CN112441922B - Method for preparing oxalate through CO oxidative coupling, catalyst and preparation method thereof - Google Patents
Method for preparing oxalate through CO oxidative coupling, catalyst and preparation method thereof Download PDFInfo
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- CN112441922B CN112441922B CN201910823841.5A CN201910823841A CN112441922B CN 112441922 B CN112441922 B CN 112441922B CN 201910823841 A CN201910823841 A CN 201910823841A CN 112441922 B CN112441922 B CN 112441922B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for producing oxalate by CO oxidative coupling, which mainly solves the problems of low conversion rate of nitrite and low selectivity and space-time yield of the target product oxalate in the prior art. The invention adopts the mixed gas containing nitrous acid ester and CO as the raw material, adopts a fixed bed reactor, and has the reaction temperature of 110-170 ℃ and the volume space velocity of 1000-10000 h ‑1 The ratio of CO to nitrous acid ester in the raw materials is (1-3): 1, under the condition that the reaction pressure is 0.1-2.0MPa, the raw material contacts with a catalyst to react to generate oxalate; the catalyst is a metal Pd catalyst loaded on copper phyllosilicate and/or nickel phyllosilicate, and comprises the following components in parts by weight: 1) 95.0 to 99.9 parts of copper/nickel phyllosilicate; 2) The technical proposal of 0.1 to 5.0 parts of noble metal Pd well solves the problem and can be used in the industrial production of oxalate through the oxidative coupling of CO.
Description
Technical Field
The invention relates to a method for producing oxalate through CO oxidative coupling, a catalyst and a preparation method thereof, in particular to a method for producing oxalate through CO oxidative coupling, a copper phyllosilicate or nickel-loaded noble metal Pd catalyst and a preparation method thereof.
Background
Oxalate is an important organic chemical raw material and is widely used for preparing various important chemical products, such as oxalic acid obtained by hydrolyzing oxalate, oxamide obtained by ammoniation and ethylene glycol obtained by hydrogenation. The preparation of oxalate by CO oxidative coupling is a key step in the technology of preparing glycol from coal, and has great industrial application value. In addition, the process has important application prospect in industrial tail gas treatment. Many industrial tail gases contain a large amount of CO, and are mainly treated by a combustion method at present, if the CO in the tail gases is collected and converted into oxalate with high added value, not only can energy conservation and emission reduction be realized, but also resources can be fully utilized, and the problem of environmental pollution is solved.
The gas phase method for preparing oxalate by CO coupling has the most advantages, and the gas phase method research is carried out in 1978 by Xingsheng corporation of Japan and Italy Monte Edison. Wherein, the oxalate synthesis process by gas phase catalysis developed by the Xingyou company of Uyu department has the reaction pressure of 0.5MPa and the reaction temperature of 80-150 ℃.
With the international development of the technological process for preparing oxalate by CO oxidative coupling, many domestic institutions also develop research. According to the resource distribution characteristics of less oil and more coal in China, the preparation of the organic oxygen-containing compound by taking CO as the raw material has very important strategic significance.
Document CN106582763 discloses a catalyst for preparing oxalate through oxidative coupling, wherein nitrogen-doped graphene is used as a carrier, and nano Pd is used as an active component, so that the problems of high Pd loading amount and low oxalate space-time yield in the prior art are solved, but the nitrogen-doped graphene is expensive and poor in stability, and needs to be improved urgently.
Document CN95116136.9 discloses a catalyst for oxalate synthesis, which selects Zr auxiliary agent and develops novel Pd-Zr/Al by an impregnation method 2 O 3 The catalyst is used for the reaction of synthesizing oxalate by gas phase catalysis of CO and nitrite, and a fixed bed reaction device is adopted. However, in the patent, the yield of oxalate is relatively low, the requirement on impurities of raw material gas is relatively high, the selectivity of the product oxalate is 95%, and the conversion per pass of nitrite is 64% at most, which are all to be further improved.
Document CN101462081 discloses a catalyst for oxidative coupling reaction of CO and methyl nitrite to produce dimethyl oxalate, which uses at least one nitrate selected from metal elements in groups VIII, IB and VB of the periodic table of elements as impregnating solution, and uses carrier r-Al 2 O 3 Soaking in the soaking solution. The selectivity of dimethyl oxalate on the catalyst is only about 92 percent。
How to use a novel oxidative coupling catalyst, which can improve the conversion rate of nitrite and ensure the selectivity of oxalate at the same time, thereby realizing the production of oxalate with high space-time yield is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to solve the technical problems of low conversion rate of nitrite and low selectivity and space-time yield of the target product oxalate in the prior art, and provides a novel method for producing oxalate through CO oxidative coupling. The method has the characteristics of high conversion rate of nitrite and high selectivity and space-time yield of oxalate.
The second technical problem to be solved by the invention is to provide a catalytic gasification reaction method corresponding to the first technical problem.
The invention provides a catalyst for producing oxalate through CO oxidative coupling, which comprises carrier phyllosilicate and supported metal Pd, wherein the phyllosilicate is copper phyllosilicate and/or nickel phyllosilicate; .
