CN101056707A - Reforming catalyst for oxygen-containing hydrocarbon, method for producing hydrogen or synthesis gas using the same, and fuel cell system - Google Patents
Reforming catalyst for oxygen-containing hydrocarbon, method for producing hydrogen or synthesis gas using the same, and fuel cell system Download PDFInfo
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- CN101056707A CN101056707A CNA2005800391127A CN200580039112A CN101056707A CN 101056707 A CN101056707 A CN 101056707A CN A2005800391127 A CNA2005800391127 A CN A2005800391127A CN 200580039112 A CN200580039112 A CN 200580039112A CN 101056707 A CN101056707 A CN 101056707A
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- catalyst
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- oxygen
- containing hydrocarbon
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- 239000001301 oxygen Substances 0.000 title claims abstract description 69
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 68
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- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910001826 goyazite Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical class [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical class CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The present invention provides a modified catalyst for oxygen-containing hydrocarbon, which comprises a metal oxide containing copper and having a spinel structure and zeolite, preferably further comprises alumina, a group VIII metal, and a rare earth element; a method for producing hydrogen or synthesis gas by subjecting an oxygen-containing hydrocarbon to (1) steam reforming, (2) autothermal reforming, (3) partial oxidation reforming, and (4) carbon dioxide reforming using the reforming catalyst; and a fuel cell system using the above reforming catalyst. The modified catalyst has high activity and excellent heat resistance, and contains alumina, a group VIII metal and a rare earth element, whereby the amount of coke produced can be suppressed and the durability can be further improved. Therefore, hydrogen or synthesis gas can be efficiently produced by subjecting the oxygen-containing hydrocarbon to various reforming treatments using the reforming catalyst, and the catalyst can be used for fuel cells and the like.
Description
Technical field
The present invention relates to oxygen-containing hydrocarbon modified catalyst, use this catalyst to make the method and the fuel cell system of hydrogen or forming gas, in detail, the present invention relates to the modified catalyst of following oxygen-containing hydrocarbon and use this modified catalyst that oxygen-containing hydrocarbon is carried out various modifications, thereby efficiently make the method for hydrogen or forming gas; And the fuel cell system that utilizes this modified catalyst, described modified catalyst contains metal oxide and zeolite, or further contain various metals, and excellent heat resistance, active big, durability improve, described metal oxide cupric and have spinel structure.
Background technology
Forming gas contains carbon monoxide and hydrogen, except the unstripped gas synthetic as methyl alcohol, that carbonyl synthetic, Fischer-Tropsch is synthetic etc., also is widely used as the raw material of ammonia synthesis or various chemical products.
This forming gas is in the past always by method manufacturing such as following: utilize the method for coal gasification or be the steam modification method of hydro carbons of raw material or partical oxidizing modifying method etc. with natural gas etc.But, in the coal gasification method, not only need the high coal gasifier of complexity and price, and have problems such as equipment scale is big.In addition, in the steam modification method of hydro carbons, reaction so carry out the high temperature of about 700～1200 ℃ of reaction needed, not only needs special modification stove with big heat absorption, also has the problems such as hear resistance height that require employed catalyst.In addition, in the partical oxidizing modifying of hydro carbons, also need high temperature, thus partial oxidation furnace that need be special, and,, also have problems such as the easy deterioration of catalyst so not only on handling, have problems because reaction generates with a large amount of coals.
Therefore,, attempted oxygen-containing hydrocarbons such as use dimethyl ether in recent years, it has been implemented various modifications make forming gas as raw material in order to address this is that.
On the other hand, because environmental problem, new energy technology receives publicity, and fuel cell is extremely gazed at as a kind of of this new energy technology.Described fuel cell changes chemical energy into electric energy by making hydrogen and oxygen generation electrochemical reaction, has the high feature of energy utilization efficiency, and its practical research as the energy of domestic energy, industry or vehicle etc. is actively being carried out.
As the hydrogen source of this fuel cell, to based on the liquefied natural gas of methyl alcohol, methane, be the town gas of main component, be that the synthetic liquid fuel and the petroleum-type hydrocarbons such as petroleum-type naphtha or kerosene of raw material are studied with the natural gas with this natural gas.
When using these petroleum-type hydrocarbons to make hydrogen, in the presence of catalyst, this hydrocarbon is carried out steam modification processing or carries out partical oxidizing modifying processing etc. usually, and just produced aforesaid problem in this case.So, in the manufacturing of hydrogen, also in the method for oxygen-containing hydrocarbons such as the various use dimethyl ether of trial as raw material.
Up to now, disclose multiple with oxygen-containing hydrocarbons such as dimethyl ether as raw material, employed catalyst when it is implemented various modifications manufacturing hydrogen or forming gas, wherein as using the Cu series catalysts to the technology that oxygen-containing hydrocarbon carries out modification, following technology being disclosed: for example uses to contain the method (for example referring to patent documentation 1) that the manufacturing of Cu catalyst is made the catalyst of forming gas and used its manufacturing forming gas by oxygen-containing hydrocarbon and carbon dioxide, use contains the Cu catalyst and makes the method (for example referring to patent documentation 2) of being made catalyst and its manufacturing hydrogen of use of hydrogen by oxygen-containing hydrocarbon and steam, the oxygen-containing hydrocarbon modified catalyst that contains the solid acid that supports copper-containing metal is (for example referring to patent documentation 3, patent documentation 4), the making the catalyst of hydrogen and use it to make the method (for example referring to patent documentation 5) of hydrogen of mixture of containing Cu material and solid acid material by oxygen-containing hydrocarbon and steam, the making the catalyst of forming gas and use its method of making forming gas (for example referring to patent documentation 6 with reference to) etc. of mixture of containing Cu material and solid acid thing by oxygen-containing hydrocarbon and steam.
Yet the hear resistance of used Cu class catalyst is all insufficient in these technology, so when improving reaction temperature in order to improve reactivity, existence can't be avoided the problem of catalyst degradation.
Patent documentation 1: the spy opens flat 10-174869 communique
Patent documentation 2: the spy opens flat 10-174871 communique
Patent documentation 3: the spy opens the 2001-96159 communique
Patent documentation 4: the spy opens the 2001-96160 communique
Patent documentation 5: the spy opens the 2003-10684 communique
Patent documentation 6: the spy opens the 2003-33656 communique
Summary of the invention
The present invention carries out in view of above-mentioned condition, its purpose is to provide a kind of modified catalyst of oxygen-containing hydrocarbon and provides uses this modified catalyst that oxygen-containing hydrocarbon is implemented various modifications, the efficient method of making hydrogen or forming gas, described modified catalyst contains copper, and excellent heat resistance, active big, durability improves.In addition, the present invention also aims to provide a kind of fuel cell system excellent, it possesses modification device with above-mentioned excellent modified catalyst and is the fuel cell of fuel with the hydrogen by this modification device manufacturing.
The inventor furthers investigate to achieve these goals, found that, by Cu-contained catalyst is made spinel structure, and in the catalyst of this cupric spinel structure combined zeolite, can obtain the hear resistance height, simultaneously active big, catalyst that durability improves, and find, by further containing aluminium oxide or group VIII metal, rare earth element, in the modification of oxygen-containing hydrocarbon, can further suppress the growing amount of burnt (コ one Network), can realize described purpose.The present invention just is being based on that this understanding finishes.
That is, the invention provides the manufacture method and the fuel cell system of following oxygen-containing hydrocarbon modified catalyst, hydrogen or forming gas.
(1) a kind of oxygen-containing hydrocarbon modified catalyst is characterized in that, it contains metal oxide and zeolite, described metal oxide cupric and have spinel structure.
(2) according to (1) described oxygen-containing hydrocarbon modified catalyst, wherein, be benchmark with the quality, cupric and metal oxide with spinel structure are 1: 1～100: 1 with the content ratio of zeolite.
(3) according to (1) or (2) described oxygen-containing hydrocarbon modified catalyst, wherein, described cupric and the metal oxide with spinel structure are Cu-Mn type spinelle.
(4) according to any described oxygen-containing hydrocarbon modified catalyst in (1)～(3), wherein, zeolite is ZSM-5.
(5) according to any described oxygen-containing hydrocarbon modified catalyst in (1)～(4), wherein, it contains metal oxide, zeolite and aluminium oxide, described metal oxide cupric and have spinel structure.
(6) according to any described oxygen-containing hydrocarbon modified catalyst in (1)～(5), wherein, contain group VIII metal and/or rare earth element in the zeolite.
(7) according to (6) described oxygen-containing hydrocarbon modified catalyst, wherein, the group VIII metal is at least a metal that is selected among Pt, Pd, Ir, Rh and the Ru.
(8) according to (6) described oxygen-containing hydrocarbon modified catalyst, wherein, the group VIII metal is at least a metal that is selected among Fe, Ni and the Co.
(9) a kind of oxygen-containing hydrocarbon modified catalyst, it obtains by any described modified catalyst in reduction (1)～(8).
(10) according to any described oxygen-containing hydrocarbon modified catalyst in (1)～(9), wherein, oxygen-containing hydrocarbon is to be selected from least a in dimethyl ether and the methyl ethyl ether.
(11) manufacture method of a kind of hydrogen or forming gas is characterized in that, any described modified catalyst carries out the steam modification to oxygen-containing hydrocarbon in use (1)～(10).
(12) manufacture method of a kind of hydrogen or forming gas is characterized in that, any described modified catalyst carries out self heat modification to oxygen-containing hydrocarbon in use (1)～(10).
(13) manufacture method of a kind of hydrogen or forming gas is characterized in that, any described modified catalyst carries out partical oxidizing modifying to oxygen-containing hydrocarbon in use (1)～(10).
(14) manufacture method of a kind of hydrogen or forming gas is characterized in that, any described modified catalyst carries out the carbon dioxide modification to oxygen-containing hydrocarbon in use (1)～(10).
(15) a kind of fuel cell system is characterized in that, the fuel cell that it has modification device and acts as a fuel with the hydrogen by this modification device manufacturing, described modification device possess any described modified catalyst in (1)～(10).
Description of drawings
The schematic flow sheet of [Fig. 1] fuel cell system of the present invention.
Symbol description
1: gasifier
11: feed pipe
12: the fuel ingress pipe
15: tube connector
21: fuel tank
23: devulcanizer
24: water pump
31: modification device
31A: modification device blowtorch
The 32:CO converter
33:CO selective oxidation device
34: fuel cell
34A: fuel cell negative pole
34B: fuel cell anode
34C: fuel cell polyelectrolyte
35: air-blast device
36: moisture trap
37: heat extraction and recovery device
37A: heat exchanger
37B: heat exchanger
37C: cooler
37D: cooling medium circulating pump
The specific embodiment
The oxygen-containing hydrocarbon modified catalyst of first aspect present invention is to contain cupric and have the metal oxide of spinel structure and the catalyst of zeolite, preferably also contains the catalyst of any one composition in aluminium oxide, group VIII metal and the rare earth element.
As oxygen-containing hydrocarbon of the present invention, can preferably enumerate alcohols such as methyl alcohol, ethanol; Ethers such as dimethyl ether, methyl ethyl ether.Wherein, preferred especially dimethyl ether and methyl ethyl ether.
Among the present invention, the metal oxide with spinel structure is at AB
2O
4One of observed representative crystalline texture type in the type composite oxide of metal, it has cubic system.Above-mentioned AB
2O
4In, A is a divalent metal usually, B is a trivalent metal.
