CN105457631A - Catalyst for preparing ethyl alcohol acid ester through oxalic ester gas phase hydrogenation and preparation method - Google Patents
Catalyst for preparing ethyl alcohol acid ester through oxalic ester gas phase hydrogenation and preparation method Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The invention belongs to the technical field of ethyl alcohol acid ester preparation, and particularly relates to a silver catalyst for preparing ethyl alcohol acid ester through oxalic ester gas phase hydrogenation and a preparation method thereof. The catalyst is prepared by taking metallic silver as an active component through a silver ammonia complexation ammonia distillation method; at least one of modified silica gel, silica sol, silicon oxide, a silicon-aluminum molecular sieve and activated carbon is adopted as a carrier of the catalyst, wherein the content of the metallic silver preferably accounts for 0.5%-35% of the weight of the carrier and optimally accounts for 5%-30% of the weight of the carrier, the carrier optimally selects nanoscale silicon dioxide-modified silica sol which does not contain sodium ions, and the average particle size of the silica sol is 1-30 nm. The obtained silver catalyst is used for a production technology for preparing the ethyl alcohol acid ester through oxalic ester gas phase hydrogenation, has the better ethyl alcohol acid ester selectivity and catalyst activity than those of an existing Cu catalyst and is long in life, stable in activity and suitable for industrialized production.
Description
Technical field
The invention belongs to the preparing technical field of ethyl glycolate, be specially a kind of catalyst and the preparation method that prepare ethyl glycolate for oxalate gas phase hydrogenation.
Background technology
Ethyl glycolate is a kind of important chemical products, is widely used in many fields such as chemical industry, medicine, agricultural chemicals, feed, dyestuff and spices.As the improvement solvent of fiber, resin and rubber; Hydrogenation is for ethylene glycol, and carbonylation malonate, ammonia solution glycine, is hydrolyzed glycolic processed etc.Wherein the market demand of glycolic is larger.
Current foreign technology mainly adopts formaldehyde carbonylation route, due to corrosion and condition of high voltage, high to equipment requirement, have high input, suitability for industrialized production difficulty, domestic, be the process route continuing to use monoxone and soda lye hybrid reaction resterification, but this method take acetic acid as raw material, chlorine method is produced, seriously corroded, pollute large, cost is high, can not large-scale production, therefore need the process route of improvement badly.
By hydrogenation of oxalate for preparing for ethyl glycolate, and then exploitation downstream product, forming good industrial chain, is the very good prospect of current chemical enterprise.Due to ethyl glycolate hydrogenation generating glycol very easily further, therefore exploitation has the catalyst that higher oxalate conversion ratio realizes ethyl glycolate high selectivity simultaneously, becomes the key of this technology commercialization application.Having document both at home and abroad and patent reports with copper is the report of the oxalate catalytic hydrogenation ethyl glycolate catalyst of main active component using metals such as silver as auxiliary agent, but prepared divided catalyst feed stock conversion and ethyl glycolate target product selective on need to improve, the active lifetime of catalyst and stability can not meet the requirement of industrialized unit application.
Japan Patent JP6135895A comparatively early disclose prepared by dimethyl oxalate plus hydrogen for methyl glycollate, take silica as carrier, supported copper and silver, adopt copper ammonia complexation ammonia still process method to be prepared into methyl glycollate, product selectivity is less than 70%.
US Patent No. 4602102 reports the method for a kind of prepared by dimethyl oxalate plus hydrogen for methyl glycollate, and adopt supported copper and silver catalyst, the conversion ratio of dimethyl oxalate is 90.2%, and the yield of methyl glycollate is 68%.
Chinese patent CN101138730A discloses and adopts a kind of Catalysts and its preparation method for oxalic ester hydrogenation synthesizing of glycolate, with metallic copper for main active component, take silver as co-catalyst, is prepared from by infusion process; Its carrier is the Ludox of modification, and wherein metallic copper content is preferably 5% ~ 45% of vehicle weight; Argent content is the 0.1%-15% of vehicle weight, and carrier preferably has the Ludox of bimodal pore distribution structure, and its specific area is 100-300m
2/ g, this catalyst reactivity worth in oxalate and hydrogen synthesizing alcohol acid esters react is steady, is easy to control, but dimethyl oxalate conversion ratio 85%, methyl glycollate is 83%.
