CN108117480B - Method for preparing isobutanol by catalytic conversion of mixed solution of methanol and ethanol - Google Patents
Method for preparing isobutanol by catalytic conversion of mixed solution of methanol and ethanol Download PDFInfo
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
- C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
Abstract
The invention relates to a novel method for preparing isobutanol by catalytically converting a mixed solution of methanol and ethanol. The method directly takes a mixed solution of methanol and ethanol as a raw material, takes an alkaline carrier carrying two or more elements of platinum, palladium, ruthenium, rhodium, cobalt, copper, nickel, tungsten and molybdenum as a catalyst, takes a fixed bed reactor as an evaluation device, and prepares the isobutanol by the catalytic conversion reaction of the mixed solution of the methanol and the ethanol. The method provides a new method for preparing isobutanol by using methanol and ethanol with serious surplus of production as raw materials. Therefore, the method has important industrial application prospect.
Description
Technical Field
The invention belongs to the field of basic chemical raw material preparation, and particularly relates to a method for preparing isobutanol by catalytic conversion of a mixed solution of methanol and ethanol.
Background
In recent years, isobutanol has been used in many fields as an important chemical raw material. Is an important raw material for synthesizing plasticizer, anti-aging agent, essential oil and medicine, and is also an important ingredient for producing paint and varnish. In addition, as an oil additive, isobutanol has the specific advantages of high calorific value, easiness in mixing, high octane number, difficulty in water absorption, low volatility and the like, and represents huge development potential.
Currently, the production of isobutanol is largely divided into two major categories, chemical synthesis and biological synthesis, with chemical synthesis being dominant. The chemical synthesis method for preparing isobutanol mainly comes from the by-product of a device for producing butanol/octanol by propylene carbonylation. The carbonylation synthesis of propylene is mainly classified into high pressure process, medium pressure process and low pressure process. The high pressure carbonylation synthesis technology has been replaced by low pressure carbonylation synthesis technology using rhodium as catalyst due to poor selectivity and more by-products. Through the development of many years, the low-pressure carbonylation technology is continuously improved. However, the method still has the problems of complicated process, high price of the rhodium catalyst and the like. The production of isobutanol by the biological synthesis method is mainly a small amount of by-products in the production of n-butanol by grain fermentation. On one hand, the method has high production cost and needs expensive biological fungi. On the other hand, the method also strives for grains with people, and a new method for efficiently converting non-grain biomass into isobutanol by using the non-grain biomass as a raw material is yet to be developed.
Methanol is the simplest saturated monohydric alcohol, the methanol productivity in 2015 in China reaches 6976 ten thousand tons, however, due to insufficient downstream application development of methanol, the operating rate is only 56%, and nearly 3000 ten thousand tons of capacity is in an idle state, and the phenomenon of production stoppage of methanol manufacturers is common. In recent years, researchers have developed a new process for preparing ethanol from methanol through methyl acetate, and a new direction is provided for upgrading and converting methanol. CN102690171B reports that methanol and CO undergo carbonylation to perform acid-acid synthesis reaction, the obtained acetic acid will further esterify with raw material methanol to generate acid methyl ester, and then hydrogenation is performed to obtain a mixture of methanol and ethanol. The above method also requires a further purification process to obtain ethanol. It would clearly be of great interest if a direct conversion of the methanol ethanol mixture described above to isobutanol could be developed which would be of higher value.
In conclusion, the existing isobutanol preparation process generally has the problems of complex process, high catalyst manufacturing cost and the like. Aiming at the problems, the invention develops a new method for directly preparing isobutanol by using a methanol-ethanol mixed solution. The method takes an alkaline carrier loaded with metal as a catalyst, and catalyzes a mixed solution of methanol and ethanol to be converted into isobutanol under an inert atmosphere. The product separation and purification problems of the existing methanol-to-ethanol process are avoided. But also can fully utilize the abundant methanol resources in China, and has important application value.
Disclosure of Invention
The invention aims to provide a novel method for preparing isobutanol, which directly takes methanol-ethanol mixed liquor as a raw material to prepare the isobutanol.
The invention provides a method for preparing isobutanol by catalytic conversion of a mixed solution of methanol and ethanol, which is characterized by comprising the following steps of: the method comprises the steps of taking a mixed solution of methanol and ethanol as a raw material, taking an alkaline carrier carrying two or more elements of platinum, palladium, ruthenium, rhodium, cobalt, copper, nickel, tungsten and molybdenum as a catalyst, and catalyzing the mixed solution of methanol and ethanol to be converted on a fixed bed reactor in an inert atmosphere to generate isobutanol.
