CN115770583B - Catalyst for producing isobutanol by using synthesis gas and methanol - Google Patents
Catalyst for producing isobutanol by using synthesis gas and methanol Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001556 precipitation Methods 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000012696 Pd precursors Substances 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004904 shortening Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011164 primary particle Substances 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
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of preparation of low-carbon alcohol catalysts, and particularly relates to a catalyst for preparing isobutanol by taking synthesis gas and methanol as raw materials and a preparation method thereof. The catalyst is prepared by adopting a precipitation method, a mixing grinding method and an impregnation method according to the total weight percentage of ：ZrO2：20-45%,MnO2：10-40%,ZnO：10-40%,CuO：1-2%,Co2O3：3-5%;PdO：0.2-0.6%;AlKO6Si2：0.5-1%., wherein Zr, zn, mn, cu, co component precursors are nitrate. The catalyst of the invention is applied to the process of preparing isobutanol by using synthesis gas, and can directly add methanol into raw materials, thereby achieving the effect of shortening the reaction path, improving the space-time yield of C 2+ alcohol and directly improving the space-time yield of isobutanol.
Description
Technical Field
The invention belongs to the technical field of preparation of low-carbon alcohol catalysts, and particularly relates to a catalyst for producing isobutanol by taking synthesis gas and methanol as raw materials and a preparation method thereof.
Background
Isobutanol is a basic organic chemical raw material, and can be used for preparing antioxidants, esters, synthetic rubber, synthetic drugs and the like, and can also be used as a high-grade solvent. Commercial isobutanol is currently derived mainly from byproducts of the carbonylation of propylene to butanol with low yields, and so research into the production of isobutanol from synthesis gas is of great economic and social importance.
CN105727982A is a catalyst for synthesizing low-carbon alcohol and a preparation method thereof, and Cu, ni and Pd auxiliary agents are added into a catalyst taking Mn, zn and Zr as carriers to obtain a catalyst for preparing low-carbon alcohol from synthesis gas with high C 2+ selectivity, and better isobutanol selectivity is obtained. However, the catalyst adopts synthesis gas as a raw material, the reaction path is longer, and the total alcohol yield and the isobutanol yield are not high.
Disclosure of Invention
The invention aims to provide a catalyst for producing isobutanol by using synthesis gas and methanol. The catalyst has the advantages of high selectivity of C 2+ alcohol, high space-time yield of C 2+ total alcohol, high space-time yield of isobutanol and the like.
The invention provides a catalyst for producing isobutanol by using synthesis gas and methanol, which is realized by the following technical scheme.
The invention provides a catalyst for producing isobutanol by using synthesis gas and methanol, which comprises the following components in percentage by mass ：ZrO2：20-45%,MnO2：10-40%,ZnO：10-40%,CuO：1-2%,Co2O3：3-5%;PdO：0.2-0.6%;AlKO6Si2：0.5-1%.
The catalyst for producing isobutanol by using synthesis gas and methanol provided by the invention is prepared by adopting a method combining a coprecipitation method, a mixed grinding method and an impregnation method.
The preparation method of the catalyst comprises the following steps:
a) Completely dissolving the precursor of Zr, mn, zn, co, cu components in deionized water according to a proportion, carrying out concurrent precipitation on the solution and an aqueous solution of NaOH or Na 2CO3, stirring and maintaining pH=6.8-7.4 in the precipitation process, and continuing stirring after the acid solution is added dropwise;
b) Continuously adding aqueous solution of NaOH or Na 2CO3 until the pH value is 9-10, and continuously stirring;
c) Heating and continuously stirring, washing the obtained precipitate with deionized water to neutrality, drying and roasting;
d) Pulverizing the materials obtained in the step c), mixing solid alkali according to a proportion, adding a pore-forming auxiliary agent, mixing, grinding, granulating, drying, forming, and roasting after forming;
e) And d) immersing the formed material in the step of Pd precursor solution in an equal volume in proportion, and drying and roasting to obtain the required catalyst.
