CN114713250B - Catalyst for preparing chlorine by catalytic oxidation of hydrogen chloride and preparation method and application thereof - Google Patents
Catalyst for preparing chlorine by catalytic oxidation of hydrogen chloride and preparation method and application thereof Download PDFInfo
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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 by hydrogen chloride catalytic oxidation, which comprises a carrier and an active ingredient loaded on the carrier, wherein the active ingredient contains CuClF. The invention also provides the preparation of the catalyst and the application of the catalyst in hydrogen chloride catalytic oxidation. The catalyst of the invention has the characteristics of high activity, high stability and low cost.
Description
Technical field:
the invention belongs to the fields of catalysts and environmental protection, and particularly relates to a catalyst for preparing chlorine by catalytic oxidation of hydrogen chloride, a preparation method and application thereof.
The background technology is as follows:
chlorine is an important chemical raw material. However, in the production of domestic chlorine-related products, there is a general problem that the utilization rate of chlorine atoms is low. One mole of byproduct hydrogen chloride is produced per mole of chlorine gas consumed. According to statistics, the total amount of byproduct hydrogen chloride in China reaches 500 ten thousand tons in 2015. At present, most of byproduct hydrogen chloride is absorbed by water to prepare hydrochloric acid. Along with the gradual supply and demand of the hydrochloric acid market and the increasingly strict environmental protection requirement, the hydrogen chloride is converted into chlorine, so that the recycling is realized, and the method becomes an important requirement for sustainable development of the chlorine industry.
The conversion of hydrogen chloride to chlorine includes direct oxidation, catalytic oxidation, and electrolytic processes. Among them, the catalytic oxidation method is the most economical and effective method recognized in the industry. Since 1870, the process of converting hydrogen chloride into chlorine gas in one step by using copper chloride as a catalyst (called the Deacon process) has been introduced for the first time by Deacon, and catalytic oxidation has been increasingly used. The types of catalysts reported so far are: copper-based, chromium-based, cerium-based, and ruthenium-based catalysts. The noble metal ruthenium-based catalyst has good low-temperature activity and stability, so that industrialization is realized. British patent GB1046313 discloses a supported RuCl with silica gel, pumice and Al2O3 as carriers 3 The catalyst and the reaction temperature is 200-500 ℃. U.S. Pat. No. 3,182 discloses a method of treating a patient with RuO 2 Catalysts based on different ruthenium componentsStarting materials, e.g. RuCl 3 、Ru 3 (CO) 12 、[Ru(NH 3 ) 6 ]Cl 3 And the like, with rutile titanium dioxide as a carrier, the conversion rate of hydrogen chloride can reach 85-90% under the continuous operation of 15000 h. European patent EP2026905 is improved on the basis of Japanese Sumitomo US5871707, and the conversion rate of hydrogen chloride can be maintained at 40% in 7000h operation by using tin dioxide and aluminum oxide as a carrier to support ruthenium dioxide. U.S. patent 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, ruthenium is a noble metal, and thus, the cost is high and the international market price is greatly floating, so that although ruthenium catalysts have been commercialized, research on non-noble metal catalysts is continued.
Copper-based catalysts are a current research hotspot because of the lack of toxicity issues with hexavalent chromium. Chinese patent CN101862663A, CN102658149A, CN104923239A, CN105268448A, CN105289631A, CN105642318A discloses a series of copper-based catalysts with non-noble metals Cu and transition metals V as main components, and alkali metals K and Na, rare earths Ce, la, sm and Pr as auxiliary agents together forming a main body part, the carrier being alumina or silica coated alumina. The conversion rate of the catalyst is higher and is more than 80%. Such patents are similar to US5707919 except that no chromium is added, but that a relatively expensive rare earth metal is required to be added, typically in an amount of about 10 wt%. To date, in order to improve the stability of copper catalysts, the strategy commonly adopted by researchers has been to add adjuvants, mainly rare earth metals with higher cost, to form complex salts with high boiling point, in order to reduce their volatility.
In view of the above, there are still a number of disadvantages in the prior art. Therefore, the copper-based catalyst with high activity, high stability and low cost is continuously developed, and the method 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 the chlorine by catalytic oxidation of hydrogen chloride, which has high activity, high stability and low cost.
The second object of the invention is to provide a method for preparing the catalyst.
The third object of the invention is to provide an application of the catalyst (namely, a method for preparing chlorine by hydrogen chloride catalytic oxidation).
