CN110560057B - Application of multi-active-component catalyst in preparation of 1, 3-propylene glycol by hydrogenolysis of glycerol - Google Patents
Application of multi-active-component catalyst in preparation of 1, 3-propylene glycol by hydrogenolysis of glycerol Download PDFInfo
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
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- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
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Abstract
The patent relates to application of a multi-active-component catalyst in preparation of 1, 3-propylene glycol by hydrogenolysis of glycerol. The preparation method of the catalyst comprises the following steps: firstly, loading a precursor of tungsten oxide on alumina by adopting an excess impregnation method, adjusting the pH value, selecting a proper surfactant, and loading one of gold, iridium, rhodium, palladium and silver (an active component is marked as A) on the carrier by adopting a deposition-precipitation method to obtain A/WOx‑Al2O3Then wet impregnating into A/WO with precursor solution of platinumx‑Al2O3Obtaining Pt/A/WOx‑Al2O3(ii) a At the same time, can be found in Pt/A/WOx‑Al2O3One or two of molybdenum, rhenium, tungsten, aluminum, sodium, lanthanum, cerium, iron, zirconium, zinc and the like are added to the catalyst as an auxiliary agent. The catalyst prepared by the patent can ensure that the glycerol aqueous solution is hydrogenolyzed under certain hydrogen pressure and temperature with high conversion rate and high selectivity to generate 1, 3-propanediol, and has good stability.
Description
Technical Field
The invention relates to a preparation method of a multi-active-component catalyst and application of the multi-active-component catalyst in preparation of 1, 3-propylene glycol by hydrogenolysis of glycerol.
Background
In recent years, the continuous development of human society has been seriously affected by the increasing exhaustion of fossil energy and the remarkable trend of environmental pollution, so that the search for renewable clean energy is highly valued by governments and scientists of various countries. Under this large background, biodiesel is receiving attention due to its non-toxicity, renewable, degradable and low polluting emissions. However, the production of 1Kg of glycerin is accompanied for every 10Kg of biodiesel, and it is expected that glycerin as a by-product will be produced in a large amount with the rapid development of the biodiesel industry. Therefore, the conversion of glycerol into high value-added chemicals has become one of the research hotspots in today's society. The glycerol can generate 1, 3-propylene glycol, 1, 2-propylene glycol, n-propanol, ethylene glycol and the like through hydrogenolysis reaction, wherein the 1, 3-propylene glycol has higher economic value and market application value.
1, 3-propanediol is a chemical raw material with high added value, is an important synthetic raw material of plasticizer, detergent, preservative, emulsifier and the like, can also be used in the industries of food, cosmetics, pharmacy and the like, and has the main application of reacting with terephthalic acid to generate novel polyester, namely poly (1, 3-trimethylene terephthalate) (PTT) with great development application. PTT is a novel polyester fiber with biodegradability, has the characteristics of excellent rebound resilience, softness, easy dyeing and the like, overcomes the defects of too hard polyethylene terephthalate (PET) and too soft polybutylene terephthalate (PBT), and has wide application prospect in the industries of carpets, textile engineering plastics and the like.
Compared with the traditional ethylene oxide carbonylation hydrogenation method (Chinese patent CN1201407A) and the acrolein hydration hydrogenation method for preparing the 1, 3-propylene glycol (US patent US5364984A), the method for preparing the 1, 3-propylene glycol by directly hydrogenizing the glycerol has the characteristics of simple process, extremely low environmental pollution and the like, and has great competitiveness and challenge. Through numerous studies, it was found that Pt/WOx/Al2O3The catalyst system has good catalytic activity for the reaction of preparing the 1, 3-propylene glycol by hydrogenolysis of the glycerol, but the catalyst system has poor tolerance to impurities in the crude glycerol and is easy to be poisoned to cause the inactivation of the catalyst.
Disclosure of Invention
Compared with the prior art, the invention effectively improves the conversion rate of the glycerol and the selectivity of the 1, 3-propanediol, and the catalyst has good stability.
