CN115121280B - Catalytic cracking catalyst and preparation method thereof - Google Patents
Catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN115121280B CN115121280B CN202210731040.8A CN202210731040A CN115121280B CN 115121280 B CN115121280 B CN 115121280B CN 202210731040 A CN202210731040 A CN 202210731040A CN 115121280 B CN115121280 B CN 115121280B
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- molecular sieve
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- rare earth
- catalytic cracking
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002808 molecular sieve Substances 0.000 claims abstract description 126
- 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 126
- -1 rare earth nitrate salt Chemical class 0.000 claims abstract description 55
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 28
- 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 16
- 239000011343 solid material Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 238000009718 spray deposition Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000008235 industrial water Substances 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 37
- 229910002651 NO3 Inorganic materials 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 16
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims description 11
- 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 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 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 6
- 229910052621 halloysite Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- JMTIXSZQYHAMLY-UHFFFAOYSA-N [P].[Zn] Chemical compound [P].[Zn] JMTIXSZQYHAMLY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 235000015110 jellies Nutrition 0.000 claims description 3
- 239000008274 jelly Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006479 redox reaction Methods 0.000 abstract description 9
- 239000003292 glue Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 description 47
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 16
- 101100372898 Caenorhabditis elegans vha-5 gene Proteins 0.000 description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 150000002910 rare earth metals Chemical class 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 8
- 239000007788 liquid 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
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 239000004005 microsphere Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 230000001360 synchronised effect Effects 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 239000002351 wastewater Substances 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 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
- 239000007921 spray Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 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
- 239000000571 coke Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012528 membrane 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate 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
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 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
- 239000010457 zeolite Substances 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a catalytic cracking catalyst, which comprises the following steps: (1) Compounding a 'two-cross-one-baking' molecular sieve and a 'two-cross-two-baking' molecular sieve, wherein the adding proportion of the 'two-cross-one-baking' molecular sieve is less than or equal to 40wt%; meanwhile, taking NH 4 + carried in the two-cross-over one-baking molecular sieve as a reference, adding rare earth nitrate salt to obtain a compound mixed molecular sieve; (2) Mixing the mixed molecular sieve, the solid material, the auxiliary solid material, the binder, the rare earth chloride salt, the hydrochloric acid solution and the industrial water to form glue; (3) The finished product of the FCC catalytic cracking catalyst is obtained through spray forming, roasting, washing, filtering and drying, NH 4 + and NO 3 ‑ mainly undergo a series of oxidation-reduction reactions in the roasting process, and finally the finished product is discharged out of the system in the form of nitrogen through a tail gas.
Description
Technical Field
The invention belongs to the field of catalytic cracking catalyst preparation, and particularly relates to a catalytic cracking catalyst which does not produce low ammonia nitrogen sewage in the preparation process and a preparation method thereof.
Background
In the process of manufacturing FCC (catalytic cracking) catalysts, active zeolite (molecular sieve) is a key active component, accounting for about 35% of the catalyst. When the FCC catalyst device does not introduce other exchange liquid carrying NH 4 +, the active component of the molecular sieve (about 10 percent of the catalyst) is not subjected to secondary roasting, NH 4 + carried in a molecular sieve filter cake enters a filtering liquid in the process of preparing and washing the FCC catalyst, so that the sewage of the FCC catalyst device contains a small amount of NH 3 -N (about 200 mg/L).
However, in the existing design scheme, the balance of a water system of a molecular sieve device and an FCC catalyst manufacturing device (a microsphere device) is optimized, and the other components except for the internal recycling of the microsphere device exchange filtering liquid are recycled to the molecular sieve device (used as the filtering machine washing water); the tail gas absorption liquid of the microsphere device is used as the drainage outside the device and is conveyed to the sewage treatment device. As the 'two-cross-one baking' molecular sieve used by the FCC catalyst manufacturing device carries part of NH 4 +, the microsphere device is sent to the sewage treatment device in the factory to lead the ammonia nitrogen in the sewage to be about 200 mg/L. However, as the requirements of society on pollutant emission are increasingly strict, the B standard of the first-level standard in GB18918-2002 requires ammonia nitrogen in sewage to be less than or equal to 8mg/L.
