CN1114916A - Multi-zeolite catalyzer for preparation of low-carbon olefines - Google Patents

Multi-zeolite catalyzer for preparation of low-carbon olefines Download PDF

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CN1114916A
CN1114916A CN94107496A CN94107496A CN1114916A CN 1114916 A CN1114916 A CN 1114916A CN 94107496 A CN94107496 A CN 94107496A CN 94107496 A CN94107496 A CN 94107496A CN 1114916 A CN1114916 A CN 1114916A
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zeolite
heavy
rare earth
catalyzer
earth
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CN1048428C (en
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施文元
张领辉
施至诚
葛星品
叶忆芳
刘舜华
谢朝钢
李再婷
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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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

Abstract

The catalyst for preparing low-carbon olefin by petroleum hydrocarbon transform is made of clay (0-70 wt.%), inorganic oxide (5-90 wt.%) and zeolite (10-35 Wt.%) and features that said zeolite content includes five-membered-ring high-silicon zeolite containing P and rare-earth (20-75 wt.%), high-silicon Y-type zeolite (20-75 Wt.%) and Y-type zeolite containing rare-earth (1-25 Wt.%). Its advantages include high stability of hydrothermal activity, transform rate and yield rate of propene, isobutene and isopentene.

Description

Produce the multi-zeolite catalyzer of low-carbon alkene
The present invention relates to the petroleum hydrocarbon cracking and produce the catalyzer of low-carbon alkene, more particularly, the present invention relates to the petroleum hydrocarbon cracking and produce the particularly catalyzer that contains crystal silicon-aluminate zeolite of iso-butylene and isopentene of ethene, propylene, butylene and amylene.
Produce low-carbon alkenes such as ethene, propylene, butylene from petroleum hydrocarbon, generally adopting with Sweet natural gas, petroleum naphtha or solar oil is the pyrolysis in tubular furnace of raw material; With the heavy hydrocarbon is the heat carrier cracking of raw material; Or be the catalysis conversion method of raw material with the low-carbon alcohol.And conventional catalytic cracking unit also by-product low-carbon alkene when producing gasoline and diesel oil, but its output only accounts for below the 15 heavy % of stock oil.
Once having many patents to introduce the employing appropriate catalyst, under certain reaction type formula and operational condition, is the method that raw material is produced low-carbon alkene with the petroleum hydrocarbon.For example, USP3 has introduced aluminum oxide, silicon oxide or other oxide compound of working load IIB, VB, VIIB and VIII family element in 541,179, USP3,647,682, DD225,135 and SU1,214,726 and has produced low-carbon alkene as catalyzer.But because the metal of these loads has dehydrogenation functionality, in the cracking reaction process, quickened condensation green coke process, so this class catalyzer only is applicable to the lightweight material of processing boiling range below 220 ℃.
At SU523, introduced use potassium vanadate, potassium stannate or potassium niobate in 133, SU487,927 and SU410,073 and gasoline has been carried out cracking as catalyzer, obtained the low-carbon alkene of about 56 heavy %, its ethylene yield reaches 36.5 heavy %, and productivity of propylene reaches 12.5 heavy %; At DD152, introduce use amorphous silicon Al catalysts in 356, in fixed bed or moving-burden bed reactor, petroleum hydrocarbon (comprising gasoline, diesel oil, gas oil or decompression fraction oil) has been carried out cracking, 600～800 ℃ of its temperature of reaction, reaction times is 0.3～0.7 second, C 2～4Olefins yield is 40～55%; At JP60-222, introduced use ZSM-5 catalyzer in 428, with C 5～C 25Paraffinic hydrocarbon is a raw material, and its temperature of reaction is 600～750 ℃, and the charging air speed is 20～300 o'clock -1, C 2～4Olefins yield reaches about 30%.The main drawback of aforesaid method is the temperature height of scission reaction, and raw materials used boiling spread is narrow.
