CN110052261A - A kind of catalysis carbon dioxide selectivity prepares solid catalyst and the application of methanol and carbon monoxide - Google Patents
A kind of catalysis carbon dioxide selectivity prepares solid catalyst and the application of methanol and carbon monoxide Download PDFInfo
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- CN110052261A CN110052261A CN201910460589.6A CN201910460589A CN110052261A CN 110052261 A CN110052261 A CN 110052261A CN 201910460589 A CN201910460589 A CN 201910460589A CN 110052261 A CN110052261 A CN 110052261A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- 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
Abstract
The invention discloses solid catalyst and applications that a kind of catalysis carbon dioxide selectivity prepares methanol and carbon monoxide, and the solid catalyst is with ZnO-ZrO2For carrier, In is loaded2O3, wherein the molar ratio of Zn and Zr is 1:6~6:1, and with ZnO-ZrO2The amount of substance be 100% meter, the load capacity of In is 1mol%~15mol%.The preparation method of catalyst of the present invention is simple, low in cost, it, which is catalyzed hydrogenation of carbon dioxide under cryogenic and prepares methanol selectivity, is up to 87%, catalysis hydrogenation of carbon dioxide prepares carbon monoxide selective and is up to 98% under the high temperature conditions, methanation byproduct reaction is controlled 1% or so, and titanium dioxide charcoal percent conversion is higher, same catalyst is realized by two kinds of preparation different products of temperature regulation, there is good prospects for commercial application.
Description
Technical field
The invention belongs to hydrogenation of carbon dioxides to utilize technical field, relate generally to a kind of hydrogenation of carbon dioxide prepare methanol and
The solid catalyst of carbon monoxide, and methanol and carbon monoxide are prepared using the catalysis of solid catalyst hydrogenation of carbon dioxide
Method.
Background technique
In recent years, CO caused by fossil energy largely consumes2Emission problem is increasingly prominent to the destruction of ecological environment,
Therefore, with CO2The relevant research and development of emission reduction, such as CO2It traps, seal up for safekeeping with technologies such as trans-utilizations by global height weight
Depending on.
Methanol is one of basic organic chemical industry raw material, itself is also good fuel, CO2Synthesizing methanol by hydrogenating is to utilize two
The important channel of carbonoxide, CO2The catalyst research of synthesizing methanol by hydrogenating it is most be CuZnO catalyst, research be mostly by
CuZnO is supported on Al2O3、ZrO2、SiO2、TiO2On equal carriers, and to catalyst addition Na, K, Ce, Cs, Ca, Zr, La, Mn,
The metals such as Ti, Th, Mg, Ba be modified as auxiliary agent (Handbook of Heterogeneous Catalysis Wiley,
2008,2920).And inverse water-gas catalyst mainly has copper-based catalysts, nickel-base catalyst, noble metal catalyst and other green woods
Material etc., copper-based catalysts are easy sintering and are oxidized since thermal stability is poor, therefore not applicable pyroreaction, and Ni-based urge
Agent is usually used in methanation catalyst, therefore when preparing carbon monoxide, is also easy to produce methane byproduct, noble metal catalyst cost
Height, easy-sintering inactivation (Appl.Catal.A:Gen.2004,257,97-106) under high temperature.Patent W09606064Al uses Zn-
Cr/Al2O3Although carbon dioxide conversion can be carbon monoxide by catalyst, methanation by-product is more serious.
J.sloczynski et al. (Appl.Catal.A.2004,278,11-23) uses Au/ZnO-ZrO2Catalyst, 220 DEG C,
8MPa, hydrogen-carbon ratio are reacted under conditions of being 3:1, and methanol selectivity is close to 100%, but conversion ratio only has 2%.A.G.kharaji
Et al. (Chem.Eng., 2013,21,1007-1014) use Fe-Mo/ γ-Al2O3Catalyst is in 600 DEG C, 1MPa, hydrogen-carbon ratio
It is reacted under 1:1, synthesis gas selectivity is close to 100%, and conversion ratio is close to 45%, but the process reaction temperature is higher is unfavorable for synthesizing
The subsequent transformation of gas reacts.Can Li et al. people (Sci.Adv., 2017,3-14) uses ZnO-ZrO2Catalyst, 320 DEG C,
5MPa, hydrogen-carbon ratio are to react under 3:1, methanol selectivity 85%, conversion ratio 13%.Chunshan Song et al. (Journal
Of Utilization, 2018,27,81-88) use In2O3-ZrO2Catalyst, it is anti-under being 3:1 in 280 DEG C, 3MPa, hydrogen-carbon ratio
It answers, methanol selectivity only 60%, CO2Conversion ratio only 8%.