In order to solve the problem of higher ammonia nitrogen content in sewage, the high ammonia nitrogen sewage generated by the molecular sieve device can be matched with a high ammonia nitrogen sewage (the ammonia nitrogen content of the design water inlet is less than or equal to 5000 mg/L) steam removal and recovery treatment facility, ammonia nitrogen cannot be removed because the FCC catalyst manufacturing device is not provided with a low ammonia nitrogen sewage treatment facility, and the sewage treatment device is subjected to concentration by a (DTRO+RO) membrane and MVR evaporation crystallization desalination treatment and then is required to enter the high ammonia nitrogen sewage treatment facility for treatment, so that the sewage treatment cost is increased, the utilization rate of the reuse water of the whole plant is influenced, and meanwhile, the capacity of the device is also improved for a long time.
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 (with an upper limit of about 200 mg/L) sewage generated by an FCC catalyst manufacturing device. In order to solve the problem, the invention breaks the previous thought of removing ammonia nitrogen in sewage from the end sewage treatment level, changes the production process and the formula from the source of FCC catalyst preparation, and generates nitrogen by introducing rare earth nitrate (rare earth nitrate is not generally adopted in the existing preparation process, and the exceeding of tail gas nitrogen oxides caused by nitrate decomposition in the subsequent spray drying and roasting drying processes) and skillfully utilizes an autocatalysis oxidation-reduction reaction mechanism to generate a series of reactions between NH 4 + carried in a 'two-stage one-baking' molecular sieve filter cake and NO 3 -.
To this end, the present invention provides a method for preparing a catalytic cracking catalyst (FCC catalyst), comprising the steps of:
(1) Compounding a 'two-cross-one-baking' molecular sieve and a 'two-cross-two-baking' molecular sieve, wherein the adding proportion of the 'two-cross-one-baking' molecular sieve is less than or equal to 40wt%; meanwhile, taking NH 4 + carried in the two-cross-over one-baking molecular sieve as a reference, adding rare earth nitrate salt to obtain a compound mixed molecular sieve;
(2) Mixing the mixed molecular sieve, the solid material, the auxiliary solid material, the binder, the rare earth chloride 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 + and NO 3 - mainly undergo a series of oxidation-reduction reactions in the roasting process, and finally the FCC catalyst is discharged out of the system through tail gas in the form of nitrogen.
Specifically, in the step (1), the types and the proportions of the two-stage and one-stage baked molecular sieves can be determined according to the compositions of different series of FCC catalyst products, the proportions of the components in each product molecular sieve are different, and rare earth chloride salts may be added after the components are subjected to nuclear subtraction in the compounding process. For example, in the production of LC-6 catalytic cracking catalyst products, the molecular sieves are formulated in the following categories and proportions: MASY (ω): 58.95%, RDY-1 (ω): 25.0%, yttrium nitrate (ω calculated as Y 2O3): 5.5%, yttrium chloride (ω calculated as Y 2O3): 3.70%, SA-5 type selective molecular sieves (ω): 12.35%, yttrium chloride (ω calculated as Y 2O3) was actually added 2.325% after the nuclear subtraction.
Specifically, in the step (1), the amount of NH 4 + carried in the "two-to-one bake" molecular sieve can be calculated, for example, during the production of the "two-to-one bake" molecular sieve, the secondary exchange ratio (molecular sieve dry basis: NH 4 +) is 1:0.076, water wash ratio of 1:5, about 3.55% NH 4 + is carried in the filter cake, i.e. NH 4 + per kg molecular sieve dry basis: 1.973mol. Therefore, in order to easily measure the amount of NH 4 + carried in the "two-to-one-bake" molecular sieve, it is preferable that the amount of washing water in each treatment step in the preparation process of the "two-to-one-bake" molecular sieve is constant to ensure that the content of NH 4 + carried in the filter cake of the "two-to-one-bake" molecular sieve is stable.
The principle process for removing ammonia nitrogen in the molecular sieve by adding rare earth nitrate in the production process of the microsphere device is as follows:
The secondary cross-over primary baked molecular sieve contains residual ammonium sulfate and ammonium oxalate, lanthanum chloride and hydrochloric acid are normally added in the gelling process, rare earth nitrate (such as lanthanum nitrate and yttrium nitrate) is specially added, partial rare earth oxalate and rare earth sulfate precipitate is generated in colloid, and more chloride ions, nitrate ions, ammonium ions and a small amount of oxalate exist in solution, namely ammonium salt in the solution mainly exists in the form of ammonium chloride, ammonium nitrate and ammonium oxalate. The colloid is quickly heated and evaporated to be more than 100 ℃ after entering a spray tower (the temperature of the tail gas is not more than 150 ℃), a small amount of nitrate and ammonium ions react to generate nitrogen gas in a short time before the moisture is evaporated, 5NH 4 ++3NO3 -＝4N2+9H2O+2H+ is generated, and the decomposition reaction of ammonium chloride, ammonium nitrate and ammonium oxalate solid salt is mainly used after the moisture is evaporated, as follows:
Decomposing ammonium chloride into ammonia gas and hydrochloric acid, decomposing ammonium oxalate into ammonia gas, carbon dioxide and water, decomposing NH 4Cl＝NH3 +.sub.L+HCl +.L, decomposing ammonium oxalate into ammonia gas, carbon dioxide and water, decomposing 2 (NH 4)2C2O4+O2＝2NH3↑+4CO2↑+2H2 O +.sub.L)
Ammonium nitrate generates N 2、O2、NH3 and NOx during solution evaporation and high temperature heating.
