CN1142019C - P-contained cracking catalyst for hydrocarbons and its preparing process - Google Patents

P-contained cracking catalyst for hydrocarbons and its preparing process Download PDF

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CN1142019C
CN1142019C CNB001093770A CN00109377A CN1142019C CN 1142019 C CN1142019 C CN 1142019C CN B001093770 A CNB001093770 A CN B001093770A CN 00109377 A CN00109377 A CN 00109377A CN 1142019 C CN1142019 C CN 1142019C
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catalyst
molecular sieve
heavy
phosphorus
zeolite
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CN1325940A (en
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达志坚
宗保宁
田辉平
罗一斌
张剑秋
张久顺
何鸣元
龙军
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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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Abstract

The present invention relates to a phosphorus-containing hydrocarbon cracking catalyst prepared from 10 to 60 wt% of Y-type molecular sieve or 10 to 60 wt% of Y-type molecular sieve and molecular sieve in an MFI structure and/or beta molecular sieve, 0 to 75 wt% of clay, 10 to 60 wt% of two kinds of aluminum oxide, 0.1 to 7.0 wt% of phosphorus (measured by P2O5) and 0 to 20 wt% of rare earth (measured by RE2O3). The catalyst is obtained by mixing a molecular sieve treated with a phosphorus-containing solution with the clay and a dialuminium binding agent after the molecular sieve treated with the phosphorus-containing solution is mixed with or not mixed with a molecular sieve not treated with a phosphorus-containing solution and by treating the mixture with a phosphorus containing solution after the mixture is calcined at the temperature of 500DEG C or dried in a spraying mode. The catalyst can reduce the content of olefins in a gasoline fraction of products to 20 to 26 wt%.

Description

A kind of phosphorous hydrocarbon cracking catalyzer and preparation
The invention relates to a kind of phosphorous hydrocarbon cracking catalyzer and preparation method thereof, specifically, about a kind of olefin(e) centent in the product gasoline fraction, phosphorus containing molecular sieve type hydrocarbon cracking catalyzer and preparation method thereof of reducing.
From the mid-1970s, countries in the world have gradually adopted fluid catalytic cracking (FCC) catalyst that contains ultra-steady Y molecular sieve (USY) to improve the octane number of catalytically cracked gasoline, this is because USY has the low characteristics of acid site density, reduced the hydrogen transfer reaction in the FCC process, increased the olefin(e) centent in the gasoline fraction, thereby having improved the octane number of gasoline, mainly is research octane number (RON).But alkene is as a kind of more active hydro carbons, and meeting photochemical reaction took place and generates ozone after not only volatilization entered atmosphere, make environment be subjected to severe contamination, and its existence can affect the stability of gasoline and the use of engine.Therefore, various countries increase day by day to the attention of olefin(e) centent in the gasoline, the olefin(e) centent in the gasoline are made restriction in the gasoline standard of many countries.
In China's gasoline blend component is FCC gasoline more than 80%, and the olefin(e) centent of FCC gasoline is very high, and this is the high main cause of olefin(e) centent in the Chinese commodity gasoline.So the olefin(e) centent that reduces in China FCC gasoline fraction is an important and real approach that reduces olefin(e) centent in the Chinese commodity gasoline.
In the last few years, people had adopted phosphorus had been introduced method in the Cracking catalyst with the abrasion resistance of improving catalyst, activity, selective and hydrothermal stability etc.These methods can be divided three classes substantially:
The first kind: earlier the precursor with molecular sieve, clay and/or high-temperature inorganic oxide mixes, and carries out post processing with the aqueous solution of phosphorus-containing compound behind the spray shaping and makes catalyst.As CN1062750A and CN1062157A.Or handle the Y zeolite catalyst of making by the carclazyte converted in-situ with dihydrogen phosphate ions, dihydrogen phosphite radical ion or its ammonium salt, to improve its catalytic activity.Such as USP4454241, USP4465780 and USP4504382.
Second class: handle matrix or, add active component then and make catalyst with phosphorus-containing compound all or part of as matrix with phosphorus-containing compound.At USP4, reported with phosphorus-containing compound in 584,091 and anticipated aluminium oxide, then this phosphorus-containing alumina is mixed and made into catalyst mutually with carclazyte, USY and silicon-aluminum sol.Reported in USP4873211 with the specific surface is 50-300 rice 2The aluminum phosphate of/gram is as matrix, and adding specific surface again is 200-1000 rice 2The Cracking catalyst that the Y zeolite of/gram is made.The boron phosphate that then contains the heavy .% of 0.1-5 in the Cracking catalyst matrix in USP5151394.
The 3rd class: process earlier molecular sieve or directly add silicoaluminophosphamolecular molecular sieves as the part of active component or active component with phosphorus-containing compound, and then adding matrix is made catalyst.Make Cracking catalyst as in EP300500, having reported the inorganic oxide matrix of the heavy % of at least a silicoaluminophosphamolecular molecular sieves and 0-99 be combined, for the production of high-knock rating gasoline.Disclosed method is that the NaY after the ammonium exchange is handled the Y zeolite that obtains the heavy % of phosphorous 0.1-4 with the phosphorus-containing compound aqueous solution of phosphoric acid or its ammonium salt among the EP397183, obtain P-USY through hydrothermal treatment consists again, make catalyst with high-temperature inorganic oxide and clay pulping, spray-drying then.This agent has preferably gasoline selective.In USP5110776, reported various molecular sieves (comprising X, Y, USY, REX, REY, RE-USY, ZSM-5, ZSM-22 etc.) are handled with phosphate solution after, drying not, mixes with the matrix precursor pull an oar after, spray-drying is made catalyst.This agent has good abrasion resistance and improved octane number.In WO9421378 be with the phosphoric acid solution of the heavy % of 0.5-4 after under 20-100 ℃ USY equimolecular sieve being carried out modification, be aided with kaolin matrix and make catalyst, can reduce dry gas and coke.Molecular sieve after will exchanging among the USP5378670, particularly USY molecular sieve obtain phosphorus modified molecular sieves successively with phosphorus-containing compound processing, hydrothermal treatment consists, again process with phosphorus-containing compound.This molecular sieve can improve cracking activity, the gasoline selective of catalyst and reduce the growing amount of dry gas, coke.
In sum, prior art is for the phosphorus modification of catalyst, and its purpose is nothing more than being hydrothermal stability and abrasion resistance for the selectivity that improves product gasoline and octane number, catalyst, and improves coke selectivity.
Up to now, have no molecular sieve and catalyst all with the phosphorus modification to reach the report that reduces olefin(e) centent in the gasoline.
Purpose of the present invention is exactly that olefin(e) centent in a kind of FCC of reduction gasoline fraction is provided on the basis of above-mentioned prior art, and has the excellent activity and the catalytic cracking catalyst and preparation method thereof of phosphorus containing molecular sieve type optionally.
