CN104014359A - Preparation method of petroleum hydrocarbon cracking catalyst - Google Patents
Preparation method of petroleum hydrocarbon cracking catalyst Download PDFInfo
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- CN104014359A CN104014359A CN201410245587.2A CN201410245587A CN104014359A CN 104014359 A CN104014359 A CN 104014359A CN 201410245587 A CN201410245587 A CN 201410245587A CN 104014359 A CN104014359 A CN 104014359A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000005336 cracking Methods 0.000 title claims abstract description 30
- 239000003209 petroleum derivative Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 55
- 239000002002 slurry Substances 0.000 claims abstract description 52
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 27
- 239000011147 inorganic material Substances 0.000 claims abstract description 27
- 239000010457 zeolite Substances 0.000 claims abstract description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 20
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 20
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 229910001593 boehmite Inorganic materials 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000010009 beating Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract 1
- 238000005360 mashing Methods 0.000 abstract 1
- 238000009718 spray deposition Methods 0.000 abstract 1
- 238000001694 spray drying Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960003589 arginine hydrochloride Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 mixes Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method of a petroleum hydrocarbon cracking catalyst. The preparation method comprises the following steps: mashing pseudo-boehmite with water while keeping the solid content percentage in the slurry within 10-25%; adding a hydrochloric acid solution according to the aluminum-acid ratio being 0.10-0.35, and sufficiently and uniformly stirring; slowly adding a water glass solution into the slurry while stirring rapidly for 10-120 minutes; adding an alumina sol solution and uniformly stirring; adding porous inorganic material slurry and kaolin slurry which are uniformly dispersed in advance to the obtained slurry, and stirring for at least 10 minutes to form a catalyst slurry; and performing spray forming and drying on the catalyst slurry, washing and baking under water steam atmosphere. According to the preparation method, the porous inorganic material is induced, the production cost is low, the catalyst has a rich pore duct structure so that the performance of the catalyst is further enriched and improved; the requirement of petroleum hydrocarbon cracking reaction is met; compared with an existing zeolite type petroleum hydrocarbon cracking catalyst, the catalyst has higher activity and stability.
Description
Technical field
The invention belongs to catalyst technical field, relate in particular to a kind of preparation method of cracking catalyst for petroleum hydrocarbon.
Background technology
Cracking catalyst for petroleum hydrocarbon is a kind of silicate porous inorganic material, for high efficiency cracking petroleum hydrocarbon, developed multiple inorganic material, as: the inorganic material of zeolite type, comprises A type zeolite, X-type zeolite, ZSM-5 series zeolite, modenite, beta zeolite etc.; And for example, amorphous porous inorganic material, comprises various silica, aluminium oxide and sieve and silica-sesquioxide, and it is actual that Cracking catalyst prepared by these materials has been widely used in industry.
Although there has been so many Cracking catalyst, in the face of growing society need, still cannot meet the actual needs of industry, be badly in need of the cracking catalyst for petroleum hydrocarbon of exploitation excellent performance.
Summary of the invention
The object of the embodiment of the present invention is to provide a kind of preparation method of cracking catalyst for petroleum hydrocarbon, be intended to solve existing Cracking catalyst, in the face of growing society need, still cannot meet the actual needs of industry, be badly in need of the problem of the cracking catalyst for petroleum hydrocarbon of exploitation excellent performance.
The embodiment of the present invention is to realize like this, a kind of preparation method of cracking catalyst for petroleum hydrocarbon, the preparation method of this cracking catalyst for petroleum hydrocarbon, catalyst comprises according to percentage by weight: 10%～70% porous inorganic material, 0%～60% kaolin, 0%～30% boehmite, 0%～15% siliceous solution, 0%～30% aluminium colloidal sol; Comprise the following steps:
Step 1, by the making beating of boehmite water, control slurry solid content between 10%～25%, according to aluminic acid, than the ratio that is 0.10～0.35, add hydrochloric acid solution, aluminic acid, than the alumina weight having in the checking computations weight/boehmite of 36% concentration, stirs;
Step 2, under rapid stirring, slowly adds water glass solution to step 1 in the slurries that obtain, stir 10～120 minutes, then add aluminium sol solution, stirs;
Step 3, adds finely dispersed porous inorganic material slurries and kaolin slurry in advance to step 2 in the slurries that obtain, stir 10 minutes above time, has formed catalyst slurry;
Step 4, is shaped catalyst slurry spraying to dry and burn under dry, washing, water vapour atmosphere.
