CN105618088B - A kind of copper fluoride base class hydrotalcite catalyst and its preparation method and application - Google Patents
A kind of copper fluoride base class hydrotalcite catalyst and its preparation method and application Download PDFInfo
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- CN105618088B CN105618088B CN201610060719.3A CN201610060719A CN105618088B CN 105618088 B CN105618088 B CN 105618088B CN 201610060719 A CN201610060719 A CN 201610060719A CN 105618088 B CN105618088 B CN 105618088B
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Abstract
The invention discloses a kind of copper fluoride base class hydrotalcite catalyst and its preparation method and application, the copper fluoride base class hydrotalcite catalyst includes Cu, ZnO, Al2O3And fluoride, the molar ratio that the molar ratio of Cu elements and Zn elements be 2, Cu elements, the total mole number of Zn elements and the molal quantity ratio of Al elements are 0.5 4, F elements and Al elements is 0.29 2.57.The copper fluoride base class hydrotalcite catalyst of the present invention has metallic element dispersion degree high, and strong basicity bit quantity is more, is conducive to H2Dissociative and CO2Stablize absorption, in CO2Performance is stablized in hydrogenation operation, is ensureing higher CO2While conversion ratio, it can be obviously improved methanol selectivity, and preparation method is simple, it is easy to operate, it is easy to accomplish industry amplification.
Description
Technical field
The present invention relates to catalyst fields, and in particular to a kind of copper fluoride base class hydrotalcite catalyst and preparation method thereof and
Using.
Background technology
CO in air2The increasingly depleted of greenhouse effects and fossil fuel caused by concentration increases is concerned.By CO2Turn
It is the effective way for being expected to solve greenhouse gas emission and fossil fuel substitute two large problems to turn to methanol, this is because methanol
Not only it is important Organic Chemicals, but also is non-petroleum base cleaning synthetic fuel.Relative to industrial synthesising gas systeming carbinol, CO2
In hydrogenation reactionHigher CO2And H2Concentration can promote reverse water-gas-shift reaction And CO is generated, cause methanol selectivity to be far below synthesis gas route.Thus, how to inhibit by-product CO's
It generates, improve the concern that methanol selectivity receives numerous researchers.Reaction mechanism is furtherd investigate, it can be more preferable geographical
Solution and design effective catalyst.Although CO2There are still many disputes for the reaction mechanism of preparing methanol by hydrogenation, however for Cu-ZnO-
(ZrO2) catalyst, the reaction mechanism of double activated position is generally satisfactory, H2Dissociative carried out on the sites Cu, and CO2
Absorption be then happened on the basic site of catalyst surface, the atom H on the sites Cu pass through overflow effect reach surface alkali position
To containing, carbon species carry out gradually plus hydrogen, the intermediate species of formation formates and surface bond formaldehyde etc. eventually form methanol.Many is ground
The person of studying carefully has found that methanol and CO can be generated by identical intermediate species, which can both be hydrogenated to methanol, can also take off
Hydrogen forms CO.Thus, many researchers think that methanol selectivity is related with the distribution of catalyst surface alkali position, catalyst surface alkali
The improvement of property is beneficial to obtain better CO2Add hydrogen effect.
Fluorine ion can promote many base catalyzed reactions, be introduced into hydrotalcite-like compound as a kind of alkali anion
In, the undersaturated F of coordination can be formed after roasting–, to improve highly basic bits number.There are many researchers to utilize houghite
" memory effect " is successfully by F–Houghite interlayer is introduced, houghite product of roasting is added to containing F–Solution
In, the reconstruction of hydrotalcite-like compound, F can occur–Interlayer can be entered, fluorine-containing houghite compound is formed, roast again
Material surface highly basic bits number afterwards obviously increases.But this method is comparatively laborious, time-consuming, is easy in dual-spectrum process
Houghite laminate is caused to grow up, reunite, the introduction volume of fluorine ion is also not easily controlled.
