CN106582755B - A kind of method of catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol and preparation method thereof and preparation by furfural gas phase hydrogenation furfuryl alcohol - Google Patents
A kind of method of catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol and preparation method thereof and preparation by furfural gas phase hydrogenation furfuryl alcohol Download PDFInfo
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- CN106582755B CN106582755B CN201510662161.1A CN201510662161A CN106582755B CN 106582755 B CN106582755 B CN 106582755B CN 201510662161 A CN201510662161 A CN 201510662161A CN 106582755 B CN106582755 B CN 106582755B
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 220
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 77
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 61
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 121
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 44
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 26
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 25
- 239000005751 Copper oxide Substances 0.000 claims abstract description 23
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims description 59
- 239000000843 powder Substances 0.000 claims description 57
- 229960004643 cupric oxide Drugs 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000000748 compression moulding Methods 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 51
- 239000000243 solution Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 6
- -1 hydrogen aldehyde Chemical class 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940035427 chromium oxide Drugs 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940093956 potassium carbonate Drugs 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940078480 calcium levulinate Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical class [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- HCAJEUSONLESMK-UHFFFAOYSA-N cyclohexylsulfamic acid Chemical compound OS(=O)(=O)NC1CCCCC1 HCAJEUSONLESMK-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- GTUVXOOHBUUGBH-UHFFFAOYSA-N furan;methanol Chemical compound OC.C=1C=COC=1 GTUVXOOHBUUGBH-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol, the catalyst contains copper oxide, chromium oxide, potassium carbonate and silica, the molar ratio 1-5:1 of copper oxide and chromium oxide, the molar ratio 20-80:1 of copper oxide and potassium carbonate, the molar ratio 1-20:1 of copper oxide and silica, the invention further relates to the preparation methods of the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol, and the catalyst of this method preparation, in addition, the invention further relates to the methods of preparation by furfural gas phase hydrogenation furfuryl alcohol, the catalyst of the preparation by furfural gas phase hydrogenation furfuryl alcohol prepared using method of the invention has greater activity and selectivity, and the method for preparing catalyst is simple, it is easily operated, catalyst performance repeatability is preferably, industry amplification application easy to accomplish, in catalyst preparation process, the waste water of pollution environment will not be generated.
Description
Technical field
The present invention relates to furfuryl alcohol production fields, and in particular, to a kind of catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol, furfural
The catalyst and preparation by furfural gas phase hydrogenation furfuryl alcohol of preparation method and this method preparation of the catalyst of gas phase hydrogenation furfuryl alcohol
Method.
Background technique
Furfuryl alcohol is a kind of important industrial chemicals, and it is nutrient drug calcium levulinate that second phthalein propionic acid, which can be made, through hydrolysis in furfuryl alcohol
Intermediate；The furan type resin, furfuryl alcohol-Lauxite and phenolic resin etc. of better performances can be produced using furfuryl alcohol as raw material；Chaff
Alcohol is the good solvent and rocket fuel of furane resins, varnish, pigment again；In addition, furfuryl alcohol synthetic fibers, rubber, pesticide and
It is also widely used in foundary industry.
The production technology of furfuryl alcohol can be divided into liquid-phase hydrogenatin technique and two kinds of gas phase hydrogenation technique at present, and the latter is highly-safe,
Furfural purity is high, catalyst long service life are the development trends of furfural hydrogenation production furfuryl alcohol technique.
The catalyst of furfural hydrogasification producing furancarbinol is broadly divided into two class of copper silicon systems and copper chromium system at present, and the two is compared,
The former has that active low and structural stability is poor, the service life is short.
