CN117753470A - Catalyst for preparing chlorine, preparation method and application thereof - Google Patents

Catalyst for preparing chlorine, preparation method and application thereof Download PDF

Info

Publication number
CN117753470A
CN117753470A CN202211122117.8A CN202211122117A CN117753470A CN 117753470 A CN117753470 A CN 117753470A CN 202211122117 A CN202211122117 A CN 202211122117A CN 117753470 A CN117753470 A CN 117753470A
Authority
CN
China
Prior art keywords
catalyst
chloride
nitrate
hours
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211122117.8A
Other languages
Chinese (zh)
Inventor
冉令卫
曹传宗
易光铨
殷艳欣
李作金
孙康
黎源
华卫琦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202211122117.8A priority Critical patent/CN117753470A/en
Publication of CN117753470A publication Critical patent/CN117753470A/en
Pending legal-status Critical Current

Links

Abstract

The invention relates to a catalyst for preparing chlorine and application thereof. The catalyst is of a structure that an inorganic nonmetallic material is doped by thallium to coat an active component; the catalyst provided by the invention has high conversion rate and good stability when being used for the reaction of preparing chlorine by hydrogen chloride oxidation, and simultaneously solves the problems of poor abrasion resistance, and reduced catalyst activity caused by easy falling and pulverization of active components during long-period operation of the catalyst used in the fluidized bed reaction process.

