CA1117549A

CA1117549A - High temperature vapor phase catalytic dimerization of acrylonitrile

Info

Publication number: CA1117549A
Application number: CA000291804A
Authority: CA
Inventors: James L. Callahan
Original assignee: Individual
Current assignee: Individual
Priority date: 1976-11-26
Filing date: 1977-11-25
Publication date: 1982-02-02
Also published as: AU517491B2; AU3089877A; GB1573281A; BE861222A; FR2372149A1; ATA851877A; DK527577A; ZA776690B; AT360502B; DE2752168A1; JPS5368724A; SE7713392L

Abstract

HIGH TEMPERATURE VAPOR PHASE CATALYTIC
DIMERIZATION OF ACRYLONITRILE

ABSTRACT OF THE DISCLOSURE
Acrylonitrile is dimerized to 1,4-dicyanobutenes and adiponitrile by contacting acrylonitrile in the vapor phase with a catalyst comprising activated alumina containing inorganic sulfide ion.

Description

BACKGROUND OF THE INVENTION
The present lnvention relates to the high temper-ature vapor phase dimerization of acrylonitrile to form ~someric 1,4-dlcyanobutenes and adiponitrile.
P~uch work has been recently done on the catalytic dimerization and hydrodimerizaticn of acrylonitrile to 1,4~
dicyanobutenes and adiponitrlle. See, for example, the following Japanese and German patent publications: JA
077686, JA 7115494, JA 7125726, JA 7121369, JA 7127729, JA
7115485, DT 1945780, JA 7139330 and DT 2446641. As disclosed in these patents, acrylonitrile can be dimerized into 1,4-dicyanobutenes and/or adiponitrile by contacting acrylonitrile in the gaseous phase optionally together with hydrogen with a catalyst selected from a wide variety of dif~erent materials.
In many of these references, ~t is necessary or preferable to sub;ect the catalys~ pri.or to use to reduction in hydrogen gas so that the metallic components of the catalyst are present essentially in elemental form. Alternatively, the metallic catalyst can be employed ln some of the processes in the form o~ a chloride, sulfate, nitrate, acetate or Gther organic compound.

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Against this background, it has been discovered tha~ a catalyst co~.prising actlvated alumi~a containing inorganic su].fide lon exhibits a substantial and unexpected activity in the catalytlc vapor phase dimerization of acrylo-nitrile.
Therefore, in accordance with the present invention, a process for the vapor phase catalytic dimer~.ation of acrylonitrile to 1,4-dicyanobutenes and adiponitrile is provided, the process comprising contacting gaseous acrylo-nitrile with a catalyst comprising activated alumina contain-lng inorganic sulfide ion. More specifically, the present invention provides a process for the vapor phase catalytic dimeri~ation of acrylonitrile to l,4-dicyanobutenes and adiponitrile in which acrylonitrile in the gas phase is contacted with an inorganic sulfide ion-containing activated alumina catalyst formed by contacting activated alumina at an elevated temperature of at least about 500F with a material capable of decomposing to liberate inorganic sulfide ion at the elevated temperature. In another embodiment, the present lnvention also provides a process for the vapor phase catalytic dimerization of acry~onitrile to 1,4-dicyano-butenes in which acrylonitrile in the gas phase is contacted with a catalyst comprising an activated alumina carrier having supported thereon a catalytically effective amount of a sulfide of a metal or metalloid, the metal or metalloid being selected from Groups IA, IIA, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIA, and IVA of the Period1c Table, the rare earth metals, scandium and hafnium.

