CN107876083B - Preparation method of spherical catalyst for preparing aromatic hydrocarbon from methanol with non-uniformly distributed active components - Google Patents
Preparation method of spherical catalyst for preparing aromatic hydrocarbon from methanol with non-uniformly distributed active components Download PDFInfo
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- CN107876083B CN107876083B CN201711086935.6A CN201711086935A CN107876083B CN 107876083 B CN107876083 B CN 107876083B CN 201711086935 A CN201711086935 A CN 201711086935A CN 107876083 B CN107876083 B CN 107876083B
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- catalyst
- methanol
- active component
- active components
- aromatic hydrocarbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005470 impregnation Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 238000011068 loading method Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 239000011265 semifinished product Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 210000002969 egg yolk Anatomy 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 18
- 239000002184 metal Substances 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 8
- 239000012798 spherical particle Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005899 aromatization reaction Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 5
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229940044658 gallium nitrate Drugs 0.000 description 3
- 238000009828 non-uniform distribution Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 235000013345 egg yolk Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- 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
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (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 spherical catalyst for preparing aromatic hydrocarbon from methanol with non-uniformly distributed active components, belonging to the technical field of deep processing of methanol. The preparation method of the invention adopts a method combining a one-step impregnation method and multi-step post-treatment to realize the control of the distribution condition of the metal active components on the catalyst, and finally the yolk-shaped spherical catalyst is prepared. The catalyst prepared by the method has higher activity, higher aromatic selectivity and lower CO in the reaction process of preparing aromatic hydrocarbon from methanolxAnd (4) selectivity.
Description
Technical Field
The invention belongs to the technical field of methanol deep processing, and particularly relates to a preparation method of a spherical catalyst for preparing aromatic hydrocarbon from methanol with non-uniformly distributed active components.
Background
Aromatic hydrocarbons (benzene, toluene and xylene) are very important basic raw materials for organic chemical industry, and are widely used for producing high-end materials such as polyester, fiber, rubber and the like. For years, the self-sufficiency rate of aromatic hydrocarbon in China is low, and the foreign dependence of domestic paraxylene reaches 55% in 2015 according to statistics. Under the influence of the energy structure of 'rich coal, lean oil and less gas' in China, the technology for preparing aromatic hydrocarbon from coal-based methanol in China is rapidly developed, the capacity of preparing aromatic hydrocarbon from methanol in China is totally 150 ten thousand tons by 2015, the capacity of establishing and planning is 120 ten thousand tons, and the specific technology mainly comprises a fixed bed technology, a fluidized bed technology and a moving bed technology in the research and development stage.
At present, methanol-to-aromatic catalysts applied at home and abroad are all M with uniformly distributed metal active componentsiDual-function catalyst (M) of/ZSM-5 molecular sieveiRepresenting one or more metal active components), because methanol molecules are extremely active under the process condition of preparing aromatic hydrocarbon by methanol, the metal active components on the catalyst can promote the cracking side reaction of the methanol molecules to generate hydrogen and carbon oxides while providing aromatization reaction activity. In additionIn addition, in the reaction process of preparing the aromatic hydrocarbon from the methanol, the reaction for directly generating the aromatic hydrocarbon mainly comprises two main types of reactions, one is aromatization of the low-carbon alkane, the other is aromatization of the low-carbon alkane, and the effect of the metal active component is mainly embodied in the aromatization process of the low-carbon alkane.
The 'egg yolk type' catalyst refers to that the content of active components in the center of catalyst particles is larger than that of the active components in the outer surfaces of the catalyst particles, and the specific definition refers to catalyst carrier preparation and application technology authored by the zhhon law. If the catalyst for preparing the aromatic hydrocarbon from the methanol is prepared into the yolk-shaped catalyst, when the methanol contacts the catalyst, a reaction process mainly comprising aromatization of olefin is firstly carried out on a ZSM-5 molecular sieve catalyst with low metal content, meanwhile, the proportion of side reaction of the methanol cracking is reduced, and then a reaction process mainly comprising aromatization of low-carbon alkane is mainly carried out in the central area of catalyst particles with high metal content. Generally speaking, the methanol-to-aromatics catalyst with the metal active component distributed in the yolk shape has higher reaction activity, aromatics selectivity and lower byproduct selectivity.
CN103480359B discloses a preparation method of a low-carbon alkane dehydrogenation catalyst with non-uniformly distributed active components, which is characterized in that the active components are pre-loaded on a pore-enlarging agent of the catalyst, and then the catalyst is prepared by extrusion molding, so that part or all of the active components are distributed on the surface of a part of pores of the catalyst in a relatively concentrated manner, and finally the low-carbon alkane dehydrogenation catalyst with non-uniformly distributed active components is obtained.
