阅读说明：本技术 Co氧化偶联制备草酸酯的方法及其催化剂和制备方法 (Method for preparing oxalate through CO oxidative coupling, catalyst and preparation method thereof ) 是由 陈梁锋 唐康健 朱俊华 于 2019-09-02 设计创作，主要内容包括：本发明涉及一种由CO氧化偶联生产草酸酯的方法,主要解决以往技术中存在的亚硝酸酯转化率低,目的产物草酸酯的选择性和时空产率低的问题。本发明通过采用以含有亚硝酸酯和CO的混合气体为原料,采用固定床反应器,在反应温度为110-170℃,体积空速为1000-10000小时~(-1),原料中CO与亚硝酸酯的比例为(1-3)：1,反应压力为0.1-2.0MPa的情况下,原料与催化剂接触,反应生成草酸酯；其中,所述的催化剂为页硅酸铜和/或页硅酸镍负载的金属Pd催化剂,以重量份数计,包括以下组分：1)95.0～99.9份的页硅酸铜/镍；2)0.1～5.0份的贵金属Pd的技术方案较好地解决了该问题,可用于CO氧化偶联生成草酸酯的工业生产中。(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 nitrite and CO as the raw material, adopts a fixed bed reactor, and has the reaction temperature of 110-class 170 ℃ and the volume space velocity of 1000-class 10000 h ‑1 The ratio of CO to nitrous acid ester in the raw material 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) 0.1-5.0 parts of noble metal PdSolves the problem and can be used in the industrial production of generating oxalate through CO oxidative coupling.)

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;

preferably, the copper or nickel content of the copper and nickel phyllosilicates is 5-40% by weight.

2. The catalyst according to claim 1, characterized in that the phyllosilicate is present in a weight fraction of 95.0 to 99.9, preferably 96.0 to 99.8, more preferably in a weight fraction of 98.0 to 99.7, the metal Pd is present in a weight fraction of 0.1 to 5.0, preferably 0.2 to 4, more preferably 0.3 to 2; the copper and/or nickel content of the carrier phyllosilicate is preferably 8 to 30% by weight.

3. The catalyst according to claim 1 or 2, characterized in that the catalyst made of copper phyllosilicate and copper nickel phyllosilicate supporting metal Pd has an infrared spectrum of 665-^-1Peak area of (A) and 795-805cm^-1The peak area ratios are (0.005-0.15): 1 and (0.01-0.3): 1, preferably (0.01-0.10): 1 and (0.02-0.20): 1; preferably, 665-^-1The peak area of (A) was 670cm^-1The peak area of (A), 795-805cm in the infrared spectrogram^-1The peak area of (A) is 800cm^-1Peak area of (d).

4. A method for preparing a catalyst according to any one of claims 1 to 3, 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 continuing 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;

s2, dissolving the salt of metal Pd in water, adding the copper phyllosilicate or nickel phyllosilicate carrier prepared in the step 1 of S1, drying overnight, and roasting to obtain the catalyst.

5. The method for preparing the catalyst according to claim 4, comprising the steps of:

s1, adding the copper salt into deionized water which accounts for 300-8000% of the weight of the copper salt, adding concentrated ammonia water which accounts for 60-300% of the weight of the copper salt, adding silica sol which accounts for 100-1500% of the weight of the copper salt, stirring for 1-10 hours, heating to 50-100 ℃, and evaporating ammonia or continuing to heat until the pH value is less than 7; filtering the obtained mixture, washing with water, drying at 80-150 ℃ overnight, and roasting at 300-700 ℃ for 2-16h to obtain carrier copper phyllosilicate; or

S1, adding the nickel salt into deionized water which accounts for 300-8000% of the weight of the nickel salt, then adding urea which accounts for 60-300% of the weight of the nickel salt, then 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 continuing to heat until the pH value is 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 carrier nickel phyllosilicate; s2, dissolving the salt of metal Pd in water, adding the copper phyllosilicate or nickel copper phyllosilicate carrier prepared in the step 1 of S1, drying at 80-150 ℃ overnight, and roasting at 300-700 ℃ for 2-16h to obtain the catalyst.

