CN107043319A - The method for preparing methanol - Google Patents
The method for preparing methanol Download PDFInfo
- Publication number
- CN107043319A CN107043319A CN201610082698.5A CN201610082698A CN107043319A CN 107043319 A CN107043319 A CN 107043319A CN 201610082698 A CN201610082698 A CN 201610082698A CN 107043319 A CN107043319 A CN 107043319A
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- China
- Prior art keywords
- catalyst
- methanol
- copper
- zinc
- reaction
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 303
- 238000000034 method Methods 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 85
- 239000007789 gas Substances 0.000 claims abstract description 44
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 36
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003426 co-catalyst Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011787 zinc oxide Substances 0.000 claims abstract description 7
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 23
- 239000011701 zinc Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 150000003751 zinc Chemical class 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 239000011686 zinc sulphate Substances 0.000 claims description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical group CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000336 copper(I) sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 159
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 28
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 28
- 239000003610 charcoal Substances 0.000 description 22
- 229910002651 NO3 Inorganic materials 0.000 description 18
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 238000011946 reduction process Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 229960004424 carbon dioxide Drugs 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ISHFYECQSXFODS-UHFFFAOYSA-M 1,2-dimethyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1C ISHFYECQSXFODS-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 description 1
- 229940023032 activated charcoal Drugs 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- YOPUATYREUZXIO-UHFFFAOYSA-N copper;methanol Chemical compound [Cu].OC YOPUATYREUZXIO-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002309 gasification Methods 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
- 239000012442 inert solvent Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method of methanol, this method is included in the presence of copper-zinc catalyst and co-catalyst, the synthesis gas of hydrogen and oxycarbide is contacted with catalyst and co-catalyst, the catalyst is made up of cupric oxide and zinc oxide, wherein the co-catalyst is C1-6Alkylol, the specific surface area of copper-zinc catalyst is 40-60m2/g.What the present invention was provided is converted into the method for methanol by synthesis gas realizes the high reaction activity under low temperature.This method, which can also be such that catalyst is up in the reaction time, can keep good catalytic activity in more than 500 hours.
Description
Technical field
The present invention relates to a kind of method for preparing methanol, more particularly, to by hydrogen and oxycarbide
The method that synthesis gas prepares methanol.
Background technology
Methanol is a kind of important Organic Chemicals and high-grade fuel.Conventional methanol synthesis technique (ICI
Method) methanol mainly is prepared from the synthesis gas of coal conversion, reaction is general to be higher than 230 DEG C, pressure in temperature
Carried out higher than under conditions of 6.0MPa.Under this reaction condition, CO conversion per pass is very low,
Be generally not more than 16% (for example, see J.C.J.Bart et al., Catal.Today, 1987 years volume 2,
1st phase, the 1-124 pages).Because the reaction is fierce exothermic reaction, vapor phase method is difficult except heat,
CO conversion per pass have to be controlled in low-level, cause substantial amounts of unreacted high pressure feed must
It must circulate, whole reaction efficiency is very low.In addition, the reaction is limited extremely serious by thermodynamical equilibrium,
Reduction reaction temperature can promote balance to be moved to the direction of generation methanol, but the activity of catalyst
Reduction.Therefore, typically by improving pressure or taking the internal circulating load of increasing unreacting gas to improve
CO conversion ratio, but this mode of operation requires high to the material of reaction unit, need to increase operating cost
With.The problem of conversion per pass for how to improve CO, industry, which is generally believed, uses low-temp methanol
Catalyst or to be taken in by the way of heat be more feasible direction.
CN1210101A discloses a kind of method of liquid phase low temperature combined production of methanol and methyl formate, the party
Method is disclosed in the liquid phase, and under 100-160 DEG C, 3.0-8.0MPa reaction condition, synthesis gas is straight
Combined production of methanol and methyl formate are connect, catalyst is Cu-Cr catalyst, and synthesis gas conversion per pass is reachable
95%.But in the method, it is necessary to add alkali alcoholate and non-polar solven.Due to unstripped gas
In contain moisture and carbon dioxide, the sodium ion in catalyst is changed into sodium carbonate.Due to urging
The composition of agent changes, and causes catalyst easily to inactivate and causes this method not industrialize.
It is generally acknowledged that super critical condition is conducive to mass transfer and heat transfer, and therefore, also useful supercritical methanol technology synthesis
Methanol.For example in Japan Kokai JP2000-336050 disclose one kind carbon dioxide and hydrogen
For raw material, the method for synthesizing methanol in supercritical phase pentane, hexane and heptane, the special permission thinks two
The reaction of carbonoxide synthesizing methanol is overcritical lower than reacting fast in general gas phase.Japanese Laid-Open
Special permission JP2000-204053 discloses a kind of method of use synthesis gas in overcritical lower synthesizing methanol,
Think that the aggregate velocity of methanol at supercritical conditions is higher than the reaction speed under general gas phase condition, but
It must be used in these methods to reacting inert solvent, and reaction temperature and pressure ratio are higher.This
Outside, the stability of catalyst also needs further raising.