The invention provides a multi-active-component catalyst for preparing 1, 3-propylene glycol by direct hydrogenolysis of glycerol, wherein the catalyst adopts an excess impregnation method to load a precursor of tungsten oxide on alumina, regulate the pH value and select a proper surfactantLoading one of gold, iridium, rhodium, palladium and silver (active component is marked as A) on the carrier by adopting a deposition-precipitation method to obtain A/WOx-Al2O3Then wet impregnating into A/WO with precursor solution of platinumx-Al2O3Obtaining Pt/A/WOx-Al2O3(ii) a At the same time, can be found in Pt/A/WOx-Al2O3One or two of molybdenum, rhenium, tungsten, aluminum, sodium, lanthanum, cerium, iron, zirconium, zinc and the like are added to the catalyst as an auxiliary agent;
said A/WOx-Al2O3The preparation process comprises the following steps: firstly, dissolving a precursor (ammonium metatungstate or ammonium paratungstate aqueous solution) of tungsten oxide in excessive water, heating in a water bath at 30-90 ℃ for 0.5-3 h, adding a proper amount of alumina powder, continuing to stir in the water bath at 30-90 ℃ for 10-18 h, adjusting the pH to 1-5 by using concentrated hydrochloric acid or concentrated nitric acid and the like, adding a proper amount of surfactant, stirring for a period of time, adding a precursor solution of the component A, continuing to age for 12-48 h, filtering, washing, drying at 80-120 ℃ for more than 10h, calcining in a muffle furnace at 500-800 ℃ for 1-10 h to obtain A/WOx-Al2O3Powder;
the A/WOx-Al2O3The surfactant added in the preparation process is one of polyvinyl alcohol, polyethylene glycol, trimethyl hexadecyl ammonium bromide, octadecylamine and the like;
the A/WOx-Al2O3In the above formula, the mass content of W is 1-30%, preferably 5-25%; the mass content of the component A is 0.01-10%, preferably 0.1-5%;
dipping a precursor solution of platinum into A/WO by adopting wet dippingx-Al2O3The Pt/A/WO is obtained by the above preparationx-Al2O3The preparation method comprises the following specific steps: preliminarily wetting and dipping the proportioned platinum precursor aqueous solution on a carrier for 10-48 h, drying in a drying oven at 60-120 ℃ for more than 10h, calcining in a muffle furnace at 300-500 ℃ for 1-5 h, and finally obtaining Pt/A/WOx-Al2O3A catalyst;
the Pt/A/WOx-Al2O3The mass content of the noble metal Pt is 0.1-10%, preferably 0.5-5%;
in Pt/A/WOx-Al2O3On the basis of the catalyst, one or two of molybdenum, rhenium, tungsten, aluminum, sodium, lanthanum, cerium, iron, zirconium, zinc and the like are added as auxiliary agents, and the preparation process comprises the following steps: and (3) carrying out incipient wetness impregnation on the carrier by using the proportioned auxiliary agent precursor aqueous solution for 10-48 h, drying in an oven at 60-120 ℃ for more than 10h, and calcining in a muffle furnace at 300-500 ℃ for 1-5 h. The mass content of the additive is 0.001-10%, preferably 0.01-5%;
the catalyst is reduced under high-purity hydrogen, the reduction pressure is 0.1-5 Mpa, the reduction temperature is 150-600 ℃, and the reduction time is 0.5-10 h;
the catalyst is used in the reaction for preparing the 1, 3-propylene glycol by hydrogenolysis of the glycerol, the reaction adopts a fixed bed reactor, the reaction raw material is glycerol aqueous solution, the mass concentration of the glycerol is 5-100%, the hydrogen pressure is 0.1-10 MPa, the reaction temperature is 80-300 ℃, the reaction time is 0.2-500 h, and the using amount of the catalyst is 0.01-5 g.