Summary of the invention
The purpose of the present invention is overcome to prepare that methanol and synthesis gas selectivity and conversion ratio are low, consume energy in art methods
Height, byproduct methane high conversion rate, the disadvantages of catalyst is at high cost, provide that a kind of preparation process is simple, at low cost, by-product first
The few carbon dioxide hydrogenation reaction catalyst of alkane, and the catalyst prepares synthesis gas in low temperature preparation methanol, high temperature, and one is urged
Agent can pass through the different selectivity of content of active principle in carrier by two kinds of preparation different products of temperature regulation
Prepare methanol and carbon monoxide.
For above-mentioned purpose, catalyst provided by the invention is with ZnO-ZrO2For carrier, In is loaded2O3, wherein Zn and Zr
Molar ratio be 1:6~6:1, and with ZnO-ZrO2The amount of substance be 100% meter, the load capacity of In be 1mol%~
15mol%.
In above-mentioned solid catalyst, the molar ratio of preferably Zn and Zr are 1:1~4:1, with ZnO-ZrO2Substance amount
For 100% meter, the load capacity of In is 5mol%~10mol%.
Catalyst of the present invention the preparation method comprises the following steps: by any one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride and nitre
Sour zinc, zinc chloride, any one or more in zinc sulfate mixture be dissolved in deionized water, alkaline solution (carbon is then added dropwise
The aqueous solution of sour ammonia, sodium hydroxide, potassium hydroxide etc.) control pH be 6~8, stirred 3~6 hours at 40~90 DEG C.Later,
Precipitating is separated by solid-liquid separation and obtains solid product, and solid product is cleaned, 80~120 DEG C of dryings 18~24 hours, 450~
550 DEG C roast 2~6 hours, obtain ZnO-ZrO2Carrier.Mixture one or two kinds of in indium nitrate, inidum chloride is dissolved in ethyl alcohol
With the in the mixed solvent of water, ZnO-ZrO is added2Carrier stirs 3~6 hours, then rotary evaporation solvent evaporated, 80~120 DEG C
18~24 hours dry, 450~550 DEG C roast 2~6 hours, grind, and are granulated, and particle crosses 20~40 mesh screens, obtains solid and urge
Agent In2O3/ZnO-ZrO2。
Solid catalyst of the present invention prepares the application in methanol in catalysis hydrogenation of carbon dioxide, and the hydrogenation of carbon dioxide is anti-
It should be carried out in the fixed bed reactors for being filled with solid catalyst, first with pure hydrogen or nitrogen or argon gas in 280~330 before reaction
DEG C 0.5~2h of activated catalyst, hydrogenation reaction temperature is 270~380 DEG C, the molar ratio of carbon dioxide and hydrogen is 1:1~1:
6, air speed is 8000~15000mL/gh, pressure is 1.0~6.0MPa.
Above-mentioned solid catalyst prepares the application in methanol in catalysis hydrogenation of carbon dioxide, and preferably hydrogenation reaction temperature is
300~330 DEG C, the carbon dioxide and molar ratio of hydrogen is 1:3~1:4, air speed is 10000~12000mL/gh, pressure is
2.0~4.0MPa.
Above-mentioned catalysis hydrogenation of carbon dioxide prepare methanol application in, in the carrier of further preferred solid catalyst Zn with
The molar ratio of Zr is 1:6~1:3.
Solid catalyst of the present invention prepares the application in carbon monoxide in catalysis hydrogenation of carbon dioxide, and the carbon dioxide adds
Hydrogen reaction carries out in the fixed bed reactors for being filled with solid catalyst, first with pure hydrogen or nitrogen or argon gas in 280 before reaction
~330 DEG C of 0.5~2h of activated catalyst, hydrogenation reaction temperature is 390~550 DEG C, the molar ratio of carbon dioxide and hydrogen is 1:1
~1:10, air speed are 8000~15000mL/gh, pressure is 1.0~6.0MPa.