Catalyst provided by the invention is by two kinds of aluminium oxide of the clay of the Y zeolite of the heavy % of 10-60 or Y zeolite and MFI structure molecular screen and/or beta-molecular sieve, the heavy % of 0-75, the heavy % of 10-60, with P 2O 5The phosphorus of the heavy % of the 0.1-7.0 of meter and with RE 2O 3The rare earth of the heavy % of the 0-20 of meter forms.
Wherein said Y zeolite is selected from one or more the mixture among HY, REY, REHY, USY, REUSY, the REDASY.Wherein contain the content of rare earth of Y zeolite of rare earth with RE 2O 3Count the heavy % of 0.5-20.
Said MFI structure molecular screen is selected from ZSM-5 or belongs to one or more molecular sieve in the MFI structure with it together, as disclosed among CN1052290A, CN1058382A, CN1147420A, the CN1194181A.
When using multiple molecular sieve in the catalyst, the weight ratio with MFI structure molecular screen and Y zeolite should be 0.025-1, preferred 0.1-0.5; The weight ratio of beta-molecular sieve and Y zeolite should be 0.025-0.8.
Said clay is a Cracking catalyst matrix clay commonly used, as kaolin, halloysite, imvite, bentonite etc.
Said two kinds of aluminium oxide are respectively from the mixture of the aluminium oxide of boehmite and aluminium colloidal sol.Wherein account for the 6-40% of catalyst weight, preferably 15-25% from the aluminium oxide of boehmite; Account for the 4-20% of catalyst weight from the aluminium oxide of aluminium colloidal sol, preferably 6-12%.Can contain take the boehmite butt as benchmark, with RE in the boehmite 2O 3The rare earth of the heavy % of the 0-40 of meter.
Catalyst provided by the invention makes according to following method: with Y zeolite or Y zeolite and have the molecular sieve of MFI structure and/or beta-molecular sieve carries out one or many with phosphorus-containing compound solution and processes, make the phosphorus content on the molecular sieve reach desired value, dry, after 350-750 ℃ of roasting 0.1-8 hour, with phosphorus containing molecular sieve and double aluminium binder, clay mixes, perhaps with phosphorus containing molecular sieve and above-mentioned molecular sieve and the double aluminium binder processed without phosphorus solution, clay mixes, homogeneous was by 500 ℃ of roasting 0.5-6 hours or spray-drying, then washing, filter, use again the post processing of phosphorus-containing compound solution, namely get phosphorous hydrocarbon cracking catalyzer provided by the invention after the drying.
Said double aluminium binder is the mixture of boehmite and aluminium colloidal sol, and wherein all or part of boehmite needs acidified and burin-in process.Concrete processing method is: with boehmite and water making beating, add with RE 2O 3Meter, accounting for rare earth compound or its solution of boehmite weight 0-40%, after stirring, is 0.15～0.50 hcl acidifying with sour aluminium weight ratio, in 40-90 ℃ of aging 0.5-5 hour.The method of boehmite acidifying and burin-in process can also be with after clay and the making beating of boehmite mixing and water adding, after adding rare earth compound or its solution stir, uses hcl acidifying, and is then aging.Whether rare earth adding quantity wherein can according to containing rare earth in the Y zeolite and content is regulated, and the rare earth in the slurries should guarantee that the content of rare earth in the final catalyst reaches predetermined value.
Above said method with phosphorus-containing compound solution-treated molecular sieve be: with molecular sieve with its butt weight ratio be 0.5-3.0, elemental phosphorous content be in the phosphorus-containing compound solution of 0.05-5.0% in 4-80 ℃ down dipping or stir 1-8 hour after, 100-120 ℃ dry 1-10 hour.So repeat one or many.Phosphorus content after dry in the molecular sieve is with P 2O 5Count the heavy % of 0.05-10.
Said process with the phosphorus-containing compound post processing be with gained roasting or spray-drying product with its butt weight ratio be 0.5-4.0, elemental phosphorous content be stirred 1-8 hour in the phosphorus-containing compound solution of 0.1-2.0% or filter carry out with the exchange of phosphorus-containing compound solution and absorption after, 100-120 ℃ dry 1-10 hour.
Said phosphorus-containing compound is the water soluble compound of phosphorus, comprise orthophosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphite, aluminum phosphate etc., be best with phosphoric acid and ammonium salt thereof wherein, this ammonium salt also can be formulated with phosphoric acid and ammoniacal liquor.The concentration of phosphorus-containing compound solution is with the elemental phosphorous heavy % of 0.05-5.0 that counts.
Compare with the phosphorus-containing catalyst of other prior art, when catalyst provided by the invention is used for catalytic cracking process, have activity stability height, heavy oil conversion performance height, the advantage that olefin(e) centent is low in the product gasoline, coke is few.
Following example will be described further Catalysts and its preparation method provided by the invention.
In example, the content of rare earth in the sample catalyst is measured with XRF, and phosphorus content is measured with chemical colorimetry, and specific surface and pore volume are measured with low-temperature nitrogen adsorption method.
The catalyst that is used for the little anti-and fixed fluidized bed evaluation of light oil is in advance through aging 4 hours or 17 hours of 800 ℃, 100% steam.
The little anti-appreciation condition of light oil is: 235～335 ℃ huge port light diesel fuel is a raw material, and oil ratio is 3.2, and weight space velocity is 16h -1, temperature is 460 ℃.
Fixed fluidized bed appreciation condition is: reaction temperature is 520 ℃, weight space velocity 20h -1, the catalyst loading amount is 90 grams, and oil ratio is 5, and reaction raw materials is the defeated VGO+20% decompression residuum of 80% pipe.
Olefin(e) centent is by gas Chromatographic Determination in the gasoline.
Example 1
With 32 gram REHY molecular sieve (RE 2O 3Content 3.4 heavy %, Na 2The heavy % of O content 4.5, silica alumina ratio is 5.6, the Shandong catalyst plant is produced) with after ammonium phosphate (chemical pure) solution of 43.8 grams, 7.8 weight % (in the ammonium phosphate amount) mix, stirred 0.5 hour, 120 ℃ after lower dry 2 hours, roasting 40 minutes in air is taken out and is pulverized under 480 ℃.
In 41 gram boehmites (solid content 34.8 heavy %, Shandong Aluminum Plant's production), add 78 gram water, after stirring, take by weighing again rare earth chloride (production of Inner Mongol Baotou rare earth factory, the RE of 3.0 grams 2O 3Content 46 heavy %, RE 2O 3Consist of La 2O 353.2%, CeO 213.0%, Pr 6O 1113.0%, Nd 2O 320.8%), is dissolved in 10 gram water, mixes with boehmite solution, stir after 10 minutes, take by weighing 15 grams, 37 heavy % hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) and dropwise add in the mixed liquor, stir.The gained pastel wore out 1.5 hours down at 90 ℃.The phosphorous REHY molecular sieve after pulverizing and 2 gram MFI structure molecular screen (Na 2The heavy % of O content 3.0, silica alumina ratio 30, the Shandong catalyst plant is produced), behind 39.4 gram kaolin (solid content 85.0 heavy %, the China Kaolin Co., Ltd's industrial products) mixing, (contain Al with aged boehmite and 24 gram aluminium colloidal sols 2O 321 heavy %, the Shandong catalyst plant is produced) mix after, in 500 ℃ of lower roastings 2 hours.
