Copper-iron double-component composite catalyst for preparing electronic-grade hydrogen chloride gas and application of copper-iron double-component composite catalyst

Abstract

The invention belongs to the technical field of high-purity gas preparation and catalysis, and discloses a copper-iron double-component composite catalyst for removing trace acetylene and ethylene in petrochemical byproduct hydrogen chloride gas to prepare electronic grade hydrogen chloride gas, and a preparation method of the copper-iron double-component composite catalyst comprises the following steps: immersing activated carbon in hydrochloric acid; washing the activated carbon carrier with deionized water until the pH is neutral, and drying to obtain the pretreated activated carbon carrier; and impregnating the active component on the pretreated active carbon carrier, carrying out ultrasonic-assisted impregnation, standing, and drying, thereby obtaining the product, the active components are Fe metal salt and Cu metal salt. According to the method, trace acetylene and ethylene in the petrochemical byproduct hydrogen chloride gas are catalyzed to react with the hydrogen chloride gas at the same time, so that acetylene and ethylene are removed at the same time, and the acetylene and ethylene removal step in the existing hydrogen chloride purification process is simplified. Compared with a traditional method, the reaction efficiency of preparing the electronic-grade hydrogen chloride gas is remarkably improved.

Description

Technical Field

[0001] The invention belongs to the technical field of high-purity gas preparation and catalysis, in particular to a copper-iron two-component composite catalyst for removing trace acetylene and ethylene from petrochemical byproduct 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 process 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] At present, the main methods for preparing electronic-grade hydrogen chloride include analytical method, hydrochloric acid stripping method, industrial by-product acid stripping method, synthetic method and petrochemical by-product hydrogen chloride purification method. Among them, the hydrogen chloride gas produced by analytical method, hydrochloric acid stripping method, industrial by-product acid stripping method and synthetic method 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 because of its simple operation, low production cost and high product purity. However, the removal of acetylene and ethylene is still 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 byproduct hydrogen chloride gas to prepare electronic grade hydrogen chloride. The method reacts acetylene with hydrogen chloride under the action of HgCl2-BaCl2 / activated carbon composite catalyst to generate halogenated hydrocarbons that are easy to remove. At the same time, ethylene reacts under the action of CuCl2-KCl-SrCl2 / activated carbon composite catalyst to generate halogenated hydrocarbons that are also easy to remove. Under the synergistic effect of these two composite catalysts, acetylene and ethylene can be effectively removed, thereby improving the purity of electronic grade hydrogen chloride.

[0005] Although the existing technology can effectively remove ethylene and acetylene impurities, the removal of ethylene and acetylene requires different catalysts for catalytic reactions, and the catalytic efficiency is low; the existing process removes acetylene and ethylene impurities in steps, which makes the process steps complicated and increases production costs; the current process catalyst uses a mercury-containing catalyst, which has significant environmental and health risks. In view of this, the present invention provides a new bifunctional catalyst and preparation method, which has the characteristics of high efficiency, green safety and low cost, and can simultaneously and efficiently remove trace acetylene and ethylene impurities in the by-product hydrogen chloride gas of petrochemical industry, greatly simplifying the process steps and improving the reaction efficiency. This catalyst design overcomes the limitations of the existing technology of removing impurities separately, and avoids the environmental and health risks caused by the use of toxic mercury catalysts. Summary of the invention

[0006] The purpose of the present invention is to overcome the deficiencies in 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 prepare 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 carrier;

[0010] (2) impregnating the active component onto the activated carbon carrier obtained by pretreatment, using ultrasound to assist the impregnation, standing and then drying to obtain;

[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] Further, 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 manner, wherein the Fe metal salt is first impregnated into the pretreated activated carbon carrier, and then the Cu metal salt is impregnated into the activated carbon carrier after drying.

