CN106268920A - A kind of catalytic cracking catalyst with big substrate specific surface area - Google Patents
A kind of catalytic cracking catalyst with big substrate specific surface area Download PDFInfo
- Publication number
- CN106268920A CN106268920A CN201610593171.9A CN201610593171A CN106268920A CN 106268920 A CN106268920 A CN 106268920A CN 201610593171 A CN201610593171 A CN 201610593171A CN 106268920 A CN106268920 A CN 106268920A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- specific surface
- surface area
- catalytic cracking
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 239000000758 substrate Substances 0.000 title claims abstract description 24
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000004927 clay Substances 0.000 claims abstract description 30
- 239000002808 molecular sieve Substances 0.000 claims abstract description 28
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 15
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 3
- 229910000632 Alusil Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 abstract description 28
- 239000005995 Aluminium silicate Substances 0.000 abstract description 25
- 235000012211 aluminium silicate Nutrition 0.000 abstract description 25
- 238000005336 cracking Methods 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 3
- 239000002010 green coke Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000295 fuel oil Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 5
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 4
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 4
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 101150116295 CAT2 gene Proteins 0.000 description 3
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 3
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 3
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 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 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of catalytic cracking catalyst with big substrate specific surface area.It is characterized in that catalyst be with have Large ratio surface, macropore volume modified clay material as main matrix, replace boehmite and all or part of Kaolin, it is mixed and made into serosity with molecular sieve, binding agent, spray-dried molding and roasting, repulped, be filtered, washed and dried to obtain catalyst prod.The substrate specific surface area of catalyst is more than 100m2/ g, pore volume are more than 0.40ml/g.The catalyst that the present invention provides has higher residual oil cracking performance, and green coke is low, dry gas is low, has higher light oil productivity and high liquid yield.And in the case of molecular sieve content is greatly lowered, still there is excellent residual oil cracking performance, catalyst low cost.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst in PETROLEUM PROCESSING field, be about having big substrate furtherly
The catalyst for heavy oil catalytic cracking of specific surface.
Background technology
Catalytic cracking is very important oil secondary operations technique, is also the important sources of petrol and diesel oil, enters catalytic cracking
The raw oil of device generally reduced crude, decompression residuum, wax tailings or have passed through hydrotreating, it just slips journey and typically exists
More than 350 DEG C, belong to the supramolecular mixture that density is big, carbon residue is high, content of beary metal is high.
The orifice diameter of Y type molecular sieve is at about 0.7nm, and much smaller than the diameter of residual oil molecule, therefore residual oil molecule cannot
Entering inside the duct of molecular sieve, can only carry out cracking on the surface of molecular sieve or stromal surface, this requires that catalyst has
Bigger substrate surface area.
Common catalyzed Cracking catalyst generally comprises substrate and activity group member two part, and substrate is by clay, active oxidation
Aluminum (boehmite or a diaspore), binding agent are made, and its substrate specific surface area is typically smaller than 80m2/g。
In order to prepare the catalytic cracking catalyst with big substrate specific surface area, W. R. Grace & Co is at CN101636227A
In propose to use there is the host material of bigger serface silicon dioxide, the catalyst substrates specific surface area obtained reaches
182m2/g。
A kind of assistant for calalytic cracking of CN101745373A report, is characterized by two kinds of aluminium oxidies containing stepped pore distribution,
One is macroporous aluminium oxide, and one is little porous aluminum oxide.
CN102078821 A discloses a kind of Cracking catalyst containing mesoporous silica-alumina materials, it is characterised in that this catalyst
By cracking activity constituent element, clay, binding agent and mesoporous silica-alumina materials composition, wherein described mesoporous silica-alumina materials be by
Prepared by CN1565733A, have boehmite crystal phase structure, and surface area is 200 ~ 400m2/ g, pore volume is 0. 5 ~ 2.0ml/
G, this catalyst with use boehmite conventional catalyst compared with, Catalyst Production low cost, have more preferable converting crude oil
Ability.
