CN114713250A - Catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride and preparation method and application thereof - Google Patents

Catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride and preparation method and application thereof Download PDF

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CN114713250A
CN114713250A CN202210356897.6A CN202210356897A CN114713250A CN 114713250 A CN114713250 A CN 114713250A CN 202210356897 A CN202210356897 A CN 202210356897A CN 114713250 A CN114713250 A CN 114713250A
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catalyst
hydrogen chloride
catalytic oxidation
cucl
cuf
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CN114713250B (en
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周永华
徐凡
龚浚
张鑫
田新
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Central South University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/122—Halides of copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/04—Preparation of chlorine from hydrogen chloride
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention belongs to the field of hydrogen chloride catalytic oxidation, and particularly relates to a catalyst for preparing chlorine through hydrogen chloride catalytic oxidation. The invention also provides the preparation of the catalyst and the application of the catalyst in the catalytic oxidation of hydrogen chloride. The catalyst of the invention has the characteristics of high activity, high stability and low cost.

Description

Catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride and preparation method and application thereof
The technical field is as follows:
the invention belongs to the field of catalysts and the field of environmental protection, and particularly relates to a catalyst for preparing chlorine through catalytic oxidation of hydrogen chloride, and a preparation method and application thereof.
Background art:
chlorine is an important chemical raw material. However, in the production of products related to chlorine in China, the problem of low utilization rate of chlorine atoms generally exists. One mole of hydrogen chloride is produced as a by-product for every mole of chlorine consumed. According to statistics, the total amount of the byproduct hydrogen chloride in 2015 in China reaches 500 million tons. At present, most of the hydrogen chloride produced as a by-product is absorbed in water to produce hydrochloric acid. With the gradual supply and demand of the hydrochloric acid market and increasingly strict environmental requirements, hydrogen chloride is converted into chlorine to realize recycling, so that the method becomes an important requirement for sustainable development of the chlorine-related industry.
The conversion of hydrogen chloride to chlorine includes direct oxidation, catalytic oxidation and electrolysis. Among them, the catalytic oxidation method is the most economically efficient method recognized in the industry. Since Deacon first introduced a process for converting hydrogen chloride into chlorine gas in one step as a catalyst (called the Deacon process) in 1870, catalytic oxidation processes have been increasingly used. The types of catalysts reported so far are: copper-based, chromium-based, cerium-based, and ruthenium-based catalysts. Among them, the noble metal ruthenium-based catalyst has been industrially realized because of its excellent low-temperature activity and stability. British patent GB1046313 discloses a supported RuCl taking silica gel, pumice and Al2O3 as carriers3A catalyst, wherein the reaction temperature is 200-500 ℃. US5871707 discloses a method of treatment with RuO2Catalysts based on different ruthenium starting materials, e.g. RuCl3、Ru3(CO)12、[Ru(NH3)6]Cl3And the conversion rate of the hydrogen chloride can reach 85-90% under the continuous operation of 15000h by taking the rutile type titanium dioxide as the carrier. European patent EP2026905 is an improvement on Japanese Sumitomo US5871707 patent, and the conversion rate of hydrogen chloride can be maintained at 40% in 7000h operation by using tin dioxide and aluminum oxide as combined carrier to load ruthenium dioxide. U.S. Pat. No. 2007292336 discloses that tin oxide is used as a carrier, RuO2 is loaded, and the single-pass conversion rate of hydrogen chloride is 15-90%. However, since ruthenium is a noble metal, it is expensive, and international market price is greatly fluctuating, research on non-noble metal catalysts is continued despite the fact that ruthenium catalysts have been commercialized.
