CN105396584A - Oxalate catalyst synthesized through CO coupling, preparation method and purpose of oxalate catalyst - Google Patents
Oxalate catalyst synthesized through CO coupling, preparation method and purpose of oxalate catalyst Download PDFInfo
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Abstract
Disclosed are an oxalate catalyst synthesized through CO coupling, a preparation method, and a purpose of the oxalate catalyst. The invention relates to the oxalate catalyst prepared from CO through gas-phase synthesis, and mainly solves the technical problem that a catalyst in the prior art is low in activity and is low in nitrite conversion rate and oxalate space-time yield during gas-phase synthesis of oxalate from CO. The oxalate catalyst comprises the following components, by weight: 1) 0.05-2.5 wt% of palladium, 2) 0.06-3 wt% of a lanthanide metal or an oxide of the lanthanide metal, and 3) 94.5-99.8 wt% of a carrier, which is selected from at least one of alumina, silica, or a molecular sieve. The technical scheme that palladium in the catalyst has a ratio of bridge-type CO adsorption to linear CO adsorption being 0.8-4.5 preferably solves the problem. The preparation method can be used in industrial production of oxalate from CO through gas-phase synthesis.
Description
Technical field
The present invention relates to a kind of catalyst for carbon monoxide vapor-phase synthesis oxalate, especially for the catalyst of carbon monoxide vapor-phase synthesis dimethyl oxalate or diethy-aceto oxalate.
Background technology
Oxalate is a kind of important Organic Chemicals, prepares various dyestuff, medicine, solvent, extractant and various intermediate in a large number for fine chemistry industry.In addition, oxalate hydrogenation can prepare very important industrial chemicals ethylene glycol, and this route can replace the method that the higher petroleum path of current cost produces ethylene glycol.
Traditional oxalate production line has starch nitric acid oxidation method, cellulose alkali fusion, sodium formate method, ethylene glycol one-step oxidation process, oxidation of propylene and oxalic acid alcohol esterification reaction method, but above-mentioned traditional handicraft exists that cost is high, energy consumption is large, seriously polluted, raw material utilizes the shortcomings such as unreasonable.So the process route of a cost low environment close friend must be found.Nineteen sixty-five American Association oil company has found that carbon monoxide, alcohol and oxygen can direct synthesis of oxalate under palladium chtalyst effect, company of Ube Industries Ltd. and ARCO company of the U.S. have carried out research and development in succession in this field since then, within 1977, Ube Industries Ltd. just proposes normal pressure gas-phase synthesis of oxalate technology, take Pd/A12O3 as catalyst, temperature 80 ~ 150 DEG C, under pressure 0.5MPa condition, the yield 98% of dimethyl oxalate.Nitrogen oxide in methyl alcohol and tail gas at high temperature uses dioxygen oxidation, and synthesis methyl nitrite recycles.
China is a coal resources relative abundance, and carbon monoxide source is sufficient, and utilizing the route of carbon monoxide gas phase coupling synthesis of oxalate repeated hydrogenation preparing ethylene glycol to tally with the national condition, is an economically viable technology path.So domestic many enterprises and research institution have done a large amount of work to this field.Such as, patent 200810035248.6 discloses a kind of Catalysts and its preparation method for oxalate synthesis and application, described catalyst take Alpha-alumina as carrier, comprise the active constituent Pd of 0.01 ~ 1wt%, the auxiliary agent Ir of 0.01 ~ 0.5wt%, this catalyst oxalate space-time yield is 750g/L.cat.Patent CN200710061392 discloses the Catalysts and its preparation method of CO low-voltage gas-phase synthesizing of oxalic ester, this catalyst with Metal Palladium for main active constituent, with titanium and cerium for co-catalyst, its carrier is the Alpha-alumina of modification is carrier, and the space-time yield of this catalyst dimethyl oxalate is 700g/L.cat.H.But the improvement aspect that mostly concentrates on catalyst formulation and carrier structure is reported in such research, the space-time yield that institute develops catalyst oxalate also need raising.
