CN113754652A - Synthesis method of metal diazolyl ion catalyst - Google Patents

Synthesis method of metal diazolyl ion catalyst Download PDF

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CN113754652A
CN113754652A CN202110985821.5A CN202110985821A CN113754652A CN 113754652 A CN113754652 A CN 113754652A CN 202110985821 A CN202110985821 A CN 202110985821A CN 113754652 A CN113754652 A CN 113754652A
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acetylene
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diazole
chloride
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高子豪
王富民
张旭斌
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HEBEI MEIBANG ENGINEERING TECHNOLOGY CO LTD
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HEBEI MEIBANG ENGINEERING TECHNOLOGY CO LTD
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Abstract

The invention relates to the technical field of high-activity catalyst preparation, in particular to a synthesis method of a metal diazolyl ion catalyst; according to the synthesis method of the metal diazolyl ion catalyst, a heterocyclic compound containing propylamine is obtained through Michael addition reaction, and is further subjected to amidation reaction with metal carboxylate containing two carboxyl groups, so that metal ions are combined together to obtain the metal diazolyl ion catalyst, the inactivation of the catalyst is effectively avoided, and high-activity and high-stability catalysis is realized.

Description

Synthesis method of metal diazolyl ion catalyst
Technical Field
The invention relates to the technical field of preparation of high-activity catalysts, in particular to a synthesis method of a metal diazole-based ionic catalyst.
Background
Polyvinyl chloride (PVC), is a polymer obtained by polymerizing Vinyl Chloride Monomer (VCM) with an initiator such as peroxide and azo compound or by a radical polymerization mechanism under the action of light and heat. Vinyl chloride homopolymers and vinyl chloride copolymers are collectively referred to as vinyl chloride resins. In the PVC industry of China, the acetylene method is mainly used for producing vinyl chloride monomer, and the yield of the vinyl chloride monomer accounts for about 80 percent of the total yield. However, the catalyst used for synthesizing vinyl chloride is mercuric chloride and mercury-free chloride with metal chloride as an active component. The mercury chloride can cause serious pollution to the environment, and the polyvinyl chloride synthesized by the mercury chloride contains a small amount of mercury, so that the application of the polyvinyl chloride is limited. Therefore, the catalyst is developed towards low-mercury and non-mercury, mercury pollution is controlled and gradually eliminated, and a clean catalyst and a process route for synthesizing chloroethylene are searched, so that the problem which needs to be solved urgently in the chlor-alkali industry at present is solved.
ZL02808687.2 reports on the preparation of hydrogen-bis (chelated) boric acid compounds and alkali metal-bis (chelated) borates, in which the bis (chelated) boric acid compounds are prepared by reacting boric acid or boron trioxide with dicarboxylic organic compounds. CN103113242B reports functionalized choline chloride ionic liquid, a preparation method thereof and application thereof in electrochemical energy storage devices, wherein anions of the functionalized choline chloride ionic liquid are mainly Cl-, Br-, BF 4-and the like, and the ionic liquid is applied to the fields of lithium ion batteries and capacitors.
CN202011171467.4 provides a chelating boron ionic liquid containing a thiadiazole structure, wherein the ionic liquid is prepared by taking choline as a cation and taking thiadiazole glycerol chelating borate as an anion. The anionic thiadiazole glycerol chelating borate is prepared by reacting 2, 5-dimercapto-1, 3, 4-thiadiazole with glycerol and then reacting with boric acid. The invention also provides application of the chelating boron ionic liquid containing the thiadiazole structure, and the ionic liquid is dissolved in polyethylene glycol base oil to prepare a lubricant composition. The invention provides a chelating boron ionic liquid containing a thiadiazole structure, and a polyethylene glycol lubricant composition containing the ionic liquid has good corrosion resistance, good wear resistance and good antifriction performance.
