CN110142006B - Device for high-temperature chlorination and dehydrogenation of alkane gas and use method - Google Patents
Device for high-temperature chlorination and dehydrogenation of alkane gas and use method Download PDFInfo
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- 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
Abstract
The invention relates to a device for high-temperature chlorination and dehydrogenation of alkane gas and a using method thereof. The device comprises a device body provided with a reaction cavity, wherein a low-melting-point metal molten layer and a molten salt layer are arranged in the reaction cavity of the device body, and the molten salt layer is arranged on the low-melting-point metal molten layer. The molten salt in the molten salt layer is introduced as a reaction solvent, has larger heat capacity than gas, can effectively and continuously provide heat generated by the reaction of chlorine and low-melting metal to the chlorination and dehydrogenation reaction of low-boiling metal chloride steam and alkane gas, improves the mass transfer and heat transfer performance of a reaction system, and is more energy-saving, controllable and higher in product selectivity.
Description
Technical Field
The invention belongs to the field of chemical production, relates to a high-temperature chlorination device and application thereof, and particularly relates to a high-temperature chlorination and dehydrogenation device for alkane gas and a using method thereof.
Background
Chlorination is a very common type of chemical reaction among organic compounds. Chlorination refers primarily to a reaction in which chlorine atoms are introduced into the molecules of a compound. Chlorine is a common chlorinating agent. However, because the chemical property of chlorine is very active, if the chlorine is directly chloridized, the chloridizing process is not easy to control, side reactions are more, the selectivity of products is poor, and the separation and purification difficulty is large, particularly, the chlorine and alkane react to obtain a mixture of various chloroalkane isomers, the boiling points of the chloroalkane isomers are very close, and the chloroalkane isomers cannot be separated.
The invention of application No. 201580056793.1 discloses chlorination of ethane at 350-700 deg.C using chlorine as chlorinating agent. Under the reaction conditions, the product produces various by-products such as 1,1, 1-trichloroethane, 1, 1-dichloroethylene, 1, 1-dichloroethane, trans-1, 2-dichloroethylene, cis-1, 2-dichloroethylene, tetrachloroethane, 1,1, 2-trichloroethane, etc., in addition to the desired products of ethylene, hydrogen chloride and vinyl chloride monomer at a content of about 90%. The method adopts the method of directly chlorinating ethane and chlorine, and has the disadvantages of low yield of target products, increased difficulty and cost of subsequent separation and purification due to more side reactions.
Compared with chlorine, the chemical activity of the metal chloride is weaker, the chlorination reaction is milder and controllable, the metal chloride is more suitable for high-temperature chlorination reaction, and the side reaction can be effectively reduced.
The invention of application No. 201510777040.1 describes a process for the chlorination coupling of methane by reacting CH4Mixing with metal chloride steam to react, and reducing the metal chloride into metal, CH4After chlorination coupling, HCl and C are obtained2H6、C2H4And C2H2The mixed gas of (1). The method utilizes the steam of the metal chloride as the chlorinating agent for the chlorination coupling of the methane, can generate stable C2 hydrocarbon, has high selectivity of the C2 hydrocarbon, almost has no chloralkane, converts the methane with low additional value into the C2 hydrocarbon with high additional value, and has good application prospect.
The invention patent with application number of 201510630923, X, relates to a method for chlorination and dehydrogenation of ethane by mixing low-boiling-point metal chloride with C2H6Mixing and reacting, reducing the low-boiling point metal chloride into liquid low-melting point metal, C2H6After chlorination dehydrogenation, the product containing HCl and C is obtained2H4、C2H2And C2H3Mixed gas of Cl, wherein C2H4The selectivity of (A) is as high as 98%. The method takes low-boiling-point metal chloride steam as a chlorination and dehydrogenation raw material, has high ethane conversion rate and good ethylene selectivity, and has the characteristics of simple process, low cost and high yield.