The invention provides a method for preparing isobutanol by catalytic conversion of a mixed solution of methanol and ethanol, which is characterized by comprising the following steps of: the catalyst for preparing isobutanol by catalytically converting the mixed solution of methanol and ethanol is a catalyst which contains two or more than three elements of platinum, palladium, ruthenium, rhodium, cobalt, copper, nickel, tungsten and molybdenum and is supported on the surface of an alkaline carrier, wherein the atomic ratio of any two metals is 0.1-5: 1; the basic carrier comprises MgO, BaO, SrO, ZrO, TiO2、ZnO、Ca3(PO4)2，CeO2Magnesium aluminum hydrotalcite, fluorapatite, hydroxyphosphorous acidLimestone, Na-Y zeolite, Na-X zeolite, etc.
The invention provides a method for preparing isobutanol by catalytic conversion of a mixed solution of methanol and ethanol, which is characterized by comprising the following steps of: the catalyst comprises Pt-Ni/MgO, Pd-Ni/MgO, Ru-Ni/BaO, Rh-Cu/MgO, Pd-Co/ZnO, Ni-Mo/MgO, Pd-W/SrO, Pt-W/ZrO, Ru-Ni/TiO2Rh-Ni/magnalium hydrotalcite, Pd-Cu/CeO2Pt-Ni/MgO, Pd-Ni/hydroxyapatite and Rh-Ni/fluorapatite; wherein the atomic molar ratio between the two metals is 0.1-5: 1 or more than two of them.
The invention provides a method for preparing isobutanol by catalytic conversion of a mixed solution of methanol and ethanol, which is characterized by comprising the following steps of: the supported catalyst for preparing isobutanol by catalyzing the conversion of methanol and ethanol mixed solution comprises 0.1-25% of active components calculated by metal.
The invention provides a method for preparing isobutanol by catalytic conversion of a mixed solution of methanol and ethanol, which is characterized by comprising the following steps of: the preparation method of the supported catalyst for preparing isobutanol by catalyzing the conversion of methanol and ethanol mixed solution can adopt one of an impregnation method, a hydrothermal synthesis method and a precipitation deposition method to support an active component on the surface of a carrier.
The invention provides a method for preparing isobutanol by catalytic conversion of a mixed solution of methanol and ethanol, which is characterized by comprising the following steps of: the conversion reaction temperature of the raw material methanol-ethanol mixed liquid on the catalyst is 200-450 ℃.
The invention provides a method for preparing isobutanol by catalytic conversion of a mixed solution of methanol and ethanol, which is characterized by comprising the following steps of: the methanol-ethanol catalytic conversion reaction is carried out in one or more than two inert atmospheres of nitrogen, argon and the like, and the reaction pressure is 0.1-2.5 MPa.
The invention provides a method for preparing isobutanol by catalytic conversion of a mixed solution of methanol and ethanol, which is characterized by comprising the following steps of: the device for preparing isobutanol by catalyzing the conversion of the methanol-ethanol mixed solution is a fixed bed reactor, and the feeding mode adopts a plunger pump feeding mode.
The invention provides a method for preparing isobutanol by catalytic conversion of a mixed solution of methanol and ethanol, which is characterized by comprising the following steps of: the molar ratio of the methanol to the ethanol in the mixed solution of the methanol and the ethanol is 0.5-50: 1.
compared with the existing isobutanol preparation method, the invention provides a new route for preparing isobutanol by directly catalyzing and converting methanol and ethanol, and expands downstream products of methanol by taking methanol with serious surplus domestic productivity as a raw material.
Detailed Description
Example 1:
the preparation of the Pd-Ni/MgO catalyst by impregnation is used as an example to detail the procedure of the supported catalyst used: according to Pd: ni ═ 1: 1, respectively weighing 0.4g of sodium chloropalladate (Na)2PdCl4) And 0.39g of nickel nitrate (Ni (NO)3)26H2O) is dissolved in 60mL deionized water to prepare an active component salt solution (the loading of the active component is 0.1-25%, Pd: the Ni ratio is 0.1-5: 1, here 1: 1) and soaking the carrier MgO in the solution for 12h, then evaporating to dryness, and roasting at 540 ℃ for 6h to obtain the Pd-Ni/MgO catalyst.
