CN101844078B - Catalyst for preparing glycol through oxalate hydrogenation and preparation method thereof - Google Patents
Catalyst for preparing glycol through oxalate hydrogenation and preparation method thereof Download PDFInfo
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- CN101844078B CN101844078B CN2009100480258A CN200910048025A CN101844078B CN 101844078 B CN101844078 B CN 101844078B CN 2009100480258 A CN2009100480258 A CN 2009100480258A CN 200910048025 A CN200910048025 A CN 200910048025A CN 101844078 B CN101844078 B CN 101844078B
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Abstract
The invention relates to a catalyst for preparing glycol through oxalate hydrogenation and a preparation method thereof. The catalyst is a copper/silica catalyst prepared by liquid phase reduction through sol-gel and a precipitation method. After forming a complex compound, the raw material copper salt is mixed with a carrier to generate the catalyst with high surface area. The catalyst can be directly applied to oxalate hydrogenation, and has very high reactivity and product selectivity.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method 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; Many research institutions have carried out the work of this respect one after another afterwards: Haruhiko Miyazaki in 1985 etc. disclose the CuMokBapOx catalyst in United States Patent (USP) 4551565, United States Patent (USP) 4585890,4440873 and 4614728 discloses in 1984 and has used the standby copper base hydrogenation catalyst of cuprammonium silica gel legal system, reported the copper Si catalyst of a kind of Cr of containing in the European patent 0060787, U.S. ARCO company adopted the Cu-Cr catalyst in 1986; Fujian thing structure institute of the domestic Chinese Academy of Sciences finishes the 200ml mould examination research work of diethy-aceto oxalate Hydrogenation ethylene glycol in the early 1990s exploitation Cu-Cr catalyst.But 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.
For Cu-series catalyst, growing up of metallic usually is the main cause that causes catalysqt deactivation.And Cu-series catalyst generally plays catalytic action under reducing condition (0 valency or 0 valency/1 valency).Therefore catalyst generally is to reduce in hydrogen before the reaction, or preparation finish after the preservation of reduction post-passivation.Operating time for the former is long, and operating condition is very strict, avoids temperature runaway, requires very meticulously, causes catalyst activity component agglomeration to avoid the catalyst overheating temperature runaway, also can produce certain negative effect to catalyst structure; And the latter needs specific installation, eremacausis, and complex procedures, complex operation step also needs simple reduction to process before the use.For these shortcomings of vapour phase reduction, also there is the researcher to carry out alternative work, comprise and use hydrogen or dilution hydrogen Reduced Copper Catalyst (cn94119605.4) in the solvent streams, but the method is still comparatively loaded down with trivial details; Utilize in addition liquid-phase reduction prepare noble metal catalyst (02108585.4, CN1631523), but this is mainly used on the catalyst of infusion process preparation.This patent has been invented the method that a kind of one-step method directly prepares the catalyst that is applicable to the oxalate hydrogenation, and easy and simple to handle, catalyst performance is superior.
Summary of the invention
Technical problem to be solved by this invention provides a kind ofly need not reduce, be directly used in the gas-solid phase reaction catalyst of high activity, high selectivity, this catalyst is applicable to hydrogenation of oxalate for preparing ethylene glycol reaction, have easy-to-use, low, the active high of reaction temperature.
The catalyst of preparing glycol through oxalate hydrogenation of the present invention, take copper/cupric oxide as active component, silica is carrier, catalyst preparation process is modified through liquid-phase reduction.
Catalyst is prepared from by collosol and gel and the precipitation method.The raw material mantoquita mixes with carrier after forming complex compound, modifies through liquid-phase reduction, generates the catalyst of high-ratio surface.
Catalyst preferable alloy copper content of the present invention is 10%～60% of total catalyst weight; The preferred specific area of catalyst is 100～600m
2/ g; The preferred pore volume of catalyst is 0.1～2.0cm
3/ g.
Above-mentioned total catalyst weight refers to the gross weight of active component and carrier.Active component copper/cupric oxide refers to: copper and/or cupric oxide.
Above-mentioned liquid-phase reduction is modified the mode that refers to add the liquid-phase reduction agent and is reduced modified catalyst.
The preparation method of catalyst of the present invention comprises the steps:
Copper salt solution is formed the complex solution of ammonia, support precursor is mixed with the former, system temperature is adjusted to 60-95 ℃, when treating that system pH is changed to 7-13, add the liquid-phase reduction agent, the hybrid reaction endpoint pH is below 6.5, to be generally pH3-6.5; After the washing of compound process, filtration, the drying, make the target catalyst.
Specifically comprise the following steps:
(1) copper salt solution is formed the complex solution of ammonia, cupric ammine complex concentration is 0.001～8.0M in the solution, and control pH value is between 10-14.