Copper-based catalysts are the current focus of research due to the absence of the toxicity problem of hexavalent chromium. Chinese patents CN101862663A, CN102658149A, CN104923239A, CN105268448A, CN105289631A and CN105642318A disclose a series of copper-based catalysts, in which non-noble metal Cu and transition metal V are used as main components, alkali metals K and Na, rare earths Ce, La, Sm and Pr are used as auxiliaries to jointly form a main body part, and the carrier is alumina or silica-coated alumina. The catalyst has high conversion rate, which is over 80 percent. This patent is similar to US5707919 except that chromium is not added, but expensive rare earth metals are added, typically in an amount of about 10 wt%. To date, in order to improve the stability of copper catalysts, researchers have generally adopted a strategy of adding an auxiliary agent, mainly rare earth metals with high cost, to form a double salt with high boiling point, so as to reduce the volatility of the double salt.
In summary, the prior art still has many disadvantages. Therefore, the copper-based catalyst with high activity, high stability and low cost is continuously developed, and still has good industrial application prospect.
Disclosure of Invention
Aiming at the defects of various catalysts for preparing chlorine by catalytic oxidation of hydrogen chloride, the invention aims to provide a catalyst for preparing chlorine by catalytic oxidation of hydrogen chloride, which has high activity, high stability and low cost.
The second purpose of the invention is to provide a preparation method of the catalyst.
The third object of the present invention is to provide the use of the above catalyst (i.e., a method for producing chlorine gas by catalytic oxidation of hydrogen chloride).
Some CuCl is present in the prior art2Application as a catalyst for catalytic oxidation of hydrogen chloride, but less involving CuF2The application of the catalyst as a main catalyst for catalytic oxidation of hydrogen chloride is reported. Furthermore, the inventor researches and discovers that CuCl2、CuF2As a hydrogen chloride catalytic oxidation catalyst, the catalytic activity is not ideal, and the resistance to high-acidity and high-temperature conditions of hydrogen chloride is not strong, aiming at the technical problem, the invention provides the following improvement scheme:
a catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride comprises a carrier and an active component loaded on the carrier, wherein the active component contains CuClF.
The research of the invention finds that CuClF is used as a catalytic active component, which can show excellent catalytic activity, more importantly, can well endure high-temperature and high-acid corrosion conditions in a catalytic process, and can show excellent catalytic stability.
Preferably, the active ingredient contains CuF2、CuCl2At least one of (1).
In the present invention, a CuClF composition comprising CuClF and at least one CuF is used2、CuCl2The catalytic activity and the catalytic stability under high-temperature and high-acid conditions can be further synergistically improved.
The active ingredient of the invention is prepared by containing CuF2、CuCl2The active ingredient raw materials are roasted in protective atmosphere to prepare;
preferably, the content of CuClF in the active ingredient is greater than or equal to 20 mol%; more preferably 50 mol% or more; still more preferably 60 mol% or more.
Preferably, in the active ingredient raw material, CuF2/CuCl2The molar ratio of (A) to (B) is 1-4: 1-2; more preferably 1-2: 1. The research of the invention finds that under the optimal proportion, the catalyst with good catalytic activity and stability can be obtained.
Preferably, the roasting temperature is 350-550 ℃, and more preferably 400-500 ℃. The baking time is, for example, 2 to 6 hours, and further 3 to 5 hours.
In the present invention, the type of the carrier is not particularly limited, and may be, for example, activated alumina (Al)2O3) Titanium dioxide (anatase type-A type), titanium dioxide (rutile type-R type), cordierite, silicon dioxide (SiO)2) One or more of (a).
In the catalyst, the weight ratio of active ingredients to a carrier is 0.05-0.35: 1; more preferably 0.1 to 0.25: 1.
The invention also provides a preparation method of the catalyst, which comprises the steps of preparing a carrier and CuF2、CuCl2The mixed raw material is baked at the temperature of 350-550 ℃ in protective atmosphereAnd (4) firing to obtain the product.
In the invention, the new catalyst loaded with the active component can be obtained by roasting the composite raw material in the atmosphere, and the prepared catalyst can show better catalytic activity and catalytic stability.