Among the present invention, use the metal oxide of the spinel structure of cupric,, can enumerate Cu-Mn type spinelle, Cu-Fe type spinelle, Cu-Cr type spinelle etc. as this metal oxide, consider preferred Cu-Mn type spinelle from catalyst activity and hear resistance equal angles.As above-mentioned Cu-Mn type spinelle, can enumerate for example CuMn
2O
4Deng, as Cu-Fe type spinelle, can enumerate for example CuFe
2O
4Deng.As Cu-Cr type spinelle, can enumerate for example CuCr
2O
4Deng.In addition, can also use CuAl
2O
4, ternary system Cu (FeCr)
2O
4, Cu (FeAl)
2O
4, Cu (MnFe)
2O
4Spinelle.As Cu (MnFe)
2O
4The type spinelle can be enumerated Cu (Mn
1.5Fe
0.5) O
4, Cu (Mn
1.0Fe
1.0) O
4, Cu (Mn
2/3Fe
4/3) O
4, Cu (Mn
0.5Fe
1.5) O
4Deng.
Compare with the metal oxide of the non-spinel structure of cupric, the excellent heat resistance of the metal oxide of the spinel structure of this cupric, and when being used for the modification of oxygen-containing hydrocarbon, the catalytic activity of per surface area is far above the metal oxide of the non-spinel structure of cupric.
In addition, in the scope that does not hinder the object of the invention, in the modified catalyst of the present invention, the copper-containing compound that can contain non-spinel structure as required is as the copper-containing metal oxide.
Then, as the preparation method's of the metal oxide of the spinel structure of the used cupric of a modified catalyst of the present invention example, with preparation CuMn
2O
4The situation of spinelle is that example describes.
At first, water-soluble mantoquitas such as use copper nitrate are as the copper source, and water-soluble manganese salts such as use manganese nitrate are as the manganese source, and the modulation aqueous solution in this aqueous solution, makes them in fact reach the chemical theory ratio, and promptly the mol ratio of Cu and Mn is essentially 1: 2.Then, add chelating agents such as citric acid in this aqueous solution, heating evaporates the water and generates gel then.Then, this gel is carried out heat treated, make decomposition such as nitrate anion in the gel, citric acid, the oxide micropowder that obtains was calcined about 1～5 hour in the temperature about 300～500 ℃ in air, further burn till about 5～15 hours then, obtain CuMn thus in the temperature about 500～1000 ℃
2O
4Spinelle.In addition, when the high temperature more than 700 ℃ burns till, allegedly form Mn
2O
3Or Mn
3O
4With Cu
1.5Mn
1.5O
4The mixture of spinelle.
In this method, can use the copper source of the ratio of the relative Mn of Cu more than the amount of chemical theory ratio.In this case, resulting metal oxide is the oxide (Cu of copper
2O or CuO or their mixture) with the mixture of spinel oxides.
In addition, preparation CuFe
2O
4During spinelle, sources of iron such as water-soluble molysite such as use ferric nitrate replace above-mentioned manganese source to get final product.In addition, use the mixture in source of iron and manganese source to replace above-mentioned manganese source then can obtain containing Cu (FeMn)
2O
4The metal oxide of spinelle.
When oxygen-containing hydrocarbon modified catalyst of the present invention contains the metal oxide of described cupric spinel structure, contain zeolite.Zeolite can be enumerated ZSM-5, modenite, X type, Y type, A type, L type, β type, ferrierite etc., considers preferred modenite and ZSM-5, preferred especially ZSM-5 from catalyst activity and durability angle.
As above-mentioned modenite and ZSM-5, consider from the catalyst activity angle, all or part of by proton exchange type than cation exchange type more preferably.
By quality ratio, the mixed proportion of Cu-Mn type spinelle and zeolite is preferably 1: 1～and 100: 1, more preferably 2: 1～50: 1.The mixed proportion of zeolite is less than this ratio, catalyst activity reduction then, and greater than this ratio, the burnt growing amount that then becomes the reason of catalyst degradation increases, so not preferred.
The oxygen-containing hydrocarbon modified catalyst of the present invention that contains metal oxide and zeolite can be by following method preparation, and described metal oxide is the metal oxide of the spinel structure of cupric.That is, adopting following method can prepare modified catalyst of the present invention, is the suitable granular method of size with the metal oxide powder of cupric spinel structure and zeolite powder mixing aftershaping; The particle and the suitable zeolite granular of the size method of mixing etc. of suitable size that perhaps will contain the metal oxide of cupric spinel structure.
As the aluminium oxide that contains in the metal oxide of the spinel structure of cupric and the zeolite, can use the aluminium oxide of the crystal habit arbitrarily among commercially available α, β, γ, η, θ, κ, the χ.In addition, hydrated aluminas such as boehmite, magnesium goyazite, gibbsite can also be burnt till the back uses.In addition, also can in aluminum nitrate, add pH and be about 8～10 alkaline buffer, generate precipitation of hydroxide, it be burnt till the back use, or also aluminium chloride can be burnt till.In addition, can also use the aluminium oxide of making by sol-gel process, in the described sol-gel process, alkoxide such as isobutanol aluminum are dissolved in the alcohol such as 2-propyl alcohol, inorganic acids such as interpolation hydrochloric acid are made alumina gel as hydrolyst, and it is carried out drying, burns till.
With respect to the mixture integral body of metal oxide, zeolite and the aluminium oxide of the spinel structure of cupric, alumina content is 5～50 quality %, is preferably 8～40 quality %, more preferably 10～30 quality %.By containing the aluminium oxide of 5～50 quality %, can be inhibited burnt growing amount and reduce active effect not significantly.
The interpolation of aluminium oxide can be added when the cupric spinel oxide mixes with zeolite simultaneously, also can add before and after the cupric spinel oxide mixes with zeolite.
As the group VIII metal that adds in this zeolite, can enumerate noble metal and iron, cobalt and nickel such as platinum, palladium.
As noble metal, can enumerate platinum, palladium, ruthenium, rhodium and iridium, preferred especially platinum.
As the platinum compounds in platinum composition source, for example can enumerate PtCl
4, H
2PtCl
6, Pt (NH
3)
4Cl
2, (NH
4)
2PtCl
2, H
2PtBr
6, NH
4[Pt (C
2Hx) Cl
3], Pt (NH
3)
4(OH)
2, Pt (NH
3)
2(NO
2)
2Deng.
These platinum compounds can be used alone, also can be with two or more and usefulness.Following palladium compound, ruthenium compound, rhodium compound and iridic compound are too.
As the palladium compound in palladium composition source, for example can enumerate (NH
4)
2PdCl
6, (NH
4)
2PdCl
4, Pd (NH
3)
4Cl
2, PdCl
2, Pd (NO
3)
2Deng.
As the ruthenium compound in ruthenium composition source, can enumerate for example RuCl
3NH
2O, Ru (NO
3)
3, Ru
2(OH)
2Cl
47NH
33H
2O, K
2(RuCl
5(H
2O)), (NH
4)
2(RuCl
5(H
2O)), Ka (RuCl
5(NO)), RuBr
3NH
2O, Na
2RuO
4, Ru (NO) (NO
3)
3, (Ru
3O (OAc)
6(H
2O)
3) OacnH
2O, K
4(Ru (CN)
6) nH
2O, K
2(Ru (NO
2)
4(OH) (NO)), (Ru (NH
3)
6) Cl
3, (Ru (NH
3)
6) Br
3, (Ru (NH
3)
6) Cl
2, (Ru (NH
3)
6) Br
2, (Ru
3O
2(NH
3)
14) Cl
6H
2O, (Ru (NO) (NH
3)
5) Cl
3, (Ru (OH) is (NH (NO)
3)
4) (NO
3)
2, RuCl
2(PPh
3)
3, RuCl
2(PPh
3)
4, (RuClH (PPh
3)
3, C
7H
8, RuH
2(PPh
3)
4, RuClH (CO) (PPh
3)
3, RuH
2(CO) (PPh
3)
3, (RuCl
2(cod))
n, Ru (CO)
12, Ru (acac)
3, (Ru (HCOO) (CO)
2)
n, Ru
2I
4(p-cymene)
2Deng ruthenium salt.In these ruthenium compounds, consider preferred RuCl from the property handled angle
3NH
2O, Ru (NO
3)
3, Ru
2(OH)
2Cl
47NH
33H
2O.
As the rhodium compound in rhodium composition source, can enumerate for example Na
3RhCl
6, (NH
4)
2RhCl
6, Rh (NH
3)
5Cl
3, RhCl
3Deng.
As the iridic compound in iridium composition source, can enumerate for example (NH
4)
2IrCl
6, IrCl
3, H
2IrCl
6Deng.
The balance equal angles that generates burnt effect and economy from suppress modified-reaction considers that with respect to 100 mass parts zeolites, the loading of noble metal composition is preferably 0.01～10 mass parts, more preferably 0.1～5 mass parts.
The method that supports the noble metal composition on zeolite is not particularly limited.Support under the above situation of two metamembers, can support each composition successively, also can support simultaneously.As the operation that supports of noble metal composition, can adopt heating impregnation method, vacuum impregnation method, normal pressure impregnation method, evaporation to do various impregnation methods such as solid method, filling perforation method, incipient wetness method; Infusion process; Spray-on process; Methods such as ion-exchange preferably contain method of impregnation and ion-exchange by what filling perforation method, incipient wetness method were carried out.
As the group VIII metal ingredient beyond the noble metal that adds in this zeolite, can enumerate Fe, Ni and Co composition.Compound for the raw material that is used as Fe, Ni and Co composition is not particularly limited, but the preferred water soluble compound is used nitrate usually.
Be not particularly limited for support the method for adding Fe, Ni, Co to zeolite.Support operation and can adopt the above-mentioned method of in the noble metal composition, putting down in writing, can adopt the method that begins to add etc. from the synthetic initial stage of zeolite in addition.Especially preferably support or utilize following method to begin to add from the synthetic initial stage of zeolite by ion-exchange.
With respect to zeolite, the content of Fe, Ni, Co composition is 0.05～20 quality %, is preferably 0.1～10 quality %.By making zeolite contain Fe, Ni, the Co composition of 0.05～20 quality %, can advantageously obtain additive effect economically.
The zeolite that is added with above-mentioned Fe, Ni, Co composition is through reduction, for example more than 30 minutes, can further improve additive effect in 200～800 ℃, preferred about 400 ℃ temperature reduction in hydrogen-containing gas streams.
Be not particularly limited the method for can application examples carrying out as organic compounds such as interpolation tetrapropyl ammonium salt, alcohols in prepare raw material for the zeolite synthetic method under the situation that begins to add Fe, Ni, Co from the synthetic initial stage of zeolite; In preparing raw material, add crystal seed such as modenite and be not added with the method etc. of organic compounds.
Except can adding various silica source, alumina source, alkali metal source, crystallization agent (template), can also add the compounds such as sulfuric acid, nitric acid, NaOH and crystallization promoter sodium chloride that are used to regulate pH in gel, colloidal sol or the solution before synthetic as the hydro-thermal of preparation raw material.
Silica source as this moment, can enumerate for example sodium metasilicate, waterglass, SiO 2 powder, silicic acid, aqueous colloidal shape silica etc., particularly the angle of the supply in micelle control, alkaline kation source and cost of material is considered preferred water glass, colloid shape silica etc. from aqueous reaction mixture.As waterglass, the waterglass of No. 3 regulation of preferred Japanese Industrial Standards.
In addition,, can use sodium aluminate, aluminum sulfate, activated alumina, hydrated alumina etc., preferred especially sodium aluminate, aluminum sulfate etc. as alumina source.
As alkali metal source, can together supply with alumina sources such as silica source such as waterglass, colloid shape silica or sodium aluminates, and can enumerate alkali metal hydroxides such as NaOH, potassium hydroxide.Especially preferably use NaOH.
Crystallization agent (template) can be used organonitrogen compound, specifically can use carbon number be 2～10 primary, secondary, tertiary amine; MEA, single Propanolamine, diglycolamine, tetrapropyl ammonium, tetraethyl ammonium and their ammonium salt; Choline; Pyrrolidines; Ethylenediamine; Diaminopropanes etc., preferred especially diglycolamine, bromination tetrapropyl ammonium.
