CN100563829C - Integral supported carbon molecular sieve catalyst and preparation method thereof is used - Google Patents
Integral supported carbon molecular sieve catalyst and preparation method thereof is used Download PDFInfo
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- CN100563829C CN100563829C CNB2008100141381A CN200810014138A CN100563829C CN 100563829 C CN100563829 C CN 100563829C CN B2008100141381 A CNB2008100141381 A CN B2008100141381A CN 200810014138 A CN200810014138 A CN 200810014138A CN 100563829 C CN100563829 C CN 100563829C
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Abstract
A kind of integral supported carbon molecular sieve catalyst, it is by integral honeycomb cordierite and CNT, and HZSM-5 type molecular sieve is formed, and wherein CNT accounts for 7～20 parts, and HZSM-5 accounts for 10～30 parts, and cordierite accounts for 60～80 parts.Preparation method: at first use chemical vapour deposition technique in-situ growing carbon nano tube on the integral honeycomb cordierite, and, adopt the diauxic growth method to grow on the carrier in the ZSM-5 molecular sieve as carrier.Integral supported carbon molecular sieve catalyst is applied in the methanol dehydration dimethyl ether synthesizing reaction.
Description
Technical field
The invention belongs to a kind of preparation of novel preparing dimethyl ether by dewatering methanol synthetic technology, particularly integral supported carbon molecular sieve catalyst and the application in methanol dehydration dimethyl ether-preparing thereof.
Background technology
The preparing dimethyl ether by dewatering methanol production method mainly contains following several at present:
A, methanol liquid-phase dehydration method.Tradition methanol liquid-phase dehydration preparing dimethy ether is to form methyl-hydrogen-sulfate monomethyl-sulfate in the presence of the concentrated sulfuric acid earlier, the regeneration dimethyl ether, though this technology reaction condition gentleness (130～160 ℃), methyl alcohol conversion per pass height (＞80%), selectivity good (＞98%), but this process equipment burn into intermediate product is poisonous, raffinate and waste water serious environment pollution in the still, has been tending towards superseded.As for patent CN1322704A, the compound acid of forming with fluid sulphuric acid and phosphoric acid generates dimethyl ether, though be successfully applied to industry, this technology is difficult to known to the external world.It is catalyst that patent CN1180064A adopts novel cationic fluid, with methanol esterification dehydration, have advantages such as conversion ratio height, quality are good, pollution-free, but this process catalyst is indeterminate, and the invention back there is no application example in nearly 10 years certainly, and also there is certain problem in explanation itself.
B, methanol gas phase dehydration method.The material (CN1164509A, CN1745894A, CN1308987A etc.) that catalyst commonly used has activated alumina (JP63056433), molecular sieve (US4177167) and gained is handled in modification on both bases.Yet these all catalyst all are granular, in fixed bed methanol dehydration dimethyl ether synthesis process, ubiquity reaction heat be difficult to the water in time shift out, generate can not be in time from catalyst surface break away from, problem such as air speed is low, the bed temperature difference is big, had a strong impact on the service life and the reaction conversion per pass of catalyst.Patent CN2723451Y, CN2928846Y, CN2900523Y etc. address the above problem from improving the consersion unit aspect, have obtained certain effect, technological process is long, equipment is complicated but exist, and invests weakness such as big.
Summary of the invention
At above problem, we have prepared a kind of novel integral supported carbon molecular sieve catalyst, utilize the active high of molecular sieve, the advantage of reaction condition gentleness, characteristics such as the bed layer pressure of the hydrophobic performance of CNT, big and modifiable surface area and integral honeycomb cordierite reduces, heat and mass transfer performance is good, enlarge-effect is little, make integral supported carbon molecular sieve catalyst, be used for the methanol dehydration dimethyl ether-preparing experiment, for industrial methanol dehydration dimethyl ether synthesis provides a kind of new method.
Integral supported carbon molecular sieve catalyst provided by the invention, it is by integral honeycomb cordierite and CNT, and HZSM-5 type molecular sieve is formed, and wherein CNT accounts for 7～20 parts, and HZSM-5 accounts for 10～30 parts, and cordierite accounts for 60～80 parts.10 parts of wherein said CNTs, HZSM-5 account for 19 parts, and the cordierite matrix accounts for 71 parts.