Chinese patent CN104923219A discloses a kind of preparing ethanol by oxalate hydrogenation acid methyl esters catalyst, preparation method and its usage, with silver for main active constituent, palladium, platinum, ruthenium, barium, zinc, copper, calcium, magnesium, nickel, cobalt, manganese, cerium, iron, lanthanum or molybdenum are aiding catalytic component, silica, aluminium oxide, zirconia, titanium oxide or Si-Al molecular sieve are carrier, adopt and be impregnated on carrier by first excessive for the solution containing active constituent silver and auxiliary agent, with precipitating reagent, it is precipitated again, fixing technical scheme solves this problem preferably, can be used in the industrial production of preparing ethanol by oxalate hydrogenation acid methyl esters catalyst.
Chinese patent CN101700496A discloses a kind of Catalysts and its preparation method of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate, described catalyst with metallic copper for main active component, silver and manganese for helping active component, Al
2o
3for carrier; Wherein metallic copper content is 25% ~ 50% of catalyst quality, argent content is 5% ~ 15% of catalyst quality, manganese metal content is 8% ~ 20% of catalyst quality, Al
2o
3content is 15% ~ 40% of catalyst quality.This invention catalyst has very high reactivity in the reaction of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate, and oxalate conversion ratio reaches 98%, but selective only 75% of methyl glycollate.
Chinese patent CN200710061391.8 discloses a kind of Catalysts and its preparation method for oxalic ester hydrogenation synthesizing of glycolate, and the described catalyst of this invention for main active component with metallic copper, is taken silver as co-catalyst, is prepared from by infusion process; Its carrier is the Ludox of modification, and wherein metallic copper content is preferably 5% ~ 45% of vehicle weight; Argent content is 0.1% ~ 15% of vehicle weight; Carrier preferably has the Ludox of bimodal pore distribution structure, and its specific area is 100-300m
2/ g, the conversion ratio of oxalate is up to 95%, and the selective of ethyl glycolate is up to 84%.
Chinese patent CN101816934 discloses and a kind ofly prepares silver-colored silicon oxide catalyst of methyl glycollate and ethylene glycol and preparation method thereof for dimethyl oxalate gas phase continuous catalytic hydrogenation.The preparation process of this invention catalyst is: soluble silver salt is made into silver ammino solution, and adds polyvinylpyrrolidone as protective agent and structure directing agent; Add reducing agent under stirring, control reaction temperature is 20-90 DEG C; Add ethyl orthosilicate again, stir 1-24hr, be warming up to 60-90 DEG C, and to control reaction end pH value be 6-10; Finally, wash, dry and under 100 ~ 900 degree roasting 1-24h.The catalyst prepared prepares methyl glycollate and ethylene glycol for dimethyl oxalate gas phase continuous catalytic hydrogenation, and the yield of methyl glycollate reaches 95%,
Chinese patent CN101954288A openly knows clearly a kind of prepared by dimethyl oxalate plus hydrogen for the Catalysts and its preparation method of methyl glycollate and application, adopt the copper-based catalysts that urea decomposition-even co-precipitation is prepared from, the conversion ratio of dimethyl oxalate can reach 94.5%, and the selective of methyl glycollate is up to 93.5%.
From content disclosed in above-mentioned document, mostly adopt Cu as catalyst activity component about hydrogenation of oxalate for preparing for ethyl glycolate catalyst, but Cu is catalyst based not high for this technique ubiquity catalytic activity, the selective lower shortcoming of ethyl glycolate, and Cu is catalyst based responsive to reaction temperature for the existence of oxalate gas phase hydrogenation ethyl glycolate, the shortcoming of catalyst life instability.At present, industrialization exploration work about oxalate gas phase hydrogenation ethyl glycolate concentrates on the research and development to catalyst mostly, and hydrogenation of oxalate for preparing is exothermic reaction for the reaction of ethyl glycolate, carrying out reaction bed temperature and can increase along with reaction, and the inactivation of the inevitable accelerator activator of too high local temperature rise, affect catalyst performance.Selecting reactor pattern and feeding manner are also very large on the impact of technique improperly, diverse location mixing of materials and air-flow in reactor can be caused uneven, catalyst can not be made full use of, finally cause the selective lower of ethyl glycolate.
Summary of the invention
The object of the invention is to for above technical problem, a kind of catalyst and the preparation method that prepare ethyl glycolate for oxalate gas phase hydrogenation be provided, this catalytic component is simple, reactivity is high, the selective height of product ethanol acid esters.
