CN103657730A - Catalyst for preparing 1,2-propylene glycol by glycerinum hydrogenation and preparation method thereof - Google Patents
Catalyst for preparing 1,2-propylene glycol by glycerinum hydrogenation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for preparing 1,2-propylene glycol by glycerinum hydrogenation and a preparation method of the catalyst, and belongs to a catalyst containing metal or a metallic oxide. The catalyst is characterized by comprising the following raw material components in percentage by weight: 10%-40% of heteropoly acid, 30%-90% of a carrier, 5%-20% of active components, and 0.5%-10% of a modified component. The catalyst and the preparation method thereof provided by the invention have the advantages that the activity is high, the selectivity is good, a reaction condition is mild, the reaction speed is high, the conversion rate of the raw materials is high, and the energy consumption is low. The catalyst provided by the invention has an acid site and a metal hydrogenation site, is a dual-function catalyst, is high in reactivity, selectivity and stability, still keeps the high efficiency at the large air speed, and has good industrial application prospect; the catalyst provided by the invention has the advantages that the operating pressure is low, the equipment investment is saved, the energy consumption is low, and the glycerinum conversion rate can achieve 90.12%.
Description
Technical field
The present invention is a kind of Catalysts and its preparation method of preparing 1,2-dihydroxypropane by glycerine hydrogenation.Belong to the catalyst that comprises metal or metal oxide.
Background technology
1,2-PD is a kind of important industrial chemicals, is mainly used in the raw material of unsaturated polyester resin, epoxy resin, polyurethane resin, and wherein unsaturated polyester (UP) is in a large number for surface coating and reinforced plastics.Because propane diols toxicity is little, there is wetability and there is good solubility property, therefore in food, medicine and cosmetics, be widely used, as producing tobacco wetting agent, young animal feed production, polymeric plasticizer and specialty plasticiser, develop again in the recent period for the new purposes of liquid detergent.
In recent years, in short supply along with world energy sources, Biodiesel has obtained development fast, and the process of preparation biodiesel produces a large amount of byproduct glycerine, rationally utilize superfluous biological base glycerol exploitation high value added product, will contribute to increase the economic benefit of whole Biodiesel.Traditional propane diols raw materials for production are mainly derived from petrochemicals expoxy propane, owing to being subject to the impact of oil price, 1, the cost of material of 2-propane diols improves constantly, for breaking away from 1, the production of 2-propane diols is depended on unduly petroleum resources, is necessary to develop the technology path that biomass resource is prepared 1,2-PD.
Preparing 1,2-dihydroxypropane by glycerine hydrogenation route had both solved the problem of glycerine surplus in Biodiesel, had broken away from again 1,2-PD and had produced the dependence to fossil energy, had great importance.
Glycerine be take as raw material in Germany Degussa company (CN93114516.3), and the glycerine water solution that uses 10%～40%wt at 250 ~ 340 ℃ is raw material, and the first step generates methacrylaldehyde and hydroxypropanone-by highly acid solid catalyst by dehydrating glycerin; Second step generates 3-HPA by methacrylaldehyde hydration in acidic catalyst; The 3rd step generates 1,3-PD and 1,2-PD by 3-HPA and hydroxypropanone-hydrogenation reaction.With respect to glycerine, the productive rate of 1,3-, third-glycol is 60%, the productive rate of 1,2-PD is 10%.Reaction time is long, and productive rate is low.
Germany BASF AG (CN 95121742.9) adopts the composite catalyst that contains metallic cobalt, copper, manganese and aluminium, can also, with the catalyst system and catalyzing that contains inorganic acid or heteropoly acid, pass through preparing 1,2-dihydroxypropane by glycerine hydrogenation.Temperature higher than 200 ° of C and pressure higher than 20MPa condition under, this method can high yield obtains 1,2-PD, but severe reaction conditions, catalyst system is complicated.
Chinese patent CN 1061968C has described the catalytic hydrogenolysis by glycerine under a kind of high temperature and high pressure and has prepared 1, the method of 2-propane diols, adopt the catalyst of containing metal cobalt, copper, molybdenum and manganese, 1, the yield of 2-propane diols can be up to 95%, but reaction pressure is 20 ~ 32MPa, higher pressure causes plant investment cost up and operation easier to strengthen.
