CN108236966A - Aromatization of methanol catalyst and preparation method thereof - Google Patents

Aromatization of methanol catalyst and preparation method thereof Download PDF

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Publication number
CN108236966A
CN108236966A CN201611207917.4A CN201611207917A CN108236966A CN 108236966 A CN108236966 A CN 108236966A CN 201611207917 A CN201611207917 A CN 201611207917A CN 108236966 A CN108236966 A CN 108236966A
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aromatization
oxide
molecular sieve
methanol
catalyst
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刘贵生
李稚松
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Compass Aerospace Satellite Application Technology Group Co Ltd
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Compass Aerospace Satellite Application Technology Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The present invention provides a kind of aromatization of methanol catalyst and preparation method thereof, the following steps performed including sequence：Minor metallic element is introduced to by fabricated in situ or infusion process in molecular sieve, obtain modified molecular screen, by after described modified molecular screen experience base extraction with binding agent molding bonded, catalyst carrier is obtained, oxide is added in the catalyst carrier is made aromatization of methanol catalyst by dry, roasting.Aromatization of methanol catalyst is made with long lifespan according to above-mentioned flow process, is not easy coking, the characteristics of activity time is long.

Description

Aromatization of methanol catalyst and preparation method thereof
Technical field
The present invention relates to a kind of aromatization of methanol preparation fields, are specifically designed a kind of aromatization of methanol catalyst and its preparation Method.
Background technology
With the development of world economy, various countries are also increasing to the demand of the energy, in current world energy sources structure In, the energy that the mankind are utilized is mainly the fossil energies such as oil, natural gas, coal, but the use of fossil fuel is to the mankind The realistic pressure of environmental pollution and energy shortage is brought, this causes the whole world to begin to focus on new energy, and it is desirable that new energy It can overcome the problems, such as the pollution that combustion of fossil fuel is brought and the lack of energy being likely to occur.Aromatization of methanol is as new petrochemical industry Raw material sources have become a kind of trend, are to alleviate China's energy shortage situation, improve comprehensive utilization of resources, are apt to ambient condition, The effective shortcut preserved the ecological environment.Aromatic hydrocarbons, particularly light aromatics BTX（Benzene,toluene,xylene）It is important organic Industrial chemicals has high added value.The main source of the aromatic hydrocarbons in China is catalysis recombination and steam cracking pair in petroleum path Drippolene is produced, what it is from coal route is only 10% or so.The coal methanol in China just gradually moves towards enlargement, and yield is continuous It is soaring, it is contemplated that China's production capacity of methanol in 2017 add up to up to 20,000,000 tons/year, improve Downstream Products of Methanol added value, Extend coal chemical industry and gas chemical industry's industrial chain, the interdependency of Imported oil is reduced, all with strategic meaning.And current first Vintage catalyst is there are short life, easy coking, the technical issues of activity time is short.
Invention content
The purpose of the present invention is to solve the above problems, provide a kind of aromatization of methanol catalyst, can effectively solve Certainly short life, easy coking, stability difference technological deficiency.
Aromatization of methanol catalyst and preparation method thereof, preparation method are：
Step 1：Minor metallic element is introduced to by fabricated in situ or infusion process in the molecular sieve that size is 150-700nm, The mass ratio 1 of minor metallic element and molecular sieve:3-8 obtains modified molecular screen, and in terms of metal component, content accounts for molecular sieve The 0.5-5% of quality.；
Step 2：The modified molecular screen is undergone into base extraction, at 20-80 DEG C, with the lye of a concentration of 1.1-1.5% It is one or many to molecular sieve processing, it is 0.1-8 hours per treatment, washing is filtered, is carried out at a temperature of 100-150 DEG C The solid-liquid mass ratio of drying, the lye and modified molecular screen is 1:3-50；
Step 3：By step 2 obtained material and binding agent molding bonded, catalyst carrier, binding agent and experience lye are obtained The mass ratio 1 of modified molecular screen:3-50；
Step 4：Oxide is added in into the catalyst carrier, aromatization of methanol catalyst is made by dry, roasting；Described Oxide and the mixing quality of catalyst carrier ratio are：1:5-6；
The lye is：Sodium hydroxide, sodium carbonate, ammonium hydroxide, organic amino one or more mixtures；
The binding agent is：Aluminium oxide, water aluminium oxide, Ludox, silica one or more mixtures, size is 200-550nm；
The oxide is：One or two kinds of mixtures of zinc oxide or gallium oxide, one kind of lanthana or cobalt oxide or Two kinds of mixture；By weight, ratio 3-7：0.5-2；
SiO in the wherein described molecular sieve2With A12O3Molar ratio is 1：100-350.