Invention content
It is an object of the invention to overcome the deficiencies of existing technologies, provide a kind of copper fluoride base class hydrotalcite catalyst and its
Preparation method and application, the copper fluoride base class hydrotalcite catalyst includes Cu, ZnO, Al2O3And fluoride, Cu elements and Zn members
The molar ratio of element is that 2, Cu elements, the total mole number of Zn elements and the molal quantity ratio of Al elements are 0.5-4, F elements and Al members
The molar ratio of element is 0.29-2.57.The copper fluoride base class hydrotalcite catalyst of the present invention has metallic element dispersion degree height, highly basic
Property bit quantity is more, is conducive to H2Dissociative and CO2Stablize absorption, in CO2Performance is stablized in hydrogenation operation, is protecting
The higher CO of card2While conversion ratio, it can be obviously improved methanol selectivity, and preparation method is simple, it is easy to operate, it is easy to accomplish
Industry amplification.
The present invention is achieved by the following technical solutions：
First aspect present invention provides a kind of copper fluoride base class hydrotalcite catalyst, and the copper fluoride base class is hydrotalcite catalyzed
Agent includes Cu, ZnO, Al2O3And fluoride, the molar ratio of Cu elements and Zn elements be 2, Cu elements, Zn elements total mole number with
The molal quantity ratio of Al elements is 0.5-4, and the molar ratio of F elements and Al elements is 0.29-2.57.
Cu elements, the total mole number of Zn elements and the molal quantity ratio of Al elements can be 0.5-2 or 2-4.
The molar ratio of F elements and Al elements can be 0.29-0.60,0.60-0.90,0.90-1.20,1.20-1.50,
1.50-1.80,1.80-2.10 or 2.10-2.57.
The fluoride is zinc fluoride and aluminum fluoride.
Second aspect of the present invention provides a kind of preparation method of copper fluoride base class hydrotalcite catalyst, includes the following steps：
1) according to proportioning is by copper soluble-salt, zinc soluble-salt, aluminium soluble-salt and fluoaluminate is soluble in water is mixed
Heshui solution；
2) sodium hydroxide solution, reacted generation sediment is added in the mixed aqueous solution；
3) by the sediment aging, washing, drying, fluorination hydrotalcite-like materials are obtained；
4) the fluorination hydrotalcite-like materials are restored under pure hydrogen atmosphere up to copper fluoride base class hydrotalcite catalyst.
Preferably, in step 1), the copper soluble-salt is Cu (NO3)2, the zinc soluble-salt is Zn (NO3)2, described
Aluminium soluble-salt is Al (NO3)3, the fluoaluminate is Na3AlF6。
Preferably, the molar ratio of Cu elements and Zn elements in zinc soluble-salt is 2 in copper soluble-salt, in copper soluble-salt
The total mole number ratio of the total mole number of Zn elements and Al elements in aluminium soluble-salt and fluoaluminate in Cu elements, zinc soluble-salt
Value is 0.5-4.
Preferably, the molar ratio of the fluoaluminate and the aluminium soluble-salt is 0.05-0.75, as 0.05-0.15,
0.15-0.25,0.25-0.3,0.3-0.4,0.4-0.65,0.65-0.7 or 0.7-0.75.
Preferably, in the step 2), reaction temperature is 10-40 DEG C, such as 10-20 DEG C, 20-25 DEG C, 25-30 DEG C or 30-
40 DEG C, the pH value of precipitation reaction terminal is 8-11, such as 8-9,9-10 or 10-11.
Preferably, in the step 2), a concentration of 0.5-2mol/L of the sodium hydroxide solution of addition, such as 0.5-1mol/L
Or 1-2mol/L.
Preferably, in the step 3), aging temperature is 60-100 DEG C, ageing time 6-48h.
Preferably, in the step 3), drying temperature is 60-120 DEG C.
Preferably, in the step 4), reduction temperature is 250-350 DEG C, such as 250-270 DEG C, 270-280 DEG C, 280-290
DEG C, 290-300 DEG C, 300-310 DEG C, 310-320 DEG C, 320-330 DEG C or 330-350 DEG C, recovery time 4-15h, as 4-6h,
6-8h, 8-10h, 10-12h or 12-15h.
Third aspect present invention provides a kind of application of copper fluoride base class hydrotalcite catalyst, the copper fluoride base class neatly
Stone catalyst is used for the synthetic reaction of methanol.
Preferably, the copper fluoride base class hydrotalcite catalyst is used for CO2And H2Mixed gas atmosphere in reaction synthesis first
Alcohol.
