A copper-iron two-component composite catalyst for preparing electronic-grade hydrogen chloride gas and its application

Abstract

The present invention belongs to the field of high-purity gas preparation and catalysis technology, and discloses a copper-iron two-component composite catalyst for removing trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to produce electronic-grade hydrogen chloride gas. The preparation method of the copper-iron two-component composite catalyst comprises the following steps: immersing activated carbon in hydrochloric acid, washing it with deionized water until the pH is neutral, and drying it to obtain a pretreated activated carbon carrier; impregnating active components onto the pretreated activated carbon carrier, performing ultrasonic-assisted impregnation, standing it for drying, and obtaining the product; the active components are Fe metal salt and Cu metal salt. The present invention catalyzes the simultaneous reaction of trace acetylene and ethylene in petrochemical by-product hydrogen chloride gas with hydrogen chloride gas, thereby achieving the simultaneous removal of acetylene and ethylene, thereby simplifying the steps of removing acetylene and ethylene in the existing hydrogen chloride purification process. Compared with traditional methods, the present invention significantly improves the reaction efficiency of preparing electronic-grade hydrogen chloride gas.

Description

Technical Field

[0001] The invention belongs to the technical field of high-purity gas preparation and catalysis, and in particular to a copper-iron two-component composite catalyst for removing trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to prepare electronic-grade hydrogen chloride gas. Background Art

[0002] Electronic-grade hydrogen chloride gas is ultra-high-purity hydrogen chloride gas, mainly used in the manufacturing processes of high-tech fields such as semiconductors, optoelectronics and solar cells. With the rapid development of the country's semiconductor industry and optoelectronics industry, the quantity and quality requirements for electronic-grade hydrogen chloride gas are becoming increasingly higher. The current domestic market is highly dependent on imports. Against the backdrop of independent chip manufacturing, domestic substitution is a major trend in the future.

[0003] Currently, the main methods for preparing electronic-grade hydrogen chloride include analytical methods, hydrochloric acid stripping methods, industrial by-product acid stripping methods, synthetic methods, and petrochemical by-product hydrogen chloride purification methods. Among them, the hydrogen chloride gas produced by analytical methods, hydrochloric acid stripping methods, industrial by-product acid stripping methods, and synthetic methods has low purity and has gradually failed to meet the needs of the electronics industry, especially integrated circuit production. In contrast, the petrochemical by-product hydrogen chloride purification method has become the mainstream technology in current industrial production due to its simple operation, low production cost, and high product purity. However, the removal of acetylene and ethylene remains a technical problem that needs to be solved in this method.

[0004] Chinese patent (CN1511780A) discloses a method for removing trace acetylene and ethylene impurities from petrochemical by-product hydrogen chloride gas to produce electronic-grade hydrogen chloride. This method involves reacting acetylene with hydrogen chloride over a HgCl2-BaCl2 / activated carbon composite catalyst to produce easily removable halogenated hydrocarbons. Simultaneously, ethylene reacts over a CuCl2-KCl-SrCl2 / activated carbon composite catalyst to produce similarly easily removable halogenated hydrocarbons. The synergistic effect of these two composite catalysts effectively removes acetylene and ethylene, thereby improving the purity of electronic-grade hydrogen chloride.

[0005] While existing technologies can effectively remove ethylene and acetylene impurities, they require different catalysts for the catalytic reactions, resulting in low catalytic efficiency. Existing processes remove acetylene and ethylene impurities in separate steps, which complicates the process and increases production costs. Current process catalysts use mercury-containing catalysts, which pose significant environmental and health risks. In light of this, the present invention provides a novel bifunctional catalyst and preparation method. This catalyst is highly efficient, environmentally friendly, safe, and low-cost, capable of simultaneously and effectively removing trace acetylene and ethylene impurities from hydrogen chloride gas, a byproduct of petrochemical production. This significantly simplifies the process steps and improves reaction efficiency. This catalyst design overcomes the limitations of existing technologies that remove impurities separately and avoids the environmental and health risks associated with the use of toxic mercury catalysts. Summary of the Invention

[0006] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a copper-iron two-component composite catalyst for removing trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to prepare electronic grade hydrogen chloride gas.

[0007] The technical solution adopted by the present invention to solve its technical problem is:

[0008] A copper-iron two-component composite catalyst for removing trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to produce electronic-grade hydrogen chloride gas. The preparation method of the copper-iron two-component composite catalyst comprises the following steps:

[0009] (1) immersing the activated carbon in hydrochloric acid, washing it with deionized water until the pH is neutral, and drying it to obtain the pretreated activated carbon support;

[0010] (2) impregnating the active component onto the activated carbon support obtained by pretreatment, using ultrasound-assisted impregnation, allowing it to stand and then drying;

[0011] Wherein, the active components are Fe metal salt and Cu metal salt.

[0012] Furthermore, in step (1), the activated carbon is immersed in the hydrochloric acid solution for 6-12 hours;

[0013] Alternatively, the activated carbon is coconut shell activated carbon.

[0014] Furthermore, the Cu metal salt is a chloride, sulfate or nitrate of Cu, and the Fe metal salt is a chloride, sulfate or nitrate of Fe;

[0015] Alternatively, the impregnation in step (2) is carried out by an equal volume impregnation method, and the impregnation is carried out in a step-by-step impregnation manner, first impregnating the Fe metal salt into the pretreated activated carbon support, and then impregnating the Cu metal salt into the activated carbon support after drying.

