United States Patent (19) Chao et al

Transcription

1 United State Patent (19) Chao et al (75) (73) (51) (52) 58) 56 SOLID PHOSPHORIC ACID CATALYST Inventor: Tai-Hiang Chao, Mt. Propect; Fiona P. Wilcher, De Plaine; Mark R. Ford, Buffalo Grove; Andrzej Z. Ringwelki, Marengo, all of Ill. Aignee:, UOP, De Plaine, Ill. Appl. No.: 288,921 Filed: Dec. 23, 1988 Int, C.... B01J 21/16; B01J 27/182; U.S. C.... 2/81: 2/80; 2/214; 585/466; 585/529 Field of Search... 2/214, 81, 80 Reference Cited U.S. PATENT DOCUMENTS 2,116,1 5/1938 Ipatieff et al.... 2/214 2,275,182 3/1942 Ipatieff et al SO2/24 2,6,201 8/1953 Mavity /.4 3,0,472 8/1962 Morrell... 2/214 3,112,0 1 1/1963 Bielawki et al / Patent Number: 4,946,8 Date of Patent: Aug. 7, ,661,801 5/1972 Gutmann et al.... 2/214 3,673,111 6/1972 Hovarth et al.... 2/.4 3,801,704 4/1974 Kobayahi et al /9 4,521,638 6/1985 Kida et al /640 FOREIGN PATENT DOCUMENTS /1961 Fed. Rep. of Germany... 2/214 Primary Examiner-Paul E. Konopka Attorney, Agent, or Firm-Thoma K. McBride; John F. Spear, Jr. 57 ABSTRACT A olid phophoric acid catalyt having a total X-ray intenity of at leat percent relative to alpha-alumina. The olid phophoric acid catalyt i produced by cry tallizing an amorphou mixture of an acid oxide of pho phoru and a iliceou material at a temperature of from 0 to 0 C. and in the preence of from 3 to mole percent water vapor baed upon the total vapor rate to the crytallizing mean. 9 Claim, 1 Drawing Sheet Saa CataAYSf Afa Aao AAPA2a 7/OAV. f2o AO2 a YN S 90 N te w w A. o 40 2 R Y 7-5 -/4 A2 // 16-y A Q 29 \ 7 2O o To fat Cryfo?/finity. O

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3 1. SOLID PHOSPHORIC ACID CATALYST BACKGROUND OF THE INVENTION Thi invention relate to an improved olid pho phoric acid catalyt compoition having a total ilicon phophate X-ray intenity greater than.0 percent relative to alpha-alumina having been prepared by pe cific calcination condition. Solid phophoric acid i a catalyt well known for it uefulne in variou hydrocarbon converion procee uch a aromatic alkylation and olefin polymerization. The catalyt i compoed of a upport or ubtrate por tion onto which i incorporated an acid fraction for catalytic activity. It i believed that the ubtrate por tion i formed from the ilica-phophoric acid reaction, principally ilicon orthophophate, Si3(PO4)4, ilicon pyrophophate, SiP2O7, a well a derivative of thee compound. The catalyt i typically prepared by mix ing ilica with phophoric acid followed by extruion and calcination. The reaction are imply illutrated a follow: The above reaction indicate that the phophoric acid will react with ilica to yield both type of phophate depending upon toichiometry and reaction condition. The ilicon orthophophate can alo be dehydrated during drying to give the ilicon pyrophophate, and thi i believed to be the alternative mechanim for the ilicon pyrophophate formation. The ilicon ortho- to pyro-phophate converion alo depend on factor uch a temperature and hydration, a illutrated by the following equation: Si3(PO4)4--heat-2SiPO7--SiO2 Thee reaction have made the catalyt manufacturing more complex. Low activity or low tability catalyt have reulted due to low crytallinity caued by poor crytallization condition. DESCRIPTION OF THE PRIOR ART Solid phophoric acid catalyt and method of opti mizing the phyical propertie uch a cruh trength of uch catalyt are well known in the art. However, improving tability by maximizing the total ilicon phophate crytallinity i heretofore unknown. U.S. Pat. No. 2,6,201 to J. Mavity decribe a pro ce for improving the tructural trength of a calcined olid phophoric acid catalyt by adding a hydrolyzable compound of a metal elected from a group coniting of titanium, zirconium, and tin to the compoite prior to calcination of the metal containing olid phophoric acid catalyt. The deirable calcination temperature range from 100 to 0 C. In ditinction, the catalyt of the intant invention doe not comprie any added metal component, nor doe the 201 dicloure mention the benefit obtained by maximizing the ilicon pho phate crytallinity. U.S. Pat. No. 3,112,0 to M. Bielawki et al. di cloe a proce for the polymerization of hydrocarbon olefin