CN107552057B - ZnO/Cu catalyst and preparation method thereof for methanol synthesis reaction - Google Patents
ZnO/Cu catalyst and preparation method thereof for methanol synthesis reaction Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 70
- 239000004094 surface-active agent Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000004064 cosurfactant Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 3
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 16
- 230000001376 precipitating effect Effects 0.000 claims description 14
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 10
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 4
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 4
- 239000001593 sorbitan monooleate Substances 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000001760 fusel oil Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- 235000013847 iso-butane Nutrition 0.000 claims description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- -1 Qula logical x-100 Chemical compound 0.000 claims 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 claims 1
- 238000011017 operating method Methods 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of ZnO/Cu catalyst for methanol synthesis reaction, this method comprises: suitable surfactant, cosurfactant and oil is selected mutually to prepare Reverse Microemulsion System；Cu(OH)2Precipitating and the acquisition of CuO particle of the nano particle in microemulsion；Zn(OH)2Precipitating of the nano particle in microemulsion on CuO；Centrifugal filtration, washing, drying, calcining；Most ZnO/Cu catalyst is obtained through reduction afterwards.The invention also discloses the ZnO/Cu catalyst that the above method is prepared.The ZnO/Cu catalyst of the method for the present invention preparation, can in high volume synthesize, have a wide range of application, and reaction process operating procedure is simple and environmentally-friendly, have high controllability.Reactivity worth of the obtained ZnO/Cu catalyst in methanol-fueled CLC is substantially better than now widely used Cu/ZnO catalyst.
Description
Technical field
The present invention relates to nanocatalyst technical field more particularly to a kind of ZnO/Cu catalysis for methanol synthesis reaction
Agent and preparation method thereof.
Background technique
Methanol is a kind of global chemical article, is commonly used for chemical raw material.Meanwhile methanol is also a kind of clean fuel,
It can mix individually or with gasoline and be used as motor vehicle fuel.As a kind of excellent liquid fuel, methanol can be transport
Convenient and fast energy storage is provided with fuel cell.Between 2014-2015, the global demand amount of methanol has reached 100,000,000 tonnes.With
The sharply consumption of fossil fuel and CO in recent years2The increase of discharge amount recycles CO2Preparing alternative fuel becomes research
Hot spot, it is desirable to pass through catalysis CO2Hydrogenation reaction prepare methanol and effectively solve the above problems.
Currently, the CO studied extensively2Synthesizing methanol by hydrogenating catalyst is Cu/ZnO/Al2O3.This catalyst is in synthesis gas
(H2, CO and CO2Mixture) industrialized decades in reaction for preparing methanol, start in recent years for CO2Hydrogenation reaction.To the greatest extent
This catalyst is managed to have excellent performance in synthesising gas systeming carbinol, but in CO2Activity is lower in synthesizing methanol by hydrogenating.In order to improve
Catalyst activity, many researchers conduct in-depth research the activated centre of this system.Although there is presently no unified
Conclusion, but as the synergistic effect between Cu and ZnO is reported, more and more researchers think ZnO in this catalyst system
It has very important effect.Also, in CO2In synthesizing methanol by hydrogenating reaction, because Reversed Water-gas Shift side reaction (RWGS,
CO2+H2→CO+H2O presence), Cu/ZnO/Al2O3The selectivity of resulting methanol is not very high on catalyst.There is researcher to grind
Cu/ZnO/Al is studied carefully2O3CO on catalyst2Synthesizing methanol by hydrogenating and RWGS reaction process.They have found: with methanol synthesis reaction
Active sites are different, and the active sites of RWGS reaction are the monometallic of high dispersive.It therefore, can be to traditional Cu/ZnO/Al2O3Catalyst
Surface carry out modification regulation, come achieve the purpose that increase methanol synthesis reaction active sites and inhibit RWGS reaction active site.Most
Eventually, it is expected to obtain the higher catalyst of methanol yield.
Traditional Cu/ZnO catalyst due to metal active position excessive exposure and to by-product CO in methanol synthesis reaction
Selectivity with higher.
