CN106311267A - Catalyst for synthesizing isobutanol from synthetic gas as well as preparation method and application thereof - Google Patents
Catalyst for synthesizing isobutanol from synthetic gas as well as preparation method and application thereof Download PDFInfo
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 8
- 239000010970 precious metal Substances 0.000 claims abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 32
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 230000015572 biosynthetic process Effects 0.000 claims description 25
- 238000003786 synthesis reaction Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 24
- 238000001556 precipitation Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000402754 Erythranthe moschata Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- -1 propenecarbonyl Chemical group 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for synthesizing isobutanol from synthetic gas as well as a preparation method and an application thereof. The catalyst is prepared by a coprecipitation method. The catalyst comprises the following components in percentages by weight: 2-35% of CuO, 10-50% of ZrO2, 10-35% of MnO2, 4-25% of NiO, 3-15% of Fe2O3, 0.01-0.2% of oxide of alkali metal and 0.01-0.3% of oxide of precious metal, wherein the oxides of alkali metal and precious metal are added and used as auxiliary agents. In the condition that the reaction temperature is 400 DEG C, the pressure is 6MPa, the air speed of synthetic gas is 8000h<-1>, the proportion of methanol to isobutanol in liquid phase products is higher than 85%, and the proportion of isobutanol is higher than 29%.
Description
Technical field
The present invention relates to a kind of catalyst and its preparation method and application, relate in particular to catalyst of a kind of synthesis gas synthesis isobutanol and its preparation method and application.
Background technology
Isobutanol is basic organic chemical industry raw material, is used for manufacturing antioxidant, synthetic rubber, synthetic musk, fruit quintessence oil and synthetic drug etc..China is rare earth resources big country, and isobutanol is widely used in the purification of the salts such as strontium in Rare Earth Production, barium and lithium as solvent.
At present, industry isobutanol is essentially from side-product during propenecarbonyl synthesis legal system butanol, owing to this method is to produce n-butyl alcohol as target, therefore, the isobutanol amount obtained is little, it is impossible to meet the needs growing to isobutanol, and the raw material producing isobutanol is petroleum-based products propylene mostly.The few oil of rich coal is the main feature of energy structure in China, and along with being gradually increased of energy shortage and people's environmental consciousness, the syngas catalytic conversion low-carbon alcohols etc. utilizing coal to produce cleans fuel becomes the study hotspot in derived energy chemical field.
CO hydrogenation highly selective is directly synthesized isobutene. and isobutanol not only technique is simple, potential economic benefits, and what is more important can obtain from Non oil-based route, thus alleviates the pressure of the huge oil breach that China exists to a certain extent.
Before the nineties in last century, in higher alcohols synthesis, the catalyst used by isobutanol height selectivity is mainly Zn/Cr2O3、Cu/A12O3Deng.Patent EP0034338A2 and US4513100 disclose by methanol synthesis catalyst (Cu/ZnO/Al2O3, Zn/Cr2O3) through catalyst obtained by appropriate alkali metal or Modified With Alkali-earth Compounds.This type of catalyst activity is higher, and in product, isobutanol content is higher, but reaction condition harsher (pressure is 14～20 MPa, and temperature is 350～450 DEG C), water content higher (generally 30～50%) in product.
In recent years, owing to the character of zirconium and oxide thereof is gradually found and utilizes, zirconium oxide is gradually applied in catalyst, zirconium oxide is the most oxidizing but also has reproducibility, and this just determines zirconium oxide both can make the carrier of catalyst, can make again active component, such as, Cu/ZrO2、ZrO2/A12O3Deng.Meanwhile, appropriate ZrO is added2It is possible not only to make catalyst to be more easy to reduction, and can make each constituent element high degree of dispersion on it, increase the specific surface area of catalyst, carry high catalytic activity.Thus have higher researching value in the application of synthesis gas synthesis isobutanol.
European patent EP 0208102A2 provides a kind of containing ZrO2、MnO2, alkali metal and appropriate precious metals pd and Pt catalyst, be 420 DEG C in reaction temperature, pressure is 250 bar and air speed is at 13600 h-1Under the conditions of, in liquid product, the content of methanol is 43.9%, and the content of isobutanol is 40.4%.