According to some preferred embodiments of the invention, the copper or nickel content of the copper nickel phyllosilicate and of the nickel phyllosilicate is 5 to 40% by weight each.
According to some preferred embodiments of the invention, the copper or nickel content of both the copper and nickel phyllosilicates is between 8 and 30% by weight.
According to some preferred embodiments of the present invention, the phyllosilicate is 95.0 to 99.9 parts by weight, and the metal Pd is 0.1 to 5.0 parts by weight.
According to some preferred embodiments of the present invention, the phyllosilicate is present in an amount of 96.0 to 99.8 parts by weight and the metal Pd is present in an amount of 0.2 to 4 parts by weight.
According to some preferred embodiments of the present invention, the phyllosilicate is present in an amount of 98.0 to 99.7 parts by weight and the metal Pd is present in an amount of 0.3 to 2 parts by weight.
According to some embodiments of the invention, the catalyst made of copper phyllosilicate and copper nickel phyllosilicate supported metal Pd has an infrared spectrum from 665 to 675cm -1 The peak area of (A) and the peak area of 795-805cm -1 The peak area ratios are (0.005-0.15): 1 and (0.01-0.3): 1.
according to some preferred embodiments of the invention, the catalyst made of copper phyllosilicate and copper nickel phyllosilicate supporting metal Pd has an infrared spectrum of 670cm -1 Peak area of (2) to 800cm -1 The peak area ratios are (0.01-0.10): 1 and (0.02-0.20): 1.
in a second aspect of the present invention, there is provided a method for preparing the catalyst of the first aspect, comprising the steps of:
s1, adding copper salt or nickel salt into water, adding concentrated ammonia water or urea, then adding silica sol, heating, and evaporating ammonia or continuously heating until the pH value is less than 7 or more than 6; filtering the obtained mixture, washing with water, drying, and roasting to obtain carrier copper phyllosilicate or nickel phyllosilicate;
and S2, dissolving a salt of metal Pd in water, adding the copper phyllosilicate or nickel phyllosilicate carrier prepared in the step 1 of S1 into the solution, drying the mixture overnight, and roasting the mixture to obtain the catalyst.
According to some embodiments of the invention, the method comprises the steps of:
s1, adding the copper salt into deionized water accounting for 300-8000 percent of the weight of the copper salt, adding concentrated ammonia water accounting for 60-300 percent of the weight of the copper salt, adding silica sol accounting for 100-1500 percent of the weight of the copper salt, stirring for 1-10 hours, heating to 50-100 ℃, and evaporating ammonia or continuously heating until the pH value is less than 7; filtering the obtained mixture, washing with water, drying at 80-150 deg.C overnight, and calcining at 300-700 deg.C for 2-16h to obtain carrier copper phyllosilicate; or
S1, adding nickel salt into deionized water accounting for 300-8000% of the weight of the nickel salt, then adding urea accounting for 60-300% of the weight of the nickel salt, then adding silica sol accounting for 100-1500% of the weight of the nickel salt, stirring for 1-10 hours, heating to 60-100 ℃, and evaporating ammonia or continuously heating until the pH value is more than 6; filtering the obtained mixture, washing with water, drying at 80-150 deg.C overnight, and roasting at 300-700 deg.C for 2-16h to obtain carrier nickel phyllosilicate; s2, dissolving a salt of metal Pd in water, adding the copper phyllosilicate or the nickel copper phyllosilicate carrier prepared in the step 1 in the step S1, drying at 80-150 ℃ overnight, and roasting at 300-700 ℃ for 2-16h to obtain the catalyst. The overnight drying is 6-14h.
According to some preferred embodiments of the present invention, the copper salt is at least one of copper nitrate, copper carbonate, basic copper carbonate, copper sulfate and copper chloride, copper bromide; the nickel salt is at least one of nickel nitrate, nickel carbonate, basic nickel carbonate, nickel sulfate, nickel chloride and nickel bromide.
According to some preferred embodiments of the present invention, the salt of metallic Pd is palladium chloride and/or palladium nitrate. .
According to some embodiments of the invention, siO in the silica sol is used 2 The content of (A) is 20-50%.
In a third aspect of the present invention, there is provided a method for producing oxalate using the catalyst of the first aspect or the catalyst prepared by the method of the second aspect, wherein a mixed gas containing nitrite and CO is used as a raw material, and a fixed bed reactor is used, and the raw material and the catalyst are contacted and reacted to produce oxalate. .
According to some preferred embodiments of the invention, the reaction temperature is in the range of 110 to 170 ℃.
According to some preferred embodiments of the invention, the reaction temperature is 120 to 160 ℃.
According to some preferred embodiments of the invention, the volume space velocity is from 1000 to 10000 hours -1 。
According to some preferred embodiments of the present invention, the volume space velocity is 2000 to 6000 hours -1 。
According to some preferred embodiments of the present invention, the molar ratio of CO to nitrite in the feedstock is preferably (1-3): 1.
According to some preferred embodiments of the present invention, the molar ratio of CO to nitrite in the feedstock is preferably (1.2-2.5): 1.
According to preferred embodiments of the present invention, the diluent nitrogen is present in an amount of 30% to 70% by volume.