A typical preparation method of the catalyst disclosed by the invention comprises the following steps:
a) Completely dissolving Zr, mn, zn, co, cu components of precursor in deionized water according to a proportion, precipitating the solution and NaOH or Na 2CO3 water solution in parallel flow at 65-70 ℃, stirring and maintaining pH=6.8-7.4 during precipitation, and continuously stirring for 15-25min, preferably 20min after the acid solution is added dropwise;
b) Continuing to add the aqueous solution of NaOH or Na 2CO3 to a ph=9-10, continuing to stir for 25-35min, preferably 30min;
c) Raising the temperature to 75-85 ℃, preferably 80 ℃, continuing stirring for 25-35min, preferably 30min, washing the obtained precipitate with deionized water at 70-80 ℃ to be neutral, drying at 100-120 ℃, and roasting at 450-500 ℃ for 3-5h;
d) Pulverizing the materials obtained in the step c), mixing solid alkali according to a proportion, adding a pore-forming auxiliary agent, mixing, grinding, granulating, drying and forming, and roasting at 450-500 ℃ for 3-5h after forming;
e) And d), soaking the formed material in Pd precursor solution in an equal volume in proportion, drying and roasting at 450-500 ℃ for 3-5h to obtain the required catalyst.
Preferably, the precursors of the Zr, mn, cu, zn, co, pd components are all nitrates.
Preferably, the solid base is AlKO 6Si2.
Preferably, the solid alkali is crushed to below 150 meshes and added for mixing and grinding.
The catalyst provided by the invention is used for the reaction of synthesis gas and methanol to produce isobutanol, and the use conditions are as follows: the pressure is 8.0MPa, the temperature is 380 ℃, the equivalent GHSV of synthetic gas=5000 h -1, the equivalent hydrogen-carbon ratio is 1, and the equivalent methanol gas space velocity GHSV is less than or equal to 1200 h -1.
The equivalent GHSV=5000 h -1 of the synthetic gas disclosed by the invention is the sum of the space velocity of the synthetic gas converted from methanol and the space velocity of the fresh synthetic gas.
The hydrogen-carbon ratio equivalent 1 is the ratio of methanol converted into synthetic gas and added with fresh synthetic gas.
The methanol equivalent gas space velocity GHSV is not more than 1200 h -1, which is the fractional space velocity of the methanol synthesis gas after the methanol is converted into the synthesis gas space velocity.
The invention uses the chemical formula CH 3 OH of methanol, wherein, two H 2 and one CO are provided, the hydrogen-carbon ratio is 2, the methanol equivalent synthetic gas space velocity can be calculated according to the methanol liquid space velocity, the methanol gas space velocity equivalent GHSV is less than or equal to 1200H -1, and the methanol liquid space velocity is less than or equal to 571 g.L -1h-1.
The beneficial effects of the invention are that
The catalyst for generating C 2+ alcohols by reacting synthesis gas with methanol is prepared by adopting a precipitation method of controlling the pH value twice and a preparation method of mixing and grinding and dipping, so that a wrapped catalyst with high dispersity is obtained, the pH value of the catalyst can be adjusted by adding solid alkali during mixing and grinding, and the alkali loss speed in the use process of the catalyst is reduced; adding a small amount of Co to improve the efficiency of the growth of the alcohol carbon chain and the CO conversion rate, and adding a small amount of copper to control the path of generating the alcohols by the synthesis gas. The catalyst of the invention is applied to the process of preparing isobutanol by using synthesis gas, and can directly add methanol into raw materials, thereby achieving the effect of shortening the reaction path, improving the space-time yield of C 2+ alcohol and directly improving the space-time yield of isobutanol.
Detailed Description
The following examples are only for further explanation of the contents and effects of the present invention, and are not to be construed as limiting the present invention.
Example 1
According to the composition of ZrO 220%,MnO234%,ZnO40%,CuO2%,Co2O3%, completely dissolving a Zr, mn, zn, co, cu nitrate precursor in deionized water to prepare 2L of solution, carrying out concurrent precipitation on the solution and Na 2CO3 aqueous solution under Zr4+=14.8g/L、Mn4+=21.5g/L、Zn2+=32.10g/L、Cu2+=1.6g/L、Co3+=2.1g/L.70℃, stirring and maintaining pH=7 in the precipitation process, and stirring for 20min after the acid solution is added dropwise; continuing to add Na 2CO3 aqueous solution until the pH value is=10, and continuing to stir for 30min; raising the temperature to 80 ℃, continuing stirring for 30min, washing the obtained precipitate with deionized water at 80 ℃ to be neutral, drying at 100 ℃, and roasting at 500 ℃ for 3h; crushing the obtained sample, mixing AlKO 6Si2 solid 1g according to the weight ratio of 0.5%, adding 4g of pore-forming auxiliary agent graphite according to the weight ratio of 2%, mixing, grinding, granulating, drying and forming, and roasting at 500 ℃ for 3 hours after forming; about 200g of the calcined sample was immersed in Pd (NO 3）2 solution) at an equal volume in a proportion of 0.5% by weight of PdO, dried and calcined at 500℃for 3 hours to obtain the desired catalyst, which was designated as sample 1.
