CN103657730B - The Catalysts and its preparation method of preparing 1,2-dihydroxypropane by glycerine hydrogenation - Google Patents
The Catalysts and its preparation method of preparing 1,2-dihydroxypropane by glycerine hydrogenation Download PDFInfo
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Abstract
The present invention is a kind of Catalysts and its preparation method of preparing 1,2-dihydroxypropane by glycerine hydrogenation.Belong to the catalyst comprising metal or metal oxide.A catalyst for preparing 1,2-dihydroxypropane by glycerine hydrogenation, is characterized in that the raw material components by being calculated in mass percent as follows is made: heteropoly acid 10 ~ 40, carrier 30 as one kind ~ 90, active component 5 ~ 20, modified component 0.5 ~ 10.Provide a kind of catalyst activity high, selective 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.The existing acidic site of catalyst of the present invention has again metal hydrogenation position, is bifunctional catalyst, has higher reactivity, selective and stability, under larger air speed, still keeps high efficiency, have good prospects for commercial application.Operating pressure is low, low equipment investment, and energy consumption is low; Glycerol conversion yield reaches 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 comprising 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 excellent solubility property, therefore be widely used in food, medicine and cosmetics, be used as to produce tobacco wetting agent, young animal feed production, polymeric plasticizer and specialty plasticiser, develop again in the recent period for liquid detergent novelty teabag.
In recent years, in short supply along with world energy sources, Biodiesel obtains and develops fast, and the process of preparation biodiesel produces a large amount of byproduct glycerine, the biological base glycerol exploitation high value added product of Appropriate application surplus, will contribute to the economic benefit increasing whole Biodiesel.Traditional propane diols raw materials for production are mainly derived from petrochemicals expoxy propane, due to the impact by oil price, 1, the cost of material of 2-propane diols improves constantly, for breaking away from 1, depending on unduly petroleum resources produced by 2-propane diols, is necessary that exploitation biomass resource prepares the technology path of 1,2-PD.
Preparing 1,2-dihydroxypropane by glycerine hydrogenation route had both solved the problem of glycerol overstock in Biodiesel, had broken away from again the dependence of 1,2-PD production to fossil energy, had had great importance.
Degussa company of Germany (CN93114516.3) take glycerine as raw material, and the glycerine water solution using 10% ~ 40%wt at 250 ~ 340 DEG C is raw material, and dehydrating glycerin is generated methacrylaldehyde and hydroxypropanone-by highly acid solid catalyst by the first step; Methacrylaldehyde hydration in acidic catalyst is generated 3-HPA by second step; 3rd step generates 1,3-PD and 1,2-PD by 3-HPA and hydroxypropanone-hydrogenation reaction.Relative 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.
BASF Corp. of Germany (CN95121742.9) adopts the composite catalyst containing metallic cobalt, copper, manganese and aluminium, with the catalyst system and catalyzing containing inorganic acid or heteropoly acid, can also pass through preparing 1,2-dihydroxypropane by glycerine hydrogenation.In temperature higher than 200 ° of C and pressure higher than under 20MPa condition, this method can high yield obtain 1,2-PD, but severe reaction conditions, catalyst system is complicated.
Chinese patent CN1061968C prepares 1 by the catalytic hydrogenolysis of glycerine under describing a kind of high temperature and high pressure, 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 up to 95%, but reaction pressure is 20 ~ 32MPa, higher pressure causes plant investment cost up and operation easier to strengthen.