It is matrix with 0～70 heavy % clay and 5～99 heavy % inorganic oxides that the applicant once disclosed a kind of in CN1043520A, the ZSM-5 of 1～50 heavy % and the mixture of Y zeolite are the catalyst for cracking of active ingredient, and this catalyzer is only applicable to produce propylene and butylene by the stock oil of multiple boiling range scope.The applicant then discloses a kind of catalyzer that is active ingredient with ZSM-5, REY and three kinds of zeolites of high silicon Y in CN1072201A, this catalyzer is used for producing propylene, butylene and high-quality gasoline by the stock oil of various boiling range scopes.The applicant also discloses another kind of with the catalyzer that to contain rare-earth five-membered ring supersiliceous zeolite, REY and three kinds of zeolites of high silicon Y be active ingredient in CN1085825A, and this catalyzer is used for the stock oil of various boiling range scopes equally and produces propylene, butylene and high-quality gasoline.
In recent years, abroad some companies are all managing to make FCC apparatus volume increase iso-butylene and isopentene to produce gasoline blend component oxycompound by changing catalyzer.Using boiling range as Grace company is that 215～556 ℃, K value are 11.51 nitrogen-containing material, when 521 ℃ temperature of reaction, transformation efficiency are 68 weight %, use the RFG catalyzer, productivity of propylene is 6.3～6.8 heavy %, the iso-butylene productive rate is 3.8～4.0 heavy %, and the isopentene productive rate is 4.7～5.1 heavy %; When catalyzer changes into when being active ingredient with 90%USY+10%ZSM-5, under identical temperature of reaction and transformation efficiency, productivity of propylene is 8.7 heavy %, and the iso-butylene productive rate is 3.6 heavy %, the isopentene productive rate be 3.9 heavy % (NPRAAM-91-34, AM-92-43).And for example Engelhard company uses middle-eastern crude gas oil to be raw material, and catalyzer is Isoplus-2000, and when transformation efficiency was 70 weight %, the iso-butylene productive rate was 3.3 heavy %, and the isopentene productive rate is 4.5 heavy %; When employing was the catalyzer of active ingredient with the REUSY zeolite, the iso-butylene productive rate was 0.58 heavy % under identical transformation efficiency, and the isopentene productive rate is 2.6 heavy % (NPRA AM-92-45).For another example Uop Inc. with the API value be 26.24, the K value is that 11.87 mixing VGO is when being raw material, USY with low content of rare earth is the activity of such catalysts component, when 549 ℃ temperature of reaction, transformation efficiency were 82.9 weight %, the iso-butylene productive rate was 2.08 heavy %, and the isopentene productive rate is 2.43 heavy %; When being the activity of such catalysts component with the USY of low content of rare earth and 5% ZSM-5, when 527 ℃ temperature of reaction, transformation efficiency were 80.8 heavy %, the iso-butylene productive rate was 2.36 heavy %, and the isopentene productive rate is 2.56 weight % (NPRA AM-92-26).Also having Mobil company in addition is catalyzer (ACSPreprints with the faujusite that contains rare earth and the mixture of ZSM-5 zeolite, 35 (4), 678～683), Hispanic Institute for Research and Technology is catalyzer (Appl.Catal. with the β zeolite, 82 (1), 37～50,1992) try hard to improve the productive rate of different propylene and iso-butylene in the FCC apparatus.
The purpose of this invention is to provide a kind of new catalyst, in the hope of obtaining the productive rate of low-carbon alkene, particularly propylene, iso-butylene and isopentene higher in the product.
Catalyzer provided by the invention has following composition: the zeolite of the inorganic oxide of the clay of 0～70 heavy %, 5～90 heavy % and 10～35 heavy %, said zeolite are that the five-ring supersiliceous zeolite of the phosphorous and rare earth of 20～75 heavy %, the type-Y high silicon zeolite and 1～25 of 20～75 heavy % weigh the mixture of the y-type zeolite that contains rare earth of %.
Clay in this catalyzer can be natural or synthetic, through or without various chemistry and/or physical treatment, usually as the various clays of cracking catalyst carrier, as kaolin, halloysite etc.
Inorganic oxide in this catalyzer is selected from amorphous Si O 2Al 2O 3, Al 2O 3, SiO 2
Type-Y high silicon zeolite in this catalyzer is with chemistry and/or physical method, as hydrothermal method, acidic treatment, aluminium-eliminating and silicon-replenishing method, SiCl 4That obtain after the processing such as method, that contain or do not contain rare earth, stabilization type-Y high silicon zeolite.