Baked catalyst is pulverized, crossed 20 mesh sieves, washing in water, ammoniacal liquor and the exhaustion of yang water in 20 times of PH3 to stem-based catalyst～4 respectively under 60 ℃, be washed till Na after sieving 2O＜0.25%, after the filtration, filter cake processed 1 hour under 20-80 ℃ in the elemental phosphorous phosphoric acid solution of counting 0.70 heavy % after, 120 ℃ lower dry 2 hours, namely get phosphorous REHY molecular sieve catalyst A provided by the invention.
Consisting of of catalyst A: kaolin 36.9%, the aluminium oxide 15.8% from boehmite, the aluminium oxide 5.6% from aluminium colloidal sol, Y zeolite 34.1%, MFI structure molecular screen 2.2%, RE 2O 32.7%, P 2O 52.7%.
Evaluation result sees Table 1.
Comparative Examples 1
Prepare catalyst by the method described in the example 1, but the roasting in the 1st step is in 100% steam.This comparative catalyst's note is made A '.
Catalyst A ' consist of: kaolin 36.9%, aluminium oxide 21.4%, Y zeolite 34.1%, MFI structure molecular screen 2.2%, RE 2O 32.7%, P 2O 52.7%.
The evaluation result data are listed in table 1.
Table 1
Catalyst A A '
Specific surface, rice 2/ gram 229 198
Pore volume, milliliter/gram 0.32 0.27
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % 82 67 79 62
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % 17.4 51.8 19.2 3.6 20.2 16.2 49.1 20.6 4.2 24.5
Data from table 1 can be found out: catalyst A has comparison than catalyst A ' higher activity stability and low coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 2
To 21 gram REY molecular sieve (RE 2O 3Content is 19.5 heavy %, Na 2O content is 1.6 heavy %, silica alumina ratio is 5.4, Chang Ling catalyst plant production) adding 32 gram concentration in is ammonium dihydrogen phosphate (ADP) (chemical pure) solution of 4.1 heavy % (in the ammonium dihydrogen phosphate (ADP) amount), stir and evenly mix 2 hours, 120 ℃ of lower dryings are after 2 hours, roasting is 3 hours in 500 ℃ of lower air, takes out and pulverizes.
Get 42.5 gram boehmites, after adding 100 gram water stir, add again 20 gram HCl, after stirring, that pastel is lower aging 2 hours at 70 ℃.Again the phosphorous REY molecular sieve after the above-mentioned pulverizing, 2 gram MFI structure molecular screen (Na 2The heavy % of O content 3.0, silica alumina ratio 30, the Shandong catalyst plant is produced), 20.1 gram kaolin with aging after boehmite and after 51.3 gram aluminium colloidal sols mix, in 500 ℃ of lower roastings 2 hours.
Same with the 3rd step in the example 1, just solution containing phosphate is the ammonium phosphate solution of phosphorous 0.30 heavy %, gets phosphorous REY molecular sieve type catalyst B provided by the invention.
Consisting of of catalyst B: kaolin 25.5%, the aluminium oxide 22.1% from boehmite, the aluminium oxide 16.1% from aluminium colloidal sol, Y zeolite 25.2%, MFI structure molecular screen 3.0%, RE 2O 36.0%, P 2O 52.0%.
Evaluation result sees Table 2.
Comparative Examples 2
Prepare catalyst by the method described in the example 2, but the solution containing phosphate that adds in the 1st step is that 32 gram concentration are the ammonium dihydrogen phosphate of 7.1 heavy % (in ammonium dihydrogen phosphate (ADP)), roasting is in 100% steam, and the 3rd solution containing phosphate of no use in the step filter cake is handled, the comparative catalyst that obtains note is made B '.
Catalyst B ' consist of kaolin 25.5%, aluminium oxide 38.2%, Y zeolite 25.2%, MFI structure molecular screen 3.0%, RE 2O 36.0%, P 2O 52.0%.
Relevant Analysis and evaluating data are listed in table 2.
Comparative Examples 3
According to disclosed preparation method in the USP5110776 example 3, the preparation comparative catalyst.
Get REY molecular sieve (RE 2O 3Content is 19.5 heavy %, Na 2O content is 1.6 heavy %, and silica alumina ratio is 5.4, and the Chang Ling catalyst plant is produced) 101.4 grams, 0.61 gram dispersant, 11.0 gram ammonium dihydrogen phosphate (ADP)s and 133.8 gram water mix and stirred 16 hours, and then add 163.8 gram deionized waters.In addition 96.5 gram kaolin, 385 gram sodium metasilicate (are contained SiO 226.8 heavy %, Na 2The heavy % of O7.8, the Qilu Petrochemical Company catalyst plant is produced) and 2134 gram water mix, add at last the molecular sieve pulp that has prepared, mix, dry, wash to there not being acid ion, reslurry, spray-drying obtains comparative catalyst B ".
Catalyst B " consist of kaolin 25.4%, silica 41.2%, Y zeolite 25.2%, RE 2O 36.1%, P 2O 52.1%.
Relevant Analysis and evaluating data are listed in table 2.
Table 2
Catalyst B B ' B "
Specific surface, rice 2/ gram 238 211 218
Pore volume, milliliter/gram 0.32 0.29 0.29
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % 83 67 78 60 81 63
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % 15.8 49.8 21.0 4.0 19.9 14.8 47.8 22.4 5.4 23.2 15.6 48.9 22.0 5.2 22.5
Can find out from table 2 data: catalyst B has comparison than catalyst B ' higher activity stability and low coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.Catalyst B has comparison than catalyst B " olefin(e) centent in higher activity, activity stability and lower coking yield, the gasoline fraction.
Example 3
To 22 gram USY molecular sieve (Na 2O content is 0.87 heavy %, and silica alumina ratio is 6.8, and the Shandong catalyst plant is produced) in to add 30 gram concentration be the ammonium dihydrogen phosphate of 1.85 heavy % (in the ammonium dihydrogen phosphate (ADP) amount), stirring and evenly mixing 4 hours, 120 ℃ drying is after 2 hours down, and 550 ℃ of following roastings 30 minutes, taking-up was pulverized.