Patent application CN1107079A discloses a kind of preparation by furfural gas phase hydrogenation and takes catalyst for furfural alcohol, consisting of:
CuO30-52%, Cr2O328-53%, CaO5-15%, and it is added with VIII race and zinc oxide；Patent application CN1978051A is public
It has opened a kind of preparation by furfural gas phase hydrogenation and has taken catalyst for furfural alcohol, consisting of: CuO25-55%, Cr2O325-60%, SiO2 5-
9% and other auxiliary agent 1-6%；Patent application CN102631930A discloses preparation by furfural gas phase hydrogenation and takes catalyst for furfural alcohol,
Composition are as follows: CuO26-50%, Cr2O322-40%, Al2O30.10-11%, SiO20.10-11%, auxiliary agent 1-15%.
Although above-mentioned catalyst all shows higher furfural activity and furfuryl alcohol selectivity, preparation method is altogether
The precipitation method.Coprecipitation prepares catalyst and generally comprises with liquid, neutralization, washing, filtering, drying, roasting, and process is more and not easily-controllable
System, reproducibility is poor, and waste water, the exhaust gas of a large amount of pollution environment furthermore can be also generated in preparation process.
Therefore, significant to be badly in need of a kind of novel furfural gas phase that the better simply activity and selectivity of preparation method is relatively high and stable
Add the catalyst of hydrogen furfuryl alcohol.
Summary of the invention
The purpose of the invention is to overcome the method for preparing catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol in the prior art compared with
Defect complicated, activity and selectivity is unstable provides a kind of preparation method compared with simple, preparation process is pollution-free and catalyst is living
Property and the higher preparation by furfural gas phase hydrogenation furfuryl alcohol of selectivity catalyst and preparation by furfural gas phase hydrogenation furfuryl alcohol catalyst system
The method of Preparation Method and preparation by furfural gas phase hydrogenation furfuryl alcohol.
To achieve the goals above, on the one hand, the present invention provides a kind of catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol, should
Catalyst contains copper oxide, chromium oxide, potassium carbonate and silica, the molar ratio 1-5:1 of copper oxide and chromium oxide, copper oxide with
The molar ratio 1-20:1 of the molar ratio 20-80:1 of potassium carbonate, copper oxide and silica.
On the other hand, the present invention also provides a kind of preparation method of the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol, the party
Method includes:
(1) mixture of cupric oxide powder, chromium oxide powder and silica solution is ground；
(2) mixture that step (1) obtains successively is dried, roasted, compression molding；
(3) mold compound that step (2) obtains is impregnated in wet chemical,
Wherein, the molar ratio of cupric oxide powder and chromium oxide powder is 1-5:1, the molar ratio of cupric oxide powder and potassium carbonate
For 20-80:1, the molar ratio of silica is 1-20:1 in cupric oxide powder and silica solution.
The third aspect, the present invention also provides the catalyst of the preparation by furfural gas phase hydrogenation furfuryl alcohol of above method preparation.
Fourth aspect, the present invention also provides a kind of methods of preparation by furfural gas phase hydrogenation furfuryl alcohol, this method comprises: by above-mentioned
It is reacted after catalyst reduction for preparation by furfural gas phase hydrogenation furfuryl alcohol, the reaction condition includes: that temperature is 110-150 DEG C, pressure
For 0.2-0.6MPa, liquid air speed is 0.2-1hr-1。
The catalyst of the preparation by furfural gas phase hydrogenation furfuryl alcohol prepared using method of the invention has greater activity and selectivity,
It is 110 DEG C, pressure 0.3MPa in reaction temperature, liquid air speed is 0.25hr-1Under conditions of, furfural conversion ratio is >=95%,
Furfuryl alcohol selectivity >=96%, and the method for preparing catalyst is simple, easily operated, catalyst performance repeatability preferably, is easy real
Existing industry amplification application will not generate waste water, the exhaust gas of pollution environment in catalyst preparation process, be that a kind of green is clear
Clean production technology.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
On the one hand, the present invention provides a kind of catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol, the catalyst contain copper oxide,
The molar ratio 20- of the molar ratio 1-5:1 of chromium oxide, potassium carbonate and silica, copper oxide and chromium oxide, copper oxide and potassium carbonate
The molar ratio 1-20:1 of 80:1, copper oxide and silica.
