CN105418344B - The technique for preparing paraxylene and propylene using mixed alcohol ether - Google Patents
The technique for preparing paraxylene and propylene using mixed alcohol ether Download PDFInfo
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- CN105418344B CN105418344B CN201510734850.9A CN201510734850A CN105418344B CN 105418344 B CN105418344 B CN 105418344B CN 201510734850 A CN201510734850 A CN 201510734850A CN 105418344 B CN105418344 B CN 105418344B
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 86
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 18
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 44
- 239000002808 molecular sieve Substances 0.000 claims description 35
- 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 35
- 238000007598 dipping method Methods 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000002372 labelling Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 16
- 239000005977 Ethylene Substances 0.000 abstract description 16
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001294 propane Substances 0.000 abstract description 8
- -1 C12 hydrocarbon Chemical class 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000004254 Ammonium phosphate Substances 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 3
- 235000019289 ammonium phosphates Nutrition 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/80—Mixtures of different zeolites
-
- 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)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the technique that a kind of utilization mixed alcohol ether prepares paraxylene and propylene, it is that alcohol ether gaseous mixture is contacted to progress catalytic reaction in fluidized-bed reactor with catalyst, it is 490~500 DEG C, 1.5~2.0MPa of pressure, 4~4.5h of alcohol ether mixed gas air speed that the temperature in fluidized-bed reactor is controlled during catalytic reaction‑1, the composition of alcohol ether gaseous mixture is methanol, the dimethyl ether of 65 parts by weight, the water of 1.5 parts by weight, the C6 C12 hydrocarbon of 2 parts by weight of 32 parts by weight.In such scheme, alcohol ether gaseous mixture is catalyzed by catalyst in a fluidized bed reactor, enable alcohol ether gaseous mixture high selectivity changes into propylene and paraxylene, oil after processing, gas phase are measured, alcohol ether conversion rate is more than 99%, paraxylene proportion in dimethylbenzene is more than ethylene/ethane in 90%, gas phase and is more than 8, propylene/propane more than 8, propylene/ethylene more than 10.
Description
It is on December 03rd, 2014, Application No. 2014107294608, entitled " mixing the applying date that the present invention, which is,
Alcohol ether for paraxylene and propylene method " patent of invention divisional application.
Technical field
The present invention relates to petrochemical industry, and in particular to a kind of utilization mixed alcohol ether prepares the work of paraxylene and propylene
Skill.
Background technology
Paraxylene and propylene are important raw materials in Chemical Manufacture, have there is substantial amounts of periodical, books, patent etc. at present
Document describes the scheme that propylene and dimethylbenzene are produced using methanol, dimethyl ether catalysis, and catalysis catalyst used is mostly
ZSM-5 and its modifier, but in disclosed method, below generally existing in one or more defect：Alcohol ether conversion rate
Less than 99%, paraxylene proportion in dimethylbenzene is less than ethylene/ethane (weight ratio, similarly hereinafter) in 90%, gas phase and is less than
8th, propylene/propane is less than 8, propylene/ethylene and is less than 10.
The content of the invention
It is an object of the invention to provide a kind of method that mixed alcohol ether prepares paraxylene and propylene, its alcohol ether conversion rate
More than 99%, it is big more than 8, propylene/propane that paraxylene proportion in dimethylbenzene is more than ethylene/ethane in 90%, gas phase
It is more than 10 in 8, propylene/ethylene.