Example 2:
the prepared 1mLPd-Ni/MgO catalyst particles (where Pd: Ni ═ 1: 1, active metal loading 5%) were loaded into a fixed bed reactor with nitrogen as the carrier gas at a reaction temperature of 350 ℃. Pumping raw material methanol-ethanol mixed liquor (the molar ratio of methanol to ethanol is 3: 1) into a reaction system by using a double-plunger pump, wherein the feeding airspeed of the mixed alcohol is 1h-1The reaction pressure is 0.1 MPa. After the reaction was equilibrated, a sample was taken and analyzed by Agilent7890 chromatography for the composition of the product, the main component being isobutanol, and also a small amount of propanol, n-butanol, etc. The selectivity of isobutanol in the product is calculated to be 75% by adopting an internal standard method, and the conversion rate of ethanol is 90%.
Example 3:
the prepared 1mL of Rh-Ni/magnesium aluminum hydrotalcite (same preparation process as example 1, except that the active metal element and the carrier are different) (wherein Rh: Ni ═ 3: 1, active metal loading is 15%) catalyst particles were loaded into a fixed bed reactor, and nitrogen gas was used as a carrier gas, and the reaction temperature was 400 ℃. Pumping raw material methanol-ethanol mixed liquor (methanol: ethanol molar ratio is 1: 1) into a reaction system by using a double-plunger pump, wherein the mixed alcohol feeding airspeed is 1h-1The reaction pressure is 0.5 MPa. After the reaction had settled, the procedure was as in example 2The product was analyzed by the method in (1) to obtain isobutanol selectivity of 85% and ethanol conversion of 82%.
Example 4:
1mL of the prepared Pd-Co/ZnO (same preparation process as example 1 except that the active metal element and the carrier are different) (wherein the Pd: Co is 5: 1, and the active metal loading is 25%) catalyst particles are loaded into a fixed bed reactor, nitrogen is used as a carrier gas, and the reaction temperature is 450 ℃. Pumping raw material methanol-ethanol mixed liquor (methanol: ethanol molar ratio is 10: 1) into a reaction system by using a double-plunger pump, wherein the mixed alcohol feeding airspeed is 1h-1The reaction pressure was 1.0 MPa. After the reaction was stabilized, the product was analyzed according to the method in example 2 to give an isobutanol selectivity of 80% and an ethanol conversion of 92%.
Example 5:
1mL of the prepared Rh-Cu/MgO (prepared according to the same procedure as in example 1 except that the active metal element was different) (wherein Rh: Cu is 0.1: 1 and the active metal loading was 5%) catalyst particles were charged into a fixed bed reactor using nitrogen as a carrier gas at a reaction temperature of 375 ℃. Pumping raw material methanol-ethanol mixed liquor (methanol: ethanol molar ratio is 1: 1) into a reaction system by using a double-plunger pump, wherein the mixed alcohol feeding airspeed is 0.5h-1The reaction pressure is 0.1 MPa. After the reaction was stabilized, the product was analyzed according to the method in example 2 to give an isobutanol selectivity of 90% and an ethanol conversion of 70%.
Example 6:
1mL of the prepared Pt-Ni/MgO (prepared according to the same procedure as in example 1 except that the active metal element is different) (wherein Pt: Ni is 5: 1 and the active metal loading is 10%) catalyst particles were loaded into a fixed bed reactor using nitrogen as a carrier gas at a reaction temperature of 350 ℃. Pumping raw material methanol-ethanol mixed liquor (methanol: ethanol molar ratio is 5: 1) into a reaction system by using a double-plunger pump, wherein the mixed alcohol feeding airspeed is 1h-1The reaction pressure is 0.5 MPa. After the reaction had leveled off, the product was analyzed according to the method in example 2 to give an isobutanol selectivity of 75% and an ethanol conversion of 65%.
Example 7:
1mL of Rh-Ni/BaO (prepared in the same manner as in example 1 except for the active metal elements anddifferent carriers) (where Rh: ni ═ 3: 1, active metal loading of 10%) catalyst particles were loaded into a fixed bed reactor, nitrogen was used as a carrier gas, and the reaction temperature was 450 ℃. Pumping raw material methanol-ethanol mixed liquor (the molar ratio of methanol to ethanol is 3: 1) into a reaction system by using a double-plunger pump, wherein the feeding airspeed of the mixed alcohol is 0.5h-1The reaction pressure is 0.5 MPa. After the reaction was stabilized, the product was analyzed according to the method in example 2 to obtain a selectivity for isobutanol of 70% and an ethanol conversion of 60%.
