CN101844079A - 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 of oxalate gas phase hydrogenation synthesizing glycol.
Background technology
Ethylene glycol is a kind of important Organic Chemicals, is mainly used in to make polyester fiber, antifreezing agent, non-ionic surface active agent, monoethanolamine and explosive etc., also is used to prepare 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, promptly first direct oxidation method is produced oxirane, makes ethylene glycol through liquid-phase catalysis or on-catalytic hydration again.All this route is disclosed as Chinese patent 02112038.2, United States Patent (USP) 5874653, Japan Patent 82106631.This method is discharged a large amount of waste water in process of production, the product separation difficulty, the energy consumption height, pollute 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, than being diethy-aceto oxalate all can be transformed under 200 the condition, glycol selectivity is 97.7% to this catalyst at 0.1MPa, 177 ℃, hydrogen ester, and 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 does not appear in the newspapers; United States Patent (USP) 4585890,4440873 discloses the copper base hydrogenation catalyst that uses the preparation of cuprammonium silica gel method in 1984, 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 selectivity high hydrogen ester ratio must 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 big, reported a kind of catalyst in the European patent 0060787, it can control the mass fraction of this accessory substance in product under 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%, the selectivity of such accessory substance is 0.1%, its shortcoming is the reaction temperature height, and copper crystal grain is easier grows up, and side reactions such as hydrogenation easily took place.
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 preparing 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 technology 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 past in the document, 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 characteristics such as low, that liquid hourly space velocity (LHSV) big, impurity content in product is low, cut down the consumption of energy, improve space-time yield, reduce production costs.
Hydrogenation of oxalate for preparing of the present invention is got the catalyst of ethylene glycol, is active component with the cupric oxide, and 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 is meant 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 ℃, mixing speed 50～500rpm stirs 30～120min down;
(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, mixing speed 50～500rpm stirred 10～48 hours down.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, 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, 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 following roastings 2～10 hours.
It is that reaction raw materials prepares polyalcohol that catalyst of the present invention can be used for the polybasic ester.After application process comprises the steps: to adopt aforementioned catalyst reduction, with the polybasic ester is reaction raw materials, and 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%, and the selectivity of ethylene glycol is more than 95%.
Experiment shows, catalyst of the present invention has very high reactivity and glycol selectivity in hydrogenation of oxalate for preparing is got the reaction of ethylene glycol, 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 have higher activity and selectivity in 1～10MPa scope, space-time yield height, feed stock conversion are 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 the one way life-span 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 technology hydrogen ester of the present invention, greatly reduces costs such as energy consumption and separation.
The specific embodiment
The Preparation of catalysts method:
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, mixing speed 50～500rpm stirs 30～120min down; 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, and then 40～120 ℃ of temperature, mixing speed 50～500rpm stirred 10～48 hours down; Generate precipitation, through filtration, the deionized water washing, 90～120 ℃ dry 4～12 hours down, promptly make catalyst of the present invention in 300～600 ℃ of following 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 to the present invention is described 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 institute restricted portion equally.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, 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 3.0,70 ℃ of temperature, mixing speed 350rpm stirs 60min down; 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, mixing speed 400rpm stirred 24 hours down, generate precipitation, filtration and deionized water clean filter cake repeatedly and obtain the catalyst filter cake while hot, drying is 4 hours under 95 ℃, promptly obtains Catalysts Cu/SiO2 (A) in 4 hours 400 ℃ of following 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 1.0,70 ℃ of temperature, mixing speed 350rpm stirs 120min down; 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, mixing speed 450rpm stirred 18 hours down, generate precipitation, filtration and deionized water clean filter cake repeatedly and obtain the catalyst filter cake while hot, drying is 4 hours under 120 ℃, promptly obtains Catalysts Cu/SiO2 (B) in 4 hours 450 ℃ of following 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,, take by weighing Na with nitre acid for adjusting pH value to 2.0