As for the mol ratio of each oxide, Si
2/ Al
2O
3Than being 10～300, be preferably 20～100.During less than this ratio, non-crystallizable or crystallinity is poor, and during greater than this ratio, because the acid amount is less and poor activity.In addition, the mol ratio of Al/M (M represents Fe/Ni/Co) is 0.5～20, is preferably 1～10.During less than this ratio, it is poor that a M composition part is separated out in crystallization outside or crystallinity, and during greater than this ratio, effect is little.
As the rare earth elements that contains in the zeolite, can enumerate Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.Composition source to these rare earth elements is not particularly limited.Preferred water misciblely maybe can be dissolved in methyl alcohol, ethanol, and use nitrate usually.
The method that supports rare earth elements is not particularly limited.Support under the above situation of binary, can support the aqueous solution of each composition or methyl alcohol, ethanolic solution successively, also can support simultaneously.As supporting operation, can adopt heating impregnation method, normal temperature impregnation method, vacuum impregnation method, normal pressure impregnation method, evaporation to do various impregnation methods such as solid method, filling perforation method, incipient wetness method; Infusion process; Spray-on process; Methods such as ion-exchange.When utilizing the aqueous solution to carry out impregnation, filling perforation method, incipient wetness method are effective, and when utilizing methyl alcohol and ethanolic solution to carry out impregnation, more preferably solid method is done in evaporation.
The loading of rare earth elements is 0.1～20 quality %, is preferably 1～10 quality %.By being 0.1～20 quality %, can advantageously obtain the effect that supports of rare earth element economically.
In the present invention, by reducing above-mentioned modified catalyst, can further improve activity.Reduction is handled gas phase reduction process of handling and the wet type reducing process of handling with reducing agent in containing the air-flow of hydrogen.The former reduction is handled usually in hydrogeneous air-flow in 150～500 ℃, preferred 200～300 ℃ temperature and was implemented 30 minutes～24 hours, preferred 1～10 hour.Except hydrogen, also can there be inert gases such as nitrogen, helium, argon simultaneously.
As the latter's wet type reducing process, the Birch reduction of use liquid ammonia/alcohol/Na, liquid ammonia/alcohol/Li is arranged; The Benkeser reduction of use methyl amine/Li etc.; With Zn/HCl, Al/NaOH/H
2O, NaH, LiAlH
4Or the method handled of reducing agent such as its substituent, silicol class, sodium borohydride or its substituent, diborane, formic acid, formalin, hydrazine.In this case, ℃ carry out in room temperature～100 usually 10 minutes～24 hours, preferably carried out 30 minutes～10 hours.
In addition, by the flowing reactive raw material, hydrogen or CO that reacting middle catalyst just is generated have reduced.
Among the present invention, catalyst is owing to be reduced or be generated gas reduction in the reduction pre-treatment, Cu or other elements break away from from spinel structure, are in the part or all of irretentive state of spinel structure, but emphasis of the present invention is to use the Cu catalyst that has spinel structure at first.
In the hydrogen of a second aspect of the present invention or the manufacture method of forming gas, the modified catalyst by using the invention described above carries out (1) steam modification, (2) self heat modification, (3) partical oxidizing modifying or (4) carbon dioxide modification to oxygen-containing hydrocarbons such as dimethyl ether and makes hydrogen or forming gas.
Then, as example each method of modifying is described with the situation of using dimethyl ether.
[steam modification]
When using modified catalyst of the present invention, the steam modification of dimethyl ether is reacted by following reaction equation.
CH
3OCH
3+H
2O→2CH
3OH ......(1)
2CH
3OH+2H
2O→2CO
2+6H
2 ......(2)
2CO
2+2H
2→2CO+2H
2O ......(3)
So when making hydrogen, as long as the choice reaction condition makes the reaction of above-mentioned (3) be difficult for carrying out, the reaction that (4) promptly take place gets final product.
CH
3OCH
3+3H
2O→2CO
2+6H
2......(4)
On the other hand, when making forming gas, the reaction of above-mentioned (1), (2) and (3) takes place in the choice reaction condition, and the reaction that (5) promptly take place gets final product.
CH
3OCH
3+H
2O→2CO+4H
2 ......(5)
When making hydrogen, the mol ratio of steam/dimethyl ether is 3 in theory, but is preferably about 3～6, and on the other hand, when making forming gas, the mol ratio of steam/dimethyl ether is 1 in theory, but is preferably about 1～2.
Reaction temperature is preferably selected 250～450 ℃ scope usually 200～500 ℃ of selections.This temperature is during less than 200 ℃, and the conversion ratio of dimethyl ether might step-down, and this temperature then becomes the reason of catalyst activity deterioration during greater than 500 ℃.With the dimethyl ether is benchmark, and GHSV (gas volume air speed) is preferably at 100～10000h
-1Scope.This GHSV is less than 100h
-1The time, production efficiency is low, and is not preferred in the practicality, and greater than 10000h
-1The time, the conversion ratio of dimethyl ether became low, and was not preferred in the practicality.In addition, reaction pressure is generally about normal pressure～1Mpa.During this hypertonia, the conversion ratio of dimethyl ether has the trend of reduction.
[self heat modification]
In the reaction of self heat modification, the oxidation reaction of dimethyl ether and with the same reactor of being reflected at of steam in take place or in continuous reactor, take place.In this case, some is different to make hydrogen and the reaction condition of making forming gas, but the mol ratio of oxygen/dimethyl ether is preferably selected in 0.1～1 scope usually, and the mol ratio of steam/dimethyl ether is preferably selected in 0.5～3 scope.The mol ratio of oxygen/dimethyl ether is less than 0.1 o'clock, and the reaction heat that utilizes heating to supply with is not enough sometimes, and this mol ratio is greater than 1 o'clock, might complete oxidation take place and causes hydrogen concentration to reduce.In addition, the mol ratio of steam/dimethyl ether is less than 0.5 o'clock, and hydrogen concentration reduces sometimes, and this mol ratio is greater than 3 o'clock, and undersupply might generate heat.
Reaction temperature is usually 200～800 ℃ of selections, preferably select 250～500 ℃ scope.In addition, GHSV is identical with the situation of above-mentioned steam modification with reaction pressure.
[partical oxidizing modifying]
In the partical oxidizing modifying reaction, dimethyl ether generation partial oxidation reaction, some is different to make hydrogen and the reaction condition of making forming gas, but the mol ratio of oxygen/dimethyl ether is preferably selected in 0.3～1.5 scope usually.The mol ratio of this oxygen/dimethyl ether was less than 0.3 o'clock, and the conversion ratio of dimethyl ether is not high enough sometimes, and this mol ratio greater than 1.5 o'clock complete oxidation takes place, and became the reason that hydrogen concentration reduces.Reaction temperature is usually 200～900 ℃ of selections, preferably select 250～600 ℃ scope.In addition, GHSV is identical with the situation of above-mentioned steam modification with reaction pressure.
[carbon dioxide modification]
In the carbon dioxide modified-reaction, dimethyl ether and carbon dioxide react, and some is different for the reaction condition of manufacturing hydrogen and manufacturing forming gas, but common CO
2The mol ratio of/dimethyl ether is preferably selected 0.8～2, is more preferably selected in 0.9～1.5 scope.This CO
2The mol ratio of/dimethyl ether is less than 0.8 o'clock, and the conversion ratio of dimethyl ether might be not high enough, and this mol ratio is greater than 2 o'clock, residual a large amount of CO in the product
2, become the reason that the hydrogen dividing potential drop reduces, and must remove CO sometimes
2So, not preferred.In this reaction, steam can be imported,, hydrogen concentration can be improved by this importing.In addition, reaction temperature, GHSV and reaction pressure are identical with the situation of above-mentioned steam modification.
A third aspect of the present invention is a fuel cell system, it is characterized in that, it has modification device and is the fuel cell of fuel with the hydrogen by this modification device manufacturing, and described modification device possesses above-mentioned modified catalyst.Utilize Fig. 1 to describe.
Fuel in the fuel tank 21 is imported devulcanizer 23.Usually, sulfur-bearing not when using preferred dimethyl ether etc. as oxygen-containing hydrocarbon, but devulcanizer is effective for containing sulfur-containing compound as situation of smell additive etc. etc.Can fill for example active carbon, zeolite or metal species adsorbent etc. in the devulcanizer 23.Through the fuel of devulcanizer 23 desulfurization with from water pot after the water that water pump 24 is supplied with mixes, be directed in the gasifier 1 and gasify, be admitted to then in the modification device 31.Be filled with above-mentioned modified catalyst in the modification device 31, make hydrogen by above-mentioned steam modified-reaction by the fuel mixture of sending into modification device 31 (oxygen-containing hydrocarbon and steam).
So the hydrogen of making is by CO converter 32, CO selective oxidation device 33, and CO concentration is reduced to the degree that does not influence characteristics of fuel cells.Example as the catalyst that uses in these reactors, in the CO converter 32, iron-chromium-based catalysts, copper-zinc system catalyst or noble metal series catalysts can be enumerated, in the CO selective oxidation device 33, ruthenium catalyst, platinum group catalyst or their mixed catalyst can be enumerated.Under the low situation of the CO concentration in the hydrogen of modified-reaction manufacturing, CO converter 32 can be installed.
At this moment, become proton, carry out the reaction of ejected electron, carry out the reaction that oxygen obtains electronics and proton generation water, between the two poles of the earth 34A, 34B, produce DC current at side of the positive electrode at negative side hydrogen.In this case, Pt catalyst that negative pole use platinum black or active carbon support or Pt-Ru alloy catalyst etc., the Pt catalyst that anodal use platinum black or active carbon support etc.
Blowtorch 31A at negative pole 34A side connection modification device 31 can act as a fuel with remaining hydrogen.In addition, anodal 34B side connects moisture trap 36, will be separated with emission gases in conjunction with the water that generates with hydrogen by the airborne oxygen that supplies to anodal 34B side, and water can be used to generate steam.In the fuel cell 34, be accompanied by generating and produce heat, reclaim this heat so set up heat extraction and recovery device 37, thereby can effectively utilize.Heat extraction and recovery device 37 is attached to fuel cell 34, have heat exchanger 37A, heat exchanger 37B, cooler 37C and pump 37D, the heat that produces when heat exchanger 37A obtains reaction, heat and water that heat exchanger 37B is used for heat exchanger 37A is obtained carry out heat exchange, pump 37D makes cooling medium heat exchanger 37A, 37B and cooler 37C circulation, and the warm water that obtains among the heat exchanger 37B can be in other effectively utilizations such as equipment.
Embodiment
Then, illustrate in greater detail the present invention, but the present invention is not subjected to any qualification of these examples by embodiment.
In addition, among following each embodiment and comparative example, the Si in the catalyst, Al, Pt, group VIII metal (Fe, Ni, Co) and rare earth metal (La, Ce, Sm) use ICP ICP Atomic Emission Spectrophotometer device to measure as follows.
(pre-treatment of ICP)
1.ZSM-5 in Si and the dissolving method of Al
Get about 0.05g sample and put into the platinum ware, add the about 0.5g of mixture (mass ratio 9: 1) of lithium tetraborate and lithium fluoride, fully mix.After 20 minutes, put and be chilled to room temperature 925 ℃ of fusions with electric furnace.To wherein adding the mixed solution 40mL that 5g tartaric acid and 40mL dissolving with hydrochloric acid are obtained in 1L distilled water, heating for dissolving, put once more be chilled to room temperature after, with the distilled water constant volume to 50mL.With ICP the Si in this solution, Al are carried out quantitatively.