However, in the prior art, only the ionic liquid is adopted to react with the metal ions under the action of the carrier, and the ionic liquid has the advantages of extremely low saturated vapor pressure, good thermal stability, good solubility of metal compounds, adjustable structure and function and the like, so that a new path is opened up for the development of acetylene hydrochlorination gas-liquid reaction. Different non-mercury metal catalysts are dissolved in imidazole and pyridine conventional ionic liquids to react, the ionic liquids take imidazole rings and pyridine rings as cations and chloride ions, bromide ions, hexafluorophosphate radicals or tetrafluoroborate radicals as anions, but the ionic liquids are low in conversion rate and have a certain difference with industrial reaction.
Disclosure of Invention
The invention aims at the defects in the prior art, discloses a synthesis method of a metal diazolyl ion catalyst, and belongs to the technical field of high-activity catalyst preparation. Compared with the gas-liquid phase reaction taking the conventional ionic liquid as a medium, the catalyst used in the invention effectively avoids the deactivation of the catalyst, and realizes high-activity and high-stability catalysis.
A synthesis method of a metal diazole-based ionic catalyst comprises the following steps:
s1: adding 5-12 parts of dimercaptothiodiazole, 3-8 parts of 4-pentenoic acid, 0.5-2.2 parts of ethylenically unsaturated monomer and 100-120 parts of organic solvent into a closed high-pressure reaction kettle by weight parts, adding 1.2-2.4 parts of sodium ethoxide, heating and stirring to 60-75 ℃, and reacting for 2-5 hours to obtain an intermediate 1;
s2: adding 15-40 parts of metal salt into the intermediate 1, continuously stirring and reacting for 2-4h at 80-90 ℃, and then drying in vacuum at 70-80 ℃ to remove the organic solvent, thereby finally obtaining the metal diazolyl ion catalyst.
Further, the ethylenically unsaturated monomer is selected from the group consisting of 1-vinylimidazole, N-allylimidazole, 4-vinylpyridine, N-methyl-N-vinylacetamide, diallylcarboxamide, N-methyl-N-allylcarboxamide, N-ethyl-N-allylcarboxamide, N-cyclohexyl-N-allylcarboxamide, 4-methyl-5-vinylthiazole, N-allyldiisooctylphenothiazine, 2-methyl-1-vinylimidazole, 3-methyl-1-vinylpyrazole, N-vinylpurine, N-vinylpiperazine, vinylpiperidine, vinylmorpholine, and combinations thereof.
Further, the ethylenically unsaturated monomer is selected from the group consisting of 1-vinylimidazole, N-allylimidazole, 4-vinylpyridine, N-methyl-N-vinylacetamide, diallylcarboxamide, and combinations thereof.
Further, the organic solvent is one of methanol, ethanol, diethyl ether, acetone, ethyl acetate, benzene, toluene, chloroform, carbon tetrachloride or N, N-dimethylformamide.
Further, the metal salt is MX, wherein M represents a cation selected from one of Pt, Al, In, Bi, Fe, Mn, Ba, Ca, K, Rb, Sr, Nd, Hf and Pr; x represents an anion selected from SO4 2-、 NO3-、Cl-、I-、Br-、ClO4-、PO4 3-、SO3 2-、NO2-、ClO3-One kind of (1).
Further, the metal salt X anion is a halide ion.
Further, the metal salt is one or a mixture of more of copper chloride, cuprous chloride, ferric chloride, ferrous chloride and zinc chloride.
Further, the preparation of vinyl chloride by using the metal diazolyl ion catalyst to catalyze acetylene hydrochlorination is carried out, the prepared catalyst is added into a bubbling reactor, acetylene and hydrogen chloride serving as reaction raw materials are mixed and then introduced into the bubbling reactor for reaction, the reaction temperature is 120-240 ℃, the reaction pressure is 0.1-0.8 MPa, the volume flow rate ratio of the hydrogen chloride to the acetylene is 1-1.5: 1, and the acetylene volume space velocity is 10-70 h-1；
Further, in the application of the method for preparing vinyl chloride by catalyzing hydrochlorination of acetylene, the volume space velocity of acetylene is controlled to be 40-50 h-1The flow rate ratio of the hydrogen chloride to the acetylene is 1-1.3: 1, the temperature is 160-200 ℃, and the pressure is 0.1-0.5 MPa.
