CN104368356A - Catalyst for preparing low-carbon mixed alcohol from synthesis gas and preparation method and application thereof - Google Patents
Catalyst for preparing low-carbon mixed alcohol from synthesis gas and preparation method and application thereof Download PDFInfo
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- CN104368356A CN104368356A CN201410617949.6A CN201410617949A CN104368356A CN 104368356 A CN104368356 A CN 104368356A CN 201410617949 A CN201410617949 A CN 201410617949A CN 104368356 A CN104368356 A CN 104368356A
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- catalyst
- preparing low
- mixed alcohol
- synthesis
- carbon mixed
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 29
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000011787 zinc oxide Substances 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 13
- -1 alkali metal salt Chemical class 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- 238000000748 compression moulding Methods 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 239000011701 zinc Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000004448 titration Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000003245 coal Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002816 fuel additive Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for preparing low-carbon mixed alcohol from synthesis gas, which comprises copper oxide, zinc oxide, zirconium oxide and an auxiliary agent, wherein the general formula of the catalyst is as follows: cuaZnbZrcMdNeOxM is at least one of metal elements of Mn, Ce, Mg, Fe, Co and Ni, N is alkali metal, a takes the value of 0.3-4.0, b takes the value of 0.5-3.5, c takes the value of 1.0-5.0, d takes the value of 0.02-0.3, e takes the value of 0.01-0.2, and x is the sum of the number of oxygen atoms required by all the metal elements in the general formula. The invention also discloses a preparation method and application of the catalyst. The method has the advantages of high selectivity of C2+ alcohol, high selectivity of isobutanol, low hydrocarbon selectivity, low water content in liquid-phase products, simple and easy preparation method and easy industrialization.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and application, especially relate to a kind of Catalysts and its preparation method for the synthesis of gas preparing low-carbon mixed alcohol and application, belong to catalysis technical field.
Background technology
The energy, as the grand strategy goods and materials of national economy and social development, is the essential condition ensureing national sustainable development and national defense safety.In recent years, along with the continuous expansion of the mankind to energy demand and the continuous consumption of natural resources, actively seek and develop new energy system to very urgent the mankind.In world's energy resource structure, oil only accounts for about 7%, and coal is then close to 80%, and the energy resource structure feature of the few oil of the rich coal of China is more obvious, therefore from the strategic concerns of energy development, the high effect cleaning technology of research and development coal resources can make up the shortage of petroleum resources.
Carbon monoxide and hydrogen is more easily prepared, by catalyzing carbon monoxide hydrogenation synthesizing low carbon mixed alcohol (C based on coal
1-C
5alcohol) be the important channel of coal resources clean utilization, be also one of important research content of C-1 chemistry, its technological process and synthesizing methanol are similar substantially.MAS can as fuel additive, wherein C
2-C
5mixed alcohol is eco-friendly liquid fuel additive, not sulfur-bearing and aromatic compound, surcharge is higher, can directly substitute methyl tertiary butyl ether(MTBE) as gasoline additive, also mixed alcohol can be separated, the single alcohols obtained directly is used as industrial chemicals.In recent years, MAS progressively shows especially in the using value of fuel and chemical field, and correlative study becomes increasingly active.
At present, the catalyst of preparing low-carbon mixed alcohol by synthetic gas is existing a lot, and different research institutions have developed the catalyst with different characteristics.As the modified synthesis catalyst for methanol that the people such as US Patent No. 4031123 and US2327066 and C.E.Hofstadt propose at patent US4513100 the people such as patent EP0034338A2, Fattore, this type of catalysis is at Cu/ZnO/Al
2o
3, Zn/Cr
2o
3appropriate alkali metal is added or Modified With Alkali-earth Compounds forms in catalyst for methanol, this type of catalyst has active high feature, in product, isobutanol content is higher, but it is harsher that shortcoming is reaction condition, pressure is between 14-20MPa, temperature is between 350-450 DEG C, and in product, water content reaches 30-50%.
US Patent No. 4882360 proposes a kind of MoS
2the preparation method of catalyst, this catalyst has resistance to sulphur property, product moisture content less, ethanol and normal propyl alcohol content higher, but the stability of such catalyst and life-span there is some problems.In addition, US Patent No. 4122110 and US4291126 also proposed a kind of preparation method of Cu/Co series catalysts, and this catalyst operating condition is gentleer, and product is based on straight chain n-alkanol, reactivity is higher, but the more hydro carbons of by-product and water in products is divided more.