Mixing the raw materials through a solid phase to prepare the mixed raw material, or mixing the raw materials through a wet method and then drying to prepare the mixed raw material;
preferably, the wet mixing solvent is at least one of water, C1-C4 alcohol and acetone;
the liquid phase mixing is, for example, impregnation mixing by, for example, impregnating the carrier with the CuF dispersed therein2、CuCl2Or an organic solution such as ethanol or acetone. The temperature of the liquid phase impregnation process is room temperature, the impregnation time is 2-12 hours, and the impregnation can be carried out for 6-24 hours at 30-120 ℃. The solid phase mixing is, for example, milling, ball milling, or the like.
Preferably, in the mixed raw materials, CuF2/CuCl2The molar ratio of (A) to (B) is 1-4: 1-2; further preferably 1-2: 1; more preferably 1 to 1.5: 1. It was found that the catalyst having the active ingredient obtained by calcination under the preferred conditions can exhibit more excellent catalytic activity and stability.
Preferably, CuF2、CuCl2The weight ratio of the total weight of the carrier to the carrier is 0.05-0.35: 1; more preferably 0.1 to 0.25: 1.
In the invention, the mixed raw materials are subjected to roasting load and transformation treatment in a protective atmosphere.
The protective atmosphere is an atmosphere without oxidation and reduction components, such as: at least one of nitrogen, inert gas (argon, helium, etc.).
In the present invention, the calcination temperature is preferably 400 to 500 ℃.
In the present invention, the time for the baking treatment is, for example, 2 to 6 hours, preferably 3 to 5 hours.
The invention also provides a method for preparing chlorine by catalytic oxidation of hydrogen chloride, which comprises the steps of contacting oxygen and hydrogen chloride with a catalyst, and carrying out catalytic oxidation reaction to prepare chlorine; the catalyst is the catalyst of the invention.
Under the catalytic oxidation process, the catalyst can be used for carrying out catalytic oxidation on the hydrogen chloride based on the existing means. For example, in the method for preparing chlorine by catalytic oxidation of hydrogen chloride, the molar ratio of hydrogen chloride to oxygen is 4: 1-1: 4; the temperature in the catalytic oxidation reaction process is 300-500 ℃; preferably, the reaction pressure is 0.1 to 1.0 MPa.
The method for preparing the chlorine gas by the catalytic oxidation of the hydrogen chloride comprises the step of carrying out the reaction for preparing the chlorine gas by the catalytic oxidation of the hydrogen chloride in a fixed bed reactor, wherein the volume space velocity of the hydrogen chloride is 2000-20000 h-1。
Preferably, the reaction for preparing chlorine by catalytic oxidation of hydrogen chloride is carried out in a fixed bed reactor, and the catalytic conditions are as follows: the reaction temperature is 300-500 ℃, preferably 350-420 ℃, the reaction pressure is 0.1-1.0 MPa, preferably 0.1-0.2 MPa, and the molar ratio of hydrogen chloride to oxygen is 4: 1-1: 4, more preferably 1: 1-1: 3, the volume space velocity of the hydrogen chloride is 2000-20000 h-1More preferably 4000 to 6000 hours-1。
Advantageous effects
1. The invention provides a method for selectively containing CuF by using CuClF2、CuCl2At least one of which is an active ingredient. The new catalyst has excellent catalytic activity and high tolerance stability under high temperature and high acid conditions.
2. The brand new catalyst provided by the invention has the hydrogen chloride conversion rate of over 82%, and more importantly, the catalyst is not inactivated in a 100-hour test and is compared with the existing CuCl2The catalyst of the same type shows excellent catalytic stability. Compared with the existing copper-based catalyst with high cost, the catalyst shows equivalent activity and stability.
3. Does not contain rare earth metal, and has higher activity of active components per unit mass, thereby having lower cost.