Description

Catalyst for preparing chlorine, preparation method and application thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst for preparing chlorine and application thereof.
Background
Chlorine is an important chemical raw material and is widely applied to the textile, medicine, petrochemical industry, drinking water disinfection, environmental protection industry and the likeMultiple fields. When chlorine is applied to chemical synthesis, most chlorine-related reactions have low utilization rate of chlorine atoms, so that a large amount of chlorine resources are lost, and the lost chlorine resources exist in the form of byproduct hydrogen chloride. According to statistics of related documents, with the development of the China chemical industry, the production scale of products such as polyvinyl chloride, MDI, TDI, methane chloride, trichloroethylene and the like is enlarged, the total amount of byproduct hydrogen chloride is over 500 ten thousand t/a, and taking toluene-2, 4-diisocyamate (TDI) as an example, the generation of 1 molecule of TDI is accompanied with the generation of 4 molecules of byproduct hydrogen chloride: CH (CH) 3 C 6 H 3 (NH 2 )2+2COCl 2 CH 3 C 6 H 3 (NCO) 2 +4HCl. The utilization of chlorine atoms is zero and all chlorine atoms are converted to hydrogen chloride by-products. The hydrogen chloride market is limited, the demand is small, the environmental cost is high, and the terminal treatment cost is high; if the waste water is not fully recycled, the development of green chemistry is not facilitated. Therefore, people hope to find an economical and applicable process for preparing chlorine from hydrogen chloride, and the closed cycle and zero emission of chlorine are realized, so that the research significance is very important.
As early as the nineteenth century, foreign researchers have begun to study the process of producing chlorine from hydrogen chloride. To date, three main approaches are involved: electrolytic, direct and catalytic oxidation processes. Among them, the catalytic oxidation method with low energy consumption and simple operation is favored by related industries, and becomes a research hot spot in recent years. The catalytic oxidation method is to convert HCl into Cl under the action of a catalyst by taking O2 as an oxidant 2 The reaction formula is as follows:
4HCl+O 2 →2H 2 O+2Cl 2
the reaction is reversible, is restricted by balance, and has higher reaction temperature, so that the requirement on the catalyst is more severe. How to obtain a catalyst with high activity and high stability has been the core of research in this field. Catalysts used in the catalytic oxidation of hydrogen chloride to produce chlorine mainly include copper-based, chromium-based, and ruthenium-based catalysts, and cerium-based catalysts developed in recent years, and the like. Among them, copper-based catalysts are excellent in activity, low in cost, easy to regenerate, and wide in industrial application prospect, and researchers have conducted extensive and intensive studies on them.
The patent CN201610625612.9 takes B, nb, P and other elements as copper-based catalyst auxiliary agents, the addition of the B element greatly slows down the loss of Cu components, prolongs the service life of the catalyst, and simultaneously obtains good catalytic performance, but the conversion rate of hydrogen chloride is only 80 percent.
The active component of the catalyst in the patent CN201711220899.8 adopts a ruthenium component, the active component is treated by hydrogen peroxide to prepare the catalyst, the hydrogen chloride conversion rate is only 35.9%, and noble metal ruthenium element is adopted.
Chinese patent CN101559374 discloses a catalyst loaded with copper chloride, potassium chloride, manganese nitrate and cerium nitrate using silica gel and ReY molecular sieve as carrier, the flow rate of hydrogen chloride and oxygen is 200ml/min, the catalyst consumption is 25g, the reaction temperature is 380 ℃, and the conversion rate of hydrogen chloride is 83.6%. However, the catalyst also has the defects of copper component loss, low space velocity and the like.
Disclosure of Invention
The invention provides a catalyst for preparing chlorine and application thereof, in order to solve the problems of poor stability and low catalytic activity of a copper catalyst in the prior art. The catalyst overcomes the defects of the existing copper catalyst, thallium is added into the copper catalyst, and the catalyst is prepared in a mode of coating active components with inorganic nonmetallic materials, so that the catalyst has the advantages of high activity, good stability, abrasion resistance and the like.
In order to solve the technical problems, in one aspect, the invention provides a catalyst for preparing chlorine, the catalyst comprises a carrier, an inorganic nonmetallic material and an active component, and the composition of the active component contained in the catalyst is represented by the following general formula (1):
Cu a Tl b X c Y d Z e C f O g (1)
wherein: x is selected from one of alkali metals; y is selected from at least one of transition metal or alkaline earth metal manganese, iron, nickel, cobalt, zinc, titanium, magnesium, calcium and barium; z is selected from one of rare earth elements;
a has a value in the range of 0.3 to 1.2, preferably 0.3 to 0.6
b has a value in the range of 0.01 to 0.2, preferably 0.03 to 0.2;
the value range of c is 0.1-0.8, preferably 0.1-0.6;
d has a value in the range of 0.1 to 0.8, preferably 0.1 to 0.4;
e has a value in the range of 0.01 to 0.3, preferably 0.01 to 0.1;
the value range of f is 1 to 2.8, preferably 1 to 2.5;
g is the number of oxygen atoms required to satisfy the valence of each element of the catalyst;
preferably, the active component is Cu 0.3～0.6 Tl 0.03～0.2 X 0.1～0.6 Y 0.10～0.4 Z 0.01～0.1 C 1～2.5 O g g is a value corresponding to the atomic valence state of each component.
Based on the total weight of the catalyst, the dosage of the carrier, the inorganic nonmetallic material and the active components is 3-15: 0.01 to 0.2:10 to 25.