Get 26 gram boehmites, add 32 gram water and stir, stir after 10 minutes, dropwise add 10.5 and restrain HCl, after stirring, that pastel is lower aging 1.5 hours at 70 ℃.Then the phosphorous USY molecular sieve after pulverizing, 1 gram MFI structure molecular screen (Na 2The heavy % of O content 3.0, silica alumina ratio 30, the Qilu Petrochemical Company catalyst plant is produced), 30 gram kaolin restrain the aluminium colloidal sols with above-mentioned boehmite and 30 after aging and mix, behind the mixing in 500 ℃ of lower roastings 2 hours.
With the 3rd step in the example 2 with, just solution containing phosphate be elemental phosphorous be the ammonium phosphite solution of 0.15 heavy %, get phosphorous USY molecular sieve type catalyst C provided by the invention.
Catalyst C consists of: kaolin 20.7%, the aluminium oxide 22.3% from boehmite, the aluminium oxide 11.1% from aluminium colloidal sol, Y zeolite 43.4%, MFI structure molecular screen 1.5%, P 2O 51.0%.
It is analyzed and evaluation result sees Table 3.
Comparative Examples 4
Prepare USY molecular sieve type comparative catalyst by the method described in the EP397183 example I-IV, this comparative catalyst C '.
Catalyst C ' consists of kaolin 20.5%, aluminium oxide 19.1%, Y zeolite 45.7%, P 2O 50.4%, aluminium oxide dry powder 14.3%.
The data of Relevant Analysis and evaluation are listed in table 3.
Table 3
Catalyst C C '
Specific surface, rice 2/ gram 252 234
Pore volume, milliliter/gram 0.34 0.32
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % 78 67 76 62
Heavy oil is little anti-, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % 16.8 48.9 20.8 3.2 25.2 15.4 47.6 21.5 4.1 33.5
Data from table 3 can be found out: catalyst C has comparison than the higher activity stability of catalyst C ' and low coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 4
To 25 gram REUSY molecular sieve (Na 2O content is 1.2 heavy %, RE 2O 3Content is 1.5 heavy %, and silica alumina ratio is 6.8, and the Shandong catalyst plant is produced) in add 45 grams in the ammonium phosphate amount, concentration is the ammonium phosphate solution of 5.1 heavy %, stirs after 3 hours, and 120 ℃ of lower dryings are after 2 hours, roasting is 2 hours in 600 ℃ of lower air, takes out and pulverizes.
Get 21.7 gram boehmites, add 42 gram water and stir, add again 0.37 gram rare earth chloride, stir after 10 minutes, dropwise add 10 and restrain HCl, after stirring, that pastel is lower aging 1.5 hours at 80 ℃.Then the phosphorous REUSY molecular sieve after the above-mentioned pulverizing, 3 gram MFI structure molecular screen (Na 2The heavy % of O content 3.0, silica alumina ratio 30, the Qilu Petrochemical Company catalyst plant is produced), 44.6 gram kaolin with aging after boehmite and after 12 gram aluminium colloidal sols mix, in 500 ℃ of lower roastings 4 hours.
Identical with the 3rd step of example 1, just solution containing phosphate be elemental phosphorous be the ammonium dihydrogen phosphate of 0.30 heavy %, obtain phosphorous REUSY molecular sieve type catalyst D provided by the invention.
Catalyst D consists of kaolin 48.8%, boehmite 9.8%, aluminium colloidal sol 3.2%, Y zeolite 31.7%, MFI structure molecular screen 3.9%, RE 2O 30.7, P 2O 51.9%.
It is analyzed and evaluation result sees Table 4.
Comparative Examples 5
Press the method Kaolinite Preparation of Catalyst described in the example 4, but with solution containing phosphate molecular sieve is not processed in the 1st step, other prepares comparative catalyst D ' all with example 4.
Catalyst D ' consists of: kaolin 49.5%, binding agent 13.2%, Y zeolite 32.2%, MFI molecular sieve 3.9, RE 2O 30.7%, P 2O 50.5%.
Relevant Analysis and evaluating data are listed in table 4.
Comparative Examples 6
Prepare comparative catalyst D by the 8 described methods of example among the CN1062750 " (this comparative catalyst's composition is adjusted in the scope that its patent comprises).
Catalyst D " consist of: kaolin 48.8%, aluminium oxide 13.0%, Y zeolite 31.7%, MFI structure molecular screen 3.9%, RE 2O 30.7%, P 2O 51.9%.
Relevant Analysis and evaluating data are listed in table 4.Table 4
Catalyst D D ' D "
Specific surface, rice 2/ gram 231 242 240
Pore volume, milliliter/gram 0.32 0.34 0.33
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % 79 66 83 62 82 64
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % 16.2 49.8 22.9 3.0 24.0 17.7 50.8 19.0 4.4 28.2 16.9 50.2 19.6 4.2 27.4
As can be seen from Table 4, catalyst D has comparison than catalyst D ', D " higher activity stability and low coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 5
With 50 gram NaY (Na 2The heavy % of O content 11, silica alumina ratio is 5.6, the Chang Ling catalyst plant is produced) at the ammonium chloride solution of 1 liter of 0.15M 60 ℃ of lower exchanges 1 hour, the filter cake after the filtration obtained Na in 2 hours 550 ℃ of roastings +Pre-exchange degree is 65% HNaY.It again by above-mentioned steps exchange twice, is obtained the HY molecular sieve.
Add 30 grams in elemental phosphorous in the 23 gram HY molecular sieves, the phosphoric acid of phosphorous 1.7 heavy %, PH4.5 and the mixed liquor of ammoniacal liquor stirred 6 hours, and after 120 ℃ of lower dryings, pulverizing is taken out in roasting 1 hour in air under 500 ℃.
After making the aging boehmite of identical weight according to example 3 the 2nd same procedure in the step, with phosphorous HY molecular sieve, the 2 gram beta-molecular sieve (Na of above-mentioned pulverizing 2The heavy % of O content 3.2, silica alumina ratio 28, Qilu Petrochemical company catalyst plant is produced), 28.5 gram kaolin, 17.2 gram aluminium colloidal sols and aging after boehmite mix after, in 500 ℃ of following roastings 1.5 hours.
After the step identical with the 3rd step in the example 1, get phosphorus containing molecular sieve type catalyst E provided by the invention.
Catalyst E consists of: kaolin 38.0%, the aluminium oxide 14.2% from boehmite, the aluminium oxide 5.7% from aluminium colloidal sol, Y zeolite 36.1%, β zeolite 3.1%, P 2O 52.9%.
It is analyzed and evaluation result sees Table 5.
Comparative Examples 7
According to disclosed preparation method in the USP4970183 example, preparation HY type comparative catalyst.
