CN100395029C - Production of liquefied gas cracking catalyst with gasoline olefin content decreasement - Google Patents
Production of liquefied gas cracking catalyst with gasoline olefin content decreasement Download PDFInfo
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- CN100395029C CN100395029C CNB2005100681776A CN200510068177A CN100395029C CN 100395029 C CN100395029 C CN 100395029C CN B2005100681776 A CNB2005100681776 A CN B2005100681776A CN 200510068177 A CN200510068177 A CN 200510068177A CN 100395029 C CN100395029 C CN 100395029C
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Abstract
The present invention relates to a preparation method of a cracking catalyst for reducing the olefine content of gasoline and increasing the yield of liquid gas. Clay, deionized water and a phosphorus-containing compound are uniformly mixed to obtain clay slurry; a molecular sieve, deionized water, a phosphorus-containing compound and a rare earth compound are uniformly mixed to obtain molecular sieve slurry; a binding agent, deionized water and optional inorganic acid are uniformly mixed to obtain binding agent slurry; the clay slurry, the molecular sieve slurry and the binding agent slurry are dried after being uniformly mixed. The cracking catalyst prepared with the method of the present invention has the advantages of high liquid gas yield and particularly high concentration of propene in the liquid gas. The content of olefine in the gasoline is reduced while high gasoline yield and a high gasoline octane number are maintained.
Description
Technical field
The invention belongs to a kind of preparation method of hydrocarbon cracking catalyzer.
Technical background
Along with the environmental protection standard increasingly stringent, it is more and more lower to require to reduce olefin content in gasoline.Developing the catalyst that reduces olefin(e) centent in catalytic cracking (FCC) gasoline fraction, is a quick feasible approach.
Along with the petrochemical industry industrial expansion, FCC technology is not only the important means that light oil is provided, also provide simultaneously a kind of processing mode of basic Organic Chemicals such as alkene, as propylene is the important source material of producing phenol-acetone, acrylic acid etc., therefore, need develop and have the higher catalyst of propylene content in higher yield of liquefied gas, the especially liquefied gas.
Improve the yield of liquefied gas yield of propylene in the liquefied gas especially in the cracked product, when keeping higher yield of gasoline and octane number, reduce olefin content in gasoline.To increase low-carbon alkene on the one hand, reduce olefin content in gasoline on the other hand again.
In recent years, the preparation method that phosphorus is introduced in the Cracking catalyst appears in the newspapers repeatly, and it mainly acts on following four classes substantially:
One, is used to improve abrasion index, activity, selectivity and the hydrothermal stability etc. of catalyst.As CN1022465C, CN1024504C, CN1062750A, CN1062157A etc. the precursor of molecular sieve, clay and/or inorganic oxide is mixed, the aqueous solution with phosphorus-containing compound after the spray-drying carries out post processing, these methods can be improved the abrasion index of catalyst, make catalyst have good hydrothermal stability and catalytic activity; USP5110776, USP5378670, EP252761, EP300500, EP397183, WO9421378A, CN1085722C etc. handle molecular sieve or directly add silicoaluminophosphamolecular molecular sieves as active component with phosphorus-containing compound, to improve the cracking activity of catalyst, improve the selectivity of product, the catalyst that is prepared by these methods has higher light oil productive rate and low coke yield.
Two, be used for increasing output of diesel oil.As CN1072030C that the aqueous solution of faujasite and phosphorus-containing compound is even, drying 450-600 ℃ of following roasting 0.5 hour, is mixed phosphorous faujasite and aluminium colloidal sol, aging boehmite slurries again, contains or argillaceous not.
Three, be used to reduce olefin content in gasoline.Provide a kind of preparation method of phosphorus containing molecular sieve Cracking catalyst as CN1325940A, molecular sieve is flooded in phosphorus-containing compound solution, stirs, dry again, so repeat one or many, make P on the molecular sieve
2O
5Content is the heavy % of 0.05-10, mixes with double aluminium binder, clay then, obtains catalyst with the post processing of phosphorus-containing compound solution again after drying, washing, the filtration.This catalyst can reduce olefin(e) centent in the FCC gasoline fraction, and has excellent activity and selectivity.
Four, be used for low-carbon olefines high-output, keep or improve the octane number of gasoline.Disclosed as CN1042201C, CN1055301C is voluminous C
3-C
5The Cracking catalyst of alkene, they can improve isobutene, iso-amylene productive rate, can make gasoline yield and octane number maintain higher level again; Disclosed Cracking catalyst such as CN1072201A, CN1085825A, CN1093101A, CN1098130A are used to improve octane number and olefins yield.
Cracking catalyst by above-mentioned prior art for preparing all can not reduce content of olefin in gasoline and voluminous liquefied gas simultaneously.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of Cracking catalyst, the catalyst that is prepared by this method will reduce content of olefin in gasoline, simultaneously voluminous liquefied gas.
Preparation of catalysts method provided by the invention comprises:
(1), the preparation of clay slurry
Clay, deionized water and phosphorus-containing compound are mixed, make clay slurry, the phosphorus-containing compound addition is counted the heavy %P of 0.1-5.0 with the butt weight of catalyst
2O
5
(2), the preparation of molecular sieve pulp
Molecular sieve, deionized water, phosphorus-containing compound, rare earth compound are mixed, make molecular sieve pulp, the addition of phosphorus-containing compound is counted the heavy %P of 0.1-3.0 with the butt weight of catalyst
2O
5, the addition of rare earth compound is counted the heavy %RE of 0.1-5.0 with the butt weight of catalyst
2O
3
(3), the preparation of binding agent slurries
Binding agent, deionized water and optional inorganic acid are mixed, make the binding agent slurries;
(4), the mixing of slurries
Above-mentioned clay slurry, molecular sieve pulp and binding agent slurries are mixed the back drying.