Some CuCl in the prior art 2 Application as hydrogen chloride catalytic oxidation catalyst, but less relates to CuF 2 The application of the catalyst as a main catalyst for the catalytic oxidation of hydrogen chloride is reported. Furthermore, the present inventors have found that CuCl 2 、CuF 2 As a hydrogen chloride catalytic oxidation catalyst, the catalytic activity is not ideal, the tolerance to the high acidity and high temperature conditions of hydrogen chloride is not strong, and aiming at the technical problem, the invention provides the following improvement scheme:
the catalyst for preparing chlorine by catalytic oxidation of hydrogen chloride comprises a carrier and an active ingredient loaded on the carrier, wherein the active ingredient contains CuClF.
The invention researches find that CuClF is adopted as a catalytic active component, and the CuClF can show excellent catalytic activity, and more importantly, the CuClF can well withstand high-temperature and high-acid etching conditions in a catalytic process and can show excellent catalytic stability.
Preferably, the active ingredient contains CuF 2 、CuCl 2 At least one of them.
In the present invention, a CuF comprising CuClF and at least one CuF is used 2 、CuCl 2 Can further synergistically improve the catalytic activity and the catalytic stability under high-temperature and high-acid conditions.
The active ingredient of the invention is prepared by the method comprising CuF 2 、CuCl 2 The active ingredient raw materials of (2) are prepared by roasting in protective atmosphere;
preferably, the content of CuClF in the active ingredient is greater than or equal to 20mol%; more preferably 50mol% or more; more preferably, the amount is 60mol% or more.
Preferably, in the active ingredient raw material, cuF 2 /CuCl 2 Molar ratio of (2) is1-4:1-2; further preferably 1 to 2:1. The present inventors have found that a catalyst having both good catalytic activity and stability can be obtained at a preferable ratio.
Preferably, the temperature of the calcination is 350 to 550 ℃, and more preferably 400 to 500 ℃. The calcination time may be, for example, 2 to 6 hours, and may be further 3 to 5 hours.
In the present invention, there is no particular limitation on the type of support, and for example, it may be activated alumina (Al 2 O 3 ) Titanium dioxide (anatase-a type), titanium dioxide (rutile-R type), cordierite, silica (SiO 2 ) One or more of the following.
In the catalyst, the weight ratio of the active ingredients to the 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 supporting and CuF 2 、CuCl 2 Is baked in protective atmosphere at 350-550 ℃.
According to the invention, the composite raw material is baked in the atmosphere, so that a new catalyst loaded with the active ingredients can be obtained, 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 materials, or mixing the raw materials through a wet method and drying to prepare the mixed raw materials;
preferably, the wet mixed solvent is at least one of water, C1-C4 alcohol and acetone;
the liquid phase mixing is, for example, impregnation mixing, and the steps are, for example, impregnation of the support with CuF dispersed therein 2 、CuCl 2 Or an organic solution such as ethanol or acetone. The temperature of the liquid phase dipping process is room temperature, the dipping time is 2-12 hours, and the dipping can be performed for 6-24 hours at 30-120 ℃. The solid phase mixing is, for example, grinding, ball milling, etc.
Preferably, in the mixed raw material, cuF 2 /CuCl 2 The molar ratio of (2) is 1-4:1-to-the-upper2; further preferably 1 to 2:1; still more preferably 1 to 1.5:1. It was found that the catalyst of the active ingredient obtained by calcination under the preferred conditions can exhibit more excellent catalytic activity and stability.
Preferably, cuF 2 、CuCl 2 The weight ratio of the total weight of the catalyst 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 which does not contain oxidation or reducing components, such as: at least one of nitrogen and inert gases (argon, helium, etc.).
In the present invention, the baking temperature is preferably 400 to 500 ℃.
In the present invention, the time for the calcination treatment is, for example, 2 to 6 hours, preferably 3 to 5 hours.
The invention also provides a method for preparing chlorine by hydrogen chloride catalytic oxidation, 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.
The catalyst can be used for catalytic oxidation of 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 to 1:4, a step of; the temperature of the catalytic oxidation reaction process is 300-500 ℃; preferably, the reaction pressure is 0.1 to 1.0MPa.
