CN101786001A - Catalyst for hydrogenation of carbon dioxide to generate methanol and preparation method thereof - Google Patents
Catalyst for hydrogenation of carbon dioxide to generate methanol and preparation method thereof Download PDFInfo
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- CN101786001A CN101786001A CN201010126677A CN201010126677A CN101786001A CN 101786001 A CN101786001 A CN 101786001A CN 201010126677 A CN201010126677 A CN 201010126677A CN 201010126677 A CN201010126677 A CN 201010126677A CN 101786001 A CN101786001 A CN 101786001A
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- carbon dioxide
- methanol
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 78
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 238000000975 co-precipitation Methods 0.000 claims abstract description 19
- 239000002086 nanomaterial Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 230000008021 deposition Effects 0.000 claims abstract description 3
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 claims abstract 3
- 238000006722 reduction reaction Methods 0.000 claims abstract 3
- 229920005862 polyol Polymers 0.000 claims abstract 2
- 150000003077 polyols Chemical class 0.000 claims abstract 2
- 239000008367 deionised water Substances 0.000 claims description 61
- 229910021641 deionized water Inorganic materials 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 239000000243 solution Substances 0.000 claims description 56
- 239000010949 copper Substances 0.000 claims description 36
- 239000011701 zinc Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 239000012065 filter cake Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000000706 filtrate Substances 0.000 claims description 17
- 230000007935 neutral effect Effects 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229940011182 cobalt acetate Drugs 0.000 claims description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 2
- 239000002244 precipitate Substances 0.000 claims 2
- 229910017518 Cu Zn Inorganic materials 0.000 claims 1
- 229910017752 Cu-Zn Inorganic materials 0.000 claims 1
- 229910017943 Cu—Zn Inorganic materials 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims 1
- 239000012527 feed solution Substances 0.000 claims 1
- 239000011344 liquid material Substances 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- -1 that is Substances 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 229910052720 vanadium Inorganic materials 0.000 description 15
- 238000001914 filtration Methods 0.000 description 14
- 239000013049 sediment Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 238000004364 calculation method Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000252095 Congridae Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
用于二氧化碳加氢制甲醇的催化剂及其制备方法，涉及催化剂，提供以碳纳米管基材料为促进剂，用于二氧化碳加氢制甲醇的催化剂及其制备方法，催化剂用于二氧化碳催化加氢制甲醇时，能有效提高二氧化碳的加氢转化率和甲醇的单程产率。催化剂包含金属主组分和碳纳米管基纳米材料促进剂，金属主组分为Cu、Zn、Or，碳纳米管基纳米材料促进剂为CNT或y％Co/CNT，化学式为CuiZnjZrk-x％(CNT或y％Co/CNT)，各组分的质量百分数为Zn5％～20％，Zr25％～50％，碳纳米管基纳米材料促进剂1％～18％，余量为Cu。催化剂采用共沉淀制备。金属钴修饰的多壁碳纳米管用多元醇液相微波助化学还原沉积法制备。Catalyst for hydrogenation of carbon dioxide to methanol and preparation method thereof, relates to catalyst, provides carbon nanotube-based material as a promoter, catalyst for hydrogenation of carbon dioxide to methanol and preparation method thereof, catalyst for catalytic hydrogenation of carbon dioxide When using methanol, it can effectively improve the hydrogenation conversion rate of carbon dioxide and the single-pass yield of methanol. The catalyst contains a metal main component and a carbon nanotube-based nanomaterial promoter, the metal main component is Cu, Zn, Or, and the carbon nanotube-based nanomaterial promoter is CNT or y%Co/CNT, and the chemical formula is Cu i Zn j Zr k -x% (CNT or y% Co/CNT), the mass percentage of each component is Zn5% ~ 20%, Zr25% ~ 50%, carbon nanotube-based nanomaterial accelerator 1% ~ 18%, the balance For Cu. The catalyst is prepared by co-precipitation. Cobalt-modified multi-walled carbon nanotubes were prepared by polyol liquid-phase microwave-assisted chemical reduction deposition.
Description
Technical field
The present invention relates to a kind of catalyst, especially relate to a kind of copper-zinc-Zr catalyst that promotes with the CNT based nano-material and preparation method thereof.
Background technology
CO
2Fixing a large amount of discharging CO in hydrogenation is considered between present short-term
2One of economical and effective method.In order to improve weather conditions and to solve the carbon resource problem, needing to develop can be with CO
2Be converted into the technology of valuable material.In the multiple option of being considered, in view of methyl alcohol is that important industrial chemicals and oil replenish alternative synthetic fuel, with CO
2By hydro-conversion is that the research of methyl alcohol receives much attention.Relevant CO over nearly 20 years
2Preparing methanol by hydrogenation has a report with on the research of catalyst or the exploitation document more; Study the earliest, be that CuO-is catalyst based the most widely.([1] Amenomiya Y., et al., Proc9 such as Amenomiya
ThIntern.Congr.Catal. (Chem.Inst.of Canada, Calgary), 1988, p.634-641), (Proc 9 for [2] Pommier B., et al. for Pommier etc.