754~

DETAI_~3 ~SCR~PTIOtJ
Process Conditions In carrying out the inventive process, acrylo-nitrile in the vapor phase is contacted with a catalyst zs described below for effecting the dimerization reaction.
The reaction can be carried out either in the batch mode or continuously and either with a fixed bed or a fluidized bed.
he reaction temperature is generally between 500 and 1100F, 800 to 1000~ being preferred. The reaction pressure is normally maintained between 1 and lO0 atmospheres with a reaction pressure of 2 to 50 atmospheres being preferred.
The apparent contact time between the catalyst and the reactant may vary from about 0.1 second to about 30 seconds.
In general, lower reaction temperatures tend to benefit from longer contact times, and at higher temperature shorter contact times tend to be optimum.
Preferably, the gaseous acrylonitrile feed fed to the reactor contains a carrier gas for sweeping the rela-tively heavy reac~ion products out of the reactor. Hydrogen, nitrogen or any gas inert to the reaction can be employed as the carrier gas. Preferably, the amount of carrier gas mixed with the acrylonitrile feed is such that the acrylo-nitr~le/carrier gas ratio in the feed is 0.5:1 to 25:1. If desired~ hydrogen sulfide in a molar ratio of gr eater than zero to 30 mole ,ol ~ preferably 2 to 20 mole ~0, and optimally 30. 15 mole %, with respect to the total amount o~ carrier gas , 5~3 ~e~, can be include~' in ~hc carr'er gas to insure that t~lP
~ r~ir.a ca~alJ~st of thC ~PsPn~ r.ven~ion rera~ns ricn ~n sul~lde ion during ~he di~erization reaction. ~he preferrPd ca~rier ~as is hydro~en since hydrogen insures th2t the metal or metallo~d in the catalyst remains in a reduced sta~e.
he reaction product obtained upon comple'ion of the reaction is composed prlmarily o~ propionitrile, adipo-nitrile, cis- and trans-1,4-d~cyanobutene-1, cis and trans-1,4-dicyanobutene-2 and unreacted acrylonitrile. Also present may ~e small amounts Or succinonitrile, acetonitrile and pyridine. The reaction product can be subjected to suitable known separation techniques to yield the desired end products, namely the 1,4-dicyanobutenes and adiponitrile.
As is well known ln the art, adiponitrile can be readily con~erted into either hexamethylenediamine or adipic acid, which are both starting materials for nylon 66, by simple and straightforward procedures. See U. S. Patents 3,056,837, 3,272,866 and 3,272,867. Also, 1,4-dicyanobutenes can be converted into adiponitrile by known hydrogenation proce-dures. See, for example, M. J. .~stle, Chemistry of Petro-che~icals, Reinhold Chemical Co., copyright 1956, pp. 240, 247 and 256; and U. S. Patent 2,518,608 and U. S. Patent

2,451,386.
Catalyst The catalyst employed in the inventive process ~or the high temperature vapor phase catalytic dimerization of acrylonitrile comprises activated alumina containing the inorganic sulfide ion, the alumina being used alone or in combination with a metal or metalloid promo~er. Thus, in one embodiment of the present invention, unpromoted ~17~
activated a'~l~ira ,lhen acti~ated SG as to contain inorganic sullide ion can be used as the catalyst in the i~ventive process. In this embodi,~.ent, activated aliu.nina is sulfur-activated by contacting the alumina at an elevated tempera-ture, normally at least about 500F, with a materi21 capableof decomposing in the presence of activated alumina at the elevated temperature to liberate sul~ide ion (hereinafter referred to as a "sulfide ion-yielding material"j. ~ny material which is capable of decomposing in the presence o activated alumina to liberate sulfide ion at a temperature of at least about 500F is useful for this purpose. For example, hydrogen sulfide, carbon disulf~de and organic sulfur-containing molecules decomposing at a temperature of at least about 500F to llberate sulfide ions can be used.
Good examples of such organic sulfur containing molecules are the mercaptans, specifically alkyl mercaptans in which the alkyl group has 1 to 12 carbon atoms (iOe. methyl mercaptan, ethyl mercaptan, propyl mercaptan, etc.). In this embodiment, the use of hydrogen sulfide or carbon disulfide is pre~erred while the use of hydrogen sulfide is most preferred.
In order to sulfur activate the activated alumina catalyst in this embodiment of the invention so that it contains inorganic sulfide ion, activated alumina is heated to an elevated temperature at or above about 500F and contacted with the sulfide ion-yielding material. The activated alumina can be heated to the elevated temperature prior to or simulaneously with contacting the sulfide lon-yielding material. ~lternately, the sulfide ion-yielding material can be heated to the elevated temperature. The time period over which the activated al~nina must be ~'7~