6. The method of claim 4, 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.

7. The method according to claim 4, wherein the salt of metallic Pd is palladium chloride and/or palladium nitrate.

8. A process as claimed in claim 4, wherein the silica sol used is SiO₂The content of (A) is 20-50%.

9. A method for producing oxalate by using the catalyst according to any one of claims 1 to 3 or the catalyst prepared by the method according to any one of claims 4 to 8, 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.

10. The process according to claim 9, characterized in that the reaction temperature is 110-^-1Preferably 2000-6000 hours^-1And/or the molar ratio of CO to nitrite in the raw material is (1-3):1, preferably (1.2-2.5):1, and/or the diluent nitrogen has a volume content of 30-70%, preferably 40-60%, and/or the reaction pressure is 0.1-2.0MPa, preferably 0.1-1.0 MPa.

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 Shikoku corporation has the reaction pressure of 0.5MPa and the reaction temperature of 80-150 ℃.

With the international development of the technology 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 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.

The document CN95116136.9 discloses a catalyst for synthesizing oxalate, selects Zr auxiliary agent and develops a novel catalyst by an impregnation methodPd-Zr/Al of₂O₃The 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-Al₂O₃Soaking 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 so as to realize 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 by 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 the copper nickel phyllosilicate and of the nickel phyllosilicate is 8 to 30% by weight each.

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 of 665-^-1Peak area of (A) and 795-805cm^-1The 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^-1Peak area of (2) to 800cm^-1The 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 continuing 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;

s2, dissolving the salt of metal Pd in water, adding the copper phyllosilicate or nickel phyllosilicate carrier prepared in the step 1 of S1, drying overnight, and roasting 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 which accounts for 300-8000% of the weight of the copper salt, adding concentrated ammonia water which accounts for 60-300% of the weight of the copper salt, adding silica sol which accounts for 100-1500% of the weight of the copper salt, stirring for 1-10 hours, heating to 50-100 ℃, and evaporating ammonia or continuing to heat until the pH value is less than 7; filtering the obtained mixture, washing with water, drying at 80-150 ℃ overnight, and roasting at 300-700 ℃ for 2-16h to obtain carrier copper phyllosilicate; or

S1, adding the nickel salt into deionized water which accounts for 300-8000% of the weight of the nickel salt, then adding urea which accounts for 60-300% of the weight of the nickel salt, then 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 continuing to heat until the pH value is 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 carrier nickel phyllosilicate; s2, dissolving the salt of metal Pd in water, adding the copper phyllosilicate or nickel copper phyllosilicate carrier prepared in the step 1 of S1, drying at 80-150 ℃ overnight, and roasting at 300-700 ℃ for 2-16h to obtain the catalyst. The drying overnight is for 6-14 h.

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 used₂The 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 present invention, the reaction temperature is 110-170 ℃.

According to some preferred embodiments of the present invention, the reaction temperature is 120-160 ℃.

According to some preferred embodiments of the present invention, the volume space velocity is 1000-^-1。

According to some preferred embodiments of the present invention, the volume space velocity is 2000-^-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 2.0 MPa.

According to some preferred embodiments of the invention, the reaction pressure is between 0.1 and 1.0 MPa.

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^-1Peak area of (2) to 800cm^-1The 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^-1Peak area of (2) to 800cm^-1The 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^-1Peak area of (2) to 800cm^-1The 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, 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 smallAt 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, stirring is carried out for 1-10 h, heating is carried out 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 ℃ overnight, roasting at 300-700 ℃ for 2-16h to obtain carrier copper phyllosilicate, adding nickel salt into deionized water accounting for 300-8000% of the weight of the nickel salt, adding urea accounting for 60-300% of the weight of the nickel salt, adding silica sol accounting for 100-1500% of the weight of the nickel salt, stirring for 1-10 h, heating to 60-100 ℃, and continuing to heat until the pH value is 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 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 noble metal Pd catalyst loaded on copper phyllosilicate and/or nickel phyllosilicate is used in the oxidative coupling reaction of CO and nitrite, and has the reaction temperature of 130 ℃ and the volume space velocity of 3000 hours^-1When 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 (1098g/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.

