CN101844079B - Catalyst for preparing glycol through oxalate hydrogenation and preparation and application thereof - Google Patents
Catalyst for preparing glycol through oxalate hydrogenation and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing glycol through oxalate hydrogenation and the preparation and the application thereof. The catalyst is a silica carrier which is prepared with copper oxide as the active component and silicon ester as the carrier. The catalyst is prepared through a sol-gel method and a coprecipitation method, and can be used for preparing polylol with polybasic ester as the reaction raw material. Experiments show that the catalyst has very high reactivity and glycol selectivity in glycol synthesis through oxalic ester and hydrogen, long service and stable reaction.
Description
Technical field
The present invention relates to a kind of catalyst and preparation and application thereof of oxalate gas phase hydrogenation synthesizing glycol.
Background technology
Ethylene glycol is a kind of important Organic Chemicals, mainly for the manufacture of polyester fiber, antifreezing agent, non-ionic surface active agent, monoethanolamine and explosive etc., also is used for preparation low-freezing cooling fluid (engine is used), also can directly be used as solvent.In addition, in tobacco industry, textile industry and cosmetic industry extensive use is arranged also.
The most of petroleum path that adopts of the existing production technology of ethylene glycol, namely first direct oxidation method is produced oxirane, makes ethylene glycol through liquid-phase catalysis or on-catalytic hydration again.All this route is disclosed such as Chinese patent 02112038.2, United States Patent (USP) 5874653, Japan Patent 82106631.The method is discharged a large amount of waste water in process of production, the product separation difficulty, and energy consumption is high, pollution is high, cost is high.
At the end of the seventies in last century, L R Jehner etc. at first proposes the technology path of oxalate gas phase hydrogenation preparing ethylene glycol in Japan Patent 5323011,5542971; Haruhiko Miyazaki in 1985 etc. disclose CuMo in United States Patent (USP) 4551565
kBa
pO
xCatalyst, this catalyst at 0.1MPa, 177 ℃, hydrogen ester than being diethy-aceto oxalate all can be transformed under 200 the condition, glycol selectivity is 97.7%, the shortcoming of this catalyst is that the reaction hydrogen ester is higher, liquid hourly space velocity (LHSV) lower (about 0.036g/g cath), catalyst life has no report; United States Patent (USP) 4585890,4440873 discloses in 1984 and has used the standby copper base hydrogenation catalyst of cuprammonium silica gel legal system, it is in diethy-aceto oxalate reduction preparation glycol reaction, at hydrogen ester than 300,0.05MPa, 188 ℃, during liquid hourly space velocity (LHSV) 0.024g/g cath, diethy-aceto oxalate 100% transforms, and glycol selectivity is 99.5%; Under the conditions of similarity, in the change condition: 215 ℃, hydrogen ester transform than 50 o'clock diethy-aceto oxalates 98%, and glycol selectivity reduces to 87%, and this catalyst shortcoming is that the liquid hourly space velocity (LHSV) that is suitable for is too low, in order to keep high conversion ratio and high hydrogen ester ratio selectively must to be arranged.
To produce the higher alcohols accessory substance in the preparing glycol by hydrogenating oxalate process, even such accessory substance content very low (0.1%wt) also can have a strong impact on product quality, and separation difficulty, energy consumption is large, reported a kind of catalyst in the European patent 0060787, it can control the mass fraction of this accessory substance in product in the situation of accurately controlling reaction condition be about 1%, but its shortcoming is Cr element and the controlled condition harshness that needs to add severe toxicity in its catalyst, is difficult to industrialization.Koichi Hirai1985 has reported a kind of Cu/NH that does not add the Cr element in United States Patent (USP) 4614728
3-Si catalyst, they are under 220 ℃, the experiment condition of 2MPa, liquid hourly space velocity (LHSV) 0.92g/mlh, the conversion ratio of dimethyl oxalate is 99.9%, glycol selectivity is 90.4%, such accessory substance selectively be 0.1%, its shortcoming is that reaction temperature is high, and copper crystal grain is easier grows up, and the side reactions such as hydrogenation easily occured.