Summary of the invention
For the deficiencies in the prior art, the purpose of the present invention is to provide a kind of for methanol synthesis reaction
ZnO/Cu catalyst and preparation method thereof, to solve existing catalyst to active, the low technical problem of selectivity of reaction, from
Fundamentally aforementioned drawback existing for existing catalyst during solution methanol synthesis reaction.
To achieve the above object, the ZnO/Cu catalyst for methanol synthesis reaction that technical solution of the present invention provides
Preparation method, its step are as follows:
1) configuration of Reverse Microemulsion System: select suitable surfactant, cosurfactant and oily phase composition anti-
Phase microemulsion system, wherein surfactant/oil is mutually 0.35~0.70mol/L, surfactant and cosurfactant matter
Amount is than being (1~3): 1；
2)Cu(OH)2Precipitating and the acquisition of CuO particle of the nano particle in microemulsion:
21) Cu (NO is dissolved3)2Yu Shuizhong is to form the Cu (NO that concentration is 0.1~0.4mol/L3)2Solution, and be added to
In the microemulsion of appropriate step 1), 1~3h is stirred；
22) while with step 21), tetramethylammonium hydroxide (TMAH) Yu Shuizhong is dissolved to form concentration as 1~3mol/
The TMAH solution of L, and be added in the microemulsion of appropriate step 1), stir 1~3h；
23) microemulsion of step 22) is added in the microemulsion of step 21), then at room temperature stand reaction 18~
For 24 hours, make precipitating completely, be centrifuged, after methanol washing and drying, in 300~400 DEG C of 2~3h of calcining, obtain CuO particle；
Wherein Cu (NO in TMAH solution and step 21) in step 22)3)2The sum of volume of solution, and in step 22) and in step 21)
The ratio of the sum of oil phase volume be 1:(5~10)；Be with the ratio between the oil phase volume in step 21) in step 22) (0.8~
1.2): 1；Cu (the NO in TMAH and step 21) in step 22)3)2The ratio between the amount of substance be (2.2~6): 1；
3)Zn(OH)2Precipitating of the nano particle in microemulsion on CuO:
31) Zn (NO is dissolved3)2Yu Shuizhong is to form the Zn (NO that concentration is 0.10~0.35mol/L3)2Solution, and with step
It is rapid 23) in obtained CuO particle be added in the microemulsion of appropriate step 1) together, stir 1~3h；
32) while with step 31), TMAH Yu Shuizhong is dissolved to form the TMAH solution that concentration is 1~3mol/L, and add
Enter into the microemulsion of appropriate step 1), stirs 1~3h；
33) microemulsion of step 32) is added in the microemulsion of step 31), then at room temperature stand reaction 18~
For 24 hours, make precipitating complete；Wherein: Zn (NO in TMAH solution and step 31) in step 32)3)2The sum of volume of solution, with step
32) ratio of the sum of the oil phase volume in and in step 31) is 1:(5~10)；In step 32) with the oily phase body in step 31)
The ratio between product is (0.8~1.2): 1；Zn (the NO in TMAH and step 31) in step 32)3)2The ratio between the amount of substance be (2.2
~6): 1；And the quality of element Zn is less than the quality of element Cu in system；
4) it centrifugal filtration, washing, drying, calcining: after centrifugal filtration, methanol washing, drying, is calcined in 300~400 DEG C
3~5h obtains ZnO/CuO sample；
5) it restores: ZnO/CuO sample obtained by step 4) being put into tube furnace, is restored in 300~350 DEG C of hydrogen atmospheres
1~3h obtains final ZnO/Cu catalyst.
Preferably, the surfactant in the step 1) is sorbitan monooleate (Span-80), Qula leads to x-
100, one of octyl phenol polyoxyethylene ether -10 (OP-10), cosurfactant be ethyl alcohol, normal propyl alcohol, isopropanol,
N-butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, 1- hexanol, 2- hexanol, 1- octanol, sec-n-octyl alcohol, fusel oil, one in n nonylphenol
Kind, oil is mutually normal heptane, ethane, propane, normal butane, iso-butane, pentane, isopentane, n-hexane, isohexane, hexamethylene, just
One of in octane, isooctane.
