CN104923219A - Methyl glycolate catalyst prepared by hydrogenation of oxalate, and preparation method and use thereof - Google Patents
Methyl glycolate catalyst prepared by hydrogenation of oxalate, and preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a methyl glycolate catalyst prepared by hydrogenation of oxalate, and a preparation method and a use thereof, and is used for mainly solving the problems of poor activity of a catalyst and low methyl glycolate selectivity in the prior art. The problems are better solved through adopting the technical schemes that sliver is used as a main active component, palladium, platinum, ruthenium, barium, zinc, copper, calcium, magnesium, nickel, cobalt, manganese, cerium, iron, lanthanum or molybdenum is used as a catalysis assisting component, silica, alumina, zirconia, titania or a silicon aluminum molecular sieve is used as a carrier, the carrier is excessively impregnated with a solution containing the active component silver and an auxiliary agent firstly, and then a depositing agent is used for precipitation and immobilization of the active component silver. The methyl glycolate catalyst can be used in industrial production of oxalate hydrogenation preparation of the methyl glycolate catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of preparing ethanol by oxalate hydrogenation acid esters catalyst, particularly produce the method for preparing catalyst of methyl glycollate about dimethyl oxalate catalytic hydrogenation.
Background technology
Methyl glycollate, due to the molecular structure of its uniqueness, has the chemical property of alcohol and ester concurrently, oxonation, hydrolysis, oxidation reaction etc. can occur, become a kind of important industrial chemicals.Many fields such as chemical industry, medicine, agricultural chemicals, feed, spices and fuel can be widely used in.
Due to methyl glycollate be widely used, market demand is high, also very many to its synthesising process research both at home and abroad, mainly contain glyoxal and methyl alcohol one-step synthesis, formaldehyde carbonylation one Lipase absobed method, ester dimethoxym ethane and formic acid method, coupling method, chloroactic acid method, formaldehyde and hydrogen cyanide addition process, dimethoxym ethane and Formaldehyde Radical addition process, oxalate hydrogenating reduction method, biology enzyme oxidizing process.Although synthetic method is more, all there is larger shortcoming in a lot of technique.
At present production line main abroad adopts formaldehyde to be the carbonylation route of raw material, under about 70.9MPa and high temperature, by formalin with CO under the catalyst action such as the concentrated sulfuric acid or boron trifluoride, first condensation generation glycolic.Again namely glycolic methanol esterification is obtained methyl glycollate.The shortcoming of this method be strong acid catalyst to consersion unit seriously corroded, and be reaction under high pressure, higher to equipment requirement, the disposable input of equipment is comparatively large, cannot large-scale production.The production of domestic methyl glycollate and glycolic mainly adopts chloroactic acid method and formaldehyde and hydrogen cyanide addition process, wherein chloroactic acid method is the process route by monoxone and Ke's property sodium solution hybrid reaction resterification, this chloroacetic production adopts acetic acid to be raw material, sulphur is catalyst, chlorine method is produced, although process is simple, seriously corroded in production process, pollute large, cost is high thus cause this method can not large-scale production.And impurity is more in the methyl glycollate produced of this kind of method, affect its application in fields such as polymerizations.Hydrogen cyanide rule under sulfuric acid catalysis, obtains hydroxyacetonitrile for raw material with formaldehyde and hydrogen cyanide, and be then hydrolyzed, esterification can obtain the methyl glycollate that gross production rate is 80%, and the method is simple, but feed hydrogen cyanic acid toxicity is larger.
20 century 70s; by the impact of world oil crisis; various countries start to carry out a large amount of based on the C1 chemical research of natural gas and coal-based feedstocks one after another; correlation technique also achieves in the nineties in last century and develops fast; to produce in ethylene glycol for raw material with coal or natural gas in research especially and achieve great breakthrough; with CO and this process route of methyl nitrite synthesis of oxalic ester by gaseous catalysis ripe, at present the pilot scale of existing many covers and industrialized unit build up.So exploitation to take oxalate as the method for raw material preparation of ethanol by hydrogenating acid methyl esters significant.
