CN108339569B - Supported quaternary phosphonium salt non-metallic catalyst, preparation method and application - Google Patents

Supported quaternary phosphonium salt non-metallic catalyst, preparation method and application Download PDF

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CN108339569B
CN108339569B CN201710050920.8A CN201710050920A CN108339569B CN 108339569 B CN108339569 B CN 108339569B CN 201710050920 A CN201710050920 A CN 201710050920A CN 108339569 B CN108339569 B CN 108339569B
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phosphonium salt
quaternary phosphonium
catalyst
bromide
supported
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CN108339569A (en
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李韡
李晓燕
张金利
赵伟
韩优
尚姗姗
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Tianjin University
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Tianjin University
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a supported quaternary phosphonium salt non-metallic catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) preparing a quaternary phosphonium salt solution; (2) stirring a catalyst carrier and a quaternary phosphonium salt solution for 0.5-2h, carrying out sealed heating in a water bath at 60-120 ℃ for 2-12h, taking out, and drying to obtain the non-metallic catalyst of the supported quaternary phosphonium salt, wherein the mass ratio of the quaternary phosphonium salt to the catalyst carrier is 1-30: 100. the supported quaternary phosphonium salt nonmetal catalyst has strong operability, good controllability and stable catalyst performance; the preparation method is simple, is applied to the catalytic addition reaction of acetylene and hydrogen chloride, and has the advantages of environmental friendliness, low cost and the like. Under the reaction condition, the acetylene conversion rate is 32-95%, and the selectivity of the product chloroethylene is more than 99%.