Example 2
According to ZrO 245%,MnO210%,ZnO37.8%,CuO1%,Co2O3%; completely dissolving Zr, mn, zn, co, cu nitrate precursor in deionized water to prepare 2L solution, wherein the solution and NaOH aqueous solution are subjected to concurrent precipitation under Zr4+=33.3g/L、Mn4+=6.32g/L、Zn2+=30.33g/L、Cu2+=0.8g/L、Co3+=3.55g/L.65℃, stirring and maintaining pH=7 in the precipitation process, and stirring for 20min after the acid solution is added dropwise; continuously adding NaOH aqueous solution until the pH value is=10, and continuously stirring for 30min; raising the temperature to 80 ℃, continuing stirring for 30min, washing the obtained precipitate with deionized water at 80 ℃ to be neutral, drying at 120 ℃ and roasting at 450 ℃ for 5h; crushing the obtained sample, mixing AlKO 6Si2 solid 2g according to the weight ratio of 1%, adding pore-forming auxiliary agent graphite 4g according to the weight ratio of 2%, mixing, grinding, granulating, drying and forming, and roasting at 450 ℃ for 5h after forming; the calcined sample was immersed in Pd (NO 3）2 solution) at an equal volume at a ratio of PdO0.2% by weight, dried and calcined at 450℃for 5 hours to obtain the desired catalyst, which was designated as sample 2.
Example 3
According to the composition of ZrO 242.9%,MnO240%,ZnO10%,CuO1.5%,Co2O3 percent, completely dissolving a nitrate precursor of Zr, mn, zn, co, cu in deionized water to prepare 2L of solution, carrying out concurrent precipitation on the solution and an aqueous NaOH solution under Zr4+=31.74g/L、Mn4+=25.39g/L、Zn2+=8.02g/L、Cu2+=3.2g/L、Co3+=2.84g/L.70℃, stirring and maintaining pH=7 in the precipitation process, and stirring for 20min after the acid solution is added dropwise; continuously adding NaOH aqueous solution until the pH value is=10, and continuously stirring for 30min; raising the temperature to 80 ℃, continuing stirring for 30min, washing the obtained precipitate with deionized water at 80 ℃ to be neutral, drying at 120 ℃ and roasting at 470 ℃ for 4h; crushing the obtained sample, mixing AlKO 6Si2 solid 1.2g according to the weight ratio of 0.6%, adding 4g of 2% by weight of pore-forming auxiliary agent graphite, mixing, grinding, granulating, drying and forming, and roasting at 470 ℃ for 4 hours after forming; the calcined sample was impregnated with Pd (NO 3）2 solution at an equal volume of PdO0.6 wt%, dried and calcined at 470℃for 4 hours to give the desired catalyst, which was designated as sample 3.
Example 4
According to the composition of ZrO 231%,MnO231%,ZnO31%,CuO1.5%,Co2O3 and 4.5%, completely dissolving Zr, mn, zn, co, cu nitrate precursor in deionized water to prepare 2L solution, carrying out cocurrent precipitation on the solution and NaOH aqueous solution under Zr4+=22.93g/L、Mn4+=19.59g/L、Zn2+=24.88g/L、Cu2+=3.6g/L、Co3+=3.20g/L.70℃, stirring and maintaining pH=7 in the precipitation process, and stirring for 20min after the acid solution is added dropwise; continuously adding NaOH aqueous solution until the pH value is=10, and continuously stirring for 30min; raising the temperature to 80 ℃, continuing stirring for 30min, washing the obtained precipitate with deionized water at 80 ℃ to be neutral, drying at 120 ℃ and roasting at 470 ℃ for 4h; crushing the obtained sample, mixing AlKO 6Si2 solid 1g according to the weight ratio of 0.5%, adding 4g of 2% by weight of pore-forming auxiliary agent graphite, mixing, grinding, granulating, drying and forming, and roasting at 470 ℃ for 4 hours after forming; the calcined sample was impregnated with Pd (NO 3）2 solution) at an equal volume at a ratio of PdO0.5 wt%, dried and calcined at 470℃for 4 hours to give the desired catalyst, which was designated sample 4.