Oxalate catalytic hydrogenation is a cascade reaction, and the first step obtains methyl glycollate, and methyl glycollate further hydrogenation can obtain ethylene glycol, and the high selectivity of the high conversion and ethyl glycolate that how to realize oxalate is the key of this synthetic method.Have document and patent reports with copper the report of the oxalate catalytic hydrogenation synthesizing methyl glycolate catalyst being main active constituent, but the catalyst oxalate conversion ratio of preparation and ethyl glycolate selective on need raising.
Patent CN101138730A discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of glycolate, and this catalyst for main active constituent 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 the 5%-45% of vehicle weight, and 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 is in oxalate and hydrogen synthesizing alcohol acid esters react, and reactivity worth is steady, is easy to control, but dimethyl oxalate conversion ratio lower be 85%, selective is 83%.
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 constituent, silver and manganese are for helping active constituent, A1203 is 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%, A1203 content of catalyst quality 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 can reach 98%, but the selective of methyl glycollate only has 75%.
Patent CN101816934 discloses a kind of dimethyl oxalate gas phase continuous catalytic hydrogenation and prepares silver-colored silicon oxide catalyst of methyl glycollate and ethylene glycol and preparation method thereof.The preparation process of described catalyst is: soluble silver salt is made into silver ammino solution, and adds polyethylene pyrrole network alkane ketone as protective agent and structure directing agent: add reducing agent under stirring, control reaction temperature is 20-90 DEG C; Add positive silicic acid second vinegar again, stir 1 ~ 24 hour, be warming up to 60 ~ 90 DEG C, and to control reaction end pH value be 6-10; Finally wash, dry and roasting 1 ~ 24 hour at 100 ~ 900 DEG C.The catalyst prepared prepares methyl glycollate and ethylene glycol for dimethyl oxalate gas phase continuous catalytic hydrogenation, and methyl glycollate yield can reach 95%.But ethyl orthosilicate must be used in this catalyst preparing as catalyst carrier, and adopt business Si0
2the conventional Ag/Si0 of preparation
2catalyst does not then almost have catalytic activity, and large-scale industrial production is more difficult in this way in institute.
Summary of the invention
One of technical problem to be solved by this invention there is poor catalyst activity and the selective low technical problem of methyl glycollate in prior art, provides the catalyst of a kind of new preparing ethanol by oxalate hydrogenation acid methyl esters.Two of technical problem to be solved by this invention is to provide a kind of new preparing ethanol by oxalate hydrogenation acid methyl esters method for preparing catalyst.It is active good that the preparing ethanol by oxalate hydrogenation acid methyl esters catalyst adopting the method to prepare has, selective high feature.Three of technical problem to be solved by this invention is to provide the method for a kind of catalyst corresponding with one of technical solution problem for preparing ethanol by oxalate hydrogenation acid methyl esters.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst of preparing ethanol by oxalate hydrogenation acid methyl esters, with weight parts, comprises following component:
A) 0.5 ~ 30 part is selected from least one active constituent in the oxide of silver or silver;
B) 0 ~ 10 part is selected from least one metal in palladium, platinum, ruthenium, barium, zinc, copper, calcium, magnesium, nickel, cobalt, manganese, cerium, iron, lanthanum or molybdenum or oxides additive;
C) 70 ~ 99 parts are selected from least one carrier in silica, aluminium oxide, zirconia, titanium oxide, Si-Al molecular sieve.
In technique scheme, weight parts, component consumption a) is preferably 2 ~ 20 parts, component b) consumption be preferably 0.05 ~ 7 part, component c) consumption be preferably 73 ~ 97.9 parts.