Preferably, in the step 1), surfactant/oil phase=0.5~0.6mol/L and helps surface at surfactant
The mass ratio of activating agent is (1~2): 1.
Preferably, in the step 21), Cu (NO3)2Concentration be 0.2~0.3mol/L.
Preferably, in the step 23), Cu (NO in the TMAH solution and step 21) in the step 22) of addition3)2Solution
The sum of volume, the ratio with the sum of oil phase volume in the step 22) of addition and in step 21) is 1:(6~8), and be added
Step 22) in the ratio between oil phase volume in step 21) be (0.9~1.1): 1
Preferably, in the step 33), in system the mass ratio of the quality and element Cu of element Zn be 1:(1.2~
6).It is highly preferred that the mass ratio of the quality and element Cu of element Zn is 1:(1.4~2 in system).
Preferably, calcination temperature is 340~360 DEG C in the step 4), and calcination time is 3.5~4.5h.
Preferably, in the step 5), the recovery time is 1~2h.
Compared with prior art, the advantages and beneficial effects of the present invention are:
1, the present invention uses the large batch of synthesis ZnO/Cu catalyst of reverse micro emulsion method for the first time, in view of reverse micro emulsion
Method prepares the high controllability of nano material, can simply accurately control the size and shape of prepared ZnO/Cu nano particle
Looks are conducive to improve the catalytic performance indexs relevant to methanol synthesis reaction such as stability, the catalytic activity of catalyst.
2, the preparation method provided in the present invention has a wide range of application, and reaction process operating procedure is simple and environmentally-friendly.It is acquired
Reactivity worth of the ZnO/Cu catalyst in methanol-fueled CLC be substantially better than now widely used Cu/ZnO catalyst, ZnO/Cu
Methanol yield is 4 times of Cu/ZnO on catalyst.It is ground by the catalyticing mechanism to methanol synthesis reaction on catalyst
Study carefully, additionally it is possible to push the development that catalyst technology is designed from atomic level.
Detailed description of the invention
Fig. 1 is the SEM figure for the ZnO/Cu catalyst that embodiment 1 is prepared.
Fig. 2 is the SEM figure for the Cu/ZnO catalyst that comparative example is prepared.
Specific embodiment
For the purpose of the present invention, technical solution, advantage and beneficial effect is more clearly understood, below in conjunction with attached drawing and tool
Body embodiment, is described in further details the method for the present invention.
Embodiment 1
The present invention is used for the ZnO/Cu catalyst of methanol synthesis reaction, and preparation methods steps are as follows:
(1) configuration of Reverse Microemulsion System: selecting Qula to lead to, x-100 is surfactant, n-hexyl alcohol is to help surface living
Property agent, normal heptane is oily phase composition Reverse Microemulsion System, and it is 76g, surfactant/oil that wherein Qula, which leads to x-100 additional amount,
The mass ratio of phase=0.55mol/L, surfactant and cosurfactant is 1.5；The reverse microemulsion liquid that will be prepared
System is divided into uniform four parts；The amount of surfactant, cosurfactant and oily phase can also all be reduced to 1/4, preparation is same
Four parts of Reverse Microemulsion Systems.
(2)Cu(OH)2Precipitating of the nano particle in microemulsion: the Cu (NO of 2.5mmol is taken3)2It is dissolved in 10mL water and being formed
Cu(NO3)2It is added thereto after solution in the microemulsion of a step (1).It is added in another microemulsion and is dissolved in water formation
Concentration is that tetramethylammonium hydroxide (TMAH) 6mL of 1.5mol/L will be added with the micro- of TMAH after two parts of microemulsions stir 1h respectively
Lotion is added to added with Cu (NO3)2Microemulsion in, static 18h makes Cu (OH)2Precipitating is complete, then by precipitating centrifuge
Separation 3 times is carried out, is washed with methanol.Precipitating after separation is placed in crucible, in an oven 100 DEG C of dry 10h.In Muffle furnace
2h is calcined in 350 DEG C of air atmospheres, obtains CuO particle.
