CN101940934A - Catalyst for preparing dimethyl ether by synthetic gas and preparation method and application thereof - Google Patents
Catalyst for preparing dimethyl ether by synthetic gas and preparation method and application thereof Download PDFInfo
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- CN101940934A CN101940934A CN2009101578728A CN200910157872A CN101940934A CN 101940934 A CN101940934 A CN 101940934A CN 2009101578728 A CN2009101578728 A CN 2009101578728A CN 200910157872 A CN200910157872 A CN 200910157872A CN 101940934 A CN101940934 A CN 101940934A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 159
- 238000006243 chemical reaction Methods 0.000 claims abstract description 93
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 66
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 66
- 239000011701 zinc Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- 238000001556 precipitation Methods 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000000975 co-precipitation Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- PPQREHKVAOVYBT-UHFFFAOYSA-H aluminium carbonate Inorganic materials [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims abstract description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 40
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 40
- 230000004048 modification Effects 0.000 claims description 33
- 238000012986 modification Methods 0.000 claims description 33
- 239000004411 aluminium Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 13
- 238000010790 dilution Methods 0.000 claims description 12
- 239000012895 dilution Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 238000009938 salting Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract 3
- 229940118662 aluminum carbonate Drugs 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 39
- 230000001588 bifunctional effect Effects 0.000 description 16
- 230000018044 dehydration Effects 0.000 description 13
- 238000006297 dehydration reaction Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000000320 mechanical mixture Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
The invention provides a catalyst for preparing dimethyl ether by synthetic gas and a preparation method and an application thereof. The preparation method comprises the following steps: a) carrying out parallel flow coprecipitation on mixed nitrate solution containing copper, zinc and aluminum and sodium carbonate solution, ageing the obtained precipitation solution to obtain slurry which is a precursor for methanol synthesis catalyst; b) carrying out backflow treatment on pseudo-boehmite with SO42-containing acid or salt solution, filtering and drying to obtain the modified pseudo-boehmite; and c) adding the modified pseudo-boehmite to the precursor for the methanol synthesis catalyst, stirring and mixing evenly, filtering, drying and roasting to obtain the target product. The preparation method of the invention has simple preparation process, good repeatability, mild reaction condition, high catalytic activity and good stability, and the method can help solve the problems of high reaction temperature and poor catalyst stability in the prior art.
Description
Technical field
The present invention relates to a kind of catalyst that is used for the synthesis gas preparation dimethyl ether.
The invention still further relates to above-mentioned Preparation of catalysts method.
The invention still further relates to the application of above-mentioned catalyst in preparing dimethylether from synthetic gas by reaction.
Background technology
Dimethyl ether is a kind of important chemical material, be widely used in fields such as pharmacy, fuel, agricultural chemicals, refrigeration, daily-use chemical industry, have nontoxic, safety, combustion thermal efficiency height, the clean no black smoke of combustion tail gas, metal had advantage such as corrosion, can be used as propellant, domestic fuel and diesel fuel etc., is desirable liquefied fuel gas substitute; Also be the important intermediate that natural gas and coal are produced liquid fuel simultaneously, it is the green fuel of a kind of putative 21st century, be a kind of clean energy resource carrier of potentialization, crucial status arranged in modern chemical industry production, thereby at home and abroad draw attention day by day.
The Dehydration of methanol that traditional commercial run of producing dimethyl ether is on solid acid catalyst to be carried out.All the catalyst progress of preparing dimethyl ether by dewatering methanol is reported as Chinese patent CN 1613558A, CN 1745894A, CN 1106219C, CN1895779A, CN 1919451A, CN 1151110C and U.S. Pat 707606, US4560807 etc. from different angles, but all there is certain defective, or reaction temperature is higher, stable unfavorable to catalyst; Or preparation process complexity; Or containing rare earth element or noble metal in the modified component, cost is higher.
