- USOO5321 171A

United States Patent (19) 11. Patent Number: 5,321,171

Morimoto et al. (45) Date of Patent: Jun. 14, 1994
54 METHOD FOR PRODUCING METHYL (56) References Cited
CHELORIDE U.S. PATENT DOCUMENTS
75 Inventors: Takeshi Morimoto; Shinsuke 3,872,175 3/1975 Robota et al. .
Morikawa; Hirokazu Takagi; Naoki OTHER PUBLICATIONS
Yoshida, all of Yokohama, Japan Chemical Abstracts, vol. 102, No. 9, Mar. 4, 1985,
73) Assignee: Asahi Glass Company Ltd., Tokyo, AN-78351j, p. 552, JP-A-59 184139, Oct. 19, 1984.
Japan Chemical Abstracts, vol. 86, No. 25, Jun. 20, 1977,
AN-189178d, p. 546, JP-A-7 705 702, Jan. 17, 1977.
(21) Appl. No.: 77,765 Primary Examiner-Howard T. Mars
Attorney, Agent, or Firm-Oblon, Spivak, McClelland,
22 Filed: Jun. 18, 1993 Maier & Neustadt
57 ABSTRACT
(30) Foreign Application Priority Data A method for producing methyl chloride, which com
Jun. 19, 1992 (JP) Japan .................................. 4-186344 prises reacting methanol and hydrogen chloride in a gas
Jun. 30, 1992 JP Japan .................................. 4-95560 phase in the presence of a catalyst, wherein a zirconium
Mar. 30, 1993 JP Japan .................................. 5-095,577 oxide catalyst or a composite catalyst comprising at
least two oxides of metals selected from the group con
51) Int. Cli.............................................. CO7C 17/16 sisting of Zr, Ti and Al, is used as the catalyst.
(52) U.S.C. .................................................... 570/258
58) Field of Search ......................................... 570/258 6 Claims, No Drawings
 5,321,171
1. 2
As the zirconium oxide, an oxide of tetravalent zirco
METHOD FOR PRODUCING METHYL nium (hereinafter referred to as zirconia) is usually em
CHELORIDE ployed, and the specific surface area is preferably at
least 10 m2/g, more preferably at least 50 m/g. The
The present invention relates to a method for produc titanium oxide may, for example, be an oxide of bivalent
ing methyl chloride which comprises reacting methanol titanium, trivalent titanium or tetravalent titanium, but
and hydrogen chloride in a gas phase in the presence of an oxide of tetravalent titanium (hereinafter referred to
a novel catalyst. as titania) is usually preferably employed. The titania is
Methyl chloride is widely recognized to be useful as preferably the one having a specific surface area of at
a starting material for silicone, butyl rubber, methyl 10 least 10 m2/g, more preferably at least 50 m2/g. As the
cellulose, chloroform, carbon tetrachloride or the like. aluminum oxide, an oxide of trivalent aluminum (here
However, no industrially satisfactory method for its inafter referred to as alumina) is usually employed, and
production has not yet been known. particularly preferred is y-alumina. The specific surface
Heretofore, as a method for producing methyl chlo area of the alumina is preferably at least 10 m2/g, more
ride, a method by means of a gas phase chlorination 15 preferably at least 50 m2/g.
reaction of methane or a method by means of a liquid In the present invention, the zirconium oxide catalyst
phase hydrochlorination reaction of methanol using a may be used alone, or a complex oxide catalyst having
Friedel Crafts catalyst such as a metal halide as the two or three types of metal oxides selected from the
catalyst, has been known. Further, a method is also above-mentioned three types of specific metal oxides,
known wherein methanol and hydrogen chloride are may be used. Specifically, a combination of zirconium
reacted in a gas phase in the presence of an alumina oxide-titanium oxide, zirconium oxide-aluminum oxide,
catalyst (Japanese Examined Patent Publications No. titanium oxide-aluminum oxide or zirconium oxide
15733/1982 and No. 30248/1973). titanium oxide-aluminum oxide) may, for example, be
However, the above conventional methods have var mentioned. The mixing ratio of these three types of
ious drawbacks, respectively. 25 specific metal oxides is not particularly limited and can
Namely, the method of the gas phase chlorination of be changed within a wide range. However, if aluminum
methane requires a large installation, and simulta oxide is too much, the effects of the present invention
neously produces methylene chloride, chloroform, car tend to be hardly observed. Accordingly, it is usually
bon tetrachloride, etc. as by-products. Accordingly, 30 preferred to use aluminum oxide in an amount of not
separation of such by-products and purification are higher than 95 wt %, preferably not higher than 80 wt
%.
required. Thus, an extremely complex operation is re In the present invention, it is possible to use a catalyst
quired, and the reaction temperature is high, whereby a having an oxide of at least one metal selected from the
side reaction such as formation of carbon is likely to group consisting of zinc, copper, manganese, cobalt,
occur, and selectivity for methyl chloride is very low. 35 chromium, iron and nickel incorporated to the above
On the other hand, the method of the liquid phase mentioned zirconium oxide catalyst or to the complex
hydrochlorination reaction of methanol has difficulties oxide catalyst. The starting material for such an addi
such that deterioration of the catalyst is remarkable tional metal oxide may be in any chemical form. For
since water is present in the system, conversion of the example, it is possible to employ a nitrate, a hydrochlo
methanol is low, the reaction rate is low, and selectivity ride, a carbonate, an acetate, a hydroxide, a complex
for methyl chloride is low since a side reaction such as salt or an alkoxide of such a metal element. A solution
formation of dimethyl ether is likely to occur. Thus, can be prepared by a preparation method suitable to the
such a method is not suitable as a method for industrial chemical form of the starting material. However, it is
application. preferred to employ a nitrate or an acetate as the start
Further, the method of reacting methanol and hydro 45 ing material, since it is thereby possible to secure a good
gen chloride in a gas phase in the presence of an alumina solubility in a solvent, a good dispersibility of the addi
catalyst, requires a high temperature reaction to attain a tional metal oxide and a good pyrolytic property during
high degree of conversion of methanol and, as such, is calcination. Such metal salts may be used in combina
disadvantageous from the viewpoint of e.g. the durabil tion as a mixture of two or more, if desired.
ity of the catalyst or the control of decomposition of 50 There is no particular restriction as to the manner of
methyl chloride. incorporating such an additional metal oxide to the
The object of the present invention is to solve the zirconium oxide catalyst or to the complex oxide cata
above described problems and to provide a means to lyst, and any method which is commonly used for the
accomplish a high methanol conversion and selectivity preparation of a catalyst, such as an impregnation
for methyl chloride even by a low temperature reaction 55 method, a coprecipitation method or a kneading
(for example, at a reaction temperature of from about method, may be employed. Namely, an impregnation
200 to 250 C.) in a method for producing methyl chlo method may be employed wherein a solution having a
ride by reacting methanol and hydrogen chloride in a salt of the additional metal dissolved in water or in an
gas phase. organic solvent such as methanol, ethanol or acetone,
The present invention provides anew a method for preferably a solution having such a salt dissolved in
producing methyl chloride, which comprises reacting water, is impregnated to the zirconium oxide catalyst or
methanol and hydrogen chloride in a gas phase in the to the complex oxide catalyst, followed by drying. Oth
presence of a catalyst, wherein a zirconium oxide cata erwise, a coprecipitation method may be employed
lyst or a composite catalyst comprising at least two wherein salts of metal sources of the above-mentioned
oxides of metals selected from the group consisting of 65 specific metal oxides and a metal source of the addi
Zr, Ti and Al, is used as the catalyst. tional metal oxide are dissolved in water or in an or
Now, the present invention will be described in detail ganic solvent such as an alcohol and then co
with reference to the preferred embodiments. precipitated with a neutralizing agent such as aqueous
 5,321,171
3 4.
ammonia or sodium carbonate, followed by washing, temperature for desorption of ammonia is usually pref
filtration and then drying. erably at least 100 C.
The amount of the additional metal oxide incorpo The starting material for the component (ZnO) as the
rated to or supported on the zirconium oxide catalyst or active component may be in any chemical form. For
the complex oxide catalyst is selected within a range of 5 example, it is possible to employ a nitrate, a hydrochlo
from 1 to 20 wt %. However, an amount of from 3 to 15 ride, an acetate, a hydroxide or a complex salt. A solu
wt % is preferred from the viewpoint of the effects. tion is prepared by a preparation method suitable for the
In the present invention, it is preferred to employ a chemical form of the starting material. However, it is
catalyst prepared by dispersing an oxide of Zn as a first usually preferred to employ a nitrate or an acetate as the
component in an oxide of at least one metal selected 10 starting material, since it is thereby possible to secure a
from the group consisting of Zr and Ti, or in a complex good solubility in a solvent, a good dispersibility on a
oxide comprising at least two oxides of metals selected support and a good pyrolytic property during calcina
from the group consisting of Zr, Ti and Al, as a second tion. Such a metal salt is dissolved in water or in an
component. organic solvent such as methanol, ethanol or acetone,
The surface of the first component (ZnO) as the ac 15 preferably in water, and the solution thereby obtained is
tive component dispersed in the specific metal oxide as impregnated to the second component (specific metal
the second component, will be chlorinated by HCl in oxides) as the support, followed by drying to obtain a
the feed gas and thus will serve as active sites. The catalyst. Catalysts prepared by a coprecipitation
higher the active component dispersed in the catalyst, method show even higher activities than those obtained
the higher the catalytic activities. Catalysts containing 20 by the impregnation method, since the first component
the first component and the second component all show as the active component can thereby be highly and
a high degree of conversion of feed material and selec stably dispersed in the catalyst.
