CN104069870A - Catalyst for preparing methyl alcohol from syngas as well as preparation method and application of catalyst - Google Patents
Catalyst for preparing methyl alcohol from syngas as well as preparation method and application of catalyst Download PDFInfo
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- CN104069870A CN104069870A CN201410318874.1A CN201410318874A CN104069870A CN 104069870 A CN104069870 A CN 104069870A CN 201410318874 A CN201410318874 A CN 201410318874A CN 104069870 A CN104069870 A CN 104069870A
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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 for preparing methyl alcohol from syngas. The preparation method of the catalyst comprises the following steps: putting a CuO/ZnO/Al2O3 catalyst into a container, adding a rhodium salt solution with the same volume, immersing for 6-48 h, and then drying for 8-16 h at 80-120 DEG C; roasting the obtained product for 3-6 h at 300-400 DEG C to obtain the catalyst comprising 40-65 percent of Cu, 25-40 percent of Zn, 2-20 percent of Al and 0.1-0.2 percent of Rh in molar ratio. The catalyst has the advantages of high activity and good stability.
Description
Technical field
The invention belongs to a kind of preparation method and application of catalyst, be specifically related to a kind of copper rhodium base catalyst and preparation method and application of synthesising gas systeming carbinol.
Background technology
Methyl alcohol is a kind of important basic chemical industry raw material, and Downstream Products of Methanol is at chemical industry, pharmacy, and the various fields such as the energy have a wide range of applications.Take synthesis gas as raw material methyl alcohol processed be one of important channel of coal high-efficiency clean utilization.At present, the catalyst of synthesizing methanol is mainly CuO/ZnO/Al
2o
3catalyst, Cu is as activated centre, and ZnO, as carrier, has played dispersion Cu species, prevents the effect of Cu sintering and loss, has synergy between Cu and ZnO simultaneously, contributes to form the Cu-Zn active sites of synthesizing methanol in catalyst.Al
2o
3contribute to improve decentralization and the specific area of catalyst, strengthened the heat endurance of catalyst simultaneously.But in existing copper-based catalysts evaluation result, synthesis gas conversion per pass is lower, it is the principal element of limiting catalyst activity.Further improving the conversion per pass of unstripped gas and the space-time yield of product, is to reduce industrial production cost, energy-saving and cost-reducing an urgent demand.
In order further to improve the activity of catalyst, at CuO/ZnO/Al
2o
3on the basis of catalyst, introduce the 4th component as auxiliary agent, to improve catalyst to CO and H
2absorption and activity function, reach the object that improves catalyst activity.Document (Peng Gao., et al., Journal of catalyst, 2013.298 (0): 51-60) report, at CuO/ZnO/Al
2o
3in catalyst, add Zr, effectively increased the specific area of catalyst and active specy Cu, promoted the dispersion of Cu, thereby strengthened catalyst to CO and H
2adsorption capacity.Chinese patent (publication number CN1810357A) discloses a kind of catalst for synthesis of methanol and preparation method thereof, and the method is at CuO/ZnO/Al
2o
3in catalyst, introduce Li, CO conversion ratio can reach 16～30%, and methyl alcohol space-time yield is 326～678mg/ (ml
cath).
Because unstripped gas is CO/CO in absorption, the activation of catalyst surface
2the committed step of hydrogenation reaction, and Rh is stronger to CO adsorption activation ability, the highly active promotion CO hydrogenation of energy, and Rh can promote H
2absorption dissociate.Therefore, using Rh as catalytic active component, can effectively improve the activity of CO hydrogenation reaction.Chinese patent (publication number CN1390638A) discloses a kind of carbon nanotube loaded rhodium base catalyst for the synthesis of methyl alcohol, utilize Rh to the storage hydrogen of CO adsorption activation ability and carrier carbon nanotube and transmit proton and characteristic electron, improved the activity of catalyst synthesizing methanol, the catalytic activity of catalyst is 1.9 times of industrial NC207 catalyst, when Rh load capacity is 5wt%, methyl alcohol space-time yield reaches maximum 411mg/ (g
cath).And the disclosed a kind of rhodium base catalyst of preparing MAS for the synthesis of gas of Chinese patent (publication number CN102029173A), that Rh is loaded on the molecular sieve with regular hexagonal pore structure, discovery can improve the selective of the conversion ratio of CO and ethanol, but the main methane gas that generates of reaction, methyl alcohol selectively below 10%.Visible, carrier is very large on the catalytic performance impact of rhodium base catalyst, and rhodium base catalyst catalyze and synthesize gas synthesizing methanol activity neither be very high.