The invention patent with application number 201510777040.1 and application number 201510630923, X, realizes high-temperature chlorination and dehydrogenation reaction by contacting metal chloride with methane or ethane, and is more economical and energy-saving compared with other prior art. However, in the engineering process, the chloride steam and methane or ethane are both gases, so that the heat capacity is small, and the heat of the chlorination and dehydrogenation reaction of the methane or ethane gas cannot be continuously and stably supplied. When the gas temperature is low, the chlorination reaction is incomplete and the efficiency is low; and the gas temperature is too high, side reactions are easy to generate, and the heat required by the chlorination reaction of methane or ethane cannot be continuously and stably supplied, so that the yield of the product is unstable.
Therefore, the constant temperature reactor is developed to solve the problems of poor mass and heat transfer effect, unstable yield and the like in the high-temperature reaction process of the gas, and has great significance for industrial popularization and application of the technology.
Disclosure of Invention
The invention mainly aims at the technical defects of patent application Nos. 201510777040.1 and 201510630923.X, and provides a device for high-temperature chlorination and dehydrogenation of alkane gas and a using method thereof.
The invention is realized by the following technical scheme:
the invention provides a device for high-temperature chlorination and dehydrogenation of alkane gas, which comprises a device body provided with a reaction cavity, wherein a low-melting-point metal molten layer and a molten salt layer are arranged in the reaction cavity of the device body, and the molten salt layer is arranged on the low-melting-point metal molten layer.
Preferably, at least one of the following technical features is also included:
1) a gas-liquid separation layer is further arranged in the reaction cavity of the device body and is arranged on the molten salt layer, and a cooling pipe is arranged on the outer wall of the device body corresponding to the gas-liquid separation layer; the cooling medium in the cooling pipe is preferably alkane gas, which not only has the cooling function on the gas-phase chlorination and dehydrogenation crude product of the reaction, but also preheats the alkane gas;
2) a first air inlet is formed in the wall of the device body corresponding to the low-melting-point metal molten layer; chlorine gas is introduced from the first gas inlet, and the first gas inlet can be arranged at the bottom of the low-melting-point metal molten layer;
3) a second air inlet is formed in the wall of the device body corresponding to the molten salt layer; the alkane gas is introduced from a second gas inlet, and the second gas inlet can be arranged in the middle of the molten salt layer;
4) a plurality of porous plates are arranged in the low-melting-point metal melt layer, so that the gas distribution condition is improved;
5) and a plurality of porous plates are arranged in the molten salt layer, so that the gas distribution condition is improved.
More preferably, in the feature 1), a product gas outlet is provided on a wall of the apparatus body corresponding to the gas-liquid separation layer.
Through the device for high-temperature chlorination and dehydrogenation of the alkane gas, chlorine can be introduced from the first gas inlet to react with low-boiling-point metal to obtain low-boiling-point metal chloride steam, and the alkane gas can be introduced from the second gas inlet to react with the low-boiling-point metal chloride steam entering the molten salt layer to obtain a gas-phase chlorination and dehydrogenation crude product. And after the gas-phase chlorination and dehydrogenation crude product is cooled by a cooling pipe in a gas-liquid separation layer, part or all of unreacted low-boiling-point metal chloride steam is condensed into liquid and then flows back to a molten salt layer, and the residual gas-phase chlorination and dehydrogenation crude product can be discharged from a product gas outlet.
The device for high-temperature chlorination and dehydrogenation of the alkane gas is particularly suitable for preparing C2 hydrocarbon by chlorination and dehydrogenation coupling of methane and ethylene by chlorination and dehydrogenation of acetylene.
A second aspect of the invention provides a method of using the apparatus described above, comprising the steps of:
1) adding Cl2Introducing the low-melting-point metal molten layer to make Cl2Reacting with low-boiling-point metal to obtain low-boiling-point metal chloride steam, wherein a molten salt layer is arranged on the low-boiling-point metal molten layer, and the low-boiling-point metal chloride steam enters the molten salt layer;
2) introducing alkane gas into a molten salt layer for dissolving low-boiling-point metal chloride steam, and reacting the alkane gas with the low-boiling-point metal chloride to obtain a gas-phase chlorination-dehydrogenation crude productA product and a low melting point metal, said low melting point metal returning to said low melting point metal molten layer, continuing with Cl2Reacting, wherein the molten salt in the molten salt layer is the molten metal chloride which is liquid at the reaction temperature of the step 2). The molten salt is chemically stable at the reaction temperature of step 2) and does not react with the reaction raw materials and reaction products of step 2).