In technique scheme, component c) be preferably silica and the mixture being selected from least one in aluminium oxide, zirconia or titanium oxide, wherein silica is preferably (100 ~ 5) with the mass ratio being selected from least one in aluminium oxide, zirconia or titanium oxide: 1.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of a kind of preparing ethanol by oxalate hydrogenation acid methyl esters catalyst, comprises the following steps:
A) soluble-salt of active constituent silver and the soluble-salt of auxiliary agent are made into mixed solution I;
B) under stirring, carrier is joined in solution I, obtain slurry II;
C) at least one be selected from carbonate, bicarbonate, alkali-metal hydroxide or inorganic ammoniacal liquor is mixed with solution III and makes precipitating reagent;
D) mixed with slurry II by solution III, the pH value of precipitation reaction terminal is 5.6 ~ 12, obtains slurry IV;
E) slurry IV filtered after ageing at 30 ~ 150 DEG C, wash, obtain filter cake;
F) by filter cake 60 ~ 130 DEG C of oven dry, 300 ~ 600 DEG C of roastings obtain the catalyst of preparing ethanol by oxalate hydrogenation acid methyl esters.
In technique scheme, the soluble-salt of active constituent silver is preferably selected from least one in silver nitrate, ester acid silver or silver oxalate; The soluble-salt of auxiliary agent is preferably selected from least one soluble-salt in palladium, platinum, ruthenium, barium, zinc, copper, calcium, magnesium, nickel, cobalt, manganese, cerium, iron, lanthanum or molybdenum; The soluble-salt concentration of active constituent silver is preferably 0.01 ~ 0.66 mol/L, and the soluble-salt concentration of auxiliary agent is preferably 0.001 ~ 0.18 mol/L.
In technique scheme, the carbonate in precipitating reagent or bicarbonate are preferably selected from least one in the carbonate of alkali metal or alkaline-earth metal or bicarbonate; Alkali-metal hydroxide is preferably selected from least one in NaOH or potassium hydroxide; Inorganic ammonia is preferably selected from least one in liquefied ammonia or ammoniacal liquor.
In technique scheme, in step d), the pH value of precipitation reaction terminal is preferably 6 ~ 11, and in step e), the Aging Temperature of slurry IV is preferably 50 ~ 115 DEG C, and digestion time is preferably 3 ~ 48 hours.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: a kind of method of preparing ethanol by oxalate hydrogenation acid methyl esters, with dimethyl oxalate and hydrogen for raw material, it is 180 ~ 230 DEG C in reaction temperature, reaction pressure is 2.0 ~ 3.5MPa, and dimethyl oxalate weight space velocity is 0.1 ~ 1.5 hour
-1, hydrogen and dimethyl oxalate mol ratio are (50 ~ 140): react with catalyst exposure under 1 condition, generate the effluent containing methyl glycollate; Used catalyst, with weight parts, comprises following component:
A) 0.5 ~ 30 part is selected from least one active constituent in the oxide of silver or silver;
B) 0 ~ 10 part is selected from least one metal in palladium, platinum, ruthenium, barium, zinc, copper, calcium, magnesium, nickel, cobalt, manganese, cerium, iron, lanthanum or molybdenum or oxides additive;
C) 70 ~ 99 parts are selected from least one carrier in silica, aluminium oxide, zirconia, titanium oxide, Si-Al molecular sieve.
In technique scheme, reaction temperature is preferably 185 ~ 215 DEG C, and reaction pressure is preferably 2.5 ~ 3MPa, and dimethyl oxalate weight space velocity is preferably 0.3 ~ 1.2 hour
-1, hydrogen and dimethyl oxalate mol ratio are preferably (60 ~ 100): 1.
Oxalate hydrogenation is the reaction of a series connection, and target product methyl glycollate is an intermediate product in this cascade reaction, if reaction can generating glycol and ethanol further.So catalyst needs to take into account high activity, improve oxalate conversion ratio, need again to control reactions steps and rest on methyl glycollate as much as possible, down do not react further.The present invention's silver is that main active constituent substitutes traditional copper catalyst, solves the selective low shortcoming of catalyst methyl glycollate in the past.And by auxiliary agent with activity silver synergy is first excessive is impregnated on carrier, then with precipitating reagent, the uniformity of silver on carrier and dispersiveness are effectively improved to its precipitation, fixing method, adopt common commercial carrier just to obtain the catalyst with greater activity.
