CN112919416B - Method for preparing hydrogen chloride by catalyzing pyrolysis of organic amine hydrochloride - Google Patents
Method for preparing hydrogen chloride by catalyzing pyrolysis of organic amine hydrochloride Download PDFInfo
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Abstract
The invention provides a method for preparing hydrogen chloride by catalyzing pyrolysis of organic amine hydrochloride, which comprises the following steps: mixing organic amine hydrochloride, a diluent and a solid acid catalyst, and placing the mixture into a reaction kettle, wherein a rectifying structure is connected above the reaction kettle; introducing nitrogen into the reaction kettle, regulating the reaction temperature to 150-190 ℃, carrying out pyrolysis reaction of organic amine hydrochloride in the reaction kettle, and carrying out rectification operation through the rectification structure; collecting hydrogen chloride gas generated by pyrolysis reaction and escaping through the rectification structure; after the reaction is finished, separating and recovering the solid acid catalyst, the diluent and the organic amine generated by the reaction. The method can recycle the organic amine extractant and generate hydrogen chloride gas with high added value, the pyrolysis rate of the organic amine hydrochloride can reach more than 95 percent, and the pyrolysis energy consumption is obviously reduced through the catalysis of the solid acid catalyst, so that a foundation is provided for industrial development.
Description
Technical Field
The invention belongs to the technical field of organic amine extractant regeneration, and particularly relates to a method for preparing hydrogen chloride by catalyzing pyrolysis of organic amine hydrochloride.
Background
As industrialized global climate warming becomes more and more severe, how to effectively control and utilize CO 2 Becomes a great challenge worldwide. Carbon capture, utilization and sequestration technologies (utilization and storage, CCUS) are believed to drastically reduce CO 2 The main route of discharge. CO 2 Mineralization is becoming more and more important as an important development direction of the CCUS technology, wherein CO is treated by a reaction-crystallization-coupling process using alkali chloride waste solutions of natural or industrial processes or the like 2 The method is converted into carbonate with high added value.
Mineralization processes generally utilize organic amines as extractants, wherein an organic tertiary amine (R 3 N) refers to an amine having in the molecule a trivalent radical linked to three hydrocarbon radicals, the extraction of which is the most widely used industrially in organic amine extractantsTaking one of the dosage. The organic tertiary amine is typically trialkylamine, and has a chemical formula N [ C ] corresponding to the foreign commodity Alamine 336, and a domestic commodity N235 or 7301 n H 2n+1 ] 3 (n=8 to 10). In the mineralization process, organic tertiary amine is used as an extractant to extract and separate metal ions in the chloride solution, so that organic amine hydrochloride is generated.
The industrial application of the mineralization process requires the effective regeneration of the organic amine serving as an extractant, and the organic amine and hydrogen chloride are generated through pyrolysis of the organic amine hydrochloride, so that the regeneration problem of the organic amine extractant can be solved, and chlorine element can be recovered in an ideal form of hydrogen chloride gas with higher added value to relieve the problem of chlorine resource shortage in China, thereby realizing the development goal of green chemistry of full utilization of atoms.
However, the pyrolysis process of the organic amine hydrochloride is a high-energy consumption process, the pyrolysis temperature is high, and the pyrolysis reaction time is long. The energy consumption of the pyrolysis process directly influences whether the process can realize industrial application. Therefore, the method for preparing the hydrogen chloride by pyrolyzing the organic amine hydrochloride reduces the pyrolysis temperature of the organic amine hydrochloride and shortens the pyrolysis reaction time, thereby achieving the purposes of recycling the organic amine and preparing the hydrogen chloride gas and reducing the energy consumption, and being beneficial to the industrialized popularization and application of the pyrolysis process of the organic amine hydrochloride.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for preparing hydrogen chloride by catalyzing pyrolysis of organic amine hydrochloride, which reduces the pyrolysis temperature of the organic amine hydrochloride by adding a proper catalyst and shortens the reaction time, thereby achieving the purposes of recycling the organic amine, preparing hydrogen chloride gas and reducing energy consumption.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method of catalyzing pyrolysis of organic amine hydrochloride to produce hydrogen chloride, the method comprising the steps of:
(1) Mixing organic amine hydrochloride, a diluent and a solid acid catalyst, and placing the mixture into a reaction kettle, wherein a rectifying structure is connected above the reaction kettle and is used for separating hydrogen chloride gas generated by pyrolysis reaction and the vaporized diluent which is condensed and reflowed to participate in the pyrolysis reaction;
(2) Introducing nitrogen into the reaction kettle, regulating the reaction temperature to 150-190 ℃, carrying out pyrolysis reaction of organic amine hydrochloride in the reaction kettle, and carrying out rectification operation through the rectification structure;
(3) Collecting hydrogen chloride gas generated by pyrolysis reaction and escaping through the rectification structure;
(4) After the reaction is finished, separating and recovering the solid acid catalyst, the diluent and the organic amine generated by the reaction.