Because CO catalyst for synthesizing oxalic ester by gas-phase is a structure sensitive catalyst, the height of this catalyst activity is not only relevant with catalyst formulation, carrier structure, relevant to the suction type of raw material carbon monoxide also with activity over catalysts component palladium, improves the bridged adsorption intensity of active component palladium to carbon monoxide in catalyst and is conducive to improving the conversion ratio of nitrites and the space-time yield of oxalate.
Summary of the invention
Technical problem to be solved by this invention is that to there is catalyst activity in prior art low, and in carbon monoxide vapor-phase synthesis oxalate process, nitrites conversion ratio and the low problem of oxalate space-time yield, provide a kind of new CO coupling catalyst for synthesizing oxalic ester.Two of technical problem to be solved by this invention is to provide a kind of preparation method of new CO coupling catalyst for synthesizing oxalic ester, adopts the catalyst prepared of the method in CO coupling synthesis of oxalate process, have methyl nitrite conversion ratio and the high feature of oxalate space-time yield.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 CO coupling synthesis of oxalate.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of for CO coupling catalyst for synthesizing oxalic ester, by weight percentage, comprises following component: 1) 0.05 ~ 2.5wt% palladium; 2) 0.06 ~ 3wt% lanthanide series metal or its oxide; 3) 94.5 ~ 99.8wt% carrier, at least one in support selected from alumina, silica or molecular sieve; Wherein, palladium bridged adsorption carbon monoxide and line formula sorbing carbon monoxide ratio are 0.8 ~ 4.5.
In technique scheme, by weight percentage, component 2) content be preferably 0.1 ~ 2wt%.
In technique scheme, in catalyst, palladium bridged adsorption carbon monoxide and line formula sorbing carbon monoxide ratio are preferably 1 ~ 4.5, are more preferably 1.5 ~ 4.5.
In technique scheme, in catalyst, the average grain diameter of palladium crystal grain is 3 ~ 21 nanometers, is preferably 3 ~ 12.
For solve the problems of the technologies described above two, the preparation method of catalyst described in the present invention, mainly comprises the following steps:
Comprise the following steps:
A) soluble-salt of active constituent palladium and auxiliary agent is dissolved in the water containing anion surfactant, to be dissolved complete after adjustment pH value of solution be 1.5 ~ 6.5, obtain maceration extract I;
B) maceration extract I flooded or be sprayed at carrier, obtaining catalyst precarsor;
C) by catalyst precarsor aging, oven dry in atmosphere, roasting, reduction, required catalyst is obtained.
In the water of anion surfactant described in technique scheme, content is preferably 0.02 ~ 0.6wt%.
PH described in technique scheme is 3 ~ 6
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 carbon monoxide vapor-phase synthesis oxalate, reaction temperature 110 ~ 170 DEG C, and reaction pressure 0 ~ 1MPa, the mol ratio of raw material carbon monoxide and nitrites is 1 ~ 4, and volume space velocity is 800 ~ 4000h
-1react with catalyst exposure described in technique scheme under condition, generate the effluent containing oxalate.
Active constituent palladium in palladium catalyst can be divided into two kinds of modes to the absorption of carbon monoxide, and one is bridged adsorption, and another kind of is the absorption of line formula.And in the reaction of carbon monoxide vapor-phase synthesis producing oxalic ester, the carbon monoxide only existed in bridged adsorption mode could participate in reaction, with methyl nitrite oxalic ester.So when ensureing that in catalyst, active constituent palladium reaches certain decentralization, the ratio improving palladium bridged adsorption carbon monoxide in catalyst is conducive to improving the conversion ratio of nitrites and the space-time yield of oxalate.