in the preence of a pecific olid phophoric acid catalyt. Thi pecific catalyt comprie a pecific 4,946,8 O 20 2 high PO to SiO2 mole ratio in exce of about The catalyt i alo required to be a calcined at a tem perature of preferably above 560'. C. The 0 diclo ure teache of the advantage of calcining the catalyt at above 560 C. to achieve a pecific crytallite ratio of crytalline form C to crytalline form B of about 28:1. However, when the P2O5 to SiO2 mole ratio exceed 1.08 a pecified by the prior art, only material with phophate content higher than ilicon pyrophophate (SiP2O7, P2O5/SiO2=1) are likely to be preent. Silicon orthophophate (Si3(PO4)4) i not likely to be preent ince it only ha the P2O5/SiO2 ratio of Although the 0 dicloure dicue catalyt crytallinity ratio a a bai for optimizing the performance, no mention on the total crytallinity amount requirement wa ob erved. U.S. Pat. No. 3,673,111 to E. Hovarth et al. dicloe a proce for the manufacture of a olid phophoric acid catalyt by two-tep calcination to improve the catalyt phyical trength. Higher cruh trength wa obtained when the unfinihed catalyt i expoed to team at temperature of from 260' to 426 C. for a period of time followed by a econd calcination in the abolute abence of team. U.S. Pat. No. 3,801,704 to M. Kobayahi et al. di cloe a olid acidic aluminum phophate catalyt. It ha no relevance to the intant invention where a high ta bility olid phophoric acid catalyt with only ilicon phophate crytalline phae are detected by X-ray. Finally, U.S. Pat. No. 4,521,638 to Kida et al. di cloe a proce for preparing tertiary olefin employing a olid phophoric acid catalyt. The ueful catalyt of the proce i calcined at a temperature of greater than 0 C., preferably above 600 C., epecially preferably above 700 C. in an inert atmophere. If the calcination temperature i lower than 0 C., a catalyt having a ufficient activity and a long life cannot be obtained (column 4, line 63 to column 5, line 2). Thi differ from that of the intant invention in which the high tability olid phophoric acid catalyt wa obtained by improv ing the total ilicon phophate crytalline content in part by calcining attemperature lower than about 0 C. OBJECTS AND EMBODIMENTS It ha been dicovered that improved catalyt tabil ity in the catalytic condenation reaction i achieved by maximizing the total and type of crytalline content in a olid phophoric acid catalyt. Furthermore, thi higher ilicon phophate crytallinity product i obtained in a controlled manner by cloely controlling team level and temperature during the crytallization tep. A principal objective of thi invention i to provide an improved olid phophoric acid catalyt. The im proved catalyt exhibit enhanced catalyt life due to improved catalyt crytallinity and crytallinity ditri bution. Accordingly, a broad embodiment of the preent invention i a olid phophoric acid catalyt. The olid phophoric acid catalyt i characterized in that it ha total ilicon phophate X-ray intenity greater than percent relative to alpha-alumina. The olid phophoric acid catalyt i further characterized in that it include crytallite of both ilicon orthophophate and ilicon pyrophophate but may not be limited to thee crytal line phae. The deired crytallinity i produced by crytallizing an amorphou mixture of an acid oxide of

4 3 phophoru and a iliceou material at controlled condi tion. The crytallizing of the catalyt i ideally con ducted in a crytallizing mean containing one or more crytallizing zone at a temperature of from 0' to 0 C. and a team level of from 3 to mole percent baed upon the total vapor in the crytallizing zone. In a narrower embodiment, the intant olid pho phoric acid catalyt i characterized in that it ha a total ilicon phophate X-ray intenity greater than 40 per cent relative to alpha-alumina by integrating the (002) peak ilicon pyrophophate and (113) peak of ilicon orthophophate and dividing the raw integrated inteni tie of ilicon phophate phae by the um of raw inte grated intenitie of (012), (104), and (113) peak of an alpha-alumina external tandard. The olid phophoric acid catalyt comprie ilicon pyrophophate crytal lite with at leat 0.1 percent X-ray intenity and ilicon