4NH 4NO3＝4NH3↑+3O2↑+4NO↑+2H2 O (dilute ammonium nitrate solution)
4NH 4NO3＝4NH3↑+O2↑+4NO2↑+2H2 O (concentrated ammonium nitrate solution)
NH 4NO3＝HNO3+NH3 ≡ (ammonium nitrate solid 110 ℃ -185 ℃)
4HNO3＝4NO2↑+O2↑+2H2O
The residence time of the materials in the spray tower is short, the above reaction is insufficient, the residence time of the materials is long (about 20-30 minutes) after the materials enter a roasting furnace (600 ℃) and the temperature can reach more than 400 ℃, and besides the decomposition reaction, the ammonium nitrate which is not reacted completely can also take place as follows:
NH3NO3＝N2O↑+2H2O(185℃～200℃)
4NH 3NO3＝3N2↑+2NO2↑+8H2 O (400 ℃ above)
N 2、CO2、O2、NH3、NO2、NO、N2 O and the like exist in the gas generated in the process. Nitrogen oxides exist mainly in the form of NO and NO 2 under high temperature conditions. The SNCR reaction temperature is not reached in the roasting furnace barrel at 400-500 ℃, but practice proves that oxidation-reduction reaction is truly carried out, most NH 3 is eliminated, and the SCR reaction is carried out, wherein the reason probably is that the FCC catalyst contains about 50% of Al 2O3, 3-4% of rare earth oxide, 0.5-0.7% of Fe 2O3 and rich molecular sieve surface area and pore channel structure, so that part of the FCC catalyst has the function of the SCR catalyst, and therefore, the SCR reaction can be carried out at high temperature, and the oxidation-reduction reaction of ammonia and nitrogen oxides is carried out to generate harmless nitrogen, and the reaction is mainly as follows: 4NH 3+4NO+O2＝4N2+6H2 O and 4NH 3+2NO2+O2＝3N2+6H2 O are named self-catalyzed oxidation-reduction reactions because they are distinguished from SCR reactions and combine with their own features as catalysts.
In all the above processes, there are 3 reaction formulas involved in the elimination reaction of ammonium/ammonia and nitrogen oxides, which are:
5NH 4 ++3NO3 -＝4N2+9H2O+2H+ (molar ratio 5:3)
4NH 3+4NO+O2＝4N2+6H2 O (molar ratio 1:1)
4NH 3+2NO2+O2＝3N2+6H2 O (molar ratio 2:1)
Therefore, the theoretical feeding ratio of NO 3 - to NH 4 + should be 1:1 to 1:2, the molar ratio of the specific NO 3 - to the NH 4 + is found to be proper when the molar ratio is 5.0 (3.5-4.5).
When the nitrate amount is insufficient, ammonium radicals carried by the two-stage-one-baking molecular sieve cannot be completely eliminated; when the nitrate amount is excessive, the NOx in the tail gas of the device can be in an out-of-standard (the NOx of new enterprises in the general area is less than or equal to 200mg/m 3) risk.
On the basis of ensuring proper adding proportion of rare earth nitrate, analysis and test post personnel need to check instruments and meters regularly, so that various influencing factors are eliminated, error rate is reduced, analysis and test reliability is improved, and an FCC catalyst manufacturing device accurately judges whether oxidation-reduction reaction is complete according to the analysis result of chemical composition of the mixed molecular sieve; and determining whether to supplement rare earth nitrate or adjust the compound proportion of the molecular sieve according to the analysis result.
The above needs to be explained, in order to ensure that the content of NH 4 + carried in the filter cake of the second-cross first-baking molecular sieve is stable, the exchange ratio of the second exchange tank, the exchange ratio of the second exchange filter and the washing water quantity of the second exchange filter must be constant during the production of the second-cross first-baking molecular sieve, so as to ensure that the content of NH 4 + carried in the filter cake of the second-cross first-baking molecular sieve is stable, and the rare earth nitrate added in proportion can react in sufficient quantity during the manufacturing process of the FCC catalyst, so that on one hand, the influence of NH 4 + in sewage on the sewage delivery index (NH 3 -N is less than or equal to 8 mg/L) is eliminated, and on the other hand, the risk of exceeding the standard (NOx of new enterprises in general areas is less than or equal to 200mg/m 3) in the tail gas of the device is avoided.