CN1565733A reports a kind of mesoporous silica-alumina materials, is by soluble aluminum source and alkali reaction, adds solubility
Silicon source, the most aging, ion exchanges, filters, be dried and be prepared from.
CN1978593B reports a kind of catalytic cracking catalyst, it is characterized by that catalyst contains one and has the thin water aluminum of plan
The mesoporous material of stone structure, this mesoporous material is salic, silicon oxide and metal-oxide, such as magnesium oxide or rare earth oxide
Deng.
CN103007981A reports a kind of Resid Fcc Catalyst;This catalytic cracking catalyst, is characterized by urge
Agent contains silicon magnesium glue, a diaspore of 15 ~ 25% of 5 ~ 25%, has big substrate specific surface area, suitable acidity and passivation
Metallic nickel and the function of vanadium, have the heavy oil conversion performance of excellence.
CN1964785A reports a kind of medium-pore catalyst, and it adds the porous material containing unformed silica-alumina
Material, is substantially free of the hole of 1 ~ 4nm.
CN103566962A reports a kind of multi-functional catalyst composition, and its feature is in the mesoporous Si-Al adding 1 ~ 50%
Material (prepared by the method basically identical with CN1565733A), the heat-resistant inorganic oxide matrix of 5% ~ 97%, can reduce hydrocarbon
The gasification temperature that oil gasification converts.
CN1186105 reports and is incorporated in catalytic cracking catalyst, the metakaolin after acid extracts to improve base
Matter specific surface area.
CN102188963A reports the preparation method of a kind of modified kaolin, by hard burned Kaolin, additional
Aluminum source and acid solution add in container under stirring, prepare solid content and starch in the mixing of 12～50% after stirring
Liquid, heats to 90～150 DEG C in confined conditions by this mixed serum and reacts, and isothermal reaction 0.5～3 hours,
Then being not required to filtration can be directly as the raw material preparing catalytic cracking catalyst.
CN104556081A provides a kind of modified kaolin and preparation method thereof, and the method includes: by kaolin starting material
Mix homogeneously with aqueous sulfuric acid, the mixture obtained is carried out the first heat treatment；By the solid washing after the first heat treatment, mistake
Filter, the solid after filtering carries out the second heat treatment.Make kaolinic pore size distribution be significantly improved, improve Kaolin
Surface area and pore volume, by the heavy oil pyrolysis ability of its Cracking catalyst made as carrier and activity and gasoline yield
It is obtained for significantly raising.
CN101745413A, CN101745412A propose a kind of catalytic cracking catalyst and preparation method thereof.Its catalysis
Cracking catalyst comprises modified clay 1～50%, and modified clay is through 800～1100 DEG C, gluing after roasting in 0.3～10 hour
Soil, and containing P 0.1～3.0%, RE2O30.1～4.0%, Na2O 0.1～1.5%, modified clay pore volume 0.1～0.5mL/
G, specific surface 50～400m2/ g, mean diameter 0.5～15 μm.This catalytic cracking catalyst can improve productivity of propylene and liquefaction
Density of propylene in gas, and effectively reduce heavy oil yield.
CN1814705A the most directly uses boehmite as substrate, adds or is not added with clay, with molecular sieve, binding agent
Prepare catalyst together so that it is there is Super matrix specific surface area.
In CN103301889A first by the aqueous solution of porous material and molecular sieve and organic film former polyvinyl alcohol first
At a temperature of mix and be dried, then pulp together with clay, boehmite, binding agent etc., then molding, wash, be dried to obtain
Big pore volume substrate catalyst.
Summary of the invention
It is an object of the invention to provide a kind of catalytic cracking catalyst with big substrate specific surface area, this catalyst is at tool
There is while having Super matrix specific surface area macropore volume and suitable acidity, slag oil cracking ability can be increased substantially, and
And do not increase coke yield and dry gas yied.
