CN114433173B - Method for preparing FCC catalyst with low apparent bulk density - Google Patents
Method for preparing FCC catalyst with low apparent bulk density Download PDFInfo
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- CN114433173B CN114433173B CN202011110620.2A CN202011110620A CN114433173B CN 114433173 B CN114433173 B CN 114433173B CN 202011110620 A CN202011110620 A CN 202011110620A CN 114433173 B CN114433173 B CN 114433173B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000001694 spray drying Methods 0.000 claims abstract description 64
- 239000002253 acid Substances 0.000 claims abstract description 55
- 238000001035 drying Methods 0.000 claims abstract description 47
- 239000002002 slurry Substances 0.000 claims abstract description 45
- 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 21
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 64
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 25
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 25
- 229910021536 Zeolite Inorganic materials 0.000 claims description 20
- 239000010457 zeolite Substances 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 19
- 239000002808 molecular sieve Substances 0.000 claims description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 17
- 238000004523 catalytic cracking Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 239000004927 clay Substances 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003546 flue gas Substances 0.000 claims description 10
- 239000005995 Aluminium silicate Substances 0.000 claims description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims description 9
- 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 description 9
- -1 rectorite Chemical compound 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 claims description 2
- 230000023556 desulfurization Effects 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 34
- 230000000052 comparative effect Effects 0.000 description 16
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 14
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 14
- 239000011148 porous material Substances 0.000 description 13
- 239000004005 microsphere Substances 0.000 description 11
- 230000020477 pH reduction Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004231 fluid catalytic cracking Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000003570 air Substances 0.000 description 2
- 229910052934 alunite Inorganic materials 0.000 description 2
- 239000010424 alunite Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 description 2
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 1
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 229940092782 bentonite Drugs 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 150000004684 trihydrates Chemical class 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/31—Density
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
A method of preparing a low apparent bulk FCC catalyst comprising: forming a first slurry comprising an alumina binder, an active component and water, and spray-drying the first slurry in a spray-drying tower, wherein a drying medium used for the spray-drying contains an acid gas, and the concentration of the acid gas in the drying medium is not less than 0.3g/m 3 . The catalyst preparation method can reduce the apparent bulk density of the FCC catalyst and ensure that the catalyst has better wear resistance.
Description
Technical Field
The present invention relates to a process for preparing a low apparent bulk FCC catalyst.
Background
Fluid Catalytic Cracking (FCC) is an important crude oil secondary processing process employing a fluidized bed reactor using microspherical catalytic cracking catalysts or catalytic cracking aides. In order to ensure good fluidization properties of the catalyst, it is desirable to have a certain apparent bulk density while also having good attrition resistance.
At present, the catalytic cracking catalyst and the auxiliary agent are mainly semisynthetic catalysts. The preparation process of the catalyst comprises the steps of mixing a binder, an active component and optional clay according to a certain proportion to prepare slurry, and then spray drying, optional roasting, washing, drying and the like. Among these, common binders include aluminum binders such as aluminum sol and/or pseudo-boehmite, but the prepared catalysts often suffer from a high apparent bulk density.
Increasing the catalyst pore volume can reduce the apparent bulk of the catalyst.
CN1831090a reports the introduction of polymer particles of 5-1500nm during the preparation of the catalyst, removal of the polymer particles after shaping, forming mesopores. However, polymers are expensive and their incineration creates environmental concerns.
CN1388214a by adding an amount of alumina of beta-alumina trihydrate, the bulk specific gravity (apparent bulk density) and pore volume of the catalyst can be adjusted within a wide range.
CN1854258A provides mesoporous silica-alumina material with pore volume of 0.5-2.0ml/g and pore diameter of 8-20 nm. However, the introduced macroporous material is filled with the binder in the pore canal of the macroporous material, so that the macropores are lost, the binder entering the macropores loses the binding capacity, and the wear resistance of the catalyst is reduced.
In the existing preparation method of the catalytic cracking catalyst, increasing the pore volume often leads to poor attrition resistance of the catalyst.
Disclosure of Invention
The invention aims to provide a preparation method for reducing apparent bulk density of an FCC catalyst.