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 specific nucleus is reduced in the gelling process according to the type and the quality of the rare earth nitrate salt added in the molecular sieve of the second cross-first baking.
Specifically, in the preparation method provided by the invention, other exchange liquid carrying NH 4 + is not introduced, water washing is adopted in the step (3), the water washing amount is increased, the quality requirement can be met, and the ammonium-containing exchange liquid is not required to be introduced.
Specifically, in the process of preparing the catalyst, the catalyst is prevented from being produced by adopting a single 'two-cross-one-baking' molecular sieve, when the catalyst is compounded with the 'two-cross-two-baking' molecular sieve, the proportion of the 'two-cross-one-baking' molecular sieve is not more than 40%, otherwise, even if the influence of NH 4 + on a sewage delivery index (NH 3 -N is less than or equal to 8 mg/L) can be eliminated through oxidation-reduction reaction, the risk that NOx in tail gas of the device exceeds standard (NOx in new enterprises in general areas is less than or equal to 200mg/m 3) exists, and the appearance of the tail gas is abnormal, so that the environment protection risk exists.
The preparation method of the catalytic cracking catalyst is characterized in that the 'two-cross-one baking' molecular sieve is preferably at least one selected from RDY-1 molecular sieve and 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 'two-cross-one-baking' molecular sieve.
The preparation method of the catalytic cracking catalyst of the invention is characterized in that the molar ratio of NH 4 + carried in the 'two-stage-one-baking' molecular sieve to nitrate ions in the rare earth nitrate salt is preferably 5.0 (3.5-4.5).
The preparation method of the catalytic cracking catalyst of the invention is characterized in that the 'two-cross-two-baking' molecular sieve is preferably at least one selected from MASY molecular sieves and HRSY-1 molecular sieves.
The preparation method of the catalytic cracking catalyst is characterized in that the solid material is preferably at least one selected from kaolin and pseudo-boehmite.
The preparation method of the catalytic cracking catalyst of the invention is characterized in that the auxiliary solid material is preferably selected from at least one of macroporous pseudo-boehmite, halloysite, boehmite, phosphorus-zinc modified low-silicon type selective molecular sieve, magnesium chloride and high-silicon type selective molecular sieve.
The preparation method of the catalytic cracking catalyst provided by the invention is characterized in that the binder is preferably at least one selected from aluminum sol, silica alumina sol and acidified pseudo-boehmite.
The preparation method of the catalytic cracking catalyst of the invention is characterized in that the roasting conditions are as follows: the temperature is 600-800 ℃, preferably 650-700 ℃; the time is 0.5 to 1h, preferably 30to 40min.
The invention also provides a catalytic cracking catalyst prepared by the preparation method, which takes solid materials and auxiliary solid materials as matrix carriers, takes a 'two-cross-one-baking' molecular sieve, a 'two-cross-two-baking' molecular sieve and rare earth chloride salt as active components, and has the specific surface area more than or equal to 250m 2/g; preferably, kaolin and halloysite are used as matrix carriers, alumina sol and acidified pseudo-boehmite are used as binders, and MASY molecular sieve, HASY-6 molecular sieve and rare earth chloride are used as active components; more preferably, kaolin (39 wt%) halloysite (10 wt%) is used as a matrix carrier, alumina sol (6 wt%) and acidified pseudo-boehmite (15 wt%) are used as binders, MASY molecular sieve (19 wt%) HASY-6 molecular sieve (8 wt%) and rare earth chloride (2.5 wt%) are used as active components, the micro-reaction activity (800 ℃ multiplied by 17 h) of the catalytic cracking catalyst product is more than or equal to 68%, and the specific surface area is more than or equal to 250m 2/g.
The invention is suitable for the manufacturing process of FCC catalyst, and solves the problem of low ammonia nitrogen (200 mg/L) sewage treatment generated by NH 4 + carried in a 'two-cross-one-baking' molecular sieve (the compound proportion is not more than 40 wt%) at the process source. When the molecular sieve is compounded or microballoon is glued, the NH 4 + carried in the 'two-cross-one-baking' molecular sieve is taken as a reference (when the FCC catalyst device does not introduce other exchange liquid carrying NH 4 +), NO 3 - is proportionally introduced, ammonia nitrogen in the sewage of the FCC catalyst manufacturing device is reduced to below 8.0mg/L, and meanwhile, NOx in the tail gas is less than 150.0mg/m 3.