2CO
390g is dissolved in the 200mL deionization, and two kinds of solution mix, and 75 ℃ of temperature, mixing speed 300rpm stirs 60min down; Choose cupric oxalate and be mixed with 2.0M aqueous solution 250mL, join in the above-mentioned solution, 90 ℃ of reaction temperatures, mixing speed 450rpm stirred 24 hours down, generate precipitation, filtration and deionized water clean filter cake repeatedly and obtain the catalyst filter cake while hot, and drying is 4 hours under 95 ℃, promptly obtained Catalysts Cu/SiO2 (C) in 4 hours 450 ℃ of following 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, mixing speed 350rpm stirred 22 hours down, generate precipitation, filtration and deionized water clean filter cake repeatedly and obtain the catalyst filter cake while hot, drying is 6 hours under 120 ℃, promptly obtains Catalysts Cu/SiO2 (D) in 6 hours 400 ℃ of following 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, mixing speed 500rpm stirred 24 hours down, generate precipitation, filtration and deionized water clean filter cake repeatedly and obtain the catalyst filter cake while hot, drying is 12 hours under 200 ℃, and moulding promptly 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 0.5,70 ℃ of temperature, mixing speed 350rpm stirs 60min down; 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, mixing speed 400rpm stirred 24 hours down, generate precipitation, filtration and deionized water clean filter cake repeatedly and obtain the catalyst filter cake while hot, drying is 4 hours under 110 ℃, promptly obtains Catalysts Cu/SiO2 (F) in 4 hours 400 ℃ of following 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 operating condition that the reaction of hydrogenation of oxalate for preparing ethylene glycol suits is as follows, 190 ℃ of reaction temperatures, reaction pressure 3.0MPa, 1.4 kilograms of/hour 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
The catalyst characterization parameter
Adopt the 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 |
| Catalyst | Specific area/(m 2/g) | Pore volume/(cm 3/g) |
| ??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 (12)
1. a hydrogenation of oxalate for preparing is got the catalyst of ethylene glycol, is active component with the cupric oxide, and carrier is the silica support of esters of silicon acis preparation.
2. catalyst according to claim 1 is characterized in that copper content is 10%～60% of total catalyst weight.
3. catalyst according to 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 according to claim 1 is characterized in that described esters of silicon acis is selected from one or more in tetramethoxy-silicane, tetraethoxysilane or the tetrapropoxysilane.
5. catalyst according to 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.
6. catalyst according to claim 1 is characterized in that, described catalyst is to adopt sol-gal process and coprecipitation to make.
7. as Preparation of catalysts method as described in arbitrary claim among the claim 1-6, 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, mixing speed 50～500rpm stirs 30～120min down;
(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 10～48 hours under mixing speed 50～500rpm, the generation precipitation is through making catalyst of the present invention after filtration, deionized water washing, drying, roasting and the moulding.
8. as Preparation of catalysts method as described in the claim 7, it is characterized in that the acidic materials among the step a are selected from nitric acid, sulfuric acid, hydrochloric acid or acetic acid.
9. as Preparation of catalysts method as described in the claim 7, it is characterized in that the mantoquita among the step b is selected from nitrate, sulfate, oxalates, acetate or the halides of metallic copper.
10. as Preparation of catalysts method as described in the claim 7, it is characterized in that the precipitating reagent among 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.
11. being used for the polybasic ester as catalyst as described in arbitrary claim among the claim 1-6 is that reaction raw materials prepares polyalcohol.
12. a hydrogenation reaction prepares the technology of polyalcohol, adopt among the claim 1-6 after the described catalyst reduction of arbitrary claim, with the polybasic ester is 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 |
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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 |
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| CN109289865A (en) * | 2018-09-30 | 2019-02-01 | 中国科学院山西煤炭化学研究所 | A silicon-containing catalyst for producing low-carbon mixed alcohol from synthesis gas and its production method and application |
| CN109433206A (en) * | 2018-11-28 | 2019-03-08 | 中触媒新材料股份有限公司 | With the radial hole channel mesoporous silicon oxide copper-loading catalyst preparation method in center |
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| 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 | A kind of method for catalyzing furfural hydrogenation to prepare 2-methylfuran |
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