CA2049522A1 - Shaped extrudate of phosphoric acid catalyst utilizable for the conversion of organic compounds - Google Patents
Shaped extrudate of phosphoric acid catalyst utilizable for the conversion of organic compoundsInfo
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- CA2049522A1 CA2049522A1 CA002049522A CA2049522A CA2049522A1 CA 2049522 A1 CA2049522 A1 CA 2049522A1 CA 002049522 A CA002049522 A CA 002049522A CA 2049522 A CA2049522 A CA 2049522A CA 2049522 A1 CA2049522 A1 CA 2049522A1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
"SHAPED EXTRUDATE OF PHOSPHORIC ACID CATALYST
UTILIZABLE FOR THE CONVERSION OF ORGANIC COMPOUNDS"
ABSTRACT
A solid catalyst composite which consists of a shaped extrudate comprising a solid binder admixed with phosphoric acid is provided in a form having a ratio of exterior surface area to catalyst volume greater than
UTILIZABLE FOR THE CONVERSION OF ORGANIC COMPOUNDS"
ABSTRACT
A solid catalyst composite which consists of a shaped extrudate comprising a solid binder admixed with phosphoric acid is provided in a form having a ratio of exterior surface area to catalyst volume greater than
Description
aSHAPED EXrRU~TE OF PHOSPH(:)RIC ACI~ ~A~L~ST
~ITILIZABLE F~R THE ~ONVERSION C)F OR~A~ 2M3~S3 FIELD OF THE INVENTIQ~I
This invention rela~es ~o ~he solution of ~Ihe problem ~ coke-indlJced swelling ~ phosphoric acid catalys~ par~icles where they are used in accelera~ing conversior or~anic compounds.
BACK~iR~UND ~F THE INVENIIQ~I
Solid catalys~ particles are utilizable for many processes involving ~he ~o conversion of or0anic compounds. A particular exampl0 of solid catalyst particles comprises solid phosphoric acid which comprises a calcined rnixture of an acid of phosphorus and a porous binder material. These solid phosphoric acid catalysts are effective in the polymerization of normally gaseous olefins ~o form normallyliquid hydrocarbons. In addition, solid phosphoric acid catalysts arc very useful in catalyzin~ the alkylation of aromatic hydrocarbons with alkylating agents such as olefins, aliphatic halides, etc. to form useful products.
The catalyst is composed of a support or substrate por~ion onto which is incorporated an acid fraction for catalytic activty. It is believed that the substrate portion is formed from the silica-phosphoric acid reaction, principaliy silicon orthophosphate, Si3(P04)4, silicon pyrophosphate, SiP207, as well as derivativesof these compounds. The catalyst is typically prepared by mixing silica with phosphoric acid followed by ex~rusion and calcination. The reactions are simply illustrated as follows:
3 SiO2 + 4 H3P04 ~ > Si3(P04)4 + 6 H20 SiO2 + 2 H3P04 > SiP207 + 3 H20 The above reactions indicate that the phosphoric acid will react with silica ~o yiel~
both types of phosphates depending upon stoichiometry and reaction conditions.
The silicon orthophosphate can also be dehydrated during drying to giva ~he silicon 3 o pyrophosphate, and this is believed to be the alternativs mechanism for the silicon pyrophosphate formation. The silicon ortho- to pyrophosphate conversion also depends on factors such as temperature and hydration, as illustrated by th0 following equations:
Sb(P~,)4 + 2 H3PO~ --~ 3 SiP207 ~ 3 7~2 Si3(PO4)4 + h~at ~ 2 SiP2O7 ~ ~i2 The preparation of ~hese catalys~s is knDwn in th0 art 85, for 0xample, ~JI.S.
Patent No. 2,5~6,852 which describes a solid phosphoric acid comprisiny a mDcture ~f kaolin, ~ crystallins silica and phosphoric acid. O~her pa~ents which describe various methods of forming ~his catalyst cc~mpos~e include U.S. Patent Nos.
~ITILIZABLE F~R THE ~ONVERSION C)F OR~A~ 2M3~S3 FIELD OF THE INVENTIQ~I
This invention rela~es ~o ~he solution of ~Ihe problem ~ coke-indlJced swelling ~ phosphoric acid catalys~ par~icles where they are used in accelera~ing conversior or~anic compounds.
BACK~iR~UND ~F THE INVENIIQ~I
Solid catalys~ particles are utilizable for many processes involving ~he ~o conversion of or0anic compounds. A particular exampl0 of solid catalyst particles comprises solid phosphoric acid which comprises a calcined rnixture of an acid of phosphorus and a porous binder material. These solid phosphoric acid catalysts are effective in the polymerization of normally gaseous olefins ~o form normallyliquid hydrocarbons. In addition, solid phosphoric acid catalysts arc very useful in catalyzin~ the alkylation of aromatic hydrocarbons with alkylating agents such as olefins, aliphatic halides, etc. to form useful products.
The catalyst is composed of a support or substrate por~ion onto which is incorporated an acid fraction for catalytic activty. It is believed that the substrate portion is formed from the silica-phosphoric acid reaction, principaliy silicon orthophosphate, Si3(P04)4, silicon pyrophosphate, SiP207, as well as derivativesof these compounds. The catalyst is typically prepared by mixing silica with phosphoric acid followed by ex~rusion and calcination. The reactions are simply illustrated as follows:
3 SiO2 + 4 H3P04 ~ > Si3(P04)4 + 6 H20 SiO2 + 2 H3P04 > SiP207 + 3 H20 The above reactions indicate that the phosphoric acid will react with silica ~o yiel~
both types of phosphates depending upon stoichiometry and reaction conditions.
The silicon orthophosphate can also be dehydrated during drying to giva ~he silicon 3 o pyrophosphate, and this is believed to be the alternativs mechanism for the silicon pyrophosphate formation. The silicon ortho- to pyrophosphate conversion also depends on factors such as temperature and hydration, as illustrated by th0 following equations:
Sb(P~,)4 + 2 H3PO~ --~ 3 SiP207 ~ 3 7~2 Si3(PO4)4 + h~at ~ 2 SiP2O7 ~ ~i2 The preparation of ~hese catalys~s is knDwn in th0 art 85, for 0xample, ~JI.S.
Patent No. 2,5~6,852 which describes a solid phosphoric acid comprisiny a mDcture ~f kaolin, ~ crystallins silica and phosphoric acid. O~her pa~ents which describe various methods of forming ~his catalyst cc~mpos~e include U.S. Patent Nos.
2,650,201, 2,833,727, 2,871,199, snd 3,112,350.
One disadvantag0 which may occur during the use of these catalyst 10 composites during a polymerization or alkylation reaction is that the catalyst particles may tend ~o disintegrate and form solid beds through which the feedstock encounters difficulty in passage through the catalyst bed. Ukewise, the catalystparticle, if not disintegrated, may also possess a tendency to increase in volume or swell due to the deposition of coke thereon, thereby further reducing the space 15 between the particles with attendant difficulty of passage through the bed.
It is therefore apparent that the amount of space between the catalyst particles is important and indeed may be considered critical in nature in order to avoid an excessive pressure drop. Inasmuch as the space between the catalyst particles or voidage is critical it is necessary to provide catalyst particles which will 20 not tend to reduce this voidage but will provide a sufficient amount of voidage to enable any expansion of the catalyst particle without excessive loss of voidage and thereby allow a concurrent stability of pressure to be maintained.
The prior art is replete with patents showing various shaped catalyst par-ticles. However, as will hereinafter be shown in great detail, these particles 25 comprise bases having a catalytically active metal deposited thereon or zeolitic catalysts which may not contain a catalytic metal. Examples of these prior patents include U.S. Patent No. 3,966,644 which shows a porous hydrotreating catalyst particle comprising a major portion of alumina and a miner portion of silica having a catalytic metal such as molybdenum, cobalt nickel, or mixtures thereof deposited on 30 this catalyst base. U.S. Patent Nos. 4,328,130 and 4,342,643 show shaped channeled catalysts which comprise a refractory oxide such as alumina, silica, silica-alumina, magnesium, etc. containing active transition metals in the form of metals, metal oxides, metal sul~ldes, and, if so desired, an aluminosilicate zeolite.
U.S. Patent No. 4,370,492 discloses a carrier such as a silicic acid having a noble 35 metal composited thereof. Likewise, U.S. Patent No. 4,495,307 also shows a shaped catalyst comprising a catalyst base such as alumina, silica or silica-alumina, having a hydrogenation rnetal selected from Group VIB and Group Vlll ~ Ihe Periodic Table composited theresn. U.S. Patent No. 4,391,740 is drawn ~o a catalyst for hydroprocessin~ heavy carbc,naceous ~eedstocks in which an elongated ex~rudate of a catalys~ of a base such as alumina or silica ha~/ing a 5 catalytic metal such as molybdenum, tungsten, nickel or cobal~ composi~ed theresn, the preferred shape for this catalyst being oval or elliptical in conFiguration with or withou~ bumps. U.S. Patent Nos. ~,394,303, 4,489,173 and 4,606,815 all disclose shaped catalysts for hydroprocessing hydrocarbon feedstocks of lobular configuration, said bases comprising refractory inorganic oxides or clays having a lC catalytic metal such as molybdenum, tungsten, nickel or cobalt composited thereon. Likewise other shaped catalyst particles having lobular shapes are set forth in U.S. Patent Nos. 4,028,227, 4,495,307 and 4,534,855. The firs~ of thesereferences utilizes a catalyst base such as alumina impregnated with cobalt and/or molybdenum while the latter two comprise only alumina.