The invention is simultaneously suitable for reducing other working conditions of NOx in the tail gas and ammonia nitrogen in the sewage, and the purposes of reducing the NOx in the tail gas and NH 4 + in the sewage can be respectively achieved by adjusting the proportion of nitrate and ammonium salt.
The beneficial effects of the invention are as follows:
The invention breaks through the previous thought of removing ammonia nitrogen in sewage from the end sewage treatment layer, changes the preparation process of the FCC catalyst from the source of FCC catalyst manufacture, skillfully utilizes the oxidation-reduction reaction mechanism by introducing nitrate, oxidizes NH 4 + carried in a 'two-phase-one-baking' molecular sieve filter cake into N 2 in the process of FCC catalyst manufacture drying roasting, and discharges the NH 4 + into the atmosphere along with device tail gas, thereby fundamentally solving the restriction factor of ammonia nitrogen sewage to an FCC catalyst manufacture water system, improving the device productivity and the reuse water utilization rate, simultaneously reducing the adding amount of rare earth chloride in the glue manufacturing process of the FCC catalyst according to the proportion, reducing the chloride content in the device sewage, finally reducing the production amount of sodium chloride in microsphere sewage evaporation crystallization (MVR) units of a matched sewage treatment device, not only reducing the end sewage treatment cost, but also remarkably improving the economic benefit and environmental protection benefit.
Drawings
FIG. 1 is a schematic flow diagram of a process for manufacturing an FCC catalyst according to the invention.
FIG. 2 is a graph comparing the NH 3 -N content of the wastewater during the catalyst manufacturing process of example 1 and comparative example 1.
FIG. 3 is a graph comparing the NH 3 -N content of the wastewater during the catalyst manufacturing process of example 2 and comparative example 2.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
Analytical test method for use in the examples
1. Chemical composition: fluorescence spectroscopy analysis QSYLS 1050-2021;
NH 3 -N: distillation-neutralization titration HJ 537-2009.
(II) specification of raw materials used in examples
RDY-1 molecular sieve (double-cross-baked molecular sieve, RE 2O3 content 1.8%, na 2 O content 1.2%, crystallinity 79%, unit cell constant 24.58X10 -10 m), MASY molecular sieve (double-cross-baked molecular sieve, RE 2O3 content 2.0%, na 2 O content 1.2%, crystallinity 73%, unit cell constant 24.53X 10 -10 m), HASY-6 molecular sieve (double-cross-baked molecular sieve, RE 2O3 content 6.0%, na 2 O content 1.1%, crystallinity 80%, unit cell constant 24.64X 10 -10 m), kaolin (29.5% burn), alumina sol (11.7% containing alumina), pseudoboehmite (38.6% burn), hydrochloric acid (32.6%), alkali liquor (31.5%), lanthanum nitrate rare earth (RE 2O3 350.0.0 g/L), yttrium nitrate rare earth (RE 2O3 350.0.0 g/L), lanthanum chloride rare earth (2O3 260.0.0 g/L), yttrium chloride rare earth (2O3 g/L), and yttrium chloride Rare Earth (RE) are industrial products.
Wherein the RDY-1 molecular sieve (two-cross-over one-baking molecular sieve) and HASY-6 molecular sieve (two-cross-over one-baking molecular sieve) have a secondary exchange ratio (molecular sieve dry basis: NH 4 +) of 1:0.076, water wash ratio of 1:5, about 3.55% NH 4 + is carried in the filter cake, i.e. NH 4 + per kg molecular sieve dry basis: 1.973mol. And (3) injection: the ammonium radical introduced by the primary exchange is removed by roasting (790 ℃) after the primary exchange, and the primary exchange operation is not required.
Specifically, when NO other exchange liquid carrying NH 4 + is introduced in the preparation of the FCC catalyst, NO 3 - required to be added in the preparation of the molecular sieve or the gelling of the microspheres is calculated based on NH 4 + carried in the "two-stage-one-bake" molecular sieve, and different series of products are manufactured according to the FCC catalyst by yttrium nitrate Y (NO 3)3 and lanthanum nitrate La (NO 3)3 replaces part of rare earth chloride, then Y (NO 3)3 and La (the ratio of introduction of NO 3)3:
1. Based on La 2O3, la 2O3 is added in theory: 6.43%;
2. Based on Y 2O3, Y 2O3 is added in theory: 4.46%.
In the actual production process, the actual adding proportion of La 2O3 is 7.0-7.5 wt% (equivalent to the molar ratio of ammonium ions to nitrate ions of 5.0:3.9-5.0:4.1) and the actual adding proportion of Y 2O3 is 5.0-5.5 wt% (equivalent to the molar ratio of ammonium ions to nitrate ions of 5.0:4.0-5.0:4.4) in consideration of the reaction efficiency and the thermal decomposition of NO 3 -.