Copper phyllosilicate as carrier

[ example a1 ]

18.9 g of copper nitrate trihydrate, 200 g of deionized water and 30g of 25% concentrated ammonia water are added into a 500 ml beaker, and 37.5 g of SiO are added₂Stirring 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^-1Peak area of (2) to 800cm^-1The 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 added₂Stirring 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 100 deg.C oven overnight, and calcining at 550 deg.C for 10 hr to obtain copper phyllosilicate carrier PS-2 with Cu content of 35 wt%, and infrared spectrum of 670cm^-1Peak area of (2) to 800cm^-1The peak area ratio of (B) was 0.04.

In a 200 ml beaker, 20 g PS-2 carrier was added, 100 ml deionized water and 0.066 g PdCl were added₂The 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 the 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 give PS-3 as the copper phyllosilicate support having a Cu content of 5% by weight and a mass of 670cm in the IR spectrum^-1Peak area of (2) to 800cm^-1The peak area ratio was 0.03.

The catalyst was prepared in the same manner as in example a1, except that the support used was PS-3 and the resulting catalyst was aOCP-3.

[ 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 42.5 g of silica sol was added to obtain a copper phyllosilicate support of PS-4 having a Cu content of 15% by weight and a 670cm IR spectrum^-1Peak area of (2) to 800cm^-1The peak area ratio of (A) was 0.05.

The catalyst was prepared in the same manner as in example a1, except that the support used was PS-4 and the resulting catalyst was aOCP-4.

[ example a5 ]

The catalyst support was prepared in the same manner as in example a1, except that the copper salt used was 17.5 g of cupric bromide, the amount of concentrated aqueous ammonia added was 20.0 g, the amount of silica sol added was 37.5 g, and the resulting copper phyllosilicate support was PS-5 having a Cu content of 25% by weight and a 670cm IR spectrum showing 670cm^-1Peak area of (2) to 800cm^-1The peak area ratio of (A) was 0.09.

The catalyst was prepared in the same manner as in example a1, except that the support used was PS-5 and the resulting catalyst was aOCP-5.

[ example a6-8 ]

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 weight 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, with Pd in an amount of 0.3, 0.8 and 1.5, respectively, and the copper phyllosilicate PS-1 as the support 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 N₂The reaction conditions are as follows: the reaction temperature is 130 ℃, and the gas volume space velocity is 3000 hours^-1The 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 1098 g/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 880 g/Lcat/h.

[ example a11 ]

The reaction conditions for the oxidative coupling of CO to prepare oxalate were the same as in [ example a9 ], except that the catalyst used was aOCP-3, the conversion of methyl nitrite was 63.2%, the selectivity to dimethyl oxalate was 99.2%, and the space-time yield of dimethyl oxalate was 990 g/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 to dimethyl oxalate was 99.0%, and the space-time yield of dimethyl oxalate was 1018 g/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 1061 g/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 for dimethyl oxalate was 99.2%, and the space-time yield of dimethyl oxalate was 832 g/Lcat/h.

[ example a15 ]

The reaction conditions for the oxidative coupling of CO to prepare oxalate 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 1154 g/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 obtained was 76.0%, the selectivity for dimethyl oxalate was 98.0%, and the space-time yield of dimethyl oxalate was 1177 g/Lcat/h.

[ example a17 ]

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 40% CO, 20% NO, 40% N by volume₂. 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 1281 g/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 used was 20% CO, 20% NO, 60% N by volume₂. The gas space velocity is 2000 hours^-1The 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 629 g/Lcat/h.

[ example a19 ]

Method for preparing oxalate by oxidative coupling of COThe reaction conditions were the same as in [ example a9 ], except that the gas composition used was 20% CO, 20% NO, 60% N by volume₂. The air space velocity is 6000 hours^-1The 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 1350 g/Lcat/h.

[ example a20 ]

The reaction conditions for preparing oxalate by oxidative coupling of CO were the same as in example a9, and the results obtained were shown in Table a1 after 3000 hours of continuous reaction.