Other prior U.S. patents disclose shaped particles such as U.S. Patent No.
4,441,990. This patent discloses hollow shaped catalytic extrudates which are essentially rectangular or triangular in cross section. The catalyst particles comprise support materials onto which metals may be added. Particular catalyst particles which are enumerated include alumina or alumina as a support in 20 admixture with a zeolite, and which may contain cobalt, molybdenum oxides, copper or zinc oxides as an added metal. Another prior U.S. Patent is No.
2,644,800 which discloses a shaped catalyst having a packed catalytic reactor comprising a plurality of flanges around a central post element, the support comprising a cylindrical metal having a catalyst surface. In addition, U.S. Patent No.
25 4,224,185 discloses a formed, shaped solid catalyst in which a solid catalyst particle is admixed with a fibrillatable polyolefin followed by mechanically shearing themixture to form a mat of catalyst particles which are entrapped in the polyolefin and thereafter mechanically shaping the mat to provide the desired catalyst particles.
Likewise, U.S. patents which disclose shaped catalyst particles include Patent Nos.
30 4,652,687 and 4,717,781. These patents show shaped particles which may be polylobular or cylindrical in configuration. However, these particles are utilized as oxidation catalysts and comprise a Group Vlll noble metal, a Group IVA metal and a Group IA or IIA metal composited on a metal oxide support such as alumina.
None of the shaped catalysts of the prior art comprise a shaped particle 35 which consists of an admixture of an acid of phosphorus with a porous binder, said admixture being formed with a desired con~lguration, as is the case of the present invention.
~RIEF S~JMMA~ QFl~!~!vENTLQ~
This invention rela~es to shaped solid particles which are ~ilizable for ~he conversion of organic compounds and particularly ~o ~he polymerization or alkyla~ion of organic hydrocarbons. In addHion, ~he invenlion ~Iso rela~e5 ~0 a process employing these shap0d catalyst particles to obtain desirable produ~s as~ resu~ of ~he processes in which ~he ca~alysts are employed. By utilizing a catalyst which possesses a shaped form such as a polylobular configuration it is possible to eff~c~ a process in such a manner wher0by ~he possibility of a disadvantageous pressure drop occurring is greatly diminished.
~o It is therefore an objec~ of ~his invention ~o provide a shaped catalyst particle ~ilizabl0 in a hydrucarbon conversion process such as polymerization or alkylation which will possess the ability ~o maintain a desired degree of voidage between the particles, thus permirting ~he uninterrupted flow of feedstock to be converted through a catalyst bed.
A further object of this invention is to provide an organic compound con-version process utilizing the shaped catalyst particles of the presen~ invention ~o obtain the desired product in an economical manner.
In one aspect an embodiment of this invention resides in a solid catalyst composite for the conversion of organic compounds, which consists of a shaped extrudate, comprising a solid binder admixed with a phosphoric acid having a ratio of exterior surface area to catalyst volume greater than ~2 L D
in which D is the largest representative diameter and L is the length of said ex-3 o trudate.
Another embodiment of this invention resides in a process for the conversion of an organic compound which comprises contactin~ said organic compound at conversion conditions with a solid catalyst, which consists of a shaped extrudate, comprisin~ a solid binder admixed with a phosplhoric acid, having a ratio of ext0rior ~uffaea araa to catalyst ~olume ~reater than ~ 2 ' 3. _.
L ~ I
~o in which D is ~ha lar0est representativs diamEIter E~nd L is ~he length ~ said ex-trudate and recovering the resultant conversion product.
A specific ernbudimen~ of ~his invention lesides in a solid cataiyst compos-lta for the conversion of organic compounds consistin0 of a polylobular shaped particle containing from 3 ~o 8 lobes comprising diatomaceous earth admix0d wlthpolyphosphoric acid in which said phosphoric acid is present in an arnount greater than 10% by weight of the compos~te.
A specific embodiment of this invention is found in a process for the con-version of organic compounds which comprises contacting an olefinic feedstream containing frorn 2 to 6 carbon atoms at a temperature in the range of from 100 to 20 400C and a pressure in the range of from 1 to 500 atmospheres (101.3 to 5065D
kPa) with a solid catalyst comprising a polylobular shaped particle comprising diatomaceous earth admixed with phosphoric acid and recovering the resultant polymerized product.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is concerned with a shaped catalyst particle which is utilizable in catalytic conversion processes whereby various organic compounds are converted to useful products. Catalyst particles when formed into a catalystbed in a reactor may tend to disintegrate or break down during the process in which they are employed. Alternatively, if the catalyst does not disintegrate or break down it may have a tendency to swell. Either the disintegration or swelling sf the eatalyst in the catalyst bed will tend to minimize the space between the particles and thus contribute to a pressure drop between the entrance to the bed and the exit from the bed. By clogging the spaces between the catalyst particles it will therefore require a continued increase in pressure or necessitate the removal of the catalyst bed and replacement thereof in order to provide a workable process. In order to minimizethe necessity for replacement of catalyst or use of increased pressure, bo~h of which will contribute to an increase in the cost of the process and thus perhaps r0nder ~h0 process unsconomical to operate il has n~w been discovered ~h~ ~hese difficulties may be overcome by employing catalys~ par~icles which possess a de~lnite configuration. By utilizing a cylindrical or polylobular shaped parlicle of ~he ~ype hereina~er set forth in greater detail it is possible to maintain ~he voidage 5 between the catalyst particles and thus preverlt a loss of pressure with an excessive pressure drop through the bed of the catalys~. Solid phosphoric acicl ca~alyst particles having the shaped form of ~he present inven~ion such as a polylobular,tubular, ridged, fluted or channeled cylindrical shape are used in either polym0rization or alkylation reactions, where even though they may swell or 1C increase in volume in an amount in the range of from 10% to 150% by volum0 of the original size, and they will still provide sufficient voidage so that there is little, ~ any, pressure drop ~hrough the catalyst bed.
The solid phosphoric acid shaped catalyst of the present invention will comprise a solid binder admixed with an acid of phosphorus, preferably one in 15 which the phosphorus has a valence of 5. The acid may constitute from 10% to 80% of the catalyst mixture ultimately produced. Of ~he various acids of phosphorus, orthophosphoric acid (H3PO4) and pyrophosphoric acid (H4P2O7) find general application in the primary mixtures, due mainly to the cheapness and to the readiness with which they may be procured, although the invention is not re-20 stricted to their use, but may employ any of the other acids of phosphorus insofaras they are adaptable. However, it is not intended to infer that the different acids of phosphorus which may be employed will produce catalysts which have identical effects upon any given organic reactions as each of the catalysts produced from different acids and by slightly varying procedures will exert its own characteristic 2 5 action.
In using orthophosphoric acid as one of the primary ingredients, different concentrations of the aqueous solutions may be employed, for example, acid containing from approximately 75 to 100% H3PO4 or orthophosphoric acid containing some free phosphorus pentoxide may be used. By this is meant that the3 o ortho acid may contain a definite percentage of the pyro acid corresponding to the primary phase of dehydration of orthophosphoric acid. Within these concentrationranges the acids will be liquids of varying viscosities and readily mixed with solid siliceous adsorbents.
Triphosphoric acid which may be represented by the formula: HsP3O~0 may 35 also be used as one of the starting materials for the preparation of the catalyst of ~his invention. These catalytic composi-~ions Imay also ibe preparecl ~rorn a phos-phoric acid mix~ure containing or~hophosphoric acid, pyrophosp`noTic acid, triphosphori1 acid and other pol\yphosphoric arids.
A phosphoric acid mix~ure which is 0enerally re~erred lo as polyp~osp~oric 5 acid may also be employed in ~his process. Polyphosphoric acid is formed by heatin0 orlhophosphoric acid or pyrophosphoric acid or mlxtures thereoF in sui~able equiprnent such as carbon lined trays heated by flue~ gases or o~her sui~able means to produce a phosphoric acid mi~ture generally analyzing from 79% ~o B~% by weight of P2Os. Such a liquicl mixture oi phosphoric acids wilh 79.4% Pl~)s ~o c:onten~ was Found by analysis to contain 2~.5% of orthophosphoric acid (~I~PO~), q5.2% oF pyrophosphoric acid (H~P2O7), 26.0% of triphosphoric acid (HsP3O10), and ~.3% by weight oF uniden~i~ied phosphoric acids. Another polyphosphoric acidmix~ure somewhat more concentra~ed than the one just referred ~o and having a P2Os con~ent of 8~% by weight was found by analysis to contain 57% by weigh~ of 15 triphosphoric acid (H5P3O10), 17% by weighl of hexametaphosphoric acid (HPO3)6, 1 i% by weighl of pyrophosphoric acid (H4P2O7), 5% by weight of orlhophosphoric acid (H3PO4) and 10% by weight of unidentified phosphoric acids.Another acid of phosphorus which may be employed in the manufacture of a composite catalyst according to the present invention is tetraphosphoric acid. It 20 has the general formula: H6P4O13 which corresponds to the double oxide formula:
3H2O.2P2Os which in turn may be considered as the acid resulting when three molecules of water are lost by four molecules of orthophosphoric acid H3PO4. Thetetraphosphoric acid may be manufactured by gradual or controlled dehydration orheating of orthophosphoric acid and pyrophosphoric acid or by adding phosphoric 25 pentoxide to these acids in proper amounts. When the latter procedure is followed, phosphoric anhydride is added gradually until it amounts to 520% by weight of total water present. After a considerable period of standing at ordinary temperature, the crystals of the tetraphosphoric acid separate from the viscous liquid and it is found that these crystals melt at approximately 93F (34C) and have a specific gravity of 30 1.1886 at a temperature of 60F (16C). However, it is unnecessary to crystallize the telraphosphoric acid before employing it in the preparation of the solid catalyst inasmuch as the crude tetraphosphoric acid mixture may be incorporated with the polycyclic aromatic hydrocarbon and the solid siliceous adsorbent.
