CN104174407A - Catalyst for preparation of glycol by oxalate hydrogenation and use thereof - Google Patents
Catalyst for preparation of glycol by oxalate hydrogenation and use thereof Download PDFInfo
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- CN104174407A CN104174407A CN201310195951.4A CN201310195951A CN104174407A CN 104174407 A CN104174407 A CN 104174407A CN 201310195951 A CN201310195951 A CN 201310195951A CN 104174407 A CN104174407 A CN 104174407A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a catalyst for preparation of glycol by oxalate hydrogenation, and mainly aims to solve the problem of low selectivity of hydrogenation product glycol and short service life of catalyst in the prior art. The catalyst uses copper metal as an active component and silicon dioxide as a carrier, and is also added with appropriate metal additives. The metal additives mainly play the role to modulate the active valence of the metal copper during reaction so as to improve the reaction conversion rate and the glycol selectivity. The selected additives play the role to improve the glycol selectivity and catalyst stability. The catalyst has the advantages of high selectivity and stability.
Description
[technical field] the present invention relates to a kind of catalyst of hydrogenation of oxalate for preparing ethylene glycol, particularly about the catalyst of dimethyl oxalate and diethy-aceto oxalate Hydrogenation ethylene glycol.
[background technology]
Ethylene glycol (EG) is a kind of important Organic Chemicals.It is not only the monomer of producing mylar, alkyd resins and polyester fiber, or the raw material of all multi-products such as lubricant, plasticizer, paint, adhesive and surfactant.Ethylene glycol demand sustainable growth in recent years.
The traditional processing technology of ethylene glycol is that epoxyethane water is legal, and the method technological process is long, and energy consumption is high, and glycol selectivity is low, simultaneously because this production technology is depended on petroleum resources unduly, so China's ethylene glycol demand relies on import mostly.And in numerous methods of Non oil-based route synthesizing glycol, synthesis gas is more through the research of oxalate preparing ethylene glycol, relatively ripe.First the method prepares synthesis gas (CO+H by non-oil resource
2), then by CO oxidative coupling oxalic ester, the further catalytic hydrogenation generating glycol of oxalate.The method is because technological process is simple, and energy consumption is low and glycol selectivity is high and have much application prospect, also thereby become a large study hotspot of China recent years coal chemical technology.
This technique mesoxalic acid ester through hydrogenation preparing ethylene glycol process is considered to committed step, is also the bottleneck place of limiting its heavy industrialization.Mainly there is following reaction in this process: (1) oxalate hydrogenation generates intermediate product methyl glycollate; (2) the further hydrogenation of methyl glycollate generates order glycol product; (3) ethylene glycol continues hydrogenation generation ethanol or other dihydroxylic alcohols accessory substance; (4) ethylene glycol reacts with other single methanols and generates ether.Therefore in hydrogenation of oxalate for preparing ethylene glycol process, it is crucial how improving product selectivity.And the glycol selectivity of this process catalyst and catalytic stability still can not meet the requirement of heavy industrialization application at present, so the exploitation of catalyst is the main study hotspot of this problem at present.
With respect to homogeneous hydrogenation catalyst, heterogeneous hydrogenation catalyst has that preparation method is simple, reaction condition is gentle and the advantage such as catalyst is easily separated, is the research emphasis of preparing ethylene glycol by using dimethyl oxalate plus hydrogen catalysts in recent years.Wherein copper-based catalysts because activity is high, cheap and easy to get, preparation simply is subject to increasing attention, but copper-based catalysts there is anti-poisoning performance a little less than, easy-sintering and easily form the shortcomings such as high polymer.For the problems referred to above, people select the preparation method of copper-based catalysts, carrier and additive modification etc. has carried out large quantity research, to reach, improve catalyst stability and object optionally.As: Ube patent (US4,229,591) adopt the standby copper-based catalysts of ammonia still process legal system at 180 ℃, hydrogen ester than being that under 300 reaction condition, oxalate conversion ratio can reach 100%, glycol selectivity is up to 99.5%.Fujian thing structure is studied Cu-Cr catalyst the earliest, at 200～230 ℃, 2.5～3MPa, gas liquid ratio is under 46～60 conditions, can obtain 99.8% oxalate conversion ratio, glycol selectivity can reach 95.3%. in addition, and the units such as Fujian thing structure institute, University Of Tianjin, East China University of Science, Zhejiang University have also carried out the research work of hydrogenation of oxalate for preparing ethylene glycol copper-based catalysts, has improved the performance of hydrogenation of oxalate for preparing ethylene glycol copper-based catalysts.