Further, siliceous solution is waterglass, and modulus is 2.9～3.2.
Further, the preparation process of porous inorganic material comprises:
The first step is dried kaolin and is burnt 0.5～5 hour at 500～1100 ℃;
Second step adds the clay after the first step is processed in water glass solution, evenly mixes;
The 3rd step, the slurries that second step is obtained at room temperature standing 12～48 hours, then crystallization 10～48 hours at sealing and 70～150 ℃, afterwards, adds metallic iron oxide, fully stirring;
The 4th step, the slurries that the 3rd step is obtained are crystallization 10～48 hours at sealing and 90～250 ℃, filters, and obtains filter cake, oven dry;
The 5th step, ammonium chlorate or aqueous ammonium chloride solution washing exchange for the filter cake that the 4th step is obtained, remove free metal ion wherein, as sodium, potassium, iron.
Further, porous inorganic material contains crystalline aluminosilicate structure.
Further, crystalline aluminosilicate structure is y-type zeolite, MFI structural zeolite or y-type zeolite, the mixture of MFI structural zeolite.
Further, MFI structural zeolite is zsm-5.
The preparation method of cracking catalyst for petroleum hydrocarbon provided by the invention, has introduced porous inorganic material, and low cost of manufacture has abundant pore passage structure, and the introducing of metallic iron has made up the deficiency of catalytic performance, further enriches and improved the performance of catalyst; Oil-containing crystalline aluminosilicate of the present invention is zeolite structured, for catalyst provides catalytic reaction required surface acidity, due to transition metal ions has been introduced in catalyst, the surface acid property of material is adjustable more flexibly, can better meet the demand of catalytic cracking of petroleum hydrocarbon reaction; The present invention not only contains crystalline aluminosilicate structure, also contain a large amount of mesopores and macroporous structure, make catalysis material Kong road Alto more not broad, can meet the diffusion needs of catalytic reaction Raw molecule, improved the accessibility in zeolite structured middle activated centre, further improve reaction efficiency and benefit, reduced the negative effect bringing because of diffusion demonstration.
The present invention, due to the zeolite component that contains kaolin crystallization apparatus, compares with existing zeolites cracking catalyst for petroleum hydrocarbon, has had higher activity and better activity stability.
Accompanying drawing explanation
Fig. 1 is preparation method's flow chart of the cracking catalyst for petroleum hydrocarbon that provides of the embodiment of the present invention.
The specific embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Below in conjunction with drawings and the specific embodiments, application principle of the present invention is further described.
As shown in Figure 1, the preparation method of the cracking catalyst for petroleum hydrocarbon of the embodiment of the present invention comprises the following steps:
The present invention, by after boehmite acidifying, adds siliceous solution, then adds aluminium colloidal sol, finally adds one or more porous inorganic materials, mixes, and sprays and is dried, washes, dries and burn.
S101: boehmite water is pulled an oar, control slurry solid content between 10%～25%, the ratio that is 0.10～0.35 than (alumina weight in the checking computations weight/boehmite of 36% concentration) according to aluminic acid adds hydrochloric acid solution, stirs;
S102: under rapid stirring, slowly add water glass solution in the slurries that obtain, stir 10～120 minutes, then add aluminium sol solution, stir;
S103: add finely dispersed porous inorganic material slurries and kaolin slurry in advance in the slurries that obtain, stir 10 minutes above time, formed catalyst slurry;
S104: catalyst slurry spraying is shaped and dries and burn under dry, washing, water vapour atmosphere.