The present invention effectively regulates the decentralization of palladium in catalyst and the suction type to carbon monoxide by the method for adding anion surfactant and adjust ph in maceration extract, Gu compared with prior art, catalyst metals palladium good dispersion of the present invention, and the bridged adsorption ratio of palladium to carbon monoxide is high, be conducive to the utilization rate and the catalytic activity that improve active constituent palladium in catalyst.Adopt the inventive method, nitrites conversion ratio can reach 89%, and oxalate space-time yield can reach 1150g/L.H
-1, achieve good technique effect.
In the inventive method, adopt following method of testing:
1) catalytic component is measured by ICP.
2) palladium crystal grain average grain diameter: the particle diameter of palladium crystal grain is recorded by x-ray diffractometer (XRD).
3) palladium measures carbon monoxide adsorbs: powder catalyst being ground to form below 500 orders, gets the good thin slice of light transmission that 20mg is pressed into diameter 12mm, thickness 0.1mm, is placed in In-situ Infrared pond.First with hydrogen 200 degree of reductase 12s hour, by sample cell pumping high vacuum after reduction terminates, then pass into CO gas, make Catalyst Adsorption saturated, utilize infrared test instrument to measure in catalyst palladium to carbon monoxide bridge-type and line formula adsorption peak intensity.
Below by concrete embodiment, the invention will be further described.
Detailed description of the invention
[embodiment 1]
Get 60g alumina support.Get 0.3g palladium bichloride and 0.12g lanthanum nitrate and be dissolved in 30ml containing in the deionized water of 0.1% aliphatic alcohol polyoxyvinethene phosphate, add after dissolving and regulate pH 4.0 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-1A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 2]
Get 60g alumina support.Get 0.3g palladium bichloride and 1g lanthanum nitrate and be dissolved in 30ml containing in the deionized water of 0.1% aliphatic alcohol polyoxyvinethene phosphate, add after dissolving and regulate pH 4.0 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-2A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 3]
Get 60g alumina support.Get 0.3g palladium bichloride and 0.56g lanthanum nitrate and be dissolved in 30ml containing in the deionized water of 0.1% aliphatic alcohol polyoxyvinethene phosphate, add after dissolving and regulate pH 4.0 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-3A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 4]
Get 60g silica support.Get 0.05g palladium bichloride and 3.7g cerous nitrate and be dissolved in 45ml containing in the deionized water of 0.1% aliphatic alcohol polyoxyvinethene phosphate, add after dissolving and regulate pH 4.0 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-4A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 5]
Get 60g4A type molecular sieve carrier.Get 0.1g palladium bichloride and 1.3g samaric nitrate and be dissolved in 35ml containing in the deionized water of 0.1% NaLS, add after dissolving and regulate pH 4.0 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-5A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 6]
Get 60gZSM-5 molecular sieve carrier.Get 2.5g palladium bichloride, 0.42g praseodymium nitrate and 0.67g sodium nitrate and be dissolved in 35ml containing in the deionized water of 0.1% aliphatic alcohol polyoxyvinethene phosphate, add after dissolving and regulate pH 4.0 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-6A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 7]
Get 60g alumina support.Get 1g palladium bichloride and 0.19g neodymium nitrate and be dissolved in 30ml containing in the deionized water of 0.1% neopelex, add after dissolving and regulate pH 4.0 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-7A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 8]
Get 60g silica support.Get 2.5g palladium bichloride and 1.1g lanthanum nitrate and be dissolved in 45ml containing in the deionized water of 0.1% odium stearate, add after dissolving and regulate pH 4.0 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-8A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 9]
Get 60g alumina support.Get 0.3g palladium bichloride and 1g lanthanum nitrate and be dissolved in 30ml containing in the deionized water of 0.1% aliphatic alcohol polyoxyvinethene phosphate, add after dissolving and regulate pH 1.5 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-10A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 10]