tivity for methyl chloride at the initial stage, but some Also in the coprecipitation method, the starting mate
catalysts having strong surface acidity exhibit a ten 25 rial salts for the first component and the second compo
dency such that the catalytic activities decrease with nent may be in any chemical forms. For example, ni
time. As a result of the analysis, it has been found that trates, hydrochlorides, carbonates, acetates, hydrox
coke precipitates due to condensation or thermal de ides, complex salts or alkoxides of these metal elements
composition of the feed material methanol or the prod may be employed. A starting material salt solution is
uct by the action of the strongly acidic sites of the cata 30 prepared by a preparation method suitable to the chemi
lyst, and it is believed that due to the precipitation of cal forms of the starting materials. However, it is partic
coke, clogging of pores of the catalyst and a decrease of ularly preferred to use nitrates or acetates as the starting
the surface area result, thus leading to a deterioration of materials, since it is thereby possible to secure good
the catalytic activities. solubilities in a solvent, good dispersibilities of the cata
lyst components and good pyrolytic properties during
The surface acidity of the catalyst can be measured as
by an ammonia TPD method (a temperature pro calcination. Salts of the specific metals may be used in
combination as a mixture of two or more of them, if
grammed desorption method). The ammonia TPD desired.
method is a method wherein ammonia is chemically Such metal salts are dissolved in water or in an or
adsorbed to the acid sites of the catalyst at a predeter ganic solvent such as an alcohol, preferably in water,
mined temperature, and then the temperature is raised, 40 and if necessary, an acid or an alkali is added to adjust
whereupon the amount of desorbed ammonia is mea the pH, to obtain a starting material salt solution having
sured, and from the peak temperature for desorption of metal elements adjusted to a predetermined composi
ammonia, the acidity is measured. The stronger the tional ratio. This starting material salt solution and a
surface acidity of the catalyst, the more strongly ammo precipitating agent such as aqueous ammonia or sodium
nia is chemically adsorbed to the acid sites of the cata 45 carbonate are simultaneously gradually dropwise added
lyst and the higher the peak temperature for the desorp under stirring to a buffer solution employing e.g. ammo
tion of ammonia. In the measuring operation by this nium nitrate, to form a co-precipitated gel. The condi
method, 150 mg of the catalyst is first heated at 500 C. tions for formation of the coprecipitated gel, such as the
for one hour in a He stream of 50 cm3/min for pretreat pH, the temperature, the concentration of the starting
ment. Then, 4% NH3/He is passed therethrough at 100' 50 material salt solution and the rate of its addition are
C. at a rate of 50 cm/min for one hour to adsorb ammo selected to be suitable for the chemical forms of the
nia on the catalyst. Then, He is passed therethrough at starting material salts. Further, by controlling these
the same temperature at a rate of 50 cm/min for one conditions, it is possible to obtain a catalyst having a
hour to remove ammonia physically adsorbed on the desired surface area, particle size and pore size distribu
catalyst. Then, the temperature is raised at a rate of 10 55 tion. The gel thus obtained may be aged, as the case
C./min in a He stream of 50 cm/min to desorb the requires, followed by washing with water and then
ammonia chemically adsorbed to the acid sites, where drying. Incorporation of a catalyst component which
upon the liberated amount is measured by TCD (a ther does not form precipitates by the coprecipitation opera
mal conductivity detector). tion, can be conducted by e.g. an impregnation method
By this method, the acidities of various catalysts were or a kneading method in a suitable form such as a pow
measured, whereby it has been confirmed that with der form after drying the coprecipitated gel.
catalysts having relatively weak acidities whereby the The amount of incorporation of the first component
peak temperature for desorption of ammonia by the in the catalyst thus prepared by the above method, is
above-mentioned ammonia TPD method is not higher selected within a range of from 0.01 to 20 wt %. How
than 350° C., preferably not higher than 300 C., no 65 ever, in the impregnation method, the amount is prefer
substantial deterioration occurs even when a continuous ably from 3 to 15 wt %, and in the coprecipitation
operation is conducted for at least 2,000 hours, and the method, the amount is preferably from 0.1 to 15 wt %,
durability has been substantially improved. The peak from the viewpoint of economy and effects.
 5,321,171
5 6
The catalyst of the present invention may further Further, with respect to the molar ratio of hydrogen
contain other additive components in addition to the chloride to methanol (HCl/CH3OH ratio), either one
first component and the second component. For exam may be in excess. However, if methanol is in large ex
ple, as an acidity suppressing component, an oxide of at cess, the conversion of hydrogen chloride tends to be
least one metal selected from the group consisting of 5 low. Therefore, the HC1/CH3OH molar ratio is prefera
alkali metals, alkaline earth metals and rare earth metals, bly from 1.0 to 1.5 for an industrial operation. Further,
may be added. Such an oxide may, for example, be an the space velocity (SV) in the reactor is preferably from
oxide of e.g. magnesium, sodium, potassium, calcium, 200 to 10,000 h-1, preferably from 300 to 3,000 h-1.
cerium, lithium or yttrium. The amount of such acidity The reaction product is usually separated from the non
suppressing component to be incorporated or supported O reacted substance and collected by a conventional
is preferably from 0.1 to 5 wt %, more preferably from method.
0.5 to 3 wt %, from the viewpoint of effects. The catalyst to be used in the present invention has
The catalyst to be used in the present invention may high catalytic activities as compared with a conven
be subjected to calcination, if desired, after drying. As 15
tional catalyst such as alumina, whereby the reaction
the calcination conditions, a temperature of from 300' can be conducted at a lower temperature, and there will
to 700 C., preferably from 400 to 600 C. and a time of be merits such that the durability of the catalyst in
from 1 to 20 hours, preferably from 2 to 10 hours, may creases, and decomposition of methyl chloride will
be employed. However, such conditions are not partic decrease. Further, the catalyst can be used in the form
ularly limited. The shape or the like of the catalyst may 20 of spherical particles, whereby the pressure difference
be the one commonly known in the art. For example, between before and after the catalyst bed during the
the catalyst may be pelletized and used in various continuous operation, can be small. Accordingly, the
shapes. power required to supply the gas to the catalytic bed
In the present invention, it is possible to produce can be saved.
methyl chloride at a low cost by using by-product hy 25 Now, the present invention will be described in fur
drogen chloride containing hydrogen fluoride or the ther detail with reference to Examples. However, it
like produced as a by-product by the fluorination reac
tion of a compound instead of expensive synthesized should be understood that the present invention is by no
means restricted by such specific Examples.
hydrogen chloride. Accordingly, the present invention
provides an effective and efficient method of utilizing EXAMPLE 1.
by-product hydrogen chloride containing hydrogen 30 Commercially available zirconia powder (specific
fluoride, which used to have a very limited use and surface area: 100 m2/g) was calcined in an electric fur
which used to require a substantial cost for fluorine nace at 500 C. for three hours, and the calcined prod
removing treatment. uct was press-molded under a gauge pressure of 120
The concentration of hydrogen fluoride in the hydro 35 kg/cm2, followed by pulverization and classification
gen chloride is preferably less than 10% from the view with sieves to obtain a catalyst having a particle size of
point of the safety and the durability of the apparatus. from 10 to 20 mesh.6 ml of this catalyst was packed into
The by-product hydrogen chloride containing hydro a glass reactor having an inner diameter of 14 mm and
gen fluoride may, for example, be hydrogen chloride heated to a predetermined temperature, whereupon a
produced in a large amount as a by-product during the 40 reaction was conducted by supplying methanol and
production of a fluorinated hydrocarbon, or a fluori hydrogen chloride in a molar ratio of
nated and chlorinated hydrocarbon, by fluorinating a HCl/CH3OH = 1.4 at a space velocity SV = 2,200 h-1.
chlorinated hydrocarbon. Such a by-product hydrogen The results are shown in Table 1.
chloride usually contains from 10 ppm to a few % of
hydrogen fluoride. 45 TABLE 1
The reaction system, the reaction apparatus, the reac Reaction Conversion Selectivity for
tion conditions, etc. are not particularly limited so long temperature of methanol methyl chloride
as the reaction can be conducted in a gas phase by (C) (mol%) (mol%)
means of the catalyst. For example, a fixed bed system 200 0. 93.5
or a fluidized bed system can usually be employed. In a 50 250
300
15.8
57.2
94.3
97.5
case where methanol and hydrogen chloride are re 300 84.2 98.5
acted in a gas phase by using the above described cata
lyst, the reaction can be conducted under atmospheric
pressure or under elevated pressure (at a level of from 2 EXAMPLE 2
to 5 atm). On the other hand, the reaction temperature 55
may be at least the temperature (108 C.) at which hy Commercially available zirconia powder (specific
drochloric acid undergoes condensation. However, the surface area: 80 m2/g) was immersed into an aqueous
reaction is preferably conducted at a temperature of at zinc nitrate solution and then dried at 120 C. for 10
least 120' C. from the viewpoint of the reactivity and hours. Then, it was calcined at 500 C. for 4 hours so
the selectivity. Otherwise, the reaction rate tends to be that zinc oxide was supported thereon in an amount of
slow, whereby the yield will be low. Further, the 10 wt %. This material was press-molded under a gauge
amount of dimethyl ether to be produced as a by-pro pressure of 150 kg/cm, followed by pulverization and
duct, will increase. Further, a non-reacted substance classification with sieves to obtain a test catalyst having
and water produced as a by-product by the reaction of a particle size of from 7 to 15 mesh. 6 ml of this catalyst
methanol and hydrogen chloride, tend to remain in the was packed into a glass reactor having an inner diame
reaction system, and they tend to adversely affect the ter of 14 mm and heated to a predetermined tempera
catalyst, or the reaction apparatus will substantially be ture. A reaction was conducted by supplying methanol
corroded. and hydrogen chloride thereto in a molar ratio of
 5,321,171
7 8
HCl/CH3OH = 1.3 at a space velocity SV=2,500 h. manganese nitrate solution, then dried at 100 C. for 12
The results are shown in Table 2. hours and then calcined at 550° C. for 4 hours so that
TABLE 2 manganese oxide was supported thereon in an amount
Reaction Conversion Selectivity for 5 of 9 wt %. The product was press-molded under a
temperature of methanol methyl chloride gauge pressure of 130 kg/cm2, followed by pulveriza
(C) (mol%) (mol%) tion and classification with sieves to obtain a test cata
200
250
98.5
100.0
99.8
100.0
lyst having a particle size of from 10 to 20 mesh. 6 ml of
300 100.0 100.0 this catalyst was packed into a glass reactor having an
3S0 100.0 000 10 inner diameter of 14 mm and heated to a predetermined
temperature, and then a reaction was conducted by
supplying hydrogen chloride and methanol in a molar
EXAMPLE 3 ratio of HCl/CH3OH = 1.4 at a space velocity
Commercially available zirconia powder (specific SV=2,300 h-1. The results are shown in Table 5.
