CN101791555B - Catalyst for gas-phase dimethyloxalate synthesis by CO and preparation method thereof - Google Patents
Catalyst for gas-phase dimethyloxalate synthesis by CO and preparation method thereof Download PDFInfo
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- CN101791555B CN101791555B CN2010101287320A CN201010128732A CN101791555B CN 101791555 B CN101791555 B CN 101791555B CN 2010101287320 A CN2010101287320 A CN 2010101287320A CN 201010128732 A CN201010128732 A CN 201010128732A CN 101791555 B CN101791555 B CN 101791555B
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Abstract
The invention discloses a catalyst for the gas-phase dimethyloxalate synthesis by CO and a preparation method thereof. In the catalyst of the invention, an alpha-type aluminum oxide is used as a carrier, an impregnation method is used to load metal palladium, lanthanum and rhenium, the palladium which serves as an active ingredient and the lanthanum and rhenium which serve as auxiliary active ingredients cooperate and interact with each other, and the stability and service life of the catalyst are improved effectively. The catalyst has extremely high reaction activity and selectivity in the reaction for the gas-phase dimethyloxalate synthesis by CO, makes reaction smooth and easily controllable and is suitable for industrial production actually.
Description
Technical field
The invention belongs to catalyst preparation technical field, further relate to a kind of Catalysts and its preparation method of the CO of being used for gas-phase dimethyloxalate synthesis.
Background technology
Carbon monoxide low pressure gas solid catalysis coupling synthesis of oxalate is the important subject of present C-1 chemistry.With the oxalate is that intermediate is produced oxalic acid, ethylene glycol, glycolic acid, oxamides and some medicine, dyestuff, compare with traditional handicraft have that production technology is simple, raw material rationally, low cost and other advantages.The exploitation of this problem has great economic benefit and social benefit.
Ube Industries Ltd. eighties is the technology of back end hydrogenation preparing ethylene glycol with regard to having developed the CO synthesis of oxalate, and obtained major progress; Meanwhile, Italian Montedison Group has carried out the research of carbon monoxide and nitrites gas solid method synthesis of oxalate; In recent years, China has also carried out C in succession
1The research of method synthesis of oxalate.The southwest PdCl of chemical research institute
2-CuCl
2Catalyst system and catalyzing liquid phase method oxidation of ethanol carbonylation synthesis of diethyl oxalate employing, ethanol conversion is 18%, the selectivity of diethy-aceto oxalate is 79%.Fujian Inst. of Matter Structure, Chinese Academy of Sciences carries out the research of carbon monoxide atmospheric gas solid catalysis synthesis of oxalate and spin-off thereof, and successfully passed through the technical appraisement of the Chinese Academy of Sciences, technological economics evaluation is thought, utilize carbon monoxide to produce oxalate and oxalic acid, economic benefit is obvious, has to realize industrialized prerequisite at no distant date.Because the coal resource of China is abundant relatively, exploitation is that the technology of raw material synthesis of oxalate and spin-off thereof can effectively be alleviated the degree of dependence of China to oil with CO, develops the effective catalyst that is used for the CO gas-phase synthesis of oxalate and has important economic implications equally.
Summary of the invention
Technical problem
Technical problem to be solved by this invention provides a kind of Catalysts and its preparation method of CO gas-phase dimethyloxalate synthesis of high activity, high selectivity and the long service life that can be applicable to actual industrial production.
Technical scheme
The present invention is achieved by the following technical programs.
A kind of catalyst of CO gas-phase dimethyloxalate synthesis, the main active component of described catalyst is a Metal Palladium, and helping active component is lanthanoid metal and rhenium metal, and the carrier of described catalyst is a α type alundum (Al; Described Metal Palladium content is 0.5～2% of carrier quality, and described lanthanoid metal content is 0.05～0.5% of carrier quality, and described rhenium metal content is 0.01～0.15% of carrier quality.
The catalyst of above-mentioned a kind of CO gas-phase dimethyloxalate synthesis, wherein, described Metal Palladium content is 1.05% of carrier quality, and described lanthanoid metal content is 0.32% of carrier quality, and described rhenium metal content is 0.10% of carrier quality.