CN102950003B discloses a preparation method of a hydrogenation catalyst with non-uniformly distributed active components, which is characterized in that an organic solvent is added as a competitive adsorbent in the active component loading process, and then the distribution of the active components is controlled by heat treatment under a closed condition.
CN100418623C discloses a preparation method of a thin shell type hydrogen oxidation catalyst, which is characterized in that an alkali metal hydroxide solution is used to pretreat a catalyst carrier, then an active component is loaded by an impregnation method, the distribution of the active component is controlled by using the precipitation reaction of the active component and the metal hydroxide, and finally the thin shell type catalyst is prepared.
CN105597756A discloses a preparation method of a copper-based core-shell catalyst for preparing methyl formate by methanol dehydrogenation, which is characterized in that a thermal decomposition method is adopted to prepare copper oxide nano core particles, and then a mesoporous silica shell layer is wrapped.
CN104399477B discloses a preparation method of a Fischer-Tropsch synthesis catalyst with non-uniform distribution of active components, which is characterized in that the distribution of the active components is controlled by modulating the saturation degree of an impregnation solution, the impregnation pressure and the carrier temperature in the impregnation process of the active components.
CN105435860A discloses a method for preparing a catalyst with non-uniform distribution of a cocatalyst, which is characterized in that in the presence of crystal nuclei, water, a carrier matrix substance, a binder and a saturated solution containing the cocatalyst are continuously mixed by a rolling ball method, the adding rate of the saturated solution containing the cocatalyst is controlled to obtain a carrier precursor, the carrier precursor is dried and roasted, and then the carrier precursor is contacted with a solution containing a main catalyst, and then the carrier precursor is dried and roasted.
CN101612583B discloses a preparation method of a saturated alkane dehydrogenation catalyst with non-uniform distribution of active components, which is characterized in that impregnation solutions containing different metal components are sequentially contacted with a carrier, and the loading of the active components is realized by a step impregnation method. The Pt distribution is controlled by adjusting the dosage of hydrochloric acid in the Pt impregnation liquid, and other active components in the catalyst are uniformly distributed.
For the preparation method of the catalyst with the active components distributed non-uniformly disclosed by the prior patent, the problems that special equipment needs to be matched, the controllability of the distribution condition of the active components is poor, or the active components and competitive adsorbents need to be highly matched and the like exist, so that the preparation method of the catalyst is complex and the implementability is poor.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a spherical catalyst for preparing aromatic hydrocarbon from methanol with non-uniformly distributed active components, which does not need special equipment, has highly controllable distribution condition of the active components on a carrier, large selection space of the active components and a post-treatment reagent and strong mutual matching property.
The invention relates to a preparation method of a spherical catalyst for preparing aromatic hydrocarbon from methanol with non-uniformly distributed active components, which modifies a catalyst carrier by adopting a one-step impregnation and multi-step post-treatment method, and finally prepares M with a metal active component in a yolk-shaped distributionithe/ZSM-5 molecular sieve bifunctional catalyst specifically comprises the following steps:
(1) taking spherical HZSM-5 molecular sieve particles, and roasting to obtain a catalyst carrier;
(2) weighing a certain amount of one or more of chloroplatinic acid solution, silver soluble salt, gallium soluble salt, zinc soluble salt, nickel soluble salt and lanthanum soluble salt, and dissolving in water to obtain active component impregnation liquid;
(3) adding the active component impregnation liquid prepared in the step (2) into the catalyst carrier obtained in the step (1), impregnating for 1-15 h at normal temperature in an equal volume mode, and then drying for 5-15 h to obtain a semi-finished product catalyst;
(4) weighing one or more of a certain amount of citric acid, oxalic acid, glacial acetic acid, tartaric acid, phosphoric acid, ethanol and glycol, dissolving in water, wherein the total solute content is 0.05-0.50 g/ml, adding the solution into the semi-finished catalyst obtained in the step (3), soaking for 1-15 h in the same volume, and drying;
(5) repeating the step (4), wherein the accumulated times are 1-10 times, and roasting the obtained sample to obtain the spherical catalyst for preparing the aromatic hydrocarbon from the methanol;
wherein the catalyst is M with active components distributed in a yolk shapeiThe total load of an active component oxide in the catalyst is 1-10 wt%, preferably 1-8 wt%.
In the above technical solution, the active component is preferably one or more of silver, gallium, zinc, nickel, and lanthanum.
In the above technical solution, the solute of the impregnation solution in step (4) is preferably one or more of citric acid, oxalic acid, glacial acetic acid, tartaric acid and ethanol.