In recent years, developed that with the synthesis gas be the new process that raw material is directly produced dimethyl ether, also more and more be subjected to researcher's attention.By the catalyst that direct synthesis of dimethyl ether from synthesis gas adopted is the bifunctional catalyst that is composited by methanol synthesis catalyst and methanol dehydration catalyst, methanol synthesis catalyst is mainly copper, zinc-base O composite metallic oxide catalyst, as composite oxides such as Cu-Zn-Al, Cu-Zn-Zr or Cu-Zn-Cr; Methanol dehydration catalyst mainly adopts γ-Al
2O
3Or solid acid catalyst such as molecular sieve.When using this bifunctional catalyst to react, there is the synthetic and methanol dehydration two classes reaction of methyl alcohol in the reaction system simultaneously, there is cooperative effect between each component of catalyst, the very fast dehydration of the methyl alcohol that generates generates dimethyl ether, feasible reaction has broken through the thermodynamics equilibrium limit in the simple methyl alcohol synthetic reaction, increase the reaction motive force, can effectively reduce the conversion per pass of operating pressure and raising CO.
Patent US 5753716 discloses a kind of directly by the method for producing dimethyl ether by synthesis gas, and this method is that one or more composite oxides of employing copper, zinc, aluminium, chromium are that methanol synthesis catalyst and aluminum phosphate are methanol dehydration catalyst.This bifunctional catalyst system has good stable, but the life-span be 934h only also, and activity of such catalysts is lower.
Patent US 4417000 discloses a kind of directly by the preparation method of the bifunctional catalyst of synthesis gas preparation dimethyl ether, and this method is to adopt the activated alumina of tungsten modification as methanol dehydration catalyst.At H
2/ CO mol ratio is 1.0, reaction pressure 6.21MPa, reaction temperature 285-300 ℃ and the about 3000h of unstripped gas air speed
-1Condition under, the CO conversion ratio is 26.7-52.5%, the DME selectivity is 98%.This shows that the reaction temperature and the reaction pressure of this catalyst are higher, the CO conversion ratio is lower, the stability problem of this patent of invention and not mentioned bifunctional catalyst.
Patent ZL 00133279.1 discloses a kind of directly by the bifunctional catalyst and the preparation technology thereof of synthesis gas preparing dimethy ether, and this catalyst comprises that mainly weight percentage is that metal oxide and the weight percentage of 30%-70% is the acidic components of 30%-70%.Wherein metal oxide is one or more mixtures in cupric oxide, zinc oxide, chromium oxide, the cerium oxide, and acidic components are one or more mixtures in molecular sieve, aluminium oxide, the aluminum phosphate.At H
2/ CO mol ratio is 3.85, reaction pressure 4.0MPa, 300 ℃ of reaction temperatures and the about 1500h of unstripped gas air speed
-1Condition under, CO conversion ratio 81.75%.The required reaction temperature of this catalyst is higher, the H in the needed raw material gas
2/ CO is than higher, and the stability problem of not mentioned catalyst in should invention.
Patent CN 101157038A discloses a kind of Catalysts and its preparation method of synthesizing dimethyl ether one-step with synthesis gas as well, be characterized in " one pot " preparation in same environment of synthetic component of methyl alcohol and methanol dehydration component, add Cu, Zn active component fully and form required silicon source, aluminium source and template agent such as Si-Al oxide, molecular sieve in liquid phase environment, preparing general formula is the slurried catalyst of CuZnMSiAl (M is an auxiliary agent).At H
2/ CO mol ratio is 1.0, under the condition of 280 ℃ of reaction pressure 4.0MPa, reaction temperature, the CO conversion ratio is 40.07%, the DME selectivity is 66.1%.The reaction temperature of this catalyst is still higher, and reactivity is very low, and is somebody's turn to do the stability problem of not mentioned catalyst in the invention.
Patent ZL 93115774.9 discloses a kind of by the process of preparation of dimethyl ether from synthesis gas reaction with catalyst and preparation dimethyl ether thereof, and this method adopts the γ-Al of the oxide modifying of boron, titanium or P elements
2O
3The bifunctional catalyst that forms for methanol dehydration component and industrial catalst for synthesis of methanol mechanical mixture.At H
2/ CO mol ratio is about 2.0, reaction pressure 3.5MPa, 260 ℃ of reaction temperatures, reaction velocity 1000h
-1Condition under, 83% before by the modification of CO conversion ratio brings up to 85%, the DME selectivity also is increased to 94% by 84% before the modification.But the reaction temperature of this catalyst still higher (being higher than 250 ℃), and the stability problem of not mentioned catalyst still in should invention.