The technical scheme is that a kind of catalytic cracking catalyst with big substrate specific surface area, it is characterised in that:
This catalytic cracking catalyst with modified clay material as main matrix, replace boehmite or activated alumina and all or
Part of clay, pulp together with active component, binding agent, spray shaping, wash, be dried to obtain catalyst, the substrate of catalyst
Specific surface area is more than 100m2/ g, pore volume are more than 0.40ml/g；Remember by butt weight 100%, containing the modified Y type molecule of 5 ~ 50%
Sieve, the modified clay material of 30 ~ 95%, type of the selecting molecular sieve of MFI structure of 0 ~ 35% or Beta molecular sieve, 2 ~ 20% inorganic
Adhesive oxides.
Described modified clay material is to be prepared with clay for primary raw material, is mainly composed of silicon oxide and oxidation
Aluminum, has the mol ratio of silicon oxide and aluminium oxide between 0.01 ~ 50:1, low temperature N2Adsorption specific surface area is at 80 ~ 800m2/ g, hole
Volume is at 0.2 ~ 3.0ml/g.More particularly press Chinese patent " a kind of modified clay new material and preparation method thereof "
(CN102091609) prepare.
Described Modified Zeolite Y is at least one of USY, PSRY, REUSY, HY, REY, REHY, REDASY.
Described inorganic oxide binder be Alumina gel, Ludox, Alusil, phosphorus aluminium glue at least one.
The catalytic cracking catalyst that the present invention provides has the following characteristics that
The first, the preparation of catalyst be with have Large ratio surface, macropore volume modified clay material as main matrix, replace
Boehmite and all or part of Kaolin, be mixed and made into serosity, spray-dried molding and roasting with molecular sieve, binding agent
Burn, repulped, be filtered, washed and dried to obtain catalyst prod.Particularly point out, prepare in the raw material of catalyst and do not contain price relatively
Expensive boehmite or activated alumina.
The second, the catalyst that the present invention provides has big substrate specific surface area and macropore volume, has higher residual oil and splits
Change ability, green coke is low, dry gas is low, has higher light oil productivity and high liquid yield.
3rd, the catalyst that the present invention provides is in the case of being greatly lowered molecular sieve content, still has excellent
Residual oil cracking performance, catalyst low cost.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described is embodied as
Mode is merely to illustrate and explains the present invention, is not limiting as the present invention.
In embodiments, Na in the composition of catalyst or material20、A1203、Si02、Rare earth oxide equal size X-ray
Fluorescence spectrometry, specific surface area uses low temperature N2Absorption BET method analysis (sees " Petrochemical Engineering Analysis method (RIPP experiment side
Method) ", Yang Cui surely waits and compiles, Science Press, and nineteen ninety publishes).
Kaolin: China Kaolin Co., Ltd produces, Inner Mongol Chao Pai Kaolin company
Alumina gel: aluminium oxide 21.2%, Yueyang is polymerized to Chemical Co., Ltd. and produces
Boehmite: aluminium oxide 67%, Shandong Aluminium Industrial Corp produces
PSRY-4 molecular sieve: rare earth 4.1%, sodium oxide 0.8%, catalyst Chang Ling factory produces
Deionized water: catalyst Chang Ling factory produces
For heavy oil micro anti-evaluation catalyst need in advance on fixed bed aging equipment in 800 DEG C, aging under 100% steam
Process 17 hours.