Detailed Description
Example 1 (comparative example)
Dissolving ammonium metatungstate in deionized water to obtain 5% ammonium salt solution, heating in 30 deg.C water bath for 1 hr, adding appropriate amount of alumina powder, stirring in 30 deg.C water bath for 15 hr, filtering, washing, drying at 100 deg.C for 12 hr, calcining in muffle furnace at 700 deg.C for 5 hr to obtain WO 10% in mass contentx-Al2O3And (3) powder. Impregnating chloroplatinic acid solution in equal volume into WOx-Al2O3Standing the carrier for 24h, drying the carrier in a 120 ℃ oven for 12h, and calcining the carrier in a muffle furnace at 500 ℃ for 10h to obtain the Pt/WOx-Al2O3The mass content of Pt in the catalyst was 4%. Reducing and activating the prepared catalyst for 3 hours at 500 ℃ in a hydrogen reduction furnace to prepare the catalyst with the mass content of 4% Pt/10% WO3-Al2O3. Selecting a fixed bed reactor with the mass concentration of the glycerol aqueous solution being 50 percent, and catalyzingThe chemical dosage is 2g, the reaction temperature is 200 ℃, the reaction pressure is 5MPa, and the reaction time is 15 h.
Example 2
Dissolving ammonium metatungstate in deionized water to obtain an ammonium salt solution with the mass content of 5%, heating in a water bath at 60 ℃ for 1h, adding a proper amount of alumina powder, continuing to stir in the water bath at 60 ℃ for 15h, adjusting the pH to 5 with concentrated hydrochloric acid, adding 20 wt% (relative to the mass of the alumina carrier) of polyvinyl alcohol (with the average molecular weight of 9000-10000), stirring for 1h, adding a chloroauric acid solution with the mass concentration of about 50mg/mL, continuing to age for 24h, filtering, washing, drying at 120 ℃ for 12h, and calcining in a muffle furnace at 700 ℃ for 5h to obtain Au/WOx-Al2O3Powder in which W and Au are contained in amounts of 10% and 1% by mass, respectively. Impregnating chloroplatinic acid solution in equal volume into WOx-Al2O3Soaking the carrier overnight, drying in a 120 ℃ oven for 12h, and calcining in a muffle furnace at 500 ℃ for 5h to obtain Pt/Au/WOx-Al2O3The mass content of Pt in the catalyst was 4%. The prepared catalyst is reduced and activated for 3 hours at 500 ℃ in a hydrogen reduction furnace to prepare the catalyst 4 percent of Pt/1 percent of Au/10 percent of WO3-Al2O3. A fixed bed reactor is selected, the mass concentration of the glycerol aqueous solution is 50%, the catalyst amount is 2g, the reaction temperature is 200 ℃, the reaction pressure is 5MPa, and the reaction time is 15 h.
Example 3
Dissolving ammonium metatungstate in deionized water to obtain an ammonium salt solution with the mass content of 5%, heating in a water bath at 60 ℃ for 1h, adding a proper amount of alumina powder, continuing to stir in the water bath at 60 ℃ for 15h, adjusting the pH to 5 with concentrated hydrochloric acid, adding 20 wt% (relative to the mass of the alumina carrier) of polyvinyl alcohol (with the average molecular weight of 9000-10000), stirring for 1h, adding a chloroauric acid solution with the mass concentration of about 50mg/mL, continuing to age for 24h, filtering, washing, drying at 120 ℃ for 12h, and calcining in a muffle furnace at 700 ℃ for 5h to obtain Au/WOx-Al2O3Powder in which W and Au are contained in amounts of 10% and 1% by mass, respectively. Impregnating chloroplatinic acid solution in equal volume into WOx-Al2O3Soaking on carrier for 24 hr, drying at 120 deg.C in oven for 12 hr, and calcining at 500 deg.C in muffle furnaceAfter 5 hours of burning, Pt/Au/WO is preparedx-Al2O3The mass content of Pt in the catalyst was 4%. The ammonium molybdate aqueous solution is dipped into Pt/Au/WO in equal volumex-Al2O3Then the mixture is dipped for 24h, dried in a 120 ℃ oven for 12h and calcined in a muffle furnace at 300 ℃ for 5h to prepare Mo/Pt/Au/WOx-Al2O3And the mass content of molybdenum in the catalyst is 0.5 percent. The prepared catalyst is reduced and activated for 3 hours at 500 ℃ in a hydrogen reduction furnace to prepare the catalyst of 0.5 percent of Mo/4 percent of Pt/1 percent of Au/10 percent of WO3-Al2O3. A fixed bed reactor is selected, the mass concentration of the glycerol aqueous solution is 50%, the catalyst amount is 2g, the reaction temperature is 200 ℃, the reaction pressure is 5MPa, and the reaction time is 15 h.