The invention provides a catalyst preparation method for reducing apparent bulk density of a catalyst, which comprises the following steps:
forming a first slurry comprising an alumina binder, an active component and water, and spray-drying the first slurry in a spray-drying tower, wherein a drying medium used for the spray-drying contains an acid gas, and the concentration of the acid gas in the drying medium is not less than 0.3g/m 3 . The concentration of the acid gas in the drying medium is, for example, 0.3 to 3g/m 3 For example 0.5-2 or 0.6-1.5 g/m 3 . Wherein the volume of the drying medium is based on the gas volume under standard conditions.
According to the method for preparing the catalyst of the invention, the acid gas is a substance which exists in a gas state in a spray-drying temperature range (above the tower outlet temperature and below the tower inlet temperature) and is dissolved in water to form acid, and the acid gas is such as HCl, SO 3 、P 2 O 5 、NO 2 In organic acidsOne or more, preferably HCl, SO 3 、P 2 O 5 、NO 2 More preferably HCl.
According to the catalyst preparation method of the present invention, the concentration of the acid gas in the drying medium in the spray drying tower is preferably 0.3 to 3g/m 3 。
According to the catalyst preparation method of the present invention, the solid content of the first slurry is preferably 5 to 35 wt%.
According to the catalyst preparation method of the present invention, an acid is further added to the first slurry to acidify the binder, the acid being an inorganic acid and/or an organic acid, preferably, the acid is added in an amount corresponding to that of Al 2 O 3 The molar ratio of the pseudo-boehmite is 0.05-0.2:1 is, for example, 0.08 to 0.16:1. the inorganic acid is, for example, one or more of hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, preferably hydrochloric acid. The organic acid is one or more of carboxylic acid with 1-10 carbon atoms, preferably one or more of formic acid and acetic acid.
According to the catalyst preparation method of the present invention, the first slurry comprises 20 to 60 wt%, for example 20 to 40 wt% or 25 to 35 wt% clay on a dry basis, 10 to 70 wt%, for example 20 to 50 or 30 to 45 wt% active component on a dry basis, 15 to 70 wt%, for example 20 to 50 wt% alumina binder on an alumina basis, the alumina binder being pseudoboehmite and optionally an alumina sol, for example an alumina sol and a pseudoboehmite.
According to the preparation method of the catalyst, the dry weight of the first slurry is taken as the reference, and Al is taken as the reference 2 O 3 The pseudo-boehmite is added in an amount of 10 to 50% by weight, for example 15 to 45% by weight or 20 to 40% by weight or 20 to 35% by weight.
According to the preparation method of the catalyst, the dry weight of the first slurry is taken as the reference, and Al is taken as the reference 2 O 3 The aluminum sol is added in an amount of 0 to 20% by weight, for example, 3 to 15% by weight.
According to the inventionThe active component can be an active component commonly used for a catalytic cracking catalyst, such as a molecular sieve. The molecular sieve may be a zeolite molecular sieve or a non-zeolite molecular sieve, and the zeolite molecular sieve is one or more of Y-type zeolite, ZSM-5 zeolite and beta zeolite, for example, Y-type zeolite or a mixture of Y-type zeolite and one or more of ZSM-5 zeolite and beta zeolite. The Y-type zeolite is, for example, HY zeolite or NH 4 Y zeolite, rare earth Y zeolite, ultrastable Y zeolite, rare earth ultrastable zeolite Y, or a mixture of a plurality thereof.
According to the catalyst preparation method of the present invention, the first slurry may further contain clay, for example, one or more of kaolin, sepiolite, rectorite, montmorillonite, rectorite, halloysite, diatomaceous earth, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite, preferably one or more of kaolin, sepiolite, rectorite, montmorillonite, rectorite, halloysite, and more preferably kaolin.
According to the catalyst preparation method of the present invention, the spray-drying inlet temperature (the temperature of the drying medium entering the spray-drying tower) is 300 to 600 ℃.
According to the catalyst preparation method of the present invention, the spray-dried outlet temperature (temperature of the drying medium leaving the spray-drying tower) is 100 to 220 ℃.
According to the catalyst preparation method of the present invention, the spray drying is carried out, the inlet temperature of the spray drying tower is preferably 300-380 ℃, and the outlet temperature of the spray drying tower is preferably 100-150 ℃.