According to preferred embodiments of the present invention, the diluent nitrogen is present in an amount of 40% to 60% by volume.
According to some preferred embodiments of the invention, the reaction pressure is between 0.1 and 2.0MPa.
According to some preferred embodiments of the invention, the reaction pressure is between 0.1 and 1.0MPa.
In the present invention, "/" denotes "or" unless otherwise specified, for distinguishing between parallel embodiments. For example, "670 cm in the infrared spectrum of the catalyst made of copper phyllosilicate/nickel supported noble metal Pd -1 Peak area of (2) to 800cm -1 The ratio of the peak area of (0.005-0.15)/(0.01-0.3) "means that" 670cm in the infrared spectrum of the catalyst made of copper phyllosilicate-supported noble metal Pd -1 Peak area of (d) to 800cm -1 The ratio of peak area of (0.005-0.15) "and" 670cm in the infrared spectrum of the catalyst made of nickel phyllosilicate supporting noble metal Pd -1 Peak area of (d) to 800cm -1 The ratio of peak area of (E) to (E) was (0.01-0.3) ". For example, adding copper/nickel salt into deionized water with the weight of 300-8000 percent of that of the copper/nickel salt, then adding concentrated ammonia water/urea with the weight of 60-300 percent of that of the copper/nickel salt, then adding silica sol with the weight of 100-1500 percent of that of the copper/nickel salt, stirring for 1-10 hours, heating to (50-100 ℃)/(60-100 ℃), and evaporating ammonia/continuing heating until the pH value is less than 7/more than 6; filtering the obtained mixture, washing with water, drying at 80-150 ℃ overnight, and roasting at 300-700 ℃ for 2-16h to obtain the carrier copper/nickel phyllosilicate, which means that copper salt is added into deionized water with the weight of 300-8000 percent of the copper salt, then concentrated ammonia water with the weight of 60-300 percent of the copper salt is added, then silica sol with the weight of 100-1500 percent of the copper salt is added, the mixture is stirred for 1-10 h, heated to 50-100 ℃, and ammonia is evaporated until the pH value is less than 7; filtering the obtained mixture, washing with water, drying at 80-150 deg.C overnight, roasting at 300-700 deg.C for 2-16h to obtain carrier copper phyllosilicate, adding nickel salt into deionized water in 300-8000 wt%, adding urea in 60-300 wt%, and adding silicon in 100-1500 wt% of nickel saltDissolving sol, stirring for 1-10 hr, heating to 60-100 deg.c, and further heating to pH value greater than 6; filtering the obtained mixture, washing with water, drying at 80-150 deg.C overnight, and calcining at 300-700 deg.C for 2-16h to obtain carrier nickel phyllosilicate ".
The invention has the beneficial effects that:
the method adopts copper phyllosilicate and/or nickel phyllosilicate as a carrier to load the noble metal Pd catalyst, the metal Pd is well dispersed, and the Pd and the carrier copper phyllosilicate and/or nickel phyllosilicate have obvious synergistic action, so that the activity and the selectivity of oxalate are improved. The copper phyllosilicate and/or nickel phyllosilicate loaded noble metal Pd catalyst is used in the oxidative coupling reaction of CO and nitrous acid ester, and the reaction temperature is 130 ℃, and the volume space velocity is 3000 hours -1 When the ratio of CO to methyl nitrite in the raw material is 1.5, the volume content of nitrogen is 50 percent, and the reaction pressure is 0.5MPa, the conversion rate of methyl nitrite is 70.1 percent/72.5 percent, the selectivity of dimethyl oxalate is 99.1 percent/98.6 percent, and the space-time yield of dimethyl oxalate is (1098 g/Lcat/h)/(1130 g/Lcat/h).
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the present invention is not limited to the examples.
1. Copper phyllosilicate as carrier
[ example a1 ]
18.9 g of copper nitrate trihydrate, 200 g of deionized water and 30g of 25% strength ammonia water are added to a 500 ml beaker, and 37.5 g of SiO are added 2 Stirring 40% silica sol Ludox AS-40 at room temperature for 3 hours, heating to 90 ℃ for ammonia evaporation until the pH is less than 7, filtering the obtained mixture, washing with deionized water for 3 times, drying in a 120 ℃ oven overnight, and roasting in a 450 ℃ oven for 4 hours to obtain the copper phyllosilicate carrier PS-1, wherein the Cu content is 25%, and 670cm in an infrared spectrogram -1 Peak area of (2) to 800cm -1 The peak area ratio of (A) was 0.08.
Adding 20 g of PS-1 carrier into a 200 ml beaker, adding 100 ml of deionized water and 0.77 g of palladium nitrate solution with the Pd mass content of 13%, drying the mixture in an oven at 120 ℃ overnight, and then roasting in the oven at 450 ℃ for 4 hours to obtain the noble metal Pd catalyst aOCP-1 loaded on the copper phyllosilicate carrier, wherein the weight part of Pd is 0.5, and the weight part of the carrier copper phyllosilicate is 99.5.
