CN106316833A - Byproduct hydrogen chloride reusing method - Google Patents

Byproduct hydrogen chloride reusing method Download PDF

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Publication number
CN106316833A
CN106316833A CN201610687639.0A CN201610687639A CN106316833A CN 106316833 A CN106316833 A CN 106316833A CN 201610687639 A CN201610687639 A CN 201610687639A CN 106316833 A CN106316833 A CN 106316833A
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Prior art keywords
hydrogen chloride
tower
chloride
product
ketenes
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CN201610687639.0A
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Chinese (zh)
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周超
周一超
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Individual
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66Silver or gold
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58Preparation of carboxylic acid halides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/38Acyl halides
    • C07C53/40Acetyl halides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/18Silver
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/20Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
    • B01J2523/23Calcium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/20Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
    • B01J2523/27Zinc

Abstract

The invention discloses a byproduct hydrogen chloride reusing method. The byproduct hydrogen chloride reusing method comprises the following steps: firstly, inflating mixed gas of acetylene and oxygen into the bottom of a ketene producing tower, and under the action of vacuum, completing synthesis of ketene CH2=C=O within one second by using a Zn0\CaO\AgO catalyst bed with silica gel as a carrier; secondly, under the action of vacuum, enabling gaseous ketene to enter an acetyl chloride producing tower, inflating dried and purified byproduct hydrogen chloride HCL gas into the bottom of the tower, and performing addition reaction on the two gases to generate acetyl chloride; thirdly, under the action of vacuum, enabling the acetyl chloride gas to enter a condensing tower, cooling and condensing into liquid acetyl chloride, and recycling into an acetyl chloride dropwise adding or collecting tank so as to recycle the byproduct hydrogen chloride as a chemical intermediate acetyl chloride product. The byproduct hydrogen chloride reusing method has the beneficial effects of a reasonable structural design and a wide application range.