The invention further provides that the pyrolysis reaction time of the organic amine hydrochloride is 2-8h.
The invention is further arranged that the flow rate of the nitrogen introduced into the reaction kettle is 200-600mL/min.
The invention is further arranged that the diluent is decalin or n-dodecane.
The invention is further arranged that the solid acid catalyst is 4A molecular sieve, 5A molecular sieve, 13X molecular sieve, 10X molecular sieve, Y molecular sieve, mordenite, ZSM-5, beta molecular sieve, phosphotungstic acid, phosphomolybdic acid and SO 4 2- /ZrO 2 And WO 3 /ZrO 2 One or more of the following.
The invention is further arranged that the mass ratio of the diluent to the organic amine hydrochloride is 2:1-5:1.
The invention is further arranged that the mass of the solid acid catalyst is 5-20% of the mass of the organic amine hydrochloride.
The invention further provides that the rectification adopts total reflux operation.
The invention further provides that the organic amine hydrochloride is obtained after the extraction and separation of the organic amine extractant in the mineralization process.
The invention is further provided that after the reaction is finished, the solid acid catalyst, the diluent and the organic amine generated by the reaction in the reaction kettle are separated in solid-liquid mode, wherein the solid phase is the solid acid catalyst, and the solid phase can be recycled after washing and drying; the liquid phase is a mixture of the organic amine and the diluent, and the organic amine and the diluent are separated through reduced pressure distillation, so that the regeneration of the organic amine and the recycling of the diluent are realized.
The invention has the beneficial effects that:
the invention provides a method for preparing hydrogen chloride by catalyzing organic amine hydrochloride pyrolysis through solid acid, which is characterized in that hydrogen chloride gas with high added value is generated while an organic amine extractant is recovered, and meanwhile, pyrolysis energy consumption is obviously reduced through the catalysis of a solid acid catalyst, so that a foundation is provided for industrial development. The pyrolysis rate of the organic amine hydrochloride can reach more than 95 percent by adopting the method disclosed by the invention, the pyrolysis temperature of the organic amine hydrochloride is obviously reduced, the reaction time is shortened, and a better technical effect is obtained.
Drawings
Fig. 1 is a schematic diagram of a reaction apparatus for pyrolysis of organic amine hydrochloride according to the present invention.
Detailed Description
The present invention is described in further detail below with reference to examples. It is to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, as will be apparent to those skilled in the art upon examination of the following, of various non-essential modifications and adaptations of the invention.
The invention provides a method for preparing hydrogen chloride by catalyzing pyrolysis of organic amine hydrochloride, which is found by a great amount of experimental researches and theoretical researches that the energy consumption can be effectively reduced by adding a solid acid catalyst into an organic amine hydrochloride pyrolysis reaction system. The solid acid catalyst has a strong acid site, and competes with HCl in organic amine hydrochloride, so that acting force of organic amine and HCl is reduced, pyrolysis temperature is reduced, reaction time is shortened, and reaction energy consumption is greatly reduced.
Fig. 1 is a schematic diagram of a reaction device for pyrolysis reaction of organic amine hydrochloride, the reaction device comprises a reaction kettle 1 for the pyrolysis reaction, a rectification structure 2 is installed above the reaction kettle 1, the rectification structure 2 comprises a rectification column 21 connected with the top end of the reaction kettle 1 and a condenser 22 connected with the top end of the rectification column 21, and the diluent is easy to volatilize at the reaction temperature and causes a great deal of loss because the diluent is required to be added in the pyrolysis reaction of the organic amine hydrochloride, so that the rectification structure 2 is used for condensing and refluxing the gasified diluent participating in the pyrolysis reaction, and separating HCl gas generated in the pyrolysis reaction; the top end of the condenser 22 is used for collecting HCl gas generated by pyrolysis reaction; the nitrogen gas inlet pipeline 3 is arranged above the reaction kettle 1 and is used for introducing nitrogen gas into the reaction kettle 1 so as to timely remove HCl gas generated by pyrolysis of the organic amine hydrochloride along with the nitrogen gas, thereby reducing the partial pressure of HCl and reducing the progress of reverse reaction.