A kind of technique of glycerine gas phase hydrogenation is reported in patent WO2007/010299.This technique adopts Cu series catalysts, and raw material is the methanol solution of glycerine, reaction temperature 160 ~ 260 ° of C, pressure 1 ~ 3MPa, hydrogen and glycerine ratio 400:1 ~ 600:1, and under glycerine 100% transforms, 1,2-PD is selective reaches 96%.But, adopt gas phase glycerine feed in this patent, due to glycerine boils up till 290 DEG C, make glycerine gasification energy consumption higher, the operating cost of device must be increased.In addition, this technique needs higher hydrogen glycerine ratio, makes the one way utilization rate of hydrogen lower, adds 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 containing metallic cobalt, copper, manganese and aluminium, reaction temperature is higher than 200 ° of C, and reaction pressure is higher than 20MPa, and 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, selective 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 be reached by following measure:
The catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention, is characterized in that the raw material components by being calculated in mass percent as follows is made:
Wherein:
Heteropoly acid is any one or its any two or more combination in phosphomolybdic acid, phosphotungstic acid, silico-tungstic acid or silicomolybdic acid;
Carrier is any one or its any two or more combination in silica gel, active carbon, aluminium oxide, zirconia, titanium oxide or molecular sieve;
Active component is any one or its any two or more combination in nickel, zinc, copper, magnesium, zirconium, molybdenum, aluminium or titanium element;
Modified component is any one or its any two or more combination of potassium, manganese, vanadium, tin, cadmium, iron, palladium or cobalt metal element.
The ratio optimization of the present inventor between the selection and each component of catalyst raw material components and synergy have paid performing creative labour.Thus solve the technical problem to be solved in the present invention, complete task of the present invention.
Object of the present invention can also be reached by following measure:
The catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention, is characterized in that the raw material components by being calculated in mass percent as follows is made:
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, described modified component is provided with the form of its aqueous solution by the water soluble salt of potassium, manganese, vanadium, tin, cadmium, iron, palladium or cobalt metal element.
The catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation of the present invention, is characterized in that the water soluble salt of 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, it is characterized in that adopting single-steeping method, step is as follows:
Be impregnated on carrier after the salt of heteropoly acid, active component and the salt of modified component are dissolved by catalyst composition distilled water, leave standstill 1 ~ 24 hour, 100 ~ 145 DEG C of oven dry, roasting 1 ~ 10 hour at 300 ~ 700 DEG C, the catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation can be obtained.
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
Be impregnated on carrier after being dissolved by catalyst composition distilled water by the salt of heteropoly acid and active metal component, leave standstill 1 ~ 24 hour, 100 ~ 145 DEG C of oven dry, at 300 ~ 700 DEG C, roasting 1 ~ 10 hour, obtains single-steeping catalyst precursor;
2. catalyst preparing
Be impregnated into after the salt of modified component is dissolved by catalyst composition distilled water on the single-steeping catalyst precursor that 1. step obtain, leave standstill 1 ~ 24 hour, 100 ~ 145 DEG C of oven dry, roasting 1 ~ 10 hour at 300 ~ 700 DEG C, obtain 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 DEG C, and reaction pressure is 1 ~ 7MPa, and the reaction time is 10 ~ 300h, and obtained product 1,2-PD, 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, selective 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, under larger air speed, still keeps high efficiency, have 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, and easy to operate, with short production cycle, product yield is high, and production cost is low.
Detailed description of the invention
The present invention will now be further detailed embodiment:
Embodiment 1
(1) catalyst preparing: take 9.44g copper nitrate respectively, 1.91g potassium chloride, 10g silico-tungstic acid be dissolved in distilled water, be impregnated on 41.5g alumina carrier, leave standstill 5h, 120 DEG C of oven dry, 400 DEG C of roasting 5h, can obtain 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, reaction temperature 185 DEG C, glycerine volume space velocity 1.0h
-1, hydrogen/glycerine mol ratio is 3:1, and reaction time 10h, result of the test is in table 1.
Embodiment 2
(1) catalyst preparing: take 17.32g nickel nitrate respectively, 7.28g cobalt nitrate, 7.5g silico-tungstic acid be dissolved in distilled water, be impregnated on 37.5g alumina carrier, leave standstill 5h, 120 DEG C of oven dry, 450 DEG C of roasting 5h, can obtain 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, reaction temperature 190 DEG C, glycerine volume space velocity 0.8h
-1, hydrogen/glycerine mol ratio is 4:1, and reaction time 15h, result of the test is in table 1.