[0016] Furthermore, the weight of the Cu metal is 1-15% of the total weight of the catalyst, and the weight of the Fe metal is 1-15% of the total weight of the catalyst;

[0017] Alternatively, the drying temperature in step (2) is 80-120° C. and the drying time is 6-12 h;

[0018] Alternatively, the ultrasonic-assisted immersion time in step (2) is 1-2 hours, and the ultrasonic frequency is one of 20-40 kHz, 40-60 kHz, 60-80 kHz, and 80-100 kHz.

[0019] Furthermore, the specific steps are as follows:

[0020] (1) Weigh activated carbon, immerse it in a 1 mol / L hydrochloric acid solution for 6 h, filter it, wash it with deionized water until the pH is neutral, and dry it at 120°C for 12 h to obtain the pretreated catalyst support;

[0021] (2) Weigh ferric chloride and dissolve it in deionized water. The ratio of ferric chloride to deionized water is 24.377:45 g:mL. Add the Fe salt solution dropwise to the pretreated catalyst support. Ultrasonic immersion is performed at 50 kHz for 2 h. The catalyst support is sealed and placed in an oven at 80°C for 6 h. The catalyst support is then dried in an oven at 120°C for 6 h.

[0022] (3) Weigh copper chloride and dissolve it in deionized water. The ratio of iron chloride to deionized water is 13.550:45 g:mL. The copper salt solution is added dropwise to the activated carbon treated in step (2). Ultrasonic immersion is performed at 50 kHz for 2 hours. The mixture is sealed and placed in an oven at 80°C for 6 hours. Finally, the mixture is dried in an oven at 120°C for 6 hours to obtain a copper-iron two-component composite catalyst.

[0023] The mass ratio of activated carbon: 1 mol / L hydrochloric acid solution: ferric chloride: cupric chloride is 50:200:24.377:13.550 in terms of g:mL:g:g.

[0024] The copper-iron two-component composite catalyst is used to remove trace acetylene and ethylene impurities from the petrochemical by-product hydrogen chloride gas to prepare electronic grade hydrogen chloride gas.

[0025] A method for producing electronic-grade hydrogen chloride gas by removing trace amounts of acetylene and ethylene from petrochemical by-product hydrogen chloride gas using the copper-iron two-component composite catalyst described above comprises the following steps: loading the copper-iron two-component composite catalyst into a fixed-bed reactor, introducing hydrogen chloride gas and a 5000 ppm acetylene-ethylene mixed gas into the reactor, and maintaining the reaction temperature at 140-180° C. to remove trace amounts of acetylene and ethylene from the reaction system.

[0026] Further, the following steps are included:

[0027] A copper-iron two-component composite catalyst was placed in a stainless steel fixed-bed reactor, and the raw gas of hydrogen chloride and a mixed gas of acetylene and ethylene was introduced to evaluate the performance of the catalyst. The specific steps include the following:

[0028] (1) The copper-iron two-component composite catalyst was loaded into the reaction tube of a stainless steel fixed-bed reactor, the temperature of the fixed-bed reactor was set to 120° C., and nitrogen was introduced into pipeline No. 2 to dry the catalyst;

[0029] (2) Turn off the nitrogen, raise the temperature of the fixed bed reactor to the reaction temperature of 140-180°C, and introduce hydrogen chloride gas into pipeline No. 1 to activate the catalyst;

[0030] (3) A mixed gas of acetylene and ethylene is introduced through pipeline No. 3. The two gases enter the reaction tube and start the reaction. The reaction tail gas flows through the alkali solution absorption bottle, and the treatment is completed;

[0031] Among them, the stainless steel fixed bed reactor can be a device in the field of acetylene hydrochlorination. Specifically, the stainless steel fixed bed reactor includes a reactor body, a reaction tube, an alkali solution absorption bottle, pipeline No. 1, pipeline No. 2 and pipeline No. 3. The reactor body and the reaction tube are arranged in a vertical direction. The reaction tube is coaxially connected in the reactor body. The top of the reaction tube is set as the reaction tube inlet, and the bottom of the reaction tube is set as the reaction tube outlet. The input end of pipeline No. 1 can input hydrogen chloride gas, the input end of pipeline No. 2 can input nitrogen, and the input end of pipeline No. 3 can input acetylene and ethylene mixed gas. The output ends of pipeline No. 1, pipeline No. 2 and pipeline No. 3 are all tightly connected to the reaction tube inlet of the reaction tube, and the reaction tube outlet of the reaction tube is connected to the alkali solution absorption bottle. The alkali solution absorption bottle can absorb the hydrogen chloride gas in the tail gas.

[0032] Furthermore, the No. 1 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4a, the dryer 5a, the mass flow meter 6a and the one-way check valve 7a in sequence;

[0033] The No. 2 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4a, the dryer 5b, the mass flowmeter 6a and the one-way check valve 7a in sequence, or the No. 2 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4a, the dryer 5b, the mass flowmeter 6b and the one-way check valve 7b in sequence;

[0034] The No. 3 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4c, the dryer 5c, the mass flow meter 6b and the one-way check valve 7b in sequence.

