WO2017054460A1 - 一种乙烷氯化脱氢的方法 - Google Patents

一种乙烷氯化脱氢的方法 Download PDF

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WO2017054460A1
WO2017054460A1 PCT/CN2016/082022 CN2016082022W WO2017054460A1 WO 2017054460 A1 WO2017054460 A1 WO 2017054460A1 CN 2016082022 W CN2016082022 W CN 2016082022W WO 2017054460 A1 WO2017054460 A1 WO 2017054460A1
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point metal
ethane
chlorination
dehydrogenation
boiling point
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PCT/CN2016/082022
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English (en)
French (fr)
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钟劲光
刘星
刘雪花
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厦门中科易工化学科技有限公司
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Priority to CA2982507A priority Critical patent/CA2982507A1/en
Priority to KR1020177030384A priority patent/KR102044350B1/ko
Priority to EP16850085.8A priority patent/EP3357899B1/en
Priority to RU2017136187A priority patent/RU2679911C1/ru
Priority to JP2018502312A priority patent/JP6505941B2/ja
Priority to US15/560,397 priority patent/US10138181B2/en
Publication of WO2017054460A1 publication Critical patent/WO2017054460A1/zh

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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/035—Preparation of hydrogen chloride from chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/04—Preparation of chlorine from hydrogen chloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/04—Halides
    • C01G19/06—Stannous chloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00—Compounds of bismuth
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/22—Aliphatic unsaturated hydrocarbons containing carbon-to-carbon triple bonds
    • C07C11/24—Acetylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
    • C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
    • C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
    • C07C19/043—Chloroethanes
    • C07C19/045—Dichloroethanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/04—Chloro-alkenes
    • C07C21/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/44—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with halogen or a halogen-containing compound as an acceptor
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a method for dehydrogenating ethane, in particular to a method for chlorination dehydrogenation of ethane, belonging to the field of chemical production.
  • Ethane is mainly found in petroleum gas, natural gas, coke oven gas and petroleum cracking gas. At present, the most widely used ethane is used to produce ethylene, and ethane is much more economical than the raw material for the cracking of ethylene.
  • the method for producing ethylene from ethane mainly includes steam pyrolysis method and oxidative dehydrogenation method.
  • Steam pyrolysis is the traditional method of ethylene from ethane.
  • the steam pyrolysis method has high energy consumption, low heat utilization rate, strict requirements on equipment materials, and high production cost.
  • other heavy olefins such as propylene, butadiene and aromatic hydrocarbons are also produced in the product to reduce the ethylene yield.
  • Ethylene oxidative dehydrogenation to ethylene technology has milder reaction conditions than steam pyrolysis process, but the introduction of oxygen by oxidative dehydrogenation technology increases the difficulty of oxygen-containing by-products and subsequent separation and purification, and the selectivity and yield of ethylene. Both are relatively low.
  • the catalytic oxidation dehydrogenation catalyst preparation process is also cumbersome.
  • a method for catalytic oxidative dehydrogenation of ethane, which uses at least one of Mo, Te, V and Nb with Cu, Ta, Sn, Se, W, Ti, is disclosed in European Patent Application No. EP20030704717.
  • the Chinese patent No. 2012100126547 provides a catalyst for oxidative dehydrogenation of ethylene to ethylene at low temperature.
  • the catalyst is mainly composed of HCl gas, TiO 2 is used as a catalytic component, and the main active component is HCl gas and reaction.
  • the raw material gas air and ethane
  • the reaction temperature is controlled at 440 ° C to 550 ° C, and the ethylene yield is 45% to 75%.
  • the present invention provides a novel method for chlorination dehydrogenation of ethane in view of the technical drawbacks of the prior art described above.
  • the invention adopts a low boiling point metal chloride as a chlorination dehydrogenation raw material, and the low melting point metal formed by the reaction is used as an intermediate medium, and has the characteristics of simple process, low cost and high yield.
  • the production control to control the ratio of ethane and chloride, it is possible to produce some acetylene and vinyl chloride by-product while producing ethylene.
