CN1055492A - Catalyst for coupling-synthesizing diethyl oxalate by catalyzing carbon monoxide - Google Patents
Catalyst for coupling-synthesizing diethyl oxalate by catalyzing carbon monoxide Download PDFInfo
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- CN1055492A CN1055492A CN 90103093 CN90103093A CN1055492A CN 1055492 A CN1055492 A CN 1055492A CN 90103093 CN90103093 CN 90103093 CN 90103093 A CN90103093 A CN 90103093A CN 1055492 A CN1055492 A CN 1055492A
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- carbon monoxide
- catalyzer
- gallium
- carrier
- palladium
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Abstract
The invention discloses under the normal pressure in current system, in the fixed-bed reactor, carbon monoxide and one step of ethyl nitrite gas-phase reaction are made the catalyzer of oxalic acid diethyl ester, and it is with α-Al
2O
3Be carrier, with palladium is main active ingredient, with the gallium is the spherical of cocatalyst or strip loaded catalyst, and it can be a reactant gas source with the carbon monoxide (CO content about 98%) of high density, also can carbon monoxide only is that the producer gas after about 30% the purification is a reactant gas source.This catalyzer is 35-55% to the per pass conversion of carbon monoxide, contains oxalic acid diethyl ester in the products therefrom and can reach 85%, and its catalytic activity height, simple for production, cost is low, is suitable for suitability for industrialized production and uses.
Description
The invention belongs to the catalyzer of coupling-synthesizing diethyl oxalate by catalyzing carbon monoxide.
At present, domestic employing oxalic acid and ethanol add toluene esterification dehydration method and produce oxalic acid diethyl ester.One of its main raw material oxalic acid is to use sodium formate method production, and at 160 ℃, under the 18-20kg pressure, synthesising acid sodium concentrates at 400 ℃ then and is dehydrogenated to sodium oxalates, generates lead oxalate with the lead sulfate effect again with carbon monoxide and sodium hydroxide.Further get the oxalic acid crude product with sulfuric acid acidation, use barium carbonate and centesimal poly-propionic acid amide flocking settling at last, get elaboration oxalic acid, its production process is long, and the cost height suddenly waits to seek new production method.
In recent years, and Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences (gas chemical industry such as Song Ruojun, 3,25(1986); 2,14(1987)) in laboratory study carbon monoxide normal pressure catalytic coupling synthesis of oxalate, its reaction formula is:
Wherein R is ethyl or methyl
Used catalyzer is a load type palladium catalyst, and the weight percentage of palladium (Pd) is 0.1-0.6%, and carrier is α-Al
2O
3And γ-Al
2O
3Two kinds, catalyzer is 16-28 purpose fine particle, only be suitable for experiment and use, and the preformed catalyst of using with suitability for industrialized production still there is a big difference.
English Patent 2003872 has disclosed by carbon monoxide and ethyl nitrite synthesis of diethyl oxalate employing, makes catalyzer (carrier is an activated carbon) with Pd/C, and this activity of such catalysts is very low, and the product yield approximately is 1%Pd/ α-Al
2O
31/10th, this shows that Pd/C is the catalyzer that is not suitable for doing synthetic oxalic acid diethyl ester under existence conditions.
Purpose of the present invention aims to provide a kind of moulding, high reactivity, high-selectivity catalyst of being used by the suitability for industrialized production of coupling-synthesizing diethyl oxalate by catalyzing carbon monoxide that be applicable to, with the innovation oxalic acid diethyl ester manufacturing process, reduce production costs.
The said catalyzer of the present invention is the α-Al with moulding
2O
3Being carrier, is main active ingredient with palladium, is the loaded catalyst of cocatalyst with the gallium, and wherein the percentage composition of palladium is 0.5-1.5%, and the percentage composition of gallium is 0-0.5%, and in preparation process, palladium and gallium add with Palladous chloride and gallium chloride solution form respectively.Solid-state Palladous chloride is mixed with certain density palladium chloride solution in the 2N hydrochloric acid soln, measures the milliliter number of required gallium chloride solution by the percentage composition of the gallium of being prepared; The cocatalyst gallium also is mixed with certain density gallium chloride solution, by the percentage composition of the gallium of being prepared measure required gallium chloride solution the milliliter number, then Palladous chloride and two kinds of solution of gallium chloride are mixed into mixing solutions, shaping carrier α-Al
2O
3Be immersed in the mixing solutions of Palladous chloride and gallium chloride, for carrier can be immersed in the solution entirely, can add certain water gaging in mixing solutions is diluted, make the cumulative volume of solution surpass the carrier cumulative volume, intermittently rock or stir the container of Sheng solution and carrier, in order to make active ingredient and cocatalyst component load on the carrier more equably, can at room temperature allow solvent slowly vapor away, also can be added in the water-bath, the volatilization of accelerated solvent, after treating that solvent evaporates is intact, under 130-150 ℃, be baked to driedly again, be finished catalyst.