ThIntern.Congr.Catal. (Chem.Inst.of Canada, Calgary), 1988, p.610-617) and ([3] Koppel R.A. such as Koeppel, et al., Appl.Catal.A:Gen.84 (1) (1992): 77-102) results reported shows, CuO/ZrO
2To CO
2The catalytic activity of preparing methanol by hydrogenation is higher than CuO/ZnO, also is higher than CuO/Al
2O
3, CuO/SiO
2, CuO/MgO and CuO/TiO
2After a while, some contain catalyst based (the comprising: Cu/ZnO/ZrO of CuO of multicomponent promoter
2, Cu-ZnO-Ga
2O
3And CuO-ZnO-ZrO
2-Ga
2O
3Deng ([4] Frohlich C., et al., Appl Catal A:Gen.106 (2) (1993): 275-293; [5] Saito M., et al., Appl Catal A:Gen.138 (2) (1996): 311-318; [6] Kilo M., et al., J.Mol.Catal.A:Chem.126 (2-3) (1997): 169-184; [7] Koppel R.A., et al., J.Catal.179 (1998): 515-527; [8] Ma Y., et al., Appl.Catal.A:General 171 (1) (1998): 45-55; [9] Joo O.S., et al., Ind.Eng.Chem.Res.38 (1999): 1808-1812; [10] Cong Y.et al., Chin.J.Catal.21 (3) (2000): 247-250; [11] Toyir J., et al., Appl.Catal.B:Env.29 (3) (2001): 207-215; [12] Sloczynski J., et al., Appl.Catal.A:Gen.249 (1) (2003): 129-138; [13] Sloczynski J., et al., Appl.Catal.A:Gen.278 (1) (2004): 11-23; [14] Yang C., et al., Catal.Today 115 (1-4) (2006): 222-227; [15] Sloczynski J., et al., Appl.Catal.A:Gen.310 (1) (2006): 127-137; [16] Arena F., et al., J.Catal.249 (2) (2007): 185-194; [17] Arena F., et al., Appl.Catal.A:Gen.350 (1) (2008): 16-23; [18] Guo X., et al., Catal.Commun.10 (13) (2009): 1661-1664)) exploitation also has report.Yet have the existing catalyst based catalysis CO of CuO-in mind from practical standpoint
2The productive rate of preparing methanol by hydrogenation is lower.The research and development of effective catalyst are the technical bottlenecks that realizes this process industrialization.
In another field, forward position, multi-walled carbon nano-tubes (MWCNTs, hereinafter be abbreviated as CNT) ([19] Iijima S., Nature 354 (1991): ([20] the Serp P. of attention day by day that 56-58) causes international catalysis educational circles over nearly 10 years, et al., Appl.Catal.A:Gen.253 (2) (2003): 337-358; [21] Zhang H.B., et at., Curr.Topics Catal.4 (2005): 1-21; [22] Zhang H.B., et at., Catal.Surv.Asia 13 (2009): 41-58).This class novel nano material with carbon element has some particular structure and physico-chemical property, such as: graphited tube wall, nano level tube chamber, sp
2The surface that-C constitutes, higher electrical and thermal conductivity, in high-grade specific area and to the adsorption/activation of hydrogen and promote the excellent properties of hydrogen overflow, or the like these make CNT get a good chance of becoming novel catalyst carrier or cocatalyst.Catalytic applications paper ([23] PlaneixJ.M. of the relevant CNT of a first piece of writing since 1994, et al., J.Am.Chem.Soc.116 (17) (1994): 7935-7936) deliver since, existing up to a hundred pieces of research papers are delivered, its involvement aspect contains: α, the selection hydrogenation of beta-unsaturated aldehyde, olefin hydroformylation ([24] Zhang Y., et al., Appl.Catal.A:Gen.187 (2) (1999): 213-224), ammonia synthesis ([25] Chen H.B., et al., Appl.Surf.Sci.180 (3-4) (2001): 328-335), FT synthesizes ([26] Steen E., et al., Catal.Today 71 (3-4) (2002): 327-334), methyl alcohol and low-carbon alcohols are synthesized ([27] Zhang H.B., et al., ACS Symp.Ser.No.852,2003, p.195-209; [28] Dong X., et al., Catal.Lett.85 (3-4) (2003): 237-246; [29] Zhang H.B., et al., Chem.Commun.40 (2005): 5094-5096; [30] Pan X.L., et al., Nature Materials 6 (2007): 507-511; [31] Dong X., et al., Catal.Today 147 (2) (2009): 158-165), select dehydrogenation ([32] Liu Z.J., et al., Catal.Lett.72 (3-4) (2001): 203-206), selective oxidation ([33] Li C.B., et al., J.Mol.Catal.A:Chem.193 (1-2) (2003): 71-75), and to electro-catalysis ([34] Shukla A.K., et al., J.Electroanal.Chem.504 (1) (2001): 111-119) and fuel cell ([35] Li W., et al., Carbon 40 (5) (2002): 791-794) wait numerous areas.Utilizing some transition metal that CNT is modified in advance is expected further to improve it some hydrogenation process is helped catalytic performance ([36] Shen B.S., et al.Acta Chimica Sinica (Chinese) 62 (18) (2004): 1721-1728; [37] Ma X.M., et al., Catal.Lett.111 (3-4) (2006): 141-151; [38] Wu X.M., et al., Appl Catal A:Gen.340 (1) (2008): 87-97).