The micro-anti-appreciation condition of heavy oil is: oil ratio 5 or 6, catalyst inventory 6g, reaction temperature 500 DEG C, regeneration temperature
600 DEG C, raw material oil properties is shown in Table 1.
Table 1 raw oil main character
| Density (20 ° of C, kg/m-3) | 0.9344 |
| Boiling range/ | |
| Fore-running | 259 |
| 50% | 448 |
| 90% | 620 |
| 500 DEG C distillate | 72 |
| Carbon residue % | 3.3 |
| Total sulfur % | 0.13 |
| Saturated hydrocarbons % | 52.2 |
| Aromatic hydrocarbon % | 30.3 |
| Colloid % | 16.4 |
| Asphalitine % | 1.1 |
| Fe mg/kg | 2.6 |
| Ni mg/kg | 11.4 |
| V mg/kg | 5.2 |
| Na mg/kg | 1.2 |
| Ca mg/kg | 4 |
| Cu mg/kg | / |
| Basic nitrogen, ppm | 1297 |
Embodiment 1 ~ 2 is to prepare modified clay material used
Embodiment 1
Prepare according to the method for patent CN102091608B embodiment 3, by 10Kg Kaolin (Inner Mongol Chao Pai Kaolin company
650 DEG C of roasted products, Al2O3Content 36.5%, igloss 3%) it is placed in 50L stirred autoclave, adding 21.8 liters of concentration is 12%
Mixed in hydrochloric acid uniform, process 2 hours at 90 DEG C, be cooled to 50 DEG C, under agitation add (the oxidation of 8 liters of sodium aluminate solutions
Aluminum 330g/l, 1.5 Crater corrosion), rear addition and 1Kg sodium carbonate solid, after mixing, pH is 10.2, is warmed up to 85 DEG C aging 4
Hour, filtering, filter for 4 times with 40 liters of deionized water wash, filter cake is dried 6 hours at 150 DEG C, and the modified clay obtained is remembered
M1, analyzes its composition and calculates SiO2: Al2O3Mol ratio is 1.64, igloss 27.3%, low temperature N2Absorption records pore volume and is
0.62ml/g, specific surface area are 380m2/g。
Embodiment 2
Prepare according to the method for patent CN102091608B embodiment 1, by 12Kg Kaolin (is produced from China Kaolin Co., Ltd Suzhou,
Al2O3Content 39.8%, igloss 28%) it is placed in 50L stirred autoclave, add 8 liters of pulps of deionized water, add 2.26 liters of concentration
It is the concentrated sulphuric acid mix homogeneously of 98%, heats up and process 3 hours at 140 DEG C, be cooled to 50 DEG C, under agitation add 8.6 liters of inclined aluminum
Acid sodium solution (aluminium oxide 330g/l, 1.5 Crater corrosion), after mix homogeneously survey PH be 7.6, be warmed up to 95 DEG C aging 2 hours, mistake
Filtering, filter for 4 times with 40 liters of deionized water wash, filter cake is dried 4 hours at 120 DEG C, and the modified clay obtained note M2 analyzes it
Composition calculates SiO2: Al2O3Mol ratio is 1.34, igloss 29.5%, low temperature N2Absorption records pore volume and is 0.85ml/g, compares table
Area is 358m2/g。
Embodiment 3
The preparation of catalyst cat-1: (content is 70 weight %, and Chinese kaolin is public by modified clay material M1, Kaolin of Suzhou
Department produce), Alumina gel (A1203Content 21. 5 weight %, Yueyang be polymerized to Chemical Co., Ltd. produce), PSRY-4 molecular sieve (RE203
4. 1 weight %, Na2O0.8 weight %, Chang Ling catalyst plant produces) and the mixing making beating of a certain amount of deionized water, colloid solid content is about
About 32%, add the hydrochloric acid of appropriate 20%, control pH to 3.0 ~ 3.3, stir 60 minutes, be then spray-dried and make microsphere catalysis
Agent, by this microspherical catalyst roasting 1 hour at 500 DEG C, with about 5 ~ 10 times of deionized water drip washing after cooling, filter filter cake in
120 DEG C of drying, obtain catalyst cat-1.
Based on butt, catalyst formulation is: modified clay material M1: Kaolin of Suzhou: Alumina gel: PSRY-4 molecular sieve
=50:12:8:30.