surface area: 80 m2/g) was immersed into an aqueous 15 TABLE 5
chromium acetate solution and then dried at 120' C. for Reaction Conversion Selectivity for
6 hours. Then, the dried product was calcined at 450° C. temperature of methanol methyl chloride
for 4 hours so that chromium oxide was supported ("C) (mol%) (mol%)
thereon in an amount of 9 wt %. The product was press 200 20.3 98.0
molded under a gauge pressure of 130 kg/cm, followed 20 250 98. 99.6
by pulverization and classification with sieves to obtain 300 100.0 100.0
a test catalyst having a particle size of from 10 to 20 350 000 99.9
mesh. 6 ml of this catalyst was packed into a glass reac
tor having an inner diameter of 14 mm and heated to a
predetermined temperature. A reaction was conducted 25 EXAMPLE 6
by supplying methanol and hydrogen chloride in a Commercially available zirconia powder (specific
molar ratio of HCl/CH3OH = 1.4 at a space velocity surface area: 80 m2/g) was immersed in an aqueous
SV = 2,200 hl. The results are shown in Table 3. cobalt nitrate solution and then dried at 110' C. for 8
TABLE 3 hours. Then, it was calcined at 500 C. for 4 hours so
Reaction
temperature
Conversion
of methanol
Selectivity for
methyl chloride
30 that cobalt oxide was supported thereon in an amount of
(C.) (mol%) (mol%)
9 wt %. The product was press-molded under a gauge
200 95.3 99.3
pressure of 120 kg/cm2, followed by pulverization and
250 98.2 99.7 classification with sieves to obtain a test catalyst having
300 99.9 99.9 a particle size of from 10 to 20 mesh.6 ml of this catalyst
35
350 100.0 99.9 was packed into a glass reactor having an inner diame
ter of 14 mm and heated to a predetermined tempera
ture. Then, a reaction was conducted by supplying
EXAMPLE 4 methanol and hydrogen chloride in a molar ratio of
Commercially available zirconia powder (specific 40 HC/CH3OH = 1.3 at a space velocity SV=2,500 hl.
surface area: 100 m2/g) was immersed in an aqueous The results are shown in Table 6.
copper acetate solution. The powder was dried at 110 TABLE 6
C. for 9 hours, and then calcined at 500 C. for 3 hours Reaction Conversion Selectivity for
so that copper oxide was supported thereon in an temperature of methanol methyl chloride
amount of 11 wt %. The product was press-molded 45 ("C.) (mol%) (mol%)
under a gauge pressure of 140 kg/cm2, followed by 200 18.2 98.0
pulverization and classification with sieves to obtain a 250 95.8 99.2
test catalyst having a particle size of from 7 to 15 mesh. 300 99.5 99.4
6 ml of this catalyst was packed into a glass reactor 350 100.0 100.0
having an inner diameter of 14 mm and heated to a 50
predetermined temperature. Then, a reaction was con
ducted by supplying thereto methanol and hydrogen EXAMPLE 7
chloride in a molar ratio of HCl/CH3OH = 1.3 at a
space velocity SV = 2,500 hl. The results are shown in surface area: 100 m2/g) waszirconia
Commercially available powder (specific
immersed in an aqueous
Table 4. 55
TABLE 4
iron nitrate solution. This powder was dried at 110' C.
for 12 hours and then calcined at 600 C. for two hours
Reaction Conversion Selectivity for so that iron oxide was supported thereon in an amount
temperature of methanol methyl chloride
(C.) (mol%) (mol%) of 10 wt %. The product was press-molded under a
200 15.3 98.0 60 gauge pressure of 150 kg/cm, followed by pulveriza
250 90.3 99.8 tion and classification with sieves to obtain a test cata
300
350
99.2
100.0
99.9
99.8
lyst having a particle size of from 7 to 15 mesh. 6 ml of
this catalyst was packed into a glass reactor having an
inner diameter of 14 mm and heated to a predetermined
EXAMPLE 5
65 temperature. Then, a reaction was conducted by sup
plying methanol and hydrogen chloride thereto in a
Commercially available zirconia powder (specific molar ratio of HCl/CH3OH = 1.5 at a space velocity
surface area: 100 m2/g) was immersed in an aqueous SV = 2,500 hl. The results are shown in Table 7.
 5,321,171
9 10
TABLE 7 TABLE 9-continued
Reaction Conversion Selectivity for Reaction Conversion Selectivity for
temperature of methanol methyl chloride temperature of methanol methyl chloride
("C) (mol%) (mol %) (C) (mol%) (mol %)
200 70,2 99.0 5 350 100.0 100.0
250 98.3 99.7
300 100,0 99.9
350 100.0 99.9
EXAMPLE 10
O Using zinc chloride as the zinc source and zirconium
EXAMPLE 8 oxychloride as the zirconium source, a mixed aqueous
Commercially available zirconia powder (specific solution was prepared so that the molar ratio of
surface area: 100 m/g) was immersed in an aqueous Zn/Zr=0.01/1. This mixed aqueous solution and 10%
nickel acetate solution. The powder was dried at 120 aqueous ammonia were gradually dropwise added to
C. for 6 hours and then calcined at 500° C. for 3 hours water under stirring to maintain pH=8, to form a co
so that nickel oxide was supported thereon in an amount precipitated gel. The gel was left to stand still for one
of 11 wt %. The product was press-molded under a day and then subjected to washing with water and fil
gauge pressure of 120 kg/cm2, followed by pulveriza tration, and it was dried at 120' C. for 15 hours. The
tion and classification with sieves to obtain a test cata product was further pulverized and calcined at 550 C.
lyst having a particle size of from 10 to 20 mesh. 6 ml of 20 for 8 hours to obtain a complex oxide catalyst of
this catalyst was packed into a glass reactor having an ZnO-ZrO2. This complex oxide catalyst had a ZnO
inner diameter of 14 mm and heated to a predetermined content of 0.6 wt % and a specific surface area of 90
temperature. Then, a reaction was conducted by sup m2/g. Then, this catalyst was press-molded under a
plying methanol and hydrogen chloride thereto in a 25 gauge pressure of 140 kg/cm, followed by pulveriza
molar ratio of HC1/CH3OH = 1.4 at a space velocity tion and classification with sieves to obtain a test cata
SV=2,300 h-1. The results are shown in Table 8. lyst having a particle size of from 7 to 15 mesh. 6 ml of
TABLE 8 this catalyst was packed into a glass reactor having an
Reaction Conversion Selectivity for inner diameter of 14 mm and heated to a predetermined
temperature of methanol methyl chloride 30 temperature. Then, a reaction was conducted by sup
("C.) (mol%) (mol%) plying methanol and hydrogen chloride thereto in a
200
250
85.3
99.9
98.9
99.8
molar ratio of HCl/CH3OH = 1.5 at a space velocity
300 100.0 100.0
SV= 1,800 hl. The results are shown in Table 10.
350 100.0 100.0 TABLE 10
35
Reaction Conversion Selectivity for
temperature of methanol methyl chloride
EXAMPLE 9 ("C) (mol%) (mol %)
200 99.8 99.9
Using zinc nitrate as the zinc source and zirconium 250 000 100.0
oxynitrate as the zirconium source, a mixed aqueous 40 300 100.0 100.0
solution was prepared so that the molar ratio of 350 100.0 100.0
Zn/Zr=0.1/1. This mixed aqueous solution and 10%
aqueous ammonia was gradually dropwise added to
water under stirring to maintain pH=8, to form a co EXAMPLE 11
precipitated gel. The gel was left to stand still for one 45
day and then subjected to washing with water and fil Using chromium nitrate as the chromium source and
tration, and it was dried at 110' C. for 20 hours. Thezirconium oxychloride as the zirconium source, a mixed
product was further pulverized and calcined at 500 C. aqueous solution was prepared so that the molar ratio of
for 10 hours to obtain a complex oxide catalyst of Cr/Zr=0.1/1. This mixed aqueous solution and 10%
ZnO-ZrO2. This complex oxide catalyst had a ZnO 50 aqueous ammonia were gradually dropwise added to
content of 6.2 wt % and a specific surface area of 95 water under stirring to maintain pH=8, to form a co
m2/g. Then, this catalyst was press-molded under a precipitated gel. The gel was left to stand still for one
gauge pressure of 150 kg/cm2, followed by pulveriza day and then subjected to washing with water and fil
tion and classification with sieves to obtain a test cata tration, and it was dried at 100' C. for 20 hours. The
lyst having a particle size of from 10 to 20 mesh. 6 ml of 55 product was further pulverized and calcined at 500' C.
this catalyst was packed into a glass reactor having an for 8 hours to obtain a complex oxide catalyst of Cr2O
inner diameter of 14 mm and heated to a predetermined 3-ZrO2. This complex oxide catalyst had a Cr2O3 con
temperature. Then, a reaction was conducted by sup tent of 11.0 wt % and a specific surface area of 85 m2/g.
plying methanol and hydrogen chloride thereto in a Then, this catalyst was press-molded under a gauge
molar ratio of HCl/CH3OH = 1.5 at a space velocity 60 pressure of 150 kg/cm, followed by pulverization and
SV=2,000 hl. The results are shown in Table 9. classification with sieves to obtain a test catalyst having
TABLE 9 a particle size of from 10 to 20 mesh.6 ml of this catalyst
Reaction Conversion Selectivity for
was packed into a glass reactor having an inner diame
temperature of methanol methyl chloride ter of 14 mm and heated to a predetermined tempera
("C) (mol%) (mol%) 65 ture. Then, a reaction was conducted by supplying
200 99.8 99.9 methanol and hydrogen chloride thereto in a molar
250 00.0 100.0 ratio of HCl/CH3OH = 1.6 at a space velocity
300 100.0 100.0 SV = 2,200 hl. The results are shown in Table 11.