Description

Supported quaternary phosphonium salt non-metallic catalyst, preparation method and application
Technical Field
The invention relates to a supported quaternary phosphonium salt non-metallic catalyst applied to the addition reaction of acetylene and hydrogen chloride.
Background
Polyvinyl chloride (PVC), the oldest and most commonly used product in the plastics industry, is one of the most important plastics in the world, plays a significant role in the development of national economy and society in China, and the demand thereof continues to increase worldwide. PVC is mainly produced by polymerization of Vinyl Chloride Monomer (VCM), and the main production methods of VCM are classified into three, ethane method, ethylene method, and acetylene method. Because of the characteristics of 'more coal, lean oil and less gas' in China, the economy of PVC production by the calcium carbide acetylene method is better than that of other two methods, and the capacity of the method accounts for 70% of the capacity of PVC in China. However, in the process of producing chloroethylene by an acetylene method, mercuric chloride is mainly used as a catalyst, and the use amount of mercury accounts for more than 60% of the mercury consumption in China, so that the method is the largest mercury consumption industry in the world and brings about a serious mercury pollution problem. The development of the mercury-free catalyst becomes the focus of attention of all countries in the world, and the method can be used for designing an environment-friendly, efficient and energy-saving vinyl chloride production process, so that the development of the mercury-free catalyst has very important significance on acetylene hydrochlorination.
At present, the research of mercury-free catalysts in acetylene hydrochlorination is mainly divided into heterogeneous catalysts and homogeneous catalysts. Heterogeneous mercury-free catalysts can be divided into two broad categories, metal-catalyzed and non-metal-catalyzed. Metal catalysts have high catalytic activity and stability, but are limited by their cost and storage, thus promoting the development of non-metal catalysts.
Chinese patent CN103894220A of the institute of chemical and physical university of chinese academy of sciences discloses a molecular sieve mercury-free catalyst for acetylene hydrochlorination. The catalyst consists of 50-100 wt% FAU type molecular sieve and 0-50% non-molecular sieve.
Chinese patent CN104549401A of tianjin university discloses a non-metal catalyst used in hydrochlorination of acetylene, which is obtained by mainly combining N, O, S and P-containing compounds with a catalyst carrier.
Chinese patent CN106238095A discloses a sulfur-doped non-metal catalyst, which is applied to acetylene hydrochlorination. The catalyst is a non-metal catalyst obtained by doping a sulfur-containing compound into a catalyst carrier.
The invention of the patent uses the non-metal catalyst in the hydrochlorination of acetylene, but still has the characteristics of low catalytic activity, poor stability and the like of the non-metal catalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a supported quaternary phosphonium salt nonmetal catalyst.
The second purpose of the invention is to provide a preparation method of the supported quaternary phosphonium salt nonmetal catalyst.
The third purpose of the invention is to provide the application of the supported quaternary phosphonium salt non-metallic catalyst in catalyzing the addition reaction of acetylene and hydrogen chloride.
The technical scheme of the invention is summarized as follows:
the preparation method of the supported quaternary phosphonium salt nonmetal catalyst comprises the following steps:
(1) preparing a quaternary phosphonium salt solution;
(2) stirring a catalyst carrier and a quaternary phosphonium salt solution for 0.5-2h, carrying out sealed heating in a water bath at 60-120 ℃ for 2-12h, taking out, and drying to obtain the non-metallic catalyst of the supported quaternary phosphonium salt, wherein the mass ratio of the quaternary phosphonium salt to the catalyst carrier is 1-30: 100.
the quaternary phosphonium salt is preferably: tetradecyltributylphosphonium bromide, tetradecyltrimethylphosphonium bromide, dodecyltrimethylphosphonium bromide, dodecyltriphenylphosphonium bromide, benzyltrimethylphosphonium bromide, ethyltriphenylphosphonium chloride, tetrabutylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetramethylphosphonium bromide or tetraphenylphosphonium tetrafluoroborate.
The solvent of the quaternary phosphonium salt solution is water, methanol, ethanol, toluene or dichloroethane.
The catalyst support is preferably: activated carbon, alumina, graphene, or carbon nanotubes.
The supported quaternary phosphonium salt nonmetal catalyst prepared by the method.
The supported quaternary phosphonium salt non-metallic catalyst is applied to catalyzing the addition reaction of acetylene and hydrogen chloride.
The reaction conditions were: the temperature range is 150 ℃ and 250 ℃, the feed gas ratio is (V)HCl/VC2H2) 0.90-1.2, the volume space velocity of the raw material gas acetylene is 10-120h-1。
The invention has the advantages that:
the supported quaternary phosphonium salt nonmetal catalyst has strong operability, good controllability and stable catalyst performance; the preparation method is simple, is applied to the catalytic addition reaction of acetylene and hydrogen chloride, and has the advantages of environmental friendliness, low cost and the like. Under the reaction condition, the acetylene conversion rate is 32-95%, and the selectivity of the product chloroethylene is more than 99%.
Detailed Description
The present invention is specifically described below by way of examples in order to enable those skilled in the art to better understand the present invention. The examples are not intended to limit the invention in any way.
Example 1
The preparation method of the supported quaternary phosphonium salt nonmetal catalyst comprises the following steps:
(1) preparing a quaternary phosphonium salt solution:
accurately weighing 0.1g of tetraphenylphosphonium bromide, and dissolving in 20m L methanol to obtain a tetraphenylphosphonium bromide solution;
(2) and (2) stirring 10g of alumina and the tetraphenylphosphonium bromide solution obtained in the step (1) for 30min, sealing and heating in a water bath at 60 ℃ for 12h, taking out, and drying to obtain the supported quaternary phosphonium salt nonmetal catalyst.
In the present example, the supported quaternary phosphonium salt non-metallic catalyst catalyzes the addition reaction of acetylene and hydrogen chloride at a reaction temperature of 250 ℃ and a feed gas ratio of (V)HCl/VC2H2)0.9, the volume space velocity of the raw material gas acetylene is 120h-1Under the condition, the acetylene conversion rate is 32 percent, and the selectivity of the product chloroethylene is more than 99 percent.
And (3) comparison: alumina blank support (acetylene conversion 13%, product vinyl chloride selectivity greater than 99%).
Example 2
The preparation method of the supported quaternary phosphonium salt nonmetal catalyst comprises the following steps:
(1) preparing a quaternary phosphonium salt solution:
1.5g of tetrabutyl phosphonium bromide is accurately weighed and dissolved in ethanol of 20m L to obtain tetrabutyl phosphonium bromide solution;
(2) and (2) stirring 10g of carbon nano tube (multi-walled carbon nano tube, the tube diameter is 10-20nm) and the tetrabutyl phosphonium bromide solution obtained in the step (1) for 1h, heating in a water bath at 100 ℃ for 4h in a sealed manner, taking out, and drying to obtain the supported quaternary phosphonium salt nonmetal catalyst.
The non-metallic catalyst of the supported quaternary phosphonium salt is applied to the addition reaction of acetylene and hydrogen chloride, the reaction temperature is 180 ℃, and the feed gas ratio is (V)HCl/VC2H2)1.1 volume space velocity of acetylene as raw material gas of 50h-1Under the condition, the acetylene conversion rate is 57%, and the selectivity of the product chloroethylene is more than 99%.
And (3) comparison: carbon nanotube blank support (acetylene conversion 24%, product vinyl chloride selectivity greater than 99%).
Example 3
The preparation method of the supported quaternary phosphonium salt nonmetal catalyst comprises the following steps:
(1) preparing a quaternary phosphonium salt solution:
accurately weighing 3.0g of tetramethyl phosphonium bromide, and dissolving in 20m L of distilled water to obtain a tetramethyl phosphonium bromide solution;
(2) stirring 10g of activated carbon (40-60 meshes) and the tetramethyl phosphonium bromide solution obtained in the step (1) for 2h, carrying out sealed heating in a water bath at 120 ℃ for 2h, taking out, and drying to obtain the supported quaternary phosphonium salt nonmetal catalyst.
The supported quaternary phosphonium salt non-metallic catalyst of the embodiment is applied to the addition reaction of acetylene and hydrogen chloride, the reaction temperature is 150 ℃, and the feed gas ratio is (V)HCl/VC2H2)1.2 volume space velocity of acetylene as raw material gas of 10h-1Under the condition, the acetylene conversion rate is 95 percent, and the selectivity of the product chloroethylene is more than 99 percent.
And (3) comparison: activated carbon blank support (acetylene conversion 43%, product vinyl chloride selectivity greater than 99%).
Experiments prove that: in the other same examples, the supported quaternary phosphonium salt non-metal catalyst prepared by the method has the catalytic effect similar to that of the example.
Experiments prove that: the catalytic effect of the supported quaternary phosphonium salt nonmetal catalyst prepared in the same way as the embodiment is similar to the embodiment by respectively using toluene or dichloroethane to replace the distilled water in the embodiment.
Experiments prove that: the graphene is used for replacing the activated carbon in the embodiment, and other similar effects to the embodiment are similar to the effect of the embodiment in the catalytic effect of the prepared supported quaternary phosphonium salt nonmetal catalyst.