Patent ZL 200410016391.2 discloses a kind of method by direct preparation of dimethyl ether by using synthesis gas, and this method is used through SO
4 2-γ-the Al of modification
2O
3The bifunctional catalyst that is composited with the synthetic component of Cu, Zn base methyl alcohol is as the synthetic catalyst of dimethyl ether.SO wherein
4 2-γ-the Al of modification
2O
3Be to adopt simple immersion process for preparing and get, be about to a certain amount of γ-Al
2O
3Pour into and flood 2h in the sulfate liquor, then elimination raffinate and oven dry, roasting.At H
2/ CO mol ratio is 2.0, reaction pressure 4.0MPa, 270 ℃ of reaction temperatures, reaction velocity 1500h
-1Condition under, CO conversion ratio 93.6%, DME selectivity 94.6%.As seen, adopt SO
4 2-γ-the Al of modification
2O
3Be methanol dehydration catalyst, can make CO conversion ratio and DME selectivity that raising is significantly arranged, but still do not mention the stability problem of catalyst in this patent of invention.
This shows that there are defectives such as reaction temperature height, CO conversion ratio be low in the disclosed bifunctional catalyst of being made up of methanol synthesis catalyst and methanol dehydration catalyst of above-mentioned several patents of invention, and most of patent equal service life of not mentioned catalyst.Therefore the catalytic activity and the stability of this bifunctional catalyst await further raising, obtain one and synthesis gas prepared directly that the dimethyl ether reaction has high CO conversion ratio and are the target directions that catalyst preparation technology develops than the catalyst of long life.
Summary of the invention
The purpose of this invention is to provide a kind of high activity of synthesis gas preparation dimethyl ether, bifunctional catalyst of high stability of being used for.
Another purpose of the present invention provides the method for the above-mentioned catalyst of preparation.
For achieving the above object, catalyst provided by the invention is to obtain by following steps:
A) preparation of methanol synthesis catalyst presoma: with the nitrate mixed solution and the sodium carbonate liquor of copper, zinc and aluminium and flow co-precipitation, the gained precipitation solution is worn out, the gained slurries are the methanol synthesis catalyst presoma; Wherein the mass ratio of institute's cupric, zinc, aluminium is 15-65: 10-40: 2-20 in the nitrate mixed solution;
B) modification boehmite preparation: the boehmite employing is contained SO
42-Acid or salting liquid reflow treatment, filter, after the drying the modification boehmite; SO wherein
4 2-Mass content be 1-15%;
C) the modification boehmite that step b is obtained joins in the methanol synthesis catalyst presoma of step a, after mixing after filtration, dry, roasting gets target product.
The method of the above-mentioned catalyst of preparation provided by the invention, its key step is
A) preparation of methanol synthesis catalyst presoma: with the nitrate mixed solution of copper, zinc and aluminium and sodium carbonate liquor under 50-80 ℃, the condition of pH=6.0-10.0 and flow co-precipitation, at 60-90 ℃ down aging 1-4 hour (h), the gained slurries are the methanol synthesis catalyst presoma with the gained precipitation solution; Wherein the mass ratio of institute's cupric, zinc, aluminium is 15-65: 10-40: 2-20 in the nitrate mixed solution.
B) modification boehmite preparation: the boehmite employing is contained SO
4 2-Acid or salting liquid at 50-90 ℃ of following reflow treatment 12-72 hour, filter, after the drying the modification boehmite; SO wherein
4 2-Mass content be 1-15%; Contain SO
4 2-Acid or salt be H
2SO
4, Al
2(SO
4)
3, ZnSO
4, FeSO
4, (NH
4)
2SO
4, Ti (SO
4)
2Or the mixture of its arbitrary proportion.
C) the modification boehmite that step b is obtained joins in the methanol synthesis catalyst presoma of step a, after filtration, 80-150 ℃ of 12-72 hour drying time, again in 350-700 ℃ of roasting 2-30 hour, gets target product after mixing.
Among the described preparation method, the mass ratio of copper, zinc, aluminium is preferably 25-50 in the nitrate mixed solution among the step a: 15-30: 5-10.
Among the described preparation method, the co-precipitation temperature among the step a is preferably 60-70 ℃, pH value and is preferably=and 7.0-9.0, ageing time be preferably 1-3h.
Among the described preparation method, SO in the modification boehmite among the step c
4 2-The quality percentage composition be preferably 3-12%.