2.ZSM-5 middle Pt dissolving method
Get about 1g sample and put into alumina crucible,, get the 0.1g sample and put into teflon (テ Off ロ Application) (registration mark) container after 60 minutes 900 ℃ of heat treated, add 1mL hydrofluoric acid and 4mL chloroazotic acid, heating is done solid.Then add 1mL hydrochloric acid, cover with surface plate and heat, put cold after, the Y standard liquid of 1000ppm that adds 0.2mL is as inner mark solution, constant volume is to 50mL.With ICP the Pt in this solution is carried out quantitatively.Also add in the calibration curve solution of Pt and measure with above-mentioned same Y standard liquid.
3.ZSM-5 the dissolving method of middle rare earth metal and group VIII metal (Fe, Ni, Co)
Get about 0.04g sample and put into the platinum ware, add 3mL ion exchange water, 0.5mL hydrofluoric acid and 0.5mL sulfuric acid, 1mL hydrochloric acid, be heated to the white cigarette of appearance.Put cold after, add the 10mL ion exchange water, further heat.Solution becomes get transparent after, stop the heating, put cold after, be settled to 50mL.With ICP rare earth metal in this solution (La, Ce, Sm) and group VIII metal (Fe, Ni, Co) are carried out quantitatively.
(ICP assay method)
1. analytical instrument
Use the SPS-5100 type of multielement simultaneous type ICP ICP Atomic Emission Spectrophotometer device セ イ コ one イ Application ス Star Le メ Application Star (strain) production of ICP JIS K 0116 regulation to analyze.
2. condition determination
Power output: 1.3kW
Argon flow amount: plasma gas ... 16L/ minute
オ キ シ ヤ リ テ イ one ガ ス ... 0.2L/ minute
Carrier gas ... 0.4～0.5L/ minute (pressure: 2.2kg/cm
2)
Photometry height: 12mm (on the actuating coil)
Measure wavelength: 214.423nm (Pt), 333.749nm (La), 418.659nm (Ce), 359.259nm (Sm), 251.618nm (Si), 396.152nm (Al), 238.204 (Fe), 231.604nm (Ni), 238.892nm (Co)
(evaluation of catalyst)
The evaluation of the catalyst that each embodiment and comparative example etc. are obtained is undertaken by the steam modified-reaction of dimethyl ether (note is made DME) is following.
(1) shaping of catalyst that each embodiment and comparative example etc. are obtained is 16～32 orders, is filled in the reactor.
(2) before the steam modified-reaction, at hydrogen (H
2: 250 ℃ of heating 1 hour, reduce 100%).
(3) activity rating is following carries out: in embodiment 1～9 and the comparative example 1～2, steam/DME mol ratio 5, be 900h based on the GHSV (gas volume air speed) of DME
-1, based on all gas (DME+H
2O) GHSV is 5400h
-1, DME conversion ratio (initial activity) and the coking after 18 hours (コ one キ Application グ) rate under 250 ℃ of the evaluation response temperature.In addition, in embodiment 1,3,14～36 and the comparative example 3～4, steam/DME mol ratio 5.0, be 333h based on the GHSV (gas volume air speed) of DME
-1, based on all gas (DME+H
2O) GHSV is 2000h
-1, DME conversion ratio (initial activity) under 280 ℃ of the evaluation response temperature and the coking rate after 18 hours.
The DME conversion ratio adopts according to reactor outlet gas forms the numerical value of representing with following formula.
DME conversion ratio (%)=(A/B) * 100
A:CO molar concentration+CO
2Molar concentration+CH
4Molar concentration
B:CO molar concentration+CO
2Molar concentration+CH
4Molar concentration+(DME molar concentration * 2)
The numerical value that coking rate (%) adopts following formula to represent.
Coking rate (%)=(D/C) * 100
C: be included in 250 ℃ of catalyst qualities (g) that react the burnt quality that generates after 18 hours down of reaction temperature
D: 250 ℃ of Jiao that generate after reacting 18 hours down measure (burnt quality: g) in reaction temperature
(4) durability evaluation is as follows: in embodiment 1～9 and comparative example 1～2, steam/DME mol ratio is 5, be 333h based on the GHSV (gas volume air speed) of DME
-1, based on all gas (DME+H
2O) GHSV is 2000h
-1, under 250 ℃ of reaction temperatures, carry out maximum 250 hours reaction, dropped to for 95% required time as the durable time with the DME conversion ratio.In addition, in embodiment 3,10～14,17,20,21,24 and comparative example 3, steam/DME mol ratio is 5.0, be 333h based on the GHSV (gas volume air speed) of DME
-1, based on all gas (DME+H
2O) GHSV is 2000h
-1, by estimating at active rate of descent after following 400 hours of 280 ℃ of reaction temperatures [(initial stage DME conversion ratio-400 hour after DME conversion ratio)/initial stage DME conversion ratio] * 100 and above-mentioned coking rate (%).
Embodiment 1 (mass ratio of Cu-Mn spinel oxides and H-ZSM-5 is 2: 1 a mixed catalyst)
In 1 liter of beaker, 300 ml distilled waters are joined 13.28g (55 mM) copper nitrate, and [Na カ ラ イ テ ス Network society produces, 99.5 quality %Cu (NO
3)
23H
2O] and 31.55g (108 mM) manganese nitrate [production of シ グ マ ア Le De リ Star チ ジ ヤ パ Application, 98.0 quality %Mn (NO
3)
26H
2O] in, stirred 2 hours at 60 ℃.Then, in this solution, add 34.65g (165 mM) citric acid first hydrate [production of シ グ マ ア Le De リ Star チ ジ ヤ パ Application], after 1 hour, be warmed up to 80 ℃, evaporate the water 60 ℃ of stirrings.
The gel that so generates was heated 7 hours at 140 ℃, nitrate anion and citric acid are decomposed, it is last to obtain oxide micropowder, 400 ℃ of calcinings 2 hours, burns till 10 hours in 900 ℃ in air in firing furnace in air again.After burning till, the Cu-Mn spinel oxides (Cu that 10g is obtained
1.5Mn
1.5Spinelle and Mn
2O
3Mixture) and 5g H-ZSM-5 (Zeolyst society produces, and CBV3020E) mixes in mortar, and the mass ratio of making Cu-Mn spinel oxides and H-ZSM-5 thus is 2: 1 a mixed catalyst.Activity of such catalysts evaluation and the durability evaluation that obtains be the results are shown in Table 1.
Embodiment 2 (mass ratio of Cu-Mn spinel oxides and H-modenite is 2: 1 a mixed catalyst)
(eastern ソ one society produces, and HSZ-640NAA) ammonium nitrate with 1 mol carries out ion-exchange in 4 hours in 60 ℃ of temperature baths, 120 ℃ of one nights of drying, burns till 3 hours at 500 ℃ with firing furnace then, obtains H type modenite with the H-modenite.The H type modenite that Cu-Mn spinel oxides that 10g is prepared similarly to Example 1 and 5g obtain mixes in mortar, and the mass ratio that obtains Cu-Mn spinel oxides and H type modenite thus is 2: 1 a mixed catalyst.The activity of such catalysts evaluation result that obtains is seen Table 1.
Comparative example 1 (mass ratio of Cu-Mn spinel oxides and aluminium oxide is 2: 1 a mixed catalyst)
(Sumitomo Chemical society produces, and AKP-G015) mixes in mortar, and the mass ratio of making Cu-Mn spinel oxides and aluminium oxide thus is 2: 1 a mixed catalyst for Cu-Mn spinel oxides that 10g is prepared similarly to Example 1 and 5g aluminium oxide.The activity of such catalysts evaluation result that obtains is seen Table 1.
Comparative example 2 (mass ratio of Cu-Zn-Al catalyst and H-ZSM-5 is 2: 1 a mixed catalyst)
(ズ one De ケ ミ one catalyst society produces the Cu-Zn-Al catalyst that 10g is commercially available, MDC-3) and 5g H-ZSM-5 (Zeolyst society produces, CBV3020E) mix in mortar, the mass ratio of making Cu-Zn-Al catalyst and H-ZSM-5 thus is 2: 1 mixed catalysts.The activity of such catalysts evaluation result that obtains is seen Table 1.
Embodiment 3 (mass ratio of Cu-Mn spinel oxides and H-ZSM-5 is 8: 1 a mixed catalyst)
(Zeolyst society produces, and CBV3020E) mixes in mortar, and the mass ratio of making Cu-Mn spinel oxides and H-ZSM-5 thus is 8: 1 a mixed catalyst for Cu-Mn spinel oxides that 20g is prepared similarly to Example 1 and 2.5g H-ZSM-5.The activity of such catalysts evaluation result that obtains is seen Table 1.
Embodiment 4 (mass ratio of Cu-Mn spinel oxides and H-ZSM-5 is 32: 1 a mixed catalyst)
(Zeolyst society produces, and CBV3020E) mixes in mortar, and the mass ratio of making Cu-Mn spinel oxides and H-ZSM-5 thus is 32: 1 a mixed catalyst for Cu-Mn spinel oxides that 32g is prepared similarly to Example 1 and 1g H-ZSM-5.Durability evaluation to the catalyst that obtains the results are shown in Table 1.
Embodiment 5 (mass ratio of Cu-Mn spinel oxides and H-ZSM-5 is 1: 2 a mixed catalyst)
(Zeolyst society produces, and CBV3020E) mixes in mortar, and the mass ratio of making Cu-Mn spinel oxides and H-ZSM-5 thus is 1: 2 a mixed catalyst for Cu-Mn spinel oxides that 5g is prepared similarly to Example 1 and 10g H-ZSM-5.Durability evaluation to the catalyst that obtains the results are shown in Table 1.
Embodiment 6 (mass ratio of Cu-Mn spinel oxides and 0.1 quality %Pt/H-ZSM-5 is 2: 1 a mixed catalyst)
[society produces 98.5 quality %H with the pure pharmaceutical worker's industry of light with 0.27g (0.51 mM) chloroplatinic acid hexahydrate
2PtCl
66H
2O] be dissolved in 35 ml distilled waters, contain then be dipped into 10g H-ZSM-5 (Zeolyst society produces, CBV3020E) in, 120 ℃ of dryings 3 hours, burnt till 3 hours at 400 ℃, prepare 0.1 quality %Pt/H-ZSM-5.
Cu-Mn spinel oxides and the above-mentioned 0.1 quality %Pt/H-ZSM-5 of 5g that 10g is prepared similarly to Example 1 mix in mortar, and the mass ratio of making Cu-Mn spinel oxides and 0.1 quality %Pt/H-ZSM-5 thus is 2: 1 a mixed catalyst.The activity of such catalysts evaluation result that obtains is seen Table 1.
Embodiment 7 (mass ratio of Cu-Mn spinel oxides and 0.1 quality %Pt/H-ZSM-5 is 8: 1 a mixed catalyst)
Cu-Mn spinel oxides and 2g 0.1 quality %Pt/H-ZSM-5 that 16g is prepared similarly to Example 1 mix in mortar, and the mass ratio of making Cu-Mn spinel oxides and 0.1 quality %Pt/H-ZSM-5 thus is 8: 1 a mixed catalyst.Activity of such catalysts evaluation and the durability evaluation that obtains be the results are shown in Table 1.
Embodiment 8 (mass ratio of Cu-Mn spinel oxides and 0.1 quality %Pt-ZSM-5 is 2: 1 a mixed catalyst)
(island chemicals society produces, Pt (NH with 0.086g (0.26 mM) chlorination four ammino platinum
3)
4Cl
2) join in 300 ml distilled waters, in bathing, 80 ℃ of temperature stir.Then, (Zeolyst society produces, and CBV3020E), carries out ion-exchange in 9 hours then in 80 ℃ of temperature are bathed, and, burns till 3 hours at 400 ℃ with firing furnace after one night 120 ℃ of dryings, obtains 0.1 quality %Pt-ZSM-5 to add 50g H-ZSM-5 in this solution.