(3) taking concentration is the Zn (NO of 1.6mmol3)2It is dissolved in the Zn in 10mL water to form concentration as 0.16mol/L
(NO3)2Solution, and be added thereto in the microemulsion of a step 1) together with CuO particle obtained in step 2), it stirs
2h；The TMAH of the 1.5mol/L of 6mL is added thereto in the microemulsion of a step 1) simultaneously, stirs 2h；Then will contain
The microemulsion of TMAH is added to containing Zn (NO3)2Microemulsion in, stand reaction 20h at room temperature, keep precipitating complete.
(4) system obtained in step (3) continues to stir 18h, is then centrifuged for filtering, after washing 3 times with methanol, in Muffle
In 100 DEG C of drying 10h, 350 DEG C of calcining 4h in furnace.Obtain ZnO/CuO sample.
(5) the ZnO/CuO sample is put into tube furnace, the reductase 12 h in 300 DEG C of hydrogen atmospheres is obtained final
ZnO/Cu catalyst.
Its SEM figure is shown in Fig. 1.
Embodiment 2
(1) configuration of Reverse Microemulsion System: select sorbitan monooleate for surfactant, isoamyl alcohol be help
Surfactant, isohexane are oily phase composition Reverse Microemulsion System, and wherein sorbitan monooleate additional amount is 60g,
Surfactant/oil phase=0.60mol/L, surfactants/cosurfactants mass ratio=2；The reverse phase that will be prepared
Microemulsion system is divided into four parts, and every part of volume ratio is followed successively by 11:10:10:9 and (is denoted as 11 parts by volume, 10 parts by volume, 10 bodies respectively
Product part and 9 parts by volume microemulsions)；The amount of surfactant, cosurfactant and oily phase can also all reduce to respectively to 11/40,
10/40,10/40,9/40, prepare four parts of Reverse Microemulsion Systems.
(2)Cu(OH)2Precipitating of the nano particle in microemulsion: the Cu (NO of 3mmol is dissolved3)2Cu is formed in 10mL water
(NO3)2It is added to after solution in 11 parts by volume microemulsions of step (1).It is wherein added in one 10 parts by volume microemulsions and is dissolved in water
The concentration of formation is tetramethylammonium hydroxide (TMAH) 4mL of 2.5mol/L, will be added with after two parts of microemulsions stir 3h respectively
The microemulsion of TMAH is added to added with Cu (NO3)2Microemulsion in, static 20h makes Cu (OH)2Precipitating completely, then will precipitating
Separation 3 times is carried out with centrifuge, is washed with methanol.Precipitating after separation is placed in crucible, in an oven 100 DEG C of dry 10h.
2h is calcined in 350 DEG C of air atmospheres of Muffle furnace, obtains CuO particle.
(3) 2mmolZn (NO is dissolved3)2To form concentration as the Zn (NO of 0.2mol/L in 10mL water3)2Solution, and with
Obtained CuO particle is added to together in 10 parts by volume microemulsions of another step 1) in step 2), stirs 2h；Simultaneously will
The TMAH of the 2.5mol/L of 4mL is added in 9 parts by volume microemulsions of step 1), stirs 2h；Then by the micro emulsion containing TMAH
Liquid is added to containing Zn (NO3)2Microemulsion in, stand reaction 20h at room temperature, keep precipitating complete.
(4) system obtained in step (3) continues to stir 20h, is then centrifuged for filtering, after washing 3 times with methanol, in Muffle
In 100 DEG C of drying 8h, 350 DEG C of roasting 4h in furnace.Obtain ZnO/CuO sample.
(5) the ZnO/CuO sample is put into tube furnace, restores 1.5h in 300 DEG C of hydrogen atmospheres, obtains final
ZnO/Cu catalyst.