Example 8:
1mL of the prepared Ni-Mo/MgO (prepared according to the same procedure as in example 1 except that the active metal element was different) (wherein Ni: Mo 5: 1, active metal loading was 15%) catalyst particles were charged into a fixed bed reactor using nitrogen as a carrier gas at a reaction temperature of 425 ℃. Pumping raw material methanol-ethanol mixed liquor (methanol: ethanol molar ratio is 5: 1) into a reaction system by using a double-plunger pump, wherein the mixed alcohol feeding airspeed is 1.0h-1The reaction pressure is 0.1 MPa. After the reaction was stabilized, the product was analyzed according to the method in example 2 to give an isobutanol selectivity of 90% and an ethanol conversion of 75%.
Example 9:
1mL of the prepared Pd-W/SrO (prepared according to the same procedure as in example 1 except that the active metal element and the carrier are different) (wherein the Pd: W is 1: 1 and the active metal loading is 25%) catalyst particles are loaded into a fixed bed reactor, nitrogen is used as a carrier gas, and the reaction temperature is 375 ℃. Pumping raw material methanol-ethanol mixed liquor (methanol: ethanol molar ratio is 1: 1) into a reaction system by using a double-plunger pump, wherein the mixed alcohol feeding airspeed is 0.5h-1The reaction pressure is 0.5 MPa. After the reaction was stabilized, the product was analyzed according to the method in example 2 to give an isobutanol selectivity of 70% and an ethanol conversion of 75%.
Example 10:
1mL of the prepared Pt-W/ZrO (prepared as in example 1 except that the active metal element and the carrier were different) (wherein Pt: W is 3: 1 and the active metal loading is 25%) were loaded into a fixed bed reactor using nitrogen as a carrier gas at a reaction temperature of 425 ℃. Pumping raw material methanol-ethanol mixed liquor (methanol: ethanol molar ratio is 1: 1) into a reaction body by using a double-plunger pumpThe air speed of mixed alcohol feeding is 0.8h-1The reaction pressure is 2.5 MPa. After the reaction was stabilized, the product was analyzed according to the method in example 2 to obtain an isobutanol selectivity of 60% and an ethanol conversion of 95%.
Example 11:
1mLRu-Ni/TiO to be prepared2(the preparation process was the same as example 1 except that the active metal element and the carrier were different) (wherein Ru: Ni 1: 1, active metal loading was 15%) catalyst particles were charged into a fixed bed reactor using nitrogen as a carrier gas at a reaction temperature of 450 ℃. Pumping raw material methanol-ethanol mixed liquor (methanol: ethanol molar ratio is 1: 1) into a reaction system by using a double-plunger pump, wherein the mixed alcohol feeding airspeed is 0.5h-1The reaction pressure is 0.5 MPa. After the reaction was stabilized, the product was analyzed according to the method in example 2 to obtain a selectivity of isobutanol of 70% and an ethanol conversion of 80%.
Example 12:
1mL of the prepared Pd-Cu/CeO2(preparation process same as example 1, except that active metal element and carrier are different) (wherein Pd: Cu is 5: 1, active metal loading is 5%) catalyst particles were charged into a fixed bed reactor, and reaction temperature was 350 ℃ with nitrogen as carrier gas. Pumping raw material methanol-ethanol mixed liquor (the molar ratio of methanol to ethanol is 1: 1) into a reaction system by using a double-plunger pump, wherein the feeding airspeed of the mixed alcohol is 1.0h-1The reaction pressure is 0.1 MPa. After the reaction had leveled off, the product was analyzed according to the method in example 2 to give an isobutanol selectivity of 74% and an ethanol conversion of 65%.
Example 13:
1mL of the prepared Pt-Ni/MgO (prepared according to the same procedure as in example 1 except that the active metal element was different) (wherein Pt: Ni ═ 3: 1, active metal loading was 5%) catalyst particles were charged into a fixed bed reactor, and the reaction temperature was 450 ℃. Pumping raw material methanol-ethanol mixed liquor (methanol: ethanol molar ratio is 5: 1) into a reaction system by using a double-plunger pump, wherein the mixed alcohol feeding airspeed is 0.5h-1The reaction pressure is 2.0 MPa. After the reaction was stabilized, the product was analyzed according to the method in example 2 to give an isobutanol selectivity of 70% and an ethanol conversion of 65%.
Example 14:
1mL of the prepared Pd-Ni/hydroxyapatite (prepared according to the same process as example 1 except that the active metal element and the carrier are different) (wherein the Pd: Ni is 1: 1, and the active metal loading is 10%) is loaded into a fixed bed reactor, and the reaction temperature is 375 ℃ with nitrogen as a carrier gas. Pumping raw material methanol-ethanol mixed liquor (the molar ratio of methanol to ethanol is 3: 1) into a reaction system by using a double-plunger pump, wherein the feeding airspeed of the mixed alcohol is 0.1h-1The reaction pressure is 0.1 MPa. After the reaction was stabilized, the product was analyzed according to the method in example 2 to give an isobutanol selectivity of 85% and an ethanol conversion of 75%.