Wherein the alkali metal is one of lithium, sodium, potassium and cesium, preferably sodium or potassium. The rare earth element is at least one of lanthanoid elements, preferably cerium, lanthanum, praseodymium and neodymium.
The carrier is one or more of molecular sieve, kaolin, diatomite, silicon dioxide, aluminum oxide, titanium dioxide and zirconium dioxide, preferably molecular sieve or kaolin, wherein the molecular sieve is more preferably Y-type molecular sieve.
In another aspect, the present invention provides a method for preparing a catalyst for preparing chlorine, comprising the steps of: 1) Dissolving a required copper-containing compound, thallium-containing compound, transition metal compound, alkali metal compound, alkaline earth metal compound and rare earth metal compound in water, adding a carrier for soaking, drying and roasting to obtain a catalyst precursor; 2) Adding the catalyst precursor in the step 1 into hydrogen peroxide solution, and then stirring, filtering and drying to obtain an initial catalyst; 3) Respectively adding an inorganic carbon material and a binder into a rotary roll coater, and coating the inorganic carbon material on the surface of an initial catalyst in the rotary roll coater by adjusting the spraying speed of the binder to obtain a medium-term catalyst; and sequentially performing alkali washing, acid washing and water washing on the medium-term catalyst, and drying and roasting to obtain the catalyst for preparing the chlorine.
The copper-containing compound in step 1) is a soluble salt of copper, preferably one or more of copper nitrate, copper chloride and copper acetate, more preferably copper nitrate and copper chloride. In general, when two or more kinds are used, there is no limitation on the proportion thereof, and a combination of any proportions may be used;
the compound containing transition metal in the step 1) is one or more of soluble salts of manganese, iron, nickel, cobalt, zinc and titanium, preferably one or more of nitrate, chloride or acetate corresponding to manganese, iron, nickel, cobalt, zinc and titanium elements, more preferably one or more of nitrate, chloride or acetate corresponding to manganese, iron, cobalt and zinc elements;
the thallium-containing compound in step 1) is thallium oxide;
the alkali metal compound in the step 1) is one or more of chloride, nitrate, acetate, carbonate or borate of lithium, sodium and potassium; preferably sodium or potassium chloride, nitrate, acetate, carbonate or borate;
the alkaline earth metal compound in the step 1) is one or more of chloride, nitrate, acetate, carbonate or borate of magnesium, calcium and barium, preferably chloride, nitrate, acetate, carbonate or borate of magnesium or calcium;
the rare earth metal compound in the step 1) is nitrate or chloride salt of cerium, lanthanum, praseodymium and neodymium, preferably nitrate;
the amount of each compound in the step 1) is not particularly limited as long as the amount ratio of the compound represented by the general formula (1) can be satisfied.
The drying temperature in the step 1) is 60-100 ℃, preferably 80-100 ℃, the roasting temperature is 500-600 ℃, preferably 500-550 ℃, and the time is 10-15 h, preferably 10-12 h;
the mass ratio of the catalyst precursor to the hydrogen peroxide solution in the step 2) is 1:1-1.5, and the concentration of the hydrogen peroxide solution is 20-40 wt%, preferably 25-36 wt%.
The stirring temperature in the step 2) is 40-80 ℃, preferably 45-75 ℃, and the stirring time is 3-8 h, preferably 4-7 h;
the filtration process in step 2) is selected from reduced pressure filtration, the drying temperature is 30-60 ℃, preferably 50-60 ℃,
the inorganic carbon material in the step 3) is selected from one or more of carbon nanofibers, carbon nanotubes, carbon quantum dots, carbon nanoplatelets and graphene, preferably carbon nanofibers, more preferably carbon nanofibers with an outer diameter of 200-600 nm and a length of 5-50 μm.
The binder in step 3) is selected from ethanol, water, methanol, preferably ethanol.
In the step 3), the mass ratio of the inorganic carbon material, the binder and the initial catalyst is 1.0-2.5: 0.55-0.95:15-25.
The specific reagent for alkaline washing in the step 3) is selected from NaOH, the reagent for acid washing is selected from sulfuric acid and nitric acid aqueous solution with the mass ratio of 1:1, the drying temperature is 40-100 ℃, preferably 80-100 ℃, the roasting temperature is 450-550 ℃ and the time is 3h.
In addition, the invention also provides application of the catalyst in the reaction of preparing chlorine by hydrogen chloride catalytic oxidation.
Finally, the invention provides a method for preparing chlorine by catalytic oxidation of hydrogen chloride, which comprises the following steps: the catalyst of the invention is applied to the reaction of preparing chlorine by hydrogen chloride catalytic oxidation in a fluidized bed reactor. The reaction conditions are as follows: the reaction temperature is 320-460 ℃, preferably 360-400 ℃; the reaction pressure is 0.1-0.6 Mpa, preferably 0.1-0.35 Mpa; the molar ratio of the hydrogen chloride to the oxygen is 0.5-9:1, preferably 1-4:1; the mass airspeed of the hydrogen chloride is 0.1 to 2.5h -1 Preferably 0.5 to 2 hours -1 。
The reaction product is absorbed by an excessive potassium iodide solution, the chlorine generated by the reaction is measured by an iodometry, and unreacted hydrogen chloride is obtained by acid-base titration, so that the yield of the chlorine is calculated.
The scheme of the invention has the following advantages:
the catalyst provided by the invention has the characteristics of simple preparation process, and meanwhile, compared with gold and ruthenium catalysts, the catalyst has relatively low price.