[0035] Alternatively, the purity of the nitrogen gas is above 99%, the purity of the hydrogen chloride gas is above 99%, and the concentrations of the acetylene and ethylene mixed gases are both 50-5000 ppm;

[0036] Alternatively, when the loading amount of the Fe-Cu two-component composite catalyst is 4 mL, the activation time of hydrogen chloride gas is 30 min, the flow rate of hydrogen chloride gas is set to 12 mL / min, and the flow rate of acetylene and ethylene mixed gas is set to 12 mL / min; the introduction time of nitrogen is 30 min, the flow rate is set to 12 mL / min, and the raw gas space velocity W=180 h -1 ;

[0037] Alternatively, the stainless steel fixed bed reactor further comprises a thermocouple, which is connected to the reaction tube, and the temperature in the reaction tube is controlled by the thermocouple.

[0038] Furthermore, in the method, the acetylene conversion rate is not less than 97%, and reaches a maximum of 99.682%; the ethylene conversion rate is not less than 95%, and reaches a maximum of 98.670%.

[0039] The advantages and positive effects achieved by the present invention are:

[0040] 1. The present invention catalyzes the simultaneous reaction of trace acetylene and ethylene in petrochemical by-product hydrogen chloride gas with hydrogen chloride gas, achieving the simultaneous removal of both acetylene and ethylene. This simplifies the acetylene and ethylene removal steps in existing hydrogen chloride purification processes. Compared to conventional methods, the present invention significantly improves the efficiency of producing electronic-grade hydrogen chloride gas (this improved efficiency refers to the effect achieved by existing processes using two catalysts, while the present invention achieves this using only one catalyst).

[0041] 2. This invention utilizes an Fe-Cu catalyst to simultaneously remove ethylene and acetylene gases without introducing additional impurities, effectively purifying hydrogen chloride gas. Specifically, in the presence of the Fe-Cu catalyst, acetylene and ethylene in the feed react with hydrogen chloride to produce halogenated hydrocarbons that are easily removed from the hydrogen chloride gas. Compared to traditional mercury-containing catalysts for removing acetylene and ethylene, the Fe-Cu bimetallic mercury-free catalyst offers superior economic and environmental benefits. Its simple and efficient preparation method makes it suitable for large-scale industrial applications.

[0042] 3. The catalyst produced by the present invention is used in the hydrochlorination of trace acetylene and ethylene, effectively removing these impurities from petrochemical by-product hydrogen chloride gas, thereby producing electronic-grade hydrogen chloride gas. Compared to existing hydrochlorination catalysts, the mercury-free catalyst of the present invention can simultaneously remove both acetylene and ethylene impurities, has a simple preparation process, and offers significant economic and environmental benefits.

[0043] 4. The catalyst of the present invention is highly efficient, green, safe, and low-cost. It can simultaneously and efficiently remove trace acetylene and ethylene impurities from hydrogen chloride gas, a by-product of petrochemical industry, greatly simplifying the process steps and improving reaction efficiency. This catalyst design overcomes the limitations of the existing technology of removing impurities separately and avoids the environmental and health risks brought about by the use of toxic mercury catalysts. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 Schematic diagram of the structure and connection of the stainless steel fixed bed reactor used in the catalyst evaluation of the present invention and a schematic diagram of the process flow;

[0045] Figure 2 This is a graph showing the conversion rates of acetylene and ethylene when the copper-iron two-component composite catalyst of the present invention is used to remove trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to produce electronic-grade hydrogen chloride gas; wherein a is the conversion rate of acetylene in Example 1; b is the conversion rate of ethylene in Example 1. DETAILED DESCRIPTION

[0046] The present invention will be further described below with reference to the embodiments. The following embodiments are descriptive rather than restrictive, and the scope of protection of the present invention cannot be limited by the following embodiments.

[0047] The various experimental operations involved in the specific embodiments are all routine techniques in the field. For parts not specifically annotated in this document, ordinary technicians in this field can refer to various commonly used reference books, scientific literature or related instructions, manuals, etc. before the filing date of this invention to implement them.

[0048] A copper-iron two-component composite catalyst for removing trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to produce electronic-grade hydrogen chloride gas. The preparation method of the copper-iron two-component composite catalyst comprises the following steps:

[0049] (1) immersing the activated carbon in hydrochloric acid, washing it with deionized water until the pH is neutral, and drying it to obtain the pretreated activated carbon support;

[0050] (2) impregnating the active component onto the activated carbon support obtained by pretreatment, using ultrasound-assisted impregnation, allowing it to stand and then drying;

[0051] Wherein, the active components are Fe metal salt and Cu metal salt.

[0052] Preferably, in step (1), the activated carbon is immersed in the hydrochloric acid solution for 6-12 hours;

[0053] Alternatively, the activated carbon is coconut shell activated carbon.

[0054] Preferably, the Cu metal salt is a chloride, sulfate or nitrate of Cu, and the Fe metal salt is a chloride, sulfate or nitrate of Fe;

[0055] Alternatively, the impregnation in step (2) is carried out by an equal volume impregnation method, and the impregnation is carried out in a step-by-step impregnation manner, first impregnating the Fe metal salt into the pretreated activated carbon support, and then impregnating the Cu metal salt into the activated carbon support after drying.

