CN112094167A - Preparation method and application of catalyst for producing durene by isomerizing mixed durene - Google Patents
Preparation method and application of catalyst for producing durene by isomerizing mixed durene Download PDFInfo
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- CN112094167A CN112094167A CN202011068678.5A CN202011068678A CN112094167A CN 112094167 A CN112094167 A CN 112094167A CN 202011068678 A CN202011068678 A CN 202011068678A CN 112094167 A CN112094167 A CN 112094167A
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- durene
- catalyst
- mixed
- molecular sieve
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- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 title claims abstract description 838
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims abstract description 118
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000002808 molecular sieve Substances 0.000 claims abstract description 54
- 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 54
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 35
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- 238000010306 acid treatment Methods 0.000 claims abstract description 5
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 229940037003 alum Drugs 0.000 claims description 20
- 230000008014 freezing Effects 0.000 claims description 19
- 238000007710 freezing Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 8
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 description 18
- 230000008025 crystallization Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 238000002791 soaking Methods 0.000 description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 4
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WGSMMQXDEYYZTB-UHFFFAOYSA-N 1,2,4,5-tetramethylbenzene Chemical compound CC1=CC(C)=C(C)C=C1C.CC1=CC(C)=C(C)C=C1C WGSMMQXDEYYZTB-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2737—Catalytic processes with 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
- 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
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- 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
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- B01J35/617—
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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
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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
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
Abstract
The invention provides a preparation method and application of a catalyst for producing durene by isomerizing mixed durene, which comprises the steps of carrying out alkali treatment, ammonium exchange, extrusion molding, acid treatment, dipping of a metal oxide solution on an H beta molecular sieve, an MCM-49 molecular sieve, a Y molecular sieve or the mixed molecular sieve of H beta and MCM-49, drying and roasting to obtain the catalyst for producing durene by isomerizing the mixed durene; the catalyst is used for mixed tetramethylbenzene isomerization to produce durene, and the reaction product obtained by the reaction contains the following components in percentage by weight: 18-25% of durene, 30-50% of durene and 2-10% of durene, the selectivity reaches more than 91%, and the yield reaches more than 41%, thus being suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of durene catalyst preparation, in particular to a preparation method and application of a catalyst for producing durene by isomerizing mixed durene.
Background
Durene (1, 2,4, 5-tetramethylbenzene) is commonly called durene, is an important organic chemical raw material and is mainly used for producing pyromellitic dianhydride (named as pyromellitic anhydride or PMDA), and the PMDA is an important raw material for high-quality plasticizers, curing agents and powder coating flatting agents. PMDA is also an important raw material for synthesizing polyimide, and the polyimide is widely applied to the aviation industry, the atomic energy industry and the electromechanical industry. With the increasing market usage of polyimide, durene is used as the main raw material for synthesizing polyimide, and the demand is increasing.
Many technologists at home and abroad explore a series of durene preparation processes and develop different process routes. The industrial production method comprises C10Rectifying heavy aromatic hydrocarbon fraction, freezing crystallization and distributed crystallization purification; c10Distilling heavy aromatic hydrocarbon fraction, and performing adsorption separation; alkylating the pseudocumene methanol; isomerizing and disproportionating trimethylbenzene; chloromethylating trimethyl benzene; isomerizing tetramethylbenzene; methanol to durene, and the like.
Because the raw material cost of the pseudocumene is high, the source is limited, the activity, the selectivity and the stability of the used catalyst are not ideal, the equipment is easy to corrode, and the environmental pollution is caused.
C solely by physical separation process10The yield of durene which is a byproduct of the heavy aromatics comprehensive utilization technology is difficult to improve under the influence of heavy aromatics treatment capacity, durene content and aromatic sales conditions. At present, C is by-produced in China10Heavy aromatics have not been fully utilized. Durene isC10The important source of the economic benefit of the comprehensive utilization technology of heavy aromatics. Therefore, C is fully utilized10The development of catalysts for isomerizing and increasing the yield of durene is urgent.