One or two kinds of mixtures of the molecular sieve for ZSM-5 or ZSM-11 molecular sieves.
The modified molecular screen is the mixture of the modified molecular screen one or two of ZSM-5 or ZSM-11.
The minor metallic element is：Ammonium molybdate and iron content, the nitrate of Zn-ef ficiency, sulfate, carbonate and grass It is one or more in hydrochlorate.
The minor metallic element is preferably：One or more mixtures of ammonium molybdate, ferric nitrate and zinc nitrate.
Aromatization of methanol catalyst provided by the invention and preparation method thereof improves the agent of methanol arenes catalytic and uses the longevity Life, the stability that increases, reduce the generation of area carbon during catalyst use；The metallic element of addition can effectively increase Service life.
For the above objects, features and advantages of the present invention is enable to be clearer and more comprehensible, special embodiment below elaborates It is as follows.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical solution in the embodiment of the present invention is clearly and completely described, Obviously, described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Reality based on the present invention Example is applied, those skilled in the art's all other embodiments obtained under the premise of creative work is not made belong to The scope of protection of the invention.
Embodiment 1
Aromatization of methanol catalyst and preparation method thereof, step 1：Will be in terms of metal component, content accounts for the 3% of molecular sieve quality Minor metallic element ammonium molybdate, ferric nitrate, zinc carbonate and zinc nitrate mixture, ruler is introduced to by fabricated in situ or infusion process In the mixture molecular sieve of very little ZSM-5, ZSM-11 for 300nm, the mass ratio 1 of minor metallic element and molecular sieve:3, it obtains Modified molecular screen；
Step 2：By the mixture of ZSM-5, ZSM-11 modified molecular screen experience lye sodium hydroxide, sodium carbonate, ammonium hydroxide, organic The solid-liquid mass ratio of the mixture processing of ammonia, lye and modified molecular screen is 1:20；At 40 DEG C, with a concentration of 1.2% lye Primary to molecular sieve processing, processing time is 2 hours, is filtered washing, is dried at a temperature of 120 DEG C.
Step 3：By step 2 obtained material and size be 300nm aluminium oxide, the binder mixtures of silica are bonded to Type, the mass ratio 1 of binding agent and the modified molecular screen of experience lye:5；Obtain catalyst carrier.
Step 4：It will be by weight 5：The mixture of 1 zinc oxide, lanthana and cobalt oxide adds in the catalyst carrier warp 350 DEG C are crossed, aromatization of methanol catalyst is made in drying in 11 hours, roasting；Oxide and the mixing quality of catalyst carrier ratio are 1：5.
SiO wherein in molecular sieve2With A12O3Molar ratio is 1：200.