Example 5
According to the composition of ZrO 232%,MnO232%,ZnO31.3%,CuO1%,Co2O3%, completely dissolving a Zr, mn, zn, co, cu nitrate precursor in deionized water to prepare 2L of solution, carrying out concurrent precipitation on the solution and an NaOH aqueous solution under Zr4+=23.67g/L、Mn4+=20.23g/L、Zn2+=25.12g/L、Cu2+=0.8g/L、Co3+=2.12g/L.70℃, stirring and maintaining pH=7 in the precipitation process, and stirring for 20min after the acid solution is added dropwise; continuously adding NaOH aqueous solution until the pH value is=10, and continuously stirring for 30min; raising the temperature to 80 ℃, continuing stirring for 30min, washing the obtained precipitate with deionized water at 80 ℃ to be neutral, drying at 120 ℃ and roasting at 470 ℃ for 4h; crushing the obtained sample, mixing AlKO 6Si2 solid 1g according to the weight ratio of 0.5%, adding 4g of pore-forming auxiliary agent graphite according to the weight ratio of 2%, mixing, grinding, granulating, drying and forming, and roasting at 470 ℃ for 4 hours after forming; the calcined sample was immersed in Pd (NO 3）2 solution) at an equal volume at a ratio of PdO0.2% by weight, dried and calcined at 470℃for 4 hours to obtain the desired catalyst, which was designated as sample 5.
Example 6
According to ZrO230.5%,MnO230.5%,ZnO30.4%,CuO2%,Co2O35%;PdO0.6%;AlKO6Si21%, completely dissolving Zr, mn, zn, co, cu nitrate precursor in deionized water to prepare 2L solution, precipitating the solution and NaOH aqueous solution in parallel flow under Zr4+=22.56g/L、Mn4+=19.28g/L、Zn2+=24.40g/L、Cu2+=1.6g/L、Co3+=3.55g/L.70℃, stirring and maintaining pH=7 during precipitation, and stirring for 20min after the acid solution is added dropwise; continuously adding NaOH aqueous solution until the pH value is=10, and continuously stirring for 30min; raising the temperature to 80 ℃, continuing stirring for 30min, washing the obtained precipitate with deionized water at 80 ℃ to be neutral, drying at 120 ℃ and roasting at 470 ℃ for 4h; crushing the obtained sample, mixing AlKO 6Si2 solid 2g according to the weight ratio of 1%, adding pore-forming auxiliary agent graphite 4g according to the weight ratio of 2%, mixing, grinding, granulating, drying and forming, and roasting at 470 ℃ for 4 hours after forming; the calcined sample was immersed in Pd (NO 3）2 solution) at a ratio of 0.6% in equal volume, dried and calcined at 470℃for 4 hours to obtain the desired catalyst, which was designated as sample 6.
Activity test conditions: the catalyst performance was evaluated by charging 50ml of the raw catalyst into a reactor having an inner diameter of 26 mm. Before the reaction, the catalyst is reduced for 12 hours in nitrogen-hydrogen atmosphere with the concentration of 5% hydrogen at 400 ℃ and 0.2MPa, and then the synthesis gas is switched in a boosting way and added into methanol for reaction. The reaction conditions are as follows: the pressure is 8.0MPa, the temperature is 380 ℃, the synthesis gas GHSV=3800 h -1, the methanol equivalent gas space velocity GHSV=1200 h -1=571 g·L-1h-1 =28.55 g/50 ml catalyst.h, and the total hydrogen-carbon ratio is converted to 1.
Table 1 results of catalyst evaluation
| CO conversion% | Methanol conversion% | Total mass of C 2+ alcohol per hour g | Isobutanol mass per hour, g | Isobutanol mass ratio in C 2+ alcohol% | |
| Sample 1 | 12.8 | 0.0 | 9.2 | 7.6 | 76.1 |
| Sample 2 | 12.1 | -2.0 | 7.0 | 4.8 | 68.6 |
| Sample 3 | 11.4 | -1.9 | 7.1 | 4.9 | 69.0 |
| Sample 4 | 15.0 | 2.4 | 12.2 | 10.1 | 82.8 |
| Sample 5 | 13.9 | 2.0 | 11.5 | 9.4 | 81.7 |
| Sample 6 | 14.2 | 1.8 | 11.7 | 9.0 | 76.9 |
Sample 4 of primary particle size catalyst was charged in an internal diameter 26mm reactor with 50ml, the catalyst was reduced at 400℃under 0.2MPa in a nitrogen-hydrogen atmosphere with a hydrogen concentration of 5% for 12 hours, and then the synthesis gas was switched under pressure and fed into methanol for reaction. The reaction conditions are as follows: the pressure is 8.0MPa, the temperature is 380 ℃, the GHSV=5000 h -1 of the synthesis gas and the hydrogen-carbon ratio is 1. No methanol was added.