The catalyst belongs to a copper-based catalyst, the surface oxygen property of the catalyst has a great relation with the catalytic reaction performance, active oxygen species are needed to be provided for reaction sites, the catalytic activity and selectivity can be greatly improved only by efficient coordination of the active oxygen species and reactants, in the reaction, reactant molecules hydrogen chloride react with lattice oxygen on the surface of the catalyst, the reactant molecules are oxidized into target products, after the lattice oxygen participates in the reaction, gas-phase oxygen is adsorbed and the lower oxides in active components on the catalyst are oxidized to an initial state to complete redox forms of Redos, so that the lattice oxygen plays a leading role in the reaction, and the adsorbed oxygen plays a synergistic role. Thallium element is introduced and treated by hydrogen peroxide, so that chloride ions are desorbed from the surface of the catalyst, and the oxidation of lattice oxygen is reduced, thereby achieving the purpose of inhibiting deep oxidation.
The problem of activity reduction caused by the falling of active components due to mutual abrasion of the catalysts in the fluidized bed is solved by adopting an inorganic nonmetallic material coating mode, and simultaneously, the catalyst is subjected to alkaline washing and acidic etching pore-forming on the surface of the catalyst, so that oxygen vacancies are increased, a material foundation and a place are provided for rapid bulk migration of lattice oxygen ions, the reaction is ensured to be carried out in a high-selectivity direction, and the service life of the catalyst is prolonged.
Detailed Description
The invention is further illustrated by the following examples, which are in no way limited to the following examples.
Raw materials and sources:
cupric chloride, dihydrate: aladin; brand number: c111685; specification of: purity 99.999%;
sodium chloride: aladin; brand number: c111544; specification of: purity 99.999%;
cerium nitrate, hexahydrate: aladin; brand number: c105378; specification of: purity 99.95%;
neodymium nitrate, hexahydrate: aladin; brand number: n119418; specification of: purity 99.9%;
magnesium nitrate, hexahydrate: testing in south; brand number: c0190530223; specification of: purity 99%;
carbon nanofibers: super-color practice; brand number: c308068; specification of: purity 99%;
sodium hydroxide: aladin; brand number: s111498; specification of: the purity was 96%.
Hydrogen peroxide: aladin; brand number: h414630; specification of: 30wt%;
ethanol: aladin; brand number: e111946; specification of: 99.8%;
the testing method comprises the following steps: the reaction product is absorbed by an excessive potassium iodide solution, the chlorine generated by the reaction is measured by an iodometry, and unreacted hydrogen chloride is obtained by acid-base titration, so that the yield of the chlorine is calculated.
Example 1
Sequentially weigh 51g of CuCl 2 ·2H 2 O、9.13g Tl 2 O 3 、5.8gNaCl、21.7gCe(NO 3 ) 3 ·6H 2 O、21.9gNd(NO 3 ) 3 ·6H 2 O、25.6gMg(NO 3 ) 2 ·6H 2 O was dissolved in 50ml of water and stirred well to form a slurry. Then 200g of HY molecular sieve is added and stirred for 6 hours at 70 ℃, the fully impregnated catalyst is placed in an oven, dried for 8 hours at 100 ℃, taken out, placed in a roasting furnace, roasted for 12 hours at 550 ℃, naturally cooled and taken out, and then the catalyst precursor is obtained. Adding a catalyst precursor into 30wt% hydrogen peroxide, stirring at 60 ℃ for 5 hours, filtering and drying at 100 ℃ for 7 hours to obtain an initial catalyst, weighing 1g of carbon nanofiber and the initial catalyst, realizing the rotary coating of the carbon nanofiber on the outer surface of the initial catalyst in a rotary roll coater by adjusting the spraying speed of ethanol, drying at 100 ℃ for 5 hours after molding to obtain a middle catalyst, adding the middle catalyst into a three-neck flask containing 1000g of 50wt% sodium hydroxide aqueous solution, refluxing and stirring at 90 ℃ for 5 hours to perform alkali modification, washing the middle catalyst obtained by filtering after alkali modification with deionized water until the pH of filtrate is 6-8, and adding the middle catalyst into the three-neck flask after washingAnd (3) carrying out acid modification, namely adding the medium-term catalyst into a three-neck flask containing 50wt% of sulfuric acid and nitric acid aqueous solution with the mass ratio of 1:1, refluxing and stirring the slurry at 90 ℃ for 5 hours to carry out acid modification, washing the catalyst obtained by filtering after acid modification by deionized water until the pH value of filtrate is 6-8, drying the catalyst in an oven at 100 ℃, and roasting the catalyst at 550 ℃ for 3 hours to obtain 293g of active catalyst. Tabletting and forming to obtain 30-60 mesh catalyst particles.
6g of 30-60 mesh catalyst is filled into a fixed bed reactor, and the reaction is carried out under the conditions that the flow rates of hydrogen chloride and oxygen are 100ml/min, the reaction temperature is 380 ℃ and the reaction pressure is 0.18 Mpa. The chlorine yield after 4 hours of reaction is 89.2%, the chlorine yield after 100 hours of reaction is 88.9%, and the catalyst activity is kept stable.
Example 2
Sequentially weigh 85g of CuCl 2 ·2H2O、27.4g Tl 2 O 3 、11.7gNaCl、34.72gCe(NO 3 ) 3 ·6H2O、35.04gNd(NO 3 ) 3 ·6H 2 O、51.2gMg(NO 3 ) 2 ·6H 2 O was dissolved in 50ml of water and stirred well to form a slurry. Then 200g of HY molecular sieve is added and stirred for 6 hours at 70 ℃, the fully impregnated catalyst is placed in an oven, dried for 8 hours at 100 ℃, taken out, placed in a roasting furnace, roasted for 12 hours at 550 ℃, naturally cooled and taken out, and then the catalyst precursor is obtained. Adding the carbon nanofiber and the initial catalyst into 30 weight percent hydrogen peroxide, stirring for 5 hours at 60 ℃, filtering and drying for 7 hours at 100 ℃ to obtain an initial catalyst, weighing 2g of carbon nanofiber and the initial catalyst, realizing the rotary coating of the carbon nanofiber on the outer surface of the initial catalyst by adjusting the spraying speed of ethanol in a rotary roll coater, drying for 5 hours at 100 ℃ after molding to obtain a