Among the described preparation method, contain SO among the step c
4 2-Acid or salt be preferably Al
2(SO
4)
3, ZnSO
4Or (NH
4)
2SO
4
Among the described preparation method, the SO among the step c
4 2-The reflux temperature of handling boehmite is preferably 60-80 ℃, and return time is preferably 24-72h.
Among the described preparation method, the mass ratio of the modification boehmite that adds in the steps d and institute's cupric, zinc, aluminium-mixed oxide is preferably 2: 1-4: 1.
Among the described preparation method, the baking temperature in the steps d is preferably 90-120 ℃, is preferably 12-48h drying time.
Among the described preparation method, the sintering temperature in the steps d is preferably 450-600 ℃, and roasting time is preferably 3-8h.
Catalyst of the present invention is used for preparing dimethylether from synthetic gas by reaction, and catalyst is seated in the fixed bed reactors, uses N under normal pressure
2The H of dilution
2In 250-280 ℃, air speed 1000-3000h
-1Reduction is 6-8 hour under the condition; After being cooled to 80-100 ℃ with N
2The H of dilution
2Switch to synthesis gas, heat up and carry out synthetic reaction, reaction condition is: temperature 200-280 ℃, and pressure 1-10MPa, air speed 500-10000h
-1, reaction time 5-10 hour, chromatogram on-line analysis product and tail gas were formed.N
2The H of dilution
2Consist of by volume: N
2/ H
2=10-20/1; Synthesis gas by volume consists of: H
2/ CO/CO
2=2/1-2/0.1-2.
Catalyst of the present invention is in preparing dimethylether from synthetic gas by reaction, and preferred reaction temperature is 230-260 ℃, and reaction pressure is 3-5MPa, air speed 1000-3000h
-1
Among the preparation method of the present invention, SO
4 2-The modification boehmite is handled with roasting heat with the compound back of catalst for synthesis of methanol precursor drying and is compared with the catalyst of present document and patent report, at first be chemical composition and physical arrangement homogeneous, obviously be different from the traditional industrial methanol catalyst and the mechanical mixture of dehydration catalyst.Adopt SO
4 2-The modification boehmite is easy on the one hand and the methanol synthesis catalyst precursor is compound, after calcination process, form the proper acidic position on the other hand, particularly under the reaction in-situ condition, induce activation, metal active center and dehydration activity center show the obvious synergistic effect, have overcome two kinds of activated centres from microcosmic mechanism and have poisoned the deactivation phenomenom that causes mutually.The overall performance of composite catalyst is embodied in has very high reactivity, particularly low temperature active, thereby has effectively suppressed the coking in the direct synthesis of dimethyl ether from synthesis gas process and the sintering of active component.Reaction test to direct synthesis of dimethyl ether from synthesis gas in fixed bed reactors illustrates that bifunctional catalyst of the present invention has shown good stable, and line duration has surpassed 1000h.Therefore, bifunctional catalyst of the present invention has the advantage that reaction temperature is low, catalytic activity is high, catalytic performance is stable.
Catalyst of the present invention is suitable for the synthesizing dimethyl ether by synthetic gas in various sources such as coal, natural gas and living beings, is suitable for various types of reactors such as fixed bed, slurry attitude bed, bubble tower, fluid bed simultaneously.
Description of drawings
Fig. 1 is the estimation of stability experimental result that embodiment 1 prepared catalyst original position is induced activation and 1000h.
The specific embodiment:
The present invention solves the problem of the not high and poor stability of the reaction temperature height, the catalyst activity that exist in the prior art, provide a kind of and have lower reaction temperature, higher CO conversion ratio and dimethyl ether, a kind of bifunctional catalyst and preparation and using method of high stability especially is provided optionally by the bifunctional catalyst and the preparation technology thereof of direct preparation of dimethyl ether by using synthesis gas.