In the method for preparing the chlorine by hydrogen chloride catalytic oxidation, the reaction for preparing the chlorine by hydrogen chloride catalytic oxidation is carried out in a fixed bed reactor, and 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 under the following catalytic conditions: the reaction temperature is 300-500 ℃, more suitably 350-420 ℃, the reaction pressure is 0.1-1.0 MPa, more suitably 0.1-0.2 MPa, and the molar ratio of hydrogen chloride to oxygen is 4:1 to 1:4, more preferably 1:1 to 1:3, the volume space velocity of the hydrogen chloride is 2000 to the upper20000h -1 More preferably 4000 to 6000 hours -1 。
Advantageous effects
1. The invention provides a method for selectively containing CuF by CuClF 2 、CuCl 2 At least one of which is an active ingredient. The novel catalyst has excellent catalytic activity and high-temperature and high-acid condition tolerance stability.
2. The brand new catalyst has the hydrogen chloride conversion rate reaching more than 82 percent, and more importantly, no deactivation is observed in the test of 100 hours, compared with the prior CuCl 2 Equivalent types of catalysts exhibit excellent catalytic stability. Compared with the existing copper-based catalyst with high cost, the catalyst has equivalent activity and stability.
3. The rare earth metal is not contained, and the activity of the active component per unit mass is higher, so that the cost is lower.
Drawings
FIG. 1 is an XRD spectrum of the catalyst of example 1
FIG. 2 shows XPS and Cu spectra of the catalyst of example 1
Detailed Description
1. CuF (Curie point) 2 -CuCl 2 Study of raw Material proportion
Example 1 (CuF) 2 With CuCl 2 Molar ratio of 1
According to the mole ratio of 1:1 weighing CuF 2 And CuCl 2 0.16g in total is added into 10ml of water, ultrasonic is carried out for 30min at room temperature, then 0.8g of active alumina carrier is added, the mixture is kept stand for 12 hours at room temperature, then dried for 12 hours in a 65 ℃ oven, and baked for 4 hours under 400 ℃ nitrogen atmosphere, thus obtaining the catalyst which is named as catalyst-1. XRD and XPS patterns of the material obtained are shown in FIGS. 1 and 2, respectively. As can be seen from FIG. 1, the catalyst is seen to be mainly CuClF as the active ingredient, except for the crystalline phase of the alumina support, and in addition to a small amount of CuF 2 . Although CuCl is not detected 2 The presence of Cl element is evident from the XPS results of FIG. 2, which illustrates CuCl 2 Is still partly present but due to very low content orHighly dispersed and thus undetectable by XRD. As can be seen from fig. 2, the elemental composition of the catalyst surface is Al, cu, F, O and Cl. The valence of Cu is mainly bivalent, and is accompanied by partial monovalent, which indicates that the interaction exists between the surface active components of the catalyst, and the catalyst is not in a single form.
The prepared catalyst was charged into a fixed bed reactor, the temperature was raised to a reaction temperature of 370℃under nitrogen protection, then the nitrogen was turned off, and a mixed gas of 16ml/min of hydrogen chloride and 32ml/min of oxygen (O2/HCl=2) was introduced, with a reaction pressure of 0.1MPa. The hydrogen chloride conversion was 85.2% after 2 hours of reaction and 85.0% after 20 hours of reaction. The reaction was continued for 100 hours with the hydrogen chloride conversion remaining at 85.0%.
Example 2 (CuF) 2 With CuCl 2 Molar ratio of 2
According to the mole ratio of 2:1 weighing CuF 2 And CuCl 2 0.16g in total is added into 10ml of water, ultrasonic is carried out for 30min at room temperature, then 0.8g of active alumina carrier is added, the mixture is kept stand for 12 hours at room temperature, then dried for 12 hours in a 65 ℃ oven, and baked for 4 hours under 400 ℃ nitrogen atmosphere, thus obtaining the catalyst, which is named as catalyst-2.
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 82.4% and after 20 hours of reaction the hydrogen chloride conversion was found to be 82.2%.
Example 3 (CuF) 2 With CuCl 2 Molar ratio of 4
According to the mole ratio of 4:1 weighing CuF 2 And CuCl 2 0.16g in total is added into 10ml of water, ultrasonic is carried out for 30min at room temperature, then 0.8g of active alumina carrier is added, the mixture is kept stand for 12 hours at room temperature, then dried for 12 hours in a 65 ℃ oven, and baked for 4 hours under 400 ℃ nitrogen atmosphere, thus obtaining the catalyst, which is denoted as catalyst-4.