Preferably, the molar ratio 40-60:1 of the molar ratio 2.4-3:1 of copper oxide and chromium oxide, copper oxide and potassium carbonate, oxygen
Change the molar ratio 3-5:1 of copper and silica, so as to further increase the activity and selectivity of catalyst.
Second aspect, the present invention also provides a kind of preparation method of the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol, the party
Method includes:
(1) mixture of cupric oxide powder, chromium oxide powder and silica solution is ground；
(2) mixture that step (1) obtains successively is dried, roasted, compression molding；
(3) mold compound that step (2) obtains is impregnated in wet chemical,
Wherein, the molar ratio of cupric oxide powder and chromium oxide powder is 1-5:1, the molar ratio of cupric oxide powder and potassium carbonate
For 20-80:1, the molar ratio of silica is 1-20:1 in cupric oxide powder and silica solution.
Method according to the present invention, it is preferable that the molar ratio of cupric oxide powder and chromium oxide powder is 2.4-3:1,
The molar ratio of cupric oxide powder and potassium carbonate is 40-60:1, and the molar ratio of silica is 3- in cupric oxide powder and silica solution
5:1, so as to further increase the activity and selectivity of catalyst.
Method according to the present invention, cupric oxide powder and chromium oxide powder can be the cupric oxide powder of this field routine
End and chromium oxide powder, it is preferable that the partial size of cupric oxide powder is less than 100 mesh, and the partial size of chromium oxide powder is less than 100 mesh.
In the present invention, silica is added in catalyst in the form of colloidal sol, skeletal support can be played the role of, it is possible to increase
The specific surface area and cellular structure of catalyst, to improve the activity and selectivity of catalyst.Wherein, silica solution can be ability
Domain routine silica solution, such as can be acidic silicasol.
Method according to the present invention, the lapping mode can be the various grinding method in this field, preferably ball milling,
It is highly preferred that it is 5-30:1 that the condition of the ball milling, which includes: ratio of grinding media to material, revolving speed is 100-800 revs/min, and the time is 1-48 hours,
It is highly preferred that ratio of grinding media to material is 8-15:1, revolving speed is 300-500 revs/min, and the time is 6-12 hours, so that catalyst
In each component equably mix, and then the activity and selectivity of catalyst can be significantly improved.
Method according to the present invention, in step (2), compression molding can be the side of the compression molding of this field routine
Method, it is preferable that the method for the compression molding includes: to press the graphite that 0.5-2 weight % is added in the product after roasting
Sheetmolding, so as to increase the intensity and lubricity of catalyst obtained.
Method according to the present invention, in step (2), the condition of the drying can be the various dried strips in this field
Part, such as can be include: drying temperature be 100-120 DEG C, drying time is 10-20 hours.
Method according to the present invention, in step (2), the condition of the roasting can be the various roasting items in this field
Part, for example, may include: maturing temperature be 300-400 DEG C, calcining time be 2-6 hours.
K is added in catalyst of the invention2CO3, due to K2CO3In alkalinity, therefore, furfural can be slowed down and reacted
Polymerization in journey, to be conducive to improve the stability of catalyst.It is not special to the concentration of wet chemical in the present invention
Requirement, as long as making in catalyst obtained the molar ratio of copper oxide and potassium carbonate within the above range.
Method according to the present invention, in step (3), it is preferable that immersion condition include: be 1-3 hours the time.Its
In, the temperature of dipping is room temperature.
Method according to the present invention, this method can also include: that the product that dipping obtains is dried；It is preferred that
Ground, the condition of the drying include: that drying temperature is 100-120 DEG C, and drying time is 10-20 hours.