According to the catalyst preparation method, a drying medium (or called hot air) is contacted with atomized first slurry in a spray drying tower to form a spray drying mixture, and the mixture is led out of the spray drying tower to be separated to obtain catalyst microspheres and gas, wherein the gas is called spray drying tail gas. The separation may be by sedimentation and/or cyclone, as is well known to those skilled in the art, and will not be described in detail herein.
According to the catalyst preparation method of the invention, the drying medium can comprise one or more of air, flue gas (flue gas for short), nitrogen, inert gas and roasting tail gas.
According to the catalyst preparation method of the invention, the drying medium contains acid gas, and the acid gas can be contained in the drying medium by adding substances capable of forming the acid gas, for example, high-concentration hydrochloric acid, HCl gas and SO gas can be added 3 、NO 2 、N 2 O 5 One or more of organic acid which can be gasified in a spray drying temperature range and roasting tail gas. The acid gas is preferably HCl. In one embodiment, the drying medium contains roasting tail gas and other gases, such as one or more of flue gas, air, and nitrogen. The roasting tail gas can be acid-containing waste gas generated during roasting in the preparation process of a catalytic cracking catalyst, a flue gas desulfurization auxiliary agent, a flue gas denitration auxiliary agent and the like, the acid-containing waste gas is separated by a cyclone separator (for short, a cyclone separator) to obtain the roasting tail gas, or the roasting tail gas is mixed with other gases such as flue gas to form a drying medium, wherein the acid gas can be further added to ensure that the acid gas content in the drying medium is more than 0.3g/m 3 Preferably 0.3-3g/m 3 。
According to the preparation method of the catalyst, after the roasting tail gas is subjected to cyclone separation, the solid carried in the roasting tail gas is separated, and the roasting tail gas is mixed with a spray-dried drying medium and then is introduced into a spray-drying tower. The acid gas is generated by roasting, so that the use amount of acid can be reduced, and the catalyst can be dried by using high-temperature gas generated by roasting, so that the energy consumption for heating a drying medium is reduced.
The catalyst preparation method according to the present invention may further comprise a step of calcination. The roasting comprises roasting the catalyst microspheres obtained by spray drying. Reference may be made to the calcination process in the production of the existing catalytic cracking catalysts. In one embodiment, the firing temperature of the firing is preferably 450-800 ℃, preferably 500-700 ℃. Preferably, the calcination time is 1 to 6 hours. Preferably, the calcination causes more than 90% of the acid in the catalyst to enter the calcination atmosphere. The calcination atmosphere may be one or more of air, flue gas, inert gas, nitrogen. The roasting is performed in a roasting furnace. The gas in the roasting atmosphere is led out of the roasting furnace to form roasting tail gas, and the temperature of the roasting tail gas is preferably 500-700 ℃.
The process for the preparation of a catalyst according to the invention may also comprise a step of washing, which may be referred to the washing methods of the prior art, for example by washing with ammonium salt solutions, the invention being not particularly limited.
The spray drying tower, the roasting furnace, the cyclone separator (for short) and the tail gas treatment system can adopt the spray drying, the roasting furnace, the cyclone separator and the tail gas treatment system in the preparation of the existing catalytic cracking catalyst and auxiliary agent, and the equipment is changed little.
The invention provides a spray drying system for the method, which comprises a spray drying tower, a drying medium supply system, a spray drying tail gas leading-out system and a slurry atomizing system, wherein the drying medium supply system also comprises an acid gas supply system. Wherein the spray drying tower is used for enabling an atomization product of the atomization system to be in contact with a drying medium for drying; the drying medium system is used for providing a hot drying medium for the spray drying tower; the spray drying tail gas extraction system is used for leading the drying medium after spray drying out of the spray drying tower; the slurry atomization system is used to form droplets of a liquid material to be dried and then enters the spray drying tower. The drying medium supply system comprises an acid gas supply system for introducing acid gas into the drying medium.