orthophophate crytallite with at leat.0 percent X-ray intenity, both relative to alpha-alumina. The deired phophoric acid crytallinity can be produced by crytallizing an amorphou mixture of an acid oxide of phophoru and a iliceou material in a crytallizing mean containing one or more crytallizing zone at a temperature of from 3 to 0 C., at a team level of from 5 to mole percent baed upon the vapor level in one or more of the crytalizing zone for a total period of time ranging from 20 to 120 minute. DESCRIPTION OF THE DRAWING The FIGURE i a graphical repreentation of the catalyt life propertie in gallon of hydrocarbon pro ceed per pound of olid phophoric acid catalyt in relation to total crytallinity of the catalyt. The propy lene condenation reaction wa ued for obtaining thi catalyt life data. DETAILED DESCRIPTION OF THE INVENTION Solid phophoric acid catalyt are well known for their utility in variou important hydrocarbon conver ion procee. However, there have alway been prob lem aociated with the ue of olid phophoric acid catalyt in uch procee including catalyt activity, catalyt diolution, catalyt trength, catalyt life, and the like. Therefore, way to produce active, trong catalyt are alway being purued. To approach thi goal, a long life catalyt formulation ha been invented by way of catalyt crytallinity optimization. The eential and active ingredient of the olid cata lyt herein contemplated i an acid of phophoru, pref. erably one in which the phophoru ha a valence of --5. The acid may contitute from about 60 to about 80 wt.% or more of the catalyt mixture ultimately pro duced, and i preferred to be over 80 wt.% thereof. Of the variou acid of phophoru, orthophophoric acid (H3PO4) and pyrophophoric acid (HP2O7) find gen eral application in the primary mixture, due mainly to their cheapne and to the readine with which they may be procured, although thi invention i not re tricted to their ue but may employ any of the other acid of phophoru inofar a they are adaptable. It i not intended to infer, however, that the different acid of phophoru, which may be employed will produce catalyt which have identical affect upon any given organic reaction a each of the catalyt produced from different acid and by lightly varied procedure will exert it own characteritic action. However, it i be lieved that the catalyt produced having the crytalliz 4,946, ing propertie dicloed herein will have uperior hy drocarbon converion propertie in comparion to cata lyt uing imilar precuror but different manufactur ing method. In uing orthophophoric acid a a primary ingredi ent, different concentration of the aqueou olution may be employed from approximately 75 to 100 percent or acid containing ome free phophoru pentoxide may even be ued. By thi i meant that the ortho acid may contain a definite percentage of the pyro acid corre ponding to the primary phae of dehydration of the orthophophoric acid. Within thee concentration range, the acid will be liquid of varying vicoitie and will readily mix with adorbent material. In prac tice, it ha been found that pyrophophoric acid corre ponding to the formula HaP2O7 can be incorporated with iliceou material at temperature omewhat above it melting point (61 C.) and that the period of heating which i given to the pyro acid adorbent mix ture may be different from that ued when the ortho acid i o employed. Triphophoric acid which may be repreented by the formula Hp3O10 may alo be ued a a tarting material for preparation of the catalyt of thi invention. Thee catalytic compoition may alo be prepared from the iliceou material mentioned herein and phophoric acid mixture containing orthophophoric, pyropho phoric, triphophoric, and other polyphophoric acid. The material which may be employed a adorbent or carrier for oxygen acid of phophoru are divided roughly into two clae. The firt comprie material of predominantly iliceou character and include diato maceou earth, kieelguhr, and artificially prepared porou ilica. The econd cla of material which may be employed either alone or in conjunction with the firt cla comprie generally certain member of the cla of alumina ilicate and include uch naturally occurring ubtance a variou fuller earth