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. After 2 hours of reaction, the conversion of hydrogen chloride was 78.1% by sampling and the conversion of hydrogen chloride after 20 hours of reaction was 78.0%.
Example 4 (CuF) 2 With CuCl 2 Molar ratio of 0.5
According to the mole ratio of 0.5:1 weighing CuF 2 And CuCl 2 0.16g in total is added into 10ml of water, ultrasonic is carried out for 30min at room temperature, then 0.8g of active alumina carrier is added, the mixture is kept stand for 12 hours at room temperature, then dried for 12 hours in a 65 ℃ oven, and baked for 4 hours under 400 ℃ nitrogen atmosphere, thus obtaining the catalyst which is named as catalyst-0.5.
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 87.3% and after 20 hours of reaction the hydrogen chloride conversion was reduced to 77.2%.
As can be seen from examples 1 to 4, component A CuF 2 With a B component CuCl 2 Has a great influence on the performance of the catalyst. CuCl 2 The higher the addition amount, the higher the initial conversion of hydrogen chloride can be obtained, but the stability is lowered; cuCl 2 The lower the amount added, the better the stability, but the lower the hydrogen chloride conversion. At CuF 2 With CuCl 2 The molar ratio is 1-2:1, and the conversion rate and the stability of the hydrogen chloride can be simultaneously achieved.
2. Calcination temperature study
Example 5
The only difference compared to example 1 is that the firing temperature was changed to 450℃as follows:
according to the mole ratio of 1:1 weighing CuF 2 And CuCl 2 0.16g in total is added into 10ml of water, ultrasonic is carried out for 30min at room temperature, then 0.8g of active alumina carrier is added, the mixture is kept stand for 12 hours at room temperature, then dried for 12 hours in a 65 ℃ oven, and baked for 4 hours under the nitrogen atmosphere at 450 ℃ to prepare the catalyst, which is named as a catalyst-450.
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 87.6% and after 20 hours of reaction the hydrogen chloride conversion was found to be 87.2%.
Example 6
The only difference compared to example 1 is that the firing temperature was changed to 500℃as follows:
according to the mole ratio of 1:1 weighing CuF 2 And CuCl 2 0.16g in total is added into 10ml of water, ultrasonic is carried out for 30min at room temperature, then 0.8g of active alumina carrier is added, the mixture is kept stand for 12 hours at room temperature, then dried for 12 hours in a 65 ℃ oven, and baked for 4 hours under the nitrogen atmosphere at 500 ℃ to prepare the catalyst, which is marked as a catalyst-500.
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 88.2% and after 20 hours of reaction the hydrogen chloride conversion was found to be 88.1%.
Examples 5 and 6 show that the activity of the catalyst is slightly improved when the calcination temperature is increased, but the variation range is not large when the temperature is 450 ℃.
Example 7
According to the mole ratio of 1:1 weighing CuF 2 And CuCl 2 A total of 0.10 g was added to 10ml of ethanol, sonicated at room temperature for 30min, then 0.8g of active alumina carrier was added, and left standing at room temperature for 24 hours to dry, then calcined at 400℃under nitrogen atmosphere for 5 hours to prepare a catalyst, designated as catalyst-1-E.
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 87.7% and after 20 hours of reaction the hydrogen chloride conversion was found to be 87.5%.
Example 8
According to the mole ratio of 1:1 weighing CuF 2 And CuCl 2 Adding 0.2 g of the total amount into 10ml of ethanol, carrying out ultrasonic treatment at room temperature for 30min, adding 0.8g of P25 titanium dioxide, standing at room temperature for 24 hours until the total amount is dry, and roasting at 400 ℃ under nitrogen atmosphere for 3 hours to obtain a catalyst which is marked as CuCl 2 +CuF 2 /P25-1-E。
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 85.7% and after 20 hours of reaction the hydrogen chloride conversion was found to be 85.6%.
Example 9
According to the mole ratio of 1:1 weighing CuF 2 And CuCl 2 Together with 0.16g of an activated alumina powder carrier, in a ball mill, for 1 hour under nitrogen protection, then in a nitrogen atmosphereRoasting for 4 hours at 400 ℃ under nitrogen atmosphere to obtain the catalyst, which is named as catalyst-1-P.
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 78.2% and after 20 hours of reaction the hydrogen chloride conversion was found to be 74.3%.