Patent CN201010131745.3 discloses and is supported a small amount of alkali metal K by cerium oxide, manganese oxide and zirconium oxide and catalyst that precious metal palladium forms, at reaction temperature 400 DEG C, pressure 8 MPa, air speed 10000 h-1, H2Under conditions of/CO volume ratio is 1:1～3:1, the conversion ratio of CO is 8.81%, and in alcohol, the selectivity (Cmol%) of isobutanol is 31.84%, and space-time yield is 70.35 g/Kg-Cat/h, and the selectivity of methane is 7.33%.
Patent CN201310217022.9 discloses a kind of catalyst by synthesis gas synthesis isobutanol and is made up of copper oxide, zinc oxide, zirconium oxide, lanthana, Disamarium trioxide, thorium oxide, cerium oxide, vanadium oxide, nickel oxide and potassium oxide, and in product, isobutanol selectivity reaches 45.37mol%.
In existing synthesis gas synthesis isobutanol technology, the conversion ratio of CO and selectivity benefit for commercial production of isobutanol are relatively low, and reaction condition is the harshest mostly.
Summary of the invention
It is an object of the invention to provide a kind of isobutanol selectivity high, preparation process is simple, relatively mild a kind of synthesis gas isobutanol catalyst of operating condition and preparation method thereof.
The catalytic component of the present invention is CuO, ZrO2、MnO2、NiO、Fe2O3Deng metal-oxide, and add the oxide of appropriate bases metal and noble metal as auxiliary agent, wherein, CuO, ZrO2、MnO2、NiO、Fe2O3, alkali metal oxide, the percentage by weight of metal oxide containing precious metals be: 2% ~ 35%:10% ~ 50%:10% ~ 35%:4% ~ 25%:3% ~ 15%:0.01 ~ 0.2%:0.01 ~ 0.3%.
Described alkali metal is any one in K, Rb, Cs, preferably K；
Described noble metal is the one in Pd, Pt, preferably Pd.
In the present invention, the preparation method of catalyst is as follows: the nitrate of Cu, Zr, Mn, Ni, Fe is configured to solution in proportion, it is co-precipitated with precipitant solution, precipitation temperature is 50 ~ 80 DEG C, and precipitation pH is 8 ~ 11, and digestion time is 20 ~ 40 min, scrubbed, filter, be dried, at 300 ~ 500 DEG C of roasting 4 ~ 6 h, then impregnate the nitrate solution of noble metal, after drying, at 200 ~ 400 DEG C of roasting 2 ~ 5 h, final impregnating K2CO3, after drying, at 200 ~ 500 DEG C of roasting 2 ~ 5 h, obtain catalyst.
Described precipitant uses NaOH, Na2CO3、KOH、K2CO3, one in ammonia, preferably NaOH.
Above-mentioned catalyst is used for synthesis gas isobutanol, uses fixed bed reactors, with H2For reducing gases, at gas space velocity 200～1000 h-1, reduce pressure 0.3～1 MPa, to catalyst reduction 10～20 h under conditions of reduction temperature 300～450 DEG C.Being passed through synthesis gas after having reduced to react, reaction temperature is 350 ~ 450 DEG C, and reaction pressure is 5 ~ 15 MPa, and synthesis gas air speed is 3000 ~ 15000 h-1, H in synthesis gas2It is 3.0 ~ 1.0 with the volume ratio of CO.
The method for preparing catalyst that the present invention provides is simple, has higher space-time yield and isobutanol selectivity.
Detailed description of the invention
In order to make those skilled in the art be more fully understood that the present invention, and enabling the above-mentioned advantage of the present invention to become apparent from understandable, below in conjunction with specific embodiment, the present invention is further detailed explanation.
Embodiment 1
Weigh 24.16 gCu (NO3)2·3H2O、85.86 gZr(NO3)4·5H2O、17.89 gMn(NO3)2、14.54 gNi(NO3)2·6H2O、20.2 gFe(NO3)3·9H2O is made into the aqueous solution of 1L, is co-precipitated with the NaOH solution of 2 mol/L, and precipitation pH is 9.0, and precipitation temperature is 70 DEG C.It is aged 20 min after having precipitated, is washed with deionized afterwards 5 times, 120 DEG C of drying, 450 DEG C of calcining 6 h.Impregnate the Pd (NO of 0.1 wt%3)2, after 120 DEG C dry, 450 DEG C of calcinings 5 h, the K of final impregnating 1 wt%2CO3, after 120 DEG C dry, 450 DEG C of roasting 5 h, this catalyst is designated as C-1.