CN103769112A discloses a kind of methanol copper-based catalysts and preparation method thereof, the catalyst
It is the 3rd element al of addition on the basis of CuO-ZnO catalyst, is ensureing certain activity and selection
Property on the premise of improve catalyst stability.But, the temperature in use of the catalyst is 245 DEG C,
Belong to the category of high temperature methanol synthetic catalyst.This method is easily limited by thermodynamical equilibrium, CO
Average conversion be usually 57.4%.
The content of the invention
The present invention be in order to solve in the existing method for preparing methanol by synthesis gas, exist reaction pressure compared with
High unfavorable operation；The higher reaction balance that is unfavorable for of reaction temperature tends to beneficial direction, and reaction temperature
It is anti-that the high defect unfavorable to catalyst stability has high methanol concurrently at a lower reaction temperature there is provided one kind
Speed, high catalyst stability are answered so that the preparation method of the low methanol of running cost.
The present inventor's in-depth study by extensive, surprisingly it has been found that：By containing oxidation of coal
During the synthesis gas of thing and hydrogen prepares methanol, if choosing to reacting the co-catalysis in catalytic activity
Agent C1-6Alkylol, uses specific surface area for 40-60m2/ g copper-zinc catalysts are higher relative to temperature
Supercritical reaction, under conditions of compared with low reaction temperatures and reaction pressure, high reaction can be kept
Speed, and the reactivity of catalyst can be kept for a long time.Find, complete based on more than
The present invention.
The invention provides a kind of preparation method of methanol, this method, which is included in copper-zinc catalyst and helped, urges
In the presence of agent, the synthesis gas of hydrogen and oxycarbide is contacted with catalyst and co-catalyst,
The catalyst is made up of cupric oxide and zinc oxide, wherein the co-catalyst is C1-6Alkylol, institute
The specific surface area for stating copper-zinc catalyst is 40-60m2/g。
The method of the present invention is realized compared with low reaction temperatures and reaction pressure compared with previous methods
Under the conditions of, high reaction speed can be kept.In addition, this method can also make the catalyst of the present invention exist
Reaction time, which is up to, can keep good catalytic activity in more than 500 hours.
Brief description of the drawings
Fig. 1 is the stability test result that the method for embodiment 19 prepares methanol.
Embodiment
" synthesis gas " as described herein is with CO and H containing a certain proportion of2For the mixed of main component
Close unstripped gas.Synthesis gas is generally by solid material (such as coal, coke), liquid charging stock (such as light oil, heavy oil)
With gas raw material (such as natural gas, casing-head gas) through gasification, cracking or conversion after again it is purified processing and make
, it can for example be selected from coke-stove gas, liquefied gas, water-gas, semiwater gas, natural gas and oil field
At least one of gas.Usually, synthesis gas should comprise about the hydrogen and oxycarbide of following ratio：
H2=40-80 volumes %
CO=3-40 volume %, and
CO2=1-20 volumes %.
The method for preparing methanol by synthesis gas that the present invention is provided is included in copper-zinc catalyst and co-catalysis
In the presence of agent, the synthesis gas of hydrogen and oxycarbide is contacted with catalyst and co-catalyst,
The catalyst is made up of cupric oxide and zinc oxide, wherein the co-catalyst is C1-6Alkylol, copper-
The specific surface area of zinc catalyst is 40-60m2/g。
The method provided according to the present invention, in the preferred case, synthesis gas and catalyst and co-catalysis
The condition of agent contact includes：Temperature is 150-220 DEG C, and pressure is 2.0-10.0MPa；Preferable temperature is
170-200 DEG C, pressure is 5.0-7.0MPa.
The method provided according to the present invention, the co-catalyst is preferably C1-4Alkylol.Described help is urged
The example of agent can be methanol, ethanol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, 2- methyl
At least one of -1- propyl alcohol and 2- methyl-2-propanols, preferably methanol, ethanol, 1- propyl alcohol and 2-
At least one of butanol.In this case, higher methanol yield can be obtained.
The method provided according to the present invention, the synthesis by hydrogen and oxycarbide to implementing the present invention
The mode that gas changes into methanol has no particular limits, therefore usable continuation method or discontinuous process,
Wherein discontinuous process for example can be implemented as batch process.However, according to the invention it is preferred to continuous
Method is implemented the synthesis gas of hydrogen and oxycarbide changing into methanol.