The catalyst of above-mentioned a kind of CO gas-phase dimethyloxalate synthesis, wherein, the specific area of described α type alundum (Al is 8～16m
2/ g is 0.01～0.06cm than pore volume
3/ g, pore radius are 30～90nm, and density is 0.68～0.85g/cm
3
The catalyst of above-mentioned a kind of CO gas-phase dimethyloxalate synthesis, wherein, the specific area of described α type alundum (Al is 9m
2/ g is 0.04cm than pore volume
3/ g, pore radius are 60nm, and density is 0.78g/cm
3
The Preparation of catalysts method of above-mentioned a kind of CO gas-phase dimethyloxalate synthesis, preparation process is as follows:
(1) γ type alundum (Al is made it to be converted into α type alundum (Al at 1200～1250 ℃ of roasting 5～7h;
(2) palladium bichloride, perrhenic acid, lanthanum chloride, hydrochloric acid and deionized water are mixed and made into maceration extract;
(3) α type alundum (Al is dissolved in the above-mentioned maceration extract, and is heated to 70～80 ℃, under this temperature, stir 2～3h, at room temperature flood 14～30h then;
(4) solution with step (3) gained filters, the catalyst that obtains is washed 10 times with deionized water, and each deionized water consumption is 500ml, then respectively at 60～80 ℃ of drying 6～10h, 100～150 ℃ of drying 15～20h, and at 450～500 ℃ of roasting 10～15h;
(5) catalyzer with water after the roasting is closed hydrazine solution and at room temperature soak 6～10h and reduce, use methanol wash again, promptly get the final catalyst product, dry standby.
The using method of catalyst of the present invention:
Described catalyst needs to carry out reduction activation with hydrogen before use, and hydrogen flowing quantity is 20～50ml/ming (cat), needs 180 ℃ of following constant temperature activation 5～8 hours.
The reaction equation of CO gas-phase dimethyloxalate synthesis is as follows:
2CO+2CH
3ONO→CH
3OOCCOOCH
3+2NO
Reaction removes and generates dimethyl oxalate, also generates surplus accessory substances such as dimethyl carbonate, methyl ethyl oxalate, methyl glycollate, and the NO that generates in the reaction turns back to the methyl nitrite synthesizing section and recycles.
Being reflected in the fixed bed reactors of CO gas-phase dimethyloxalate synthesis carried out, and feed gas volume compares CH
3ONO: CO is between 1: 9～1: 3, and reaction temperature is 100～150 ℃, and reaction pressure is 0.08～0.15MPa, and the total air speed of unstripped gas is 1880h
-1～4200h
-1
Beneficial effect
Catalyst of the present invention selects for use α type alundum (Al as carrier, by infusion process carried metal palladium, lanthanoid metal and rhenium metal, main active component palladium with help the effect of cooperatively interacting of active component lanthanum and rhenium, improved the stability and the life-span of catalyst effectively.This catalyst has very high reactivity and selectivity in the reaction of CO gas-phase dimethyloxalate synthesis, and reacting balance, be easy to control, can be applicable to actual industrial production.
The specific embodiment
A kind of Preparation of catalysts method of CO gas-phase dimethyloxalate synthesis, preparation process is as follows: (1) makes it to be converted into α type alundum (Al with γ type alundum (Al at 1200～1250 ℃ of roasting 5～7h; (2) palladium bichloride, perrhenic acid, lanthanum chloride, hydrochloric acid and deionized water are mixed and made into maceration extract; (3) α type alundum (Al is dissolved in the above-mentioned maceration extract, and is heated to 70～80 ℃, under this temperature, stir 2～3h, at room temperature flood 14～30h then; (4) solution with step (3) gained filters, the catalyst that obtains is washed 10 times with deionized water, and each deionized water consumption is 500ml, then respectively at 60～80 ℃ of drying 6～10h, 100～150 ℃ of drying 15～20h, and at 450～500 ℃ of roasting 10～15h; (5) catalyzer with water after the roasting being closed hydrazine solution and at room temperature soak 6～10h and reduce, is 100% methanol wash again with mass percent concentration, promptly gets the final catalyst product, dries standby.
Embodiment 1
A kind of Preparation of catalysts method of CO gas-phase dimethyloxalate synthesis, preparation process is as follows: γ type alundum (Al is made it to be converted into α type alundum (Al at 1200 ℃ of roasting 5h, with palladium bichloride, perrhenic acid, lanthanum chloride, hydrochloric acid and deionized water are mixed and made into maceration extract, the quality percentage composition of Pd is 1.9% in the maceration extract, the quality percentage composition of Re is 0.6%, the quality percentage composition of La is 0.3%, the volume ratio of maceration extract and carrier is 1.5: 1, the α type alundum (Al of getting 90g is dissolved in the above-mentioned maceration extract, and be heated to 70 ℃, under this temperature, stir 2h, at room temperature flood 14h then; Filter then, the catalyst that obtains is washed 10 times with deionized water, and each deionized water consumption is 500ml, then respectively at 60 ℃ of dry 6h, and at 100 ℃ of dry 15h, and at 450 ℃ of roasting 10h.At last the catalyzer with water after the roasting being closed hydrazine solution and at room temperature soak 6h and reduce, is that 100% methyl alcohol washs with mass percent concentration again, promptly gets the final catalyst product A, dries standby.