Especially the density of propylene in the liquefied gas is very high to have higher yield of liquefied gas by the Cracking catalyst of method of the present invention preparation, when keeping higher yield of gasoline and octane number, has reduced olefin content in gasoline.
The specific embodiment
Preparation of catalysts method provided by the invention comprises:
(1), the preparation of clay slurry
Clay, deionized water and phosphorus-containing compound are mixed, make clay slurry, the phosphorus-containing compound addition is counted the P of the heavy % of the 0.1-5.0 preferred 0.3-3.5 of heavy % with the butt weight of catalyst
2O
5
(2), the preparation of molecular sieve pulp
Molecular sieve, deionized water, phosphorus-containing compound solution, rare earth compound are mixed, make molecular sieve pulp, the addition of phosphorus-containing compound is counted the P of the heavy % of the 0.1-3.0 preferred 0.3-2.5 of heavy % with the butt weight of catalyst
2O
5, the addition of rare earth compound is counted the RE of the heavy % of the 0.1-5.0 preferred 0.3-4.8 of heavy % with the butt weight of catalyst
2O
3
(3), the preparation of binding agent slurries
Binding agent, deionized water and optional inorganic acid are mixed, make the binding agent slurries;
(4), the mixing of slurries
After above-mentioned clay slurry, molecular sieve pulp and binding agent slurries are mixed, again through the drying or the spray-drying of routine.
The preparation of clay slurry, molecular sieve pulp and binding agent slurries does not have strict precedence, can prepare simultaneously, can be by different order preparations yet.
Cracking catalyst by method preparation of the present invention comprises the heavy % clay of 20-70, the heavy % molecular sieve of 15-50, and the heavy % binding agent of 7-45 adds the heavy %P of 0.2-8.0
2O
5, add the heavy %RE of 0.1-5.0
2O
3, all in catalyst butt weight.
Described clay is selected from one or more the mixture in kaolin, halloysite, imvite, diatomite, bentonite, the sepiolite, preferred kaolin.
One or more the mixture of described molecular screening in faujasite, zeolite, modenite, β zeolite with MFI structure, described faujasite is selected from y-type zeolite or/and X type zeolite, and wherein y-type zeolite is selected from one or more the mixture in phosphorous y-type zeolite, REY type zeolite, phosphorous REY type zeolite, HY type zeolite, phosphorous HY type zeolite, REHY type zeolite, phosphorous REHY type zeolite, USY type zeolite, phosphorous USY type zeolite, REUSY type zeolite, the phosphorous REUSY type zeolite; Described mesopore zeolite is selected from the zeolite with MFI structure, the mixture of one or more in the zeolite with MFI structure of phosphorous, iron and/or rare earth.
When using y-type zeolite in the catalyst, when having the multiple molecular sieves such as zeolite of MFI structure, having the zeolite of MFI structure and the weight ratio of y-type zeolite and should be the preferred 0.2-2.5 of 0.1-2.7.
In described clay slurry and molecular sieve pulp preparation process, all add phosphorus-containing compound, this phosphorus-containing compound comprises the compound of various phosphorus, as one or more in phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphoric acid, pyrophosphate, polymer phosphate, polymeric phosphate, metaphosphoric acid, the metaphosphate, be preferably in phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphorous acid, ammonium phosphite, sodium pyrophosphate, potassium pyrophosphate, sodium phosphate trimer, PTPP, calgon, the hexa metaphosphoric acid potassium one or more.The mixture of one or more in phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphorous acid, ammonium phosphite, sodium pyrophosphate, sodium phosphate trimer, the calgon more preferably.The solution that in described clay slurry and molecular sieve pulp preparation process, also can add above-mentioned phosphorus-containing compound.
The solution that adds rare earth compound in described molecular sieve pulp preparation process, described rare earth compound are that rare earth chloride is or/and nitric acid rare earth, preferably rare earth chloride.
Described binding agent is selected from a kind of or wherein several mixture in the silica-alumina gel of silicon-aluminum sol, silica-alumina gel, modification of aluminium colloidal sol, Ludox, boehmite, silicon-aluminum sol, modification, a kind of or wherein several mixture in preferred aluminium colloidal sol, Ludox, the boehmite.
When binding agent contains boehmite, must add inorganic acid and carry out acidifying, described inorganic acid is hydrochloric acid, nitric acid or phosphoric acid, preferred hydrochloric acid.
Preparation method provided by the invention has following characteristics:
1, the Cracking catalyst of this method preparation has higher yield of liquefied gas, and especially the density of propylene in the liquefied gas is very high, when keeping higher yield of gasoline and octane number, has reduced olefin content in gasoline.The affiliation that adds in right amount of phosphorus makes the surface acidity of molecular sieve and clay that favourable variation take place, and this is the result owing to different conditions phosphorus and surfaces of aluminum effect, the hydrogen migration moderate performance of catalyst, and coke yield is lower.
2, this method is clay, molecular sieve and three strands of slurries of binding agent to be mixed generate catalyst slurry, and this one-tenth glue mode makes the one-tenth glue mode of Cracking catalyst become more flexible, and is quick and easy to control; Before drying, any one part of catalyst slurry does not all need to heat up aging, has shortened the Preparation of catalysts time, has improved production efficiency, has reduced energy consumption and production cost.