Embodiment 2
Aromatization of methanol catalyst and preparation method thereof, step 1：Will be in terms of metal component, content accounts for the 5% of molecular sieve quality Minor metallic element ammonium molybdate, ferric carbonate, zinc carbonate mixture, being introduced to size by fabricated in situ or infusion process is In the molecular sieve of the ZSM-11 of 150nm, the mass ratio 1 of minor metallic element and molecular sieve:5 obtain modified molecular screen；
Step 2：ZSM-11 modified molecular screens are undergone into the organic ammonia treatment of lye, at 60 DEG C, with a concentration of 1.5% lye pair Molecular sieve processing three times, 1 hour per treatment, is filtered washing, is dried at a temperature of 100 DEG C, the lye Solid-liquid mass ratio with modified molecular screen is 1:10；
Step 3：It is 400nm water aluminium oxide by step 2 obtained material and size, the mixture molding bonded of Ludox, obtains Catalyst carrier, the mass ratio 1 of binding agent and the modified molecular screen of experience lye:10；
Step 4：It will be by weight 3:0.5 zinc oxide, cobalt oxide mixture add in the catalyst carrier by 450 DEG C, 8 Aromatization of methanol catalyst is made in hour drying, roasting；The oxide and the mixing quality ratio of catalyst carrier are：1:6；
SiO wherein in molecular sieve2With A12O3Molar ratio is 1：300.
Embodiment 3
Aromatization of methanol catalyst and preparation method thereof：
Step 1：Will be in terms of metal component, content accounts for 2% minor metallic element ammonium molybdate, ferric nitrate, the nitre of molecular sieve quality Sour zinc, ferric oxalate, zinc sulfate mixture, by fabricated in situ or infusion process be introduced to size be 500nm ZSM-5, ZSM- In 11 mixture molecular sieve, the mass ratio 1 of minor metallic element and molecular sieve:8, obtain modified molecular screen；
Step 2：By the mixture experience lye sodium carbonate of ZSM-5, ZSM-11 modified molecular screen, the mixture of ammonium hydroxide Processing at 50 DEG C, handles molecular sieve No. 5 times with a concentration of 1.1% lye, 3 hours per treatment, is filtered washing, It is dried at a temperature of 130 DEG C, the solid-liquid mass ratio of the lye and modified molecular screen is 1:35；
Step 3：Step 2 obtained material and size for 450nm alumina bounds are molded, obtain catalyst carrier, binding agent Mass ratio 2 with the modified molecular screen for undergoing lye:6；
Step 4：It will be by weight 6:1 zinc oxide, lanthana mixture add in the catalyst carrier by 550 DEG C, 3 is small When aromatization of methanol catalyst is made；Oxide and the mixing quality of catalyst carrier ratio are：1:5.5；
SiO wherein in molecular sieve2With A12O3Molar ratio is 1：220.
Embodiment 4
Aromatization of methanol catalyst and preparation method thereof：
Step 1：Will be in terms of metal component, content accounts for 4.5% minor metallic element zinc nitrate, the ammonium molybdate of molecular sieve quality, It is introduced to by fabricated in situ or infusion process in the ZSM-5 molecular sieve that size is 600nm, the matter of minor metallic element and molecular sieve Measure ratio 1:7, obtain modified molecular screen；
Step 2：By mixture experience lye sodium hydroxide, sodium carbonate, ammonium hydroxide, the organic amino of the ZSM-5 modified molecular screens Mixture processing, at 80 DEG C, with a concentration of 1.3% lye to molecular sieve handle 1 time, handle 7 hours, be filtered and wash It washs, is dried at a temperature of 140 DEG C, the solid-liquid mass ratio of the lye and modified molecular screen is 1:50；
Step 3：It is 550nm water aluminium oxide molding bondeds by step 2 obtained material and size, obtains catalyst carrier, bonds Agent and the mass ratio 1 of the modified molecular screen of experience lye:23；
Step 4：It will be by weight 7：Described in the mixture of the mixture of 2 zinc oxide and gallium oxide, lanthana and cobalt oxide adds in Catalyst carrier passes through 500 DEG C, and aromatization of methanol catalyst is made in drying in 5 hours, roasting；The oxide is carried with catalyst The mixing quality ratio of body is：1:5.5；
SiO wherein in molecular sieve2With A12O3Molar ratio is 1：350.
