United States Patent Office 3,506,552

Patented Apr. 14, 1970

2
3,506,552 and chlorine, and the resulting vapor reaction mixture is
PREPARATION OF WNYL CHLORIDE FROM allowed to become heated, said heated vapor reaction mix
ETHANE USNG CHLORINE WITH ACTENIC ture is found to contain varying, but substantial, amounts
LIGHT of vinyl chloride, ethyl chloride, dichloroethane and hy
James P. Russell, Berkeley Heights, N.J., assignor to Air drogen chloride. The relative amounts of these products de
Reduction Company, Incorporated, New York, N.Y., pends in large measure on the relative amounts of chlorine
a corporation of New York w and ethane in the feed mixture, the intensity of incident
No Drawing. Filed Mar. 31, 1967, Ser. No. 627,294 light thereupon, and the temperature of the heated reac
int. C. B01j 1/10; C07c 21/06, 17/00 tion mixture, as will be described in more detail herein
U.S. C. 204-163 9 Claims after. The process is particularly suited to being carried
10
out in continuous fashion, and it is preferred to do so.
ABSTRACT OF THE DISCLOSURE In carrying out the process of the present invention the
vapor mixture feed of chlorine and ethane is introduced,
Vinyl chloride is prepared by the photochemical chlor preferably continuously, into a suitable reactor and ex
ination of ethane with chlorine at 250 to 400° C. With 5 posed to chemically-active light. It is preferred that the
a contact time of 2 to 20 seconds. exposition be effected by dispersing the vapor feed mix
ture in a suitable liquid medium. This may be achieved
by providing a suitable liquid within the reactor system,
This invention relates to the preparation of halogenated continuously flowing the vapor feed mixture through the
hydrocarbons and more particularly to the preparation of 20 liquid medium, thereby forming a vapor-liquid dispersion
vinyl chloride. Specifically, it relates to a photochemical from which a vapor reaction mixture, continuously ema
process for producing vinyl chloride and other halo nates. Both the gas-liquid dispersion, and the vapor phase
genated hydrocarbons such as ethylchloride and dichloro emanating therefrom are exposed to the chemically-active
ethanes useful in preparing vinyl chloride. light.
Vinyl chloride is an extremely versatile material and 25 When carried out in the preferred mode described, the
finds major use in a wide variety of applications such as effect of the chemically-active light is to induce photo
in the preparation of polymers for coatings, textile fin chemically an exothermic reaction between the chlorine
ishes, rigid products such as pipes, and the like. At present and ethane in the vapor feed mixture which results in a
vinyl chloride is made commercially from either acetylene heated vapor reaction mixture. As stated above, the tem
or ethylene or a combination of both depending on 30 perature to which the reaction mixture is heated is an
economics of the particular location of the manufacturing important characteristic in the process. Variations in prod
plant. One method of major commercial importance in uct distribution are observed depending on how this tem
volves the hydrochlorination of acetylene using anhy perature varies. In general, it may be said that good yields
drous hydrogen chloride in the presence of a mercuric of commercially useable materials are obtained at vapor
chloride catalyst. In another method, ethylene is first 35 reaction mixture temperatures varying from 150 to 500
chlorinated to ethylene dichloride which is then thermally C. It is preferred, for best results, to employ vapor tem
or catalytically dehydrochlorinated to vinyl chloride. As peratures of the order of 250° C. to 400° C. in which
can be seen, each of these processes commences from range the vapor reaction mixture, after removal of by
either acetylene or ethylene, material which are at least produced hydrogen chloride, contains vinyl chloride in
one step, and usually a difficulty practiced step, removed 40
amounts as much as 10% by weight and large amounts of
from the basic, widely available hydrocarbon raw mate ethyl chloride (about 40-45% by weight), and dichloro
rials from which they are prepared. In view of this, a great ethanes (about 40-50% by weight).