contacted wlth the sul~ide ion-yielding material is the time necessary ~or the sulfide ion-yielding material to react with the ~lu~in~ and ~o~m si~ni~icant inorg~nic sulfide ion. Normally this takes about 0.1 to 5 hours.
In accordance with another embodiment o~ the present invention, the activated alu~ina support can be promoted with a suitable metal or metalloid promoker ele-ment. In accordance with the present invention, it has ~een found that sul,ur-activated activated alumina promoted ~Jith a wide variety of different metals or metalloids will also exhibit a significant catalytic effect in the catalytic dimerization of acrylonitrile to 1,4-dicyanobutenes and adiponitrile. In accordance with this embodiment of the invention, elements found useful in exhibiting a promoter effect are metals and metalloids of Groups IA, IIA, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA5 and IVA of the Periodic Table, rare earth metal, scandium and hafnium. A broadly preferred class of promoter metal or metalloids is lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, - 20 strontium, barium, chromium, molybdenum, manganese, iron, cobalt, nickel, pallad~um, platinum, copper, silver, zinc, cadmium, tellurium, tin and lead. A more preferred class of metal or metalloid promoters is composed of those of the foregoing elements in Groups IA, IIA, IB and IIB of the Periodic Table and lead, namely lithium, sodium, potassium, rubidium, cesium, manganese, calcium, strontium, barium, copper, silver, zinc, cadmium and lead. ~ost preferred metal or metalloid promoters are sodium, strontium, and silver. In each of the above-noted classes, the indicated metals and metalloid can be used individually or in ad-mixture with one another.

3 ~L75~
~e s~ ur-ac~iva~ed ac~l~ated alu~n~ ca~'ysts o2 ~his emboc~ment ol ~h~ preser~.t invention can contain from a creat de~l to a ver~ llttle metal or metallold promo~Pr.
The m~nlmal amount Or pro~.oter is that amount nece~sary for the presence of~ the promoter to exert an influence on the catalytic activ~ty o~ the sulfur-activated catalyst. The ma~lmum zmount is approximately 90 ~Jeight percent, based on the total weight of the catalyst. Normally, the amount of metal or metalloid promoter is greater than zero percent to 90 weight percent, preferably 0.1 to 50 weight percent, while the most preferred amount is about 1 to 10 weight percent.
The catalyst o~ this embodiment o~ the p~esent invent~on can be prepared by depositing the metal or metal-loid promoter in elemental form or in the form o~ an oxide~
hydroxide or salt on an activated alumina support or carrier and thereafter subjecting the composites ~ormed to sulfur-activating conditions as described above. Promoter metals or metalloids can be deposited on an activated alumina support by depositing on the activated alumina support a reducible or irreducible salt, hydroxlde or oxide of the metal or metalloid and thereafter reducing the salt or oxide by contact with elemental hydrogen. Examples of compounds useful for this purpose are Ni(No3)2~6H2o, P205-24MoO3-48H20 (for Mo), CetN03)3~6H20, CrO3, Cu(N03)2 3H20, ( 3 3 2 MntN3)2~6H2~ KOH~ Uo2(No3?2'6H20~ Mg(No3)2~6H2o~ ~lN03, AgN03~ and PdC12. Techniques ~or depositing metals or metalloids on supports are well known in the art and thoroughly described ln the various Japanese patents listed above.