Embodiment 3
(1) configuration of Reverse Microemulsion System: to select octyl phenol polyoxyethylene ether -10 be surfactant, isoamyl
Alcohol is cosurfactant, and isohexane is oily phase composition Reverse Microemulsion System, and wherein octyl phenol polyoxyethylene ether -10 adds
Entering amount is 80g, surfactant/oil phase=0.6mol/L, surfactants/cosurfactants mass ratio=2.5；It will preparation
Obtained Reverse Microemulsion System is divided into four parts, and every part of volume ratio is followed successively by 8:10:11:9 and (is denoted as 8 parts by volume, 10 volumes respectively
Part, 11 parts by volume and 9 parts by volume microemulsions)；The amount of surfactant, cosurfactant and oily phase can also all be reduced to respectively
8/38,10/38,11/38,9/38, prepare four parts of Reverse Microemulsion Systems.
(2)Cu(OH)2Precipitating of the nano particle in microemulsion: the Cu (NO of 4mmol is dissolved3)2Cu is formed in 10mL water
(NO3)2It is added to after solution in 8 parts by volume microemulsions of step (1).It is added in another 10 parts by volume microemulsion and is dissolved in water shape
At concentration be 2.5mol/L tetramethylammonium hydroxide (TMAH) 5mL will be added with TMAH after two parts of microemulsions stir 2h respectively
Microemulsion be added to added with Cu (NO3)2Microemulsion in, static 20h makes Cu (OH)2Precipitating completely, then will precipitating with from
Scheming carries out separation 3 times, is washed with methanol.Precipitating after separation is placed in crucible, in an oven 100 DEG C of dry 10h.In horse
2h not is calcined in 350 DEG C of air atmospheres of furnace, obtains CuO particle.
(3) 2.8mmolZn (NO is dissolved3)2To form concentration as the Zn (NO of 0.28mol/L in 10mL water3)2Solution, and
It is added to together with CuO particle obtained in step 2) in 11 parts by volume microemulsions of step 1), stirs 2h；Simultaneously by 6mL
The TMAH of 2.5mol/L be added in 9 parts by volume microemulsions of step 1), stir 2h；Then the microemulsion containing TMAH is added
Enter to containing Zn (NO3)2Microemulsion in, stand reaction 20h at room temperature, keep precipitating complete.
(4) system obtained in step (3) continues stirring for 24 hours, is then centrifuged for filtering, after washing 3 times with methanol, in Muffle
In 100 DEG C of drying 8h, 350 DEG C of roasting 4h in furnace.Obtain ZnO/CuO sample.
(5) the ZnO/CuO sample is put into tube furnace, the reductase 12 .5h in 300 DEG C of hydrogen atmospheres is obtained final
ZnO/Cu catalyst.
Comparative example
Unlike the first embodiment, that step (2) preparation in the comparative example is Zn (OH)2Precipitating is received through calcining
Rice ZnO particle, precipitating obtains Cu (OH) to step (3) on nano ZnO particles again2, just in embodiment 1 step (2) and
Step (3) on the contrary, remaining condition with embodiment 1, the additional amount including each substance, therefore obtained in comparative example and embodiment 1
Element Zn and the mass ratio of element Cu are also identical in final product, and what only the comparative example was prepared is Cu/ZnO catalysis
Agent, and what embodiment 1 obtained is ZnO/Cu catalyst.
Its SEM figure is shown in Fig. 2.
It can be seen that ZnO/Cu is urged from the SEM of two kinds of given different catalysts figure (i.e. Fig. 1 and Fig. 2) and table 2~5
Agent has biggish Cu particle, but ZnO particle is smaller；On the contrary, Cu particle is smaller in Cu/ZnO, but ZnO particle compared with
Greatly, that is to say, that ZnO/Cu catalyst subtracts while the interface Cu-ZnO for keeping having greater activity to methanol synthesis reaction
The presence for the high dispersion metal Cu that there is greater activity to RWGS reaction is lacked.It is anti-that two catalyst are applied to methanol-fueled CLC simultaneously
It answers, used reaction condition are as follows: P=2.0MPa, GHSV=3600h-1, CO2/H2=3:1 (volume ratio), catalytic effect is shown in
Table 1.