Adopting the oxalate hydrogenation catalyst prepared of the present invention, in the reaction of oxalate and hydrogen synthesizing methyl glycolate, take dimethyl oxalate as raw material, reaction temperature 180 ~ 230 DEG C, and weight space velocity 0.1 ~ 1.5 hour
-1, hydrogen ester is than being (50 ~ 140): 1, and reaction pressure is under the condition of 2.0 ~ 3.0MPa, and the conversion ratio of oxalate reaches 95%, and the selective of methyl glycollate reaches 90%, obtains good technique effect.
Below by embodiment and comparative example, the present invention is further elaborated, but be not limited only to the present embodiment.
Detailed description of the invention
[embodiment 1]
Using 0.5 liter of solution containing 0.26 mol/L silver nitrate as solution I, under stirring, 80 grams of silica are joined in solution I and obtain slurry II, again the sodium carbonate of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 7,60 DEG C of ageings 30 hours, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 500 DEG C of roastings 5 hours, the catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 12.6 parts of silver, 2.64 parts of silver oxides and 84.76 parts of silica.
[embodiment 2]
Using 0.5 liter of solution containing 0.03 mol/L silver nitrate, 0.0012 mol/L palladium nitrate as solution I, under stirring, 80g aluminium oxide is joined in solution I and obtain slurry II, again the NaOH of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 8,60 DEG C of ageings 1 hour, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 300 DEG C of roastings 5 hours, the catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 1.56 parts of silver+0.44 part of silver oxide+0.05 part of palladium oxide+97.95 parts of aluminium oxide.
[embodiment 3]
Using 0.5 liter of solution containing 0.031 mol/L silver nitrate, 0.023 mol/L ammonium molybdate as solution I, under stirring, 78g silica and 2g aluminium oxide are joined in solution I and obtain slurry II, again the sodium carbonate of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 8,70 DEG C of ageings 3 hours, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 300 DEG C of roastings 5 hours, the catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 1.43 parts of silver, 0.57 part of silver oxide, 2 parts of molybdenum oxides and 94.1 parts of silica, 1.9 parts of aluminium oxide.
[embodiment 4]
Using 0.5 liter of solution containing 0.01 mol/L silver nitrate, 0.16 mol/L copper nitrate as solution I, under stirring, 79.2g silica and 0.8g zirconia are joined in solution I and obtain slurry II, again the ammoniacal liquor of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 7,115 DEG C of ageings 20 hours, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 400 DEG C of roastings 5 hours, the catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 0.5 part of silver, 7 parts of cupric oxide and 92 parts of silica and 0.5 part of zirconium dioxide.
[embodiment 5]
Using 0.5 liter of solution containing 0.062 mol/L silver nitrate, 0.0012 mol/L nitric acid ruthenium as solution I, under stirring, 76.2g silica and 3.8g titanium oxide are joined in solution I and obtain slurry II, again the carbonic hydroammonium of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 11,50 DEG C of ageings 48 hours, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 400 DEG C of roastings 5 hours, the catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 2.98 parts of silver, 1.02 parts of silver oxides, 0.05 ruthenium-oxide and 92.3 parts of silica, 4.65 parts of titanium oxide.
[embodiment 6]
Using 0.5 liter of solution containing 0.129 mol/L silver nitrate, 0.012 mol/L barium nitrate as solution I, under stirring, 72.7g silica and 7.3g aluminium oxide are joined in solution I and obtain slurry II, again the ammonium carbonate of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 6,95 DEG C of ageings 24 hours, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 600 DEG C of roastings 5 hours, the catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 5.87 parts of silver, 2.13 parts of silver oxides, 1 part of barium monoxide and 82.7 parts of silica, 8.3 parts of aluminium oxide.
[embodiment 7]
Using 0.5 liter of solution containing 0.27 mol/L silver nitrate, 0.02 mol/L ammonium molybdate as solution I, under stirring, 66.7g silica and 13.7g titanium oxide are joined in solution I and obtain slurry II, again the ammoniacal liquor of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 9,80 DEG C of ageings 20 hours, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 500 DEG C of roastings 5 hours, the catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 8.14 parts of silver, 6.86 parts of silver oxides, 1.5 parts of lanthanas and 69.6 parts of silica, 13.9 parts of titanium oxide.