The present invention is for implementing not having the reactor that the synthesis gas of hydrogen and oxycarbide changes into methanol
There is special limitation.Reactor can use flowing bed reactor or fixed bed reactors.
For this embodiment of continuation method, the present invention does not have to air speed selected in continuation method
There is any limitation, condition is can to implement the synthesis gas of hydrogen and oxycarbide to the conversion of methanol.
Wherein in the embodiment of continuation method, the Feed space velocities of such as co-catalyst can be 0.01-40h-1,
Preferably 0.1-20h-1, more preferably 2.0-12h-1。
The method provided according to the present invention, in the preferred case, the Feed space velocities of wherein synthesis gas are
500-2500h-1；Preferably 650-2200h-1；More preferably 800-2000h-1。
According to the present invention, term " air speed " referred to based on synthesis gas or co-catalyst within the unit interval
During by the small volume of volume/catalyst of per volume of catalyst bed.
The total moles of the molal quantity of copper and copper and zinc in the method provided according to the present invention, copper-zinc catalyst
Several ratio can be selected in the larger context, for example, copper rubs in the copper-zinc catalyst
Your ratio of number and copper and the total mole number of zinc can be 0.1-0.9：1；Preferably 0.3-0.7：1；Enter
One step is preferably 0.4-0.7：1.In this case, when preparing methanol by synthesis gas, it can have concurrently
High reactivity, high methanol yield and good catalyst stability.
The method provided according to the present invention, it is preferable that the specific surface area of copper-zinc catalyst is 45-55m2/g。
The method provided according to the present invention, in the preferred case, copper-zinc catalyst are prepared using urea method.
The method for preparing copper-zinc catalyst using urea method is known to those skilled in the art, for example this method
It may comprise steps of：By water-soluble mantoquita and water-soluble zinc salt deionized water dissolving, mixed
Close solution；Then urea is added in gained mixed solution and produces precipitation, obtain mixture；By institute
Obtain mixture and carry out separation of solid and liquid, and solid product obtained by separation of solid and liquid is washed, dried and roasted
Burn.
In the preparation method of copper-zinc catalyst, the species of water-soluble mantoquita can be in the larger context
Selected, for example, the water-soluble mantoquita can be Cu (NO3)2、CuSO4、Cu2SO4、
CuNO3And CuCl2At least one of；Preferably Cu (NO3)2、CuSO4And CuCl2In
At least one, more preferably Cu (NO3)2。
In the preparation method of above-mentioned copper-zinc catalyst, the species of water-soluble zinc salt can be in larger model
Enclose it is interior selected, for example, the water-soluble zinc salt can be Zn (NO3)2、ZnSO4、
Zn(CH3COO)2And ZnCl2At least one of；Preferably Zn (NO3)2、ZnSO4And ZnCl2
At least one of, more preferably Zn (NO3)2。
In the preparation method of above-mentioned copper-zinc catalyst, in copper-zinc catalyst the molal quantity of copper and copper and
The ratio of the total mole number of zinc can be selected in the larger context, for example, the copper-zinc catalysis
The ratio of the molal quantity of copper and copper and the total mole number of zinc can be 0.1-0.9. in agent：1；Preferably
0.3-0.7：1；More preferably 0.4-0.7：1.
In the preparation method of above-mentioned copper-zinc catalyst, the use of water-soluble mantoquita and zinc salt and deionized water
Amount is not specially required, for example, the total moles and the mol ratio of deionized water of water-soluble mantoquita and zinc salt
Can be 1：300-1000, preferably 1：500-800.
In order that material mixes more uniform, the preferably addition of all materials is stirred in stirring such as machinery
Mix lower progress.Specifically, speed of agitator can be 50-600rpm, preferably 350-450rpm.
The present invention is mixed for urea is added in the mixed solution of containing water-soluble mantoquita and zinc salt
Temperature be not particularly limited, for example, the mixing that urea is added into containing water-soluble mantoquita and zinc salt is molten
Temperature in liquid can be 5-35 DEG C, preferably 10-25 DEG C；At this temperature, containing water-soluble mantoquita
The time mixed with the mixed solution of zinc salt with urea can be 0.1-1.0 hours, preferably 0.3-0.7
Hour is so that the material added fully dissolves.
In order to accelerate reaction, it is preferable that the mixing that urea is added into containing water-soluble mantoquita and zinc salt is molten
Heating is precipitated with promoting to produce after in liquid.The present invention by urea to being added to containing water-soluble mantoquita and zinc salt
Mixed solution in after heating be not particularly limited with the temperature for producing precipitation, for example, urea is added
Being heated after to the mixed solution of containing water-soluble mantoquita and zinc salt can be with the temperature for producing precipitation
90-98 DEG C, preferably 92-98 DEG C；The mixing of the mixed solution and urea of containing water-soluble mantoquita and zinc salt
Heating afterwards can be for 1-5 hour, preferably 1-3 hours with the time of precipitation.