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. At normal temperature, the solution A, B is dripped into 50mL deionized water at the speed of 10 mL per minute under stirring, the obtained mixture is aged for 2 hours at 60 ℃ and then filtered, the filter cake is washed for 5 times by the deionized water, and then is dried at 120 ℃ overnight and then is roasted for 4 hours at 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 ] to give a methyl nitrite conversion of 45.5%, a dimethyl oxalate selectivity of 95.1% and an hourly space yield of 684 g/Lcat/h.

Nickel disilicate 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 added₂Stirring 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^-1Peak area of (2) to 800cm^-1The peak area ratio of (A) 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-supported 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 added₂Stirring 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^-1Peak area of (2) to 800cm^-1The 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 added₂And 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 ]

Method for preparing catalyst carrier and [ implementation ]Example b1 the same 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 PS-3 with a Ni content of 5% by weight and 670cm in the IR spectrum^-1Peak area of (2) to 800cm^-1The 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 a nickel phyllosilicate support PS-4 having a Ni content of 15% by weight and a spectrum of 670cm in infrared^-1Peak area of (2) to 800cm^-1The peak area ratio was 0.10.

The catalyst was prepared in the same manner as in example b1, except that the support used was PS-4 and the resulting catalyst was bOCP-4.

[ 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 nickel phyllosilicate support having a Ni content of 25% by weight and a size of 670cm in an infrared spectrum^-1Peak area of (2) to 800cm^-1The peak area ratio of (A) was 0.18.

The catalyst was prepared in the same manner as in example b1, except that the support used was PS-5 and the resulting catalyst was bOCP-5.

[ example b6-8 ]

The preparation of the catalyst support and the catalyst were carried out in the same manner as in example b1, except that the palladium nitrate solution containing 13% by weight 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, with 0.3, 0.8 and 1.5 parts by weight of Pd, and 99.7, 99.2 and 98.5 parts by weight of the support, nickel phyllosilicate PS-1.

[ 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 N₂The reaction conditions are as follows: the reaction temperature is 130 ℃, and the gas volume space velocity is 3000 hours^-1The 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 1130 g/Lcat/h.

[ example b10 ]

The reaction conditions for the oxidative coupling of CO to give 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 to dimethyl oxalate was 98.4%, and the space-time yield of dimethyl oxalate was 890 g/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 996 g/Lcat/h.

[ example b12 ]

The reaction conditions for the preparation of oxalate by oxidative coupling of CO were identical to [ example b9 ], except that the catalyst used was bOCP-4, giving a conversion of methyl nitrite of 66.5%, a selectivity for dimethyl oxalate of 98.7% and a space-time yield of dimethyl oxalate of 1037 g/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 1074 g/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 obtained was 53.9%, the selectivity for dimethyl oxalate was 99.1%, and the space-time yield of dimethyl oxalate was 844 g/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 1161 g/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 was 78.0%, the selectivity for dimethyl oxalate was 97.5%, and the space-time yield of dimethyl oxalate was 1201 g/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 was 40% CO, 20% NO, 40% N by volume₂. The air space velocity is 5000 hours^-1The 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 1278 g/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 used was 20% CO, 20% NO, 60% N by volume₂. The gas space velocity is 2000 hours^-1The 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 635 g/Lcat/h.

[ example b19 ]

The reaction conditions for preparing the oxalate through CO oxidative coupling are the same as that in example b9,except that the gas composition by volume used was 20% CO, 20% NO, 60% N₂. The air space velocity is 6000 hours^-1The 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 1345 g/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. At normal temperature, the solution A, B is dripped into 50mL deionized water at the speed of 10 mL per minute under stirring, the obtained mixture is aged for 2 hours at the temperature of 60 ℃ and then filtered, the filter cake is washed for 5 times by the deionized water, and then is dried at the temperature of 120 ℃ overnight, and then is roasted for 4 hours at the temperature of 450 ℃, so as 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 nickel phyllosilicate carrier-supported noble metal Pd catalyst PNS-1, wherein the weight part of Pd is 0.5, and the weight part of 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 568 g/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 with reference to exemplary embodiments, but 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.