[0016] Further, 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) Weighing activated carbon, immersing it in a 1 mol / L hydrochloric acid solution for 6 h, filtering it, washing the activated carbon with deionized water until the pH is neutral, and drying it at 120° C. for 12 h to obtain a pretreated catalyst carrier;

[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, and drop the Fe salt solution into the pretreated catalyst support, ultrasonically immerse it for 2 h at 50 KHZ, seal it and place it in an oven at 80 °C for 6 h, and then dry it 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, add the copper salt solution dropwise to the activated carbon treated in step (2), ultrasonically immerse for 2 h at 50 KHZ, seal and place in an oven at 80° C. for 6 h, and finally dry in an oven at 120° C. for 6 h to obtain a copper-iron two-component composite catalyst;

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

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

[0025] The invention discloses a method for removing trace acetylene and ethylene in the by-product hydrogen chloride gas of petrochemical industry by using the copper-iron two-component composite catalyst as described above to prepare electronic grade hydrogen chloride gas. The method comprises the following steps: loading the copper-iron two-component composite catalyst into a fixed bed reactor, introducing hydrogen chloride gas and a mixed gas of acetylene and ethylene with a concentration of 5000 ppm, and reacting at a temperature of 140-180° C. to remove trace acetylene and ethylene gas in the reaction system.

[0026] Further, the following steps are included:

[0027] A copper-iron 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 evaluate the performance of the catalyst, which specifically includes the following steps:

[0028] (1) a copper-iron two-component composite catalyst is loaded into a reaction tube of a stainless steel fixed bed reactor, the temperature of the fixed bed reactor is set to 120° C., and nitrogen is 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, and the two gases enter the reaction tube to start the reaction. After the reaction tail gas flows through the alkali solution absorption bottle, the treatment is completed;

[0031] 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 arranged as the reaction tube inlet, and the bottom of the reaction tube is arranged 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 flow meter 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 flow meter 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 nitrogen is above 99%, the purity of hydrogen chloride gas is above 99%, and the concentration of acetylene and ethylene mixed gas is 50-5000ppm;

[0036] Alternatively, when the loading amount of the Fe-Cu two-component composite catalyst is 4 mL, the activation time of the hydrogen chloride gas is 30 min, the flow rate of the hydrogen chloride gas is set to 12 mL / min, and the flow rate of the 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 the maximum is 99.682%; the ethylene conversion rate is not less than 95%, and the maximum is 98.670%.

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

[0040] 1. The present invention catalyzes the reaction of trace acetylene and ethylene in the petrochemical byproduct hydrogen chloride gas with hydrogen chloride gas to achieve simultaneous removal of acetylene and ethylene, thereby simplifying the steps of removing acetylene and ethylene in the existing hydrogen chloride purification process. Compared with the traditional method, the present invention significantly improves the reaction efficiency of preparing electronic grade hydrogen chloride gas (here, improving the reaction efficiency means that the existing process uses two catalysts to achieve the effect, while the present invention only uses one catalyst to achieve it.).

[0041] 2. The present invention uses Fe-Cu catalyst to remove ethylene and acetylene gas simultaneously without introducing other impurities, and efficiently purifies hydrogen chloride gas. Specifically, in the presence of Fe-Cu catalyst, acetylene and ethylene in the feed react with hydrogen chloride to generate halogenated hydrocarbons that are easily removed from hydrogen chloride gas. Compared with traditional mercury-containing catalysts for removing acetylene and ethylene, Fe-Cu bimetallic mercury-free catalysts have higher economic and environmental benefits, and the preparation method is simple and efficient, and is suitable for large-scale industrial applications.

[0042] 3. The catalyst prepared by the present invention is used for the hydrochlorination reaction of trace acetylene and ethylene, and can effectively remove trace acetylene and ethylene impurities in the by-product hydrogen chloride gas of petrochemical industry, thereby preparing electronic grade hydrogen chloride gas. Compared with the existing hydrochlorination reaction catalyst, the mercury-free catalyst of the present invention can remove acetylene and ethylene impurities at the same time, has a simple preparation process, and has significant economic and environmental benefits.

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

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

[0045] Figure 2 The figure 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 in the petrochemical by-product hydrogen chloride gas to prepare electronic grade hydrogen chloride gas; wherein a is the conversion rate of acetylene in Example 1; and b is the conversion rate of ethylene in Example 1. DETAILED DESCRIPTION

[0046] The present invention will be further described below in conjunction with the embodiments. The following embodiments are descriptive rather than restrictive, and the protection scope 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 art. For parts not specially annotated in this document, ordinary technicians in the art can implement them by referring to various commonly used reference books, scientific and technological literature or related instructions, manuals, etc. before the filing date of this invention.