 5,321,171
11 12
TABLE TABLE 13-continued
Reaction Conversion Selectivity for Reaction Conversion Selectivity for
temperature of methanol methyl chloride temperature of methanol methyl chloride
("C) (mol%) (mol%) ("C.) (mol%) (mol %)
200 95.5 99.5 5 activi- 250 100.0 000
250 98.5 99.7 ties 300 100.0 000
300 1000 99.9 350 100.0 100.0
350 1000 99.9 After 200 98.8 99.8
2,000
10 - he
COMPARATIVE EXAMPLE 1.
Commercially available y-alumina powder (specific EXAMPLE 13
surface area: 140 m2/g) was calcined at 500 C. for 4 Using zirconium oxychloride as the zirconium source
hours in an electric furnace. The powder was then
press-molded under a gauge pressure of 120 kg/cm2, 5 and titanium isopropoxide as the titanium source, a
mixed aqueous solution was prepared so that the molar
followed by pulverization and classification with sieves ratio of Zr/Tis- 1.5. This solution and 10% aqueous
to obtain a test catalyst having a particle size of from 10 ammonia were gradually dropwise added to water
to 20 mesh. 6 ml of this catalyst was packed into a glass under stirring
reactor having an inner diameter of 14 mm and heated to maintain pH=7, to form a coprecipi
to a predetermined temperature. Then, a reaction was 0 then
tated gel. This gel was left to stand still for one day and
conducted by supplying methanol and hydrogen chlo it wassubjected
dried at
to washing with water and filtration, and
100° C. for 20 hours. The product was
ride thereto in a molar ratio of HC/CH3OH = 1.3 at a
space velocity SV = 2,000 hl. The results are shown in further pulverized and calcined at 550° C. for 5 hours to
obtain a complex oxide catalyst of ZrO2-TiO2. The
Table 12.
25 obtained ZrO2 complex oxide catalyst had a specific
TABLE 12 surface area of 96 m2/g. This complex oxide catalyst
Reaction
temperature
Conversion
of methanol
Selectivity for
methyl chloride
was immersed in an aqueous zinc nitrate solution and
("C) (mol%) (mol%)
then dried at 110' C. for 12 hours. Then, it was calcined
200 15.8 98.3 30
at 500 C. for 4 hours so that zinc oxide was supported
250 77.5 99.1 thereon in an amount of 10 wt %. Then, the product
300 96.3 99.8 was press-molded under a gauge pressure of 140
350 99.8 99.8 kg/cm2, followed by pulverization and classification
with sieves to obtain a test catalyst having a particle size
of from 7 to 15 mesh. 6 ml of this catalyst was packed
EXAMPLE 2 35 into a glass reactor having an inner diameter of 14 mm
Using zirconium oxynitrate as the zirconium source and heated to a predetermined temperature. Then, a
and aluminum nitrate as the aluminum source, a mixed reaction was conducted by supplying methanol and
hydrogen chloride thereto in a molar ratio of
aqueous solution was prepared so that the molar ratio of HCl/CH3OHs 1.4 at a space velocity SV=2,300 h-l.
Zr/Al=2. This mixed aqueous solution and 10% aque 40
ous ammonia were gradually dropwise added to water The results are shown in Table 14.
under stirring to maintain pH=8, to form a coprecipi TABLE 14
tated gel. The gel was left to stand still for one day and Reaction Conversion Selectivity for
then subjected to washing with water and filtration, and temperature of methanol methyl chloride
it was dried at 110° C. for 20 hours. The product was 45 (C) (mol%) (mol%)
further pulverized and then calcined at 500 C. for 6 Initial 200 98.9 99.9
hours to obtain a complex oxide catalyst of ZrO2-Al activi-
ties
250
300
100.0
100.0
100.0
OO.O
2O3. This complex oxide catalyst had a specific surface 350 100.0 000
area of 95 m2/g. This ZrO2-Al2O3 complex oxide After 200 98.9 99.8
catalyst was immersed in an aqueous zinc acetate solu SO 2,000
tion and then dried at 100° C. for 15 hours. Then, it was hrs
calcined at calcined at 550 C. for 3 hours so that zinc
oxide was supported thereon in an amount of 11 wt %.
Then, this product was press-molded under a gauge EXAMPLE 1.4
pressure of 130 kg/cm2, followed by pulverization and 55 Using titanium chloride as the titanium source and
classification with sieves to obtain a test catalyst having aluminum nitrate as the aluminum source, a mixed aque
a particle size of from 10 to 20 mesh. 6 ml of this catalyst ous solution was prepared so that the molar ratio of
was packed into a glass reactor having an inner diame Al/Ti=1 and adjusted to pH=0.9 with hydrochloric
ter of 14 mm and heated to a predetermined tempera acid. This solution and 10% aqueous ammonia were
ture. Then, a reaction was conducted by supplying gradually dropwise added to water under stirring to
methanol and hydrogen chloride thereto in a molar adjust pH=8, to form a coprecipitated gel. The gel was
ratio of HC1/CH3OH = 1.5 at a space velocity left to standstill for one day and then subjected to wash
SV= 1,600 hl. The results are shown in Table 13. ing with water and filtration, and it was dried at 100 C.
TABLE 13 for 20 hours. The product was further pulverized and
Reaction Conversion Selectivity for 65 then calcined at 500 C. for 6 hours to obtain a complex
temperature of methanol methyl chloride oxide catalyst of Al2O3-TiO2. The obtained complex
(C.) (mol%) (mol%) oxide catalyst had a specific surface area of 85 m2/g.
initial 200 98.7 99.9 The complex oxide catalyst was immersed in an aque
 5,321,171
13 14
ous zinc acetate solution and then dried at 110 C. for 10 solution and 10% aqueous ammonia were gradually
hours. Then, it was calcined at 500 C. for 3 hours so dropwise added to water under stirring to maintain
that zinc oxide was supported thereon in an amount of pH=8, to form a coprecipitated gel. The gel was left to
9 wt %. Then, the product was press-molded under a stand still for one day and then subjected to washing
gauge pressure of 130 kg/cm2, followed by pulveriza 5 with water and filtration, and then it was dried at 100
tion and classification with sieves to obtain a test cata C. for 24 hours. The product was further pulverized and
lyst having a particle size of from 10 to 20 mesh. 6 ml of then calcined at 500 C. for 6 hours to obtain a complex
this catalyst was packed into a glass reactor having an oxide catalyst of ZnO-ZrO2-TiO2. This complex
inner diameter of 14 mm and heated to a predetermined oxide catalyst had a specific surface area of 70 m/g.
temperature. Then, a reaction was conducted by sup 10 Then, this catalyst was press-molded under a gauge
plying methanol and hydrogen chloride thereto in a pressure of 120 kg/cm2, followed by pulverization and
molar ratio of HC1/CH3OH = 1.5 at a space velocity classification with sieves to obtain a test catalyst having
SV=2,100 hl. The results are shown in Table 15. a particle size of from 7 to 15 mesh. 6 ml of this catalyst
TABLE 1.5 was packed into a glass reactor having an inner diame
Reaction Conversion Selectivity for 15 ter of 14 mm and heated to a predetermined tempera
temperature of methanol methyl chloride ture. Then, a reaction was conducted by supplying
(C.) (mol %) (mol%) methanol and hydrogen chloride thereto in a molar
Initial
activi-
200
250
98.8
100.0
99.8
100.0
ratio of HCl/CH3OH = 1.4 at a space velocity
ties 300 000 100.0
SV=2,300 hl. The results are shown in Table 17.
20
350 100.0 100.0 TABLE 17
After 200 98.7 99.7
1,000 Reaction Conversion Selectivity for
hrs temperature of methanol methyl chloride
(C) (mol%) (mol%)
25 Initial 200 99. 99.9
activi- 250 100,0 100.0
EXAMPLE 1.5 ties 300 1000 000
350 100.0 100.0
Using zinc nitrate as the zinc source, zirconium ox After 200 99.2 99.9
ynitrate as the zirconium source and aluminum nitrate 1,000
as the aluminum source, a mixed aqueous solution was 30
hrs
prepared so that the molar ratio of Zn/Zr/Al=0.3/1/1.
This solution and 10% aqueous ammonia were gradu
ally dropwise added to water under stirring to maintain EXAMPLE 17
pH=8, to form a coprecipitated gel. The gel was left to Using zirconium oxychloride as the zirconium source
stand still for one day and then subjected to washing 35 and aluminum nitrate as the aluminum source, a mixed
with water and filtration, and then it was dried at 110 aqueous solution was prepared so that the molar ratio of
C. for 20 hours. The product was further pulverized and Zr/Als= 1. This solution and 10% aqueous ammonia
then calcined at 550 C. for 6 hours to obtain a complex were gradually dropwise added to water under stirring
oxide catalyst of ZnO-ZrO2-Al2O3. The complex to maintain pH = 8, to form a coprecipitated gel. The gel
oxide catalyst had a specific surface area of 62 m2/g. was left to stand still for one day and then subjected to
Then, this catalyst was press-molded under a gauge washing with water and filtration, and then it was dried
pressure of 140 kg/cm, followed by pulverization and at 110° C. for 15 hours. The product was pulverized and
classification with sieves to obtain a test catalyst having then calcined at 500 C. for 6 hours to obtain a complex
a particle size of from 10 to 20 mesh. 6 ml of this catalyst oxide catalyst of Al2O3-ZrO2. This catalyst had a
was packed into a glass reactor having an inner diame 45 specific surface area of 95 m2/g. Then, the catalyst was
ter of 14 mm and heated to a predetermined tempera press-molded under a gauge pressure of 130 kg/cm2,
ture. Then, a reaction was conducted by supplying followed by pulverization and classification with sieves
methanol and hydrogen chloride thereto in a molar to obtain a test catalyst having a particle size of from 10
ratio of HC/CH3OH = 1.6 at a space velocity to 20 mesh, 6 ml of this catalyst was packed into a glass
SV=2,300 hl. The results are shown in Table 16. 0 reactor having an inner diameter of 14 mm and heated
TABLE 6 to a predetermined temperature. Then, a reaction was
Reaction Conversion Selectivity for conducted by supplying methanol and hydrogen chlo
temperature of methanol methyl chloride ride thereto in a molar ratio of HC/CH3OH = 1.5 at a
(C) (mol%) (mol%) space velocity SV=2,000h-l. The results are shown in
Initial 200 98.0 99.9 55 Table 8.