[0056] Preferably, the weight of the Cu metal is 1-15% of the total weight of the catalyst, and the weight of the Fe metal is 1-15% of the total weight of the catalyst;

[0057] Alternatively, the drying temperature in step (2) is 80-120° C. and the drying time is 6-12 h;

[0058] Alternatively, the ultrasonic-assisted immersion time in step (2) is 1-2 hours, and the ultrasonic frequency is one of 20-40 kHz, 40-60 kHz, 60-80 kHz, and 80-100 kHz.

[0059] Preferably, the specific steps are as follows:

[0060] (1) Weigh activated carbon, immerse it in a 1 mol / L hydrochloric acid solution for 6 h, filter it, wash it with deionized water until the pH is neutral, and dry it at 120°C for 12 h to obtain the pretreated catalyst support;

[0061] (2) Weigh ferric chloride and dissolve it in deionized water. The ratio of ferric chloride to deionized water is 24.377:45 g:mL. Add the Fe salt solution dropwise to the pretreated catalyst support. Ultrasonic immersion is performed at 50 kHz for 2 h. The catalyst support is sealed and placed in an oven at 80°C for 6 h. The catalyst support is then dried in an oven at 120°C for 6 h.

[0062] (3) Weigh copper chloride and dissolve it in deionized water. The ratio of iron chloride to deionized water is 13.550:45 g:mL. The copper salt solution is added dropwise to the activated carbon treated in step (2). Ultrasonic immersion is performed at 50 kHz for 2 hours. The mixture is sealed and placed in an oven at 80°C for 6 hours. Finally, the mixture is dried in an oven at 120°C for 6 hours to obtain a copper-iron two-component composite catalyst.

[0063] The mass ratio of activated carbon: 1 mol / L hydrochloric acid solution: ferric chloride: cupric chloride is 50:200:24.377:13.550 in terms of g:mL:g:g.

[0064] The copper-iron two-component composite catalyst is used to remove trace acetylene and ethylene impurities from the petrochemical by-product hydrogen chloride gas to prepare electronic grade hydrogen chloride gas.

[0065] A method for producing electronic-grade hydrogen chloride gas by removing trace amounts of acetylene and ethylene from petrochemical by-product hydrogen chloride gas using the copper-iron two-component composite catalyst described above comprises the following steps: loading the copper-iron two-component composite catalyst into a fixed-bed reactor, introducing hydrogen chloride gas and a 5000 ppm acetylene-ethylene mixed gas into the reactor, and maintaining the reaction temperature at 140-180° C. to remove trace amounts of acetylene and ethylene from the reaction system.

[0066] Preferably, the method comprises the following steps:

[0067] A copper-iron two-component composite catalyst was placed in a stainless steel fixed-bed reactor, and the raw gas of hydrogen chloride and a mixed gas of acetylene and ethylene was introduced to evaluate the performance of the catalyst. The specific steps include the following:

[0068] (1) The copper-iron two-component composite catalyst was loaded into the reaction tube of a stainless steel fixed-bed reactor, the temperature of the fixed-bed reactor was set to 120° C., and nitrogen was introduced into pipeline No. 2 to dry the catalyst;

[0069] (2) Turn off the nitrogen, raise the temperature of the fixed bed reactor to the reaction temperature of 140-180°C, and introduce hydrogen chloride gas into pipeline No. 1 to activate the catalyst;

[0070] (3) A mixed gas of acetylene and ethylene is introduced through pipeline No. 3. The two gases enter the reaction tube and start the reaction. The reaction tail gas flows through the alkali solution absorption bottle, and the treatment is completed;

[0071] Among them, the stainless steel fixed bed reactor can be a device in the field of acetylene hydrochlorination. Specifically, the stainless steel fixed bed reactor includes a reactor body, a reaction tube, an alkali solution absorption bottle, pipeline No. 1, pipeline No. 2 and pipeline No. 3. The reactor body and the reaction tube are arranged in a vertical direction. The reaction tube is coaxially connected in the reactor body. The top of the reaction tube is set as the reaction tube inlet, and the bottom of the reaction tube is set as the reaction tube outlet. The input end of pipeline No. 1 can input hydrogen chloride gas, the input end of pipeline No. 2 can input nitrogen, and the input end of pipeline No. 3 can input acetylene and ethylene mixed gas. The output ends of pipeline No. 1, pipeline No. 2 and pipeline No. 3 are all tightly connected to the reaction tube inlet of the reaction tube, and the reaction tube outlet of the reaction tube is connected to the alkali solution absorption bottle. The alkali solution absorption bottle can absorb the hydrogen chloride gas in the tail gas.

[0072] Preferably, the No. 1 pipeline is connected to the reaction tube inlet of the reaction tube through a valve 4a, a dryer 5a, a mass flow meter 6a and a one-way check valve 7a in sequence;

[0073] The No. 2 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4a, the dryer 5b, the mass flowmeter 6a and the one-way check valve 7a in sequence, or the No. 2 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4a, the dryer 5b, the mass flowmeter 6b and the one-way check valve 7b in sequence;

[0074] The No. 3 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4c, the dryer 5c, the mass flow meter 6b and the one-way check valve 7b in sequence.

