USOO8796498B2

(12) United States Patent (10) Patent No.: US 8,796.498 B2

Butler et al. (45) Date of Patent: Aug. 5, 2014

(54) METHOD FOR PRODUCTION OF STYRENE (52) U.S. Cl.

FROM TOLUENE AND METHANE USPC ............ 585/437; 585/313; 585/319; 585/323
(58) Field of Classification Search
(71) Applicant: Fina Technology, Inc., Houston, TX CPC ...... C07C2/867; CO7C 45/002; C07C 15/46;
(US) CO7C 47/04
USPC .................................. 585/313, 323,319, 437
(72) Inventors: James R. Butler, Spicewood, TX (US); See application file for complete search history.
Joseph E. Pelati, Hosuton, TX (US)
(56) References Cited
(73) Assignee: Fina Technology, Inc., Houston, TX
(US) U.S. PATENT DOCUMENTS

(*) Notice: Subject to any disclaimer, the term of this i.S. A 88: Siants et al.
patent is extended or adjusted under 35 2003/0065228 A1 4/2003 Schweers et al.
U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS
(21) Appl. No.: 14/093,667 Taiwanese Office Action and Search Report issued in Taiwanese
1-1. Patent Application No. 098 139965 dated Dec. 11, 2013, and English
(22) Filed: Dec. 2, 2013 translation thereof (10 pages).
O O Song et. al., “Formaldehyde production from methanol using a
(65) Prior Publication Data porous Vycor glass membrane reactor'. Journal of Membrane Sci
US 2014/0094631 A1 Apr. 3, 2014 ence, 1991, 57. 1, pp. 95-113.
O O Primary Examiner — Thuan D Dang
Related U.S. Application Data
(63) Continuation of application No. 12/345,550, filed on (57) ABSTRACT
Dec. 29, 2008, now Pat. No. 8,686,205. A process is disclosed for making styrene by converting
methanol to formaldehyde in a reactor then reacting the form
(51) Int. Cl. aldehyde with toluene to form styrene in a separate reactor.
C07C I/20 (2006.01)
C07C I/207 (2006.01) 17 Claims, 2 Drawing Sheets

Separator 14
9
Reactor
U.S. Patent Aug. 5, 2014 Sheet 1 of 2 US 8,796.498 B2
U.S. Patent Aug. 5, 2014 Sheet 2 of 2 US 8,796.498 B2

20
 US 8,796.498 B2
1. 2
METHOD FOR PRODUCTION OF STYRENE one or more first reactors to form a first product stream com
FROM TOLUENE AND METHANE prising formaldehyde and reacting the formaldehyde with
toluene in one or more second reactors to form a second
CROSS-REFERENCE TO RELATED product stream comprising styrene. The first product stream
APPLICATIONS can include one or more of hydrogen, water, or methanol. The
methanol, if any is present, can be separated from the first
This application is a Continuation of U.S. application Ser. product stream and recycled to the one or more first reactors.
No. 12/345,550, filed on Dec. 29, 2008. The process can include utilizing one or more oxidation
10
reactors to convert methanol into formaldehyde and water to
FIELD form the first product stream. The process can optionally
include utilizing one or more dehydrogenation reactors to
The present invention relates to a method for the produc convert methanol into formaldehyde and hydrogen to form
tion of styrene. the first product stream.
