CN115121280A - Catalytic cracking catalyst and preparation method thereof - Google Patents
Catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN115121280A CN115121280A CN202210731040.8A CN202210731040A CN115121280A CN 115121280 A CN115121280 A CN 115121280A CN 202210731040 A CN202210731040 A CN 202210731040A CN 115121280 A CN115121280 A CN 115121280A
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- molecular sieve
- baking
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- rare earth
- catalytic cracking
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002808 molecular sieve Substances 0.000 claims abstract description 132
- 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 131
- -1 rare earth nitrate Chemical class 0.000 claims abstract description 60
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 51
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000013329 compounding Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000011343 solid material Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 238000009718 spray deposition Methods 0.000 claims abstract description 7
- 239000008235 industrial water Substances 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 21
- 101100372898 Caenorhabditis elegans vha-5 gene Proteins 0.000 claims description 14
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 14
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- 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 10
- 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 5
- 239000000969 carrier Substances 0.000 claims description 5
- 229910052621 halloysite Inorganic materials 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 235000015110 jellies Nutrition 0.000 claims description 3
- 239000008274 jelly Substances 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 239000007789 gas Substances 0.000 abstract description 33
- 230000008569 process Effects 0.000 abstract description 16
- 238000006479 redox reaction Methods 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 3
- 239000003292 glue Substances 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract 1
- 239000010865 sewage Substances 0.000 description 42
- 238000004231 fluid catalytic cracking Methods 0.000 description 40
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 150000002910 rare earth metals Chemical class 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000004005 microsphere Substances 0.000 description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 230000001360 synchronised effect Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010841 municipal wastewater Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical group [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JMTIXSZQYHAMLY-UHFFFAOYSA-N [P].[Zn] Chemical compound [P].[Zn] JMTIXSZQYHAMLY-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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
- 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
- B01J29/80—Mixtures of different zeolites
-
- B01J35/61—
-
- 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
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a preparation method of a catalytic cracking catalyst, which comprises the following steps: (1) compounding the 'double-cross once-baking' molecular sieve and the 'double-cross twice-baking' molecular sieve, wherein the adding proportion of the 'double-cross once-baking' molecular sieve is less than or equal to 40 wt%; simultaneously using NH carried in the 'two-way one-baking' molecular sieve 4 + Adding rare earth nitrate as a reference to obtain a compounded mixed molecular sieve; (2) mixing the mixed molecular sieve, the solid material, the auxiliary solid material, the binder, the chlorinated rare earth salt, the hydrochloric acid solution and the industrial water to form glue; (3) spray forming, roasting, washing, filtering and drying to obtain FCC catalytic cracking catalyst finished product, NH 4 + With NO 3 ‑ PrimaryA series of oxidation-reduction reactions occur during the firing process, and finally the nitrogen gas passes through the tail gas exhaust system.
Description
Technical Field
The invention belongs to the field of preparation of catalytic cracking catalysts, and particularly relates to a catalytic cracking catalyst which does not generate low ammonia nitrogen sewage in the preparation process and a preparation method thereof.
Background
In the manufacture of FCC (catalytic cracking) catalysts, active zeolites (molecular sieves) are the key active components and constitute around 35% of the catalyst. No other entrained NH is introduced into the FCC catalyst unit 4 + When the exchange liquid is used, the active component of the 'two-way one-baking' molecular sieve (accounting for about 10 percent of the catalyst) is not subjected to secondary baking, and NH carried in the filter cake of the molecular sieve 4 + The filtering washing liquid enters the FCC catalyst preparation and washing process, so that the sewage of the FCC catalyst device contains a small amount of NH 3 -N (around 200 mg/L).
However, in the existing design scheme, through the balance optimization of the water systems of the molecular sieve device and the FCC catalyst manufacturing device (microsphere device), the exchange filtration washing liquid of the microsphere device is recycled to the molecular sieve device (used as the filter washing water) except the interior of the device; and conveying the tail gas absorption liquid of the microsphere device serving as the external drainage of the device to a sewage treatment device. The "two-way one-baking" molecular sieve used in the FCC catalyst manufacturing plant carries part of NH 4 + So that the ammonia nitrogen in the sewage of the microsphere device is about 200mg/L when the microsphere device is delivered to the factory sewage treatment device. However, with the increasingly strict requirements of society on pollutant discharge, the B standard of the primary standard in GB18918-2002 requires that the ammonia nitrogen in sewage is less than or equal to 8 mg/L.
In order to solve the problem of high ammonia nitrogen content in sewage, the high ammonia nitrogen sewage generated by a molecular sieve device can be matched with a high ammonia nitrogen sewage (the ammonia nitrogen content of the designed inlet water is less than or equal to 5000mg/L) steam removal recovery treatment facility, and ammonia nitrogen cannot be removed because a low ammonia nitrogen sewage treatment facility is not configured in an FCC (fluid catalytic cracking) catalyst manufacturing device.