Further, the condenser 22 is filled with cooling water from bottom to top for condensing the gasified diluent participating in the pyrolysis reaction; the condensed condensate flows down from the condenser 22, part of the condensate flows back to the reaction kettle 1 through the rectifying column 21 according to the reflux ratio controlled by rectification, and part of the condensate flows out from the condenser 22 and is collected. When the rectification is controlled to be the total reflux operation, all condensate flows back to the reaction kettle 1 through the rectification column 21.
Further, stirring required by the reaction is provided above the reaction kettle 1 through mechanical stirring 4 or other conventional technical means in the field; the reaction vessel 1 provides the heat required for the reaction by means conventional in the art.
The invention relates to a method for preparing hydrogen chloride by catalyzing organic amine hydrochloride pyrolysis, which comprises the following steps of:
(1) Mixing organic amine hydrochloride, a diluent and a solid acid catalyst, and putting the mixture into the reaction kettle 1;
(2) Introducing nitrogen into the reaction kettle 1, regulating the reaction temperature to 150-190 ℃, carrying out pyrolysis reaction of organic amine hydrochloride in the reaction kettle 1, and carrying out rectification operation through the rectification structure 2;
(3) Collecting HCl gas generated by pyrolysis reaction and escaping through the rectification structure 2;
(4) After the reaction is finished, separating and recovering the solid acid catalyst, the diluent and the organic amine generated by the reaction.
Further, the flow rate of the nitrogen introduced into the reaction kettle is 200-600mL/min; the pyrolysis reaction time is 2-8h.
Further, the diluent is decalin or n-dodecane.
Further, the solid acid catalyst is 4A molecular sieve, 5A molecular sieve, 13X molecular sieve, 10X molecular sieve, Y molecular sieve, mordenite, ZSM-5, beta molecular sieve, phosphotungstic acid, phosphomolybdic acid, SO 4 2- /ZrO 2 And WO 3 /ZrO 2 One or more of the following.
Preferably, the A-type molecular sieve has a silica-alumina ratio of 1.5-2.0, the X-type molecular sieve has a silica-alumina ratio of 2.1-3.0, the Y-type molecular sieve has a silica-alumina ratio of 3.1-6.0, the mordenite has a silica-alumina ratio of 9.0-1.0, the ZSM-type molecular sieve has a silica-alumina ratio of 10-500, and the beta-type molecular sieve has a silica-alumina ratio of 10-150.
Further, the mass ratio of the diluent to the organic amine hydrochloride is 2:1-5:1.
Further, the mass of the solid acid catalyst is 5% -20% of the mass of the organic amine hydrochloride.
Further, the rectification adopts total reflux operation.
Further, the organic amine hydrochloride is obtained after the extraction and separation of the organic amine extractant in the mineralization process.
Further, HCl gas generated by the pyrolysis reaction is collected by a sodium hydroxide solution, and the pyrolysis rate of the organic amine hydrochloride can be calculated by analyzing the chloride ion content in the solution.
Further, after the reaction is finished, solid acid catalyst, diluent and organic amine generated by the reaction in the reaction kettle are subjected to solid-liquid separation through filtration or other conventional solid-liquid separation technical means in the field, wherein the solid phase after the solid-liquid separation is the solid acid catalyst, and the solid phase can be recycled after washing and drying; the liquid phase is a mixture of the organic amine and the diluent, and the organic amine and the diluent are separated through reduced pressure distillation, so that the regeneration of the organic amine and the recycling of the diluent are realized.
The pyrolysis reaction of the organic amine hydrochloride is carried out by using the reaction device and the method, wherein experimental data of no solid acid catalyst is added in the pyrolysis reaction are shown in comparative examples 1-3, and experimental data of solid acid catalyst is shown in examples 1-23.
