CN112916049A - Oxygen-containing polydentate ligand modified copper-based catalyst for acetylene hydrochlorination reaction and preparation method and application thereof - Google Patents
Oxygen-containing polydentate ligand modified copper-based catalyst for acetylene hydrochlorination reaction and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an oxygen-containing polydentate ligand modified copper-based catalyst for acetylene hydrochlorination and a preparation method and application thereof. The catalyst takes activated carbon as a carrier and copper salt as a main active component, and the catalytic activity and stability of the catalyst are improved by adding oxygen-containing polydentate ligands. The oxygen-containing polydentate ligand does not contain other heteroatoms except oxygen and can form a stable complex with copper; the copper salt is selected from one or more of copper chloride, copper bromide, copper nitrate and copper sulfate; the mass ratio of the copper element in the catalyst is 2.5-16%. Copper ions can be firmly combined with oxygen-containing polydentate ligands to prevent reduction to inactive zero-valent copper during the catalytic process. In addition, if the two are coordinated to form a five-membered cyclic complex, the electrons of the copper ions can be regulated and controlled, and the space distribution of the copper ions is more favorable for catalysis.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and particularly relates to an oxygen-containing polydentate ligand modified copper-based catalyst for acetylene hydrochlorination, and a preparation method and application thereof.
Background
Polyvinyl chloride (PVC) is one of five general resins in the world, and is widely applied to multiple industries such as chemical industry, building materials, agriculture, medical appliances and the like. In 2018, the total yield of the Chinese PVC exceeds 2400 ten thousand tons, and the total yield of the PVC accounts for more than 40% of the total yield of the PVC in the world. By 2026, the global PVC total demand is expected to reach 5620 million tons. The production of polyvinyl chloride (PVC) needs Vinyl Chloride Monomer (VCM), and in view of the special energy structure of rich coal, poor oil and less gas in China, the acetylene method production route based on coal is selected in China with mature technology, less water consumption and low production cost, but the core link of the production route depends on mercury-containing catalysts, and the production of polyvinyl chloride (PVC) becomes the industry with the largest mercury consumption in China and accounts for more than 60% of the total mercury consumption in China.
The mercury-containing catalyst for industrial hydrochlorination of acetylene contains HgCl as main active component2It is easy to sublimate and run off at high temperature, and can cause serious environmental pollution and serious harm to human health. With the positive effect of 'water guarantee for mercury' in 2017 in the contracting prescriptions in China and the like, the use of products containing mercury is strictly limited, and the mercury-free process in the industry of preparing vinyl chloride by calcium carbide becomes a necessary way for the development of the industry. Since the 70 s of the last century, research on mercury-free catalysts for acetylene hydrochlorination has begun by relevant researchers at home and abroad. A large number of research results show that the mercury-free catalyst with industrial application conditions at the present stage mainly uses a catalyst with noble metals (such as Au, Pt and Ru) as active components and a catalyst with non-noble metals (such as Cu, Sn and Bi) as active components. Based on economy, a non-noble metal mercury-free catalyst is in the heat trend of research in recent years, particularly a Cu-based catalyst, and a large number of documents and patent reports appear.
The invention patent with the publication number of CN107008465B discloses a copper-based catalyst for acetylene hydrochlorination, which takes copper salt as an active component and is added with a stabilizer to improve the stability of the catalyst. The copper salt is selected from one or more of copper chloride, copper nitrate, copper sulfate and copper phosphate, the stabilizer is selected from one or more of guanidine hydrochloride, tetramethylethylenediamine hydrochloride, tetramethylammonium chloride, tetraethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, methyltriphenylphosphonium chloride and 1-butyltriphenylphosphonium chloride, the stability of the copper-based catalyst is effectively improved, but the reaction activity is not improved, and the highest initial reaction activity is only 74%.
Application 201910933364.8 proposes a method for the preparation of a trivalent copper catalyst and its use in the hydrochlorination of acetylene. Adding a nitrogen-containing heterocyclic compound and a copper salt into a trichloromethane solution, and mixing to obtain a mixed solution containing a divalent copper compound; adding ionic liquid into the obtained mixed solution, and obtaining mixed solution containing a trivalent copper compound under the action of an oxidant; and (3) soaking the porous solid carrier in the obtained mixed liquid containing the trivalent copper compound for 0.5-5 h, taking out the treated solid, and heating and drying under the condition of blue light irradiation to obtain the trivalent copper catalyst. Although the catalyst has certain activity and stability in the reaction, the preparation process is complicated, and the industrial production is not easy to realize.