[0075] Alternatively, the purity of the nitrogen gas is above 99%, the purity of the hydrogen chloride gas is above 99%, and the concentrations of the acetylene and ethylene mixed gases are both 50-5000 ppm;

[0076] Alternatively, when the loading amount of the Fe-Cu two-component composite catalyst is 4 mL, the activation time of hydrogen chloride gas is 30 min, the flow rate of hydrogen chloride gas is set to 12 mL / min, and the flow rate of acetylene and ethylene mixed gas is set to 12 mL / min; the introduction time of nitrogen is 30 min, the flow rate is set to 12 mL / min, and the raw gas space velocity W=180 h -1 ;

[0077] Alternatively, the stainless steel fixed bed reactor further comprises a thermocouple, which is connected to the reaction tube, and the temperature in the reaction tube is controlled by the thermocouple.

[0078] Preferably, in the method, the acetylene conversion rate is not less than 97%, and can reach a maximum of 99.682%; the ethylene conversion rate is not less than 95%, and can reach a maximum of 98.670%.

[0079] Specifically, the relevant preparation and detection are as follows:

[0080] Example 1

[0081] A copper-iron two-component composite catalyst for removing trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to produce electronic-grade hydrogen chloride gas, the preparation method of which comprises the following steps:

[0082] (1) Weigh 50 g of coconut shell activated carbon and immerse it in 200 mL of 1 mol / L hydrochloric acid solution for 6 h. After filtering, the coconut shell activated carbon was washed with deionized water until the pH was neutral and dried at 120 °C for 12 h to obtain the pretreated catalyst support.

[0083] (2) Weigh 24.377 g of ferric chloride and dissolve it in 45 mL of deionized water. Add the Fe salt solution dropwise to the pretreated catalyst support, ultrasonically immerse it for 2 h at 50 kHz, seal it, and heat it in an 80 °C oven for 6 h. Then, dry it in a 120 °C oven for 6 h.

[0084] (3) Weigh 13.550 g of copper chloride and dissolve it in 45 mL of deionized water. Add the Cu salt solution dropwise to the activated carbon treated in step (2), ultrasonically immerse it for 2 h at 50 kHz, seal it, and heat it in an 80°C oven for 6 h. Finally, dry it in an oven at 120°C for 6 h to obtain a Fe-Cu two-component composite catalyst B1.

[0085] (4) The B1 catalyst was loaded into a fixed bed reactor and the reaction temperature was set at 160°C to evaluate the catalyst performance.

[0086] A method for removing trace amounts of acetylene and ethylene from petrochemical by-product hydrogen chloride gas using the copper-iron two-component composite catalyst to produce electronic-grade hydrogen chloride gas comprises the following steps:

[0087] The following reactions mainly occur between acetylene and ethylene and hydrogen chloride on Fe-Cu catalyst:

[0088]

[0089] The Fe-Cu two-component composite catalyst is placed in a stainless steel fixed bed reactor, and raw gas hydrogen chloride and acetylene-ethylene mixed gas are introduced to perform a performance evaluation of the catalyst, specifically comprising the following steps:

[0090] (1) The Fe-Cu catalyst was loaded into the reaction tube of a stainless steel fixed-bed reactor, the temperature of the fixed-bed reactor was set to 120°C, and nitrogen was introduced into pipeline No. 2 to dry the catalyst;

[0091] (2) Turn off the nitrogen, raise the temperature of the fixed bed reactor to the reaction temperature of 140-180°C, and introduce hydrogen chloride gas into pipeline No. 1 to activate the catalyst;

[0092] (3) A mixture of acetylene and ethylene is introduced through line 3. The two gases enter the reaction tube and begin the reaction. The reaction tail gas flows through the alkali solution absorption bottle 11, and the treatment is completed. The material in the alkali solution absorption bottle can be fed into a gas chromatograph to evaluate and analyze the catalyst performance.

[0093] The stainless steel fixed bed reactor can be a device in the field of acetylene hydrochlorination, specifically, Figure 1As shown, the stainless steel fixed bed reactor includes a reactor body 8, a reaction tube 9, an alkali solution absorption bottle 11, pipeline 1 No. 1, pipeline 2 No. 2 and pipeline 3 No. 3. The reactor body and the reaction tube are arranged in a vertical direction. The reaction tubes are coaxially connected in the reactor body. The top of the reaction tube is set as the reaction tube inlet (not numbered in the figure), and the bottom of the reaction tube is set as the reaction tube outlet (not numbered in the figure). The input end of pipeline No. 1 can input hydrogen chloride gas, the input end of pipeline No. 2 can input nitrogen, and the input end of pipeline No. 3 can input acetylene and ethylene mixed gas. The output ends of pipeline No. 1, pipeline No. 2 and pipeline No. 3 are all tightly connected to the reaction tube inlet of the reaction tube, and the reaction tube outlet of the reaction tube is connected to the alkali solution absorption bottle. The alkali solution absorption bottle can absorb the hydrogen chloride gas in the tail gas to prevent the tail gas from corroding the chromatographic detection device.