3, the catalyst of this method preparation can be in a wide in range scope some physical property of regulating catalyst, keep good abrasion resistance simultaneously, for example, bulk density is the 0.60-0.82 grams per milliliter, pore volume is 0.25-0.45 milliliter/gram.Bigger pore volume means the green coke trend that can reduce crackate, improves product and distributes; Different bulk densities means the demand of Cracking catalyst applicable to different catalytic cracking units.
The following examples will the present invention will be further described, but therefore do not limit the present invention.
Among the embodiment, content of rare earth in the catalyst sample is measured with XRF, phosphorus content is measured with chemical colorimetry, bulk density, pore volume and abrasion index adopt " petrochemical industry analytical method (RIPP test method) " respectively, and (Yang Cuiding, Gu Kanying compile, 1990, Science Press) RIPP31-90, the RIPP28-90 in, RIPP29-90 method are measured.
The catalyst that is used for the little anti-and fixed fluidized bed evaluation of light oil is in advance through aging 8 hours or 17 hours of 800 ℃, 100% steam.
The little anti-appreciation condition of light oil is: it is the particle of 420-841 micron that catalyst breakage is become particle diameter, and loading amount is 5 grams, and reaction raw materials is that boiling range is 235-337 ℃ a straight distillation light diesel oil, 460 ℃ of reaction temperatures, and weight space velocity is 16 hours
-1, oil ratio 3.2.
Be lower than gasoline yield+gas yield+coke yield of 204 ℃ in light oil microactivity MA=(being lower than gasoline output+gas yield+coke output of 204 ℃ in the product)/charging total amount * 100%=product.
Fixed fluidized bed appreciation condition is: the catalyst loading amount is 90 grams, and reaction raw materials is a 80%VGO+20% decompression residuum, 520 ℃ of reaction temperatures, and weight space velocity is 20 hours
-1, oil ratio 5.
Embodiment 1
1.3 kilograms of kaolin (dry basis, China Kaolin Co., Ltd produces) are added in ammonium dihydrogen phosphate (ADP) (chemical pure, the Beijing Chemical Plant produces) solution of 0.3 kilogram of 24 heavy % (in the ammonium dihydrogen phosphate (ADP) amount), stirred 1.5 hours, form kaolin slurry.
Get boehmite (in aluminium oxide, Shandong Aluminum Plant's product) 1.1 kilogram, aluminium colloidal sol is (in aluminium oxide, Shandong catalyst plant product) 0.8 kilogram, hydrochloric acid (the chemical pure of 5.6 kilograms and 282 milliliter 36 heavy % of deionized water, the Beijing Chemical Plant produces) mix and stirred 1.5 hours, needn't heat up wears out can obtain the binding agent slurries.
Get 1.3 kilograms of REY molecular sieve (RE
2O
3Content 18.5 heavy %, Na
2O content is 1.6 heavy %, and silica alumina ratio 5.4, the Shandong catalyst plant is produced), 0.4 kilogram of ZRP-1 molecular sieve (a kind of zeolite of phosphorous and rare earth, Na with MFI structure
2O content 0.1 heavy %, silica alumina ratio 25, the content of rare earth oxide are 1.5 weight %, wherein, La
2O
3Account for 53.2 weight %, the CeO of rare earth oxide
2Account for 13.0 weight %, the Pr of rare earth oxide
6O
11Account for 13.0 weight %, the Nd of rare earth oxide
2O
3Account for 20.8 weight % of rare earth oxide, in element phosphor, phosphorus content is 1.1 weight %, the Shandong catalyst plant is produced, down together) mix with 2.0 kilograms of deionized waters that add 69 gram phosphoric acid (chemical pure, the Beijing Chemical Plant produces), add 114 milliliters of re chlorides (self-control, RE again
2O
3Concentration is 219 grams per liters, and the solid rare earth chloride is produced by Inner Mongol Baotou rare earth factory, RE
2O
3Content 46 heavy %, RE
2O
3Consist of La
2O
353.2 heavy %, CeO
213.0 heavy %, Pr
6O
1113.0 heavy %, Nd
2O
320.8 heavy %, down together) and 5 milliliters of ammoniacal liquor (chemical pure, the Beijing Chemical Plant produces), make molecular sieve pulp.
Above-mentioned three strands of slurries are mixed, promptly obtain catalyst A 1 by the present invention's preparation.
Consisting of of catalyst A 1: kaolin 26.4 heavy %, boehmite 22.0 heavy %, aluminium colloidal sol 16.1 heavy %, REY type molecular sieve 25.0 heavy %, ZRP-1 molecular sieve 8.0 heavy % add P
2O
52.0 heavy %, RE
2O
30.5%.The fixed fluidized bed evaluation result of catalyst A 1 is listed in the table 1.
Embodiment 2
1.3 kilograms of kaolin are added in the solution of 0.9 kilogram of deionized water and 139 gram diammonium hydrogen phosphates (chemical pure, the Beijing Chemical Plant produces) generation, stir and obtained the binding agent slurries in 1.5 hours.
Get 1.1 kilograms of boehmites, 0.8 kilogram of aluminium colloidal sol, the mixed in hydrochloric acid of 3.6 kilograms and 94 milliliter 36 heavy % of deionized water stirred 1.5 hours, obtained the binding agent slurries.