As shown in comparative examples 1-3, the pyrolysis reaction of the organic amine hydrochloride can reach a higher pyrolysis rate (more than 95 percent) under the conditions that the reaction temperature is 190 ℃ and the reaction time is 8 hours without adding a solid acid catalyst. However, the reaction temperature is higher, the reaction time is longer, the total energy consumption is higher, the industrialized application of the organic amine hydrochloride is not facilitated, and when the reaction temperature is reduced or the reaction time is shortened, the pyrolysis rate is obviously reduced, and the requirement of the pyrolysis rate of the organic amine hydrochloride cannot be met. As shown in examples 1-23, the addition of the solid acid catalyst to the pyrolysis reaction of the organic amine hydrochloride can significantly reduce the reaction temperature and/or shorten the reaction time compared with the comparative example, and the pyrolysis rate is still kept at a higher level (more than 95%), which significantly reduces the reaction energy consumption as a whole and is beneficial to the industrial application and popularization of the pyrolysis reaction.
Comparative example 1
Mixing 30g of organic amine hydrochloride and 150g of decalin, then placing the mixture into a reaction kettle, adjusting the reaction temperature to 190 ℃, introducing nitrogen into the kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 8 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 97%.
Comparative example 2
Mixing 30g of organic amine hydrochloride and 150g of decalin, then placing the mixture into a reaction kettle, regulating the reaction temperature to 170 ℃, introducing nitrogen into the kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 8 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 85%.
Comparative example 3
Mixing 30g of organic amine hydrochloride and 150g of decalin, then placing the mixture into a reaction kettle, adjusting the reaction temperature to 190 ℃, introducing nitrogen into the kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 4 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 90%.
Example 1
Mixing 30g of organic amine hydrochloride, 150g of decalin and 6g of 4A molecular sieve, then placing the mixture into a reaction kettle, regulating the reaction temperature to 150 ℃, introducing nitrogen into the reaction kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 8 hours, thereby carrying out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 95%.
Example 2
Mixing 30g of organic amine hydrochloride, 150g of decalin and 6g of 5A molecular sieve, then placing the mixture into a reaction kettle, adjusting the reaction temperature to 160 ℃, introducing nitrogen into the kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 7 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 95%.
Example 3
Mixing 30g of organic amine hydrochloride, 150g of decalin and 3g of 13X molecular sieve, then placing the mixture into a reaction kettle, regulating the reaction temperature to 170 ℃, introducing nitrogen into the reaction kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 6 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 97%.
Example 4
Mixing 30g of organic amine hydrochloride, 150g of decalin and 3g of 10X molecular sieve, then placing the mixture into a reaction kettle, regulating the reaction temperature to 180 ℃, introducing nitrogen into the reaction kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 3 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 97%.
Example 5
30g of organic amine hydrochloride, 150g of decalin and a 1.5gY type molecular sieve are mixed and then put into a reaction kettle, the reaction temperature is regulated to 190 ℃, the nitrogen gas is introduced into the kettle at the flow rate of 300mL/min, the stirring speed is 100-200rpm, and the reaction time is 2 hours, so that the pyrolysis reaction of the organic amine hydrochloride is carried out.
And collecting the generated gas by using sodium hydroxide solution, analyzing the content of chloride ions, and calculating the pyrolysis rate, wherein the pyrolysis rate is 98%.
Example 6
30g of organic amine hydrochloride, 150g of decalin and 6g of ZSM-5 are mixed and then put into a reaction kettle, the reaction temperature is regulated to 150 ℃, the nitrogen gas is introduced into the kettle at the flow rate of 300mL/min, the stirring speed is 100-200rpm, and the reaction time is 8 hours, so that the pyrolysis reaction of the organic amine hydrochloride is carried out.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 96%.
Example 7
Mixing 30g of organic amine hydrochloride, 150g of decalin and 5g of mordenite, then placing the mixture into a reaction kettle, regulating the reaction temperature to 160 ℃, introducing nitrogen into the reaction kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 8 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 95%.
Example 8
Mixing 30g of organic amine hydrochloride, 150g of decalin and 5g of beta molecular sieve, then placing the mixture into a reaction kettle, regulating the reaction temperature to 170 ℃, introducing nitrogen into the reaction kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 6 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
And collecting the generated gas by using sodium hydroxide solution, analyzing the content of chloride ions, and calculating the pyrolysis rate, wherein the pyrolysis rate is 98%.
Example 9
Mixing 30g of organic amine hydrochloride, 150g of decalin and 1.5g of phosphotungstic acid, then placing the mixture into a reaction kettle, adjusting the reaction temperature to 180 ℃, introducing nitrogen into the kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 4 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 95%.
Example 10
Mixing 30g of organic amine hydrochloride, 150g of decalin and 3g of phosphomolybdic acid, then placing the mixture into a reaction kettle, adjusting the reaction temperature to 190 ℃, introducing nitrogen into the kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 2 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
And collecting the generated gas by using sodium hydroxide solution, analyzing the content of chloride ions, and calculating the pyrolysis rate, wherein the pyrolysis rate is 98%.