Disclosure of Invention
Based on the above, the present invention aims to provide a catalytic cracking catalyst and a preparation method thereof, so as to solve the problem of low ammonia nitrogen (upper limit is about 200mg/L) sewage generated by an FCC catalyst manufacturing device. In order to solve the problem, the invention breaks through the previous thought of removing ammonia nitrogen in the sewage from the terminal sewage treatment layer surface, changes the production process and the formula from the source of FCC catalyst preparation, and introduces dilute nitric acidEarth salt (rare earth nitrate is not generally adopted in the prior preparation process, which prevents the over standard of tail gas nitrogen oxide caused by the decomposition of nitrate radical in the subsequent spray drying and roasting drying process), and NH carried in the filter cake of the 'two-way one-baking' molecular sieve is ingeniously utilized by utilizing the autocatalysis redox reaction mechanism 4 + With NO 3 - A series of reactions take place to generate nitrogen.
To this end, the present invention provides a method for preparing a catalytic cracking catalyst (FCC catalyst), comprising the steps of:
(1) compounding the 'double-cross once-baked' molecular sieve and the 'double-cross twice-baked' molecular sieve, wherein the adding proportion of the 'double-cross once-baked' molecular sieve is less than or equal to 40 wt%; simultaneously using NH carried in the 'two-way one-baking' molecular sieve 4 + Adding rare earth nitrate as a reference to obtain a compounded mixed molecular sieve;
(2) mixing the mixed molecular sieve, the solid material, the auxiliary solid material, the binder, the chlorinated rare earth salt, the hydrochloric acid solution and the industrial water into jelly;
(3) the coke is subjected to spray forming, roasting, washing, filtering and drying to obtain the FCC catalyst, NH 4 + With NO 3 - A series of oxidation-reduction reactions mainly occur in the roasting process, and finally the nitrogen gas is discharged out of the system through tail gas.
Specifically, in the step (1), the type and the proportion of the 'two-way and one-baking' molecular sieve can be determined according to different series of FCC catalyst product compositions, the proportion of each component in each product molecular sieve is different, and in the compounding process, the components are added according to the proportion, and after nuclear reduction, chlorinated rare earth salt may be added. For example, in the production of an LC-6 catalytic cracking catalyst product, the molecular sieve compound types and proportions are as follows: MASY (ω): 58.95%, RDY-1(ω): 25.0% yttrium nitrate (as Y) 2 O 3 Meter, ω): 5.5% yttrium chloride (as Y) 2 O 3 Meter, ω): 3.70%, SA-5 type molecular sieve (omega): 12.35% by weight, after nucleation, yttrium chloride (in Y) 2 O 3 Omega) was added in an amount of 2.325%.
Specifically, the stepsIn step (1), NH carried in the 'two-way one-baking' molecular sieve 4 + The amount of (A) can be calculated, for example, as the secondary exchange ratio (molecular sieve dry basis: NH) during the production of the "two-way one-bake" molecular sieve 4 + ) Is 1: 0.076, water washing ratio of 1: 5 when stabilized, the filter cake carried about 3.55% NH 4 + I.e. containing NH per kg of molecular sieve dry basis 4 + : 1.973 mol. Therefore, to easily estimate the NH carried in the 'two-way one-baking' molecular sieve 4 + Preferably, the amount of wash water in each treatment step during the preparation of the "two-way one-bake" molecular sieve is constant to ensure that the NH carried in the cake of the "two-way one-bake" molecular sieve is constant 4 + The content is stable.
The principle process of removing ammonia nitrogen in the molecular sieve by adding nitric acid rare earth in the production process of the microsphere device is as follows:
the two-cross one-baking molecular sieve contains residual ammonium sulfate and ammonium oxalate, and in the course of gelatinizing, lanthanum chloride and hydrochloric acid are normally added, and the rare earth nitrate salt (for example lanthanum nitrate and yttrium nitrate) is specially added, so that the partial rare earth oxalate and rare earth sulfate are precipitated in the colloid, at the same time, the solution can contain more chloride ions, nitrate ions and ammonium ions and small quantity of oxalate radical, i.e. the ammonium salt in the solution mainly exists in the form of ammonium chloride, ammonium nitrate and ammonium oxalate. The colloid is heated and evaporated to above 100 deg.C (not exceeding 150 deg.C) in spray tower, and a small amount of nitrate and ammonium ions react to generate nitrogen, 5NH 4 + +3NO 3 - ＝4N 2 +9H 2 O+2H + After the water is evaporated to dryness, the decomposition reaction of ammonium chloride, ammonium nitrate and ammonium oxalate solid salt is mainly used as follows:
decomposition of ammonium chloride into ammonia gas and hydrochloric acid, NH 4 Cl＝NH 3 ℃ + HCl ℃,. ammonium oxalate is decomposed into ammonia, carbon dioxide and water, 2 (NH) 4 ) 2 C 2 O 4 +O 2 ＝2NH 3 ↑+4CO 2 ↑+2H 2 O↑
The ammonium nitrate generates N in the process of evaporating the solution to dryness and heating at high temperature 2 、O 2 、NH 3 And NOx.