deal of interest has developed in recent years in alternate Attending this are high conversions of ethane to chlori
routes to vinyl chloride. Unfortunately, most of these nated hydrocarbons, the conversion figures usually rang
routes suffer one or more disadvantages in that they re 45 ing from 75-88%. Trichloroethanes are obtained in the
quire drastic conditions, or large excesses of non-hydro reaction mixture in amounts generally less than 7% by
carbon starting materials, or yield large amounts of by weight and usually around 4-5% by weight. The use of
products which are not commercially desirable. It would lower reaction mixture temperatures tends to increase the
thus be very desirable, indeed, if a basic, low cost hydro 50
amount of the trichlorinated products obtained.
carbon starting material could be converted in a direct The temperature of the reaction mixture is conveniently
one stage process to vinyl chloride and commercially obtained, in accordance with a feature of this invention,
useable by-products. It is an object of this invention by utilizing the heat of reaction generated as a result of
to provide such a process. the photochemical combination of chlorine and ethane.
By commercially desirable by-products are meant those If the self-generated temperature is too high, suitable
products which are of use within the technology of vinyl cooling means may be introduced into the reactor to
chloride production, or are eminently useful in their own achieve proper values. Similarly, if it is too low, auxiliary
right. For example, both 1,1 dichloro and 1,2 dichloro heating means can be introduced. As a further added
ethanes are considered commercially desirable since they features of the invention, however, an interrelationship
can be converted into vinyl chloride. Ethyl chloride is has been noted between the relative proportion of chlo
likewise useful, though not as desirable as the dichloro 60
rine and ethane in the feed mixture on the one hand,
ethanes, since it may be converted to dichloroethane by and the intensity of incident light upon said mixture
chlorination. On the other hand, trichloroethane, al on the other, each with respect to the temperature which
though suitable for preparing vinylidene chloride; and the reaction mixture attains. Thus, by utilizing variations
other higher halogenated hydrocarbons, are considered in feed mixture constituent concentrations and incident
to be not as desirable as the dichloroethanes and ethyl 65 light intensities, sufficient heat is generated to produce
chloride. Hydrogen chloride, useful in a variety of indus desirable reaction mixtures. For example, and with ref
trial applications, is a desirable by-product. erence to the vapor feed mixture, when chlorine:ethane
In accordance with the present invention, it has been mole ratios of from 1.5-2:1 are employed, reaction mix
discovered that when a vapor feed mixture of chlorine and 70 ture temperatures ranging from 85-255° C. are obtained
ethane is exposed to light of sufficient intensity and qual when incident light intensity is above about 135 foot
ity to cause a photochemical reaction between the ethane candles. Mole ratios below this range tend to produce
 3,506,552 4
3
vapor reaction mixtures gradually decreasing in tempera example, when the vapor feed mixture is introduced into
ture with decreasing mole ratios to the point where said the bottom of a vertical reactor containing the liquid, the
temperature is about the same as the gas-liquid disper vapor will pass through the entire length of liquid depth,
sions of which more will be recited hereinafter. Never in which case the effective depth is the same as the
the less, such mole ratios are employable, as are higher actual depth. If it were introduced at the mid-point, the
ratios since it is preferred in the process to utilize pri effective depth would be about one-half the actual depth.
marily the incident light intensity as a means for achiev The liquid used as the dispersing medium may be either
ing desirable temperatures. With regard to the mole aqueous or organic and is preferably inert with respect
ratios, although values of from 0.9 to 2.2:1 may be em to its reactivity with chlorine, ethane, vinyl chloride and