Preferably, the method further comprises the following steps: a gas-liquid separation layer (13) is arranged on the molten salt layer, the gas-phase chlorination and dehydrogenation crude product obtained in the step 2) is subjected to condensation separation, part or all of unreacted low-boiling-point metal chloride steam in the chlorination and dehydrogenation crude product is condensed into liquid low-boiling-point metal chloride and flows back to the molten salt layer, and the residual gas-phase chlorination and dehydrogenation crude product is discharged.
More preferably, the temperature of condensation separation is 250-600 ℃.
Preferably, the low-melting metal is liquid at the reaction temperature of step 1), the low-melting metal chloride is gaseous at the reaction temperature of step 1), and the low-boiling metal chloride can be reacted with H at the reaction temperature of step 1)2Reducing metal simple substance and hydrogen chloride.
Preferably, step 1) further comprises at least one of the following technical features:
1) the low melting point metal is selected from at least one of Sn, Bi and Pb;
2) the reaction temperature in the step 1) is 600-950 ℃.
Preferably, step 2) further comprises at least one of the following technical features:
1) the molten salt is selected from one or more of alkali metal chloride, alkaline earth metal chloride and transition metal chloride; the alkali metal chloride is selected from one or more of chlorides of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr), the alkaline earth metal chloride is selected from one or more of chlorides of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra), transition metal elements in the transition metal chloride refer to d-zone and ds-zone elements in the periodic table (the d-zone elements comprise elements in groups III B-VIIB and VIII of the periodic table, and the ds-zone comprises elements in groups IB-IIB of the periodic table, and does not comprise one or more of lanthanide and actinide);
2) the alkane gas is methane or ethane;
3) the reaction temperature of the step 2) is 600-950 ℃.
The device and the using method of the invention introduce the molten salt in the molten salt layer as a reaction medium when the alkane gas is subjected to high-temperature chlorination dehydrogenation such as methane chlorination coupling and ethane chlorination dehydrogenation, and have at least one of the following beneficial effects:
(1) the molten salt layer is arranged on the low-melting-point metal molten layer in the device, the molten salt in the molten salt layer is a metal chloride molten mass which is liquid at the reaction temperature, and the molten salt has larger heat capacity than gas, so that heat generated by the reaction of chlorine and the low-melting-point metal can be effectively and continuously provided for the chlorination and dehydrogenation reaction of low-boiling-point metal chloride steam and alkane gas such as methane or ethane gas, the heat transfer performance of a reaction system is improved, the energy is saved, the controllability is realized, and the product selectivity is higher.
(2) The molten salt can dissolve the low-boiling-point metal chloride steam, the concentration of the low-boiling-point metal chloride steam can be increased, and the mass transfer performance of a reaction system is improved, so that the system can maintain sufficient low-boiling-point chloride to react with alkane gas, and the high-temperature chlorination and dehydrogenation processes of the alkane gas such as methane or ethane gas are more stable and higher in efficiency.
(3) The gas-phase chlorination and dehydrogenation crude product obtained by high-temperature chlorination and dehydrogenation is well separated by a gas-liquid separation layer.
Drawings
FIG. 1 shows a device for high-temperature chlorination and dehydrogenation of alkane gases.