BACKGROUND 15 The second product stream can include one or more of
toluene, water, or formaldehyde. The toluene and/or formal
Styrene is an important monomer used in the manufacture dehyde, if any is present, can be separated from the second
of many plastics. Styrene is commonly produced by making product stream and recycled to the one or more second reac
ethylbenzene, which is then dehydrogenated to produce Sty tors. The one or more second reactors can include a reaction
rene. Ethylbenzene is typically formed by one or more aro Zone under reaction conditions containing a catalyst for react
matic conversion processes involving the alkylation of ben ing toluene and formaldehyde to form styrene. The process
Z. can include passing the first product stream to a separation
Aromatic conversion processes, which are typically car stage for separating formaldehyde from the first product
ried out utilizing a molecular sieve type catalyst, are well stream. The separation stage can comprise a membrane sepa
known in the chemical processing industry. Such aromatic 25 ration capable of removing hydrogen from the formaldehyde
conversion processes include the alkylation of aromatic com Stream.
pounds such as benzene with ethylene to produce alkylaro Another embodiment of the present invention is a process
matics such as ethylbenzene. Typically an alkylation reactor, for making styrene by converting methanol to formaldehyde
which can produce a mixture of monoalkyl and polyalkyl in one or more first reactors to form a first product stream
benzenes, will be coupled with a transalkylation reactor for 30
comprising one or more of formaldehyde, hydrogen, water, or
the conversion of polyalkylbenzenes to monoalkylbenzenes. methanol. The first product stream proceeds to a first separa
The transalkylation process is operated under conditions to tion stage for separating formaldehyde from the first product
cause disproportionation of the polyalkylated aromatic frac stream. The separation stage can include a membrane sepa
tion, which can produce a product having an enhanced ethyl ration unit capable of removing hydrogen from the formal
benzene content and reduced polyalkylated content. When 35
dehyde stream prior to the Seccion reactor.
both alkylation and transalkylation processes are used, two
separate reactors, each with its own catalyst, can be employed Toluene and formaldehyde are reacted in one or more
for each of the processes. second reactors to form a second product stream comprising
Ethylene is obtained predominantly from the thermal one or more of styrene, toluene, water, or formaldehyde. The
cracking of hydrocarbons, such as ethane, propane, butane, or 40 second product stream then passes to a second separation
naphtha. Ethylene can also be produced and recovered from stage for separating styrene from the second product stream.
various refinery processes. Thermal cracking and separation Methanol, of present, can be separated from the first product
technologies for the production of relatively pure ethylene stream and recycled to the one or more first reactors. Toluene
can account for a significant portion of the total ethylbenzene and formaldehyde, if present, can be separated from the sec
production costs. 45 ond product stream and recycled to the one or more second
Benzene can be obtained from the hydrodealkylation of reactOrS.
toluene that involves heating a mixture of toluene with excess The process can include utilizing one or more oxidation
hydrogen to elevated temperatures (for example 500° C. to reactors to convert methanol into formaldehyde and water to
600°C.) in the presence of a catalyst. Under these conditions, form the first product stream. The process can optionally
toluene can undergo dealkylation according to the chemical 50 include utilizing one or more dehydrogenation reactors to
equation: CHCH+H >CH+CH. This reaction requires convert methanol into formaldehyde and hydrogen to form
energy input and as can be seen from the above equation, the first product stream. The one or more second reactors can
produces methane as a byproduct, which is typically sepa comprise a reaction Zone under reaction conditions contain
rated and may used as heating fuel for the process. ing a catalyst for reacting toluene and formaldehyde to form
In view of the above, it would be desirable to have a process 55 styrene. The catalyst can be a basic or neutral catalyst, and can
of producing styrene that does not rely on thermal crackers be a basic or neutral Zeolite catalyst. The catalyst can com
and expensive separation technologies as a source of ethyl prise one or more promoters chosen from the group of alkali
ene. It would further be desirable to avoid the process of elements, alkaline earth elements, rare earth elements, Y, Zr,
converting toluene to benzene with its inherent expense and and Nb.
loss of a carbonatom to form methane. It would be desirable 60
to produce styrene without the use of benzene and ethyleneas BRIEF DESCRIPTION OF DRAWINGS
feedstreams.
FIG. 1 illustrates a flow chart for the production of styrene
SUMMARY by the reaction of formaldehyde and toluene, wherein the
65 formaldehyde is first produced in a separate reactor by either
An embodiment of the present invention is a process for the dehydrogenation or oxidation of methanol and is then
making styrene by converting methanol to formaldehyde in reacted with toluene to produce styrene.