It is furthermore preferred that H in the mixed gas atmosphere2With CO2Molar ratio be 2-4, such as 2-3 or 3-4, volume space velocity is
2000-10000h-1, such as 2000-3000h-1、3000-4000h-1、4000-5000h-1、5000-6000h-1、6000-7000h-1、
7000-8000h-1Or 8000-10000h-1, reaction pressure 2.0-6.0MPa, such as 2.0-3.0MPa, 3.0-4.0MPa, 4.0-
5.0MPa or 5.0-6.0MPa, reaction temperature is 200-320 DEG C, such as 200-230 DEG C, 230-250 DEG C, 250-260 DEG C, 260-
270 DEG C, 270-280 DEG C, 280-300 DEG C or 300-320 DEG C.
The present invention one of at least has the advantages that：
1) copper fluoride base class hydrotalcite catalyst of the invention has metallic element dispersion degree high, and strong basicity bit quantity is more,
Be conducive to H2Dissociative and CO2Stablize absorption, in CO2Performance is stablized in hydrogenation operation, is ensureing higher CO2Turn
While rate, methanol selectivity can be obviously improved；
2) preparation method of copper fluoride base class hydrotalcite catalyst of the invention uses (AlF6)3–Octahedron is in houghite
Fluorine ion is introduced directly into veneer structure in building-up process, the introduction volume of fluorine ion can be adjusted in wider range
Control, the preparation method is simple, easy to operate, it is easy to accomplish industry amplification.
Specific implementation mode
Illustrate technical scheme of the present invention below by way of specific specific example.It should be understood that mention one of the present invention or
Multiple method and steps do not repel before and after the combination step that there is also other methods step or the steps specifically mentioned at these
It can also be inserted into other methods step between rapid；It should also be understood that these embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Moreover, unless otherwise indicated, the number of various method steps is only to differentiate the convenient tool of various method steps,
Rather than to limit the ordering of various method steps or limiting the scope of the invention, the change of relativeness or tune
It is whole, without material changes in technical content, when being also considered as the enforceable scope of the present invention.
The technology of the present invention details is subject to detailed description by following embodiments.It should be noted that for embodiment, make
With the only technical characteristic that further illustrates the present invention, rather than limit the present invention.
(Cu+Zn)/Al refers to Cu elements in copper soluble-salt in following embodiment, Zn elements always rubs in zinc soluble-salt
The ratio of your number and the total mole number of Al elements in aluminium soluble-salt and fluoaluminate.
Embodiment 1
According to Cu/Zn=2, (Cu+Zn)/Al=2, Na3AlF6/Al(NO3)3=0.05 ratio (molar ratio), by nitric acid
Copper, zinc nitrate, aluminum nitrate and Na3AlF6It is dissolved in deionized water and is made into mixed aqueous solution, be added dropwise at a temperature of 20 DEG C
In the sodium hydroxide solution of 1.0mol/L, dropwise addition process need to be sufficiently stirred, and final ph is maintained at 8, will after precipitation reaction
Products therefrom aging under 70 DEG C of stirring conditions for 24 hours, then gained precipitation is washed with deionized for several times, then at 70 DEG C
It is dried in vacuum overnight, obtains fluorination hydrotalcite-like materials.Resulting materials are heat-treated 12h for 270 DEG C under pure hydrogen atmosphere, obtain fluorine
Change copper-based houghite catalyst.Synthesizing methanol by hydrogenating carbon dioxide reaction carries out in the stainless steel reactor of 6mm internal diameters, instead
Answer condition as follows：P=5.0MPa, T=230 DEG C, GHSV=3000h-1, n (H2)/n(CO2Liquid phase production is collected in)=3 with ice-water bath
Object, gas chromatographic analysis product composition, evaluation results are shown in Table 1.