U.S. ARCO company in 1986 adopts the Cu-Cr catalyst, and under loaded catalyst 100ml, 3.0MPa pressure, the ethylene glycol yield is 95%, the long running 466h of catalyst.Chinese Academy of Sciences's Fujian thing structure finish the 200ml mould examination research work of diethy-aceto oxalate Hydrogenation ethylene glycol in the early 1990s.They use the Ec-13 Cu-Cr catalyst, under 0.6MPa～3.0MPa, 205 ℃～240 ℃, liquid hourly space velocity (LHSV) 0.327g/g cath condition, and running 1134h, space-time yield 142g/lh.Above catalyst is short service life, and the oxalate gas phase hydrogenation prepares ethylene glycol technique does not have the industrial applications precedent at present.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the previous literature, hydrogen ester than too high, liquid hourly space velocity (LHSV) is little, impurity defective such as content height in product, the gas-solid phase reaction catalyst of a kind of high activity, high selectivity is provided, this catalyst is applicable to hydrogenation of oxalate for preparing ethylene glycol, have that reaction temperature is low, active high, the active temperature scope is wide, hydrogen ester is than the characteristics such as low, that liquid hourly space velocity (LHSV) large, impurity content in product is low, reduce energy consumption, improve space-time yield, reduce production costs.
The catalyst of preparing glycol through oxalate hydrogenation of the present invention, take cupric oxide as active component, carrier is the silica support of esters of silicon acis preparation.
In the described catalyst, copper content is 10%～60% of total catalyst weight, and preferred value is 20%-40%.Total catalyst weight refers to the gross weight of active component and carrier.
The specific area of described catalyst is 100～600m
2/ g, preferred value is 250-450m
2/ g.
The pore volume of described catalyst is 0.1～2.0cm
3/ g, preferred value is 0.3～1.0cm
3/ g.
Described catalyst needs to reduce 4～12 hours in 200～350 ℃ hydrogen stream or hydrogen and nitrogen mixture stream before use.
Described esters of silicon acis includes but not limited to tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane.
Catalyst of the present invention adopts sol-gal process and coprecipitation preparation, comprises the steps:
(1) esters of silicon acis is dissolved in methyl alcohol or the ethanol, adds deionized water, regulate the pH value between 0.1～5.0 with acidic materials, then 40～120 ℃ of temperature, preferred 70-110 ℃, stir 30～120min under mixing speed 50～500rpm;
(2) mantoquita is mixed with the aqueous solution, the concentration of mantoquita is 0.001～2.0M in the solution;
(3) precipitating reagent is made into the aqueous solution, concentration is 0.001～8.0M, and step (1) is mixed with the solution of (2) preparation, and the aqueous solution of precipitating reagent is added;
(4) 40～120 ℃ of temperature, stirred under mixing speed 50～500rpm 10～48 hours.The generation precipitation is through making catalyst of the present invention after filtration, deionized water washing, drying, roasting and the moulding.
Above-mentioned precipitating reagent includes but not limited to NaOH, Na
2CO
3, (NH
4)
2CO
3, NaHCO
3, NH
4HCO
3, NH
3H
2O and urea etc.The addition manner of precipitating reagent comprises and once all feeds intake and drip, and the dropping mode just comprises and adding, counter add and and stream add.
Above-mentioned mantoquita comprises nitrate, sulfate, oxalates, acetate or the halides of metallic copper, such as copper nitrate, and copper sulphate, Schweinfurt green, cupric oxalate or copper halide, wherein copper halide can be selected from copper chloride, copper bromide.
Acidic materials in the above-mentioned steps 1 are selected from but are not limited to inorganic acid or organic acid, such as nitric acid, sulfuric acid, hydrochloric acid, acetic acid etc.
Drying condition is to descend dry 4～12 hours at 90～120 ℃ in the above-mentioned steps 4, and roasting condition is 300～600 ℃ of lower roastings 2～10 hours.
Catalyst of the present invention can be used for preparing polyalcohol take polybasic ester as reaction raw materials.After application process comprises the steps: to adopt aforementioned catalyst reduction, take polybasic ester as reaction raw materials, range of reaction temperature is 160～260 ℃, and the reaction pressure scope is 1～10MPa, the liquid hourly space velocity (LHSV) of described polybasic ester is 0.01～3g/g cat.h, and hydrogen ester is than 30～400: 1.