activi- 250 100.0 100.0
ties 300 100.0 000 TABLE 8
350 100.0 000 Reaction Conversion Selectivity for
After 200 99.1 99.9 temperature of nethanol methyl chloride
1,000 (C) (mol%) (mol%)
hrs
200 75.3 99.0
250 77.5 99.9
300 98.8 100.0
EXAMPLE 16 350 100.0 O0.0
Using zinc acetate as the zinc source, zirconium oxy
chloride as the zirconium source and titanium isopro 65
EXAMPLE 1.8
poxide as the titanium source, a mixed aqueous solution
was prepared so that the molar ratio of Zn/Zr/Ti= Using zirconium oxychloride as the zirconium source
0.25/1/1 and adjusted to pH = 1 with nitric acid. This and titanium isopropoxide as the titanium source, a
 5,321,171
15 16
mixed aqueous solution was prepared so that the molar thereon in an amount of 10 wt %. The product was
ratio of Zr/Ti=1 and adjusted to pH = 1 with nitric press-molded under a gauge pressure of 140 kg/cm,
acid. This solution and 10% aqueous ammonia were followed by pulverization and classification with sieves
gradually dropwise added to water under stirring to to obtain a test catalyst having a particle size of from 10
maintain pH=8, to form a coprecipitated gel. The gel to 20 mesh. 6 ml of this catalyst was packed into a glass
was left to stand still for one day and then subjected to reactor having an inner diameter of 14 mm and heated
washing with water and filtration, and then it was dried to a predetermined temperature. Then, a reaction was
at 100 C. for 20 hours. The product was pulverized and conducted by supplying methanol and hydrogen chlo
then calcined at 500' C. for 5 hours to obtain a complex O ride in a molar ratio of HCl/CH3OH = 1.3 at a space
oxide catalyst of TiO2-ZrO2. The obtained catalyst velocity SV=2,000 hl. The results are shown in Table
had a specific surface area of 96 m2/g. Then, the cata 21.
lyst was press-molded under a gauge pressure of 140 TABLE 21
kg/cm, followed by pulverization and classification Reaction Conversion Selectivity for
with sieves to obtain a test catalyst having a particle size 15 temperature of methanol methyl chloride
of from 7 to 15 mesh. 6 ml of this catalyst was packed ("C) (mol%) (mol%)
into a glass reactor having an inner diameter of 14 mm 200 98.8 99.8
and heated to a predetermined temperature. Then, a 250 100.0 100.0
reaction was conducted by supplying methanol and 300 100.0 100.0
hydrogen chloride thereto in a molar ratio of 20 350 100.0 100.0
HCl/CH3OH = 1.4 at a space velocity SV=2,300 h 1.
The results are shown in Table 19.
TABLE 19 COMPARATIVE EXAMPLE 2
Reaction Conversion Selectivity for 25 Commercially available y-Al2O3 powder (specific
temperature of methanol methyl chloride surface area: 140 m2/g) was calcined at 500 C. for 4
("C) (mol%) (mol%) hours in an electric furnace, and the product was press
200 20.5 98.1 molded under a gauge pressure of 150 kg/cm, followed
250 95.5 99.8 by pulverization and classification with sieves to obtain
300 97.4 100.0 30
350 100.0 100.0 a test catalyst having a particle size of from 10 to 20
mesh. 6 ml of this catalyst was packed into a glass reac
tor having an inner diameter of 14 mm and heated to a
EXAMPLE 19 predetermined temperature. Then, a reaction was con
A complex oxide catalyst of Al2O3-ZrO2 prepared 35 ducted by supplying methanol and hydrogen chloride
in a molar ratio of HCl/CH3OH = 1.4 at a space veloc
and calcined in the same manner as in Example 6, was ity SV = 2,000 hl. The results are shown in Table 22.
immersed in an aqueous zinc acetate solution and then
dried at 120° C. for 8 hours. Then, it was calcined at
500 C. for three hours so that zinc oxide was supported TABLE 22
thereon in an amount of 10 wt %. The product was Reaction Conversion Selectivity for
press-moided under a gauge pressure of 150 kg/cm2, temperature
(C.)
of methanol
(mol%)
methyl chloride
(mol%)
followed by pulverization and classification with sieves
to obtain a test catalyst having a particle size of from 10 Initial
activi-
200
250
15.8
77.5
98.3
99.1
to 20 mesh. 6 ml of this catalyst was packed into a glass 45 ties 300 96.3 99.8
reactor having an inner diameter of 14 mm and heated 350 99.8 99.9
to a predetermined temperature. Then, a reaction was After 200 10.3 97.5
conducted by supplying methanol and hydrogen chlo 200
hrs
ride in a molar ratio of
HC1/CH3OH = 1.5 at a space velocity SV=2,400 SO
hi. The results are shown in Table 20.
EXAMPLES 21 to 26
TABLE 20
Reaction Conversion Selectivity for Various test catalysts as shown in the following Table
temperature of methanol methyl chloride 55 23 was prepared in the same manner as in Example 12.
("C) (mol%) (mol%) In the column for "Test catalyst" in Table 11, metal
200 99.1 99.7 species of each complex oxide catalyst and their molar
250 100.0 00.0 ratio, and the type of the additional metal oxide are
300 000 100.0 indicated. The amount of the additional metal oxide
350 00.0 100.0
60 supported, was 10 wt %. 6 ml of such a test catalyst was
packed into a glass reactor having an inner diameter of
EXAMPLE 20
14 mm and heated to a predetermined temperature.
Then, a reaction was conducted by supplying methanol
A complex oxide catalyst of TiO2-ZrO2 prepared and hydrogen chloride in a molar ratio of
and calcined in the same manner as in Example 7, was 65 HCl/CH3OH = 1.3 at a space velocity SV = 2,000 hl.
immersed in an aqueous zinc nitrate solution and then The results are shown in Table 23. The reaction results
dried at 110' C. for 10 hours. Then, it was calcined at after 500 hours in Table 23 are the results of the reaction
500 C. for 3 hours so that zinc oxide was supported conducted at a temperature of 200° C.
 5,321,171
17 18
TABLE 23
Test catalyst Reaction result (mol%)
Metal (Upper column: CH3OH conversion,
Exam- molar Kind of Lower column: CH3C selectivity)
No. ratio additives 200 C. 250 C. 300 C. 350 C. After S00 hrs
21 Zr/Ti = 2 Copper 7.2. 85.5 99.0 100.0 20.2
oxide 98. 99.0 99.7. 99.9 98.2
22 Zr/Ti = 1 Manganese 25.2 98.5 000 100.0 26.3
oxide 98.2 99.7 00.0 99.9 98.3
23 TivA = Cobalt 23.8 96.2 99.7 100.0 23.5
oxide 98.1 99.4 99.8 100.0 97.9
24 Tival as 2 Chronium 96.0 98.5 100.0 1000 95.9
oxide 99.4 99.8 100.0 000 99.4
25 A/Zr s 1 Iron oxide 74.8 98.5 100.0 100.0 75.
- 99.0 99.8 99.9 99.9 99.1
26 AZr = 2 Nickel 88.7 99.9 000 000 88.9
oxide 99.1 99.8 99.9 00.0 99.2

EXAMPLES 27 TO 30 TABLE 25
20 Reaction Conversion Selectivity for
Various test catalysts as shown in the following Table temperature of methanol methyl chloride
24 were prepared in the same manner as in Example 12. ("C) (mol%) (mol%)
In thes column for "Test catalyst” in Table 24, metal Initi
nitial 200 96.5 99.8
species of each complex oxide catalyst and their molar activities 250 99.9 99.9
ratio, and the type of the additional metal oxide are 300 100.0 100.0
indicated. The amount of the additional metal oxide f 350 100.0 000
supported, was 10 wt %. 6 ml of such a test catalyst was S. 200 85.6 98.7
packed into a glass reactor having an inner diameter of
14 mm and heated to a predetermined temperature.
Then, a reaction was conducted by supplying methanol EXAMPLE 32
and hydrogen chloride in a molar ratio of 30
HCl/CH3OH = 1.3 at a space velocity SV=2,000 h-1. Commercially available zirconia powder (specific
The results are shown in Table 24. The reaction results surface area: 80 m2/g) was immersed in an aqueous zinc
after 500 hours in Table 24 are the results of the reaction. nitrate solution and then dried at 120° C. for 12 hours.
conducted at a temperature of 200 C. Then, the dried product was calcined at 500 C, for 3
TABLE 24
Test catalyst Reaction result (mol%)
Metal (Upper column: CH3OH conversion,
Exan- molar Kind of Lower column: CH3C selectivity)
No. ratio additives 200 C. 250 C. 300 C. 350 C. After 500 hrs
27 ZAl 3 Zinc oxide 98.5 100.0 100.0 100.0 98.7
99.9 100.0 100.0 100.0 99.9
28 AlAZr = 3 Zinc oxide 97.3 100.0 000 100.0 97.5
99.8 99.9 000 100.0 99.8
29 TimA = 3 Zinc oxide 97.5 100.0 100.0 100.0 97.7
99.9 100.0 100.0 100.0 99.9
30 Al/Ti = 3 Zinc oxide 96.2 100,0 100.0 100.0 96.3
99.6 99.9 100.0 100.0 99.5

hours so that zinc oxide was supported thereon in an

EXAMPLE 31
50 amount of 9 wt %. The product
p
was ppress-molded
under a gauge pressure of 150 kg/cm, followed by
Commercially available titania powder (specific sur pulverization and classification with sieves to obtain a
face area: 50 m/g) was immersed in an aqueous zinc test catalyst having a particle size of from 7 to 15 mesh.
acetate solution and then dried at 110 C. for 15 hours. The peak temperature for liberation of ammonia by the
Then, the dried product was calcined at 500 C. for 4. 55 ammonia TPD method was 230 C, 6 cm3 of this cata
hours so that zinc oxide was supported thereon in an lyst was packed into a glass reactor having an inner
amount of 10 wt %. The product was press-molded diameter of 14 mm and heated to a predetermined tem
under a gauge pressure of 120 kg/cm2, followed by perature. Then, a reaction was conducted by supplying
pulverization and classification with sieves to obtain a methanol and hydrogen chloride thereto in a molar
catalyst having a particle size of from 10 to 20 mesh. 60 ratio of HC1/CH3OH = 1.3 at a space velocity
The peak temperature for desorption of ammonia by the SV=2,500 h. The results are shown in Table 26.