 US 8,796.498 B2
3 4
FIG. 2 is a schematic illustration of an aspect of an embodi ating conditions and the efficiency of the reaction system. If
ment of the present invention having the capability for con excess toluene or formaldehyde is fed to the reaction Zone, the
tinuous reaction with catalyst regeneration. unreacted portion can be Subsequently separated and recycled
back into the process. In one embodiment the ratio oftoluene:
DETAILED DESCRIPTION formaldehyde can range from between 100:1 to 1:100. In
alternate embodiments the ratio oftoluene:formaldehyde can
Toluene has been used to produce styrene by reactions with range between from 50:1 to 1:50: from 20:1 to 1:20; from
either methanol or methane/oxygen as the co-feed. Theoreti 10:1 to 1:10: from 5:1 to 1:5; from 2:1 to 1:2.
cally methanol (CHOH) and toluene (CHCH) can be In FIG. 1 there is a simplified flow chart of one embodiment
reacted together to form styrene, water and hydrogen gas, as 10 of the styrene production process described above. The first
shown below: reactor (2) is either a dehydrogenation reactor oran oxidation
reactor. This reactor is designed to convert the first methanol
feed (1) into formaldehyde. The gas product (3) of the reactor
In practice, however, the methanol (CHOH) often dehy is then sent to a gas separation unit (4) where the formalde
drogenates into formaldehyde (CHO) and hydrogen gas 15 hyde is separated from any unreacted methanol and unwanted
(H). Often the toluene conversion is low or the selectivity to byproducts. Any unreacted methanol (6) can then be recycled
products of the methanol is too low to make the process back into the first reactor (2). The byproducts (5) are sepa
economical. Conversion of methanol to COX or methane can rated from the clean formaldehyde (7).
result in an undesirable by-product stream that is not easily In one embodiment the first reactor (2) is a dehydrogena
recovered. In order to avoid this undesirable side reaction, a tion reactor that produces formaldehyde and hydrogen and
method of producing styrene utilizing a separate reactor to the separation unit (4) is a membrane capable of removing
convert methanol into formaldehyde is disclosed. Toluene hydrogen from the product stream (3).
can then be reacted directly with formaldehyde to produce In an alternate embodiment the first reactor (2) is an oxi
styrene and water. This process avoids the instability aspects dative reactor that produces product stream (3) comprising
of the methanol. 25 formaldehyde and water. The product stream (3) comprising
Formaldehyde can be produced either by the oxidation or formaldehyde and water can then be sent to the second reactor
dehydrogenation of methanol. Silver-based catalysts are most (9) without a separation unit (4).
commonly used for this process but copper can also be used. The formaldehyde feed stream (7) is then reacted with a
Iron-molybdenum-oxide catalysts are typically used for the feed stream of toluene (8) in the second reactor (9). The
dehydrogenation route. A separate process for the dehydro 30 toluene and formaldehyde react to produce styrene. The prod
genation or oxidation of methanol into formaldehyde gas uct (10) of the second reactor (9) may then be sent to an
could be utilized. optional separation unit (11) where any unwanted byproducts
A separation unit may then be used if needed in order to (15) Such as water can separated from the styrene, unreacted
separate the formaldehyde from the hydrogen gas or water formaldehyde and unreacted toluene. Any unreacted formal
from the formaldehyde and unreacted methanol prior to react 35 dehyde (12) and the unreacted toluene (13) can be recycled
ing it with toluene for the production of styrene. This sepa back into the reactor (9). A styrene product stream (14) can be
ration would inhibit the hydrogenation of the formaldehyde removed from the separation unit (11) and subjected to fur
back to methanol. Purified formaldehyde could then be sent to ther treatment or processing if required.
the second reactor and the unreacted methanol could be The operating conditions of the reactors and separators will
recycled. The use of formaldehyde for the side chain alkyla 40 be system specific and can vary depending on the feedstream
tion of toluene is shown below: composition and the composition of the product streams. The
reactor (9) for the reaction of toluene and formaldehyde will
operate at elevated temperatures and pressures, such as for a
Formaldehyde can be produced by the oxidation of metha non-limiting example from 250° C. to 750° C. and from 1 atm
nol to produce formaldehyde and water. The oxidation of 45 to 70 atm in pressure and may contain a basic or neutral
methanol is described in the equation below: catalyst system.