Get 1.3 kilograms of MOY molecular sieves (a kind of y-type zeolite of phosphorous and rare earth, RE according to CN1325940A preparation
2O
3Content 8.0 heavy %, Na
2O content is 1.3 heavy %, and phosphorus content 1.1 heavy %, silica alumina ratio 5.6, the Shandong catalyst plant is produced), 0.4 kilogram of ZSP-1 molecular sieve (a kind of MFI type zeolite of phosphorous and iron, Fe
2O
3Content 2.5 heavy %, P
2O
54.0 heavy %, Na
2O content is 0.1 heavy %, silica alumina ratio 25, the Shandong catalyst plant is produced), mix with 2.5 kilograms of deionized waters that add 34.5 gram phosphoric acid, add 115 milliliters of re chlorides and 6 milliliters of ammoniacal liquor again, obtain molecular sieve pulp.
Above-mentioned three strands of slurries are mixed, promptly obtain catalyst A 2 by the present invention's preparation.
Consisting of of catalyst A 2: kaolin 26.0 heavy %, boehmite 22.2 heavy %, aluminium colloidal sol 16.1 heavy %, MOY molecular sieve 25.2 heavy %, ZRP-1 molecular sieve 8.0 heavy % add P
2O
52.0 heavy %, RE
2O
30.5 heavy %.The fixed fluidized bed evaluation result of catalyst A 2 is listed in the table 1.
Comparative Examples 1
According to disclosed preparation method in the CN1325940A example 2, the preparation comparative catalyst.
Get 1.3 kilograms of REY molecular sieves, add in 2.8 kilograms of deionized waters and 162 solution that are made into of gram ammonium dihydrogen phosphate (ADP)s, stirs 2 hours mixings, 120 ℃ down after dry 2 hours, roasting is 3 hours in 500 ℃ of air, takes out pulverizing.
Get 1.1 kilograms of boehmites, 7.0 kilograms of deionized waters of adding, hydrochloric acid stir, wore out 2 hours down at 70 ℃, again the phosphorous REY molecular sieve after the above-mentioned pulverizing, 0.4 kilogram of ZRP-1 molecular sieve, 1.3 kilograms of kaolin with aging after boehmite and 0.8 kg aluminium colloidal sol mix, 500 ℃ of following roastings 2 hours.
Press the 3rd step of the example 2 and handle catalyst, promptly get comparative catalyst A3.
Comparative catalyst A3 consists of: kaolin 26.5 heavy %, and boehmite 22.2 heavy %, aluminium colloidal sol 16.1 heavy %, Y zeolite 25.2 heavy %, ZRP-1 molecular sieve 8.0 heavy % add P
2O
52.0 heavy %.The fixed fluidized bed evaluation result of catalyst A 3 is listed in the table 1.
Table 1
| Catalyst | A1 | A2 | A3 |
| MA(800℃/8h) | 78 | 76 | 69 |
| Conversion ratio, heavy % | 83.6 | 83.7 | 79.2 |
| The product productive rate, heavy % | |||
| Liquefied gas | 28.7 | 28.3 | 25.0 |
| Gasoline | 43.3 | 42.8 | 41.1 |
| Diesel oil | 11.8 | 12.1 | 11.4 |
| Coke | 7.6 | 7.9 | 8.9 |
| Productivity of propylene in the liquefied gas, heavy % | 11.2 | 10.8 | 9.6 |
| Olefin(e) centent in the gasoline, heavy % | 24.2 | 23.5 | 30.2 |
From table 1 data as can be seen, catalyst A 1, A2 comparison has higher activity level than catalyst A 3, and the olefin(e) centent in the gasoline fraction and coke yield are lower, and liquefied gas the and wherein productive rate of propylene is higher.
Embodiment 3
683 gram kaolin are added in the solution of 467 gram deionized waters and 53.9 gram calgons (chemical pure, the Beijing Chemical Plant produces) formation, stir and obtained kaolin slurry in 1.5 hours.
Get 225 gram ZRP-1 molecular sieves, 225 gram REY and 75 gram DASY
0.0Zeolite (a kind of USY zeolite, Na
2O content is 0.98 heavy %, silica alumina ratio 6.2, the Shandong catalyst plant is produced, down with) add in the 600 gram deionized waters, add 41.8 gram diammonium hydrogen phosphates again, 103 milliliters of re chlorides and 10 milliliters of ammoniacal liquor stir it are mixed, and form molecular sieve pulp.
Above-mentioned two strands of slurries and aluminium colloidal sol 210 grams are mixed, promptly obtain catalyst B 1 by the present invention's preparation.
Consisting of of catalyst B 1: kaolin 45.5 heavy %, aluminium colloidal sol 14.0 heavy %, ZRP-1 molecular sieve 15.0 heavy %, REY molecular sieve 15.0 heavy %, DASY
0.0Molecular sieve 5.0 heavy % add RE
2O
31.5 heavy %, P
2O
54.0 heavy %.The fixed fluidized bed evaluation result of catalyst B 1 is listed in the table 2.
Comparative Examples 2
According to disclosed preparation method among the CN1072201A embodiment 6, the preparation comparative catalyst.
Get 765 gram kaolin and add in the 210 gram aluminium colloidal sols and stir, promptly get carrier pulp.
With 225 gram ZSM-5 (Na
2The heavy % of O content 0.2, silica alumina ratio 60, the Shandong catalyst plant is produced), 225 gram REY and 75 gram DASY
0.0The type zeolite adds in the 1100 gram deionized waters, mixes with above-mentioned carrier pulp behind the making beating homogeneous, drying, washs, is drying to obtain comparative catalyst B2.