and clay uch a bentonite, montmorillonite, acid treated clay, and the like. Each adorbent or upporting material which may be ued will exert it own pecific influence upon the net effectivene of the catalyt compoite which will not necearily be identical with that of other member of the cla. In producing the catalyt compoite which are uti lized in the preent invention, an oxygen acid of pho phoru and a olid ilaceou material are mixed at a temperature of from about 10 to about 232 C. and preferably at a temperature of from about 95 to about 180 C. to form a compoite. Thu, atifactory reult have been obtained by heating polyphophoric acid (82% PO content) at a temperature of about 170 C. and then mixing thi hot acid with diatomaceou earth. The polyphophoric acid and diatomaceou earth form a compoite in which the weight ratio of phophoru pentoxide to diatomaceou adorbent i from about 1.8 to about 6.0. Thi compoite i lightly moit to almot dry in appearance but become platic when ubjected to preure in a hydraulic pre-type or auger-type ex truder by which the compoite i formed into piece that are cut into haped particle. Thi amorphou ex trudate i then crytallized to produce the final catalyt with deired propertie. The crytallization of the amorphou extrudate may be accomplihed in any known crytallizing mean known in the art in which temperature, team rate, and time in the crytallizing apparatu may be controlled. Condition of temperature, team addition rate, and

5 5 time in the crytallization apparatu all directly impact on the final type and amount of crytallite in the fin ihed olid phophoric acid catalyt. A mentioned, it i preferred that the finihed olid phophoric acid cata lyt have a total ilicon phophate X-ray intenity of at leat percent relative to an alpha-alumina tandard, and comprie crytallite of both ilicon orthopho phate and ilicon pyrophophate. The term "crytallization' mean apparatu or pro ce a ued in the intant application and refer to any type of apparatu in which one may control tempera ture, team rate, and time in the apparatu in order to optimize the deired crytallinity propertie of the olid phophoric acid catalyt of thi invention. Specifically, uch crytallizing mean will be an oven or furnace. Typical of uch apparatue known in the art are muffle oven or furnace, kiln, and batch or continuou calciner. The crytallization can obviouly be accomplihed in a batch or continuou manner. Such a crytallizing mean may contain one or more zone where temperature, time, and team level can be con trolled. Temperature i the firt critical crytallization condi tion. Temperature i important in both dehydrating the amorphou material and in controlling the type of cry tallite produced a a reult of the crytallizing proce dure. It i well known that high temperature, epe cially thoe above 0 C. reult in a olid phophoric acid catalyt compriing eentially only crytallite of ilicon pyrophophate. A a reult of deiring a catalyt with crytallite of both ilicon orthophophate and ilicon pyrophophate, it wa determined that crytalli zation temperature ranging from 0 to 0 C. were mot deirable and epecially temperature between 3 and 0 C. In conjunction with a pecific crytallizing tempera ture, it i alo an important apect of thi invention that the team, or moiture content of the crytallizing mean be controlled cloely to reult in the deired crytallinity propertie of the catalyt. It i deired that the team content of the vapor of the crytallization zone or zone range from 3 to mole percent baed upon the total vapor content of the crytallization zone. It i mot preferred that the team level range from 5.0 to 0 mole percent baed on the total vapor rate to the crytallization zone. It hould be noted that controlling the team content of the crytallization zone vapor doe not necearily mean that all or even part of the team to the crytalliza tion zone mut be added from an outide ource. It i quite poible that much of the team will be preent in the vapor in the crytallization zone a a reult of evapo ration of water from the catalyt during the crytalliza tion. Steam addition to the crytallization zone or zone will likely be required but the variable might alo be controlled by