Embodiment 4 ~ 6 is the performance change that different content modification clay material replaces the catalyst that molecular sieve prepares.
Embodiment 4
Based on butt, catalyst cat-2 formula is: modified clay material M1: Kaolin of Suzhou: Alumina gel: PSRY-4 molecule
Sieve=45:12:8:35.
Embodiment 5
Based on butt, catalyst cat-3 formula is: modified clay material M1: Kaolin of Suzhou: Alumina gel: PSRY-4 molecule
Sieve=55:12:8:25.
Embodiment 6
Based on butt, catalyst cat-4 formula is: modified clay material M1: Kaolin of Suzhou: Alumina gel: PSRY-4 molecule
Sieve=60:12:8:20.
The character of catalyst cat-1, cat-2, cat-3, cat-4 is shown in Table 2, and its evaluating data is shown in Table 3.
Comparative example 1
Based on butt, catalyst formulation is: boehmite: Kaolin of Suzhou: Alumina gel: PSRY-4 molecular sieve=20:37:
8:35.It is prepared as comparative catalyst by catalyst process same in embodiment 3, is denoted as D-1.
Comparative example 2
Based on butt, catalyst formulation is: boehmite: Kaolin of Suzhou: Alumina gel: PSRY-4 molecular sieve=20:47:
8:25.It is prepared as comparative catalyst by catalyst process same in embodiment 3, is denoted as D-2.
Comparative example 3
Boehmite is added in quantitative deionized water, after stirring, add the hydrochloric acid that concentration is 36% and carry out at acidifying
Reason, acid aluminum ratio controls 0.10 ~ 0.12, after stirring 10 minutes, is warming up to 65 DEG C of static acidifyings 1 ~ 2 hour, and slurry pH value is raised to
It is about 3. 0.After stopping heating, then it is separately added into Kaolin of Suzhou and Alumina gel, after stirring 30 minutes, then in mixed serum
Add PSRY-4 molecular sieve, continue stirring 30 minutes, be then spray-dried and make microspherical catalyst.This microspherical catalyst is existed
Roasting 1 hour at 500 DEG C, with 5 ~ 10 times of deionized water drip washing after cooling, in 120 DEG C of drying after filtration, obtains comparative catalyst
D-3。
Comparative catalyst D-3 consists of: PSRY-4 molecular sieve 35.0 %, Kaolin 20.0 %, Alumina gel 10.0%, plan
Boehmite 35.0 %.
Comparative example 4
By Kaolin of Suzhou (content is 70 weight %, and China Kaolin Co., Ltd produces), Alumina gel, mesoporous silica-alumina materials SA-1, and
PSRY-4 molecular sieve and the mixing making beating of a certain amount of deionized water, colloid solid content about about 35%, stir 60 minutes, then
Spray drying makes microspherical catalyst.By this microspherical catalyst roasting 1 hour at 500 DEG C, with 5 ~ 10 times of deionized water drip washing,
In 120 DEG C of drying after filtration, obtain comparative catalyst D-4.
During wherein mesoporous silica-alumina materials SA-1 uses CN1565733A prepared by embodiment 1 method, mesoporous silica-alumina materials SA-1
Chemical composition be 0.12Na20:72.8A1203: 27.0Si02, its specific surface area is 382m2/ g, pore volume is 1. 1m1/g, averagely
Aperture is 11. 8nm, and most probable pore size is 9.5nm.
Comparative catalyst D-4 consists of: PSRY-4 molecular sieve 35%, Kaolin 47%, Alumina gel 8%, mesoporous silica-alumina materials
SA-1 10%。
The character of comparative catalyst D-1, D-2, D-3, D-4 is shown in Table 2, and its evaluating data is shown in Table 3.