At present, the acetylene hydrochlorination copper-based catalyst mainly has the disadvantages of activity and poor stability or the preparation method is not easy to realize industrial production. Based on the background, the application discloses an acetylene hydrochlorination mercury-free catalyst which takes activated carbon as a carrier and copper salt as an active component and improves the activity and stability through oxygen-containing polydentate ligand.
Disclosure of Invention
Aiming at the defects of the technology and the defects in the aspect of industrial application, the invention provides an oxygen-containing polydentate ligand modified copper-based catalyst for acetylene hydrochlorination, and a preparation method and application thereof.
Aiming at the problems of low activity and poor stability commonly existing in the existing copper-based catalyst, a large number of experiments and researches find that the oxygen-containing polydentate ligand can enable high-valence copper active species to be more stable and reduce the generation of a reduction product, namely zero-valence copper in the catalytic process. According to the theory of soft and hard acid-base, electron donors such as carboxyl, hydroxyl and the like are oxygen atoms, are difficult to polarize and belong to hard base, copper ions are hard acid and can form stable coordination compounds with the hard base, and the oxygen atoms of the electron donors such as carboxyl, hydroxyl and the like can be stably coordinated with the copper ions serving as boundary acid, so that the copper ions can be firmly combined with oxygen-containing polydentate ligand, and are prevented from being reduced into inactive zero-valent copper in the catalytic process, and the activity and the stability of the copper-based catalyst are further improved. Furthermore, if the two are coordinated to form a five-membered cyclic complex, the electrons of the copper ions can be regulated and controlled to tend to have a more favorable spatial distribution for catalysis.
The oxygen-containing polydentate ligand refers to a ligand in which two or more oxygen atoms are contained as a coordinating atom in one ligand. There are 6 electrons around the oxygen. Two of which form a covalent bond with carbon and then have two lone pair electrons which can coordinate with transition metal. The oxygen atom in the furan ring, the carbonyl oxygen and the hydroxyl oxygen in the carboxyl group are all sp2 hybridized, and the oxygen of the alcoholic hydroxyl group is sp3 hybridized, but all can be used as coordination atoms. The oxygen-containing polydentate ligands to which this patent relates are free of heteroatoms other than oxygen.
The invention is realized by the following method:
the oxygen-containing polydentate ligand modified copper-based catalyst for the hydrochlorination of acetylene consists of copper salt, oxygen-containing polydentate ligand and a carrier. Copper salt and one or more oxygen-containing ligands are loaded on the surface of a carbon carrier, wherein the cation of the copper salt is mainly Cu2+(ii) a The coordinated oxygen atom of the oxygen-containing ligand is from one or more of furan ring, ester group, carboxyl and hydroxyl.
A preparation method of an oxygen-containing polydentate ligand modified copper-based catalyst for acetylene hydrochlorination comprises the following steps:
1) dissolving a copper salt and an oxygen-containing polydentate ligand into a specific solvent at a certain temperature according to a certain proportion to obtain a mixed solution, wherein the ligand can be completely dissolved at the temperature to obtain a uniform and stable mixed solution;
2) uniformly loading active components in the mixed solution on an active carbon carrier by adopting methods such as dipping, spraying, precipitation, ion exchange, spray evaporation and the like at the same temperature;
3) drying for a certain time under a certain temperature and pressure environment to obtain the catalyst.
Preferably, step 1) further comprises one or more of the following features:
1) the copper salt is selected from one or more of copper chloride, copper bromide, copper nitrate and copper sulfate; more preferably, the copper salt is copper chloride;
2) the ligand is selected from one or more of oxygen-containing organic matters with furan rings (such as 2-acetylfuran, furfuryl alcohol, furfural and hydroxymethyl furfural), ester groups (ethyl carbonate, 1, 4-butyrolactone, methyl pyruvate, dimethyl maleate, diethyl oxalate, 4-hydroxycoumarin), carboxyl groups (mandelic acid, 1-hydroxycyclohexyl formic acid, trimethylpyruvic acid, lactic acid, malonic acid and 2-tetrahydrofuran formic acid); wherein 2-acetylfuran, furfuryl alcohol, furfural, hydroxymethyl furfural, methyl pyruvate, diethyl oxalate, mandelic acid, 1-hydroxycyclohexyl formic acid, trimethylpyruvic acid, lactic acid, 2-tetrahydrofurfuryl formic acid and the like can form a five-membered ring complex structure with copper.