controlling uch variable a total vapor rate through the crytallization zone or zone, tempera ture, and green catalyt moiture content among other. Time in the crytallization proce i alo important. Typically, the total crytallization time will vary from 20 to 120 minute. When more than one crytallization zone i ued, the total time in each may vary uch that the total crytallization time range from 20 to 120 min ute. It i a further preferred apect of thi invention that where there i more than one crytallization zone, at leat one crytallization zone mut be operated at the condition above. It i further preferred that the termi 4,946,8 O 20 6 nal or final crytallization zone in a multiple tep cry tallization proce i operated at the deired proce condition detailed above. Keeping in mind that the deired temperature range will typically be the highet crytallization temperature the catalyt will ee, it be come reaonable to operate the terminal crytallization zone at the temperature and team condition that will optimize the catalyt total crytallinity and crytallite type. Thi i not to ay that other crytallization zone beide the terminal zone cannot be operated at the preferred operating condition. It i believed that thi i the mot efficient way of producing the catalyt di cloed herein. A olid phophoric acid catalyt produced by the method above will have a total ilicon phophate X-ray intenity greater than percent and preferably 40 per cent or greater relative to an alpha-alumina tandard. The preferred catalyt alo will comprie pyropho phate crytallite with preferably at leat 0.1 percent X-ray intenity relative to alpha-alumina. The crytallinity type and total crytallinity of the finihed olid phophoric acid catalyt i determined by X-ray diffraction uing a National Bureau of Standard alpha-alumina reference material. Thi analyi pro vide relative value of ilicon orthophophate and ili con pyrophophate both with repect to alpha-alumina not relative to each other and not abolute value of crytallinity. To determine the relative crytallinity of a finihed olid phophoric acid catalyt ample, the ample i firt ground to fine powder (-3 meh). The ample i then inerted into an X-ray diffractometer equipped with preferably copper anode X-ray tube and a quantitative diffraction can i acquired. Raw integrated intenitie of ilicon phophate phae are acquired by integrating the (002) peak of ilicon pyrophophate and (113) peak of ilicon orthophophate. Alo obtained i the raw integrated intenity of an alpha-alumina external tan dard by integrating the (012), (104), and (113) peak. Relative X-ray intenitie of ilicon phophate phae are obtained by dividing their repective raw integrated intenitie by the um of raw integrated intenitie of three peak of an alpha-alumina external tandard. The reult i multiplied by 100 and expreed in percent unit. The X-ray diffraction reult reported herein are expreed in value uch a total relative crytallinity, ilicon orthophophate crytallinity and ilicon pyro phophate crytallinity, and finally in term of a relative intenity ratio. Total relative crytallinity i ynonymou to total crytallinity. The total crytallinity of the olid pho phoric acid catalyt i the um of the ilicon orthopho phate crytallinity relative to alpha-alumina, and ilicon pyrophophate crytallinity relative to alpha-alumina. The relative intenity ratio refer to the ratio of the ilicon orthophophate crytallinity relative to alpha alumina divided by the ilicon pyrophophate crytal linity relative to alpha-alumina. The catalyt of thi invention i ueful in catalytic condenation, aromatic alkylation, and other type of hydrocarbon converion procee. When employed in the converion of olefinic hydrocarbon into polymer, the catalyt formed a heretofore et forth i preferably employed a a granular layer in a heated reactor which i generally made from teel and through which the preheated hydrocarbon fraction i directed. Thu, the olid catalyt of thi proce may be employed for treat