  • a method for chlorination dehydrogenation of ethane wherein a low boiling point metal chloride is mixed with C 2 H 6 , a low boiling point metal chloride is reduced to a liquid low melting point metal, and C 2 H 6 is dechlorinated to obtain a HCl. a mixed gas of C 2 H 6 , C 2 H 4 , C 2 H 2 and C 2 H 3 Cl.
  • the low-boiling metal chloride is gaseous at the reaction temperature, and the reaction temperature in H 2 can be reduced to a liquid low melting point metal and hydrogen chloride. More preferably, the low boiling metal chloride is BiCl 3 or SnCl 2 .
  • the reaction temperature is 500 to 800 °C. More preferably, the reaction temperature is 550 to 650 °C.
  • the reaction temperature may be 500 to 600 ° C, 600 to 650 ° C, 650 to 700 ° C or 700 to 800 ° C.
  • the molar ratio of chlorine element to C 2 H 6 in the low boiling point metal chloride is from 1 to 4:1.
  • the molar ratio of chlorine element to C 2 H 6 in the low boiling point metal chloride may be from 1 to 2:1, from 2 to 3:1 or from 3 to 4:1.
  • the reaction time is controlled such that the conversion of C 2 H 6 reaches 50 to 99.9%.
  • the reaction time is controlled so that the conversion rate of C 2 H 6 reaches 50 to 99.9%, which is controlled by the following method: collecting the gas after dehydrogenation tail gas to remove hydrogen chloride per unit time, and determining the amount of unreacted ethane therein, according to the following formula Calculate the conversion of C 2 H 6 . If the conversion of C 2 H 6 is less than 50%, the conversion can be increased by prolonging the reaction time, and the reaction time can be extended by reducing the flow rate of ethane; if the conversion of C 2 H 6 is higher than 99.9% can reduce the conversion rate by shortening the reaction time, shortening the reaction time by increasing the ethane flow rate.
  • the method further comprises reacting a low melting point metal to obtain a low boiling point metal chloride, and returning to a mixed reaction with C 2 H 6 .
  • the method of reacting the low melting point metal to obtain a low boiling point metal chloride is selected from any of the following methods:
  • Method 1 reacting a low melting point metal with chlorine gas to obtain a low boiling point metal chloride
  • Method 2 a low melting point metal reacts with oxygen or air to obtain a metal oxide; the metal oxide absorbs HCl obtained by chlorination dehydrogenation of C 2 H 6 to obtain a low boiling point metal chloride;
  • Method three When the low boiling point when metal chloride SnCl 2, SnCl 2 reduction reaction with hydrochloric acid to give a low melting point of Sn, to obtain a low-boiling metal chloride SnCl 2 and H 2.
  • the method further comprises a mixed gas containing HCl, C 2 H 6 , C 2 H 4 , C 2 H 2 and C 2 H 3 Cl selected from any of the following methods using HCl:
  • Method 1 obtaining hydrochloric acid product by absorbing HCl with water
  • Method 3 Catalytic oxidation of HCl with oxygen or air to Cl 2 , and returning to react with a low melting point metal to obtain a low boiling point metal chloride.
  • the mixed gas after HCl separation is separated to obtain C 2 H 4 , C 2 H 2 and C 2 H 3 Cl products, respectively.
  • the mixed gas after the separation of HCl can obtain C 2 H 4 , C 2 H 2 and C 2 H 3 Cl products by a conventional separation method, and a conventional separation method such as rectification.
  • the intermediate of the reaction is a liquid low-melting metal, which is easy to transport and separate in the process, and the reaction device is simple and easy to operate;
  • Different ratios of C 2 H 4 , C 2 H 2 and C 2 H 3 Cl can be obtained by controlling the C 2 H 6 single pass conversion.
  • the single pass conversion rate of C 2 H 6 can reach over 98%, and the selectivity of ethylene can reach over 95% when ethylene is the target product.
  • more than 10% of C 2 H 2 or C 2 H 3 Cl can be obtained, which is an effective method for directly synthesizing C 2 H 3 Cl;
  • step 1) oxygen into step 1) obtained in the molten bismuth, the Bi is converted to Bi 2 O 3, Bi 2 O 3 subsequent absorption step (1) obtained in HCl, to give ethane and BiCl 3 to continue the reaction;
  • step 1 The mixed gas containing HCl, C 2 H 6 , C 2 H 4 , C 2 H 2 and C 2 H 3 Cl obtained in step 1) passes through the Bi 2 O 3 layer, and absorbs HCl to obtain C 2 H 6.