In patent WO2007/010299, reported a kind of technique of glycerine gas phase hydrogenation.This process using Cu series catalysts, the methanol solution that raw material is glycerine, 160 ~ 260 ° of C of reaction temperature, pressure 1 ~ 3MPa, hydrogen and glycerine ratio 400:1 ~ 600:1, under glycerine 100% transforms, 1,2-PD selectively can reach 96%.But, in this patent, adopt gas phase glycerine feed, because glycerine boiling point is up to 290 ℃, make glycerine gasification energy consumption higher, must increase the operating cost of device.In addition, this technique needs higher hydrogen glycerine ratio, makes the one way utilization rate of hydrogen lower, has increased hydrogen material consumption.
In sum, the catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the prior art exists following not enough:
1. hydrogenation preparing 1,2-dihydroxypropane by glycerine hydrogenation, the production cycle is long, and product yield is low.
2. the composite catalyst that contains metallic cobalt, copper, manganese and aluminium, reaction temperature is higher than 200 ° of C, and reaction pressure is higher than 20MPa, severe reaction conditions, catalyst system is complicated.
3. the catalyst of containing metal cobalt, copper, molybdenum and manganese, reaction pressure is up to 20 ~ 32MPa, and higher pressure causes plant investment cost up and operation easier to strengthen.
4. adopt Cu series catalysts, adopt gas phase glycerine feed, need higher hydrogen glycerine ratio, cause energy consumption higher, cost of material is high.
Summary of the invention
The object of the invention is to avoid above-mentioned weak point of the prior art, and provide a kind of catalyst activity high, selectively good, reaction condition is gentle, reaction speed is fast, feed stock conversion is higher, the Catalysts and its preparation method for preparing 1,2-dihydroxypropane by glycerine hydrogenation that energy consumption is lower.
The present invention also aims to provide a kind of reaction pressure lower, easy to operate, the using method of the catalyst for preparing 1,2-dihydroxypropane by glycerine hydrogenation that product yield is higher.
Object of the present invention can reach by following measure:
The catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention, is characterized in that being made by the raw material components being calculated in mass percent as follows:
Wherein:
Heteropoly acid is any one or its any two or more combinations in phosphomolybdic acid, phosphotungstic acid, silico-tungstic acid or silicomolybdic acid;
Carrier is any one or its any two or more combinations in silica gel, active carbon, aluminium oxide, zirconia, titanium oxide or molecular sieve;
Active component is any one or its any two or more combinations in nickel, zinc, copper, magnesium, zirconium, molybdenum, aluminium or titanium element;
Modified component is any one or its any two or more combinations of potassium, manganese, vanadium, tin, cadmium, iron, palladium or cobalt metal element.
The present inventor has paid performing creative labour in the selection of catalyst raw material component and ratio optimization and the synergy between each component.Thereby solved the technical problem to be solved in the present invention, completed task of the present invention.
Object of the present invention can also reach by following measure:
The catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention, is characterized in that being made by the raw material components being calculated in mass percent as follows:
It is preferred technical scheme.
The catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention, described active component is provided with its aqueous solution form by the water soluble salt of nickel, zinc, copper, magnesium, zirconium, molybdenum, aluminium or titanium element.
The catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention, the water soluble salt of described metallic element is its nitrate, hydrochloride or sulfate.
The catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention, by the water soluble salt of potassium, manganese, vanadium, tin, cadmium, iron, palladium or cobalt metal element, the form with its aqueous solution provides described modified component.
The catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention, the water soluble salt that it is characterized in that described metallic element is its nitrate, hydrochloride or sulfate.
A preparation method for the catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention, is characterized in that adopting single-steeping method, and step is as follows:
The salt of the salt of heteropoly acid, active component and modified component is formed with being impregnated on carrier after distilled water dissolving by catalyst, standing 1 ~ 24 hour, 100 ~ 145 ℃ of oven dry, roasting was 1 ~ 10 hour at 300 ~ 700 ℃, can make the catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation.