Integral supported carbon molecular sieve catalyst preparation method provided by the invention, at first use chemical vapour deposition technique (CVD method) in-situ growing carbon nano tube on the integral honeycomb cordierite (CNTs), and, adopt the diauxic growth method to grow on the carrier in the ZSM-5 molecular sieve as carrier.Specific embodiments is as follows: (1) cordierite carrier preliminary treatment.Get the integral honeycomb cordierite of commercially available 400cpsi, cut and wear into
The column type sample of (about 0.5g), deionized water is cleaned oven dry.(2) growth of CNT and preliminary treatment, preparation CNT-cordierite monoblock type composite catalyzing agent carrier.Cordierite with step (1) gained is a matrix, 700～850 ℃ with iron catalytic pyrolysis acetylene multi-walled carbon nano-tubes (CNTs) the preparation CNTs/ cordierite monoblock type composite catalyzing agent carrier of growing in its surface, preferred 750～800 ℃ of acetylene cracking temperature, preferred 750 ℃.Place 30% dilute nitric acid solution to boil and boil 0.5～2.0h, preferred 1.0h spends deionised water to filtrate and is neutral, oven dry.(3) precoating HZSM-5 molecular sieve crystal seed.Get step (2) gained CNT-cordierite monoblock type composite catalyzing agent carrier and place ultrasonic in advance scattered 0.2～2.0%HZSM-5 molecular sieve suspension, take out behind the 30s and blow down raffinate in the hole, dry in the shade.After the repetition above-mentioned steps 2～3 times, place 500 ℃ of roasting 2～6h of Muffle furnace.(4) diauxic growth molecular sieve.(synthetic liquid mole consists of: Al with NaOH, sodium metaaluminate, tetrapropyl ammonia bromide (TPABr), ethyl orthosilicate (TEOS) and the deionized water of certain proportioning
2O
3: aSiO
2: bNa
2O:cH
2O:dTPABr, a=20～100, preferred 40～80; B=2～30, preferred 7～15; C=3000～16000, preferred 3000～10000; D=5～25 preferred 8～17) put into autoclave, the CNT that scribbles HZSM-5 molecular sieve crystal seed in advance-cordierite monoblock type composite catalyzing agent carrier that step (3) is obtained places clear liquid in the still, at 150～190 ℃ of crystallization 24～48h, preferred 170 ℃ of crystallization 48h; Take out washing, oven dry.After the repetition above-mentioned steps 2～3 times, 550 ℃ of roasting 3～6h remove the masterplate agent and obtain the Na-ZSM-5/CNTs/ cordierite.NH with 0.5～2.0mol/L
3NO
3Solution carries out ion-exchange 2～4 times to the Na-ZSM-5/CNTs/ cordierite, NH
3NO
3The preferred 1.0mol/L of solution concentration; After spending deionised water, oven dry slowly is warming up to 500～550 ℃ of roasting 3～6h, obtains load capacity and be 10%～30% HZSM-5/CNTs/ cordierite.
A kind of application of integral supported carbon molecular sieve catalyst is characterized in that integral supported carbon molecular sieve catalyst is applied in the methanol dehydration dimethyl ether synthesizing reaction.The reaction temperature that is adopted is 170～240 ℃, air speed 6～12h
-1
Integral supported carbon molecular sieve catalyst is put into tubular reactor carry out the preparing dimethyl ether by dewatering methanol experiment, reaction equation is as follows:
2CH
3OH→CH
3OCH
3+H
2O
Catalytic reaction is carried out in tubular reactor, and reaction temperature is 150～260 ℃, and reaction pressure is 0.1～0.4MPa, and mass space velocity is 8～16h
-1Product enters the GC-6890 gas-chromatography by six-way valve and carries out on-line analysis.
The monoblock type carbon molecular sieve catalyst that the present invention adopts has following advantage:
(1) compare with the HZSM-5/ cordierite, the HZSM-5/CNTs/ cordierite has higher low-temperature reactivity.Compare catalyst ZHC-8 and ZH-12, ZHC-8 just reaches 94% at 190 ℃ of methanol conversions, and ZH-12 is 84%.
(2) adopt diauxic growth method growth molecular sieve than adopting the growth in situ method can reduce the growth number of times, economize in raw materials.Relatively catalyst ZH-12 and YZH-13 adopt the load capacity amount of No. 10 molecular sieves of growth in situ method growth just to reach 58% of diauxic growth method growth 3 times.