To achieve the above object, the present invention is implemented using following scheme：
A kind of utilization mixed alcohol ether prepares the technique of paraxylene and propylene, operates as follows：
ZSM-5 molecular sieve, ZSM-11 molecular sieves are respectively placed in sodium hydroxide solution progress one-level and impregnate modified, hydroxide
The mass concentration of sodium solution is 5%, and the modified temperature of one-level dipping is 30~35 DEG C, duration 2.5h, is then utilized in kettle
Acid modification liquid carries out second steepwater modification, during acid modification liquid is the mixed aqueous solution of hydrochloric acid and fluosilicic acid, mixed aqueous solution
The content of hydrochloric acid is that the content of 2%, fluosilicic acid is 6%, second steepwater be modified temperature for 110 DEG C, duration 2.5h, control sealing
Pressure 0.25MPa in kettle, second steepwater reclaims ZSM-5 molecular sieve and ZSM-11 molecular sieves and is washed and dried after being modified
It is dry；By ZSM-5 molecular sieve, ZSM-11 molecular sieves and clay according to 10:0.1:1.5 mass ratio is mixed, and then will be mixed
1~2mm of diameter particle is made in thing in granulator, and 4.5h is then calcined under the conditions of 550-600 DEG C, by product mark after roasting
Be designated as ZSM- I, ZSM- I be placed in the first mixed liquor and impregnates 2h, dipping terminate after carry out successively the first filtering, first dry and
First roasting, the Product Labeling that the first roasting is obtained is ZSM- II, and the first temperature dried is 100 DEG C, the temperature of the first roasting
Spend for 650 DEG C, duration 5h, ZSM- II is placed in 45 DEG C of dipping 1h in the second mixed liquor, dipping carries out the second mistake successively after terminating
Filter, the second drying and the second roasting can obtain catalyst, and the second temperature dried is 100 DEG C, and the second temperature being calcined is 550
DEG C, duration 6h, the first mixed liquor for 0.75mol/L copper chloride solution and 0.5mol/L manganese chloride solution according to 1:1 body
Product is obtained than mixed preparing；Magnesium chloride solution, 4mol/L ferric chloride solution, positive silicic acid second that second mixed liquor is 1.5mol/L
Ester solution is according to volume ratio 1:1:2 mixed configurations are obtained；
Catalyst obtained above is loaded in fluidized-bed reactor, alcohol ether gaseous mixture is passed through into fluidized-bed reactor is carried out
Catalytic reaction, urges and oil phase and gas phase is separated after catalytic reaction, control during catalytic reaction the temperature in fluidized-bed reactor be 490~
500 DEG C, 1.5~2.0MPa of pressure, 4~4.5h of alcohol ether mixed gas air speed-1, the composition of alcohol ether gaseous mixture is the first of 32 parts by weight
Alcohol, the dimethyl ether of 65 parts by weight, the water of 1.5 parts by weight, the C6-C12 hydrocarbon of 2 parts by weight.
In such scheme, alcohol ether gaseous mixture is catalyzed by catalyst in a fluidized bed reactor so that alcohol ether is mixed
That closes that gas is capable of high selectivity changes into propylene and paraxylene, the oil after processing, gas phase is measured, alcohol ether conversion rate is big
In 99%, paraxylene proportion in dimethylbenzene is more than ethylene/ethane in 90%, gas phase and is more than more than 8, propylene/propane
8th, propylene/ethylene is more than 10.
The reasonably combined and I and II dipping of alcohol ether gaseous mixture component is modified to ZSM-5 molecular sieve and ZSM-11 molecules
The improvement of the pore structure of sieve, is easy to the attachment of subsequent metal element, silicon, P elements, improves alcohol ether conversion rate.ZSM-5 molecular sieve,
The mix and match and lanthanum of ZSM-11 molecular sieves, phosphorous oxides can significantly improve the selectivity of propylene conversion in catalysis, copper,
The oxides such as manganese significantly improve the selectivity of paraxylene conversion in catalysis, meanwhile, above-mentioned catalyst can also be significantly improved
The selectivity of alkane, alkene, in addition, after catalyst structure is improved, it is more firm, silica is difficult for drop-off, life 2~
3 times, reduce production cost.
Embodiment
In order that objects and advantages of the present invention are more clearly understood, the present invention is carried out specifically with reference to embodiments
It is bright.It should be appreciated that following word is only to describe one or more of specific embodiments of the invention, not to the present invention
The protection domain specifically asked carries out considered critical, and agents useful for same unless otherwise instructed, can be by business by way of being commercially available.