Embodiment 2
Weigh 24.06 gCu (NO3)2·3H2O、64.4 gZr(NO3)4·5H2O、26.83 gMn(NO3)2、4.4 gNi(NO3)2·6H2O、10.1 gFe(NO3)3·9H2O is made into the aqueous solution of 1L, is co-precipitated with the NaOH solution of 2 mol/L, and precipitation pH is 9.5, and precipitation temperature is 75 DEG C.It is aged 20 min after having precipitated, is washed with deionized afterwards 5 times, 120 DEG C of drying, 450 DEG C of roasting 6 h.Impregnate the Pd (NO of 0.2 wt%3)2, after 120 DEG C dry, 420 DEG C of roasting 5 h, the K of final impregnating 0.8 wt%2CO3, after 120 DEG C dry, 450 DEG C of roasting 3 h, this catalyst is designated as C-2.
Embodiment 3
Weigh 18.05 gCu (NO3)2·3H2O、42.93 gZr(NO3)4·5H2O、8.94 gMn(NO3)2、7.33 gNi(NO3)2·6H2O、16.16 gFe(NO3)3·9H2O is made into the aqueous solution of 1L, is co-precipitated with the NaOH solution of 2 mol/L, and precipitation pH is 10.0, and precipitation temperature is 75 DEG C.It is aged 40 min after having precipitated, is washed with deionized afterwards 5 times, 120 DEG C of drying, 400 DEG C of roasting 6 h.Impregnate the Pd (NO of 0.08 wt%3)2, after 120 DEG C dry, 420 DEG C of roasting 5 h, the K of final impregnating 1.2 wt%2CO3, after 120 DEG C dry, 450 DEG C of roasting 4 h, this catalyst is designated as C-3.
Comparative example 1
Weigh 24.16 gCu (NO3)2·3H2O、85.86 gZr(NO3)4·5H2O、17.89 gMn(NO3)2、20.2 gFe(NO3)3·9H2O is made into the aqueous solution of 1L, is co-precipitated with the NaOH solution of 2 mol/L, and precipitation pH is 9.0, and precipitation temperature is 70 DEG C.It is aged 20 min after having precipitated, is washed with deionized afterwards 5 times, 120 DEG C of drying, 450 DEG C of calcining 6 h.Impregnate the Pd (NO of 0.1 wt%3)2, after 120 DEG C dry, 450 DEG C of calcinings 5 h, the K of final impregnating 1 wt%2CO3, after 120 DEG C dry, 450 DEG C of roasting 5 h, this catalyst is designated as B-1.
Comparative example 2
Weigh 24.06 gCu (NO3)2·3H2O、64.4 gZr(NO3)4·5H2O、26.83 gMn(NO3)2、4.4 gNi(NO3)2·6H2O is made into the aqueous solution of 1L, is co-precipitated with the NaOH solution of 2 mol/L, and precipitation pH is 9.5, and precipitation temperature is 75 DEG C.It is aged 20 min after having precipitated, is washed with deionized afterwards 5 times, 120 DEG C of drying, 450 DEG C of roasting 6 h.Impregnate the Pd (NO of 0.2 wt%3)2, after 120 DEG C dry, 420 DEG C of roasting 5 h, the K of final impregnating 0.8 wt%2CO3, after 120 DEG C dry, 450 DEG C of roasting 3 h, this catalyst is designated as B-2.
Comparative example 3
Weigh 18.05 gCu (NO3)2·3H2O、42.93 gZr(NO3)4·5H2O、8.94 gMn(NO3)2、7.33 gNi(NO3)2·6H2O、16.16 gFe(NO3)3·9H2O is made into the aqueous solution of 1L, is co-precipitated with the NaOH solution of 2 mol/L, and precipitation pH is 10.0, and precipitation temperature is 75 DEG C.It is aged 40 min after having precipitated, is washed with deionized afterwards 5 times, 120 DEG C of drying, 400 DEG C of roasting 6 h.Impregnate the Pd (NO of 0.08 wt%3)2, after 120 DEG C dry, 420 DEG C of roasting 5 h, this catalyst is designated as B-3.
By above-mentioned Catalyst packing in fixed bed reactors, with H2For reducing gases, at gas space velocity 400 h-1, reduction pressure 0.3 MPa, to catalyst reduction 12 h under conditions of reduction temperature 350 DEG C.