4~

~ ice the ~e~a or r~etalloid ~o~o~er ~ de~osited cn the support, t~e co~pos~tes so rormed can be sub~ected to sul~ur-activatlrlg cor.ditions as described above. As in the previous e~.bodiment, the composite c~n be activ~ted by contacting the composite wlth a material capable of decomposing in the presence of the activated alumina composite to liberate sul~ide ~on at an elevated tem~erature, preferably at least about 500F. Such materials as hydrogen sulflde~ carbon disulfide and decomposable organic sulfur-containing molecules, such as the mercaptans mentioned above, are also use~ul in this embodiment o~ the invent~on. Moreover, the contact time should, in general, also be about 0.1 to 5 hours.
In this connection, in this embodiment of the ~nvention the sulfur activation procedure is accomplished for a time and at a temperature sufficient so that the metal or metalloid in the composite is converted to the corresponding ~norganic sulfide. Accordingly, in this embodiment of the present invention the catalyst can be characterized as comprisin~ an activated alumina support having thereon a metal or metalloid promoter in the form of an inorganic sulflde.
From the foregoing, it will be appreciated that the present invention provides a novel process for the catalytic dimerization of acrylonitrile to 1,4-dlcyano-butenes and adiponitrile. An important aspect of thisprocess is that the cakalyst employed is activated alumin~
either alone or in combination with a suitable metal or metalloid promoter which has been subjected to a sulfur-activation treatment. Although not wishing to be bound to 3 any theory, it is believed that the novel catalytic -75i~

e~ect re~'iz~d ir. accor~a~ce wi~h the pre~ent invention occurs when sulfur is present in the activated all~mina catalyst in the form of inorganic s~lfide ion. In the second embodiment of the present invention in which the activated alumina is promoted with a metal or metalloid promoter, sul~ur-activation of the alumina/promoter com-posite has the effect of causing the metal or metalloid in the composite to take the form of a sulfide. Therefore, in this embodiment sulfide ion is present as part of the metal compound containing the metal promoter.
In a similar manner, it is believed that small but significant amounts of sulfide ion are present in the activated alumina catalyst of the first embodiment of the present invention in which no metal or metalloid promoter is combined with the activated alumlna support. Thermodynamic studies tend to show that alumina, A12O3, will not be trans-formed in major amount to aluminum sulfide by contact with hydrogen sulfide. However, such studies are based on macroscopic analysis. It is believed that although the entire body of an alumina mass sub~ected to sulfiding conditions may not form aluminum sulfide, small but signif-icant amounts of aluminum sulfide are formed on the surfaces of the alumina body. It i5 believed, therefore, that in-organic sulfide ion is also present in the activated alumina catalyst of the first embodiment of the present invention in which no metal or metalloid promoter is added to the alu~.ina.
To further support the view that it is the pres-ence of inorganic sulfide ion in the alumina catalyst of the present invention which provides the novel catalytic effects 3o herein described, it has also been found in accordance with the present invention that sulfide ion can be introduced 5a~9 into the alumina cava~yst c,f the p~esen~ invent~on b~
technlques other than the sulfur~activation treatment discussed above. For exar.~le, it has been ~ound that an e~. ective catalyst can also be obtained by introducin~
sulfide ion during the wet chemistry stage o~ preparir.g the catalyst. This may be accompl~shed by bubbling H2S g2s through an aqueous slurry o~ activated alumina particles and a salt of the metal or metalloid promoter, whereby a sulfide of the metal or metalloid forms on the activated alumina particles. Still another way of producing an effective catalyst comprises m~xing elemental sulfur with a composite comprising the metal or metalloid promoter in reduced or ele-mental form on an activated alumina support and thereafter heating the mixture to calcining temperatures (e.g. above 500F) in an inert atmosphere.
Any activated alumina having a surface area of 0.5 to 800 m2/g can be employed as the starting material to form the sulfide ion-containing catalyst em~loyed in the inventive process. For example, activated alumina having a surface ,~ 20 area of 2 to 500 m2/g can be used to advantage in the present invention. As a practical matter, the most common surface area of commercially available alumina is about 200 m /g, and therefore the activated alumina used in the inventive process preferably has a surface area of 2 to 200 m2/g. The particle size of the activated alumina starting material used to make the catalyst of the inventive process as well as the particle size of the catalyst itself is unimportant, any particle size being effective. When the inventive process is carried out in a fixed-bed reactor on a commercial scale, the particle size of the catalyst ~75~