Embodiment 5
Aromatization of methanol catalyst and preparation method thereof：
Step 1：Will be in terms of metal component, content accounts for 1% minor metallic element ammonium molybdate, ferric nitrate and the nitre of molecular sieve quality The mixture of sour zinc is introduced to by fabricated in situ or infusion process in the ZSM-11 molecular sieves that size is 700nm, trace meter member The mass ratio 1 of element and molecular sieve:6, obtain modified molecular screen；
Step 2：The mixture of the ZSM-11 modified molecular screens is undergone into the organic ammonia treatment of lye, at 75 DEG C, uses concentration Lye for 1.4% handles molecular sieve No. 6 times, 3 hours per treatment, is filtered washing, is dried at a temperature of 150 DEG C Dry, the lye and the solid-liquid mass ratio of modified molecular screen are 1:25；
Step 3：It is 330nm aluminium oxide by step 2 obtained material and size, water aluminium oxide, silicon solution molding bonded, is urged Agent carrier, the mass ratio 1 of binding agent and the modified molecular screen of experience lye:45；
Step 4：It will be by weight 4:1 gallium oxide, lanthana mixture add in the catalyst carrier by 400 DEG C, 9 is small When dry, roasting aromatization of methanol catalyst is made；The oxide and the mixing quality ratio of catalyst carrier are：1:6；
SiO wherein in molecular sieve2With A12O3Molar ratio is 1：120.
Embodiment 6
Aromatization of methanol catalyst and preparation method thereof：
Step 1：Will be in terms of metal component, content accounts for 2.5% minor metallic element ammonium molybdate of molecular sieve quality, passes through original position Synthesis or infusion process are introduced in the ZSM-11 molecular sieves that size is 550nm, the mass ratio 1 of minor metallic element and molecular sieve: 4, obtain modified molecular screen；
Step 2：By the mixtures of ZSM-11 modified molecular screens experience lye sodium hydroxide, sodium carbonate, ammonium hydroxide, organic The mixture processing of ammonia at 30 DEG C, handles molecular sieve 2 times with a concentration of 1.1% lye, 5 hours per treatment, carries out Filtration washing is dried at a temperature of 110 DEG C, and the solid-liquid mass ratio of the lye and modified molecular screen is 1:15；
Step 3：It is 250nm water aluminium oxide molding bondeds by step 2 obtained material and size, obtains catalyst carrier, bonds Agent and the mass ratio 1 of the modified molecular screen of experience lye:6；
Step 4：It will be by weight 7：The mixture addition catalyst load of 2 zinc oxide and gallium oxide, lanthana and cobalt oxide Body passes through 360 DEG C, and aromatization of methanol catalyst is made in drying in 6 hours, roasting；The mixing of oxide and the catalyst carrier Mass ratio is：1:5.5；
SiO wherein in molecular sieve2With A12O3Molar ratio is 1：150.
It is provided below under same experimental conditions, uses the experimental result of the catalyst of different component provided by the present invention （It is shown in Table 1）, i.e., using component, that is, experiment condition of aromatization of methanol catalyst.2-7 row have corresponded to same experimental conditions respectively Under, use the concrete outcome of catalyst progress gasoline component preparation obtained in embodiment 1-6）.