Embodiment 2
According to Cu/Zn=2, (Cu+Zn)/Al=2, Na3AlF6/Al(NO3)3=0.15 ratio (molar ratio), by nitric acid
Copper, zinc nitrate, aluminum nitrate and Na3AlF6It is dissolved in deionized water and is made into mixed aqueous solution, be added dropwise at a temperature of 20 DEG C
In the sodium hydroxide solution of 1.0mol/L, dropwise addition process need to be sufficiently stirred, and final ph is maintained at 9, will after precipitation reaction
Products therefrom aging under 70 DEG C of stirring conditions for 24 hours, then gained precipitation is washed with deionized for several times, then at 80 DEG C
It is dried in vacuum overnight, obtains fluorination hydrotalcite-like materials.Resulting materials are heat-treated 8h for 290 DEG C under pure hydrogen atmosphere, obtain fluorine
Change copper-based houghite catalyst.Synthesizing methanol by hydrogenating carbon dioxide reaction carries out in the stainless steel reactor of 6mm internal diameters, instead
Answer condition as follows：P=5.0MPa, T=250 DEG C, GHSV=4000h-1, n (H2)/n(CO2Liquid phase production is collected in)=3 with ice-water bath
Object, gas chromatographic analysis product composition, evaluation results are shown in Table 1.
Embodiment 3
According to Cu/Zn=2, (Cu+Zn)/Al=2, Na3AlF6/Al(NO3)3=0.25 ratio (molar ratio), by nitric acid
Copper, zinc nitrate, aluminum nitrate and Na3AlF6It is dissolved in deionized water and is made into mixed aqueous solution, be added dropwise at a temperature of 25 DEG C
In the sodium hydroxide solution of 1.0mol/L, dropwise addition process need to be sufficiently stirred, and final ph is maintained at 9, will after precipitation reaction
Products therefrom aging 12h under 80 DEG C of stirring conditions then gained precipitation is washed with deionized for several times, then at 90 DEG C
It is dried in vacuum overnight, obtains fluorination hydrotalcite-like materials.Resulting materials are heat-treated 8h for 300 DEG C under pure hydrogen atmosphere, obtain fluorine
Change copper-based houghite catalyst.Synthesizing methanol by hydrogenating carbon dioxide reaction carries out in the stainless steel reactor of 6mm internal diameters, instead
Answer condition as follows：P=4.0MPa, T=270 DEG C, GHSV=5000h-1, n (H2)/n(CO2Liquid phase production is collected in)=3 with ice-water bath
Object, gas chromatographic analysis product composition, evaluation results are shown in Table 1.
Embodiment 4
According to Cu/Zn=2, (Cu+Zn)/Al=2, Na3AlF6/Al(NO3)3=0.3 ratio (molar ratio), by nitric acid
Copper, zinc nitrate, aluminum nitrate and Na3AlF6It is dissolved in deionized water and is made into mixed aqueous solution, be added dropwise at a temperature of 30 DEG C
In the sodium hydroxide solution of 2.0mol/L, dropwise addition process need to be sufficiently stirred, and final ph is maintained at 10, will after precipitation reaction
Products therefrom aging 12h under 80 DEG C of stirring conditions then gained precipitation is washed with deionized for several times, then at 100 DEG C
Under be dried in vacuum overnight, obtain fluorination hydrotalcite-like materials.310 DEG C of heat treatment 8h, acquisition under pure hydrogen atmosphere by resulting materials
Copper fluoride base class hydrotalcite catalyst.Synthesizing methanol by hydrogenating carbon dioxide reaction carries out in the stainless steel reactor of 6mm internal diameters,
Reaction condition is as follows：P=4.0MPa, T=300 DEG C, GHSV=6000h-1, n (H2)/n(CO2Liquid phase is collected in)=3 with ice-water bath
Product, gas chromatographic analysis product composition, evaluation results are shown in Table 1.
Embodiment 5
According to Cu/Zn=2, (Cu+Zn)/Al=2, Na3AlF6/Al(NO3)3=0.4 ratio (molar ratio), by nitric acid
Copper, zinc nitrate, aluminum nitrate and Na3AlF6It is dissolved in deionized water and is made into mixed aqueous solution, be added dropwise at a temperature of 30 DEG C
In the sodium hydroxide solution of 1.0mol/L, dropwise addition process need to be sufficiently stirred, and final ph is maintained at 10, will after precipitation reaction
Products therefrom aging 8h under 90 DEG C of stirring conditions then gained precipitation is washed with deionized for several times, then at 110 DEG C
It is dried in vacuum overnight, obtains fluorination hydrotalcite-like materials.Resulting materials are heat-treated 6h for 330 DEG C under pure hydrogen atmosphere, obtain fluorine
Change copper-based houghite catalyst.Synthesizing methanol by hydrogenating carbon dioxide reaction carries out in the stainless steel reactor of 6mm internal diameters, instead
Answer condition as follows：P=3.0MPa, T=320 DEG C, GHSV=8000h-1, n (H2)/n(CO2Liquid phase production is collected in)=3 with ice-water bath
Object, gas chromatographic analysis product composition, evaluation results are shown in Table 1.