4NH 4 NO 3 ＝4NH 3 ↑+3O 2 ↑+4NO↑+2H 2 O (dilute ammonium nitrate solution)
4NH 4 NO 3 ＝4NH 3 ↑+O 2 ↑+4NO 2 ↑+2H 2 O (concentrated ammonium nitrate solution)
NH 4 NO 3 ＝HNO 3 +NH 3 ℃ (ammonium nitrate solid 110 ℃ -185 ℃ C.)
4HNO 3 ＝4NO 2 ↑+O 2 ↑+2H 2 O
The retention time of the materials in the spray tower is short, the reaction is not sufficient, the retention time of the materials is long (about 20-30 minutes) and the temperature can reach more than 400 ℃ after the materials enter a roasting furnace (600 ℃), and the ammonium nitrate which does not completely react can also react as follows besides the decomposition reaction:
NH 3 NO 3 ＝N 2 O↑+2H 2 O(185℃～200℃)
4NH 3 NO 3 ＝3N 2 ↑+2NO 2 ↑+8H 2 o (above 400 ℃ C.)
The presence of N in the gases generated in the process 2 、CO 2 、O 2 、NH 3 、NO 2 、NO、N 2 O, and the like. Nitrogen oxides mainly comprising NO and NO under high temperature conditions 2 The form exists. The temperature of the roasting furnace in the furnace cylinder is 400-500 ℃ and the SNCR reaction temperature cannot be reached, but practice proves that the oxidation-reduction reaction does occur, and most NH 3 Eliminated by the reaction, indicating that the SCR reaction occurred, probably because the FCC catalyst itself contained about 50% Al 2 O 3 3 to 4 percent of rare earth oxide and 0.5 to 0.7 percent of Fe 2 O 3 And abundant molecular sieve surface area and pore structure, make its part possess the function of SCR catalyst, consequently can take place the SCR reaction at high temperature, make ammonia and nitrogen oxide take place the redox reaction and generate harmless nitrogen gas, the reaction mainly is: 4NH 3 +4NO+O 2 ＝4N 2 +6H 2 O and 4NH 3 +2NO 2 +O 2 ＝3N 2 +6H 2 O is different from SCR reaction and is named as autocatalytic oxidation-reduction reaction by combining the characteristic of the O as a catalyst.
There are 3 equations involved in the elimination of ammonium/ammonia and nitrogen oxides in all the above processes, which are:
5NH 4 + +3NO 3 - ＝4N 2 +9H 2 O+2H + (molar ratio 5: 3)
4NH 3 +4NO+O 2 ＝4N 2 +6H 2 O (molar ratio 1: 1)
4NH 3 +2NO 2 +O 2 ＝3N 2 +6H 2 O (molar ratio 2: 1)
Thus NO 3 - And NH 4 + The theoretical feed ratio of (1): 1 to 1: 2, finding out specific NO after groping 3 - And NH 4 + The feeding molar ratio is suitable when the feeding molar ratio is 5.0 (3.5-4.5).
When the nitrate radical amount is insufficient, the ammonium radical carried by the 'two-way one-baking' molecular sieve can not be completely eliminated; when the amount of nitric acid is excessive, NOx in tail gas of the device exceeds the standard (NOx of a new enterprise in a general area is less than or equal to 200 mg/m) 3 ) And (4) risks.
On the basis of ensuring that the addition proportion of the nitric acid rare earth salt is proper, a person at an analysis and test post needs to regularly check instruments and meters, eliminate various influence factors, reduce the error rate and improve the analysis and test reliability, and an FCC catalyst manufacturing device accurately judges whether the oxidation-reduction reaction is complete or not according to the analysis result of the chemical composition of the mixed molecular sieve; and determining whether to supplement rare earth nitrate or adjust the compounding ratio of the molecular sieve and the like according to the analysis result.
The above description is to ensure the NH carried in the filter cake of the 'two-way one-baking' molecular sieve 4 + The content is stable, and the exchange ratio of the secondary exchange tank, the exchange ratio of the secondary exchange filter and the washing water quantity of the secondary exchange filter are required to be constant during the production of the 'two-way and one-baking' molecular sieve, so that the NH carried in the filter cake of the 'two-way and one-baking' molecular sieve is ensured 4 + Has stable contentDefinitely, the rare earth nitrate added in proportion in the process of manufacturing the FCC catalyst can react sufficiently, so that NH in the sewage is eliminated on one hand 4 + For the sewage delivery index (NH) 3 -N is less than or equal to 8mg/L), and on the other hand, the NOx in the tail gas of the device is prevented from exceeding the standard (the NOx of new enterprises in general areas is less than or equal to 200 mg/m) 3 ) And (4) risks.
Specifically, because the rare earth nitrate salt is added in the step (1), the rare earth chloride salt is added in the step (2), and the nucleus is specifically reduced in the gelling process according to the species and the mass of the rare earth nitrate salt added in the 'two-way one-baking' molecular sieve.
Specifically, in the preparation method provided by the invention, other carried NH is not introduced 4 + The exchange liquid in the step (3) is washed by water, the quality requirement can be met by increasing the washing amount, and the exchange liquid containing ammonium does not need to be introduced.