ammonia TPD method was 330 C, 6 cm3 of this cata TABLE 26
lyst was packed into a glass reactor having an inner Reaction Conversion Selectivity for
diameter of 14 mm and heated to a predetermined tem temperature of methanol methyl chloride
perature, and a reaction was conducted by supplying 65 ("C) (mol %) (mol%)
methanol and hydrogen chloride thereto in a molar Initial 200 98.6 99.8
ratio of HCl/CH3OH = 1.4 at a space velocity activities 250 99.9 OO.O
SV=2,200 h-1. The results are shown in Table 25. 300 100.0 00.0
 5,321,171
19
TABLE 26-continued 10 wt %. Then, the product was press-molded under a
Reaction Conversion Selectivity for
gauge pressure of 140 kg/cm, followed by pulveriza
temperature of methanol methyl chloride tion and classification with sieves to obtain a test cata
(C.) (mol%) (mol%) lyst having a particle size of from 7 to 15 mesh. The
350 100.0 100.0 5 peak temperature for desorption of ammonia by the
After 200 98.6 99.7 ammonia TPD method was 200 C. 6 cm of this cata
2,000 lyst was packed into a glass reactor having an inner
hrs
diameter of 14 mm and heated to a predetermined tem
O
perature. Then, a reaction was conducted by supplying
EXAMPLE 33 methanol and hydrogen chloride thereto in a molar
ratio of HCl/CH3OH = 1.4 at a space velocity
Using zirconium oxynitrate as the zirconium source SV=2,300 h-l. The results are shown in Table 28.
and aluminum nitrate as the aluinum source, a mixed
aqueous solution was prepared so that the molar ratio of TABLE 28
Zr/Al=2. This solution and 10% aqueous ammonia 15 Reaction Conversion Selectivity for
were gradually dropwise added to water under stirring temperature of methanol methyl chloride
to maintain pH=8, to form a coprecipitated gel. The gel ("C) (mol%) (mol%)
was left to stand still for one day and then subjected to Initial 200 98.9 99.9
washing with water and filtration, and it was dried at activities 250
300
00.0
100.0
100.0
00.0
110' C. for 20 hours. The dried product was further 20 350 100.0 100.0
pulverized and then calcined at 500' C. for 6 hours to After 200 98.9 99.8
obtain a complex oxide of ZrO2-Al2O3. The obtained 2,000
powder had a specific surface area of 95 m2/g. This hrs
powder was immersed into an aqueous zinc acetate
solution and then dried at 100° C. for 15 hours. Then, 25
the dried product was calcined at 550° C. for 3 hours so EXAMPLE 35
that zinc oxide was supported thereon in an amount of Using titanium chloride as the titanium source and
11 wt %. Then, the product was press-molded under a aluminum nitrate as the aluminum source, a mixed aque
gauge pressure of 130 kg/cm, followed by pulveriza
tion and classification with sieves to obtain a test cata 30 ous solution was prepared so that the molar ratio of
lyst having a particle size of from 10 to 20 mesh. The Al/Ti=1 and adjusted to pH=0.9 with hydrochloric
peak temperature for desorption of ammonia by the acid. This solution and 10% aqueous ammonia were
ammonia TPD method was 200° C. 6 cm3 of this cata gradually dropwise added to water under stirring to
lyst was packed into a glass reactor having an inner maintain pH=8, to form a coprecipitated gel. The gel
diameter of 14 mm and heated to a predetermined tem 35 was left to stand still for one day and then subjected to
perature. Then, a reaction was conducted by supplying washing with water and filtration, and it was dried at
methanol and hydrogen chloride thereto in a molar 100° C. for 20 hours. The dried product was further
ratio of HC1/CH3OH = 1.5 at a space velocity pulverized and then calcined at 500 C. for 6 hours to
SV = 1,600 hl. The results are shown in Table 27. obtain a complex oxide of Al2O3-TiO2. The obtained
TABLE 27 40 powder had a specific surface area of 85 m2/g. This
Reaction Conversion Selectivity for powder was immersed into an aqueous zinc acetate
temperature of methanol methyl chloride solution and then dried at 110° C. for 10 hours. Then,
("C) (mol %) (mol%) the dried product was calcined at 500 C. for 3 hours so
Initia 200 98.7 99.9 that zinc oxide was supported thereon in an amount of
activities 250 100.0 100.0 45 9 wt %. Then, the product was press-molded under a
300
350
100.0
100.0
100.0
100.0
gauge pressure of 130 kg/cm2, followed by pulveriza
After 200 98.8 99.8 tion and classification with sieves to obtain a test cata
2,000 lyst having a particle size of from 10 to 20 mesh. The
hrs peak temperature for desorption of ammonia by the
50 ammonia TPD method was 200' C. 6 cm3 of this cata
EXAMPLE 34
lyst was packed into a glass reactor having an inner
diameter of 14 mm and heated to a predetermined tem
Using zirconium oxychloride as the zirconium source perature. Then, a reaction was conducted by supplying
and titanium isopropoxide as the titanium source, a methanol and hydrogen chloride thereto in a molar
mixed aqueous solution was prepared so that the molar 55 ratio of HCl/CH3OH = 1.5 at a space velocity
ratio of Zr/Ti=1.5. This solution and 10% aqueous SV=2,100 hl. The results are shown in Table 29.
ammonia were gradually dropwise added to water TABLE 29
under stirring to maintain pH=7, to form a coprecipi Reaction Conversion Selectivity for
tated gel. The gel was left to stand still for one day and temperature of methanol Inethyl chloride
then subjected to washing with water and filtration, and ("C) (mol%) (mol%)
it was dried at 100° C. for220 hours. The dried product Initial 200 98.8 99.8
was further pulverized and then calcined at 550° C. for activities 250 000 000
5 hours to obtain a complex oxide of ZrO2-TiO2. The 300 100.0 00.0
obtained powder had a specific surface area of 96 m2/g. 350 000 OO.O
This powder was immersed into an aqueous zinc nitrate 65 After 200 98.7 99.7
solution and then dried at 110° C. for 12 hours. Then, 1,000
hrs
the dried product was calcined at 500 C. for 4 hours so
that zinc oxide was supported thereon in an amount of
 5,321,171
21 22
EXAMPLE 36 TABLE 31
Reaction Conversion Selectivity for
Using zinc nitrate as the zinc source and zirconium temperature of methanol methyl chloride
oxychloride as the zirconium source, a mixed aqueous ("C) (mol%) (mol%)
solution was prepared so that the molar ratio of 5 Initial 200 98.5 99.8
Zn/Zr=0.17. This solution and 10% aqueous ammonia activities 250
300
100.0
100.0
100.0
100.0
were gradually dropwise added to water under stirring 350 100.0 100.0
to maintain pH=8, to form a coprecipitated gel. The gel After 200 98.5 99.6
was left to stand still for one day and then subjected to 10
500 hrs
washing with water and filtration, and it was dried at
100° C. for 24 hours. The dried product was further EXAMPLE 38
pulverized and then calcined at 500' C. for 8 hours to
obtain a complex oxide of ZnO-ZrO2. The obtained Using zinc nitrate as the zinc source, zirconium ox
powder had a specific surface area of 69 m2/g. Then, 15 ynitrate as the zirconium source and aluminum nitrate
the power was press-molded under a gauge pressure of as the aluminum source, a mixed aqueous solution was
140 kg/cm2, followed by pulverization and classifica prepared so that the molar ratio of Zn/Zr/Al-0.3/1/1.
tion with sieves to obtain a test catalyst having a particle The mixed aqueous solution and 10% aqueous ammonia
were gradually dropwise added to water under stirring
size of from 10 to 20 mesh. The peak temperature for 20 to
desorption of ammonia by the ammonia TPD method wasmaintain left to
pH=8, to form a coprecipitated gel. The gel
stand still for one day and then subjected to
was 250' C. 6 cm3 of this catalyst was packed into a washing with water and filtration, and it was dried at
glass reactor having an inner diameter of 14 mm and 110° C. for 20 hours. The dried product was further
heated to a predetermined temperature. Then, a reac pulverized and then calcined at 550° C. for 6 hours to
tion was conducted by supplying methanol and hydro- 25 obtain a complex oxide of ZnO-ZrO2-Al2O3. The
gen chloride thereto in a molar ratio of obtained powder had a specific surface area of 62 m2/g.
HCl/CH3OH = 1.4 at a space velocity SV = 2,200 h-1. Then, the power was press-molded under a gauge pres
The results are shown in Table 30. sure of 140 kg/cm2, followed by pulverization and clas
TABLE 30
sification with sieves to obtain a test catalyst having a
30 particle size of from 10 to 20 mesh. The peak tempera
Reaction Conversion Selectivity for ture for desorption of ammonia by the ammonia TPD
temperature of methanol methyl chloride method was 200 C. 6 cm of this catalyst was packed
("C) (mol%) (mol%) into a glass reactor having an inner diameter of 14 mm
Initial 200 98.8 99.8 and heated to a predetermined temperature. Then, a
activities 250 000 100.0 35 reaction was conducted by supplying methanol and
300 100.0 100.0
350 100.0 100.0
hydrogen chloride thereto in a molar ratio of
After 200 98.8 99.7 HC1/CH3OH = 1.6 at a space velocity SV=2,300 hl.
500 hrs The results are shown in Table 32.