The technical solution used in the present invention is as follows:
(1) Preparation of catalysts
The preparation method of the bifunctional catalyst of the high activity by direct preparation of dimethyl ether by using synthesis gas provided by the invention, high stability may further comprise the steps successively:
1. the preparation of methanol synthesis catalyst presoma: the nitrate mixed solution of copper, zinc, aluminium and sodium carbonate liquor are under 50-80 ℃, the condition of pH=6.0-10.0 and flow co-precipitation in temperature, with gained precipitation solution aging 1-4h under 60-90 ℃, the gained slurries are the methanol synthesis catalyst presoma, and wherein the mass ratio of institute's cupric, zinc, aluminium is 15-65: 10-40: 2-20 in the nitrate mixed solution;
2. modification boehmite preparation: adopt commercial boehmite and contain SO
4 2-Acid or salting liquid reflow treatment 12-72h under 50-90 ℃ condition, filter then solid sample, will obtain the modification boehmite after the washing of the solid sample of gained, the drying, wherein SO
4 2-Mass content be 1-15%;
3. the modification boehmite that step is obtained in 2. joins in the methanol synthesis catalyst presoma that step obtains in 1., after mixing after filtration, washing, 80-150 ℃ dry 12-72h, a 350-700 ℃ roasting 2-30h make dimethyl ether synthetic catalyst.
(2) use of catalyst
Be crushed to the 40-60 order behind the catalyst compression molding, be seated in the pressurization static bed reactor of stainless steel of 5mm internal diameter, under normal pressure, use N
2The H of dilution
2In 250-280 ℃, air speed 1000-3000h
-1Reduce 6-8h under the condition, be cooled to 80-100 ℃ after with N
2The H of dilution
2Switch to the high pressure synthesis gas, synthetic reaction is carried out in temperature programming then, and reaction condition is: temperature 200-280 ℃, and pressure 1-10MPa, air speed 500-10000h
-1Reach the optimum response state induce 5-10h under reaction condition after, chromatogram on-line analysis product and tail gas are formed.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
With 48.3g Cu (NO
3)
2.3H
2O, 24.3g Zn (NO
3)
2.6H
2O and 17.4g Al (NO
3)
3.9H
2O is dissolved in the 600ml distilled water, be made into the mixed solution of stable homogeneous after, under the condition of 70 ℃ of temperature of control and pH=7.5, (take by weighing the 50g anhydrous Na with sodium carbonate liquor
2CO
3Be dissolved in the 800mL deionized water) and flow co-precipitation, make precipitation evenly mixed, after precipitation was complete, precipitation solution continued at 70 ℃ of aging 1h, and the gained slurries are the precursor of methanol synthesis catalyst.Wherein the mass ratio of copper, zinc, aluminium is 43: 18: 4.24.
With 50.8g (NH
4)
2SO
4Be dissolved in the 320ml distilled water, be made into SO
4 2-Mass content is 7.5% (NH
4)
2SO
4Solution, then toward wherein pouring the commercial boehmite powder of 20g into, reflow treatment 24h under 65 ℃ condition, filter then solid sample, with the solid sample washing back of gained in 110 ℃ of dry 12h.With the SO that makes
4 2-The boehmite of modification joins in the precursor slurries of methanol synthesis catalyst of preparation, mixes after filtration washing in 110 ℃ of dry 12h, is transferred in the Muffle furnace then in 500 ℃ of following roasting 4h, promptly gets dimethyl ether synthetic catalyst.
To be crushed to the 40-60 order behind the dimethyl ether synthetic catalyst compression molding, be seated in the pressurization static bed reactor of stainless steel of 5mm internal diameter, under normal pressure, use N
2The H of dilution
2(H
2Molar content: 5%, air speed 1500h
-1) 270 ℃ of reduction 6 hours.Cool to 100 ℃ and switch to synthesis gas (H
2/ CO/CO
2=1: 1: 0.16) synthetic reaction is carried out in pressurization, temperature programming again, and reaction condition is as follows: 250 ℃ of temperature, pressure 4.0MPa, air speed 1500h
-1, reaction time 1000h.Reach the optimum response state induce 5-10h under reaction condition after, chromatogram on-line analysis product and tail gas are formed.Reaction result is seen Fig. 1.
Embodiment 2
With 48.3g Cu (NO
3)
2.3H
2O, 24.3g Zn (NO
3)
2.6H
2O and 17.4g Al (NO
3)
3.9H
2O is dissolved in the 600ml distilled water, be made into the mixed solution of stable homogeneous after, under the condition of 60 ℃ of temperature of control and pH=9, (take by weighing the 50g anhydrous Na with sodium carbonate liquor
2CO
3Be dissolved in the 800mL deionized water) and flow co-precipitation, make precipitation evenly mixed, after precipitation was complete, precipitation solution continued at 70 ℃ of aging 3h, and the gained slurries are the precursor of methanol synthesis catalyst.Wherein the mass ratio of copper, zinc, aluminium is 43: 18: 4.24.