In the preparation method of above-mentioned copper-zinc catalyst, dry method, the method for roasting and catalyst
The method of shaping can be carried out using mode well known in the art.Drying can be conventional drying means,
Such as oven for drying, dry temperature can be 80-160 DEG C, preferably 100-140 DEG C；Dry
Time can be 4-20 hours, preferably 10-14 hours.Roasting can be to prepare copper-zinc catalyst
Conventional roasting condition, for example, the temperature of roasting can be 300-450 DEG C, preferably 350-400 DEG C；
The time of roasting can be 1-10 hours, preferably 3-7 hours.For example, the method for shaping can be
Compression molding.
Under the method provided according to the present invention, preferable case, this method is additionally included in be contacted with synthesis gas
Before, used catalyst is reduced.The method of reduction, which is included in reactor, loads catalyst,
First the reactor for accommodating catalyst is purged at normal temperatures with nitrogen before reaction, also Primordial Qi is then passed to,
And temperature is raised, reduction activation is carried out to the catalyst.Also the composition of Primordial Qi is hydrogen and inert gas
Mixture, inert gas can be at least one of for nitrogen, helium and argon gas, also hydrogen in Primordial Qi
The content of gas is 1-10 weight %.
The present invention is described in detail by embodiment and comparative example below, but the scope of the present invention is not limited to
These embodiments.
CO conversion ratios, CO described in following examples and comparative example2Conversion ratio, C conversion ratios,
Formic acid esters selectivity, methanol selectivity and methanol yield are calculated as follows respectively.
● the CO in CO conversion ratios (%)=1- (the CO molal quantitys reclaimed after reaction)/reaction raw materials rubs
That number) * 100
●CO2Conversion ratio (%)=1- (CO reclaimed after reaction2Molal quantity) CO in/reaction raw materials2
Molal quantity) * 100
● C conversion ratios (%)=CO conversion ratios (%) * (the CO molal quantitys in reaction raw materials)/(reaction raw materials
In CO molal quantitys+CO2Molal quantity)+CO2Conversion ratio (%) * (CO in reaction raw materials2Mole
Number)/(CO+CO in reaction raw materials2Molal quantity)
● formic acid esters selectivity (%)=(the formic acid esters molal quantity reclaimed after reaction)/{ (C conversion ratios
(%) * (CO+CO in reaction raw materials2Molal quantity) } * 100
● methanol selectivity (%)=(moles of methanol reclaimed after reaction)/{ (C conversion ratios (%) * (reactions
CO+CO in raw material2Molal quantity) } * 100
● methanol yield (%)=(moles of methanol of the generation)/(CO molal quantitys+CO of reaction2Mole
Number) * 100
Specific surface area is determined using Japan's BELCAT-B devices.
Gases used use Shimadzu GC-8 type chromatograms in course of reaction, chromatographic column is activated-charcoal column (TCD)
Analysis.
Product liquid produced by reaction uses chromatographic column for OV-101 Shimadzu GC-14A type gas
Phase chromatogram (FID) chromatography.
Prepare embodiment 1
14.98g Cu (NO are added in 2L beaker3)2·3H2O and 18.28g Zn (NO3)2·6H2O,
Then 1500g deionized waters are added, 130g urea is added, stirs at room temperature, fully dissolving.
Said mixture is transferred in the oil bath that oil temperature is 95 DEG C, constantly stirred under low whipping speed 400rpm
Mix 2 hours, until metal salt is fully precipitated.Then beaker is taken out from oil bath, is cooled to after room temperature,
Reaction gained mixture is subjected to separation of solid and liquid.Solid obtained by separation of solid and liquid is washed to it with water
Without nitrate, dried 12 hours in 120 DEG C.Then it is calcined 5 hours in 370 DEG C of air.Pressure
Piece, broken, sieve take the fraction of 20-40 mesh numbers.The performance data of gained catalyst is referring to table 1.
Prepare embodiment 2
Using with preparing the identical experiment condition of embodiment 1 and process, simply by Cu (NO3)2·3H2O
Amount be changed to 17.98g and by Zn (NO3)2·6H2O amount is changed to 14.62g.The property of gained catalyst
Energy data are referring to table 1.
Prepare embodiment 3
Using with preparing the identical experiment condition of embodiment 1 and process, simply by Cu (NO3)2·3H2O
Amount be changed to 20.97g and by Zn (NO3)2·6H2O amount is changed to 10.97g.The property of gained catalyst
Energy data are referring to table 1.