Suitable catalysts for the reaction of toluene and formal
dehyde can include as non-limiting examples metal oxides
Alternately formaldehyde can be produced by the dehy such as: CuO, ZnO CuO; ZnO CuO Al-O, CuCrO3:
drogenation of methanol to produce formaldehyde and 50 ZnCrO; or ZnO CuO CrOs. Other catalysts that can be
hydrogen gas. This method produces a dry formaldehyde used include metals Supported on a substrate such as silica or
stream that may be preferred as it would not require the titania, for example: Ru; Rh; Ni; Co: Pd; or Pt. These can also
separation of the water prior to the reaction of the formalde contain promoters such as Mn,Ti, Zr, V.Nb, K, Cs, or Na. Still
hyde with toluene. The dehydrogenation process is described another group of catalysts that can be used for the present
in the equation below: 55 invention include sulfide based catalysts such as: MoS:WS:
CHOH->CHO+H,
MoWS; CoMoS; or NoMoS. These sulfide catalysts can
include promoters such as K, Rb, Cs, Ca, Sr., Ba, La, or Ce.
In order to prevent the hydrogenation of formaldehyde The above catalysts can have toluene promoters added
back to methanol, it is desirable to have the separation of Such as the alkali, alkaline earth, and/or rare earth elements.
formaldehyde from either water or hydrogen gas prior to its 60 Other toluene promoters that can be added include Y, Zr,
reaction with toluene. Separating the formaldehyde from the and/or Nb.
other byproducts of the oxidation or dehydrogenation reac Improvement in side chain alkylation selectivity may be
tion would result in a stable formaldehyde stream that could achieved by treating a molecular sieve Zeolite catalyst with
be used in the production of styrene. proper chemical compounds to inhibit the external acidic
Although the reaction has a 1:1 molar ratio of toluene and 65 sites and minimize aromatic alkylation on the ring positions.
formaldehyde, the ratio of the feedstreams is not limited Another means of improvement of side chain alkylation
within the present invention and can vary depending on oper selectivity can be to impose restrictions on the catalyst struc
 US 8,796.498 B2
5 6
ture to facilitate side chain alkylation. In one embodiment the The catalyst can be continuously circulated from the reac
catalyst used in an embodiment of the present invention is a tion Zone (21) to the regeneration vessel (22) and then again
basic or neutral catalyst. to the reaction Zone (21). The catalyst can therefore act as a
The catalytic reaction systems suitable for this invention vehicle for the transfer of heat from Zone to Zone as well as
can include one or more of the Zeolite or amorphous materials providing the necessary catalytic activity. Catalyst from the
modified for side chain alkylation selectivity. A non-limiting reaction Zone (21) that is being transferred to the regeneration
example can be a zeolite promoted with one or more of the Zone (22) can be referred to as “spent catalyst'. The term
following: Ru, Rh, Ni, Co, Pd, Pt, Mn,Ti, Zr, V. Nb, K, Cs, or “spent catalyst” is not intended to be indicative of a total lack
Na. of catalytic activity by the catalyst particles. Catalyst, which
Zeolite materials suitable for this invention may include
10 is being withdrawn from the regeneration vessel (22), is
silicate-based Zeolites and amorphous compounds such as referred to as “regenerated catalyst. The catalyst can be
faujasites, mordenites, pentasils, etc. Silicate-based Zeolites regenerated in the regeneration vessel (22) by heat and con
tact with a regeneration stream (30). The regeneration stream
are made of alternating SiO, and MO, tetrahedra, where M is (30) can comprise oxygen and can comprise steam. The
an element selected from the Groups 1 through 16 of the 15 regenerated catalyst can be separated from the regeneration
Periodic Table (new IUPAC). These types of zeolites have 8-, stream by the use of one or more cyclones (31) that can enable
10-, or 12-membered oxygen ring channels. An example of the removal of the regeneration vessel (22) via line (32). The
Zeolites of this invention can include 10- and 12-membered regenerated catalyst can be transferred via line (33) to the
ring zeolites, such as ZSM-5, ZSM-11, ZSM-22, ZSM-48, lower section of the riser (23) where it is again in contact with
ZSM-57, etc. the feed stream (25) and can flow up the riser (23).