[embodiment 8]
Using 0.5 liter of solution containing 0.66 mol/L silver oxalate, 0.133 mol/L nickel nitrate as solution I, under stirring, 80g silica is joined in solution I and obtain slurry II, again the potassium hydroxide of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 8,30 DEG C of ageings 24 hours, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 550 DEG C of roastings 5 hours, the catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 19.05 parts of silver, 10.95 parts of silver oxides, 4 parts of nickel oxide and 66 parts of silica.
[embodiment 9]
Using 0.5 liter of solution containing 0.13 mol/L silver acetate, 0.013 mol/L cobalt acetate as solution I, under stirring, 70g silica and 10g aluminium oxide are joined in solution I and obtain slurry II, again the carbonic hydroammonium of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 6,70 DEG C of ageings 15 hours, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 400 DEG C of roastings 5 hours, the catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 5.66 parts of silver, 2.34 parts of silver oxides, 0.5 cobalt oxide and 80 parts of silica, 10.4 parts of aluminium oxide.
[embodiment 10]
Using 0.5 liter of solution containing 0.132 mol/L silver nitrate, 0.032 mol/L cerous nitrate as solution I, under stirring, 80g silica is joined in solution I and obtain slurry II, again the sodium carbonate of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 7,85 DEG C of ageings 4 hours, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 350 DEG C of roastings 5 hours, the catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 5.2 parts of silver, 2.8 parts of silver oxides, 3 parts of cerium oxide and 89 parts of silica.
[embodiment 11]
Using 0.5 liter of solution containing 0.13 mol/L silver acetate, 0.001 mol/L palladium nitrate, 0.05 mol/L nickel nitrate as solution I, under stirring, 80gZSM-5 molecular sieve is joined in solution I and obtain slurry II, again the carbonic hydroammonium of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 8,65 DEG C of ageings 3 hours, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 450 DEG C of roastings 5 hours, the catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 5.33 parts of silver, 2.67 parts of silver oxides, 0.05 part of palladium oxide, 2 parts of nickel oxide and 89.95 parts of molecular sieves.
[comparative example 1]
According to the preparation method of embodiment 3, the content just changing silver nitrate in solution 1 contains the solution of 0.005 mol/L silver nitrate and 0.023 mol/L ammonium molybdate as solution I by 0.5L, under stirring, 78g silica and 2g aluminium oxide are joined in solution I and obtain slurry II, again the sodium carbonate of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 7, 60 DEG C of ageings 10 hours, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 500 DEG C of roastings 5 hours, catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 0.3 part of silver, 2 parts of molybdenum oxides and 95.8 parts of silica, 2.4 parts of aluminium oxide.
[comparative example 2]
According to the preparation method of embodiment 3, the content just changing silver nitrate in solution 1 contains the solution of 0.82 mol/L silver nitrate and 0.023 mol/L ammonium molybdate as solution I by 0.5L, under stirring, 78g silica and 2g aluminium oxide are joined in solution I and obtain slurry II, again the sodium carbonate of 3 mol/L is joined in slurry II as precipitating reagent, controlling terminal pH is 7, 60 DEG C of ageings 10 hours, then slip after filtration, washing, the filter cake obtained 80 ~ 120 DEG C is dried 10 hours, 500 DEG C of roastings 5 hours, catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 14.8 parts of silver, 20.2 parts of silver oxides, 1.5 parts of molybdenum oxides and 61.9 parts of silica, 1.6 parts of aluminium oxide.
[comparative example 3]
0.5 liter of solution containing 0.26 mol/L silver nitrate is prepared according to embodiment 1; by the method for patent CN101816934, soluble silver salt is made into silver ammino solution again; and add polyethylene pyrrole network alkane ketone as protective agent and structure directing agent; reducing agent is added under stirring; control reaction temperature is 20-90 DEG C; add general silica again; stir 10 hours; be warming up to 60 ~ 90 DEG C; and to control reaction end pH value be 7; finally wash, dry and under 500 degree roast 5 hours, the catalyst tablet forming after roasting is catalyst.Through X-fluorometric investigation, it consists of: 12.6 parts of silver, 2.64 parts of silver oxides and 84.76 parts of silica.