The preparation method of the catalyst of another kind of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention, is characterized in that adopting secondary dipping process, comprises the steps:
1. single-steeping Kaolinite Preparation of Catalyst presoma
The salt of heteropoly acid and active metal component is formed after dissolving with distilled water and is impregnated on carrier by catalyst, and standing 1 ~ 24 hour, 100 ~ 145 ℃ of oven dry, roasting was 1 ~ 10 hour at 300 ~ 700 ℃, obtains single-steeping catalyst precursor;
2. catalyst preparation
The salt of modified component is formed and to be impregnated into after dissolving with distilled water on the single-steeping catalyst precursor that 1. step make by catalyst, standing 1 ~ 24 hour, 100 ~ 145 ℃ of oven dry, roasting was 1 ~ 10 hour at 300 ~ 700 ℃, make the catalyst for preparing 1,2-dihydroxypropane by glycerine hydrogenation.
The using method of the catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention, is characterized in that for fixed bed reactors, and hydrogen/glycerine mol ratio is 3:1 ~ 10:1, and glycerine air speed is 0.1 ~ 1.3h
-1, reaction temperature is 180 ~ 260 ℃, and reaction pressure is 1 ~ 7MPa, and the reaction time is 10 ~ 300h, makes product 1,2-PD, and glycerol conversion yield reaches 90.12/%.
The Catalysts and its preparation method of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention has following good effect compared to existing technology:
1. provide a kind of catalyst activity high, selectively good, reaction condition is gentle, and reaction speed is fast, and feed stock conversion is higher, the Catalysts and its preparation method for preparing 1,2-dihydroxypropane by glycerine hydrogenation that energy consumption is lower.
2. provide a kind of reaction pressure lower, easy to operate, the using method of the catalyst for preparing 1,2-dihydroxypropane by glycerine hydrogenation that product yield is higher.
3.. the existing acidic site of catalyst of the present invention has again metal hydrogenation position, is bifunctional catalyst, has higher reactivity, selective and stability, still keeps high efficiency under larger air speed, has good prospects for commercial application.
4. operating pressure is low, low equipment investment, and energy consumption is low; Glycerol conversion yield reaches 90.12/%.
5. technique is simple, easy to operate, with short production cycle, and product yield is high, and production cost is low.
The specific embodiment
The present invention will now be further detailed embodiment:
Embodiment 1
(1) catalyst preparation: take respectively 9.44g copper nitrate, 1.91g potassium chloride, 10g silico-tungstic acid and be dissolved in distilled water, be impregnated on 41.5g alumina carrier, standing 5h, 120 ℃ of oven dry, 400 ℃ of roasting 5h, can make the catalyst containing 5% bronze medal, 2% potassium, 10% silico-tungstic acid, 83% alundum (Al2O3).
(2) reaction is carried out in continuous fixed bed reactor: loaded catalyst 10ml, reaction pressure 6MPa, 185 ℃ of reaction temperatures, glycerine volume space velocity 1.0h
-1, hydrogen/glycerine mol ratio is 3:1, reaction time 10h, and result of the test is in Table 1.
Embodiment 2
(1) catalyst preparation: take respectively 17.32g nickel nitrate, 7.28g cobalt nitrate, 7.5g silico-tungstic acid and be dissolved in distilled water, be impregnated on 37.5g alumina carrier, standing 5h, 120 ℃ of oven dry, 450 ℃ of roasting 5h, can make the catalyst containing 7% nickel, 3% cobalt, 15% silico-tungstic acid, 75% alundum (Al2O3).
(2) reaction is carried out in continuous fixed bed reactor: loaded catalyst 10ml, reaction pressure 5MPa, 190 ℃ of reaction temperatures, glycerine volume space velocity 0.8h
-1, hydrogen/glycerine mol ratio is 4:1, reaction time 15h, and result of the test is in Table 1.