6 7 ing mixture of olefin-containing hydrocarbon vapor to effect olefin polymerization, but the ame catalyt may alo be ued at operating condition uitable for maintaining liquid phae operation during polymeriza tion of olefinic hydrocarbon, uch a butylene, to produce gaoline fraction. When employed in the poly merization of normally gaeou olefin, the formed cata lyt particle are generally placed in a vertical, cylindri cal treating tower and the olefin-containing ga mixture i paed downwardly therethrough at a temperature of from about 140 to about 290 C. and at a preure of from about 6.8 to about 102 atmophere. Thee condi tion are particularly applicable when dealing with olefin-containing material which may contain from approximately 10 to percent or more of propylene and butylene. When operating on a mixture compriing eentially propylene and butylene, thi catalyt i ef fective attemperature from about 140' to about 0' C. and at a preure of from about 34 to about 102 atmo phere. When employed in the alkylation of aromatic hydro carbon, the catalyt of thi invention may be located in tubular reactor or ingle, fixed bed of catalyt. Tem perature which are uitable for the alkylation of aro matic with the intant catalyt are thoe temperature which initiate a reaction between an aromatic ubtrate and the particular olefin ued to electively produce the deired monoalkylaromatic compound. Generally, tem perature uitable for ue are from about 100 to about 390 C., epecially from about 0' to about 275 C. Preure which are uitable for ue herein preferably are above about 1 atmophere but hould not be in ex ce of about 1 atmophere. An epecially deirable preure range i from about 10 to about 40 atmophere with a liquid hourly pace velocity (LHSV) baed upon the aromatic feed rate of from about 0.1 to about hr", and epecially from about 0.5 to about 5 hr 1. It hould be noted that the temperature and preure com bination ued herein i to be uch that the alkylation reaction take place in eentially the liquid phae. In an eentially liquid phae proce for producing alkylaro matic, the catalyt i continuouly wahed with reac tant, thu preventing buildup of coke precuror on the catalyt. Thi reult in reduced amount of carbon forming on aid catalyt in which cae, catalyt cycle life i extended a compared to a ga phae alkylation proce in which coke formation and catalyt deactiva tion i a major problem. By "eentially liquid phae, it i meant that all of the active reactant are in the liquid phae, however, there may be inert compound that exit in the vapor phae uch a light paraffin. During ue of thi catalyt in hydrocarbon conver ion procee, it i often of value to add mall amount of moiture to prevent exceive dehydration and ube quent decreae in catalyt activity and in order to ub tantially prevent lo of water from the catalyt. An amount of water or water vapor uch a team i added to the charged hydrocarbon o a to ubtantially bal ance the water content of the catalyt. Thi amount of water vapor varie from about 0.1 to about 6.0 percent by volume of the organic material charged. 4,946,8 The following example are preented in illutration of the method of thi invention and are not intended a an undue limitation on the generally broad cope of the invention a et out in the appended claim. EXAMPLE I Thi example illutrate the general preparation method for the amorphou form phophoric acid cata lyt extrudate that i converted by variou crytalliza tion method of the ubequent example into crytalline form of olid phophoric acid catalyt. Kieelguhr clay and phophoric acid have a P205 content of 82 percent or greater were combined at a 0 weight ratio of 1 to 2 at a temperature of 170 C. Thi material wa extruded with an extruder through a die to produce extrudate approximately 5 mm diameter. Only amorphou character wa detected by X-ray with the 60 8 green extrudate. The extrudate thu produced were then ued in the crytallization experiment decribed in the following Example II to VIII. The crytallinity of the finihed catalyt wa determined by X-ray diffrac tion. The method employed ued tandard X-ray dif fraction technique uing NBS alpha-alumina a a refer ence material (ee the pecification for the exact tet method). Therefore, the crytallinity value of ortho phophate and pyrophophate reported in the following example are not abolute crytallinity value but are intead relative to alpha-alumina. EXAMPLE I A batch of amorphou