The reaction mechanism is as follows:
dimercapto thiodiazole, 4-pentenoic acid and an ethylenic bond unsaturated monomer are subjected to Michael addition reaction to obtain a heterocyclic compound containing thiodiazole, and the heterocyclic compound is further subjected to complexation reaction with metal salt to combine metal ions together to obtain the metal diazolyl ion catalyst.
The partial reaction scheme is shown in FIG. 2, which is only for explaining the reaction principle and does not represent the whole reaction form.
The technical effects are as follows:
1. the dimercapto thiodiazole, the 4-pentenoic acid and the ethylenic bond unsaturated monomer are subjected to Michael addition reaction to obtain a heterocyclic compound containing thiodiazole, and the heterocyclic compound is further subjected to complexation reaction with metal salt.
2. In the metal chelating carboxylic acid ion catalyst system provided by the invention, the acetylene conversion rate of the acetylene hydrochlorination reaction is as high as 95.1%, the vinyl chloride selectivity is more than 99%, the catalytic activity is not reduced within 120h of a test, and the catalyst system has good stability.
Drawings
Fig. 1 is a trend chart of the catalytic effect of the iron-based carboxylic acid ion catalyst prepared in example 5.
FIG. 2 shows the reaction mechanism of Michael addition reaction of dimercaptothiodiazole, 4-pentenoic acid and ethylenically unsaturated monomer.
Detailed Description
Catalyst preparation example 1
S1: adding 5g of dimercaptothiodiazole, 3g of 4-pentenoic acid, 0.5g of 1-vinylimidazole and 100g of ethanol into a closed high-pressure reaction kettle, adding 1.2g of sodium ethoxide, heating and stirring to 60 ℃, and reacting for 2 hours to obtain an intermediate 1;
s2: and continuously stirring the intermediate 1 and copper chloride for reaction for 2 hours at the temperature of 80 ℃, and then drying in vacuum at the temperature of 70 ℃ to remove the organic solvent, thereby finally obtaining the copper-based carboxylic acid ion catalyst.
Evaluation of catalyst Performance
Preparing chloroethylene by using the metal diazolyl ion catalyst to catalyze the hydrochlorination of acetylene, adding a copper-based carboxylic acid ion catalyst into a bubbling reactor, mixing acetylene and hydrogen chloride serving as reaction raw materials, introducing the mixture into the bubbling reactor to react, wherein the reaction temperature is 120 ℃, the reaction pressure is 0.1Mpa, the volume flow rate ratio of the hydrogen chloride to the acetylene is 1:1, and the volume space velocity of the acetylene is 10h-1. After 120 hours of reaction, the catalytic activity is not reduced, the conversion rate of acetylene is 88.4 percent, and the selectivity of chloroethylene is 99.32 percent.
Catalyst preparation example 2
S1: adding 7g of dimercaptothiodiazole, 5g of 4-pentenoic acid, 0.9g of 4-vinylpyridine and 100g of ethanol into a closed high-pressure reaction kettle, adding 1.5g of sodium ethoxide, heating and stirring to 65 ℃, and reacting for 3 hours to obtain an intermediate 1;
s2: and (3) continuously stirring the intermediate 1 and ferric chloride for reaction for 3 hours at the temperature of 80 ℃, and then drying in vacuum at the temperature of 80 ℃ to remove the organic solvent, thereby finally obtaining the iron-based carboxylic acid ionic catalyst.