Embodiment 2
A kind of Preparation of catalysts method of CO gas-phase dimethyloxalate synthesis, preparation process is as follows: γ type alundum (Al is made it to be converted into α type alundum (Al at 1230 ℃ of roasting 6h, with palladium bichloride, perrhenic acid, lanthanum chloride, hydrochloric acid and deionized water are mixed and made into maceration extract, the quality percentage composition of Pd is 2.0% in the maceration extract, the quality percentage composition of Re is 0.5%, the quality percentage composition of La is 0.25%, the volume ratio of maceration extract and carrier is 1.5: 1, the α type alundum (Al of getting 90g is dissolved in the above-mentioned maceration extract, and be heated to 75 ℃, under this temperature, stir 2.5h, at room temperature flood 20h then; Filter then, the catalyst that obtains is washed 10 times with deionized water, and each deionized water consumption is 500ml, then respectively at 70 ℃ of dry 8h, and at 120 ℃ of dry 18h, and at 480 ℃ of roasting 12h.At last the catalyzer with water after the roasting being closed hydrazine solution and at room temperature soak 8h and reduce, is that 100% methyl alcohol washs with mass percent concentration again, promptly gets the final catalyst product B, dries standby.
Embodiment 3
A kind of Preparation of catalysts method of CO gas-phase dimethyloxalate synthesis, preparation process is as follows: γ type alundum (Al is made it to be converted into α type alundum (Al at 1250 ℃ of roasting 7h, with palladium bichloride, perrhenic acid, lanthanum chloride, hydrochloric acid and deionized water are mixed and made into maceration extract, the quality percentage composition of Pd is 1.5% in the maceration extract, the quality percentage composition of Re is 0.8%, the quality percentage composition of La is 0.20%, the volume ratio of maceration extract and carrier is 1.5: 1, the α type alundum (Al of getting 90g is dissolved in the above-mentioned maceration extract, and be heated to 80 ℃, under this temperature, stir 3h, at room temperature flood 30h then; Filter then, the catalyst that obtains is washed 10 times with deionized water, and each deionized water consumption is 500ml, then respectively at 80 ℃ of dry 10h, and at 150 ℃ of dry 20h, and at 500 ℃ of roasting 15h.At last the catalyzer with water after the roasting being closed hydrazine solution and at room temperature soak 10h and reduce, is that 100% methyl alcohol washs with mass percent concentration again, promptly gets the final catalyst products C, dries standby.
The catalyst activity property testing:
Catalyst is inserted in the fixed bed reactors, and reactor inside diameter is 32mm, and long 500mm feeds N
2Protection, heat temperature raising to 60 ℃ stops logical N then
2, and use H
2Catalyst is carried out reduction activation, H
2Flow is 40ml/ming (cat), is warming up to 180 ℃, constant temperature activation 6 hours.Activation finishes the logical N in back
2Displacement is compared CH with feed gas volume
3ONO: CO feeds in reactor at 1: 4, and the total air speed of unstripped gas is 3670h
-1, reaction temperature is 135 ℃, reaction pressure 0.12MPa, and the high energy of the space-time yield of dimethyl oxalate reaches 1200g/L
CatalystH, the selectivity of dimethyl oxalate 〉=99.5%, this catalyst moves 2000h in fixed bed reactors, stable reaction, catalyst does not have deactivation phenomenom.Below be respectively the The performance test results of the catalyst that three embodiment make:
| Catalyst prod | Selectivity/the % of dimethyl oxalate | Space-time yield/the g/L of dimethyl oxalate Catalyst·h |
| A | 99.8 | 1100 |
| B | 99.5 | 1200 |
| C | 99.6 | 1061 |
Claims (5)
1. the catalyst of a CO gas-phase dimethyloxalate synthesis is characterized in that, the main active component of described catalyst is a Metal Palladium, and helping active component is lanthanoid metal and rhenium metal, and the carrier of described catalyst is a α type alundum (Al; Described Metal Palladium content is 0.5～2% of carrier quality, and described lanthanoid metal content is 0.05～0.5% of carrier quality, and described rhenium metal content is 0.01～0.15% of carrier quality.