The materials which may be employed as adsorbents or carriers IFor oxygen 3 5 acids of phosphorus are divided roughly into two classes. The first class cornprises materials of predominantly siliceous character and includes diatomaceous earth, kieselguhr, and artificially prepared porous silica. The second class oF materials which may be employed either along with or in conJunctinn with iha Firs~ class cornprises ~enerally certain mernbers of Ihle class of aluminum sili(,~es and includes such naturally occurring substances as various fuller's ear~hs and clays such as bentonrte, montmorillonite, acid treated clays and the like. ~ach adsorben-~
5 or supporting material which rnay be used will exert its own specific influence uponlhe net effectiveness of the catalys~ composite which will not necessarily be iclentical with tha~ of other members of the class.
The catalyst composites which are utilized in the present inven~ion are prepared by admixing an oxygerl acid of phosphorus and a solid binder which, in ~o ~he pr0ferred embodimen~ of the invention, comprises a siliceous material, at a temperature in -~he range of from 10 to 230C, and preferably at a temperature of from 95~ ~o 200C to form a cornposite, the oxygen acid of phosphorus being present in said composit0 in an amount greater than 10% by weight. As an exampleof this, a composite may be formed by heating polyphosphorus acid (82% P2Os 15 content) to a temperature of about 170C and thereafrter mixing this hot acid with diatomaceous earth which has previously been at room ~emperature. The polyphosphorus acid and diatomaceous earth form a composite which has the weight ratio of phosphorus pentoxide to diatomaceous earth in a range of from 2.5 to ~.5. This composite is slightly moist to almost dry in appearance but becomes2 o plastic when subjected to pressure in a hydraulic press type or auger type extrudate by which the composite is formed into the desired shaped par~icles.
The catalyst particles may be polylobular in configuration and may contain from 3 to 8 lobes, thus enabling the catalyst, when loaded into a bed, to maintain a sufficient voidage in the bed whereby an uninterrupted flow of feedstock will pass 25 through the bed without a depreciable loss of pressure even though the catalyst particle will swell and increase in volume. The catalytic particles may range in length from 0.075 to 0.75 inches (1.9 to 19 mm) and will have a ratio of exterior surface to catalyst volume greater than [4/D+2/L], where D is the largest representative diameter and L the length of the extrudate. Typically, D is selected so that it is less 30 or equal to L and more typically from 1/4 to 3/4 of L. In addition, the die through which the dough is extruded will be configured to form lobes, the length of eachlobe ranging from 0.01 D to 0.3 D while the average width of ~he lobe will range from 0.01 D to 0.5 D. By forming a catalyst which possesses these particular configurations, it is possible to obtain a catalyst which possesses a greater ef-35 fectiveness factor with a corresponding stability than was obtained when utili~ingcatalysts of more conventional shapes. The finished particles may be either solid or, if so desired, possesses an aperture through the central part of the particle. The res~ an~ ca~alysl compos~e whiGh is 0x~rudecl ~hrou~h ~h0 die is ~ill Jn a heated ~onclrtion and ~he die ~hrou~h wllieh ~he catalys~ Is extruded ~Nili ~Ise~ be preheated ~o a predetermined ~empera~ure as, for exarnpie, absu~ 170C. ~he ~?x~ruded ~talys~ parlicles in polylobular shape are then oaicined by heatin0 in air, nr~ro~en, 5 ~lu~ ~as, or som0 uther iner~ ~as ~ ra ~emper~ure of from ~00~ ~o ~00C, and preferably a~ a temper~ure of from ~0 ~o ~,75e~ or a period ~ ~ime which may ran~e from U.25 ~o 8 hours, and preferably from 0.5 lo 2 hours.
Ano~her catalys~ cornposi~e of the presen~ invention eomprisin0 an admixlure of a solid binder and an acid of phosphorus may be simply tubular in eor)fi~uration or may comprisQ a tube having ~he interior sec~ion of ~he tube filled wrth a plurality of in~ersec~ing veins Iha~ give Ihe particle a carhNheel shape. The catalytic parlicles may range in length frorn 0.050 Io 0.75 inches (1.3 to 19 mm) and will have a ratio of shape surFace ~o gross ca~alys~ volume 0reater than ~/D ~ 2/L~, wher0 D is ~he average oulside diame~er of the entire par~icle and L is the lenyth of ~he e~rudate.
The ~erm shape surFace refers ~o ~he macroscopic sur~ace area o~ ~he ca~alysl for all surfaces of ~he ca~alyst, including the interior walls of the channels and excludes ~he surface area associated with any microscopic pores. The ~erm grt)ss voluma means the solid catalyst volume which includes the volume of the channels. Tha relative inside and outside diameters of the channels are limited to provide to a ratio of do/dj which is between 1.1 and 8.0 where dj is the largest transverse dimension across the inside of any channel and do is the dimension to the outside of wallssurrounding the channel, taken along the line of dimension dj. This ratio of channe diameters is chosen to provide channels large enough for flow purposes and ade-quate wall thickness around the channels for structural integrity of the support.
Still another form or shape of the catalyst comprising an admixture of a solid binder and an acid of phosphorous will comprise a cylinder having ridges, flutes or channels, the number of ridges, flutes or channels on the surface of the cylinder ranging from 2 to 10. As in the case of ~he polylobular catalyst particles they may be solid or possess an aper~ure and will have a ratio of exterior sur~ace to catalyst 3 o volume greater than 4 + 2 L D L
rne resulting catalyst which has been calcined is activa for promoting the polymerization of olefinic hydrocarbons, particularly for polymerizing normally gaseous olefinic hydrocarbons ~o form norrnally liquid hydrocarbons sui~able for use as constituents of gasolirle. ~hen employed in ~he conYersion of olefinic hydrocarbons into polymers, the calcined catalyst formed as hereinbe~ore sel ~orth is preferably employed as a bed in a heated reactor which is yenerally macle ~rom steel, and ~hrou0h which the preheated hydrocarbon fraction is clirec~ed. Thus, the 5 solid ~talyst of this process may be employed for treating mixtures of olefin-containing hydrocarbon vapors to effect olefin polymerization, bu~ the same catalyst may also ba used at operating conditions suitable for maintaining liquid phase operation during polymerization of olefinic hydrocarbons such as bu~ylenes, to produce gasoline ~ractions. When employed in the polymerization of normally l0 gaseous olefins, the formed and calcined ca~alyst particles are generally placed in a vertical, cylindrical treatiny tower and the olefin-containing gas mixture is passed downwardly therethrough at a temperature of from 150 to 400C and at a pressure of from 1 to 100 atmospheres (101.3 to 10130 kPa). These conditions areparticularly applicable when dealing with olefin-containing material such as stabilizer 15 reflux which may contain from approximatelylO to 50% or more of propylene andbutylenes. When operating on a mixture comprising essentially butanes and butylenes, this catalyst is effective at conditions favoring the maximum utilization of both normal butylenes and isobutylene which involves mixed polymerization at temperatures from 100 to 400C and a pressure from about 5 to about 500 at-2 o mospheres (506 to 50650 kPa).
The catalyst of this invention is also useful in the alkylation of aromatichydrocarbons with an alkylating agent. The alkylating agent which may be charged to the alkylation reaction zone may be selected from a group of diverse materials including monoolefins, diolefins, polyolefins, acetylenic hydrocarbons, and also2 5 alkylhalides, alcohols, ethers, esters, the latter including the alkylsulfates, alkylphosphates, and various esters of carboxylic acids. The preferred olefin-acting compounds are olefinic hydrocarbons which comprise monoolefins containing one double bond per molecule. Monoolefins which may be utilized as olefin-acting compounds in the process of the present invention are either normally gaseous or30 normally liquid and include ethylene, propylene, 1-butene, 2-butene, isobutylene, and the higher molecular weight normally liquid olefins such as the various pentenes, hexenes, heptenes, octenes, and mixtures thereof, and still higher molecular weight liquid olefins, the latter including various olefin polymers having 9 to 18 carbon atoms per molecule including propylene trimer, propylene tetramer, 35 propylene pentamer, etc. Cycloolefins such as cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, etc., may also be utilized, although not necessarily with equivalent results. Other hydrocarbons such as para~lns, naphthenes, and the like containing 2 to 18 carbon atoms may also be present in ehe alkylating agent. When the c~alyst of the present invenlion is used for catalyzing an aromatic alkylation reaction, it is preferred that ~he monoolefin contains at least 2 and not more than 14 carbon atoms. More sp0cffilcally, i~ is5 praferred that the monoolefin is propylene.