Although these researchs have obtained good effect in laboratory, the domestic industrial amplification test device of many covers synthesis gas through preparing ethylene glycol from oxalic ester of also having built of while, but its product ethylene glycol still cannot meet the standard of downstream polyester spent glycol, the impact that impurity in product is larger the ultraviolet permeability of ethylene glycol product, and this catalyst problem such as also existence and stability is poor.SiO in the catalyst based preparation process of Cu of simultaneously reporting in document
2what carrier was all used is Ludox, take Ludox as carrier source, although can improve the decentralization of catalyst, if catalyst amplifies on a large scale, can increase production cost and environmental pressure undoubtedly.White carbon is a kind of large industrial materials, is widely used in the aspects such as rubber, coating, weaving, papermaking, agricultural chemicals and food additives.It is the first that the white carbon volume of production and marketing of China occupies the whole world.Wherein the synthetic white carbon of vapor phase method, referred to as gas-phase silica, is a kind of nanometer SiO
2powder, its specific area is very large, and adsorption power is strong, and dispersive property is good and chemical purity is high, the very suitable carrier as catalyst of these special natures.Catalyst carrier using it as this process of preparing glycol through oxalate hydrogenation, not only can utilize its above-mentioned advantage, can simplify catalyst preparation process simultaneously, reduces catalyst preparation cost.And white carbon is also seldom had to report so far for the carrier of hydrogenation of oxalate for preparing ethylene glycol catalyst.
Have bibliographical information, n-type semiconductor oxide is in hydrogen atmosphere, and its electrical conductivity increases along with the increase of hydrogen dividing potential drop, has the special nature that significantly can transmit electronics, utilizes this character can promote significantly the Hydrogenation of catalyst.P-type semiconductor oxide has character in contrast.So n-type semiconductor oxide is often used as the auxiliary agent of hydrogenation catalyst, p-type semiconductor oxide is often used in oxidation reaction.The object of the invention using n-type semiconductor oxide as auxiliary agent, add to Cu catalyst based in, be applied in the reaction of preparing glycol through oxalate hydrogenation, be intended to utilize its unique electronics auxiliary agent effect, improve selectively its stability particularly of catalyst.
[summary of the invention]
Technical problem to be solved by this invention is for the deficiencies in the prior art, and a kind of catalyst of hydrogenation of oxalate for preparing ethylene glycol is provided.
This catalyst be take Cu as active component, SiO
2for carrier, preferred white carbon carrier, wherein white carbon is nanometer SiO prepared by vapor phase method
2powder, n-type semiconductor oxide is auxiliary agent, preferably CeO
2auxiliary agent.While being applied to catalytic reaction because Cu is catalyst based, the activated centre of the corresponding differential responses of the Cu particle of different valence state, also has cooperative effect between different valence state Cu particle.By adding auxiliary agent, can effectively regulate the ratio of Cu particle different valence state, and then improve corresponding reactivity.Auxiliary agent can be stablized the valence state of Cu particle simultaneously, and then improves its stability.The n-type semiconductor oxide electronics auxiliary agent that the applicant adds can make the active component Cu of catalyst
+/ Cu
0with Ce
4+/ Ce
3+under the atmosphere of reactor feed gas (ester/hydrogen), form redox cycle, improve and maintain the Cu in copper-based catalysts
+/ Cu
0cu in ratio, particularly course of reaction
+/ Cu
0stablizing of ratio, and then improve copper-based catalysts reactivity worth and the reaction stability of hydrogenation of oxalate for preparing ethylene glycol.
The technical problem existing for solving existing oxalate hydrogenation, the technical solution used in the present invention is:
A catalyst for hydrogenation of oxalate for preparing ethylene glycol, take metal Cu as active component, it is characterized in that:
Above-mentioned catalyst is with SiO
2for carrier, n-type semiconductor oxide is auxiliary agent; In described catalyst, the quality percentage composition of each component is: active metal Cu is that 10～70%, n-type semiconductor oxide auxiliary agent is 0.01%～10%, and surplus is carrier S iO
2.