Example 1
Introducing yttrium nitrate rare earth according to the molar ratio of ammonium ions to nitrate ions of 5.0 (3.5-4.5) based on dry basis of RDY-1 molecular sieve
RDY-1 molecular sieve and MASY molecular sieve are mixed according to the mass ratio of 1:2, introducing yttrium nitrate rare earth according to Y 2O3 (5.3 wt%, equivalent to the mole ratio of ammonium ion to nitrate ion of 5.0:4.2) based on dry basis of RDY-1 molecular sieve, and 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 as follows: MASY (omega): 58.95), RDY-1 (omega): 25.0%, yttrium chloride (calculated as Y 2O3), omega): 3.70% and SA-5 type selective molecular sieve (omega): 12.35%) according to the actual compounding ratio of the molecular sieve, wherein the added yttrium nitrate rare earth (calculated as Y 2O3) is subjected to nuclear subtraction, and the compounding ratio of the yttrium chloride rare earth after nuclear subtraction is adjusted as 5.3% of yttrium nitrate rare earth is added to RDY-1: 2.375% (different series of products, specifically reduced according to the compounding proportion). According to the specific glue proportion of the FCC catalytic cracking catalyst, the production water, the alumina sol, the lanthanum chloride, the kaolin, the pseudo-boehmite, the hydrochloric acid and the compound molecular sieve are sequentially added, and after the processes of spray forming, drying and roasting (the roasting temperature is 680 ℃, the roasting time is 35 min), washing with water, filtering and re-drying, the FCC catalytic cracking catalyst finished product is obtained, wherein the NH 3 -N and the contemporaneous tail gas NOx content in the sewage generated by the device are shown in the table 1:
Table 1: NH 3 -N and synchronous tail gas NOx content in sewage of device after yttrium nitrate rare earth is introduced according to proportion
The serial numbers in table 1 are simplified code numbers, and represent consecutive data points of one stage in sequence, for example, the data corresponding to serial numbers 1,2, and 3 represent the data acquisition result within 24 hours (8 hours is a shift).
Comparative example 1
The conventional production uses RDY-1 molecular sieve for compounding, and rare earth nitrate is not added
RDY-1 molecular sieve and MASY molecular sieve are mixed according to the following ratio of 1:2, according to the actual compound proportion requirements of the molecular sieve, according to different series products, the compound proportion requirements of the molecular sieve are different, and during the production of the LC-6 product, the compound proportion of the molecular sieve is as follows: MASY (ω): 58.95%, RDY-1 (ω): 25.0%, yttrium chloride (ω calculated as Y 2O3): 3.70%, SA-5 type selective molecular sieves (ω): 12.35%. According to the gelling proportion of the FCC catalytic cracking catalyst, the production water, the alumina sol, the lanthanum chloride, the kaolin, the pseudo-boehmite, the hydrochloric acid and the compound molecular sieve are sequentially added, and after the processes of spray forming, drying and roasting (the roasting temperature is 680 ℃, the roasting time is 35 min), washing, filtering and re-drying, the finished product of the FCC catalytic cracking catalyst is obtained, and the NH 3 -N content in sewage generated by the device is shown in the table 2: (NOx in the tail gas of the synchronous device is less than or equal to 10mg/m 3)
Table 2: NH 3 -N content in plant wastewater during conventional production (compounding with RDY-1 molecular sieves)
| Sequence number | NH3-N,mg/L | Sequence number | NH3-N,mg/L | Sequence number | NH3-N,mg/L |
| 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 serial numbers in table 2 are simplified code numbers, and represent consecutive data points of one stage in turn, for example, the data corresponding to serial numbers 1,2, and 3 represent the data acquisition result within 24 hours (8 hours is a shift). In addition, the NOx in the tail gas of the synchronous device is less than or equal to 10mg/m 3, and no statistics is made.