The aromatic substrate which is charged to the alkylation reaction zone in admixture with the alkylating agent may be selected from the group of aromatic compounds which include individually and in admixture benzene, monocyclic alkyl substituted benzenes such as toluene, o-xylene, m-xylene, p-xylene, mesitylene lO (1,3,5-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), hemimellitene (~,2,3-trimethylhenzene), ethylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, etc., and polycyclic aromatic compounds such as naphthalene, alkyl substituted naphthalenes, anthrcenes, etc.
In a continuous process for alkylating aromatic hydrocarbons with olefins, 15 the previously described reactants are continuously fed into a pressure vessel containing solid phosphoric acid catalyst of this invention. The feed admixture may be introduced into the alkylation reaction zone containing the alkylation catalyst at a constant rate, or alternatively, at a variable rate. Normally, the aromatic substrate and olefinic alkylating agent are contacted at a molar ratio of from 1:1 to 20:1 and 20 preferably from 2:1 to 10:1. The preferred molar feed ratios help to maximize the catalyst life cycle by minimizing the deactivation of the catalyst by coke and heavy material deposition upon the catalyst. The catalyst may be contained in one bed within a reactor vessel or divided up among a plurality of beds within a reactor. T'ne alkylation reaction system may contain one or more reaction vessels in series. The 25 feed to the reaction zone can flow vertically upwards, or downwards through the catalyst bed in a typical plug flow reactor, or horizontally across the catalyst bed in a radial flow type reactor.
In some cases, in order to maintain the reaction temperature in the preferred range and thus reduce the formation of unwanted polyalkylaromatics, it may be 30 desirable to quench the reactants to dissipate heat of reaction. A quench stream comprised of the aromatic substrate olefin, the alkylating agent or a portion of the reactor effluent stream, or mixtures thereof may be injected into the alkylationreactor system in order to dissipate heat and supply additional amounts of olefin alkylating agent and unreacted aromatic substrate at various locations within the 35 reaction zone. This is accomplished for example in a single-stage reactor by multiple injection of the aforementioned quench stream components into the reaction zone via strategically placed inlet lines leading into said reaction zone. The amoun~ and composi~ion of ~uench ma~erial injec~ed in~o ei-~her a single s~age reac~ion system or multi-s~age reaction system may be varied accorc3ing lo need.Benefits resulting from multiple quench injec~ior1 include elimina~ion of cosll\J cooling apparatus in the process, improved selectivity to forma~ion of ~he desired 5 alkylarom~ic compound, provision for a larger heat sink and op~imiza~ion ~F the olefin to aromatic compound molar ratio throughou~ the r0ac~ion zone, thus resulting in increased yieid of the clesired monoalkylated aromalic compound.
lremperatures vvhich are suitable for use in the process herein ar0 those temperatures which ini~ia~e a reac~ion between an aromatic subs~rat0 and the ~o par~icular olefin used Io selectively produce ~he desired monoalkylaromatic compound. Generall\/, temperatures sui~able for use are from 100 lo 390C, especially from 1 5C) to 275C. Pressures which are suitabl0 for use herein preferably are above 1 atmosphere (101.3 kPa) but should not be in excess oF 130atmospheres (13269 kPa). An especially desirable pressure range is from 10 to 4û:L5 a~mospheres ~1013 to ~052 kPa); with a liquid hourly space velocity (LHSV) based upon the benzene feed rate of from 0.5 to 50 hr~1. It should be noted tha~ the lemperature and pressure combination used herein is to be such that the alkylation reaction takes place in essentially the liquid phase. In a liquid phase process for producing alkylaromatics, the catalyst is continuously washed with reactants, thus 20 preventing buildup of coke precursors on the catalyst. This results in reduced amounts of carbon forming on said catalyst in which case, catalyst cycle life isextended as compared to a gas phase alkylation process in which coke formation and catalyst deactivation is a major problem.
Additionally, a regulated amount of water is preferably added to the alkylation 25 reaction zone. In order to substantially prevent loss of water from the catalyst and subsequent decrease in catalyst activities, an amount of water or water vapor such as steam is added to the charge so as to substantially balance the water vapor pressure of the alkylation catalyst hereinabove described. This amount of water varies from 0.01 to 6% by volurne of the organic material charged to the alkylation 3 o reaction zone. The water is then typically removed with the light by-product stream recovered in the first separation zone.
When employing a continuous type of operation in which the solid phosphoric acid catalysts are disposed as a fixed bed in a reaction zone by utili7ing the tubular or polylobular shaped particle of the present invention, it is possible to 35 maintain a proper operating condition involving pressure. This proper operating pressure will remain fairly constant even though the catalyst par~icle will swell during the USB thereof due to various conditions including the deposition of coke on the surFace of ~he catalyst parlicle. ven thol.lgh ~he par~icle size or ~/olume may be increased From 10% ~o 150% O~ ttle original size or volume of ~h2 particle F~ will still be possible to re~ain a sufficient amount o~ voidag0 in ~he reactor and ~hus enable the process to be maintained over fairly constant operating condilions.
While She above c0iscussion has cen~erecl mainly on ~he use of a con~inuous type o7 operation it is also con~emplated ~ha~ ~he conversion of organic compounds may be effecled in a batch type operation. When this type of operation is 0mployed a quantity of ~he desired catalyst is placed in a suitable apparatus, one example of vvhich comprises an autoclave oF the rotaling or stirred type, the organic compound or compounds to be converted may then be charged to the apparatus while the apparatus is heated ~o lhe desired operating ~emperature of from 100 to ~00C
and al pressures ransing From atmospheric to 100 atmospheres or more (101.3 to 10130 kPa). The pressure does no~ appear lo be a critical variable inasmuch as ~he process may be carriecl out in either a liquid or vapor phase, thus the pressurewhich is u~ilized to efFect the reaction may be selected purely from the most aclvan~ageous pressure based upon economic consideration and obtain the stability of the particular reactants which are charged to the process under thenecessary processing conditions. At the end of a predetermined residence time the apparatus and contents thereof are allowed to cool to room temperature, any 2 0 excess pressure is vented and the desired reaction product comprising, for example, the polymerized olefinic hydrocarbon or the alkylaromatic compound is recovered, separated from the catalyst by conventional means such as filtration,centrifugation, etc., further separated from any other unreacted starting materials by conventional means such as fractional distillation, crystallization, etc. and 2 5 recovered.
The following examples are given as illustrative embodiments of the present invention with relation to the shaped catalyst particles.
EXAMPLE I - PRIOR ART
Cylindrical extrudates of solid catalyst composite comprised of polyphosphoric acid and a kieselguhr binder and containing 73.1 weight percent phosphoric acid as polyphosphoric acid were loaded into a reactor and contacted with a feed stream consisting of C3 and C4 paraffins and olefins with about 250 ppm H2O to maintain catalyst hydration For sufficient time to produce 40 gallons of olefin polymer product per pound of catalyst. During the run the pressur~ drop 35 across the reactor increased From 2 psig to 36 psig (i.e. frorn 13.8 to 7~ kPa). At 1~
the completion of this run the spen~ catalyst was removed from the reac~or ~ube and inspec~ed. Representative sarnples from 5 foot and 10 foot (152~ ~o 3048 mm) depths in the reactor tube showed substantial swelling compared wi~h a retained sample of the fresh catalyst such tha~ the catalyst particles wers compressed in~o a 5 single solid mass with greatly reduced voidage.
EXAMPLE 2 - INVENTIQ~I
A laboratory plant test has been employed to quan~itate the amount of swelling that occurs with catalys~ particles of the formulation of the current invention during use for olefin polymerization. For each test 20 pellets of an extrudated solid l0 catalyst composite comprised of polyphosphoric acid and a kieselguhr binder were shaped into 0.3x0.4 cm cubes. Each cube was measured, weighed and loaded into a 7/8 inch (19.6 mm) ID reactor using five stainless steel baskets to isolate each catalyst cube from all others. Three tests were conducted in which a hydrocarbonfeed comprised of equal amounts by weight of propylene and a commercially-15 produced propylene polymer product with 1 weight percent added H2O was fed tothe rear,tor at 375C, 300 psig (2172 kPa), and 17hr-1 WHSV for 4, 20 and 30 hours. At the end of the specified time the spent catalyst cubes were recovered and weighed and measured. The weight and volume gains as percent of fresh catalyst weight and volume are tabulated in Table 1.
2 o Table 1 Test Number Hours on Stream /O Weiaht Gain % Volume Gain 4 9+ 7 26+ 11 2 20 34~ 12 91 + 25 3 30 55+ 15 122~ 32 According to engineering calculations and engineering design information which has been developed over the years, the physical properties of solid phosphoric acid catalysts comprising an admixture of acid of phosphorus and a solid binder will possess the following properties.
-~k 9 ~ n I
el~ p o~? . , t''l I L ~ C3 0 5 ~ 9 'D
1~
.~
O ~ f3 J ~n 6q 8. N ~ Y~ ~ IID
11 ~
o ~ ` o o c:~
_~ C ~ N V~
I ~ ~ ~ g `D
1~ ~ æ ~0 $o ~ o ~
I ., ~ ~ C ~ ~ V~ ~
.,~ 3 ~ ~ B D ~ _ -- ,~
~ 7 0 ~ ~ ~ g ~
O
ln additisn, when L~ilizec~ as a catalys~ in a reacgor ~he ca~alys~ par~icles will possess a voidage accordin0 to Ihe followiny table.