Comparative catalyst B2 consists of: kaolin 51.0 heavy %, aluminium colloidal sol 14.0 heavy %, ZSM-5 molecular sieve 15.0 heavy %, REY molecular sieve 15.0 heavy %, DASY
0.0Molecular sieve 5.0 heavy %.The fixed fluidized bed evaluation result of comparative catalyst B2 is listed in the table 2.
Comparative Examples 3
According to disclosed preparation method among the CN1085825A embodiment 6, the preparation comparative catalyst.
Get 765 gram kaolin and add in the 210 gram aluminium colloidal sols and stir, promptly get carrier pulp.
With 225 gram ZRP-1,225 gram REY and 75 gram DASY
0.0The type zeolite adds in the 1100 gram deionized waters, mixes with above-mentioned carrier pulp behind the making beating homogeneous, drying, washs, is drying to obtain comparative catalyst B3.
Comparative catalyst B3 consists of: kaolin 51.0 heavy %, aluminium colloidal sol 14.0 heavy %, ZRP-1 molecular sieve 15.0 heavy %, REY molecular sieve 15.0 heavy %, DASY
0.0Molecular sieve 5.0 heavy %.The fixed fluidized bed evaluation result of comparative catalyst B3 is listed in the table 2.
Table 2
| Catalyst | B1 | B2 | B3 |
| MA(800℃/8h) | 72 | 66 | 67 |
| Conversion ratio, heavy % | 77.7 | 72.5 | 72.7 |
| The product productive rate, heavy % | |||
| Liquefied gas | 34.9 | 30.7 | 31.4 |
| Gasoline | 32.8 | 31.6 | 31.1 |
| Diesel oil | 12.2 | 11.9 | 11.6 |
| Coke | 7.1 | 7.9 | 7.8 |
| Productivity of propylene in the liquefied gas, heavy % | 12.5 | 10.6 | 11.0 |
| Olefin(e) centent in the gasoline, heavy % | 25.1 | 30.6 | 30.9 |
From table 2 data as can be seen: catalyst B 1 has comparison than catalyst B 2, activity level that B3 is higher, and the olefin(e) centent in the gasoline fraction and coke yield are lower, and the productive rate of liquefied gas and propylene is higher.
Embodiment 4
1.8 kilograms of kaolin are added in the solution of 1.2 kilograms of deionized waters and 31.5 gram ammonium phosphate (chemical pure, the Beijing Chemical Plant produces) formation, stir and obtained kaolin slurry in 1.5 hours.
Get 1.0 kilograms of boehmites, 0.5 kilogram of aluminium colloidal sol, the mixed in hydrochloric acid of 3.4 kilograms and 85 milliliter 36 heavy % of deionized water stirred 1.0 hours, obtained the binding agent slurries.
Get 0.15 kilogram of REHY molecular sieve (RE
2O
3Content 3.6 heavy %, Na
2O content is 4.6 heavy %, silica alumina ratio 5.6, the Shandong catalyst plant is produced), 0.6 kilogram of ZRP-1 molecular sieve, 0.9 kilogram of DASY
2.0Molecular sieve (a kind of REUSY zeolite, RE
2O
3Content 1.5 heavy %, Na
2O content is 1.2 heavy %, silica alumina ratio 6.8, the Shandong catalyst plant is produced, down together), mix with 2.0 kilograms of deionized waters that add 73.5 gram ammonium phosphate, add 457 milliliters of re chlorides again, make molecular sieve pulp.
Above-mentioned three strands of slurries are mixed, promptly obtain catalyst C1 by the present invention's preparation.
Catalyst C1 consists of: kaolin 35.0 heavy %, boehmite 20.0 heavy %, aluminium colloidal sol 10.0 heavy %, REHY molecular sieve 3.0 heavy %, ZRP-1 molecular sieve 12.0 heavy %, DASY
2.0Molecular sieve 17.0 heavy % add RE
2O
32.0 heavy %, P
2O
51.0 heavy %.The fixed fluidized bed evaluation result of catalyst C1 is listed in the table 3.
Comparative Examples 4
According to disclosed preparation method among the CN1055301C embodiment 6, the preparation comparative catalyst.
0.5 kg aluminium colloidal sol, 1.9 kilograms of kaolin and deionized water and stirring is even, add 1.0 kilograms of boehmites again, mix, 62 ℃ aging 2 hours, promptly get carrier pulp.Get 0.3 kilogram of ZRP-1,0.4 kilogram of ZSM-5,0.2 kilogram of REHY and 0.9 kilogram of DASY respectively
2.0Zeolite adds in the deionized water, mixes with above-mentioned carrier pulp behind the making beating homogeneous, drying, washs, is drying to obtain comparative catalyst C2.
Comparative catalyst C2 consists of: kaolin 37.0 heavy %, boehmite 20.0 heavy %, aluminium colloidal sol 10.0 heavy %, ZRP-1 molecular sieve 6.0 heavy %, ZSM-5 molecular sieve 7.0 heavy %, REHY molecular sieve 3.0 heavy %, DASY
2.0Molecular sieve 17.0 heavy %.The fixed fluidized bed evaluation result of comparative catalyst C2 is listed in the table 3.
From table 3 data as can be seen, catalyst C1 has the comparison activity level higher than catalyst C2, and the olefin(e) centent in the gasoline fraction and coke yield are lower, and the productive rate of liquefied gas and propylene is higher.
