CN101550051B - Process for preparing arene selectivity by enhancing methanol aromatizatian and process for preparation of catalyst thereof - Google Patents
Process for preparing arene selectivity by enhancing methanol aromatizatian and process for preparation of catalyst thereof Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 230000002708 enhancing effect Effects 0.000 title abstract 2
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- 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 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000005899 aromatization reaction Methods 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 241001120493 Arene Species 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims 3
- 239000013543 active substance Substances 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 2
- 238000007605 air drying Methods 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 229940044658 gallium nitrate Drugs 0.000 claims 1
- 229910001961 silver nitrate Inorganic materials 0.000 claims 1
- 238000007667 floating Methods 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 2
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 8
- 238000011161 development Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910005183 Ga(NO3)3.9H2O Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 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
- 239000012263 liquid product Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Chemical group 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a process for preparing arene selectivity by enhancing methanol aromatizatian. The process uses methanol as raw material, compositely modifies HZSM-5 molecular sieve catalyst by active ions like Ga, Zn, Cu, Cr and Ag for catalyzing methanol aromatizatian, employs the fixed bed continuous process or the floating bed continuous process, wherein the reaction pressure is 0.1-3.5Mpa; the reaction temperature is 380-500 DEG C; the space velocity of raw material liquid is 0.1-10.0 h<-1>; and N2 space velocity is 120-800 h<-1>. The advantages of the invention lie in collocation combination of mixing ion modification, and arene selectivity reaches to 70%.
Description
Technical field
The present invention relates to a kind of technology and Preparation of catalysts method thereof that aromatization of methanol is produced arenes selectivity that improve.
Background technology
Aromatic hydrocarbons is a kind of strategic goods and materials, is the raw material of medicine, agricultural chemicals, dyestuff, organic materials and basic chemical industry.In medical agricultural chemicals, contain the aromatic hydrocarbons elementary cell in the most medicine, nearly all dyestuff all adopts aroamtic hydrocarbon raw material, and various auxiliary agents in the organic materials and advanced electronic material also all be unable to do without aroamtic hydrocarbon raw material.Aromatic hydrocarbons is mainly derived from refining of petroleum at present, and along with disposable petroleum resources tap/dip deep into and widely-used, output day by day reduces, and therefore develops new aromatic hydrocarbons production process, has important strategic meaning and realistic meaning.
Methyl alcohol is a kind of important chemical material, wide material sources.In recent years, the coal chemical industry engineering project starts comprehensively, and a collection of project that with the coal is raw material is produced methyl alcohol is built up one after another and gone into operation, and the production of methyl alcohol has got into a fast-developing period, and increase of production is huge.Along with progress of science and technology, be that chemical industry sintetics and new organic chemical industry's technology of raw material obtains paying attention to and development day by day with methyl alcohol, new chemical plant installations constantly is born, and Downstream Products of Methanol constantly produces, and impels the positive develop rapidly of methyl alcohol scientific and technological development.
At present, the Downstream Products of Methanol development field is wide, and speed is quite fast.Like preparing gasoline by methanol (MTG), methyl alcohol system ethene (MTF) and methanol conversion are alkene (MTO) etc., and methyl alcohol prepares propylene and ethene is the importance achievement of the vertical deep development of methyl alcohol.The technology of the direct aromizing of methyl alcohol is demanded Application and Development urgently.