At present, domesticly prepared by low carbon mixed alcohol catalyst to synthesis gas also carried out the deep research of system, but majority is the modification abroad catalyst system basis carried out.The people such as Sun Yuhan, Fang Kegong of such as Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences propose in patent CN201210342290.9 has the ferro element of stronger chain growth ability and the method for potassium element and the structural promoter such as zinc oxide, chromium oxide, to improve C a kind of adding on silicon dioxide carried copper Mn catalyst
2 +alcohol is selective, mitigation process conditions, but this catalyst alcohols selectivity is low, the hydro carbons that by-product is more and CO
2.Propose in patent CN201310428824.4 and add the method that the elements such as Mn, La, Ce, Rh, Pd carry out modification in Cu/Co series catalysts, through the catalyst of modification, there are higher higher alcohols selective.Propose a kind of by Fe in patent CN201310095284.2
2o
3with the catalyst with copper iron nucleocapsid structure of CuO composition, this catalyst can prevent iron from sintering, and the selective height of alcohol, stability is better.A kind of transition metal modified MoS is proposed in patent CN200410064554.4
2the preparation method of catalyst, the catalyst of acquisition has higher C
2 +the hydrocarbon-selective that alcohol is selective and lower.A kind of M-M is proposed in patent CN200910175310.6
1-M
2the preparation method of catalyst, wherein M is the one of Mo, W, V, M
1the one of Fe, Co, Ni, Cr, Mn, La or Ce, M
2be one or more in K, Na, Be, Mg, this catalyst sulfur tolerance is better, and good stability, activity is higher.
Patent CN200610097869.8 proposes and a kind ofly prepares by coprecipitation the method that Cu/Zn/Al/Cr catalyzes and synthesizes MAS, this good catalyst activity, and the life-span is long, and alcohols selectivity is high, C
2 +above alcohol content can reach 40.97%.
Above catalyst respectively has feature, when CO conversion ratio is higher, and C
2 +alcohol is selective may lower or hydro carbons that by-product is more, works as C
2 +alcohol selective high time, the conversion ratio of CO may be lower again, and namely allowing to industrially to be applied economy neither be fine, and thus people constantly improve catalyst for a long time, expect to obtain CO conversion ratio high while C
2 +the catalyst that alcohol is selective and alcohol space-time yield is all higher.
Summary of the invention
The invention solves deficiency of the prior art, the invention provides a kind of higher C
2 +alcohol and isobutanol selective, effectively can solve C
2 +alcohol is the selective low problem of isobutanol especially.
Technical scheme of the present invention is:
For the synthesis of the catalyst of gas preparing low-carbon mixed alcohol, it is characterized in that, comprise cupric oxide, zinc oxide, zirconia and auxiliary agent, and the general formula of described catalyst is: Cu
azn
bzr
cm
dn
eo
xwherein, M is at least one (at least one in preferred Mn, Ce, Co, Ni metallic element) in Mn, Ce, Mg, Fe, Co, Ni metallic element, and described N is auxiliary agent, and described auxiliary agent is alkali metal, and the span of a is 0.3-4.0, the span of the span of b to be the span of 0.5-3.5, c be 1.0-5.0, d is 0.02-0.3, the span of e is 0.01-0.2, the x oxygen atom number summation needed for metallic elements all in general formula.
Further, described alkali metal is any one in Rb, Cs, K.
And the preferred 0.02-0.15 of span of span preferred 0.03-0.25, the e of span preferred 2.0-4.2, the d of span preferred 0.6-3.2, the c of the span of described a preferred 0.8-3.6, b.