Description

By-product hydrogen chloride reuse method
Technical field
The present invention relates to chemical by-product and recycle field, particularly a kind of by-product hydrogen chloride reuse method.
Background technology
In chemical industry, many medium-sized and small enterprises produce substantial amounts of by-product hydrogen chloride in process of production, at present, domestic It is that hydrogen chloride simply adsorbs into low content hydrochloric acid (about 29%) that the hydrogen chloride of these enterprises reclaims way;At current chemical industry In industry, the whole nation just has the by-product hydrochloric acid of nearly million tons every year, not only causes raw-material waste, limits the product of enterprise Can, cause serious three-waste pollution simultaneously.
Process as a example by the production of monomer medicament by water, in the production producing the products such as monomer medicament " hydroxy ethylidene-diphosphate " During just have substantial amounts of by-product hydrochloric acid to produce, when by-product hydrochloric acid stock's swell-warehouse, would have to stopping production process, major part enterprise All with the price of 200 yuans of subsidy per ton, give intermetallic composite coating enterprise or extensive chemical enterprise is used as raw material, these enterprises Industry fails to reach to deal carefully with the technical capability of spent acid, causes serious environmental pollution.
Summary of the invention
The invention aims to solve the problems referred to above, devise a kind of by-product hydrogen chloride reuse method.
Realize above-mentioned purpose, the technical scheme is that, a kind of by-product hydrogen chloride reuse method, the method include as Lower step:
The first step, is passed through the mixed gas of acetylene and oxygen, under vacuum, by with silica gel being at the bottom of ketenes generates tower The ZnO Ca0 AgO catalyst bed body of carrier, can complete ketenes CH in one second2The synthesis of=C=O.
Second step, the ketenes of gaseous state under vacuum, enters chloroacetic chloride and generates tower, simultaneously by the by-product of dry decontamination Hydrogen chloride HCL gas is passed through at the bottom of tower, two kinds of gas generation additive reaction, generates chloroacetic chloride.
3rd step, gas chloroacetic chloride under vacuum, enters condensing tower, and cooling is condensed into liquid chloroacetic chloride, is recovered to Chloroacetic chloride dropping fills or collection is received and filled, and completes the recycling of by-product hydrogen chloride, is converted into product chemical intermediate " chloroacetic chloride ".
In described mixed gas, the mol ratio of acetylene and oxygen is 2:1.
The temperature of described mixed gas is 98 DEG C---110 DEG C.
The reaction equation of the described first step is: 2C2H2+O2=2C2H2O。
The reaction equation of described second step is: C2H2O+HCL=CH3COCL。
A kind of by-product hydrogen chloride reuse means, this device be generated tower by ketenes, chloroacetic chloride generates tower, condensing tower and Chloroacetic chloride receives tank and is sequentially connected with composition, and chloroacetic chloride generates to connect on tower HCL dry decontamination tank, is dried in dry decontamination tank Agent is H2SO4
The bottom of described ketenes generation tower is passed through the mixed gas of acetylene and oxygen, and ketenes is the most logical in generating tower chuck Enter steam mixed gas is heated.
Described chloroacetic chloride is passed through steam in generating tower chuck and heats chloroacetic chloride reaction of formation.
Described hydrogen chloride gas is the side-product of Chemical Manufacture.
Utilize the by-product hydrogen chloride reuse method that technical scheme makes, can be by fast for the hydrogen chloride gas of by-product Speed reacts into chloroacetic chloride product, only need to be connected to by native system in by-product hydrogen chloride system, can be achieved with recycling, structure Design is simple, practical, is suitable for large-scale promotion.
Accompanying drawing explanation
Fig. 1 is the structural representation of by-product hydrogen chloride reuse means of the present invention;
In figure, 1, ketenes generate tower;2, chloroacetic chloride generates tower;3, condensing tower;4, chloroacetic chloride receives tank;5, hydrogen chloride is dried only Change tank.
Detailed description of the invention
Being specifically described the present invention below in conjunction with the accompanying drawings, a kind of by-product hydrogen chloride reuse method, the method includes Following steps:
The first step, is passed through the mixed gas of acetylene and oxygen, under vacuum, by with silica gel being at the bottom of ketenes generates tower The ZnO CaO AgO catalyst bed body of carrier, can complete ketenes CH in one second2The synthesis of=C=O.
Second step, the ketenes of gaseous state under vacuum, enters chloroacetic chloride and generates tower, simultaneously by the by-product of dry decontamination Hydrogen chloride HCL gas is passed through at the bottom of tower, two kinds of gas generation additive reaction, generates chloroacetic chloride.
3rd step, gas chloroacetic chloride under vacuum, enters condensing tower, and cooling is condensed into liquid chloroacetic chloride, is recovered to Chloroacetic chloride dropping fills or collection is received and filled, and completes the recycling of by-product hydrogen chloride, is converted into product chemical intermediate " chloroacetic chloride ".Its In, in described mixed gas, the mol ratio of acetylene and oxygen is 2:1;The temperature of described mixed gas is 98 DEG C---110 DEG C;Institute The reaction equation stating the first step is: 2C2H2+O2=2C2H2O;The reaction equation of described second step is: C2H2O+HCL=CH3COCL。
As it is shown in figure 1, a kind of by-product hydrogen chloride reuse means, this device is to be generated tower 1, chloroacetic chloride generation by ketenes Tower 2, condensing tower 3 and chloroacetic chloride receive tank 4 and are sequentially connected with composition, and chloroacetic chloride generates to connect on tower HCL dry decontamination tank 5, Dry decontamination tank internal desiccant is H2SO4.Wherein, the bottom of described ketenes generation tower 1 is passed through the gaseous mixture of acetylene and oxygen Body, ketenes is also passed through steam and heats mixed gas in generating tower chuck;Described chloroacetic chloride is passed through steam in generating tower 2 chuck Chloroacetic chloride reaction of formation is heated;Described hydrogen chloride gas is the side-product of Chemical Manufacture.
The know-why of native system is, the hydrogen chloride gas drying of by-product is purified, directly and ketenes is at catalyst Chloroacetic chloride product is reacted into rapidly under effect.Only native system need to be connected in by-product hydrogen chloride system, can be achieved with reclaiming again Utilize.
Chloroacetic chloride is chemical intermediate, is important industrial chemicals, is widely used in medicine intermediate, pesticide intermediate Deng, process as a example by monomer medicament production industry by water, when producing the products such as monomer medicament " hydroxy ethylidene-diphosphate ", just have A large amount of hydrogen chloride by-products, can be converted into the hydrogen chloride of by-product chloroacetic chloride as leading portion raw materials for production, make production system not By-product hydrochloric acid again, brings great economic benefit to enterprise.
Know-why:
One, at the bottom of ketenes generates tower, it is passed through acetylene and the mixed gas of oxygen (mol ratio 2:1), keeps temperature 98 DEG C---110 DEG C, under vacuum, by the ZnO CaO AgO catalyst bed body with silica gel as carrier, within one second, ketenes can be completed CH2The synthesis of=C=O.Reaction equation is: 2C2H2+O2=2C2H2O
Two, the ketenes of gaseous state is under vacuum, enters chloroacetic chloride and generates tower, simultaneously by the by-product hydrogen chloride of dry decontamination HCL gas is passed through at the bottom of tower, two kinds of gas generation additive reaction, generates chloroacetic chloride.
Reaction equation is: C2H2O+HCL=CH3COCL
Three, gas chloroacetic chloride is under vacuum, enters condensing tower, and cooling is condensed into liquid chloroacetic chloride, is recovered to chloroacetic chloride and drips Add filling or collection is received and filled, complete the recycling of by-product hydrogen chloride, be converted into product chemical intermediate " chloroacetic chloride ".
Technique scheme only embodies the optimal technical scheme of technical solution of the present invention, those skilled in the art Some variations may made some of which part all embody the principle of the present invention, belong to protection scope of the present invention it In.