Utilize aromatization of methanol; Be methyl alcohol under the effect of catalyzer, be the process of aromatic hydrocarbon through dehydration, polymerization and cyclisation, be to make rational use of resources to produce one of new effective way of aromatic hydrocarbons; Be one of new problem that derives along with the development of Coal Chemical Industry in recent years, have certain strategic importance.Originally aromatization of methanol is a kind of sub product in the preparing gasoline by methanol product; At present, specializing in the aromatization of methanol report only has 6 pieces, and wherein one piece is Chinese patent (application number 200610012703.1); Aromatics yield is only 30～40%.In the aromatization of methanol research process, like simple use HZSM-5 catalyzer, though produced aromatic hydrocarbons; But in aromatization process with side reactions such as cracking, hydrogenolysis, hydrogen transferences; Produced other a large amount of hydrocarbon compounds simultaneously, restricted the raising of arenes selectivity, yield is not high.And with part or all of silicon or aluminium among the heteroatoms isomorphous substitution HZSM-5 such as copper, zinc, gallium, phosphorus, silver; In chemical constitution that has changed molecular sieve and pore structure size; The type property of selecting to its surface acid property and molecular sieve is carried out modulation, with obtaining the excellent sieve catalyst of catalytic performance and selectivity.The present invention is through the mixed and modified HZSM-5 sieve catalyst of different activities ion; Be intended to improve the selectivity of aromatization of methanol preparing aromatic hydrocarbon by converting; Simultaneously find that in a large amount of research lanthanum has little effect for the modified HZSM-5 molecular sieve, different with in the past achievement in research.
Summary of the invention
The objective of the invention is to propose a kind of selectivity and yield that can improve aromatic hydrocarbon product, the aromatization of methanol that is suitable for suitability for industrialized production is again produced the preparation technology of aromatic hydrocarbons.
For realizing above-mentioned purpose, the present invention has adopted following technical scheme: be raw material with methyl alcohol, under the certain reaction condition, with the composite modified HZSM-5 sieve catalyst of the active ion of different concns, catalysis methanol is produced aromatic hydrocarbons; HZSM-5 catalyzer (Si/Al is 25-100) wherein.Reaction can adopt fixed bed continuous processing or floating bed continuous processing to carry out, and as carrier gas, carries the flow through HZSM-5 sieve catalyst of modification of methanol steam with the nitrogen of certain air speed, produces aromatic hydrocarbon product through catalysis.In catalytic process, used the active ion modified HZSM-5 sieve catalyst of different concns; Use therein active ion one of has in copper, zinc, gallium, phosphorus, the silver or mixed assemblage, and the usage quantity of each active ion (load concentration) by weight is the 1-15% of molecular sieve.Catalytic reaction condition is: working pressure: 0.1-3.5Mpa; Service temperature: 380-500 ℃; Raw material liq air speed: 0.1-10.0h
-1N
2Air speed: 120-800h
-1
Technique effect of the present invention is: the kind and the concentration limit of the active ion that in the past is used for the modified HZSM-5 molecular sieve broken in (1); And the matched combined mode of hybrid ionic modification; Thereby expanded the method for modified catalyst greatly, made the yield of aromatic hydrocarbon product that very significantly increase arranged.(2) two components, three components or more polycomponent is mixed and modified have been given full play to the meliority of each component, can not only obviously improve the yield of aromatic hydrocarbons, and can improve the selectivity of aromatic hydrocarbon product by a relatively large margin.
Description of drawings
Fig. 1 is fluidizing reactor and revivifier synoptic diagram.
Embodiment
Below in conjunction with specific embodiment the present invention is done to further describe, but be not limited to this.
Embodiment 1:
1. Preparation of catalysts
(1) taking by weighing commercially available Si/Al (atomic ratio) is 38 powdery HZSM-5 molecular sieve, 30 grams, 520 ℃ of following roastings 4 hours, to remove volatile constituent.
(2) get (1) molecular sieve 15 that obtains of step and restrain in mortar, add 5 gram pseudo-boehmite thorough mixing, grind evenly.
(3) nitric acid with 5Wt% drips in the good material of mill, mixes and pinches suitably, crosses 100 order sub-sieves, uses the Rotarytabletpress compressing tablet, puts into baking oven in 110 ℃ of oven dry.
(4) the sheet molecular sieve that makes is put into High Temperature Furnaces Heating Apparatus, adopt the ladder-elevating temperature method to be warming up to 120 ℃ earlier, constant temperature 0.5 hour; Be warming up to 300 ℃ then, kept 1 hour, be warming up to 520 ℃ at last; Kept 4 hours; To remove nitric acid and moisture etc., reduce to room temperature afterwards naturally and take out, being processed into tap density is that every gram is equivalent to the bulk about 1 milliliter.