(2) support precursor is evenly mixed with the complex solution of step 1.
(3) system temperature is adjusted to 60-95 ℃, mixing speed 50-500rmp.
When (4) treating that system pH is changed to 7-13, add the liquid-phase reduction agent, reducing agent: copper=0.5-20: 1 (mol ratio).
(5) the control pH value of reaction system is 6.5 to be reaction end when following, and reaction stops.
(6) after the compound process filtration that step 5 is obtained, washing, the drying, make the target catalyst.
Above-mentioned mantoquita is selected from one or more in copper nitrate, Schweinfurt green or the cupric oxalate.
Copper salt solution refers to the aqueous solution of mantoquita.
The method that above-mentioned copper salt solution forms the complex solution of ammonia can adopt conventional method, makes as drip ammoniacal liquor in the aqueous solution of mantoquita.
Above-mentioned carrier precursor is Ludox, estersil or white carbon.
Above-mentioned reducing agent is selected from one or more in hydrazine hydrate, formaldehyde or senior aldehyde, the ascorbic acid etc.The liquid-phase reduction agent refers to the aqueous solution of reducing agent.
The mode of above-mentioned adding liquid-phase reduction agent is for dripping the aqueous solution of reducing agent, and the concentration of reducing agent is 1-8w% in the reducing agent aqueous solution.
Catalyst of the present invention need not reduction, directly efficient catalytic oxalate hydrogenation under reaction condition after making.
The present invention also further provides a kind of hydrogenation of oxalate for preparing ethylene glycol technique, comprise: the catalyst that preceding method is made need not reduction and is directly used in hydrogenation of oxalate for preparing ethylene glycol technique, take polybasic ester as reaction raw materials, the reaction Operating condition is as follows, 160～260 ℃ of reaction temperatures, reaction pressure 1～10MPa, catalyst loading (charging rate of reaction raw materials oxalate) 0.01～3g/g cat.h, hydrogen/oxalate=30～400: 1 (molecular proportion).In this technique, the conversion ratio of oxalate is more than 95%, ethylene glycol selectively more than 95%.
Experiment shows, the catalyst that preparation method of the present invention makes has very high reactivity and glycol selectivity in the reaction of preparing glycol through oxalate hydrogenation, and the life-span is long, reacting balance.
The specific embodiment
Copper salt solution is formed the complex solution of ammonia, the concentration of solution is 0.001～8.0M, and control pH value is between 10-14.Support precursor is evenly mixed with the former.System temperature is adjusted to 60-95 ℃, mixing speed 50-500rmp.When treating that system pH is changed to 7-13, add the liquid-phase reduction agent, liquid-phase reduction agent: copper=0.5-20: 1 (mol ratio).The control pH value of reaction system is reaction end when being 3-6.5, and reaction stops.After the filtration of compound process, washing, the drying, make the target catalyst.
Embodiment 1:
Take by weighing copper nitrate 150g, add the 200mL deionized water dissolving; Dripping ammoniacal liquor has precipitation to generate, and continue to drop to precipitation and dissolve fully, be 13.0 by ammoniacal liquor addition control pH value.Add Ludox 100 grams, stir 60min under the mixing speed 350rpm.System temperature rises to 75 ℃.Treat that system pH was down at 9.0 o'clock, drip hydrazine hydrate (the hydrazine content 5wt%) 200mL (mol ratio of conversion reducing agent and Cu is: 1: 2) of dilution, kept mixing speed 8 hours, system pH drops to 6.5 naturally, generates and precipitates.Filter, washing obtains the catalyst filter cake, and drying is 12 hours under 95 ℃.Namely obtain Catalysts Cu/SiO2 (A), the specific area of catalyst is 300m
2/ g; Pore volume is 1.1cm
3/ g.With the broken screening of Catalysts Cu/SiO2 (A) compressing tablet 40-60 order; Under reaction condition, carry out the reaction of preparing glycol by hydrogenating oxalate.
Embodiment 2:
Take by weighing copper nitrate 150g, add the 200mL deionized water dissolving; Dripping ammoniacal liquor has precipitation to generate, and continues to drop to precipitation and dissolves fully, and control pH value is 13.0.Add Ludox 100 grams, stir 60min under the mixing speed 350rpm.System temperature rises to 75 ℃.Treat that system pH was down at 9.0 o'clock, drip formalin (content of formaldehyde 5wt%) 200mL (mol ratio of conversion reducing agent and Cu is: 1: 1) of dilution, keep mixing speed to system pH to be down to 6.5, generate and precipitate.Filter, washing obtains the catalyst filter cake, and drying is 12 hours under 95 ℃.Namely obtain Catalysts Cu/SiO2 (B), the specific area of catalyst is 400m
2/ g; Pore volume is 1.5cm
3/ g.With the broken screening of Catalysts Cu/SiO2 (B) compressing tablet 40-60 order; Under reaction condition, carry out the reaction of preparing glycol by hydrogenating oxalate.