Embodiment 3
(1) catalyst preparing: take 22.88g zinc nitrate respectively, 8.99g manganese chloride, 7.5g phosphotungstic acid be dissolved in distilled water, be impregnated on 35g silica supports, leave standstill 5h, 120 DEG C of oven dry, 400 DEG C of roasting 5h, can obtain 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, reaction temperature 195 DEG C, glycerine volume space velocity 1.2h
-1, hydrogen/glycerine mol ratio is 5:1, and reaction time 20h, result of the test is in table 1.
Embodiment 4
(1) catalyst preparing: take 53.4g magnesium nitrate respectively, 5.49g stannic chloride, 10g phosphomolybdic acid be dissolved in distilled water, be impregnated on 32.5g silica supports, leave standstill 9h, 120 DEG C of oven dry, 600 DEG C of roasting 5h, can obtain 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, reaction temperature 195 DEG C, glycerine volume space velocity 1.2h
-1, hydrogen/glycerine mol ratio is 5:1, and reaction time 20h, result of the test is in table 1.
Embodiment 5
(1) catalyst preparing: take 9.44g copper nitrate respectively, 4.58g zinc nitrate, 7.21g ferric nitrate, 5g silico-tungstic acid be dissolved in distilled water, be impregnated on 40.5g alumina carrier, leave standstill 10h, 140 DEG C of oven dry, 650 DEG C of roasting 6h, can obtain 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, reaction temperature 200 DEG C, glycerine volume space velocity 1.3h
-1, hydrogen/glycerine mol ratio is 6:1, and reaction time 30h, result of the test is in table 1.
Embodiment 6
(1) catalyst preparing: take 18.88g copper nitrate respectively, 34.73g aluminum nitrate, 6g phosphotungstic acid be dissolved in distilled water, be impregnated on 35g silica supports, leave standstill 12h, 120 DEG C of oven dry, 600 DEG C 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, leave standstill 10h, 120 DEG C of oven dry, 600 DEG C of roasting 5h, can obtain 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, reaction temperature 210 DEG C, glycerine volume space velocity 0.9h
-1, hydrogen/glycerine mol ratio is 6:1, and reaction time 40h, result of the test is in table 1.
Embodiment 7
(1) catalyst preparing: take 22.65g copper nitrate respectively, 26.71g magnesium nitrate, 7.5g phosphotungstic acid be dissolved in distilled water, be impregnated on 17.5g titanium dioxide and 15g zirconia carrier, leave standstill 10h, 110 DEG C of oven dry, 550 DEG C 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, leave standstill 12h, 110 DEG C of oven dry, 550 DEG C of roasting 7h, can obtain containing 12% bronze medal, 5% magnesium, 3% cadmium, 15% phosphotungstic acid, 35% titanium dioxide and 30% zirconia catalyst.
(2) reaction is carried out in continuous fixed bed reactor: loaded catalyst 10ml, reaction pressure 6MPa, reaction temperature 205 DEG C, glycerine volume space velocity 0.9h
-1, hydrogen/glycerine mol ratio is 5:1, and reaction time 35h, result of the test is in table 1.
Embodiment 8
(1) catalyst preparing: take 67.95g copper nitrate, 14.17g ammonium dimolybdate, 15g phosphotungstic acid and 15g silico-tungstic acid respectively and be dissolved in distilled water, be impregnated on 43g alumina carrier, leave standstill 4h, 100 DEG C of oven dry, 700 DEG C 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 18.8ml0.5mol/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), leave standstill 6h, 140 DEG C of oven dry, 700 DEG C of roasting 9h, can obtain 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, reaction temperature 250 DEG C, glycerine volume space velocity 0.2h
-1, hydrogen/glycerine mol ratio is 9:1, and reaction time 80h, result of the test is in table 1.