The catalyst used for the isomerization of tetramethylbenzene at present takes mordenite or ultrastable zeolite as an active component, and the reaction form is gas-solid or liquid-solid reaction. However, the catalyst has disadvantages such as low activity and poor stability.
In conclusion, durene has wide application and high added value, and is an important fine chemical raw material. Therefore, the development of the catalyst for preparing durene by isomerizing mixed durene has potential and huge social and economic benefits; but also can meet the requirements of the aviation industry of China on novel engineering materials, and has extremely important strategic significance on the economy and national defense construction of China.
Disclosure of Invention
The invention aims to disclose a preparation method and application of a catalyst for producing durene by isomerizing mixed durene so as to overcome the defects in the prior art.
The technical scheme of the invention is as follows:
a preparation method of a catalyst for producing durene by isomerizing mixed durene comprises the following steps:
carrying out alkali treatment, ammonium exchange, extrusion molding, acid treatment, dipping of a metal oxide solution on an H beta molecular sieve, an MCM-49 molecular sieve, a Y molecular sieve or a mixed molecular sieve of H beta and MCM-49, drying and roasting to obtain a catalyst for producing durene by isomerizing mixed durene; the mass ratio of the H beta molecular sieve to the MCM-49 molecular sieve in the H beta and MCM-49 mixed molecular sieve is 1: 0.5 to 3; the alkali treatment time is 0-200min, and the dipping time of the metal oxide solution is 0-24 h; the mixed tetramethylbenzene includes durene, durene and durene.
The specific surface area of the molecular sieve is more than or equal to 550m2The grain size is 100nm-5 μm.
The alkali treatment is to perform alkali treatment on the molecular sieve at 30-90 ℃, the alkali solution is one or two of a sodium hydroxide solution and a potassium hydroxide solution, and the concentration of the alkali solution is 0.05-0.6 mol/L.
The ammonium exchange is to carry out ion exchange on the molecular sieve carrier subjected to alkali treatment for 10-500min at 30-90 ℃ by using ammonium nitrate, ammonium sulfate, ammonium chloride or ammonium carbonate, wherein the concentration of an ammonium solution is 0.05-0.6 mol/L.
The acid treatment is to soak the molecular sieve carrier which is subjected to ion exchange and extrusion molding in an acid solution at 50-90 ℃ for 0-5h, wherein the acid solution is one or more of sulfuric acid, hydrochloric acid, hydrofluoric acid, acetic acid, citric acid and oxalic acid, and the concentration of the acid solution is 0.1-2.0 mol/L.
The weight percentage of the metal oxide in the catalyst is as follows: 0-5% of nickel or palladium oxide, 0-4% of cerium oxide, 0-2.5% of vanadium oxide, 0-3% of copper oxide, 0-1% of magnesium oxide and 0-4% of potassium oxide; the metal oxide solution impregnation is to dissolve one or more of nickel or palladium soluble salt, cerium soluble salt, alum soluble salt, copper soluble salt, magnesium soluble salt and potassium soluble salt by water, the amount of the water is determined according to the water absorption rate of the carrier, then the carrier is added, and the impregnation is carried out at 30-90 ℃.
The drying temperature is 90-140 ℃, and the drying time is 6-20 h; the roasting temperature is 400-700 ℃, and the roasting time is 3-12 h.
The mixed tetramethylbenzene comprises the following components in percentage by weight:
0 to 10 percent of durene
30 to 50 percent of durene
2-10% of durene.
The durene, the partial durene and the continuous durene in the mixed durene account for not less than 50 percent by weight of the total substance.