Drawings
FIG. 1 is an XRD spectrum of the catalyst of example 1
FIG. 2 shows XPS Total and Cu spectra of the catalyst of example 1
Detailed Description
One, CuF2-CuCl2Raw material ratio study
Example 1 (CuF)2With CuCl2The molar ratio is 1)
According to a molar ratio of 1: 1 weighing CuF2And CuCl2Adding 0.16g of the total amount of the components into 10ml of water, performing ultrasonic treatment at room temperature for 30min, then adding 0.8g of active alumina carrier, standing at room temperature for 12 hours, then drying in an oven at 65 ℃ for 12 hours, and roasting at 400 ℃ for 4 hours in a nitrogen atmosphere to obtain the catalyst, wherein the catalyst is marked as catalyst-1. The XRD and XPS patterns of the prepared material are shown in fig. 1 and 2, respectively. As can be seen from FIG. 1, the catalyst, in addition to the crystalline phase of the supported alumina, can be seen to have an active ingredient of mainly CuClF, in addition to which a small amount of CuF is present2. Although no CuCl was detected2But the existence of Cl element can be seen from the XPS result of FIG. 2, indicating that CuCl is present2Still partially present but not detectable by XRD due to low or highly dispersed content. As can be seen from fig. 2, the elemental composition of the catalyst surface was Al, Cu, F, O and Cl. The valence state of Cu is mainly divalent, and is accompanied by partial univalent, which indicates that the surface active components of the catalyst have interaction and are not in a single form.
The prepared catalyst is loaded into a fixed bed reactor, the temperature is raised to the reaction temperature of 370 ℃ under the protection of nitrogen, then the nitrogen is cut off, and mixed gas of 16ml/min hydrogen chloride flow and 32ml/min oxygen flow (O2/HCl is 2) is introduced, and the reaction pressure is 0.1 MPa. After 2 hours of reaction, the hydrogen chloride conversion was 85.2%, and after 20 hours of reaction, the hydrogen chloride conversion was 85.0%. The reaction was continued for 100 hours while the hydrogen chloride conversion remained at 85.0%.
Example 2 (CuF)2With CuCl2The molar ratio is 2)
According to a molar ratio of 2:1 weighing CuF2And CuCl2Adding 0.16g of the total amount of the raw materials into 10ml of water, performing ultrasonic treatment at room temperature for 30min, then adding 0.8g of active alumina carrier,standing for 12 hours at room temperature, then drying in an oven at 65 ℃ for 12 hours, and roasting at 400 ℃ for 4 hours in a nitrogen atmosphere to obtain the catalyst, which is marked as catalyst-2.
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the hydrogen chloride conversion was 82.4% and the hydrogen chloride conversion after 20 hours of the reaction was 82.2%.
Example 3 (CuF)2With CuCl2The molar ratio is 4)
According to a molar ratio of 4:1 weighing CuF2And CuCl2Adding 0.16g of the total amount of the components into 10ml of water, performing ultrasonic treatment at room temperature for 30min, then adding 0.8g of active alumina carrier, standing at room temperature for 12 hours, then drying in an oven at 65 ℃ for 12 hours, and roasting at 400 ℃ for 4 hours under the nitrogen atmosphere to obtain the catalyst, wherein the catalyst is marked as catalyst-4.
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. After 2 hours of reaction, the hydrogen chloride conversion rate was 78.1% by sampling and was 78.0% after 20 hours of reaction.
Example 4 (CuF)2With CuCl2The mol ratio is 0.5)
According to a molar ratio of 0.5: 1 weighing CuF2And CuCl2Adding 0.16g of the total amount of the components into 10ml of water, performing ultrasonic treatment at room temperature for 30min, then adding 0.8g of active alumina carrier, standing at room temperature for 12 hours, then drying in an oven at 65 ℃ for 12 hours, and roasting at 400 ℃ for 4 hours in a nitrogen atmosphere to obtain a catalyst, wherein the catalyst is marked as catalyst-0.5.