Cu-Mn spinel oxides and 0.1 above-mentioned quality %Pt-ZSM-5 of 5g that 10g is prepared similarly to Example 1 mix in mortar, and the mass ratio of making Cu-Mn spinel oxides and 0.1 quality %Pt-ZSM-5 thus is 2: 1 a mixed catalyst.The activity of such catalysts evaluation result that obtains is seen Table 1.
Embodiment 9 (mass ratio of Cu-Mn spinel oxides and 0.1 quality %Pt-ZSM-5 is 8: 1 a mixed catalyst)
The 0.1 quality %Pt-ZSM-5 that Cu-Mn spinel oxides that 16g is prepared similarly to Example 1 and 2g prepare similarly to Example 8 mixes in mortar, and the mass ratio of making Cu-Mn spinel oxides and 0.1 quality %Pt-ZSM-5 thus is 8: 1 a mixed catalyst.Activity of such catalysts evaluation and the durability evaluation that obtains be the results are shown in Table 1.
[table 1]
| Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| The catalyst component mass ratio | |||||||||||
| (copper component) | |||||||||||
| The Cu-Mn spinelle | 2 | 2 | 2 | 8 | 32 | 1 | 2 | 8 | 2 | 8 | |
| The Cu-Zn-Al catalyst | 2 | ||||||||||
| (solid acid composition) | |||||||||||
| H-ZSM-5 | 1 | 1 | 1 | 1 | 2 | ||||||
| The H-modenite | 1 | ||||||||||
| Aluminium oxide | 1 | ||||||||||
| 0.1wt％Pt/H-ZSM-5 | 1 | 1 | |||||||||
| 0.1wt％Pt-ZSM-5 | 1 | 1 | |||||||||
| Activity rating (250 ℃, 900h -1) | |||||||||||
| DME conversion ratio (%) | 85 | 81 | 3 | 70 | 75 | 86 | 82 | 90 | 82 | ||
| Coking rate (%) | 0.24 | 1.8 | 0.18 | 0.20 | 0.10 | 0.19 | 0.07 | ||||
| Durability evaluation | |||||||||||
| The durable time (h) | ＞250 | ＞250 | ＞250 | 5 | ＞250 | ＞250 |
By the activity rating result of table 1 as can be known, compare with the catalyst that aluminium oxide forms with mixed C u-Mn spinel oxides, be mixed with the DME steam modified active height of the catalyst of zeolites such as H-ZSM-5, H-modenite in the Cu-Mn spinel oxides, in addition, even compare with the mixed catalyst of existing C u class catalyst and H-ZSM-5, this catalyst has also shown equal above DME steam modified active, and reacted burnt growing amount is few.(embodiment 1～2, comparative example 1～2)
In addition, the mixing ratio that makes Cu-Mn spinel oxides and H-ZSM-5 in table 1 was 1: 2～32: 1 range, the durability of evaluate catalysts, as a result, mixing ratio is 1: 2 o'clock, because coking, durability only is 5 hours, and mixing ratio is 2: 1～32: 1 o'clock, and durability is all more than 250 hours, and the mixing ratio of Cu-Mn spinel oxides and zeolite preferably sets more than 1 as can be known.(embodiment 3～5)
In addition, from the activity rating result of table 1 as can be known, the situation of Cu-Mn spinel oxides and the zeolite that contains noble metal (Pt) catalyst that mixes and the zeolite that does not contain noble metal specific activity mutually improves, and the coking rate descends.(comparison of the comparison of embodiment 6,8 and embodiment 1 and embodiment 7,9 and embodiment 3)
Embodiment 10 (mass ratio of Cu-Mn spinel oxides and H-ZSM-5 is to add 5 quality % aluminium oxide in 8: 1 the mixed catalyst)
(Zeolyst society produces for Cu-Mn spinel oxides, 2g H-ZSM-5 that 16g is prepared similarly to Example 1, CBV3020E) and the 0.95g aluminium oxide (Sumitomo Chemical society produces, AKP-G015) in mortar, mix, obtain being added with the Cu-Mn spinel oxides of 5 quality % aluminium oxide and the mixed catalyst (8: 1) of H-ZSM-5 thus.Durability evaluation to the catalyst that obtains the results are shown in Table 2.
Embodiment 11 (mass ratio of Cu-Mn spinel oxides and H-ZSM-5 is to add 8 quality % aluminium oxide in 8: 1 the mixed catalyst)
(Zeolyst society produces for Cu-Mn spinel oxides, 2g H-ZSM-5 that 16g is prepared similarly to Example 1, CBV3020E) and 1.6g aluminium oxide (Sumitomo Chemical society produce AKP-G015) in mortar, mix, obtain being added with the Cu-Mn spinel oxides of 8 quality % aluminium oxide and the mixed catalyst (8: 1) of H-ZSM-5 thus.Durability evaluation to the catalyst that obtains the results are shown in Table 2.
Embodiment 12 (mass ratio of Cu-Mn spinel oxides and H-ZSM-5 is to add 20 quality % aluminium oxide in 8: 1 the mixed catalyst)
(Zeolyst society produces for Cu-Mn spinel oxides, 2g H-ZSM-5 that 16g is prepared similarly to Example 1, CBV3020E) and 4.5g aluminium oxide (Sumitomo Chemical society produce AKP-G015) in mortar, mix, obtain being added with the Cu-Mn spinel oxides of 20 quality % aluminium oxide and the mixed catalyst (8: 1) of H-ZSM-5 thus.Durability evaluation to the catalyst that obtains the results are shown in Table 2.
Embodiment 13 (mass ratio of Cu-Mn spinel oxides and H-ZSM-5 is to add 50 quality % aluminium oxide in 8: 1 the mixed catalyst)
(Zeolyst society produces for Cu-Mn spinel oxides, 2g H-ZSM-5 that 16g is prepared similarly to Example 1, CBV3020E) and 18g aluminium oxide (Sumitomo Chemical society produce AKP-G015) in mortar, mix, obtain being added with the Cu-Mn spinel oxides of 50 quality % aluminium oxide and the mixed catalyst (8: 1) of H-ZSM-5 thus.Durability evaluation to the catalyst that obtains the results are shown in Table 2.
Comparative example 3 (mass ratio of Cu-Zn-Al catalyst and H-ZSM-5 is 8: 1 a mixed catalyst)
(ズ one De ケ ミ one catalyst society produces the Cu-Zn-Al catalyst that 16g is commercially available, MDC-3) and 2g H-ZSM-5 (Zeolyst society produces, CBV3020E) mix in mortar, the mass ratio of making Cu-Zn-Al catalyst and H-ZSM-5 thus is 8: 1 a mixed catalyst.Durability evaluation to the catalyst that obtains the results are shown in Table 2.
[table 2]
| Embodiment 10 | | | Embodiment 13 | Comparative example 3 | Embodiment 3 | |
| The catalyst component mass ratio | ||||||
| (copper component) | ||||||
| The Cu-Mn spinelle | 8 | 8 | 8 | 8 | 8 | |
| The Cu-Zn-Al catalyst | 8 | |||||
| (solid acid composition) | ||||||
| H-ZSM-5 | 1 | 1 | 1 | 1 | 1 | 1 |
| Aluminium oxide addition (quality %) | 5 | 8 | 20 | 50 | ||
| Durability evaluation (333h -1) | ||||||
| Conversion ratio (280 ℃, %) | ||||||
| Initial stage | 100 | 100 | 100 | 88 | 60 | 100 |
| Behind the 400h | 70 | 78 | 89 | 79 | 14 | 52 |
| Active reduced rate is (behind the 400h, %) | 30.0 | 22.0 | 11.0 | 10.2 | 76.7 | 48.0 |
| The coking rate is (behind the 400h, %) | 0.46 | 0.29 | 0.15 | 0.12 | 1.8 | 0.79 |
Be noted that to give in the table 2 embodiment 3 is adopted result when carrying out durability evaluation with the same method of embodiment 10～13.From the result of embodiment 10～13 and embodiment 3 as can be known, by adding aluminium oxide in the mixed catalyst of Cu-Mn spinel oxides and H-ZSM-5, actively reduce fewly, the coking rate descends.
Embodiment 14 (Cu-Mn spinel oxides+1 quality %Fe/H-ZSM-5 (Si-Al, impregnation supports) catalyst (mass ratio 8: 1))
[society produces 99 quality %Fe (NO with the pure pharmaceutical worker's industry of light with 1.47g (3.6 mM) ferric nitrate nonahydrate
3)
39H
2O] be dissolved in 11 milliliters the distilled water, contain be dipped into 20g H-ZSM-5 (Zeolyst society produces, CBV3020E) in,, carry out burning till in 3 hours after 3 hours 120 ℃ of dryings at 400 ℃, obtain 1 quality %Fe/H-ZSM-5 (Si-Al).With before the Cu-Mn spinel oxides mixes, at 500 ℃ the 1 quality %Fe/H-ZSM-5 (Si-Al) that obtains is carried out hydrogen reduction in 3 hours and handle.
The 1 quality %Fe/H-ZSM-5 (Si-Al) that the hydrogen reduction that Cu-Mn spinel oxides that 16g is prepared similarly to Example 1 and 2g obtain by above-mentioned steps was handled mixes in mortar, obtain Cu-Mn spinel oxides+1 quality %Fe/H-ZSM-5 (Si-Al, impregnation supports) catalyst (mass ratio 8: 1) thus.The activity of such catalysts evaluation that obtains and durability evaluation be the results are shown in Table 3.
Embodiment 15 (Cu-Mn spinel oxides+1 quality %Ni/H-ZSM-5 (Si-Al, impregnation supports) catalyst (mass ratio 8: 1))
[society produces 98%Ni (NO with the pure pharmaceutical worker's industry of light with 1.02g (3.4 mM) nickel nitrate hexahydrate
3)
26H
2O] be dissolved in 11 ml distilled waters, contain be dipped into 20g H-ZSM-5 (Zeolyst society produces, CBV3020E) in,, burnt till 3 hours after 3 hours 120 ℃ of dryings at 400 ℃, obtain 1 quality %Ni/H-ZSM-5 (Si-Al).Before the Cu-Mn spinel oxides mixes, handle 500 ℃ of hydrogen reductions that the 1 quality %Ni/H-ZSM-5 (Si-Al) that obtains was carried out 3 hours.
The 1 quality %Ni/H-ZSM-5 (Si-Al) that the hydrogen reduction that Cu-Mn spinel oxides that 16g is prepared similarly to Example 1 and 2g obtain by above-mentioned steps was handled mixes in mortar, obtain Cu-Mn spinel oxides+1 quality %Ni/H-ZSM-5 (Si-Al, impregnation supports) catalyst (mass ratio 8: 1) thus.The activity of such catalysts evaluation result that obtains is seen Table 3.
Embodiment 16 (Cu-Mn spinel oxides+1 quality %Co/H-ZSM-5 (Si-Al, impregnation supports) catalyst (mass ratio 8: 1))
[society produces 98%Co (NO with the pure pharmaceutical worker's industry of light with 1.02g (3.4 mM) Cobalt(II) nitrate hexahydrate
3)
26H
2O] be dissolved in 11 ml distilled waters, contain be dipped into 20gH-ZSM-5 (Zeolyst society produces, CBV3020E) in,, burnt till 3 hours after 3 hours 120 ℃ of dryings at 400 ℃, obtain 1 quality %Co/H-ZSM-5 (Si-Al).Before the Cu-Mn spinel oxides mixes, at 500 ℃ the 1 quality %Co/H-ZSM-5 (Si-Al) that obtains is carried out hydrogen reduction in 3 hours and handle.
The 1 quality %Ni/H-ZSM-5 (Si-Al) that the hydrogen reduction that Cu-Mn spinel oxides that 16g is prepared similarly to Example 1 and 2g obtain by above-mentioned steps was handled mixes in mortar, obtain Cu-Mn spinel oxides+1 quality %Co/H-ZSM-5 (Si-Al, impregnation supports) catalyst (mass ratio 8: 1) thus.The activity of such catalysts evaluation result that obtains is seen Table 3.