Example 4
The other conditions were the same as in example 2 except that the chlorine was replaced with chloroiridic acid.
Example 5
The gold chloride was exchanged for silver nitrate and the other conditions were the same as in example 2.
Example 6
The ammonium molybdate was replaced with lanthanum nitrate and the other conditions were the same as in example 3.
Example 7
The ammonium molybdate was replaced with zirconyl nitrate and the other conditions were the same as in example 3.
Example 8
The ammonium molybdate was replaced with ferric nitrate and the other conditions were the same as in example 3.
TABLE 1 comparison of catalytic Performance for the hydrogenolysis of glycerol to 1, 3-propanediol
Others include small amounts of propane, methanol, ethanol, ethylene glycol, overall material conservation.
The above description is of the preferred embodiment of the present invention and is not intended to limit the invention in any way or manner. It should be understood that all changes, modifications and equivalents that can be made by one skilled in the art without departing from the spirit and scope of the invention as described above are equivalent embodiments of the invention; meanwhile, any changes, modifications and evolution of the equivalent changes of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention.
Claims (12)
1. The application of the multi-active component catalyst in the preparation of 1, 3-propylene glycol by the hydrogenolysis of glycerol is characterized in that the catalyst is used for preparing WOx-Al2O3A carrier, x is 23; then adopting a deposition-precipitation method to load gold serving as an active component, namely A on the carrier to obtain A/WOx-Al2O3Then wet impregnating into A/WO with precursor solution of platinumx-Al2O3Obtaining Pt/A/WOx-Al2O3(ii) a At the same time, in Pt/A/WOx-Al2O3One or two of molybdenum and iron are added on the catalyst of (1) as an auxiliary agent; the specific preparation process comprises the following steps: firstly, dissolving a precursor of tungsten oxide in deionized water to obtain an ammonium salt solution with the mass content of 5-10%, and dissolving the ammonium salt solution in 30-90% by massoC, heating in water bath for 0.5-3 h, adding aluminum oxide powder, and continuing for 30-90 hoC, stirring for 10-18 h in water bath, adjusting the pH to 1-5 by using concentrated hydrochloric acid or concentrated nitric acid, adding a surfactant accounting for 10-20 wt% of the mass of the alumina carrier, stirring for more than 30 min, adding a precursor solution of the component A, continuously aging for 12-48 h, filtering, washing, and performing 80-120oDrying the C for more than 10 hours in a muffle furnace for 500-800 hoursoCalcining for 1-10 h under C to obtain A/WOx-Al2O3Powder; wherein the precursor of tungsten oxide is one or two of ammonium metatungstate or ammonium paratungstate;
dipping a precursor solution of platinum into A/WO by adopting wet dippingx-Al2O3Preparation of Pt/A/WOx-Al2O3The preparation method comprises the following specific steps: preliminarily wetting and soaking the proportioned platinum precursor aqueous solution on a carrier for 10-48 h and 60-120 hoC, drying in a drying oven for more than 10 hours in a muffle furnace for 300-500 hoursoCalcining for 1-5 h under C to finally obtain Pt/A/WOx-Al2O3A catalyst.
