CN108339569A - Support type quaternary alkylphosphonium salt non-metallic catalyst and preparation method and application - Google Patents

Support type quaternary alkylphosphonium salt non-metallic catalyst and preparation method and application Download PDF

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CN108339569A
CN108339569A CN201710050920.8A CN201710050920A CN108339569A CN 108339569 A CN108339569 A CN 108339569A CN 201710050920 A CN201710050920 A CN 201710050920A CN 108339569 A CN108339569 A CN 108339569A
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alkylphosphonium salt
phosphonium
support type
quaternary alkylphosphonium
metallic catalyst
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CN108339569B (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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  • Chemical & Material Sciences (AREA)
  • 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 support type quaternary alkylphosphonium salt non-metallic catalyst and preparation method and application, preparation method includes the following steps：(1) quaternary phosphine salting liquid is prepared；(2) by catalyst carrier and quaternary phosphine salting liquid, 0.5 2h is stirred, in 60 120 DEG C of 2 12h of water-bath heated sealed, is taken out, it is dry, obtain the non-metallic catalyst of support type quaternary alkylphosphonium salt, the mass ratio of the quaternary alkylphosphonium salt and catalyst carrier is 1 30：100.A kind of support type quaternary alkylphosphonium salt non-metallic catalyst strong operability of the present invention, controllability is good, catalyst performance stabilised；Preparation method is simple, is applied in the addition reaction of catalyzing acetylene and hydrogen chloride, have many advantages, such as it is environmentally friendly, it is at low cost.At reaction conditions, conversion of alkyne is 32 95%, and the selectivity of product vinyl chloride is more than 99%.