ca~. be the CGn~ention~ par~icle size for fi~ed-bed com-mercial cara1ytic reactors, namel~ 1/16 inch to 1/2 inch in diameter. Similarly, w-hen the in~entive ~rocess is carried out in a fluid-bed, the particle size of the catalyst is advantageously the conventional particle size ~or cor~mercial fluid-bed reactor~, namely 20 to 300 mi crons. In the following workin~ examples the catalyst had a particle size of 9 to 40 mesh, Tyler, since this is a convenient size for laboratory scale testing.
Examples In order to more thoroughly describe the present invention, the following working examples are presented. In each o~ these examples, acrylonitrile was dimerized in a reactor constructed of an 8.0 mm inside diameter stainless steel tube. The reactor had a 10 cc reaction zone, an inlet for reactants and an outlet for products. The reactor was heated in a salt bath to give the desired reaction tempera-ture. In ~eneral, the experimental method consisted of pre reducing a supported metal oxide catalyst with hydrogen and then passing a mixture of hydrogen and acrylonitrile over the catalyst at 800F at one atmosphere total pressure.
Standard run conditions in all the examples unless otherwise indicated comprised a feed rate of 40 STP cc/min. H2, 0.2 cc liquid acrylontrile per minute and a run time of 5 minutes. In a large number of runs, the used catalyst was sulfided with a mixture of 15% H2S in H2 and a second run was made with an acrylonitrile/hydrogen mixture.
In all runs, the off-gas was scrubbed in 11.0 cc of acetone at ice temperature and an aliquot was analyzed by ~2S liquid chromotography and mass spectroscopy for the degree of acrylonitrile conversion and the composition of the converted product.

3L13L75q~
For the ?urDoses of th1s applicat~srl, the fol-lo~ir,E definitions are used:

moles of acrYlni ri e reacted ~ 100 % Yield = moles of acrylonitrile converted to a s~ecific product x 100 moles of acrylonitrile reacted The following experiments, some of which represent the ~resent invention and others of which are outside the scope of the invention and presented for the purposes of comparison, were conducted:

Exam An aqueous solution of NH4OH was added to an aqueous copper nitrate solution to produce a preci~itate of hydrous CuO. The precipitate was recovered, filtered, washed, dried, crushed, screened, calcined and reduced at 800F in H2 to produce 9 to 40 mesh (Tyler) copper particles.
The reactor was charged with 3 cc of copper particles, and the charge was ~ulfided by passing a 20% H2S in H2 stream through the reactor for one hour at 800F. A total of 1.0 oc acrylonitrile was then fed through the reactor over a period of fi~e minutes. Along with the acrylonitrile, H2 was ~ed through the reactor at a rate of 40 STP cc/min.
The reaction temperature was maintained at 800F. The reaction product was recovered and analyzed wlth the following results:
acrylonitrile conversion = 0%
propionitrile yield = 0%
adiponitrile yield = 0,~
1,4-dicyanobutene-1 yield = 0%
1,4 dicyanobutene-2 yield = 0%

7~i49 _xam ~_ 4 cc ~amma activated alumina having a surface area of 180 to 200 m2/g and a particle size of 9 -to 40 rnesh ~as fed .into the reactor and the reactor heated to a ternperature o~ 800F. A gas mixture comprisiny 15% H2S in H2 was fed to the reactor to effect sulfiding of the alumina catalyst.
After 15 minutes, acrylonitrile was also fed to the rèactor, a total of 1 cc acrylonitrile being uniformly fed to the reactor over a period of 5 minutes. The reaction product 10 was recovered and analyzed with the following results:
acrylonitrile conversion = 35.2%
propionitrile yield = 1.1%
adiponitrile yield = 0%
1,4-dicyanobutene-1 yield = 5.6%
1,4-dicyanobutene-2 yield = 0%

_ample 3 Example 2 was repeated except that the reactor was charged with 4 cc of 14 to 2~ mesh (Tyler) Alundum ~ (Alcoa T-61). The following results were obtained:
acrylonitrile conversion = 0%
propionitrile yield = 0%
adiponitrile yield = 0%
1,4-dicyanobutene-1 yield = 0%
1,4-dicyanobutene-2 yield = 0%
material balance 100%

Example 4 ___ _ 2.47 g. Co(NO3)2 6H20 was dissolved in S cc water, and the solution obtained thereby was used to impregnate 5