2. Use according to claim 1, characterized in that: the surfactant added in the preparation process is one or more than two of polyvinyl alcohol with the average molecular weight of 9000-10000, polyethylene glycol with the average molecular weight of 380-420, hexadecyl trimethyl ammonium bromide and octadecylamine.
3. Use according to claim 1, characterized in that: the precursor of the tungsten oxide is one or two of ammonium metatungstate and ammonium paratungstate.
4. Use according to claim 1, characterized in that: the prepared A/WOx-Al2O3In the method, the mass content of W is 1-30%; the mass content of the component A is 0.01-10%.
5. Use according to claim 4, characterized in that: the prepared A/WOx-Al2O3In the method, the mass content of W is 5-25%; the mass content of the component A is 0.1-5%.
6. Use according to claim 1, characterized in that: the mass content of the noble metal Pt is 0.1-10%.
7. Use according to claim 1, characterized in that: the mass content of the noble metal Pt is 0.5-5%.
8. Use according to claim 1, characterized in that: in Pt/A/WOx-Al2O3On the basis of the catalyst, one or two of molybdenum and iron are added as an auxiliary agent, and the specific preparation process comprises the following steps: preliminarily wetting and dipping the proportioned water solution of the soluble acid or salt auxiliary agent precursor of the metal on the carrier for 10-48 h and 60-120 hoC, drying in a drying oven for more than 10 hours in a muffle furnace for 300-500 hoursoCalcining for 1-5 h under C.
9. Use according to claim 1 or 8, characterized in that: the mass content of the additive in the catalyst is 0.001-10%.
10. Use according to claim 1 or 8, characterized in that: the mass content of the additive in the catalyst is 0.01-5%.
11. Use according to claim 9, characterized in that: the catalyst is preferably reduced under high-purity hydrogen before use, the reduction pressure is 0.1-5 Mpa, and the reduction temperature is 150-600 MpaoAnd C, the reduction time is 0.5-10 h.
12. Use according to claim 9, characterized in that: the catalyst is used in the reaction for preparing 1, 3-propylene glycol by hydrogenolysis of glycerol, the reaction adopts a fixed bed reactor, the reaction raw material is glycerol aqueous solution, the mass concentration of the glycerol is 5-100%, the hydrogen pressure is 0.1-10 MPa, and the reaction temperature is 80-300%oC, the reaction time is 0.2-500 h, and the dosage of the catalyst is 0.01-5 g.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101723801A (en) * | 2008-10-24 | 2010-06-09 | 中国科学院大连化学物理研究所 | Method for preparing 1,3-propylene glycol by directly hydrogenizing glycerol |
CN104507896A (en) * | 2012-04-27 | 2015-04-08 | 纳幕尔杜邦公司 | Production of alpha, omega-diols |
CN104661988A (en) * | 2012-09-20 | 2015-05-27 | 纳幕尔杜邦公司 | Process for making linear long-chain alkanes using renewable feedstocks |
CN105618045A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Application of bimetallic catalyst in glycerol hydrogenolysis for preparation of 1,3-propylene glycol |
CN106883098A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | Application of the multiple active components catalyst in hydrogenolysis of glycerin prepares 1,3- propane diols |
-
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101723801A (en) * | 2008-10-24 | 2010-06-09 | 中国科学院大连化学物理研究所 | Method for preparing 1,3-propylene glycol by directly hydrogenizing glycerol |
CN104507896A (en) * | 2012-04-27 | 2015-04-08 | 纳幕尔杜邦公司 | Production of alpha, omega-diols |
CN104661988A (en) * | 2012-09-20 | 2015-05-27 | 纳幕尔杜邦公司 | Process for making linear long-chain alkanes using renewable feedstocks |
CN105618045A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Application of bimetallic catalyst in glycerol hydrogenolysis for preparation of 1,3-propylene glycol |
CN106883098A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | Application of the multiple active components catalyst in hydrogenolysis of glycerin prepares 1,3- propane diols |
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