Claims (9)

1. a by-product hydrogen chloride reuse method, it is characterised in that the method comprises the steps:
The first step, is passed through the mixed gas of acetylene and oxygen, under vacuum, by with silica gel being at the bottom of ketenes generates tower The ZnO CaO AgO catalyst bed body of carrier, can complete ketenes CH in one second2The synthesis of=C=O;
Second step, the ketenes of gaseous state under vacuum, enters chloroacetic chloride and generates tower, simultaneously by the by-product chlorination of dry decontamination Hydrogen HCL gas is passed through at the bottom of tower, two kinds of gas generation additive reaction, generates chloroacetic chloride;
3rd step, gas chloroacetic chloride under vacuum, enters condensing tower, and cooling is condensed into liquid chloroacetic chloride, is recovered to acetyl Chlorine dropping fills or collection is received and filled, and completes the recycling of by-product hydrogen chloride, is converted into product chemical industry intermediate acetyl chlorine.
By-product hydrogen chloride reuse method the most according to claim 1, it is characterised in that in described mixed gas acetylene and The mol ratio of oxygen is 2:1.
By-product hydrogen chloride reuse method the most according to claim 2, it is characterised in that the temperature of described mixed gas is 98℃---110℃。
4. according to described by-product hydrogen chloride reuse method arbitrary in claim 1-3, it is characterised in that the described first step Reaction equation is: 2C2H2+O2=2C2H2O。
5. according to described by-product hydrogen chloride reuse method arbitrary in claim 1-3, it is characterised in that described second step Reaction equation is: C2H2O+HCL=CH3COCL。
6. the by-product hydrogen chloride reuse means that method makes according to claim 1, it is characterised in that this device is Generated tower (1) by ketenes, chloroacetic chloride generates tower (2), condensing tower (3) and chloroacetic chloride reception tank (4) are sequentially connected with and constitute, second On acyl chlorides generation tower, connection has HCL dry decontamination tank (5), dry decontamination tank internal desiccant is H2SO4
By-product hydrogen chloride reuse means the most according to claim 6, it is characterised in that described ketenes generates tower (1) Bottom be passed through the mixed gas of acetylene and oxygen, ketenes is also passed through steam and heats mixed gas in generating tower chuck.
By-product hydrogen chloride reuse means the most according to claim 6, it is characterised in that described chloroacetic chloride generates tower (2) It is passed through steam in chuck chloroacetic chloride reaction of formation is heated.
By-product hydrogen chloride reuse means the most according to claim 6, it is characterised in that described hydrogen chloride gas is chemical industry The side-product produced.
CN201610687639.0A 2016-08-19 2016-08-19 Byproduct hydrogen chloride reusing method Pending CN106316833A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647871A (en) * 1968-04-10 1972-03-07 Wacker Chemie Gmbh Process for producing acetylchloride
DE2060807A1 (en) * 1970-12-10 1972-06-15 Basf Ag Acetyl chloride prepn - by ketene/hydrogenchloride reaction in absence of catalysts
CN200964388Y (en) * 2006-10-28 2007-10-24 周烜 Preparation device for acetyl chloride cogeneration hydroxyl ethidene diphosphoric acid
CN102295517A (en) * 2011-07-05 2011-12-28 镇江市东煌化工有限公司 Process of synthesizing methyl chloride with hydrogen chloride gas by-produced in production of phosphorous acid from phosphorus trichloride

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647871A (en) * 1968-04-10 1972-03-07 Wacker Chemie Gmbh Process for producing acetylchloride
DE2060807A1 (en) * 1970-12-10 1972-06-15 Basf Ag Acetyl chloride prepn - by ketene/hydrogenchloride reaction in absence of catalysts
CN200964388Y (en) * 2006-10-28 2007-10-24 周烜 Preparation device for acetyl chloride cogeneration hydroxyl ethidene diphosphoric acid
CN102295517A (en) * 2011-07-05 2011-12-28 镇江市东煌化工有限公司 Process of synthesizing methyl chloride with hydrogen chloride gas by-produced in production of phosphorous acid from phosphorus trichloride

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JONES I T N ET AL: "Kinetics and mechanism of the reaction of atomic oxygen with acetylene", 《PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON, SERIES A:MATHEMATICAL, PHYSICAL AND ENGINEERING SCIENCES》 *
刘志海等: "乙烯酮氯化法合成氯乙酰氯的反应器研究", 《湖南化工》 *

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