Summary of the invention
It is promoter with the carbon nanotube-based material that purpose of the present invention aims to provide a kind of, the Catalysts and its preparation method that is used for hydrogenation of carbon dioxide to generate methanol, when prepared catalyst is used for catalytic hydrogenation of carbon dioxide system methyl alcohol, can effectively improve the hydrogenation conversion of carbon dioxide and the one-pass yield of methyl alcohol.
The described catalyst that is used for hydrogenation of carbon dioxide to generate methanol comprises master metal component and CNT based nano-material promoter, the master metal component is Cu, Zn, Zr, CNT based nano-material promoter is the multi-walled carbon nano-tubes (y%Co/CNT) that multi-walled carbon nano-tubes (CNT) or metallic cobalt are modified, and chemical formulation is: Cu
iZn
jZr
k-x% (CNT or y%Co/CNT), subscript i, j, k are the molar ratio coefficient of associated metal elemental constituent in the Cu-Zn-Zr major constituent in the formula, x% is the mass percent of CNT based nano-material promoter in catalyst, and y% is the mass percent of Co in y%Co/CNT.
The mass percent of each component is respectively in the catalyst: Zn:5%～20%, preferred 8%～16%; Zr:25%～50%, preferred 30%～44%; CNT based nano-material promoter 1%～18%, preferred 8%～16%; Surplus is Cu.
When CNT based nano-material promoter was y%Co/CNT, the mass percent y% of metal Co was 1%～10%, preferred 3%～8%.
The outer tube diameter of above-mentioned CNT can be 10～60nm, and interior caliber can be 2～12nm, phosphorus content 〉=95%, graphite-like carbon content 〉=80%, specific area 100～250m
2/ g; Preferred outer tube diameter is 10～50nm, interior caliber 2.5～9nm, phosphorus content 〉=98%, graphite-like carbon content 〉=85%, specific area 120～200m
2/ g.
The described Preparation of catalysts method that is used for hydrogenation of carbon dioxide to generate methanol may further comprise the steps:
1) copper nitrate, zinc nitrate and the zirconyl nitrate three with amount of calculation mixes, and adds deionized water and makes solution A;
2) sodium carbonate of amount of calculation is dissolved in deionized water and makes solution B;
3) solution A and solution B injected in the reaction vessel that is equipped with amount of calculation CNT or y%Co/CNT carried out coprecipitation reaction, sediment;
4) sediment is filtered, the filter cake washing, centrifugal filtration, the filter cake oven dry, roasting again gets the catalyst that hydrogenation of carbon dioxide to generate methanol is used, i.e. Cu
iZn
jZr
k-x% (CNT or y%Co/CNT) (oxidation state).
In step 2) in, the amount of described deionized water preferably makes Na in the solution B
+Cu in the equivalent concentration of ion and the solution A
2+, Zn
2+, ZrO
2+The total yield concentration of metal ion equates.
In step 3), described solution A and solution B are injected in the reaction vessel that is equipped with amount of calculation CNT or y%Co/CNT carried out coprecipitation reaction, its concrete steps can be: under 65～75 ℃, with solution A and solution B constant speed, and stream inject and be equipped with in the reaction vessel of amount of calculation CNT or y%Co/CNT, under 65～75 ℃ of constant temperature, stirring condition, carry out coprecipitation reaction, the pH value that keeps the liquid bed of material is 6.5～8.0, and the reinforced back of finishing continues to stir 0.5～1h, allows it reduce to room temperature naturally then.
In step 4), described filter cake washing can adopt filter cake to wash to the electrical conductivity of filtrate consistent with deionized water through deionized water; The temperature of described oven dry can be 105～115 ℃, and the time of oven dry can be 5～6h; Described roasting can be at pure N
2300～360 ℃ of roasting temperature 2～4h in the atmosphere.
The multi-walled carbon nano-tubes (y%Co/CNT) that described metallic cobalt is modified can adopt polyalcohol liquid phase microwave to help the preparation of electronation sedimentation, and its concrete steps are:
1) cobalt acetate with amount of calculation joins in the ethylene glycol, is stirred to cobalt acetate and dissolves fully, adds concentration and be pH value that the KOH aqueous solution of 4mol/L regulates feed liquid 9.0～9.5, magnetic agitation 30～40min;
2) CNT of adding amount of calculation carries out the electronation deposition reaction of cobalt acetate by the heating using microwave program behind ultrasonic processing 20～40min, and reaction is finished, and cooling is filtered, and filters Pie and is neutral after acetone and deionized water wash to filtrate earlier; The heating using microwave program is carry out microwave radiation heating 100s, stops to heat 20s, heats 10s again, stops to heat 20s, heats 10s again;
3) filter Pie promptly gets the multi-walled carbon nano-tubes (y%Co/CNT) that y% modifies at the metallic cobalt of 1%～10% scope in 105～115 ℃ of oven dry down.