The y-type zeolite that contains rare earth in this catalyzer is selected from Rare Earth Y (REY), rare earth hydrogen Y (REHY).
The five-ring supersiliceous zeolite of the phosphorous and rare earth in this catalyzer be with aluminum phosphate handle the five-ring supersiliceous zeolite that contains rare earth, phosphorous in this zeolite (with P 2O 5Meter) 2～20 heavy %, best 2～10 heavy % contain rare earth (with RE 2O 3Meter) 2～10 heavy %.
The five-ring supersiliceous zeolite (trade names ZRP) that contains rare earth be the applicant at USP5, the zeolite disclosed in 232,675, it has the x-ray diffraction spectra of ZSM-5 zeolite family, its anhydrous chemical constitution expression formula is: 0.01～0.30RE 2O 30.4～1.0NaOAl 2O 320～60SiO 2, the used faujasite seeds that contains rare earth when synthetic of the rare earth in this composition, the duct of this zeolite is narrow than the ZSM-5 zeolite, it is 2～4 times of ZSM-5 zeolite to the ratio of the adsorptive capacity of normal hexane and hexanaphthene.This zeolite is to be raw material with water glass, aluminum phosphate, mineral acid, is crystal seed with REY or REHY zeolite, makes in 12～60 hours at 130～200 ℃ of following crystallizations.
The method of handling the ZRP zeolite with aluminum phosphate is as follows: zeolite is exchanged processing in advance with ammonium ion make its content (with Na 2O meter) reduces to and be not more than 0.1 heavy %, will consist of Al 2O 3: P 2O 5=1: 1～3 aluminum phosphate colloid is according to P 2O 5: weight ratio and this zeolite of zeolite (butt)=1: 5～99 mix, and have roasting down 0.5～6 hour in 300～600 ℃, 10～100% water vapors.
Catalyzer method for making provided by the invention is as follows: with the precursor of inorganic oxide, as aluminium colloidal sol, pseudo-boehmite, silicon sol or its mixture and silicon-aluminum sol or gel, mix by preset blending ratio with clay, and it is mixed with the slurries that solid content is 10～50 heavy % with decationized Y sieve water, stir, use mineral acid, example hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid transfer to 2～4 with slurries PH, keep this pH value, the zeolite that after leaving standstill aging 0～2 hour under 20～80 ℃, adds predetermined amount, homogeneous, spraying drying, the flush away free sodium ion, drying.
Catalyzer provided by the invention have when being used for catalytic pyrolysis hydro-thermal activity stability height, transformation efficiency height, heavy oil conversion rate high and
Figure A9410749600071
, particularly iso-butylene and the high characteristics of isopentene productive rate.On the small fixed flowing bed device, be raw material for example with the paraffinic base wax oil, catalyst sample through 800 ℃, 100% steam-treated after 6 hours 520 ℃, when agent-oil ratio 5, weight space velocity 1 -1Condition under carry out cracking performance when evaluation, when transformation efficiency is 82～86 heavy %
Figure A9410749600081
With Productive rate can reach 32～34% and 8.3～9.3% of raw material weight respectively.
Following example will give further instruction to the present invention.
Being prepared as follows of five-ring supersiliceous zeolite (following brief note is P-ZRP) of used phosphorous and rare earth in the example: get 100 gram (butt) ZRP zeolite (Zhou village, Shandong catalyst plant product, SiO 2/ Al 2O 330, RE 2O 32.0%), according to zeolite (butt): ammonium sulfate: the weight ratio of decationized Y sieve water=100: 25: 2000 exchanges after the filtration 1 time 90 ℃ of following ion-exchanges 1 hour again.Atomic absorption spectrum records in this zeolite sodium content (with Na 2The O meter) be 0.04%.With 13.8 gram pseudo-boehmite (Shandong Aluminum Plant's product, Al 2O 395%, solid content 30%), 9.0 gram industrial phosphoric acids (content 85%) and 200 gram decationized Y sieve water mix the back add above-mentioned ammonium exchange zeolite in, stir, 110 ℃ of dry backs promptly got phosphorus content (with P in aging 4 hours in 800 ℃, 100% water vapour atmosphere 2O 5Meter) is the five-ring supersiliceous zeolite P-ZRP of 5% phosphorous and rare earth.