As can be seen from the comparison of the above tables 1 and 2, in comparative example 1, the NH 3 -N content of the sewage is about 200mg/L, in example 1, the NH 3 -N content of the sewage is below 8.0mg/L, the B standard of the first-level standard in the pollutant emission Standard of urban sewage treatment plant (GB 18918-2002) is satisfied, and the NH 3 -N is less than or equal to 8mg/L; the integral control of NOx in the tail gas of the synchronous device is below 150.0mg/m 3, which accords with the execution standard of new enterprises in general areas in emission Standard of pollutants for inorganic chemistry industry (GB 31573-2015), the NOx is less than or equal to 200mg/m 3, and the appearance of the tail gas of the device is normal, thereby achieving the industrial application effect of removing ammonia nitrogen in the FCC catalyst 'double-alternating-first-baking' molecular sieve, and simultaneously avoiding the environmental protection hidden trouble caused by the exceeding of the NOx in the tail gas.
Example 2
Introducing lanthanum nitrate rare earth according to the molar ratio of ammonium ion to nitrate ion of 5.0 (3.5-4.5) based on HASY-6 molecular sieve dry basis
HASY-6 molecular sieves and MASY molecular sieves were combined in a 1:2, introducing lanthanum rare earth nitrate according to La 2O3 (7.3 wt%, equivalent to the mol ratio of ammonium ions to nitrate ions of 5.0:4.0) and according to the gel forming proportion of FCC catalytic cracking catalyst, sequentially adding production water, alumina sol and lanthanum chloride (simultaneously, the added lanthanum rare earth nitrate is subjected to nuclear subtraction), wherein the compounding proportion of HASY-6 molecular sieve is 29.24% (w) in the process of producing LZR-60C according to La 2O3, the compounding proportion of the compound molecular sieve is 28% (w) in the gel forming process, the adding proportion of lanthanum rare earth chloride is 1.5% (w), and after the nuclear subtraction, the adding proportion of lanthanum chloride in the gel forming process is adjusted to be 0.90% (w), according to the gel forming proportion, the concrete subtraction), kaolin, pseudo-boehmite, hydrochloric acid and the compound molecular sieve are subjected to spray forming, drying roasting (the temperature 680 ℃ for 35 min), washing filtering and re-drying processes, and obtaining the finished product, wherein the finished product is produced by the FCC catalytic cracking catalyst, and the content of the tail gas is 34-34N and the same as that shown in the end gas in the table of the final product is shown in the following stage of 34-34N-3:
Table 3: NH 3 -N and synchronous tail gas NOx content in sewage of device after lanthanum nitrate rare earth is introduced in proportion
| Sequence number | NH3-N,mg/L | NOx in exhaust gas, mg/m 3 | Sequence number | NH3-N,mg/L | NOx in exhaust gas, mg/m 3 |
| 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 serial numbers in table 3 are simplified code numbers, and represent consecutive data points of one stage in sequence, for example, the data corresponding to serial numbers 1,2, and 3 represent the data acquisition result within 24 hours (8 hours is a shift).
Comparative example 2
The conventional production is carried out by compounding HASY-6 molecular sieves without adding rare earth nitrate
HASY-6 molecular sieves and MASY molecular sieves were combined in a 1:2, according to the glue proportion of the FCC catalytic cracking catalyst, sequentially adding production water, alumina sol, lanthanum chloride, kaolin, pseudo-boehmite, hydrochloric acid and a compound molecular sieve, and carrying out spray forming, drying and roasting (the roasting temperature is 680 ℃, the roasting time is 35 min), washing, filtering and re-drying processes on the device to obtain a finished product of the FCC catalytic cracking catalyst, wherein the NH 3 -N content in sewage generated by the device is shown in a table 4, and the NOx in tail gas of the same-period device is less than or equal to 10mg/m 3.
Table 4: NH 3 -N content in plant wastewater during conventional production (compounding by HASY-6 molecular sieves)
| Sequence number | NH3-N,mg/L | Sequence number | NH3-N,mg/L | Sequence number | NH3-N,mg/L |
| 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 that: the NOx in the tail gas of the synchronous device is less than or equal to 10mg/m 3, and no statistics is made. The serial numbers in table 4 are simplified code numbers, and represent consecutive data points of one stage in sequence, for example, the data corresponding to serial numbers 1,2, and 3 represent the data acquisition result within 24 hours (8 hours is a shift).