olid phophoric acid green extrudate from Example I wa ubjected to a crytalli zation proce in a mall oven in batche of 100 to 0 gram. The oven contained a mean of allowing once through air and team to be added at a controled rate a well a a mean for cloely controlling the oven temper ature. After about 20 minute under 3 percent team level at an oven temperature of 0 C., the catalyt wa removed and analyzed for it crytallinity, Only crytal line ilicon orthophophate wa detected with an X-ray intenity of 10.7 percent relative to an alpha-alumina tandard. No crytalline ilicon pyrophophate were detected. EXAMPLE III A batch of amorphou olid phophoric acid green extrudate from Example I wa ubjected to a crytalli zation proce in the ame mall oven a in Example II. After about 20 minute under 22 percent team level at 0 C. oven temperature, the catalyt wa removed and analyzed for it crytallinity. Only crytalline form of ilicon orthophophate wa detected with a relative X-ray intenity of 6.4 percent relative to an alpha alumina tandard. The reult of thi example and the reult of Example II indicate that team ha no effect on the production of crytalline ilicon pyrophophate at temperature below 0 C. EXAMPLE IV A batch of amorphou olid phophoric acid green extrudate from Example I wa ubjected to a crytalli zation proce in the ame mall oven a in Example II. After about minute under 3 percent team level at 392 C. oven temperature, the catalyt wa removed and analyzed for it crytallinity. Only crytalline form of ilicon orthophophate wa detected with a relative X-ray intenity of 44.9 percent relative to an alpha alumina tandard. EXAMPLE V A portion of the crytalline olid phophoric acid catalyt from Example IV wa ubjected to a recondi

7 4,946,8 tioning proce in the ame mall oven a in Example II for an additional 20 minute at 392 C. under 26 percent team. Thi additional treatment reduced the total ili con phophate X-ray intenity to 41.7 percent relative to the alpha-alumina tandard with the relative intenity 5 ratio between ilicon orthophophate and ilicon pyro phophate of 7.1. Thi example how that both team and a temperature are critical factor in producing a olid phophoric acid catalyt having crytallite of ortho and pyrophophate 10 EXAMPLE VI A batch of amorphou olid phophoric acid green extrudate from Example I wa ubjected to a crytalli zation proce in the ame mall oven a in Example II. After about minute in an 18 percent team atmo phere at 392 C. oven temperature, the catalyt wa removed and analyzed for it crytallinity. Crytallite of both ilicon orthophophate and ilicon pyropho phate were detected with a total X-ray intenity of 40 percent relative to an alpha-alumina tandard. The rela tive intenity ratio between the ilicon orthophophate and ilicon pyrophophate wa Thi reult indi cate that a high team rate at temperature above 0 C. promote the formation of crytalline ilicon pyro phophate in a crytalline olid phophoric acid cata lyt. EXAMPLE VII A portion of the crytalline olid phophoric acid catalyt from Example VI wa ubjected to a recondi tioning proce in the ame mall oven a in Example II for an additional 20 minute at 392 C. in a 3 percent team atmophere. Thi additional treatment reduced the total ilicon phophate X-ray intenity to 38.0 per cent relative to the alpha-alumina tandard while the relative intenity ratio between ilicon orthophophate and ilicon pyrophophate dropped to EXAMPLE VIII A batch of amorphou olid phophoric acid green extrudate from Example I wa ubjected to a crytalli zation proce in the ame mall oven a in Example II. After about 70 minute in a 27 percent team atmo phere at 4' C. oven temperature, the catalyt wa removed and analyzed for it crytallinity. Crytalline form of both ilicon orthophophate and ilicon pyro phophate were detected with a total X-ray intenity of 47.7 percent relative to an alpha-alumina tandard. The relative intenity ratio between the ilicon orthopho phate and ilicon pyrophophate wa EXAMPLE IX A number of olid phophoric acid catalyt prepared eentially a et forth in Example I and finihed at variou calcination condition were analyzed for rela tive ilicon orthophophate and ilicon pyrophophate X-ray intenity. The reult of thi analyi can be found in Table 1 below. The analyzed catalyt were then teted for catalyt life by placing the catalyt in an olefin polymerization proce plant. The tet wa conducted at a preure of about 68.0 atmophere, with propylene feed, at a liquid hourly pace velocity of from , and at a tempera ture of from 149' to 2' C. The catalyt life wa deter mined a gallon of polymer product produced per pound of catalyt. 