Table 2 catalyst property contrast table
Table 3 catalyst heavy oil evaluating data table
| Catalyst is numbered | cat-1 | cat-2 | cat-3 | cat-4 | D-1 | D-2 | D-3 | D-4 |
| Reaction temperature, DEG C | 500 | 500 | 500 | 500 | 500 | 500 | 500 | 500 |
| Oil ratio | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Air speed, 1/h | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 |
| Material balance, m% | ||||||||
| Dry gas | 1.22 | 1.24 | 1.21 | 1.16 | 1.08 | 0.99 | 1.17 | 1.16 |
| Liquefied gas | 12.76 | 13.44 | 12.06 | 12.56 | 11.69 | 10.73 | 10.76 | 11.57 |
| C5 gasoline | 48.98 | 50.67 | 47.24 | 46.38 | 43.17 | 39.6 | 45.99 | 47.25 |
| Diesel oil | 21.43 | 19.65 | 22.11 | 22.22 | 22.48 | 24.75 | 22.5 | 21.7 |
| Heavy oil | 9.18 | 8.28 | 11.06 | 11.59 | 15.29 | 18.15 | 12.73 | 11.57 |
| Coke | 6.43 | 6.72 | 6.32 | 6.09 | 6.29 | 5.78 | 6.85 | 6.75 |
| Amount to | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Conversion ratio, m% | 69.39 | 72.07 | 66.83 | 66.19 | 62.23 | 57.1 | 64.77 | 66.73 |
| Total liquid yield, m% | 83.17 | 83.76 | 81.41 | 81.16 | 77.34 | 75.08 | 79.25 | 80.52 |
| Light receipts, m% | 70.41 | 70.32 | 69.35 | 68.6 | 65.65 | 64.35 | 68.49 | 68.95 |
Embodiment 7 ~ 9 investigates the performance of low molecule sieve content catalyst
Embodiment 7
Preparing catalyst by the technique of embodiment 3, in terms of butt, catalyst cat-5 formula is: modified clay material M2: Soviet Union
State Kaolin: Alumina gel: PSRY-4 molecular sieve=60:8:12:20.
Embodiment 8
Preparing catalyst by the technique of embodiment 3, in terms of butt, catalyst cat-6 formula is: modified clay material M2: Soviet Union
State Kaolin: Alumina gel: PSRY-4 molecular sieve=70:0:10:20.
Embodiment 9
Preparing catalyst by the technique of embodiment 3, in terms of butt, catalyst cat-7 formula is: modified clay material M2: Soviet Union
State Kaolin: Alumina gel: PSRY-4 molecular sieve=70:4:10:16.
The character of catalyst cat-5, cat-6, cat-7 is shown in Table 4, and its heavy oil evaluating data is shown in Table 5.
Table 4 catalyst property contrast table
| Catalyst is numbered | cat-5 | cat-6 | cat-7 |
| Specific surface area m2/g | 297 | 340 | 304 |
| Substrate specific surface m2/g | 182 | 212 | 208 |
| Micropore specific surface m2/g | 115 | 118 | 96 |
| Pore volume ml/g | 0.44 | 0.46 | 0.43 |
| Abrasion index % | 1.8 | 2.1 | 1.6 |
| Re2O3 wt% | 0.81 | 0.83 | 0.65 |
| Na2O wt% | 0.16 | 0.15 | 0.12 |
| MAT 800℃/17h | 58 | 60 | 57 |
Table 5 catalyst heavy oil evaluating data table
| Catalyst is numbered | cat-5 | cat-6 | cat-7 |
| Reaction temperature, DEG C | 500 | 500 | 500 |
| Oil ratio | 6 | 6 | 6 |
| Air speed, 1/h | 18 | 18 | 18 |
| Material balance, m% | |||
| Dry gas | 1.11 | 1.14 | 1.09 |
| Liquefied gas | 12.07 | 12.62 | 10.97 |
| C5 gasoline | 47.89 | 50.08 | 46.44 |
| Diesel oil | 20.93 | 19.59 | 19.76 |
| Heavy oil | 11.97 | 10.31 | 15.81 |
| Coke | 6.03 | 6.26 | 5.93 |
| Amount to | 100.00 | 100.00 | 100.00 |
| Conversion ratio, m% | 67.10 | 70.10 | 64.43 |
| Total liquid yield, m% | 80.89 | 82.29 | 77.17 |
| Light receipts, m% | 68.82 | 69.67 | 66.20 |
In the case of molecular sieve content is reduced to 16 ~ 20%, catalyst still has excellent cracking performance.