As can be seen from the comparison of the above tables 3 and 4, in comparative example 2, the NH 3 -N content of the sewage is about 200mg/L, in example 2, the NH 3 -N content of the sewage is below 8.0mg/L, and the sewage meets the B standard (NH 3 -N must be less than or equal to 8 mg/L) of the first-level standard in the pollutant emission standard of urban sewage treatment plant (GB 18918-2002); the integral control of NOx in the tail gas of the synchronous device is below 150.0mg/m 3, which accords with the execution standard of new enterprises in general areas in emission Standard of pollutants for inorganic chemistry industry (GB 31573-2015), the NOx is less than or equal to 200mg/m 3, and the appearance of the tail gas of the device is normal, thereby achieving the industrial application effect of removing ammonia nitrogen in the FCC catalyst 'double-alternating-first-baking' molecular sieve, and simultaneously avoiding the environmental protection hidden trouble caused by the exceeding of the NOx in the tail gas.
According to the embodiment and the comparative example, in the manufacturing process of the FCC catalyst, according to different series of catalyst products, in the process of compounding the molecular sieve, according to the standard of a 'two-cross one-baking' molecular sieve, after La 2O3 (7.0% -7.5%) and Y 2O3 (5.0% -5.5%) are respectively introduced into NO 3 -, ammonia nitrogen in the sewage of the device is integrally controlled to be below 8.0mg/L (B standard of the first-level standard in pollutant emission standard of municipal sewage treatment plants (GB 18918-2002), ammonia nitrogen is required to be below 8 mg/L), NOx in the tail gas of the same device is integrally controlled to be below 150.0mg/m 3 (newly built enterprises in the general areas in emission standard of inorganic chemical industry pollutants (GB 31573-2015)), NOx is below 200mg/m 3), and the appearance of the tail gas of the device is normal.
In conclusion, the invention thoroughly solves the restriction factor of the 'two-cross-one-baking' molecular sieve on a water system in the manufacturing process of the FCC catalyst, releases the productivity of a main device, reduces the chloride content in sewage of the device, simultaneously reduces the production amount of sodium chloride salt of an evaporation crystallization (MVR) unit of a matched sewage treatment device, reduces the sewage treatment cost, ensures that the utilization rate of reuse water reaches 100%, and has remarkable upgrading and synergy results.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (6)
1. A method for preparing a catalytic cracking catalyst, comprising the steps of:
(1) Compounding a 'two-cross-one-baking' molecular sieve and a 'two-cross-two-baking' molecular sieve, wherein the adding proportion of the 'two-cross-one-baking' molecular sieve is less than or equal to 40wt%; meanwhile, taking NH 4+ carried in the two-cross-over one-baking molecular sieve as a reference, adding rare earth nitrate salt to obtain a compound mixed molecular sieve;
(2) Mixing the molecular sieve, solid material, auxiliary solid material, binder, rare earth chloride salt, hydrochloric acid solution and industrial process
Mixing industrial water into jelly;
(3) The jelly is subjected to spray forming, roasting, washing, filtering and drying to obtain the catalytic cracking catalyst;
the solid material is selected from kaolin and pseudo-boehmite;
the auxiliary solid material is selected from at least one of macroporous pseudo-boehmite, halloysite, boehmite, phosphorus-zinc modified low-silicon shape selective molecular sieve, magnesium chloride and high-silicon shape selective molecular sieve;
The binder is at least one selected from aluminum sol, silica alumina sol and acidified pseudo-boehmite;
In the step (3), the roasting conditions are as follows: the temperature is 600-800 ℃; the time is 0.5 to 1 hour.
2. The method according to claim 1, wherein the amount of washing water used in each treatment step is constant during the preparation of the "two-stage one-bake" molecular sieve.
3. The method according to claim 1, wherein in the step (1), the molar ratio of NH 4+ carried in the "two-stage one-bake" molecular sieve to nitrate ions in the rare earth nitrate salt is 5.0 (3.5 to 4.5).
4. The method according to claim 1, wherein in the step (3), the condition of the firing is: the temperature is 650-700 ℃; the time is 30-40 min.
5. A catalytic cracking catalyst prepared by the process according to any one of claims 1 to 4, wherein the catalyst is solid
The body material and the auxiliary solid material are used as matrix carriers, a 'two-cross-one-baking' molecular sieve, a 'two-cross-two-baking' molecular sieve and rare earth chloride salt are used as active components, and the specific surface area of the catalytic cracking catalyst is more than or equal to 250m 2/g; the solid material is selected from kaolin and pseudo-boehmite; the auxiliary solid material is selected from at least one of macroporous pseudo-boehmite, halloysite, boehmite, phosphorus-zinc modified low-silicon shape selective molecular sieve, magnesium chloride and high-silicon shape selective molecular sieve.
6. The catalytic cracking catalyst of claim 5, wherein kaolin and halloysite are used as matrix supports and alumina sol and acidified pseudo-boehmite are used as binders.
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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 of catalytic cracking cocatalyst |
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