Reference numerals:
1 device body with reaction cavity
11 low melting point metal melt layer
12 molten salt layer
13 gas-liquid separation layer
14 first air inlet
15 second air inlet
16 product gas outlet
Detailed Description
The technical solution of the present invention is illustrated by specific examples below. It is to be understood that one or more method steps mentioned in the present invention do not exclude the presence of other method steps before or after the combination step or that other method steps may be inserted between the explicitly mentioned steps; it should also be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Comparative example 1
(1) Adding Cl2Introducing a metal Sn molten layer, controlling the chlorination temperature to be 870 ℃ to lead Cl2Reaction with metallic Sn to obtain SnCl2Steam;
(2) will CH4Introducing gas above the Sn melt layer to make CH4Gas and SnCl2Steam contact, control of CH4With Cl introduced in step 1)2In a molar ratio of 10: 1, the reaction temperature is 850 ℃ to ensure that CH4With SnCl2Chlorination, dehydrogenation and coupling to obtain HCl and CH4、C2H6、C2H4、C2H2，SnCl2Reducing to liquid Sn, returning to the metal molten layer, continuing to react with Cl2And (4) reacting.
(3) Mixing HCl and C of the mixed gas obtained in the step (2)2H6、C2H4、C2H2After separation, CH is recovered4Circulating to the step (1) to continue SnCl2And (4) reacting. The main components of the tail gas after HCl removal of methane chlorination dehydrogenation coupling are shown in the table 1-1.
Table 1-1 comparative example 1 table (molar concentration) of gas phase components after HCl removal of methane chlorination-dehydrogenation coupling tail gas
Comparative example 2
(1) Adding Cl2Introducing a metal Bi molten layer, controlling the chlorination temperature to be 700 ℃ and leading Cl to be added2Reaction with metallic Bi to obtain SnCl3Steam;
(2) will CH4Gas is introduced above the metal Bi melt layer to make CH4Gas and BiCl3Steam contact, control of CH4With Cl introduced in step 1)2In a molar ratio of 10: 1, the reaction temperature is 700 ℃, so that CH is generated4With BiCl3Chlorination, dehydrogenation and coupling to obtain HCl and CH4、C2H6、C2H4、C2H2，BiCl3Reducing the Bi into liquid state to return to the metal molten layer, continuing to react with Cl2And (4) reacting.
(3) Mixing HCl and C of the mixed gas obtained in the step (2)2H6、C2H4、C2H2After separation, CH is recovered4Recycling to the step (1) for continuing and adding BiCl3And (4) reacting. The main components of the tail gas after HCl removal of methane chlorination dehydrogenation coupling are shown in the table 2-1.
Table 2-1 comparative example 2 gas phase composition table (molar concentration) of methane chlorination dehydrogenation coupling tail gas after HCl removal
Comparative example 3
(1) Adding Cl2Introducing a metal Bi molten layer, controlling the chlorination temperature to be 720 ℃ and leading Cl to be2Reacting with metal Bi to obtain BiCl3Steam;
(2) c is to be2H6Gas is introduced above the metal Bi melt layer to cause C2H6Gas and BiCl3Steam contact, control C2H6With Cl introduced in step 1)2In a molar ratio of 1: 1.1, reaction temperature 700 ℃ to C2H6With BiCl3Chlorination and dehydrogenation to obtain HCl and CH4、C2H6、C2H4、C2H2、C2H3Cl，BiCl3Reducing the Bi into liquid state to return to the metal molten layer, continuing to react with Cl2And (4) reacting.
(3) And (3) absorbing and separating HCl in the mixed gas obtained in the step (2), wherein the main components of the obtained ethane chlorination dehydrogenation tail gas are shown in a table 3-1.
Table 3-1 comparative example 3 gas phase composition table (molar concentration) of ethane chlorination dehydrogenation tail gas after HCl removal
Comparative example 4
(1) Adding Cl2Introducing a metal Bi molten layer, controlling the chlorination temperature to be 620 ℃ and leading Cl to be2Reacting with metal Bi to obtain BiCl3Steam;
(2) c is to be2H6Gas is introduced above the metal Bi melt layer to cause C2H6Gas and BiCl3Steam contact, control C2H6With Cl introduced in step 1)2In a molar ratio of 1: 1.1, reaction temperature 600 ℃ to C2H6With BiCl3Chlorination and dehydrogenation to obtain HCl and CH4、C2H6、C2H4、C2H2、C2H3Cl，BiCl3Reducing the Bi into liquid state to return to the metal molten layer, continuing to react with Cl2And (4) reacting.