The described catalyst of hydrogenation of carbon dioxide to generate methanol that is used for is to CO
2The catalytically active assessment of preparing methanol by hydrogenation carries out on pressurization static bed continuous flow reactor-GC combined system.Each evaluation test catalyst amount is 0.2～0.5g.CO
2Hydro-conversion is the 2.0～5.0MPa that is reflected at of methyl alcohol, and 190～270 ℃, reactor feed gas consists of V (H
2)/V (CO
2)/V (N
2)=69/23/8, corresponding air speed are to carry out under the reaction condition of GHSV=3000～25000mL/ (hg).Before the reaction, oxidation forerunner attitude catalyst often forces down earlier hydrogen reduction gas (V (H
2)/V (N
2)=5/95, air speed are 3600mL/ (hg)) carry out original position prereduction by certain heating schedule, last 16h, after to transfer to reaction temperature required, switch to import reactor feed gas and under uniform temperature, pressure, unstripped gas air speed condition, react.The reaction end gas of discharging from reactor outlet unloads immediately to normal pressure, take a sample through utilidor (temperature remains on 110 ℃) direct sending gas chromatograph six-way valve, unite by the thermal conductivity detector (TCD) (TCD) of GC-950 type gas chromatograph (Shanghai sea glad chromatographic apparatus company) and hydrogen flame detector (FID) and do on-line analysis.The former chromatographic column filler is TDX-201 carbon molecular sieve (a Tianjin chemical reagent Co., Ltd product), and column length 1.2m uses H
2Do carrier gas, at room temperature work, be used for separating detection CO, N
2(as interior mark) and CO
2Latter's chromatographic column filler is Porapak Q-S (a USA product), and column length 2m uses N
2Do carrier gas, operating temperature remains on 130 ℃, is used for separating detection lower carbon number hydrocarbons, low-carbon alcohol ether and other oxygen-bearing organic matter.CO
2Conversion ratio and against the current the gas conversion side reaction generate the selectivity of CO by N
2The internal standard method measuring and calculating, CO such as alcohol, ether, hydrocarbon
2The C-based selective of hydrogenation carbonaceous products and space-time yield are calculated by C base normalization method.The prepared catalyst activity of the present invention is high and stablize the selectivity height of product methyl alcohol, CO
2The space-time yield of hydrogenation conversion and methyl alcohol is all apparently higher than existing similar catalyst, and simple for production, good reproducibility.
The specific embodiment
The invention will be further described by embodiment below.
Embodiment 1
Cobalt acetate (Co (CH with 0.311g
3COO)
24H
2O, purity is the AR level) drop into and to fill in the beaker of 50mL ethylene glycol (purity is the AR level), being stirred to cobalt acetate dissolves fully, add an amount of KOH aqueous solution (concentration is 4mol/L), with the pH value of regulating and keeping feed liquid in 9.3～9.4 scopes, stir 30min, the back adds the CNT of 1.228g, feed liquid is through ultrasonic processing 30min, after be placed on micro-wave oven (2450MHz, 640W), carry out microwave radiation heating 100s stops to heat 20s, heat 10s again, repeat " stopping to heat 20s; heat 10s again " operation once, the back is taken out feed liquid and is placed cold bath allow its rapid cooling, and after filtration, filter Pie is earlier after acetone and deionized water washing, be washed till filtrate and be neutral, under 110 ℃ of temperature, dry, promptly get the CNT that metal Co is modified; Analyzing definite its stoichiometric equation through EDX is 4.5%Co/CNT.
Cu (NO with 7.00g
3)
23H
2O, 2.16g Zn (NO
3)
26H
2O and 4.84g ZrO (NO
3)
22H
2O (purity is the AR level) three mixes, and adds the 100mL deionized water and makes solution A; Other is with the Na of 5.77g
2CO
3(purity is the AR level) is dissolved in the deionized water of 100mL and makes solution B; Under 70 ℃ of temperature, solution A and B constant speed and drip are added in the beaker of 4.5%Co/CNT that 0.570g is housed in advance and 200mL deionized water, at 70 ℃ of constant temperature, constantly stir and keep the pH value of the liquid bed of material under the condition about 7.5, to carry out coprecipitation reaction, reinforced finishing continues to stir 0.5h, after stop heating and allow it reduce to room temperature naturally, sediment is through centrifugal filtration, deionized water washs to filtrate and is neutral, and filter cake is dried 6h under 110 ℃ of temperature, pure N
2350 ℃ of roasting temperature 2h in the atmosphere, promptly getting stoichiometric equation is Cu
8Zn
2Zr
5The catalyst of-12.5% (4.5%Co/CNT) (oxidation state).