The preparation method of cracking catalyst for petroleum hydrocarbon of the present invention, catalyst comprises according to percentage by weight: 10%～70% porous inorganic material, 0%～60% kaolin, 0%～30% boehmite, 0%～15% siliceous solution, 0%～30% aluminium colloidal sol; Comprise following method:
The present invention specifically comprises the following steps:
(1) boehmite water is pulled an oar, control slurry solid content between 10%～25%, the ratio that is 0.10～0.35 than (alumina weight in the checking computations weight/boehmite of 36% concentration) according to aluminic acid adds hydrochloric acid solution, stirs;
(2) under rapid stirring, in the slurries that obtain to (1), slowly add water glass solution, stir 10～120 minutes, then add aluminium sol solution, stir;
(3) in the slurries that obtain to (2), add finely dispersed porous inorganic material slurries and kaolin slurry in advance, stir 10 minutes above time, formed catalyst slurry;
(4) catalyst slurry spraying is shaped and dries and burn under dry, washing, water vapour atmosphere.
(1) of the present invention-(4) can be adjusted boring order of addition flexibly;
The siliceous solution that the present invention introduces is waterglass, and its modulus is 2.9～3.2, and the object of introducing silicon is acidity and the pore distribution that regulates catalyst substrates, makes catalyst have better petroleum hydrocarbon cracking selective;
Method provided by the present invention, the porous inorganic material of introducing is to prepare by following step:
(1) kaolin is dried at 500～1100 ℃ and burn 0.5～5 hour;
(2) in water glass solution, add the clay after above-mentioned (1) processing, evenly mix;
(3) slurries that (2) obtained at room temperature standing 12～48 hours, then crystallization 10～48 hours at sealing and 70～150 ℃, afterwards, adds metallic iron oxide, fully stirring wherein;
(4) slurries that (3) obtained are crystallization 10～48 hours at sealing and 90～250 ℃, filters, and obtains filter cake, oven dry;
(5) ammonium chlorate or aqueous ammonium chloride solution washing exchange for the filter cake (4) being obtained, remove free metal ion wherein, as sodium, potassium, iron etc.;
Method provided by the present invention, the porous inorganic material of introducing contains crystalline aluminosilicate structure, and in particular, this crystalline aluminosilicate structure is y-type zeolite, MFI structural zeolite or their mixture, wherein said MFI structural zeolite is zsm-5;
The chemical composition and structure parameter of the porous inorganic material of preparing by the inventive method, as table 1, is introduced two or more porous inorganic material;
The present invention carries out hydro-thermal by the dried catalyst of spraying shaping and dries burning, its objective is the zeolite structured suitable dealuminzation super stabilizing of the crystalline aluminosilicate making in catalyst, further the structure of rugged catalyst; Be applicable to have the cracking catalyst for petroleum hydrocarbon of following composition: 10%～70% porous inorganic material, 0%～60% kaolin, 0%～30% boehmite, 0%～15% containing Ludox, 0%～30% aluminium colloidal sol, its element compositing range is as follows: the patent content of aluminium oxide is 20%～70%, and silica weight content is 30%～70%; Adopting its specific area of the present invention is 150～350 meters squared per gram, and pore volume is 0.20～0.48 milligram/gram, and wear strength is qualified, and average grain diameter is 55～90 microns.