Embodiment 3:
Take by weighing copper nitrate 150g, add the 200mL deionized water dissolving; Dripping ammoniacal liquor has precipitation to generate, and continues to drop to precipitation and dissolves fully, and control pH value is 13.0.Add Ludox 100 grams, stir 60min under the mixing speed 350rpm.System temperature rises to 75 ℃.Treat that system pH was down at 9.0 o'clock, drip hydrazine hydrate solution (the hydrazine content 5wt%) 100mL (mol ratio of conversion reducing agent and Cu is: 1: 2) of dilution, keep mixing speed to system pH to be down to 6.5, generate and precipitate.Filter, washing obtains the catalyst filter cake, and drying is 12 hours under 95 ℃.Namely obtain Catalysts Cu/SiO2 (C), the specific area of catalyst is 350m
2/ g; Pore volume is 1.2cm
3/ g.With the broken screening of Catalysts Cu/SiO2 (C) compressing tablet 40-60 order; Under reaction condition, react.
Embodiment 4:
Take by weighing Schweinfurt green 21g, add the 200mL deionized water dissolving; Dripping ammoniacal liquor has precipitation to generate, and continues to drop to precipitation and dissolves fully, and control pH value is 13.0.Add Ludox 54 grams, stir 60min under the mixing speed 350rpm.System temperature rises to 75 ℃.Treat that system pH was down at 7.0 o'clock, drip hydrazine hydrate solution (the hydrazine content 5wt%) 100mL (mol ratio of conversion reducing agent and Cu is: 20: 1) of dilution, keep mixing speed to system pH to be down to below 6, generate and precipitate.Filter, washing obtains the catalyst filter cake, and drying is 12 hours under 95 ℃.Namely obtain Catalysts Cu/SiO2 (D), the specific area of catalyst is 500m
2/ g; Pore volume is 2.0cm
3/ g.With the broken screening of Catalysts Cu/SiO2 (D) compressing tablet 40-60 order; Under reaction condition, react.
Embodiment 5:
Take by weighing cupric oxalate 10g, add the 200mL deionized water dissolving; Dripping ammoniacal liquor has precipitation to generate, and continues to drop to precipitation and dissolves fully, and control pH value is 13.0.Add Ludox 54 grams, stir 60min under the mixing speed 350rpm.System temperature rises to 75 ℃.Treat that system pH was down at 10.0 o'clock, drip hydrazine hydrate solution (the hydrazine content 5wt%) 100mL (mol ratio of conversion reducing agent and Cu is: 10: 1) of dilution, keep mixing speed to system pH to be down to below 6, generate and precipitate.Filter, washing obtains the catalyst filter cake, and drying is 12 hours under 95 ℃.Namely obtain Catalysts Cu/SiO2 (E), the specific area of catalyst is 550m
2/ g; Pore volume is 1.8cm
3/ g.With the broken screening of Catalysts Cu/SiO2 (E) compressing tablet 40-60 order; Under reaction condition, react.
Comparative example 1:
Take by weighing copper nitrate 150g, add the 200mL deionized water dissolving; Dripping ammoniacal liquor has precipitation to generate, and continues to drop to precipitation and dissolves fully, and control pH value is 13.0.Add Ludox 100 grams, stir 60min under the mixing speed 350rpm.System temperature rises to 75 ℃.Keep mixing speed to system pH to be down to 6.5, generate precipitation.Filter, washing obtains the catalyst filter cake, and drying is 12 hours under 95 ℃.Namely obtain Catalysts Cu/SiO2 (F).With Catalysts Cu/SiO
2(F) the broken screening of compressing tablet 40-60 order; Under reaction condition, react.
The catalyst performance test
Catalyst is placed stainless steel reactor, reactor inside diameter 10mm, inside reactor dress thermocouple sheath, loaded catalyst is 5mL, 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, and reaction temperature 185-200 ℃, reaction pressure 3.0MPa, liquid hourly space velocity (LHSV) 0.7g/ (gcat h), hydrogen/oxalate=100 (molecular proportion).Reaction result is as shown in table 1.
Table 1, the different catalysts reactivity worth.
As seen from the above table, compare with Comparative Examples, catalyst of the present invention selectively can reach respectively 99% and 95% at 185 ℃ of conversion ratios and principal product, and the Catalyst Conversion of processing without liquid-phase reduction under the same reaction conditions only is 80%, and principal product selectively also only is 82%.Utilize Catalysts and its preparation method disclosed in this invention can omit catalyst vapour phase reduction step.