5~9 ,-c-a~s Or 9 ~o 4fS rr,esh activate~ r,ina having a surface rea of 180 to 200 ~2/g The resultant corr.posite was dried at 2 ~emDeratUre o~ 153C, heated in air for one hour at 500C and then c~ar~e~ into the reactor. ~2 was fed to the reactor for a period of one hour at 800F to reduce the cobalt in the composite. Thereafter, the com~osite was sulfided by passing a mixture of 15% H2S in H2 ~hrough the reactor for 30 minutes at 800F. The dimerization reaction was accomplished by passing 1.0 cc acrylonitrile through the reactor uniformly over a period of five minutes~ Along with the acrylonitrile a carrier gas comprising 15% H2S in H2 was fed to the reactor at a rate of 40-STP cc/min. The reaction temperature was 800F. mhe reaction product was recovered and the ~ollowing results were obta~ned:
acrylonitrile conversion =31.5%
propionitrile yield =13.8%
adiponitrile yield = 0%
1,4-dicyanobutene-1 yield =7.5%
1,4-dicyanobutene-2 yield = 0%

After completion of ~xample 4, the catalyst was left in the reactor and stripped with H2 for one hour at 800F. After the stripping operation, 1.0 cc acrylonitrile was fed to the reactor uniformly over a period of five minutes. Along with the acrylonitrile, 40 STP cc/min H2 was fed to the reactor. The reaction temperature was maintained at 800F. The reaction product was r-ecovered and the following results were obtained:

75~3 2crylon1lr le conversion = 12.9~
?ro?ionitrile yield ~ 35.5%
adiponitrile yield = 0 19 4-dicyanobutene-1 yield = 12.5~
1,4-dicyanobutene-2 yield a 0%

Exam~le 6 Example 4 was repeated except that the catalyst in the reactor was not sub~ected to sulfiding condltions with 15% H2S in H2 after cobalt was reduced. Also, H2S was not 10 included in the carrier gas. The following results were obtained:
acrylonitrile conversion = 5~.9%
propionitrile yield = 23. 8/o adiponitrile yield = 0%
1,4-dicyanobutene-1 yield - 1.7%
1~4-dicyanobutene-2 yield = 0,0 Example_7 5.0 grams of 9 to 40 mesh (Tyler) high surface area (180 to 200 m2~g~ gamma alumina particles were impreg-nated with 0.97 grams P2o5~24MoO3~48H20 in sufficient amount of water to ~us~ wet the surface of the alumina particles.
The alumina particles so impregnated were dried ~or two hours at 150C and calcined in air at 500C for one hour to yield activated alumina particles having thereon 9.1%
Mo in the ~orm of molydena. 3 cc of the catalyst were charged into the reactor and sub~ected to hydrogen reduction conditions at 800F for two hours. 1.0 cc acrylonitrile was uniformly fed to the reactor over a period of five minutes, H2 also being ~ed to the reactor during the reaction ~7~
at 40 STP cc/min. The reaction tem~erature ~las ~OO~F. The reactlon product was recovered and the ~ollowing recults were obtained:
acrylonitrile converslon = 49.0 pro~ionitrile yield ~ 58.5~
adiponi~rile yield ~ 0%
1,4-d~cyanobutene-1 yield = 2.0%
1,4-dicyanobutene-2 yield = 0%

Example 8 After the completion of Example 7, the catalyst in the reactor was sulfided by passing 15~ H2S in H2 over the catalyst for two hours at 800F. 1.0 cc acrylonitrile was then fed to the reactor uniformly over a period of five minutes, H2 at a rate of 40 STP cc/min also being fed to the reactor during this period. The reaction temperature was 800F. The reaction product was recovered and the following results were obtained:
acrylonitrile ccnversion = 70.1 propionitrile yield = 96.3~
adiponitrile yield = o%
1,4-dicyanobutene-1 yield = 2.3%
1,4-dicyanobutène-2 yield - 0%