(3) And (3) absorbing and separating HCl in the mixed gas obtained in the step (2), wherein the main components of the obtained ethane chlorination dehydrogenation tail gas are shown in a table 3-1.
Table 3-1 comparative example 3 gas phase composition table (molar concentration) of ethane chlorination dehydrogenation tail gas after HCl removal
The following embodiment uses the device for high-temperature chlorination and dehydrogenation of alkane gas as shown in fig. 1, which includes a device body 1 provided with a reaction cavity, a low-melting-point metal molten layer 11, a molten salt layer 12 and a gas-liquid separation layer 13 are arranged in the reaction cavity of the device body 1, the molten salt layer 12 is arranged on the low-melting-point metal molten layer 11, the gas-liquid separation layer 13 is arranged on the molten salt layer 12, a cooling pipe is arranged on the outer wall of the device body 1 corresponding to the gas-liquid separation layer 13, and a first gas inlet 14 is arranged on the wall of the device body 1 corresponding to the low-melting-point metal molten layer 11; a second air inlet 15 is arranged on the wall of the device body 1 corresponding to the molten salt layer 12, and a product air outlet 16 is arranged on the wall of the device body 1 corresponding to the gas-liquid separation layer 13.
Example 1
(1) Adding Cl2Introducing a Pb molten layer from a chlorine inlet of the low-melting-point metal molten layer at the bottom of the tower, controlling the temperature of the low-melting-point metal molten layer to 950 ℃ and enabling Cl to be in contact with the low-melting-point metal molten layer2Reacting with metallic Pb to obtain PbCl2Steam, PbCl2Steam enters a chloride molten salt layer consisting of CuCl-KCl (the molar ratio of CuCl to KCl is 1: 1);
(2) will CH4Gas is introduced from a molten salt layer alkane gas inlet to dissolve PbCl2Molten salt layer of steam CuCl-KCl, control of CH4With Cl introduced in step 1)2In a molar ratio of 5: 1, controlling the temperature of a molten salt layer to be 950 ℃ to ensure that CH4With PbCl2Chloridizing, dehydrogenating and coupling to obtain crude product gas, PbCl2Reducing to liquid Pb back to the molten metal layer, continuing to react with Cl2And (4) reacting.
(3) Controlling the temperature of a cooling pipe of the gas-liquid separation layer at the top of the tower to be 550 ℃, and enabling the crude product gas obtained in the step 2) to pass through the gas-liquid separation layer and then to be liquid PbCl2Returning to the molten salt layer, returning the liquid metal Pb to the metal molten layer, containing HCl and C2H6、C2H4、C2H2Is discharged from the gas-liquid separation layer gas-discharge port. The main components of the discharged gas phase components after HCl removal are shown in Table 1.
Table 1 example 1 table of gas phase composition (molar concentration) of HCl-removed methane chlorination-dehydrogenation coupling tail gas
Example 2
(1) Adding Cl2Introducing a metal Sn molten layer from a chlorine inlet of the low-melting-point metal molten layer at the bottom of the tower, controlling the temperature of the low-melting-point metal molten layer to be 870 ℃, and enabling Cl to be contained2Reaction with metallic Sn to obtain SnCl2Steam, SnCl2The steam enters into CuCl-CsCl-CaCl2(CuCl, CsCl and CaCl)2The molar ratio is 1: 0.1: 0.1) a molten chloride salt layer;
(2) will CH4Gas is introduced from a molten salt layer alkane gas inlet to dissolve SnCl2Vaporous CuCl-CsCl-CaCl2Molten salt layer of composition, control of CH4With Cl introduced in step 1)2In a molar ratio of 10: 1, controlling the temperature of a molten salt layer to be 850 ℃ to enable CH4With SnCl2The chlorination and dehydrogenation are coupled to obtain crude product gas, SnCl2Reducing to liquid Sn, returning to the metal molten layer, continuing to react with Cl2And (4) reacting.