Embodiment 9
(1) catalyst preparing: take 18.88g copper nitrate, 22.88g zinc nitrate, 69.47g aluminum nitrate and 7.5g phosphotungstic acid respectively and be dissolved in distilled water, be impregnated on 27g absorbent charcoal carrier, leave standstill 4h, 100 DEG C of oven dry, the lower 400 DEG C 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, leave standstill 7h, 145 DEG C of oven dry, the lower 500 DEG C of roasting 4h of nitrogen atmosphere, can obtain 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, reaction temperature 220 DEG C, glycerine volume space velocity 0.6h
-1, hydrogen/glycerine mol ratio is 7:1, and reaction time 100h, result of the test is in table 1.
Embodiment 10
(1) catalyst preparing: take 33.98g copper nitrate respectively, 3.11g potassium nitrate, 6g silico-tungstic acid be dissolved in distilled water, be impregnated on 43.8g alumina carrier, leave standstill 10h, 120 DEG C of oven dry, 600 DEG C of roasting 5h, can obtain 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, reaction temperature 200 DEG C, glycerine volume space velocity 0.9h
-1, hydrogen/glycerine mol ratio is 4:1, and reaction time 300h, result of the test is in table 1.
Table 1 result of the test
Claims (5)
1. a preparation method for preparing 1,2-dihydroxypropane by glycerine hydrogenation catalyst, is characterized in that the raw material components by being calculated in mass percent as follows is made:
Wherein:
Heteropoly acid is any one or its any two or more combination in phosphomolybdic acid, phosphotungstic acid, silico-tungstic acid or silicomolybdic acid;
Carrier is any one or its any two or more combination in silica gel, active carbon, aluminium oxide, zirconia, titanium oxide or molecular sieve;
Active component is any one or its any two or more combination in nickel, zinc, copper, magnesium, zirconium, molybdenum, aluminium or titanium element;
Modified component is any one or its any two or more combination of potassium, manganese, vanadium, tin, cadmium, iron, palladium or cobalt metal element;
The preparation method of the catalyst of described preparing 1,2-dihydroxypropane by glycerine hydrogenation, adopts secondary dipping process, comprises the steps:
1. single-steeping Kaolinite Preparation of Catalyst presoma
Be impregnated on carrier after being dissolved by catalyst composition distilled water by the salt of heteropoly acid and active metal component, leave standstill 1 ~ 24 hour, 100 ~ 145 DEG C of oven dry, at 300 ~ 700 DEG C, roasting 1 ~ 10 hour, obtains single-steeping catalyst precursor;
2. catalyst preparing
Be impregnated into after the salt of modified component is dissolved by catalyst composition distilled water on the single-steeping catalyst precursor that 1. step obtain, leave standstill 1 ~ 24 hour, 100 ~ 145 DEG C of oven dry, roasting 1 ~ 10 hour at 300 ~ 700 DEG C, obtain the catalyst for preparing 1,2-dihydroxypropane by glycerine hydrogenation;
The using method of the catalyst of described preparing 1,2-dihydroxypropane by glycerine hydrogenation, for fixed bed reactors, hydrogen/glycerine mol ratio is 3:1 ~ 10:1, and glycerine air speed is 0.1 ~ 1.3h
-1, reaction temperature is 180 ~ 260 DEG C, and reaction pressure is 1 ~ 7MPa, and the reaction time is 10 ~ 300h, and obtained product 1,2-PD, glycerol conversion yield reaches 90.12%.
2. the preparation method of preparing 1,2-dihydroxypropane by glycerine hydrogenation catalyst according to claim 1, 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.
3. the preparation method of preparing 1,2-dihydroxypropane by glycerine hydrogenation catalyst according to claim 2, is characterized in that the water soluble salt of described metallic element is its nitrate, hydrochloride or sulfate.
4. the preparation method of preparing 1,2-dihydroxypropane by glycerine hydrogenation catalyst according to claim 1, is characterized in that described modified component is provided with the form of its aqueous solution by the water soluble salt of potassium, manganese, vanadium, tin, cadmium, iron, palladium or cobalt metal element.
5. the preparation method of preparing 1,2-dihydroxypropane by glycerine hydrogenation catalyst according to claim 4, is characterized in that the water soluble salt of described modified component is its nitrate, hydrochloride or sulfate.
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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 |
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