Being passed through synthesis gas after having reduced to react, reaction condition is reaction temperature 400 DEG C, pressure 6 MPa, air speed 8000 h-1。
Obtaining mixed alcohol product after reacted gas is condensed, product enters chromatography the most again, result is as shown in table 1:
Table 1 product space-time yield and alcohol distribution
As shown in Table 1, after adding Ni, Fe, K, the space-time yield of product increased and beneficially methanol and the generation of isobutanol.At reaction temperature 400 DEG C, pressure 6 MPa, synthesis gas air speed 8000 h-1Reaction condition under, in liquid product the ratio of methanol and isobutanol be higher than 85%, the ratio of isobutanol be higher than 29%.
Claims (9)
1. the catalyst being synthesized isobutanol by synthesis gas, it is characterised in that: catalytic component is CuO, ZrO2、MnO2、NiO、Fe2O3, and add alkali metal oxide and metal oxide containing precious metals as auxiliary agent, and wherein, CuO, ZrO2、MnO2、NiO、Fe2O3, alkali metal oxide, the percentage by weight of metal oxide containing precious metals be: 2% ~ 35%:10% ~ 50%:10% ~ 35%:4% ~ 25%:3% ~ 15%:0.01 ~ 0.2%:0.01 ~ 0.3%.
2. catalyst as claimed in claim 1, it is characterised in that described alkali metal is any one in K, Rb, Cs.
3. catalyst as claimed in claim 2, it is characterised in that described alkali metal is K.
4. catalyst as claimed in claim 1, it is characterised in that described noble metal is the one in Pd, Pt.
5. catalyst as claimed in claim 4, it is characterised in that described noble metal is Pd.
6. the preparation method being synthesized isobutanol catalyst as described in the appended claim 1 by synthesis gas, it is characterized in that comprising the following steps: the nitrate of Cu, Zr, Mn, Ni, Fe is configured to solution in proportion, it is co-precipitated with precipitant solution, precipitation temperature is 50 ~ 80 DEG C, precipitation pH value is 8 ~ 11, digestion time is 20 ~ 40 min, scrubbed, filter, be dried, at 300 ~ 500 DEG C of roasting 4 ~ 6 h, then the nitrate solution of noble metal is impregnated, after drying, at 200 ~ 400 DEG C of roasting 2 ~ 5 h, final impregnating K2CO3, after drying, at 200 ~ 500 DEG C of roasting 2 ~ 5 h, obtain catalyst.
7. the preparation method of catalyst as claimed in claim 6, it is characterised in that described precipitant uses NaOH, Na2CO3、KOH、K2CO3, one in ammonia.
8. the preparation method of catalyst as claimed in claim 7, it is characterised in that described precipitant uses NaOH.
9. the application of a catalyst as claimed in claim 1, it is characterised in that use fixed bed reactors, with H2For reducing gases, at gas space velocity 200～1000 h-1, reduce pressure 0.3～1 MPa, to catalyst reduction 10～20 h under conditions of reduction temperature 300～450 DEG C；Being passed through synthesis gas after having reduced to react, reaction temperature is 350 ~ 450 DEG C, and reaction pressure is 5 ~ 15 MPa, and synthesis gas air speed is 3000 ~ 15000 h-1, H in synthesis gas2It is 3.0 ~ 1.0 with the volume ratio of CO.
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| CN201510389572.8A CN106311267A (en) | 2015-07-06 | 2015-07-06 | Catalyst for synthesizing isobutanol from synthetic gas as well as preparation method and application thereof |
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| CN110508300A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Catalyst NdNiO3/SiC-SiO2-Foam for Biogas Total Component Conversion Biomethanol and Its Preparation Method |
| CN115770583A (en) * | 2021-09-06 | 2023-03-10 | 中石化南京化工研究院有限公司 | Catalyst for producing isobutanol by using synthesis gas and methanol |
| CN116368114A (en) * | 2020-09-14 | 2023-06-30 | 环球油品有限责任公司 | Catalyst for the synthesis of isobutanol from synthesis gas and ethanol or propanol |
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| CN110508300A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Catalyst NdNiO3/SiC-SiO2-Foam for Biogas Total Component Conversion Biomethanol and Its Preparation Method |
| CN116368114A (en) * | 2020-09-14 | 2023-06-30 | 环球油品有限责任公司 | Catalyst for the synthesis of isobutanol from synthesis gas and ethanol or propanol |
| CN115770583A (en) * | 2021-09-06 | 2023-03-10 | 中石化南京化工研究院有限公司 | Catalyst for producing isobutanol by using synthesis gas and methanol |
| CN115770583B (en) * | 2021-09-06 | 2024-05-14 | 中石化南京化工研究院有限公司 | Catalyst for producing isobutanol by using synthesis gas and methanol |
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