Embodiment 1
ZSM-5 molecular sieve, ZSM-11 molecular sieves are respectively placed in sodium hydroxide solution progress one-level and impregnate modified, hydroxide
The mass concentration of sodium solution is 5%, and the modified temperature of one-level dipping is 30~35 DEG C, duration 2.5h, is then utilized in kettle
Acid modification liquid carries out second steepwater modification, during acid modification liquid is the mixed aqueous solution of hydrochloric acid and fluosilicic acid, mixed aqueous solution
The content of hydrochloric acid is 2% (mass concentration, similarly hereinafter), the content of fluosilicic acid are 6%, the temperature that second steepwater is modified is 110 DEG C, when
Pressure 0.25MPa in long 2.5h, control seal pot body, second steepwater reclaims ZSM-5 molecular sieve and ZSM-11 molecules after being modified
Sieve and washed and dried；By ZSM-5 molecular sieve, ZSM-11 molecular sieves and clay according to 10:0.1:1.5 mass ratio carry out
Mix, then homomixture is made to 1~2mm of diameter particle in granulator, be then calcined under the conditions of 550-600 DEG C
4.5h, is ZSM- I by Product Labeling after roasting, ZSM- I is placed in the first mixed liquor and impregnates 2h, dipping is carried out successively after terminating
First filtering, first are dried and the first roasting, and the Product Labeling that the first roasting is obtained is ZSM- II, and the first temperature dried is
100 DEG C, the temperature of the first roasting is 650 DEG C, duration 5h, and ZSM- II is placed in into 45 DEG C of dipping 1h in the second mixed liquor, dipping knot
The second filtering, the second drying and the second roasting are carried out after beam successively and can obtain catalyst, the second temperature dried is 100 DEG C,
The temperature of second roasting is 550 DEG C, duration 6h, and the first mixed liquor is the chlorination of 0.75mol/L copper chloride solution, 0.5mol/L
The ammonium phosphate solution of manganese solution, 0.02mol/L lanthanum nitrate hexahydrate and 1mol/L is according to 1:1:1:1 volume ratio mixed preparing is obtained
Arrive；Second mixed liquor is pressed for 1.5mol/L magnesium chloride solution, 4mol/L ferric chloride solution, teos solution (anhydrous)
According to volume ratio 1:1:2 mixed configurations are obtained.
Catalyst obtained above is loaded in fluidized-bed reactor, alcohol ether gaseous mixture is passed through into fluidized-bed reactor is carried out
Oil phase and gas phase are separated after catalytic reaction, catalytic reaction, control during catalytic reaction the temperature in fluidized-bed reactor be 490~
500 DEG C, 1.5~2.0MPa of pressure, 4~4.5h of alcohol ether mixed gas air speed-1, the composition of alcohol ether gaseous mixture is the first of 32 parts by weight
Alcohol, the dimethyl ether of 65 parts by weight, the water of 1.5 parts by weight, the C6-C12 hydrocarbon of 2 parts by weight.
Oil after processing, gas phase are measured, alcohol ether conversion rate is more than 99.9%, and paraxylene is shared in dimethylbenzene
Ratio is more than ethylene/ethane in 99%, gas phase and is more than 8, propylene/propane more than 10, propylene/ethylene more than 10.
Embodiment 2
ZSM-5 molecular sieve, ZSM-11 molecular sieves are respectively placed in sodium hydroxide solution progress one-level and impregnate modified, hydroxide
The mass concentration of sodium solution is 5%, and the modified temperature of one-level dipping is 30~35 DEG C, duration 2.5h, is then utilized in kettle
Acid modification liquid carries out second steepwater modification, during acid modification liquid is the mixed aqueous solution of hydrochloric acid and fluosilicic acid, mixed aqueous solution
The content of hydrochloric acid is 2% (mass concentration, similarly hereinafter), the content of fluosilicic acid are 6%, the temperature that second steepwater is modified is 110 DEG C, when
Pressure 0.25MPa in long 2.5h, control seal pot body, second steepwater reclaims ZSM-5 molecular sieve and ZSM-11 molecules after being modified
Sieve and washed and dried；By ZSM-5 molecular sieve, ZSM-11 molecular sieves and clay according to 10:0.1:1.5 mass ratio is carried out
Mix, then homomixture is made to 1~2mm of diameter particle in granulator, be then calcined under the conditions of 550-600 DEG C
4.5h, is ZSM- I by Product Labeling after roasting, ZSM- I is placed in the first mixed liquor and impregnates 2h, dipping is carried out successively after terminating
First filtering, first are dried and the first roasting, and the Product Labeling that the first roasting is obtained is ZSM- II, and the first temperature dried is
100 DEG C, the temperature of the first roasting is 650 DEG C, duration 5h, and ZSM- II is placed in into 45 DEG C of dipping 1h in the second mixed liquor, dipping knot
The second filtering, the second drying and the second roasting are carried out after beam successively and can obtain catalyst, the second temperature dried is 100 DEG C,
The temperature of second roasting is 550 DEG C, duration 6h, and the first mixed liquor is the chlorination of 0.75mol/L copper chloride solution, 0.5mol/L
The ammonium phosphate solution of manganese solution, 0.02mol/L lanthanum nitrate hexahydrate and 1mol/L is according to 1:1:1:1 volume ratio mixed preparing is obtained
Arrive；The magnesium chloride solution, 4mol/L ferric chloride solution, teos solution that second mixed liquor is 1.5mol/L are according to volume
Than 1:1:2 mixed configurations are obtained.
