CN105854880A - Catalyst for synthesizing ethyl ethoxyacetate through hydrogenation of diethyl oxalate and preparation method and application of catalyst - Google Patents
Catalyst for synthesizing ethyl ethoxyacetate through hydrogenation of diethyl oxalate and preparation method and application of catalyst Download PDFInfo
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- CN105854880A CN105854880A CN201610237182.3A CN201610237182A CN105854880A CN 105854880 A CN105854880 A CN 105854880A CN 201610237182 A CN201610237182 A CN 201610237182A CN 105854880 A CN105854880 A CN 105854880A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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Abstract
A catalyst for synthesizing ethyl ethoxyacetate through hydrogenation of diethyl oxalate is prepared from, by mass, 2.0-65.0wt% of CuO serving as a main active component and 3.5-98.0wt% of Al2O3 serving as a carrier. The catalyst for synthesizing ethyl ethoxyacetate through hydrogenation of diethyl oxalate has the advantages of being high in selectivity, good in stability and suitable for industrial production.
Description
Technical field
The invention belongs to catalyst and its preparation method and application, synthesize catalyst of ethoxy ethyl acetate and its preparation method and application particularly to a kind of diethy-aceto oxalate gas phase hydrogenation.
Background technology
Ethoxy ethyl acetate can be dissolved in water, is soluble in ethanol, ether, is miscible in most organic solvents such as aromatic hydrocarbons, as alembroth, has extremely strong solvability, especially higher to the dissolving power of polymeric, has the character of fatty ether and acetic acid esters.Be mainly used in metal, solvent that furniture sprays paint; brush lacquer solvent; also can make protective coating, dyestuff, resin, leather, ink solvent it can also be used to the hard surface cleaner such as metal, glass formula in, and chemical reagent or organic synthesis intermediate can be made.Therefore, the market demand of ethoxy ethyl acetate is bigger.
The tradition preparation of ethoxy ethyl acetate is with monoxone as raw material, ethoxyacetic acid is produced after adding the ethanol solution of caustic alcohol, blast HCl gas subsequently it to be esterified with ethanol in reactant mixture, add alkali lye afterwards filter and remove the impurity such as ethanol, extract, distill after obtain ethoxy ethyl acetate.But this method causes great environmental pollution and the health hazard to operating personnel because using strong acid, highly basic etc., simultaneously because using the raw materials such as caustic alcohol to make the with high costs of industrialized production, furthermore, this method reaction process is complicated and loaded down with trivial details, process conditions are required more harsh, limits the mass market supply of ethoxy ethyl acetate.
Currently, along with the day by day exhausted of world petroleum resource and the clean and efficient increase day by day utilizing demand of coal, find and exploitation prepares other industrial chemicals on a large scale with coal and living beings for base stock and multi-chemical has had become as and known together widely, and meet active demand and the needs of increasingly serious Environmental Protection Situation of society.At present, the synthesis gas obtained by coal and gasification of biomass is produced diethy-aceto oxalate and has been realized in industrialization, and its yield ensure that the demand in market.Thermodynamics of reactions is analyzed and numerous result of study shows, diethy-aceto oxalate catalytic hydrogenation can generate intermediate product ethyl glycolate, and ethyl glycolate is hydrogenated to end-product ethylene glycol or ethanol further.Therefore, the product that this reaction is traditional is ethyl glycolate, ethylene glycol and ethanol.However, it has been found that use some to have the catalyst of special construction can be hydrogenated with one-step synthesis ethoxy ethyl acetate by diethy-aceto oxalate.But, the selectivity synthesis difficulty controlling ethoxy ethyl acetate under corresponding reaction condition is very big, so by carbon one degradation pathways through the design that key technology is catalyst of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate.CN101700496A discloses a kind of Al2O3Carrier loaded Cu base catalyst, but primary product is ethyl glycolate, and catalyst needs to add noble metal component Ag.Other major part research all concentrates on the traditional product such as preparing glycol by hydrogenating oxalate and ethanol.Although copper-based catalysts prepared in this series of studies has higher activity and selectivity, but product is single and is easily caused the production capacity surplus of Related product, limits coal and living beings are converted into the development of other fine chemicals technology and the popularization of related industries.What is more important, by the end of at present, does not also have document to report the catalyst of diethy-aceto oxalate gas phase hydrogenation synthesis ethoxy ethyl acetate.Therefore exploitation have high selectively and the catalyst of high stability is one of diethy-aceto oxalate key technical problems of selecting Hydrogenation ethoxy ethyl acetate.