~LÇ ABD Piece Dens tv Solicl Cylinder 0.990 1.65 0.400 Quadralobe 0.9081.65 0.450 Tubular Cylinder 0.795 1.65 0.518 According to engineering calculations the performance of solid phosphoric acid catalysts having various shapes will perform according to Table 3 if u~ilized as a polymerization catalyst in a reactor in which a feed comprising a mixture of about 2 o 50/50% of propylene and propane or a feed of approximately 50/50% butylene and butane or a feed in approximately the same ratio of a mixture of propylene and butylene with propane and butane.is passed over the catalyst in a tubular reactor which is maintained at an inlet temperature of about 200C and a pressure of 1,000 psig (6998 kPa) LHSV of 2.5 hr.~1.
~ o D ~~o ~o ID
,~
~. ~ In ~ C~ O
u ~ a m I m ~ ~n In U~
O ~ O
~, u~ ?~ '' '' -' P~ a n U
t,) ~
It is to b0 noted from the above calculations tha~ catalyst particles which possess a quadralobe or tubular cylindrical shape will maintain a sufficienl amount of voidage t9 permit passage of the feed over ~he catalys~ without resul~ing isl a pressur0 drop sufficient to r0nder the process inoperable. For example, at a rslative 5 tim0 of 100 ths pressure drop when utilizing a solid cylinder shaped particle will resuH in a pressur0 drop of 50 psi (3q5 kPa) as compared to a pressure drsp of 17.8 psi (123 kPa) for the quadralobular shaped particle and a pressure drop of only 5.9 psi 141 kPa) for a tubular cylindrical shaped particle. The pressure drop or P at a relative time of 150 shows that the solid cylinder is over 1,000 psi (6~95 kPa) as lO compared to 102 psi (703 kPa) for the quadralobe and 15.1 psi (104 kPa) for the tubular cylinder. This pressure drop would effectively halt the flow of the feedthrough the reactor in the case when utilizing a solid cylinder. Similar calculations should also show the same results could be obtained when using catalyst particles which possess configurations such as ridged, fluted or channeled cylindrical 15 shapes.
It is therefore readily apparent from the above calculations that the use of catalyst particles which possess a desired configuration will permit a sufficient amount of voidage to be maintained during the operation when compared to catalyst particles which have heretofore been employed in this type of reaction.
One disadvantag0 which may occur during the use of these catalyst 10 composites during a polymerization or alkylation reaction is that the catalyst particles may tend ~o disintegrate and form solid beds through which the feedstock encounters difficulty in passage through the catalyst bed. Ukewise, the catalystparticle, if not disintegrated, may also possess a tendency to increase in volume or swell due to the deposition of coke thereon, thereby further reducing the space 15 between the particles with attendant difficulty of passage through the bed.
It is therefore apparent that the amount of space between the catalyst particles is important and indeed may be considered critical in nature in order to avoid an excessive pressure drop. Inasmuch as the space between the catalyst particles or voidage is critical it is necessary to provide catalyst particles which will 20 not tend to reduce this voidage but will provide a sufficient amount of voidage to enable any expansion of the catalyst particle without excessive loss of voidage and thereby allow a concurrent stability of pressure to be maintained.
The prior art is replete with patents showing various shaped catalyst par-ticles. However, as will hereinafter be shown in great detail, these particles 25 comprise bases having a catalytically active metal deposited thereon or zeolitic catalysts which may not contain a catalytic metal. Examples of these prior patents include U.S. Patent No. 3,966,644 which shows a porous hydrotreating catalyst particle comprising a major portion of alumina and a miner portion of silica having a catalytic metal such as molybdenum, cobalt nickel, or mixtures thereof deposited on 30 this catalyst base. U.S. Patent Nos. 4,328,130 and 4,342,643 show shaped channeled catalysts which comprise a refractory oxide such as alumina, silica, silica-alumina, magnesium, etc. containing active transition metals in the form of metals, metal oxides, metal sul~ldes, and, if so desired, an aluminosilicate zeolite.
U.S. Patent No. 4,370,492 discloses a carrier such as a silicic acid having a noble 35 metal composited thereof. Likewise, U.S. Patent No. 4,495,307 also shows a shaped catalyst comprising a catalyst base such as alumina, silica or silica-alumina, having a hydrogenation rnetal selected from Group VIB and Group Vlll ~ Ihe Periodic Table composited theresn. U.S. Patent No. 4,391,740 is drawn ~o a catalyst for hydroprocessin~ heavy carbc,naceous ~eedstocks in which an elongated ex~rudate of a catalys~ of a base such as alumina or silica ha~/ing a 5 catalytic metal such as molybdenum, tungsten, nickel or cobal~ composi~ed theresn, the preferred shape for this catalyst being oval or elliptical in conFiguration with or withou~ bumps. U.S. Patent Nos. ~,394,303, 4,489,173 and 4,606,815 all disclose shaped catalysts for hydroprocessing hydrocarbon feedstocks of lobular configuration, said bases comprising refractory inorganic oxides or clays having a lC catalytic metal such as molybdenum, tungsten, nickel or cobalt composited thereon. Likewise other shaped catalyst particles having lobular shapes are set forth in U.S. Patent Nos. 4,028,227, 4,495,307 and 4,534,855. The firs~ of thesereferences utilizes a catalyst base such as alumina impregnated with cobalt and/or molybdenum while the latter two comprise only alumina.
Other prior U.S. patents disclose shaped particles such as U.S. Patent No.
4,441,990. This patent discloses hollow shaped catalytic extrudates which are essentially rectangular or triangular in cross section. The catalyst particles comprise support materials onto which metals may be added. Particular catalyst particles which are enumerated include alumina or alumina as a support in 20 admixture with a zeolite, and which may contain cobalt, molybdenum oxides, copper or zinc oxides as an added metal. Another prior U.S. Patent is No.
2,644,800 which discloses a shaped catalyst having a packed catalytic reactor comprising a plurality of flanges around a central post element, the support comprising a cylindrical metal having a catalyst surface. In addition, U.S. Patent No.
25 4,224,185 discloses a formed, shaped solid catalyst in which a solid catalyst particle is admixed with a fibrillatable polyolefin followed by mechanically shearing themixture to form a mat of catalyst particles which are entrapped in the polyolefin and thereafter mechanically shaping the mat to provide the desired catalyst particles.
Likewise, U.S. patents which disclose shaped catalyst particles include Patent Nos.
30 4,652,687 and 4,717,781. These patents show shaped particles which may be polylobular or cylindrical in configuration. However, these particles are utilized as oxidation catalysts and comprise a Group Vlll noble metal, a Group IVA metal and a Group IA or IIA metal composited on a metal oxide support such as alumina.
None of the shaped catalysts of the prior art comprise a shaped particle 35 which consists of an admixture of an acid of phosphorus with a porous binder, said admixture being formed with a desired con~lguration, as is the case of the present invention.
~RIEF S~JMMA~ QFl~!~!vENTLQ~
This invention rela~es to shaped solid particles which are ~ilizable for ~he conversion of organic compounds and particularly ~o ~he polymerization or alkyla~ion of organic hydrocarbons. In addHion, ~he invenlion ~Iso rela~e5 ~0 a process employing these shap0d catalyst particles to obtain desirable produ~s as~ resu~ of ~he processes in which ~he ca~alysts are employed. By utilizing a catalyst which possesses a shaped form such as a polylobular configuration it is possible to eff~c~ a process in such a manner wher0by ~he possibility of a disadvantageous pressure drop occurring is greatly diminished.
~o It is therefore an objec~ of ~his invention ~o provide a shaped catalyst particle ~ilizabl0 in a hydrucarbon conversion process such as polymerization or alkylation which will possess the ability ~o maintain a desired degree of voidage between the particles, thus permirting ~he uninterrupted flow of feedstock to be converted through a catalyst bed.
A further object of this invention is to provide an organic compound con-version process utilizing the shaped catalyst particles of the presen~ invention ~o obtain the desired product in an economical manner.
In one aspect an embodiment of this invention resides in a solid catalyst composite for the conversion of organic compounds, which consists of a shaped extrudate, comprising a solid binder admixed with a phosphoric acid having a ratio of exterior surface area to catalyst volume greater than ~2 L D
in which D is the largest representative diameter and L is the length of said ex-3 o trudate.
Another embodiment of this invention resides in a process for the conversion of an organic compound which comprises contactin~ said organic compound at conversion conditions with a solid catalyst, which consists of a shaped extrudate, comprisin~ a solid binder admixed with a phosplhoric acid, having a ratio of ext0rior ~uffaea araa to catalyst ~olume ~reater than ~ 2 ' 3. _.
L ~ I
~o in which D is ~ha lar0est representativs diamEIter E~nd L is ~he length ~ said ex-trudate and recovering the resultant conversion product.
A specific ernbudimen~ of ~his invention lesides in a solid cataiyst compos-lta for the conversion of organic compounds consistin0 of a polylobular shaped particle containing from 3 ~o 8 lobes comprising diatomaceous earth admix0d wlthpolyphosphoric acid in which said phosphoric acid is present in an arnount greater than 10% by weight of the compos~te.