Embodiments of reactors that can be used with the present Use of broader terms such as comprises, includes, having,
invention can include, by non-limiting examples: fixed bed etc. should be understood to provide support for narrower
reactors; fluid bed reactors; and entrained bed reactors. Reac terms such as consisting of consisting essentially of com
tors capable of the elevated temperature and pressure as prised Substantially of, etc.
described herein, and capable of enabling contact of the reac 25 The term “molecular sieve” refers to a material having a
tants with the catalyst, can be considered within the scope of fixed, open-network structure, usually crystalline, that may
the present invention. Embodiments of the particular reactor be used to separate hydrocarbons or other mixtures by selec
system may be determined based on the particular design tive occlusion of one or more of the constituents, or may be
conditions and throughput, as by one of ordinary skill in the used as a catalyst in a catalytic conversion process.
art, and are not meant to be limiting on the scope of the present 30 Use of the term “optionally with respect to any element of
invention. An example of a fluid bed reactor having catalyst a claim is intended to mean that the Subject element is
regeneration capabilities that may be employed with the required, or alternatively, is not required. Both alternatives
present invention is illustrated in FIG. 2. This type of reactor are intended to be within the scope of the claim. Use of
system employing a riser can be modified as needed, for broader terms such as comprises, includes, having, etc.
example by insulating or heating the riser if thermal input is 35 should be understood to provide support for narrower terms
needed, or by jacketing the riser with cooling water if thermal Such as consisting of consisting essentially of comprised
dissipation is required. These designs can also be used to Substantially of, etc.
replace catalyst while the process is in operation, by with The term “regenerated catalyst” refers to a catalyst that has
drawing catalyst from the regeneration vessel from an exit regained enough activity to be efficient in a specified process.
line (not shown) or adding new catalyst into the system while 40 Such efficiency is determined by individual process param
in operation. eters.
FIG. 2 is a schematic illustration of an aspect of an embodi The term “spent catalyst” refers to a catalyst that has lost
ment of the present invention having the capability for con enough catalyst activity to no longer be efficient in a specified
tinuous reaction with catalyst regeneration. The reaction pro process. Such efficiency is determined by individual process
cess (20) generally comprises two main Zones for reaction 45 parameters.
(21) and regeneration (22). A reaction Zone can be comprised The term “Zeolite' refers to a molecular sieve containing a
of a vertical conduit, or riser (23), as the main reaction site, silicate lattice, usually in association with Some aluminum,
with the effluent of the conduit emptying into a large volume boron, gallium, iron, and/or titanium, for example. In the
process vessel, which may be referred to as a separation following discussion and throughout this disclosure, the
vessel (24). In the reaction riser (23), a feed stream (25), such 50 terms molecular sieve and Zeolite will be used more or less
as toluene and formaldehyde, is contacted with a fluidized interchangeably. One skilled in the art will recognize that the
catalyst, which can be a relatively large fluidized bed of teachings relating to Zeolites are also applicable to the more
catalyst, at reactor conditions. The residence time of catalyst general class of materials called molecular sieves.