middle catalyst, adding the middle catalyst into a three-neck flask containing 1000g of 50 weight percent sodium hydroxide aqueous solution, refluxing and stirring for 5 hours at 90 ℃ for alkali modification, washing the middle catalyst obtained after the alkali modification by deionized water until the pH value of filtrate is 6-8, carrying out acid modification on the middle catalyst after washing, and adding the middle catalyst into a three-neck flask containing 1000g of 50 weight percent sulfuric acid and nitric acid aqueous solution with the mass ratio of 1:1, wherein the slurry is subjected to alkali modificationThe slurry is refluxed and stirred for 5 hours at 90 ℃ for acid modification, the catalyst obtained by filtering after acid modification is washed by deionized water until the pH value of filtrate is 6-8, and then dried in an oven at 100 ℃ and baked for 3 hours at 550 ℃ to obtain 369g of active catalyst. Tabletting and forming to obtain 30-60 mesh catalyst particles.
6g of 30-60 mesh catalyst is filled into a fixed bed reactor, and the reaction is carried out under the conditions that the flow rates of hydrogen chloride and oxygen are 100ml/min, the reaction temperature is 380 ℃ and the reaction pressure is 0.18 Mpa. The chlorine yield after 4 hours of reaction is 89.1%, the chlorine yield after 100 hours of reaction is 89.6%, and the catalyst activity is kept stable.
Example 3
Sequentially weigh 102gCuCl 2 ·2H 2 O、45.7g Tl 2 O 3 、17.5gNaCl、43.4gCe(NO 3 ) 3 ·6H 2 O、43.8gNd(NO 3 ) 3 ·6H 2 O、102.4gMg(NO 3 ) 2 ·6H 2 O was dissolved in 50ml of water and stirred well to form a slurry. Then 200g of HY molecular sieve is added and stirred for 6 hours at 70 ℃, the fully impregnated catalyst is placed in an oven, dried for 8 hours at 100 ℃, taken out, placed in a roasting furnace, roasted for 12 hours at 550 ℃, naturally cooled and taken out, and then the catalyst precursor is obtained. Adding the mixture into hydrogen peroxide with the equal mass concentration of 30wt%, stirring for 5 hours at 60 ℃, filtering and drying for 7 hours at 100 ℃ to obtain an initial catalyst, weighing 2.5g of carbon nano fibers and the initial catalyst, realizing the rotary coating of the carbon nano fibers on the outer surface of the initial catalyst by adjusting the spraying speed of ethanol in a rotary roll coater, drying for 5 hours at 100 ℃ after molding to obtain a middle catalyst, adding the middle catalyst into a three-mouth flask containing 1000g of 50wt% sodium hydroxide aqueous solution, refluxing and stirring for 5 hours at 90 ℃ to perform alkali modification, washing the middle catalyst obtained after alkali modification by deionized water until the pH value of filtrate is 6-8, performing acid modification on the middle catalyst after washing, adding the middle catalyst into a three-mouth flask containing 1000g of 50wt% sulfuric acid and nitric acid aqueous solution with the mass ratio of 1:1, refluxing and stirring for 5 hours at 90 ℃, performing acid modification, and filtering to obtain the catalyst, and using deionized water after acid modificationCleaning until the pH value of the filtrate is 6-8, drying in a baking oven at 100 ℃, and roasting at 550 ℃ for 3 hours to obtain 428g of active catalyst. Tabletting and forming to obtain 30-60 mesh catalyst particles.
6g of 30-60 mesh catalyst is filled into a fixed bed reactor, and the reaction is carried out under the conditions that the flow rates of hydrogen chloride and oxygen are 100ml/min, the reaction temperature is 380 ℃ and the reaction pressure is 0.18 Mpa. The chlorine yield after 4 hours of reaction is 88.5%, the chlorine yield after 100 hours of reaction is 88.1%, and the activity of the catalyst is kept stable.
Example 4
Sequentially weigh 51g of CuCl 2 ·2H 2 O、9.13g Tl 2 O 3 、5.8gNaCl、21.8gPr(NO 3 ) 3 ·6H 2 O、21.7gLa(NO 3 ) 3 ·6H 2 O、25.6gMg(NO 3 ) 2 ·6H 2 O was dissolved in 50ml of water and stirred well to form a slurry. Then 200g of HY molecular sieve is added and stirred for 6 hours at 70 ℃, the fully impregnated catalyst is placed in an oven, dried for 8 hours at 100 ℃, taken out, placed in a roasting furnace, roasted for 12 hours at 550 ℃, naturally cooled and taken out, and then the catalyst precursor is obtained. Adding a catalyst precursor into 30wt% hydrogen peroxide, stirring at 60 ℃ for 5 hours, filtering and drying at 100 ℃ for 7 hours to obtain an initial catalyst, weighing 1g of carbon nanofiber and the initial catalyst, realizing the rotary coating of the carbon nanofiber on the outer surface of the initial catalyst in a rotary roll coater by adjusting the spraying speed of ethanol, drying at 100 ℃ for 5 hours after molding to obtain a middle catalyst, adding the middle catalyst into a three-mouth flask containing 1000g of 50wt% sodium hydroxide aqueous solution, refluxing and stirring the slurry at 90 ℃ for 5 hours for alkali modification, washing the middle catalyst obtained after alkali modification by deionized water until the pH value of a filtrate is 6-8, performing acid modification on the middle catalyst after washing, adding the middle catalyst into a three-mouth flask containing 1000g of 50wt% sulfuric acid and nitric acid aqueous solution with the mass ratio of 1:1, refluxing and stirring at 90 ℃ for 5 hours, washing the catalyst obtained after acid modification by deionized water until the pH value of a filtrate is 6-8, and placing the three-mouth flask at 100 ℃ for 3 hours for baking to obtain the catalyst after acid modification, and baking at 550 ℃ for 3 hours273g of sex catalyst. Tabletting and forming to obtain 30-60 mesh catalyst particles.
6g of 30-60 mesh catalyst is filled into a fixed bed reactor, and the reaction is carried out under the conditions that the flow rates of hydrogen chloride and oxygen are 100ml/min, the reaction temperature is 380 ℃ and the reaction pressure is 0.18 Mpa. The chlorine yield after 4 hours of reaction is 89.9%, the chlorine yield after 100 hours of reaction is 88.6%, and the catalyst activity is kept stable.
Example 5