Claims (6)

1. The preparation method of the supported quaternary phosphonium salt nonmetal catalyst is characterized by comprising the following steps:
(1) preparing a quaternary phosphonium salt solution;
(2) stirring a catalyst carrier and a quaternary phosphonium salt solution for 0.5-2h, carrying out sealed heating in a water bath at 60-120 ℃ for 2-12h, taking out, and drying to obtain the non-metallic catalyst of the supported quaternary phosphonium salt, wherein the mass ratio of the quaternary phosphonium salt to the catalyst carrier is 1-30: 100, respectively;
the quaternary phosphonium salt is tetradecyltributylphosphonium bromide, tetradecyltrimethylphosphonium bromide, dodecyltrimethylphosphonium bromide, dodecyltriphenylphosphonium bromide, benzyltrimethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, tetramethylphosphonium bromide or tetraphenylphosphonium tetrafluoroborate.
2. The process as claimed in claim 1, wherein the solvent for the quaternary phosphonium salt solution is water, methanol, ethanol, toluene or dichloroethane.
3. The method as set forth in claim 1, wherein the catalyst support is activated carbon, alumina, graphene or carbon nanotubes.
4. A supported quaternary phosphonium salt non-metallic catalyst prepared by the process of any of claims 1-3.
5. The use of the supported quaternary phosphonium salt non-metallic catalyst of claim 4 for catalyzing the addition reaction of acetylene and hydrogen chloride.
6. Use according to claim 5, characterized in that the reaction conditions are: the temperature range is 150 ℃ and 250 ℃, and the feed gas ratio is VHCl/VC2H20.90-1.2, the volume space velocity of the raw material gas acetylene is 10-120h-1。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012113778A1 (en) * 2011-02-24 2012-08-30 Solvay Sa Process for the hydrohalogenation of an alkyne and for the manufacture of vinyl chloride by hydrochlorination of acetylene
TW201236758A (en) * 2010-12-22 2012-09-16 Solvay Catalytic system and its use for the manufacture of vinyl chloride by hydrochlorination of acetylene
CN104109076A (en) * 2014-06-30 2014-10-22 浙江大学 Method for preparing vinyl chloride by hydrochlorinating acetylene through using quaternary phosphonium long-chain ionic liquid as medium
CN104549401A (en) * 2013-10-28 2015-04-29 天津大学 Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application
CN104974128A (en) * 2015-07-24 2015-10-14 大连理工大学 Method for preparing cyclic carbonate by using supported quaternary phosphonium salt catalyst
CN105983428A (en) * 2015-01-30 2016-10-05 天津大学 Catalyst used in low-temperature removal of hydrogen chloride from dichloroethane for preparation of vinyl chloride, and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201236758A (en) * 2010-12-22 2012-09-16 Solvay Catalytic system and its use for the manufacture of vinyl chloride by hydrochlorination of acetylene
WO2012113778A1 (en) * 2011-02-24 2012-08-30 Solvay Sa Process for the hydrohalogenation of an alkyne and for the manufacture of vinyl chloride by hydrochlorination of acetylene
CN104549401A (en) * 2013-10-28 2015-04-29 天津大学 Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application
CN104109076A (en) * 2014-06-30 2014-10-22 浙江大学 Method for preparing vinyl chloride by hydrochlorinating acetylene through using quaternary phosphonium long-chain ionic liquid as medium
CN105983428A (en) * 2015-01-30 2016-10-05 天津大学 Catalyst used in low-temperature removal of hydrogen chloride from dichloroethane for preparation of vinyl chloride, and preparation method and application thereof
CN104974128A (en) * 2015-07-24 2015-10-14 大连理工大学 Method for preparing cyclic carbonate by using supported quaternary phosphonium salt catalyst

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