Table 1
1 2 3 4 5 6
Methanol flow (g/h) 13.74 13.74 13.74 13.74 13.74 13.74
Water flow (g/h) 2.4 2.4 2.4 2.4 2.4 2.4
Gas velocity (h-1) 1444 1444 1444 1444 1444 1444
Methanol weight air speed (WHSV) (h-1) 2.0 2.0 2.0 2.0 2.0 2.0
Temperature (0C) 380 380 380 380 380 380
Pressure (MPa) 0.8 0.8 0.8 0.8 0.8 0.8
Methanol conversion (%) 99.91 99.69 99.78 99.91 99.80 99.59
Gas phase yield (wt%) 26.60 21.34 19.96 12.93 10.65 10.68
The ratios of C5 in the gas phase（wt%) 10.84 12.21 9.14 7.77 6.72 7.56
Liquid yield (wt%) 73.41 78.76 79.15 83.79 87.90 85.36
Aromatics yield (wt%) 19.72 35.06 23.03 42.06 31.59 31.10
Benzene, toluene and paraxylene yield (wt%) 9.43 18.87 9.52 9.02 7.71 8.57
Benzene, toluene and paraxylene content (wt%) in oil 12.85 23.93 12.01 10.77 8.77 10.05
Dimethylbenzene yield (wt%) 7.21 13.77 7.36 7.07 5.99 6.69
Paraxylene content (%) in dimethylbenzene 40.68 34.48 37.68 33.58 32.59 31.27
Hydrocarbon balance (%) 100.01 100.10 99.11 96.72 98.55 96.04
The content (wt%) of benzene in oil 0.30 0.53 0.29 0.26 0.48 0.34
Hydrogen 0.02 0.02 0.02 0.01 0.01 0.01
Carbon monoxide (only meter wherein C） 0.07 0.08 0.09 0.13 0.27 0.11
Carbon dioxide (only meter wherein C） 0.01 0.00 0.01 0.01 0.00 0.00
Methane 0.77 0.57 0.90 0.95 1.07 0.73
Ethane 0.22 0.23 0.26 0.27 0.41 0.34
Ethylene 4.16 1.50 2.91 1.62 0.53 0.76
Propane 4.68 5.13 4.53 3.67 4.16 4.27
Propylene 3.14 1.96 2.05 1.00 0.35 0.34
Iso-butane 6.49 6.75 4.93 3.09 2.40 2.70
Normal butane 1.25 1.42 0.95 0.62 0.53 0.57
Anti- butylene 0.59 0.32 0.28 0.10 0.04 0.03
1- butylene 0.35 0.19 0.18 0.07 0.02 0.02
Isobutene 1.60 0.85 0.84 0.33 0.11 0.08
Maleic 0.38 0.21 0.18 0.07 0.02 0.02
Isopentane 2.68 2.36 1.70 0.94 0.68 0.68
Carbon 5 0.20 0.24 0.13 0.06 0.04 0.03
Carbon 5- carbon 9 47.35 42.91 55.52 56.45 55.55 53.80
Benzene 0.22 0.42 0.23 0.22 0.43 0.29
Carbon 10 0.72 0.61 0.80 0.71 0.75 0.35
Toluene 2.00 4.66 1.92 1.73 1.29 1.60
Ethylbenzene 0.50 1.20 0.51 0.47 0.35 0.44
Paraxylene 2.93 4.73 2.77 2.36 1.95 2.09
Meta-xylene 3.08 6.43 3.28 3.22 2.80 3.23
Ortho-xylene 1.20 2.55 1.31 1.48 1.24 1.37
Carbon 11- carbon 12 0.01 0.05 0.09 0.03 0.01 0.10
Trimethylbenzene 2.81 3.88 3.65 4.63 6.00 6.06
Aromatic series (>Carbon 8)+hydrocarbon (>Carbon 13) 6.99 11.18 9.35 12.48 17.53 16.03
Illustrated in the relevant technologies with different comparative examples below, the aromatization of methanol catalyst that is provided.From experimental result point From the point of view of analysis, in the result for preparing experiment, benzene content ＜ 0.5%；Methanol conversion ＞ 99%；Catalyst single pass life：25~30d, Catalyst entire life：>=2 years, therefore, methanol aromatic hydrocarbons new catalyst can effectively solve fixed bed and fluid catalyst During for aromatization of methanol, the technical problems such as short catalyst service life, easy coking, activity time are improved, enhance first During alcohol aromatisation can with the high life, be not easy the harvest aromatic hydrocarbons of coking.
The above, not to the present invention do in any form with substantial restriction, all technology people for being familiar with the industry Member, without departing from the scope of the present invention, when using disclosed above technology contents, and a little change made More, the equivalent variations with developing are modified, are the equivalent embodiment of the present invention.