In the preparation process of the catalyst, the invention should avoid using single 'double cross and one baking' molecular sieve to produce the catalyst, when the catalyst is compounded with the 'double cross and two baking' molecular sieve, the proportion of the 'double cross and one baking' molecular sieve is not more than 40 percent, otherwise, NH can be eliminated through oxidation-reduction reaction 4 + For the sewage delivery index (NH) 3 N is less than or equal to 8mg/L), NOx in tail gas of the device exceeds standard (NOx of newly built enterprises in general areas is less than or equal to 200 mg/m) 3 ) Risks, and the appearance of the tail gas is abnormal, so that the environmental protection risk exists.
In the preparation method of the catalytic cracking catalyst, the 'double-exchange and single-roasting' molecular sieve is preferably selected from at least one of an RDY-1 molecular sieve and a HASY-6 molecular sieve.
In the preparation method of the catalytic cracking catalyst, the washing water consumption of each treatment step is preferably constant in the preparation process of the 'double-exchange and single-roasting' molecular sieve.
In the preparation method of the catalytic cracking catalyst, NH carried in the 'double-cross one-baking' molecular sieve is preferable 4 + The molar ratio of the nitrate ions to the nitrate ions in the rare earth nitrate is 5.0 (3.5-4.5).
In the preparation method of the catalytic cracking catalyst, the 'double-cross double-baking' molecular sieve is preferably selected from at least one of MASY molecular sieve and HRSY-1 molecular sieve.
In the preparation method of the catalytic cracking catalyst according to the present invention, preferably, the solid material is at least one selected from kaolin and pseudo-boehmite.
In the preparation method of the catalytic cracking catalyst, the auxiliary solid material is preferably at least one selected from macroporous pseudo-boehmite, halloysite, boehmite, a phosphorus-zinc modified low-silicon type molecular sieve, a low-silicon type molecular sieve, magnesium chloride and a high-silicon type molecular sieve.
In the method for preparing the catalytic cracking catalyst, the binder is preferably at least one selected from the group consisting of an aluminum sol, a silica-alumina sol, and an acidified pseudo-boehmite.
In the preparation method of the catalytic cracking catalyst, preferably, the calcination conditions are as follows: the temperature is 600-800 ℃, preferably 650-700 ℃; the time is 0.5 to 1 hour, preferably 30 to 40 min.
The invention also provides a catalytic cracking catalyst prepared by the preparation method, which takes a solid material and an auxiliary solid material as matrix carriers, takes the 'two-cross one-baking' molecular sieve, the 'two-cross two-baking' molecular sieve and chlorinated rare earth salt as active components, and has a specific surface area of more than or equal to 250m 2 (ii)/g; preferably, kaolin and halloysite are used as matrix carriers, alumina sol and acidified pseudo-boehmite are used as binders, and MASY molecular sieves, HASY-6 molecular sieves and rare earth chloride are used as active components; more preferably, kaolin (39wt percent) and halloysite (10wt percent) are used as matrix carriers, alumina sol (6wt percent) and acidified pseudo-boehmite (15wt percent) are used as binders, MASY molecular sieve (19wt percent), HASY-6 molecular sieve (8wt percent) and rare earth chloride (2.5wt percent) are used as active components, the micro-reactivity (800 ℃ multiplied by 17h) of the catalytic cracking catalyst product is more than or equal to 68 percent, and the specific surface area is more than or equal to 250m 2 /g。
The invention is suitable for the FCC catalyst manufacturing process, and solves 'two-way-one-way' at the process sourceNH carried in the baked molecular sieve (the compounding proportion is not more than 40wt percent) 4 + The produced sewage with low ammonia nitrogen (200mg/L) is treated. Through compounding molecular sieve or preparing colloid from microballs, the NH carried by "two-exchange one-baking" molecular sieve 4 + On a basis (no other entrained NH is introduced into the FCC catalyst unit 4 + Exchange liquid of) proportionally introducing NO 3 - The ammonia nitrogen in the sewage of the FCC catalyst manufacturing device is reduced to below 8.0mg/L, and the NOx in the tail gas is less than 150.0mg/m 3 。
The invention is simultaneously suitable for reducing NOx in tail gas and other working conditions of ammonia nitrogen in sewage, and can respectively reduce NOx in tail gas and NH in sewage by adjusting the proportion of nitrate and ammonium salt 4 + The purpose of (1).
The invention has the following beneficial effects:
the invention breaks through the conventional thought of removing ammonia nitrogen in the sewage from the tail end sewage treatment layer surface, changes the preparation process of the FCC catalyst from the source of FCC catalyst preparation, and skillfully utilizes an oxidation-reduction reaction mechanism by introducing nitrate radicals to carry NH carried in a filter cake of the 'two-way-over-one-baking' molecular sieve 4 + Oxidation to N during dry calcination in FCC catalyst manufacture 2 The tail gas is discharged into the atmosphere along with the tail gas of the device, so that the restriction factor of the ammonia nitrogen sewage on a water system for producing the FCC catalyst is fundamentally solved, the yield of the device and the utilization rate of the reuse water are improved, the dosage of rare earth chloride in the process of producing glue by the FCC catalyst is reduced proportionally, the chloride content in the sewage of the device is reduced, the generation amount of sodium chloride salt in a microsphere sewage evaporative crystallization (MVR) unit of a matched sewage treatment device is finally reduced, the tail end sewage treatment cost is reduced, and the economic benefit and the environmental protection benefit are obviously improved.