As can be seen from Table 1, the CO of reversed ZnO/Cu catalyst2Conversion ratio (12.0%) is urged much larger than tradition Cu/ZnO
Agent (5.5%)；And ZnO/Cu catalyst has lower CO selectivity and higher CH3OH selectivity, finally makes
ZnO/Cu catalyst has highest methanol yield (3.2mmolg-1·h-1), it is 4 times of Cu/ZnO catalyst methanol yield.
The methanol synthesis reaction catalytic result of 1 catalyst of table
The constituent content 1. located in 2 Fig. 1 of table
The constituent content 2. located in 3 Fig. 1 of table
The constituent content 1. located in 4 Fig. 2 of table
The constituent content 2. located in 5 Fig. 2 of table
Above-described each specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail.It should be understood that the above is only a specific embodiment of the present invention, it is not intended to restrict the invention,
All within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in of the invention
Within protection scope.
Claims (10)
1. a kind of preparation method of the ZnO/Cu catalyst for methanol synthesis reaction, it is characterised in that: this method includes as follows
Step:
1) configuration of Reverse Microemulsion System: select suitable surfactant, cosurfactant and oily phase composition reverse phase micro-
Emulsion system, wherein surfactant/oil is mutually 0.35~0.7mol/L, and surfactant is with cosurfactant mass ratio
(1~3): 1；
2)Cu(OH)2Precipitating and the acquisition of CuO particle of the nano particle in microemulsion:
21) Cu (NO is dissolved3)2Yu Shuizhong is to form the Cu (NO that concentration is 0.1~0.4mol/L3)2Solution, and it is added to appropriate step
In rapid microemulsion 1), 1~3h is stirred；
22) while with step 21), TMAH Yu Shuizhong is dissolved to form concentration and be the TMAH solution of 1~3mol/L, and be added to
In the microemulsion of appropriate step 1), 1~3h is stirred；
23) microemulsion of step 22) is added in the microemulsion of step 21), then at room temperature stand reaction 18~for 24 hours,
Make precipitating completely, is centrifuged, after methanol washing and drying, in 300~400 DEG C of 2~3h of calcining, obtains CuO particle；Wherein
Cu (NO in TMAH solution and step 21) in step 22)3)2The sum of volume of solution and the oily phase in step 22) and in step 21)
The ratio of the sum of volume is 1:(5~10), and be (0.8~1.2) with the ratio between the oil phase volume in step 21) in step 22): 1；
And the TMAH in the step 22) and Cu (NO in step 21)3)2The ratio between the amount of substance be (2.2~6): 1；
3)Zn(OH)2Precipitating of the nano particle in microemulsion on CuO:
31) Zn (NO is dissolved3)2Yu Shuizhong is to form the Zn (NO that concentration is 0.10~0.35mol/L3)2Solution, and with step 23)
In obtained CuO particle be added in the microemulsion of appropriate step 1) together, stir 1~3h；
32) while with step 31), TMAH Yu Shuizhong is dissolved to form concentration and be the TMAH solution of 1~3mol/L, and be added to
In the microemulsion of appropriate step 1), 1~3h is stirred；
33) microemulsion of step 32) is added in the microemulsion of step 31), then at room temperature stand reaction 18~for 24 hours,
Keep precipitating complete；Wherein: Zn (NO in TMAH solution and step 31) in step 32)3)2The sum of volume of solution in step 32)
And the ratio of the sum of oil phase volume in step 31) is 1:(5~10)；In step 32) with the ratio between the oil phase volume in step 31)
For (0.8~1.2): 1；Zn (the NO in TMAH and step 31) in step 32)3)2The ratio between the amount of substance be (2.2~6): 1；
And the quality of element Zn is less than the quality of element Cu in system；
4) centrifugal filtration, washing, drying, calcining: through centrifugal filtration, methanol washing, drying after, in 300~400 DEG C calcine 3~
5h obtains ZnO/CuO sample；
5) it restores: ZnO/CuO sample obtained by step 4) is put into tube furnace, restore 1 in 300~350 DEG C of hydrogen atmospheres~
3h obtains final ZnO/Cu catalyst.