Compared with the prior art, the preparation method of the spherical catalyst for preparing aromatic hydrocarbon from methanol with the unevenly distributed active component adopts a one-step impregnation and multi-step post-treatment method to modify the catalyst carrier, and finally prepares the Mi/ZSM-5 molecular sieve dual-function catalyst with the metal active component distributed in a yolk shape.
The specific implementation mode is as follows:
the invention is further illustrated by the following comparative examples and examples, without thereby restricting the content of the invention.
The invention relates to a methanol-to-aromatics spherical catalyst with non-uniformly distributed active components, which is prepared by the following preparation method and performance measurement method, and the specific operation is as follows:
(1) taking 100g of spherical HZSM-5 molecular sieve particles, wherein the sphere diameter is 1.9-2.1 mm, roasting at 550 ℃ for 4h to obtain a catalyst carrier ZT, and testing the water absorption rate of the catalyst carrier ZT to be sigma and the unit of the catalyst carrier ZT to be ml/g;
(2) weighing a certain amount of one or more of chloroplatinic acid solution, silver soluble salt, gallium soluble salt, zinc soluble salt, nickel soluble salt and lanthanum soluble salt, dissolving in water, and diluting the water solution to constant volume of VZTObtaining an active component impregnation liquid, wherein VZT＝σ×100g；
(3) Adding the impregnation liquid prepared in the step (2) into the ZT obtained in the step (1), impregnating for 1-15 h at normal temperature, and then drying for 5-15 h at 120 ℃ to obtain a semi-finished catalyst;
(4) weighing a certain amount of one or more of citric acid, oxalic acid, glacial acetic acid, tartaric acid, phosphoric acid, ethanol and ethylene glycol, dissolving in water, and fixing the volume of the water solution to VZTObtaining an impregnation liquid with the total solute content of 0.05-0.50 g/ml, then adding the impregnation liquid into the semi-finished product catalyst obtained in the step (3), impregnating for 1-15 h, and then drying for 5-15 h at 120 ℃;
(5) repeating the step (4) for 1-10 times, and roasting the obtained sample at 550 ℃ for 4 hours to obtain a final catalyst, wherein the label is CA, and the total load of the active component oxide is 1-10 wt%;
the specific operation of the catalyst structure and performance measurement method is as follows:
(1) cutting the sample CA spherical particles into a semispherical shape, and detecting the distribution condition of the active component along the section by SEM-EDX;
(2) the reaction performance of the sample CA for preparing the aromatic hydrocarbon by the methanol is inspected on a 30ml micro reaction evaluation device, the reaction temperature is 480 ℃, the reaction pressure is 2MPa, and the mass space velocity of the methanol is 3.0h-1And respectively collecting a gaseous product, a liquid oil sample and a water sample, and analyzing the composition of the gaseous product, the aromatic hydrocarbon content of the oil sample and the methanol content of the water sample.
Comparative example 1
100g of catalyst carrier ZT was taken and tested to have a water absorption of 0.6 ml/g. Weighing a certain amount of silver nitrate, zinc nitrate and lanthanum chloride, dissolving in water, fixing the volume of an aqueous solution to 60ml to obtain an active component impregnation solution, adding the impregnation solution into 100g of a carrier ZT, impregnating for 6h at normal temperature, drying for 8h at 120 ℃, and finally roasting for 4h at 550 ℃ to obtain a final catalyst sample CA-0. Wherein Ag is2O loading of 1 wt%, ZnO loading of 4%, La2O3The loading is 1 wt%, and the total loading of the active component oxides is 6 wt%. The sample CA-0 spherical particles are cut into a hemispherical shape, the distribution condition of metal components on the cross section of the hemispherical particles is detected by SEM-EDX, the detection result is shown in table 1, wherein r is the distance between the detection point on the cross section of the particles and the center point of the cross section.
Example 1
100g of catalyst carrier ZT was taken and tested to have a water absorption of 0.6 ml/g. Weighing a certain amount of silver nitrate, zinc nitrate and lanthanum chloride, dissolving in water, fixing the volume of the water solution to 60ml to obtain an active component impregnation liquid, adding the impregnation liquid into 100g of a carrier ZT, impregnating for 6h at normal temperature, and drying for 8h at 120 ℃ to obtain a semi-finished product catalyst. Weighing 9g of citric acid, dissolving in water, adding water solution to a constant volume of 60ml, adding the solution into the semi-finished catalyst, soaking for 6h, drying at 120 deg.C for 8h, and calcining at 550 deg.C4h, catalyst sample CA-1 was obtained. Wherein Ag is2O loading of 1 wt%, ZnO loading of 4%, La2O3The loading is 1 wt%, and the total loading of the active component oxides is 6 wt%. The spherical particles of the sample CA-1 are cut into a semispherical shape, and the distribution condition of the metal components on the section of the semispherical particles is detected by SEM-EDX, and the detection results are shown in Table 1.