[ example a2 ]
24.2 g of basic copper carbonate, 200 g of deionized water and 40 g of 25% concentrated ammonia water are added into a 500 ml beaker, and 43.3 g of SiO is added 2 Stirring 30% silica sol SW-30 at room temperature for 6 hr, heating to 60 deg.C for ammonia evaporation until pH is less than 7, filtering the obtained mixture, washing with deionized water for 3 times, drying in oven at 100 deg.C overnight, and calcining at 550 deg.C for 10 hr to obtain copper phyllosilicate carrier PS-2 with Cu content of 35% by weight -1 Peak area of (2) to 800cm -1 The peak area ratio of (B) was 0.04.
In a 200 ml beaker was added 20 g of PS-2 carrier, 100 ml of deionized water and 0.066 g of PdCl 2 The mixture is dried in a 120 ℃ oven overnight and then roasted in a 450 ℃ oven for 4 hours to obtain the noble metal Pd catalyst aOCP-2 loaded on a copper phyllosilicate carrier, wherein the weight part of Pd is 0.2, and the weight part of the carrier copper phyllosilicate is 99.8.
[ example a3 ]
The catalyst support was prepared in the same manner as in example a1 except that 3.8 g of copper nitrate trihydrate was added, 8.0 g of concentrated aqueous ammonia was added, and 47.5 g of silica sol was added to obtain PS-3 as a copper phyllosilicate support having a Cu content of 5% by weight and a depth of 670cm in the IR spectrum -1 Peak area of (2) to 800cm -1 The peak area ratio was 0.03.
The catalyst was prepared in the same manner as in example a1, except that PS-3 was used as the support and aOCP-3 was used as the catalyst.
[ example a4 ]
The catalyst support was prepared in the same manner as in example a1 except that 11.3 g of copper nitrate trihydrate was added, 15.0 g of concentrated aqueous ammonia was added, and silica solution was addedThe amount of the glue was 42.5 g, and the obtained copper phyllosilicate carrier was PS-4, in which the Cu content by weight was 15%, 670cm in an IR spectrum -1 Peak area of (2) to 800cm -1 The peak area ratio of (A) was 0.05.
The catalyst was prepared in the same manner as in example a1, except that PS-4 was used as the support and aOCP-4 was obtained as the catalyst.
[ example a5 ]
The catalyst support was prepared in the same manner as in example a1 except that 17.5 g of cupric bromide was used as the copper salt, 20.0 g of concentrated aqueous ammonia was added, 37.5 g of silica sol was added, and PS-5 was obtained as the copper phyllosilicate support having a Cu content of 25% by weight and a concentration of 670cm in the IR spectrum -1 Peak area of (2) to 800cm -1 The peak area ratio of (A) was 0.09.
The catalyst was prepared in the same manner as in example a1, except that PS-5 was used as the support and aOCP-5 was used as the catalyst.
[ examples a6 to 8 ]
The preparation of the catalyst support and the catalyst were carried out in the same manner as in example a1, except that the palladium nitrate solution containing 13% by mass of Pd was used in an amount of 0.46, 1.23 and 2.31 g, respectively, to obtain catalysts aOCP-6, aOCP-7 and aOCP-8, respectively, in which Pd was present in an amount of 0.3, 0.8 and 1.5, respectively, and the copper phyllosilicate PS-1 as the support was present in an amount of 99.7, 99.2 and 98.5, respectively.
[ example a9 ]
Adding 10.0 g of aOCP-1 catalyst into a fixed bed continuous reactor, and activating for 5 hours at the normal pressure by pure hydrogen at 200 ℃ with the volume space velocity of the hydrogen of 1000 hours -1 . The volume composition of the catalyst is 30.0 percent of CO, 20 percent of NO and 50 percent of N 2 The reaction conditions are as follows: the reaction temperature is 130 ℃, and the gas volume space velocity is 3000 hours -1 The ratio of CO to methyl nitrite in the raw material is 1.5, the volume content of nitrogen is 50%, when the reaction pressure is 0.5MPa, the conversion rate of methyl nitrite is 70.1%, the selectivity of dimethyl oxalate is 99.1%, and the space-time yield of dimethyl oxalate is 1098g/Lcat/h.
[ example a10 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example a9, except that the catalyst used was aOCP-2, the conversion of methyl nitrite obtained was 56.2%, the selectivity for dimethyl oxalate was 99.0%, and the space-time yield of dimethyl oxalate was 880g/Lcat/h.
[ example a11 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example a9, except that the catalyst used was aOCP-3, the conversion of methyl nitrite obtained was 63.2%, the selectivity to dimethyl oxalate was 99.2%, and the space time yield of dimethyl oxalate was 990g/Lcat/h.
[ example a12 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example a9, except that the catalyst used was aOCP-4, the conversion of methyl nitrite was 65.1%, the selectivity for dimethyl oxalate was 99.0%, and the space-time yield of dimethyl oxalate was 1018g/Lcat/h.
[ example a13 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example a9, except that the catalyst used was aOCP-5, the conversion of methyl nitrite obtained was 68.2%, the selectivity for dimethyl oxalate was 98.5%, and the space-time yield of dimethyl oxalate was 1061g/Lcat/h.