The invention also provides an application of the catalyst obtained by the preparation method of the catalyst for producing durene by isomerizing mixed durene, which comprises the following steps: heating mixed tetramethylbenzene solution containing durene, durene and durene to 280-370 deg.C, feeding into fixed bed reactor filled with catalyst, reaction pressure is 1-3MPa, and reaction space velocity is 0.5-1.0h-1(ii) a Then the reaction product is fed intoThe rectifying device is used for further improving the concentration of durene and then entering a freezing crystallization device for separating and collecting durene and durene;
the space velocity of the reaction is the amount of reactants treated per unit volume of catalyst per unit time under the specified conditions, and is expressed in m3/（m3Catalyst h) to h)-1。
The invention has the beneficial effects that: the invention adopts a fixed bed reactor filled with the catalyst, and under the condition that the durene content is not more than 10 percent, the weight percentage of each component in the reaction product obtained by the reaction is as follows: 18-25% of durene, 30-50% of durene and 2-10% of durene, the selectivity reaches more than 91%, and the yield reaches more than 41%. The catalyst which is suitable for the isomerization pore channel structure, the acid center and the acid strength is obtained through modification treatment, and the catalyst has higher selectivity; the internal structure and acidity of the catalyst obtained by modifying the H beta and MCM-49 mixed molecular sieve can better meet the requirement of macromolecular isomerization, and the catalyst conversion rate is improved while higher selectivity is kept; the selectivity and yield of durene obtained from low-concentration durene in the raw materials are effectively improved; the catalyst can be obtained under the condition of alkali treatment or no alkali treatment, and the catalyst can be obtained under the condition of a small amount of supported metal oxide or no supported metal oxide, so that the selectivity and the yield can achieve similar effects, and the production cost is effectively saved; the reaction effect is still good after the catalyst is regenerated, and the method is suitable for industrial production. In addition, the invention makes full use of C10The content of the heavy aromatics is higher than that of the durene and the durene, and the durene is increased by isomerization; solves the problem of C in industrial production10The difficulty that the durene content in heavy aromatic hydrocarbon is low and cannot be utilized; on the premise of not changing the existing technological device for freezing and separating durene, the yield of durene is increased through isomerization, the utilization rate of byproducts is improved, and the cost for device modification of production enterprises is reduced.
Detailed Description
Example 1
The catalyst for producing durene by isomerizing mixed durene comprises the following components in percentage by weight:
1% of nickel oxide
0.5% of cerium oxide
Oxide of alum 0.3%
0.2% of magnesium oxide
1% of oxide of potassium
Balance of carrier
The carrier is an H beta molecular sieve with the specific surface area of 550m2G, grains (200 nm);
the preparation method comprises the following steps:
soaking the H beta molecular sieve in 0.1mol/L sodium hydroxide solution at 80 deg.C for 120min, exchanging with 0.5mol/L ammonium nitrate solution for 120min, and extruding to form strips. The extruded carrier is treated with 0.2mol/L hydrofluoric acid solution at 40 deg.c for 4 hr. Dissolving nickel soluble salt, cerium soluble salt, alum soluble salt, magnesium soluble salt and potassium soluble salt with water, determining the amount of water according to the water absorption of the carrier, then adding the carrier, dipping for 24h at 80 ℃, drying for 12h at 100 ℃, and roasting for 6h at 550 ℃, thus obtaining the catalyst for producing durene by isomerization of mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 280 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1.2 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 0.8 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
5.1 percent of durene
45.6 percent of durene
7.2 percent of the durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 20.1%, the weight percentage content of durene is 32.2%, and the weight percentage content of durene is 3.8%. The selectivity reaches 89.3 percent, and the yield reaches 28.4 percent.
Example 2
The catalyst for producing durene by isomerizing mixed durene comprises the following components in percentage by weight:
1.5% of nickel oxide
1% of cerium oxide
0.8 percent of alum oxide
0.7 percent of potassium oxide
Balance of carrier
The carrier is a Y molecular sieve with a specific surface area of 620 m2G, grains (500 nm);
the preparation method comprises the following steps:
soaking the Y molecular sieve in 0.05mol/L sodium hydroxide solution at 80 deg.C for 120min, exchanging with 0.6mol/L ammonium nitrate solution for 120min, and extruding to form. The extruded carrier is treated with 0.2mol/L hydrofluoric acid solution at 40 deg.c for 4 hr. Dissolving nickel soluble salt, cerium soluble salt, alum soluble salt and potassium soluble salt with water, determining the amount of water according to the water absorption of the carrier, then adding the carrier, dipping for 24h at 80 ℃, drying for 12h at 100 ℃, and roasting for 6h at 550 ℃, thus obtaining the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 350 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 1 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
7.8 percent of durene
48.1 percent of durene
8.6 percent of durene.