Embodiment 3
(1) catalyst preparation: take respectively 22.88g zinc nitrate, 8.99g manganese chloride, 7.5g phosphotungstic acid and be dissolved in distilled water, be impregnated on 35g silica supports, standing 5h, 120 ℃ of oven dry, 400 ℃ of roasting 5h, can make the catalyst containing 10% zinc, 5% manganese, 15% phosphotungstic acid, 70% silica.
(2) reaction is carried out in continuous fixed bed reactor: loaded catalyst 10ml, reaction pressure 5.5MPa, 195 ℃ of reaction temperatures, glycerine volume space velocity 1.2h
-1, hydrogen/glycerine mol ratio is 5:1, reaction time 20h, and result of the test is in Table 1.
Embodiment 4
(1) catalyst preparation: take respectively 53.4g magnesium nitrate, 5.49g stannic chloride, 10g phosphomolybdic acid and be dissolved in distilled water, be impregnated on 32.5g silica supports, standing 9h, 120 ℃ of oven dry, 600 ℃ of roasting 5h, can make the catalyst containing 10% magnesium, 5% tin, 20% phosphomolybdic acid, 65% silica.
(2) reaction is carried out in continuous fixed bed reactor: loaded catalyst 10ml, reaction pressure 7MPa, 195 ℃ of reaction temperatures, glycerine volume space velocity 1.2h
-1, hydrogen/glycerine mol ratio is 5:1, reaction time 20h, and result of the test is in Table 1.
Embodiment 5
(1) catalyst preparation: take respectively 9.44g copper nitrate, 4.58g zinc nitrate, 7.21g ferric nitrate, 5g silico-tungstic acid and be dissolved in distilled water, be impregnated on 40.5g alumina carrier, standing 10h, 140 ℃ of oven dry, 650 ℃ of roasting 6h, can make the catalyst containing 5% bronze medal, 2% zinc, 2% iron, 10% silico-tungstic acid, 81% alundum (Al2O3).
(2) reaction is carried out in continuous fixed bed reactor: loaded catalyst 10ml, reaction pressure 6MPa, 200 ℃ of reaction temperatures, glycerine volume space velocity 1.3h
-1, hydrogen/glycerine mol ratio is 6:1, reaction time 30h, and result of the test is in Table 1.
Embodiment 6
(1) catalyst preparation: take respectively 18.88g copper nitrate, 34.73g aluminum nitrate, 6g phosphotungstic acid and be dissolved in distilled water, be impregnated on 35g silica supports standing 12h, 120 ℃ of oven dry, 600 ℃ of roasting 5h, can obtain the catalyst precarsor of cupric, aluminium, phosphotungstic acid and silica; Then taking 2.87g potassium chloride is dissolved in distilled water, be impregnated on the catalyst precarsor of cupric, aluminium, phosphotungstic acid and silica standing 10h, 120 ℃ of oven dry, 600 ℃ of roasting 5h, can make the catalyst containing 10% bronze medal, 5% aluminium, 3% potassium, 12% phosphotungstic acid, 70% silica.
(2) reaction is carried out in continuous fixed bed reactor: loaded catalyst 10ml, reaction pressure 6.5MPa, 210 ℃ of reaction temperatures, glycerine volume space velocity 0.9h
-1, hydrogen/glycerine mol ratio is 6:1, reaction time 40h, and result of the test is in Table 1.
Embodiment 7
(1) catalyst preparation: take respectively 22.65g copper nitrate, 26.71g magnesium nitrate, 7.5g phosphotungstic acid and be dissolved in distilled water, be impregnated on 17.5g titanium dioxide and 15g zirconia carrier, standing 10h, 110 ℃ of oven dry, 550 ℃ of roasting 7h, can obtain the catalyst precarsor of cupric, magnesium, phosphotungstic acid, titanium dioxide and zirconium dioxide; Then taking 4.13g cadmium nitrate is dissolved in distilled water, be impregnated on the catalyst precarsor of cupric, magnesium, phosphotungstic acid, titanium dioxide and zirconium dioxide, standing 12h, 110 ℃ of oven dry, 550 ℃ of roasting 7h, can make the zirconia catalyst containing 12% bronze medal, 5% magnesium, 3% cadmium, 15% phosphotungstic acid, 35% titanium dioxide and 30%.