ployed, values of from 0.9-1.8 and preferably from 1.0- O other reaction products. Illustrative of aqueous media are
1.7:1 moles chlorine per mole ethane produce substan aqueous solutions of acids such as hydrochloric acid, and
tial amounts of commercially useable material, while phosphoric acid, acetic acid and the like. Acetic acid
production of other material is substantially suppressed. gradually chlorinates under the photochlorination condi
Values above this range tend to yield pronounced amounts tions and is therefore not preferred. Illustrative of or
of the trihalogenated materials whereas values below 5 ganic media are perfluoro-tri-n-butylamine, fluoro-chloro
the range favor production of large amounts of ethyl compounds, - such as "Halocarbon' and "Kel-F,” oils
chloride relative to dichloroethanes. Most preferred is (low polymers of trifluoro-chloro ethylene) and carbon
a mole ratio of from 1.2-1.4 moles chlorine per mole tetrachloride, and the like. The preferred medium is hy
ethane. drochloric acid in concentrations ranging from 10 to
As stated, it is preferred to utilize the intensity of 20 39% with the concentrated hydrochloric acid, i.e. about
light incident upon the gas-liquid dispersion and the 38% being preferred.
vapor reaction mixture continuously emanating there When an aqueous liquid medium is employed, best re
from as the primary means by which desirable tempera sults are obtained when the temperature of the liquid
tures of the vapor reaction mixture is obtained. In this phase is between 30° C. and 70° C. and preferably from
regard, suitable results are obtained when the intensity 40 to 60° C. Higher temperatures may be used for or
is between 50 to 500 foot candles, and preferably be ganic liquids, but in general it is preferred to operate in
tween 80 to 200 foot candles. In practice, the values at the range of 40 to 70° C. Similarly, the pressure under
the lower end of the preferred range, for example 80-150 which the process is carried out is suitably above atmos
foot candles, are most preferred and result in good yields pheric, the kinetic pressure of the flowing system being
of vinyl chloride, ethyl chloride and dichloroethanes. In 30 convenient. Ordinarily, pressures in the range of from
this connection, and while it is not intended to limit the 800-1000 mm. Hg are encountered.
invention to theoretical considerations, it is believed that As a result of carrying out the above described proc
at the most preferred conditions of incident light and ess, there is obtained a vapor reaction mixture containing
vapor feed mixture constituent mole ratios, the reaction predominantly commercially usable materials such as
rate in the liquid dispersion, relative to that in the vapor 35 vinyl chloride, hydrogen chloride, ethyl chloride and di
phase above the dispersion is reduced somewhat com chloroethanes, the latter being obtained in the form of
pared to those rates developed at other conditions. This both 1, 1 dichloro and 1,2 dichloroethane isomers in the
causes some, although probably a small amount of re mole ratio of about 3.3-3.5:1, respectively. When carried
action to occur in the vapor phase leading to a vapor out at 350° C. for vapor reaction mixture temperatures
temperature which is increased over that of the liquid at contact times of 10 seconds, 8:6 for chlorine:ethane
dispersion, probably in consequence of the lower capacity mole ratios, and 135 foot candles of incident light, the
of the gases, relative to the liquid, to absorb the heat of process surprisingly produces large amounts of vinyl
reaction. chloride and may be regarded as a vinyl chloride process.
The period of contact time that the vapor reaction The products may be separated and recovered by tech
mixture remains heated is suitably controlled by adjust niques well known in the art. For example, the hot vapor
ing the flow rate of the gases in consideration of the di 45 reaction gases are first preferably rapidly quenched to
mensions of the reacting equipment to give suitable space minimize side reactions and then submitted to a water
velocities. In general, contact times ranging from 2 to 20 scrubbing to remove hydrogen chloride. The scrubbed