In sum, CuO/ZnO/Al
2o
3catalyst has been compared comparatively significantly advantage in the synthetic field of methyl alcohol with other types catalyst, in order further to improve the activity of catalyst, need to increase auxiliary agent and improve the adsorption activation ability of catalyst to CO.And Rh has stronger absorption and activation capacity to CO, but using the catalyst synthesizing methanol that Rh prepared as main active component, be subject to the impact of carrier very large, catalytic activity and stability neither be fine.
Summary of the invention
The copper rhodium base catalyst and the preparation method and application that the object of this invention is to provide the synthesising gas systeming carbinol of a kind of high activity and good stability.
The present invention adopts following technical scheme to realize: by rhodium salt solution impregnation at CuO/ZnO/Al
2o
3on catalyst, through drying roasting, obtain CuO-Rh
2o
3/ ZnO/Al
2o
3catalyst.
Catalyst of the present invention is comprised of copper rhodium zinc-aluminium metal oxide, and in metallic element, its mole consists of Cu40～65%, Zn25～40%, Al2～20%, Rh0.1～2%.
Catalyst of the present invention is prepared by following methods:
By CuO/ZnO/Al
2o
3catalyst is placed in container, adds equal-volume rhodium salting liquid, and dipping 6～48h is then dried 8～16h, then by products therefrom roasting 3～6h at 300～400 ℃, obtained CuO-Rh at 80～120 ℃
2o
3/ ZnO/Al
2o
3catalyst.
CuO/ZnO/Al as above
2o
3catalyst, for take a kind of of CuZnAl catalyst that Cu-Zn-Al is main component, may contain a small amount of Cr, Mg, V etc. and metal promoter simultaneously.The for example graduate C207 of Nanjing of China chemical industry group, C301, C302 catalyst series, the XNC-98 catalyst of southwest chemical research institute, the LC308 catalyst of Xibei Chemical Inst, 51 catalyst series of Britain ICI company, the LG104 catalyst of German Lurgi etc.
Rhodium salt as above is one or more of rhodium nitrate, rhodium acetate, acetylacetone,2,4-pentanedione rhodium, radium chloride and chlorine rhodium acid ammonium.
Catalyst of the present invention is in the technique for the synthesis of methyl alcohol, and its reduction and reaction process condition are: in reducing gases, consist of H
2/ N
2volume ratio is 1/10～3/10, reduces 6～12h under 200～350 ℃ of conditions of reduction temperature, 200～280 ℃ of reaction temperatures, and reaction pressure 3～6MPa, reaction raw materials forms: (H
2-CO
2)/(CO+CO
2) mol ratio is 1～4, air speed 500～20000L/ (kg
cath) under condition, react.
The technology of the present invention advantage is as follows:
(1) copper rhodium base catalyst of the present invention is by past CuO/ZnO/Al
2o
3in catalyst, introduce rhodium salt again roasting prepare, can utilize existing cheap industrial CuZnAl catalyst as raw material, only add a small amount of rhodium salt, just can significantly improve the yield of synthesising gas systeming carbinol.Catalyst preparation process is simple.
(2) in catalyst of the present invention, can significantly improve absorption, the activation capacity of CO adding of Rh, meanwhile, promote H
2at the generation hydrogen ion adsorption that dissociates of catalyst surface, further, can there is rapidly catalytic reaction methanol with the hydrogen atom dissociating in the CO after Rh adsorption activation in Cu-Zn active sites.The existence of Rh greatly reduces the activated energy barrier that synthesising gas systeming carbinol speed control step CO hydrogenation generates CHO intermediate reaction, thereby has accelerated rate of catalysis reaction, and CO conversion per pass obviously improves, and methyl alcohol space-time yield also significantly improves.
The specific embodiment
Comparative example 1
The graduate C302 catalyst of Nanjing of China chemical industry group.With metallic element note, its constitutive molar ratio is Cu:Zn:Al=56.8:36.5:6.7.
Catalyst reduction and appreciation condition are in Table 1, and catalyst activity the results are shown in Table 2.
Embodiment 1
10ml C302 catalyst is placed in to crucible, adds equal-volume 0.5mol/L Rh (NO
3)
3solution, dipping 12h is then dried 12h at 100 ℃, and roasting 4h at 350 ℃, obtains CuO-Rh
2o
3/ ZnO/Al
2o
3catalyst.With metallic element note, its constitutive molar ratio is Cu:Zn:Al:Rh=55.7:35.8:6.6:1.9.
Catalyst reduction and appreciation condition are in Table 1, and catalyst activity the results are shown in Table 2.