Above-mentioned solid catalyst prepares the application in carbon monoxide, preferably hydrogenation reaction temperature in catalysis hydrogenation of carbon dioxide
For 420~510 DEG C, the carbon dioxide and molar ratio of hydrogen is 1:1~1:7, air speed is 10000~12000mL/gh, pressure
For 2.0~4.0MPa.
Above-mentioned catalysis hydrogenation of carbon dioxide is prepared in the application of carbon monoxide, in the carrier of further preferred solid catalyst
The molar ratio of Zn and Zr is 3:1~6:1.
The invention has the following beneficial effects:
Catalyst of the present invention is cheap and easy to get, which under cryogenic can highly selective catalysis hydrogenation of carbon dioxide system
Standby methanol, under the high temperature conditions can highly selective catalysis hydrogenation of carbon dioxide preparation first carbon monoxide, and the conversion of carbon dioxide
Rate is higher, realizes same catalyst by two kinds of preparation different products of temperature regulation, and can be by effective in carrier
Two kinds of preparation different products of the different selectivity of the content of component, have good prospects for commercial application.
Specific embodiment
Below with reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities
Apply example.
Embodiment 1
It is 3:7 according to the molar ratio of Zn and Zr, and with ZnO-ZrO2The amount of substance be 100% meter, the load capacity of In is
9mol%, by 2.17g Zr (NO3)4·5H2O and 3.5g Zn (NO3)2·6H2O is dissolved in 100mL water, by 3g (NH3)2CO3It is molten
In 100mL water, above-mentioned two solution is instilled in coprecipitation reaction device with 3mL/min, control pH is 7.5.After dripping
70 DEG C are stirred to react 3h, are filtered with milli-Q water, 110 DEG C of dry 12h, 500 DEG C of calcining 3h, and grinding obtains ZnO-ZrO2.It will
0.759g In(NO3)3·4.5H2O is dissolved in 24mL water and 70mL ethyl alcohol, and 2g ZnO-ZrO is then added2, stirring 5 hours, so
After be placed on revolving instrument and be evaporated for 65 DEG C, 110 DEG C of dry 12h, 500 DEG C of calcining 3h, grinding, granulation, particle crosses 20~40 mesh screens,
Obtain solid catalyst In2O3/ZnO-ZrO2。
Embodiment 2
It is 1:1 according to the molar ratio of Zn and Zr, and with ZnO-ZrO2The amount of substance be 100% meter, the load capacity of In is
9mol%, by 3.61g Zr (NO3)4·5H2O and 2.5g Zn (NO3)2·6H2O is dissolved in 100mL water, by 3g (NH3)2CO3It is molten
In 100mL water, above-mentioned two solution is instilled in coprecipitation reaction device with 3mL/min, control pH is 7.5.After dripping
70 DEG C are stirred to react 3h, are filtered with milli-Q water, 110 DEG C of dry 12h, 500 DEG C of calcining 3h, and grinding obtains ZnO-ZrO2.It will
0.702g In(NO3)3·4.5H2O is dissolved in 24mL water and 70mL ethyl alcohol, and 2g ZnO-ZrO is then added2, stirring 5 hours, so
After be placed on revolving instrument and be evaporated for 65 DEG C, 110 DEG C of dry 12h, 500 DEG C of calcining 3h, grinding, granulation, particle crosses 20~40 mesh screens,
Obtain solid catalyst In2O3/ZnO-ZrO2。
Embodiment 3
It is 7:3 according to the molar ratio of Zn and Zr, and with ZnO-ZrO2The amount of substance be 100% meter, the load capacity of In is
9mol%, by 5.05g Zr (NO3)4·5H2O and 1.5g Zn (NO3)2·6H2O is dissolved in 100mL water, by 3g (NH3)2CO3It is molten
In 100mL water, above-mentioned two solution is instilled in coprecipitation reaction device with 3mL/min, control pH is 7.5.After dripping
70 DEG C are stirred to react 3h, are filtered with milli-Q water, 110 DEG C of dry 12h, 500 DEG C of calcining 3h, and grinding obtains ZnO-ZrO2.It will
0.644g In(NO3)3·4.5H2O is dissolved in 24mL water and 70mL ethyl alcohol, and 2g ZnO-ZrO is then added2, stirring 5 hours, so