Description

Support type quaternary alkylphosphonium salt non-metallic catalyst and preparation method and application
Technical field
The present invention relates to support type quaternary alkylphosphonium salt non-metallic catalysts to be applied to acetylene and chlorination addition reaction of hydrogen.
Background technology
Polyvinyl chloride (PVC) is used as most ancient and most common product in plastics industry, is most important plastics in the world One of, great effect is played in Chinese national economy and social development, demand continues growing in the world. The production of PVC is mainly by the polymerization of vinyl chloride monomer (VCM), and the main production process of VCM is divided into three kinds, ethane method, second Alkene method and carbide acetylene method.The characteristics of due to China " more coals, oil-poor, few gas ", carbide acetylene method produces the economy of PVC more Better than other two methods, production capacity accounts for the 70% of China's PVC production capacities.But it is mainly used during acetylene method produces vinyl chloride Mercury chloride is catalyst, and the usage amount of mercury accounts for 60% or more of China's mercury consumption, is the world's largest consumption mercury industry, therewith band Carry out serious mercury pollution problem.The exploitation of catalyst without mercury will become countries in the world focus of attention, have only and take this method Environmentally friendly, energy-efficient vinyl chloride production technology can be designed, therefore, the exploitation of catalyst without mercury is to acetylene hydrogen chlorine Change reaction to have a very important significance.
Currently, in acetylene hydrochlorination reaction, the research of catalyst without mercury is broadly divided into heterogeneous catalyst and homogeneous catalysis Agent.Multiphase catalyst without mercury can be divided into two major classes, metal catalytic and nonmetal catalyzed.Metallic catalyst is lived with greater catalytic Property and stability, but it is limited to its cost and reserves, therefore pushed the development of non-metallic catalyst.
The Chinese patent CN103894220A of Dalian Inst of Chemicophysics, Chinese Academy of Sciences disclose a kind of molecular sieve without Mercury catalyst is reacted for acetylene hydrochlorination.The catalyst is by the FAU types molecular sieve of 50-100wt% and the non-molecule of 0-50% Screen banks at.
It is anti-for acetylene hydrochlorination that the Chinese patent CN104549401A of University Of Tianjin discloses a kind of non-metallic catalyst Ying Zhong, the mainly non-metallic catalyst obtained from catalyst carrier is combined by the compound containing N, O, S and P.
Chinese patent CN106238095A discloses a kind of non-metallic catalyst of doping element sulphur, is applied to second In alkynes hydrochlorination.Sulfur-containing compound is mainly doped in catalyst carrier and obtains one kind and nonmetallic urge by the catalyst Agent.
Non-metallic catalyst has been invented in above-mentioned patent to be applied in acetylene hydrochlorination reaction, but still has been urged there are nonmetallic The features such as agent catalytic activity is low, and stability is poor.
Invention content
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of support type quaternary alkylphosphonium salt non-metallic catalyst.
Second object of the present invention is to provide a kind of preparation method of support type quaternary alkylphosphonium salt non-metallic catalyst.
Third object of the present invention is to provide support type quaternary alkylphosphonium salt non-metallic catalysts to add in catalyzing acetylene and hydrogen chloride At the application in reaction.
Technical scheme of the present invention is summarized as follows：
The preparation method of support type quaternary alkylphosphonium salt non-metallic catalyst, includes the following steps：
(1) quaternary phosphine salting liquid is prepared；
(2) by catalyst carrier and quaternary phosphine salting liquid, stirring 0.5-2h takes in 60-120 DEG C of water-bath heated sealed 2-12h Go out, it is dry, obtain the non-metallic catalyst of support type quaternary alkylphosphonium salt, the mass ratio of the quaternary alkylphosphonium salt and catalyst carrier is 1-30： 100。
The quaternary alkylphosphonium salt is preferably：Myristyl San butyl phosphonium bromide, tetradecyltrimethylammonium phosphonium bromide, dodecyl three First base phosphonium bromide, three phenyl-bromide Phosphonium of dodecyl, benzyl trimethyl bromide phosphine, ethyl triphenyl phosphonium chloride, tetrabutyl phosphonium bromide Phosphonium, tetraphenyl phosphonium chloride, four fluorine boron acid Phosphonium of 4-phenyl phosphonium bromide, four methyl bromide Phosphonium or tetraphenyl.
The solvent of the quaternary phosphine salting liquid is water, methanol, ethyl alcohol, toluene or dichloroethanes.
The catalyst carrier is preferred：Activated carbon, aluminium oxide, graphene or carbon nanotube.
Support type quaternary alkylphosphonium salt non-metallic catalyst prepared by the above method.
Application of the above-mentioned support type quaternary alkylphosphonium salt non-metallic catalyst in catalyzing acetylene and chlorination addition reaction of hydrogen.
The condition of reaction is：150-250 DEG C of temperature range, unstripped gas proportioning are (VHCl/VC2H2) 0.90~1.2, unstripped gas Acetylene volume space velocity 10-120h-1。
Advantages of the present invention：
A kind of support type quaternary alkylphosphonium salt non-metallic catalyst strong operability of the present invention, controllability is good, catalyst performance stabilised； Preparation method is simple, is applied in the addition reaction of catalyzing acetylene and hydrogen chloride, have many advantages, such as it is environmentally friendly, it is at low cost. At reaction conditions, the selectivity of conversion of alkyne 32-95%, product vinyl chloride are more than 99%.
Specific implementation mode
The present invention is specifically described below by embodiment, to keep those skilled in the art better Understand the present invention.But illustrated embodiment is not intended as being limited in any way the present invention.
Embodiment 1
The preparation method of support type quaternary alkylphosphonium salt non-metallic catalyst, includes the following steps：
(1) quaternary phosphine salting liquid is prepared：
0.1g 4-phenyl phosphonium bromides accurately are weighed, is dissolved in 20mL methanol, obtains 4-phenyl phosphonium bromide solution；
(2) the 4-phenyl phosphonium bromide solution for taking 10g aluminium oxide to be obtained with step (1) stirs 30min, close in 60 DEG C of water-baths Envelope heating 12h, takes out, dry, obtains the non-metallic catalyst of support type quaternary alkylphosphonium salt.
The non-metallic catalyst of the support type quaternary alkylphosphonium salt of the present embodiment is in catalyzing acetylene and chlorination addition reaction of hydrogen, reaction Temperature is 250 DEG C, unstripped gas proportioning is (VHCl/VC2H2) 0.9, unstripped gas acetylene volume space velocity is 120h-1Under the conditions of, acetylene turns Rate is 32%, and the selectivity of product vinyl chloride is more than 99%.
Comparison：(99%) selectivity of conversion of alkyne 13%, product vinyl chloride is more than aluminium oxide empty vectors.
Embodiment 2
The preparation method of support type quaternary alkylphosphonium salt non-metallic catalyst, includes the following steps：
(1) quaternary phosphine salting liquid is prepared：
1.5g tetra- butyl phosphonium bromides accurately are weighed, are dissolved in 20mL ethyl alcohol, Si butyl phosphonium bromide solution is obtained；
(2) the Si butyl phosphonium bromides for taking 10g carbon nanotubes (multi-walled carbon nanotube, caliber 10-20nm) to be obtained with step (1) Solution stirs 1h, in 100 DEG C of water-bath heated sealed 4h, takes out, dry, obtains the non-metallic catalyst of support type quaternary alkylphosphonium salt.
The non-metallic catalyst of the support type quaternary alkylphosphonium salt of the present embodiment is applied in acetylene and chlorination addition reaction of hydrogen, reaction Temperature is 180 DEG C, unstripped gas proportioning is (VHCl/VC2H2) 1.1, unstripped gas acetylene volume space velocity is 50h-1Under the conditions of, acetylene conversion Rate is 57%, and the selectivity of product vinyl chloride is more than 99%.
Comparison：(99%) selectivity of conversion of alkyne 24%, product vinyl chloride is more than carbon nanotube empty vectors.
Embodiment 3
The preparation method of support type quaternary alkylphosphonium salt non-metallic catalyst, includes the following steps：
(1) quaternary phosphine salting liquid is prepared：
Tetra- methyl bromide Phosphonium of 3.0g accurately is weighed, is dissolved in 20mL distilled water, four methyl bromide Phosphonium solution are obtained；
(2) the four methyl bromide Phosphonium solution for obtaining 10g activated carbons (activated carbon, 40-60 mesh) and step (1), stir 2h, In 120 DEG C of water-bath heated sealed 2h, take out, it is dry, obtain support type quaternary alkylphosphonium salt non-metallic catalyst.
The support type quaternary alkylphosphonium salt non-metallic catalyst of the present embodiment is applied in acetylene and chlorination addition reaction of hydrogen, reaction temperature Degree is 150 DEG C, unstripped gas proportioning is (VHCl/VC2H2) 1.2, unstripped gas acetylene volume space velocity is 10h-1Under the conditions of, conversion of alkyne It is 95%, the selectivity of product vinyl chloride is more than 99%.
Comparison：(99%) selectivity of conversion of alkyne 43%, product vinyl chloride is more than activated carbon empty vectors.
Experiments have shown that：With myristyl San butyl phosphonium bromide, tetradecyltrimethylammonium phosphonium bromide, trimethyl bromine Change Phosphonium, three phenyl-bromide Phosphonium of dodecyl, benzyl trimethyl bromide phosphine, ethyl triphenyl phosphonium chloride, four methyl bromide Phosphonium or four Four fluorine boron acid Phosphonium of phenyl substitutes the four methyl bromide Phosphonium of the present embodiment, and the support type quaternary alkylphosphonium salt of other same the present embodiment, preparation is non- The catalytic effect of metallic catalyst is similar to the effect of the present embodiment.
Experiments have shown that：The distilled water of the present embodiment is substituted with toluene or dichloroethanes respectively, prepared by other same the present embodiment Support type quaternary alkylphosphonium salt non-metallic catalyst catalytic effect it is similar to the effect of the present embodiment.
Experiments have shown that：The activated carbon of the present embodiment, other same the present embodiment, the support type quaternary phosphine of preparation are substituted with graphene The catalytic effect of salt non-metallic catalyst is similar to the effect of the present embodiment.