2. the catalyst of a kind of CO gas-phase dimethyloxalate synthesis as claimed in claim 1, it is characterized in that, described Metal Palladium content is 1.05% of carrier quality, and described lanthanoid metal content is 0.32% of carrier quality, and described rhenium metal content is 0.10% of carrier quality.
3. the catalyst of a kind of CO gas-phase dimethyloxalate synthesis as claimed in claim 1 is characterized in that, the specific area of described α type alundum (Al is 8～16m
2/ g is 0.01～0.06cm than pore volume
3/ g, pore radius are 30～90nm, and density is 0.68～0.85g/cm
3
4. the catalyst of a kind of CO gas-phase dimethyloxalate synthesis as claimed in claim 3 is characterized in that, the specific area of described α type alundum (Al is 9m
2/ g is 0.04cm than pore volume
3/ g, pore radius are 60nm, and density is 0.78g/cm
3
5. the Preparation of catalysts method of a kind of CO gas-phase dimethyloxalate synthesis as claimed in claim 1 is characterized in that preparation process is as follows:
(1) γ type alundum (Al is made it to be converted into α type alundum (Al at 1200～1250 ℃ of roasting 5～7h;
(2) palladium bichloride, perrhenic acid, lanthanum chloride, hydrochloric acid and deionized water are mixed and made into maceration extract;
(3) α type alundum (Al is dissolved in the above-mentioned maceration extract, and is heated to 70～80 ℃, under this temperature, stir 2～3h, at room temperature flood 14～30h then;
(4) solution with step (3) gained filters, the catalyst that obtains is washed 10 times with deionized water, and each deionized water consumption is 500ml, then respectively at 60～80 ℃ of drying 6～10h, 100～150 ℃ of drying 15～20h, and at 450～500 ℃ of roasting 10～15h;
(5) catalyzer with water after the roasting is closed hydrazine solution and at room temperature soak 6～10h and reduce, use methanol wash again, promptly get the final catalyst product, dry standby.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649058B (en) * | 2011-02-25 | 2015-04-08 | 中国石油化工股份有限公司 | Fluid catalyst for preparation of oxalate through CO coupling |
| CN102649059B (en) * | 2011-02-25 | 2015-01-07 | 中国石油化工股份有限公司 | Fluid catalyst for preparation of oxalate through CO coupling |
| CN102649080B (en) * | 2011-02-25 | 2015-04-08 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing oxalic ester from CO by coupling |
| CN102649735B (en) * | 2011-02-25 | 2014-04-23 | 中国石油化工股份有限公司 | Method for producing oxalate through carbon monoxide gas phase-coupled catalytic reaction |
| CN102649751A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing dimethyl carbonate through CO coupling |
| CN107262091A (en) * | 2011-03-11 | 2017-10-20 | 宇部兴产株式会社 | Oxalate diester catalyst for producing and used the catalyst oxalate diester manufacture method |
| CN106423151A (en) * | 2016-09-14 | 2017-02-22 | 中国科学院福建物质结构研究所 | Method for preparing catalyst for synthesizing oxalate from CO through multiphase in-situ reduction |
| CN106423152A (en) * | 2016-09-26 | 2017-02-22 | 中国科学院福建物质结构研究所 | High-dispersion load type catalyst and preparation method and application thereof |
| CN106378128B (en) * | 2016-09-30 | 2018-12-21 | 中国科学院福建物质结构研究所 | A kind of CO synthesis of oxalate Pd/Al2O3The preparation method of catalyst |
| CN110846091B (en) * | 2017-06-06 | 2021-05-18 | 厦门大学 | Oxalate novel oxygen-containing fuel oil or fuel oil additive and application thereof |
Citations (3)
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|---|---|---|---|---|
| CN1381310A (en) * | 2002-05-09 | 2002-11-27 | 华东理工大学 | Catalyst for gas-phase synthesis of oxalate and its preparing process |
| CN101138722A (en) * | 2007-10-10 | 2008-03-12 | 天津大学 | Catalyzer for CO low-voltage gas-phase synthesizing of oxalic ester and method of preparing the same |
| CN101596455A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of Catalysts and its preparation method of synthesis of oxalate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381310A (en) * | 2002-05-09 | 2002-11-27 | 华东理工大学 | Catalyst for gas-phase synthesis of oxalate and its preparing process |
| CN101138722A (en) * | 2007-10-10 | 2008-03-12 | 天津大学 | Catalyzer for CO low-voltage gas-phase synthesizing of oxalic ester and method of preparing the same |
| CN101596455A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of Catalysts and its preparation method of synthesis of oxalate |
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