Evaluation of catalyst Performance
Preparing chloroethylene by using the metal diazolyl ionic catalyst to catalyze the hydrochlorination of acetylene, adding an iron-based carboxylic acid ionic catalyst into a bubbling reactor, mixing acetylene and hydrogen chloride serving as reaction raw materials, introducing the mixture into the bubbling reactor for reaction, wherein the reaction temperature is 160 ℃, the reaction pressure is 0.2Mpa, the volume flow rate ratio of the hydrogen chloride to the acetylene is 1.1:1, and the volume space velocity of the acetylene is 30h-1. After 120h of reaction, the catalytic activity is not reduced, the acetylene conversion rate is 92.8 percent, and the vinyl chloride selectivity is 99.41 percent.
Catalyst preparation example 3
S1: adding 9g of dimercaptothiodiazole, 6g of 4-pentenoic acid, 1.2g N-methyl-N-vinyl acetamide and 110g of ethanol into a closed high-pressure reaction kettle, adding 1.8g of sodium ethoxide, heating and stirring to 70 ℃, and reacting for 4 hours to obtain an intermediate 1;
s3: and continuously stirring the intermediate 1 and zinc chloride for reaction for 3 hours at the temperature of 80 ℃, and then drying in vacuum at the temperature of 80 ℃ to remove the organic solvent, thereby finally obtaining the zinc-based carboxylic acid ion catalyst.
Evaluation of catalyst Performance
Preparing chloroethylene by using the metal diazole-based ionic catalyst to catalyze hydrochlorination of acetylene, adding a zinc-based carboxylic acid ionic catalyst into a bubbling reactor, mixing acetylene and hydrogen chloride serving as reaction raw materials, introducing the mixture into the bubbling reactor for reaction, wherein the reaction temperature is 180 ℃, the reaction pressure is 0.3Mpa, the volume flow rate ratio of the hydrogen chloride to the acetylene is 1.2:1, and the volume space velocity of the acetylene is 40h-1. After 120 hours of reaction, the catalytic activity is not reduced, the conversion rate of acetylene is 93.7 percent, and the selectivity of chloroethylene is 99.55 percent.
Catalyst preparation example 4
S1: adding 10g of dimercaptothiodiazole, 8g of 4-pentenoic acid, 1.8g of diallyl formamide and 110g of ethanol into a closed high-pressure reaction kettle, adding 2.0g of sodium ethoxide, heating and stirring to 70 ℃, and reacting for 4 hours to obtain an intermediate 1;
s3: and (3) continuously stirring the intermediate 1 and cuprous chloride to react for 3 hours at 80 ℃, and then carrying out vacuum drying at 80 ℃ to remove the organic solvent, thereby finally obtaining the cuprous carboxylic acid ion catalyst.
Evaluation of catalyst Performance
Preparing chloroethylene by using the metal diazolyl ionic catalyst to catalyze the hydrochlorination of acetylene, adding a cuprous carboxylic acid ionic catalyst into a bubbling reactor, mixing acetylene and hydrogen chloride serving as reaction raw materials, and introducing the mixture into the bubbling reactor to react, wherein the reaction temperature is 200 ℃, the reaction pressure is 0.4Mpa, the volume flow rate ratio of the hydrogen chloride to the acetylene is 1.3:1, and the volume space velocity of the acetylene is 50h-1. After 120h of reaction, the catalytic activity is not reduced, the acetylene conversion rate is 93.9 percent, and the vinyl chloride selectivity is 99.61 percent.
Catalyst preparation example 5
S1: adding 12g of dimercaptothiodiazole, 8g of 4-pentenoic acid, 2.0g of 2.0g N-allylimidazole and 120g of ethanol into a closed high-pressure reaction kettle, adding 2.2g of sodium ethoxide, heating and stirring to 75 ℃, and reacting for 5 hours to obtain an intermediate 1;
s2: and continuously stirring the intermediate 1 and ferrous chloride for reaction for 4 hours at the temperature of 90 ℃, and then drying in vacuum at the temperature of 80 ℃ to remove the organic solvent, thereby finally obtaining the ferrous carboxylic acid ion catalyst.