The object of the invention is realized by following technical proposals:
A kind of catalyst preparing ethyl glycolate for oxalate gas phase hydrogenation, this catalyst take argent as active component, be prepared from by silver-colored ammonia complexing ammonia still process method, its carrier is any one or a few the mixture in modified silica-gel, Ludox, silica, Si-Al molecular sieve and active carbon, wherein argent content is the 0.5%-35% of vehicle weight, be preferably 5%-30%, carrier is preferably selected not containing the nanometer grade silica modified silicasol of sodium ion.Its average grain diameter is 1-30nm.
Prepare a preparation method for the catalyst of ethyl glycolate for oxalate gas phase hydrogenation, the method comprises the steps:
(1) acetate of argent, oxalates or nitrate deionized water dissolving are mixed with aqueous solution I, the concentration of solution is 0.001-3.0M;
(2) instill in the silver salt solution I that step (1) is obtained by inorganic ammonia or By Amine Solutions, obtain silver-colored ammonia complexing solution II, the mol ratio of inorganic ammonia or organic amine and solution I argent element is 0.1-10:1;
(3) under stirring, at least one in modified silica-gel, Ludox, silica, Si-Al molecular sieve, active carbon is added in solution II, and stir aging 1-10 hour, by most of inorganic ammonia or organic amine removing at 60-100 DEG C.Filter and wash and obtain solids;
(4) the solids dry 2-12 hour at 90-130 DEG C (3) obtained, then obtains catalyst precursor after roasting 2-8 hour at 200-500 DEG C.
(5) be 10-80mL/min g Cat with flow, in volume content, hydrogeneous tolerance is the catalyst precursor reduction 1-24 hour that (4) obtain by the nitrogen of 0-100% and the mist of hydrogen at 120-600 DEG C of temperature, just can be made into the silver catalyst that described oxalate gas phase hydrogenation prepares ethyl glycolate.
Good effect of the present invention is:
(1) catalyst that, the present invention obtains is prepared in the production technology of ethyl glycolate for oxalate gas phase hydrogenation, there is and catalyst activity more selective than the better ethyl glycolate of existing Cu catalyst, catalytic component is simple, production technology is easy, catalyst life is long, activity stabilized, be suitable for suitability for industrialized production.
(2), do not need to add second component metal as auxiliary agent, the catalyst obtained can reach the conversion ratio to the higher selective and oxalate of preparing ethanol by oxalate hydrogenation acid esters, can reduce again the consumption to noble metals such as rare earth metal and palladium, platinum, ruthenium, Lao.
Detailed description of the invention
All features disclosed in this description, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
The halide salt of containing metal silver, acetate, sulfate or nitrate deionized water dissolving are mixed with aqueous solution I, and the concentration of solution is 0.001-3.0M.In the silver salt solution obtain inorganic ammonia or By Amine Solutions instillation, obtain silver-colored ammonia complexing solution, the mol ratio of inorganic ammonia or organic amine and argent element is 0.1-10:1.Under stirring, at least one in modified silica-gel, Ludox, silica, Si-Al molecular sieve, active carbon is added in silver-colored ammonia complexing solution.And stir aging 1-10 hour, by most of inorganic ammonia or organic amine removing at 60-100 DEG C.Filter and wash, then dry 2-12 hour at 90-130 DEG C, at 200 ~ 500 DEG C, obtaining catalyst precursor after roasting 2-8 hour.Be 10-80mL/min g Cat. with flow, hydrogen be the mist of the nitrogen of 0-100% (v%) and hydrogen at 120-600 DEG C of temperature to catalyst precursor reduction 1-24 hour, just can be made into the silver catalyst that described oxalate gas phase hydrogenation prepares ethyl glycolate.
Embodiment 1:
Silver nitrate deionized water is mixed with the liquor argenti nitratis ophthalmicus I of 200mL0.4 mol/L, under stirring, 20mL ammoniacal liquor is joined in solution I and obtain silver-colored ammonia complexing solution II.Take the silica-gel carrier 48g through ammoniacal liquor modification, under agitation join in solution II by modified silica-gel, aged at room temperature 3 hours, then in 80 DEG C of water-baths, ammonia still process is 7.5 to pH value, filters and washs.Dry cake 6 hours at 110 DEG C, roasting 8 hours at 500 DEG C, 1. the solids after roasting is catalyst.Through atomic absorption spectrum detecting catalyst machine component, the percentage by weight that silver accounts for carrier silicas is: 17.6%.