Table 3
| Catalyst | C1 | C2 |
| MA(800℃/8h) | 71 | 67 |
| Conversion ratio, heavy % | 75.2 | 71.5 |
| The product productive rate, heavy % | ||
| Liquefied gas | 32.5 | 29.2 |
| Gasoline | 33.2 | 30.8 |
| Diesel oil | 11.7 | 11.3 |
| Coke | 6.8 | 7.6 |
| Productivity of propylene in the liquefied gas, heavy % | 11.8 | 10.1 |
| Olefin(e) centent in the gasoline, heavy % | 26.3 | 31.2 |
Embodiment 5
1.6 kilograms of kaolin are added in the solution of 1.2 kilograms of deionized waters and 36 gram calgons formation, stir and obtained kaolin slurry in 1.5 hours.
Get 1.4 kilograms of boehmites, 0.3 kilogram of aluminium colloidal sol, the mixed in hydrochloric acid of 5.5 kilograms and 239 milliliter 36 heavy % of deionized water stirred 1.0 hours, obtained the binding agent slurries.
Get 0.5 kilogram of DASY
0.0Molecular sieve, 1.0 kilograms of ZSM-5 molecular sieves mix with 2.0 kilograms of deionized waters that add 144 gram calgons, add 799 milliliters of re chlorides and 15 milliliters of ammoniacal liquor again, make molecular sieve pulp.
Above-mentioned three strands of slurries are mixed, promptly obtain catalyst D1 by the present invention's preparation.
Catalyst D1 consists of: kaolin 31.0 heavy %, boehmite 28.0 heavy %, aluminium colloidal sol 5.0 heavy %, DASY
0.0Molecular sieve 10.0 heavy %, ZSM-5 molecular sieve 20.0 heavy % add RE
2O
33.5 heavy %, P
2O
52.5 heavy %.The fixed fluidized bed evaluation result of catalyst D1 is listed in the table 4.
Comparative Examples 5
According to disclosed preparation method in the CN1042201C example 1, the preparation comparative catalyst.
1.8 kilograms of kaolin are added in 0.3 kg aluminium colloidal sol and the 5 kilograms of deionized waters, stir, add 360 milliliters of hydrochloric acid, add 1.5 kilograms of boehmites again and mix, 60 ℃ aging 1 hour, promptly get carrier pulp.Get 0.5 kilogram of DASY respectively
0.0, (1 kilogram of ZSM-5 molecular sieve adds in 10 kilograms of deionized waters the P-ZSM-5 molecular sieve, add 110 milliliters, phosphoric acid and 88 milliliters of ammoniacal liquor of 85% in the water), add in 2 kilograms of deionized waters, ball milling mixed with above-mentioned carrier pulp after 30 minutes, and drying promptly gets comparative catalyst D2.
Comparative catalyst D2 consists of: kaolin 35.0%, boehmite 30.0 heavy %, aluminium colloidal sol 5.0 heavy %, DASY
0.0Molecular sieve 10.0 heavy %, P-ZSM-5 molecular sieve 20.0 heavy %.The fixed fluidized bed evaluation result of comparative catalyst D2 is listed in the table 4.
Embodiment 6
1.6 kilograms of kaolin are added in the solution of 1.2 kilograms of deionized waters and 336 gram ammonium phosphate formation, stirred 1.5 hours, obtain kaolin slurry.
Get 1.2 kilograms of boehmites, Ludox is 0.5 kilogram (produce, SiO by Changhong chemical plant, Beijing
225 heavy %), the mixed in hydrochloric acid of 5.5 kilograms and 239 milliliter 36 heavy % of deionized water stirred 1.0 hours, obtained the binding agent slurries.
Get 0.2 kilogram of DASY
0.0Molecular sieve, 0.8 kilogram ZSM-5 molecular sieve, 0.2 kilogram of (Na2O content 3.2 heavy % of beta-molecular sieve, silica alumina ratio 28, the Shandong catalyst plant is produced), mix with 2.0 kilograms of deionized waters that add 124 gram phosphoric acid, add 1027 milliliters of re chlorides and 15 milliliters of ammoniacal liquor again, make molecular sieve pulp.
Above-mentioned three strands of slurries are mixed, promptly obtain catalyst E by the present invention's preparation.
Catalyst E consists of: kaolin 32.5 heavy %, boehmite 24.0 heavy %, Ludox 10.0 heavy %, DASY
0.0Molecular sieve 4.0 heavy %, ZSM-5 molecular sieve 16.0 heavy %, beta-molecular sieve 4.0 heavy % add RE
2O
34.5 heavy %, P
2O
55.0 heavy %.The fixed fluidized bed evaluation result of catalyst E is listed in the table 4.
Table 4
| Catalyst | D1 | D2 | E |
| MA(800℃/8h) | 64 | 61 | 63 |
| Conversion ratio, heavy % | 68.5 | 65.0 | 67.4 |
| The product productive rate, heavy % | |||
| Liquefied gas | 35.8 | 32.5 | 33.2 |
| Gasoline | 24.0 | 22.3 | 24.7 |
| Diesel oil | 8.1 | 8.3 | 8.4 |
| Coke | 6.7 | 7.4 | 6.5 |
| Productivity of propylene in the liquefied gas, heavy % | 13.3 | 11.9 | 12.8 |
| Olefin(e) centent in the gasoline, heavy % | 27.2 | 31.0 | 26.9 |
From table 4 data as can be seen, catalyst D1 has the comparison activity level higher than catalyst D2, and the olefin(e) centent in the gasoline fraction and coke yield are lower, and the productive rate of liquefied gas and propylene is higher; Catalyst E also has higher activity level, and the olefin(e) centent in the gasoline fraction and coke yield are lower, and the productive rate of liquefied gas and propylene is higher.