In the reaction product obtained by the reaction in the fixed bed reactor, the weight percentage content of durene is 24.6%, the weight percentage content of durene is 34.9%, and the weight percentage content of durene is 3.2%. The selectivity reaches 90.3 percent, and the yield reaches 29.6 percent.
Example 3
The catalyst for producing durene by isomerizing mixed durene comprises the following components in percentage by weight:
2% of palladium oxide
0.5% of cerium oxide
0.1 percent of alum oxide
0.5% of magnesium oxide
0.6 percent of oxide of potassium
Balance of carrier
The carrier is MCM-49 molecular sieve with specific surface area of 590 m2G, grains (300 nm);
the preparation method comprises the following steps:
soaking the MCM-49 molecular sieve in 0.05mol/L sodium hydroxide solution at 80 ℃ for 120min, exchanging with 0.5mol/L ammonium nitrate solution for 120min, and extruding and forming. Treating the carrier formed by extruding with 0.1mol/L hydrofluoric acid solution at 40 ℃ for 3 h. Dissolving palladium soluble salt, cerium soluble salt, alum soluble salt, magnesium soluble salt and potassium soluble salt with water, determining the amount of water according to the water absorption of the carrier, adding the carrier, soaking at 80 ℃ for 24h, drying at 100 ℃ for 12h, and roasting at 550 ℃ for 8h to obtain the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 370 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 0.8 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
5.5 percent of durene
45.8 percent of durene
7.5 percent of the durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 21.1%, the weight percentage content of durene is 32.2%, and the weight percentage content of durene is 4%. The selectivity reaches 91.2 percent, and the yield is 29.9 percent.
Example 4
The catalyst for producing durene by isomerizing mixed durene comprises the following components in percentage by weight:
1.5% of nickel oxide
0.5% of cerium oxide
Oxide of alum 0.3%
0.5% of potassium oxide
Balance of carrier
The carrier is H beta and MCM-49 mixed molecular sieve (mechanically mixed, the mass ratio is 1: 0.5);
the preparation method comprises the following steps:
soaking the mixed molecular sieve of the H beta and the MCM-49 in a sodium hydroxide solution with the concentration of 0.1mol/L for 120min at the temperature of 80 ℃, exchanging for 120min by an ammonium nitrate solution with the concentration of 0.5mol/L, and extruding and forming. The extruded carrier is treated with 0.2mol/L hydrofluoric acid solution at 40 deg.c for 4 hr. Dissolving nickel soluble salt, cerium soluble salt, alum soluble salt and potassium soluble salt with water, determining the amount of water according to the water absorption of a carrier, adding the carrier, soaking at 80 ℃ for 24 hours, drying at 100 ℃ for 12 hours, and roasting at 550 ℃ for 8 hours to obtain the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 330 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 1 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
6.6 percent of durene
45.6 percent of durene
7.5 percent of the durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 23.1%, the weight percentage content of durene is 31.2%, and the weight percentage content of durene is 3.8%. The selectivity reaches 91.2 percent, and the yield reaches 31.1 percent.