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the hydrogen chloride conversion was 87.3%, and the hydrogen chloride conversion after 20 hours of reaction was 77.2%.
As can be seen from examples 1 to 4, the A component CuF2With component B CuCl2The molar ratio of (A) has a large influence on the performance of the catalyst. CuCl2The higher the addition amount, the higher the initial conversion rate of hydrogen chloride can be obtained, but the stability is reduced; CuCl2The lower the amount added, the better the stability, but the lower the hydrogen chloride conversion. In CuF2With CuCl2Mole ofThe molar ratio is about 1-2: 1, and the conversion rate and stability of the hydrogen chloride can be considered at the same time.
2. Study of calcination temperature
Example 5
Compared with example 1, the only difference is that the roasting temperature is changed to 450 ℃, and the steps are as follows:
according to a molar ratio of 1: 1 weighing CuF2And CuCl2Adding 0.16g of the total amount of the mixed solution into 10ml of water, performing ultrasonic treatment at room temperature for 30min, then adding 0.8g of active alumina carrier, standing at room temperature for 12 hours, then drying in an oven at 65 ℃ for 12 hours, and roasting at 450 ℃ for 4 hours in a nitrogen atmosphere to obtain the catalyst, which is recorded as catalyst-450.
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the conversion of hydrogen chloride was 87.6% and the conversion of hydrogen chloride after 20 hours of the reaction was 87.2%.
Example 6
Compared with the example 1, the difference is only that the roasting temperature is changed to 500 ℃, and the steps are as follows:
according to a molar ratio of 1: 1 weighing CuF2And CuCl2Adding 0.16g of the total amount of the mixed solution into 10ml of water, performing ultrasonic treatment at room temperature for 30min, then adding 0.8g of active alumina carrier, standing at room temperature for 12 hours, then drying in an oven at 65 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours in a nitrogen atmosphere to obtain the catalyst, wherein the catalyst is marked as catalyst-500.
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the conversion of hydrogen chloride was 88.2% and the conversion of hydrogen chloride after 20 hours of the reaction was 88.1%.
As seen from examples 5 and 6, the activity of the catalyst was slightly improved by increasing the calcination temperature, but the variation range was not so large at 450 ℃ or higher.
Example 7
According to a molar ratio of 1: 1 weighing CuF2And CuCl2Adding 0.10 g of the catalyst into 10ml of ethanol, performing ultrasonic treatment for 30min at room temperature, adding 0.8g of active alumina carrier, standing for 24 hours at room temperature until the active alumina carrier is dried, and roasting for 5 hours at 400 ℃ in a nitrogen atmosphere to obtain the catalystThe agent, denoted as catalyst-1-E.
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the hydrogen chloride conversion was 87.7% and the hydrogen chloride conversion after 20 hours of the reaction was 87.5%.
Example 8
According to a molar ratio of 1: 1 weighing CuF2And CuCl2Adding 0.2 g of the catalyst into 10ml of ethanol, performing ultrasonic treatment at room temperature for 30min, adding 0.8g of P25 titanium dioxide, standing at room temperature for 24 h to dry, and roasting at 400 ℃ for 3 h in nitrogen atmosphere to obtain the catalyst, which is recorded as CuCl2+CuF2/P25-1-E。
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the conversion of hydrogen chloride was 85.7% and the conversion of hydrogen chloride after 20 hours of the reaction was 85.6%.
Example 9
According to a molar ratio of 1: 1 weighing CuF2And CuCl2And grinding 0.16g of the active alumina powder and 0.8g of active alumina powder carrier in a ball mill for 1 hour in a nitrogen protection atmosphere, and then roasting for 4 hours at 400 ℃ in a nitrogen atmosphere to obtain the catalyst, which is marked as catalyst-1-P.
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the conversion of hydrogen chloride was 78.2% and the conversion of hydrogen chloride after 20 hours of the reaction was 74.3%.