Embodiment 17 (Cu-Mn spinel oxides+0.1 quality %Fe-H-ZSM-5 (Si-Al, ion-exchange supports) catalyst (mass ratio 8: 1))
[society produces 99 quality %Fe (NO with the pure pharmaceutical worker's industry of light with 0.365g (0.89 mM) ferric nitrate nonahydrate
3)
39H
2O] join in 300 ml distilled waters, in bathing, 80 ℃ of temperature stir.Then, (Zeolyst society produces, and CBV3020E), carries out ion-exchange in 9 hours in 80 ℃ temperature are bathed, and after the cooling, carries out suction filtration with 5 liters of distilled water to add 50g H-ZSM-5 in this solution.After carrying out above-mentioned ion-exchange, suction filtration once more,, burnt till 3 hours at 400 ℃ with firing furnace then, obtain 0.1 quality %Fe-H-ZSM-5 (Si-Al) 120 ℃ of one nights of drying.Before the Cu-Mn spinel oxides mixes, at 500 ℃ the 0.1 quality %Fe-H-ZSM-5 (Si-Al) that obtains is carried out hydrogen reduction in 3 hours and handle.
The 0.1 quality %Fe-H-ZSM-5 (Si-Al) that the hydrogen reduction that Cu-Mn spinel oxides that 16g is prepared similarly to Example 1 and 2g obtain by above-mentioned steps was handled mixes in mortar, obtains the mixed catalyst (mass ratio 8: 1) of Cu-Mn spinel oxides and 0.1 quality %Fe-H-ZSM-5 thus.Activity of such catalysts evaluation and the durability evaluation that obtains be the results are shown in Table 3.
Embodiment 18 (Cu-Mn spinel oxides+0.1 quality %Ni-H-ZSM-5 (Si-Al, ion-exchange supports) catalyst (mass ratio 8: 1))
[society produces 98 quality %Ni (NO with the pure pharmaceutical worker's industry of light with 0.253g (0.85 mM) nickel nitrate hexahydrate
3)
26H
2O] be added in 300 ml distilled waters, in bathing, 80 ℃ of temperature stir.Then, (Zeolyst society produces, and CBV3020E), carries out ion-exchange in 9 hours in 80 ℃ temperature are bathed, and after the cooling, carries out suction filtration with 5 liters of distilled water to add 50g H-ZSM-5 in this solution.Carry out above-mentioned ion-exchange, suction filtration once more,, burnt till 3 hours at 400 ℃ with firing furnace then, obtain 0.1 quality %Ni-H-ZSM-5 (Si-Al) 120 ℃ of one nights of drying.Before the Cu-Mn spinel oxides mixes, at 500 ℃ the 0.1 quality %Ni-H-ZSM-5 (Si-Al) that obtains is carried out hydrogen reduction in 3 hours and handle.
The 0.1 quality %Ni-H-ZSM-5 (Si-Al) that the hydrogen reduction that Cu-Mn spinel oxides that 16g is prepared similarly to Example 1 and 2g obtain by above-mentioned steps was handled mixes in mortar, obtains the mixed catalyst (mass ratio 8: 1) of Cu-Mn spinel oxides and 0.1 quality %Ni-H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 3.
Embodiment 19 (Cu-Mn spinel oxides+0.1 quality %Co-H-ZSM-5 (Si-Al, ion-exchange supports) catalyst (mass ratio 8: 1))
[society produces 98 quality %Co (NO with the pure pharmaceutical worker's industry of light with 0.252g (0.85 mM) Cobalt(II) nitrate hexahydrate
3)
26H
2O] be added in 300 ml distilled waters, in bathing, 80 ℃ of temperature stir.Then, (Zeolyst society produces, and CBV3020E), carries out ion-exchange in 9 hours in 80 ℃ temperature are bathed, and after the cooling, carries out suction filtration with 5 liters of distilled water to add 50g H-ZSM-5 in this solution.Carry out above-mentioned ion-exchange, suction filtration once more,, burnt till 3 hours at 400 ℃ with firing furnace then, obtain 0.1 quality %Co-H-ZSM-5 (Si-Al) 120 ℃ of one nights of drying.Before the Cu-Mn spinel oxides mixes, at 500 ℃ the 0.1 quality %Co-H-ZSM-5 (Si-Al) that obtains is carried out hydrogen reduction in 3 hours and handle.
The 0.1 quality %Co-H-ZSM-5 (Si-Al) that the hydrogen reduction that Cu-Mn spinel oxides that 16g is prepared similarly to Example 1 and 2g obtain by above-mentioned steps was handled mixes in mortar, obtains the mixed catalyst (mass ratio 8: 1) of Cu-Mn spinel oxides and 0.1 quality %Co-H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 3.
Embodiment 20 (Cu-Mn spinel oxides+H-ZSM-5 (Si-Al-Fe, Al: Fe=5: add Fe when 5, ZSM-5 is synthetic) catalyst (mass ratio 8: 1))
[society produces 99.5 quality %Al with the pure pharmaceutical worker's industry of light with 9.15g (13.7 mM) aluminum sulfate
2(SO
4)
318H
2O], [society produces 99 quality %Fe (NO to 11.2g (27.4 mM) ferric nitrate nonahydrate with the pure pharmaceutical worker of light industry
3)
39H
2O], [society produces 97%H to 10g (99.0 mM) sulfuric acid with the pure pharmaceutical worker of light industry
2SO
4], [society produces 98 quality % (CH to 26.8g (98.9 mM) bromination tetrapropyl ammonium with the pure pharmaceutical worker of light industry
3CH
2CH
2)
4NBr] and 250 ml distilled waters mix, with the homogeneous solution that obtains as A liquid.In addition, with 215g waterglass (No. 3, the Japanese chemical industry production JIS of society, SiO
2: 29 quality %, Na
2O:9.4 quality %, water: 61.6 quality %) and 60g distilled water mix, with the homogeneous solution that obtains as B liquid.In addition, with 40.2g (684 mM) sodium chloride [society produces 99.5 quality %NaCl with the pure pharmaceutical worker of light industry] and the mixing of 120 ml distilled waters, with the homogeneous solution that obtains as C liquid.
This C liquid is stirred on the limit, and the limit slowly is added drop-wise to above-mentioned A liquid and B liquid in the C liquid simultaneously, mixes.[society produces 97 quality %H with the pure pharmaceutical worker's industry of light to add 2.0g (19.8 mM) sulfuric acid in this raw mix
2SO
4], be adjusted to pH9.5, be in 1 liter the autoclave with the mixture that the obtains internal volume of packing into, stir down with the rotating speed that changes 300rpm on the limit, and reacted 20 hours under 170 ℃, self pressure on the limit.After the reaction, mixture is cooled to room temperature, by pressure filtration solid-state product is carried out filtration washing then, wash to the pH of filtrate be below 9.5.Then with the solid content that reclaims 120 ℃ of dryings 6 hours, then in air, burnt till 6 hours at 550 ℃.
Then, the above-mentioned burned material of every 1g is used 10 milliliters of 1 mole/L aqueous ammonium nitrate solutions, at 60 ℃ above-mentioned burned material is carried out ion-exchange in 4 hours, after the cooling, carries out suction filtration with distilled water.Carry out above-mentioned ion-exchange, filtering and washing once more, the ion-exchange thing that obtains 120 ℃ of dryings 6 hours, was burnt till 3 hours at 400 ℃ then, obtain H-ZSM-5 (Si-Al-Fe, Al: Fe=5: add Fe when 5, ZSM-5 is synthetic).Confirm the SiO of this burned material by ICP
2/ Al
2O
3=57.7, Al/Fe=1.11, and confirm that by XRD this burned material is the ZSM-5 structure.Before the Cu-Mn spinel oxides mixes, at 500 ℃ of H-ZSM-5 (Si-Al-Fe, Al: Fe=5: 5) carry out hydrogen reduction in 3 hours and handle to obtaining.
H-ZSM-5 (the Si-Al-Fe that the hydrogen reduction that Cu-Mn spinel oxides that 16g is prepared similarly to Example 1 and 2g obtain by above-mentioned steps was handled, Al: Fe=5: 5) in mortar, mix, obtain Cu-Mn spinel oxides and H-ZSM-5 (Si-Al-Fe, Al: Fe=5: mixed catalyst 5) (mass ratio 8: 1) thus.Activity of such catalysts evaluation and the durability evaluation that obtains be the results are shown in Table 3.
Embodiment 21 (Cu-Mn spinel oxides+H-ZSM-5 (Si-Al-Fe, Al: Fe=9: 1, add Fe when ZSM-5 is synthetic) catalyst (mass ratio 8: 1))
[society produces 99.5 quality %Al with the pure pharmaceutical worker's industry of light with 16.5g (24.6 mM) aluminum sulfate
2(SO
4)
318H
2O], [society produces 99 quality %Fe (NO to 2.23g (5.47 mM) ferric nitrate nonahydrate with the pure pharmaceutical worker of light industry
3)
39H
2O], [society produces 97 quality %H to 10g (99.0 mM) sulfuric acid with the pure pharmaceutical worker of light industry
2SO
4], [society produces 98 quality % (CH to 26.8g (98.9 mM) bromination tetrapropyl ammonium with the pure pharmaceutical worker of light industry
3CH
2CH
2)
4NBr] and 250 ml distilled waters mix, with the homogeneous solution that obtains as A liquid.Prepare B liquid and C liquid similarly to Example 20.
Stir this C liquid on one side, on one side above-mentioned A liquid and B liquid slowly are added drop-wise in the C liquid simultaneously, mix.[society produces 97 quality %H with the pure pharmaceutical worker's industry of light to add 1.4g (13.9 mM) sulfuric acid in this raw mix
2SO
4], being adjusted to pH is 9.5.Preparation similarly to Example 20 below obtains H-ZSM-5 (Si-Al-Fe, Al: Fe=9: add Fe when 1, ZSM-5 is synthetic).Confirm the SiO of this burned material by ICP
2/ Al
2O
3=35.7, Al/Fe=9.11, and confirm that by XRD this burned material is the ZSM-5 structure.Before the Cu-Mn spinel oxides mixes, at 500 ℃ of H-ZSM-5 (Si-Al-Fe, Al: Fe=9: 1) carry out hydrogen reduction in 3 hours and handle to obtaining.
H-ZSM-5 (the Si-Al-Fe that the hydrogen reduction that Cu-Mn spinel oxides that 16g is prepared similarly to Example 1 and 2g obtain by above-mentioned steps was handled, Al: Fe=9: 1) in mortar, mix, obtain Cu-Mn spinel oxides and H-ZSM-5 (Si-Al-Fe, Al: Fe=9: mixed catalyst 1) (mass ratio 8: 1) thus.Activity of such catalysts evaluation and the durability evaluation that obtains be the results are shown in Table 3.
Embodiment 22 (Cu-Mn spinel oxides+H-ZSM-5 (Si-Al-Ni, Al: Ni=9: 1, add Ni when ZSM-5 is synthetic) catalyst (mass ratio 8: 1))
[society produces 99.5 quality %Al with the pure pharmaceutical worker's industry of light with 16.5g (24.6 mM) aluminum sulfate
2(SO
4)
318H
2O], [society produces 98 quality %Ni (NO to 1.62g (5.47 mM) nickel nitrate hexahydrate with the pure pharmaceutical worker of light industry
3)
26H
2O], [society produces 97%H to 10g (99.0 mM) sulfuric acid with the pure pharmaceutical worker of light industry
2SO
4], [society produces 98 quality % (CH to 26.8g (98.9 mM) bromination tetrapropyl ammonium with the pure pharmaceutical worker of light industry
3CH
2CH
2)
4NBr] and 250 ml distilled waters mix, with the homogeneous solution that obtains as A liquid.Prepare B liquid and C liquid similarly to Example 20.