40 TABLE 32
Reaction Conversion Selectivity for
EXAMPLE 37 temperature of methanol methyl chloride
(C) (mol%) (mol%)
Using zinc nitrate as the zinc source and titanium Initial 200 99.0 99.9
chloride as the titanium source, a mixed aqueous solu activities 250 100.0 100.0
tion was prepared so that the molar ratio of 45 300 100.0 100.0
350 100.0 100.0
Zn/Ti- 0.11. The mixed aqueous solution and 10% After 200 99. 99.9
aqueous ammonia were gradually dropwise added to 1,000
water under stirring to maintain pH=8, to form a co hrs
precipitated gel. The gel was left to stand still for one so
day and then subjected to washing with water and fil
tration, and it was dried at 120' C. for 20 hours. The EXAMPLE 39
dried product was further pulverized and then calcined Using zinc acetate as the zinc source, zirconium oxy
at 500' C. for 6 hours to obtain a complex oxide of chloride as the zirconium source and titanium isopro
ZnO-TiO2. The obtained powder had a specific sur-55 poxide as the titanium source, a mixed aqueous solution
face area of 88 m2/g. Then, the power was press was prepared so that the molar ratio of
molded under a gauge pressure of 130 kg/cm, followed Zn/Zr/Ti=0.25/1/1 and adjusted to pH = 1 with
HNO3. This solution and 10% aqueous ammonia were
by pulverization and classification with sieves to obtain gradually
a test catalyst having a particle size of from 10 to 20 60 dropwise added to water under stirring to
maintain pH=8,
mesh. The peak temperature for desorption of ammonia was left to stand stillto form a coprecipitated gel. The gel
by the ammonia TPD method was 250 C. 6 cm3 of this washing with water and for one day and then subjected to
catalyst was packed into a glass reactor having an inner 100° C. for 24 hours. Thefiltration, and it was dried at
diameter of 14 mm and heated to a predetermined tem pulverized and then calcined at 500 C. forwas
dried product
6
further
hours to
perature. Then, a reaction was conducted by supplying obtain a complex oxide of ZnO-ZrO2-TiO2. The
methanol and hydrogen chloride thereto in a molar obtained powder had a specific surface area of 70 m2/g.
ratio of HC1/CH3OH = 1.5 at a space velocity Then, the powder was press-molded under a gauge
SV = 1,800 h-1. The results are shown in Table 31. pressure of 120 kg/cm, followed by pulverization and
 5,321,171
23 24
classification with sieves to obtain a test catalyst having TABLE 35
a particle size of from 7 to 15 mesh. The peak tempera Reaction Conversion Selectivity
ture for desorption of ammonia by the ammonia TPD tempera- of methanol for methyl
method was 200 C. 6 cm3 of this catalyst was packed ture ("C.) (mol%) chloride (mol %)
into a glass reactor having an inner diameter of 14 mm Example Initial 200 0. 93.5
and heated to a predetermined temperature. Then, a 40 activities 250 5.8 94.3
reaction was conducted by supplying methanol and 300
350
57.2
84.2
97.5
98.5
hydrogen chloride thereto in a molar ratio of After 250 15.7 94.3
HCl/CH3OH = 1.4 at a space velocity SV=2,300 h-1. 10 1,000 hrs
The results are shown in Table 33. Example Initial 200 98.5 99.8
41 activities 250 100,0 000
TABLE 33 300 1000 100.0
Reaction Conversion Selectivity for 350 100.0 100.0
temperature of methanol methyl chloride After 200 98.6 99.8
("C) (mol%) (mol %) 15 2,000 hrs
Initial 200 99.1 99.9
activities 250 100.0 100.0
300 100.0 100.0 EXAMPLE 41
350 100,0 1000 Commercially available zirconia powder (specific
After 200 99.2 99.9 2O
1,000 surface area: 80 m2/g) was immersed in an aqueous zinc
hrs nitrate solution and then dried at 120° C. for 10 hours.
Then, the dried powder was clacined at 500 C. for 4
hours so that zinc oxide was supported thereon in an
COMPARATIVE EXAMPLE 3 25 amount of 10 wt %. This product was press-molded
Commercially available y-alumina powder (specific under a gauge pressure of 150 kg/cm2, followed by
pulverization and classification with sieves to obtain a
surface area: 140 m2/g) was calcined at 500 C. for 4 test catalyst having a particle size of from 7 to 15 mesh.
hours in an electric furnace. This powder was press 6 ml of this catalyst was packed into an Inconel reactor
molded under a gauge pressure of 150 kg/cm2, followed having an inner diameter of 14 mm and heated to a
by pulverization and classification with sieves to obtain 30
predetermined temperature. Then, a reaction was con
a test catalyst having a particle size of from 10 to 20 ducted by supplying methanol and hydrogen chloride
mesh. The peak temperature for desorption of ammonia containing hydrogen fluoride (HF=200 ppm) thereto in
by the ammonia TPD method was 380 C. 6 cm3 of this a molar ratio of HCl/CH3OH = 1.3/1 at a space veloc
catalyst was packed into a glass reactor having an inner 35 ity SV=2,500 hl. The results are shown in Table 35.
diameter of 14 mm and heated to a predetermined tem EXAMPLE 42
perature. Then, a reaction was conducted by supplying
methanol and hydrogen chloride thereto in a molar Commercially available zirconia powder (specific
ratio of HC1/CH3OH = 1.4 at a space velocity surface area: 80 m2/g) was immersed in an aqueous
SV=2,000 hl. The results are shown in Table 34. 40 chromium acetate solution and then dried at 120° C. for
TABLE 34 6 hours. Then, the dried powder was clacined at 450° C.
Reaction Conversion Selectivity for
for 4 hours so that chromium oxide was supported
temperature of methanol methyl chloride thereon in an amount of 9 wt %. The product was press
("C) (mol%) (mol%) molded under a gauge pressure of 130 kg/cm2, followed
Initial 200 5.8 98.3 45 by pulverization and classification with sieves to obtain
activities 250 77.5 99, a test catalyst having a particle size of from 10 to 20
300 96.3 99.8 mesh. 6 ml of this catalyst was packed into an Inconel
350 99.8 99.9 reactor having an inner diameter of 14 mm and heated
After 200 10.3 97.5 to a predetermined temperature. Then, a reaction was
200 hrs 50 conducted by supplying methanol and hydrogen chlo
ride containing hydrogen fluoride (HF= 100 ppm)
EXAMPLE 40
thereto in a molar ratio of HCl/CH3OH = 1.4/1 at a
space velocity SV = 2,200 hl. The results are shown in
Commercially available zirconia powder (specific 55
Table 36.
surface area: 100 m2/g) was calcined at 500 C. for 3 TABLE 36
hours in an electric furnace. This powder was press Reaction Conversion Selectivity
molded under a gauge pressure of 120 kg/cm2, followed tempera- of methanol for methyl
by pulverization and classification with sieves to obtain ture ("C.) (mol %) chloride (mol%)
a test catalyst having a particle size of from 10 to 20 60 Example Initial 200 95.3 99.3
mesh. 6 ml of this catalyst was packed into an Inconel 42 activities 250
300
98.2
99.9
99.7
99.9
reactor having an inner diameter of 14 mm and heated 350 100.0 99.9
to a predetermined temperature. Then, a reaction was Example Initial 200 15.3 98.0
conducted by supplying methanol and hydrogen chlo 43 activities 250 90.3 98.8
ride containing hydrogen fluoride (HF= 100 ppm) 65 300
350
99.2
100.0
99.9
99.8
thereto in a molar ratio of HCl/CH3OH = 1.4/1 at a Example Initial 200 20.3 98.0
space velocity SV = 2,200 hl. The results are shown in 44 activities 250 98. 99.6
Table 35. 300 OOO 100.0
 5,321,171
25 26
TABLE 36-continued TABLE 37-continued
Reaction Conversion Selectivity Reaction Conversion Selectivity
tempera- of methanol for methyl tempera- of methanol for methyl
ture (C) (mol%) chloride (mol%) ture (C) (mol %) chloride (mol%)
5 45 activities 250 95.8 99.2
350 100.0 99.9
300 99.5 99.4
350 100.0 100.0
Example Initial 200 70.2 99.0
EXAMPLE 43 46 activities 250 98.3 99.7
300 100.0 99.9
Commercially available zirconia powder (specific O 350 100.0 99.9
surface area: 100 m/g) was immersed in an aqueous Example Initial 200 85.3 98.9
copper acetate solution and then dried at 110 C. for 9 47 activities 2SO
300
99.9
100.0
99.8
100.0
hours. The dried powder was clacined at 500 C. for 3 350 100.0 100.0
hours so that copper oxide was supported thereon in an
amount of 11 wt %. The product was press-molded 15
under a gauge pressure of 140 kg/cm2, followed by EXAMPLE 46
pulverization and classification with sieves to obtain a
test catalyst having a particle size of from 7 to 15 mesh. Commercially available zirconia powder (specific
6 ml of this catalyst was packed into an Inconel reactor surface area: 100 m2/g) was immersed in an aqueous
having an inner diameter of 14 mm and heated to a 20 iron nitrate solution and then dried at 110' C. for 12
predetermined temperature. Then, a reaction was con hours. Then, the dried product was calcined at 600 C.
ducted by supplying methanol and hydrogen chloride for2 hours so that iron oxide was supported thereon in
containing hydrogen fluoride (HF=150 ppm) thereto in an amount of 10 wt %. The product was press-molded
a molar ratio of HCl/CH3OH = 1.3/1 at a space veloc under a gauge pressure of 150 kg/cm2, followed by
ity SV=2,500 hl. The results are shown in Table 36. 25 pulverization and classification with sieves to obtain a
test catalyst having a particle size of from 7 to 15 mesh.