Example 5
The catalyst for producing durene by isomerizing mixed durene comprises the following components in percentage by weight:
1.5% of nickel oxide
0.5% of cerium oxide
Oxide of alum 0.3%
0.5% of potassium oxide
Balance of carrier
The carrier is H beta and MCM-49 mixed molecular sieve (mechanically mixed, the mass ratio is 1: 1);
the preparation method comprises the following steps:
exchanging the mixed molecular sieve of the H beta and the MCM-49 for 120min by using ammonium nitrate solution with the concentration of 0.4mol/L, and extruding and forming. The extruded carrier is treated with 0.2mol/L hydrofluoric acid solution at 40 deg.c for 4 hr. Dissolving nickel soluble salt, cerium soluble salt, alum soluble salt and potassium soluble salt with water, determining the amount of water according to the water absorption of a carrier, adding the carrier, soaking at 80 ℃ for 24 hours, drying at 100 ℃ for 12 hours, and roasting at 550 ℃ for 8 hours to obtain the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 350 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 1 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
0.9 percent of durene
48.6 percent of durene
9.1 percent of durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 24.7%, the weight percentage content of durene is 30.2%, and the weight percentage content of durene is 1.5%. The selectivity reaches 91.5 percent, and the yield reaches 41.2 percent.
Example 6
The catalyst for producing durene by isomerizing mixed durene comprises the following components in percentage by weight:
1.5% of nickel oxide
0.5% of cerium oxide
Oxide of alum 0.3%
0.5% of potassium oxide
Balance of carrier
The carrier is H beta and MCM-49 mixed molecular sieve (mechanically mixed, the mass ratio is 1: 2);
the preparation method comprises the following steps:
soaking the mixed molecular sieve of the H beta and the MCM-49 in a sodium hydroxide solution with the concentration of 0.1mol/L for 120min at the temperature of 80 ℃, exchanging for 120min by an ammonium nitrate solution with the concentration of 0.4mol/L, and extruding and forming. The extruded carrier is treated with 0.2mol/L hydrofluoric acid solution at 40 deg.c for 4 hr. Dissolving nickel soluble salt, cerium soluble salt, alum soluble salt and potassium soluble salt with water, determining the amount of water according to the water absorption of a carrier, adding the carrier, soaking at 80 ℃ for 24 hours, drying at 100 ℃ for 12 hours, and roasting at 550 ℃ for 8 hours to obtain the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 350 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 1 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
7.1 percent of durene
46.9 percent of durene
7.4 percent of the durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 24.7%, the weight percentage content of durene is 30.5%, and the weight percentage content of durene is 4.2%. The selectivity reaches 89.8 percent, and the yield reaches 32.4 percent.
Example 7
The catalyst for producing durene by isomerizing mixed durene comprises the following components in percentage by weight:
1.5% of nickel oxide
0.5% of cerium oxide
Oxide of alum 0.3%
0.5% of potassium oxide
Balance of carrier
The carrier is H beta and MCM-49 mixed molecular sieve (mechanically mixed, the mass ratio is 1: 2);
the preparation method comprises the following steps:
exchanging the mixed molecular sieve of the H beta and the MCM-49 for 120min by using ammonium nitrate solution with the concentration of 0.4mol/L, and extruding and forming. The extruded carrier is treated with 0.2mol/L hydrofluoric acid solution at 40 deg.c for 4 hr. Dissolving nickel soluble salt, cerium soluble salt, alum soluble salt and potassium soluble salt with water, determining the amount of water according to the water absorption of a carrier, adding the carrier, soaking at 80 ℃ for 24 hours, drying at 100 ℃ for 12 hours, and roasting at 550 ℃ for 8 hours to obtain the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 350 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 1 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
6.4 percent of durene
48.3 percent of durene
6.8 percent of continuous tetramethylbenzene.
In the reaction product obtained by the reaction in the fixed bed reactor, the weight percentage content of durene is 23.6%, the weight percentage content of durene is 32.6%, and the weight percentage content of durene is 3.2%. The selectivity reaches 89.1 percent, and the yield reaches 31.2 percent.