The preparation method of the above-mentioned catalyst for the synthesis of gas preparing low-carbon mixed alcohol, is characterized in that, comprise the following steps:
(1) preparing metal salting liquid: after the slaine of other metallic elements in the general formula of catalyst except alkali metal is uniformly mixed, adds water and be mixed with metal salt solution;
(2) precipitation and post processing: the metal salt solution described in step (1) is joined in precipitating reagent, and precipitate under the temperature conditions of 40-85 DEG C, until the pH value of solution is 7.0-9.5, then 20min is stirred, aging 30min under the temperature conditions of 55-90 DEG C again, then after filtration, wash, dry, to be precipitated thing for subsequent use;
(3) alkali metal salt soln is prepared: added water by alkali metal salt and be mixed with alkali metal salt soln;
(4) Kaolinite Preparation of Catalyst: the sediment that step (2) obtains is pulverized last, impregnated in 12h in the alkali metal soln described in step (3), then after filtration, oven dry, roasting, brokenly after compression molding cross 20-40 mesh sieve, obtain the catalyst for the synthesis of gas preparing low-carbon mixed alcohol.
Further, the metal salt solution described in step (1) is nitrate solution.
Precipitating reagent described in step (2) is Na
2cO
3, NaHCO
3, ammoniacal liquor or NH
4hCO
3in any one.
The concentration of the alkali metal salt soln described in step (3) is 5-10%, and described alkali metal salt is nitrate or carbonate.
And the temperature of roasting described in step (4) is 300-550 DEG C.
And above-mentioned catalyst is for the synthesis of gas preparing low-carbon mixed alcohol.And in the process of preparing low-carbon mixed alcohol by synthetic gas, evaluating apparatus used is fixed bed reactors, reaction temperature is 250-450 DEG C, and reaction pressure is 3.0-12.0MPa, and gas space velocity is 4000-12000h
-1, H
2be 1.0-3.0 with the volume ratio of CO.
The defect solving prior art of the present invention, has following beneficial effect:
1, the catalyst activity prepared by the present invention is high, has higher C
2 +alcohol is selective, has higher isobutanol selective simultaneously;
2, the catalyst prepared by the present invention has lower hydrocarbon-selective, and in liquid product, water content is less;
3 and in preparation process, reaction pressure is low, reaction condition is gentle, strong adaptability, can use under working condition comparatively widely;
4, not containing noble metal in the catalyst prepared by the present invention, cost of material is low, and preparation is simple, and catalyst dry powder is easy to shaping, and mechanical strength is good, is suitable for industry and amplifies, be easy to industrialization;
5, the primary raw material of catalyst is the nitrate of copper, zinc, zirconium, heavy metal free, and basic nontoxic pollution-free, has environment amenable feature.
Detailed description of the invention
In order to make those skilled in the art person understand the present invention better, and above-mentioned advantage of the present invention is become apparent more, below in conjunction with specific embodiment, the present invention is further detailed explanation.
Embodiment 1
Weigh 7.95gCu (NO
3)
23H
2o, 8.84gZn (NO
3)
26H
2o, 3.56gZr (NO
3)
45H
2o, 1.56gFe (NO
3)
39H
2o, adds 0.82gMn (NO simultaneously
3)
2be made into 80ml solution, under 60 DEG C of conditions, this dropwise is joined in ammoniacal liquor, the pH controlling titration end-point is 8.0, continue after titration completes to stir 20min, aging 30min at 70 DEG C again, filter 5 times with deionized water cyclic washing again, after drying 12h at 120 DEG C, catalyst grind into powder be impregnated in the CsNO that mass fraction is 6%
312h in solution, dries 12h at having flooded latter 120 DEG C again, finally roasting 6h at 300 DEG C again, and compression molding, by catalyst breakage to 20-40 order, this catalyst is labeled as C-1.
Embodiment 2
Weigh 5.48gCu (NO
3)
23H
2o, 9.23gZn (NO
3)
26H
2o, 1.95gZr (NO
3)
45H
2o, adds 1.59gCe (NO simultaneously
3)
36H
2o is made into 70ml solution, under 50 DEG C of conditions, this dropwise is joined in sodium carbonate liquor, the pH controlling titration end-point is 7.5, continue after titration completes to stir 20min, aging 30min at 60 DEG C again, filter 5 times with deionized water cyclic washing again, after drying 12h at 120 DEG C, catalyst grind into powder be impregnated in the K that mass fraction is 8%
2cO
312h in solution, dries 12h at having flooded latter 120 DEG C again, finally roasting 6h at 350 DEG C again, and compression molding, by catalyst breakage to 20-40 order, this catalyst is labeled as C-2.