[0048] 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. 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 carrier;

[0050] (2) impregnating the active component onto the activated carbon carrier obtained by pretreatment, using ultrasound to assist the impregnation, standing and then drying to obtain;

[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 manner, wherein the Fe metal salt is first impregnated into the pretreated activated carbon carrier, and then the Cu metal salt is impregnated into the activated carbon carrier 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) Weighing activated carbon, immersing it in a 1 mol / L hydrochloric acid solution for 6 h, filtering it, washing the activated carbon with deionized water until the pH is neutral, and drying it at 120° C. for 12 h to obtain a pretreated catalyst carrier;

[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, and drop the Fe salt solution into the pretreated catalyst support, ultrasonically immerse it for 2 h at 50 KHZ, seal it and place it in an oven at 80 °C for 6 h, and then dry it 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, add the copper salt solution dropwise to the activated carbon treated in step (2), ultrasonically immerse for 2 h at 50 KHZ, seal and place in an oven at 80° C. for 6 h, and finally dry in an oven at 120° C. for 6 h to obtain a copper-iron two-component composite catalyst;

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

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

[0065] The invention discloses a method for removing trace acetylene and ethylene in the by-product hydrogen chloride gas of petrochemical industry by using the copper-iron two-component composite catalyst as described above to prepare electronic grade hydrogen chloride gas. The method comprises the following steps: loading the copper-iron two-component composite catalyst into a fixed bed reactor, introducing hydrogen chloride gas and a mixed gas of acetylene and ethylene with a concentration of 5000 ppm, and reacting at a temperature of 140-180° C. to remove trace acetylene and ethylene gas in the reaction system.

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

[0067] A copper-iron 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 evaluate the performance of the catalyst, which specifically includes the following steps:

[0068] (1) a copper-iron two-component composite catalyst is loaded into a reaction tube of a stainless steel fixed bed reactor, the temperature of the fixed bed reactor is set to 120° C., and nitrogen is 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, and the two gases enter the reaction tube to start the reaction. After the reaction tail gas flows through the alkali solution absorption bottle, the treatment is completed;

[0071] 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 arranged as the reaction tube inlet, and the bottom of the reaction tube is arranged 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 flow meter 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 flow meter 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 nitrogen is above 99%, the purity of hydrogen chloride gas is above 99%, and the concentration of acetylene and ethylene mixed gas is 50-5000ppm;

[0076] Alternatively, when the loading amount of the Fe-Cu two-component composite catalyst is 4 mL, the activation time of the hydrogen chloride gas is 30 min, the flow rate of the hydrogen chloride gas is set to 12 mL / min, and the flow rate of the 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 the maximum is 99.682%; the ethylene conversion rate is not less than 95%, and the maximum is 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 prepare electronic grade hydrogen chloride gas, and the preparation method thereof comprises the following steps:

[0082] (1) Weigh 50 g of coconut shell activated carbon, immerse it in 200 mL of 1 mol / L hydrochloric acid solution for 6 h, filter it, wash the coconut shell activated carbon with deionized water until the pH is neutral, and dry it at 120° C. for 12 h to obtain a 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 oven at 80 °C for 6 h, and then dry it in an oven at 120 °C 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 oven at 80° C. for 6 h, and 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 prepare electronic-grade hydrogen chloride gas comprises the following steps:

[0087] The main reactions of acetylene and ethylene with hydrogen chloride on Fe-Cu catalyst are as follows:

[0088]

[0089] The Fe-Cu two-component composite catalyst is loaded into a stainless steel fixed bed reactor, and raw gas hydrogen chloride and acetylene, ethylene mixed gas are introduced to evaluate the performance of the catalyst, which specifically includes 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 mixed gas of acetylene and ethylene is introduced through pipeline No. 3, and the two gases enter the reaction tube to start the reaction. After the reaction tail gas flows through the alkali solution absorption bottle 11, the treatment is completed. The material in the alkali solution absorption bottle can enter the 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 comprises 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 tube is coaxially connected in the reactor body, the top of the reaction tube is arranged as a reaction tube inlet (not numbered in the figure), the bottom of the reaction tube is arranged as a reaction tube outlet (not numbered in the figure), the input end of pipeline 1 can input hydrogen chloride gas, the input end of pipeline 2 can input nitrogen, the input end of pipeline 3 can input acetylene and ethylene mixed gas, the output ends of pipelines 1, 2 and 3 are all tightly connected to the reaction tube inlet of the reaction tube, the reaction tube outlet of the reaction tube is connected to the alkali solution absorption bottle, and 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 valve 4a, dryer 5a, mass flow meter 6a and 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 flow meter 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 flow meter 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%, the concentration of acetylene and ethylene impurities in the by-product hydrogen chloride gas of petrochemical industry is 50-5000ppm, and 5000ppm is selected as the concentration of acetylene and ethylene mixed gas 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 prepare electronic grade hydrogen chloride gas, and the preparation method thereof comprises the following steps:

[0102] (1) Weigh 50 g of coconut shell activated carbon, immerse it in 200 mL of 1 mol / L hydrochloric acid solution for 6 h, filter it, wash the coconut shell activated carbon with deionized water until the pH is neutral, and dry it at 120° C. for 12 h to obtain a 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 oven at 80 °C for 6 h, and then dry it in an oven at 120 °C 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 heat 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 a 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 that 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 prepare electronic grade hydrogen chloride gas, and the preparation method thereof comprises the following steps:

[0108] (1) Weigh 50 g of coconut shell activated carbon, immerse it in 200 mL mol / L hydrochloric acid solution for 6 h, filter it, wash the coconut shell activated carbon with deionized water until the pH is neutral, and dry it at 120 ° C for 12 h to obtain a pretreated catalyst carrier;

[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 oven at 80 °C for 6 h, and then dry it in an oven at 120 °C 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 oven at 80° C. for 6 h, and finally dry it in an oven at 120° C. for 6 h to obtain a Fe-Cu two-component composite catalyst B3.

[0111] (4) The B3 catalyst was loaded into a fixed bed reactor and the reaction temperature was set to 180° C. to evaluate the catalyst performance. The evaluation method was the same as that 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 prepare electronic grade hydrogen chloride gas, and the preparation method thereof comprises the following steps:

[0114] (1) Weigh 50 g of coconut shell activated carbon, immerse it in 200 mL of 1 mol / L hydrochloric acid solution for 6 h, filter it, wash the coconut shell activated carbon with deionized water until the pH is neutral, and dry it at 120° C. for 12 h to obtain a 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 oven at 80 °C for 6 h, and then dry it in an oven at 120 °C 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 heat 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 a 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 to 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 prepare electronic grade hydrogen chloride gas, and the preparation method thereof comprises the following steps:

[0120] (1) Weigh 50 g of coconut shell activated carbon, immerse it in 200 mL of 1 mol / L hydrochloric acid solution for 6 h, filter it, wash the coconut shell activated carbon with deionized water until the pH is neutral, and dry it at 120° C. for 12 h to obtain a 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 place it in an oven at 80 °C for 6 h, and then dry it in an oven at 120 °C 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 heat 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 a Fe-Cu two-component composite catalyst B5.

[0123] (4) The B5 catalyst was loaded into a fixed bed reactor and the reaction temperature was set to 140° C. to evaluate the catalyst performance. The evaluation method was the same as that 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 prepare electronic grade hydrogen chloride gas, comprising the following steps:

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

[0127] (2) Weigh 13.550 g of copper chloride and dissolve it in 45 mL of deionized water. Add the Cu salt solution dropwise to the pretreated catalyst support, perform ultrasonic immersion at 50 kHz for 2 h, seal the support and heat in an oven at 80 °C for 6 h, and finally dry 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 to 160° C. to evaluate the catalyst performance. The evaluation method was the same as that 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 prepare electronic grade hydrogen chloride gas, comprising the following steps:

[0131] (1) Weigh 50 g of coconut shell activated carbon, immerse it in 200 mL of 1 mol / L hydrochloric acid solution for 6 h, filter it, wash the coconut shell activated carbon with deionized water until the pH is neutral, and dry it at 120° C. for 12 h to obtain a 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, and finally dry it in an oven at 120 °C for 6 h to obtain a 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 to 160° C. to evaluate the catalyst performance. The evaluation method was the same as that 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 reaction 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 the metal Fe is used as the active component metal element alone;

[0140] It can be seen 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 in the preparation method of the catalyst of the present invention, there is a synergistic effect between the Fe metal salt and the Cu metal salt, 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: cupric 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 are no similar products 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 appreciate 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 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, characterized in that: The preparation method of the copper-iron two-component composite catalyst comprises the following steps: (1) immersing the 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; (2) impregnating the active component onto the activated carbon carrier obtained by pretreatment, using ultrasound to assist the impregnation, allowing it to stand and then drying to obtain the activated carbon carrier; Wherein, the active components are Fe metal salt and Cu metal salt.