and hydrocarbons in the riser (23) needed for substantial Depending on the context, all references herein to the
completion of the reaction may vary as needed for the specific 55 “invention' may in some cases refer to certain specific
reactor design and throughput design. The flowing vapor/ embodiments only. In other cases it may refer to subject
catalyst stream leaving the riser (23) may pass from the riser matter recited in one or more, but not necessarily all, of the
to a solids-vapor separation device. Such as a cyclone (26), claims. While the foregoing is directed to embodiments, ver
normally located within and at the top of the separation vessel sions and examples of the present invention, which are
(24). The products of the reaction can be separated from the 60 included to enable a person of ordinary skill in the art to make
portion of catalyst that is carried by the vapor stream by and use the inventions when the information in this patent is
means of one or more cyclone (26) and the products can exit combined with available information and technology, the
the cyclone (26) and separation vessel (24) via line (27). The inventions are not limited to only these particular embodi
spent catalyst falls downward to a stripper (28) located in a ments, versions and examples. Other and further embodi
lower part of the separation vessel (24). Catalyst can be trans 65 ments, versions and examples of the invention may be devised
ferred to a regeneration vessel (22) by way of a conduit (29) without departing from the basic scope thereof and the scope
connected to the stripper (28). thereof is determined by the claims that follow.
 US 8,796.498 B2
7 8
What is claimed is: 8. The process of claim 2, wherein the toluene is reacted
1. A process for making styrene comprising: with the formaldehyde at a pressure ranging from 1 atm to 70
reacting toluene and formaldehyde in one or more reactors atm.
over a sulfide catalyst to form a product stream compris 9. The process of claim 2, wherein the first product stream
ing styrene, wherein the sulfide catalyst comprises further comprises one or more of hydrogen, water, or metha
MoS2, WS., Mo., WS., CoMoS, or NoMoS. nol.
2. A process for making styrene comprising: 10. The process of claim 2, wherein methanol is separated
converting methanol to formaldehyde in one or more first from the first product stream and recycled to the one or more
first reactors.
reactors to form a first product stream comprising form 10 11. The process of claim 2, further comprising utilizing one
aldehyde:
passing the first product stream to a separation stage for or more oxidation reactors to convert methanol into formal
separating formaldehyde from the first product stream; dehyde and water to form the first product stream.
and 12. The process of claim 2, further comprising utilizing one
reacting toluene and formaldehyde in one or more second or more dehydrogenation reactors to convert methanol into
reactors over a sulfide catalyst to form a second product 15 formaldehyde and hydrogen to form the first product stream.
stream comprising styrene, wherein the sulfide catalyst 13. The process of claim 2, wherein the second product
comprises MoS, WS, Mo, WS. CoMoS, or stream further comprises one or more of toluene, water, or
NoMoS. formaldehyde.
3. The process of claim 2, wherein the sulfide catalyst is 14. The process of claim 2, further comprising passing the
promoted with K, Rb, Cs, Ca, Sr., Ba, La, or Ce. Second product stream to a second separation stage for sepa
4. The process of claim 2, wherein the sulfide catalyst rating styrene from the second product stream.
comprises one or more promoters chosen from the group of 15. The process of claim 14, wherein toluene is separated
alkali elements, alkaline earth elements, and rare earth ele from the second product stream and recycled to the one or
mentS. more second reactors.
5. The process of claim 2, wherein the sulfide catalyst 25 16. The process of claim 14, wherein formaldehyde is
comprises one or more promoters chosen from Y, Zr, and Nb. separated from the second product stream and recycled to the
one or more second reactors.
6. The process of claim 2, wherein the sulfide catalyst is 17. The process of claim 2, wherein the first separation
basic or neutral.
7. The process of claim 2, wherein the toluene is reacted stage comprises a membrane to remove hydrogen from the
with the formaldehyde at a temperature ranging from 250° C. 30 first product stream.
to 750° C.