Drawings
FIG. 1 is a schematic flow diagram of a process for making an FCC catalyst according to the invention.
FIG. 2 shows NH effluents generated during the production of catalysts in example 1 and comparative example 1 3 -comparative plot of the variation of N content.
FIG. 3 shows NH effluents generated during the production of catalysts in example 2 and comparative example 2 3 -comparative plot of the variation of N content.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and experimental methods without specific conditions noted in the following examples are generally performed under conventional conditions.
Analytical test methods used in the examples
1. The chemical composition is as follows: QSY LS1050-2021 is analyzed by fluorescence spectroscopy;
2.NH 3 -N: distillation-neutralization titration method HJ 537-2009.
Specification of raw materials used in the second example
RDY-1 molecular sieve (two-way one-baking molecular sieve, RE) 2 O 3 Content of 1.8%, Na 2 O content 1.2%, crystallinity 79%, cell constant, 24.58X 10 -10 m), MASY molecular sieves (double cross double calcined molecular sieves, RE) 2 O 3 2.0% of Na 2 O content 1.2%, crystallinity, 73%, cell constant, 24.53X 10 -10 m), HASY-6 molecular sieve (two-way one-baking molecular sieve, RE) 2 O 3 Content 6.0%, Na 2 O content 1.1%, crystallinity, 80%, cell constant, 24.64X 10 -10 m), kaolin (ignition 29.5%), alumina sol (containing alumina 11.7%), pseudo-boehmite (ignition 38.6%), hydrochloric acid (32.6%), alkali liquor (31.5%), lanthanum nitrate Rare Earth (RE) 2 O 3 350.0g/L), yttrium rare earth nitrate (RE) 2 O 3 350.0g/L), lanthanum chloride Rare Earth (RE) 2 O 3 260.0g/L), yttrium chloride Rare Earth (RE) 2 O 3 220.0g/L) are all industrial products.
Wherein the RDY-1 molecular sieve (two-way one-baking molecular sieve) and the HASY-6 molecular sieve (two-way one-baking molecular sieve) are subjected to secondary exchange ratio (molecular sieve dry basis: NH) during production 4 + ) Is 1: 0.076, water washing ratio of 1: 5 when stabilized, the filter cake carried about 3.55% NH 4 + I.e. containing NH per kg of molecular sieve dry basis 4 + ：1.973 mol. Note: because the ammonium radical introduced by the primary exchange is removed after the primary exchange is carried out through roasting (790 ℃), the primary exchange operation is not required.
In particular, no other NH carrying gas is introduced in the preparation of the FCC catalyst 4 + When the exchange liquid is used, NH carried in the 'two-way one-baking' molecular sieve is used 4 + For reference, the NO added for preparing molecular sieve or gelatinizing microsphere is calculated 3 - According to FCC catalyst, different series of products are produced by respectively passing yttrium nitrate Y (NO) 3 ) 3 And lanthanum nitrate La (NO) 3 ) 3 Replacing part of the rare earth chloride. Then Y (NO) 3 ) 3 And La (NO) 3 ) 3 The introduction ratio of (A) is as follows:
1. with La 2 O 3 Measuring, theory needs to add La 2 O 3 ：6.43％；
2. With Y 2 O 3 Adding Y theoretically 2 O 3 ：4.46％。
In the actual production process, the reaction efficiency and NO are taken into consideration 3 - Thermal decomposition of La 2 O 3 The actual addition ratio of (B) is 7.0 wt% to 7.5 wt% (corresponding to a molar ratio of ammonium ions to nitrate ions of 5.0: 3.9 to 5.0: 4.1), and Y is 2 O 3 The actual addition ratio of (B) is 5.0 wt% to 5.5 wt% (corresponding to a molar ratio of ammonium ions to nitrate ions of 5.0: 4.0 to 5.0: 4.4).