Catalyst obtained above is loaded in fluidized-bed reactor, alcohol ether gaseous mixture is passed through into fluidized-bed reactor is carried out
Oil phase and gas phase are separated after catalytic reaction, catalytic reaction, control during catalytic reaction the temperature in fluidized-bed reactor be 490~
500 DEG C, 1.5~2.0MPa of pressure, 4~4.5h of alcohol ether mixed gas air speed-1, the composition of alcohol ether gaseous mixture is the first of 32 parts by weight
Alcohol, the dimethyl ether of 60 parts by weight, the water of 1.5 parts by weight, the C6-C12 hydrocarbon of 3 parts by weight.
Oil after processing, gas phase are measured, alcohol ether conversion rate is more than 99.9%, and paraxylene is shared in dimethylbenzene
Ratio is more than ethylene/ethane in 95%, gas phase and is more than 8, propylene/propane more than 8, propylene/ethylene more than 10.
Embodiment 3
ZSM-5 molecular sieve, ZSM-11 molecular sieves are respectively placed in sodium hydroxide solution progress one-level and impregnate modified, hydroxide
The mass concentration of sodium solution is 5%, and the modified temperature of one-level dipping is 30~35 DEG C, duration 2.5h, is then utilized in kettle
Acid modification liquid carries out second steepwater modification, during acid modification liquid is the mixed aqueous solution of hydrochloric acid and fluosilicic acid, mixed aqueous solution
The content of hydrochloric acid is 2% (mass concentration, similarly hereinafter), the content of fluosilicic acid are 6%, the temperature that second steepwater is modified is 110 DEG C, when
Pressure 0.25MPa in long 2.5h, control seal pot body, second steepwater reclaims ZSM-5 molecular sieve and ZSM-11 molecules after being modified
Sieve and washed and dried；By ZSM-5 molecular sieve, ZSM-11 molecular sieves and clay according to 10:0.1:1.5 mass ratio is carried out
Mix, then homomixture is made to 1~2mm of diameter particle in granulator, be then calcined under the conditions of 550-600 DEG C
4.5h, is ZSM- I by Product Labeling after roasting, ZSM- I is placed in the first mixed liquor and impregnates 2h, dipping is carried out successively after terminating
First filtering, first are dried and the first roasting, and the Product Labeling that the first roasting is obtained is ZSM- II, and the first temperature dried is
100 DEG C, the temperature of the first roasting is 650 DEG C, duration 5h, and ZSM- II is placed in into 45 DEG C of dipping 1h in the second mixed liquor, dipping knot
The second filtering, the second drying and the second roasting are carried out after beam successively and can obtain catalyst, the second temperature dried is 100 DEG C,
The temperature of second roasting is 550 DEG C, duration 6h, and the first mixed liquor is the chlorination of 0.75mol/L copper chloride solution, 0.5mol/L
The ammonium phosphate solution of manganese solution, 0.02mol/L lanthanum nitrate hexahydrate and 1mol/L is according to 1:1:1:1 volume ratio mixed preparing is obtained
Arrive；The magnesium chloride solution, 4mol/L ferric chloride solution, teos solution that second mixed liquor is 1.5mol/L are according to volume
Than 1:1:2 mixed configurations are obtained.
Catalyst obtained above is loaded in fluidized-bed reactor, alcohol ether gaseous mixture is passed through into fluidized-bed reactor is carried out
Oil phase and gas phase are separated after catalytic reaction, catalytic reaction, control during catalytic reaction the temperature in fluidized-bed reactor be 490~
500 DEG C, 1.5~2.0MPa of pressure, 4~4.5h of alcohol ether mixed gas air speed-1, the composition of alcohol ether gaseous mixture is the first of 30 parts by weight
Alcohol, the dimethyl ether of 65 parts by weight, the water of 1.5 parts by weight, the C6-C12 hydrocarbon of 2 parts by weight.
Oil after processing, gas phase are measured, alcohol ether conversion rate is more than 99.9%, and paraxylene is shared in dimethylbenzene
Ratio is more than ethylene/ethane in 98%, gas phase and is more than 10, propylene/propane more than 8, propylene/ethylene more than 10.