Table 2 catalyst use comparative example
| CO conversion% | Methanol conversion% | Total mass of C 2+ alcohol per hour g | Isobutanol mass per hour, g | Isobutanol mass ratio in C 2+ alcohol% | |
| Sample 4 (methanol addition) | 15.0 | 2.4 | 12.2 | 10.1 | 82.8 |
| Sample 4 (without methanol) | 17.8 | Without any means for | 9.7 | 7.8 | 80.4 |
Claims (8)
1. The catalyst for producing isobutanol by using synthesis gas and methanol is characterized in that the catalyst is prepared by adopting a method of combining a coprecipitation method, a mixed grinding method and an impregnation method and comprises the following steps of:
a) Completely dissolving the precursor of Zr, mn, zn, co, cu components in deionized water according to a proportion, carrying out concurrent precipitation on the solution and an aqueous solution of NaOH or Na 2CO3, stirring and maintaining pH=6.8-7.4 in the precipitation process, and continuing stirring after the acid solution is added dropwise;
b) Continuously adding aqueous solution of NaOH or Na 2CO3 until the pH value is 9-10, and continuously stirring;
c) Heating and continuously stirring, washing the obtained precipitate with deionized water to neutrality, drying and roasting;
d) Pulverizing the materials obtained in the step c), mixing solid alkali according to a proportion, adding a pore-forming auxiliary agent, mixing, grinding, granulating, drying, forming, and roasting after forming;
e) And d) immersing the formed material in the step of Pd precursor solution in an equal volume in proportion, and drying and roasting to obtain the required catalyst.
2. The catalyst of claim 1, prepared by the steps of:
a) Completely dissolving Zr, mn, zn, co, cu components of precursors in deionized water according to a proportion, carrying out concurrent precipitation on the solution and an aqueous solution of NaOH or Na 2CO3 at 65-70 ℃, stirring and maintaining pH=6.8-7.4 in the precipitation process, and continuing stirring for 15-25min after the acid solution is added dropwise;
b) Continuously adding aqueous solution of NaOH or Na 2CO3 until the pH value is 9-10, and continuously stirring for 25-35min;
c) Raising the temperature to 75-85 ℃, continuing stirring for 25-35min, washing the obtained precipitate with deionized water at 70-80 ℃ to be neutral, drying at 100-120 ℃, and roasting at 450-500 ℃ for 3-5h;
d) Pulverizing the materials obtained in the step c), mixing solid alkali according to a proportion, adding a pore-forming auxiliary agent, mixing, grinding, granulating, drying and forming, and roasting at 450-500 ℃ for 3-5h after forming;
e) And d), soaking the formed material in Pd precursor solution in an equal volume in proportion, drying and roasting at 450-500 ℃ for 3-5h to obtain the required catalyst.
3. The catalyst of claim 1 or claim 2 wherein the precursor of Zr, mn, cu, zn, co, pd component is a nitrate.
4. The catalyst of claim 1 or 2, wherein the solid base is AlKO 6Si2.
5. The catalyst of claim 1 or 2, wherein the solid base is crushed to less than 150 mesh and added for mixing and grinding.
6. The catalyst of claim 2 wherein in step a) the agitation time is 20 minutes; stirring time in step b) was 30min and stirring time in step c) was 30min.
7. The catalyst of claim 2 wherein in step c) the temperature is raised to 80 ℃.
8. The use of the catalyst according to claim 1, wherein the catalyst is used for the reaction of synthesis gas and methanol to produce isobutanol under the following conditions: the pressure is 8.0MPa, the temperature is 380 ℃, the equivalent GHSV of synthetic gas=5000 h -1, the equivalent hydrogen-carbon ratio is 1, and the equivalent methanol gas space velocity GHSV is less than or equal to 1200 h -1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111038285.4A CN115770583B (en) | 2021-09-06 | 2021-09-06 | Catalyst for producing isobutanol by using synthesis gas and methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111038285.4A CN115770583B (en) | 2021-09-06 | 2021-09-06 | Catalyst for producing isobutanol by using synthesis gas and methanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115770583A CN115770583A (en) | 2023-03-10 |
| CN115770583B true CN115770583B (en) | 2024-05-14 |
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| CN115770583A (en) | 2023-03-10 |
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