Example 10
The only difference compared to example 1 is that the temperature of the catalytic oxidation stage was changed to 410 ℃ and the steps were:
the catalyst of example 1 was subjected to a catalytic reaction under the reaction conditions of example 1 except that the reaction temperature was changed to 410 ℃. It was found that the conversion of hydrogen chloride was 90.2% and the conversion of hydrogen chloride after 20 hours of the reaction was 89.5%.
Comparative example 1
Compared with example 1, the difference is that CuCl is not added in the raw material2Preparation of CuF2/Al2O3A catalyst, comprising the steps of:
weighing CuF2(Mo)The same amount of CuCl as in example 12-CuF2Total molar amount) was added to 10ml of water, sonicated at room temperature for 30min, then 0.8g of activated alumina support was added, allowed to stand at room temperature for 12 hours, then dried in an oven at 65 ℃ for 12 hours, and calcined at 400 ℃ for 4 hours under nitrogen atmosphere to give a catalyst, designated as CuF2/Al2O3。
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the hydrogen chloride conversion was 75.2% and the hydrogen chloride conversion after 20 hours of the reaction was 72.0%.
Comparative example 2
Compared with example 1, the difference is that CuF is not added in the raw material2Preparation of CuCl2/Al2O3The catalyst comprises the following steps:
weighing CuCl2(molar quantity same as CuCl of example 1)2-CuF2Total molar weight) was added to 10ml of water, sonicated at room temperature for 30min, then 0.8g of activated alumina support was added, allowed to stand at room temperature for 12 hours, then dried in an oven at 65 ℃ for 12 hours, and calcined at 400 ℃ under nitrogen for 4 hours to produce the catalyst, designated as CuCl2/Al2O3。
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the conversion of hydrogen chloride was 80.2% and the conversion of hydrogen chloride after 20 hours of the reaction was 45.0%.
Comparative example 3
Compared with the example 1, the difference is that the preparation process of the catalyst is carried out under the air, and other parameters and the catalytic oxidation process are the same as those of the example 1;
according to a molar ratio of 1: 1 weighing CuF2And CuCl2Adding 0.16g of the total amount of the catalyst into 10ml of water, performing ultrasonic treatment for 30min at room temperature, adding 0.8g of active alumina carrier, standing for 12 hours at room temperature, drying in an oven at the temperature of 65 ℃ for 12 hours, and roasting at the temperature of 400 ℃ for 4 hours in the air atmosphere to obtain the catalyst, which is recorded as CuO-CuCl2//Al2O3-1。
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the conversion of hydrogen chloride was 55.4% and the conversion of hydrogen chloride after 20 hours of the reaction was 38.9%.
Comparative example 4 (without Carrier, CuF)2-CuCl2The mixture is used as a catalyst)
According to a molar ratio of 1: 1 weighing CuF2And CuCl2Totally 0.48 g, ball milling for 1 hour under the protection of nitrogen, then taking 1/3 to roast for 4 hours under the atmosphere of nitrogen at 400 ℃, obtaining the catalyst which is marked as CuCl2+CuF2-1。
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the conversion of hydrogen chloride was 81.1% and the conversion of hydrogen chloride after 20 hours of the reaction was 24.6%.
Comparative example 5 (without Carrier, CuF)2As a catalyst)
0.16g of CuF was weighed out2The powder was used as a catalyst, and the catalytic reaction was carried out under the reaction conditions of example 1. It was found that the conversion of hydrogen chloride was 65.2% and the conversion of hydrogen chloride after 20 hours of the reaction was 3.4%.
Comparative example 6
Compared with the example 1, the difference is that the sintering treatment is not carried out, and the steps are as follows:
according to a molar ratio of 1: 1 weighing CuF2And CuCl2A total of 0.16 grams was added to 10ml of water, sonicated at room temperature for 30min, then 0.8 grams of the activated alumina support was added, allowed to stand at room temperature for 12 hours, and then dried in an oven at 65 ℃ for 12 hours. The catalyst was prepared and reported as catalyst-1-unburned.