and preferably from 8 to 12 seconds are suitable. These gases may then be cooled to liquid form and separated
may be achieved by directing the vapor reaction mixture by low temperature fractionation.
emanating from the liquid medium through a space, the 50 The light used for initiating the photochemical reaction
dimensions of which are easily calculated by one skilled may be any normally used in reactions of this type. It has
in the art, considering the volume flow rate of vapor been termed chemically-active which is meant to include
and the time desired. Space velocities of the vapor re daylight, sunlight, or any chemically-active artificial light,
action mixture, calculated as volume of vapor flowing e.g. radiation in the ultra-violet, visible, and infrared re
per unit volume of space through which it flows per 55 gions, having a wave length in the 2000-8000 A. range.
unit time, ranging from 150 to 800 and preferably from It may be derived from any source normally employed
200 to 550 liter/liter/hour, are suitable for producing in this art, but it is preferred, purely for reasons of econ
contact times within the above ranges. omy and ease of control to use fluoroescent light Sources,
With regard to the space velocity through the liquid, which have good light intensity in the region of 2400
it is convenient to represent this as the unit volume of 60
3500 A.
gas flowed through a unit volume of liquid (measured The following examples are given for purposes of illus
at rest) per hour. So defined, suitable space velocities tration only and are not to be construed as limiting the
through the liquid range from 100-800 and preferably invention.
200-550 liters vapor feed mixture/liter of dispersion EXAMPLES 1-4
liquid measured at rest/hour. In practice, it is convenient 65
to use reactor equipment having a uniform cross section A. Pyrex reactor tube, 48 in. by 2 in., is fitted at the
so that at a given space velocity through the liquid, the bottom with a drain stopcock, two gas inlet tubes with
desirable space velocity through the vapor space may coarse porosity sintered glass thimbles, a 24 in. by 1/2
be achieved merely by providing appropriate length in. internal cooling coil of 6 mm. Pyrex tubing, a ther
above the liquid surface. Suitable results are obtained 70 mometer for measuring vapor phase temperatures mount
when this length is about twice as long as the effective. ed 17 in. above the top of the cooling coil, and, at the
liquid depth. top of the reactor, a 10 in. by 1 in. still packed with /8
By effective liquid depth is meant the depth of liquid in. glass helices which act as a spray trap. The still head
through which the vapor feed mixture actually traverses is fitted with a U-tube manometer to read the reactor
rather than the actual depth of liquid as charged. For 75 pressure.
 3,506,552
5 6
The still head is connected to a product collection sys by gas chromatography by allowing the samples to warm
ten which consists of a 50 cm. coil condenser connected up to room temperature and vaporize, with added heat
to a jacketed produce receiver which is equipped with a treatment of the residue to remove any high boilers left
bottom drain and a gas outlet at the top. The gas outlet at room temperature.
is conncted to a 42 cm. coil condenser of which the off The foregoing procedure is followed in runs in which
gas side leads to the scrubbing section. The entire prod 5
the intensity of incident light is varied as shown in the
uct collection system is operated at -5 to -10° C. by table below, and as determined by a standard photocel
use of a cooling system which consists of a pump to cir measuring device. The chlorinated hydrocarbon produc
culate methanol which is cooled in a coil immersed in tion in weight percent of total vapor reaction mixture,
a Dry Ice-water-methanol mixture. after removal of hydrogen chloride, is indicated.
TABLE
Percent con
Incident version
light Vapor ethane to
foot temp. C2H5Ol C2H3Cl C2H4C2 CH3Cl31 cholorinated
Ex. candles (° C) (wt. percent) (wt. percent) (wt. percent) (wt. percent) products 2
360 275 42.8 .. 2 48.9 7.3 84.5
225 290 44.4 3.5 46.4 5.6 82.0
135 325 42.0 9.8 43.9 4.4 75.3
85 >350 44.7 5.6 44.3 4.0 80.0