The foregoing general procedure was repeated with many di~ferent catalysts, and the results of these experi-ments are set forth in the following Table 1. In most of these experiments, a starting material comprising a support and an amount of decomposable salt, decomposable hydroxide or oxide thereon was first procluced, and then the starting material was calcined in air at elevated temperakure so that -the metal or metalloid was present in -the composite in oxide form. The composite was then subjected to an atmosphere of hydrogen at 800F to reduce the metal or metalloid oxide.
The catalyst so produced was used in a first dimerization reaction. After completion of the first dimerization reaction, the catalyst remaining in the reactor was subjected to sulfiding with H2S at elevated temperature and used in a second dimerization reaction. Unless-otherwise indicated in Table 1:
-~ the catalyst support was 9 to 40 mesh, Tyler;
-- activated alumina was a gamma activated alumina having a surface area of 180 to 200 m2/g;
-- activated carbon supports were about 10 mesh, Tyler (Nitco ~3 Grade 718);
-- in those cases in which the support was silica, the usual method of preparation was by forming a solutior~ of decomposable metal salt in a silica sol (Nalco ~ 1034 A), gelling with ammonium nitrate and calcining the dry gel in air at a temperature o~ 350 to 500C;
-- in those experiments in which the catalyst contained more than one promoter and the support was other than silica, the promotors were applied individually by aqueous solution in the order noted in the table, the composite being dried after each promoter application;

!~

~i~75~

-- irl those exrseriments in which the catal~st con~a~.~e~ ~ore than one pro~.oter and the sup~ort was si.li.ca, an aqueous solution contalnin~
all Or the indicate~ lmpregnan~ materials was made and mlxed ~ith a sllica sol, ~hich in turn was gelled and dried as described above;
-- in the column labeled "Starting ~aterial1' the indicated percent is the weight percent of the metal or metalloid in the catalyst ultimately obtained, with the weig~t of the metal or metallold plus the wei~ht of the support being taken as 100~ (for exam~le, in Example 4 the catalyst ultimately produced contained 9.1 weight % Co and 90.9 wei~ht ~0 A12O3);
-- calcination was done in air;
-- hydrogen reduction was done at 800~ with 100 mole percent H2i -- the total amount of catalyst char~ed into the reactor was 3 cc;
-- sulfiding of the catalyst wàs done at 800F
with a gas comprisin~ 15 mole percent H2S
and 85 mole percent H2;
-- a total of 1.0 cc liauld acrylonitrile was fe~ to the reactor uniformly over a period of flve minutes so that the acrylonitrile feed rate was 0.2 cc/min;
--- 40 STP cc/min. H2 was also fed to the reactor during the dimerization reaction; and -- the ~ndicated percents ~or gases are mole percents.

l7~

Also, in ~able 1 the fcllowing abbrcviations are used:
"AN" reans 'acrylonitrile"
"propio" means "~ropionitrile"
"adipo" means "adiponitrile"
"1,4-~CB-l" means "1~4-dic~yanobutene-1"
"1,4-~CB-2" reans "1,4-dicyanobutene-2"
"succino" r.eans "succinonitrile"
"aceto" means "acetorlitrile"
"act" means "activated"
"TR" means "trace"
"RT" means - "retention time"
Also, the term "Ex 7 catalyst" as in, for example Example ~, means "the catalyst obtained from Example 7 a~ter the experiment of Example 7 was finished."

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t~j - 29a 7~'3 In many of t:he runs the yield fiyures fall far short of totaling 100~. In these cases it rnay be assumed that losses to gas and particularly coke were extensive. Chemical analysis for yas and coke ~as not performed but rniCroscopiC exa~rlination of spent catalysts confirmed the presence of carbon in cases of low material balance.
From the foregoing examples it ca~ be seen that catalysts comprising activated alumina which have been sulfided so as to contain inorganic sulfide ion exhibit a significant activity in the catalytic dimerization of acrylonitrile to 1,4-dicyanobutenes and adiponitrile. Moreover, it will further be noted that in most instances sulfided activated alumina catalysts containing a metal or metalloid promoter exhibit catalytic activity superior to unsul~ided catalysts made from the same support and promoter.
Although only a few embodiments of the present invention have been specifically described above, it should be appreciated that many additions and modifications can be made without departing from the spirit and scope of the invention.
For example, it has been found that in some instances sulfiding of the promoted or unpromoted activated alumina support to produce the inorganic sulfide ion-containing catalyst used in the inventive process can be conducted 75~