(3) Controlling the temperature of a cooling pipe of the gas-liquid separation layer at the top of the tower to be 400 ℃, and enabling the crude product gas obtained in the step 2) to pass through the gas-liquid separation layer and then to be in liquid SnCl2Returning to the molten salt layer, returning the liquid metal Sn to the metal molten layer, containing HCl and C2H6、C2H4、C2H2Is discharged from the gas-liquid separation layer gas-discharge port. The major components of the discharged gas phase components after HCl removal are shown in Table 2.
Table 2 example 2 table of gas phase components (molar concentration) of HCl-removed methane chlorination-dehydrogenation coupling tail gas
Example 3
(1) Adding Cl2Introducing a metal Bi molten layer from a chlorine inlet of the low-melting-point metal molten layer at the bottom of the tower, controlling the temperature of the low-melting-point metal molten layer to be 700 ℃ and enabling Cl to be contained2Reacting with metal Bi to obtain BiCl3Steam, BiCl3Steam enters KCl-ZnCl2(KCl and ZnCl)2The molar ratio is 1: 0.5) a molten chloride salt layer;
(2) will CH4Gas is introduced from a molten salt layer alkane gas inlet to dissolve BiCl3KCl-ZnCl of steam2Molten salt layer of composition, control of CH4With Cl introduced in step 1)2In a molar ratio of 1:1, controlling the temperature of a molten salt layer to be 700 ℃ to enable CH4With BiCl3Chloridizing, dehydrogenating and coupling to obtain crude gas BiCl3Reducing the Bi into liquid state to return to the metal molten layer, continuing to react with Cl2And (4) reacting.
(3) Controlling the temperature of a cooling pipe of the gas-liquid separation layer at the top of the tower to be 350 ℃, and enabling the crude product gas obtained in the step 2) to pass through the gas-liquid separation layer and then to be in liquid BiCl state3Returning to the molten salt layer, returning the liquid metal Bi to the metal molten layer, containing HCl and C2H6、C2H4、C2H2Is discharged from the gas-liquid separation layer gas-discharge port. The major components of the discharged gas phase components after HCl removal are shown in Table 3.
Table 3 example 3 table of gas phase composition (molar concentration) of HCl removed methane chlorination dehydrogenation coupling tail gas
Example 4
(1) Adding Cl2Introducing a metal Bi molten layer from a chlorine inlet of the low-melting-point metal molten layer at the bottom of the tower, controlling the temperature of the low-melting-point metal molten layer to be 620 ℃, and enabling Cl to be contained2Reacting with metal Bi to obtain BiCl3Steam, BiCl3The steam enters a chloride molten salt layer consisting of CuCl-MgCl (the molar ratio of CuCl to MgCl is 1: 0.3);
(2) c is to be2H6Gas is introduced from a molten salt layer alkane gas inlet to dissolve BiCl3A molten salt layer consisting of steam CuCl-MgCl, controlling C2H6With Cl introduced in step 1)2In a molar ratio of 1:1, controlling the temperature of the molten salt layer to be 600 ℃ to ensure that C is2H6With BiCl3Chlorination and dehydrogenation to obtain crude product gas, BiCl3Reducing the Bi into liquid state to return to the metal molten layer, continuing to react with Cl2And (4) reacting.
(3) Controlling the temperature of a cooling pipe of the gas-liquid separation layer at the top of the tower to be 300 ℃, and enabling the crude product gas obtained in the step 2) to pass through the gas-liquid separation layer and then to be in liquid BiCl state3Returning to the molten salt layer, returning the liquid metal Bi to the metal molten layer, containing HCl and CH4、C2H6、C2H4、C2H2、C2H3The gas phase component of Cl is discharged from the gas-liquid separation layer discharge port. The major components of the discharged gas phase fraction after removal of HCl are shown in Table 4.