Embodiment 4
ZSM-5 molecular sieve, ZSM-11 molecular sieves are respectively placed in sodium hydroxide solution progress one-level and impregnate modified, hydroxide
The mass concentration of sodium solution is 5%, and the modified temperature of one-level dipping is 30~35 DEG C, duration 2.5h, is then utilized in kettle
Acid modification liquid carries out second steepwater modification, during acid modification liquid is the mixed aqueous solution of hydrochloric acid and fluosilicic acid, mixed aqueous solution
The content of hydrochloric acid is 2% (mass concentration, similarly hereinafter), the content of fluosilicic acid are 6%, the temperature that second steepwater is modified is 110 DEG C, when
Pressure 0.25MPa in long 2.5h, control seal pot body, second steepwater reclaims ZSM-5 molecular sieve and ZSM-11 molecules after being modified
Sieve and washed and dried；By ZSM-5 molecular sieve, ZSM-11 molecular sieves and clay according to 10:0.1:1.5 mass ratio is carried out
Mix, then homomixture is made to 1~2mm of diameter particle in granulator, be then calcined under the conditions of 550-600 DEG C
4.5h, is ZSM- I by Product Labeling after roasting, ZSM- I is placed in the first mixed liquor and impregnates 2h, dipping is carried out successively after terminating
First filtering, first are dried and the first roasting, and the Product Labeling that the first roasting is obtained is ZSM- II, and the first temperature dried is
100 DEG C, the temperature of the first roasting is 650 DEG C, duration 5h, and ZSM- II is placed in into 45 DEG C of dipping 1h in the second mixed liquor, dipping knot
The second filtering, the second drying and the second roasting are carried out after beam successively and can obtain catalyst, the second temperature dried is 100 DEG C,
The temperature of second roasting is 550 DEG C, duration 6h, and the first mixed liquor is 0.75mol/L copper chloride solution and 0.5mol/L chlorine
Change manganese solution according to 1:1 volume ratio mixed preparing is obtained；Second mixed liquor is 1.5mol/L magnesium chloride solution, 4mol/L
Ferric chloride solution, teos solution are according to volume ratio 1:1:2 mixed configurations are obtained.
Catalyst obtained above is loaded in fluidized-bed reactor, alcohol ether gaseous mixture is passed through into fluidized-bed reactor is carried out
Oil phase and gas phase are separated after catalytic reaction, catalytic reaction, control during catalytic reaction the temperature in fluidized-bed reactor be 490~
500 DEG C, 1.5~2.0MPa of pressure, 4~4.5h of alcohol ether mixed gas air speed-1, the composition of alcohol ether gaseous mixture is the first of 32 parts by weight
Alcohol, the dimethyl ether of 65 parts by weight, the water of 1.5 parts by weight, the C6-C12 hydrocarbon of 2 parts by weight.
Oil after processing, gas phase are measured, alcohol ether conversion rate is more than 99.9%, and paraxylene is shared in dimethylbenzene
Ratio is more than ethylene/ethane in 98%, gas phase and is more than 4, propylene/ethylene between 3~6 more than 8, propylene/propane.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, after content described in the present invention is known, under the premise without departing from the principles of the invention, it can also be made some
Equal conversion and replacement, these, which convert and substituted on an equal basis, also should be regarded as belonging to protection scope of the present invention.