[ example a14 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example a9, except that the catalyst used was aOCP-6, the conversion of methyl nitrite obtained was 53.1%, the selectivity of dimethyl oxalate was 99.2% and the space time yield of dimethyl oxalate was 832g/Lcat/h.
[ example a15 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example a9, except that the catalyst used was aOCP-7, the conversion of methyl nitrite was 74.2%, the selectivity for dimethyl oxalate was 98.4%, and the space-time yield of dimethyl oxalate was 1154g/Lcat/h.
[ example a16 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example a9, except that the catalyst used was aOCP-8, the conversion of methyl nitrite was 76.0%, the selectivity for dimethyl oxalate was 98.0%, and the space-time yield of dimethyl oxalate was 1177g/Lcat/h.
[ example a17 ]
The reaction conditions for the oxidative coupling of CO to produce oxalate were the same as in [ example a9 ], except that the gas composition was 40% CO, 20% NO, 40% N by volume 2 . The gas space velocity is 5000 h < -1 >, the reaction temperature is 150 ℃, the reaction pressure is 0.2MPa, the conversion rate of the obtained methyl nitrite is 51.1 percent, the selectivity of the dimethyl oxalate is 95.2 percent, and the space-time yield of the dimethyl oxalate is 1281g/Lcat/h.
[ example a18 ]
The reaction conditions for the oxidative coupling of CO to prepare oxalate were the same as in example a9, except that the gas composition was 20% CO, 20% NO, 60% N by volume 2 . The gas space velocity is 2000 hours -1 The reaction temperature is 120 ℃, the reaction pressure is 0.9MPa, the conversion rate of the obtained methyl nitrite is 60.1 percent, the selectivity of the dimethyl oxalate is 99.4 percent, and the space-time yield of the dimethyl oxalate is 629g/Lcat/h.
[ example a19 ]
The reaction conditions for the oxidative coupling of CO to produce oxalate were the same as in [ example a9 ], except that the gas composition was 20% CO, 20% NO, 60% N by volume 2 . The air space velocity is 6000 hours -1 The reaction temperature is 140 ℃, the reaction pressure is 0.1MPa, the conversion rate of the obtained methyl nitrite is 43.2 percent, the selectivity of the dimethyl oxalate is 98.9 percent, and the space-time yield of the dimethyl oxalate is 1350g/Lcat/h.
[ example a20 ]
The reaction conditions for preparing oxalate by oxidative coupling of CO were the same as in example a9, and the reaction was continued for 3000 hours, and the results were shown in Table a 1.
TABLE a1
Comparative example a1
Dissolving 48.4 g of copper nitrate trihydrate in 200 ml of deionized water to obtain a solution A; an additional 24.4 grams of sodium silicate was dissolved in 200 milliliters of deionized water to provide solution B. And (2) dropping the solutions A and B into 50mL of deionized water at the speed of 10 milliliters per minute under stirring at normal temperature, aging the obtained mixture for 2 hours at the temperature of 60 ℃, filtering, washing a filter cake for 5 times by using the deionized water, drying the filter cake at the temperature of 120 ℃ overnight, and roasting the filter cake for 4 hours at the temperature of 450 ℃ to obtain the copper silicate carrier CS-1.
Adding 20 g of CS-1 carrier into a 200 ml beaker, adding 100 ml of deionized water and 0.77 g of palladium nitrate solution with the Pd mass content of 13%, drying the mixture in an oven at 120 ℃ overnight, and then roasting in the oven at 450 ℃ for 4 hours to obtain the noble metal Pd catalyst PCS-1 loaded by the copper phyllosilicate carrier, wherein the weight part of Pd is 0.5, and the weight part of the carrier copper metasilicate is 99.5.
Evaluation of the catalyst PCS-1 was carried out in the same manner as in example a9, giving a methyl nitrite conversion of 45.5%, a dimethyl oxalate selectivity of 95.1% and an hourly space yield of 684g/Lcat/h.
2. Nickel phyllosilicate as carrier
[ example b1 ]
24.8 g of nickel nitrate hexahydrate, 200 g of deionized water and 25 g of urea were added in a 500 ml beaker, and 37.5 g of SiO were added 2 Stirring 40% silica sol Ludox AS-40 at room temperature for 3 hours, heating to 90 ℃ to decompose urea until pH is higher than 6, filtering the obtained mixture, washing with deionized water for 3 times, drying in a 120 ℃ oven overnight, and roasting in a 450 ℃ oven for 4 hours to obtain the nickel phyllosilicate carrier PS-1 with the Ni content of 25% and the infrared spectrum of 670cm -1 Peak area of (d) to 800cm -1 The peak area ratio of (b) was 0.16.
Adding 20 g of PS-1 carrier into a 200 ml beaker, adding 100 ml of deionized water and 0.77 g of palladium nitrate solution with the Pd mass content of 13%, drying the mixture in a 120 ℃ oven overnight, and then roasting in a 450 ℃ oven for 4 hours to obtain the nickel phyllosilicate carrier loaded noble metal Pd catalyst bOCP-1, wherein the weight part of Pd is 0.5, and the weight part of carrier nickel phyllosilicate is 99.5.