Summary of the invention
It is an object of the invention to provide a kind of the highest, good stability, it is adaptable to diethy-aceto oxalate gas phase hydrogenation catalyst producing ethoxy ethyl acetate of industrialized production and its preparation method and application.
The present invention is achieved by the following technical programs.
The catalyst of a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate is to be main active component with cupric oxide, Al2O3For carrier, catalyst quality ratio consists of: the content of CuO is 2.0 ~ 65.0 wt%, Al2O3For 35.0-98.0 wt%.
The best in quality content of above-mentioned cupric oxide is 5.0 ~ 58.0 wt%.
The preparation method of the catalyst of above-mentioned a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate comprises the following steps:
(1) it is that 0.02 ~ 2.4:1 mixes by soluble copper salt and aluminum soluble salt by Cu/Al atomic ratio；
(2) organic carboxyl acid complexing agent is that 1:1 ~ 2 calculate by copper ion and aluminum ions total ion concentration and complexing agent mole coordination ratio, is added into step (1) mixed metal salt and at room temperature strong stirring 2 ~ 6 h；
(3) by step (2) gains 30 ~ 65oC and 70 ~ 120oSuccessively it is dried 2 ~ 10 h under C, obtains catalyst precursor powder；
(4) step (3) made catalyst precursor powder is warming up to 400 ~ 800 in airoC calcines 1 ~ 10 h, heating rate 1 ~ 20oC/min, i.e. prepares CuO/Al2O3Diethy-aceto oxalate hydrogenation catalyst.
Soluble copper salt used includes copper acetate, copper sulphate or copper nitrate；Aluminum soluble salt includes aluminum sulfate, aluminum nitrate or aluminum acetate；Complexing agent used includes oxalic acid, tartaric acid, citric acid or salicylic acid.
The application of catalyst of the present invention, comprises the steps:
Putting in fixed bed reactors by catalyst of the present invention, carry out in-situ reducing in pure hydrogen, reduction pressure is 0 ~ 0.5 MPa, H2Volume space velocity is 500 ~ 5000 h-1, with 1 ~ 5oThe ramp of C/min is to 150 ~ 300oC, reductase 12 ~ 6 h；After reduction terminates, control reaction temperature to 180 ~ 270oC, control pressure 1.5 ~ 3.0 MPa, diethy-aceto oxalate solution after being gasificated into gas with H2Be mixed into reactor carry out hydrogenation reaction generate ethoxy ethyl acetate, diethy-aceto oxalate liquid hourly space velocity (LHSV) be 0.2 ~ 2.0 h-1, H2: the mol ratio of diethy-aceto oxalate is 30 ~ 150.
The present invention compared with prior art, has the advantages that
The preparation method of catalyst of the present invention is simple, and raw material is sufficient, has high selectivity (nearly 80%) and stability (stable operation is more than 60 h) in the reaction of catalysis diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate.Being applicable to the industrialized production of reality, catalytic performance is excellent.
Detailed description of the invention
Embodiment 1
The preparation method of the catalyst of a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate, comprises the steps: that 0.223 g copper acetate and 3.422 g aluminum sulfate are mixed by (1)；(2) it is that 1:1.6 calculates by copper ion and aluminum ions total ion concentration and oxalic acid mole coordination ratio, 4.41 g oxalic acid is added to above-mentioned steps (1) mixed metal salt and at room temperature strong stirring 6 h；(3) step (2) gains are moved into 50o8 h it are dried, afterwards then at 100 under CoIt is dried 5 h under C, obtains catalyst precursor powder；Step (3) made powder sample is risen to 400 in airoC calcines 10 h, heating rate 1oC/min, i.e. prepares the CuO/Al that mass content is 5.0 wt% of cupric oxide2O3Diethy-aceto oxalate hydrogenation catalyst.