Embodiment 2:
Silver nitrate deionized water is mixed with the liquor argenti nitratis ophthalmicus I of 200ml0.4 mol/L, under stirring, 20mL ammoniacal liquor is joined in solution I and obtain silver-colored ammonia complexing solution II.Take Ludox carrier 200g, join in solution II by Ludox under the state stirred, controlling endpoint pH is 10, and aging 2 hours in 40 DEG C, then in 80 DEG C of water-baths, ammonia still process to pH value is 7.5, filters and washing leaching cake.Dry cake 6 hours at 110 DEG C, roasting 8 hours at 500 DEG C, 2. the catalyst tablet forming after roasting is catalyst.Through atomic absorption spectrum detecting catalyst machine component, the percentage by weight that silver accounts for carrier silicas is: 15.6%.
Embodiment 3:
Silver oxalate deionized water is mixed with the silver-colored solution I of oxalic acid acid of 200ml0.2 mol/L, under stirring, 20mL ammoniacal liquor is joined in solution I and obtain silver-colored ammonia complexing solution II.Take Ludox carrier 200g, by Ludox stir state under join in solution II, control endpoint pH be 9.6,50 DEG C aging 2 hours, then in 80 DEG C of water-baths, ammonia still process to pH value is 7.5, filter and washing leaching cake.Dry cake 6 hours at 110 DEG C, roasting 6 hours at 450 DEG C, 3. the catalyst tablet forming after roasting is catalyst.Through atomic absorption spectrum detecting catalyst machine component, the percentage by weight that silver accounts for carrier silicas is: 9.2%.
Embodiment 4:
Silver acetate deionized water is mixed with 200ml, and the silver-colored solution I of acetic acid acid of 1.5 mol/L, joins 20mL diethylamine in solution I under stirring and obtains silver-colored ammonia complexing solution II.Take Ludox carrier 400g, by Ludox stir state under join in solution II, control endpoint pH be 9.2,35 DEG C aging 7 hours, then in 80 DEG C of water-baths, ammonia still process to pH value is 7.8, filter and washing leaching cake.Dry cake 6 hours at 120 DEG C, roasting 6 hours at 500 DEG C, 4. the catalyst tablet forming after roasting is catalyst.Through atomic absorption spectrum detecting catalyst machine component, the percentage by weight that silver accounts for carrier silicas is: 31.8%.
Embodiment 5:
Silver nitrate deionized water is mixed with 200ml, the liquor argenti nitratis ophthalmicus I of 0.4 mol/L, under stirring, 20mL ammoniacal liquor is joined in solution I and obtain silver-colored ammonia complexing solution II.Take Si-Al molecular sieve 170g, will change Si-Al molecular sieve and join in solution II, 40 DEG C aging 5 hours, and then in 80 DEG C of water-baths, ammonia still process is 7.8 to pH value, filters and washs.Drying 6 hours at 110 DEG C, roasting 6 hours at 400 DEG C, 5. the solids after roasting is catalyst.Through atomic absorption spectrum detecting catalyst machine component, silver accounts for vehicle weight percentage and is: 5.2%.
Embodiment 6:
Silver nitrate deionized water is mixed with 200ml, the liquor argenti nitratis ophthalmicus I of 0.4 mol/L, under stirring, 20mL ammoniacal liquor is joined in solution I and obtain silver-colored ammonia complexing solution II.Take active carbon 78g, join in solution II under stirring by active carbon, 30 DEG C aging 4 hours, and then in 80 DEG C of water-baths, ammonia still process is 7.8 to pH value, filters and washs.Drying 6 hours at 110 DEG C, roasting 9 hours at 400 DEG C, 6. the solids after roasting is catalyst.Through atomic absorption spectrum detecting catalyst machine component, the percentage by weight that silver accounts for carrier silicas is: 7.8%.
Catalyst performance is tested:
Catalyst is placed in high pressure micro fixed-bed reactor, reactor inside diameter 20mm, the in-built thermocouple sheath of reactor, loaded catalyst is 5mL,. be first 20mL/min g Cat with flow, in volume content, hydrogen be the nitrogen of 5% and the mist of hydrogen at 120-600 DEG C of temperature by catalyst reduction 1-24 hour.Then reaction bed temperature is down to reaction temperature 210 DEG C.Unstripped gas passes through beds, reacts thick product and is drawn by reactor bottom, in sampling jar sample analysis after condensing gas condensation.The mol ratio of reaction gas hydrogen and ethyl glycolate adopts 100, reaction pressure 1.5Mpa, and reaction result is as shown in table 1.