With 11.85g Al
2(SO
4)
3Be dissolved in the 320ml distilled water, be made into SO
4 2-Mass content is 3% Al
2(SO
4)
3Solution, then toward wherein pouring the commercial boehmite powder of 20g into, reflow treatment 24h under 75 ℃ condition, filter then solid sample, with the solid sample washing back of gained in 110 ℃ of dry 12h.With the SO that makes
4 2-The boehmite of modification joins in the precursor slurries of methanol synthesis catalyst of preparation, mixes after filtration washing in 110 ℃ of dry 12h, is transferred in the Muffle furnace then in 500 ℃ of following roasting 4h, promptly gets dimethyl ether synthetic catalyst.
To be crushed to the 40-60 order behind the dimethyl ether synthetic catalyst compression molding, be seated in the pressurization static bed reactor of stainless steel of 5mm internal diameter, under normal pressure, use N
2The H of dilution
2(H
2Molar content: 10%, air speed 1500h
-1) 270 ℃ of reduction 6 hours.Cool to 100 ℃ and switch to synthesis gas (H
2/ CO/CO
2=1: 1: 0.16) synthetic reaction is carried out in pressurization, temperature programming again, and reaction condition is as follows: 260 ℃ of temperature, pressure 4.0MPa, air speed 1000h
-1, reaction time 40h.Reach the optimum response state induce 5-10h under reaction condition after, chromatogram on-line analysis product and tail gas are formed.Reaction result sees Table 1.
Embodiment 3
With 48.3g Cu (NO
3)
2.3H
2O, 24.3g Zn (NO
3)
2.6H
2O and 17.4g Al (NO
3)
3.9H
2O is dissolved in the 600ml distilled water, be made into the mixed solution of stable homogeneous after, under the condition of 60 ℃ of temperature of control and pH=8, (take by weighing the 50g anhydrous Na with sodium carbonate liquor
2CO
3Be dissolved in the 800mL deionized water) and flow co-precipitation, make precipitation evenly mixed, after precipitation was complete, precipitation solution continued at 70 ℃ of aging 2h, and the gained slurries are the precursor of methanol synthesis catalyst.Wherein the mass ratio of copper, zinc, aluminium is 43: 18: 4.24.
With 76.2g (NH
4)
2SO
4Be dissolved in the 320ml distilled water, be made into SO
4 2-Mass content is 10% (NH
4)
2SO
4Solution, then toward wherein pouring the commercial boehmite powder of 20g into, reflow treatment 24h under 75 ℃ condition, filter then solid sample, with the solid sample washing back of gained in 110 ℃ of dry 12h.With the SO that makes
4 2-The boehmite of modification joins in the precursor slurries of methanol synthesis catalyst of preparation, mixes after filtration washing in 110 ℃ of dry 12h, is transferred in the Muffle furnace then in 500 ℃ of following roasting 4h, promptly gets dimethyl ether synthetic catalyst.
To be crushed to the 40-60 order behind the dimethyl ether synthetic catalyst compression molding, be seated in the pressurization static bed reactor of stainless steel of 5mm internal diameter, under normal pressure, use N
2The H of dilution
2(H
2Molar content: 5%, air speed 1000h
-1) 260 ℃ of reduction 6 hours.Cool to 100 ℃ and switch to synthesis gas (H
2/ CO/CO
2=1: 1: 0.16) synthetic reaction is carried out in pressurization, temperature programming again, and reaction condition is as follows: 250 ℃ of temperature, pressure 4.0MPa, air speed 1500h
-1, reaction time 40h.Reach the optimum response state induce 5-10h under reaction condition after, chromatogram on-line analysis product and tail gas are formed.Reaction result sees Table 1.
Embodiment 4
With 48.3g Cu (NO
3)
2.3H
2O, 24.3g Zn (NO
3)
2.6H
2O and 17.4g Al (NO
3)
3.9H
2O is dissolved in the 600ml distilled water, be made into the mixed solution of stable homogeneous after, under the condition of 60 ℃ of temperature of control and pH=7.5, (take by weighing the 50g anhydrous Na with sodium carbonate liquor
2CO
3Be dissolved in the 800mL deionized water) and flow co-precipitation, make precipitation evenly mixed, after precipitation was complete, precipitation solution continued at 70 ℃ of aging 1h, and the gained slurries are the precursor of methanol synthesis catalyst.Wherein the mass ratio of copper, zinc, aluminium is 43: 18: 4.24.