By above-mentioned CuO/Al2O3Catalyst 1 mL is filled in fixed-bed tube reactor.By catalyst at volume space velocity 1800 h-1、0.3 MPa、H2With 2 under atmosphereoC/min is warming up to 150oC, reduces 6 h at this temperature, and then the temperature of fixed bed is reduced to temperature required when reaction occurs.Diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate reaction condition is as follows: reaction temperature 180oC, reaction pressure 3.0 MPa, liquid air speed is 0.2 h-1, H2: diethy-aceto oxalate mol ratio is 150:1.Reaction liquid product is by gas chromatographic analysis, and reaction end gas is by gas-chromatography on-line checking.Under the above-described reaction conditions, conversion ratio 63.6 wt% of diethy-aceto oxalate, selectivity 48.2 wt% of ethoxy ethyl acetate, selectivity 17.3 wt% of ethyl glycolate, selectivity 17.1 wt%(of ethanol are shown in Table 1).
Embodiment 2
The preparation method of the catalyst of a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate, comprises the steps: that 0.798 g copper sulphate and 5.009 g aluminum nitrates are mixed by (1)；(2) it is that 1:1.9 calculates by copper ion and aluminum ions total ion concentration and citric acid mole coordination ratio, 11.242 g citric acids is rapidly joined to above-mentioned steps (1) mixed metal salt and at room temperature strong stirring 3 h；(3) step (2) gains are moved into 30o10 h it are dried, afterwards then at 80 under CoIt is dried 8 h under C, obtains catalyst precursor powder；(4) step (3) made powder sample is warming up to 800 in airoC calcines 1 h, heating rate 1oC/min, i.e. prepares the CuO/Al that mass content is 25.0 wt% of cupric oxide2O3Diethy-aceto oxalate hydrogenation catalyst.
By above-mentioned CuO/Al2O3Catalyst 1 mL is filled in fixed-bed tube reactor.By catalyst at volume space velocity 4000 h-1, normal pressure, H2With 4 under atmosphereoC/min is warming up to 300oC, at this temperature reductase 12 h, be then reduced to temperature required when reaction occurs by the temperature of fixed bed.Diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate reaction condition is as follows: reaction temperature 270oC, reaction pressure 1.5 MPa, liquid air speed is 0.8 h-1, H2: diethy-aceto oxalate mol ratio is 100:1.Under upper described reaction condition, conversion ratio 62.8 wt% of diethy-aceto oxalate, selectivity 45.1 wt% of ethoxy ethyl acetate, selectivity 12.1 wt% of ethyl glycolate, selectivity 21.3 wt%(of ethanol are shown in Table 1)；Catalyst stabilization runs 60 h.
Embodiment 3
The preparation method of the catalyst of a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate, comprises the steps: that 1.876 g copper nitrates and 5.115 g aluminum nitrates are mixed by (1)；(2) it is that 1:1 calculates by copper ion and aluminum ions total ion concentration and tartaric acid mole coordination ratio, 6.904 g tartaric acid is rapidly joined to above-mentioned steps (1) mixed metal salt and at room temperature strong stirring 4 h；(3) step (2) gains are moved into 50o6 h it are dried, afterwards then at 70 under CoIt is dried 10 h under C, obtains catalyst precursor powder；(4) step (3) made powder sample is warming up to 700 in airoC calcines 2 h, heating rate 15oC/min, i.e. prepares the CuO/Al that mass content is 40.0 wt% of cupric oxide2O3Diethy-aceto oxalate hydrogenation catalyst.