Embodiment 3
Weigh 6.85gCu (NO
3)
23H
2o, 5.72gZn (NO
3)
26H
2o, 5.64gZr (NO
3)
45H
2o, 0.23gMn (NO
3)
2, add 0.53gCe (NO simultaneously
3)
36H
2o is made into 75ml solution, under 85 DEG C of conditions, this dropwise is joined in sodium carbonate liquor, the pH controlling titration end-point is 7.0, continue after titration completes to stir 20min, aging 30min at 90 DEG C again, filter 5 times with deionized water cyclic washing again, after drying 12h at 120 DEG C, catalyst grind into powder be impregnated in the RbNO that mass fraction is 8%
312h in solution, dries 12h at having flooded latter 120 DEG C again, finally roasting 6h at 450 DEG C again, and compression molding, by catalyst breakage to 20-40 order, this catalyst is labeled as C-3.
Embodiment 4
Weigh 6.79gCu (NO
3)
23H
2o, 8.52gZn (NO
3)
26H
2o, 5.37gZr (NO
3)
45H
2o, 0.42gMn (NO
3)
2, 0.95gMg (NO
3)
26H
2o is made into 65ml solution, under 65 DEG C of conditions, this dropwise is joined in sodium bicarbonate solution, the pH controlling titration end-point is 8.5, continue after titration completes to stir 20min, aging 30min at 75 DEG C again, filter 5 times with deionized water cyclic washing again, after drying 12h at 120 DEG C, catalyst grind into powder be impregnated in the KNO that mass fraction is 10%
312h in solution, dries 12h at having flooded latter 120 DEG C again, finally roasting 6h at 400 DEG C again, and compression molding, by catalyst breakage to 20-40 order, this catalyst is labeled as C-4.
Embodiment 5
Weigh 5.67gCu (NO
3)
23H
2o, 5.83gZn (NO
3)
26H
2o, 3.64gZr (NO
3)
45H
2o, 0.42gMn (NO
3)
2, the Co (NO of 0.6g
3)
26H
2o, adds 0.17gCe (NO simultaneously
3)
36H
2o is made into 75ml solution, under 75 DEG C of conditions, this dropwise is joined in sodium bicarbonate solution, the pH controlling titration end-point is 9.0, continue after titration completes to stir 20min, aging 30min at 85 DEG C again, filter 5 times with deionized water cyclic washing again, after drying 12h at 120 DEG C, catalyst grind into powder be impregnated in the CsNO that mass fraction is 8%
312h in solution, dries 12h at having flooded latter 120 DEG C again, finally roasting 6h at 320 DEG C again, and compression molding, by catalyst breakage to 20-40 order, this catalyst is labeled as C-5.
Embodiment 6
Weigh 7.42gCu (NO
3)
23H
2o, 6.48gZn (NO
3)
26H
2o, 4.23gZr (NO
3)
45H
2o, 1.48gNi (NO
3)
26H
2o, 1.79gMg (NO
3)
26H
2o is made into 90ml solution, under 70 DEG C of conditions, this dropwise is joined NH
4hCO
3in solution, controlling the pH of titration end-point is 7.5, continues to stir 20min after titration completes, then at 75 DEG C aging 30min, filter 5 times with deionized water cyclic washing again, after drying 12h at 120 DEG C, catalyst grind into powder be impregnated in the RbNO that mass fraction is 6%
312h in solution, dries 12h at having flooded latter 120 DEG C again, finally roasting 6h at 500 DEG C again, and compression molding, by catalyst breakage to 20-40 order, this catalyst is labeled as C-6.
Above-mentioned obtained catalyst is seated in the fixed bed reactors of Φ 16X4mm respectively and carries out performance test, and in the process of preparing low-carbon mixed alcohol by synthetic gas, evaluating apparatus used is fixed bed reactors, reaction temperature is 250-450 DEG C, reaction pressure is 3.0-12.0MPa, and gas space velocity is 4000-12000h
-1, the unstripped gas of employing is the gaseous mixture prepared, therefore H
22.0 are fixed as with the volume ratio of CO.Reacted gas obtains mixed alcohol product after condensation, and then product is entered chromatography, and result is as shown in table 1:
Table 1 different catalysts product slates
As shown in Table 1: the catalyst that the present embodiment prepares, in the reaction of preparing low-carbon mixed alcohol by synthetic gas, not only has higher C
2 +alcohol is selective, also have higher isobutanol selective, and have lower hydrocarbon-selective, in liquid product, water content is less.And in MAS, except methyl alcohol, isobutanol comparision contents height, the content of ethanol, normal propyl alcohol is also higher, it is mixed alcohol truly.