Sequentially weigh 102gCuCl 2 ·2H 2 O、45.7g Tl 2 O 3 、17.5gNaCl、43.4gCe(NO 3 ) 3 ·6H 2 O、43.5gPr(NO 3 ) 3 ·6H 2 O、102.4gMg(NO 3 ) 2 6H2O was dissolved in 50ml of water and stirred well to form a slurry. Then 200g of HY molecular sieve is added and stirred for 6 hours at 70 ℃, the fully impregnated catalyst is placed in an oven, dried for 8 hours at 100 ℃, taken out, placed in a roasting furnace, roasted for 12 hours at 550 ℃, naturally cooled and taken out, and then the catalyst precursor is obtained. Adding the carbon nanofiber and the initial catalyst into hydrogen peroxide with the equal mass concentration of 30wt%, stirring for 5 hours at 60 ℃, filtering and drying for 7 hours at 100 ℃ to obtain an initial catalyst, weighing 2.5g of carbon nanofiber and the initial catalyst, realizing the rotary coating of the carbon nanofiber on the outer surface of the initial catalyst by adjusting the spraying speed of ethanol in a rotary roll coater, drying for 5 hours at 100 ℃ after molding to obtain a middle catalyst, adding the middle catalyst into a three-mouth flask containing 1000g of 50wt% sodium hydroxide aqueous solution, refluxing and stirring for 5 hours at 90 ℃ for alkali modification, washing the middle catalyst obtained after alkali modification by deionized water until the pH of filtrate is 6-8, carrying out acid modification on the middle catalyst after washing, adding the middle catalyst into a three-mouth flask containing 1000g of 50wt% sulfuric acid and nitric acid aqueous solution, refluxing and stirring for 5 hours at 90 ℃, washing the catalyst obtained after filtering by deionized water until the pH of filtrate is 6-8, and drying for 3g at 550 ℃ in an oven to obtain the active catalyst. Tabletting and forming to obtain 30-60 mesh catalyst particles.
6g of 30-60 mesh catalyst is filled into a fixed bed reactor, and the reaction is carried out under the conditions that the flow rates of hydrogen chloride and oxygen are 100ml/min, the reaction temperature is 380 ℃ and the reaction pressure is 0.18 Mpa. The chlorine yield after 4 hours of reaction is 88.5%, the chlorine yield after 100 hours of reaction is 88.1%, and the activity of the catalyst is kept stable.
Comparative example 1
Catalyst preparation reference example 1: except that the thallium oxide component was not added at the time of supporting the active component, the catalyst was prepared in the same manner as in example 1. The chlorine yield after 4 hours of reaction was 86.1%, and the chlorine yield after 100 hours of reaction was 80.6%.
Comparative example 2
Catalyst preparation reference example 1: except that no carbon nanofibers were added, the preparation was performed as follows:
sequentially weigh 51g of CuCl 2 ·2H 2 O、9.13g Tl 2 O 3 、5.8gNaCl、21.7gCe(NO 3 ) 3 ·6H 2 O、21.9gNd(NO 3 ) 3 ·6H 2 O、25.6gMg(NO 3 ) 2 ·6H 2 O was dissolved in 50ml of water and stirred well to form a slurry. Then 200g of HY molecular sieve is added and stirred for 6 hours at 70 ℃, the fully impregnated catalyst is placed in an oven, dried for 8 hours at 100 ℃, taken out, placed in a roasting furnace, roasted for 12 hours at 550 ℃, naturally cooled and taken out, and then the catalyst precursor is obtained. Adding the catalyst into 30wt% hydrogen peroxide, stirring at 60 ℃ for 5 hours, filtering, drying at 100 ℃ for 7 hours to obtain an initial catalyst, and roasting at 550 ℃ for 3 hours to obtain 292g of active catalyst. Tabletting and forming to obtain 30-60 mesh catalyst particles. 6g of 30-60 mesh catalyst is filled into a fixed bed reactor, and the reaction is carried out under the conditions that the flow rates of hydrogen chloride and oxygen are 100ml/min, the reaction temperature is 380 ℃ and the reaction pressure is 0.18 Mpa. The chlorine yield after 4 hours of reaction was 86.6%, and the chlorine yield after 100 hours of reaction was 82.0%.
Comparative example 3
Catalyst preparation reference example 1: the preparation method is characterized in that the active component is not added with carbon nanofibers, and is not subjected to acid washing and alkali washing, and the preparation operation is as follows:
sequentially weigh 102gCuCl 2 ·2H 2 O、45.7g Tl 2 O 3 、17.5gNaCl、43.4gCe(NO 3 ) 3 ·6H 2 O、43.8gNd(NO 3 ) 3 ·6H 2 O、102.4gMg(NO 3 ) 2 ·6H 2 O was dissolved in 50ml of water and stirred well to form a slurry. Then adding 200gHY molecular sieve and stirring at 70 ℃ for 6 hours, placing the fully impregnated catalyst in a baking oven, drying at 100 ℃ for 8 hours, taking out, and roasting at 550 ℃ for 3 hours to obtain 380g of active catalyst. Tabletting and forming to obtain 30-60 mesh catalyst particles. 6g of 30-60 mesh catalyst is filled into a fixed bed reactor, and the reaction is carried out under the conditions that the flow rates of hydrogen chloride and oxygen are 100ml/min, the reaction temperature is 380 ℃ and the reaction pressure is 0.18 Mpa. The chlorine yield after 4 hours of reaction was 83.6%, and the chlorine yield after 100 hours of reaction was 80.0%.
By comparing the example 1 with the comparative example 1, it is found that the arsenic trioxide is added into the active component and treated by hydrogen peroxide, thereby facilitating the desorption of chloride ions from the surface of the catalyst, reducing the oxidation of lattice oxygen, achieving the purpose of inhibiting deep oxidation, and improving the yield and activity of chlorine.
The comparison of the embodiment 3 with the comparative examples 2 and 3 shows that the preparation of the catalyst in the form of coating by inorganic nonmetallic materials can reduce the problem of activity reduction caused by the falling of active components due to mutual abrasion of the catalyst in a fluidized bed, and simultaneously, the catalyst is subjected to alkaline washing and acidic etching for pore formation on the surface of the catalyst, so that oxygen vacancies are increased, the material basis and the place are provided for rapid bulk migration of lattice oxygen ions, the reaction is ensured to be carried out in a high-selectivity direction, and the service life of the catalyst is prolonged.