Embodiment 6
According to Cu/Zn=2, (Cu+Zn)/Al=2, Na3AlF6/Al(NO3)3=0.65 ratio (molar ratio), by nitric acid
Copper, zinc nitrate, aluminum nitrate and Na3AlF6It is dissolved in deionized water and is made into mixed aqueous solution, be added dropwise at a temperature of 40 DEG C
In the sodium hydroxide solution of 2.0mol/L, dropwise addition process need to be sufficiently stirred, and final ph is maintained at 11, will after precipitation reaction
Products therefrom aging 6h under 100 DEG C of stirring conditions then gained precipitation is washed with deionized for several times, then at 120 DEG C
Under be dried in vacuum overnight, obtain fluorination hydrotalcite-like materials.350 DEG C of heat treatment 4h, acquisition under pure hydrogen atmosphere by resulting materials
Copper fluoride base class hydrotalcite catalyst.Synthesizing methanol by hydrogenating carbon dioxide reaction carries out in the stainless steel reactor of 6mm internal diameters,
Reaction condition is as follows：P=2.0MPa, T=320 DEG C, GHSV=10000h-1, n (H2)/n(CO2)=4, with ice-water bath collection liquid
Phase product, gas chromatographic analysis product composition, evaluation results are shown in Table 1.
Embodiment 7
According to Cu/Zn=2, (Cu+Zn)/Al=0.5, Na3AlF6/Al(NO3)3=0.7 ratio (molar ratio), by nitre
Sour copper, zinc nitrate, aluminum nitrate and Na3AlF6It is dissolved in deionized water and is made into mixed aqueous solution, be added dropwise at a temperature of 40 DEG C
In the sodium hydroxide solution of 0.5mol/L, dropwise addition process need to be sufficiently stirred, and final ph is maintained at 11, will after precipitation reaction
Products therefrom aging under 90 DEG C of stirring conditions for 24 hours, then gained precipitation is washed with deionized for several times, then at 90 DEG C
It is dried in vacuum overnight, obtains fluorination hydrotalcite-like materials.Resulting materials are heat-treated 10h for 280 DEG C under pure hydrogen atmosphere, obtain fluorine
Change copper-based houghite catalyst.Synthesizing methanol by hydrogenating carbon dioxide reaction carries out in the stainless steel reactor of 6mm internal diameters, instead
Answer condition as follows：P=4.0MPa, T=260 DEG C, GHSV=5000h-1, n (H2)/n(CO2Liquid phase production is collected in)=2 with ice-water bath
Object, gas chromatographic analysis product composition, evaluation results are shown in Table 1.
Embodiment 8
According to Cu/Zn=2, (Cu+Zn)/Al=4, Na3AlF6/Al(NO3)3=0.75 ratio (molar ratio), by nitric acid
Copper, zinc nitrate, aluminum nitrate and Na3AlF6It is dissolved in deionized water and is made into mixed aqueous solution, be added dropwise at a temperature of 10 DEG C
In the sodium hydroxide solution of 1.0mol/L, dropwise addition process need to be sufficiently stirred, and final ph is maintained at 11, will after precipitation reaction
Products therefrom aging 18h under 90 DEG C of stirring conditions then gained precipitation is washed with deionized for several times, then at 80 DEG C
It is dried in vacuum overnight, obtains fluorination hydrotalcite-like materials.Resulting materials are heat-treated 6h for 320 DEG C under pure hydrogen atmosphere, obtain fluorine
Change copper-based houghite catalyst.Synthesizing methanol by hydrogenating carbon dioxide reaction carries out in the stainless steel reactor of 6mm internal diameters, instead
Answer condition as follows：P=4.0MPa, T=280 DEG C, GHSV=7000h-1, n (H2)/n(CO2Liquid phase production is collected in)=3 with ice-water bath
Object, gas chromatographic analysis product composition, evaluation results are shown in Table 1.