Get 60g alumina support.Get 0.3g palladium bichloride and 1g lanthanum nitrate and be dissolved in 30ml containing in the deionized water of 0.1% aliphatic alcohol polyoxyvinethene phosphate, add after dissolving and regulate pH 6.5 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-10A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 11]
Get 60g alumina support.Get 0.3g palladium bichloride and 1g lanthanum nitrate and be dissolved in 30ml containing in the deionized water of 0.1% aliphatic alcohol polyoxyvinethene phosphate, add after dissolving and regulate pH 3 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-11A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 12]
Get 60g alumina support.Get 0.3g palladium bichloride and 1g lanthanum nitrate and be dissolved in 30ml containing in the deionized water of 0.1% aliphatic alcohol polyoxyvinethene phosphate, add after dissolving and regulate pH 6 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-12A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 13]
Get 60g alumina support.Get 0.3g palladium bichloride and 1g lanthanum nitrate and be dissolved in 30ml containing in the deionized water of 0.02% aliphatic alcohol polyoxyvinethene phosphate, add after dissolving and regulate pH 4.5 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-13A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 14]
Get 60g alumina support.Get 0.3g palladium bichloride and 1g lanthanum nitrate and be dissolved in 30ml containing in the deionized water of 0.3% aliphatic alcohol polyoxyvinethene phosphate, add after dissolving and regulate pH 4.5 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-14A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[embodiment 15]
Get 60g alumina support.Get 0.3g palladium bichloride and 1g lanthanum nitrate and be dissolved in 30ml containing in the deionized water of 0.6% aliphatic alcohol polyoxyvinethene phosphate, add after dissolving and regulate pH 4.5 to obtain maceration extract I with sodium carbonate.Maceration extract I is slowly joined in carrier, and stirs carrier and make solution impregnation even, obtained catalyst precarsor.By 80 DEG C of oven dry after catalyst precarsor in atmosphere aging 20 hours, then be put in 450 DEG C of roastings in Muffle furnace, then put into reactor internal program and be warmed up to 300 DEG C of hydrogen reducings and after 8 hours, obtain carbon monoxide vapor-phase synthesis oxalate catalyst cat-15A.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[comparative example 1]
According to embodiment 2 formula namely: get 60g alumina support, 0.3g palladium bichloride and 1g lanthanum nitrate and prepare catalyst cat1B according to the method for patent 200810035248.6.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[comparative example 2]
According to embodiment 2 formula namely: get 60g alumina support, 0.3g palladium bichloride and 1g lanthanum nitrate, then prepare carbon monoxide vapor-phase synthesis oxalate catalyst cat-2B by the method for patent 200810114383.X.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[comparative example 3]
According to the preparation method of [embodiment 1], just do not add lanthanide Group species, prepare catalyst cat-3B.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[comparative example 4]
According to the preparation method of [embodiment 2], just in maceration extract, do not add anion surfactant, prepare catalyst cat-4B.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
[comparative example 5]
According to the preparation method of [embodiment 2], just do not regulate the pH value of maceration extract (pH value is 0.8), prepare catalyst cat-5B.
On the constituent content of analytical test catalyst, palladium crystal grain average grain diameter and catalyst, palladium is to carbon monoxide adsorbs, and test result is in table 1.
Table 1
Wherein A
cO bridge-type/ A
cO line formulafor palladium bridged adsorption carbon monoxide and line formula sorbing carbon monoxide ratio
[embodiment 16]
The present embodiment illustrates the application of embodiment 1 ~ 15 gained catalyst in the good synthesizing dimethyl oxalate reaction of CO coupling.
Get the embodiment of the present invention 1 ~ 15 gained catalyst and carry out reaction examination, reaction temperature 140 DEG C, reaction pressure is 0.2MPa, CO and methyl nitrite mol ratio are 1.5, volume space velocity is carry out the reaction of CO coupling synthesizing dimethyl oxalate under the condition of 2500 hours-1, reaction afterproduct is by methanol absorption condensation, and gas-liquid separation, does sample analysis to gas phase and liquid phase respectively.Reaction result is in table 2.