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the conversion of hydrogen chloride was 81.4% and the conversion of hydrogen chloride after 20 hours of the reaction was 29.9%.
Comparative example 7
Compared with the example 1, the difference is that the calcination temperature in the catalyst preparation process is 300 ℃, other parameters are the same as the example 1, and the steps are as follows:
according to a molar ratio of 1: 1 weighing CuF2And CuCl2Adding 0.16g of the total amount of the raw materials into 10ml of water, performing ultrasonic treatment at room temperature for 30min, then adding 0.8g of active alumina carrier, and performing ultrasonic treatment at room temperatureStanding for 12 hours, drying in an oven at 65 ℃ for 12 hours, and roasting at 300 ℃ for 4 hours in a nitrogen atmosphere to obtain the catalyst, which is recorded as catalyst-1-300.
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the hydrogen chloride conversion was 75.2% and the hydrogen chloride conversion after 20 hours of the reaction was 38.0%.
Comparative example 8
Compared with the example 1, the difference is that the calcination temperature in the catalyst preparation process is 600 ℃, other parameters are the same as the example 1, and the steps are as follows:
according to a molar ratio of 1: 1 weighing CuF2And CuCl2Adding 0.16g of the total amount of the mixed solution into 10ml of water, performing ultrasonic treatment at room temperature for 30min, then adding 0.8g of active alumina carrier, standing at room temperature for 12 hours, then drying in a 65 ℃ oven for 12 hours, and roasting at 600 ℃ for 4 hours under the nitrogen atmosphere to obtain the catalyst, wherein the catalyst is marked as catalyst-1-600.
The prepared catalyst was subjected to catalytic reaction according to the reaction conditions of example 1. It was found that the hydrogen chloride conversion was 45.9%, and the hydrogen chloride conversion after 20 hours of the reaction was 45.2%.
Discussion:
from examples 1-4, comparative examples 1-2, it can be seen that CuF was used2-CuCl2The catalyst with completely new catalytic active components can be obtained by roasting, and the catalyst can show excellent catalytic activity and stability.
From example 1 and comparative example 3, it can be seen that the calcination atmosphere during the preparation of the catalyst is also critical to the activity and stability of the catalyst. Calcination in an air atmosphere will cause CuF2The required active component is not obtained, which is not beneficial to the performance of the catalyst.
From example 1, comparative examples 4 to 5, it can be seen that the role of the carrier is obvious and is essential, in particular, in improving stability.
From examples 1, 5 and 6 and comparative examples 6, 7 and 8, it can be seen that the calcination treatment of the catalyst of the present invention is critical to the chemical phase transition, calcination is an essential step, and the calcination temperature has a suitable range. Too low a temperature to obtain satisfactory activity and stability may result from failure to form the desired crystalline phase; at too high a temperature, satisfactory activity and stability cannot be obtained, which is generally caused by the agglomeration of grains due to too high a temperature.

Claims (10)

1. A catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride comprises a carrier and an active component loaded on the carrier, and is characterized in that the active component contains CuClF.
2. The catalyst for preparing chlorine by catalytic oxidation of hydrogen chloride as claimed in claim 1, wherein the active ingredient comprises CuF2、CuCl2At least one of (1).
3. The catalyst for the catalytic oxidation of hydrogen chloride to chlorine as claimed in claim 1, wherein the active ingredient is formed by a catalyst comprising CuF2、CuCl2The active ingredient raw materials are roasted in protective atmosphere to prepare;
preferably, the content of CuClF in the active ingredient is greater than or equal to 20 mol%; more preferably 50 mol% or more; still more preferably 60 mol% or more;
preferably, in the active ingredient raw material, CuF2/CuCl2The molar ratio of (1-4: 1-2); further preferably 1-2: 1;
preferably, the roasting temperature is 350-550 ℃.