α type Al in the catalyzer
2O
3Shaping carrier is normally with γ type Al
2O
3For raw material is transformed into, γ type Al
2O
3Through 1400-1450 ℃ of high temperature sintering 8-10 hour, make its most of γ-Al
2O
3In high temperature, be converted into the most stable α-Al
2O
3, and, have γ-Al at least greater than 80% according to ASTM card 10-173 its thing phase of reflecting
2O
3Be transformed into α-Al
2O
3, granulating and forming becomes 3-4mm diameter sphere or strip then, and its specific surface is 5-20m
2/ g, broken pure intensity is greater than 5kg/cm, and bulk density is 1.0-1.2ml/g.
Catalyzer of the present invention must be handled through hydrogen reducing before participating in catalyzed reaction, and hydrogen flowing quantity is 50-70ml/min, and reduction temperature is 260-320 ℃, and time 2.5-3 hour, under hydrogen stream, cool to temperature of reaction 80-120 ℃ then, catalyzer should not reveal sky.
Table 1 is the catalysis specific activity of preformed catalyst, and the best proportioning of each component of catalyzer of the present invention is that the content of palladium is 0.8-1.2%, and the content of gallium is 0.25-0.4%.Test shows catalyst levels 10-50 milliliter, and the per pass conversion of carbon monoxide is 35-55%, and generating oxalic acid diethyl ester is about 85% at the content of crude product.This catalyzer not only catalytic activity height, selectivity is good, simple for production, and because of catalyzer balling-up shape or strip, so being suitable for suitability for industrialized production uses, the present invention can be with the carbon monoxide (CO content about 98%) of high density as reactant gas source, also can carbon monoxide only is that producer gas after about 30% the purification is as source of the gas.
Further specify the present invention by the following examples.
Embodiment 1, takes by weighing the spheroiding that the 54g bulk density is 1.12ml/g (or bar shaped) carrier α-Al
2O
3, volume is 48 milliliters, presses 1%Pd+0.33%Ga/ α-Al
2O
3Content preparation catalyzer, its step is as follows: measure and contain the palladium chloride solution 11.5ml that the palladium amount is 0.048g/ml, place beaker; Measure again and contain the solution 8.5ml that the gallium amount is 0.021g/ml, place beaker to be made into mixing solutions; The water that adds again about 40ml comes diluted mixture solution, then the 54g carrier is slowly added in the mixing solutions after the dilution and flood, intermittently stir or rock beaker, allow solvent slowly volatilize, also can place water-bath (70-80 ℃) to beaker, accelerated solvent volatilization, treat that solvent evaporates is intact after, baking promptly got preformed catalyst to doing in 8-10 hour in 130-150 ℃ of baking oven.
Embodiment 2, take by weighing shaping carrier 20g, press 1%Pd/ α-Al
2O
3Content preparation catalyzer does not promptly contain the cocatalyst gallium.The steps include: to measure that to contain the palladium amount be that the palladium chloride solution 4.6ml of 0.048g/ml places beaker, add 30ml water dilution palladium chloride solution again, then carrier slowly be impregnated in the palladium chloride solution after the dilution, intermittently stir or rock beaker, allow solvent slowly volatilize, after treating that solvent evaporates is intact, baking was extremely done in 8-10 hour in 130-150 ℃ of baking oven again.
Embodiment 3, the test of reacting middle catalyst catalytic activity:
Catalyzer places the fixed-bed reactor of stainless steel tube, reactor inside diameter-25mm, and dress thermocouple sheath in the catalyzer loading amount 10-25ml, reactor, axially by beds, by catalyst bed bottom drawn from top to bottom by the product oxalic acid diethyl ester for unstripped gas.
Catalyzer must be handled through hydrogen reducing before participating in reaction, 300 ℃ of reduction temperatures, time-3 hour, hydrogen (H
2) flow is 50-70ml/min, under hydrogen stream, drops to 80-120 ℃ in temperature of reaction district then, can not reveal sky.
The optimum flow ratio of carbon monoxide and ethyl nitrite be 50ml/min than 50ml/min, normal pressure, temperature of reaction 80-120 ℃; Optimum temps is 100-110 ℃, and the transformation efficiency of its one way carbon monoxide is 35-55%, and the content of the liquid crude product mesoxalic acid of gained diethyl ester is about 85%.In the catalyst stability test about 300 hours, can keep the yield of the transformation efficiency and the oxalic acid diethyl ester of above-mentioned carbon monoxide.