Catalyst of the present invention is used for oxalate hydrogenation prepares ethylene glycol, application process comprises the steps:
(1) catalyst was reduced 4～12 hours in 200～350 ℃ hydrogen stream or hydrogen and nitrogen mixture stream;
(2) oxalate is contacted with hydrogen in the presence of described catalyst, 160～260 ℃ of reaction temperatures, reaction pressure 1～10MPa, catalyst loading (charging rate of reaction raw materials oxalate) 0.01～3g/gcat.h, hydrogen/oxalate=30～400: 1 (molecular proportion), the conversion ratio of oxalate is more than 95%, ethylene glycol selective more than 95%.
Experiment shows that catalyst of the present invention has very high reactivity and glycol selectivity in the reaction of preparing glycol through oxalate hydrogenation, and the life-span is long, reacting balance, and reaction temperature is low, and temperature range is wide.Catalyst of the present invention has splendid operating flexibility, at 160-260 ℃, all has higher activity and selectivity in 1～10MPa scope, space-time yield is high, and feed stock conversion is that target product selectivity is more than 95% more than 95%, the impurity content that accessory substance especially has a strong impact on the target product performance is lower than 0.1%, catalyst stability is good, and the life-span is long, and single pass life reaches 4000 hours.Adopt catalyst of the present invention can significantly reduce heat and power consumption, reduce subsequent product separation equipment and operation, reduce production costs.Relatively document is lower for technique hydrogen ester of the present invention, greatly reduces the costs such as energy consumption and separation.
The specific embodiment
The preparation method of catalyst:
Esters of silicon acis is dissolved in the ethanol, adds deionized water, regulate the pH value between 0.1～5.0 with acidic materials, then 40～120 ℃ of temperature, stir 30～120min under mixing speed 50～500rpm; Nitrate, sulfate, oxalates, acetate or the halides of metallic copper are mixed with the aqueous solution, and the concentration of solution is 0.001～2.0M; Precipitating reagent is mixed with the aqueous solution, and the concentration of solution is 0.001～8.0M, and solution and this aqueous solution of above-mentioned preparation evenly made mixed solution; The several solns of above-mentioned preparation is mixed, then 40～120 ℃ of temperature, stirred under mixing speed 50～500rpm 10～48 hours; Generate precipitation, through filtration, the deionized water washing, 90～120 ℃ lower dry 4～12 hours, namely make catalyst of the present invention in 300～600 ℃ of lower roastings 2～10 hours and moulding.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, such as the catalyst chemical operation manual, or the condition of advising according to manufacturer.
Embodiment 1:
Take by weighing tetraethoxysilane 100g, be dissolved in the 100mL absolute ethyl alcohol, add the 200mL deionized water, with nitre acid for adjusting pH value to 3.0, at temperature 70 C, stir 60min under the mixing speed 350rpm; Take by weighing urea 70g, be dissolved in the 150mL deionized water; Choose copper nitrate and be mixed with 1.0M aqueous solution 500mL; Above-mentioned several solns is mixed, 95 ℃ of reaction temperatures, stirred 24 hours under the mixing speed 400rpm, generate precipitation, filtration and deionized water are repeatedly cleaned filter cake and are obtained the catalyst filter cake while hot, drying is 4 hours under 95 ℃, namely obtains Catalysts Cu/SiO2 (A) in 4 hours 400 ℃ of lower roastings after the moulding, and the weight content of copper in catalyst is 40w%.With the broken screening of Catalysts Cu/SiO2 (A) 40-60 order, after 330 ℃ of pure hydrogen reduction activation in 6 hours, be adjusted to reaction process condition and react.