  • a mixed gas of C 2 H 4 , C 2 H 2 and C 2 H 3 Cl; the main components of the ethane chlorination dehydrogenation tail gas after dehydrochlorination are shown in Table 2.
  • step 1) oxygen into step 1) obtained in the molten bismuth, the Bi is converted to Bi 2 O 3, Bi 2 O 3 subsequent absorption step (1) obtained in HCl, to give ethane and BiCl 3 to continue the reaction;

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

本发明涉及一种乙烷氯化脱氢的方法，将低沸点金属氯化物与C2H6混合反应，低沸点金属氯化物还原成液态的低熔点金属，C2H6氯化脱氢后得到含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体。该方法以低沸点金属氯化物作为氯化脱氢原料，反应生成的低熔点金属作为中间介质，具有工艺简单、成本低、收率高的特点。同时根据生产所需控制乙烷和氯化物的配比，可在生产乙烯的同时副产部分乙炔和氯乙烯。

Description

一种乙烷氯化脱氢的方法 技术领域
本发明涉及一种乙烷脱氢的方法，特别是一种乙烷氯化脱氢的方法，属于化工生产领域。
背景技术
乙烷主要存在于石油气、天然气、焦炉气及石油裂解气中，经分离而得。目前乙烷用途最广的是用来生产乙烯，乙烷作为制备乙烯的裂解原料在经济上要比重质原料合算得多。乙烷制乙烯的方法主要有蒸汽热裂解法，氧化脱氢法。
蒸汽热裂解法是乙烷制乙烯的传统方法。但蒸汽热裂解法能耗大，热量利用率低，对设备材质要求苛刻，生产成本高。同时，产品中也会产生其他重的烯烃如丙烯、丁二烯以及芳香烃等，降低乙烯收率。
乙烷氧化脱氢制乙烯技术相对于蒸汽热裂解工艺有更温和的反应条件，但由于氧化脱氢技术引进氧，增加了含氧副产品及后续分离提纯的难度，且乙烯的选择性和收率都比较低。特别是催化氧化脱氢技术催化剂制备过程也比较繁琐。如申请号为EP20030704717的欧洲专利，发明了一种乙烷催化氧化脱氢的方法，该发明用Mo，Te，V和Nb中至少一种氧化物与Cu，Ta，Sn，Se，W，Ti，Fe，Co，Ni，Cr，Zr，Sb，Bi中的一种元素结合，通过一系列工序制备乙烷氧化脱氢的催化剂，该方法乙烷的单程转化率为40～60％，乙烯的收率为20～60％。申请号为2012100126547的中国专利提供了一种低温乙烷氧化脱氢制乙烯的催化剂，该催化剂以HCl气体为主活性组分，以TiO2为助催化组分，主活性组分HCl气体与反应原料气(空气和乙烷)混合后进入反应器，反应温度控制在440℃～550℃，乙烯收率在45％～75％。
发明内容
本发明针对以上所述现有技术存在的技术缺陷，提供一种乙烷氯化脱氢的新方法。本发明以低沸点金属氯化物作为氯化脱氢原料，反应生成的低熔点金属作为中间介质，具有工艺简单、成本低、收率高的特点。同时根据生产所需控制乙烷和氯化物的配比，可在生产乙烯的同时副产部分乙炔和氯乙烯。
本发明是通过以下技术方案实现的：
一种乙烷氯化脱氢的方法，将低沸点金属氯化物与C2H6混合反应，低沸点金属氯化物还原成液态的低熔点金属，C2H6氯化脱氢后得到含有HCl、C2H6、C2H4、C2H2和C2H3Cl 的混合气体。
优选的，所述低沸点金属氯化物在反应温度下为气态，且在反应温度下能被H2还原成液态的低熔点金属和氯化氢。更优选的，所述低沸点金属氯化物为BiCl3或SnCl2。
优选的，反应温度为500～800℃。更优选的，反应温度为550～650℃。
反应温度可为500～600℃、600～650℃、650～700℃或700～800℃。
优选的，所述低沸点金属氯化物中氯元素与C2H6的摩尔比为1～4:1。
所述低沸点金属氯化物中氯元素与C2H6的摩尔比可为1～2:1、2～3:1或3～4:1。
优选的，控制反应时间使C2H6的转化率达到50～99.9％。