After be placed on revolving instrument and be evaporated for 65 DEG C, 110 DEG C of dry 12h, 500 DEG C of calcining 3h, grinding, granulation, particle crosses 20~40 mesh screens,
Obtain solid catalyst In2O3/ZnO-ZrO2。
Embodiment 4
It is 17:3 according to the molar ratio of Zn and Zr, and with ZnO-ZrO2The amount of substance be 100% meter, the load capacity of In is
9mol%, by 6.14g Zr (NO3)4·5H2O and 0.75g Zn (NO3)2·6H2O is dissolved in 100mL water, by 3g (NH3)2CO3It is molten
In 100mL water, above-mentioned two solution is instilled in coprecipitation reaction device with 3mL/min, control pH is 7.5.After dripping
70 DEG C are stirred to react 3h, are filtered with milli-Q water, 110 DEG C of dry 12h, 500 DEG C of calcining 3h, and grinding obtains ZnO-ZrO2.It will
0.601g In(NO3)3·4.5H2O is dissolved in 24mL water and 70mL ethyl alcohol, and 2g ZnO-ZrO is then added2, stirring 5 hours, so
After be placed on revolving instrument and be evaporated for 65 DEG C, 110 DEG C of dry 12h, 500 DEG C of calcining 3h, grinding, granulation, particle crosses 20~40 mesh screens,
Obtain solid catalyst In2O3/ZnO-ZrO2。
In order to prove beneficial effects of the present invention, inventor uses the solid catalyst and titanium dioxide of Examples 1 to 4 preparation
Carbon adds hydrogen low temperature preparation methanol, and high temperature prepares synthesis gas, and specific test is as follows:
1,2,4 catalyst of 0.3g embodiment is placed in fixed bed reactors respectively, is first activated with pure argon in 300 DEG C
1h, then carries out carbon dioxide hydrogenation reaction, control reaction temperature is 330 DEG C, the molar ratio of hydrogen and carbon dioxide be 4:1,
Air speed is 10000mL/gh, pressure 3.0MPa.With the yield of gas-chromatography on-line analysis measurement carbon monoxide, cold well is collected anti-
Output liquid phase is answered, with liquid chromatogram measuring methanol yield, the results are shown in Table 1.
The catalyst of the present invention of table 1 is used for carbon dioxide hydrogenation reaction result
| Catalyst | Temperature | Carbon monoxide selective | Methanol selectivity | Carbon dioxide conversion |
| Embodiment 1 | 330℃ | 49.18% | 50.82% | 27.20% |
| Embodiment 2 | 330℃ | 17.5% | 82.50% | 22.77% |
| Embodiment 4 | 330℃ | 57.14% | 42.86% | 39.68% |
3 catalyst of 0.3g embodiment is placed in fixed bed reactors, first with pure argon in 300 DEG C of activation 1h, then into
Row carbon dioxide hydrogenation reaction, control reaction temperature is respectively 300 DEG C, 330 DEG C, 360 DEG C, 390 DEG C, 420 DEG C, 450 DEG C, 480
DEG C, 510 DEG C, the molar ratio for controlling hydrogen and carbon dioxide is 4:1, air speed 10000mL/gh, pressure 3.0MPa.Use gas phase
On-line chromatographic analysis measures the yield of carbon monoxide, and cold well collects reaction output liquid phase, with liquid chromatogram measuring methanol yield, knot
Fruit is shown in Table 2.
2 embodiment of table, 3 catalyst is catalyzed carbon dioxide hydrogenation reaction result at different temperatures
3 catalyst of 0.3g embodiment is placed in fixed bed reactors, first with pure argon in 300 DEG C of activation 1h, then into
Row carbon dioxide hydrogenation reaction, control reaction temperature is respectively 390 DEG C, 420 DEG C, 450 DEG C, 480 DEG C, 510 DEG C, control hydrogen and
The molar ratio of carbon dioxide is 6.5:1, air speed 10000mL/gh, pressure 3.0MPa.It is measured with gas-chromatography on-line analysis
The yield of carbon monoxide, cold well collect reaction output liquid phase and the results are shown in Table 3 with liquid chromatogram measuring methanol yield.