Embodiment 2:
Take by weighing tetramethoxy-silicane 100g, add the 200mL deionized water, with nitre acid for adjusting pH value to 1.0, at temperature 70 C, stir 120min under the mixing speed 350rpm; Take by weighing (NH
4)
2CO
3144g is dissolved in the 200mL deionized water; Choose Schweinfurt green and be mixed with 0.5M aqueous solution 800mL; Above-mentioned several solns is mixed, 110 ℃ of reaction temperatures, stirred 18 hours under the mixing speed 450rpm, generate precipitation, filtration and deionized water are repeatedly cleaned filter cake and are obtained the catalyst filter cake while hot, drying is 4 hours under 120 ℃, namely obtains Catalysts Cu/SiO2 (B) in 4 hours 450 ℃ of lower roastings after the moulding, and the weight content of copper in catalyst is 30w%.With the broken screening of Catalysts Cu/SiO2 (B) 20-40 order; Being adjusted to reaction process condition after 300 ℃ of pure hydrogen reduction activation in 6 hours reacts.
Embodiment 3:
Take by weighing tetrapropoxysilane 100g, add the 200mL deionized water, with nitre acid for adjusting pH value to 2.0, take by weighing Na
2CO
390g is dissolved in the 200mL deionization, and two kinds of solution mix, and 75 ℃ of temperature, stir 60min under the mixing speed 300rpm; Choose cupric oxalate and be mixed with 2.0M aqueous solution 250mL, join in the mentioned solution, 90 ℃ of reaction temperatures, stirred 24 hours under the mixing speed 450rpm, generate precipitation, filtration and deionized water are repeatedly cleaned filter cake and obtained the catalyst filter cake while hot, and be lower dry 4 hours at 95 ℃, namely obtained Catalysts Cu/SiO2 (C) in 4 hours 450 ℃ of lower roastings after the moulding, the specific area of catalyst is 360m
2/ g, pore volume are 0.8cm
3/ g, the copper weight content in catalyst is 50w%.With the broken screening of Catalysts Cu/SiO2 (C) 20-40 order; Being adjusted to reaction process condition after 300 ℃ of hydrogen and nitrogen mixture reduction activation in 12 hours reacts.
Embodiment 4:
Take by weighing tetraethoxysilane 100g, add the 150mL deionized water, with nitre acid for adjusting pH value to 2.5; Measure dense NH
3H
2O100mL is dissolved in the 250mL deionized water; Choose copper chloride and be mixed with 2.0M aqueous solution 200mL; Above-mentioned several solns is mixed, 95 ℃ of reaction temperatures, stirred 22 hours under the mixing speed 350rpm, generate precipitation, filtration and deionized water are repeatedly cleaned filter cake and are obtained the catalyst filter cake while hot, drying is 6 hours under 120 ℃, namely obtains Catalysts Cu/SiO2 (D) in 6 hours 400 ℃ of lower roastings after the moulding, and the weight content of copper in catalyst is 37w%.With the broken screening of Catalysts Cu/SiO2 (D) 40-60 order; Being adjusted to reaction process condition after 300 ℃ of pure hydrogen reduction activation in 8 hours reacts.
Embodiment 5:
Take by weighing tetraethoxysilane 100g, add the 150mL deionized water, with nitre acid for adjusting pH value to 5.0; Take by weighing NH
4HCO
3100g is dissolved in the 250mL deionized water; Choose copper nitrate and be mixed with 0.05M aqueous solution 1600mL; Above-mentioned several solns is mixed, 90 ℃ of reaction temperatures, stirred 24 hours under the mixing speed 500rpm, generate precipitation, filtration and deionized water are repeatedly cleaned filter cake and are obtained the catalyst filter cake while hot, drying is 12 hours under 200 ℃, and moulding namely obtains Catalysts Cu/SiO2 (E), and the specific area of catalyst is 370m
2/ g, pore volume are 120cm
3/ g, the copper weight content in catalyst is 15w%.With the broken screening of Catalysts Cu/SiO2 (E) 40-60 order; Being adjusted to reaction process condition after 250 ℃ of pure hydrogen reduction activation in 12 hours reacts.