控制反应时间使C2H6的转化率达到50～99.9％，是通过下面的方法来控制：单位时间内收集脱氢尾气去除氯化氢后的气体，测定其中未反应的乙烷量，按下面公式计算C2H6转化率，如果C2H6转化率低于50％，可通过延长反应时间使转化率增大，延长反应时间通过减小乙烷流速；如果C2H6转化率高于99.9％，可通过缩短反应时间使转化率减小，缩短反应时间通过增大乙烷流速。
C2H6转化率＝100％‐脱氢尾气去除氯化氢后乙烷摩尔浓度。
优选的，所述方法还包括将低熔点金属反应得到低沸点金属氯化物，返回与C2H6混合反应。
更优选的，将低熔点金属反应得到低沸点金属氯化物的方法选自以下方法之任一：
方法一：低熔点金属和氯气反应，得到低沸点金属氯化物；
方法二：低熔点金属与氧气或空气反应，得到金属氧化物；金属氧化物吸收C2H6氯化脱氢后得到的HCl，得到低沸点金属氯化物；
方法三：当低沸点金属氯化物为SnCl2时，SnCl2还原得到的低熔点Sn与盐酸反应，得到低沸点金属氯化物SnCl2和H2。
优选的，所述方法还包括含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体选自以下方法之任一利用HCl：
方法一：用水吸收HCl制得盐酸产品；
方法二：将HCl与C2H4氧氯化得到二氯乙烷产品；
方法三：将HCl与氧气或空气催化氧化成Cl2，返回与低熔点金属反应得到低沸点金属氯化物。
优选的，将HCl分离后的混合气体经分离分别得到C2H4、C2H2和C2H3Cl产品。HCl分离后的混合气体可通过常规的分离方法分别得到C2H4、C2H2和C2H3Cl产品，常规的 分离方法如精馏。
本发明乙烷氯化脱氢的方法，基本原理如下：
Figure PCTCN2016082022-appb-000001
Figure PCTCN2016082022-appb-000002
Figure PCTCN2016082022-appb-000003
或
Figure PCTCN2016082022-appb-000004
Figure PCTCN2016082022-appb-000005
Figure PCTCN2016082022-appb-000006
本发明至少具有以下有益效果之一：
(1)用低沸点金属氯化物作脱氢材料与乙烷氯化脱氢，采用气相反应，反应速度快，效率高，可在几秒之内瞬间完成反应，适于大型工业化生产；
(2)反应的中间物是液态的低熔点金属，过程中易于输送和分离，反应装置简单易行；
(3)通过控制C2H6单程转化率可获得不同比例的C2H4、C2H2和C2H3Cl。C2H6的单程转化率可达98％以上，以乙烯为目标产品时，乙烯的选择性可达95％以上。采用深度脱氢时，可得到10％以上的C2H2或C2H3Cl，是直接合成C2H3Cl的有效方法；
(4)金属氧化或氯化产生的热量可以直接用于氯化物的汽化和乙烷脱氢反应，可节约能耗。
具体实施方式
以下通过特定的具体实例说明本发明的技术方案。应理解，本发明提到的一个或多个方法步骤并不排斥在所述组合步骤前后还存在其他方法步骤或在这些明确提到的步骤之间还可以插入其他方法步骤；还应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。而且，除非另有说明，各方法步骤的编号仅为鉴别各方法步骤的便利工具，而非为限制各方法步骤的排列次序或限定本发明可实施的范围，其相对关系的改变或调整，在无实质变更技术内容的情况下，当亦视为本发明可实施的范畴。
实施例1
(1)将BiCl3蒸汽与C2H6混合，控制反应时间，使C2H6的转化率为50％，BiCl3中氯元素与C2H6的摩尔比为1:1，反应温度为500℃。C2H6氯化脱氢后得到含有HCl、C2H6、 C2H4、C2H2和C2H3Cl的混合气体，BiCl3还原成液态Bi；
(2)将氯气通入步骤1)得到的金属铋熔液中，使Bi转化成BiCl3后继续和乙烷反应；
(3)将步骤1)得到的含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体用水吸收掉HCl，即得含有C2H6、C2H4、C2H2和C2H3Cl的混合气体，同时副产盐酸；乙烷氯化脱氢尾气脱HCl后主要成分参见表1。
表1实施例1乙烷氯化脱氢尾气脱HCl后气相主要成分表
组分名 保留时间(min) 峰面积 峰高 摩尔浓度(％)
甲烷 0.86 9666 7364 0.023