1. Obtained as both isomers in mole ratio of approximately 3.4 moles of 1,1 dichloroethane
to one mole of 1,2 dichloroethane.
2 Total conversion of ethane is somewhat higher, some of the ethane being converted to
ethylene. Cillorine conversion is essentially quantitative, approximately 50 mole percent going
to chlorinated hydrocarbons and 50 percent going to hydrogen chloride.
The scrubbing section consists of two 4 in. by 48 in. What is claimed is:
tubes fitted at the bottom with gas inlet and drain. Each 25 1. The process for producing vinyl chloride which com
scrubbing tower is filled to a depth of 6 in. with 4 in. prises dispersing a vapor feed mixture comprising chlo
ceramic Berle saddles. Each Srubber contains 5 liters of rine and ethane in mole ratios of about 0.9 to 2.2:1 in a
water. These scrubbing towers are connected in series with relatively inert liquid and exposing the dispersed vapor
a third scrubber of similar design but made of 36 in. of feed mixture to actinic light to produce a vapor reaction
1% in. Pyrex tubing and holding 750 cc. of water. This 30 mixture, and maintaining said vapor reaction mixture at
scrubbing prevents carry-over of aqueous HCl spray to a temperature in the range of from 250 C. to 400 C.
the drying tower which is connected in series with the and at a contact time from 2 to 20 seconds.
scrubbers. The drying tower consists of a tower of sim 2. The process according to claim 1 wherein the method
ilar design as the small scrubber but completely filled with is carried out under continuous gas flow conditions.
10-20 mesh anhydrous CaSO4. The entire scrubbing and 35 3. The process according to claim 1 wherein the mole
drying section is interconnected with Black Tygon tub ratio of chlorine to ethane is between 1.0-1.7:1, the in
ing and the towers themselves painted black to prevent tensity of light incident upon said vapor feed mixture and
light from initiating reactions between unreacted ethane vapor reaction mixture is between 80-200 foot candles,
and chlorine which might be carried over from the re 40 whereby substantial amounts of vinyl chloride, ethyl chlo
actor. The drying tower is connected to a trap system ride, hydrogen chloride and dichloroethanes are produced.
held at Dry Ice temperatures to catch any unreacted chlo 4. The process according to claim 4 wherein the vapor
rine and small amounts of volatile chloroethanes which feed mixture is continuously dispersed through said rela
might carry through the system. tively inert liquid thereby to form a vapor-liquid disper
The trap system consists of three coil-type bulb traps. sion and a vapor reaction mixture continuously emanat
Two are in parallel and the third in series. The parallel ing therefrom.
traps are connected to the drying tower through a three 5. The process according to claim 4 wherein the vapor
way stopcock which permits operation of one or the feed mixture is flowed at a space velocity of from 150 to
other or both traps simultaneously. The third trap is 800 liters/liter of liquid phase/hr.
connected to a gas washing bottle containing 500 cc. of 6. The process of claim 5 wherein the relatively inert
10% NaOH solution and this is connected to a gas wash 50 liquid is hydrochloric acid.
ing bottle containing 500 cc. of distilled water. This, in 7. The process of claim 6 wherein the mole ratio of
turn, is connected to a 1 liter/rev. wet test meter which chlorine to ethane is from 1.2-1.4:1, and the temperature
is used to measure the volume of any off-gas. of the vapor reaction mixture of the vapor phase is be
The reactor section is positioned between two conven tween 300° C. and 375 C.
tional 48 in. 40 watt fluorescent tubes in such a manner 55 8. The process according to claim 4 for producing vinyl
that the tubes and the reactor form an isosceles triangle chloride wherein the mole ratio of chlorine:ethane is
having 5 in. base and 3 in. sides with the reactor at the from 1.2-1.4:1, the temperature of the vapor reaction
apex. mixture is between 300-375 C., the contact time at said
One liter of concentrated hydrochloric acid is placed in temperature is between 8-12 seconds, and the intensity
the reactor tube, the acid filling about 15 in. of the tube. 60 of incident light is from 80-200 foot candles.
The entire system is then purged for 5 minutes with 9. The process according to claim 8 wherein the rela
nitrogen. Thereafter, the product collection system is tively inert liquid is hydrochloric acid.
cooled to -10° C. Ethane is then started through the
hydrochloric acid at a rate of 100 liters/hr. After 5 References Cited
minutes chlorine is started at 50 liters/hr. The rates are UNITED STATES PATENTS
then gradually adjusted to supply a total of 350 liters per
hour of chlorine-ethane mixture in the mole ratio of 1,520,506 12/1924 Payne et al. -------- 204-163
1.33 moles chlorine per mole ethane. During this time, 2,393,509 1/1946 Archibald ----------- 204-163
the temperature in the reactor rises to 35-38 C. Cooling 2,453,691 11/1948 Hill ---------------- 204 -163
water is then turned on at a flow of 180–220 cc./min. 70 2,589,689 3/1952 Governale et al. 204-163
After 15-20 min., the gas flows and reactor temperatures 3,287,240 1 1/1966 Tsutsumi ----------- 204-163
reach steady state conditions. All scrubbers and traps BENJAMEN R. PADGETT, Primary Examiner
are on and sampling is begun. The product receiver is
drained hourly into a bottle pre-cooled to -78 C. to U.S. C. X.R.
provide samples for analysis. The samples are analyzed 75 204-162
 UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3,506,552 Dated April 14, 197O

it it; "r firl that error appears in the above-identified patent

and that said Letters Patent are hereby corrected as shown below:

Col. l, line 39, "material" should read -- materials --;

line 4O, "difficulty" should read -- difficultly --.
Col. 2, line 58, "features" should read -- feature --.

Col. 5 line 3, "produce" should read -- product -- ;

line 27, 's rubber" should read -- scrubber --.
Col. 6, line 4l, "claim " should read -- claim l --.

SIGNED AND
SEAE)
AUG251970

(SEAL)
Attest
Edward M. Fletchere WA. E. SCUYER, JR
Attesting Officer Cormissioner of attents

FORM PO-1050 1 0-69) sCOMMedic O38-39

A U. S. Gover NMENT PRNTNG office : is O-38-334