Preparation method of the invention is the method for solid phase mechanically and chemically, and one side catalyst components solid powder is outside
It is further crushed under power effect, so that its surface area increases sharply and forms fine particle, while different material is able in molecule
Reach on scale and comes into full contact with；Under the static(al) shearing force collective effect of reaction shape occurs for another aspect catalyst components particle
Become, to generate a large amount of lattice defects, is conducive to enhance the interaction in catalyst between copper oxide and chromium oxide to improve
The activity of catalyst.Although Traditional liquid phase coprecipitation also can be realized mixing of the different component on molecular scale, due to
External force very little and be difficult to generate biggish lattice defect, additionally there may be precipitation by metallic ion not exclusively or because precipitating
Precursor constituent is uneven caused by speed is different and particle agglomeration and the disadvantages of cause specific surface area to decline.Therefore,
The catalyst activity and selectivity with higher of the more existing coprecipitation preparation of method of the invention.
The third aspect, the present invention also provides the catalyst of the preparation by furfural gas phase hydrogenation furfuryl alcohol of above method preparation.
Fourth aspect, the present invention also provides a kind of methods of preparation by furfural gas phase hydrogenation furfuryl alcohol, this method comprises: by above-mentioned
Catalyst reduction after for preparation by furfural gas phase hydrogenation furfuryl alcohol react, the reaction condition include: temperature be 110-150 DEG C, pressure
Power is 0.2-0.6MPa, and liquid air speed is 0.2-1hr-1。
Method according to the present invention, wherein above-mentioned reaction condition can also include: hydrogen aldehyde molar ratio 9-11:1.Its
In, the specific method of gas phase Furfural hydrogenation to furfural alcohol reaction is the method for this field routine, and details are not described herein.
Method according to the present invention, wherein the restoring method of catalyst can be with the catalyst reduction of this field routine
Method, such as may include: to be restored 5-7 hours at 260-280 DEG C with nitrogen hydrogen mixture.
Embodiment 1
The present embodiment is for illustrating catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol of the invention and preparation method thereof and furfural
The method of gas phase hydrogenation furfuryl alcohol.
(1) 30g CuO powder (granularity is less than 100 mesh), 22.1g Cr are weighed2O3Powder (granularity is less than 100 mesh), 25.9g
The acidic silica gel of 25 weight % is placed in ball grinder, is 400 revs/min in revolving speed, and ratio of grinding media to material is ball under the ball milling condition of 15:1
Mill 12 hours takes out mixture, 12 hours dry through 120 DEG C, and then 350 DEG C roasting 4 hours in Muffle furnace, are then added 1
Preformed catalyst is made in the graphite tabletting of weight %, and molding catalyst is impregnated in the K containing 0.94g at room temperature2CO3It is water-soluble
In liquid, dip time is 2 hours, most obtains preparation by furfural gas phase hydrogenation through 110 DEG C afterwards for catalyst for furfural alcohol within dry 12 hours.This is urged
CuO and Cr in agent2O3Molar ratio be 2.6:1, CuO and SiO2Molar ratio be 3.5:1, CuO and K2CO3Molar ratio be
55:1.
(2) in stainless steel reactor, catalyst obtained is small with the reduction 6 of nitrogen hydrogen mixture at a temperature of 270 DEG C
When, then at 110 DEG C of temperature, pressure 0.3MPa, liquid air speed 0.25hr-1, react under conditions of hydrogen aldehyde molar ratio 10:1 and carry out
Preparation by furfural gas phase hydrogenation furfuryl alcohol, furfural conversion ratio are 100%, and furfuryl alcohol average selectivity is 99.83%.
Embodiment 2
The present embodiment is for illustrating catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol of the invention and preparation method thereof and furfural
The method of gas phase hydrogenation furfuryl alcohol.
(1) 30g CuO powder (granularity is less than 90 mesh), 23.89g Cr are weighed2O3Powder (granularity is less than 95 mesh), 30.2g
The acidic silica gel of 25 weight % is placed in ball grinder, is 300 revs/min in revolving speed, and ratio of grinding media to material is ball under the ball milling condition of 10:1
Mill 6 hours takes out mixture, 12 hours dry through 120 DEG C, and then 350 DEG C roasting 4 hours in Muffle furnace, are then added 1 weight
Preformed catalyst is made in the graphite tabletting for measuring %, and molding catalyst is impregnated in the K containing 1.3g at room temperature2CO3Aqueous solution
In, dip time is 2 hours, most obtains preparation by furfural gas phase hydrogenation through 110 DEG C afterwards for catalyst for furfural alcohol within dry 12 hours.The catalysis
CuO and Cr in agent2O3Molar ratio be 2.4:1, CuO and SiO2Molar ratio be 3:1, CuO and K2CO3Molar ratio be 40:1.