[comparative example 4]
In preparation process, active constituent, auxiliary agent component content carrier are with [embodiment 1], and just the pH value of precipitation reaction terminal is 5.Through X-fluorometric investigation, it consists of: 8.4 parts of silver, 1.79 parts of silver oxides and 89.91 parts of silica.
[comparative example 5]
In preparation process, active constituent, auxiliary agent component content carrier are with [embodiment 1], just do not have aging step.Through X-fluorometric investigation, it consists of: 11.5 parts of silver, 3.74 parts of silver oxides and 84.86 parts of silica.
[comparative example 6]
In preparation process, active constituent, auxiliary agent component content carrier are with [embodiment 1], and just sintering temperature changes 700 DEG C into.Through X-fluorometric investigation, it consists of: 13.5 parts of silver, 1.59 parts of silver oxides and 84.91 parts of silica.
[embodiment 13]
The present embodiment illustrates the application of embodiment 1 ~ 12 gained catalyst in the reaction of preparing ethanol by oxalate hydrogenation acid methyl esters.
Get the embodiment of the present invention 1 ~ 12 gained catalyst and carry out reaction examination.With dimethyl oxalate and hydrogen for raw material, reaction temperature 205 DEG C, weight space velocity 1 hour
-1, hydrogen ester is than being 80:1, and reaction pressure is check and rate catalyst under the condition of 0.28MPa.Catalyst is before examination, and passing into hydrogen at volume space velocity is 1500 hours
-1temperature programming to 300 DEG C is reduced.Reaction result is in table 1.
[comparative example 7]
Get comparative example 1 ~ 6 gained catalyst and carry out reaction examination, adopt reducing condition, raw material and the reaction condition identical with embodiment 13.Reaction result is in table 1.
Table 1
As can be seen from test result, the preparing ethanol by oxalate hydrogenation acid methyl esters catalyst activity and selectivity prepared by the inventive method is all apparently higher than reference sample.Show that catalyst prepared by the inventive method has significantly progressive and advantage.
[embodiment 14]
The present embodiment illustrates that embodiment 1 gained catalyst changes the result of the test of process conditions in the reaction of preparing ethanol by oxalate hydrogenation acid methyl esters.
Get the embodiment of the present invention 1 gained catalyst and carry out reaction examination, change process conditions and test, reaction condition and the results are shown in Table 2.
Table 2
Claims (10)
1. a catalyst for preparing ethanol by oxalate hydrogenation acid methyl esters, with weight parts, comprises following component:
A) 0.5 ~ 30 part is selected from least one active constituent in the oxide of silver or silver;
B) 0 ~ 10 part is selected from least one metal in palladium, platinum, ruthenium, barium, zinc, copper, calcium, magnesium, nickel, cobalt, manganese, cerium, iron, lanthanum or molybdenum or oxides additive;
C) 70 ~ 99 parts are selected from least one carrier in silica, aluminium oxide, zirconia, titanium oxide, Si-Al molecular sieve.
2. according to claim 1 preparing ethanol by oxalate hydrogenation acid methyl esters catalyst, it is characterized in that with weight parts, component consumption a) is 2 ~ 20 parts, component b) consumption be 0.05 ~ 7 part, component c) consumption be 73 ~ 97.9 parts.
3. according to claim 1 preparing ethanol by oxalate hydrogenation acid methyl esters catalyst, it is characterized in that component c) be silica and the mixture being selected from least one in aluminium oxide, zirconia or titanium oxide, wherein silica and the mass ratio that is selected from least one in aluminium oxide, zirconia or titanium oxide are 100 ~ 5:1.
4. a preparation method for preparing ethanol by oxalate hydrogenation acid methyl esters catalyst, comprises the following steps:
A) soluble-salt of active constituent silver and the soluble-salt of auxiliary agent are made into mixed solution I;
B) under stirring, carrier is joined in solution I, obtain slurry II;
C) at least one be selected from carbonate, bicarbonate, alkali-metal hydroxide or inorganic ammoniacal liquor is mixed with solution III and makes precipitating reagent;
D) mixed with slurry II by solution III, the pH value of precipitation reaction terminal is 5.6 ~ 12, obtains slurry IV;
E) slurry IV filtered after ageing at 30 ~ 150 DEG C, wash, obtain filter cake;
F) by filter cake 60 ~ 130 DEG C of oven dry, 300 ~ 600 DEG C of roastings obtain the catalyst of preparing ethanol by oxalate hydrogenation acid methyl esters.