Embodiment 2
By the LG104 catalyst (CuO-V of 10ml Germany Lurgi
2o
5/ ZnO/Al
2o
3, with metallic element note, its constitutive molar ratio is Cu:Zn:Al:V=55.4:34.8:4.3:5.5) and be placed in crucible, add equal-volume 0.4mol/L RhCl
3solution, dipping 6h is then dried 10h at 110 ℃, and roasting 3h at 380 ℃, obtains CuO-Rh
2o
3-V
2o
5/ ZnO/Al
2o
3catalyst.With metallic element note, its constitutive molar ratio is Cu:Zn:Al:V:Rh=54.5:34.1:4.3:5.3:1.8.
Catalyst reduction and appreciation condition are in Table 1, and catalyst activity the results are shown in Table 2.
Embodiment 3
The graduate C301 catalyst of 20ml Nanjing of China chemical industry group (with metallic element note, its constitutive molar ratio is Cu:Zn:Al=62.5:31.2:6.3) is placed in to crucible, adds equal-volume 0.42mol/LRh (NO
3)
3solution, dipping 12h is then dried 14h at 110 ℃, and roasting 4h at 400 ℃, obtains CuO-Rh
2o
3/ ZnO/Al
2o
3catalyst.With metallic element note, its constitutive molar ratio is Cu:Zn:Al:Rh=62.0:30.9:6.3:0.8.
Catalyst reduction and appreciation condition are in Table 1, and catalyst activity the results are shown in Table 2.
Embodiment 4
The XNC-98 catalyst of 11ml southwest chemical research institute (with metallic element note, its constitutive molar ratio is Cu:Zn:Al=63.6:25.2:11.2) is placed in to crucible, adds equal-volume 0.6mol/L Rh (CH
3cOO)
3
Solution, dipping 36h is then dried 16h at 80 ℃, and roasting 5h at 350 ℃, obtains CuO-Rh
2o
3/ ZnO/Al
2o
3catalyst.With metallic element note, its constitutive molar ratio is Cu:Zn:Al:Rh=62.3:24.7:11.0:2.0.
Catalyst reduction and appreciation condition are in Table 1, and catalyst activity the results are shown in Table 2.
Embodiment 5
By the 51-7 catalyst (CuO-MgO/ZnO/Al of 50ml Britain ICI company
2o
3, with metallic element note, its constitutive molar ratio is Cu:Zn:Al:Mg=56.4:24.4:16.2:3.0) and be placed in crucible, add equal-volume 0.75mol/L Rh (C
5h
7o
2)
3solution, dipping 48h is then dried 12h at 100 ℃, and roasting 4h at 320 ℃, obtains CuO-Rh
2o
3-MgO/ZnO/Al
2o
3catalyst.With metallic element note, its constitutive molar ratio is Cu:Zn:Al:Mg:Rh=56.1:24.2:16.1:0.6.
Catalyst reduction and appreciation condition are in Table 1, and catalyst activity the results are shown in Table 2.
Embodiment 6
50ml C302 catalyst is placed in to crucible, adds equal-volume 1.5mol/L (NH
4)
3rhCl
6solution, dipping 24h is then dried 15h at 90 ℃, and roasting 6h at 300 ℃, obtains CuO-Rh
2o
3/ ZnO/Al
2o
3catalyst.With metallic element note, its constitutive molar ratio is Cu:Zn:Al:Rh=56.2:36.1:6.6:1.0.
Catalyst reduction and appreciation condition are in Table 1, and catalyst activity the results are shown in Table 2.
Table 1 catalyst reduction and reaction condition
The active result of table 2 catalyst synthesising gas systeming carbinol
| ? | CO conversion ratio (v%) | Methyl alcohol space-time yield (g/kg cat·h) | Deactivation rate (%/sky) |
| Comparative example 1 | 22.3 | 371.8 | 0.32 |
| Embodiment 1 | 40.5 | 778.9 | 0.05 |
| Embodiment 2 | 43.8 | 1633.4 | 0.03 |
| Embodiment 3 | 38.7 | 853.7 | 0.05 |
| Embodiment 4 | 46.3 | 1947.5 | 0.04 |
| Embodiment 5 | 37.4 | 762.4 | 0.02 |
| Embodiment 6 | 50.7 | 1097.6 | 0.03 |
Claims (7)
1. a catalyst for synthesising gas systeming carbinol, is characterized in that catalyst is comprised of copper rhodium zinc-aluminium metal oxide, and in metallic element, its mole consists of Cu 40～65%, and Zn 25～40%, and Al 2～20%, and Rh 0.1～2%.