Example 11
30g of organic amine hydrochloride, 150g of decalin and 1.5g of SO 4 2- /ZrO 2 Mixing, placing the mixture into a reaction kettle, regulating the reaction temperature to 160 ℃, introducing nitrogen into the reaction kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 6 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 95%.
Example 12
30g of organic amine hydrochloride, 150g of decalin and 6gWO 3 /ZrO 2 Mixing, placing the mixture into a reaction kettle, regulating the reaction temperature to 170 ℃, introducing nitrogen into the reaction kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 2 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 95%.
Example 13
Mixing 30g of organic amine hydrochloride, 150g of decalin, 1g of 4A molecular sieve and 0.5g of phosphotungstic acid, then placing the mixture into a reaction kettle, adjusting the reaction temperature to 150 ℃, introducing nitrogen into the kettle at the flow rate of 300mL/min, stirring at the rotation speed of 100-200rpm, and reacting for 8 hours, thereby carrying out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 96%.
Example 14
Mixing 30g of organic amine hydrochloride, 150g of decalin, 0.5g of mordenite and 1g of phosphotungstic acid, then placing the mixture into a reaction kettle, adjusting the reaction temperature to 160 ℃, introducing nitrogen into the kettle at the flow rate of 300mL/min, stirring at the rotation speed of 100-200rpm for 6 hours, and carrying out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 95%.
Example 15
30g of organic amine hydrochloride, 150g of decalin, 2g of ZSM-5 and 1g of phosphomolybdic acid are mixed and then put into a reaction kettle, the reaction temperature is regulated to 170 ℃, the nitrogen gas is introduced into the kettle at the flow rate of 300mL/min, the stirring speed is 100-200rpm, and the reaction time is 2 hours, so that the pyrolysis reaction of the organic amine hydrochloride is carried out.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 97%.
Example 16
Mixing 30g of organic amine hydrochloride, 150g of decalin, 1g of 13X molecular sieve and 0.5g of phosphomolybdic acid, then placing the mixture into a reaction kettle, adjusting the reaction temperature to 180 ℃, introducing nitrogen into the kettle at the flow rate of 300mL/min, stirring at the rotation speed of 100-200rpm, and reacting for 2 hours, thereby carrying out pyrolysis reaction of the organic amine hydrochloride.
And collecting the generated gas by using sodium hydroxide solution, analyzing the content of chloride ions, and calculating the pyrolysis rate, wherein the pyrolysis rate is 99%.
Example 17
30g of organic amine hydrochloride, 150g of decalin, 2g of 10X molecular sieve and 1g of ZSM-5 are mixed and then put into a reaction kettle, the reaction temperature is regulated to 150 ℃, the nitrogen gas inlet flow is 300mL/min, the stirring speed is 100-200rpm, the reaction time is 6 hours, and the pyrolysis reaction of the organic amine hydrochloride is carried out.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 95%.
Example 18
30g of organic amine hydrochloride, 150g of decalin, 2g of ZSM-5 and 1g of SO 4 2- /ZrO 2 Mixing, placing the mixture into a reaction kettle, regulating the reaction temperature to 160 ℃, introducing nitrogen into the reaction kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 6 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 97%.
Example 19
30g of organic amine hydrochloride, 150g of decalin, 4g of phosphotungstic acid and 2g of SO 4 2- /ZrO 2 Mixing, placing the mixture into a reaction kettle, regulating the reaction temperature to 170 ℃, introducing nitrogen into the reaction kettle at a flow rate of 300mL/min, stirring at a rotation speed of 100-200rpm, and reacting for 2 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
And collecting the generated gas by using sodium hydroxide solution, analyzing the content of chloride ions, and calculating the pyrolysis rate, wherein the pyrolysis rate is 99%.
Example 20
30g of organic amine hydrochloride, 150g of decalin, 4g of ZSM-5 and 2gWO 3 /ZrO 2 Mixing, placing the mixture into a reaction kettle, regulating the reaction temperature to 180 ℃, introducing nitrogen into the reaction kettle at the flow rate of 300mL/min, stirring at the rotation speed of 100-200rpm, and reacting for 2 hours to carry out pyrolysis reaction of the organic amine hydrochloride.