Catalyst is to CO
2The catalytically active assessment of preparing methanol by hydrogenation carries out on pressurization static bed continuous flow reactor (φ 8mm)-gas-chromatography combined system.Catalyst amount is 0.5g.Before the reaction, oxidized catalyst is at normal pressure, low hydrogen reducing gases (V (H
2)/V (N
2)=5/95, flow velocity is 3600mL/h) in carry out original position prereduction by certain heating schedule, last 16h, after transfer to the reaction temperature required, switch to import material synthesis gas and react, product is done on-line analysis by the GC-950 type gas chromatograph that is equipped with TCD and FID dual detector, two chromatographic columns.The evaluation result demonstration, at 2.0MPa, 230 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and 3000mL/ (hg), CO
2Hydrogenation conversion reaches 7.2%, and the selectivity of methyl alcohol is 98.0% in the hydrogenation products, and corresponding methyl alcohol space-time yield is 70mg/ (hg); And at 5.0MPa, 250 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and GHSV=25000mL/ (hg), CO
2Hydrogenation conversion reaches 8.7%, and the selectivity of methyl alcohol is 97.9% in the hydrogenation products, and corresponding methyl alcohol space-time yield is 699mg/ (hg), is the former matrix catalyst (Cu that does not add CNT-promoter
8Zn
2Zr
5) 1.1 times (seeing Table 1) of (former matrix Preparation of catalysts method the is the same) space-time yield of methyl alcohol under same reaction conditions (638mg/ (hg)).
The reactivity of hydrogenation of carbon dioxide to generate methanol on table 1 catalyst
Reaction condition: a) 2.0MPa, 230 ℃, V (H
2)/V (CO
2)/V (N
2)=69/23/8, GHSV=3000mL/ (hg);
b)5.0MPa，250℃，V(H
2)/V(CO
2)/V(N
2)＝69/23/8，GHSV＝25000mL/(h·g)
Embodiment 2
Cu (NO with 7.00g
3)
23H
2O, 2.16g Zn (NO
3)
26H
2O and 4.84g ZrO (NO
3)
22H
2O (purity is the AR level) three mixes, and adds the 100mL deionized water and makes solution A; Other is with the Na of 5.77g
2CO
3(purity is the AR level) is dissolved in the deionized water of 100mL and makes solution B; Under 70 ℃ of temperature, solution A and B constant speed and drip added be equipped with in advance in the beaker of 0.570g CNT and 200mL deionized water, at 70 ℃ of constant temperature, constantly stir and keep the pH value of the liquid bed of material under the condition about 7.5, to carry out coprecipitation reaction, reinforced finishing continues to stir 0.5h, after stop heating and allow it reduce to room temperature naturally, sediment is through centrifugal filtration, deionized water washs, is washed till filtrate and is neutral, and filter cake is dried 6h under 110 ℃ of temperature, pure N
2350 ℃ of roasting temperature 2h in the atmosphere, promptly getting stoichiometric equation is Cu
8Zn
2Zr
5The catalyst of-12.5%CNT (oxidation state).
Catalyst is to CO
2The catalytically active assessment experiment of preparing methanol by hydrogenation is with embodiment 1.The evaluation result demonstration, at 5.0MPa, 250 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and 25000mL/ (hg), CO
2Hydrogenation conversion reaches 8.2%, and the selectivity of methyl alcohol is 99.6% in the hydrogenation products, and corresponding methyl alcohol space-time yield reaches 671mg/ (hg) (seeing Table 2).
Embodiment 3
Cu (NO with 7.00g
3)
23H
2O, 0.54g Zn (NO
3)
26H
2O and 4.84g ZrO (NO
3)
22H
2O (purity is the AR level) three mixes, and adds the 100mL deionized water and makes solution A; Other is with the Na of 5.19g
2CO
3(purity is the AR level) is dissolved in the deionized water of 100mL and makes solution B; Under 70 ℃ of temperature, solution A and B constant speed and drip are added in the beaker of 4.5%Co/CNT that 0.520g is housed in advance and 200mL deionized water, at 70 ℃ of constant temperature, constantly stir and keep the pH value of the liquid bed of material under the condition about 7.5, to carry out coprecipitation reaction, reinforced finishing continues to stir 0.5h, after stop heating and allow it reduce to room temperature naturally, sediment is through centrifugal filtration, deionized water washs, is washed till filtrate and is neutral, and filter cake is dried 6h under 110 ℃ of temperature, pure N
2350 ℃ of roasting temperature 2h in the atmosphere, promptly getting stoichiometric equation is Cu
8Zn
0.5Zr
5The catalyst of-12.5% (4.5%Co/CNT) (oxidation state).
Catalyst is to CO
2The catalytically active assessment experiment of preparing methanol by hydrogenation is with embodiment 1.The evaluation result demonstration, at 2.0MPa, 230 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and 3000mL/ (hg), CO
2Hydrogenation conversion reaches 5.1%, and the selectivity of methyl alcohol is 99.0% in the hydrogenation products, and corresponding methyl alcohol space-time yield is 50mg/ (hg) (seeing Table 2).