Table 1 catalyst performance test result
The present invention is not limited to aforesaid detailed description of the invention.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.
Claims (5)
1. prepare the silver catalyst of ethyl glycolate for oxalate gas phase hydrogenation for one kind, this catalyst comprises active component and carrier, it is characterized in that: this catalyst take argent as active component, be prepared from by silver-colored ammonia complexing ammonia still process method, its carrier is any one or a few the mixture in modified silica-gel, Ludox, silica, Si-Al molecular sieve and active carbon, wherein argent content is the 0.5%-35% of carrier quality, and gross mass percentage composition is 100%.
2. the silver catalyst preparing ethyl glycolate for oxalate gas phase hydrogenation according to claim 1, it is characterized in that: argent content is the 0.5%-35% of vehicle weight, carrier is selected not containing the nanometer grade silica modified silicasol of sodium ion, and its average grain diameter is 1-30nm.
3. the silver catalyst preparation method preparing ethyl glycolate for oxalate gas phase hydrogenation according to claim 1 or claim 2, is characterized in that comprising the following steps:
(1) acetate of containing metal silver, oxalates or nitrate deionized water dissolving are mixed with aqueous solution I, the concentration of solution is 0.001-3.0M;
(2) inorganic ammonia or By Amine Solutions are instilled in the silver salt solution I that step (1) is obtained, obtain silver-colored ammonia complexing solution II;
(3) under stirring, carrier is added in solution II, and stir aging 1-10 hour, by most of inorganic ammonia or organic amine removing at 60-100 DEG C, filter and wash and obtain solids;
(4) the solids dry 2-12 hour at 90-130 DEG C (3) obtained, then obtains catalyst precursor after roasting 2-8 hour at 200-500 DEG C;
(5) be 10-80mL/mingCat with flow, in volumn concentration, hydrogeneous tolerance is the catalyst precursor reduction 1-24 hour that (4) obtain by the nitrogen of 0-100% and the mist of hydrogen at 120-600 DEG C of temperature, just makes the silver catalyst that described oxalate gas phase hydrogenation prepares ethyl glycolate.
4. the preparation method preparing the silver catalyst of ethyl glycolate for oxalate gas phase hydrogenation according to claim 3, it is characterized in that: described in step (2) by inorganic ammonia or By Amine Solutions instillation in the silver salt solution I that step (1) is obtained, in inorganic ammonia or organic amine and solution I, the mol ratio of argent element is 0.1-10:1.
5. the preparation method preparing the silver catalyst of ethyl glycolate for oxalate gas phase hydrogenation according to claim 3, is characterized in that: described inorganic ammonia comprises liquefied ammonia or ammoniacal liquor, and organic amine is urea, monoethyl amine, diethylamine, a propylamine or tert-butylamine.
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Cited By (5)
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|---|---|---|---|---|
| CN105921173A (en) * | 2016-04-21 | 2016-09-07 | 河南大学 | Nano-silver composite textile catalyst and application thereof |
| CN111774050A (en) * | 2020-07-17 | 2020-10-16 | 兰州理工大学 | Preparation method and application of supported catalyst for catalyzing dimethyl oxalate hydrogenation |
| CN112206775A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst and application of prepared catalyst |
| CN113333000A (en) * | 2021-06-11 | 2021-09-03 | 高化学（江苏）化工新材料有限责任公司 | Preparation method and device of catalyst for synthesizing dimethyl carbonate |
| CN114950416A (en) * | 2022-02-25 | 2022-08-30 | 上海应用技术大学 | Catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921173A (en) * | 2016-04-21 | 2016-09-07 | 河南大学 | Nano-silver composite textile catalyst and application thereof |
| CN112206775A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst and application of prepared catalyst |
| CN111774050A (en) * | 2020-07-17 | 2020-10-16 | 兰州理工大学 | Preparation method and application of supported catalyst for catalyzing dimethyl oxalate hydrogenation |
| CN111774050B (en) * | 2020-07-17 | 2023-05-09 | 兰州理工大学 | Preparation method and application of supported catalyst for catalyzing hydrogenation of dimethyl oxalate |
| CN113333000A (en) * | 2021-06-11 | 2021-09-03 | 高化学（江苏）化工新材料有限责任公司 | Preparation method and device of catalyst for synthesizing dimethyl carbonate |
| CN114950416A (en) * | 2022-02-25 | 2022-08-30 | 上海应用技术大学 | Catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate and preparation method and application thereof |
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