Prepare embodiment 4
Using with preparing the identical experiment condition of embodiment 1 and process, simply by Cu (NO3)2·3H2O
Amount be changed to 11.98g and by Zn (NO3)2·6H2O amount is changed to 21.94g.The property of gained catalyst
Energy data are referring to table 1.
Prepare embodiment 5
Using with preparing the identical experiment condition of embodiment 1 and process, simply by Cu (NO3)2·3H2O
Amount be changed to 8.99g and by Zn (NO3)2·6H2O amount is changed to 25.59g.The property of gained catalyst
Energy data are referring to table 1.
Prepare comparative example 1
14.98g Cu (NO are added in 2L beaker3)2·3H2O's and 18.28g
Zn(NO3)2·6H2O, then adds 300g deionized waters, and stirring and dissolving obtains solution A.Will
21.2g Na2CO3300g deionized waters are dissolved in, stirring and dissolving obtains solution B, 80 DEG C and filled
Divide under stirring, solution A and solution B are slowly dropped into the beaker equipped with 100g deionized waters, control
The pH value of solution processed is 8.5, after solution A is dripped, and stops the addition of solution B, and pH value is
8.5, continue to stir 1 hour, beaker is taken out from oil bath, static 24 hours in room temperature, filtering,
It is washed with deionized water, repeated washing and filtering, until pH value is 7.0, then dries 12 in 120 DEG C
Hour, 370 DEG C be calcined 5 hours.Tabletting, broken, sieve take the catalyst of 20-40 mesh numbers.Sunk
Shallow lake method CuO-ZnO methanol synthesis catalysts.The performance data of gained catalyst is referring to table 1.
Prepare comparative example 2
Repeat to prepare comparative example 1, except that, simply by Cu (NO3)2·3H2O amount is changed to 8.99g
With by Zn (NO3)2·6H2O amount is changed to 25.59g, and the performance data of gained catalyst is referring to table 1.
Table 1
Embodiment 1
Load 2.0g in tubular fixed-bed flow reactor and prepare catalyst prepared by embodiment 1, first
20mL/min nitrogen is passed through, purges 10 minutes, then catalyst is reduced, also Primordial Qi is
5% hydrogen and 95% He, flow velocity is 40mL/min.
In reduction process, 230 DEG C are begun to warm to from room temperature, programming rate is 4 DEG C/min, 230 DEG C
Kept for 6 hours.Reduction stops being passed through also Primordial Qi after terminating, and reduces the temperature to the reaction temperature of setting
190 DEG C, it is passed through synthesis gas (the volume % of CO 31.8；CO25.0 volume %；H260.2 volume %；Ar 3
Volume %), the air speed of synthesis gas is 1260h-1, reacting system pressure reaches 5.0MPa, co-catalyst
Methanol is squeezed into high-pressure pump, and methanol air speed is 4.5h-1, reaction temperature is 190 DEG C.Under reaction product is used
Cold-trap separation is swum, the gas part after separation is analyzed using online TCD, and product liquid takes from cold-trap
Go out, with offline FID chromatography.CO conversion ratios are 42.2%, CO2Conversion ratio is 8.9%, always
Charcoal conversion ratio is 36.67%, and methanol selectivity is 99.68%, and methyl formate is selectively 0.32%,
Methanol yield is 36.55%.
Embodiment 2
Repetition embodiment 1, but prepared with the catalyst replaced embodiment 1 for preparing the preparation of embodiment 2
Catalyst.CO conversion ratios are 37.7%, CO2Conversion ratio is 5.8%, and total charcoal conversion ratio is 33.37%,
Methanol selectivity is 99.52%, and Ethyl formate is selectively 0.48%, and methanol yield is 33.21%.
Embodiment 3
Repetition embodiment 1, but prepared with the catalyst replaced embodiment 1 for preparing the preparation of embodiment 3
Catalyst.CO conversion ratios are 33.2%, CO2Conversion ratio is 2.7%, and total charcoal conversion ratio is 48.15%,
Methanol selectivity is 99.63%, and Ethyl formate is selectively 0.37%, and methanol yield is 47.97%.
Embodiment 4
Repetition embodiment 1, but prepared with the catalyst replaced embodiment 1 for preparing the preparation of embodiment 4
Catalyst.CO conversion ratios are 34.8%, CO2Conversion ratio is 0.6%, and total charcoal conversion ratio is 29.06%,
Methanol selectivity is 99.39%, and Ethyl formate is selectively 0.61%, and methanol yield is 28.88%.
Embodiment 5
Repetition embodiment 1, but prepared with the catalyst replaced embodiment 1 for preparing the preparation of embodiment 5
Catalyst.CO conversion ratios are 28.1%, CO2Conversion ratio is -2.7%, and total charcoal conversion ratio is 23.92%,
Methanol selectivity is 99.12%, and Ethyl formate is selectively 0.88%, and methanol yield is 23.71%.