Embodiment 4
Cu (NO with 7.00g
3)
23H
2O, 4.31g Zn (NO
3)
26H
2O and 4.84g ZrO (NO
3)
22H
2O (purity is the AR level) three mixes, and adds the 100mL deionized water and makes solution A; Other is with the Na of 6.53g
2CO
3(purity is the AR level) is dissolved in the deionized water of 100mL and makes solution B; Under 70 ℃ of temperature, solution A and B constant speed and drip are added in the beaker of 4.5%Co/CNT that 0.636g is housed in advance and 200mL deionized water, at 70 ℃ of constant temperature, constantly stir and keep the pH value of the liquid bed of material under the condition about 7.5, to carry out coprecipitation reaction, reinforced finishing continues to stir 0.5h, after stop heating and allow it reduce to room temperature naturally, sediment is through centrifugal filtration, deionized water washs, is washed till filtrate and is neutral, and filter cake is dried 6h under 110 ℃ of temperature, pure N
2350 ℃ of roasting temperature 2h in the atmosphere, promptly getting stoichiometric equation is Cu
8Zn
4Zr
5The catalyst of-12.5% (4.5%Co/CNT) (oxidation state).
Catalyst is to CO
2The catalytically active assessment experiment of preparing methanol by hydrogenation is with embodiment 1.The evaluation result demonstration, at 2.0MPa, 230 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and 3000mL/ (hg), CO
2Hydrogenation conversion reaches 6.1%, and the selectivity of methyl alcohol is 96.0% in the hydrogenation products, and corresponding methyl alcohol space-time yield reaches 58mg/ (hg) (seeing Table 2).
Embodiment 5
Cu (NO with 8.19g
3)
23H
2O, 2.52g Zn (NO
3)
26H
2O and 3.39g ZrO (NO
3)
22H
2O (purity is the AR level) three mixes, and adds the 100mL deionized water and makes solution A; Other is with the Na of 5.84g
2CO
3(purity is the AR level) is dissolved in the deionized water of 100mL and makes solution B; Under 70 ℃ of temperature, solution A and B constant speed and drip are added in the beaker of 4.5%Co/CNT that 0.550g is housed in advance and 200mL deionized water, at 70 ℃ of constant temperature, constantly stir and keep the pH value of the liquid bed of material under the condition about 7.5, to carry out coprecipitation reaction, reinforced finishing continues to stir 0.5h, after stop heating and allow it reduce to room temperature naturally, sediment is through centrifugal filtration, deionized water washs, is washed till filtrate and is neutral, and filter cake is dried 6h under 110 ℃ of temperature, pure N
2350 ℃ of roasting temperature 2h in the atmosphere, promptly getting stoichiometric equation is Cu
8Zn
2Zr
3The catalyst of-12.5% (4.5%Co/CNT) (oxidation state).
Catalyst is to CO
2The catalytically active assessment experiment of preparing methanol by hydrogenation is with embodiment 1.The evaluation result demonstration, at 2.0MPa, 230 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and 3000mL/ (hg), CO
2Hydrogenation conversion reaches 6.5%, and the selectivity of methyl alcohol is 97.0% in the hydrogenation products, and corresponding methyl alcohol space-time yield reaches 62mg/ (hg) (seeing Table 2).
Embodiment 6
Cu (NO with 6.14g
3)
23H
2O, 1.89g Zn (NO
3)
26H
2O and 5.93g ZrO (NO
3)
22H
2O (purity is the AR level) three mixes, and adds the 100mL deionized water and makes solution A; Other is with the Na of 5.72g
2CO
3(purity is the AR level) is dissolved in the deionized water of 100mL and makes solution B; Under 70 ℃ of temperature, solution A and B constant speed and drip are added in the beaker of 4.5%Co/CNT that 0.583g is housed in advance and 200mL deionized water, at 70 ℃ of constant temperature, constantly stir and keep the pH value of the liquid bed of material under the condition about 7.5, to carry out coprecipitation reaction, reinforced finishing continues to stir 0.5h, after stop heating and allow it reduce to room temperature naturally, sediment is through centrifugal filtration, deionized water washs, is washed till filtrate and is neutral, and filter cake is dried 6h under 110 ℃ of temperature, pure N
2350 ℃ of roasting temperature 2h in the atmosphere, promptly getting stoichiometric equation is Cu
8Zn
2Zr
7The catalyst of-12.5% (4.5%Co/CNT) (oxidation state).
Catalyst is to CO
2The catalytically active assessment experiment of preparing methanol by hydrogenation is with embodiment 1.The evaluation result demonstration, at 2.0MPa, 230 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and 3000mL/ (hg), CO
2Hydrogenation conversion reaches 5.6%, and the selectivity of methyl alcohol is 98.0% in the hydrogenation products, and corresponding methyl alcohol space-time yield reaches 54mg/ (hg) (seeing Table 2).