The catalyst of above-mentioned hydrogenation of oxalate for preparing ethylene glycol, its carrier S iO
2for Ludox and white carbon.
The catalyst of above-mentioned hydrogenation of oxalate for preparing ethylene glycol, the preferred white carbon of its carrier.
The catalyst of above-mentioned hydrogenation of oxalate for preparing ethylene glycol, its n-type semiconductor oxide auxiliary agent refers to the oxides additive that electronics can be provided, preferably CeO
2.
The catalyst of above-mentioned hydrogenation of oxalate for preparing ethylene glycol, catalyst promoter content is 0.1～5%, is preferably 0.2～3%.
Above-mentioned oxalate, refers to oxalic acid mono-methyl, oxalic acid mono ethyl ester, dimethyl oxalate, diethy-aceto oxalate, excellent finger dimethyl oxalate and diethy-aceto oxalate.
Described catalyst is used for the reaction condition of the reaction of catalysis hydrogenation of oxalate for preparing ethylene glycol: temperature is 180-300 ℃, and pressure is 1.0-3.0Mpa, and the mol ratio of hydrogen ester (hereinafter to be referred as hydrogen ester ratio) is 50～220.
While adopting fixed bed reactors, liquid hourly space velocity (LHSV) is 0.5h
-1.
The present invention relates to a kind of catalyst of hydrogenation of oxalate for preparing ethylene glycol, mainly solve the problem that hydrogenation products glycol selectivity is low, catalyst life is short existing in conventional art.Catalyst of the present invention be take metallic copper as active component, take silica as carrier, and suitable metal auxiliary agent in addition.The metal promoter adding in the present invention mainly plays and regulates the active state of metallic copper when reaction, with this, improves the selective of the conversion ratio of reaction and ethylene glycol.Several auxiliary agents that the present invention selects have all played raising glycol selectivity and have improved catalyst stability object.Catalyst of the present invention has higher selective and stability.
Concrete catalyst performance evaluation adopts following scheme:
For the shortcoming of product analysis aspect in document, the present invention utilizes application of gas chromatorgraphy/mass technology, and hydrogenation products has been carried out to full constituent analysis simultaneously.In continuous-flow gas-solid phase reactor, carry out, catalyst filling amount is that 1.0g. adopts 350 ℃ of reducing catalysts of pure hydrogen normal pressure, and flow velocity is 100 mL/min, is warming up to 350 ℃, and keeps 4h with the speed of 1～2 ℃/min from room temperature, passes into H after being down to reaction temperature
2, with constant-flux pump, squeeze into the methanol solution of 15wt.%DMO, system pressure is that 2.0MPa. product is analyzed by gas-chromatography, chromatographic column is 30m FFAP type polarity capillary column, hydrogen flame detector (FID) detection reaction raw material and product.
GC-MS analyzes DMO hydrogenation products, detect altogether and find five kinds of product: methyl glycollate (MG), ethylene glycol (EG), glycol monoethyl ether (2-MEO), 1,2-propane diols (1,2-POD), 1,2-butanediol (1,2-BOD), wherein EG is target product, and other are accessory substance.
Catalyst Conversion and selective calculation method are as follows:
In above formula, M refers to product, as EG, MG, 2-MEO, 1,2-POD, 1,2-BOD etc.
The present invention has the following advantages compared with the prior art:
1. adopt white carbon as catalyst carrier, simplify catalyst preparation process and reduce preparation cost, and be easy to large-scale industrialization application.
2. add n-type semiconductor oxide as auxiliary agent, its special electronic action in hydrogen atmosphere, can stablize the valence state of main active metal Cu, and then improves performance, the especially stability of catalyst.
3. product analysis adopts application of gas chromatorgraphy/mass technology, and full constituent is analyzed, and calculates the selectively more true and reliable of products obtained therefrom.
The technology of the present invention details is by following embodiment detailed description in addition.It should be noted that lifted embodiment, its effect just further illustrates technical characterictic of the present invention, rather than limits the present invention.
The specific embodiment
Embodiment 1
By deionized water by Cu (NO
3)
2be mixed with the 0.3mol/L aqueous solution, measure this solution of 157ml and be placed in beaker, slowly drip while stirring mass concentration and be 25%～28% ammoniacal liquor, to pH value of solution in beaker be to stop for 9.5～10.5 o'clock.