Claims (9)
1. the catalyst of a preparing glycol through oxalate hydrogenation, take copper as active component, silica is carrier, catalyst preparation process is modified through liquid-phase reduction, and the method for the catalyst of described preparing glycol through oxalate hydrogenation through comprising the following steps makes: copper salt solution is formed the complex solution of ammonia, support precursor is mixed with the former, system temperature is adjusted to 60-95 ℃, when treating that system pH is changed to 7-13, add the liquid-phase reduction agent, the hybrid reaction endpoint pH is below 6.5; After the washing of compound process, filtration, the drying, make the target catalyst, described mantoquita is selected from one or more in copper nitrate, Schweinfurt green or the cupric oxalate.
2. the catalyst of preparing glycol through oxalate hydrogenation as claimed in claim 1 is characterized in that, in the described catalyst, metallic copper content is 10%～60% of total catalyst weight; Specific surface area of catalyst is 100～600m
2/ g; The catalyst pore volume is 0.1～2.0cm
3/ g.
3. the catalyst of preparing glycol through oxalate hydrogenation as claimed in claim 1 is characterized in that, described liquid-phase reduction is modified and referred in the process of Kaolinite Preparation of Catalyst, adds liquid-phase reduction agent reduction and modifies, and wherein, the mol ratio of reducing agent and copper is 0.5-20: 1.
4. the preparation method of the catalyst of the described preparing glycol through oxalate hydrogenation of arbitrary claim among the claim 1-3, comprise the steps: copper salt solution is formed the complex solution of ammonia, support precursor is mixed with the former, system temperature is adjusted to 60-95 ℃, when treating that system pH is changed to 7-13, add the liquid-phase reduction agent, the hybrid reaction endpoint pH is below 6.5; After the washing of compound process, filtration, the drying, make the target catalyst, described mantoquita is selected from one or more in copper nitrate, Schweinfurt green or the cupric oxalate.
5. the preparation method of the catalyst of preparing glycol through oxalate hydrogenation as claimed in claim 4 is characterized in that, when adding the liquid-phase reduction agent, the mol ratio of reducing agent and copper is 0.5-20 in the solution: 1.
6. the preparation method of the catalyst of preparing glycol through oxalate hydrogenation as claimed in claim 4 is characterized in that, described carrier precursor is Ludox, estersil or white carbon.
7. the preparation method of the catalyst of preparing glycol through oxalate hydrogenation as claimed in claim 4 is characterized in that, described reducing agent is selected from one or more in hydrazine hydrate, formaldehyde or senior aldehyde, the ascorbic acid.
8. the application of the catalyst of the described preparing glycol through oxalate hydrogenation of arbitrary claim among the claim 1-3 is characterized in that, need not reduction after catalyst is made, directly catalysis oxalate hydrogenation under reaction condition.
9. hydrogenation of oxalate for preparing ethylene glycol technique, comprise: the described catalyst of arbitrary claim among the claim 1-3 be need not reduction be directly used in hydrogenation of oxalate for preparing ethylene glycol technique, take oxalate as reaction raw materials, 160～260 ℃ of control reaction temperatures, reaction pressure 1～10MPa, catalyst loading 0.01～3g/g cat.h, the molecular proportion of hydrogen and oxalate is 30～400: 1.
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| CN106336345B (en) * | 2015-07-10 | 2019-11-22 | 华东理工大学 | The method for preparing 1,3- propylene glycol |
| CN105435791B (en) * | 2015-12-03 | 2021-08-10 | 上海华谊能源化工有限公司 | Catalyst for preparing 1, 3-propanediol by hydrogenating dialkyl malonate and preparation method and application thereof |
| CN107866224A (en) * | 2016-09-26 | 2018-04-03 | 上海华谊能源化工有限公司 | Catalyst and its production and use |
| CN106563449B (en) * | 2016-11-07 | 2019-04-16 | 中国科学院福建物质结构研究所 | Oxalic ester hydrogenation synthesizing of ethylene glycol catalyst and preparation method thereof and start-up method |
| CN109225281B (en) * | 2018-09-19 | 2022-04-15 | 中国天辰工程有限公司 | Catalyst containing multivalent copper active component, preparation method and application |
| CN114054022A (en) * | 2021-12-14 | 2022-02-18 | 河南能源化工集团研究总院有限公司 | Catalyst, preparation method and application |
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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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| CN101342489A (en) * | 2007-07-12 | 2009-01-14 | 上海焦化有限公司 | Hydrogenation reaction catalyst, preparation and application thereof |
Non-Patent Citations (4)
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