Claims (4)
1. a catalytic cracking catalyst with big substrate specific surface area, it is characterised in that: this catalytic cracking catalyst is to change
Property clay-like material be main matrix, replace boehmite or activated alumina and all or part of clay, with active component,
Binding agent pulp together, spray shaping, washs, is dried to obtain catalyst, and the substrate specific surface area of catalyst is more than 100m2/g、
Pore volume is more than 0.40ml/g；Remember by butt weight 100%, the Modified Zeolite Y containing 5 ~ 50%, the modified clay of 30 ~ 95%
Material, type of the selecting molecular sieve of MFI structure of 0 ~ 35% or Beta molecular sieve, the inorganic oxide binder of 2 ~ 20%.
2. the catalytic cracking catalyst with big substrate specific surface area as described in claim 1, it is characterised in that: described changes
Property clay-like material be to be prepared with clay for primary raw material, be mainly composed of silicon oxide and aluminium oxide, have silicon oxide with
The mol ratio of aluminium oxide between 0.01 ~ 50:1, low temperature N2Adsorption specific surface area is at 80 ~ 800m2/ g, pore volume 0.2 ~
3.0ml/g。
3. the catalytic cracking catalyst with big substrate specific surface area as described in claim 1, it is characterised in that: described changes
Property Y type molecular sieve is at least one of USY, PSRY, REUSY, HY, REY, REHY, REDASY.
4. the catalytic cracking catalyst with big substrate specific surface area as described in claim 1, it is characterised in that: described nothing
Machine adhesive oxides be Alumina gel, Ludox, Alusil, phosphorus aluminium glue at least one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610593171.9A CN106268920A (en) | 2016-07-26 | 2016-07-26 | A kind of catalytic cracking catalyst with big substrate specific surface area |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610593171.9A CN106268920A (en) | 2016-07-26 | 2016-07-26 | A kind of catalytic cracking catalyst with big substrate specific surface area |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106268920A true CN106268920A (en) | 2017-01-04 |
Family
ID=57652429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610593171.9A Pending CN106268920A (en) | 2016-07-26 | 2016-07-26 | A kind of catalytic cracking catalyst with big substrate specific surface area |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106268920A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686785A (en) * | 2019-03-12 | 2020-09-22 | 中国石油天然气股份有限公司 | Heavy oil catalytic cracking catalyst and preparation method thereof |
| CN112169828A (en) * | 2020-10-14 | 2021-01-05 | 岳阳明科催化技术有限公司 | Clay-type catalytic cracking catalyst and preparation method thereof |
| CN115025806A (en) * | 2022-05-19 | 2022-09-09 | 青岛惠城环保科技集团股份有限公司 | Preparation method of iron pollution resistant catalytic cracking catalyst |
| CN115582141A (en) * | 2021-07-06 | 2023-01-10 | 中国石油天然气股份有限公司 | Catalyst for oil slurry cracking and coke gasification and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353165A (en) * | 2000-11-02 | 2002-06-12 | 中国石油化工股份有限公司 | Cocatalyst for cracking hydrocarbons |
| CN102091609A (en) * | 2010-12-03 | 2011-06-15 | 于向真 | Modified clay new material and preparation method thereof |
| CN105728028A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Catalyst for highly-producing olefin isomer and high-octane gasoline |
-
2016
- 2016-07-26 CN CN201610593171.9A patent/CN106268920A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353165A (en) * | 2000-11-02 | 2002-06-12 | 中国石油化工股份有限公司 | Cocatalyst for cracking hydrocarbons |