4. The catalyst for producing chlorine through catalytic oxidation of hydrogen chloride according to any one of claims 1 to 3, wherein the carrier is one or more of activated alumina, anatase-A type titania, rutile-R type titania, cordierite, and silica;
preferably, in the catalyst, the weight ratio of the active component to the carrier is 0.05-0.35: 1; more preferably 0.1 to 0.25: 1.
5. A method for preparing the catalyst according to any one of claims 1 to 4, wherein the catalyst comprises a carrier and CuF2、CuCl2The mixed raw materials are roasted at the temperature of 350-550 ℃ in protective atmosphere to obtain the composite material.
6. The method for preparing a catalyst according to claim 5, wherein the mixed raw materials are prepared by mixing the respective raw materials in a solid phase, or by mixing in a wet process and then drying;
preferably, the wet mixing solvent is at least one of water, C1-C4 alcohol and acetone;
preferably, in the mixed raw materials, CuF2/CuCl2The molar ratio of (1-4: 1-2); further preferably 1-2: 1;
CuF2、CuCl2the weight ratio of the total weight of the carrier to the carrier is 0.05-0.35: 1; more preferably 0.1 to 0.25: 1.
7. The method for preparing a catalyst according to any one of claims 5 to 6, wherein the protective atmosphere is at least one of nitrogen gas and inert gas;
preferably, the roasting temperature is 400-500 ℃;
preferably, the roasting time is 2-6 h, preferably 3-5 h.
8. A method for preparing chlorine by catalytic oxidation of hydrogen chloride is characterized in that oxygen and hydrogen chloride are contacted with a catalyst to carry out catalytic oxidation reaction to prepare chlorine; the catalyst is the catalyst as described in any one of claims 1 to 4 or the catalyst prepared by the preparation method as described in any one of claims 5 to 7.
9. The process for preparing chlorine by catalytic oxidation of hydrogen chloride according to claim 8, wherein the molar ratio of hydrogen chloride to oxygen is from 4: 1-1: 4; the temperature in the catalytic oxidation reaction process is 300-500 ℃; preferably, the reaction pressure is 0.1 to 1.0 MPa.
10. The method for preparing chlorine through catalytic oxidation of hydrogen chloride as claimed in claim 9, wherein the reaction for preparing chlorine through catalytic oxidation of hydrogen chloride is carried out in a fixed bed reactor, and the volume space velocity of hydrogen chloride is 2000-20000 h-1。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2818163A1 (en) * 2000-12-19 2002-06-21 Renault Catalyst preparation, for burning-off diesel soot, includes reaction between copper chloride and copper difluoride, followed by hot oxidation
CN101125297A (en) * 2007-09-03 2008-02-20 清华大学 Oxychlorination catalyst and application thereof
CN102264674A (en) * 2008-12-22 2011-11-30 纳幕尔杜邦公司 Method of hydrodechlorination to produce dihydrofluorinated olefins
CN111013614A (en) * 2019-11-06 2020-04-17 浙江师范大学 Catalyst carrier and catalyst for preparing chlorine by oxidizing hydrogen chloride, and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2818163A1 (en) * 2000-12-19 2002-06-21 Renault Catalyst preparation, for burning-off diesel soot, includes reaction between copper chloride and copper difluoride, followed by hot oxidation
CN101125297A (en) * 2007-09-03 2008-02-20 清华大学 Oxychlorination catalyst and application thereof
CN102264674A (en) * 2008-12-22 2011-11-30 纳幕尔杜邦公司 Method of hydrodechlorination to produce dihydrofluorinated olefins
CN111013614A (en) * 2019-11-06 2020-04-17 浙江师范大学 Catalyst carrier and catalyst for preparing chlorine by oxidizing hydrogen chloride, and preparation method and application thereof

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