Embodiment 6
Embodiment 1 is repeated, it is 6.488h that reaction condition, which is removed with air speed,-1Ethanol substitution methanol urge as helping
Agent, other reaction conditions are identical.CO conversion ratios are 53.6%, CO2Conversion ratio is 13.5%,
Total charcoal conversion ratio is 48.15%, and methanol selectivity is 96.47%, and Ethyl formate is selectively 3.53%,
Methanol yield is 46.45%.
Embodiment 7
Embodiment 1 is repeated, it is 8.112h that reaction condition, which is removed with air speed,-1Normal propyl alcohol substitution methanol as helping
Catalyst, other reaction conditions are identical.CO conversion ratios are 71.63%, CO2Conversion ratio is 20.1%,
Total charcoal conversion ratio is 64.63%, and methanol selectivity is 91.27%, and propyl formate is selectively 8.73%,
Methanol yield is 58.99%.
Embodiment 8
Embodiment 1 is repeated, it is 10.42h that reaction condition, which is removed with air speed,-12- butanol substitution methanol conduct
Co-catalyst, other reaction conditions are identical.CO conversion ratios are 81.8%, CO2Conversion ratio is 17.6%,
Total charcoal conversion ratio is 73.08%, and methanol selectivity is 80.1%, and butyl formate is selectively 19.9%,
Methanol yield is 58.53%.
Embodiment 9
Embodiment 8 is repeated, but reaction pressure is changed to 6.0MPa, and CO conversion ratios are 98.8%, CO2
Conversion ratio is 78.0%, and total charcoal conversion ratio is 95.97%, and methanol selectivity is 66.5%, butyl formate
Selectivity is 33.5%, and methanol yield is 63.82%.
Embodiment 10
Except reaction condition except system pressure be 6.0MPa in addition to, other reaction conditions and the phase of embodiment 1
Together.CO conversion ratios are 69.79%, CO2Conversion ratio is 8.45%, and total charcoal conversion ratio is 61.46%,
Methanol selectivity is 99.5%, and butyl formate is selectively 0.5%, and methanol yield is 61.15%.
Embodiment 11
Except reaction condition except system pressure be 7.0MPa in addition to, other reaction conditions and the phase of embodiment 1
Together.CO conversion ratios are 80.25%, CO2Conversion ratio is 18.25%, and total charcoal conversion ratio is 71.83%,
Methanol selectivity is 99.43%, and methyl formate is selectively 0.57%, and methanol yield is 71.42%.
Embodiment 12
Except reaction temperature is 170 DEG C, other reaction conditions and embodiment 11 are identical.CO conversion ratios are
48.39%, CO2Conversion ratio is 13.64%, and total charcoal conversion ratio is 43.67%, and methanol selectivity is
99.78%, methyl formate is selectively 0.22%, and methanol yield is 43.57%.
Embodiment 13
Except reaction temperature is 180 DEG C, other reaction conditions and embodiment 11 are identical.CO conversion ratios are
58.59%, CO2Conversion ratio is 14.71%, and total charcoal conversion ratio is 52.55%, and methanol selectivity is
99.68%, methyl formate is selectively 0.32%, and methanol yield is 52.38%.
Embodiment 14
Except reaction temperature is 200 DEG C, other reaction conditions and embodiment 11 are identical.CO conversion ratios are
85.85%, CO2Conversion ratio is 28.84%, and total charcoal conversion ratio is 78.10%, and methanol selectivity is
99.23%, methyl formate is selectively 0.77%, and methanol yield is 77.5%.
Embodiment 15
Reduction process and embodiment 11 are identical, and reaction condition is 830h except the air speed of synthesis gas-1, help and urge
The air speed of agent methanol is 2.25h-1Outside, other reaction conditions and embodiment 11 are identical.Reaction result
It is 88.61%, CO for CO conversion ratios2Conversion ratio is 20.14%, and total charcoal conversion ratio is 79.31%,
Methanol selectivity is 99.94%, and methyl formate is selectively 0.06%, and methanol yield is 79.26%.
Embodiment 16
Reduction process and embodiment 11 are identical, and reaction condition is 945h except the air speed of synthesis gas-1, help and urge
The air speed of agent methanol is 3.38h-1Outside, other reaction conditions and embodiment 11 are identical.Reaction result
It is 87.37%, CO for CO conversion ratios2Conversion ratio is 17.38%, and total charcoal conversion ratio is 77.86%,
Methanol selectivity is 99.98%, and methyl formate is selectively 0.02%, and methanol yield is 77.84%.