The preparation method of the catalyst provided by the invention can provide the microspherical catalytic cracking catalyst with lower apparent bulk density by acidifying slurry containing the alumina binder in a spray drying process. Preferably, the solid content and the acidification degree of catalyst slurry before spray drying are controlled, the spray drying temperature is controlled, and meanwhile, acid gas is utilized to realize secondary acidification of pseudo-boehmite at the outer layer of the fog drops, so that gradient acidification of pseudo-boehmite in the catalyst microspheres can be realized, the particle size of colloid particles is distributed from the surface layer to the inside of the microspheres in a gradient manner from small to large, the apparent bulk density of the catalyst can be reduced, and meanwhile, the strength of the catalyst is not reduced. Preferably, the spray drying tower can prolong the drying time of the fog drops, and can have better secondary acidification effect.
The catalyst preparation method provided by the invention is used for preparing the catalytic cracking catalyst, and the activity of the catalyst is not affected. The method provided by the invention has low cost, and can be realized by adding an acid gas adding device into the existing catalyst production device. The preferred method can recover the acid by introducing the roasting tail gas into a spray drying tower, reduces the acid consumption and is easy to implement. The catalyst preparation method provided by the invention can be used for producing catalytic cracking catalysts and auxiliaries. The catalyst preparation method provided by the invention is particularly suitable for preparing catalytic cracking catalysts or assistants suitable for alumina-containing binders, especially for preparing catalysts containing pseudo-boehmite binders, can reduce apparent bulk density of the catalyst without changing catalyst composition, and can maintain good catalyst abrasion resistance.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a catalyst according to the present invention. Wherein,,
1. the device comprises a blower, a roasting furnace, a cyclone separator, a blower, a hot blast stove, a spray drying tower, a cyclone separator, a draught fan, a recycling fan, a tail gas treatment system and a tail gas treatment system.
Detailed Description
According to the preparation method of the catalyst for reducing the apparent bulk density of the catalyst, one embodiment comprises the steps of mixing clay, pseudo-boehmite, an active component, optional alumina sol and inorganic acid, pulping to form first slurry, spray-drying and forming the first slurry, and roasting at a high temperature to obtain catalyst microspheres; wherein the solid content of the first slurry is preferably 5 to 35 wt%, and the inorganic acid is added in an amount corresponding to Al 2 O 3 The molar ratio (acid aluminum ratio) of the calculated pseudo-boehmite addition amount is preferably 0.05:1-0.2:1; in the air flow of the spray drying towerThe concentration of the inorganic acid is 0.3-3g/m 3 Spray drying at inlet temperature of 300-600deg.C and outlet temperature of 100-220deg.C. Preferably, the catalyst after spray drying is calcined, and the temperature of the roasting furnace atmosphere for calcination is 500-700 ℃. Preferably, the calcination separates more than 90% of the inorganic acid in the catalyst from the catalyst into the calcination tail gas. Preferably, the roasting tail gas is introduced into a cyclone separator, separated from the catalyst, mixed with a spray drying tower drying medium and introduced into a spray drying tower.
According to the catalyst preparation method for reducing apparent bulk density of the catalyst of the present invention, in one embodiment, molecular sieves, clay, pseudo-boehmite, and mineral acid are slurried in the following manner: mixing molecular sieve and water to form slurry, adding clay and pseudo-boehmite, mixing uniformly, and adding inorganic acid, mixing uniformly to obtain first slurry.
According to the catalyst preparation method for reducing apparent bulk density of the catalyst, according to one embodiment, molecular sieves, alumina sol, clay, pseudo-boehmite and mineral acid are pulped in the following manner: mixing molecular sieve and water to form slurry, adding aluminum sol, clay and pseudo-boehmite, mixing uniformly, and adding inorganic acid, mixing uniformly to obtain first slurry.
The catalyst preparation method for reducing apparent bulk density of the catalyst can be used for preparing microsphere catalysts, such as microsphere catalytic cracking catalysts or catalytic cracking assistants, and in one embodiment, the average diameter of the catalyst or the assistants is 60-80 microns, the volume of particles with diameters smaller than 149 microns is more than 90% of the total particle volume, and the volume of particles with diameters smaller than 40 microns is less than 40% of the total particle volume.