Earlier with 80 gram NaY (Na 2O content 11 weighs %, silica alumina ratio 5.6, the Chang Ling catalyst plant is produced) and carry out ion-exchange with ammonium ion solution, make 75 gram HY molecular sieves, again itself and 45 grams 20 are weighed % (with phosphorous acidimeter) H 3PO 4(the NH of solution and 50 grams, 20 heavy % 4) 2SO 4The mixed solution of solution, filters after 0.5 hour at 90 ℃ of lower stirring reactions, and washing obtains phosphorous NH 4Y processes this phosphorous NH in 700 ℃ of lower steam atmospheres 4Y2 hour, obtain phosphorous HY.(Changhong chemical plant, Beijing commercial product contains 12%SiO 40 gram Ludox earlier then 2), 20.4 gram kaolin, 14 gram hydrated aluminas (the heavy % of solid content 34.8, Qilu Petrochemical company catalyst plant is produced) mix, the more phosphorous HY of 17.6 grams is mixed with it, drying, washing, dry again, obtain HY type comparative catalyst E '.
Catalyst E ' consists of: kaolin 38.9%, sial binding agent 21.6%, Y zeolite 36.6%, P 2O 52.9%.
Relevant Analysis and evaluating data are listed in table 5.
Comparative Examples 8
Prepare catalyst by the method described in the example 5, but in the 3rd step not to the filter cake post processing that phosphorates, obtain phosphorous comparative catalyst E ".
Catalyst E " consist of kaolin 38.4%, aluminium oxide 20.0%, Y zeolite 36.5%, β zeolite 3.2, P 2O 51.9%.
Relevant Analysis and evaluating data are listed in table 5.
Table 5
Catalyst E E ' E "
Specific surface, rice 2/ gram 233 208 238
Pore volume, milliliter/gram 0.30 0.27 0.31
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % 76 64 73 59 77 61
Heavy oil is little anti-, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % 16.2 48.1 19.8 3.8 24.8 14.5 45.8 22.2 4.5 29.2 16.8 48.8 19.3 4.7 29.3
Can find out from table 5 data: catalyst E has comparison than catalyst E ', E " higher activity stability and low coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 6
Respectively to 8 gram REHY (RE 2O 3Content is 3.4 heavy %, and the Chang Ling catalyst plant is produced) and 8 gram REY molecular sieve (RE 2O 3Content is 19.5 heavy %, the production of Qilu Petrochemical Company catalyst plant) adding 24 gram concentration in is the ammonium dihydrogen phosphate of 2.0 heavy % (in the ammonium dihydrogen phosphate (ADP) amount), stirs 5 hours, and 120 ℃ of dryings are after 2 hours, roasting 1 hour in air under 600 ℃ is taken out and is pulverized.
Make 20 phosphorous REHY and the REY molecular sieve (RE that restrain after aging boehmite will be pulverized by method described in the second step of example 3 2O 319.5 heavy %, the Qilu Petrochemical Company catalyst plant is produced), 2 gram MFI structure molecular screen (Na 2The heavy % of O content 3.2, silica alumina ratio 33, the Chang Ling catalyst plant is produced), after 30 gram kaolin, the boehmite after aging and 40 gram aluminium colloidal sols mix, in 500 ℃ of lower roastings 2 hours.
With the 3rd step same steps as of example 1, but solution containing phosphate obtains phosphorous mixed molecular sieve type catalyst F provided by the invention for being the diammonium hydrogen phosphate of 0.40 heavy % in elemental phosphorous concentration.
Catalyst F consists of: kaolin 35.2%, the aluminium oxide 27.6% from boehmite, the aluminium oxide 11.6% from aluminium colloidal sol, Y zeolite 19.5%, MFI structure molecular screen 2.8%, RE 2O 32.5%, P 2O 50.8%.
Relevant Analysis and evaluating data are listed in table 6.
Comparative Examples 9
Prepare catalyst by the method described in the example 6, but do not add ZSM-5 in second step, and add REHY, reach same molecular sieve content, this comparative catalyst F '.
Catalyst F ' consists of: kaolin 35.2%, aluminium oxide 39.2%, Y zeolite 22.2%, RE 2O 32.6%, P 2O 50.8%.
Relevant Analysis and evaluating data are listed in table 6.
Data can be found out from table 6, and catalyst F has comparison than the higher activity stability of catalyst F ' and low coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.Table 6
Catalyst F F '
Specific surface, rice 2/ gram 218 196
Pore volume, milliliter/gram 0.30 0.29
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % 77 66 74 61
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % 17.2 47.2 21.1 4.2 22.8 16.1 46.3 22.0 5.6 26.5
Example 7
With 30 gram REHY molecular sieve (RE 2O 3Content is 3.4 heavy %, and the Qilu Petrochemical Company catalyst plant is produced) with 45.3 grams in elemental phosphorous, behind the ammonium dibasic phosphate solution mixing of 3.0 heavy %, stirred 6 hours, after 120 ℃ of lower dryings, 650 ℃ of lower roastings were taken out pulverizing after 2 hours in air.
In 20 gram boehmites, add 40 gram water, after stirring, add 7 and restrain HCl, stir after 30 minutes, acidification pseudo-boehmite is lower aging 2 hours in 80 ℃.Then the phosphorous REHY molecular sieve after the above-mentioned pulverizing, 70.5 gram kaolin with aging after boehmite and after 14.3 gram aluminium colloidal sols mix, 500 ℃ of lower roastings 2.5 hours.
With example 2 in the 3rd the step same steps as after, get molecular sieve type catalyst G provided by the invention.
Catalyst G consists of: kaolin 57.6%, the aluminium oxide 6.7% from boehmite, the aluminium oxide 2.9% from aluminium colloidal sol, Y zeolite 27.9%, RE 2O 30.9%, P 2O 54.0%.
Relevant Analysis and evaluating data are listed in table 7.
Comparative Examples 10
Prepare catalyst by the method described in the example 7, but roasting is in 100% steam in the first step, and solution containing phosphate of no use is handled to filter cake in the 3rd step, obtains comparative catalyst G '.
Catalyst G consists of: kaolin 58.1%, aluminium oxide 9.7%, Y zeolite 28.2%, RE 2O 30.9%, P 2O 53.1%.
Relevant Analysis and evaluating data are listed in table 7.
Table 7
Catalyst G G '
Specific surface, rice 2/ gram 212 205
Pore volume, milliliter/gram 0.28 0.26
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % 77 69 78 63
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % 16.0 47.6 20.8 4.0 22.2 16.8 48.0 20.2 4.8 26.4
Data can be found out from table 7, and catalyst G has comparison than catalyst G ' more high-activity stable and lower coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 8
With 36 gram USY molecular sieve (Na 2O content 0.87 heavy %, silica alumina ratio 6.8, the Qilu Petrochemical Company catalyst plant is produced) with the ammonium dihydrogen phosphate mixing of 49.8 grams, 6.5 heavy % (in the ammonium dihydrogen phosphate (ADP) amount) after, continue to stir 3 hours, 120 ℃ lower dry 2 hours, then under 500 ℃ in air roasting take out and pulverize after 1.5 hours.