Embodiment 17
Reduction process and embodiment 11 are identical, and reaction condition is 1590h except the air speed of synthesis gas-1, help
The air speed of catalyst methanol is 5.63h-1Outside, other reaction conditions and embodiment 11 are identical.As a result it is
CO conversion ratios are 68.52%, CO2Conversion ratio is 2.73%, and total charcoal conversion ratio is 59.58%, first
Alcohol is selectively 99.43%, and methyl formate is selectively 0.57%, and methanol yield is 59.24%.
Embodiment 18
Reduction process and embodiment 11 are identical, and reaction condition is 1990h except the air speed of synthesis gas-1,
The air speed of co-catalyst methanol is 6.75h-1Outside, other reaction conditions and embodiment 11 are identical.As a result
It is 55.45%, CO for CO conversion ratios2Conversion ratio is 2.07%, and total charcoal conversion ratio is 47.20%,
Methanol selectivity is 98.32%, and methyl formate is selectively 1.68%, and methanol yield is 46.41%.
Comparative example 1
In tubular fixed-bed flow reactor, load catalyst prepared by 2.0g comparative examples 1, react bar
Part and embodiment 1 are identical, and CO conversion ratios are 32.3%, CO2Conversion ratio is -5.7%, total charcoal conversion
Rate is 27.14%, and methanol selectivity is 89.5%, and methyl formate is selectively 10.5%, methanol yield
For 24.29%.
Comparative example 2
Embodiment 1 is repeated, but co-catalyst is changed to n-hexane.CO conversion ratios are 22.1%, CO2
Conversion ratio is 31.2%, and total charcoal conversion ratio is 23.3%, and methanol selectivity is 99.9%, methane selection
Property is 0.1%, and methanol yield is 23.28%.
Comparative example 3
Embodiment 1 is repeated, catalyst is changed to industrial methanol synthesis catalyst
CuO-ZnO-Al2O3(Top rope MK-101, wherein CuO content are 50 weight %, ZnO
Content is 40 weight %, Al2O3Content be 10 weight %), CO conversion ratios be 25.6%, CO2
Conversion ratio is 3.3%, and total charcoal conversion ratio is 22.57%, and methanol selectivity is 98.5%, methane selection
Property be 0.1%, the selectivity of methyl formate is 1.4%, and methanol yield is 22.23%.
Comparative example 4
In tubular fixed-bed flow reactor, load 2.0g and prepare catalyst prepared by comparative example 2, instead
Answer condition and embodiment 1 identical, CO conversion ratios are 19.6%, CO2Conversion ratio is -4.4%, total charcoal
Conversion ratio is 16.34%, and methanol selectivity is 96.3%, and methyl formate is selectively 3.7%, methanol
Yield is 15.74%.
Embodiment 19
Using the experiment condition of embodiment 7, unlike, the time extended to 500 hours from 8 hours.
As a result Fig. 1 is seen.As can be seen from Figure 1 CO conversion ratio is at 500 hours, be always held at 80% with
On, CO2Conversion ratio be also maintained at more than 16%, the selectivity of methanol does not also change, and says
The bright method using the present invention, under the conditions of low-temp reaction, in the presence of co-catalyst, not only CO
And CO2High conversion rate, the selectivity of methanol is also high, and the stability of catalyst is also fine.Catalyst
Specific surface area from the 51.6m before reaction2/ g drops to 50.2M2/ g, does not change substantially, illustrates catalysis
Agent is highly stable.
Claims (10)
1. a kind of preparation method of methanol, this method is included in depositing for copper-zinc catalyst and co-catalyst
Under, the synthesis gas of hydrogen and oxycarbide is contacted with catalyst and co-catalyst, it is described to urge
Agent is made up of cupric oxide and zinc oxide, it is characterised in that the co-catalyst is C1-6Alkylol, copper-
The specific surface area of zinc catalyst is 40-60m2/g。
2. according to the method described in claim 1, its conditional includes：Temperature is 150-220 DEG C,
Pressure is 2.0-10.0MPa；Preferable temperature is 170-200 DEG C, and pressure is 5.0-7.0MPa.
3. according to the method described in claim 1, wherein the co-catalyst is C1-4Alkylol；It is excellent
Elect methanol, ethanol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, 2- methyl isophthalic acids-propyl alcohol and 2- as
At least one of methyl-2-propanol；More preferably in methanol, ethanol, 1- propyl alcohol and 2- butanol
At least one.