Take 12g white carbon and add the above-mentioned Cu of filling (NO
3) in the beaker of solution, at 30 ℃ of aging 4h of stirred in water bath, be warming up to 90 ℃ of ammonia still processs, until the pH value of beaker solution is to stop at 7～8 o'clock.The sediment of gained is filtered, washed to the pH of filtrate and be about 7.
120 ℃ of dry 12h of sediment after washing, 450 ℃ of roasting 4h, compressing tablet is crushed to 20～40 orders, and reaction pre reduction obtains catalyst A: 20wt%Cu/SiO
2.
Embodiment 2
Preparation process is with embodiment 1, and difference is: take 11.925g white carbon as carrier, and the Cu (NO that is 0.3mol/L to 157ml concentration
3)
2in solution, add the Ce (NO of 0.2324g
3)
36H
2o, then adds ammoniacal liquor to regulate pH with embodiment 1.This embodiment prepares catalyst B: 20wt%Cu-0.5wt%Ce/SiO
2.
Embodiment 3
Preparation process is with embodiment 1, and difference is: take 40g Ludox (containing 30wt.%SiO
2, all the other are water) and replace white carbon as carrier.Prepare catalyst C:20wt%Cu/SiO
2.
Embodiment 4
Preparation process is with embodiment 2, and difference is: take 11.25g white carbon as carrier, take the Ce (NO of 2.3263g simultaneously
3)
36H
2o adds in beaker.This embodiment prepares catalyst D:20wt%Cu-5wt%CeO
2/ SiO
2.
Embodiment 5
Preparation process is with embodiment 1, and difference is: take 13.5g white carbon as carrier, measuring 78.7ml concentration is the Cu (NO of 0.3mol/L
3)
2solution.This embodiment prepares catalyst E:10wt%Cu/SiO
2.
Embodiment 6
Preparation process is with embodiment 1, and difference is: take 10.5g white carbon as carrier, measuring 236.2ml concentration is the Cu (NO of 0.3mol/L
3)
2solution.This embodiment prepares catalyst F:30wt%Cu/SiO
2.
Embodiment 7
Preparation process is with embodiment 1, and difference is: take 9g white carbon as carrier, measuring 314.9ml concentration is the Cu (NO of 0.3mol/L
3)
2solution.This embodiment prepares catalyst G:40wt%Cu/SiO
2.
Comparing embodiment 1
Preparation process is with embodiment 2, and difference is: the Co (NO that takes 0.3705g
3)
26H
2o.This embodiment prepares catalyst H:20wt%Cu-0.5wt%Co/SiO
2.
Embodiment 8:
The catalyst of embodiment 1 and 3 preparations are for the reaction of hydrogenation of oxalate for preparing ethylene glycol, and its reaction condition is 220 ℃, 2MPa, 150 hydrogen ester ratios, 0.5h
-1lHSV
dMOtime reactivity worth list in table 1.
Preparing ethylene glycol by using dimethyl oxalate plus hydrogen reactivity worth on table 1 copper-based catalysts
Table 1 can find out, the catalyst that the white carbon of take is carrier as carrier and Ludox has similar hydrogenation activity.But there is difference slightly on selective, it is selective that the catalyst that the white carbon of take is carrier has higher EG, simultaneously its 1,2POD and 1, the Main By product of reporting in two kinds of documents of 2BOD selective all significantly lower than take the catalyst that Ludox is carrier, and these two kinds of accessory substances are generally considered to be the one of the main reasons that affects EG product quality.Simultaneously because white carbon is as a kind of common raw material of industry, compared to Ludox, it is cheap and easy to get is suitable for large-scale production and application, is more suitable catalyst carrier.
Embodiment 9:
The preparing ethylene glycol by using dimethyl oxalate plus hydrogen of embodiment 1,2,4 and comparing embodiment 1 Kaolinite Preparation of Catalyst is at 220 ℃, 2MPa, 150 hydrogen ester ratios, 0.5h
-1lHSV
dMOreactivity worth under condition is listed in table 2.