By above-mentioned CuO/Al2O3Catalyst 1 mL is filled in fixed-bed tube reactor.By catalyst at volume space velocity 3600 h-1、0.2 MPa、H2With 3 under atmosphereoC/min is warming up to 260oC, at this temperature reductase 12 h, be then reduced to temperature required when reaction occurs by the temperature of fixed bed.Diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate reaction condition is as follows: reaction temperature 240oC, reaction pressure 2.7 MPa, liquid air speed is 0.6 h-1, H2: diethy-aceto oxalate mol ratio is 120:1.Under reaction condition described above, conversion ratio 67.6 wt% of diethy-aceto oxalate, selectivity 39.4 wt% of ethoxy ethyl acetate, selectivity 19.9 wt% of ethyl glycolate, selectivity 20.3 wt%(of ethanol are shown in Table 1)；Catalyst stabilization runs 60 h.
Embodiment 4
The preparation method of the catalyst of a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate, comprises the steps: that 3.376 g copper nitrates and 2.041 g aluminum acetates are mixed by (1)；(2) it is that 1:2 calculates by copper ion and aluminum ions total ion concentration and salicylic acid mole coordination ratio, 14.530 g salicylic acids is added in above-mentioned steps (1) mixed metal salts and at room temperature strong stirring 5 h；(3) step (2) gains are moved into 60o4 h it are dried, afterwards then at 100 under CoIt is dried 4 h under C, obtains catalyst precursor powder；(4) step (3) made powder sample is warming up to 550 in airoC calcines 5 h, heating rate 2oC/min, i.e. prepares the CuO/Al that mass content is 48.0 wt% of cupric oxide2O3Diethy-aceto oxalate hydrogenation catalyst.
By above-mentioned CuO/Al2O3Catalyst 1 mL is filled in fixed-bed tube reactor.By catalyst at volume space velocity 5000 h-1、0.3 MPa、H2With 5 under atmosphereoC/min is warming up to 240oC, reduces 3 h at this temperature, and then the temperature of fixed bed is reduced to temperature required when reaction occurs.Diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate reaction condition is as follows: reaction temperature 220oC, reaction pressure 2.1 MPa, liquid air speed is 2.0 h-1, H2: diethy-aceto oxalate mol ratio is 30:1.Under reaction condition described above, conversion ratio 74.6 wt% of diethy-aceto oxalate, selectivity 55.7 wt% of ethoxy ethyl acetate, selectivity 11.2 wt% of ethyl glycolate, selectivity 18.6 wt%(of ethanol are shown in Table 1)；Catalyst stabilization runs 60 h.
Embodiment 5
The preparation method of the catalyst of a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate, comprises the steps: that 3.993 g copper acetates and 4.899 g aluminum acetates are mixed by (1)；(2) it is that 1:1 calculates by copper ion and aluminum ions total ion concentration and salicylic acid mole coordination ratio, 15.469 g salicylic acids is added in above-mentioned steps (1) mixed metal salts and at room temperature strong stirring 2 h；(3) step (2) gains are moved into 65o2 h it are dried, afterwards then at 120 under CoIt is dried 2 h under C, obtains catalyst precursor powder；(4) step (3) made powder sample is warming up to 650 in airoC calcines 3 h, heating rate 5oC/min, i.e. prepares the Cu/Al that mass content is 58.0 wt% of cupric oxide2O3Diethy-aceto oxalate hydrogenation catalyst.
By above-mentioned CuO/Al2O3Catalyst 1 mL is filled in fixed-bed tube reactor.By catalyst at volume space velocity 500 h-1、0.4 MPa、H2With 1 under atmosphereoC/min is warming up to 250oC, reduces 6 h at this temperature, and then the temperature of fixed bed is reduced to temperature required when reaction occurs.Diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate reaction condition is as follows: reaction temperature 220oC, reaction pressure 2.4 MPa, liquid air speed is 1.2 h-1, H2: diethy-aceto oxalate mol ratio is 50:1.Under reaction condition described above, conversion ratio 73.4 wt% of diethy-aceto oxalate, selectivity 79.7 wt% of ethoxy ethyl acetate, selectivity 6.7 wt% of ethyl glycolate, selectivity 5.3 wt%(of ethanol are shown in Table 1)；Catalyst stabilization runs 60 h.