Embodiment 6:
Take by weighing tetraethoxysilane 100g, be dissolved in the 100mL absolute ethyl alcohol, add the 200mL deionized water, with nitre acid for adjusting pH value to 0.5, at temperature 70 C, stir 60min under the mixing speed 350rpm; Take by weighing NaHCO
390g is dissolved in the 150mL deionized water; Choose copper bromide and be mixed with 0.5M aqueous solution 800mL; Above-mentioned several solns is mixed, 90 ℃ of reaction temperatures, stirred 24 hours under the mixing speed 400rpm, generate precipitation, filtration and deionized water are repeatedly cleaned filter cake and are obtained the catalyst filter cake while hot, drying is 4 hours under 110 ℃, namely obtains Catalysts Cu/SiO2 (F) in 4 hours 400 ℃ of lower roastings after the moulding, and the weight content of copper in catalyst is 28w%.With the broken screening of Catalysts Cu/SiO2 (F) 40-60 order; Being adjusted to reaction process condition after 300 ℃ of pure hydrogen reduction activation in 8 hours reacts.
The catalyst performance test
Catalyst is placed stainless steel reactor, reactor inside diameter 10mm, inside reactor dress thermocouple sheath, loaded catalyst is 10mL, and unstripped gas passes through beds from top to bottom, and glycol product is drawn by reactor bottom.The reaction Operating condition of hydrogenation of oxalate for preparing ethylene glycol is as follows, 190 ℃ of reaction temperatures, reaction pressure 3.0MPa, 1.4 kg/hours of liter catalyst of catalyst loading (charging rate of reaction raw materials oxalate), hydrogen/oxalate=100 (molecular proportion).Reaction result is as shown in table 1.
Table 1 catalyst performance test result
| Catalyst | Dimethyl oxalate conversion ratio/% | Glycol selectivity/% | Diethy-aceto oxalate conversion ratio/% | Glycol selectivity/% |
| Cu/SiO2 | ＞98 | 95 | ＞99 | 96 |
| (A) | ||||
| Cu/SiO2 (B) | ＞98 | 94 | ＞99 | 95 |
| Cu/SiO2 (C) | ＞98 | 95 | ＞99 | 95 |
| Cu/SiO2 (D) | ＞98 | 93 | ＞99 | 92 |
| Cu/SiO2 (E) | ＞98 | 87 | ＞99 | 88 |
| Cu/SiO2 (F) | ＞98 | 90 | ＞99 | 91 |
The catalyst characterization parameter
Adopt specific area and the pore volume of the ASAP2020M+C physical and chemical adsorption instrument mensuration catalyst of U.S. Merck ﹠ Co., Inc.Measurement result is as shown in table 2.
Table 2 catalyst characterization test result
| Catalyst | Specific area/(m 2/g) | Pore volume/(cm 3/g) |
| Cu/SiO2(A) | 450 | 0.6 |
| Cu/SiO2(B) | 400 | 0.7 |
| Cu/SiO2(C) | 360 | 0.8 |
| Cu/SiO2(D) | 390 | 0.3 |
| Cu/SiO2(E) | 370 | 1.2 |
| Cu/SiO2(F) | 250 | 0.8 |
Claims (10)
1. the catalyst of a preparing glycol through oxalate hydrogenation, take cupric oxide as active component, carrier is the silica support of esters of silicon acis preparation, described esters of silicon acis is selected from one or more in tetramethoxy-silicane, tetraethoxysilane or the tetrapropoxysilane, and described catalyst is to adopt the sol-gal process and the coprecipitation that comprise the following steps to make:
(a) esters of silicon acis is dissolved in methyl alcohol or the ethanol, adds deionized water, regulate the pH value between 0.1～5.0 with acidic materials, then 40～120 ℃ of temperature, stir 30～120min under mixing speed 50～500rpm;
(b) mantoquita is mixed with the aqueous solution, the concentration of mantoquita is 0.001～2.0M in the solution;
(c) precipitating reagent is made into the aqueous solution, concentration is 0.001～8.0M, and step (a) is mixed with the solution of (b) preparation, and this aqueous solution is added;
(d) 40～120 ℃ of temperature, stirred under mixing speed 50～500rpm 10～48 hours, the generation precipitation is through making described catalyst after filtration, deionized water washing, drying, roasting and the moulding.
2. catalyst as claimed in claim 1 is characterized in that copper content is 10%～60% of total catalyst weight.