Comparative example
According to Cu/Zn=2, (Cu+Zn)/Al=0.5, Na3AlF6/Al(NO3)3=0 ratio (molar ratio), by nitric acid
Copper, zinc nitrate and aluminum nitrate, which are dissolved in deionized water, is made into mixed aqueous solution, and 0.5mol/L is added dropwise at a temperature of 10 DEG C
Sodium hydroxide solution in, dropwise addition process need to be sufficiently stirred, and final ph is maintained at 8, by products therefrom after precipitation reaction
Gained precipitation is then washed with deionized for several times, is then dried in vacuo at 60 DEG C by the aging 48h under 60 DEG C of stirring conditions
Overnight, hydrotalcite-like materials are obtained.Resulting materials are heat-treated 15h for 250 DEG C under pure hydrogen atmosphere, obtain copper-based catalysts.Two
The reaction of carbonoxide synthesizing methanol by hydrogenating carries out in the stainless steel reactor of 6mm internal diameters, and reaction condition is as follows：P=6.0MPa, T
=200 DEG C, GHSV=2000h-1, n (H2)/n(CO2Liquid product, gas chromatographic analysis product group are collected in)=2 with ice-water bath
At evaluation results are shown in Table 1.
1 embodiment catalyst reaction result of table
Ensureing higher CO by evaluating the copper-based catalysts modified through fluorine known to data in table 12While conversion ratio, significantly
Improve methanol selectivity.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of not departing from the method for the present invention, can also make
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are the equivalent embodiment of the present invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations made by above-described embodiment, still fall within the range of technical scheme of the present invention
It is interior.
Claims (10)
1. a kind of copper fluoride base class hydrotalcite catalyst, which is characterized in that the copper fluoride base class hydrotalcite catalyst include Cu,
ZnO、Al2O3And fluoride, the molar ratio of Cu elements and Zn elements are total mole number and the Al elements of 2, Cu elements, Zn elements
Molal quantity ratio is 2, F elements and the molar ratio of Al elements is 0.29-2.57.
2. a kind of preparation method of copper fluoride base class hydrotalcite catalyst as described in claim 1, which is characterized in that including with
Lower step：
1) according to proportioning is by copper soluble-salt, zinc soluble-salt, aluminium soluble-salt and fluoaluminate is soluble in water obtains mixing water
Solution；
2) sodium hydroxide solution, reacted generation sediment is added in the mixed aqueous solution；
3) by the sediment aging, washing, drying, fluorination hydrotalcite-like materials are obtained；
4) the fluorination hydrotalcite-like materials are restored under pure hydrogen atmosphere up to copper fluoride base class hydrotalcite catalyst.
3. the preparation method of copper fluoride base class hydrotalcite catalyst as claimed in claim 2, it is characterised in that：The step 2)
In, reaction temperature is 10-40 DEG C, and the pH value of precipitation reaction terminal is 8-11.
4. the preparation method of copper fluoride base class hydrotalcite catalyst as claimed in claim 2, it is characterised in that：The step 2)
In, a concentration of 0.5-2mol/L of the sodium hydroxide solution of addition.
5. the preparation method of copper fluoride base class hydrotalcite catalyst as claimed in claim 2, it is characterised in that：The step 3)
In, aging temperature is 60-100 DEG C, ageing time 6-48h.
6. the preparation method of copper fluoride base class hydrotalcite catalyst as claimed in claim 2, it is characterised in that：The step 3)
In, drying temperature is 60-120 DEG C.
7. the preparation method of copper fluoride base class hydrotalcite catalyst as claimed in claim 2, it is characterised in that：The step 4)
In, reduction temperature is 250-350 DEG C, recovery time 4-15h.
8. a kind of application of copper fluoride base class hydrotalcite catalyst as described in claim 1, which is characterized in that the copper fluoride
Base class hydrotalcite catalyst is used for the synthetic reaction of methanol.
9. the application of copper fluoride base class hydrotalcite catalyst as claimed in claim 8, which is characterized in that the copper fluoride base class
Hydrotalcite catalyst is used for CO2And H2Mixed gas atmosphere in react synthesizing methanol.
10. the application of copper fluoride base class hydrotalcite catalyst as claimed in claim 9, which is characterized in that the mixed gas
H in atmosphere2With CO2Molar ratio be 2-4, volume space velocity 2000-10000h-1, reaction pressure 2.0-6.0MPa, reaction temperature
Degree is 200-320 DEG C.
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