2. The copper-iron two-component composite catalyst according to claim 1, characterized in that: In step (1), the activated carbon is immersed in the hydrochloric acid solution for 6-12 hours; Alternatively, the activated carbon is coconut shell activated carbon.

3. The copper-iron two-component composite catalyst according to claim 1, characterized in that: 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; 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 manner, wherein the Fe metal salt is first impregnated into the pretreated activated carbon carrier, and then the Cu metal salt is impregnated into the activated carbon carrier after drying.

4. The copper-iron two-component composite catalyst according to claim 1, characterized in that: 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; Alternatively, the drying temperature in step (2) is 80-120° C. and the drying time is 6-12 h; 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.

5. The copper-iron two-component composite catalyst according to any one of claims 1 to 4, characterized in that: The specific steps are as follows: (1) Weighing activated carbon, immersing it in a 1 mol / L hydrochloric acid solution for 6 h, filtering it, washing the activated carbon with deionized water until the pH is neutral, and drying it at 120° C. for 12 h to obtain a pretreated catalyst carrier; (2) Weigh ferric chloride and dissolve it in deionized water, the ratio of ferric chloride to deionized water is 24.377:45 g:mL, and drop the Fe salt solution into the pretreated catalyst support, ultrasonically immerse it for 2 h at 50 KHZ, seal it and place it in an oven at 80 °C for 6 h, and then dry it in an oven at 120 °C for 6 h; (3) Weigh copper chloride and dissolve it in deionized water, the ratio of iron chloride to deionized water is 13.550:45, add the copper salt solution dropwise to the activated carbon treated in step (2), ultrasonically immerse for 2 h at 50 KHZ, seal and place in an oven at 80° C. for 6 h, and finally dry in an oven at 120° C. for 6 h to obtain a copper-iron two-component composite catalyst; Among them, the mass ratio of activated carbon: 1 mol / L hydrochloric acid solution: ferric chloride: cupric chloride is 50:200:24.377:13.550 in g:mL:g:g.

6. Use of the copper-iron two-component composite catalyst according to any one of claims 1 to 5 in removing trace acetylene and ethylene impurities from petrochemical by-product hydrogen chloride gas to prepare electronic grade hydrogen chloride gas.

7. A method for preparing electronic grade hydrogen chloride gas by removing trace amounts of acetylene and ethylene from the by-product hydrogen chloride gas of petrochemical industry using the copper-iron two-component composite catalyst as claimed in any one of claims 1 to 5, characterized in that: The method comprises the following steps: loading a copper-iron two-component composite catalyst into a fixed bed reactor, introducing hydrogen chloride gas and acetylene-ethylene mixed gas with a concentration of 5000 ppm, and removing trace acetylene-ethylene gas in the reaction system at a reaction temperature of 140-180°C.

8. The method according to claim 7, characterized in that: The steps include: A copper-iron 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 evaluate the performance of the catalyst, which specifically includes the following steps: (1) a copper-iron two-component composite catalyst is loaded into a reaction tube of a stainless steel fixed bed reactor, the temperature of the fixed bed reactor is set to 120° C., and nitrogen is 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, and the two gases enter the reaction tube to start the reaction. After the reaction tail gas flows through the alkali solution absorption bottle, the treatment is completed; The stainless steel fixed bed reactor comprises 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 arranged as a reaction tube inlet, and the bottom of the reaction tube is arranged as a 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 with the reaction tube inlet of the reaction tube, and the reaction tube outlet of the reaction tube is connected with the alkali solution absorption bottle, which can absorb hydrogen chloride gas in the tail gas.

9. The method according to claim 8, characterized in that: The No. 1 pipeline is connected to the reaction tube inlet of the reaction tube through valve 4a, dryer 5a, mass flow meter 6a and 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 flow meter 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 flow meter 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 nitrogen is above 99%, the purity of hydrogen chloride gas is above 99%, and the concentration of acetylene and ethylene mixed gas is 50-5000ppm; Alternatively, when the loading amount of the Fe-Cu two-component composite catalyst is 4 mL, the activation time of the hydrogen chloride gas is 30 min, the flow rate of the hydrogen chloride gas is set to 12 mL / min, and the flow rate of the 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.

10. The method according to any one of claims 7 to 9, 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%.

Images