Table 4 example 4 table of gas phase composition (molar concentration) of ethane chlorination dehydrogenation tail gas after HCl removal
Example 5
(1) Adding Cl2Introducing a metal Bi molten layer from a chlorine inlet of the low-melting-point metal molten layer at the bottom of the tower, controlling the temperature of the low-melting-point metal molten layer to be 720 ℃ and enabling Cl to be contained2Reacting with metal Bi to obtain BiCl3Steam, BiCl3Steam enters a chloride molten salt layer consisting of CuCl;
(2) c is to be2H6Gas is introduced from a molten salt layer alkane gas inlet to dissolve BiCl3A molten salt layer of CuCl of steam, and C2H6With Cl introduced in step 1)2In a molar ratio of 1: 1.1, controlling the temperature of the molten salt layer to be 700 ℃ to ensure that C is2H6With BiCl3Chlorination and dehydrogenation to obtain crude product gas, BiCl3Reducing the Bi into liquid state to return to the metal molten layer, continuing to react with Cl2And (4) reacting.
(3) Controlling the temperature of a cooling pipe of the gas-liquid separation layer at the top of the tower to be 350 ℃, and enabling the crude product gas obtained in the step 2) to pass through the gas-liquid separation layer and then to be in liquid BiCl state3Returning to the molten salt layer, returning the liquid metal Bi to the metal molten layer, containing HCl and CH4、C2H6、C2H4、C2H2、C2H3The gas phase component of Cl is discharged from the gas-liquid separation layer discharge port. The major components of the discharged gas phase fraction after removal of HCl are shown in Table 5.
Table 5 example 5 table of gas phase composition (molar concentration) of ethane chlorination dehydrogenation tail gas after HCl removal
Example 6
(1) Adding Cl2Introducing a metal Bi molten layer from a chlorine inlet of the low-melting-point metal molten layer at the bottom of the tower, controlling the temperature of the low-melting-point metal molten layer to be 780 ℃ and enabling Cl to be contained2Reacting with metal Bi to obtain BiCl3Steam, BiCl3The steam enters a molten salt layer consisting of CuCl-LiCl (the molar ratio of CuCl to LiCl is 1: 0.2);
(2) c is to be2H6Gas is introduced from a molten salt layer alkane gas inlet to dissolve BiCl3A molten salt layer of steam CuCl-KCl, and control of C2H6With Cl introduced in step 1)2In a molar ratio of 1: 1.2, controlling the temperature of the molten salt layer to be 780 ℃ to ensure that C2H6With BiCl3Chlorination and dehydrogenation to obtain crude product gas, BiCl3Reducing the Bi into liquid state to return to the metal molten layer, continuing to react with Cl2And (4) reacting.
(3) Controlling the temperature of a cooling pipe of the gas-liquid separation layer at the top of the tower to be 300 ℃, and enabling the crude product gas obtained in the step 2) to pass through the gas-liquid separation layer and then to be in liquid BiCl state3Returning to the molten salt layer, returning the liquid metal Bi to the metal molten layer, containing HCl and CH4、C2H6、C2H4、C2H2、C2H3The gas phase component of Cl is discharged from the gas-liquid separation layer discharge port. The major components of the discharged gas phase fraction after removal of HCl are shown in Table 6.
Table 6 example 6 table of gas phase composition (molar concentration) of ethane chlorination dehydrogenation tail gas after HCl removal
Example 7
(1) Adding Cl2Introducing a metal Sn molten layer from a chlorine inlet of the low-melting-point metal molten layer at the bottom of the tower, controlling the temperature of the low-melting-point metal molten layer to be 870 ℃, and enabling Cl to be contained2Reacting with metal Bi to obtain BiCl3Steam, BiCl3Steam enters a molten salt layer consisting of CuCl-KCl (the molar ratio of CuCl to KCl is 1: 1);
(2) c is to be2H6Gas is introduced from a molten salt layer alkane gas inlet to dissolve SnCl2A molten salt layer of steam CuCl-KCl, and control of C2H6With Cl introduced in step 1)2In a molar ratio of 1: 1.1, controlling the temperature of the molten salt layer to be 850 ℃ to ensure that C is2H6With SnCl2Chlorination and dehydrogenation to obtain crude product gas, SnCl2Reducing to liquid Sn, returning to the metal molten layer, continuing to react with Cl2And (4) reacting.