[comparative example 6]
Get comparative example 1 ~ 5 gained catalyst and carry out reaction examination, adopt the reducing condition raw material identical with embodiment 16 and reaction condition.Reaction result is in table 2.
Table 2
As can be seen from test result and synthetic reaction effect, catalyst of the present invention, in the reaction of carbon monoxide vapor-phase synthesis oxalate, to the space-time yield of nitrites conversion ratio, oxalate apparently higher than reference sample, has significantly progressive and advantage.
[embodiment 17]
The present embodiment illustrates that embodiment 2 gained catalyst changes the result of the test of process conditions in the reaction of carbon monoxide gas phase coupling synthesis of oxalate, reaction condition and the results are shown in Table 3.
Table 3
Claims (10)
1. for a CO coupling catalyst for synthesizing oxalic ester, by weight percentage, comprise following component: 1) 0.05 ~ 2.5wt% palladium; 2) 0.06 ~ 3wt% lanthanide series metal or its oxide; 3) 94.5 ~ 99.8wt% carrier, at least one in support selected from alumina, silica or molecular sieve; Wherein, in catalyst, palladium bridged adsorption carbon monoxide and line formula sorbing carbon monoxide ratio are 0.8 ~ 4.5.
2., according to claim 1 for CO coupling catalyst for synthesizing oxalic ester, it is characterized in that by weight percentage, component 2) content be 0.1 ~ 2wt%.
3., according to claim 1 for CO coupling catalyst for synthesizing oxalic ester, it is characterized in that in catalyst, palladium bridged adsorption carbon monoxide and line formula sorbing carbon monoxide ratio are 1 ~ 4.5.
4., according to claim 3 for CO coupling catalyst for synthesizing oxalic ester, it is characterized in that in catalyst, palladium catalyst bridged adsorption carbon monoxide and line formula sorbing carbon monoxide ratio are 1.5 ~ 4.5.
5., according to claim 1 for CO catalyst for synthesizing oxalic ester by gas-phase, it is characterized in that the average grain diameter of palladium crystal grain in catalyst is nanometer 3 ~ 21.
6., according to claim 5 for CO catalyst for synthesizing oxalic ester by gas-phase, it is characterized in that the average grain diameter of palladium crystal grain in catalyst is nanometer 3 ~ 12.
7. the preparation method for CO catalyst for synthesizing oxalic ester by gas-phase described in any one of claim 1 ~ 6, comprises the following steps:
A) soluble-salt of active constituent palladium and auxiliary agent is dissolved in the water containing anion surfactant, to be dissolved complete after adjustment pH value of solution be 1.5 ~ 6.5, obtain maceration extract I;
B) maceration extract I flooded or be sprayed at carrier, obtaining catalyst precarsor;
C) by catalyst precarsor aging, oven dry in atmosphere, roasting, reduction, required catalyst is obtained.
8. the preparation method for CO catalyst for synthesizing oxalic ester by gas-phase according to claim 7, is characterized in that described anion surfactant content in water is 0.02 ~ 0.6wt%.
9. the preparation method of carbon monoxide vapor-phase synthesis oxalate catalyst according to claim 7, is characterized in that maceration extract pH is 3 ~ 6.
10. a method for carbon monoxide vapor-phase synthesis oxalate, reaction temperature 110 ~ 170 DEG C, reaction pressure 0 ~ 1MPa, the mol ratio of raw material carbon monoxide and nitrites is 1 ~ 4, and volume space velocity is 800 ~ 4000h
-1react with catalyst exposure described in any one of claim 1 ~ 6 under condition, generate the effluent containing oxalate.
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| CN106423151A (en) * | 2016-09-14 | 2017-02-22 | 中国科学院福建物质结构研究所 | Method for preparing catalyst for synthesizing oxalate from CO through multiphase in-situ reduction |
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