[0094] The No. 1 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4a, the dryer 5a, the mass flow meter 6a and the one-way check valve 7a in sequence;

[0095] The No. 2 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4a, the dryer 5b, the mass flowmeter 6a and the one-way check valve 7a in sequence, or the No. 2 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4a, the dryer 5b, the mass flowmeter 6b and the one-way check valve 7b in sequence;

[0096] The No. 3 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4c, the dryer 5c, the mass flow meter 6b and the one-way check valve 7b in sequence.

[0097] The purity of nitrogen is above 99%, the purity of hydrogen chloride gas is above 99%, and the concentration of acetylene and ethylene impurities in the petrochemical by-product hydrogen chloride gas is 50-5000 ppm. 5000 ppm is selected as the acetylene and ethylene mixed gas concentration in the catalyst evaluation reaction device of the present invention to better reflect the catalyst effect.

[0098] When the loading amount of Fe-Cu two-component composite catalyst is 4 mL, the activation time of hydrogen chloride gas is 30 min, the flow rate of hydrogen chloride gas is set to 12 mL / min, and the flow rate of acetylene and ethylene mixed gas is set to 12 mL / min; the introduction time of nitrogen is 30 min, the flow rate is set to 12 mL / min, and the raw gas space velocity W=180 h -1 .

[0099] Preferably, the stainless steel fixed bed reactor further comprises a thermocouple 10, which is connected to the reaction tube. The temperature in the reaction tube is controlled by the thermocouple, and the temperature change can be monitored in real time to ensure that the temperature remains constant.

[0100] Example 2

[0101] A copper-iron two-component composite catalyst for removing trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to produce electronic-grade hydrogen chloride gas, the preparation method of which comprises the following steps:

[0102] (1) Weigh 50 g of coconut shell activated carbon and immerse it in 200 mL of 1 mol / L hydrochloric acid solution for 6 h. After filtering, the coconut shell activated carbon was washed with deionized water until the pH was neutral and dried at 120 °C for 12 h to obtain the pretreated catalyst support.

[0103] (2) Weigh 1.457 g of ferric sulfate and dissolve it in 45 mL of deionized water. Add the Fe salt solution dropwise to the pretreated catalyst support, ultrasonically immerse it for 2 h at 50 kHz, seal it, and heat it in an 80 °C oven for 6 h. Then, dry it in a 120 °C oven for 6 h.

[0104] (3) Weigh 19.065 g of copper nitrate and dissolve it in 45 mL of deionized water. Add the Cu salt solution dropwise to the activated carbon treated in step (2), ultrasonically immerse it for 2 h at 50 kHz, seal it and place it in an oven at 80 ° C. for 6 h, and finally dry it in an oven at 120 ° C. for 6 h to obtain Fe-Cu two-component composite catalyst B2.

[0105] (4) Catalyst B2 was loaded into a fixed bed reactor and the reaction temperature was set at 170° C. to evaluate the catalyst performance. The evaluation method was the same as in Example 1.

[0106] Example 3

[0107] A copper-iron two-component composite catalyst for removing trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to produce electronic-grade hydrogen chloride gas, the preparation method of which comprises the following steps:

[0108] (1) Weigh 50 g of coconut shell activated carbon and immerse it in 200 mL mol / L hydrochloric acid solution for 6 h. After filtering, the coconut shell activated carbon is washed with deionized water until the pH is neutral and dried at 120 ° C for 12 h to obtain the pretreated catalyst support.

[0109] (2) Weigh 10.906 g of ferric nitrate and dissolve it in 45 mL of deionized water. Add the Fe salt solution dropwise to the pretreated catalyst support, ultrasonically immerse it for 2 h at 50 kHz, seal it, and heat it in an 80 °C oven for 6 h. Then, dry it in a 120 °C oven for 6 h.

[0110] (3) Weigh 19.897 g of copper sulfate and dissolve it in 45 mL of deionized water. Add the Cu salt solution dropwise to the activated carbon treated in step (2), ultrasonically immerse it for 2 h at 50 kHz, seal it, and heat it in an 80°C oven for 6 h. Finally, dry it in a 120°C oven for 6 h to obtain a Fe-Cu two-component composite catalyst B3.

[0111] (4) Catalyst B3 was loaded into a fixed bed reactor and the reaction temperature was set at 180° C. to evaluate the catalyst performance. The evaluation method was the same as in Example 1.

[0112] Example 4

[0113] A copper-iron two-component composite catalyst for removing trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to produce electronic-grade hydrogen chloride gas, the preparation method of which comprises the following steps:

[0114] (1) Weigh 50 g of coconut shell activated carbon and immerse it in 200 mL of 1 mol / L hydrochloric acid solution for 6 h. After filtering, the coconut shell activated carbon was washed with deionized water until the pH was neutral and dried at 120 °C for 12 h to obtain the pretreated catalyst support.

[0115] (2) Weigh 7.313 g of ferric chloride and dissolve it in 45 mL of deionized water. Add the Fe salt solution dropwise to the pretreated catalyst support, ultrasonically immerse it for 2 h at 50 kHz, seal it, and heat it in an 80 °C oven for 6 h. Then, dry it in a 120 °C oven for 6 h.

[0116] (3) Weigh 29.846 g of copper nitrate and dissolve it in 45 mL of deionized water. Add the Cu salt solution dropwise to the activated carbon treated in step (2), ultrasonically immerse it for 2 h at 50 kHz, seal it and place it in an oven at 80 ° C. to heat it for 6 h. Finally, dry it in an oven at 120 ° C. for 6 h to obtain Fe-Cu two-component composite catalyst B4.