A specific embodiment of this invention is found in a process for the con-version of organic compounds which comprises contacting an olefinic feedstream containing frorn 2 to 6 carbon atoms at a temperature in the range of from 100 to 20 400C and a pressure in the range of from 1 to 500 atmospheres (101.3 to 5065D
kPa) with a solid catalyst comprising a polylobular shaped particle comprising diatomaceous earth admixed with phosphoric acid and recovering the resultant polymerized product.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is concerned with a shaped catalyst particle which is utilizable in catalytic conversion processes whereby various organic compounds are converted to useful products. Catalyst particles when formed into a catalystbed in a reactor may tend to disintegrate or break down during the process in which they are employed. Alternatively, if the catalyst does not disintegrate or break down it may have a tendency to swell. Either the disintegration or swelling sf the eatalyst in the catalyst bed will tend to minimize the space between the particles and thus contribute to a pressure drop between the entrance to the bed and the exit from the bed. By clogging the spaces between the catalyst particles it will therefore require a continued increase in pressure or necessitate the removal of the catalyst bed and replacement thereof in order to provide a workable process. In order to minimizethe necessity for replacement of catalyst or use of increased pressure, bo~h of which will contribute to an increase in the cost of the process and thus perhaps r0nder ~h0 process unsconomical to operate il has n~w been discovered ~h~ ~hese difficulties may be overcome by employing catalys~ par~icles which possess a de~lnite configuration. By utilizing a cylindrical or polylobular shaped parlicle of ~he ~ype hereina~er set forth in greater detail it is possible to maintain ~he voidage 5 between the catalyst particles and thus preverlt a loss of pressure with an excessive pressure drop through the bed of the catalys~. Solid phosphoric acicl ca~alyst particles having the shaped form of ~he present inven~ion such as a polylobular,tubular, ridged, fluted or channeled cylindrical shape are used in either polym0rization or alkylation reactions, where even though they may swell or 1C increase in volume in an amount in the range of from 10% to 150% by volum0 of the original size, and they will still provide sufficient voidage so that there is little, ~ any, pressure drop ~hrough the catalyst bed.
The solid phosphoric acid shaped catalyst of the present invention will comprise a solid binder admixed with an acid of phosphorus, preferably one in 15 which the phosphorus has a valence of 5. The acid may constitute from 10% to 80% of the catalyst mixture ultimately produced. Of ~he various acids of phosphorus, orthophosphoric acid (H3PO4) and pyrophosphoric acid (H4P2O7) find general application in the primary mixtures, due mainly to the cheapness and to the readiness with which they may be procured, although the invention is not re-20 stricted to their use, but may employ any of the other acids of phosphorus insofaras they are adaptable. However, it is not intended to infer that the different acids of phosphorus which may be employed will produce catalysts which have identical effects upon any given organic reactions as each of the catalysts produced from different acids and by slightly varying procedures will exert its own characteristic 2 5 action.
In using orthophosphoric acid as one of the primary ingredients, different concentrations of the aqueous solutions may be employed, for example, acid containing from approximately 75 to 100% H3PO4 or orthophosphoric acid containing some free phosphorus pentoxide may be used. By this is meant that the3 o ortho acid may contain a definite percentage of the pyro acid corresponding to the primary phase of dehydration of orthophosphoric acid. Within these concentrationranges the acids will be liquids of varying viscosities and readily mixed with solid siliceous adsorbents.
Triphosphoric acid which may be represented by the formula: HsP3O~0 may 35 also be used as one of the starting materials for the preparation of the catalyst of ~his invention. These catalytic composi-~ions Imay also ibe preparecl ~rorn a phos-phoric acid mix~ure containing or~hophosphoric acid, pyrophosp`noTic acid, triphosphori1 acid and other pol\yphosphoric arids.
A phosphoric acid mix~ure which is 0enerally re~erred lo as polyp~osp~oric 5 acid may also be employed in ~his process. Polyphosphoric acid is formed by heatin0 orlhophosphoric acid or pyrophosphoric acid or mlxtures thereoF in sui~able equiprnent such as carbon lined trays heated by flue~ gases or o~her sui~able means to produce a phosphoric acid mi~ture generally analyzing from 79% ~o B~% by weight of P2Os. Such a liquicl mixture oi phosphoric acids wilh 79.4% Pl~)s ~o c:onten~ was Found by analysis to contain 2~.5% of orthophosphoric acid (~I~PO~), q5.2% oF pyrophosphoric acid (H~P2O7), 26.0% of triphosphoric acid (HsP3O10), and ~.3% by weight oF uniden~i~ied phosphoric acids. Another polyphosphoric acidmix~ure somewhat more concentra~ed than the one just referred ~o and having a P2Os con~ent of 8~% by weight was found by analysis to contain 57% by weigh~ of 15 triphosphoric acid (H5P3O10), 17% by weighl of hexametaphosphoric acid (HPO3)6, 1 i% by weighl of pyrophosphoric acid (H4P2O7), 5% by weight of orlhophosphoric acid (H3PO4) and 10% by weight of unidentified phosphoric acids.Another acid of phosphorus which may be employed in the manufacture of a composite catalyst according to the present invention is tetraphosphoric acid. It 20 has the general formula: H6P4O13 which corresponds to the double oxide formula:
3H2O.2P2Os which in turn may be considered as the acid resulting when three molecules of water are lost by four molecules of orthophosphoric acid H3PO4. Thetetraphosphoric acid may be manufactured by gradual or controlled dehydration orheating of orthophosphoric acid and pyrophosphoric acid or by adding phosphoric 25 pentoxide to these acids in proper amounts. When the latter procedure is followed, phosphoric anhydride is added gradually until it amounts to 520% by weight of total water present. After a considerable period of standing at ordinary temperature, the crystals of the tetraphosphoric acid separate from the viscous liquid and it is found that these crystals melt at approximately 93F (34C) and have a specific gravity of 30 1.1886 at a temperature of 60F (16C). However, it is unnecessary to crystallize the telraphosphoric acid before employing it in the preparation of the solid catalyst inasmuch as the crude tetraphosphoric acid mixture may be incorporated with the polycyclic aromatic hydrocarbon and the solid siliceous adsorbent.
The materials which may be employed as adsorbents or carriers IFor oxygen 3 5 acids of phosphorus are divided roughly into two classes. The first class cornprises materials of predominantly siliceous character and includes diatomaceous earth, kieselguhr, and artificially prepared porous silica. The second class oF materials which may be employed either along with or in conJunctinn with iha Firs~ class cornprises ~enerally certain mernbers of Ihle class of aluminum sili(,~es and includes such naturally occurring substances as various fuller's ear~hs and clays such as bentonrte, montmorillonite, acid treated clays and the like. ~ach adsorben-~
5 or supporting material which rnay be used will exert its own specific influence uponlhe net effectiveness of the catalys~ composite which will not necessarily be iclentical with tha~ of other members of the class.
The catalyst composites which are utilized in the present inven~ion are prepared by admixing an oxygerl acid of phosphorus and a solid binder which, in ~o ~he pr0ferred embodimen~ of the invention, comprises a siliceous material, at a temperature in -~he range of from 10 to 230C, and preferably at a temperature of from 95~ ~o 200C to form a cornposite, the oxygen acid of phosphorus being present in said composit0 in an amount greater than 10% by weight. As an exampleof this, a composite may be formed by heating polyphosphorus acid (82% P2Os 15 content) to a temperature of about 170C and thereafrter mixing this hot acid with diatomaceous earth which has previously been at room ~emperature. The polyphosphorus acid and diatomaceous earth form a composite which has the weight ratio of phosphorus pentoxide to diatomaceous earth in a range of from 2.5 to ~.5. This composite is slightly moist to almost dry in appearance but becomes2 o plastic when subjected to pressure in a hydraulic press type or auger type extrudate by which the composite is formed into the desired shaped par~icles.
The catalyst particles may be polylobular in configuration and may contain from 3 to 8 lobes, thus enabling the catalyst, when loaded into a bed, to maintain a sufficient voidage in the bed whereby an uninterrupted flow of feedstock will pass 25 through the bed without a depreciable loss of pressure even though the catalyst particle will swell and increase in volume. The catalytic particles may range in length from 0.075 to 0.75 inches (1.9 to 19 mm) and will have a ratio of exterior surface to catalyst volume greater than [4/D+2/L], where D is the largest representative diameter and L the length of the extrudate. Typically, D is selected so that it is less 30 or equal to L and more typically from 1/4 to 3/4 of L. In addition, the die through which the dough is extruded will be configured to form lobes, the length of eachlobe ranging from 0.01 D to 0.3 D while the average width of ~he lobe will range from 0.01 D to 0.5 D. By forming a catalyst which possesses these particular configurations, it is possible to obtain a catalyst which possesses a greater ef-35 fectiveness factor with a corresponding stability than was obtained when utili~ingcatalysts of more conventional shapes. The finished particles may be either solid or, if so desired, possesses an aperture through the central part of the particle. The res~ an~ ca~alysl compos~e whiGh is 0x~rudecl ~hrou~h ~h0 die is ~ill Jn a heated ~onclrtion and ~he die ~hrou~h wllieh ~he catalys~ Is extruded ~Nili ~Ise~ be preheated ~o a predetermined ~empera~ure as, for exarnpie, absu~ 170C. ~he ~?x~ruded ~talys~ parlicles in polylobular shape are then oaicined by heatin0 in air, nr~ro~en, 5 ~lu~ ~as, or som0 uther iner~ ~as ~ ra ~emper~ure of from ~00~ ~o ~00C, and preferably a~ a temper~ure of from ~0 ~o ~,75e~ or a period ~ ~ime which may ran~e from U.25 ~o 8 hours, and preferably from 0.5 lo 2 hours.