Claims (7)

1. the preparation method of support type quaternary alkylphosphonium salt non-metallic catalyst, feature include the following steps：
(1) quaternary phosphine salting liquid is prepared；
(2) by catalyst carrier and quaternary phosphine salting liquid, 0.5-2h is stirred, in 60-120 DEG C of water-bath heated sealed 2-12h, is taken out, It is dry, obtain the non-metallic catalyst of support type quaternary alkylphosphonium salt, the mass ratio of the quaternary alkylphosphonium salt and catalyst carrier is 1-30：100.
2. according to the method described in claim 1, it is characterized in that the quaternary alkylphosphonium salt is myristyl San butyl phosphonium bromide, the tetradecane Three first base phosphonium bromide of base, trimethyl phosphonium bromide, three phenyl-bromide Phosphonium of dodecyl, benzyl trimethyl bromide phosphine, second Base triphenyl phosphonium chloride, four butyl phosphonium bromides, tetraphenyl phosphonium chloride, 4-phenyl phosphonium bromide, four methyl bromide Phosphonium or tetraphenyl four Fu Peng Suan Phosphonium.
3. according to the method described in claim 1, it is characterized in that the solvent of the quaternary phosphine salting liquid is water, methanol, ethyl alcohol, toluene Or dichloroethanes.
4. according to the method described in claim 1, it is characterized in that the catalyst carrier be activated carbon, aluminium oxide, graphene or Carbon nanotube.
5. support type quaternary alkylphosphonium salt non-metallic catalyst prepared by the method for one of claim 1-4.
6. application of the support type quaternary alkylphosphonium salt non-metallic catalyst of claim 5 in catalyzing acetylene and chlorination addition reaction of hydrogen.
7. application according to claim 6, it is characterized in that the condition of the reaction is：150-250 DEG C of temperature range, raw material Gas proportioning is (VHCl/VC2H2) 0.90~1.2, unstripped gas acetylene volume space velocity 10-120h-1。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110605130A (en) * 2019-10-12 2019-12-24 内蒙古中谷矿业有限责任公司 Composite metal salt catalyst for acetylene hydrochlorination

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110605130A (en) * 2019-10-12 2019-12-24 内蒙古中谷矿业有限责任公司 Composite metal salt catalyst for acetylene hydrochlorination

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