[ example b2 ]
23.6 g of basic nickel carbonate, 200 g of deionized water and 35g of urea were added to a 500 ml beaker, and 43.3 g of SiO were added 2 Stirring 30% silica sol SW-30 at room temperature for 6 hr, heating to 70 deg.C to decompose urea until pH is greater than 6, filtering the obtained mixture, washing with deionized water for 3 times, drying in oven at 100 deg.C overnight, and calcining at 550 deg.C for 10 hr to obtain nickel phyllosilicate carrier PS-2 with Ni content of 35 wt%, and infrared spectrum of 670cm -1 Peak area of (d) to 800cm -1 The peak area ratio of (A) was 0.08.
In a 200 ml beaker, 20 g PS-2 carrier was added, 100 ml deionized water and 0.066 g PdCl were added 2 And drying the mixture in a 120 ℃ oven overnight, and then roasting in a 450 ℃ oven for 4 hours to obtain the nickel phyllosilicate carrier-loaded noble metal Pd catalyst bOCP-2, wherein the weight part of Pd is 0.2, and the weight part of carrier nickel phyllosilicate is 99.8.
[ example b3 ]
The preparation of the catalyst support was the same as in example b1, except that 4.6 g of nickel nitrate hexahydrate, 6.1 g of urea and 47.5 g of silica sol were added to obtain a nickel phyllosilicate support of PS-3 with a Ni content of 5% by weight and a spectrum of 670cm in IR spectrum -1 Peak area of (d) to 800cm -1 The peak area ratio of (b) was 0.06.
The catalyst was prepared in the same manner as in example b1, except that the support used was PS-3 and the resulting catalyst was bOCP-3.
[ example b4 ]
The catalyst support was prepared in the same manner as in example b1, except that 13.6 g of nickel nitrate hexahydrate, 14.5 g of urea and 42.5 g of silica sol were added to obtain nickel phyllosilicateThe carrier is PS-4, wherein the weight content of Ni is 15%, and 670cm in an infrared spectrogram -1 Peak area of (2) to 800cm -1 The peak area ratio was 0.10.
The catalyst was prepared in the same manner as in example b1, except that PS-4 was used as the support and bOCP-4 was obtained as the catalyst.
[ example b5 ]
The catalyst support was prepared in the same manner as in example b1, except that 17.1 g of nickel bromide was used as the nickel salt, 25.0 g of urea was added, 37.5 g of silica sol was added, and PS-5 was obtained as the phyllosilicate nickel support having a Ni content of 25% by weight and a spectrum of 670cm in infrared -1 Peak area of (d) to 800cm -1 The peak area ratio of (A) was 0.18.
The catalyst was prepared in the same manner as in example b1, except that PS-5 was used as the support and bOCP-5 was obtained as the catalyst.
[ examples b6 to 8 ]
The catalyst support and the catalyst were prepared according to the same method as in example b1, except that the palladium nitrate solution containing 13% by mass of Pd was used in an amount of 0.46, 1.23 and 2.31 g, respectively, to obtain bOCP-6, bOCP-7 and bOCP-8, respectively, in terms of Pd in an amount of 0.3, 0.8 and 1.5, respectively, and the nickel phyllosilicate PS-1 was used as the support in an amount of 99.7, 99.2 and 98.5, respectively.
[ example b9 ]
Adding 10.0 g bOCP-1 catalyst into a fixed bed continuous reactor, activating for 5 hours at the normal pressure by pure hydrogen at 200 ℃, wherein the volume space velocity of the hydrogen is 1000 hours -1 . The volume composition of the catalyst is 30.0 percent of CO, 20 percent of NO and 50 percent of N 2 The reaction conditions are as follows: the reaction temperature is 130 ℃, and the gas volume space velocity is 3000 hours -1 The ratio of CO to methyl nitrite in the raw material is 1.5, the volume content of nitrogen is 50%, when the reaction pressure is 0.5MPa, the conversion rate of methyl nitrite is 72.5%, the selectivity of dimethyl oxalate is 98.6%, and the space-time yield of dimethyl oxalate is 1130g/Lcat/h.
[ example b10 ]
The reaction conditions for the oxidative coupling of CO to prepare oxalate were the same as in example b9, except that the catalyst used was bOCP-2, the conversion of methyl nitrite was 57.2%, the selectivity for dimethyl oxalate was 98.4%, and the space-time yield of dimethyl oxalate was 890g/Lcat/h.
[ example b11 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example b9, except that the catalyst used was bOCP-3, the conversion of methyl nitrite obtained was 64.2%, the selectivity for dimethyl oxalate was 98.2%, and the space-time yield of dimethyl oxalate was 996g/Lcat/h.
[ example b12 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example b9, except that the catalyst used was bOCP-4, the conversion of methyl nitrite obtained was 66.5%, the selectivity for dimethyl oxalate was 98.7%, and the space-time yield of dimethyl oxalate was 1037g/Lcat/h.
[ example b13 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example b9, except that the catalyst used was bOCP-5, the conversion of methyl nitrite was 69.2%, the selectivity for dimethyl oxalate was 98.2%, and the space-time yield of dimethyl oxalate was 1074g/Lcat/h.