In conjunction with embodiments of the invention, effect of the present invention is described further:
Embodiment 1:
Take 20kg porous inorganic material MY (butt), its the Nomenclature Composition and Structure of Complexes parameter is as shown in table 1, add in 40kg acid water, pull an oar 30 minutes, under stirring condition, slowly adding wherein 4kg solid content is 8% water glass solution (butt), stir 20 minutes, the aluminium colloidal sol (butt) that adds wherein 23kg, stir 30 minutes, then adding wherein 53kg solid content is 25% kaolin slurry (butt), stir 45 minutes, go spraying to be shaped, with earth solution exchange, process, washing and dry, at 650 ℃ and under water vapour atmosphere, dry and burn 2 hours, obtain catalyst sample A, its physical property is as table 2,
Embodiment 2:
Take 15kg boehmite (butt), add water 135kg, stir 20 minutes, by sour aluminum ratio 0.18, add 36% hydrochloric acid solution, under agitation acidifying 40 minutes, under strong agitation condition, add wherein 30kg porous inorganic material MYZ and 15kgMZ porous material, continue to stir 90 minutes, adding wherein 20kg solid content is 15% aluminium sol solution (butt), stir 20 minutes, adding 12kg solid content is 10% water glass solution (butt) again, stir 110 minutes, adding subsequently 8kg solid content is 30% kaolin slurry (butt), stir 60 minutes, go spraying to be shaped, with earth solution exchange, process, washing and dry, at 600 ℃, dry and burn 3 hours, obtain catalyst sample B, its physical property is as shown in table 2,
Embodiment 3:
Take 5kg boehmite 9 (butt), add 100kg decationized Y sieve water, stir 60 minutes, by sour aluminum ratio 0.30, add 36% hydrochloric acid solution, stir 20 minutes, static acidifying 60 minutes, under rapid stirring, to it, adding 8kg solid content is 25 water glass solution, stir 49 minutes, adding wherein 60kg solid content is 30% MYZ porous material again, stir 30 minutes, the last 7kg solid content that adds is wherein 10% aluminium sol solution (butt), stir 40 minutes, go spraying to be shaped, repeatedly wash and be dried, under 550 ℃ and hydro-thermal atmosphere, dry and burn 5 hours, obtain catalyst sample C, its physical property is as table 2,
Embodiment 4:
Take 14kg kaolin (butt), add water 30kg, fully stir, the boehmite slurries (butt) that the solid content that adds 18kg to be 0.25 preparation by sour aluminum ratio is in advance 15%, stir 45 minutes, adding wherein 18kg solid content is 10% aluminium sol solution (butt), stir 20 minutes, add wherein the MZ porous material slurries (butt) that solid content that 50kg prepares is in advance 20%, strong agitation 90 minutes, send spraying to be shaped, repeatedly dry and washing, slough unnecessary zwitterion, then sending into high temperature furnace, at 600 ℃, dry and burn 4 hours, obtain catalyst sample D, its physical property is as table 2,
Embodiment 5:
Take 32kg kaolin (butt), with 160kg water, be made into slurries, abundant pulp homogeneous, add wherein 40kgMYZ porous material (butt), stir, add wherein again the boehmite slurries (butt) that 10kg is 15% with the solid content of arginine hydrochloride aluminum ratio 0.25 acidifying in advance, stir 30 minutes, adding 16kg solid content, it is 15% aluminium sol solution (butt), stir 45 minutes, adding subsequently 2kg solid content is 10% water glass solution (butt), stir 90 minutes, send spraying to be shaped, with earth solution exchange, process, washing and dry, in high temperature furnace, at 620 ℃ and under water vapour atmosphere, dry and burn 3 hours, obtain catalyst sample E, its physical property is as table 2,
Embodiment 6:
Take 31kgmz to empty material, add 100kg water to be made into slurries, fully stir homogeneous, adding 25kg with 36% hydrochloric acid, according to sour aluminum ratio 0.15 acidifying water, to adjust the boehmite slurries (butt) that solid content is 15% in advance, stir 30 minutes, adding wherein 40kg solid content is 20% kaolin slurry (butt) again, stir 40 minutes, then, slowly and uniformly adding 4kg solid content is 8% water glass solution (butt), stir 60 minutes, send and be spray dried to shape, repeatedly wash and be dried, in high temperature furnace, at 620 ℃, dry and burn 1 hour, obtain catalyst sample F, its physical property is as table 2,