Example 2
100g of catalyst carrier ZT was taken and tested to have a water absorption of 0.6 ml/g. Weighing a certain amount of silver nitrate, zinc nitrate and lanthanum chloride, dissolving in water, fixing the volume of the water solution to 60ml to obtain an active component impregnation liquid, adding the impregnation liquid into 100g of a carrier ZT, impregnating for 6h at normal temperature, and drying for 8h at 120 ℃ to obtain a semi-finished product catalyst. 9g of citric acid are weighed out, dissolved in water and the aqueous solution is brought to a volume of 60ml, this solution is then added to the semifinished catalyst, impregnated for 6h and then dried for 8h at 120 ℃. The dipping process of the citric acid solution is repeated for 2 times, and finally, the catalyst sample CA-2 is obtained by roasting at 550 ℃ for 4 hours. Wherein Ag is2O loading of 1 wt%, ZnO loading of 4%, La2O3The loading is 1 wt%, and the total loading of the active component oxides is 6 wt%. The spherical particles of the sample CA-2 are cut into a semispherical shape, and the distribution condition of the metal components on the section of the semispherical particles is detected by SEM-EDX, and the detection results are shown in Table 1.
Example 3
100g of catalyst carrier ZT was taken and tested to have a water absorption of 0.6 ml/g. Weighing a certain amount of silver nitrate, zinc nitrate and lanthanum chloride, dissolving in water, fixing the volume of the water solution to 60ml to obtain an active component impregnation liquid, adding the impregnation liquid into 100g of a carrier ZT, impregnating for 6h at normal temperature, and drying for 8h at 120 ℃ to obtain a semi-finished product catalyst. 9g of citric acid are weighed out, dissolved in water and the aqueous solution is brought to a volume of 60ml, this solution is then added to the semifinished catalyst, impregnated for 6h and then dried for 8h at 120 ℃. The dipping process of the citric acid solution is repeated for 6 times, and finally, the catalyst sample CA-3 is obtained by roasting at 550 ℃ for 4 hours. Wherein Ag is2O loading of 1 wt%, ZnO loading of 4%, La2O3The loading amount is 1 wt%,the total loading of active component oxide was 6 wt%. The sample CA-3 spherical particles are cut into a semispherical shape, and the distribution condition of the metal components on the section of the semispherical particles is detected by SEM-EDX, and the detection results are shown in Table 1.
Example 4
100g of catalyst carrier ZT was taken and tested to have a water absorption of 0.6 ml/g. Weighing a certain amount of silver nitrate, zinc nitrate and lanthanum chloride, dissolving in water, fixing the volume of the water solution to 60ml to obtain an active component impregnation liquid, adding the impregnation liquid into 100g of a carrier ZT, impregnating for 6h at normal temperature, and drying for 8h at 120 ℃ to obtain a semi-finished product catalyst. 9g of citric acid are weighed out, dissolved in water and the aqueous solution is brought to a volume of 60ml, this solution is then added to the semifinished catalyst, impregnated for 6h and then dried for 8h at 120 ℃. The impregnation process with the citric acid solution was repeated 7 times, and finally calcined at 550 ℃ for 4 hours to obtain catalyst sample CA-4. Wherein Ag is2O loading of 1 wt%, ZnO loading of 4%, La2O3The loading is 1 wt%, and the total loading of the active component oxides is 6 wt%. The sample CA-4 spherical particles are cut into a semispherical shape, and the distribution condition of the metal components on the section of the semispherical particles is detected by SEM-EDX, and the detection results are shown in Table 1.
Example 5
100g of catalyst carrier ZT was taken and tested to have a water absorption of 0.6 ml/g. Weighing a certain amount of gallium nitrate, dissolving the gallium nitrate in water, fixing the volume of an aqueous solution to 60ml to obtain an active component impregnation liquid, adding the impregnation liquid into 100g of carrier ZT, impregnating for 1h at normal temperature, and drying for 5h at 120 ℃ to obtain a semi-finished product catalyst. Oxalic acid and glacial acetic acid are weighed, 1.5g of each are dissolved in water, the volume of the aqueous solution is fixed to be 60ml, then the solution is added into the semi-finished catalyst, the semi-finished catalyst is soaked for 1h, and then the semi-finished catalyst is dried for 5h at 120 ℃. The oxalic acid and glacial acetic acid solution impregnation process is repeated for 2 times, and finally the catalyst sample CA-5 is obtained by roasting at 550 ℃ for 4 h. Wherein Ga2O3The loading is 1 wt%, and the total loading of the active component oxides is 1 wt%. The sample CA-5 spherical particles are cut into a semispherical shape, and the distribution condition of the metal components on the section of the semispherical particles is detected by SEM-EDX, and the detection results are shown in Table 1.