Evaluation of catalyst Performance
Preparing chloroethylene by using the metal diazolyl ionic catalyst to catalyze the hydrochlorination of acetylene, adding a ferrous carboxylic acid ionic catalyst into a bubbling reactor, mixing acetylene and hydrogen chloride serving as reaction raw materials, and introducing the mixture into the bubbling reactor for reaction, wherein the reaction temperature is 220 ℃, the reaction pressure is 0.5Mpa, the volume flow rate ratio of the hydrogen chloride to the acetylene is 1.4:1, and the volume space velocity of the acetylene is 60h-1. After 120 hours of reaction, the catalytic activity is not reduced, the conversion rate of acetylene is 94.2 percent, and the selectivity of chloroethylene is 99.74 percent.
Catalyst preparation example 6
S1: adding 12g of dimercaptothiodiazole, 8g of 4-pentenoic acid, 2.0g of 1-vinylimidazole and 120g of ethanol into a closed high-pressure reaction kettle, adding 2.4g of sodium ethoxide, heating and stirring to 75 ℃, and reacting for 5 hours to obtain an intermediate 1;
s3: and continuously stirring the intermediate 1 and zinc chloride for reaction for 4 hours at the temperature of 90 ℃, and then drying in vacuum at the temperature of 80 ℃ to remove the organic solvent, thereby finally obtaining the zinc-based carboxylic acid ion catalyst.
Evaluation of catalyst Performance
The zinc-based carboxylic acid ion catalyst is used for catalyzing hydrochlorination of acetylene to prepare vinyl chloride, the zinc-based carboxylic acid ion catalyst is added into a bubbling reactor, reaction raw material gases of acetylene and hydrogen chloride are mixed and then introduced into the bubbling reactor for reaction, the reaction temperature is 240 ℃, the reaction pressure is 0.6Mpa, the volume flow rate ratio of the hydrogen chloride to the acetylene is 1.5:1, and the acetylene volume space velocity is 70h-1. After 120 hours of reaction, the catalytic activity is not reduced, the conversion rate of acetylene is 95.1 percent, and the selectivity of chloroethylene is 99.81 percent.
Comparative example 1
In a bubbling reactor, a metal diazolyl ion catalyst is not added, acetylene and hydrogen chloride which are reaction raw material gases are mixed and then introduced into the bubbling reactor for reaction, the reaction temperature is 120 ℃, the reaction pressure is 0.1Mpa, the volume flow rate ratio of the hydrogen chloride to the acetylene is 1:1,the volume space velocity of the acetylene is 10h-1. After 120h of reaction, the conversion rate of acetylene was 48.9% and the selectivity of vinyl chloride was 94.11%.
Comparative example 2
In a bubbling reactor, a metal diazolyl ion catalyst is not added, acetylene and hydrogen chloride which are reaction raw material gases are mixed and then introduced into the bubbling reactor for reaction, the reaction temperature is 240 ℃, the reaction pressure is 0.8Mpa, the volume flow rate ratio of the hydrogen chloride to the acetylene is 1.5:1, and the volume space velocity of the acetylene is 70h-1. After 120h of reaction time, the acetylene conversion was 54.98% and the vinyl chloride selectivity was 95.74%.

Claims (10)

1. A synthesis method of a metal diazole-based ionic catalyst comprises the following steps:
s1: adding 5-12 parts of dimercaptothiodiazole, 3-8 parts of 4-pentenoic acid, 0.5-2.2 parts of ethylenically unsaturated monomer and 100-120 parts of organic solvent into a closed high-pressure reaction kettle by weight parts, adding 1.2-2.4 parts of sodium ethoxide, heating and stirring to 60-75 ℃, and reacting for 2-5 hours to obtain an intermediate 1;
s2: adding 15-40 parts of metal carboxylate into the intermediate 1, continuously stirring and reacting for 2-4h at 80-90 ℃, and then drying in vacuum at 70-80 ℃ to remove the organic solvent, thus obtaining the metal diazolyl ion catalyst.