5. the preparation method of preparing ethanol by oxalate hydrogenation acid methyl esters catalyst according to claim 4, is characterized in that the soluble-salt of active constituent silver is selected from least one in silver nitrate, ester acid silver or silver oxalate; The soluble-salt of auxiliary agent is selected from least one soluble-salt in palladium, platinum, ruthenium, barium, zinc, copper, calcium, magnesium, nickel, cobalt, manganese, cerium, iron, lanthanum or molybdenum.
6. the preparation method of preparing ethanol by oxalate hydrogenation acid methyl esters catalyst according to claim 4, it is characterized in that the soluble-salt concentration of active constituent silver is 0.01 ~ 0.66 mol/L, the soluble-salt concentration of auxiliary agent is 0.001 ~ 0.18 mol/L.
7. the preparation method of preparing ethanol by oxalate hydrogenation acid methyl esters catalyst according to claim 4, is characterized in that carbonate in precipitating reagent or bicarbonate are selected from least one in the carbonate of alkali metal or alkaline-earth metal or bicarbonate; Alkali-metal hydroxide is selected from least one in NaOH or potassium hydroxide; Inorganic ammonia is selected from least one in liquefied ammonia or ammoniacal liquor.
8. the preparation method of preparing ethanol by oxalate hydrogenation acid methyl esters catalyst according to claim 4, it is characterized in that the pH value of precipitation reaction terminal in step d) is 6 ~ 11, in step e), the Aging Temperature of slurry IV is 50 ~ 115 DEG C, and digestion time is 3 ~ 48 hours.
9. a method for preparing ethanol by oxalate hydrogenation acid methyl esters, with dimethyl oxalate and hydrogen for raw material, be 180 ~ 230 DEG C in reaction temperature, reaction pressure is 2.0 ~ 3.5MPa, and dimethyl oxalate weight space velocity is 0.1 ~ 1.5 hour
-1, hydrogen and dimethyl oxalate mol ratio are (50 ~ 140): react with catalyst exposure under the condition of 1, generate the effluent containing methyl glycollate; Used catalyst, with weight parts, comprises following component:
A) 0.5 ~ 30 part is selected from least one active constituent in the oxide of silver or silver;
B) 0 ~ 10 part is selected from least one metal in palladium, platinum, ruthenium, barium, zinc, copper, calcium, magnesium, nickel, cobalt, manganese, cerium, iron, lanthanum or molybdenum or oxides additive;
C) 70 ~ 99 parts are selected from least one carrier in silica, aluminium oxide, zirconia, titanium oxide, Si-Al molecular sieve.
10. according to claim 9 preparing ethanol by oxalate hydrogenation acid methyl esters method, it is characterized in that reaction temperature is 185 ~ 215 DEG C, reaction pressure is 2.5 ~ 3MPa, and dimethyl oxalate weight space velocity is 0.3 ~ 1.2 hour
-1, hydrogen and dimethyl oxalate mol ratio are (60 ~ 100): 1.