Example 10
The only difference compared to example 1 is that the temperature of the catalytic oxidation stage is changed to 410 ℃, the steps are:
the catalyst of example 1 was subjected to catalytic reaction in accordance with the reaction conditions of example 1, except that the reaction temperature was changed to 410 ℃. The hydrogen chloride conversion was found to be 90.2% and 89.5% after 20 hours of reaction.
Comparative example 1
Compared with example 1, the difference is that CuCl is not added into the raw materials 2 Preparation of CuF 2 /Al 2 O 3 The catalyst comprises the following steps:
weighing CuF 2 (molar amount of CuCl of example 1) 2 -CuF 2 Total molar amount) was added to 10ml of water, sonicated at room temperature for 30min, then 0.8g of an activated alumina support was added, left to stand at room temperature for 12 hours, then dried in an oven at 65℃for 12 hours, and calcined under nitrogen atmosphere at 400℃for 4 hours to prepare a catalyst, designated CuF 2 /Al 2 O 3 。
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 75.2% and after 20 hours of reaction the hydrogen chloride conversion was found to be 72.0%.
Comparative example 2
In comparison with example 1, the only difference is that no CuF was added to the raw material 2 Preparation of CuCl 2 /Al 2 O 3 The catalyst comprises the following steps:
weighing CuCl 2 (molar amount of CuCl of example 1) 2 -CuF 2 Total molar amount) was added to 10ml of water, sonicated at room temperature for 30min, then 0.8g of activated alumina support was added, left to stand at room temperature for 12 hours, then dried in an oven at 65℃for 12 hours, and baked under nitrogen atmosphere at 400 ℃Burning for 4 hours to obtain a catalyst, which is named as CuCl 2 /Al 2 O 3 。
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 80.2% and 45.0% after 20 hours of reaction.
Comparative example 3
The only difference compared with example 1 is that the catalyst preparation process is carried out under air, other parameters and the catalytic oxidation process are the same as in example 1;
according to the mole ratio of 1:1 weighing CuF 2 And CuCl 2 Adding 0.16g of the total amount into 10ml of water, carrying out ultrasonic treatment at room temperature for 30min, adding 0.8g of active alumina carrier, standing at room temperature for 12 hours, drying in a 65 ℃ oven for 12 hours, and roasting for 4 hours in an air atmosphere at 400 ℃ to obtain a catalyst which is named as CuO-CuCl 2 //Al 2 O 3 -1。
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 55.4% and after 20 hours of reaction the hydrogen chloride conversion was found to be 38.9%.
Comparative example 4 (no support, cuF) 2 -CuCl 2 The mixture is used as a catalyst
According to the mole ratio of 1:1 weighing CuF 2 And CuCl 2 Ball milling under nitrogen protection for 1 hr, and roasting at 400 deg.c for 4 hr in 1/3 to obtain catalyst named CuCl 2 +CuF 2 -1。
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 81.1% and 24.6% after 20 hours of reaction.
Comparative example 5 (no support, cuF) 2 As a catalyst
0.16g of CuF was weighed out 2 The powder was used as a catalyst and the catalytic reaction was carried out according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 65.2% and after 20 hours of reaction the hydrogen chloride conversion was found to be 3.4%.
Comparative example 6
The only difference from example 1 is that no sintering treatment was performed, the steps being:
according to the mole ratio of 1:1 weighing CuF 2 And CuCl 2 A total of 0.16g was added to 10ml of water and sonicated at room temperature for 30min, then 0.8g of 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 obtained and designated as catalyst-1-unburnt.
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 81.4% and after 20 hours of reaction the hydrogen chloride conversion was found to be 29.9%.
Comparative example 7
The only difference compared to example 1 is that the calcination temperature during the catalyst preparation is 300℃and the other parameters are the same as in example 1, the steps are:
according to the mole ratio of 1:1 weighing CuF 2 And CuCl 2 0.16g in total is added into 10ml of water, ultrasonic is carried out for 30min at room temperature, then 0.8g of active alumina carrier is added, the mixture is kept stand for 12 hours at room temperature, then dried for 12 hours in a 65 ℃ oven, and baked for 4 hours under the nitrogen atmosphere at 300 ℃ to prepare the catalyst, which is marked as the catalyst-1-300.
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 75.2% and after 20 hours of reaction the hydrogen chloride conversion was found to be 38.0%.