| CN102091609A (en) * | 2010-12-03 | 2011-06-15 | 于向真 | Modified clay new material and preparation method thereof |
| CN105728028A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Catalyst for highly-producing olefin isomer and high-octane gasoline |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686785A (en) * | 2019-03-12 | 2020-09-22 | 中国石油天然气股份有限公司 | Heavy oil catalytic cracking catalyst and preparation method thereof |
| CN112169828A (en) * | 2020-10-14 | 2021-01-05 | 岳阳明科催化技术有限公司 | Clay-type catalytic cracking catalyst and preparation method thereof |
| CN112169828B (en) * | 2020-10-14 | 2022-11-15 | 岳阳明科催化技术有限公司 | Clay-type catalytic cracking catalyst and preparation method thereof |
| CN115582141A (en) * | 2021-07-06 | 2023-01-10 | 中国石油天然气股份有限公司 | Catalyst for oil slurry cracking and coke gasification and preparation method thereof |
| CN115582141B (en) * | 2021-07-06 | 2023-08-22 | 中国石油天然气股份有限公司 | Catalyst for slurry cracking and coke gasification thereof and preparation method thereof |
| CN115025806A (en) * | 2022-05-19 | 2022-09-09 | 青岛惠城环保科技集团股份有限公司 | Preparation method of iron pollution resistant catalytic cracking catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102078821B (en) | Cracking catalyst containing mesoporous silica-alumina materials | |
| CN106268920A (en) | A kind of catalytic cracking catalyst with big substrate specific surface area | |
| CN101745417B (en) | Catalytic cracking catalyst | |
| CN105813740A (en) | Phosphorus-containing fcc catalyst | |
| CN109304210B (en) | Preparation method of catalytic cracking catalyst for cracking coking wax oil to produce diesel oil in high yield | |
| CN102079986A (en) | Cracking method of heavy hydrocarbon oil | |
| WO2020078434A1 (en) | Mfi structure molecular sieve rich in mesopore, preparation method therefor, and catalyst containing same and application thereof | |
| WO2020078437A1 (en) | Phosphorus-containing rare-earth-containing mfi structure molecular sieve rich in mesopore, preparation method, and catalyst containing same and application thereof | |
| CN104014361B (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN108452838A (en) | A kind of catalytic cracking catalyst | |
| RU2509605C1 (en) | Method of preparing catalyst with low content of rare-earth elements for cracking oil fractions | |
| CN109304212A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN108452837A (en) | A kind of catalytic cracking catalyst | |
| TW202041280A (en) | Catalytic-cracking catalyst and method for preparation thereof | |
| CN109304206B (en) | Preparation method of catalytic cracking catalyst for cracking coker gas oil to produce gasoline in high yield | |
| CN108452833A (en) | A kind of catalytic cracking catalyst | |
| CN105728014B (en) | A kind of preparation method of catalytic cracking catalyst | |
| CN107345161B (en) | A kind of method for hydrogen cracking of coal tar | |
| CN109746039B (en) | Hierarchical pore silicon-aluminum catalytic material and preparation method and application thereof | |
| CN109304222B (en) | Catalytic cracking catalyst for cracking coking wax oil to produce more liquefied gas and preparation method thereof | |
| CN111686785A (en) | Heavy oil catalytic cracking catalyst and preparation method thereof | |
| CN107971014A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN109675616A (en) | A kind of catalytic converting catalyst of fecund butylene and the catalysis conversion method of preparation method and voluminous butylene | |
| TWI812772B (en) | Modified Y-type molecular sieve, catalytic cracking catalyst containing it, and its preparation and use | |
| CN104556081A (en) | Modified kaolin as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170104 |