Embodiment 7
1.7 kilograms of kaolin are added in the solution of 2.1 kilograms of deionized waters and 50 gram ammonium phosphate formation, stir and obtained kaolin slurry in 1.5 hours.
Get 0.1 kilogram of boehmite, 0.8 kilogram of aluminium colloidal sol, the mixed in hydrochloric acid of 0.7 kilogram and 2 milliliter 36 heavy % of deionized water stirred 1.0 hours, obtained the binding agent slurries.
Get 0.8 kilogram of REHY molecular sieve, 0.4 kilogram of ZRP-5 molecular sieve (a kind of zeolite, Na with MFI structure
2O content 0.1 heavy %, silica alumina ratio 50, the Shandong catalyst plant is produced, down together), mix with 2.0 kilograms of deionized waters that add 34 gram ammonium phosphate, add 457 milliliters of re chlorides again, make molecular sieve pulp.
Above-mentioned three strands of slurries are mixed, promptly obtain catalyst F by the present invention's preparation.
Catalyst F consists of: kaolin 43.5 heavy %, and boehmite 3.0 heavy %, aluminium colloidal sol 20.0 heavy %, REHY molecular sieve 20.0 heavy %, ZRP-5 molecular sieve 10.0 heavy % add RE
2O
32.5 heavy %, P
2O
51.0 heavy %.The physical property of catalyst F and fixed fluidized bed evaluation result are listed in respectively in the table 5,6.
Embodiment 8
1.3 kilograms of kaolin are added in the solution of 1.2 kilograms of deionized waters and 33 gram phosphoric acid formation, stir and obtained kaolin slurry in 1.5 hours.
Get 0.5 kilogram of boehmite, 0.6 kilogram of aluminium colloidal sol, the mixed in hydrochloric acid of 1.8 kilograms and 6 milliliter 36 heavy % of deionized water stirred 1.0 hours, obtained the binding agent slurries.
Get 1.0 kilograms of REHY molecular sieves, 0.4 kilogram of ZSP-2 molecular sieve (a kind of MFI type zeolite of phosphorous and iron, Fe
2O
32.5 heavy %, P
2O
54.0 heavy %, Na
2O content is 0.1 heavy %, silica alumina ratio 50, the Shandong catalyst plant is produced), mix with 2.0 kilograms of deionized waters that add 23 gram calgons, add 457 milliliters of re chlorides and 8 milliliters of ammoniacal liquor again, make molecular sieve pulp.
Above-mentioned three strands of slurries are mixed, promptly obtain catalyst G by the present invention's preparation.
Catalyst G consists of: kaolin 33.5 heavy %, and boehmite 13.0 heavy %, aluminium colloidal sol 15.0 heavy %, REHY molecular sieve 25.0 heavy %, ZRP-5 molecular sieve 10.0 heavy % add RE
2O
32.5 heavy %, P
2O
51.0 heavy %.The physical property of catalyst G and fixed fluidized bed evaluation result are listed in respectively in the table 5,6.
Embodiment 9
0.7 kilogram of kaolin is added in the solution of 1.3 kilograms of deionized waters and 17 gram phosphoric acid and 17 gram calgons formation, stir and obtained kaolin slurry in 2.0 hours.
Get 0.9 kilogram of boehmite, 0.4 kilogram of aluminium colloidal sol, the mixed in hydrochloric acid of 3.4 kilograms and 9 milliliter 36 heavy % of deionized water stirred 1.0 hours, obtained the binding agent slurries.
Get 1.4 kilograms of REHY molecular sieves, 0.4 kilogram of ZRP-5 molecular sieve mixes with 2.0 kilograms of deionized waters that add 30 gram diammonium hydrogen phosphates, adds 457 milliliters of re chlorides and 8 milliliters of ammoniacal liquor again, makes molecular sieve pulp.
Above-mentioned three strands of slurries are mixed, promptly obtain catalyst H by the present invention's preparation.
Catalyst H consists of: kaolin 18.5 heavy %, and boehmite 23.0 heavy %, aluminium colloidal sol 10.0 heavy %, REHY molecular sieve 35.0 heavy %, ZRP-5 molecular sieve 10.0 heavy % add RE
2O
32.5 heavy %, P
2O
51.0 heavy %.The physical property of catalyst H and fixed fluidized bed evaluation result are listed in respectively in the table 5,6.
Table 5
| Embodiment | Catalyst | Bulk density, grams per milliliter | Pore volume, milliliter/gram | Abrasion index, %/hour |
| 7 | F | 0.80 | 0.28 | 1.8 |
| 8 | G | 0.72 | 0.37 | 2.1 |
| 9 | H | 0.61 | 0.43 | 3.2 |
Table 6
| Catalyst | F | G | H |
| MA(800℃/8h) | 75 | 73 | 72 |
| Conversion ratio, heavy % | 80.5 | 80.4 | 79.2 |
| The product productive rate, heavy % | |||
| Liquefied gas | 29.7 | 30.3 | 30.3 |
| Gasoline | 39.7 | 38.6 | 38.3 |
| Diesel oil | 10.5 | 10.5 | 10.9 |
| Coke | 7.9 | 8.3 | 8.7 |
| Productivity of propylene in the liquefied gas, heavy % | 10.6 | 11.1 | 11.4 |
| Olefin(e) centent in the gasoline, heavy % | 21.1 | 23.0 | 24.0 |
Can find out from table 6 data, in F, G, three catalyst of H, catalyst F has slightly high activity level, olefin content in gasoline is lower, coke yield is lower, and the productive rate of liquefied gas and propylene is also lower, and the H agent has olefin(e) centent, coke yield in the higher gasoline fraction, and the productive rate of liquefied gas and propylene is also higher, and the G agent is placed in the middle.