Claims (5)

1. aromatization of methanol catalyst and preparation method thereof, it is characterised in that：Preparation method is：
Step 1：Minor metallic element is introduced to by fabricated in situ or infusion process in the molecular sieve that size is 150-700nm, The mass ratio 1 of minor metallic element and molecular sieve:3-8 obtains modified molecular screen, and in terms of metal component, content accounts for molecular sieve The 0.5-5% of quality；
Step 2：The modified molecular screen is undergone into base extraction, at 20-80 DEG C, with the lye of a concentration of 1.1-1.5% It is one or many to molecular sieve processing, it is 0.1-8 hours per treatment, washing is filtered, is carried out at a temperature of 100-150 DEG C The solid-liquid mass ratio of drying, the lye and modified molecular screen is 1:3-50；
Step 3：By step 2 obtained material and binding agent molding bonded, catalyst carrier, binding agent and experience lye are obtained The mass ratio 1 of modified molecular screen:3-50；
Step 4：Oxide is added in into the catalyst carrier by 350-550 DEG C, 3-12 hours, methanol is made in dry, roasting Aromatized catalyst；The oxide and the mixing quality ratio of catalyst carrier are：1:5-6；
The lye is：Sodium hydroxide, sodium carbonate, ammonium hydroxide, organic amino one or more mixtures；
The binding agent is：Aluminium oxide, water aluminium oxide, Ludox, silica one or more mixtures, size is 200-550nm；
The oxide is：One or two kinds of mixtures of zinc oxide or gallium oxide, one kind of lanthana or cobalt oxide or Two kinds of mixture；By weight, ratio 3-7：0.5-2；
SiO2 and A12O3 molar ratios in the wherein described molecular sieve are 1：100-350.
2. aromatization of methanol catalyst according to claim 1 and preparation method thereof, it is characterised in that：The molecular sieve One or two kinds of mixtures for ZSM-5 or ZSM-11 molecular sieves.
3. aromatization of methanol catalyst according to claim 1 and preparation method thereof, it is characterised in that：The modification point Mixture of the son sieve for the modified molecular screen one or two of ZSM-5 or ZSM-11.
4. aromatization of methanol catalyst according to claim 1, it is characterised in that：The minor metallic element is：Molybdenum It is one or more in sour ammonium and iron content, the nitrate of Zn-ef ficiency, sulfate, carbonate and oxalates.
5. aromatization of methanol catalyst according to claim 1 or 2 and preparation method thereof, it is characterised in that：Described is micro- Measuring metallic element is preferably：One or more mixtures of ammonium molybdate, ferric nitrate and zinc nitrate.
CN201611207917.4A 2016-12-23 2016-12-23 Aromatization of methanol catalyst and preparation method thereof Pending CN108236966A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109967118A (en) * 2019-05-05 2019-07-05 北京化工大学 A kind of Method in situ modification of the HZSM-5 molecular sieve catalyst for methanol conversion for preparing arene
CN111777480A (en) * 2019-04-03 2020-10-16 中国科学院大连化学物理研究所 Method for preparing coronene compound by using molecular sieve catalyst
CN114733562A (en) * 2022-03-21 2022-07-12 大连理工大学 High-activity methane-methanol oxygen-free co-aromatization catalyst and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111777480A (en) * 2019-04-03 2020-10-16 中国科学院大连化学物理研究所 Method for preparing coronene compound by using molecular sieve catalyst
CN111777480B (en) * 2019-04-03 2021-06-15 中国科学院大连化学物理研究所 Method for preparing coronene compound by using molecular sieve catalyst
CN109967118A (en) * 2019-05-05 2019-07-05 北京化工大学 A kind of Method in situ modification of the HZSM-5 molecular sieve catalyst for methanol conversion for preparing arene
CN114733562A (en) * 2022-03-21 2022-07-12 大连理工大学 High-activity methane-methanol oxygen-free co-aromatization catalyst and preparation method and application thereof

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