乙烷 1.04 20614375 14146103 48.38
乙烯 1.13 21798544 13254713 51.16
乙炔 1.46 185413 116140 0.44
氯乙烯 5.01 2260 140 0.0053
全部   42610258 27524460 100.01
实施例2
(1)将BiCl3蒸汽与C2H6混合，控制反应时间，使C2H6的转化率为74％，控制BiCl3中氯元素与C2H6的摩尔比为2:1，反应温度为600℃。C2H6氯化脱氢后得到含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体，BiCl3还原成液态Bi；
(2)将氧气通入步骤1)得到的金属铋熔液中，使Bi转化成Bi2O3，Bi2O3吸收后续步骤(1)得到的HCl，得到BiCl3继续和乙烷反应；
(3)步骤1)得到的含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体通过Bi2O3层，吸收掉HCl，即得C2H6、C2H4、C2H2和C2H3Cl等的混合气体；乙烷氯化脱氢尾气脱HCl后主要成分参见表2。
表2实施例2乙烷氯化脱氢尾气脱HCl后气相主要成分表
组分名 保留时间(min) 峰面积 峰高 摩尔浓度(％)
甲烷 0.85 184217 134826 0.45
乙烷 1.03 10747164 7560033 26.16
乙烯 1.12 29432421 16559447 71.40
乙炔 1.45 424604 261458 1.03
氯乙烯 5.04 369146 692598 0.92
全部   41157554 24463623 99.96
实施例3
(1)将BiCl3蒸汽与C2H6混合，控制反应时间，使C2H6的转化率为97％，BiCl3中氯元素与C2H6的摩尔比为3:1，反应温度为650℃。C2H6氯化脱氢后得到含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体，BiCl3还原成液态Bi；
(2)将氯气通入步骤1)得到的金属铋熔液中，使Bi转化成BiCl3后继续和乙烷反应；
(3)将步骤1)得到的含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体用水吸收掉HCl，即得C2H6、C2H4、C2H2和C2H3Cl等的混合气体，同时副产盐酸；乙烷氯化脱氢尾气脱HCl后主要成分参见表3。
表3实施例3乙烷氯化脱氢尾气脱HCl后气相主要成分表
组分名 保留时间(min) 峰面积 峰高 摩尔浓度(％)
甲烷 0.86 532721 407419 1.31
乙烷 1.05 1053504 785805 2.61
乙烯 1.13 34063085 18044507 83.96
乙炔 1.45 3108821 1846049 7.68
氯乙烯 4.96 1805211 322805 4.46
全部   40563342 21406585 100.02
实施例4
(1)将BiCl3蒸汽与C2H6混合，控制反应时间，使C2H6的转化率为98％，BiCl3中氯元素与C2H6的摩尔比为4:1，反应温度为700℃。C2H6氯化脱氢后得到含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体，BiCl3还原成液态Bi；
(2)将氧气通入步骤1)得到的金属铋熔液中，使Bi转化成Bi2O3，Bi2O3吸收后续步骤(1)得到的HCl，得到BiCl3继续和乙烷反应；
(3)将步骤1)得到的含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体通过Bi2O3层，吸收掉HCl，即得C2H6、C2H4、C2H2和C2H3Cl等的混合气体；乙烷氯化脱氢尾气脱HCl后主要成分参见表4。
表4实施例4乙烷氯化脱氢尾气脱HCl后气相主要成分表
组分名 保留时间(min) 峰面积 峰高 摩尔浓度(％)
甲烷 0.86 532055 412012 1.31
乙烷 1.05 618220 468862 1.53
乙烯 1.13 30433728 16630354 75.12
乙炔 1.45 6019903 3423861 14.86
氯乙烯 4.94 2879373 471988 7.11