Claims (1)
1. a kind of utilization mixed alcohol ether prepares the technique of paraxylene and propylene, operate as follows：
ZSM-5 molecular sieve, ZSM-11 molecular sieves are respectively placed in sodium hydroxide solution and carry out that one-level dipping is modified, sodium hydroxide is molten
The mass concentration of liquid is 5%, and the modified temperature of one-level dipping is 30~35 DEG C, duration 2.5h, and acidity is then utilized in kettle
Modification liquid carries out second steepwater modification, and acid modification liquid is hydrochloric acid in the mixed aqueous solution of hydrochloric acid and fluosilicic acid, mixed aqueous solution
Content be that the content of 2%, fluosilicic acid is 6%, the temperature that second steepwater is modified is 110 DEG C, duration 2.5h, control sealing kettle
Interior pressure 0.25MPa, second steepwater reclaims ZSM-5 molecular sieve and ZSM-11 molecular sieves and is washed and dried after being modified；
By ZSM-5 molecular sieve, ZSM-11 molecular sieves and clay according to 10:0.1:1.5 mass ratio is mixed, and then homomixture exists
1~2mm of diameter particle is made in granulator, 4.5h is then calcined under the conditions of 550-600 DEG C, is by Product Labeling after roasting
ZSM- I, ZSM- I is placed in the first mixed liquor and impregnates 2h, and dipping carries out the first filtering, the first drying and first successively after terminating
Roasting, the Product Labeling that the first roasting is obtained is ZSM- II, and the first temperature dried is 100 DEG C, and the temperature of the first roasting is
650 DEG C, duration 5h, 45 DEG C of dipping 1h are placed in the second mixed liquor by ZSM- II, and dipping carries out the second filtering, the successively after terminating
Two dry and the second roasting can obtain catalyst, and the second temperature dried is 100 DEG C, the temperature of the second roasting is 550 DEG C, when
Long 6h, the first mixed liquor is 0.75mol/L copper chloride solution and 0.5mol/L manganese chloride solution according to 1:1 volume ratio is mixed
Preparation is closed to obtain；Second mixed liquor is 1.5mol/L magnesium chloride solution, 4mol/L ferric chloride solution, teos solution
According to volume ratio 1:1:2 mixed configurations are obtained；
Catalyst obtained above is loaded in fluidized-bed reactor, alcohol ether gaseous mixture is passed through fluidized-bed reactor and is catalyzed
Reaction, separation oil phase and gas phase after catalytic reaction, the temperature in fluidized-bed reactor control during catalytic reaction is 490~500 DEG C,
1.5~2.0MPa of pressure, 4~4.5h of alcohol ether mixed gas air speed-1, the composition of alcohol ether gaseous mixture is the methanol of 32 parts by weight, 65
The dimethyl ether of parts by weight, the water of 1.5 parts by weight, the C6-C12 hydrocarbon of 2 parts by weight.
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| CN201410729460.8A CN104387225B (en) | 2014-12-03 | 2014-12-03 | Mixed alcohol ether prepares the method for p-Xylol and propylene |
| CN201510734850.9A CN105418344B (en) | 2014-12-03 | 2014-12-03 | The technique for preparing paraxylene and propylene using mixed alcohol ether |
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| CN201510734754.4A Expired - Fee Related CN105175215B (en) | 2014-12-03 | 2014-12-03 | A kind of technique that mixed alcohol ether prepares paraxylene and propylene |
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| CN1721378A (en) * | 2004-07-14 | 2006-01-18 | 中国科学院大连化学物理研究所 | A kind of method of toluene methylation system p-Xylol co-producing light olefins |
| CN1915512A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalyst for alkylation of toluene methanol |
| CN101456786A (en) * | 2007-12-12 | 2009-06-17 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing light olefins by toluene and methylating reagent |
| CN103272633A (en) * | 2013-06-07 | 2013-09-04 | 清华大学 | Catalyst for converting alcohol ether into high p-xylene content aromatic hydrocarbon, preparation method and reaction process thereof |
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| WO2002042245A1 (en) * | 2000-11-21 | 2002-05-30 | Exxonmobil Chemical Patents Inc. | Process for producing light olefins |
| CN101347743B (en) * | 2007-07-18 | 2010-11-10 | 中国石油化工股份有限公司 | Method for preparing catalyst for producing propylene transformed from methanol with high ratio of propylene/ethylene |
| CN101607858B (en) * | 2009-07-24 | 2013-07-24 | 中国海洋石油总公司 | Method for preparing aromatic hydrocarbons and propylene simultaneously employing methanol/dimethyl ether |
| CN101602643B (en) * | 2009-07-24 | 2013-07-24 | 中国海洋石油总公司 | Method for preparing ethylene and propylene and co-producing p-xylene through methanol/dimethyl ether conversion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721378A (en) * | 2004-07-14 | 2006-01-18 | 中国科学院大连化学物理研究所 | A kind of method of toluene methylation system p-Xylol co-producing light olefins |
| CN1915512A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalyst for alkylation of toluene methanol |
| CN101456786A (en) * | 2007-12-12 | 2009-06-17 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing light olefins by toluene and methylating reagent |
| CN103272633A (en) * | 2013-06-07 | 2013-09-04 | 清华大学 | Catalyst for converting alcohol ether into high p-xylene content aromatic hydrocarbon, preparation method and reaction process thereof |
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| CN105175204B (en) | 2020-06-16 |
| CN105175204A (en) | 2015-12-23 |
| CN104387225B (en) | 2016-03-02 |
| CN105418344A (en) | 2016-03-23 |
| CN105175215B (en) | 2018-10-16 |
| CN104387225A (en) | 2015-03-04 |
| CN105175215A (en) | 2015-12-23 |
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