The above; be only the specific embodiment of the present invention, protection scope of the present invention is not limited thereto, and is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should define with claim is as the criterion.
Claims (10)
1. for the synthesis of the catalyst of gas preparing low-carbon mixed alcohol, it is characterized in that, comprise cupric oxide, zinc oxide, zirconia and auxiliary agent, and the general formula of described catalyst is: Cu
azn
bzr
cm
dn
eo
xwherein, M is at least one in Mn, Ce, Mg, Fe, Co, Ni metallic element, and described N is auxiliary agent, and described auxiliary agent is alkali metal, and the span of a is 0.3-4.0, the span of the span of b to be the span of 0.5-3.5, c be 1.0-5.0, d is 0.02-0.3, the span of e is 0.01-0.2, the x oxygen atom number summation needed for metallic elements all in general formula.
2. the catalyst for the synthesis of gas preparing low-carbon mixed alcohol according to claim 1, is characterized in that, described alkali metal is any one in Rb, Cs, K.
3. the catalyst for the synthesis of gas preparing low-carbon mixed alcohol according to claim 1, is characterized in that, the span of described a is 0.8-3.6, the span of b is 0.6-3.2, the span of the span of c to be the span of 2.0-4.2, d be 0.03-0.25, e is 0.02-0.15.
4., as claimed in claim 1 for the synthesis of the preparation method of the catalyst of gas preparing low-carbon mixed alcohol, it is characterized in that, comprise the following steps:
(1) preparing metal salting liquid: after the slaine of other metallic elements in the general formula of catalyst except alkali metal is uniformly mixed, adds water and be mixed with metal salt solution;
(2) precipitation and post processing: the metal salt solution described in step (1) is added in precipitating reagent, and precipitate under the temperature conditions of 40-85 DEG C, until the pH value of solution is 7.0-9.5, then 20min is stirred, aging 30min under the temperature conditions of 55-90 DEG C again, then after filtration, wash, dry, to be precipitated thing for subsequent use;
(3) alkali metal salt soln is prepared: added water by alkali metal salt and be mixed with alkali metal salt soln;
(4) Kaolinite Preparation of Catalyst: the sediment that step (2) obtains is pulverized last, impregnated in 12h in the alkali metal soln described in step (3), then after filtration, oven dry, roasting, brokenly after compression molding cross 20-40 mesh sieve, obtain the catalyst for the synthesis of gas preparing low-carbon mixed alcohol.
5. the preparation method of the catalyst for the synthesis of gas preparing low-carbon mixed alcohol according to claim 4, is characterized in that, the metal salt solution described in step (1) is nitrate solution.
6. the preparation method of the catalyst for the synthesis of gas preparing low-carbon mixed alcohol according to claim 4, is characterized in that, the precipitating reagent described in step (2) is Na
2cO
3, NaHCO
3, ammoniacal liquor or NH
4hCO
3in any one.
7. the preparation method of the catalyst for the synthesis of gas preparing low-carbon mixed alcohol according to claim 4, is characterized in that, the concentration of the alkali metal salt soln described in step (3) is 5-10%, and described alkali metal salt is nitrate or carbonate.
8. the preparation method of the catalyst for the synthesis of gas preparing low-carbon mixed alcohol according to claim 4, is characterized in that, the temperature of the roasting described in step (4) is 300-550 DEG C.
9. the catalyst described in any one of claim 1-3 claim is for the synthesis of gas preparing low-carbon mixed alcohol.
10. catalyst according to claim 9 is for the synthesis of gas preparing low-carbon mixed alcohol, it is characterized in that, in the process of preparing low-carbon mixed alcohol by synthetic gas, evaluating apparatus used is fixed bed reactors, reaction temperature is 250-450 DEG C, reaction pressure is 3.0-12.0MPa, and gas space velocity is 4000-12000h
-1, H
2be 1.0-3.0 with the volume ratio of CO.
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