(3) Si/Al=38 has higher high-temperature selective, and catalyst ZHC-1 reduces to 95% 210 ℃ of dimethyl ether selectivity, and ZHC-8 is still very high 220 ℃ of dimethyl ether selectivity.
(4) compare with beaded catalyst, the integer catalyzer consumption is few, and low temperature active is good, the production efficiency height.Compare with H-1 with catalyst ZHC-1, ZHC-1 molecules of active components sieve load capacity is 0.117g, at 210 ℃, 8.5h
-1Methanol conversion can reach 95%, and the H-1 catalyst amount is 1.0g, at 240 ℃, 1.0h
-1Methanol conversion is 89%.
The specific embodiment
The present invention is described further below in conjunction with embodiment.
Embodiment 1:(1) the integral honeycomb cordierite matrix of experiment employing, hole density is 400cpsi, matrix is worn into through cutting
The column type sample after, deionized water is cleaned oven dry.(2) vacuum impregnation Fe (NO
3)
3Solution is put into carbon nano-tube growth apparatus after the oven dry, 500 ℃ of logical hydrogen nitrogen mixed gas reductase 12 h directly are warming up to 750 ℃ and feed acetylene 30min, switch to nitrogen and reduce to room temperature.There is the cordierite carrier of the thick product of CNT to put into 30%HNO with long
3Solution boils handles 1.0h, and deionized water is cleaned oven dry, and carbon nanotube loaded amount is 15%.(3) acid-treated CNT/ green stone is placed ultrasonic in advance scattered 1.0%HZSM-5 molecular sieve suspension, take out behind the 30s and blow down raffinate in the hole, dry in the shade.After the repetition above-mentioned steps 2 times, place 500 ℃ of roasting 3h of Muffle furnace, obtain to scribble the CNT-cordierite monoblock type composite catalyzing agent carrier of HZSM-5 molecular sieve crystal seed.(4) taking by weighing a certain amount of NaOH is dissolved in the deionized water, stirring and dissolving adds sodium metaaluminate, after continuing stirring and dissolving, add tetrapropyl ammonia bromide (TPABr), add deionized water after stirring a period of time, measure a certain amount of ethyl orthosilicate (TEOS) and slowly splash in the above-mentioned mixed solution, fully stir, the mole of each component consists of 1Al in the last mixed liquor
2O
3: 25SiO
2: 8Na
2O:6000H
2O:17TPABr.
(5) the HZSM-5/CNTs/ cordierite that will scribble HZSM-5 molecular sieve crystal seed is in advance vertically put into the reactor of inner liner polytetrafluoroethylene, pour reactant liquor into, at 170 ℃ of crystallization 48h, water-cooled is to room temperature, the powder molecular sieve is collected simultaneously and is used for making specific activity with the monoblock type molecular sieve, the deionized water washing is dried to neutral.Behind the repeating step (4) (5) 2 times, 550 ℃ of roasting 6h remove the masterplate agent and get the Na-ZSM-5/CNTs/ cordierite.Then use the NH of 1.0mol/L
3NO
3Solution carries out ion-exchange 2 times to the Na-ZSM-5/CNTs/ cordierite, and after the deionized water washing, oven dry slowly is warming up to 500 ℃ of roasting 3h, obtains load capacity and be 15.7% HZSM-5/CNTs/ cordierite.
Embodiment 2～3: method for preparing catalyst is with embodiment 1, and just adjusting the carbon nano tube growth time is 10～30min, and other synthesis condition is constant.Methanol conversion and dimethyl ether selectivity see Table 2, are 8%～16% scope in carbon nanotube loaded amount, and carbon nanotube loaded amount does not have much affect to methanol conversion and dimethyl ether selectivity.
Embodiment 4～5: method for preparing catalyst is with embodiment 1, and just adjusting the carbon nano tube growth temperature is 700～800 ℃, and growth time is fixed as 10min, and other synthesis condition is constant.Methanol conversion and dimethyl ether selectivity see Table 2, and the acetylene cracking temperature is very big to the carbon nano tube growth influence, is lower than 700 ℃, and what obtain is carbon distribution substantially, can not promote methanol conversion.