Embodiment 7:
Take 31kgMY porous material (butt) and 24kg kaolin (butt), add 150kg water, pull an oar 60 minutes, make slurries, adding 20kg acid aluminum ratio is that 0.15 solid content is 15% boehmite slurries (butt) again, stir 30 minutes, finally adding 25kg solid content is 18% aluminium sol solution (butt), fully stir 50 minutes, then spraying is shaped, and with earth solution exchange, processes, washing and dry, in high temperature furnace, at 600 ℃ and under water vapour atmosphere, dry and burn 3 hours, obtain catalyst sample G, its physical property is as table 2;
Respectively according to the preparation method of embodiment 1-7, but according to the composition of porous material, use respectively equivalent kaolin or imvite and y-type zeolite and (or: the mixture of zsm-5 zeolite replaces porous material, has prepared comparative catalyst's sample, the corresponding A that is numbered
/-G
/, its physical property is as table 3:
The chemical composition and structure parameter of table 1 porous inorganic material
The physical and chemical performance of each embodiment catalyst sample of table 2
A): fresh catalyst;
B): the catalyst after 790 ℃, 100% water vapour, 24 hours are aging;
The physical and chemical performance of a table 3 comparative example catalyst sample
A): fresh catalyst;
B): the catalyst after 790 ℃, 100% water vapour, 24 hours are aging;
From the data of table 2 and table 3, can find out, the catalyst that catalyst Billy prepared by the inventive method prepares by prior art has better structural stability, can in hydro-thermal and hot environment, keep Stability Analysis of Structures, catalyst of the present invention has better catalytic cracking activity simultaneously.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. the preparation method of a cracking catalyst for petroleum hydrocarbon, it is characterized in that, the preparation method of this cracking catalyst for petroleum hydrocarbon, catalyst comprises according to percentage by weight: 10%～70% porous inorganic material, 0%～60% kaolin, 0%～30% boehmite, 0%～15% siliceous solution, 0%～30% aluminium colloidal sol; Comprise the following steps:
Step 1, by the making beating of boehmite water, control slurry solid content 10%～25%, according to aluminic acid, than the ratio that is 0.10～0.35, add hydrochloric acid solution, aluminic acid, than the alumina weight having in the checking computations weight/boehmite of 36% concentration, stirs;
Step 2, under rapid stirring, slowly adds water glass solution to step 1 in the slurries that obtain, stir 10～120 minutes, then add aluminium sol solution, stirs;
Step 3, adds finely dispersed porous inorganic material slurries and kaolin slurry in advance to step 2 in the slurries that obtain, stir 10 minutes above time, has formed catalyst slurry;
Step 4, is shaped catalyst slurry spraying to dry and burn under dry, washing, water vapour atmosphere.
2. the preparation method of cracking catalyst for petroleum hydrocarbon as claimed in claim 1, is characterized in that, siliceous solution is waterglass, and modulus is 2.9～3.2.
3. the preparation method of cracking catalyst for petroleum hydrocarbon as claimed in claim 1, is characterized in that, the preparation process of porous inorganic material comprises:
The first step is dried kaolin and is burnt 0.5～5 hour at 500～1100 ℃;
Second step adds the clay after the first step is processed in water glass solution, evenly mixes;
The 3rd step, the slurries that second step is obtained at room temperature standing 12～48 hours, then crystallization 10～48 hours at sealing and 70～150 ℃, afterwards, adds metallic iron oxide, fully stirring;
The 4th step, the slurries that the 3rd step is obtained are crystallization 10～48 hours at sealing and 90～250 ℃, filters, and obtains filter cake, oven dry;
The 5th step, ammonium chlorate or aqueous ammonium chloride solution washing exchange for the filter cake that the 4th step is obtained, remove free metal ion wherein, as sodium, potassium, iron.