[0117] (4) The B4 catalyst was loaded into a fixed bed reactor and the reaction temperature was set at 150° C. to evaluate the catalyst performance. The evaluation method was the same as that in Example 1.

[0118] Example 5

[0119] A copper-iron two-component composite catalyst for removing trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to produce electronic-grade hydrogen chloride gas, the preparation method of which comprises the following steps:

[0120] (1) Weigh 50 g of coconut shell activated carbon and immerse it in 200 mL of 1 mol / L hydrochloric acid solution for 6 h. After filtering, the coconut shell activated carbon was washed with deionized water until the pH was neutral and dried at 120 °C for 12 h to obtain the pretreated catalyst support.

[0121] (2) Weigh 5.453 g of ferric nitrate and dissolve it in 45 mL of deionized water. Add the Fe salt solution dropwise to the pretreated catalyst support, ultrasonically immerse it for 2 h at 50 kHz, seal it, and heat it in an 80 °C oven for 6 h. Then, dry it in a 120 °C oven for 6 h.

[0122] (3) Weigh 20.325 g of copper nitrate and dissolve it in 45 mL of deionized water. Add the Cu salt solution dropwise to the activated carbon treated in step (2), ultrasonically immerse it for 2 h at 50 kHz, seal it and place it in an oven at 80 ° C. for 6 h, and finally dry it in an oven at 120 ° C. for 6 h to obtain Fe-Cu two-component composite catalyst B5.

[0123] (4) Catalyst B5 was loaded into a fixed bed reactor and the reaction temperature was set at 140° C. to evaluate the catalyst performance. The evaluation method was the same as in Example 1.

[0124] Comparative Example 1

[0125] A method for preparing a composite catalyst for removing trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to produce electronic-grade hydrogen chloride gas comprises the following steps:

[0126] (1) Weigh 50 g of coconut shell activated carbon and immerse it in 200 mL of 1 mol / L hydrochloric acid solution for 6 h. After filtering, the coconut shell activated carbon was washed with deionized water until the pH was neutral and dried at 120 °C for 12 h to obtain the pretreated catalyst support.

[0127] (2) Weigh 13.550 g of copper chloride and dissolve it in 45 mL of deionized water. Add the copper salt solution dropwise to the pretreated catalyst support, ultrasonically immerse it for 2 h at 50 kHz, seal it, and heat it in an oven at 80 °C for 6 h. Finally, dry it in an oven at 120 °C for 6 h to obtain the Fe-Cu two-component composite catalyst B6.

[0128] (3) The B6 catalyst was loaded into a fixed bed reactor and the reaction temperature was set at 160° C. to evaluate the catalyst performance. The evaluation method was the same as in Example 1.

[0129] Comparative Example 2

[0130] A method for preparing a composite catalyst for removing trace acetylene and ethylene from petrochemical by-product hydrogen chloride gas to produce electronic-grade hydrogen chloride gas comprises the following steps:

[0131] (1) Weigh 50 g of coconut shell activated carbon and immerse it in 200 mL of 1 mol / L hydrochloric acid solution for 6 h. After filtering, the coconut shell activated carbon was washed with deionized water until the pH was neutral and dried at 120 °C for 12 h to obtain the pretreated catalyst support.

[0132] (2) Weigh 24.377 g of ferric chloride and dissolve it in 45 mL of deionized water. Add the Fe salt solution dropwise to the pretreated catalyst support, ultrasonically immerse it for 2 h at 50 kHz, seal it, and heat it in an oven at 80 °C for 6 h. Finally, dry it in an oven at 120 °C for 6 h to obtain the Fe-Cu two-component composite catalyst B7.

[0133] (3) The B7 catalyst was loaded into a fixed bed reactor and the reaction temperature was set at 160° C. to evaluate the catalyst performance. The evaluation method was the same as in Example 1.

[0134] The catalyst evaluation results are shown in Table 1.

[0135] Table 1

[0136] Catalyst No. Reaction temperature (℃) Acetylene conversion rate (%) Ethylene conversion rate (%) B1 160 99.012 98.670 B2 170 99.453 96.760 B3 180 99.682 95.692 B4 150 98.560 98.605 B5 140 97.452 97.828 B6 160 99.950 10.80 B7 160 41.739 99.432

[0137] The following conclusions can be drawn from Examples 1-5 and Comparative Examples 1-2:

[0138] Comparison between Example 1 and Comparative Example 1 shows that, in the absence of the active component Fe, the activity of ethylene hydrochlorination is significantly reduced when Cu is used alone as the active component metal element.

[0139] Comparison between Example 1 and Comparative Example 2 shows that, in the absence of the active component Cu, the activity of acetylene hydrochlorination reaction is significantly reduced when Fe is used alone as the active component metal element.

[0140] It can be seen from this that the active components used in the preparation process of the catalyst of the present invention are indispensable, and a single metal cannot meet the effect of removing acetylene and ethylene at the same time.