3) The molar ratio of the copper salt to the ligand in the mixed solution is 0.25-2; more preferably, the molar ratio of the copper salt to the ligand in the mixed solution is 0.5-1;
4) the mixed solution solvent is a common polar solvent; more preferably, the solvent is selected from one or more of deionized water, absolute ethyl alcohol, acetone, dichloromethane, acetonitrile, chloroform, N-dimethylformamide;
5) the mass of the Cu element in the mixed solution accounts for 2.5-16% of the mass fraction of the finished catalyst product, such as 2.5-5 wt%, 5-8.5 wt% and 12-15 wt%;
6) the stirring and dissolving temperature of the mixed solution is 15-80 ℃, such as 15-30 ℃, 40-65 ℃ and 65-80 ℃.
Preferably, step 2) should include one or more of the following features:
1) the active carbon carrier is one or more of coconut shell active carbon, coal active carbon, wood active carbon and asphalt-based active carbon;
2) the water capacity of the activated carbon is 60-130%, and the bulk density is 0.3-0.8 g/mL;
3) the loading temperature and the stirring and dissolving temperature are 15-80 ℃.
Preferably, step 3) should include one or more of the following features:
1) the drying treatment process of the catalyst comprises the following steps: drying for 6-20 h under the condition that the temperature is 5-20 ℃ higher than the boiling point of the solvent and the pressure is 0.1 MPa.
More preferably, the drying in step 3) is carried out for 20h at 15 ℃ above the boiling point of the solvent.
The prepared oxygen-containing polydentate ligand modified copper-based catalyst is applied to acetylene hydrochlorination.
Preferably, the reaction conditions are: the temperature is 90-250 ℃, and the volume space velocity of acetylene is 5-200 h-1The pressure is 0.01 to 0.2 MPa.
The product consisted of gas chromatographic analysis and the reactivity was expressed as acetylene conversion.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the catalyst, a neutral oxygen-containing polydentate ligand is added into copper salt and is used for forming a stable complex with copper, and the oxygen-containing polydentate ligand is introduced to form a complex with copper, so that high-valence copper active species are stabilized;
2) the stability of copper ions can reduce the generation of inactive zero-valent copper in the catalytic process, thereby improving the activity of the copper-based catalyst;
3) oxygen-containing ligands such as 2-tetrahydrofuran formic acid and furfuryl alcohol coordinate with copper ions to form a five-membered cyclic complex, and the electrons of the copper ions are regulated and controlled to tend to be more favorable for catalysis in spatial distribution, so that the catalytic activity is better. The five-membered cyclic complex structure is shown below:
4) the oxygen-containing polydentate ligand modified copper-based catalyst prepared by the preparation method has high catalytic activity and good stability, and the acetylene airspeed is 40h under the reaction condition of 130 DEG C-1Volume ratio of hydrogen chloride to acetylene is 1.2: at 1 hourThe acetylene conversion rate is over 80 percent, the stability is good, and the acetylene conversion rate has good industrial application potential.
Detailed Description
The technical solution of the present invention is illustrated by specific examples below. The following examples are intended to provide those skilled in the art with a more detailed understanding of the present invention and are not intended to limit the scope of the present invention. The scope of protection of the invention is set forth in the appended claims.
Example 1
(1) At 50 ℃, 1.7g of anhydrous copper chloride and 0.61g of methyl pyruvate are stirred and dissolved in 5.5g of anhydrous ethanol to obtain a steeping liquor containing copper ions and ligands;
(2) soaking the soaking solution on 10g of active carbon by an isometric soaking method, sealing and standing for 1 hour at 50 ℃;
(3) drying the activated carbon at 95 ℃ for 20 hours to obtain the catalyst A1.
A1 at 130 deg.C and acetylene space velocity of 40 hr-1Volume ratio of hydrogen chloride to acetylene is 1.2: at 1, the acetylene conversion was 84.5%.
Comparative example 1
(1) Dissolving 1.7g of anhydrous copper chloride in 5.5g of anhydrous ethanol at 50 ℃ under stirring to obtain a steeping liquor only containing copper ions;
(2) soaking the soaking solution on 10g of active carbon by an isometric soaking method, sealing and standing for 1 hour at 50 ℃;
(3) drying the activated carbon at 95 ℃ for 20 hours to obtain the catalyst A2.
