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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- 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
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Abstract
The invention relates to a catalyst, in particular to the catalyst for hydrogenation of carbon dioxide to generate methanol and a preparation method thereof. A carbon nanotube-based material is adopted as an accelerating agent. When being used for the catalytic hydrogenation of the carbon dioxide to generate the methanol, the catalyst can effectively increase the hydrogenation converting rate of the carbon dioxide and the one-path yield rate of the methanol. The catalyst comprises main metal components and the accelerating agent of the carbon nanotube-based material. The main metal components include Cu, Zn and Or. The accelerating agent of the carbon nanotube-based material means CNT or y% Co/CNT, and the chemical formula is CuiZnjZrk-x% (CNT or y% Co/CNT). The mass percent of each component is as follows: Zn: 5 to 20%; Zr: 25 to 50%; the accelerating agent of the carbon nanotube-based material: 1 to 18%; and the rest is Cu. The catalyst is prepared through coprecipitation. A multi-wall carbon nanotube modified by metal cobalt is prepared by utilizing liquid-phase microwaves of polyalcohol to assist in chemical reduction and 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)
1. the catalyst that is used for hydrogenation of carbon dioxide to generate methanol, it is characterized in that comprising 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 that multi-walled carbon nano-tubes or metallic cobalt are modified, and chemical formula 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.
2. the catalyst that is used for hydrogenation of carbon dioxide to generate methanol as claimed in claim 1 is characterized in that the mass percent of described master metal component and each component of CNT based nano-material promoter is respectively 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.
3. the catalyst that is used for hydrogenation of carbon dioxide to generate methanol as claimed in claim 1 or 2 is characterized in that when CNT based nano-material promoter was y%Co/CNT, the mass percent y% of metal Co was 1%～10%, preferred 3%～8%.
4. the catalyst that is used for hydrogenation of carbon dioxide to generate methanol as claimed in claim 1, the outer tube diameter that it is characterized in that described multi-walled carbon nano-tubes is 10～60nm, and interior caliber is 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.
5. the Preparation of catalysts method that is used for hydrogenation of carbon dioxide to generate methanol as claimed in claim 1 is characterized in that 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).
6. the Preparation of catalysts method that is used for hydrogenation of carbon dioxide to generate methanol as claimed in claim 5 is characterized in that in step 2) in, the amount of described deionized water makes Na in the solution B
+Cu in the equivalent concentration of ion and the solution A
2+, Zn
2+, Zr0
2+The total yield concentration of metal ion equates.
7. the Preparation of catalysts method that is used for hydrogenation of carbon dioxide to generate methanol as claimed in claim 5, it is characterized in that 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 are: under 65～75 ℃, with solution A and solution B constant speed, and the stream injection is equipped with in the reaction vessel of amount of calculation CNT or y%Co/CNT, at 65～75 ℃ of constant temperature, carry out coprecipitation reaction under the stirring condition, the pH value that keeps the liquid bed of material is 6.5～8.0, the reinforced back of finishing continues to stir 0.5～1h, allows it reduce to room temperature naturally then.
8. the Preparation of catalysts method that is used for hydrogenation of carbon dioxide to generate methanol as claimed in claim 5 is characterized in that in step 4), and described filter cake washing adopts filter cake to wash to the electrical conductivity of filtrate consistent with deionized water through deionized water.
9. the Preparation of catalysts method that is used for hydrogenation of carbon dioxide to generate methanol as claimed in claim 5 is characterized in that in step 4) the temperature of described oven dry is 105～115 ℃, and the time of oven dry is 5～6h; Described roasting is at pure N
2300～360 ℃ of roasting temperature 2～4h in the atmosphere.
10. the Preparation of catalysts method that is used for hydrogenation of carbon dioxide to generate methanol as claimed in claim 5 is characterized in that the multi-walled carbon nano-tubes that described metallic cobalt is modified adopts 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.
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