2. the preparation method of the catalyst of a kind of synthesising gas systeming carbinol as claimed in claim 1, is characterized in that comprising the following steps:
By CuO/ZnO/Al
2o
3catalyst is placed in container, adds equal-volume rhodium salting liquid, and dipping 6～48h is then dried 8～16h, then by products therefrom roasting 3～6h at 300～400 ℃, obtained CuO-Rh at 80～120 ℃
2o
3/ ZnO/Al
2o
3catalyst.
3. the preparation method of the catalyst of a kind of synthesising gas systeming carbinol as claimed in claim 2, is characterized in that described CuO/ZnO/Al
2o
3catalyst is to comprise take the CuZnAl catalyst that Cu-Zn-Al is main component.
4. the preparation method of the catalyst of a kind of synthesising gas systeming carbinol as claimed in claim 3, is characterized in that described CuO/ZnO/Al
2o
3catalyst is to comprise take the copper zinc-aluminium that Cu-Zn-Al is main component, contains the metal promoter of a small amount of Cr, Mg, V simultaneously.
5. the preparation method of the catalyst of a kind of synthesising gas systeming carbinol as claimed in claim 3, is characterized in that described CuO/ZnO/Al
2o
3catalyst is the graduate C207 of Nanjing of China chemical industry group, C301 or C302 catalyst series, the XNC-98 catalyst of southwest chemical research institute, the LC308 catalyst of Xibei Chemical Inst, 51 catalyst series of Britain ICI company or the LG104 catalyst of German Lurgi.
6. the preparation method of the catalyst of a kind of synthesising gas systeming carbinol as claimed in claim 2, is characterized in that described rhodium salt is one or more in rhodium nitrate, rhodium acetate, acetylacetone,2,4-pentanedione rhodium, radium chloride, chlorine rhodium acid ammonium.
7. the application of the catalyst of a kind of synthesising gas systeming carbinol as claimed in claim 1, is characterized in that catalyst is in the technique for the synthesis of methyl alcohol, and its reduction and reaction process condition are: in reducing gases, consist of H
2/ N
2volume ratio is 1/10～3/10, reduces 6～12h under 200～350 ℃ of conditions of reduction temperature, 200～280 ℃ of reaction temperatures, and reaction pressure 3～6MPa, reaction raw materials forms: (H
2-CO
2)/(CO+CO
2) mol ratio is 1～4, air speed 500～20000 L/ (kg
cath) under condition, react.
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| CN201410318874.1A CN104069870B (en) | 2014-07-07 | 2014-07-07 | A kind of catalyst of synthesising gas systeming carbinol and preparation method and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437510A (en) * | 2014-10-30 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of copper-zinc-based catalyst for preparing methanol by virtue of CO2 hydrogenation |
| CN107970937A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of preparation method of carbon dioxide enriched synthesising gas systeming carbinol catalyst |
| CN109289855A (en) * | 2018-11-01 | 2019-02-01 | 四川天科技股份有限公司 | A kind of synthesis gas catalyst for methanol and preparation method thereof |
| CN109420509A (en) * | 2017-08-23 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of synthesising gas systeming carbinol bimetallic catalyst and preparation method thereof |
| CN110314698A (en) * | 2018-03-28 | 2019-10-11 | 中国科学院大连化学物理研究所 | A kind of preparation method of composite catalyst, preparation method and ethane |
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2014
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437510A (en) * | 2014-10-30 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of copper-zinc-based catalyst for preparing methanol by virtue of CO2 hydrogenation |
| CN107970937A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of preparation method of carbon dioxide enriched synthesising gas systeming carbinol catalyst |
| CN109420509A (en) * | 2017-08-23 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of synthesising gas systeming carbinol bimetallic catalyst and preparation method thereof |
| CN110314698A (en) * | 2018-03-28 | 2019-10-11 | 中国科学院大连化学物理研究所 | A kind of preparation method of composite catalyst, preparation method and ethane |
| CN110314698B (en) * | 2018-03-28 | 2021-03-02 | 中国科学院大连化学物理研究所 | Composite catalyst, preparation method thereof and preparation method of ethane |
| CN109289855A (en) * | 2018-11-01 | 2019-02-01 | 四川天科技股份有限公司 | A kind of synthesis gas catalyst for methanol and preparation method thereof |
| CN109289855B (en) * | 2018-11-01 | 2020-11-03 | 西南化工研究设计院有限公司 | Methanol catalyst for synthesis gas and preparation method thereof |
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| CN104069870B (en) | 2016-05-18 |
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