EXAMPLE 44 6 ml of this catalyst was packed into an Inconel reactor
Commercially available zirconia powder (specific having an inner diameter of 14 mm and heated to a
surface area: 100 m2/g) was immersed in an aqueous predetermined temperature. Then, a reaction was con
manganese nitrate solution and then dried at 100° C. for 30 ducted by supplying methanol and hydrogen chloride
12 hours. The dried powder was clacined at 550° C. for containing hydrogen fluoride (HF=200 ppm) thereto in
4 hours so that manganese oxide was supported thereon a molar ratio of HCl/CH3OH = 1.5/1 at a space veloc
in an amount of 10 wt %. The product was press ity SV=2,500 hl. The results are shown in Table 37.
molded under a gauge pressure of 130 kg/cm2, followed EXAMPLE 47
by pulverization and classification with sieves to obtain 35 Commercially available zirconia powder (specific
a test catalyst having a particle size of from 10 to 20
mesh. 6 ml of this catalyst was packed into an Inconel surface area: 100 m2/g) was immersed in an aqueous
reactor having an inner diameter of 14 nm and heated nickel acetate solution and then dried at 120 C. for 6
to a predetermined temperature. Then, a reaction was 40 hours. Then, the dried product was calcined at 500 C.
conducted by supplying methanol and hydrogen chlo for 3 hours so that nickel oxide was supported thereon
ride thereto in a molar ratio of HC/CH3OH = 1.4/1 at in an amount of 11 wt %. The product was press
a space velocity SV=2,300 hl. The results are shown molded under a gauge pressure of 120 kg/cm, followed
in Table 36. by pulverization and classification with sieves to obtain
a test catalyst having a particle size of from 10 to 20
EXAMPLE 45 45 mesh. 6 ml of this catalyst was packed into an Inconel
Commercially available zirconia powder (specific reactor having an inner diameter of 14 mm and heated
surface area: 80 m2/g) was immersed in an aqueous to a predetermined temperature. Then, a reaction was
cobalt nitrate solution and then dried at 10' C. for 8 conducted by supplying methanol and hydrogen chlo
hours. Then, the dried product was calcined at 500 C. ride containing hydrogen fluoride (HF = 100 ppm)
for 4 hours so that cobalt oxide was supported thereon SO thereto in a molar ratio of HC1/CH3OHs 1.4/1 at a
in an amount of 9 wt %. The product was press-molded space velocity SV=2,300h. The results are shown in
under a gauge pressure of 120 kg/cm, followed by Table 37.
pulverization and classification with sieves to obtain a EXAMPLE 48
test catalyst having a particle size of from 10 to 20 mesh. 55 Using zinc nitrate as the zinc source and zirconium
6 ml of this catalyst was packed into an Inconel reactor oxynitrate as the zirconium source, a mixed aqueous
having an inner diameter of 14 mm and heated to a solution was prepared so that the molar ratio of
predetermined temperature. Then, a reaction was con Zn/Zr=0.1/1. This mixed aqueous solution and 10%
ducted by supplying methanol and hydrogen chloride aqueous ammonia were gradually dropwise added to
containing hydrogen fluoride (HF=200 ppm) thereto in
a molar ratio of HC1/CH3OH = 1.3/1 at a space veloc 60 water under stirring to maintain pH=8, to form a co
precipitated gel. The coprecipitated gel was left to
ity SV = 2,500 hl. The results are shown in Table 37. stand still for one day and then subjected to washing
with water and filtration, and it was dried at 110 C. for
TABLE 37 20 hours. The dried product was further pulverized and
Reaction Conversion Selectivity 65 calcined at 500 C. for 10 hours to obtain a complex
tempera- of methanol for methyl oxide catalyst of ZnO-ZrO2. The complex oxide cata
ture (C.) (mol%) chloride (mol%) lyst had a ZnO content of 6.2 wt % and a specific sur
Example Initial 200 18.2 98.0 face area of 95 m2/g. Then, the complex oxide catalyst
 5,321,171
27 28
was press-molded under a gauge pressure of 150 area of 85 m2/g. Then, the composite catalyst was
kg/cm2, followed by pulverization and classification press-molded under a gauge pressure of 150 kg/cm,
with sieves to obtain a test catalyst having a particle size followed by pulverization and classification with sieves
of from 10 to 20 mesh. 6 ml of this catalyst was packed to obtain a test catalyst having a particle size of from 10
into an Inconel reactor having an inner diameter of 14 5 to 20 mesh. 6 ml of this catalyst was packed into an
mm and heated to a predetermined temperature. Then, Inconel reactor having an inner diameter of 14 mm and
a reaction was conducted by supplying methanol and heated
hydrogen chloride containing hydrogen fluoride tion wastoconducted a predetermined temperature. Then, a reac
by supplying methanol and hydro
(HF=150 ppm) thereto in a molar ratio of gen chloride containing hydrogen fluoride (HF=200
HCl/CH3OH = 1.5/1 at a space velocity SV=2,000 O ppm) thereto in a molar ratio of HCl/CH3OH=1.6/1 at
hi. The results are shown in Table 38.
a space velocity SV=2,200 hl. The results are shown
TABLE 38 in Table 38.
Reaction Conversion Selectivity
tempera- of methanol for methyl COMPARATIVE EXAMPLE 4
ture ("C.) (mol%) chloride (mol%) 15 Commercially available y-alumina powder (specific
Example Initial 200 99.8 99.9 surface area: 140 m2/g) was calcined at 500 C. for 4
48 activities 250 100.0 100.0
300 100.0 00.0 hours in an electric furnace. This powder was press
350 100,0 100.0 molded under a gauge pressure of 120 kg/cm, followed
Example Initial
49 activities
200
250
99.8
100.0
99.9
100.0 20 by pulverization and classification with sieves to obtain
300 100.0 100,0 a test catalyst having a particle size of from 10 to 20
350 100,0 100.0 mesh. 6 ml of this catalyst was packed into an Inconel
Example Initial
50 activities
200
250
95.5
98.5
99.5
99.7
reactor having an inner diameter of 14 mm and heated
300 100.0 99.9
to a predetermined temperature. Then, a reaction was
350 00.0 99.9 25 conducted by supplying methanol and hydrogen chlo
ride containing hydrogen fluoride (HF=200 ppm)
thereto in a molar ratio of HCl/CH3OH = 1.3/1 at a
EXAMPLE 49 space velocity SV=2,000 hl. The results are shown in
Table 39.
Using zinc chloride as the zinc source and zirconium
oxychloride as the zirconium source, a mixed aqueous 30 TABLE 39
solution was prepared so that the molar ratio of Reaction Conversion Selectivity
Zn/Zr=0.01/1. This mixed aqueous solution and 10% tempera- of methanol for methyl
aqueous ammonia were gradually dropwise added to ture ('C) (mol%) chloride (mol%)
water under stirring to maintain pH=8, to form a co 35 Compar- Initial 200 7.1 93.3
precipitated gel. The coprecipitated gel was left to ative
Example
activities 250
300
13.2
50.5
94.
97.3
stand still for one day and then subjected to washing 4. 350 78.3 98.3
with water and filtration, and it was dried at 120° C. for After 250 6.5 92.5
15 hours. The dried product was further pulverized and 1,000 hrs
calcined at 550 C. for 8 hours to obtain a complex oxide Compar- Initial
ative activities
200
250
57.3
79.8
98.3
98.5
catalyst of ZnO-ZrO2. The complex oxide catalyst Example 300 88.2 98.9
had a ZnO content of 0.6 wt % and a specific surface 5 350 90.5 99.3
area of 90 m2/g. Then, the complex oxide catalyst was After 200 20.1 93.7
press-molded under a gauge pressure of 140 kg/cm2, 1,000 hrs
followed by pulverization and classification with sieves
to obtain a test catalyst having a particle size of from 7 45
to 15 mesh. 6 ml of this catalyst was packed into an COMPARATIVE EXAMPLE 5
Inconel reactor having an inner diameter of 14 mm and Commercially available y-alumina powder (specific
heated to a predetermined temperature. Then, a reac surface area: 140 m2/g) was immersed in an aqueous
tion was conducted by supplying methanol and hydro
gen chloride containing hydrogen fluoride (HF= 100 50 zinc nitrate solution and then dried at 120° C. for 10
ppm) thereto in a molar ratio of HC1/CH3OH = 15/1 at hours. Then, the dried product was calcined at 500 C.
a space velocity SV= 1,800 hl. The results are shown for 4 hours so that zinc oxide was supported thereon in
in Table 38. an amount of 10 wt %. The product was press-molded
under a gauge pressure of 150 kg/cm, followed by
EXAMPLE 50 55 pulverization and classification with sieves to obtain a
Using chronium nitrate as the chromium source and test catalyst having a particle size of from 7 to 15 mesh.
zirconium oxychloride as the zirconium source, a mixed 6 ml of this catalyst was packed into an Inconel reactor
aqueous solution was prepared so that the molar ratio of having an inner diameter of 14 mm and heated to a
Cr/Zr=0.1/1. This mixed aqueous solution and 10% predetermined temperature. Then, a reaction was con
aqueous ammonia were gradually dropwise added to 60 ducted by supplying methanol and hydrogen chloride
water under stirring to maintain pH=8, to form a co containing hydrogen fluoride (HF=200 ppm) thereto in
precipitated gel. The coprecipitated gel was left to a molar ratio of HCl/CH3OH = 1.3/1 at a space veloc
stand still for one day and then subjected to washing ity SV = 2,500 h-i. The results are shown in Table 39.
with water and filtration, and it was dried at 100 C. for We claim:
20 hours. The dried product was further pulverized and 65 1. A method for producing methyl chloride, which
calcined at 500 C. for 8 hours to obtain a complex oxide comprises reacting methanol and hydrogen chloride in
catalyst of Cr2O3-ZrO2. The complex oxide catalyst a gas phase in the presence of a catalyst, wherein a
had a Cr2O3 content of 11.0 wt % and a specific surface zirconium oxide catalyst or a complex oxide catalyst
 5,321,171
29 30
comprising at least two oxides of metals selected from 3. The method for producing methyl chloride ac
cording to claim 1, wherein the zirconium oxide is an
the group consisting of Zr, Ti and Al, is used as the oxide of tetravalent zirconium.
catalyst. 4. The method for producing methyl chloride ac
cording to claim 1, wherein the oxide of Ti is an oxide
2. The method for producing methyl chloride ac of tetravalent titanium.
cording to claim 1, wherein the zirconium oxide cata 5. The method for producing methyl chloride ac
lyst or the complex oxide catalyst is used which has at cording to claim 1, wherein the oxide of Al is an oxide
of trivalent aluminum.
least one oxide of metal selected from the group consist 6. The method for producing methyl chloride ac
ing of zinc, copper, manganese, cobalt, chromium, iron cording to claim 1, wherein the hydrogen chloride
contains from 10 ppm to 10 wt % of hydrogen fluoride.
and nickel incorporated therein.
15

25

30

35

45

50

55