[ example b14 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example b9, except that the catalyst used was bOCP-6, the conversion of methyl nitrite was 53.9%, the selectivity to dimethyl oxalate was 99.1%, and the space-time yield of dimethyl oxalate was 844g/Lcat/h.
[ example b15 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example b9, except that the catalyst used was bOCP-7, the conversion of methyl nitrite was 74.9%, the selectivity for dimethyl oxalate was 98.1%, and the space-time yield of dimethyl oxalate was 1161g/Lcat/h.
[ example b16 ]
The reaction conditions for the preparation of oxalate by oxidative coupling of CO were the same as in example b9, except that the catalyst used was bOCP-8, the conversion of methyl nitrite obtained was 78.0%, the selectivity to dimethyl oxalate was 97.5%, and the space time yield of dimethyl oxalate was 1201g/Lcat/h.
[ example b17 ]
The reaction conditions for the oxidative coupling of CO to prepare oxalate were the same as in example b9, except that the gas composition by volume was 40% CO, 20% NO, 40% N 2 . The air space velocity is 5000 hours -1 The reaction temperature is 150 ℃, the reaction pressure is 0.2MPa, the conversion rate of the obtained methyl nitrite is 52.1 percent, the selectivity of the dimethyl oxalate is 96.8 percent, and the space-time yield of the dimethyl oxalate is 1278g/Lcat/h.
[ example b18 ]
The reaction conditions for the oxidative coupling of CO to prepare oxalate were the same as in example b9, except that the gas composition was 20% CO, 20% NO, 60% N by volume 2 . The gas space velocity is 2000 hours -1 The reaction temperature is 120 ℃, the reaction pressure is 0.9MPa, the conversion rate of the obtained methyl nitrite is 61.1 percent, the selectivity of the dimethyl oxalate is 99.1 percent, and the space-time yield of the dimethyl oxalate is 635g/Lcat/h.
[ example b19 ]
The reaction conditions for the oxidative coupling of CO to prepare oxalate were the same as in example b9, except that the gas composition was 20% CO, 20% NO, 60% N by volume 2 . The air space velocity is 6000 hours -1 The reaction temperature is 140 ℃, the reaction pressure is 0.1MPa, the conversion rate of the obtained methyl nitrite is 43.5 percent, the selectivity of the dimethyl oxalate is 98.5 percent, and the space-time yield of the dimethyl oxalate is 1345g/Lcat/h.
[ example b20 ]
The reaction conditions for preparing oxalate by oxidative coupling of CO were the same as in example b9, and the reaction was continued for 3000 hours, and the results were shown in Table b 1.
TABLE b1
Comparative example b1
Dissolving 58.2 g of nickel nitrate hexahydrate in 200 ml of deionized water to obtain a solution A; an additional 24.4 grams of sodium silicate was dissolved in 200 milliliters of deionized water to provide solution B. And (2) dripping the solutions A and B into 50mL of deionized water at the speed of 10 milliliters per minute under stirring at normal temperature, aging the obtained mixture for 2 hours at the temperature of 60 ℃, filtering, washing a filter cake for 5 times by using the deionized water, drying the filter cake at the temperature of 120 ℃ overnight, and roasting the filter cake for 4 hours at the temperature of 450 ℃ to obtain the nickel silicate carrier NS-1.
Adding 20 g of NS-1 carrier into a 200 ml beaker, adding 100 ml of deionized water and 0.77 g of palladium nitrate solution with the Pd mass content of 13%, drying the mixture in a 120 ℃ oven overnight, and then roasting in a 450 ℃ oven for 4 hours to obtain the noble metal Pd catalyst PNS-1 loaded by the nickel phyllosilicate carrier, wherein the weight part of Pd is 0.5, and the weight part of the carrier nickel silicate is 99.5.
The catalyst PNS-1 was evaluated in the same manner as in [ example b9 ] to obtain a methyl nitrite conversion of 38.5%, a dimethyl oxalate selectivity of 93.3% and an hourly space yield of 568g/Lcat/h.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described in relation to an exemplary embodiment, and it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (16)
1. A catalyst for producing oxalate through CO oxidative coupling comprises carrier phyllosilicate and metal Pd, wherein the phyllosilicate is copper phyllosilicate and/or nickel phyllosilicate;
the weight content of copper or nickel in the copper phyllosilicate and the nickel phyllosilicate is 5-40%.
2. The catalyst according to claim 1, wherein the weight part of the phyllosilicate is 95.0 to 99.9, and the weight part of the metal Pd is 0.1 to 5.0.
3. The catalyst according to claim 1, wherein the weight part of the phyllosilicate is 96.0 to 99.8, and the weight part of the metal Pd is 0.2 to 4.
4. The catalyst according to claim 1, wherein the weight fraction of the phyllosilicate is 98.0 to 99.7 and the weight fraction of the metallic Pd is 0.3 to 2.
5. The catalyst according to claim 1, characterized in that the carrier phyllosilicate has a copper and/or nickel content in the range from 8 to 30% by weight.