(2) reaction is carried out in continuous fixed bed reactor: loaded catalyst 10ml, reaction pressure 6MPa, 205 ℃ of reaction temperatures, glycerine volume space velocity 0.9h
-1, hydrogen/glycerine mol ratio is 5:1, reaction time 35h, and result of the test is in Table 1.
Embodiment 8
(1) catalyst preparation: take respectively 67.95g copper nitrate, 14.17g ammonium dimolybdate, 15g phosphotungstic acid and 15g silico-tungstic acid and be dissolved in distilled water, be impregnated on 43g alumina carrier, standing 4h, 100 ℃ of oven dry, 700 ℃ of roasting 8h, can obtain the catalyst precarsor of cupric, molybdenum, phosphotungstic acid, phosphotungstic acid, silico-tungstic acid and alundum (Al2O3); Then measure the palladium chloride solution of 18.8ml 0.5mol/L and add appropriate distilled water, be impregnated on the catalyst precarsor of cupric, molybdenum, phosphotungstic acid, phosphotungstic acid, silico-tungstic acid and alundum (Al2O3), standing 6h, 140 ℃ of oven dry, 700 ℃ of roasting 9h, can make the catalyst containing 18% bronze medal, 8% molybdenum, 1% palladium, 15% phosphotungstic acid, 15% silico-tungstic acid and 43% alundum (Al2O3).
(2) reaction is carried out in continuous fixed bed reactor: loaded catalyst 10ml, reaction pressure 6MPa, 250 ℃ of reaction temperatures, glycerine volume space velocity 0.2h
-1, hydrogen/glycerine mol ratio is 9:1, reaction time 80h, and result of the test is in Table 1.
Embodiment 9
(1) catalyst preparation: take respectively 18.88g copper nitrate, 22.88g zinc nitrate, 69.47g aluminum nitrate and 7.5g phosphotungstic acid and be dissolved in distilled water, be impregnated on 27g absorbent charcoal carrier, standing 4h, 100 ℃ of oven dry, the lower 400 ℃ of roasting 4h of nitrogen atmosphere, can obtain the catalyst precarsor of cupric, zinc, aluminium, phosphotungstic acid and active carbon; Then taking 2.59g potassium nitrate is dissolved in distilled water, be impregnated on the catalyst precarsor of cupric, zinc, aluminium, phosphotungstic acid and active carbon, standing 7h, 145 ℃ of oven dry, the lower 500 ℃ of roasting 4h of nitrogen atmosphere, can make the catalyst containing 10% bronze medal, 10% zinc, 10% aluminium, 2% potassium, 15% phosphotungstic acid and 53% active carbon.
(2) reaction is carried out in continuous fixed bed reactor: loaded catalyst 10ml, reaction pressure 4MPa, 220 ℃ of reaction temperatures, glycerine volume space velocity 0.6h
-1, hydrogen/glycerine mol ratio is 7:1, reaction time 100h, and result of the test is in Table 1.
Embodiment 10
(1) catalyst preparation: take respectively 33.98g copper nitrate, 3.11g potassium nitrate, 6g silico-tungstic acid and be dissolved in distilled water, be impregnated on 43.8g alumina carrier, standing 10h, 120 ℃ of oven dry, 600 ℃ of roasting 5h, can make the catalyst containing 15% bronze medal, 2% potassium, 10% silico-tungstic acid, 73% alundum (Al2O3).
(2) reaction is carried out in continuous fixed bed reactor: loaded catalyst 10ml, reaction pressure 6MPa, 200 ℃ of reaction temperatures, glycerine volume space velocity 0.9h
-1, hydrogen/glycerine mol ratio is 4:1, reaction time 300h, and result of the test is in Table 1.