With 4 gram MFI structure molecular screen (Na 2The heavy % of O content 3.0, silica alumina ratio 30, the Qilu Petrochemical Company catalyst plant is produced) with the mixed liquor mixing of 12 grams in the phosphoric acid of elemental phosphorous 1.1 heavy %, PH4.5 and ammoniacal liquor after, stirred 6 hours, after 120 ℃ of lower dryings, 700 ℃ of lower roastings were taken out and are pulverized after 2 hours in air.
In 115 gram boehmites, add 230 gram water, after stirring, add successively 41 and restrain hydrochloric acid, stir after 30 minutes, acidification pseudo-boehmite is lower aging 2.5 hours in 50 ℃.Then the phosphorous USY molecular sieve after the above-mentioned pulverizing, phosphorous MFI structure molecular screen, 2 gram beta-molecular sieve (Na 2The heavy % of O content 3.2, silica alumina ratio 28, Qilu Petrochemical company catalyst plant is produced), after the boehmite after aging and 95 gram aluminium colloidal sols mix, 500 ℃ of following roastings 3 hours.
With the 3rd step same steps as in the example 1, just the concentration of solution containing phosphate is the ammonium dihydrogen phosphate in elemental phosphorous 0.50 heavy %, gets phosphorus containing molecular sieve type catalyst H provided by the invention.
Catalyst H consists of: from aluminium oxide 38.2%, the aluminium oxide 19.0% from aluminium colloidal sol, Y zeolite 34.3%, MFI molecular sieve 3.8, β zeolite 1.9%, the P of boehmite 2O 52.8%.
Relevant Analysis and evaluating data are listed in table 8.
Comparative Examples 11
Press the method Kaolinite Preparation of Catalyst described in the example 8, but roasting is in 100% steam in the first step, and the 3rd the step in not with solution containing phosphate to the capable processing of filter cake, obtain the comparative catalyst and be denoted as H '.
Catalyst H ' consists of: aluminium oxide 57.5%, Y zeolite 34.5%, MFI molecular sieve 3.8, β zeolite 1.9%, P 2O 52.2%.
Relevant Analysis and evaluating data are listed in table 8.
Comparative Examples 12
According to disclosed method among the EP252761, with 50 gram USY molecular sieve (Na 2O content 0.87 heavy %, silica alumina ratio 6.8, the Qilu Petrochemical Company catalyst plant is produced) 700 ℃ of lower processing after 16 hours in 100% steam, get wherein 30 grams, in the ammonium dihydrogen phosphate of 1096.3 grams, 6.3 heavy % (in the ammonium dihydrogen phosphate (ADP) amount) 65.6 ℃ lower process 2 hours after, filter, drying in 538 ℃ of lower roastings 2 hours, is mixed with 47 gram (butt weight) silica-alumina gels that contain 25 heavy % aluminium oxide again, make phosphorous comparative catalyst, be denoted as H ".
Catalyst H " consist of: sial binding agent 59.3%, Y zeolite 37.9%, P 2O 52.8%.
Relevant Analysis and evaluating data are listed in table 8.
Table 8
Catalyst H H ' H "
Specific surface, rice 2/ gram 248 230 232
Pore volume, milliliter/gram 0.34 0.32 0.31
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % 80 68 79 63 79 64
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % 17.6 49.8 19.9 4.1 26.3 16.6 49.3 20.8 5.4 31.7 17.1 49.3 20.2 5.0 31.2
Data can be found out from table 8, and catalyst H has comparison than catalyst H ' and H " higher activity stability and lower coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 9
Will be in elemental phosphorous, the 450ml ammonium dibasic phosphate solution of phosphorous 100 grams per liters adds 2 kilograms (dry basis) wetting REHY molecular sieve (RE without washing 2O 3Content is 3.4 heavy %, and the Chang Ling catalyst plant is produced) after, mixing stirred 8 hours, in 100 ℃ lower dry 2 hours, then roasting 2 hours in air under 500 ℃.
In the making beating tank, in 2.74 kilograms boehmite, add 4 kg of water, pull an oar after 30 minutes, add again the hydrochloric acid of 705 grams, 37 heavy %, stir after 1 hour, 85 ℃ of lower wearing out 2 hours, add then 1.86 kilograms of kaolin, 2 kilograms in water, 1.14 kilograms of aluminium colloidal sols, pulled an oar 30 minutes.
With phosphorous rare earth hydrogen Y zeolite and the 200 gram MFI structure molecular screen (Nas of roasting after 2 hours 2The heavy % of O content 3.2, silica alumina ratio 33, the Chang Ling catalyst plant is produced), 3 kg of water add another making beating tank, pull an oar after 2 hours, join in the making beating tank that second step mentions, the homogeneous 5 hours of pulling an oar again, then spray-drying.
The catalyst that spray-drying is obtained washs at filter under 60 ℃, and is that the diammonium hydrogen phosphates of 1.0 heavy % are processed in order to elemental phosphorous meter solution containing phosphate concentration, and after the filtration, 100 ℃ lower dry, namely gets phosphorus containing molecular sieve catalyst I provided by the invention.
Consisting of of catalyst I: kaolin 30.5%, the aluminium oxide 18.4% from boehmite, the aluminium oxide 4.6% from aluminium colloidal sol, Y zeolite 37.4%, MFI structure molecular screen 3.9%, RE 2O 31.3%, P 2O 53.9%.
Relevant Analysis and evaluating data are listed in table 9.
Comparative Examples 13
Press the method Kaolinite Preparation of Catalyst described in the example 9, but the amount of the ammonium dibasic phosphate solution that adds in the first step is 877ml, roasting is in 100% steam, and the 4th the step in not with solution containing phosphate to the capable processing of filter cake.This comparative catalyst's note is made I '.
Catalyst I ' consist of: kaolin 30.5%, aluminium oxide 23.0%, Y zeolite 37.4%, MFI structure molecular screen 3.9%, RE 2O 31.3%, P 2O 53.9%.
Relevant Analysis and evaluating data are listed in table 9.Table 9
Catalyst I I '
Specific surface, rice 2/ gram 238 203
Pore volume, milliliter/gram 0.30 0.27
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % 81 73 75 64
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % 16.8 49.2 20.2 4.4 23.1 15.8 47.2 21.3 4.9 26.8
Data can be found out from table 9, and catalyst I has comparison than catalyst I ' more high-activity stable and lower coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 10
Will be in elemental phosphorous amount, the 400ml phosphoric acid of phosphorous 150g/l and ammoniacal liquor mixed solution add the wetting REHY molecular sieve (RE through washing of 2.7 (with the butt restatements) kilogram 2O 3Content is 6.0 heavy %, and the Qilu Petrochemical Company catalyst plant is produced) after, mixing stirred 5 hours, in 100 ℃ lower dry 2 hours, then roasting 4 hours in air under 500 ℃.