3. catalyst as claimed in claim 1 is characterized in that the specific area of described catalyst is 100～600m
2/ g, pore volume are 0.1～2.0cm
3/ g.
4. catalyst as claimed in claim 1 is characterized in that the copper source of described active component is selected from copper nitrate, copper sulphate, Schweinfurt green, cupric oxalate or copper halide.
5. such as the preparation method of catalyst as described in arbitrary claim among the claim 1-4, adopt sol-gal process and coprecipitation to prepare, comprise the steps:
(a) esters of silicon acis is dissolved in methyl alcohol or the ethanol, adds deionized water, regulate the pH value between 0.1～5.0 with acidic materials, then 40～120 ℃ of temperature, stir 30～120min under mixing speed 50～500rpm;
(b) mantoquita is mixed with the aqueous solution, the concentration of mantoquita is 0.001～2.0M in the solution;
(c) precipitating reagent is made into the aqueous solution, concentration is 0.001～8.0M, and step (a) is mixed with the solution of (b) preparation, and this aqueous solution is added;
(d) 40～120 ℃ of temperature, stirred under mixing speed 50～500rpm 10～48 hours, the generation precipitation is through making described catalyst after filtration, deionized water washing, drying, roasting and the moulding.
6. preparation method as claimed in claim 5 is characterized in that, the acidic materials in the step (a) are selected from nitric acid, sulfuric acid, hydrochloric acid or acetic acid.
7. preparation method as claimed in claim 5 is characterized in that, the mantoquita in the step (b) is selected from nitrate, sulfate, oxalates, acetate or the halides of metallic copper.
8. preparation method as claimed in claim 5 is characterized in that, the precipitating reagent in the step (c) is selected from NaOH, Na
2CO
3, (NH
4)
2CO
3, NaHCO
3, NH
4HCO
3, NH
3H
2In O or the urea one or more.
9. be used for preparing polyalcohol take polybasic ester as reaction raw materials such as catalyst as described in arbitrary claim among the claim 1-4.
10. a hydrogenation reaction prepares the technique of polyalcohol, adopt among the claim 1-4 after the described catalyst reduction of arbitrary claim, take polybasic ester as reaction raw materials, range of reaction temperature is 160～260 ℃, the reaction pressure scope is 1～10MPa, the liquid hourly space velocity (LHSV) of described polybasic ester is 0.01～3g/g cat.h, and hydrogen ester is than 30～400: 1.
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| CN102380382A (en) * | 2011-11-01 | 2012-03-21 | 沈阳化工大学 | Catalyst used in synthesis of ethylene glycol by hydrogenating dimethyl oxalate under normal pressure and preparation method for catalyst |
| CN105727956A (en) * | 2014-12-09 | 2016-07-06 | 上海华谊能源化工有限公司 | Catalyst for preparing ethylene glycol through dimethyl oxalate gas phase hydrogenation, and preparation method and application thereof |
| CN109289865A (en) * | 2018-09-30 | 2019-02-01 | 中国科学院山西煤炭化学研究所 | The silicon-containing catalyst and preparation method of a kind of preparing low-carbon mixed alcohol by synthetic gas and application |
| CN109433206B (en) * | 2018-11-28 | 2021-07-23 | 中触媒新材料股份有限公司 | Preparation method of mesoporous silica supported copper catalyst with central radial pore passage |
| CN109482184B (en) * | 2018-11-28 | 2021-09-17 | 中触媒新材料股份有限公司 | Preparation method of catalyst for synthesizing ethylene glycol by dimethyl oxalate hydrogenation |
| CN111686742A (en) * | 2019-03-14 | 2020-09-22 | 上海诺哈尔化工技术有限公司 | Copper-based catalyst and preparation method thereof |
| CN111085203A (en) * | 2019-08-20 | 2020-05-01 | 中国科学院广州能源研究所 | Method for preparing 2-methylfuran by catalyzing hydrogenation of furfural |
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| CN101342489A (en) * | 2007-07-12 | 2009-01-14 | 上海焦化有限公司 | Hydrogenation reaction catalyst, preparation and application thereof |
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