Comparative example 8
The only difference compared to example 1 is that the calcination temperature during the catalyst preparation is 600 ℃, and other parameters are the same as in example 1, the steps are:
according to the mole ratio of 1:1 weighing CuF 2 And CuCl 2 0.16g in total is added into 10ml of water, ultrasonic is carried out for 30min at room temperature, then 0.8g of active alumina carrier is added, the mixture is kept stand for 12 hours at room temperature, then dried for 12 hours in a 65 ℃ oven, and baked for 4 hours under the atmosphere of 600 ℃ nitrogen, thus obtaining the catalyst, which is named as catalyst-1-600.
The catalyst prepared was subjected to catalytic reaction according to the reaction conditions of example 1. The hydrogen chloride conversion was found to be 45.9% and after 20 hours of reaction the hydrogen chloride conversion was found to be 45.2%.
Discussion:
from examples 1-4, comparative examples 1-2, it can be seen that CuF was used 2 -CuCl 2 The calcination can be performed to obtain a catalyst having a novel catalytic active ingredient, and the catalyst can exhibit excellent catalytic activity and stability.
From example 1, comparative example 3, it can be seen that the calcination atmosphere during the catalyst preparation process is also critical to the activity and stability of the catalyst. Calcination in an air atmosphere will cause CuF 2 The oxidation of (3) does not result in the desired active component, which is detrimental to the catalyst performance.
From example 1, comparative examples 4-5, it can be seen that the effect of the carrier is evident, in particular, indispensable in improving stability.
From examples 1, 5, 6, and comparative examples 6, 7, 8, it can be seen that the catalysts of the present invention, the calcination treatment is critical for chemical phase transformation, calcination is an essential step, and the calcination temperature has a proper range. Too low a temperature to obtain satisfactory activity and stability may result from the inability to form the desired crystalline phase; too high a temperature, which generally results from agglomeration of the grains, does not give satisfactory activity and stability.
Claims (16)
1. 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 perform catalytic oxidation reaction to prepare chlorine;
the catalyst comprises a carrier and an active ingredient loaded on the carrier, wherein the active ingredient contains CuClF;
the catalyst is prepared by the steps of containing a carrier and CuF 2 、CuCl 2 Roasting the mixed raw materials of (2) in a protective atmosphere at the temperature of 350-550 ℃;
CuF 2 /CuCl 2 the molar ratio of (1-4) to (1-2);
CuF 2 、CuCl 2 the weight ratio of the total weight of the catalyst to the carrier is 0.05-0.35:1;
roasting for 2-6 hours;
the molar ratio of the hydrogen chloride to the oxygen is (4:1) - (1:4); the temperature of the catalytic oxidation reaction process is 300-500 ℃; the reaction pressure is 0.1-1.0 MPa.
2. The method of claim 1, wherein the mixed raw materials are obtained by solid phase mixing of the raw materials or by wet mixing and drying of the mixed raw materials.
3. The method of claim 2, wherein the wet mixed solvent is at least one of water, a C1 to C4 alcohol, and acetone.
4. The method of claim 1, wherein the mixed raw material is CuF 2 /CuCl 2 The molar ratio of (1) to (2) is 1.
5. The method of claim 1, wherein CuF 2 、CuCl 2 The weight ratio of the total weight of the carrier to the carrier is 0.1-0.25:1.
6. The method of claim 1, wherein the protective atmosphere is at least one of nitrogen and an inert gas.
7. The method of claim 1, wherein the firing temperature is 400 to 500 ℃.
8. The method of claim 1, wherein the firing time is 3 to 5 hours.
9. The method of claim 1, wherein said active ingredient further comprises CuF 2 、CuCl 2 At least one of them.
10. The method of claim 1, wherein the CuClF is present in an amount greater than or equal to 20 mole percent of the active component of the catalyst.
11. The method of claim 1, wherein the CuClF is present in an amount greater than or equal to 50 mole percent of the active component of the catalyst.
12. The method of claim 1, wherein the CuClF is present in an amount greater than or equal to 60 mole percent of the active component of the catalyst.
13. The method of claim 1, wherein the support is one or more of activated alumina, anatase-a titania, rutile-R titania, cordierite, silica.
14. The method of claim 1, wherein the weight ratio of active ingredient to carrier in the catalyst is 0.05-0.35:1.
15. The method of claim 1, wherein the weight ratio of active ingredient to carrier in the catalyst is 0.1-0.25:1.
16. The process according to claim 1, wherein the reaction for preparing chlorine by 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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