Example 1
Based on the dry weight of the RDY-1 molecular sieve, introducing yttrium nitrate rare earth according to the molar ratio of ammonium ions to nitrate ions of 5.0 (3.5-4.5)
Mixing an RDY-1 molecular sieve and an MASY molecular sieve according to the mass ratio of 1: 2 mixing, based on the dry weight of the RDY-1 molecular sieve, according to Y 2 O 3 (5.3 wt%, corresponding to a molar ratio of ammonium ions to nitrate ions of 5.0: 4.2) introducing yttrium rare earth nitrate according to the actual compounding ratio of the molecular sieve (during the production of LC-6 product, the compounding ratio of the molecular sieve is MASY (omega): 58.95%, RDY-1 (omega): 25.0%), yttrium chloride (Y is Y) to obtain the product 2 O 3 Meter, ω): 3.70% and SA-5 type selectionSub-sieve (ω): 12.35 percent. ) By nuclear subtraction of added yttrium rare earth nitrate (in terms of Y) 2 O 3 Calculated), because 5.3% of yttrium nitrate rare earth is added into RDY-1, the compounding ratio of yttrium chloride rare earth after nuclear reduction is adjusted as follows: 2.375 percent (different series products, the core is reduced according to the compounding proportion). Adding production water, alumina sol, lanthanum chloride, kaolin, pseudo-boehmite, hydrochloric acid and a compound molecular sieve in sequence according to the specific gelling proportion of the FCC catalytic cracking catalyst, and performing spray forming, drying roasting (roasting temperature is 680 ℃, roasting time is 35min), washing with water, filtering and re-drying processes by using a device to obtain a finished product of the FCC catalytic cracking catalyst, wherein NH in sewage generated by the device 3 -N and contemporaneous tail gas NOx contents are shown in table 1:
table 1: after yttrium rare earth nitrate is introduced in proportion, NH is put in the sewage 3 N and contemporaneous tail gas NOx content
The numbers in table 1 are simplified codes and sequentially represent consecutive data points of one stage, for example, the data corresponding to the numbers 1, 2 and 3 represent data acquisition results within 24 hours (8 hours is one shift).
Comparative example 1
The RDY-1 molecular sieve is compounded in the conventional production without adding rare earth nitrate
Mixing the RDY-1 molecular sieve and the MASY molecular sieve according to the weight ratio of 1: 2, mixing the materials according to the actual compounding ratio requirements of the molecular sieves, wherein the compounding ratio requirements of the molecular sieves are different according to different series of products, and the compounding ratio of the molecular sieves is as follows during the production of LC-6 products: MASY (ω): 58.95%, RDY-1(ω): 25.0% yttrium chloride (as Y) 2 O 3 Meter, ω): 3.70%, SA-5 type molecular sieve (ω): 12.35 percent. Adding production water, alumina sol, lanthanum chloride, kaolin, pseudo-boehmite, hydrochloric acid and a compound molecular sieve in sequence according to the gelling proportion of the FCC catalytic cracking catalyst, and performing spray forming, drying roasting (roasting temperature is 680 ℃, roasting time is 35min), washing, filtering and re-drying processes by using a device to obtain a finished product of the FCC catalytic cracking catalyst, wherein the finished product of the FCC catalytic cracking catalyst is produced by the deviceNH in raw sewage 3 The N content is shown in Table 2: (NOx in tail gas of synchronous device is less than or equal to 10mg/m 3 )
Table 2: NH in sewage of device during conventional production (compounding by using RDY-1 molecular sieve) 3 Content of-N
| Serial number | NH 3 -N,mg/L | Serial number | NH 3 -N,mg/L | Serial number | NH 3 -N,mg/ |
| 1 | 212.1 | 7 | 116.60 | 13 | 50.9 |
| 2 | 151.20 | 8 | 157.7 | 14 | 111.2 |
| 3 | 167.70 | 9 | 170.5 | 15 | 205.4 |
| 4 | 198.10 | 10 | 131.1 | 16 | 129.2 |
| 5 | 177.10 | 11 | 124.5 | 17 | 165.8 |
| 6 | 141.10 | 12 | 164.1 | 18 | 194.1 |
The numbers in table 2 are simplified codes and sequentially represent consecutive data points of one stage, for example, the data corresponding to numbers 1, 2, and 3 represent data acquisition results within 24 hours (8 hours is one shift). Moreover, NOx in tail gas of the synchronous device is less than or equal to 10mg/m 3 No statistics are made.
As is clear from the comparison between tables 1 and 2, in comparative example 1, NH in the wastewater 3 The content of-N is about 200mg/L, in example 1, sewage NH 3 The N content is below 8.0mg/L, and the standard B, NH, of the primary standard in the discharge Standard of pollutants for municipal wastewater treatment plant (GB18918-2002) is met 3 -N whiskers is less than or equal to 8 mg/L;the NOx in tail gas of the synchronous device is integrally controlled to be 150.0mg/m 3 The method meets the execution standard of a newly built enterprise in a general area in the discharge Standard of pollutants for inorganic chemical industry (GB31573-2015)) and NOx is less than or equal to 200mg/m 3 And the tail gas appearance of the device is normal, the industrial application effect of removing ammonia nitrogen in the FCC catalyst 'two-way one-baking' molecular sieve is achieved, and the environmental protection hidden trouble caused by the over standard of tail gas NOx is avoided.