Claims (15)
1. one kind is reduced the also production of cracking catalyst of voluminous liquefied gas of content of olefin in gasoline, it is characterized in that this method comprises:
(1), the preparation of clay slurry
Clay, deionized water and phosphorus-containing compound are mixed, make clay slurry, the phosphorus-containing compound addition is counted the heavy %P of 0.1-5.0 with the butt weight of catalyst
2O
5
(2), the preparation of molecular sieve pulp
Molecular sieve, deionized water, phosphorus-containing compound, rare earth compound are mixed, make molecular sieve pulp, the addition of phosphorus-containing compound is counted the heavy %P of 0.1-3.0 with the butt weight of catalyst
2O
5, the addition of rare earth compound is counted the heavy %RE of 0.1-5.0 with the butt weight of catalyst
2O
3
(3), the preparation of binding agent slurries
Binding agent, deionized water and optional inorganic acid are mixed, make the binding agent slurries;
(4), the mixing of slurries
Above-mentioned clay slurry, molecular sieve pulp and binding agent slurries are mixed the back drying.
2. method according to claim 1 is characterized in that described clay is selected from one or more the mixture in kaolin, imvite, diatomite, bentonite, the sepiolite.
3. method according to claim 1 is characterized in that one or more the mixture of described molecular screening in faujasite, the zeolite with MFI structure, modenite, β zeolite.
4. method according to claim 3 is characterized in that described faujasite is selected from y-type zeolite or/and X type zeolite.
5. method according to claim 4 is characterized in that described y-type zeolite is selected from one or more the mixture in phosphorous y-type zeolite, REY type zeolite, HY type zeolite, REHY type zeolite, USY type zeolite, the REUSY type zeolite.
6. method according to claim 3 is characterized in that the zeolite of the described MFI of having structure is selected from ZSM-5, the mixture of one or more in the zeolite with MFI structure of one or more among phosphorous, iron, zinc, the rare earth.
7. method according to claim 3 is characterized in that having the zeolite of MFI structure and the weight ratio of y-type zeolite is 0.1-2.7.
8. method according to claim 1 is characterized in that described phosphorus-containing compound is selected from one or more mixtures in phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphoric acid, pyrophosphate, polymer phosphate, polymeric phosphate, metaphosphoric acid, the metaphosphate.
9. method according to claim 8 is characterized in that described phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphorous acid, ammonium phosphite, sodium pyrophosphate, sodium phosphate trimer, the calgon.
10. method according to claim 1 is characterized in that described rare earth compound is that rare earth chloride is or/and nitric acid rare earth.
11. method according to claim 1 is characterized in that described binding agent is selected from one or more the mixture in aluminium colloidal sol, Ludox, boehmite, silicon-aluminum sol, the silica-alumina gel.
12. method according to claim 11 is characterized in that when binding agent contains boehmite, must add inorganic acid and carry out acidifying, described inorganic acid is hydrochloric acid, nitric acid or phosphoric acid.
13. method according to claim 2 is characterized in that described kaolin is halloysite.
14. method according to claim 5, it is characterized in that described REY type zeolite is phosphorous REY type zeolite, described HY type zeolite is phosphorous HY type zeolite, described REHY type zeolite is phosphorous REHY type zeolite, described USY type zeolite is phosphorous USY type zeolite, and described REUSY type zeolite is phosphorous REUSY type zeolite.
15. method according to claim 11 is characterized in that described silicon-aluminum sol is the silicon-aluminum sol of modification, described silica-alumina gel is the silica-alumina gel of modification.
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| US9309467B2 (en) | 2007-12-20 | 2016-04-12 | China Petroleum And Chemical Corp. | Integrated process for hydrogenation and catalytic cracking of hydrocarbon oil |
| CN102008976B (en) * | 2010-11-09 | 2013-07-31 | 中国海洋石油总公司 | Method for preparing olefin-removing catalyst |
| CN102059139B (en) * | 2010-12-28 | 2013-02-20 | 洛阳市科创石化科技开发有限公司 | Catalyst used for preparing propylene and ethylene by cracking and preparation method thereof |
| CN106179470A (en) * | 2016-08-08 | 2016-12-07 | 青岛惠城环保科技股份有限公司 | A kind of catalytic cracking improves the preparation method of octane number auxiliary agent |
| CN106925336A (en) * | 2017-05-08 | 2017-07-07 | 青岛惠城环保科技股份有限公司 | A kind of Resid Fcc Catalyst and preparation method thereof |
| CN108097303B (en) * | 2017-11-22 | 2021-06-11 | 青岛惠城环保科技股份有限公司 | Preparation method of catalyst for preparing low-carbon olefin by catalytic cracking of diesel oil |
| CN112473725B (en) * | 2020-11-12 | 2022-09-20 | 万华化学集团股份有限公司 | Preparation method of modified molecular sieve catalyst and method for continuously synthesizing 3-methoxy-3-methyl butanol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5456821A (en) * | 1991-03-12 | 1995-10-10 | Mobil Oil Corp. | Catalytic conversion with improved catalyst |
| CN1436836A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Cracking catalyst preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5456821A (en) * | 1991-03-12 | 1995-10-10 | Mobil Oil Corp. | Catalytic conversion with improved catalyst |
| CN1436836A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Cracking catalyst preparing process |
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