6. The catalyst according to any one of claims 1 to 5, characterized in that the catalyst made of copper phyllosilicate and nickel phyllosilicate supporting metal Pd has an infrared spectrum from 665 to 675cm -1 Peak area of (A) and 795-805cm -1 The peak area ratios are (0.005-0.15): 1 and (0.01-0.3): 1.
7. the catalyst according to claim 6, characterized in that the catalyst made of copper phyllosilicate and nickel phyllosilicate supporting metal Pd has an infrared spectrum ranging from 665 cm to 675cm -1 The peak area of (A) and the peak area of 795-805cm -1 The peak area ratios are (0.01-0.10): 1 and (0.02-0.20): 1.
8. the catalyst of claim 6, wherein the IR spectrum is from 665 cm to 675cm -1 The peak area of (A) was 670cm -1 Peak area of (b), 795-805cm in said infrared spectrum -1 The peak area of (A) is 800cm -1 Peak area of (d).
9. A method of preparing a catalyst according to any one of claims 1 to 8, comprising the steps of:
s1, adding copper salt or nickel salt into water, adding concentrated ammonia water or urea, then adding silica sol, heating, and evaporating ammonia or continuously heating until the pH value is less than 7 or more than 6; filtering the obtained mixture, washing with water, drying, and roasting to obtain carrier copper phyllosilicate or nickel phyllosilicate;
and S2, dissolving a salt of metal Pd in water, adding the copper phyllosilicate or nickel phyllosilicate carrier prepared in the step 1 of S1 into the solution, drying the mixture overnight, and roasting the mixture to obtain the catalyst.
10. The method for preparing the catalyst according to claim 9, comprising the steps of:
s1, adding the copper salt into deionized water accounting for 300-8000 percent of the weight of the copper salt, adding concentrated ammonia water accounting for 60-300 percent of the weight of the copper salt, adding silica sol accounting for 100-1500 percent of the weight of the copper salt, stirring for 1-10 hours, heating to 50-100 ℃, and evaporating ammonia or continuously heating until the pH value is less than 7; filtering the obtained mixture, washing with water, drying at 80-150 deg.C overnight, and calcining at 300-700 deg.C for 2-16h to obtain carrier copper phyllosilicate; or
S1, adding nickel salt into deionized water which accounts for 300-8000% of the weight of the nickel salt, adding urea which accounts for 60-300% of the weight of the nickel salt, adding silica sol which accounts for 100-1500% of the weight of the nickel salt, stirring for 1-10 hours, heating to 60-100 ℃, and evaporating ammonia or continuously heating until the pH value is more than 6; filtering the obtained mixture, washing with water, drying at 80-150 deg.C overnight, and roasting at 300-700 deg.C for 2-16h to obtain carrier nickel phyllosilicate; s2, dissolving a salt of metal Pd in water, adding the copper phyllosilicate or nickel phyllosilicate carrier prepared in the step 1 in the step S1, drying at 80-150 ℃ overnight, and roasting at 300-700 ℃ for 2-16h to obtain the catalyst.
11. The method of claim 9, wherein the copper salt is at least one of copper nitrate, copper carbonate, basic copper carbonate, copper sulfate and copper chloride, copper bromide; the nickel salt is at least one of nickel nitrate, nickel carbonate, basic nickel carbonate, nickel sulfate, nickel chloride and nickel bromide.
12. The method according to claim 9, wherein the salt of metallic Pd is palladium chloride and/or palladium nitrate.
13. A process according to claim 9, characterized in that the silica sol used is SiO 2 The content of (A) is 20-50%.
14. A method for producing oxalate by using the catalyst according to any one of claims 1 to 8 or the catalyst prepared by the method according to any one of claims 9 to 13, wherein a mixed gas containing nitrite and CO is used as a raw material, a fixed bed reactor is used, and the raw material and the catalyst are in contact reaction to generate oxalate.
15. The process according to claim 14, wherein the reaction temperature is 110 to 170 ℃ and/or the volume space velocity is 1000 to 10000 hours -1 And/or the molar ratio of CO to nitrite in the raw material is (1-3): 1, and/or the volume content of diluent nitrogen is 30-70%, and/or the reaction pressure is 0.1-2.0MPa.
16. The process according to claim 14, wherein the reaction temperature is 120 to 160 ℃ and/or the volume space velocity is 2000 to 6000 hours -1 And/or the molar ratio of CO to nitrous acid ester in the raw material is (1.2-2.5): 1, and/or the volume content of diluent nitrogen is 40-60%, and/or the reaction pressure is 0.1-1.0MPa.
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| CN101993364A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing oxalic ester by gas phase CO coupling |
| CN105435779A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A catalyst for gas-phase synthesis of oxalate from carbon monoxide |
| CN109529850A (en) * | 2018-12-19 | 2019-03-29 | 山西大学 | A kind of nisiloy catalyst and its preparation method and application |
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| CN101993364A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing oxalic ester by gas phase CO coupling |
| CN105435779A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A catalyst for gas-phase synthesis of oxalate from carbon monoxide |
| CN109529850A (en) * | 2018-12-19 | 2019-03-29 | 山西大学 | A kind of nisiloy catalyst and its preparation method and application |
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