Ano~her catalys~ cornposi~e of the presen~ invention eomprisin0 an admixlure of a solid binder and an acid of phosphorus may be simply tubular in eor)fi~uration or may comprisQ a tube having ~he interior sec~ion of ~he tube filled wrth a plurality of in~ersec~ing veins Iha~ give Ihe particle a carhNheel shape. The catalytic parlicles may range in length frorn 0.050 Io 0.75 inches (1.3 to 19 mm) and will have a ratio of shape surFace ~o gross ca~alys~ volume 0reater than ~/D ~ 2/L~, wher0 D is ~he average oulside diame~er of the entire par~icle and L is the lenyth of ~he e~rudate.
The ~erm shape surFace refers ~o ~he macroscopic sur~ace area o~ ~he ca~alysl for all surfaces of ~he ca~alyst, including the interior walls of the channels and excludes ~he surface area associated with any microscopic pores. The ~erm grt)ss voluma means the solid catalyst volume which includes the volume of the channels. Tha relative inside and outside diameters of the channels are limited to provide to a ratio of do/dj which is between 1.1 and 8.0 where dj is the largest transverse dimension across the inside of any channel and do is the dimension to the outside of wallssurrounding the channel, taken along the line of dimension dj. This ratio of channe diameters is chosen to provide channels large enough for flow purposes and ade-quate wall thickness around the channels for structural integrity of the support.
Still another form or shape of the catalyst comprising an admixture of a solid binder and an acid of phosphorous will comprise a cylinder having ridges, flutes or channels, the number of ridges, flutes or channels on the surface of the cylinder ranging from 2 to 10. As in the case of ~he polylobular catalyst particles they may be solid or possess an aper~ure and will have a ratio of exterior sur~ace to catalyst 3 o volume greater than 4 + 2 L D L
rne resulting catalyst which has been calcined is activa for promoting the polymerization of olefinic hydrocarbons, particularly for polymerizing normally gaseous olefinic hydrocarbons ~o form norrnally liquid hydrocarbons sui~able for use as constituents of gasolirle. ~hen employed in ~he conYersion of olefinic hydrocarbons into polymers, the calcined catalyst formed as hereinbe~ore sel ~orth is preferably employed as a bed in a heated reactor which is yenerally macle ~rom steel, and ~hrou0h which the preheated hydrocarbon fraction is clirec~ed. Thus, the 5 solid ~talyst of this process may be employed for treating mixtures of olefin-containing hydrocarbon vapors to effect olefin polymerization, bu~ the same catalyst may also ba used at operating conditions suitable for maintaining liquid phase operation during polymerization of olefinic hydrocarbons such as bu~ylenes, to produce gasoline ~ractions. When employed in the polymerization of normally l0 gaseous olefins, the formed and calcined ca~alyst particles are generally placed in a vertical, cylindrical treatiny tower and the olefin-containing gas mixture is passed downwardly therethrough at a temperature of from 150 to 400C and at a pressure of from 1 to 100 atmospheres (101.3 to 10130 kPa). These conditions areparticularly applicable when dealing with olefin-containing material such as stabilizer 15 reflux which may contain from approximatelylO to 50% or more of propylene andbutylenes. When operating on a mixture comprising essentially butanes and butylenes, this catalyst is effective at conditions favoring the maximum utilization of both normal butylenes and isobutylene which involves mixed polymerization at temperatures from 100 to 400C and a pressure from about 5 to about 500 at-2 o mospheres (506 to 50650 kPa).
The catalyst of this invention is also useful in the alkylation of aromatichydrocarbons with an alkylating agent. The alkylating agent which may be charged to the alkylation reaction zone may be selected from a group of diverse materials including monoolefins, diolefins, polyolefins, acetylenic hydrocarbons, and also2 5 alkylhalides, alcohols, ethers, esters, the latter including the alkylsulfates, alkylphosphates, and various esters of carboxylic acids. The preferred olefin-acting compounds are olefinic hydrocarbons which comprise monoolefins containing one double bond per molecule. Monoolefins which may be utilized as olefin-acting compounds in the process of the present invention are either normally gaseous or30 normally liquid and include ethylene, propylene, 1-butene, 2-butene, isobutylene, and the higher molecular weight normally liquid olefins such as the various pentenes, hexenes, heptenes, octenes, and mixtures thereof, and still higher molecular weight liquid olefins, the latter including various olefin polymers having 9 to 18 carbon atoms per molecule including propylene trimer, propylene tetramer, 35 propylene pentamer, etc. Cycloolefins such as cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, etc., may also be utilized, although not necessarily with equivalent results. Other hydrocarbons such as para~lns, naphthenes, and the like containing 2 to 18 carbon atoms may also be present in ehe alkylating agent. When the c~alyst of the present invenlion is used for catalyzing an aromatic alkylation reaction, it is preferred that ~he monoolefin contains at least 2 and not more than 14 carbon atoms. More sp0cffilcally, i~ is5 praferred that the monoolefin is propylene.
The aromatic substrate which is charged to the alkylation reaction zone in admixture with the alkylating agent may be selected from the group of aromatic compounds which include individually and in admixture benzene, monocyclic alkyl substituted benzenes such as toluene, o-xylene, m-xylene, p-xylene, mesitylene lO (1,3,5-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), hemimellitene (~,2,3-trimethylhenzene), ethylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, etc., and polycyclic aromatic compounds such as naphthalene, alkyl substituted naphthalenes, anthrcenes, etc.
In a continuous process for alkylating aromatic hydrocarbons with olefins, 15 the previously described reactants are continuously fed into a pressure vessel containing solid phosphoric acid catalyst of this invention. The feed admixture may be introduced into the alkylation reaction zone containing the alkylation catalyst at a constant rate, or alternatively, at a variable rate. Normally, the aromatic substrate and olefinic alkylating agent are contacted at a molar ratio of from 1:1 to 20:1 and 20 preferably from 2:1 to 10:1. The preferred molar feed ratios help to maximize the catalyst life cycle by minimizing the deactivation of the catalyst by coke and heavy material deposition upon the catalyst. The catalyst may be contained in one bed within a reactor vessel or divided up among a plurality of beds within a reactor. T'ne alkylation reaction system may contain one or more reaction vessels in series. The 25 feed to the reaction zone can flow vertically upwards, or downwards through the catalyst bed in a typical plug flow reactor, or horizontally across the catalyst bed in a radial flow type reactor.
In some cases, in order to maintain the reaction temperature in the preferred range and thus reduce the formation of unwanted polyalkylaromatics, it may be 30 desirable to quench the reactants to dissipate heat of reaction. A quench stream comprised of the aromatic substrate olefin, the alkylating agent or a portion of the reactor effluent stream, or mixtures thereof may be injected into the alkylationreactor system in order to dissipate heat and supply additional amounts of olefin alkylating agent and unreacted aromatic substrate at various locations within the 35 reaction zone. This is accomplished for example in a single-stage reactor by multiple injection of the aforementioned quench stream components into the reaction zone via strategically placed inlet lines leading into said reaction zone. The amoun~ and composi~ion of ~uench ma~erial injec~ed in~o ei-~her a single s~age reac~ion system or multi-s~age reaction system may be varied accorc3ing lo need.Benefits resulting from multiple quench injec~ior1 include elimina~ion of cosll\J cooling apparatus in the process, improved selectivity to forma~ion of ~he desired 5 alkylarom~ic compound, provision for a larger heat sink and op~imiza~ion ~F the olefin to aromatic compound molar ratio throughou~ the r0ac~ion zone, thus resulting in increased yieid of the clesired monoalkylated aromalic compound.
lremperatures vvhich are suitable for use in the process herein ar0 those temperatures which ini~ia~e a reac~ion between an aromatic subs~rat0 and the ~o par~icular olefin used Io selectively produce ~he desired monoalkylaromatic compound. Generall\/, temperatures sui~able for use are from 100 lo 390C, especially from 1 5C) to 275C. Pressures which are suitabl0 for use herein preferably are above 1 atmosphere (101.3 kPa) but should not be in excess oF 130atmospheres (13269 kPa). An especially desirable pressure range is from 10 to 4û:L5 a~mospheres ~1013 to ~052 kPa); with a liquid hourly space velocity (LHSV) based upon the benzene feed rate of from 0.5 to 50 hr~1. It should be noted tha~ the lemperature and pressure combination used herein is to be such that the alkylation reaction takes place in essentially the liquid phase. In a liquid phase process for producing alkylaromatics, the catalyst is continuously washed with reactants, thus 20 preventing buildup of coke precursors on the catalyst. This results in reduced amounts of carbon forming on said catalyst in which case, catalyst cycle life isextended as compared to a gas phase alkylation process in which coke formation and catalyst deactivation is a major problem.
Additionally, a regulated amount of water is preferably added to the alkylation 25 reaction zone. In order to substantially prevent loss of water from the catalyst and subsequent decrease in catalyst activities, an amount of water or water vapor such as steam is added to the charge so as to substantially balance the water vapor pressure of the alkylation catalyst hereinabove described. This amount of water varies from 0.01 to 6% by volurne of the organic material charged to the alkylation 3 o reaction zone. The water is then typically removed with the light by-product stream recovered in the first separation zone.