The salient features of the used stock oil of evaluate catalysts sees Table 1 in the example.
Table 1
The intermediate base wax oil The paraffinic base wax oil Straight-run diesel oil
Density (20 ℃), gram per centimeter 3The electric furnace process carbon residue, heavy % alkali nitrogen, ppm boiling range, ℃ UOP K value ????0.8808 ????0.10 ????537 ????256～545 ????12.0 ????0.8560 ????0.69 ????420 ????319～504 ??????— ????0.8454 ????0.05 ????40 ????229～340
Example 1～4
Provided by the invention is that active ingredient, clay are that matrix, pseudo-boehmite are the Preparation of Catalyst and the cracking performance thereof of binding agent with P-ZRP, REY and REUSY.
With 340 kilograms of decationized Y sieve water with 168 kilograms of halloysites (Suzhou china clay company Industrial products, solid content 80%) making beating, add a certain amount of pseudo-boehmite again, transfer pH2～4 with hydrochloric acid, stir, under 75 ℃, left standstill aging 1 hour, keep pH2～4, cool the temperature to below 60 ℃, add P-ZRP, REY (Zhou village, Shandong catalyst plant product, SiO with different ratios 2/ Al 2O 3≮ 4.7, RE 2O 3≮ 17%) and REUSY (Zhou village, Shandong catalyst plant product, RE 2O 3≤ 3%) zeolite mixture and 70 kilograms of decationized Y sieve water stir, spray drying forming, the flush away Na that dissociates +, be drying to obtain catalyst sample A, B, C, D.
Table 2 has been listed used pseudo-boehmite and the consumption of mixed zeolite in the above-mentioned catalyst preparation process, the composition and the physical and chemical performance of catalyzer finished product.
On the small fixed flowing bed device, be that raw material is estimated above-mentioned catalyst sample with the paraffinic base wax oil, temperature of reaction is 520 ℃, agent-oil ratio 5 is during weight space velocity 1 1, through 800 ℃, 100% steam-treated 6 hours, the catalyzer loading amount was 180 grams to catalyst sample in advance, evaluation result sees Table 3.
Table 2
Catalyzer ??????A ??????B ???????C ???????D
The pseudo-boehmite consumption, kilogram mixed zeolite consumption, the kilogram catalyzer is formed, heavy % kaolin alumina zeolites is P-ZRP REY REUSY specific surface wherein, rice 2/ gram pore volume, milliliter/gram ????160 ????47.8 ????59.0 ????20.0 ????21.0 ????47.62 ????4.76 ????47.62 ????146 ????0.20 ????150 ????51.0 ????59.0 ????19.0 ????22.0 ????45.45 ????9.10 ????45.45 ????139 ????0.19 ????150 ????51.0 ????59.0 ????19.0 ????22.0 ????22.73 ????9.09 ????68.18 ????144 ????0.21 ????150 ????51.0 ????59.0 ????19.0 ????22.0 ????68.18 ????9.09 ????22.73 ????150 ????0.19
Table 3
Example 5～7
Provided by the invention is that active ingredient, clay are that matrix, pseudo-boehmite are the Preparation of Catalyst and the cracking performance thereof of binding agent with P-ZRP, REHY and high silicon Y.
According to the Preparation of catalysts method described in the example 1～4, with REHY (Zhou village, Shandong catalyst plant product, RE 2O 3≤ 7%) replace REY, (trade(brand)name, Zhou village, Shandong catalyst plant product are the SiO that makes with the dealumination complement silicon method with RSY 2/ Al 2O 3≮ 11 high silicon Y) replace REUSY to make catalyst sample E, F, G.
Table 4 has been listed the composition of above-mentioned catalyzer.