A2 at 130 deg.C and acetylene space velocity of 40 hr-1Volume ratio of hydrogen chloride to acetylene is 1.2: at 1, the acetylene conversion was 80.6%. However, under the same conditions, the copper ions are only used as active components, so that the overall performances such as stability and service life are poor, and the industrial application cannot be met.
Example 2
(1) At 50 ℃, 1.7g of anhydrous copper chloride and 0.54g of lactic acid are stirred and dissolved in 5.5g of N, N-dimethylformamide to obtain a steeping liquor containing copper ions and ligands;
(2) soaking the soaking solution on 10g of active carbon by an isometric soaking method, sealing and standing for 1 hour at 50 ℃;
(3) drying the activated carbon at 170 ℃ for 20 hours to obtain the catalyst A3.
A3 at 130 deg.C and acetylene space velocity of 40 hr-1Volume ratio of hydrogen chloride to acetylene is 1.2: at 1, the acetylene conversion was 87.1%.
Example 3
(1) At 50 ℃, 1.7g of anhydrous copper chloride and 0.61g of methyl pyruvate are stirred and dissolved in 5.5g of N, N-dimethylformamide to obtain a steeping liquor containing copper ions and ligands;
(2) soaking the soaking solution on 10g of active carbon by an isometric soaking method, sealing and standing for 1 hour at 50 ℃;
(3) drying the activated carbon at 170 ℃ for 20 hours to obtain the catalyst A4.
A4 at 130 deg.C and acetylene space velocity of 40 hr-1Volume ratio of hydrogen chloride to acetylene is 1.2: at 1, the acetylene conversion was 86.9%.
Example 4
(1) At 50 ℃, 1.7g of anhydrous copper chloride and 0.66g of 2-acetylfuran are stirred and dissolved in 5.5g of N, N-dimethylformamide to obtain impregnation liquid containing copper ions and ligands;
(2) soaking the soaking solution on 10g of active carbon by an isometric soaking method, sealing and standing for 1 hour at 50 ℃;
(3) drying the activated carbon at 170 ℃ for 20 hours to obtain the catalyst A5.
A5 at 130 deg.C and acetylene space velocity of 40 hr-1Volume ratio of hydrogen chloride to acetylene is 1.2: at 1, the acetylene conversion was 87.3%.
Example 5
(1) At 50 ℃, 1.7g of anhydrous copper chloride and 0.59g of furfuryl alcohol are stirred and dissolved in 5.5g of N, N-dimethylformamide to obtain impregnation liquid containing copper ions and ligands;
(2) soaking the soaking solution on 10g of active carbon by an isometric soaking method, sealing and standing for 1 hour at 50 ℃;
(3) drying the activated carbon at 170 ℃ for 20 hours to obtain the catalyst A6.
A6 acetylene at 130 deg.CSpace velocity of 40h-1Volume ratio of hydrogen chloride to acetylene is 1.2: at 1, the acetylene conversion was 87.7%.
Example 6
(1) At 50 ℃, 1.7g of anhydrous copper chloride and 0.70g of 2-tetrahydrofuran formic acid are stirred and dissolved in 5.5g of N, N-dimethylformamide to obtain impregnation liquid containing copper ions and ligands;
(2) soaking the soaking solution on 10g of active carbon by an isometric soaking method, sealing and standing for 1 hour at 50 ℃;
(3) drying the activated carbon at 170 ℃ for 20 hours to obtain the catalyst A7.
A7 at 130 deg.C and acetylene space velocity of 40 hr-1Volume ratio of hydrogen chloride to acetylene is 1.2: at 1, the acetylene conversion was 88.8%.
Example 7
(1) At 50 ℃, 1.7g of anhydrous copper chloride and 0.53g of ethyl carbonate are stirred and dissolved in 5.5g of N, N-dimethylformamide to obtain impregnation liquid containing copper ions and ligands;
(2) soaking the soaking solution on 10g of active carbon by an isometric soaking method, sealing and standing for 1 hour at 50 ℃;
(3) drying the activated carbon at 170 ℃ for 20 hours to obtain the catalyst A8.
A8 at 130 deg.C and acetylene space velocity of 40 hr-1Volume ratio of hydrogen chloride to acetylene is 1.2: at 1, the acetylene conversion was 88.1%.