Example 15:
1mL of Rh-Ni/fluorapatite (prepared in the same manner as example 1 except that the active metal element and the carrier are different) (wherein Rh: Ni is 5: 1, and the active metal loading is 20%) was loaded into a fixed bed reactor, and the reaction temperature was 350 ℃ with nitrogen as the carrier gas. Pumping raw material methanol-ethanol mixed liquor (methanol: ethanol molar ratio is 1: 1) into a reaction system by using a double-plunger pump, wherein the mixed alcohol feeding airspeed is 0.5h-1The reaction pressure is 0.1 MPa. After the reaction was stabilized, the product was analyzed according to the method in example 2 to give an isobutanol selectivity of 80% and an ethanol conversion of 65%.
The above description is only a part of the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and the present invention is not limited in any way by the order of the embodiments. Any person skilled in the art of the present invention can easily make changes or substitutions within the technical scope reported in the present invention, and shall be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention is not limited to the above embodiments, and the protection scope of the claims should be subject to.
Claims (7)
1. A method for preparing isobutanol by catalytically converting a mixed solution of methanol and ethanol is characterized by comprising the following steps: the method comprises the steps of taking a mixed solution of methanol and ethanol as a raw material, taking an alkaline carrier with two or more elements of platinum, palladium, ruthenium, rhodium, cobalt, copper, nickel, tungsten and molybdenum loaded on the surface as a catalyst, and catalyzing the mixed solution of methanol and ethanol to be converted on a fixed bed reactor to generate isobutanol under an inert atmosphere;
the catalyst comprises Pd-Ni/SrO, Ru-Ni/BaO, Rh-Cu/MgO, Pd-Co/ZnO, Ni-Mo/MgO, Pd-W/SrO, Pt-W/ZrO, Ru-Ni/TiO2Rh-Ni/magnalium hydrotalcite, Pd-Cu/CeO2One or more than two of Pd-Ni/hydroxyapatite and Rh-Ni/fluorapatite; wherein the atomic molar ratio between the two metals is 0.1-5: 1.
2. the method of claim 1, wherein: the supported catalyst for preparing isobutanol by catalyzing the conversion of methanol and ethanol mixed solution comprises 0.1-25% of active components calculated by metal.
3. The method of claim 1, wherein: the preparation method of the supported catalyst for preparing isobutanol by catalyzing the conversion of methanol and ethanol mixed solution can adopt one of an impregnation method, a hydrothermal synthesis method and a precipitation deposition method to support an active component on the surface of a carrier.
4. The method of claim 1, wherein: the conversion reaction temperature of the raw material methanol-ethanol mixed liquid on the catalyst is 200-450 ℃.
5. The method of claim 1, wherein: the methanol-ethanol catalytic conversion reaction is carried out in inert atmosphere of one or more than two of nitrogen and argon, and the reaction pressure is 0.1-2.5 MPa.
6. The method of claim 1, wherein: the device for preparing isobutanol by catalyzing the conversion of the methanol-ethanol mixed solution is a fixed bed reactor, and the feeding mode adopts a plunger pump feeding mode.
7. The method of claim 1, wherein: the molar ratio of the methanol to the ethanol in the mixed solution of the methanol and the ethanol is 0.5-50: 1.
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| CN109111343B (en) * | 2018-09-10 | 2021-05-07 | 大连理工大学 | Method for preparing benzyl alcohol and homologues through catalytic conversion of low-carbon alcohol and used catalyst |
| CN110743557A (en) * | 2019-10-24 | 2020-02-04 | 浙江工业大学 | Catalyst for synthesizing isobutanol by continuous catalytic dehydrogenation and condensation of methanol and ethanol fixed bed and preparation method and application thereof |
| CN113731413A (en) * | 2021-08-31 | 2021-12-03 | 浙江工业大学 | MOFs (metal organic frameworks) limited-area metal catalyst and preparation method and application thereof |
| CN113967473B (en) * | 2021-11-10 | 2024-03-29 | 北京化工大学 | Heterogeneous catalyst of composite oxide loaded with single atom Ru, preparation method and application |
| CN115872836A (en) * | 2022-12-30 | 2023-03-31 | 北京化工大学 | Method for synthesizing isobutanol by taking methanol and calcium carbide as raw materials |
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