(3) Controlling the temperature of a cooling pipe of the gas-liquid separation layer at the top of the tower to be 250 ℃, and enabling the crude product gas obtained in the step 2) to pass through the gas-liquid separation layer and then to be in liquid SnCl2Returning to the molten salt layer, returning the liquid metal Sn to the metal molten layer, containing HCl and CH4、C2H6、C2H4、C2H2、C2H3The gas phase component of Cl is discharged from the gas-liquid separation layer discharge port. The gas phase composition after discharge was freed from HCl and the main components are shown in Table 7.
Table 7 example 7 table of gas phase composition (molar concentration) of ethane chlorination dehydrogenation tail gas after HCl removal
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (7)
1. The use method of the high-temperature chlorination and dehydrogenation of the alkane gas is characterized by comprising a device body (1) provided with a reaction cavity, wherein a low-melting-point metal molten layer (11) and a molten salt layer (12) are arranged in the reaction cavity of the device body (1), and the molten salt layer (12) is arranged on the low-melting-point metal molten layer (11); a gas-liquid separation layer (13) is further arranged in the reaction cavity of the device body (1), the gas-liquid separation layer (13) is arranged on the molten salt layer (12), and a cooling pipe is arranged on the outer wall of the device body (1) corresponding to the gas-liquid separation layer (13); the cooling medium in the cooling pipe is selected from alkane gas;
the using method comprises the following steps:
1) adding Cl2Introducing the low-melting-point metal molten layer to make Cl2Reacting with low-boiling-point metal to obtain low-boiling-point metal chloride steam, wherein a molten salt layer is arranged on the low-boiling-point metal molten layer, and the low-boiling-point metal chloride steam enters the molten salt layer;
2) introducing alkane gas into a molten salt layer for dissolving low-boiling-point metal chloride steam, so that the alkane gas and the low-boiling-point metal chloride react to obtain a gas-phase chlorination and dehydrogenation crude product and low-melting-point metal, wherein the low-melting-point metal returns to the low-melting-point metal molten layer to continue to react with Cl2Reacting, wherein the molten salt in the molten salt layer is a metal chloride melt which is liquid at the reaction temperature of the step 2);
a gas-liquid separation layer (13) is arranged on the molten salt layer, the gas-phase chlorination and dehydrogenation crude product obtained in the step 2) is subjected to condensation separation, part or all of unreacted low-boiling-point metal chloride steam in the chlorination and dehydrogenation crude product is condensed into liquid low-boiling-point metal chloride and flows back to the molten salt layer, and the residual gas-phase chlorination and dehydrogenation crude product is discharged.
2. The use of claim 1, further comprising at least one of the following 1) to 3):
1) a first air inlet (14) is arranged on the wall of the device body (1) corresponding to the low-melting-point metal molten layer (11); a second air inlet (15) is formed in the wall of the device body (1) corresponding to the molten salt layer (12);
2) a plurality of porous plates are arranged in the low-melting-point metal molten layer (11);
3) a plurality of porous plates are arranged in the molten salt layer (12).
3. Use according to claim 1, wherein the gas-liquid separation layer (13) is provided with a product gas outlet (16) on the wall of the device body (1) corresponding thereto.
4. The use according to claim 1, wherein the temperature of the condensation separation is 250 to 600 ℃.
5. The use according to claim 1, wherein the low-melting metal is liquid at the reaction temperature of step 1), the low-boiling metal chloride is gaseous at the reaction temperature of step 1), and the low-boiling metal chloride is reacted with H at the reaction temperature of step 1)2Reducing metal simple substance and hydrogen chloride.
6. The use method of claim 1, wherein the step 1) further comprises at least one of the following steps 1) to 2):
1) the low melting point metal is selected from at least one of Sn, Bi and Pb;
2) the reaction temperature in the step 1) is 600-950 ℃.
7. The use method of claim 1, wherein the step 2) further comprises at least one of the following steps 1) to 3):
1) the molten salt is selected from one or more of alkali metal chloride, alkaline earth metal chloride and transition metal chloride;
2) the alkane gas is methane or ethane;
3) the reaction temperature of the step 2) is 600-950 ℃.
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