Preparing ethylene glycol by using dimethyl oxalate plus hydrogen reactivity worth on table 2. copper-based catalysts
It can be seen from the table, the catalyst performance that to have added n-type semiconductor oxide be auxiliary agent approaches the catalyst performance that does not add auxiliary agent, and even more excellent in some aspects, and is obviously better than adding the catalyst that p-type semiconductor oxide is auxiliary agent.Illustrate that n-type semiconductor oxide auxiliary agent is really obviously better than the catalyst that p-type semiconductor oxide is auxiliary agent aspect Hydrogenation.Auxiliary agent CeO
2content while being 0.5% and 5%, its DMO conversion ratio is more than 99%, target product EG selectively also more than 80%.
In document, it was reported that adding auxiliary agent cobalt oxide has the effect that improves catalyst performance, as can be seen from the table, it is more that the selective lower reason that interpolation cobalt oxide is auxiliary agent is exactly the 2-MEO and the MG amount that generate, and document is not considered these two kinds of accessory substances completely in calculating selectivity of product process mostly.
Embodiment 10:
The preparing ethylene glycol by using dimethyl oxalate plus hydrogen of embodiment 2 and comparing embodiment 1 Kaolinite Preparation of Catalyst is at 220 ℃, 2MPa, 150 hydrogen ester ratios, 0.5h
-1lHSV
dMOunder condition, carried out stability test.Reaction result demonstration, the catalyst of embodiment 2 DMO conversion ratio in more than 20 hours remains on more than 99%, and EG selectively maintains 84% left and right.And comparing embodiment 1 is under identical reaction condition, after 7 hours, DMO conversion ratio just reduces to 87% by 99%, and EG selectively reduces to 37% left and right by 78%.Illustrate and add catalyst that n-type semiconductor oxide is auxiliary agent compared to adding the catalyst that p-type semiconductor oxide is auxiliary agent, its improved stability is obvious.
Embodiment 11:
The preparing ethylene glycol by using dimethyl oxalate plus hydrogen of embodiment 1,5～7 Kaolinite Preparation of Catalysts is at 220 ℃, 2MPa, 150 hydrogen ester ratios, 0.5h
-1lHSV
dMOunder condition, carried out reactivity worth test, reaction result is listed in table 3.
Preparing ethylene glycol by using dimethyl oxalate plus hydrogen reactivity worth on table 3. copper-based catalysts
As can be seen from Table 3, Cu content is larger on the impact of catalyst performance.Along with the increase of Cu content, the hydrogenation activity of catalyst strengthens gradually, at Cu content, is increased to 20% when above, and what DMO conversion ratio reached 100%, EG selectively also reaches optimum value 84.2% simultaneously.And along with the continuation of Cu content increases, the selective decline of EG, selectively increasing of the accessory substance such as EO and 2-MEO, MG's selectively declines simultaneously, this is due to the increase along with Cu content, the Hydrogenation of catalyst strengthens gradually, and the further hydrogenation of target product EG meeting generates the accessory substance of secondary response.
Embodiment 12:
The preparing ethylene glycol by using dimethyl oxalate plus hydrogen of embodiment 1 Kaolinite Preparation of Catalyst is at 2MPa, 150 hydrogen ester ratios, 0.5h
-1lHSV
dMOunder condition, investigated the impact of reaction temperature, reaction result is listed in table 4.
Preparing ethylene glycol by using dimethyl oxalate plus hydrogen reactivity worth on table 4. copper-based catalysts
The experimental result of table 4 shows, changes reaction temperature, and the conversion ratio of DMO and each product selective had to larger impact.In the time of 220 ℃, the conversion ratio of DMO reached～and 100%, and along with temperature increase does not have significant change.But the distribution of hydrogenation products, but the change along with temperature has a greater change, as can be seen from the table, in the time of 220 ℃, the selective maximum of product EG, be 84%, but after reaction temperature raises, the amount of product EG reduces rapidly, accessory substance EO selectively increases gradually, in the time of 300 ℃, selectively having reached of EO～90%.Can illustrate thus, DMO hydrogenation be one to the highstrung reaction of temperature, and temperature is distributed with considerable influence to the product of hydrogenation reaction.During lower than 220 ℃, Hydrogenation is not enough, mainly selects to generate MG, and when reaction temperature, hydrogenation is excessive during higher than 220 ℃, and in product, EO's is selectively higher.While only having 220 ℃, target product EG's is selectively the highest.
Embodiment 13:
The preparing ethylene glycol by using dimethyl oxalate plus hydrogen of embodiment 1 Kaolinite Preparation of Catalyst is at 220 ℃, 2MPa, 0.5h
-1lHSV
dMOunder condition, investigated the impact of hydrogen ester ratio, reaction result is listed in table 5.