On the light oil micro-reactor, be that raw material is estimated above-mentioned catalyst sample with straight-run diesel oil, temperature of reaction is 520 ℃, agent-oil ratio 3.2 is during weight space velocity 16 -1, feed time 70 seconds, through 800 ℃, 100% steam-treated 6 hours, the catalyzer loading amount was 5.0 grams to catalyst sample in advance, evaluation result sees Table 5.
Table 4
Catalyzer ??????E ???????F ??????G
Catalyzer is formed, and heavy % kaolin alumina zeolites is P-ZRP REHY RSY wherein ????59.0 ????20.0 ????21.0 ????47.62 ????4.76 ????47.62 ????59.0 ????19.0 ????22.0 ????47.62 ????9.09 ????43.29 ????59.0 ????19.0 ????22.0 ????22.73 ????9.09 ????68.18
Table 5
Figure A9410749600131
Example 8
Provided by the invention is that active ingredient, clay are that matrix, aluminium colloidal sol are the Preparation of Catalyst and the cracking performance thereof of binding agent with P-ZRP, REY and USY.
At 218 kilograms of aluminium colloidal sols (Zhou village, Shandong catalyst plant product, Al 2O 311.4 heavy %, pH2～3) 98.6 kilograms of halloysites of middle adding, stirred 90 minutes, add 29.3 kilograms of (butt) P-ZRP, REY and USY (Zhou village, Shandong catalyst plant product, SiO again 2/ Al 2O 3≮ 10) mixture of zeolite and 72 kilograms of decationized Y sieve water stir, and spray drying forming promptly gets catalyst sample H.
Listed the composition of this catalyzer in the table 6.For the purpose of contrast, listed file names with the catalyzer (note is done contrast 1) described in the example 1 of CN1072201A in the table 6, this comparative catalyst is to be that matrix, aluminium colloidal sol are that binding agent is formed with HZSM-5, REY and DASY (Zhou village, Shandong catalyst plant product is the type-Y high silicon zeolite of the silica alumina ratio 8～9 made with the hydrothermal method dealuminzation) for active ingredient, clay.
On the small fixed flowing bed device, be that raw material is estimated above-mentioned two catalyst samples with the paraffinic base wax oil, operational condition is controlled so that the transformation efficiency of two samples is close, through 800 ℃, 100% steam-treated 6 hours, evaluation result saw Table 7 to catalyst sample in advance.
Table 6
Catalyzer ??????H Contrast 1
Catalyst forms, and heavy % kaolin alumina zeolites is P-ZRP USY REY ZSM-5 DASY wherein ????59.3 ????18.7 ????22.0 ????45.45 ????45.45 ????9.10 ????0.0 ????0.0 ????53.2 ????16.8 ????30.0 ????0.0 ????0.0 ????50.0 ????16.6 ????33.4
Table 7
Figure A9410749600151
Example 9
Provided by the invention is that active ingredient, clay are that matrix, silicon-aluminum sol are the Preparation of catalysts and the cracking performance thereof of binding agent with P-ZRP, REY and USY.
The sulphuric acid soln of 644 grams 22% is joined in the 43 gram water purification, add 0.19 liter of Al again 2O 3Content is Tai-Ace S 150 (Zhou village, the Shandong catalyst plant product) solution of 90 grams per liters, stirs, and is cooled to below 10 ℃, stirs to add 2.36 premium on currency glass (Zhou village, Shandong catalyst plant product, modulus 3.2 ± 0.1, SiO down again 2Content is 124 ± 2.0 grams per liters) and 356 gram halloysites, stirring promptly gets carrier pulp.Zeolite mixture is mixed spray drying forming behind the homogeneous, the flush away Na that dissociates with above-mentioned carrier pulp with the slurries of decationized Y sieve water +, promptly get catalyst sample I after the drying.
Listed the composition of this catalyzer in the table 8.For the purpose of contrast, listed file names with the catalyzer (note is done contrast 2 and contrast 3 respectively) described in the example 12 of the example 12 of CN1072201A and CN1085825A in the table 8, the high silicon Y of the active ingredient in this two contrast medium uses USP4,503,023 example, 3 described methods, i.e. liquid phase (NH 4) 2SiF 6The dealumination complement silicon method makes, and its silica alumina ratio is 12.