2. The method for synthesizing the metal diazole-based ionic catalyst according to claim 1, wherein: the ethylenically unsaturated monomer is selected from the group consisting of 1-vinylimidazole, N-allylimidazole, 4-vinylpyridine, N-methyl-N-vinylacetamide, diallylcarboxamide, N-methyl-N-allylcarboxamide, N-ethyl-N-allylcarboxamide, N-cyclohexyl-N-allylcarboxamide, 4-methyl-5-vinylthiazole, N-allyldiisooctylphenothiazine, 2-methyl-1-vinylimidazole, 3-methyl-1-vinylpyrazole, N-vinylpurine, N-vinylpiperazine, vinylpiperidine, vinylmorpholine, and combinations thereof.
3. The method for synthesizing the metal diazole-based ionic catalyst according to claim 1, wherein: the ethylenically unsaturated monomer is preferably 1-vinylimidazole, N-allylimidazole, 4-vinylpyridine, N-methyl-N-vinylacetamide, diallylcarboxamide, and combinations thereof.
4. The method for synthesizing the metal diazole-based ionic catalyst according to claim 1, wherein: the organic solvent is one of methanol, ethanol, diethyl ether, acetone, ethyl acetate, benzene, toluene, chloroform, carbon tetrachloride or N, N-dimethylformamide.
5. The method for synthesizing the metal diazole-based ionic catalyst according to claim 1, wherein: the organic solvent is preferably one of ethanol, chloroform or N, N-dimethylformamide.
6. The method for synthesizing the metal diazole-based ionic catalyst according to claim 1, wherein: the metal salt is MX, wherein M represents cation and is selected from one of Pt, Al, In, Bi, Fe, Mn, Ba, Ca, K, Rb, Sr, Nd, Hf and Pr; x represents an anion selected from SO4 2-、NO3-、Cl-、I-、Br-、ClO4-、PO4 3-、SO3 2-、NO2-、ClO3-One kind of (1).
7. The method for synthesizing the metal diazole-based ionic catalyst according to claim 6, wherein: the metal salt X anion is Cl-、I-、Br-。
8. The method for synthesizing the metal diazole-based ionic catalyst according to claim 6, wherein: the metal salt is one or a mixture of more of cupric chloride, cuprous chloride, ferric chloride, ferrous chloride and zinc chloride.
9. The metallic diazole of claim 1The synthesis method of the base ion catalyst is characterized by comprising the following steps: preparing chloroethylene by using the metal diazolyl ionic catalyst to catalyze hydrochlorination of acetylene, adding the prepared catalyst into a bubbling reactor, mixing acetylene and hydrogen chloride serving as reaction raw materials, introducing the mixture into the bubbling reactor for reaction, wherein the reaction temperature is 120-240 ℃, the reaction pressure is 0.1-0.8 MPa, the volume flow rate ratio of the hydrogen chloride to the acetylene is 1-1.5: 1, and the volume space velocity of the acetylene is 10-70 h-1。
10. The method for synthesizing the metal diazole-based ionic catalyst according to claim 1, wherein: in the application of preparing vinyl chloride by catalyzing acetylene hydrochlorination, the volume airspeed of acetylene is controlled to be 40-50 h-1The flow rate ratio of the hydrogen chloride to the acetylene is 1-1.3: 1, the temperature is 160-200 ℃, and the pressure is 0.1-0.5 MPa.
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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LASZLO KURTI ET AL.: "《有机合成中命名反应的战略性应用》", 31 August 2007 *
STN: "RN号分别为"127522-05-8、1072-71-5"的化合物", 《STN》 *
司建鑫 等: "离子液体在乙炔氢氯化合成氯乙烯中的应用进展", 《石油化工》 *

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Application publication date: 20211207