Preparing ethylene glycol by using dimethyl oxalate plus hydrogen reactivity worth on table 5. copper-based catalysts
Experimental result from table 5 can be found out, at hydrogen ester ratio, is 80 o'clock, and in hydrogenation products, MG's is selectively higher, and along with the increase of hydrogen ester ratio, target product EG selectively increases thereupon, and when hydrogen ester ratio is greater than 150, selectively reaching of target product EG is maximum.This explanation, under certain reaction condition, increases hydrogen ester comparison generation target product EG favourable, but arrives after certain value, continues to increase hydrogen ester comparison distribution of reaction products and there is no too large impact.
Embodiment 14:
The preparing ethylene glycol by using dimethyl oxalate plus hydrogen of embodiment 2 Kaolinite Preparation of Catalysts is at 220 ℃, 2MPa, 0.5h
-1lHSV
dMOunder condition, investigated the impact of hydrogen ester ratio, reaction result is listed in table 6.
Preparing ethylene glycol by using dimethyl oxalate plus hydrogen reactivity worth on table 6. copper-based catalysts
According to the experimental data of table 6, can find out, add n-type semiconductor oxide auxiliary agent CeO
2catalyst have the rule similar with embodiment 14.But its Hydrogenation is slightly better than the catalyst without auxiliary agent.Target product EG's is selective a little more than the catalyst without auxiliary agent.Its accessory substance 1 simultaneously, 2POD and 1,2BOD selectively hydrogen ester than from 80 to 220 excursion in, keep stablizing and always lower.
Claims (9)
1. a catalyst for hydrogenation of oxalate for preparing ethylene glycol, take metal Cu as active component, it is characterized in that: described catalyst is with SiO
2for carrier, n-type semiconductor oxide is auxiliary agent;
In described catalyst, the quality percentage composition of each component is: active metal Cu is that 10～70%, n-type semiconductor oxide auxiliary agent is 0.1%～10%, and surplus is carrier S iO
2.
2. catalyst according to claim 1, is characterized in that: described carrier S iO
2for a kind of or two kinds of mixing in Ludox and white carbon.
3. catalyst according to claim 1, is characterized in that: the preferred white carbon of described carrier.
4. catalyst according to claim 1, is characterized in that: described n-type semiconductor oxide auxiliary agent refers to the oxides additive that electronics can be provided, preferably CeO
2.
5. it is characterized in that according to claim 1: in described catalyst, auxiliary agent mass content is preferably 0.5～5%.
6. an application for the arbitrary described catalyst of claim 1-5, is characterized in that: described catalyst is for the reaction of catalysis hydrogenation of oxalate for preparing ethylene glycol.
7. application according to claim 6, is characterized in that: described oxalate refers to a kind of in oxalic acid mono-methyl, oxalic acid mono ethyl ester, dimethyl oxalate, diethy-aceto oxalate or two kinds; A kind of in excellent finger dimethyl oxalate and diethy-aceto oxalate or two kinds.
8. according to the application described in claim 6 or 7, it is characterized in that: described catalyst is used for the reaction condition of the reaction of catalysis hydrogenation of oxalate for preparing ethylene glycol: temperature is 180-300 ℃, pressure is 1.0-3.0Mpa, and the mol ratio of hydrogen ester (hereinafter to be referred as hydrogen ester ratio) is 50～220.
9. application according to claim 8, is characterized in that: while adopting fixed bed reactors, liquid hourly space velocity (LHSV) is 0.5h
-1.
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| CN111875335A (en) * | 2020-08-09 | 2020-11-03 | 苏州智本工程技术有限公司 | Mortar special for building floor and floating building floor and production method thereof |
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| CN109772321B (en) * | 2017-11-13 | 2021-07-16 | 中国科学院福建物质结构研究所 | Copper-silicon catalyst based on metal organic framework and preparation and application thereof |
| CN111875335A (en) * | 2020-08-09 | 2020-11-03 | 苏州智本工程技术有限公司 | Mortar special for building floor and floating building floor and production method thereof |
| CN111875335B (en) * | 2020-08-09 | 2021-11-16 | 苏州智本工程技术有限公司 | Mortar special for building floor and floating building floor and production method thereof |
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