Stir this C liquid on one side, on one side above-mentioned A liquid and B liquid slowly are added drop-wise in the C liquid simultaneously, mix.[society produces 97 quality %H with the pure pharmaceutical worker's industry of light to add 2.4g (23.8 mM) sulfuric acid in this raw mix
2SO
4], being adjusted to pH is 9.5.Be prepared similarly to Example 20 below, obtain H-ZSM-5 (Si-Al-Ni, Al: Ni=9: 1, ZSM-5 adds Ni when synthetic).Confirm the SiO of this burned material by ICP
2/ Al
2O
3=35.1, Al/Ni=9.06.Before the Cu-Mn spinel oxides mixes, at 500 ℃ of H-ZSM-5 (Si-Al-Ni, Al: Ni=9: 1) carry out hydrogen reduction in 3 hours and handle to obtaining.
H-ZSM-5 (the Si-Al-Ni that the hydrogen reduction that Cu-Mn spinel oxides that 16g is prepared similarly to Example 1 and 2g obtain by above-mentioned steps was handled, Al: Ni=9: 1) in mortar, mix, obtain Cu-Mn spinel oxides and H-ZSM-5 (Si-Al-Ni, Al: Ni=9: mixed catalyst 1) (mass ratio 8: 1) thus.The activity of such catalysts evaluation result that obtains is seen Table 3.
Embodiment 23 (Cu-Mn spinel oxides+H-ZSM-5 (Si-Al-Co, Al: Co=9: 1, add Co when ZSM-5 is synthetic) catalyst (mass ratio 8: 1))
[society produces 99.5 quality %Al with the pure pharmaceutical worker's industry of light with 16.5g (24.6 mM) aluminum sulfate
2(SO
4)
318H
2O], [society produces 98 quality %Co (NO to 1.62g (5.47 mM) Cobalt(II) nitrate hexahydrate with the pure pharmaceutical worker of light industry
3)
26H
2O], [society produces 97%H to 10g (99.0 mM) sulfuric acid with the pure pharmaceutical worker of light industry
2SO
4], [society produces 98 quality % (CH to 26.8g (98.9 mM) bromination tetrapropyl ammonium with the pure pharmaceutical worker of light industry
3CH
2CH
2)
4NBr] and 250 ml distilled waters mix, with the homogeneous solution that obtains as A liquid.Prepare B liquid and C liquid similarly to Example 20.
Stir this C liquid on one side, on one side above-mentioned A liquid and B liquid slowly are added drop-wise in the C liquid simultaneously, mix.[society produces 97 quality %H with the pure pharmaceutical worker's industry of light to add 2.2g (21.8 mM) sulfuric acid in this raw mix
2SO
4], being adjusted to pH is 9.5.Be prepared similarly to Example 20 below, obtain H-ZSM-5 (Si-Al-Co, Al: Co=9: 1, ZSM-5 adds Co when synthetic).Confirm the SiO of this burned material by ICP
2/ Al
2O
3=35.9, Al/Co=9.10.Before the Cu-Mn spinel oxides mixes, at 500 ℃ of H-ZSM-5 (Si-Al-Co, Al: Co=9: 1) carry out hydrogen reduction in 3 hours and handle to obtaining.
H-ZSM-5 (the Si-Al-Co that the hydrogen reduction that Cu-Mn spinel oxides that 16g is prepared similarly to Example 1 and 2g obtain by above-mentioned steps was handled, Al: Co=9: 1) in mortar, mix, obtain Cu-Mn spinel oxides and H-ZSM-5 (Si-Al-Co, Al: Co=9: mixed catalyst 1) (mass ratio 8: 1) thus.The activity of such catalysts evaluation result that obtains is seen Table 3.
[table 3]
| Embodiment 14 | Embodiment 15 | | Embodiment 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | | Embodiment 22 | | Embodiment 3 | |
| The catalyst component mass ratio | |||||||||||
| (copper component) | |||||||||||
| The Cu-Mn spinelle | 8 | 8 | 8 | 8 | 8 | 8 | 8 | 8 | 8 | 8 | 8 |
| (solid acid composition) | |||||||||||
| ZSM-5 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| The carrying metal name | Fe | Ni | Co | Fe | Ni | Co | Fe | Fe | Ni | Co | |
| Carrying metal amount (quality %) | 1 | 1 | 1 | 0.10 | 0.10 | 0.10 | 2.5 | 0.50 | 0.56 | 0.55 | |
| Loading method | |||||||||||
| Impregnation | ○ | ○ | ○ | ||||||||
| Ion-exchange | ○ | ○ | ○ | ||||||||
| Add when ZSM-5 is synthetic | ○ | ○ | ○ | ○ | |||||||
| Activity rating (280 ℃, 333h -1) | |||||||||||
| DME conversion ratio (%) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Coking rate (quality %) | 0.07 | 0.09 | 0.1 | 0.04 | 0.04 | 0.09 | 0.03 | 0.02 | 0.05 | 0.07 | 0.24 |
| Durability evaluation (333h -1) | |||||||||||
| Conversion ratio (280 ℃, %) | |||||||||||
| Initial stage | 100 | 100 | 100 | 100 | 100 | ||||||
| Behind the 400h | 68 | 73 | 80 | 78 | 52 | ||||||
| Active reduced rate is (behind the 400h, %) | 32.0 | 27.0 | 20.0 | 22.0 | 48.0 | ||||||
| The coking rate is (behind the 400h, %) | 0.43 | 0.32 | 0.22 | 0.29 | 0.79 |
Be noted that the activity rating and the durability evaluation result that in table 3, give embodiment 3.According to this result as can be known, by add the group VIII metal in the mixed catalyst of Cu-Mn spinel oxides and H-ZSM-5, can suppress burnt generation, durability further improves.
Embodiment 24 (Cu-Mn spinel oxides+5 quality %La/H-ZSM-5 catalyst (mass ratio 8: 1))
[society produces 99.9%La (NO with the pure pharmaceutical worker's industry of light with 1.64g (3.80 mM) lanthanum nitrate hexahydrate
3)
36H
2O] [society produces 99.5 quality %C with the pure pharmaceutical worker's industry of light to be dissolved in 75 milliliters of ethanol
2H
5OH] in, add 10g H-ZSM-5 (CBV3020E that Zeolyst society produces) therein, in 30 ℃ of temperature are bathed, wave to loose with evaporimeter and remove ethanol, 40 ℃ of dryings after one night, further 120 ℃ of dryings 3 hours, and burnt till 10 hours at 500 ℃, obtain 5 quality %La/H-ZSM-5.
Cu-Mn spinel oxides and 2g that 16g is prepared similarly to Example 1 mix in mortar by the 5 quality %La/H-ZSM-5 that above-mentioned steps obtains, and obtain the mixed catalyst (8: 1) of Cu-Mn spinel oxides and 5 quality %La/H-ZSM-5 thus.Activity of such catalysts evaluation and the durability evaluation that obtains be the results are shown in Table 4.
Embodiment 25 (Cu-Mn spinel oxides+5 quality %Ce/H-ZSM-5 catalyst (mass ratio 8: 1))
[society produces 98 quality %Ce (NO with the pure pharmaceutical worker's industry of light with 1.66g (3.91 mM) cerous nitrate hexahydrate
3)
36H
2O] [society produces 99.5 quality %C with the pure pharmaceutical worker's industry of light to be dissolved in 75 milliliters of ethanol
2H
5OH] in, add 10g H-ZSM-5 (CBV3020E that Zeolyst society produces) therein, in bathing, 30 ℃ of temperature wave the diffusing ethanol of removing with evaporimeter, 40 ℃ of dryings after one night, burnt till 10 hours further 120 ℃ of dryings 3 hours, and at 500 ℃, obtain 5 quality %Ce/H-ZSM-5.
Cu-Mn spinel oxides and 2g that 16g is prepared similarly to Example 1 mix in mortar by the 5 quality %Ce/H-ZSM-5 that above-mentioned steps obtains, and obtain the mixed catalyst (8: 1) of Cu-Mn spinel oxides and 5 quality %Ce/H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 4.
Embodiment 26 (Cu-Mn spinel oxides+5 quality %Sm/H-ZSM-5 catalyst (mass ratio 8: 1))
[society produces 99.5 quality %Sm (NO with the pure pharmaceutical worker's industry of light with 1.56g (3.54 mM) samaric nitrate hexahydrate
3)
36H
2O] [society produces 99.5 quality %C with the pure pharmaceutical worker's industry of light to be dissolved in 75 milliliters of ethanol
2H
5OH] in, add 10g H-ZSM-5 (CBV3020E that Zeolyst society produces) therein, in bathing, 30 ℃ of temperature wave the diffusing ethanol of removing with evaporimeter, 40 ℃ of dryings after one night, burnt till 10 hours further 120 ℃ of dryings 3 hours, and at 500 ℃, obtain 5 quality %Sm/H-ZSM-5.
Cu-Mn spinel oxides and 2g that 16g is prepared similarly to Example 1 mix in mortar by the 5 quality %Sm/H-ZSM-5 that above-mentioned steps obtains, and obtain the mixed catalyst (8: 1) of Cu-Mn spinel oxides and 5 quality %Sm/H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 4.
Embodiment 27 (Cu-Mn spinel oxides+1 quality %La/H-ZSM-5 catalyst (mass ratio 2: 1))
[society produces 99.9%La (NO with the pure pharmaceutical worker's industry of light with 0.32g (0.73 mM) lanthanum nitrate hexahydrate
3)
36H
2O] [society produces 99.5 quality %C with the pure pharmaceutical worker's industry of light to be dissolved in 75 milliliters of ethanol
2H
5OH] in, add 10g H-ZSM-5 (CBV3020E that Zeolyst society produces) therein, in bathing, 30 ℃ of temperature wave the diffusing ethanol of removing with evaporimeter, 40 ℃ of dryings after one night, burnt till 10 hours further 120 ℃ of dryings 3 hours, and at 500 ℃, obtain 1 quality %La/H-ZSM-5.
Cu-Mn spinel oxides and 5g that 10g is prepared similarly to Example 1 mix in mortar by the 1 quality %La/H-ZSM-5 that above-mentioned steps obtains, and obtain the mixed catalyst (2: 1) of Cu-Mn spinel oxides and 1 quality %La/H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 4.
Embodiment 28 (Cu-Mn spinel oxides+10 quality %La/H-ZSM-5 catalyst (mass ratio 2: 1))
[society produces 99.9%La (NO with the pure pharmaceutical worker's industry of light with 3.47g (8.02 mM) lanthanum nitrate hexahydrate
3)
36H
2O] [society produces 99.5 quality %C with the pure pharmaceutical worker's industry of light to be dissolved in 75 milliliters of ethanol
2H
5OH] in, add 10g H-ZSM-5 (CBV3020E that Zeolyst society produces) therein, in bathing, 30 ℃ of temperature wave the diffusing ethanol of removing with evaporimeter, 40 ℃ of dryings after one night, further, burnt till 10 hours, obtain 10 quality %La/H-ZSM-5 at 500 ℃ 120 ℃ of dryings 3 hours.
Cu-Mn spinel oxides and 5g that 10g is prepared similarly to Example 1 mix in mortar by the 10 quality %La/H-ZSM-5 that above-mentioned steps obtains, and obtain the mixed catalyst (2: 1) of Cu-Mn spinel oxides and 10 quality %La/H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 4.
Embodiment 29 (Cu-Mn spinel oxides+5 quality %La/H-ZSM-5 catalyst (mass ratio 2: 1))
The 5 quality %La/H-ZSM-5 that Cu-Mn spinel oxides that 10g is prepared similarly to Example 1 and 5g prepare similarly to Example 24 mix in mortar, obtain the mixed catalyst (2: 1) of Cu-Mn spinel oxides and 5wt%La/H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 4.