(5) accurately take by weighing following reagent:
Cu(NO
3)
2.3H
2O 1.5～6.0g
Zn(NO
3)
2.6H
2O 4.0～14.0g
Ga(NO
3)
3.9H
2O 2.0～8.0g
(6) mentioned reagent is put into same beaker, complete with isopyknic water heating for dissolving, stir with glass stick.
(7) molecular sieve with step (4) adds in the solution of step (6) preparation, and 80 ℃ flooded 1 hour down, stir during this on time.To remain steeping fluid and incline to, and flood by the volume of the molecular sieve water-intake rate calculating of predicting, in the present embodiment, 15 mol sieve is used 14 milliliters of steeping fluids (explaining: can adopt repeatedly dipping method) approximately.
(8) after the molecular sieve drying of dipping, with residue also diluted steeping fluid set by step (7) carry out double-steeping.
(9) treat that double-steeping liquid soaks fully and evaporate to dryness after, place 110 ℃ baking oven baking 2 hours, put into High Temperature Furnaces Heating Apparatus then, adopt gradient heating; Be warming up to 150 ℃ earlier, constant temperature 0.5 hour continues to be warming up to 300 ℃; Constant temperature 1 hour is warming up to 450 ℃ at last, is incubated 4 hours.The catalyzer that finally makes is formed (Wt%) as follows:
Powdery HZSM-5 57.7～69.4
Zn 4.0～14.0
Cu 1.8～7.4
Ga 1.6～6.2
Pseudo-boehmite 19.2～23.1.
(10) in order to ensure the quality of catalyzer, guarantee the better completion of technology of aromatization, the traditional performance of detection molecules sieve catalyst was after roasting finished:
Hardness: 50～70N
Acid density: 0.2012～0.2531mmol/g
Strength of acid: 0.3986～0.7018mmol/g.
2. Aromatizatian catalytic reaction
Use fixed bed continuous processing (referring to Fig. 1), methyl alcohol with in certain flow injected system, after vaporization, is carried the HZSM-5 sieve catalyst of the modification of flowing through down at the nitrogen of certain air speed, obtaining with aromatic hydrocarbons through catalysis is main product; Wherein reaction conditions is:
Reaction pressure 2.3Mpa
400 ℃ of temperature of reaction
Raw material liq air speed 4.0h
-1
N
2Air speed 430h
-1
Product separates the gas phase lower carbon number hydrocarbons through refrigerated separation with liquid product.Isolate aromatic hydrocarbon product, yield is 60%-65Wt%.
Embodiment 2:
In the step (3), the material behind the 100 order sub-sieves can also use the spiral banded extruder to be squeezed into the bar column type of diameter as 2-3mm excessively.
Utilize copper, zinc, gallium, phosphorus, silver-colored different kinds of ions mixed assemblage, press the foregoing description 1 and adopt fluidized-bed mode catalyzed reaction, the gained aromatics yield can reach 55-70Wt%.