The tail gas composition was analyzed using gas chromatography, sampling every 0.5 hours. Data samples were taken, represented by the 4 hour reaction point, comparing acetylene conversion and vinyl chloride selectivity for copper-based catalysts incorporating different oxygen-containing multidentate ligands, and the results are shown in the table:
the better activity of the cyclic ethyl carbonate is probably because the structure has special electronic effect, and the oxygen at two alpha positions reduces the electron cloud density on carbonyl carbon, so that the nucleophilicity of the carbonyl oxygen is enhanced, and the coordination with copper is more stable than that of the common carbonyl.
The oxygen-containing ligands in examples 1 to 6 can form five-membered cyclic complexes after coordination with copper ions, under the same conditions, the acetylene conversion rate is significantly improved compared with a copper catalyst without the oxygen-containing ligands, and the stability and the service life of the catalyst are also significantly improved due to the firm bonding of the copper ions and the oxygen-containing polydentate ligands, which indicates that the oxygen-containing ligands have significant gain effects after addition.
Nothing in this specification is said to apply to the prior art.
Claims (10)
1. An oxygen-containing polydentate ligand-modified copper-based catalyst for use in the hydrochlorination of acetylene, characterized in that the catalyst comprises a copper salt, an oxygen-containing polydentate ligand and a support.
2. The catalyst of claim 1, wherein the oxygen-containing polydentate ligand is free of heteroatoms other than oxygen and is capable of forming stable complexes with copper; the copper salt is selected from one or more of copper chloride, copper bromide, copper nitrate and copper sulfate; the mass ratio of the copper element in the catalyst is 2.5-16%.
3. The catalyst of claim 1, wherein copper coordinates to oxygen in the oxygen-containing polydentate ligand to form a five-membered ring complex.
4. The catalyst of claim 1, wherein the coordinating oxygen atoms of the oxygen-containing polydentate ligand are derived from one or more of furan rings, ester groups, carboxyl groups, hydroxyl groups; the oxygen-containing polydentate ligand is one or more of 2-acetylfuran, furfuryl alcohol, furfural, hydroxymethyl furfural, ethyl carbonate, 1, 4-butyrolactone, methyl pyruvate, dimethyl maleate, diethyl oxalate, 4-hydroxycoumarin, mandelic acid, 1-hydroxycyclohexyl formic acid, trimethylpyruvic acid, lactic acid, malonic acid and 2-tetrahydrofuran formic acid.
5. The catalyst of claim 1 wherein the support is one or more of coconut shell activated carbon, coal based activated carbon, wood based activated carbon, pitch based activated carbon.
6. The catalyst of claim 5, wherein the activated carbon has a water capacity of 60 to 130% and a bulk density of 0.3 to 0.8 g/mL.
7. A preparation method of an oxygen-containing ligand modified copper-based catalyst for acetylene hydrochlorination is characterized by comprising the following preparation steps:
(1) dissolving a copper salt and an oxygen-containing polydentate ligand into a solvent according to a certain proportion to obtain a mixed solution, wherein the molar ratio of the copper salt to the ligand in the mixed solution is 0.25-2;
(2) uniformly loading active components in the mixed solution onto an active carbon carrier by adopting a dipping method, a spraying method, a precipitation method, an ion exchange method or a spray evaporation method at the same temperature as the dissolving temperature of the mixed solution obtained in the step (1);
(3) drying at a temperature of 5-20 ℃ higher than the boiling point of the solvent to obtain the catalyst of claim 1.
8. The method according to claim 7, wherein in the step (1), the molar ratio of the copper salt to the ligand is 0.25 to 2; in the step (1), the solvent is a polar solvent; preferably, the solvent is selected from one or more of deionized water, absolute ethyl alcohol, acetone, dichloromethane, acetonitrile, chloroform, and N, N-dimethylformamide; the dissolving temperature of the mixed solution is 15-80 ℃.
9. The manufacturing method according to claim 7, wherein the drying process in the step (3) is a process of: drying for 6-20 h under the condition that the temperature is 5-20 ℃ higher than the boiling point of the solvent and the pressure is 0.1 MPa.
10. The application of the catalyst of claim 1, which is characterized in that the catalyst is used for hydrochlorination of acetylene, the reaction temperature is 90-250 ℃, and the volume space velocity of acetylene is 5-200 h-1The reaction pressure is 0.01-0.2 MPa.
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| CN112916049B (en) | 2022-05-10 |
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