The catalysis specific activity of table 1 preformed catalyst
| Catalyzer | Consumption | DE OYield g/Lhr |
| 0.5%Pd-0.35%Ga/α-Al 2O 3 | 10ml | 650 |
| 1%Pd-0.33%Ga/α-Al 2O 3(spherical) | 25ml | 1100 |
| 1%Pd-0.33%Ga/α-Al 2O 3(strip) | 25ml | 900 |
| 1.5%Pd-0.3%Ga/α-Al 2O 3 | 10ml | 600 |
| 1%Pd/α-Al 2O 3(spherical) | 10ml | 250 |
| 1%Pd/α-Al 2O 3(strip) | 10ml | 190 |
Claims (5)
1, the catalyzer of coupling-synthesizing diethyl oxalate by catalyzing carbon monoxide is characterized in that it is α-Al with moulding
2O
3Being carrier, is main active ingredient with palladium, is the loaded catalyst of cocatalyst with the gallium, with shaping carrier α-Al
2O
3Be immersed in entirely in the mixing solutions of palladium chloride solution and gallium chloride solution, intermittently rock or stir, treat that solvent slowly is evaporated completely after, under 130 °～150 ℃, be baked to dried again.
2, by the described catalyzer of claim 1, the percentage composition that it is characterized in that main active component palladium is 0.5-1.5%, and the percentage composition of cocatalyst gallium is 0-0.5%.
3, by the described catalyzer of claim 1, it is characterized in that the best percentage composition of main active component palladium is 0.8-1.2%, the best percentage composition of cocatalyst gallium is 0.25-0.4%.
4,, it is characterized in that the α-Al of moulding by the described catalyzer of claim 1
2O
3Carrier is by γ-Al
2O
3For raw material is transformed through high temperature (1400-1450 ℃) calcination, wherein the content of α-phase is greater than 80%, and the specific surface of granulating and forming carrier is 5-20m
2/ g, broken pure intensity is greater than 5kg/cm, and bulk density is 1.0-1.2ml/g.
5, by the described catalyzer of claim 1 to 4, it is characterized in that catalyzer is before participating in catalyzed reaction, must handle through hydrogen reducing, its reduction temperature is 260-320 ℃, time 2.5-3 hour, hydrogen flowing quantity 50-70ml/min was then under hydrogen stream, cool to temperature of reaction 80-120 ℃, its optimal reaction temperature is 100-110 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90103093 CN1055492A (en) | 1990-04-10 | 1990-04-10 | Catalyst for coupling-synthesizing diethyl oxalate by catalyzing carbon monoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90103093 CN1055492A (en) | 1990-04-10 | 1990-04-10 | Catalyst for coupling-synthesizing diethyl oxalate by catalyzing carbon monoxide |
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| Publication Number | Publication Date |
|---|---|
| CN1055492A true CN1055492A (en) | 1991-10-23 |
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|---|---|---|---|
| CN 90103093 Pending CN1055492A (en) | 1990-04-10 | 1990-04-10 | Catalyst for coupling-synthesizing diethyl oxalate by catalyzing carbon monoxide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101579635B (en) * | 2009-06-18 | 2011-07-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Room temperature catalytic oxidation carbon monoxide catalyst and preparation method thereof |
| CN101543784B (en) * | 2009-04-28 | 2011-07-20 | 华烁科技股份有限公司 | Preparation method for catalyst for synthesizing oxalic ester by gas-phase |
| CN102649054A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for preparation of oxalate through CO coupling |
| CN102649728A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing oxalate through gas-phase reaction of carbon monoxide |
-
1990
- 1990-04-10 CN CN 90103093 patent/CN1055492A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101543784B (en) * | 2009-04-28 | 2011-07-20 | 华烁科技股份有限公司 | Preparation method for catalyst for synthesizing oxalic ester by gas-phase |
| CN101579635B (en) * | 2009-06-18 | 2011-07-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Room temperature catalytic oxidation carbon monoxide catalyst and preparation method thereof |
| CN102649054A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for preparation of oxalate through CO coupling |
| CN102649728A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing oxalate through gas-phase reaction of carbon monoxide |
| CN102649728B (en) * | 2011-02-25 | 2014-04-23 | 中国石油化工股份有限公司 | Method for producing oxalate through gas-phase reaction of carbon monoxide |
| CN102649054B (en) * | 2011-02-25 | 2015-01-07 | 中国石油化工股份有限公司 | Catalyst for preparation of oxalate through CO coupling |
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