(2) in stainless steel reactor, catalyst obtained is small with the reduction 6 of nitrogen hydrogen mixture at a temperature of 270 DEG C
When, then at 110 DEG C of temperature, pressure 0.3MPa, liquid air speed 0.25hr-1, react under conditions of hydrogen aldehyde molar ratio 10:1 and carry out
Preparation by furfural gas phase hydrogenation furfuryl alcohol, furfural conversion ratio are 100%, and furfuryl alcohol average selectivity is 99.43%.
Embodiment 3
The present embodiment is for illustrating catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol of the invention and preparation method thereof and furfural
The method of gas phase hydrogenation furfuryl alcohol.
(1) 30g CuO powder (granularity is less than 90 mesh), 19.1g Cr are weighed2O3Powder (granularity is less than 95 mesh), 18.1g
The acidic silica gel of 25 weight % is placed in ball grinder, is 500 revs/min in revolving speed, and ratio of grinding media to material is ball under the ball milling condition of 30:1
Mill 10 hours takes out mixture, 12 hours dry through 120 DEG C, and then 350 DEG C roasting 4 hours in Muffle furnace, are then added 1
Preformed catalyst is made in the graphite tabletting of weight %, and molding catalyst is impregnated in the K containing 0.86g at room temperature2CO3It is water-soluble
In liquid, dip time is 2 hours, most obtains preparation by furfural gas phase hydrogenation through 110 DEG C afterwards for catalyst for furfural alcohol within dry 12 hours.This is urged
CuO and Cr in agent2O3Molar ratio be 3:1, CuO and SiO2Molar ratio be 5:1, CuO and K2CO3Molar ratio be 60:1.
(2) in stainless steel reactor, catalyst obtained is small with the reduction 6 of nitrogen hydrogen mixture at a temperature of 270 DEG C
When, then at 110 DEG C of temperature, pressure 0.3MPa, liquid air speed 0.25hr-1, react under conditions of hydrogen aldehyde molar ratio 10:1 and carry out
Preparation by furfural gas phase hydrogenation furfuryl alcohol, furfural conversion ratio are 100%, and furfuryl alcohol average selectivity is 99.32%.
Embodiment 4
The present embodiment is for illustrating catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol of the invention and preparation method thereof and furfural
The method of gas phase hydrogenation furfuryl alcohol.
Catalyst is prepared according to the method for embodiment 1 and carries out preparation by furfural gas phase hydrogenation furfuryl alcohol, unlike, CuO powder
Dosage be 30g, Cr2O3The dosage of powder is 57.34g, and the dosage of the acidic silica gel of 25 weight % is 90.7g, K2CO3Dosage
For 2.6g, CuO and Cr in catalyst obtained2O3Molar ratio be 1:1, CuO and SiO2Molar ratio be 1:1, CuO and K2CO3
Molar ratio be 20:1, furfural conversion ratio be 97.24%, furfuryl alcohol selectivity 99.14%.
Embodiment 5
The present embodiment is for illustrating catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol of the invention and preparation method thereof and furfural
The method of gas phase hydrogenation furfuryl alcohol.
Catalyst is prepared according to the method for embodiment 1 and carries out preparation by furfural gas phase hydrogenation furfuryl alcohol, unlike, CuO powder
Dosage be 30g, Cr2O3The dosage of powder is 11.5g, and the dosage of the acidic silica gel of 25 weight % is 4.5g, K2CO3Dosage is
0.65g, CuO and Cr in catalyst obtained2O3Molar ratio be 5:1, CuO and SiO2Molar ratio be 20:1, CuO and K2CO3
Molar ratio be 80:1, furfural conversion ratio be 99.82%, furfuryl alcohol selectivity 97.56%.