The invention is further described with reference to the process flow of fig. 1:
as shown in fig. 1, natural gas is combusted with air introduced by a blower 4 in a hot blast stove 5 to form hot air. The air provided by the blower 1 enters the roasting furnace 2, acid in the catalyst in the roasting furnace 2 is roasted and removed, then enters the roasting atmosphere, gas in the roasting atmosphere is led out of the roasting furnace to form acid-containing tail gas, the acid-containing tail gas is mixed with hot air from the hot blast stove 5 after being separated by the cyclone separator 3, the mixed gas enters the spray drying tower 6 to be contacted with atomized first slurry for drying, the dried hot air carries the catalyst to enter the cyclone separator 7 to separate the catalyst therein, and part of dried hot air is recycled to the outlet of the hot blast stove 5 by the recycling fan 9. An acid gas transfer line is added to the drying medium transfer line between the hot blast stove 5 and the spray drying tower 6 for introducing acid gas into the drying medium transfer line. At the same time, the first slurry is atomized through the nozzle and enters the spray drying tower 6 to be contacted with the drying medium entering the spray drying tower 6. The surface of the atomized initial liquid drop is wet, the mixed gas containing acid in the tower can be gradually contacted with the surface of the fog drop, the pseudo-boehmite on the surface of the formed initial fog drop is subjected to secondary acidification, the peptization degree of the pseudo-boehmite on the surface layer of the fog drop is improved, the gradient acidification of the pseudo-boehmite in the catalyst microsphere is realized, and the particle size of colloid particles is distributed from the surface layer to the inside of the microsphere in a gradient manner from small to large.
In the present invention, the water droplet pore volume, the abrasion index and the apparent bulk density (bulk ratio) were measured according to the methods (NB/SH/T0955-2017, NB/SH/T0964-2017, NB/SH/T0954-2017) respectively.
Example 1
Adding 300.4kg of water into a gel forming kettle, and adding 40 wt% of uniformly dispersed SOY-8 molecular sieve (the product produced by Mitsubishi catalyst Qilun Co., ltd., is Y-type molecular sieve containing rare earth, RE) 2 O 3 The content is 8.0 wt%, the same applies hereinafter) 92.5Kg of slurry, 23.3Kg of alumina sol (product produced by Mitsui catalyst Qilu division, alumina content 21.5 wt%, the same applies hereinafter) is added, stirred for 10 minutes, 42.9Kg of kaolin (product of Suzhou kaolin division, reduced by 23 wt%, the same applies hereinafter), beaten for 90 minutes, 41Kg of pseudo-boehmite (product of Shanxi division, limited by China aluminum industry, reduced by 39 wt%, the same applies hereinafter, abbreviated as aluminum stone) is added, stirred for 30 minutes, acidified for 90 minutes with industrial hydrochloric acid with a concentration of 36 wt% for forming a first slurry, and then sprayed dry under pressureThe dryer is spray-dried and molded at the inlet temperature of a spray drying tower of 370 ℃ and the outlet temperature of the spray drying tower of 110 ℃ to obtain the catalyst microsphere, wherein the drying medium of the spray drying tower is flue gas, and the concentration of HCl is 0.72g/m 3 The induced draft air quantity is 3000m 3 And (3) roasting, washing and drying a spray sample (namely the catalyst microspheres obtained by spray drying) to obtain a catalyst CAT-1, wherein the atmosphere temperature in a roasting furnace is 550 ℃, and the roasting time is 2 hours; the washing (same below) was carried out twice with an ammonium sulphate solution having a concentration of 1% by weight, each washing having a weight ratio of ammonium sulphate solution to catalyst of 10:1, washing temperature 60 ℃, washing time 20 minutes, and then filtering.
Table 1 the formulations of the examples and comparative examples are weight percent on a dry basis.
| Examples | Molecular sieve | Kaolin clay | Aluminum stone | Aluminum sol | First slurry solids content, wt% | Ratio of acid to aluminum |
| Example 1 | 37 | 33 | 25 | 5 | 20 | 0.15 |
| Example 2 | 37 | 33 | 25 | 5 | 35 | 0.15 |
| Example 3 | 35 | 25 | 37 | 3 | 20 | 0.2 |
| Example 4 | 42 | 25 | 22 | 11 | 35 | 0.15 |
| Comparative example 1 | 37 | 33 | 25 | 5 | 20 | 0.15 |
| Comparative example 2 | 37 | 33 | 25 | 5 | 20 | 0.2 |
| Comparative example 3 | 35 | 25 | 37 | 3 | 20 | 0.2 |
| Comparative example 4 | 35 | 25 | 37 | 3 | 20 | 0.3 |
In table 1, the acid aluminum ratio is the molar ratio of HCl added to pseudo-boehmite (abbreviated as "alunite") in terms of alumina during the formation of the first slurry.