Example 2
Taking the dry basis weight of the HASY-6 molecular sieve as a reference, introducing lanthanum nitrate rare earth according to the molar ratio of ammonium ions to nitrate ions of 5.0 (3.5-4.5)
Mixing HASY-6 molecular sieve and MASY molecular sieve according to the ratio of 1: 2, mixing, based on the dry weight of the HASY-6 molecular sieve, according to La 2 O 3 (7.3 wt%, which is equivalent to the mol ratio of ammonium ions to nitrate ions of 5.0: 4.0) introducing lanthanum nitrate rare earth, and adding production water, aluminum sol and lanthanum chloride (simultaneously nuclear reduction of the added lanthanum nitrate rare earth and La) in sequence according to the gelatinization proportion of the FCC catalytic cracking catalyst 2 O 3 In the production period of the LZR-60C, the compounding proportion of the HASY-6 molecular sieve is 29.24% (w), the input proportion of the compounding molecular sieve is 28% (w) and the input proportion of the lanthanum chloride rare earth is 1.5% (w) in the gelling process, and then the input proportion of the lanthanum chloride is adjusted to be 0.90% (w) in the gelling process after the nucleation. Different series of products, according to the colloid input proportion, concretely carrying out nuclear reduction), kaolin, pseudo-boehmite, hydrochloric acid and a compound molecular sieve are subjected to spray forming, drying roasting (roasting temperature is 680 ℃, roasting time is 35min), washing, filtering and re-drying processes by a device to obtain finished products of the FCC catalytic cracking catalyst, and NH in sewage generated by the device 3 -N and contemporaneous tail gas NOx contents are shown in table 3:
table 3: after lanthanum nitrate rare earth is introduced according to a certain proportion, NH is placed in the sewage 3 -N and contemporaneous tail gas NOx content
| Serial number | NH 3 -N,mg/L | Exhaust gas NOx, mg/m 3 | Serial number | NH 3 -N,mg/L | Exhaust gas NOx, mg/ |
| 1 | 3.1 | 99 | 10 | 5.6 | 125.8 |
| 2 | 2.0 | 125 | 11 | 1.1 | 134.6 |
| 3 | 2.8 | 125.4 | 12 | 1.0 | 110 |
| 4 | 0.7 | 132.5 | 13 | 5.6 | 102 |
| 5 | 2.5 | 115.2 | 14 | 0.4 | 98.9 |
| 6 | 2.0 | 134.8 | 15 | 5.9 | 115.4 |
| 7 | 2.7 | 125.9 | 16 | 3.9 | 123.1 |
| 8 | 3.6 | 115.4 | 17 | 3.9 | 110.5 |
| 9 | 3.1 | 100.2 | 18 | 0.6 | 101.7 |
The numbers in table 3 are simplified codes and sequentially represent consecutive data points of one stage, for example, the data corresponding to the numbers 1, 2 and 3 represent data acquisition results within 24 hours (8 hours is one shift).
Comparative example 2
In the conventional production, HASY-6 molecular sieve is compounded without adding rare earth nitrate
Mixing HASY-6 molecular sieve and MASY molecular sieve according to the ratio of 1: 2 mixing, adding production water, alumina sol, lanthanum chloride, kaolin, pseudo-boehmite, hydrochloric acid and a compound molecular sieve in sequence according to the gelling proportion of the FCC catalytic cracking catalyst, and performing spray forming, drying roasting (roasting temperature is 680 ℃, roasting time is 35min), washing, filtering and re-drying processes by using a device to obtain a finished product of the FCC catalytic cracking catalyst, wherein NH in sewage generated by the device 3 The content of-N is shown in Table 4, and NOx in tail gas of the synchronous device is less than or equal to 10mg/m 3 。
Table 4: NH in sewage of device during conventional production period (compounded by HASY-6 molecular sieve) 3 Content of-N
| Serial number | NH 3 -N,mg/L | Serial number | NH 3 -N,mg/L | Serial number | NH 3 -N,mg/ |
| 1 | 117.0 | 7 | 146.8 | 13 | 159.7 |
| 2 | 99.5 | 8 | 212.0 | 14 | 112.1 |
| 3 | 84.1 | 9 | 124.0 | 15 | 189.1 |
| 4 | 163.4 | 10 | 112.1 | 16 | 131.7 |
| 5 | 186.3 | 11 | 154.1 | 17 | 140.1 |
| 6 | 201.7 | 12 | 173.2 | 18 | 182.1 |
Note: NOx in tail gas of synchronous device is less than or equal to 10mg/m 3 No statistics are made. The numbers in table 4 are simplified codes and sequentially represent consecutive data points of one stage, for example, the data corresponding to numbers 1, 2, and 3 represent data acquisition results within 24 hours (8 hours is one shift).
As can be seen from the comparison of tables 3 and 4, in comparative example 2, NH-sewage 3 The content of-N is about 200mg/L, in example 2, sewage NH 3 The N content is below 8.0mg/L, and the standard B (NH) meeting the primary standard in the discharge Standard of pollutants for municipal wastewater treatment plants (GB18918-2002) 3 -N must be less than or equal to 8 mg/L); the NOx in the tail gas of the synchronous device is integrally controlled at 150.0mg/m 3 The following meets the execution standard of new enterprises in general areas in the discharge Standard of pollutants for inorganic chemical industry (GB31573-2015), NOx is less than or equal to 200mg/m 3 And the tail gas appearance of the device is normal, the industrial application effect of removing ammonia nitrogen in the FCC catalyst 'two-exchange one-baking' molecular sieve is achieved, and the environmental protection hidden trouble caused by the over standard of tail gas NOx is avoided.