[0141] It can also be seen that the Fe metal salt and the Cu metal salt in the catalyst preparation method of the present invention have a synergistic effect, and the Fe metal salt and the Cu metal salt can synergistically improve the relevant properties of the prepared catalyst. In particular, when the mass ratio of ferric chloride:copper chloride is 24.377:13.550, the Fe metal salt and the Cu metal salt can significantly synergistically improve the relevant properties of the prepared catalyst.

[0142] In addition, there is no similar product in the currently disclosed art. The method of the present invention is a significant advancement.

[0143] Although the embodiments of the present invention are disclosed for illustrative purposes, those skilled in the art will understand that various substitutions, changes and modifications are possible without departing from the spirit and scope of the present invention and the appended claims. Therefore, the scope of the present invention is not limited to the contents disclosed in the embodiments.

Claims

1. A method for producing electronic-grade hydrogen chloride gas by removing trace amounts of acetylene and ethylene from petrochemical by-product hydrogen chloride gas using a copper-iron two-component composite catalyst, characterized in that: The method comprises the following steps: placing a copper-iron two-component composite catalyst in a fixed bed reactor, introducing hydrogen chloride gas and a 5000 ppm acetylene-ethylene mixed gas, and removing trace acetylene-ethylene gas from the reaction system at a reaction temperature of 140-180° C. The preparation method of the copper-iron two-component composite catalyst comprises the following steps: (1) Immerse the activated carbon in hydrochloric acid, wash it with deionized water until the pH is neutral, and dry it to obtain the pretreated activated carbon carrier; (2) impregnating the active component onto the activated carbon carrier obtained by pretreatment, using ultrasound-assisted impregnation, allowing it to stand and then drying; Wherein, the active components are Fe metal salt and Cu metal salt; The weight of Cu metal in the catalyst is 1-15% of the total weight of the catalyst, and the weight of Fe metal is 1-15% of the total weight of the catalyst.

2. The method according to claim 1, wherein: The steps include: A copper-iron two-component composite catalyst was placed in a stainless steel fixed-bed reactor, and the raw gas of hydrogen chloride and a mixed gas of acetylene and ethylene was introduced to evaluate the performance of the catalyst. The specific steps include the following: (1) The copper-iron two-component composite catalyst was loaded into the reaction tube of a stainless steel fixed-bed reactor. The temperature of the fixed-bed reactor was set to 120 °C, and nitrogen was introduced into pipeline No. 2 to dry the catalyst. (2) Turn off the nitrogen, raise the temperature of the fixed bed reactor to the reaction temperature of 140-180 °C, and introduce hydrogen chloride gas into pipeline No. 1 to activate the catalyst; (3) A mixed gas of acetylene and ethylene is introduced through pipeline No.

3. The two gases enter the reaction tube and start to react. After the reaction tail gas flows through the alkali solution absorption bottle, the treatment is completed; The stainless steel fixed bed reactor includes a reactor body, a reaction tube, an alkali solution absorption bottle, pipeline No. 1, pipeline No. 2 and pipeline No.

3. The reactor body and the reaction tube are arranged in a vertical direction. The reaction tube is coaxially connected in the reactor body. The top of the reaction tube is set as the reaction tube inlet, and the bottom of the reaction tube is set as the reaction tube outlet. The input end of pipeline No. 1 can input hydrogen chloride gas, the input end of pipeline No. 2 can input nitrogen, and the input end of pipeline No. 3 can input acetylene and ethylene mixed gas. The output ends of pipeline No. 1, pipeline No. 2 and pipeline No. 3 are all tightly connected to the reaction tube inlet of the reaction tube, and the reaction tube outlet of the reaction tube is connected to the alkali solution absorption bottle. The alkali solution absorption bottle can absorb the hydrogen chloride gas in the tail gas.

3. The method according to claim 2, wherein: The No. 1 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4a, the dryer 5a, the mass flow meter 6a and the one-way check valve 7a in sequence; The No. 2 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4a, the dryer 5b, the mass flowmeter 6a and the one-way check valve 7a in sequence, or the No. 2 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4a, the dryer 5b, the mass flowmeter 6b and the one-way check valve 7b in sequence; The No. 3 pipeline is connected to the reaction tube inlet of the reaction tube through the valve 4c, the dryer 5c, the mass flow meter 6b and the one-way check valve 7b in sequence; Alternatively, the purity of the nitrogen gas is 99% or higher, the purity of the hydrogen chloride gas is 99% or higher, and the concentrations of the acetylene and ethylene mixed gases are both 5000 ppm; Alternatively, when the loading amount of the Fe-Cu two-component composite catalyst is 4 mL, the activation time of hydrogen chloride gas is 30 min, the flow rate of hydrogen chloride gas is set to 12 mL / min, and the flow rate of acetylene and ethylene mixed gas is set to 12 mL / min; the introduction time of nitrogen is 30 min, the flow rate is set to 12 mL / min, and the raw gas space velocity W=180 h -1 ; Alternatively, the stainless steel fixed bed reactor further comprises a thermocouple, which is connected to the reaction tube, and the temperature in the reaction tube is controlled by the thermocouple.

4. The method according to any one of claims 1 to 3, characterized in that: In the method, the acetylene conversion rate is not less than 97%, and the maximum reaches 99.682%; the ethylene conversion rate is not less than 95%, and the maximum reaches 98.670%.

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