Example 8
The catalyst for producing durene by isomerizing mixed tetramethylbenzene is a mixed molecular sieve of H beta and MCM-49 (mechanically mixed with the mass ratio of 1: 1);
the preparation method comprises the following steps:
exchanging the mixed molecular sieve of the H beta and the MCM-49 for 120min by using ammonium nitrate solution with the concentration of 0.5mol/L, and extruding and forming. The extruded carrier is treated with 0.4mol/L hydrofluoric acid solution at 40 deg.c for 4 hr. Drying at 100 deg.C for 12h, and calcining at 550 deg.C for 8h to obtain the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 350 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 1 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
0.3 percent of durene
49.7 percent of durene
9.7 percent of durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 24.8%, the weight percentage content of durene is 31.4%, and the weight percentage content of durene is 1.3%. The selectivity reaches 91.8 percent, and the yield reaches 41.3 percent.
Example 9
The catalyst for producing durene by isomerizing mixed tetramethylbenzene is a mixed molecular sieve of H beta and MCM-49 (mechanically mixed with the mass ratio of 1: 1);
the preparation method comprises the following steps:
exchanging the mixed molecular sieve of H beta and MCM-49 with ammonium sulfate solution with the concentration of 0.5mol/L for 120min, extruding and forming. The extruded carrier is treated with 0.4mol/L citric acid solution at 40 deg.C for 4 h. Drying at 100 deg.C for 12h, and calcining at 550 deg.C for 8h to obtain the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 350 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the isomerization catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 1 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
6.6 percent of durene
45.6 percent of durene
7.5 percent of the durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 23.1%, the weight percentage content of durene is 31.2%, and the weight percentage content of durene is 3.8%. The selectivity reaches 91.2 percent, and the yield reaches 31.1 percent.
Example 10
The catalyst for producing durene by isomerizing mixed tetramethylbenzene comprises a carrier of H beta and MCM-49 mixed molecular sieve (mechanically mixed, the mass ratio is 1: 1);
the preparation method comprises the following steps:
exchanging the mixed molecular sieve of the H beta and the MCM-49 with an ammonium chloride solution with the concentration of 0.5mol/L for 120min, extruding and forming. The extruded carrier is treated with oxalic acid solution with concentration of 0.4mol/L at 40 deg.c for 4 hr. Drying at 100 deg.C for 12h, and calcining at 550 deg.C for 8h to obtain the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 350 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 1 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
4.6 percent of durene
46.6 percent of durene
8.5 percent of durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 23.1%, the weight percentage content of durene is 31.2%, and the weight percentage content of durene is 3.8%. The selectivity reaches 92 percent, and the yield reaches 33.6 percent.
Example 11
The catalyst for producing durene by isomerizing mixed tetramethylbenzene is a mixed molecular sieve of H beta and MCM-49 (mechanically mixed with the mass ratio of 1: 1);
the preparation method comprises the following steps:
exchanging the mixed molecular sieve of the H beta and the MCM-49 with ammonium carbonate solution with the concentration of 0.5mol/L for 120min, extruding and forming. The extruded carrier is treated with 0.4mol/L hydrochloric acid solution at 40 deg.C for 4 h. Drying at 100 deg.C for 12h, and calcining at 550 deg.C for 8h to obtain the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 350 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 1 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
5.2 percent of durene
48.6 percent of durene
7.9 percent of the durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 24.2%, the weight percentage content of durene is 30.2%, and the weight percentage content of durene is 4.1%. The selectivity reaches 85.6 percent, and the yield reaches 33.6 percent.
Example 12
The catalyst for producing durene by isomerizing mixed durene comprises the following components in percentage by weight:
1.5% of nickel oxide
0.5% of cerium oxide
Oxide of alum 0.3%
0.5% of potassium oxide
Balance of carrier
The carrier is H beta and MCM-49 mixed molecular sieve (mechanically mixed, the mass ratio is 1: 3);
the preparation method comprises the following steps:
soaking the mixed molecular sieve of the H beta and the MCM-49 in a sodium hydroxide solution with the concentration of 0.1mol/L for 120min at the temperature of 80 ℃, exchanging for 120min by an ammonium nitrate solution with the concentration of 0.4mol/L, and extruding and forming. The extruded carrier is treated with 0.2mol/L hydrofluoric acid solution at 40 deg.c for 4 hr. Dissolving nickel soluble salt, cerium soluble salt, alum soluble salt and potassium soluble salt with water, determining the amount of water according to the water absorption of a carrier, adding the carrier, soaking at 80 ℃ for 24 hours, drying at 100 ℃ for 12 hours, and roasting at 550 ℃ for 8 hours to obtain the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 350 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 1 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
8.2 percent of durene
44.3 percent of durene
7.4 percent of the durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 24.5%, the weight percentage content of durene is 30.2%, and the weight percentage content of durene is 3.3%. The selectivity reaches 89.6 percent, and the yield reaches 31.5 percent.