Embodiment 6～7: method for preparing catalyst is with embodiment 1, just adjusts the amount of water in the synthetic liquid, i.e. c=3000～8000, and other parameter immobilizes.Methanol conversion and dimethyl ether selectivity see Table 3, and the c value has influenced methanol conversion, and in this scope, under the same reaction conditions, the c value is big more, and methanol conversion is high more.
Embodiment 8～9: method for preparing catalyst is with embodiment 1, just adjusts Si/Al ratio in the synthetic liquid, i.e. a=25～52, and other parameter immobilizes.Methanol conversion and dimethyl ether selectivity see Table 3, and Si/Al ratio has determined the acidic zeolite size, when a=38, are that 190 ℃ of methanol conversions can reach 94% in reaction temperature, and the dimethyl ether selectivity reaches 100%.
Embodiment 10～11: method for preparing catalyst is with embodiment 1, and just adjusting molecular sieve crystallization time t is 24～60h, and Si/Al is fixed as 38.Methanol conversion and dimethyl ether selectivity see Table 3, and crystallization time influences perfect degree, particle size and the molecular sieve carried amount of molecular sieve crystal formation, and when crystallization time was controlled at 48h, methanol conversion was the highest, reached 94%.
Embodiment 12: method for preparing catalyst is with embodiment 1, and just carbon-free nanoscale pipe original position synthesis step, and synthetic liquid mole composition is fixed as 1Al
2O
3: 38SiO
2: 8Na
2O:6000H
2O:17TPABr.Methanol conversion and dimethyl ether selectivity see Table 3, and methanol conversion only is 84%.
Embodiment 13:(1) the integral honeycomb cordierite matrix of experiment employing, hole density is 400cpsi, matrix is worn into through cutting
The column type sample after, deionized water is cleaned oven dry.
(2) taking by weighing a certain amount of NaOH is dissolved in the deionized water, stirring and dissolving adds sodium metaaluminate, after continuing stirring and dissolving, add tetrapropyl ammonia bromide (TPABr), add deionized water after stirring a period of time, measure a certain amount of ethyl orthosilicate (TEOS) and slowly splash in the above-mentioned mixed solution, fully stir, the mole of each component consists of 1Al in the last mixed liquor
2O
3: 38SiO
2: 8Na
2O:6000H
2O:17TPABr.
(3) cordierite is vertically put into the reactor of inner liner polytetrafluoroethylene, poured into reactant liquor, at 170 ℃ of crystallization 48h, water-cooled is to room temperature, and the deionized water washing is to neutral.Behind the repeating step (2) (3) 10 times, 550 ℃ of roasting 6h remove the masterplate agent and get the Na-ZSM-5/ cordierite.Then use the NH of 1.0mol/L
3NO
3Solution carries out ion-exchange 2 times to the Na-ZSM-5/ cordierite, and after the deionized water washing, oven dry slowly is warming up to 500 ℃ of roasting 3h, obtains load capacity and be 12.3% HZSM-5/ cordierite.
Embodiment 14: the foregoing description 1 resulting catalyst pipe type micro reactor (powder molecular sieve loadings is 1.0g, compressing tablet, be crushed to 20～40 orders) of packing into is carried out the active testing experiment that methanol dehydration generates dimethyl ether.Reaction temperature is 170～240 ℃, integer catalyzer air speed 6.5～12h
-1, the beaded catalyst air speed is 1.0h
-1, pressure 0.1MPa.Methyl alcohol passes through catalytic bed by micro-injection pump from top to bottom from reaction tube, and product the results are shown in Table 1 by gas chromatographic detection.Wherein integer catalyzer is designated as ZHC-1, and beaded catalyst is designated as HC-1.
Table 1 be monoblock type carbon molecular sieve catalyst and granulin molecule sieve catalyst at 170～240 ℃, 1.0～12h
-1The selectivity of methanol conversion and dimethyl ether under the air speed.