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| CN (1) | CN104923219A (en) |
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| CN107442113A (en) * | 2017-06-30 | 2017-12-08 | 天津大学 | The multi-stage porous nanometer flower structure Ag catalyst of preparing ethanol by oxalate hydrogenation acid methyl esters |
| CN108690648A (en) * | 2017-04-11 | 2018-10-23 | 中国人民大学 | A kind of titanium dichloride load copper zinc Complex denitrogenation agent and the preparation method and application thereof |
| CN109678658A (en) * | 2019-01-15 | 2019-04-26 | 中国科学技术大学 | Fatty acid and/or aliphatic ester catalytic hydrodeoxygenation prepare the method with carbon number fatty alcohol |
| CN110142048A (en) * | 2019-06-11 | 2019-08-20 | 宁波中科远东催化工程技术有限公司 | A kind of silver-bearing copper catalyst for Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and preparation method thereof and application method |
| CN110856817A (en) * | 2018-08-22 | 2020-03-03 | 上海浦景化工技术股份有限公司 | Catalyst for producing methyl glycolate and preparation method and application thereof |
| CN111437828A (en) * | 2020-03-25 | 2020-07-24 | 中国科学院福建物质结构研究所 | Silver-based catalyst for synthesizing methyl glycolate and preparation method thereof |
| CN112209831A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester |
| CN112206772A (en) * | 2020-10-15 | 2021-01-12 | 江苏金聚合金材料有限公司 | Preparation and application of catalyst for synthesizing methyl glycolate |
| CN112209832A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for synthesizing glycolate from oxalate |
| 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 |
| CN112206774A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN113368867A (en) * | 2021-06-24 | 2021-09-10 | 新疆至臻化工工程研究中心有限公司 | Catalyst for ultrasonic-assisted synthesis of methyl glycolate and preparation method thereof |
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| CN105457631A (en) * | 2015-12-16 | 2016-04-06 | 西南化工研究设计院有限公司 | Catalyst for preparing ethyl alcohol acid ester through oxalic ester gas phase hydrogenation and preparation method |
| CN108690648A (en) * | 2017-04-11 | 2018-10-23 | 中国人民大学 | A kind of titanium dichloride load copper zinc Complex denitrogenation agent and the preparation method and application thereof |
| CN108690648B (en) * | 2017-04-11 | 2020-08-04 | 中国人民大学 | Titanium dioxide loaded copper-zinc complex denitrifier and preparation method and application thereof |
| CN107442113A (en) * | 2017-06-30 | 2017-12-08 | 天津大学 | The multi-stage porous nanometer flower structure Ag catalyst of preparing ethanol by oxalate hydrogenation acid methyl esters |
| AU2019323492B2 (en) * | 2018-08-22 | 2022-03-31 | Pujing Chemical Industry Co., Ltd | Catalyst used for producing methyl glycolate and preparation method and application thereof |
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| CN109678658B (en) * | 2019-01-15 | 2020-08-25 | 中国科学技术大学 | Method for preparing fatty alcohol with same carbon number by catalytic hydrodeoxygenation of fatty acid and/or fatty acid ester |
| CN110142048A (en) * | 2019-06-11 | 2019-08-20 | 宁波中科远东催化工程技术有限公司 | A kind of silver-bearing copper catalyst for Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and preparation method thereof and application method |
| CN112209831A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for producing glycolic acid ester |
| CN112209832A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Method for synthesizing glycolate from oxalate |
| 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 |
| CN112206774A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN112209832B (en) * | 2019-07-12 | 2023-08-04 | 中国石油化工股份有限公司 | Method for synthesizing glycollate from oxalate |
| CN112209831B (en) * | 2019-07-12 | 2023-05-02 | 中国石油化工股份有限公司 | Method for producing glycolate |
| CN111437828A (en) * | 2020-03-25 | 2020-07-24 | 中国科学院福建物质结构研究所 | Silver-based catalyst for synthesizing methyl glycolate and preparation method thereof |
| CN111437828B (en) * | 2020-03-25 | 2022-10-14 | 中国科学院福建物质结构研究所 | Silver-based catalyst for synthesizing methyl glycolate and preparation method thereof |
| CN112206772A (en) * | 2020-10-15 | 2021-01-12 | 江苏金聚合金材料有限公司 | Preparation and application of catalyst for synthesizing methyl glycolate |
| CN113398983A (en) * | 2021-06-15 | 2021-09-17 | 中石化南京化工研究院有限公司 | Catalyst for preparing methyl glycolate by dimethyl oxalate hydrogenation and preparation method thereof |
| CN113368867A (en) * | 2021-06-24 | 2021-09-10 | 新疆至臻化工工程研究中心有限公司 | Catalyst for ultrasonic-assisted synthesis of methyl glycolate and preparation method thereof |
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