3 embodiment of table, 3 catalyst is catalyzed carbon dioxide hydrogenation reaction result at different temperatures
3 catalyst of 0.3g embodiment is placed in fixed bed reactors, first with pure argon in 300 DEG C of activation 1h, then into
Row carbon dioxide hydrogenation reaction, control reaction temperature is respectively 300 DEG C, 330 DEG C, 360 DEG C, 390 DEG C, 420 DEG C, 450 DEG C, 480
DEG C, 510 DEG C, the molar ratio for controlling hydrogen and carbon dioxide is 1:1, air speed 10000mL/gh, pressure 3.0MPa.Use gas phase
On-line chromatographic analysis measures the yield of carbon monoxide, and cold well collects reaction output liquid phase, with liquid chromatogram measuring methanol yield, knot
Fruit is shown in Table 4.
4 embodiment of table, 3 catalyst is catalyzed carbon dioxide hydrogenation reaction result at different temperatures
In summary the result of table 1~4 is as it can be seen that solid catalyst of the present invention is used for hydrogenation of carbon dioxide low temperature preparation first
The catalytic activity that alcohol, high temperature prepare synthesis gas is good.Wherein when low temperature preparation methanol, the more first of Zr content in solid catalyst carrier
Alcohol selectivity is better；When high temperature prepares synthesis gas, the more synthesis gas selectivity of Zn content are better in solid catalyst carrier.
Claims (9)
1. the solid catalyst that a kind of catalysis carbon dioxide selectivity prepares methanol and carbon monoxide, it is characterised in that: described solid
Body catalyst is with ZnO-ZrO2For carrier, In is loaded2O3, wherein the molar ratio of Zn and Zr is 1:6~6:1, and with ZnO-ZrO2
The amount of substance be 100% meter, the load capacity of In is 1mol%~15mol%.
2. solid catalyst according to claim 1, it is characterised in that: the molar ratio of the Zn and Zr is 1:1~4:1.
3. solid catalyst according to claim 1, it is characterised in that: with ZnO-ZrO2Substance amount be 100% meter,
The load capacity of In is 5mol%~10mol%.
4. solid catalyst described in claim 1 prepares the application in methanol in catalysis hydrogenation of carbon dioxide, it is characterised in that:
The carbon dioxide hydrogenation reaction carries out in the fixed bed reactors for being filled with solid catalyst described in claim 1, instead
In 280~330 DEG C of 0.5~2h of activated catalyst, hydrogenation reaction temperature is 270~380 for the pure hydrogen of Ying Qianxian or nitrogen or argon gas
DEG C, the molar ratio of carbon dioxide and hydrogen be 1:1~1:6, air speed is 8000~15000mL/gh, pressure be 1.0~
6.0MPa。
5. solid catalyst as claimed in claim 4 prepares the application in methanol in catalysis hydrogenation of carbon dioxide, it is characterised in that:
The hydrogenation reaction temperature is 300~330 DEG C, the molar ratio of carbon dioxide and hydrogen is 1:3~1:4, air speed be 10000~
12000mL/gh, pressure are 2.0~4.0MPa.
6. solid catalyst described in claim 4 or 5 prepares the application in methanol in catalysis hydrogenation of carbon dioxide, feature exists
In: in the carrier of the solid catalyst, the molar ratio of Zn and Zr are 1:6~1:3.
7. solid catalyst described in claim 1 prepares the application in carbon monoxide, feature in catalysis hydrogenation of carbon dioxide
Be: the carbon dioxide hydrogenation reaction in the fixed bed reactors for being filled with solid catalyst described in claim 1 into
Row, first with pure hydrogen or nitrogen or argon gas in 280~330 DEG C of 0.5~2h of activated catalyst before reaction, hydrogenation reaction temperature is 390
~550 DEG C, the carbon dioxide and molar ratio of hydrogen is 1:1~1:10, air speed is 8000~15000mL/gh, pressure 1.0
~6.0MPa.
8. solid catalyst as claimed in claim 7 prepares the application in carbon monoxide, feature in catalysis hydrogenation of carbon dioxide
Be: the hydrogenation reaction temperature is 420~510 DEG C, the carbon dioxide and molar ratio of hydrogen is 1:1~1:7, air speed is
10000~12000mL/gh, pressure are 2.0~4.0MPa.
9. solid catalyst described in claim 7 or 8 prepares the application in carbon monoxide in catalysis hydrogenation of carbon dioxide, special
Sign is: in the carrier of the solid catalyst, the molar ratio of Zn and Zr are 3:1~6:1.
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Application publication date: 20190726 |