Table 2 example and comparative example preparation process conditions
Table 3 evaluation of the properties of examples and comparative examples
| Wear index%/h | Pore volume ml/g | Apparent bulk g/ml | Light oil micro-reaction activity | |
| Example 1 | 1.2 | 0.40 | 0.72 | 68 |
| Example 2 | 1.1 | 0.39 | 0.73 | 68 |
| Example 3 | 1.2 | 0.42 | 0.71 | 69 |
| Example 4 | 2 | 0.41 | 0.72 | 70 |
| Comparative example 1 | 2.5 | 0.41 | 0.71 | 68 |
| Comparative example 2 | 1.2 | 0.36 | 0.80 | 64 |
| Comparative example 3 | 2.8 | 0.43 | 0.70 | 69 |
| Comparative example 4 | 1.2 | 0.37 | 0.79 | 63 |
Example 2
The catalyst was prepared with reference to example 1, except for the solids content of the first slurry and the HCl concentration in the drying medium.
Example 3
Catalyst was prepared with reference to example 1, except that the catalyst formulation of example 3 was as shown in Table 1, the HCl concentration in the drying medium, the spray-dried inlet and outlet temperatures were as shown in Table 2, and the remaining preparation conditions were the same as in example 1.
Example 4
A catalytic cracking catalyst was prepared by the method of reference example 1, and the formulation of the catalyst is shown in Table 1, among others. The operating conditions are shown in Table 2, and the HCl concentration in the drying medium, the spray-drying inlet and outlet temperatures are shown in Table 2.
Comparative example 1
The procedure of example 1 was followed, except that HCl was not introduced into the spray-dried drying medium, and the aluminum acid ratio was the same as in example 1. It can be seen that the catalyst pore volume and apparent bulk density are similar to those of example, but the attrition index is higher than that of example 1, and the attrition resistance is poor.
Comparative example 2
With reference to the method of example 1, except that HCl was not introduced into the drying medium during spray drying, the degree of alanate acidification (i.e., the acid to aluminum ratio) was increased during the gelling process (the process of forming the first slurry). As can be seen from Table 3, the apparent bulk density of the catalyst is high, the attrition index is reduced, example 1 is comparable, the pore volume is reduced, the catalyst activity is lower,
comparative example 3
According to the method of example 3, no secondary acidification technique is adopted, i.e. no hydrogen chloride is introduced into the drying medium, the ratio of aluminum acid to aluminum acid which is acidified by aluminum stone in the gelling process is the same as that of example 3, the pore volume and apparent bulk density of the catalyst are similar to those of the example, but the catalyst has poor abrasion resistance.
Comparative example 4
The catalyst was prepared according to the method of example 3 without secondary acidification (no HCl was introduced during spray drying), and the degree of alunite acidification in the gelling process was increased, i.e. the acid to aluminium ratio was increased, with better strength, but the apparent bulk density (also called the bulk ratio) of the catalyst was higher, the pore volume was smaller, and the catalyst activity was lower.
Examples 1-4 and comparative examples 1-4, the formulation for preparing the catalyst is shown in Table 1, the process conditions and calcination temperatures for spray drying are shown in Table 2, and the properties of the resulting catalyst are shown in Table 3.
As can be seen from tables 1-3, the process of the present invention reduces the apparent bulk of the catalyst while maintaining good catalyst strength while increasing the catalyst pore volume, and surprisingly also increases catalyst activity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
The individual technical features described in the above embodiments may be combined in any suitable manner without contradiction.
Any combination of the various embodiments of the invention is possible without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (14)
1. A method of preparing a low apparent bulk catalyst comprising:
forming a first slurry comprising an alumina binder, clay, molecular sieve and water, and spray-drying the first slurry in a spray-drying tower, wherein a drying medium used for the spray-drying contains an acid gas, and the concentration of the acid gas in the drying medium is not less than 0.3g/m 3 Wherein the volume of the drying medium is based on the gas volume under standard conditions; the alumina binder comprises pseudo-boehmite and optional alumina sol, wherein acid is added into the first slurry, the acid is inorganic acid and/or organic acid, and the addition amount of the acid is equal to that of the alumina sol 2 O 3 The molar ratio of the pseudo-boehmite is 0.05-0.2.