Embodiment 6
The present embodiment is for illustrating catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol of the invention and preparation method thereof and furfural
The method of gas phase hydrogenation furfuryl alcohol.
Catalyst is prepared according to the method for embodiment 1 and carries out preparation by furfural gas phase hydrogenation furfuryl alcohol, unlike, the item of ball milling
Part are as follows: ratio of grinding media to material 5:1, revolving speed are 150 revs/min, and the time is 1 hour, and furfural conversion ratio is 97.47%, furfuryl alcohol selectivity
98.53%.
Embodiment 7
The present embodiment is for illustrating catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol of the invention and preparation method thereof and furfural
The method of gas phase hydrogenation furfuryl alcohol.
Catalyst is prepared according to the method for embodiment 1 and carries out preparation by furfural gas phase hydrogenation furfuryl alcohol, unlike, do not use ball
The mode of mill, but use strength mechanical stirring mode by CuO powder, Cr2O3Powder, acidic silica gel are mixed, furfural conversion
Rate is 95%, furfuryl alcohol selectivity 96.43%.
The catalyst of the preparation by furfural gas phase hydrogenation furfuryl alcohol prepared using method of the invention has greater activity and selectivity,
It is 110 DEG C, pressure 0.3MPa in reaction temperature, liquid air speed is 0.25hr-1Under conditions of, furfural conversion ratio is >=95%,
Furfuryl alcohol selectivity >=96%, and the method for preparing catalyst is simple, easily operated, catalyst performance repeatability preferably, is easy real
Existing industry amplification application will not generate waste water, the exhaust gas of pollution environment in catalyst preparation process, be that a kind of green is clear
Clean production technology.
By embodiment 1 as can be seen that the molar ratio of cupric oxide powder and chromium oxide powder is 2.4- compared with embodiment 4-5
The molar ratio of 3:1, cupric oxide powder and potassium carbonate is 40-60:1, the molar ratio of silica in cupric oxide powder and silica solution
When for 3-5:1, the activity and selectivity of the catalyst of preparation can be further increased.
By embodiment 1 compared with Example 6 as can be seen that it is 8-15:1, revolving speed that the condition of the ball milling, which includes: ratio of grinding media to material,
It is 300-500 revs/min, when the time is 6-12 hours, the activity and selectivity of the catalyst of preparation can be further increased.
By embodiment 1 compared with Example 7 as can be seen that when the lapping mode is ball milling, system can be further increased
The activity and selectivity of standby catalyst.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (16)
1. a kind of catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol, which is characterized in that the catalyst contains copper oxide, chromium oxide, carbon
The molar ratio of sour potassium and silica, copper oxide and chromium oxide is 1-5:1, and the molar ratio of copper oxide and potassium carbonate is 20-80:1,
The molar ratio of copper oxide and silica is 1-20:1, and the preparation method of the catalyst includes:
(1) mixture of cupric oxide powder, chromium oxide powder and silica solution is ground；
(2) mixture that step (1) obtains successively is dried, roasted, compression molding；
(3) mold compound that step (2) obtains is impregnated in wet chemical,
Wherein, the molar ratio of cupric oxide powder and chromium oxide powder is 1-5:1, and the molar ratio of cupric oxide powder and potassium carbonate is
The molar ratio of silica is 1-20:1 in 20-80:1, cupric oxide powder and silica solution.
2. catalyst according to claim 1, wherein the molar ratio of copper oxide and chromium oxide be 2.4-3:1, copper oxide with
The molar ratio of potassium carbonate is 40-60:1, and the molar ratio of copper oxide and silica is 3-5:1.