Claims (3)
1. one kind is improved the technology that aromatization of methanol is produced arenes selectivity; It is characterized in that: be raw material with methyl alcohol; Under the certain reaction condition, with the composite modified HZSM-5 sieve catalyst of Ga, Zn, Cu, Ag active ion of different concns, catalysis methanol is produced aromatic hydrocarbon product; The preparation technology of described HZSM-5 sieve catalyst may further comprise the steps:
(1),, removes volatile constituent 450-550 ℃ of following roasting 4 hours with powdery HZSM-5 molecular sieve;
(2) get an amount of (1) the HZSM-5 molecular sieve and a certain proportion of tackiness agent that obtain of step and put into the mortar thorough mixing, grind evenly;
(3) nitric acid with 1-5% drips in the good material of mill, mixes and pinches suitably, crosses 100 order sub-sieves, uses the spiral banded extruder to be squeezed into the bar column type of diameter as 2-3mm, and natural air drying changes over to then and carries out the gradient oven dry in the baking oven, and temperature controlling range is 90-120 ℃;
(4) the strip molecular sieve that makes is put into High Temperature Furnaces Heating Apparatus, adopt the ladder-elevating temperature method to be warming up to 100-120 ℃ earlier, constant temperature 0.5 hour; Be warming up to 280-330 ℃ then, kept 1 hour, be warming up to 480-530 ℃ at last; Kept 4 hours; To remove nitric acid and moisture, reduce to room temperature afterwards naturally and take out, being processed into tap density is that every gram is equivalent to the bulk about 1 milliliter;
(5) quantitatively take by weighing be used for the modified HZSM-5 molecular sieve active substance in same beaker, complete with isopyknic water heating for dissolving, stir with glass stick;
(6) molecular sieve of step (4) gained is added in the solution of step (5) preparation, 80 ℃ of dippings 1 hour down stir during this on time, and heat and will remain the steeping fluid evaporation, and flood by the equal-volume of the molecular sieve water-intake rate calculating of prediction;
(7) steeping fluid soak fully and evaporate to dryness after, place 100-120 ℃ baking oven baking 2 hours, put into High Temperature Furnaces Heating Apparatus then; Adopt gradient heating, be warming up to 120-160 ℃ earlier, constant temperature 0.5 hour; Continue to be warming up to 280-320 ℃, constant temperature 1 hour is warming up to 430-490 ℃ at last; Be incubated 4 hours, finally make the HZSM-5 sieve catalyst of modification; Wherein, the described active substance that is used for the modified HZSM-5 molecular sieve is several kinds of mixed assemblages of gallium nitrate, zinc nitrate, cupric nitrate, Silver Nitrate, and load concentration is 1-15Wt%.
2. raising aromatization of methanol according to claim 1 is produced the technology of arenes selectivity, it is characterized in that:
Described reaction conditions is:
Reaction pressure: 0.1-3.5MPa;
Temperature of reaction: 380-500 ℃;
Liquid methanol air speed ratio: 0.1-10.0h
-1
N
2Air speed ratio: 120-800h
-1
3. raising aromatization of methanol according to claim 2 is produced the technology of arenes selectivity, it is characterized in that: described tackiness agent can be pseudo-boehmite, γ-Al
2O
3Or any in the zeyssatite.
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| CN103055928A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing arene via direct methanol conversion and preparation method thereof |
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| CN105949019B (en) * | 2016-04-29 | 2019-12-03 | 浙江大学 | A kind of catalyst and method improving methanol preparing aromatic hydrocarbon selectivity of product |
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| CN1048379A (en) * | 1989-06-28 | 1991-01-09 | 抚顺石油学院 | Technology of aromatization of low carbon hydrocarbon |
| CN1880288A (en) * | 2006-05-12 | 2006-12-20 | 中国科学院山西煤炭化学研究所 | Process of methanol conversion for preparing arene and catalyst and catalyst preparation method |
| CN101270297A (en) * | 2008-05-19 | 2008-09-24 | 中国科学院山西煤炭化学研究所 | Technique for synthesis of gas cobalt base Fischer-Tropsch synthetic liquid fuel and byproduct of aromatic hydrocarbons with coal base |
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| CN1048379A (en) * | 1989-06-28 | 1991-01-09 | 抚顺石油学院 | Technology of aromatization of low carbon hydrocarbon |
| CN1880288A (en) * | 2006-05-12 | 2006-12-20 | 中国科学院山西煤炭化学研究所 | Process of methanol conversion for preparing arene and catalyst and catalyst preparation method |
| CN101270297A (en) * | 2008-05-19 | 2008-09-24 | 中国科学院山西煤炭化学研究所 | Technique for synthesis of gas cobalt base Fischer-Tropsch synthetic liquid fuel and byproduct of aromatic hydrocarbons with coal base |
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| EP3718623A4 (en) * | 2017-11-30 | 2020-12-02 | Dalian Institute of Chemical Physics, Chinese Academy of Sciences | Molecular sieve-based catalyst modification apparatus, and method |
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