Embodiment 7
Cu (NO with 7.00g
3)
23H
2O, 2.16g Zn (NO
3)
26H
2O and 4.84g ZrO (NO
3)
22H
2O (purity is the AR level) three mixes, and adds the 100mL deionized water and makes solution A; Other is with the Na of 5.77g
2CO
3(purity is the AR level) is dissolved in the deionized water of 100mL and makes solution B; Under 70 ℃ of temperature, solution A and B constant speed and drip are added in the beaker of 4.5%Co/CNT that 0.327g is housed in advance and 200mL deionized water, at 70 ℃ of constant temperature, constantly stir and keep the pH value of the liquid bed of material under the condition about 7.5, to carry out coprecipitation reaction, reinforced finishing continues to stir 0.5h, after stop heating and allow it reduce to room temperature naturally, sediment is through centrifugal filtration, deionized water washs, is washed till filtrate and is neutral, and filter cake is dried 6h under 110 ℃ of temperature, pure N
2350 ℃ of roasting temperature 2h in the atmosphere, promptly getting stoichiometric equation is Cu
8Zn
2Zr
5The catalyst of-7.6% (4.5%Co/CNT) (oxidation state).
Catalyst is to CO
2The catalytically active assessment experiment of preparing methanol by hydrogenation is with embodiment 1.The evaluation result demonstration, at 2.0MPa, 230 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and 3000mL/ (hg), CO
2Hydrogenation conversion reaches 5.9%, and the selectivity of methyl alcohol is 99.0% in the hydrogenation products, and corresponding methyl alcohol space-time yield reaches 58mg/ (hg) (seeing Table 2).
Embodiment 8
Cu (NO with 7.00g
3)
23H
2O, 2.16g Zn (NO
3)
26H
2O and 4.84g ZrO (NO
3)
22H
2O (purity is the AR level) three mixes, and adds the 100mL deionized water and makes solution A; Other is with the Na of 5.77g
2CO
3(purity is the AR level) is dissolved in the deionized water of 100mL and makes solution B; Under 70 ℃ of temperature, solution A and B constant speed and drip are added in the beaker of 4.5%Co/CNT that 0.835g is housed in advance and 200mL deionized water, at 70 ℃ of constant temperature, constantly stir and keep the pH value of the liquid bed of material under the condition about 7.5, to carry out coprecipitation reaction, reinforced finishing continues to stir 0.5h, after stop heating and allow it reduce to room temperature naturally, sediment is through centrifugal filtration, deionized water washs, is washed till filtrate and is neutral, and filter cake is dried 6h under 110 ℃ of temperature, pure N
2350 ℃ of roasting temperature 2h in the atmosphere, promptly getting stoichiometric equation is Cu
8Zn
2Zr
5The catalyst of-17.4% (4.5%Co/CNT) (oxidation state).
Catalyst is to CO
2The catalytically active assessment experiment of preparing methanol by hydrogenation is with embodiment 1.The evaluation result demonstration, at 2.0MPa, 230 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and 3000mL/ (hg), CO
2Hydrogenation conversion reaches 5.8%, and the selectivity of methyl alcohol is 96.0% in the hydrogenation products, and corresponding methyl alcohol space-time yield reaches 55mg/ (hg) (seeing Table 2).
Embodiment 9
Prepare Co by embodiment 1 described method and modify CNT, used Co (CH
3COO)
24H
2O (purity is the AR level) and the inventory of CNT are respectively 0.311g and 3.683g, and analyzing the stoichiometric equation of determining obtained Co modification CNT through EDX is 1.5%Co/CNT.
Cu (NO with 7.00g
3)
23H
2O, 2.16g Zn (NO
3)
26H
2O and 4.84g ZrO (NO
3)
22H
2O (purity is the AR level) three mixes, and adds the 100mL deionized water and makes solution A; Other is with the Na of 5.77g
2CO
3(purity is the AR level) is dissolved in the deionized water of 100mL and makes solution B; Under 70 ℃ of temperature, solution A and B constant speed and drip are added in the beaker of 1.5%Co/CNT that 0.570g is housed in advance and 200mL deionized water, at 70 ℃ of constant temperature, constantly stir and keep the pH value of the liquid bed of material under the condition about 7.5, to carry out coprecipitation reaction, reinforced finishing continues to stir 0.5h, after stop heating and allow it reduce to room temperature naturally, sediment is through centrifugal filtration, deionized water washs, is washed till filtrate and is neutral, and filter cake is dried 6h under 110 ℃ of temperature, pure N
2350 ℃ of roasting temperature 2h in the atmosphere, promptly getting stoichiometric equation is Cu
8Zn
2Zr
5The catalyst of-12.5% (1.5%Co/CNT) (oxidation state).
Catalyst is to CO
2The catalytically active assessment experiment of preparing methanol by hydrogenation is with embodiment 1.The evaluation result demonstration, at 5.0MPa, 250 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and 25000mL/ (hg), CO
2Hydrogenation conversion reaches 6.3%, and the selectivity of methyl alcohol is 99.3% in the hydrogenation products, and corresponding methyl alcohol space-time yield reaches 514mg/ (hg) (seeing Table 2).
Embodiment 10
Method by embodiment 1 prepares Co modification CNT, Co (CH
3COO)
24H
2The inventory of the CNT of O (purity is the AR level) and purified processing is respectively 0.311g and 0.921g, and analyzing the stoichiometric equation of determining obtained Co modification CNT through EDX is 6.0%/CNT.