3. a kind of preparation method of the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol, which is characterized in that this method comprises:
(1) mixture of cupric oxide powder, chromium oxide powder and silica solution is ground；
(2) mixture that step (1) obtains successively is dried, roasted, compression molding；
(3) mold compound that step (2) obtains is impregnated in wet chemical,
Wherein, the molar ratio of cupric oxide powder and chromium oxide powder is 1-5:1, and the molar ratio of cupric oxide powder and potassium carbonate is
The molar ratio of silica is 1-20:1 in 20-80:1, cupric oxide powder and silica solution.
4. according to the method described in claim 3, wherein, the molar ratio of cupric oxide powder and chromium oxide powder is 2.4-3:1, oxygen
The molar ratio for changing copper powders and potassium carbonate is 40-60:1, and the molar ratio of silica is 3-5 in cupric oxide powder and silica solution:
1。
5. according to the method described in claim 3, wherein, the partial size of cupric oxide powder is less than 100 mesh, the partial size of chromium oxide powder
Less than 100 mesh, the silica solution is acidic silicasol.
6. according to the method described in claim 3, wherein, the lapping mode is ball milling.
7. according to the method described in claim 6, wherein, the condition of the ball milling includes: that ratio of grinding media to material is 5-30:1, and revolving speed is
100-800 revs/min, the time is 1-48 hours.
8. according to the method described in claim 7, wherein, the condition of the ball milling includes: that ratio of grinding media to material is 8-15:1, and revolving speed is
300-500 revs/min, the time is 6-12 hours.
9. the method according to any one of claim 3-5, wherein in step (2), the method packet of the compression molding
It includes: the graphite that 0.5-2 weight % is added in the product after roasting is subjected to compression molding.
10. the method according to any one of claim 3-5, wherein in step (3), immersion condition includes: the time to be
1-3 hours.
11. the method according to any one of claim 3-5, wherein in step (2), the condition of the drying includes:
Drying temperature is 100-120 DEG C, and drying time is 10-20 hours.
12. the method according to any one of claim 3-5, wherein in step (2), the condition of the roasting includes:
Maturing temperature is 300-400 DEG C, and calcining time is 2-6 hours.
13. the method according to any one of claim 3-5, wherein this method further include: the product for obtaining dipping
It is dried；The condition of the drying includes: that drying temperature is 100-120 DEG C, and drying time is 10-20 hours.
14. the catalyst of the preparation by furfural gas phase hydrogenation furfuryl alcohol of any one of claim 3-13 the method preparation.
15. a kind of method of preparation by furfural gas phase hydrogenation furfuryl alcohol, which is characterized in that this method comprises: by described in claim 14
It is reacted after catalyst reduction for preparation by furfural gas phase hydrogenation furfuryl alcohol, the reaction condition includes: that temperature is 110-150 DEG C, pressure
For 0.2-0.6MPa, liquid air speed is 0.2-1hr-1。
16. according to the method for claim 15, wherein the restoring method includes: mixed with nitrogen hydrogen at 260-280 DEG C
Object is closed to restore 5-7 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978051A (en) * | 2005-12-07 | 2007-06-13 | 南化集团研究院 | Catalyst for alduronic gas-phase hydrogenation to prepare alditol and preparing method |
| CN102603681A (en) * | 2012-03-05 | 2012-07-25 | 中国石油大学(华东) | Method for preparing furfuryl alcohol through furfural liquid-phase catalytic hydrogenation |
| CN102631930A (en) * | 2012-03-30 | 2012-08-15 | 南京熙辉新材料有限公司 | Catalyst for preparing furfuryl alcohol from furfural by vapor phase hydrogenation and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978051A (en) * | 2005-12-07 | 2007-06-13 | 南化集团研究院 | Catalyst for alduronic gas-phase hydrogenation to prepare alditol and preparing method |
| CN102603681A (en) * | 2012-03-05 | 2012-07-25 | 中国石油大学(华东) | Method for preparing furfuryl alcohol through furfural liquid-phase catalytic hydrogenation |
| CN102631930A (en) * | 2012-03-30 | 2012-08-15 | 南京熙辉新材料有限公司 | Catalyst for preparing furfuryl alcohol from furfural by vapor phase hydrogenation and preparation method thereof |
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