Embodiment 30 (Cu-Mn spinel oxides+5 quality %La/H-ZSM-5 catalyst (mass ratio aqueous solution impregnation in 2: 1))
[society produces 99.9%La (NO with the pure pharmaceutical worker's industry of light with 3.28g (7.59 mM) lanthanum nitrate hexahydrate
3)
36H
2O] be dissolved in 11 ml distilled waters, contain and be dipped among the 20g H-ZSM-5 (Zeolyst society produce CBV3020E), after 3 hours, burnt till 10 hours preparation 5wt%La/H-ZSM-5 at 500 ℃ 120 ℃ of dryings.
Cu-Mn spinel oxides and 5g that 10g is prepared similarly to Example 1 mix in mortar by the 5 quality %La/ZSM-5 that above-mentioned steps obtains, obtain the mixed catalyst (2: 1, aqueous solution impregnation) of Cu-Mn spinel oxides and 5wt%La/H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 4.
Embodiment 31 (Cu-Mn spinel oxides+5 quality %Ce/H-ZSM-5 catalyst (mass ratio 2: 1))
The 5 quality %Ce/H-ZSM-5 that Cu-Mn spinel oxides that 10g is prepared similarly to Example 1 and 5g prepare similarly to Example 25 mix in mortar, obtain the mixed catalyst (2: 1) of Cu-Mn spinel oxides and 5 quality %Ce/H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 4.
Embodiment 32 (Cu-Mn spinel oxides+5 quality %Sm/H-ZSM-5 catalyst (mass ratio 2: 1))
The 5 quality %Sm/H-ZSM-5 that Cu-Mn spinel oxides that 10g is prepared similarly to Example 1 and 5g prepare similarly to Example 26 mix in mortar, obtain the mixed catalyst (2: 1) of Cu-Mn spinel oxides and 5 quality %Sm/H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 4.
Embodiment 33 (Cu-Mn spinel oxides+5 quality %La/H-ZSM-5 catalyst (mass ratio 1: 1))
The 5 quality %La/H-ZSM-5 that Cu-Mn spinel oxides that 10g is prepared similarly to Example 1 and 10g prepare similarly to Example 24 mix in mortar, obtain the mixed catalyst (1: 1) of Cu-Mn spinel oxides and 5 quality %La/H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 5.
Embodiment 34 (Cu-Mn spinel oxides+5 quality %Ce/H-ZSM-5 catalyst (mass ratio 1: 1))
The 5 quality %Ce/H-ZSM-5 that Cu-Mn spinel oxides that 10g is prepared similarly to Example 1 and 10g prepare similarly to Example 25 mix in mortar, obtain the mixed catalyst (1: 1) of Cu-Mn spinel oxides and 5 quality %Ce/H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 5.
Embodiment 35 (Cu-Mn spinel oxides+5 quality %Sm/H-ZSM-5 catalyst (mass ratio 1: 1))
The 5 quality %Sm/H-ZSM-5 that Cu-Mn spinel oxides that 10g is prepared similarly to Example 1 and 10g prepare similarly to Example 26 mix in mortar, obtain the mixed catalyst (1: 1) of Cu-Mn spinel oxides and 5 quality %Sm/H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 5.
Embodiment 36 (Cu-Mn spinel oxides+H-ZSM-5 catalyst (mass ratio 1: 1))
Cu-Mn spinel oxides and 10g H-ZSM-5 (CBV3020E that Zeolyst society produces) that 10g is prepared similarly to Example 1 mix in mortar, obtain the mixed catalyst (1: 1) of Cu-Mn spinel oxides and H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 5.
Comparative example 4 (Cu-Zn-Al+H-ZSM-5 catalyst (mass ratio 8: 1))
Cu-Zn-Al catalyst that 16g is commercially available (MDC-3 that ズ one De ケ ミ one society produces) and 2g H-ZSM-5 (CBV3020E that Zeolyst society produces) mix in mortar, obtain the mixed catalyst (8: 1) of Cu-Zn-Al and H-ZSM-5 thus.The activity of such catalysts evaluation result that obtains is seen Table 5.
[table 4]
| | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | Embodiment 29 | Embodiment 30 | | | Embodiment 1 | |
| The catalyst component mass ratio | ||||||||||
| (copper component) | ||||||||||
| The Cu-Mn spinelle | 8 | 8 | 8 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| (solid acid composition) | ||||||||||
| ZSM-5 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| The carrying metal name | La | Ce | Sm | La | La | La | La | Ce | Sm | |
| Carrying metal amount (quality %) | 5 | 5 | 5 | 1 | 10 | 5 | 5 | 5 | 5 | |
| Loading method | ||||||||||
| The ethanolic solution impregnation | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ||
| Aqueous solution impregnation | ○ | |||||||||
| Activity rating (280 ℃, 333h -1) | ||||||||||
| DME conversion ratio (%) | 99 | 100 | 100 | 100 | 98 | 100 | 100 | 100 | 100 | 100 |
| Coking rate (quality %) | 0.08 | 0.09 | 0.13 | 0.18 | 0.11 | 0.14 | 0.16 | 0.14 | 0.16 | 0.36 |
| Durability evaluation (333h -1) | ||||||||||
| Conversion ratio (280 ℃, %) | ||||||||||
| Initial stage | 99 | |||||||||
| Behind the 400h | 70 | |||||||||
| Active reduced rate is (behind the 400h, %) | 29.3 | |||||||||
| The coking rate is (behind the 400h, %) | 0.28 |
[table 5]
| | | | | Comparative example 4 | Embodiment 3 | |
| The catalyst component mass ratio | ||||||
| (copper component) | ||||||
| The Cu-Mn spinelle | 1 | 1 | 1 | 1 | 8 | |
| The Cu-Zn-Al catalyst | 8 | |||||
| (solid acid composition) | ||||||
| ZSM-5 | 1 | 1 | 1 | 1 | 1 | 1 |
| The carrying metal name | La | Ce | Sm | |||
| Carrying metal amount (quality %) | 5 | 5 | 5 | |||
| Loading method | ||||||
| The ethanolic solution impregnation | ○ | ○ | ○ | |||
| Activity rating (280 ℃, 333h -1) | ||||||
| DME conversion ratio (%) | 100 | 100 | 100 | 100 | 60 | 100 |
| Coking rate (quality %) | 0.25 | 0.25 | 0.23 | 0.67 | 0.58 | 0.24 |
Be noted that the activity rating result who gives embodiment 1 and embodiment 3 in above-mentioned table 4 and the table 5.By the result of embodiment 24～26, comparative example 4 and embodiment 3 as can be known, compare with the mixed catalyst of Cu-Zn-Al and H-ZSM-5, the DME of the mixed catalyst of Cu-Mn spinel oxides and H-ZSM-5 (dimethyl ether) conversion ratio improves, the coking rate is low, and, by further interpolation rare earth element, can further suppress coking.In addition, by the comparison of embodiment 27～32 and embodiment 1, embodiment 33～35 and embodiment 36, confirm to have suppressed coking by in the mixed catalyst of Cu-Mn spinel oxides and H-ZSM-5, adding rare earth element.
Industrial applicability
Contain cupric and have the metal oxide of spinel structure and the catalyst of aluminium oxide is compared with existing, of the present invention contain cupric and have the metal oxide of spinel structure and the catalyst of zeolite high to the steam modified active of the oxygen-containing hydrocarbons such as dimethyl ether, and the growing amount that becomes Jiao of catalyst degradation reason also lacks than the mixed catalyst of existing copper class catalyst and zeolite. In addition, further contain aluminium oxide, group VIII metal, rare earth element by making the metal oxide that contains cupric and have spinel structure and the catalyst of zeolite, in the modification of oxygen-containing hydrocarbon, can further suppress burnt growing amount.
So, use modified catalyst of the present invention that oxygen-containing hydrocarbon is implemented various modifications, can be steady in a long-term and make efficiently hydrogen or forming gas. And, can construct and have modification device and the fuel cell system take the hydrogen by this modification device manufacturing as the excellence of the fuel cell of fuel, described modification device possesses the modified catalyst of above-mentioned excellence.
Claims (15)
1, a kind of oxygen-containing hydrocarbon modified catalyst is characterized in that, it contains metal oxide and zeolite, described metal oxide cupric and have spinel structure.
2, oxygen-containing hydrocarbon modified catalyst according to claim 1 wherein, is a benchmark with the quality, and cupric and metal oxide with spinel structure are 1: 1～100: 1 with the content ratio of zeolite.
3, oxygen-containing hydrocarbon modified catalyst according to claim 1 and 2, wherein, cupric and the metal oxide with spinel structure are Cu-Mn type spinelle.
4, according to any described oxygen-containing hydrocarbon modified catalyst in the claim 1～3, wherein, zeolite is ZSM-5.
5, according to any described oxygen-containing hydrocarbon modified catalyst in the claim 1～4, wherein, it contains metal oxide, zeolite and aluminium oxide, described metal oxide cupric and have spinel structure.
6, according to any described oxygen-containing hydrocarbon modified catalyst in the claim 1～5, wherein, contain group VIII metal and/or rare earth element in the zeolite.
7, oxygen-containing hydrocarbon modified catalyst according to claim 6, wherein, the group VIII metal is at least a metal that is selected among Pt, Pd, Ir, Rh and the Ru.
8, oxygen-containing hydrocarbon modified catalyst according to claim 6, wherein, the group VIII metal is at least a metal that is selected among Fe, Ni and the Co.
9, a kind of modified catalyst of oxygen-containing hydrocarbon, it obtains by any described modified catalyst in the reduction claim 1～8.
10, according to any described oxygen-containing hydrocarbon modified catalyst in the claim 1～6, wherein, oxygen-containing hydrocarbon is to be selected from least a in dimethyl ether and the methyl ethyl ether.
11, the manufacture method of a kind of hydrogen or forming gas is characterized in that, uses any described modified catalyst of claim 1～10 that oxygen-containing hydrocarbon is carried out the steam modification.
12, the manufacture method of a kind of hydrogen or forming gas is characterized in that, any described modified catalyst carries out self heat modification to oxygen-containing hydrocarbon in the use claim 1～10.
13, the manufacture method of a kind of hydrogen or forming gas is characterized in that, any described modified catalyst carries out partical oxidizing modifying to oxygen-containing hydrocarbon in the use claim 1～10.
14, the manufacture method of a kind of hydrogen or forming gas is characterized in that, any described modified catalyst carries out the carbon dioxide modification to oxygen-containing hydrocarbon in the use claim 1～10.
15, a kind of fuel cell system is characterized in that, the fuel cell that it has modification device and acts as a fuel with the hydrogen by this modification device manufacturing, described modification device possess any described modified catalyst in the claim 1～10.
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| JP331422/2004 | 2004-11-16 | ||
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108465481A (en) * | 2018-02-07 | 2018-08-31 | 厦门大学 | A kind of multifunctional nano composite catalyst and its preparation method and application |
| CN111744488A (en) * | 2020-07-01 | 2020-10-09 | 太原理工大学 | Catalyst for preparing dimethyl ether from slurry bed synthesis gas and preparation method thereof |
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2005
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108465481A (en) * | 2018-02-07 | 2018-08-31 | 厦门大学 | A kind of multifunctional nano composite catalyst and its preparation method and application |
| CN108465481B (en) * | 2018-02-07 | 2020-07-10 | 厦门大学 | Multifunctional nano composite catalyst and preparation method and application thereof |
| CN111744488A (en) * | 2020-07-01 | 2020-10-09 | 太原理工大学 | Catalyst for preparing dimethyl ether from slurry bed synthesis gas and preparation method thereof |
| CN111744488B (en) * | 2020-07-01 | 2022-04-19 | 太原理工大学 | Catalyst for preparing dimethyl ether from slurry bed synthesis gas and preparation method thereof |
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