2. the preparation method of the ZnO/Cu catalyst according to claim 1 for methanol synthesis reaction, it is characterised in that:
Surfactant in the step 1) is sorbitan monooleate, Qula logical x-100, octyl phenol polyoxyethylene
One of ether -10, cosurfactant are ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, 1-
One of hexanol, 2- hexanol, 1- octanol, sec-n-octyl alcohol, fusel oil, n nonylphenol, oil are mutually normal heptane, ethane, propane, positive fourth
Alkane, iso-butane, pentane, isopentane, n-hexane, isohexane, hexamethylene, normal octane, one of in isooctane.
3. the preparation method of the ZnO/Cu catalyst according to claim 1 or 2 for methanol synthesis reaction, feature exist
In: in the step 1), surfactant/oil phase=0.5~0.6mol/L, the quality of surfactant and cosurfactant
Than for (1~2): 1.
4. the preparation method of the ZnO/Cu catalyst according to claim 1 or 2 for methanol synthesis reaction, feature exist
In: in the step 21), Cu (NO3)2Concentration be 0.2~0.3mol/L.
5. the preparation method of the ZnO/Cu catalyst according to claim 1 or 2 for methanol synthesis reaction, feature exist
In: in the step 23), Cu (NO in the TMAH solution and step 21) in the step 22) of addition3)2The sum of volume of solution with
The ratio of the sum of oil phase volume in the step 22) of addition and in step 21) be 1:(6~8), and be added step 22) in
The ratio between oil phase volume in step 21) is (0.9~1.1): 1.
6. the preparation method of the ZnO/Cu catalyst according to claim 1 or 2 for methanol synthesis reaction, feature exist
In: in the step 5), the mass ratio of the quality and element Cu of element Zn is 1:(1.2~6 in system).
7. the preparation method of the ZnO/Cu catalyst according to claim 6 for methanol synthesis reaction, it is characterised in that:
In the step 33), the mass ratio of the quality and element Cu of element Zn is 1:(1.4~2 in system).
8. the preparation method of the ZnO/Cu catalyst according to claim 1 or 2 for methanol synthesis reaction, feature exist
In: calcination temperature is 340~360 DEG C in the step 4), and calcination time is 3.5~4.5h.
9. the preparation method of the ZnO/Cu catalyst according to claim 1 or 2 for methanol synthesis reaction, feature exist
In: in the step 5), the recovery time is 1~2h.
10. the ZnO/Cu catalyst that any one of claim 1~9 the method is prepared.
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| CN1660490A (en) * | 2004-12-21 | 2005-08-31 | 中国科学院广州能源研究所 | Preparation method of synthesizing catalyst of methyl alcohol |
| CN105498779A (en) * | 2014-10-11 | 2016-04-20 | 中国石油化工股份有限公司 | Preparation method of nano copper based catalyst for CO2 hydrogenation for producing methanol |
| CN106423171A (en) * | 2016-08-01 | 2017-02-22 | 中南民族大学 | Ni/Cu/M catalyst for catalytic methanol synthesis reaction and preparation method thereof |
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| CN1660490A (en) * | 2004-12-21 | 2005-08-31 | 中国科学院广州能源研究所 | Preparation method of synthesizing catalyst of methyl alcohol |
| CN105498779A (en) * | 2014-10-11 | 2016-04-20 | 中国石油化工股份有限公司 | Preparation method of nano copper based catalyst for CO2 hydrogenation for producing methanol |
| CN106423171A (en) * | 2016-08-01 | 2017-02-22 | 中南民族大学 | Ni/Cu/M catalyst for catalytic methanol synthesis reaction and preparation method thereof |
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