10 TABLE 1. Soild Phophoric Acid Catalyt Tet Reult - Relative Silicon Orthophophate Catalyt Sample Total X-ray to Silicon Pyrophophate Life Code Intenity Relative Intenity Ratio (gal/lb) , , S , The total crytallinity value of Table 1 were plotted againt the catalyt life value to demontrate that total crytallinity i directly related to catalyt tability a hown in the FIGURE. The greater the total ilicon phophate X-ray intenity of the olid phophoric acid catalyt, the more table the olid phophoric acid cata lyt will be during the olefin polymerization procee a meaured by the catalyt life. What i claimed i: 1. A olid phophoric acid catalyt having a total ilicon phophate X-ray intenity greater than 40 per cent relative to alpha-alumina and compriing ilicon pyrophophate crytallite with at leat 1.0 percent x-ray intenity and ilicon orthophophate crytallite with at leat percent x-ray intenity, both relative to alpha-alumina, with the deired phophoric acid cata lyt crytallinity produced by crytallizing an amor phou mixture of an acid oxide of phophoru and a iliceou material in a crytallizing mean where the crytallizing mean i operated at a temperature of from 0 to 0 C., and at a team concentration of from 10 to mole percent baed upon the total vapor in the crytallizing mean. 2. The olid phophoric acid catalyt of claim 1 fur ther characterized in that the amorphou mixture of phophoru oxide and a iliceou material i crytallized in the preence of from 10 to mole percent team baed upon the total vapor in the crytallizing mean. 3. The olid phophoric acid catalyt of claim 1 fur ther characterized in that the catalyt i crytallized for a total period of time ranging from 20 to 120 minute or Oe. 4. A olid phophoric acid catalyt having a total ilicon phophate X-ray intenity greater than 40 per cent relative to alpha-alumina and compriing ilicon pyrophophate crytallite with at leat 1.0 percent X-ray intenity and ilocon orthophophate crytallite with at leat percent X-ray intenity, both relative to alpha-alumina with the deired phophoric acid catalyt crytallinity produced by crytallizing an amorphou mixture of an acid oxide of phophoru and a iliceou material in a crytallizing mean compriing a crytalli zation zone which operate at a temperature of from 0 to 0 C. and contain from 10 to mole percent team baed upon the total vapor in the crytallizing zone and for a total time period ranging from 20 to 120 minute or more. 5. The olid phophoric acid catalyt of claim 4 fur ther characterized in that the iliceou material compo

8 11. nent of the olid phophoric acid catalyt i elected from the group coniting of kieelguhr clay, diatoma ceou earth, and artificially prepared porou ilica. 6. The olid phophoric acid catalyt of claim 4 fur ther characterized in that the weight ratio of phopho ru oxide to iliceou material of the amorphou mixture range from 1 to The olid phophoric acid catalyt of claim 4 fur ther characterized in that the catalyt i crytallized in a ingle Zone crytallizing mean. 8. The olid phophoric acid catalyt of claim 4 fur ther characterized in that the acid oxide of phophoru i a polyphophoric acid. 4,946, A method of preparing a olid phophoric acid catalyt having a total ilicon phophate X-ray intenity greater than 40 percent relative to alpha-alumina and compriing ilicon pyrophophate crytallite with at leat 1.0 percent x-ray intenity and ilicon orthopho phate crytallite with at leat percent x-ray intenity, both relative to alpha-alumina, the method compriing crytallizing an amorphou mixture of an acid oxide of phophoru and a iliceou material in a crytallizing mean compriing a crytallizing zone operated at a temperature of from 0' to 0 C. and at a team rate of from 10 to mole percent baed upon the total vapor in the ame crytallizing zone. 20