4. the Feed space velocities of the method according to any one of claim 1-3, wherein synthesis gas are
500-2500h-1；Preferably 650-2200h-1；More preferably 800-2000h-1。
5. the Feed space velocities of the method according to any one of claim 1-4, wherein co-catalyst
For 0.01-40h-1, preferably 0.1-20h-1, more preferably 2.0-12h-1。
6. the method according to any one of claim 1-5, wherein copper in the copper-zinc catalyst
Molal quantity and copper and the ratio of total mole number of zinc be 0.1-0.9：1；Preferably 0.3-.0.7：1；Enter
One step is preferably 0.4-0.7：1.
7. the method according to any one of claim 1-6, wherein the copper-zinc catalyst
Specific surface area is 45-55m2/g。
8. the method according to any one of claim 1-7, wherein copper-zinc catalyst are using bag
It is prepared by the method for including following steps：By water-soluble mantoquita and water-soluble zinc salt deionized water dissolving, obtain
To mixed solution；Then urea is added in gained mixed solution and produces precipitation, obtain mixture；
Gained mixture is subjected to separation of solid and liquid, and solid product obtained by separation of solid and liquid is washed, dried
And roasting.
9. method according to claim 8, wherein water-soluble mantoquita is Cu (NO3)2、CuSO4、
Cu2SO4、CuNO3And CuCl2At least one of；Preferably Cu (NO3)2、CuSO4And CuCl2
At least one of；More preferably Cu (NO3)2。
10. method according to claim 8, wherein water-soluble zinc salt are Zn (NO3)2、ZnSO4、
Zn(CH3COO)2And ZnCl2At least one of；Preferably Zn (NO3)2、ZnSO4And ZnCl2
At least one of, more preferably Zn (NO3)2。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111167492A (en) * | 2018-11-12 | 2020-05-19 | 中国科学院上海硅酸盐研究所 | Copper-modified carbon nitride, preparation method thereof and application of copper-modified carbon nitride in photocatalytic methane conversion |
| CN111545209A (en) * | 2020-04-30 | 2020-08-18 | 鞍钢股份有限公司 | Method for synthesizing Cu/ZnO catalyst based on hard template copper oxide nanosheets |
| CN115364863A (en) * | 2021-05-18 | 2022-11-22 | 中国科学院大连化学物理研究所 | Bifunctional catalyst, preparation method and application in methanol synthesis and hydrogen production by reforming |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489340A (en) * | 2011-12-02 | 2012-06-13 | 北京化工大学 | Method for preparing catalyst used for one-carbon chemical reactions through coprecipitation |
| CN103769112A (en) * | 2014-01-22 | 2014-05-07 | 新疆大学 | Copper-base catalyst for synthesizing methanol and preparation method thereof |
-
2016
- 2016-02-05 CN CN201610082698.5A patent/CN107043319B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489340A (en) * | 2011-12-02 | 2012-06-13 | 北京化工大学 | Method for preparing catalyst used for one-carbon chemical reactions through coprecipitation |
| CN103769112A (en) * | 2014-01-22 | 2014-05-07 | 新疆大学 | Copper-base catalyst for synthesizing methanol and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| I. ATAKE等: "Catalytic behavior of ternary Cu/ZnO/Al2O3 systems prepared by homogeneous precipitation in water-gas shift reaction", 《J. MOL. CATAL. A CHEM.》 * |
| JIANQING ZENG等: "A New Low-Temperature Synthesis Route of Methanol:Catalytic Effect of the Alcoholic Solvent", 《ENERGY & FUELS》 * |
| P. REUBROYCHAROEN等: "Development of a new low-temperature methanol synthesis process", 《CATALYSIS TODAY》 * |
| T. SHISHIDO等: "Active Cu/ZnO and Cu/ZnO/Al2O3 catalysts prepared by homogeneous precipitation method in steam reforming of methanol", 《APPL. CATAL. A GEN.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111167492A (en) * | 2018-11-12 | 2020-05-19 | 中国科学院上海硅酸盐研究所 | Copper-modified carbon nitride, preparation method thereof and application of copper-modified carbon nitride in photocatalytic methane conversion |
| CN111167492B (en) * | 2018-11-12 | 2022-12-13 | 中国科学院上海硅酸盐研究所 | Copper-modified carbon nitride, preparation method thereof and application of copper-modified carbon nitride in photocatalytic methane conversion |
| CN111545209A (en) * | 2020-04-30 | 2020-08-18 | 鞍钢股份有限公司 | Method for synthesizing Cu/ZnO catalyst based on hard template copper oxide nanosheets |
| CN115364863A (en) * | 2021-05-18 | 2022-11-22 | 中国科学院大连化学物理研究所 | Bifunctional catalyst, preparation method and application in methanol synthesis and hydrogen production by reforming |
| CN115364863B (en) * | 2021-05-18 | 2024-03-26 | 中国科学院大连化学物理研究所 | Double-function catalyst, preparation method and application thereof in methanol synthesis and hydrogen production by reforming |
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