Table 1 result of the test
Claims (9)
1. a catalyst for preparing 1,2-dihydroxypropane by glycerine hydrogenation, is characterized in that being made by the raw material components being calculated in mass percent as follows:
Wherein:
Heteropoly acid is any one or its any two or more combinations in phosphomolybdic acid, phosphotungstic acid, silico-tungstic acid or silicomolybdic acid;
Carrier is any one or its any two or more combinations in silica gel, active carbon, aluminium oxide, zirconia, titanium oxide or molecular sieve;
Active component is any one or its any two or more combinations in nickel, zinc, copper, magnesium, zirconium, molybdenum, aluminium or titanium element;
Modified component is any one or its any two or more combinations of potassium, manganese, vanadium, tin, cadmium, iron, palladium or cobalt metal element.
2. according to the catalyst of the preparing 1,2-dihydroxypropane by glycerine hydrogenation of claim 1, it is characterized in that being made by the raw material components being calculated in mass percent as follows:
3. according to the catalyst of the preparing 1,2-dihydroxypropane by glycerine hydrogenation of claim 1, it is characterized in that described active component is provided with its aqueous solution form by the water soluble salt of nickel, zinc, copper, magnesium, zirconium, molybdenum, aluminium or titanium element.
4. according to the catalyst of the preparing 1,2-dihydroxypropane by glycerine hydrogenation of claim 3, the water soluble salt that it is characterized in that described metallic element is its nitrate, hydrochloride or sulfate.
5. according to the catalyst of the preparing 1,2-dihydroxypropane by glycerine hydrogenation of claim 1, it is characterized in that the form with its aqueous solution provides described modified component by the water soluble salt of potassium, manganese, vanadium, tin, cadmium, iron, palladium or cobalt metal element.
6. according to the catalyst of the preparing 1,2-dihydroxypropane by glycerine hydrogenation of claim 5, the water soluble salt that it is characterized in that described metallic element is its nitrate, hydrochloride or sulfate.
7. a preparation method for the catalyst of the preparing 1,2-dihydroxypropane by glycerine hydrogenation of claim 1, is characterized in that adopting single-steeping method, and step is as follows:
The salt of the salt of heteropoly acid, active component and modified component is formed with being impregnated on carrier after distilled water dissolving by catalyst, standing 1 ~ 24 hour, 100 ~ 145 ℃ of oven dry, roasting was 1 ~ 10 hour at 300 ~ 700 ℃, can make the catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation.
8. a preparation method for the catalyst of the preparing 1,2-dihydroxypropane by glycerine hydrogenation of claim 1, is characterized in that adopting secondary dipping process, comprises the steps:
1. single-steeping Kaolinite Preparation of Catalyst presoma
The salt of heteropoly acid and active metal component is formed after dissolving with distilled water and is impregnated on carrier by catalyst, and standing 1 ~ 24 hour, 100 ~ 145 ℃ of oven dry, roasting was 1 ~ 10 hour at 300 ~ 700 ℃, obtains single-steeping catalyst precursor;
2. catalyst preparation
The salt of modified component is formed and to be impregnated into after dissolving with distilled water on the single-steeping catalyst precursor that 1. step make by catalyst, standing 1 ~ 24 hour, 100 ~ 145 ℃ of oven dry, roasting was 1 ~ 10 hour at 300 ~ 700 ℃, make the catalyst for preparing 1,2-dihydroxypropane by glycerine hydrogenation.
9. the using method of the catalyst of the preparing 1,2-dihydroxypropane by glycerine hydrogenation of claim 1, is characterized in that for fixed bed reactors, and hydrogen/glycerine mol ratio is 3:1 ~ 10:1, and glycerine air speed is 0.1 ~ 1.3h
-1, reaction temperature is 180 ~ 260 ℃, and reaction pressure is 1 ~ 7MPa, and the reaction time is 10 ~ 300h, makes product 1,2-PD, and glycerol conversion yield reaches 90.12/%.
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| CN115445652B (en) * | 2022-10-09 | 2023-11-10 | 山东京博石油化工有限公司 | Catalyst for preparing 1, 3-propylene glycol by selective hydrogenation of glycerin, preparation method and application thereof |
| CN115700146A (en) * | 2022-11-24 | 2023-02-07 | 广西民族师范学院 | Preparation method and application of photocatalyst |
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