| Sample | Temperature (℃) | Air speed (h -1) | Methanol conversion (%) | Dimethyl ether selectivity (%) |
| ZHC-1 | 170 | 8.5 | 72 | 100 |
| ZHC-1 | 190 | 8.5 | 92 | 96 |
| ZHC-1 | 210 | 8.5 | 95 | 95 |
| ZHC-1 | 230 | 8.5 | 99 | 87 |
| ZHC-1 | 190 | 6.5 | 99 | 95 |
| ZHC-1 | 190 | 12 | 86 | 97 |
| ZHC-8 | 220 | 8.5 | 95 | 100 |
| HC-1 | 220 | 1.0 | 30 | 100 |
| HC-1 | 240 | 1.0 | 89 | 99 |
Embodiment 15: the foregoing description 2～5 resulting catalyst pipe type micro reactor of packing into is carried out the active testing experiment that methanol dehydration generates dimethyl ether.Reaction temperature is 190 ℃, air speed 8.5h
-1, pressure 0.1MPa.Methyl alcohol passes through catalytic bed by micro-injection pump from top to bottom from reaction tube, and product the results are shown in Table 2 by gas chromatographic detection.Wherein integer catalyzer is designated as ZHC-m (m=2～5).
Table 2 is the influence of carbon nano tube growth condition to monoblock type carbon molecular sieve catalyst catalytic activity
| Sample | The carbon nano tube growth temperature (℃) | The carbon nano tube growth time (min) | Carbon nanotube loaded amount (%) | Methanol conversion (%) | Dimethyl ether selectivity (%) |
| ZHC-2 | 750 | 10 | 8.2 | 92 | 96 |
| ZHC-3 | 750 | 20 | 10.8 | 92 | 96 |
| ZHC-4 | 700 | 10 | * | 84 | 96 |
| ZHC-5 | 800 | 10 | 8.0 | 93 | 96 |
*: the carbon-free nanoscale pipe is carbon distribution basically
Embodiment 16: the foregoing description 6～11 and embodiment 12～13 resulting catalyst pipe type micro reactor of packing into is carried out the active testing experiment that methanol dehydration generates dimethyl ether.Reaction temperature is 190 ℃, air speed 8.5h
-1, pressure 0.1MPa.Methyl alcohol passes through catalytic bed by micro-injection pump from top to bottom from reaction tube, and product the results are shown in Table 2 by gas chromatographic detection.Wherein embodiment 6～11 catalyst are designated as ZHC-m (m=6～11), and embodiment 12～13 catalyst are designated as ZH-12 and YZH-13 respectively.
Table 3 is the influence of molecular sieve preparation parameter to monoblock type carbon molecular sieve catalyst catalytic activity.
| Sample | c | a | t(h) | Molecular sieve carried amount (%) | Methanol conversion (%) | Dimethyl ether selectivity (%) |
| ZHC-6 | 3000 | 25 | 48 | 20.1 | 89 | 94 |
| ZHC-7 | 8000 | 25 | 48 | 13.9 | 93 | 96 |
| ZHC-8 | 6000 | 38 | 48 | 16.0 | 94 | 100 |
| ZHC-9 | 6000 | 52 | 48 | 15.7 | 82 | 100 |
| ZHC-10 | 6000 | 38 | 24 | 13.5 | 77 | 100 |
| ZHC-11 | 6000 | 38 | 60 | 24.5 | 93 | 97 |
| ZH-12 | 6000 | 38 | 48 | 11.1 | 84 | 100 |
| YZH-13 | 6000 | 38 | 48 | 12.3 | 84 | 100 |
Claims (10)
1, a kind of integral supported carbon molecular sieve catalyst is characterized in that it by integral honeycomb cordierite and CNT, and HZSM-5 type molecular sieve is formed, and wherein CNT accounts for 7～20 parts, and HZSM-5 accounts for 10～30 parts, and cordierite accounts for 60～80 parts.
2, integral supported carbon molecular sieve catalyst according to claim 1 is characterized in that 10 parts of described CNTs, and HZSM-5 accounts for 19 parts, and the cordierite matrix accounts for 71 parts.
3, the preparation method of the described integral supported carbon molecular sieve catalyst of claim 1, it is characterized in that at first using chemical vapour deposition technique in-situ growing carbon nano tube on the integral honeycomb cordierite, and, adopt the diauxic growth method to grow on the carrier in the ZSM-5 molecular sieve as carrier.
4, the preparation method of integral supported carbon molecular sieve catalyst according to claim 3 is characterized in that it may further comprise the steps: (1) cordierite carrier preliminary treatment; (2) growth of CNT and preliminary treatment, preparation CNT-cordierite monoblock type composite catalyzing agent carrier; (3) precoating HZSM-5 molecular sieve crystal seed; (4) diauxic growth molecular sieve.