The reaction result of table 1 diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate
Claims (7)
1. the catalyst of a diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate, it is characterised in that catalyst is to be main active component with cupric oxide, Al2O3For carrier, catalyst quality ratio consists of: the content of CuO is 2.0 ~ 65.0 wt%, Al2O3For 35.0-98.0 wt%.
The catalyst of a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate the most as claimed in claim 1, it is characterised in that the mass content of cupric oxide is 5.0 ~ 58.0
wt%。
The preparation method of the catalyst of a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate the most as claimed in claim 1 or 2, it is characterised in that comprise the following steps:
(1) it is that 0.02 ~ 2.4:1 mixes by soluble copper salt and aluminum soluble salt by Cu/Al atomic ratio；
(2) organic carboxyl acid complexing agent is that 1:1 ~ 2 calculate by copper ion and aluminum ions total ion concentration and complexing agent mole coordination ratio, is added into step (1) mixed metal salt and at room temperature strong stirring 2 ~ 6 h；
(3) by step (2) gains 30 ~ 65oC and 70 ~ 120oSuccessively it is dried 2 ~ 10 h under C, obtains catalyst precursor powder；
(4) step (3) made catalyst precursor powder is warming up to 400 ~ 800 in airoC calcines 1 ~ 10 h, heating rate 1 ~ 20oC/min, i.e. prepares CuO/Al2O3Diethy-aceto oxalate hydrogenation catalyst.
The preparation method of the catalyst of a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate the most as claimed in claim 3, it is characterised in that soluble copper salt includes copper acetate, copper sulphate or copper nitrate.
The preparation method of the catalyst of a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate the most as claimed in claim 3, it is characterised in that aluminum soluble salt includes aluminum sulfate, aluminum nitrate or aluminum acetate.
The preparation method of the catalyst of a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate the most as claimed in claim 3, it is characterised in that complexing agent used includes oxalic acid, tartaric acid, citric acid or salicylic acid.
The application of the catalyst of a kind of diethy-aceto oxalate hydrogenation synthesis ethoxy ethyl acetate the most as claimed in claim 1 or 2, it is characterised in that comprise the steps:
Being put into by catalyst in fixed bed reactors, carry out in-situ reducing in pure hydrogen, reduction pressure is 0 ~ 0.5 MPa, H2Volume space velocity is 500 ~ 5000 h-1, with 1 ~ 5oThe ramp of C/min is to 150 ~ 300oC, reductase 12 ~ 6 h；After reduction terminates, control reaction temperature to 180 ~ 270oC, control pressure 1.5 ~ 3.0 MPa, diethy-aceto oxalate solution after being gasificated into gas with H2Be mixed into reactor carry out hydrogenation reaction generate ethoxy ethyl acetate, diethy-aceto oxalate liquid hourly space velocity (LHSV) be 0.2 ~ 2.0 h-1, H2: the mol ratio of diethy-aceto oxalate is 30 ~ 150.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1837076A1 (en) * | 2006-03-20 | 2007-09-26 | Ford Global Technologies, LLC | Diesel particulate filter catalyst with low no2 emissions |
| CN102031401A (en) * | 2011-01-04 | 2011-04-27 | 合肥工业大学 | Preparation method of nano-alumina reinforcing copper-based composite |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1837076A1 (en) * | 2006-03-20 | 2007-09-26 | Ford Global Technologies, LLC | Diesel particulate filter catalyst with low no2 emissions |
| CN102031401A (en) * | 2011-01-04 | 2011-04-27 | 合肥工业大学 | Preparation method of nano-alumina reinforcing copper-based composite |
Non-Patent Citations (2)
| Title |
|---|
| MUHAMMAD F. IRFAN等: "Modeling of NO Removal over CuO/γ-Al2O3 Catalyst in a Bubbling Fluidized Bed Reactor", 《IND. ENG. CHEM. RES.》 * |
| 阎建辉等: "纳米CuO-CuAl2O4的制备及其模拟太阳光催化产氢", 《第八届全国工业催化技术及应用年会论文集》 * |
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