Cu (NO with 7.00g
3)
23H
2O, 2.16g Zn (NO
3)
26H
2O and 4.84g ZrO (NO
3)
22H
2O (purity is the AR level) three mixes, and adds the 100mL deionized water and makes solution A; Other is with the Na of 5.77g
2CO
3(purity is the AR level) is dissolved in the deionized water of 100mL and makes solution B; Under 70 ℃ of temperature, solution A and B constant speed and drip are added in the beaker of 6.0%Co/CNT that 0.570g is housed in advance and 200mL deionized water, at 70 ℃ of constant temperature, constantly stir and keep the pH value of the liquid bed of material under the condition about 7.5, to carry out coprecipitation reaction, reinforced finishing continues to stir 0.5h, after stop heating and allow it reduce to room temperature naturally, sediment is through centrifugal filtration, deionized water washs, is washed till filtrate and is neutral, and filter cake is dried 6h under 110 ℃ of temperature, pure N
2350 ℃ of roasting temperature 2h in the atmosphere, promptly getting stoichiometric equation is Cu
8Zn
2Zr
5The catalyst of-12.5% (6.0%Co/CNT) (oxidation state).
Catalyst is to CO
2The catalytically active assessment experiment of preparing methanol by hydrogenation is with embodiment 1.The evaluation result demonstration, at 5.0MPa, 250 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and 25000mL/ (hg), CO
2Hydrogenation conversion reaches 6.7%, and the selectivity of methyl alcohol is 98.7% in the hydrogenation products, and corresponding methyl alcohol space-time yield reaches 543mg/ (hg) (seeing Table 2).
Embodiment 11
Prepare Co by embodiment 1 described method and modify CNT, used Co (CH
3COO)
24H
2O (purity is the AR level) and the inventory of CNT are respectively 0.311g and 0.737g, and analyzing the stoichiometric equation of determining obtained Co modification CNT through EDX is 7.5%Co/CNT.
Cu (NO with 7.00g
3)
23H
2O, 2.16g Zn (NO
3)
26H
2O and 4.84g ZrO (NO
3)
22H
2O (purity is the AR level) three mixes, and adds the 100mL deionized water and makes solution A; Other is with the Na of 5.77g
2CO
3(purity is the AR level) is dissolved in the deionized water of 100mL and makes solution B; Under 70 ℃ of temperature, solution A and B constant speed and drip are added in the beaker of 7.5%Co/CNT that 0.570g is housed in advance and 200mL deionized water, at 70 ℃ of constant temperature, constantly stir and keep the pH value of the liquid bed of material under the condition about 7.5, to carry out coprecipitation reaction, reinforced finishing continues to stir 0.5h, after stop heating and allow it reduce to room temperature naturally, sediment is through centrifugal filtration, deionized water washs, is washed till filtrate and is neutral, and filter cake is dried 6h under 110 ℃ of temperature, pure N
2350 ℃ of roasting temperature 2h in the atmosphere, promptly getting stoichiometric equation is Cu
8Zn
2Zr
5The catalyst of-12.5% (7.5%Co/CNT) (oxidation state).
Catalyst is to CO
2The catalytically active assessment experiment of preparing methanol by hydrogenation is with embodiment 1.The evaluation result demonstration, at 5.0MPa, 250 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and 25000mL/ (hg), CO
2Hydrogenation conversion reaches 6.5%, and the selectivity of methyl alcohol is 97.8% in the hydrogenation products, and corresponding methyl alcohol space-time yield reaches 522mg/ (hg) (seeing Table 2).
Embodiment 12
Cu (NO with 7.00g
3)
23H
2O, 2.16g Zn (NO
3)
26H
2O and 4.84g ZrO (NO
3)
22H
2O (purity is the AR level) three mixes, and adds the 100mL deionized water and makes solution A; Other is with the Na of 5.77g
2CO
3(purity is the AR level) is dissolved in the deionized water of 100mL and makes solution B; Under 70 ℃ of temperature, solution A and B constant speed and drip added be equipped with in advance in the beaker of 0.570g CNT and 200mL deionized water, at 70 ℃ of constant temperature, constantly stir and keep the pH value of the liquid bed of material under the condition about 7.5, to carry out coprecipitation reaction, reinforced finishing continues to stir 0.5h, after stop heating and allow it reduce to room temperature naturally, sediment is through centrifugal filtration, deionized water washs, is washed till filtrate and is neutral, and filter cake is dried 6h under 110 ℃ of temperature, pure N
2300 ℃ of roasting temperature 2h in the atmosphere, promptly getting stoichiometric equation is Cu
8Zn
2Zr
5The catalyst of-12.5%CNT (oxidation state).
Catalyst is to CO
2The catalytically active assessment experiment of preparing methanol by hydrogenation is with embodiment 1.The evaluation result demonstration, at 2.0MPa, 230 ℃, V (H
2)/V (CO
2)/V (N
2Under the reaction condition of)=69/23/8 and 3000mL/ (hg), CO
2Hydrogenation conversion reaches 6.4%, and the selectivity of methyl alcohol is 96.0% in the hydrogenation products, and corresponding methyl alcohol space-time yield reaches 60mg/ (hg) (seeing Table 2).
Claims (10)
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