Example 6
100g of catalyst carrier ZT was taken and tested to have a water absorption of 0.6 ml/g. Weighing a certain amount of gallium nitrate and nickel sulfate, dissolving in water, fixing the volume of the water solution to 60ml to obtain an active component impregnation liquid, adding the impregnation liquid into 100g of carrier ZT, impregnating for 12h at normal temperature, and drying for 12h at 120 ℃ to obtain a semi-finished catalyst. 10g of tartaric acid and 8g of ethanol are weighed and dissolved in water, the volume of the aqueous solution is fixed to be 60ml, then the solution is added into the semi-finished catalyst, the semi-finished catalyst is soaked for 12 hours, and then the semi-finished catalyst is dried for 12 hours at 120 ℃. The tartaric acid and ethanol solution impregnation process was repeated 3 times, and finally calcined at 550 ℃ for 4h to obtain catalyst sample CA-6. Wherein Ga2O3The loading amount is 4 wt%, the NiO loading amount is 4 wt%, and the total loading amount of the active component oxide is 8 wt%. The sample CA-6 spherical particles are cut into a semispherical shape, and the distribution condition of the metal components on the section of the semispherical particles is detected by SEM-EDX, and the detection results are shown in Table 1.
TABLE 1 statistical table of distribution of active components of catalyst
Catalyst evaluation experiment
Weighing 10g of catalyst sample, filling the catalyst sample on a 30ml micro reaction evaluation device, and inspecting the reaction performance of the sample in the preparation of aromatic hydrocarbon from methanol, wherein the reaction temperature is 480 ℃, the reaction pressure is 2MPa, and the mass space velocity of the methanol is 3.0h-1. And when the feeding time reaches 24 hours, respectively collecting a gaseous product, a liquid oil sample and a water sample, and analyzing the composition of the gaseous product, the content of aromatic hydrocarbon in the oil sample and the content of methanol in the water sample. The results of the catalyst performance evaluation are shown in Table 2.
TABLE 2 statistics table of reaction performance of catalyst methanol to aromatics
Claims (4)
1. A preparation method of a spherical catalyst for preparing aromatic hydrocarbon from methanol with non-uniformly distributed active components is characterized by comprising the following steps:
(1) taking spherical HZSM-5 molecular sieve particles, and roasting to obtain a catalyst carrier;
(2) weighing a certain amount of one or more of chloroplatinic acid solution, silver soluble salt, gallium soluble salt, zinc soluble salt, nickel soluble salt and lanthanum soluble salt, and dissolving in water to obtain active component impregnation liquid;
(3) adding the active component impregnation liquid prepared in the step (2) into the catalyst carrier obtained in the step (1), impregnating for 1-15 h at normal temperature in an equal volume mode, and then drying for 5-15 h to obtain a semi-finished product catalyst;
(4) weighing one or more of a certain amount of citric acid, oxalic acid, glacial acetic acid, tartaric acid, phosphoric acid, ethanol and glycol, dissolving in water to obtain an impregnation solution with the total solute content of 0.05-0.50 g/ml, adding the impregnation solution into the semi-finished catalyst obtained in the step (3), impregnating for 1-15 h in equal volume, and drying;
(5) repeating the step (4), wherein the accumulated times are 1-10 times, and roasting the obtained sample to obtain the spherical catalyst for preparing the aromatic hydrocarbon from the methanol;
wherein the catalyst is M with active components distributed in a yolk shapeiThe catalyst has a double function of a/ZSM-5 molecular sieve, and the total load of an active component oxide in the catalyst is 1-10 wt%.
2. The method of claim 1, wherein the active component is one or more of silver, gallium, zinc, nickel, and lanthanum.
3. The method according to claim 1, wherein the solute of the impregnation solution in the step (4) is one or more of citric acid, oxalic acid, glacial acetic acid, tartaric acid and ethanol.
4. The method according to claim 1, wherein the total loading of the active component oxide is 1 to 8 wt%.
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| US4835131A (en) * | 1986-08-29 | 1989-05-30 | Shell Oil Company | Catalyst and process for the preparation of the catalyst |
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