In the making beating jar, add 2 kilograms of kaolin, pull an oar after adding 4 kg of water, the boehmite that in the making beating jar, adds 4.9 kilograms then, pull an oar after 2 hours, add the hydrochloric acid of 1.26 kilogram of 37 heavy %, stir after 1 hour, wore out 2 hours down at 75 ℃, add 3.4 kilograms of aluminium colloidal sols then, pulled an oar 1 hour.
With phosphorous REHY type molecular sieve and the 300 gram MFI structure molecular screen (Nas of roasting after 4 hours 2The heavy % of O content 3.0, silica alumina ratio 30, Qilu Petrochemical company catalyst plant is produced), 4.5 kg of water add another making beating jar, pull an oars after 2 hours, join the 2nd and go on foot in the making beating jar of mentioning, the homogeneous 5 hours of pulling an oar again, spray-drying then.
The catalyst that spray-drying is obtained washs in order to the elemental phosphorous phosphoric acid solution of counting 1.0 heavy % on filter under 60 ℃, and after the filtration, 100 ℃ lower dry, namely gets phosphorus containing molecular sieve catalyst J provided by the invention.
Catalyst J consists of: kaolin 23.1%, the aluminium oxide 23.2% from boehmite, the aluminium oxide 9.7% from aluminium colloidal sol, Y zeolite 34.5%, MFI structure molecular screen 4.1%, RE 2O 32.2%, P 2O 53.2%.
Relevant Analysis and evaluating data are listed in table 10.
Comparative Examples 14
Press the method Kaolinite Preparation of Catalyst described in the example 10, but the amount of the mixed solution that adds in the first step is 691ml, and the 4th the step in not with solution containing phosphate to the capable processing of filter cake.This comparative catalyst's note is made J '.
Catalyst J ' consists of: kaolin 23.1%, aluminium oxide 32.9%, Y zeolite 34.5%, MFI molecular sieve 4.1%, RE 2O 32.2%, P 2O 53.2%.
Relevant Analysis and evaluating data are listed in table 10.Table 10
Catalyst J J '
Specific surface, rice 2/ gram 235 209
Pore volume, milliliter/gram 0.31 0.27
800 ℃/17hr of 800 ℃/4hr 79 70 75 63
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % 17.4 50.1 19.8 5.1 22.6 16.2 47.8 22.3 5.8 25.8
Data can be found out from table 10, and catalyst J has comparison than catalyst J ' more high-activity stable and lower coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 11
To add 3.8 kilograms (dry basis) wetting REHY molecular sieve (RE through washing in 400ml phosphoric acid and the ammoniacal liquor mixed solution of elemental phosphorous amount 150 grams per liters 2O 3Content is 6.0 heavy %, and the Qilu Petrochemical Company catalyst plant is produced) after, mixing continues to stir 3 hours, in 100 ℃ lower dry 2 hours, then roasting 3 hours in air under 650 ℃.
The boehmite that adds 6.5 kilograms in the making beating tank, add again 10 kg of water, pull an oar after 2 hours, the hydrochloric acid that adds 1.67 kilogram of 37 heavy %, stir after 2 hours, 65 ℃ of lower wearing out 1 hour, in the making beating tank, add 12.7 kilograms of aluminium colloidal sols making beating 1 hour then, add again 4 kilograms of kaolin, pulled an oar 2 hours.
With phosphorous REHY type molecular sieve and the 250 gram MFI structure molecular screen (Nas of roasting after 3 hours 2The heavy % of O content 3.0, silica alumina ratio 30, Qilu Petrochemical company catalyst plant is produced), 250 gram beta-molecular sieve (Na 2The heavy % of O content 3.2, silica alumina ratio 28, Qilu Petrochemical company catalyst plant is produced), 6.5 kg of water add another making beating jar, pull an oars after 3 hours, join the 2nd and go on foot in the making beating jar of mentioning, the homogeneous 4 hours of pulling an oar again, spray-drying then.
The catalyst that spray-drying is obtained washs in order to the elemental phosphorous phosphoric acid solution of counting 0.80 heavy % on filter under 60 ℃, and after the filtration, 100 ℃ lower dry, namely gets phosphorus containing molecular sieve catalyst K provided by the invention.
Catalyst K consists of: kaolin 26.4%, the aluminium oxide 17.5% from boehmite, the aluminium oxide 20.7% from aluminium colloidal sol, Y zeolite 27.7%, MFI structure molecular screen 1.9%, RE 2O 31.8%, β zeolite 1.9%, P 2O 52.1%.
Relevant Analysis and evaluating data are listed in table 11.
Comparative Examples 15
Prepare catalyst by the method described in the example 11, but the roasting of molecular sieve is in 100% steam atmosphere in the first step.This comparative catalyst's note is made K '.
Catalyst K ' consists of: kaolin 26.4%, aluminium oxide 38.2%, Y zeolite 27.7%, MFI structure molecular screen 1.9%, RE 2O 31.8%, β zeolite 1.9%, P 2O 52.1%.
Relevant Analysis and evaluating data are listed in table 11.Table 11
Catalyst K K '
Specific surface, rice 2/ gram 230 211
Pore volume, milliliter/gram 0.31 0.28
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % 79 68 76 62
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % 16.9 48.6 19.6 5.0 23.7 16.4 47.4 21.8 5.9 26.2
Data can be found out from table 11, and catalyst K has comparison than catalyst K ' more high-activity stable and lower coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 12
Will be in elemental phosphorous amount, the 540ml phosphoric acid of phosphorous 150g/l and ammoniacal liquor mixed solution add 4 kilograms (with butt restatement) wetting REHY (RE through washing 2O 3Content is 3.4 heavy %, and the Chang Ling catalyst plant is produced) behind the molecular sieve, mixing stirred 2 hours, in 100 ℃ lower dry 2 hours, then roasting 2 hours in air under 700 ℃.
In the making beating jar, add 4.7 kilograms of kaolin, pull an oar after adding 6 kg of water, the boehmite, the 724 gram rare earth chlorides that in the making beating jar, add 11.9 kilograms then, pull an oar after 3 hours, add the hydrochloric acid of 3.1 kilogram of 37 heavy %, stir after 1 hour, wore out 2 hours down at 70 ℃, add 15.87 kilograms of aluminium colloidal sols then, pulled an oar 1 hour.
With roasting phosphorous REHY molecular sieve and 1 kilogram of REHY molecular sieve (RE after 2 hours 2O 3Content is 3.4 heavy %, and the Chang Ling catalyst plant is produced), 667 gram MFI structure molecular screen (Na 2The heavy % of O content 3.2, silica alumina ratio 33, the Chang Ling catalyst plant is produced), 7 kg of water add another making beating tank, pull an oars after 2 hours, join the 2nd and go on foot in the making beating tank of mentioning, the homogeneous 5 hours of pulling an oar again, then spray-drying.