Claims (10)

1. A catalyst for producing chlorine, the catalyst comprising a carrier, an inorganic nonmetallic material, and an active component, the catalyst comprising an active component having a composition represented by the following general formula (1):
Cu a Tl b X c Y d Z e C f O g (1)
wherein: x is selected from one of alkali metals; y is selected from at least one of transition metal or alkaline earth metal manganese, iron, nickel, cobalt, zinc, titanium, magnesium, calcium and barium; z is selected from one of rare earth elements;
a has a value in the range of 0.3 to 1.2, preferably 0.3 to 0.6
b has a value in the range of 0.01 to 0.2, preferably 0.03 to 0.2;
the value range of c is 0.1-0.8, preferably 0.1-0.6;
d has a value in the range of 0.1 to 0.8, preferably 0.1 to 0.4;
e has a value in the range of 0.01 to 0.3, preferably 0.01 to 0.1;
the value range of f is 1 to 2.8, preferably 1 to 2.5;
g is the number of oxygen atoms required to satisfy the valence of each element of the catalyst;
preferably, the active component is Cu 0.3～0.6 Tl 0.03～0.2 X 0.1～0.6 Y 0.10～0.4 Z 0.01～0.1 C 1～2.5 O g g is a value corresponding to the atomic valence state of each component.
2. The catalyst of claim 1, wherein the carrier, inorganic nonmetallic material, and active components are used in an amount of 3 to 15, based on the total weight of the catalyst: 0.01 to 0.2:10 to 25.
3. The catalyst according to claim 1 or 2, wherein the alkali metal is one of lithium, sodium, potassium, cesium, preferably sodium or potassium. The rare earth element is at least one of lanthanoid elements, preferably cerium, lanthanum, praseodymium and neodymium.
4. A catalyst according to any of claims 1 to 3 wherein the support is one or more of molecular sieves, kaolin, diatomaceous earth, silica, alumina, titania, zirconia, preferably molecular sieves or kaolin, wherein the molecular sieves are more preferably Y-type molecular sieves.
5. The method for preparing a catalyst according to any one of claims 1 to 4, comprising the steps of: 1) Dissolving a required copper-containing compound, thallium-containing compound, transition metal compound, alkali metal compound, alkaline earth metal compound and rare earth metal compound in water, adding a carrier for soaking, drying and roasting to obtain a catalyst precursor; 2) Adding the catalyst precursor in the step 1 into hydrogen peroxide solution, and then stirring, filtering and drying to obtain an initial catalyst; 3) Respectively adding an inorganic carbon material and a binder into a rotary roll coater, and coating the inorganic carbon material on the surface of an initial catalyst in the rotary roll coater by adjusting the spraying speed of the binder to obtain a medium-term catalyst; and sequentially performing alkali washing, acid washing and water washing on the medium-term catalyst, and drying and roasting to obtain the catalyst for preparing the chlorine.
6. The method of claim 5, wherein the copper-containing compound in step 1) is a soluble salt of copper, preferably one or more of copper nitrate, copper chloride and copper acetate, more preferably copper nitrate and copper chloride; and/or the compound containing transition metal in the step 1) is one or more of soluble salts of manganese, iron, nickel, cobalt, zinc and titanium, preferably one or more of nitrate, chloride or acetate corresponding to manganese, iron, nickel, cobalt, zinc and titanium elements, more preferably one or more of nitrate, chloride or acetate corresponding to manganese, iron, cobalt and zinc elements; and/or the thallium-containing compound in step 1) is thallium oxide.
7. The method of claim 5 or 6, wherein the alkali metal compound in step 1) is one or more of lithium, sodium, potassium chloride, nitrate, acetate, carbonate or borate; preferably sodium or potassium chloride, nitrate, acetate, carbonate or borate; and/or, the alkaline earth metal compound in the step 1) is one or more of chloride, nitrate, acetate, carbonate or borate of magnesium, calcium and barium, preferably chloride, nitrate, acetate, carbonate or borate of magnesium or calcium; and/or, the rare earth metal compound in the step 1) is nitrate or chloride salt of cerium, lanthanum, praseodymium and neodymium, preferably nitrate.
8. The process according to any one of claims 5 to 7, wherein the drying in step 1) is carried out at a temperature of 60 to 100 ℃, preferably 80 to 100 ℃, and the calcination is carried out at a temperature of 500 to 600 ℃, preferably 500 to 550 ℃, for a time of 10 to 15 hours, preferably 10 to 12 hours; and/or the temperature of stirring in the step 2) is 40-80 ℃, preferably 45-75 ℃, and the stirring time is 3-8 h, preferably 4-7 h; and/or the filtration process in step 2) is selected from reduced pressure filtration, the drying temperature being 30-60 ℃, preferably 50-60 ℃.
9. The method according to any one of claims 5 to 8, wherein the inorganic carbon material in step 3) is selected from one or more of carbon nanofibers, carbon nanotubes, carbon quantum dots, carbon nanoplatelets and graphene, preferably carbon nanofibers, further preferably carbon nanofibers with an outer diameter of 200 to 600nm and a length of 5 to 50 μm; and/or, in the step 3), the mass ratio of the inorganic carbon material, the binder and the initial catalyst is 1.0-2.5: 0.55-0.95:15-25.
10. Use of the catalyst according to any one of claims 1 to 4 or the catalyst prepared by the preparation method according to any one of claims 5 to 9 in a reaction for preparing chlorine by catalytic oxidation of hydrogen chloride.
CN202211122117.8A 2022-09-15 2022-09-15 Catalyst for preparing chlorine, preparation method and application thereof Pending CN117753470A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211122117.8A CN117753470A (en) 2022-09-15 2022-09-15 Catalyst for preparing chlorine, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211122117.8A CN117753470A (en) 2022-09-15 2022-09-15 Catalyst for preparing chlorine, preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN117753470A true CN117753470A (en) 2024-03-26