4. the preparation method of cracking catalyst for petroleum hydrocarbon as claimed in claim 1, is characterized in that, porous inorganic material contains crystalline aluminosilicate structure.
5. the preparation method of cracking catalyst for petroleum hydrocarbon as claimed in claim 4, is characterized in that, crystalline aluminosilicate structure is y-type zeolite, MFI structural zeolite or y-type zeolite, the mixture of MFI structural zeolite.
6. the preparation method of cracking catalyst for petroleum hydrocarbon as claimed in claim 5, is characterized in that, MFI structural zeolite is zsm-5.
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| CN201410245587.2A CN104014359B (en) | 2014-06-04 | 2014-06-04 | A kind of preparation method of cracking catalyst for petroleum hydrocarbon |
| US14/685,819 US20160008797A1 (en) | 2014-06-04 | 2015-04-14 | Method for the synthesis of porous inorganic material, catalytic cracking of petroleum hydrocarbons and preparation of catalyst thereof |
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| CN201410245587.2A CN104014359B (en) | 2014-06-04 | 2014-06-04 | A kind of preparation method of cracking catalyst for petroleum hydrocarbon |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179469A (en) * | 2016-06-30 | 2016-12-07 | 青岛惠城环保科技股份有限公司 | A kind of preparation method of catalytic cracking propylene catalyst with yield increase |
| CN109806906A (en) * | 2017-11-20 | 2019-05-28 | 中国石油化工股份有限公司 | The preparation method of catalytic cracking catalyst |
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| JPH024452A (en) * | 1988-01-20 | 1990-01-09 | Engelhard Corp | Method for producing a zeolite catalyst |
| CN1570030A (en) * | 2003-07-17 | 2005-01-26 | 中国石油天然气股份有限公司 | Modified double-component molecular sieve and catalytic cracking catalyst |
| CN1676579A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | A zeolite-containing hydrocarbon conversion catalyst and its preparation method |
| CN101239327A (en) * | 2008-03-25 | 2008-08-13 | 北京惠尔三吉绿色化学科技有限公司 | Kaolinite-clay-containing in situ crystallizing ZSM-5 and Y type molecular sieve static bed catalyst and preparation thereof |
| CN101767028A (en) * | 2008-12-31 | 2010-07-07 | 中国石油化工股份有限公司 | Preparation method of fluid catalytic cracking catalyst |
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2014
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| JPH024452A (en) * | 1988-01-20 | 1990-01-09 | Engelhard Corp | Method for producing a zeolite catalyst |
| CN1570030A (en) * | 2003-07-17 | 2005-01-26 | 中国石油天然气股份有限公司 | Modified double-component molecular sieve and catalytic cracking catalyst |
| CN1676579A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | A zeolite-containing hydrocarbon conversion catalyst and its preparation method |
| CN101239327A (en) * | 2008-03-25 | 2008-08-13 | 北京惠尔三吉绿色化学科技有限公司 | Kaolinite-clay-containing in situ crystallizing ZSM-5 and Y type molecular sieve static bed catalyst and preparation thereof |
| CN101767028A (en) * | 2008-12-31 | 2010-07-07 | 中国石油化工股份有限公司 | Preparation method of fluid catalytic cracking catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179469A (en) * | 2016-06-30 | 2016-12-07 | 青岛惠城环保科技股份有限公司 | A kind of preparation method of catalytic cracking propylene catalyst with yield increase |
| CN106179469B (en) * | 2016-06-30 | 2019-02-19 | 青岛惠城环保科技股份有限公司 | A kind of preparation method of catalytic cracking propylene catalyst with yield increase |
| CN109806906A (en) * | 2017-11-20 | 2019-05-28 | 中国石油化工股份有限公司 | The preparation method of catalytic cracking catalyst |
| CN109806906B (en) * | 2017-11-20 | 2022-02-15 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst |
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| CN104014359B (en) | 2016-03-16 |
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