When employing a continuous type of operation in which the solid phosphoric acid catalysts are disposed as a fixed bed in a reaction zone by utili7ing the tubular or polylobular shaped particle of the present invention, it is possible to 35 maintain a proper operating condition involving pressure. This proper operating pressure will remain fairly constant even though the catalyst par~icle will swell during the USB thereof due to various conditions including the deposition of coke on the surFace of ~he catalyst parlicle. ven thol.lgh ~he par~icle size or ~/olume may be increased From 10% ~o 150% O~ ttle original size or volume of ~h2 particle F~ will still be possible to re~ain a sufficient amount o~ voidag0 in ~he reactor and ~hus enable the process to be maintained over fairly constant operating condilions.
While She above c0iscussion has cen~erecl mainly on ~he use of a con~inuous type o7 operation it is also con~emplated ~ha~ ~he conversion of organic compounds may be effecled in a batch type operation. When this type of operation is 0mployed a quantity of ~he desired catalyst is placed in a suitable apparatus, one example of vvhich comprises an autoclave oF the rotaling or stirred type, the organic compound or compounds to be converted may then be charged to the apparatus while the apparatus is heated ~o lhe desired operating ~emperature of from 100 to ~00C
and al pressures ransing From atmospheric to 100 atmospheres or more (101.3 to 10130 kPa). The pressure does no~ appear lo be a critical variable inasmuch as ~he process may be carriecl out in either a liquid or vapor phase, thus the pressurewhich is u~ilized to efFect the reaction may be selected purely from the most aclvan~ageous pressure based upon economic consideration and obtain the stability of the particular reactants which are charged to the process under thenecessary processing conditions. At the end of a predetermined residence time the apparatus and contents thereof are allowed to cool to room temperature, any 2 0 excess pressure is vented and the desired reaction product comprising, for example, the polymerized olefinic hydrocarbon or the alkylaromatic compound is recovered, separated from the catalyst by conventional means such as filtration,centrifugation, etc., further separated from any other unreacted starting materials by conventional means such as fractional distillation, crystallization, etc. and 2 5 recovered.
The following examples are given as illustrative embodiments of the present invention with relation to the shaped catalyst particles.
EXAMPLE I - PRIOR ART
Cylindrical extrudates of solid catalyst composite comprised of polyphosphoric acid and a kieselguhr binder and containing 73.1 weight percent phosphoric acid as polyphosphoric acid were loaded into a reactor and contacted with a feed stream consisting of C3 and C4 paraffins and olefins with about 250 ppm H2O to maintain catalyst hydration For sufficient time to produce 40 gallons of olefin polymer product per pound of catalyst. During the run the pressur~ drop 35 across the reactor increased From 2 psig to 36 psig (i.e. frorn 13.8 to 7~ kPa). At 1~
the completion of this run the spen~ catalyst was removed from the reac~or ~ube and inspec~ed. Representative sarnples from 5 foot and 10 foot (152~ ~o 3048 mm) depths in the reactor tube showed substantial swelling compared wi~h a retained sample of the fresh catalyst such tha~ the catalyst particles wers compressed in~o a 5 single solid mass with greatly reduced voidage.
EXAMPLE 2 - INVENTIQ~I
A laboratory plant test has been employed to quan~itate the amount of swelling that occurs with catalys~ particles of the formulation of the current invention during use for olefin polymerization. For each test 20 pellets of an extrudated solid l0 catalyst composite comprised of polyphosphoric acid and a kieselguhr binder were shaped into 0.3x0.4 cm cubes. Each cube was measured, weighed and loaded into a 7/8 inch (19.6 mm) ID reactor using five stainless steel baskets to isolate each catalyst cube from all others. Three tests were conducted in which a hydrocarbonfeed comprised of equal amounts by weight of propylene and a commercially-15 produced propylene polymer product with 1 weight percent added H2O was fed tothe rear,tor at 375C, 300 psig (2172 kPa), and 17hr-1 WHSV for 4, 20 and 30 hours. At the end of the specified time the spent catalyst cubes were recovered and weighed and measured. The weight and volume gains as percent of fresh catalyst weight and volume are tabulated in Table 1.
2 o Table 1 Test Number Hours on Stream /O Weiaht Gain % Volume Gain 4 9+ 7 26+ 11 2 20 34~ 12 91 + 25 3 30 55+ 15 122~ 32 According to engineering calculations and engineering design information which has been developed over the years, the physical properties of solid phosphoric acid catalysts comprising an admixture of acid of phosphorus and a solid binder will possess the following properties.
-~k 9 ~ n I
el~ p o~? . , t''l I L ~ C3 0 5 ~ 9 'D
1~
.~
O ~ f3 J ~n 6q 8. N ~ Y~ ~ IID
11 ~
o ~ ` o o c:~
_~ C ~ N V~
I ~ ~ ~ g `D
1~ ~ æ ~0 $o ~ o ~
I ., ~ ~ C ~ ~ V~ ~
.,~ 3 ~ ~ B D ~ _ -- ,~
~ 7 0 ~ ~ ~ g ~
O
ln additisn, when L~ilizec~ as a catalys~ in a reacgor ~he ca~alys~ par~icles will possess a voidage accordin0 to Ihe followiny table.
~LÇ ABD Piece Dens tv Solicl Cylinder 0.990 1.65 0.400 Quadralobe 0.9081.65 0.450 Tubular Cylinder 0.795 1.65 0.518 According to engineering calculations the performance of solid phosphoric acid catalysts having various shapes will perform according to Table 3 if u~ilized as a polymerization catalyst in a reactor in which a feed comprising a mixture of about 2 o 50/50% of propylene and propane or a feed of approximately 50/50% butylene and butane or a feed in approximately the same ratio of a mixture of propylene and butylene with propane and butane.is passed over the catalyst in a tubular reactor which is maintained at an inlet temperature of about 200C and a pressure of 1,000 psig (6998 kPa) LHSV of 2.5 hr.~1.
~ o D ~~o ~o ID
,~
~. ~ In ~ C~ O
u ~ a m I m ~ ~n In U~
O ~ O
~, u~ ?~ '' '' -' P~ a n U
t,) ~
It is to b0 noted from the above calculations tha~ catalyst particles which possess a quadralobe or tubular cylindrical shape will maintain a sufficienl amount of voidage t9 permit passage of the feed over ~he catalys~ without resul~ing isl a pressur0 drop sufficient to r0nder the process inoperable. For example, at a rslative 5 tim0 of 100 ths pressure drop when utilizing a solid cylinder shaped particle will resuH in a pressur0 drop of 50 psi (3q5 kPa) as compared to a pressure drsp of 17.8 psi (123 kPa) for the quadralobular shaped particle and a pressure drop of only 5.9 psi 141 kPa) for a tubular cylindrical shaped particle. The pressure drop or P at a relative time of 150 shows that the solid cylinder is over 1,000 psi (6~95 kPa) as lO compared to 102 psi (703 kPa) for the quadralobe and 15.1 psi (104 kPa) for the tubular cylinder. This pressure drop would effectively halt the flow of the feedthrough the reactor in the case when utilizing a solid cylinder. Similar calculations should also show the same results could be obtained when using catalyst particles which possess configurations such as ridged, fluted or channeled cylindrical 15 shapes.
It is therefore readily apparent from the above calculations that the use of catalyst particles which possess a desired configuration will permit a sufficient amount of voidage to be maintained during the operation when compared to catalyst particles which have heretofore been employed in this type of reaction.
Claims (9)
1. A solid catalyst composite for the conversion of organic compounds, which insists of a shaped extrudate, comprising a solid binder admixed with a phosphoric acid having a ratio of exterior surface area to catalyst volume greater than in which D is the largest representative diameter and L is the length of said ex-trudate.
2. The solid catalyst composite of Claim 1 in which said shaped extrudate consists of a polylobular, tubular, ridged, fluted or channeled cylindrical shaped particles.
3. The solid catalyst composite of Claims 1 or 2 in which said binder com-prises diatomaceous earth, kieselguhr or artificially prepared silica.
4. The solid catalyst composite of Claims 1, 2 or 3 in which said shaped extrudate possesses an aperture through the central part thereof.
5. The solid catalyst of any of Claims 1 to 4 in which said shaped extrudate is capable of increasing the dimensions thereof whereby the volume of said extrudate is increased from 10% to 150% of the original volume of said extrudate.
6. A process for the conversion of an organic compound which comprises contacting said organic compound at conversion conditions with a solid catalyst composite which consists of the shaped extrudate defined in any one of Claims 1 to 5 and recovering the resultant conversion product.
7. The process of Claim 6 in which said conversion conditions include a temperature in the range of from 100° to 400°C and a pressure in the range of from about 1 to 500 atmospheres (101.3 to 50650 kPa).
8. The process of Claim 6 or 7 in which said conversion process comprises the alkylation of an aromatic compound with an alkylating agent.
9. The process of Claim 6 or 7 in which said conversion process comprises the polymerization of an olefinic hydrocarbon containing from 2 to about 4 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002049522A CA2049522A1 (en) | 1991-08-20 | 1991-08-20 | Shaped extrudate of phosphoric acid catalyst utilizable for the conversion of organic compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002049522A CA2049522A1 (en) | 1991-08-20 | 1991-08-20 | Shaped extrudate of phosphoric acid catalyst utilizable for the conversion of organic compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2049522A1 true CA2049522A1 (en) | 1993-02-21 |
Family
ID=4148215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002049522A Abandoned CA2049522A1 (en) | 1991-08-20 | 1991-08-20 | Shaped extrudate of phosphoric acid catalyst utilizable for the conversion of organic compounds |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2049522A1 (en) |
-
1991
- 1991-08-20 CA CA002049522A patent/CA2049522A1/en not_active Abandoned
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