With 107.6g ZnSO
4Be dissolved in the 320ml distilled water, be made into SO
4 2-Mass content is 15% ZnSO
4Solution, then toward wherein pouring the commercial boehmite powder of 20g into, reflow treatment 24h under 75 ℃ condition, filter then solid sample, with the solid sample washing back of gained in 110 ℃ of dry 12h.With the SO that makes
4 2-The boehmite of modification joins in the precursor slurries of methanol synthesis catalyst of preparation, mixes after filtration washing in 110 ℃ of dry 12h, is transferred in the Muffle furnace then in 500 ℃ of following roasting 4h, promptly gets dimethyl ether synthetic catalyst.
To be crushed to the 40-60 order behind the dimethyl ether synthetic catalyst compression molding, be seated in the pressurization static bed reactor of stainless steel of 5mm internal diameter, under normal pressure, use N
2The H of dilution
2(H
2Molar content: 5%, air speed 3000h
-1) 280 ℃ of reduction 6 hours.Cool to 100 ℃ and switch to synthesis gas (H
2/ CO/CO
2=1: 1: 0.16) synthetic reaction is carried out in pressurization, temperature programming again, and reaction condition is as follows: 250 ℃ of temperature, pressure 6.0MPa, air speed 1500h
-1, reaction time 40h.Reach the optimum response state induce 5-10h under reaction condition after, chromatogram on-line analysis product and tail gas are formed.Reaction result sees Table 1.
Embodiment 5
Preparation of catalysts method and appreciation condition be with embodiment 1, and the mass ratio of copper, zinc, aluminium is 25.8: 12: 4.24 in the precursor slurries of different is methanol synthesis catalyst.Reaction time 40h, reaction result sees Table 1.
Embodiment 6
Preparation of catalysts method and appreciation condition are with embodiment 1, and different is to pour (NH into
4)
2SO
4The quality of the boehmite in the solution is 30g.Reaction time 40h, reaction result sees Table 1.
Embodiment 7
Preparation of catalysts method and appreciation condition are with embodiment 1, and that different is (NH
4)
2SO
4The time of solution reflow treatment boehmite is 48h.Reaction time 60h, reaction result sees Table 1.
Embodiment 8
Preparation of catalysts method and appreciation condition are with embodiment 1, and that different is the SO that makes
4 2-The precursor slurry mixture of the methanol synthesis catalyst among the boehmite of modification and the embodiment 1 after filtration, transfer in the Muffle furnace in 400 ℃ of following roasting 4h after the washing, drying.Reaction temperature is 230 ℃, air speed 1000h
-1, pressure 5.0Mpa, reaction time 40h, reaction result sees Table 1.
Embodiment 9
Preparation of catalysts method and appreciation condition are with embodiment 1, and that different is the SO that makes
4 2-The precursor slurry mixture of the methanol synthesis catalyst among the boehmite of modification and the embodiment 1 after filtration, transfer in the Muffle furnace in 700 ℃ of following roasting 4h after the washing, drying.Reaction time 40h, reaction result sees Table 1.
Embodiment 10
Preparation of catalysts method and service condition be with embodiment 3, and the reaction condition of different is catalyst is: 250 ℃ of temperature, pressure 6.0MPa, air speed 3000h
-1Reaction time 40h, reaction result sees Table 1.
Embodiment 11
Preparation of catalysts method and service condition be with embodiment 3, and the reaction condition of different is catalyst is: 250 ℃ of temperature, pressure 3.0MPa, air speed 1000h
-1Reaction time 40h, reaction result sees Table 1.
Embodiment 12
Preparation of catalysts method and service condition be with embodiment 3, and the reaction condition of different is catalyst is: synthesis gas consists of H
2/ CO/CO
2=1: 1: 1,250 ℃ of temperature, pressure 4.0MPa, air speed 1000h
-1Reaction time 40h, reaction result sees Table 1.
Embodiment 13
Preparation of catalysts method and service condition are with embodiment 3, and that different is the reaction pressure 5.0MPa of catalyst.Reaction time 40h, reaction result sees Table 1.