Example 13
The catalyst for producing durene by isomerizing mixed durene is the catalyst regenerated from the catalyst in the embodiment 7, the regeneration condition is that the catalyst is roasted for 8 hours at the temperature of 600 ℃, and the regenerated catalyst is obtained after natural temperature reduction.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 350 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with a regenerated catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 1 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
0.5 percent of durene
49.0 percent of durene
9.2 percent of durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 24.4%, the weight percentage content of durene is 30.3%, and the weight percentage content of durene is 1.7%. The selectivity reaches 91.2 percent, and the yield reaches 41.0 percent.
Comparative example 1
The catalyst for producing durene by isomerizing mixed durene is MCM-49 molecular sieve with specific surface area of 590 m2G, grains (300 nm);
the preparation method comprises the following steps:
extruding MCM-49 molecular sieve into strips, drying at 100 ℃ for 12h, and roasting at 550 ℃ for 8h to obtain the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 370 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 0.8 h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
5.5 percent of durene
45.8 percent of durene
7.5 percent of the durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 10.5%, the weight percentage content of durene is 35.2%, and the weight percentage content of durene is 6.2%. The selectivity was 42.0% and the yield was 9.4%.
Comparative example 2
The catalyst for producing durene by isomerizing mixed durene comprises the following components in percentage by weight:
nickel oxide or palladium oxide 7%
2% of cerium oxide
Oxide of alum 3%
Copper oxide and manganese oxide 3%
Wherein: oxide of copper: oxide of manganese = 1: 3, weight ratio
5% of oxide of potassium
Balance of carrier
The carrier is MCM-49 molecular sieve with specific surface area of 590 m2G, grains (300 nm);
the preparation method comprises the following steps:
dissolving nickel or palladium soluble salt, cerium soluble salt, alum soluble salt, copper soluble salt and manganese soluble salt with water, wherein the using amount of the water is determined according to the water absorption rate of the carrier, then adding the carrier, sequentially heating and stirring at 80 ℃ for 4h, standing at the constant temperature of 50 ℃ for 8h, drying at 120 ℃ for 8h, roasting at the constant temperature of 300 ℃ for 2h, and roasting at 600 ℃ for 3h to obtain the catalyst for producing durene by isomerizing mixed durene.
The method for producing durene by isomerizing mixed durene comprises the following steps:
heating mixed tetramethylbenzene solution containing durene, durene and durene to 350 ℃, and feeding the mixed tetramethylbenzene solution into a fixed bed reactor filled with the catalyst for reaction;
then the reaction product is sent into a rectifying device to further improve the concentration of durene, and then the durene enters a freezing crystallization device to separate and collect durene and durene;
the reaction pressure is 1 MPa;
the mass space velocity of the material in the isomerization fixed bed reactor is 1.0h-1；
The mixed tetramethylbenzene solution containing durene, durene and durene comprises the following components in percentage by weight;
7.5 percent of durene
48.8 percent of durene
7.5 percent of the durene.
In the reaction product obtained by the reaction of the fixed bed reactor, the weight percentage content of durene is 16.8%, the weight percentage content of durene is 37.2%, and the weight percentage content of durene is 4%. The selectivity reaches 61.6 percent, and the yield is 16.5 percent.