On heavy oil microreactor, be that raw material is estimated above-mentioned catalyst sample with the intermediate base wax oil, temperature of reaction is 500 ℃, agent-oil ratio 3 is during weight space velocity 16 -1, catalyst sample through 800 ℃, 100% steam-treated 8 hours, the results are shown in table 9 in advance.
Table 8
Catalyzer ??????I Contrast 2 Contrast 3
Catalyst forms, and heavy % kaolin aluminium oxide silica zeolite is the high silicon Y of P-ZRP USY REY ZSM-5 ZRP wherein ????35.0 ????2.1 ????35.9 ????27.0 ????45.45 ????45.45 ????9.10 ????0.0 ????0.0 ????0.0 ????48.3 ????1.2 ????20.5 ????30.0 ????0.0 ????0.0 ????50.0 ????16.6 ????0.0 ????33.4 ????48.3 ????1.2 ????20.5 ????30.0 ????0.0 ????0.0 ????50.0 ????0.0 ????16.6 ????33.4
Table 9
Figure A9410749600181
Example 10
Provided by the invention is that active ingredient, amorphous aluminum silicide are the Preparation of catalysts and the cracking performance thereof of matrix with P-ZRP, REY and USY.
With of the decationized Y sieve water dilution of 373 premium on currency glass, add 97 liters of Al with 398 kilograms 2O 3Content is the alum liquor of 50 grams per liters, stirs, and its temperature is controlled at 15～25 ℃, adds 136 liters of Al more successively 2O 3Content is alum liquor and 95 liters of ammoniacal liquor of 90 grams per liters, and stirring promptly gets carrier pulp.Zeolite mixture is mixed spray drying forming behind the homogeneous, the flush away Na that dissociates with above-mentioned carrier pulp with the slurries of decationized Y sieve water +, be drying to obtain catalyst sample J.
Table 10 has been listed the composition of this catalyzer.For the purpose of contrast, listed file names with the catalyzer (note is done contrast 4 and contrast 5 respectively) described in the example 16 of the example 16 of CN1072201A and CN1085825A in the table 10.
On heavy oil microreactor, be that raw material is estimated above-mentioned each catalyst sample with the intermediate base wax oil, appreciation condition the results are shown in table 11 with example 9.
Table 10
Catalyzer ??????J Contrast 4 Contrast 5
Catalyzer is formed, heavy % SiO 2·Al 2O 3Zeolite is P-ZRP USY REY ZSM-5 ZRP DASY wherein ????78.0 ????22.0 ????45.45 ????45.45 ????9.10 ????0.0 ????0.0 ????0.0 ????75.0 ????25.0 ????0.0 ????0.0 ????60.1 ????8.1 ????0.0 ????31.8 ????75.0 ????25.0 ????0.0 ????0.0 ????60.1 ????0.0 ????8.1 ????31.8
Table 11

Claims (10)

1. catalyzer that is used to produce low-carbon alkene, form by the clay of 0～70 heavy %, the inorganic oxide of 5～90 heavy % and the zeolite of 10～35 heavy %, it is characterized in that said zeolite is that the five-ring supersiliceous zeolite of the phosphorous and rare earth of 20～75 heavy %, the type-Y high silicon zeolite and 1～25 of 20～75 heavy % weigh the mixture of the y-type zeolite that contains rare earth of %.
2. according to the described catalyzer of claim 1, it is characterized in that said clay is selected from kaolin and/or halloysite.
3. according to the described catalyzer of claim 1, it is characterized in that said inorganic oxide is selected from SiO 2Al 2O 3, Al 2O 3, SiO 2
4. according to the described catalyzer of claim 1, it is characterized in that said high-silicon Y-Zeolite with chemistry and/or physical method handle, contain or do not contain the y-type zeolite of the stabilization of rare earth.
5. according to the described catalyzer of claim 1, it is characterized in that the said rare earth Y type zeolite that contains is selected from Rare Earth Y, rare earth hydrogen Y.
6. according to the described catalyzer of claim 1, it is characterized in that said phosphorous and five-ring supersiliceous zeolite rare earth is to handle obtain phosphorous (with P with aluminum phosphate 2O 5Meter) 2～20 heavy %'s contains the rare-earth five-membered ring supersiliceous zeolite.