As can be seen from the above examples and comparative examples, in the preparation of FCC catalysts, according to different series of catalyst products, the molecular sieve compounding process of the present invention uses "two-way one-baking" molecular sieve as the reference, and the La is respectively used according to the respective 2 O 3 (7.0% to 7.5%) and Y 2 O 3 (5.0% -5.5%) introduction of NO 3 - Then, the ammonia nitrogen in the sewage of the device is integrally controlled to be below 8.0mg/L (the ammonia nitrogen is required to be less than or equal to 8mg/L according to the B standard of the primary standard in the discharge Standard of pollutants for municipal wastewater treatment plant (GB 18918-2002)), and the NOx in the tail gas of the device is integrally controlled to be 150.0mg/m 3 The standard of execution of new enterprises in general areas is that NOx is less than or equal to 200mg/m (GB31573-2015) 3 ) And the tail gas appearance of the device is normal.
In conclusion, the invention thoroughly solves the restriction factor of the 'two-way and one-baking' molecular sieve on a water system in the FCC catalyst manufacturing process, releases the capacity of a main device, reduces the chloride content in the sewage of the device, simultaneously reduces the generation amount of sodium chloride salt of an evaporative crystallization (MVR) unit of a matched sewage treatment device, reduces the sewage treatment cost, achieves the reuse water utilization rate of 100 percent and has obvious upgrading and synergy effects.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (10)
1. A preparation method of a catalytic cracking catalyst is characterized by comprising the following steps:
(1) compounding the 'double-cross once-baking' molecular sieve and the 'double-cross twice-baking' molecular sieve, wherein the adding proportion of the 'double-cross once-baking' molecular sieve is less than or equal to 40 wt%; simultaneously using NH carried in the 'two-way one-baking' molecular sieve 4 + Adding rare earth nitrate as a reference to obtain a compounded mixed molecular sieve;
(2) mixing the mixed molecular sieve, the solid material, the auxiliary solid material, the binder, the chlorinated rare earth salt, the hydrochloric acid solution and the industrial water into jelly;
(3) and spray forming, roasting, washing, filtering and drying the jelly to obtain the catalytic cracking catalyst.
2. The method of claim 1, wherein the "double cross-over single calcined" molecular sieve is selected from at least one of RDY-1 molecular sieve and HASY-6 molecular sieve.
3. The method according to claim 1, wherein the washing water consumption of each treatment step is constant in the preparation process of the 'two-way and one-baking' molecular sieve.
4. The method according to claim 1, wherein in step (1), the "double cross-over single-roasting" molecular sieve carriesNH of the belt 4 + The molar ratio of the nitrate ions to the nitrate ions in the rare earth nitrate is 5.0 (3.5-4.5).
5. The method according to claim 1, wherein the "double-cross double-baked" molecular sieve is at least one selected from the group consisting of MASY molecular sieve and HRSY-1 molecular sieve.
6. The method of claim 1, wherein the solid material is selected from at least one of kaolin and pseudoboehmite.
7. The method of claim 1, wherein the auxiliary solid material is at least one selected from the group consisting of macroporous pseudoboehmite, halloysite, boehmite, phosphozinc-modified low silicon-selective molecular sieve, magnesium chloride, and high silicon-selective molecular sieve.
8. The method of claim 1, wherein the binder is selected from at least one of an aluminum sol, a silica-alumina sol, and an acidified pseudo-boehmite.
9. The production method according to claim 1, wherein in the step (3), the roasting conditions are as follows: the temperature is 600-800 ℃, preferably 650-700 ℃; the time is 0.5 to 1 hour, preferably 30 to 40 min.
10. The catalytic cracking catalyst prepared by the preparation method of any one of claims 1 to 9, which is characterized in that a solid material and an auxiliary solid material are used as matrix carriers, a 'double-cross once-baked' molecular sieve, a 'double-cross twice-baked' molecular sieve and a chlorinated rare earth salt are used as active components, and the specific surface area of the catalytic cracking catalyst is more than or equal to 250m 2 (iv) g; preferably, kaolin and halloysite are used as matrix carriers, alumina sol and acidified pseudo-boehmite are used as binders, and MASY molecular sieves, HASY-6 molecular sieves and rare earth chloride are used as active components.
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| CN103055916A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN103301870A (en) * | 2012-03-09 | 2013-09-18 | 中国石油天然气股份有限公司 | Preparation method for catalytic cracking cocatalyst |
| US20150165428A1 (en) * | 2012-06-01 | 2015-06-18 | Petrochina Company Limited | Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof |
| CN104415779A (en) * | 2013-09-04 | 2015-03-18 | 中国石油天然气股份有限公司 | Molecular sieve based catalyst for catalytic cracking regenerated flue gas denitration and preparation method of molecular sieve based catalyst |
| CN105618107A (en) * | 2014-10-29 | 2016-06-01 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN114433181A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
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