Claims (9)
1. A preparation method of a catalyst for producing durene by isomerizing mixed durene is characterized by comprising the following steps: the method comprises the following steps: carrying out alkali treatment, ammonium exchange, extrusion molding, acid treatment, dipping of a metal oxide solution on an H beta molecular sieve, an MCM-49 molecular sieve, a Y molecular sieve or a mixed molecular sieve of H beta and MCM-49, drying and roasting to obtain a catalyst for producing durene by isomerizing mixed durene; the mass ratio of the H beta molecular sieve to the MCM-49 molecular sieve in the H beta and MCM-49 mixed molecular sieve is 1: 0.5 to 3; the alkali treatment time is 0-200min, and the dipping time of the metal oxide solution is 0-24 h; the mixed tetramethylbenzene includes durene, durene and durene.
2. A process for the preparation of a catalyst for the isomerization of durene to durene according to claim 1, wherein: the specific surface area of the molecular sieve is more than or equal to 550m2The grain size is 100nm-5 μm.
3. A process for the preparation of a catalyst for the isomerization of durene to durene according to claim 1, wherein: the alkali treatment is to perform alkali treatment on the molecular sieve at 30-90 ℃, the alkali solution is one or two of a sodium hydroxide solution and a potassium hydroxide solution, and the concentration of the alkali solution is 0.05-0.6 mol/L.
4. A process for the preparation of a catalyst for the isomerization of durene to durene according to claim 1, wherein: the ammonium exchange is to carry out ion exchange on the molecular sieve carrier subjected to alkali treatment for 10-500min at 30-90 ℃ by using ammonium nitrate, ammonium sulfate, ammonium chloride or ammonium carbonate, wherein the concentration of an ammonium solution is 0.05-0.6 mol/L.
5. A process for the preparation of a catalyst for the isomerization of durene to durene according to claim 1, wherein: the acid treatment is to soak the molecular sieve carrier which is subjected to ion exchange and extrusion molding in an acid solution at 50-90 ℃ for 0-5h, wherein the acid solution is one or more of sulfuric acid, hydrochloric acid, hydrofluoric acid, acetic acid, citric acid and oxalic acid, and the concentration of the acid solution is 0.1-2.0 mol/L.
6. A process for the preparation of a catalyst for the isomerization of durene to durene according to claim 1, wherein: the weight percentage of the metal oxide in the catalyst is as follows: 0-5% of nickel or palladium oxide, 0-4% of cerium oxide, 0-2.5% of vanadium oxide, 0-3% of copper oxide, 0-1% of magnesium oxide and 0-4% of potassium oxide; the metal oxide solution impregnation is to dissolve one or more of nickel or palladium soluble salt, cerium soluble salt, alum soluble salt, copper soluble salt, magnesium soluble salt and potassium soluble salt by water, the amount of the water is determined according to the water absorption rate of the carrier, then the carrier is added, and the impregnation is carried out at 30-90 ℃.
7. A process for the preparation of a catalyst for the isomerization of durene to durene according to claim 1, wherein: the mixed tetramethylbenzene comprises the following components in percentage by weight: 0-10% of durene, 30-50% of durene and 2-10% of durene.
8. The process for preparing the catalyst for the isomerization of durene to durene according to claim 7, wherein: the durene, the partial durene and the continuous durene in the mixed durene account for not less than 50 percent by weight of the total substance.
9. Use of a catalyst obtained by the preparation process according to claim 1, characterized in that: heating mixed tetramethylbenzene solution containing durene, durene and durene to 280-370 deg.C, feeding into fixed bed reactor filled with catalyst, reaction pressure is 1-3MPa, and reaction space velocity is 0.5-1.0h-1(ii) a Then will be reversedThe reaction product is fed into a rectifying device to further increase the concentration of durene, and then the reaction product is fed into a freezing and crystallizing device to separate and collect durene and durene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115433051A (en) * | 2022-10-09 | 2022-12-06 | 连云港鹏辰特种新材料有限公司 | Method for separating durene from durene enrichment liquid |
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