2. The method of claim 1, wherein the pseudoboehmite is present in the first slurry in an amount of Al based on the dry weight of the first slurry 2 O 3 10-50 wt% of aluminum sol with Al content 2 O 3 0-20 wt%.
3. The method according to claim 1 or 2, characterized in that: the first slurry comprises, based on a first slurry dry basis: 20-60 wt% clay on dry basis, 10-70 wt% molecular sieve on dry basis and Al 2 O 3 15-70 wt% of an alumina binder.
4. The method of claim 1, wherein the first slurry has a solids content of 5 to 35 wt%.
5. The method of claim 1, wherein the acid is added to the first slurry in an amount equivalent to that of Al 2 O 3 The calculated molar ratio of the pseudo-boehmite is 0.08-0.16:1, a step of; the organic acid is one or more of carboxylic acids with 1-10 carbon atoms in the molecule.
6. The method according to claim 1, wherein the organic acid is one or more of formic acid and acetic acid; the inorganic acid is one or more of hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid.
7. The method of claim 1, wherein the first slurry is prepared by: mixing a molecular sieve with water to form slurry, adding kaolin and pseudo-boehmite, uniformly mixing, and adding inorganic acid, and uniformly mixing to obtain first slurry; or mixing the molecular sieve with water to form slurry, adding the aluminum sol, the kaolin and the pseudo-boehmite, uniformly mixing, and adding the inorganic acid, and uniformly mixing to obtain first slurry.
8. The method according to claim 1, wherein the concentration of the acid gas in the drying medium is 0.3-3g/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The acid gas is HCl or SO 3 、P 2 O 5 、NO 2 One or more of organic acids.
9. The method of claim 1, wherein the spray-dried feed tower temperature is 300-600 ℃; the outlet temperature of the spray drying is 100-220 ℃.
10. The method of claim 9, wherein the spray drying is performed at a spray drying tower inlet temperature of 300-380 ℃ and a spray drying tower outlet temperature of 100-150 ℃.
11. The method according to claim 1, wherein the spray-dried catalyst is further calcined, and the temperature of the atmosphere in the calcining furnace is controlled to be 500-700 ℃.
12. The method according to claim 1 or 11, wherein the drying medium comprises roasting tail gas, and the roasting tail gas is catalytic cracking catalyst or flue gas desulfurization auxiliary agent or gas obtained by separating solid substances from acid-containing waste gas generated during roasting of flue gas denitration auxiliary agent.
13. The method of claim 1, wherein the clay is one or more of kaolin, sepiolite, rectorite, montmorillonite, rectorite, halloysite; the molecular sieve is one or more of Y-type zeolite, ZSM-5 zeolite and beta zeolite.
14. The method of claim 13, wherein the Y-zeolite is HY, NH 4 Y, rare earth Y, ultrastable Y and one or more of rare earth ultrastable Y.
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| US5135756A (en) * | 1989-03-10 | 1992-08-04 | Thiele Kaolin Company | Process for improving the physical and catalytic properties of a fluid cracking catalyst |
| CN1246515A (en) * | 1998-09-03 | 2000-03-08 | 中国石油化工集团公司 | Process for preparing catalyst for catalytic cracking |
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| CN104549550A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing microsphere FCC (fluid catalytic cracking) catalyst |
| CN104549551A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing microsphere FCC (fluid catalytic cracking) catalyst |
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| CN101134905B (en) * | 2006-08-30 | 2012-01-11 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
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| US5135756A (en) * | 1989-03-10 | 1992-08-04 | Thiele Kaolin Company | Process for improving the physical and catalytic properties of a fluid cracking catalyst |
| CN1246515A (en) * | 1998-09-03 | 2000-03-08 | 中国石油化工集团公司 | Process for preparing catalyst for catalytic cracking |
| CN101134906A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for increasing solid content of catalytic cracking catalyst slurry |
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