The catalyst that spray-drying is obtained washs in order to the elemental phosphorous phosphoric acid solution of counting 1.2 heavy % on filter under 60 ℃, and after the filtration, 100 ℃ lower dry, namely gets phosphorus containing molecular sieve catalyst L provided by the invention.
Catalyst L consists of: kaolin 22.4%, the aluminium oxide 23.1% from boehmite, the aluminium oxide 18.6% from aluminium colloidal sol, Y zeolite 27.0%, MFI structure molecular screen 3.7%, RE 2O 32.8%, P 2O 52.4%.
Relevant Analysis and evaluating data are listed in table 12.
Comparative Examples 16
Prepare catalyst by the method described in the example 12, but solution containing phosphate of no use is handled to molecular sieve in the first step, just the water with equivalent replaces solution containing phosphate, makes comparative catalyst L '.
Catalyst L ' consists of: kaolin 22.6%, aluminium oxide 43.2%, Y zeolite 27.3%, MFI structure molecular screen 3.7%, RE 2O 32.8%, P 2O 51.4%.
Relevant Analysis and evaluating data are listed in table 12.Table 12
Catalyst L L '
Specific surface, rice 2/ gram 236 249
Pore volume, milliliter/gram 0.31 0.33
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % 80 68 81 65
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % 17.2 49.2 19.9 4.9 23.7 17.6 49.5 19.3 6.1 27.3
Data can be found out from table 12, and catalyst L has comparison than catalyst L ' more high-activity stable and lower coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.

Claims (16)

1, a kind of phosphorous hydrocarbon cracking catalyzer is characterized in that:
(1) this catalyst is by the 1. Y zeolite of the heavy % of 10-60, or 2. Y zeolite, MFI structure molecular screen and beta-molecular sieve, or 3. Y zeolite and beta-molecular sieve; The clay of the heavy % of 0-75; The heavy % of 10-60 respectively from the mixture of two kinds of aluminium oxide of boehmite and aluminium colloidal sol; With P 2O 5The phosphorus of the heavy % of the 0.1-7.0 of meter and with RE 2O 3The rare earth of the heavy % of the 0-20 of meter forms;
(2) its preparation method is as follows: incite somebody to action 1. Y zeolite, or 2. Y zeolite, MFI structure molecular screen and beta-molecular sieve, or 3. Y zeolite and beta-molecular sieve, handle with phosphorus-containing compound solution, dry, 350-750 ℃ after roasting 0.1-8 hour, with itself and the double aluminium binder of forming by boehmite and aluminium colloidal sol, clay mixes, perhaps with itself and above-mentioned molecular sieve and the double aluminium binder handled without phosphorus solution, clay mixes, homogeneous is after 500 ℃ of roasting 0.5-6 hour or spray-dryings, and washing is filtered, use the post processing of phosphorus-containing compound solution again, drying.
2,, it is characterized in that wherein said Y zeolite is selected from one or more the mixture among HY, REY, REHY, USY, REUSY, the REDASY according to the described catalyst of claim 1.
3, according to the described catalyst of claim 2, it is characterized in that wherein containing the content of rare earth of Y zeolite of rare earth with RE 2O 3Weight is counted 0.5-20%.
4,, it is characterized in that wherein said MFI structure molecular screen is selected from ZSM-5 or belong to one or more molecular sieve in the MFI structure with it together according to the described catalyst of claim 1.
5,, it is characterized in that having the molecular sieve of MFI structure and the weight ratio of Y zeolite is 0.025-1 when using multiple molecular sieve in the catalyst according to the described catalyst of claim 1; The weight ratio of beta-molecular sieve and Y zeolite is 0.025-0.8.
6, according to the described catalyst of claim 5, the weight ratio that it is characterized in that having MFI structure molecular screen and Y zeolite is 0.1-0.5.
7,, it is characterized in that said clay is selected from kaolin, halloysite, imvite, bentonite according to the described catalyst of claim 1.
8, according to the described catalyst of claim 1, it is characterized in that saidly respectively from two kinds of aluminium oxide of boehmite and aluminium colloidal sol, they account for the 6-40% and the 4-20% of catalyst weight separately.
9,, it is characterized in that the aluminium oxide from boehmite and aluminium colloidal sol accounts for the 15-25% and the 6-12% of catalyst weight separately according to the described catalyst of claim 8.
10, according to claim 8 or 9 described catalyst, it is characterized in that containing in the said boehmite take boehmite butt weight as benchmark, with RE 2O 3The rare earth of the 0-40% of meter.
11, according to the described catalyst of claim 1, it is characterized in that following acidifying and the burin-in process of all or part of process of said boehmite:, add with RE boehmite and water making beating 2O 3Meter, accounting for rare earth compound or its solution of boehmite weight 0-40%, after stirring, is 0.15～0.50 hcl acidifying with sour aluminium weight ratio, in 40-90 ℃ of aging 0.5-5 hour.
12, according to the described catalyst of claim 1, it is characterized in that following acidifying and the burin-in process of all or part of process of said boehmite: after clay and the making beating of boehmite mixing and water adding, add with RE 2O 3Meter, account for rare earth compound or its solution of boehmite weight 0-40%, after stirring, with the sour aluminium weight ratio hcl acidifying that is 0.15-0.50, in 40-90 ℃ of aging 0.5-5 hour.
13, according to the described catalyst of claim 1, it is characterized in that with the method for phosphorus-containing compound solution-treated molecular sieve being: with molecular sieve with its butt weight ratio be that 0.5-3.0, elemental phosphorous content are in 4-80 ℃ of lower dipping or after stirring 1-8 hour in the phosphorus-containing compound solution of 0.05-5.0%, 100-120 ℃ dry 1-10 hour, repeat one or many after dry phosphorus content in the molecular sieve with P 2O 5Count the heavy % of 0.05-10.
14, according to the described catalyst of claim 1, it is characterized in that said process with the post processing of phosphorus-containing compound solution be with the roasting of gained or spray-drying product be 0.5～4.0 with its butt weight ratio, elemental phosphorous content be stirred 1～8 hour in 0.1～2.0% the phosphorus-containing compound solution or carrying out on the filter with the exchange of phosphorus-containing compound solution and absorption after, 100-120 ℃ dry 1-10 hour.
15,, it is characterized in that said phosphorus-containing compound is selected among orthophosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphite, the aluminum phosphate one or more mixture according to claim 1, one of 13 and 14 described catalyst.
16, according to claim 1, one of 13 and 14 described catalyst, it is characterized in that the concentration of said phosphorus-containing compound solution is counted 0.05-5.0% with elemental phosphorous weight.
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TW202138301A (en) * 2020-04-13 2021-10-16 大陸商中國石油化工科技開發有限公司 Phosphorus-modified MFI structural molecular sieve, catalytic cracking auxiliary agent and catalytic cracking catalyst containing phosphorus-modified MFI structural molecular sieve, and preparation method thereof capable of obtaining excellent cracking conversion rate and low-carbon olefin yield

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