And collecting the generated gas by using sodium hydroxide solution, analyzing the content of chloride ions, and calculating the pyrolysis rate, wherein the pyrolysis rate is 99%.
Example 21
30g of organic amine hydrochloride, 90g of decalin, 2g of ZSM-5 and 1g of phosphomolybdic acid are mixed and then put into a reaction kettle, the reaction temperature is regulated to 170 ℃, the nitrogen gas is introduced into the kettle at the flow rate of 200mL/min, the stirring speed is 100-200rpm, and the reaction time is 2 hours, so that the pyrolysis reaction of the organic amine hydrochloride is carried out.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 95%.
Example 22
30g of organic amine hydrochloride, 60g of decalin, 2g of ZSM-5 and 1g of phosphomolybdic acid are mixed and then put into a reaction kettle, the reaction temperature is regulated to 170 ℃, the nitrogen gas is introduced into the kettle at the flow rate of 600mL/min, the stirring speed is 100-200rpm, and the reaction time is 4 hours, so that the pyrolysis reaction of the organic amine hydrochloride is carried out.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 96%.
Example 23
30g of organic amine hydrochloride, 150g of n-dodecane, 2g of ZSM-5 and 1g of phosphomolybdic acid are mixed and then put into a reaction kettle, the reaction temperature is regulated to 170 ℃, the nitrogen gas is introduced into the kettle at the flow rate of 300mL/min, the stirring speed is 100-200rpm, and the reaction time is 2 hours, so that the pyrolysis reaction of the organic amine hydrochloride is carried out.
The generated gas was collected with sodium hydroxide solution, and the content of chloride ions was analyzed to calculate the pyrolysis rate, which was 96%.
The respective reaction condition parameters and the pyrolysis rate data of the above comparative examples 1 to 3 and examples 1 to 23 are shown in the following table.
Claims (9)
1. A method for preparing hydrogen chloride by catalyzing pyrolysis of organic amine hydrochloride, comprising the steps of:
(1) Mixing organic amine hydrochloride, a diluent and a solid acid catalyst, and placing the mixture into a reaction kettle, wherein a rectifying structure is connected above the reaction kettle and is used for separating hydrogen chloride gas generated by pyrolysis reaction and the vaporized diluent which is condensed and reflowed to participate in the pyrolysis reaction;
(2) Introducing nitrogen into the reaction kettle, regulating the reaction temperature to 150-190 ℃, carrying out pyrolysis reaction of organic amine hydrochloride in the reaction kettle, and carrying out rectification operation through the rectification structure;
(3) Collecting hydrogen chloride gas generated by pyrolysis reaction and escaping through the rectification structure;
(4) After the reaction is finished, separating and recycling the solid acid catalyst, the diluent and the organic amine generated by the reaction;
the solid acid catalyst is 4A molecular sieve, 5A molecular sieve, 13X molecular sieve, 10X molecular sieve, Y molecular sieve, mordenite, ZSM-5, beta molecular sieve, phosphotungstic acid, phosphomolybdic acid, SO 4 2- /ZrO 2 And WO 3 /ZrO 2 One or more of the following.
2. The method of claim 1, wherein the organic amine hydrochloride pyrolysis reaction time is 2 to 8 hours.
3. The method according to claim 1, wherein the nitrogen flow rate into the reaction kettle is 200-600mL/min.
4. The method of claim 1, wherein the diluent is decalin or n-dodecane.
5. The method of claim 1, wherein the mass ratio of diluent to organic amine hydrochloride is from 2:1 to 5:1.
6. The method according to claim 1, wherein the mass of the solid acid catalyst is 5% -20% of the mass of the organic amine hydrochloride.
7. The method of claim 1, wherein the rectifying is performed using total reflux.
8. The method according to claim 1, wherein the organic amine hydrochloride is obtained after extraction and separation of an organic amine extractant in a mineralization process.
9. The method of claim 1, wherein after the reaction is finished, solid acid catalyst, diluent and organic amine generated by the reaction in the reaction kettle are separated in solid-liquid mode, wherein the solid phase is the solid acid catalyst, and the solid acid catalyst is recycled after washing and drying; the liquid phase is a mixture of the organic amine and the diluent, and the organic amine and the diluent are separated through reduced pressure distillation, so that the regeneration of the organic amine and the recycling of the diluent are realized.
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| WO2010026572A1 (en) * | 2008-09-02 | 2010-03-11 | Hcl Cleantech Ltd. | A process for the production of hcl gas from chloride salts and for the production of carbohydrates |
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