5, the preparation method of integral supported carbon molecular sieve catalyst according to claim 4 is characterized in that described cordierite carrier preliminary treatment is meant the integral honeycomb cordierite of getting commercially available 400cpsi, and deionized water is cleaned oven dry.
6, the preparation method of integral supported carbon molecular sieve catalyst according to claim 4, it is characterized in that the growth of described CNT and preliminary treatment are meant being matrix through pretreated cordierite, prepare CNT-cordierite monoblock type composite catalyzing agent carrier with the iron catalytic pyrolysis acetylene multi-walled carbon nano-tubes of growing in its surface at 750～800 ℃; After placing 30% dilute nitric acid solution to boil to boil 1.5h, spend deionised water to filtrate and be neutral, oven dry, 550 ℃ of roasting 4h.
7, the preparation method of integral supported carbon molecular sieve catalyst according to claim 4, it is characterized in that described precoating HZSM-5 molecular sieve crystal seed is meant that getting CNT-cordierite monoblock type composite catalyzing agent carrier places ultrasonic in advance scattered 1%HZSM-5 molecular sieve suspension, take out behind the 30s and blow down raffinate in the hole, dry in the shade;
After repeating this step 2～3 time, place 500 ℃ of roasting 3h of Muffle furnace.
8, the preparation method of integral supported carbon molecular sieve catalyst according to claim 4, it is characterized in that described diauxic growth molecular sieve is meant puts into autoclave with NaOH, sodium metaaluminate, tetrapropyl ammonia bromide, ethyl orthosilicate and the deionized water of certain proportioning, and synthetic liquid mole consists of: Al
2O
3: aSiO
2: bNa
2O: cH
2O: dTPABr, a=20～100, b=2～30, c=3000～10000, d=5～20; CNT-cordierite monoblock type composite catalyzing the agent carrier that scribbles HZSM-5 molecular sieve crystal seed is in advance placed clear liquid in the still, at 170 ℃ of crystallization 48h, take out washing, oven dry; After the repetition above-mentioned steps 2 times, 550 ℃ of roasting 4h; NH with 1.0mol/L
3NO
3Solution carries out ion-exchange 2～4 times, spend deionised water after, oven dry slowly is warming up to 540 ℃ of roasting 6h, obtains load capacity and be 10%～25% integral supported carbon molecular sieve catalyst.
9, the purposes of integral supported carbon molecular sieve catalyst according to claim 1 is characterized in that integral supported carbon molecular sieve catalyst is applied in the methanol dehydration dimethyl ether synthesizing reaction.
10, the purposes of integral supported carbon molecular sieve catalyst according to claim 9 is characterized in that the reaction temperature that is adopted is 170～240 ℃, air speed 6～12h
-1
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Families Citing this family (33)
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| CN116535239A (en) * | 2023-05-10 | 2023-08-04 | 广东比沃新能源有限公司 | Preparation method of carbon-loaded nano honeycomb ceramic and reactor equipment for carbon loading |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4800187A (en) * | 1987-10-28 | 1989-01-24 | Corning Glass Works | Method of crystallizing a zeolite on the surface of a monolithic ceramic substrate |
| CN1171294A (en) * | 1996-07-22 | 1998-01-28 | 中国石油化工总公司 | Catalytic ZSM-5/metal or ceramic compounded material and its preparation |
| CN1269262A (en) * | 1999-04-07 | 2000-10-11 | 中国科学院大连化学物理研究所 | In-site molecular sieve synthesizing process on lumpy honeycomb cordierite ceramic carrier |
| CN1683076A (en) * | 2004-04-16 | 2005-10-19 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether from synthetic gas by one step |
-
2008
- 2008-02-03 CN CNB2008100141381A patent/CN100563829C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4800187A (en) * | 1987-10-28 | 1989-01-24 | Corning Glass Works | Method of crystallizing a zeolite on the surface of a monolithic ceramic substrate |
| CN1171294A (en) * | 1996-07-22 | 1998-01-28 | 中国石油化工总公司 | Catalytic ZSM-5/metal or ceramic compounded material and its preparation |
| CN1269262A (en) * | 1999-04-07 | 2000-10-11 | 中国科学院大连化学物理研究所 | In-site molecular sieve synthesizing process on lumpy honeycomb cordierite ceramic carrier |
| CN1683076A (en) * | 2004-04-16 | 2005-10-19 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether from synthetic gas by one step |
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