全部   40483279 17983216 99.90
实施例5
(1)将SnCl2蒸汽与C2H6混合，控制反应时间，使C2H6的转化率为77％，SnCl2中氯元素与C2H6的摩尔比为2:1，反应温度为800℃。C2H6氯化脱氢后得到含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体，SnCl2还原成液态Sn；
(2)将步骤1)得到的金属锡与后续步骤1)得到的盐酸反应，得到SnCl2继续和乙烷反应；
(3)将步骤1)得到的含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体用水吸收掉HCl，即得C2H6、C2H4、C2H2和C2H3Cl等的混合气体，同时副产盐酸；乙烷氯化脱氢尾气脱HCl后主要成分参见表5。
表5实施例5乙烷氯化脱氢尾气脱HCl后气相主要成分表
组分名 保留时间(min) 峰面积 峰高 摩尔浓度(％)
甲烷 0.86 1681688 1111058 5.99
乙烷 1.05 6545196 4367150 23.24
乙烯 1.14 19506153 10995253 69.07
乙炔 1.47 405920 235319 1.46
氯乙烯 4.94 39475 3749 0.14
全部   28178432 16712529 99.90
以上所述，仅为本发明的较佳实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。凡熟悉本专业的技术人员，在不 脱离本发明的精神和范围的情况下，当可利用以上所揭示的技术内容而做出的些许更动、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明的实质技术对上述实施例所作的任何等同变化的更动、修饰与演变，均仍属于本发明的技术方案的范围内。

Claims (10)

  1. 一种乙烷氯化脱氢的方法，其特征在于，将低沸点金属氯化物与C2H6混合反应，低沸点金属氯化物还原成液态的低熔点金属，C2H6氯化脱氢后得到含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体。
  2. 根据权利要求1所述的乙烷氯化脱氢的方法，其特征在于，所述低沸点金属氯化物在反应温度下为气态，且在反应温度下能被H2还原成液态的低熔点金属和氯化氢。
  3. 根据权利要求2所述的乙烷氯化脱氢的方法，其特征在于，所述低沸点金属氯化物为BiCl3或SnCl2。
  4. 根据权利要求1所述的乙烷氯化脱氢的方法，其特征在于，反应温度为500～800℃。
  5. 根据权利要求1所述的乙烷氯化脱氢的方法，其特征在于，所述低沸点金属氯化物中氯元素与C2H6的摩尔比为1～4:1。
  6. 根据权利要求1所述的乙烷氯化脱氢的方法，其特征在于，控制反应时间使C2H6的转化率达到50～99.9％。
  7. 根据权利要求1所述的乙烷氯化脱氢的方法，其特征在于，所述方法还包括将低熔点金属反应得到低沸点金属氯化物，返回与C2H6混合反应。
  8. 根据权利要求7所述的乙烷氯化脱氢的方法，其特征在于，将低熔点金属反应得到低沸点金属氯化物的方法选自以下方法之任一：
    方法一：低熔点金属和氯气反应，得到低沸点金属氯化物；
    方法二：低熔点金属与氧气或空气反应，得到金属氧化物；金属氧化物吸收C2H6氯化脱氢后得到的HCl，得到低沸点金属氯化物；
    方法三：当低沸点金属氯化物为SnCl2时，SnCl2还原得到的低熔点Sn与盐酸反应，得到低沸点金属氯化物SnCl2和H2。
  9. 根据权利要求1所述的乙烷氯化脱氢的方法，其特征在于，所述方法还包括含有HCl、C2H6、C2H4、C2H2和C2H3Cl的混合气体选自以下方法之任一利用HCl：
    方法一：用水吸收HCl制得盐酸产品；
    方法二：将HCl与C2H4氧氯化得到二氯乙烷产品；
    方法三：将HCl与氧气或空气催化氧化成Cl2，返回与低熔点金属反应得到低沸点金属氯化物。
  10. 根据权利要求9所述的乙烷氯化脱氢的方法，其特征在于，将HCl分离后的混合气 体经分离分别得到C2H4、C2H2和C2H3Cl产品。
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