simul-taneously with rather than prior to the dimerization reaction. In such instances, hydroyen sulfide, carbon disulfide or other sulEiding gas as discussed above is included in the carrier yas in sui-table amount (preferably 15%) and fed to the reac-tor along with acryloni-trile, whereby the support is sulfided simultaneously with the commencement of the dimerization reaction. This and all other modifications are intended to be included within the scope of the present invention, which is to be limited only by the following claims:

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for forming l,4-dicyanobutene by catalytically dimerizing under vapor phase conditions at a temperature of 500° to 1100°F. acrylonitrile comprising con-tacting acrylonitrile with a catalyst comprising activated alumina containing inorganic sulfide ion.

2. The process of claim 1 wherein acrylonitrile is contacted with said catalyst for an apparent contact time of 0.1 to 30 seconds at a pressure of 1 to 100 atmospheres.

3. The process of claim 1 wherein said alumina has a surface area from 0.5 to 800 m2/g.

4. The process of claim 3 wherein said catalyst is formed by contacting activated alumina at an elevated tempera-ture of at least about 500°F with a material capable of decom-posing to liberate sulfide ion at said elevated temperature.

5. The process of claim 4 wherein said catalyst is formed by contacting activated alumina with a member selected from the group consisting of H2S, CS2 and an organic sulfur-containing molecule decompositing at said elevated temperature to liberate a sulfide ion.

6. The process of claim 5 wherein said member is selected from the group consisting of H2S and CS2.

7. The process of claim 6 wherein alumina is con-tacted with said member for 0.1 to 5 hours.

8. The process of claim 7 wherein said member is H2S.

9. The process of claim 3 wherein said catalyst consists essentially of alumina and an inorganic sulfide of a metal or metalloid selected from a) metals and metalloids of Groups IA, IIA, IVB, VB, VIB, VIIB, IB, IIB, IIIA and IVA of the Periodic Table;

(b) Rare Earth metals;
(c) scandium; and (d) hafnium.

10. The process of claim 9, wherein said inorganic sulfide is present in said catalyst in an amount such that the amount of metal in said catalyst is 0.1 to 50 percent by weight, based on the total weight of such catalyst.

11. The process of claim 10 wherein the amount of sulfide in said catalyst is such that the amount of metal in said catalyst is 1 to 10 percent by weight, based on the total weight of said catalyst.

12. The process of claim 10 wherein said metal or metalloid is selected from metals in Groups IA, IIA, IB and IIB of the Periodic Table and lead.

13. The process of claim 12 wherein said metal or metalloid is selected from the group consisting of sodium, strontium and silver.

14. The process of claim 10 wherein said catalyst is formed by depositing said metal or metalloid on said alumina to form a composite and thereafter contacting said composite at an elevated temperature of at least about 500°F with a material capable of decomposing to liberate sulfide ion at said elevated temperature so that said metal or metalloid is converted at least in part to a sulfide.

15. The process of claim 14 wherein said material is a member selected from the group consisting of H2S, CS2 and an organic sulfur-containing molecule decomposing at an elevated temperature to liberate a sulfide ion.

16. The process of claim 15 wherein said member is selected from the group consisting of H2S and CS2.

17. The process of claim 16 wherein said composite is contacted with said member for 0.1 to 5 hours.

18. The process of claim 17 wherein said member is H2S.

19. The process of claim 9 wherein said metal or metalloid is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, chromium, molybdenum, manganese, iron, cobalt, nickel, paladium, platinum, copper, silver, zinc, cadmium, tellurium, tin, lead and cerium.

20. The process of claim 3 wherein said catalyst is formed by contacting a support consisting of activated alumina at an elevated temperature of at least 500°F. with a material capable of decomposing to liberate sulfide ion at said elevated temperature.