7. according to the described catalyzer of claim 1, it is characterized in that said phosphorous and five-ring supersiliceous zeolite rare earth is to handle obtain phosphorous (with P with aluminum phosphate 2O 5Meter) 2～10 heavy %'s contains the rare-earth five-membered ring supersiliceous zeolite.
8. according to claim 6 or 7 described catalyzer, it is characterized in that the said X-ray diffractogram that the rare-earth five-membered ring supersiliceous zeolite has ZSM-5 zeolite family that contains, its anhydrous chemical constitution formula is 0.01～0.30RE 2O 30.4～1.0Na 2OAl 20 320～60SiO 2, the used crystal seed when synthetic of the rare earth in the composition, this zeolite are 2～4 times of ZSM-5 zeolite to the ratio of normal hexane and hexanaphthene adsorptive capacity.
9. according to claim 6 or 7 described catalyzer, it is characterized in that the said rare-earth five-membered ring supersiliceous zeolite that contains is that employing water glass, aluminum phosphate and mineral acid are raw material, with Rare Earth Y or rare earth hydrogen Y zeolite is crystal seed, makes in 12～60 hours at 130～200 ℃ of following crystallizations.
10. according to claim 6 or 7 described catalyzer, it is characterized in that saidly handling the method that contains the rare-earth five-membered ring supersiliceous zeolite with aluminum phosphate and being: zeolite is exchanged processing in advance with ammonium ion, make its sodium content (with Na 2O meter) reduces to and be not more than 0.1 heavy %, will consist of Al 2O 3: P 2O 5=1: 1～3 aluminum phosphate colloid is according to P 2O 5: weight ratio and this zeolite of zeolite (butt)=1: 5～99 mix, and roasting is 0.5～6 hour in the presence of 300～600 ℃, 10～100% water vapors.
CN94107496A 1994-07-15 1994-07-15 Multi-zeolite catalyzer for preparation of low-carbon olefines Expired - Lifetime CN1048428C (en)

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CN1087652C (en) * 1996-02-29 2002-07-17 中国科学院大连化学物理研究所 Catalyst for reaction of alpha-olefines prepared through ether cracking
WO2008028343A1 (en) 2006-08-31 2008-03-13 China Petroleum & Chemical Corporation A process for catalytic converting hydrocarbons
WO2008034299A1 (en) 2006-08-31 2008-03-27 China Petroleum & Chemical Corporation A catalyst for converting hydrocarbons
EP2161077A1 (en) * 2007-06-27 2010-03-10 China Petroleum & Chemical Corporation A catalytic cracking catalyst, its preparation and use
CN108262062A (en) * 2016-12-30 2018-07-10 中国石油天然气股份有限公司 A kind of catalyst for cracking heavy oil of fecund isomeric olefine and preparation method thereof

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CN1087652C (en) * 1996-02-29 2002-07-17 中国科学院大连化学物理研究所 Catalyst for reaction of alpha-olefines prepared through ether cracking
WO2008028343A1 (en) 2006-08-31 2008-03-13 China Petroleum & Chemical Corporation A process for catalytic converting hydrocarbons
WO2008034299A1 (en) 2006-08-31 2008-03-27 China Petroleum & Chemical Corporation A catalyst for converting hydrocarbons
US8716163B2 (en) 2006-08-31 2014-05-06 China Petroleum & Chemical Corporation Hydrocarbon conversion catalyst
US8900445B2 (en) 2006-08-31 2014-12-02 China Petroleum & Chemical Corporation Process for the catalytic conversion of hydrocarbons
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US9486795B2 (en) 2007-06-27 2016-11-08 China Petroleum & Chemical Corporation Catalytic cracking catalyst, its preparation and use
CN108262062A (en) * 2016-12-30 2018-07-10 中国石油天然气股份有限公司 A kind of catalyst for cracking heavy oil of fecund isomeric olefine and preparation method thereof
CN108262062B (en) * 2016-12-30 2021-09-28 中国石油天然气股份有限公司 Heavy oil cracking catalyst for producing more isoolefins and preparation method thereof

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