Embodiment 14
Preparation of catalysts method and service condition are with embodiment 3, and different is that synthesis gas consists of H
2/ CO/CO
2=2: 1: 0.16.Reaction time 40h, reaction result sees Table 1.
Subordinate list 1: embodiment catalyst reaction result
* CO
2Do not count, other minor by-products is methyl alcohol, carbon two and carbon three hydro carbons.
Claims (10)
1. catalyst that is used for the synthesis gas preparing dimethy ether obtains by following steps:
A) preparation of methanol synthesis catalyst presoma: with the nitrate mixed solution and the sodium carbonate liquor of copper, zinc and aluminium and flow co-precipitation, the gained precipitation solution is worn out, the gained slurries are the methanol synthesis catalyst presoma; Wherein the mass ratio of institute's cupric, zinc, aluminium is 15-65: 10-40: 2-20 in the nitrate mixed solution;
B) modification boehmite preparation: the boehmite employing is contained SO
4 2-Acid or salting liquid reflow treatment, filter, after the drying the modification boehmite; SO wherein
4 2-Mass content be 1-15%;
C) the modification boehmite that step b is obtained joins in the methanol synthesis catalyst presoma of step a, after mixing after filtration, dry, roasting gets target product.
2. one kind prepares the described Preparation of catalysts method of claim 1, and its key step is
A) preparation of methanol synthesis catalyst presoma: with the nitrate mixed solution of copper, zinc and aluminium and sodium carbonate liquor under 50-80 ℃, the condition of pH=6.0-10.0 and flow co-precipitation, the gained precipitation solution was worn out 1-4 hour down at 60-90 ℃, and the gained slurries are the methanol synthesis catalyst presoma; Wherein the mass ratio of institute's cupric, zinc, aluminium is 15-65: 10-40: 2-20 in the nitrate mixed solution;
B) modification boehmite preparation: the boehmite employing is contained SO
4 2-Acid or salting liquid at 50-90 ℃ of following reflow treatment 12-72 hour, filter, after the drying the modification boehmite; SO wherein
4 2-Mass content be 1-15%;
C) the modification boehmite that step b is obtained joins in the methanol synthesis catalyst presoma of step a, and the mass ratio of modification boehmite and institute's cupric, zinc, aluminium-mixed oxide is 1: 1-5: 1; After mixing after filtration, 80-150 ℃ dry 12-72 hour, again in 350-700 ℃ of roasting 3-30 hour, target product.
3. preparation method as claimed in claim 2, wherein, the mass ratio of institute's cupric, zinc, aluminium is 25-50: 15-30: 5-10 in the nitrate mixed solution.
4. preparation method as claimed in claim 2 wherein, contains SO among the step b
4 2-Acid or salt be H
2SO
4, Al
2(SO
4)
3, ZnSO
4, FeSO
4, (NH
4)
2SO
4, Ti (SO
4)
2Or the mixture of its arbitrary proportion.
5. preparation method as claimed in claim 2, wherein, co-precipitation temperature is 60-70 ℃ among the step a, pH value=7.0-9.0, ageing time is 1-3 hour.
6. preparation method as claimed in claim 2, wherein, SO among the step b
4 2-The reflux temperature of handling boehmite is 60-80 ℃, and return time is 24-72 hour.
7. preparation method as claimed in claim 2, wherein, the mass ratio of the modification boehmite that adds among the step c and institute's cupric, zinc, aluminium-mixed oxide is 2: 1-4: 1.
8. the application of the described catalyst of claim 1 in preparing dimethylether from synthetic gas by reaction is seated in catalyst in the fixed bed reactors, uses N under normal pressure
2The H of dilution
2In 250-280 ℃, air speed 1000-3000h
-1Under the condition reduction 6-8 hour, be cooled to 80-100 ℃ after with N
2The H of dilution
2Switch to synthesis gas, the intensification synthetic reaction, synthetic reaction condition is: temperature 200-280 ℃, pressure 1-10MPa, air speed 500-10000h
-1, reaction time 5-10 hour.
9. application as claimed in claim 8, wherein, N
2The H of dilution
2Consist of by volume: N
2/ H
2=10-20/1; Synthesis gas by volume consists of: H
2/ CO/CO
2=2/1-2/0.1-2.
10. application as claimed in claim 8, wherein, synthetic reaction condition is: temperature 230-260 ℃, pressure 3-5MPa, air speed 1000-6000h
-1
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