Family

ID=90320502

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211122117.8A Pending CN117753470A (en) 2022-09-15 2022-09-15 Catalyst for preparing chlorine, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN117753470A (en)

Similar Documents

Publication Publication Date Title
CN102000583B (en) Catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof
US9089838B2 (en) Catalyst and method for the production of chlorine by gas phase oxidation
CN101448735A (en) Method for producing chlorine by gas phase oxidation
CN101357337B (en) Heavy oil hydrogenating treatment catalyst and preparation method thereof
CN108722420A (en) A kind of preparation method of copper silicon systems catalyst
CN111992213B (en) Preparation method of core-shell catalyst for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol
CN106560239B (en) A kind of catalyst and its preparation method and application of catalytic chlorination hydroxide
JP5015057B2 (en) Catalyst for synthesis of chlorine and method for producing the same, and method for synthesizing chlorine using the catalyst
CN117753470A (en) Catalyst for preparing chlorine, preparation method and application thereof
CN103347607B (en) Catalyst And Method for manufacturing chlorine by gaseous oxidation
CN111054384B (en) Catalyst for organic liquid hydrogen storage material dehydrogenation and preparation method thereof
WO2019176247A1 (en) Method for producing indane
CN113135552B (en) Method for preparing chlorine by catalytic oxidation of hydrogen chloride
CN108067266B (en) Core-shell type catalyst and preparation method and application thereof
CN112441922B (en) Method for preparing oxalate through CO oxidative coupling, catalyst and preparation method thereof
CN112044440B (en) Catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride and preparation method and application thereof
JP7029346B2 (en) Indene manufacturing method
CN112427038A (en) Preparation method of catalyst for preparing neopentyl glycol by hydrogenation of hydroxypivalaldehyde
KR101780840B1 (en) Amide compound production catalyst, and process for production of amide compound
CN114904561A (en) Catalyst for preparing chlorine and application thereof
JP3788530B2 (en) Catalyst regeneration method
CN112517021B (en) Cobalt-doped modified tin dioxide catalyst, preparation method and application thereof
KR101049276B1 (en) Catalyst for the preparation of gamma-butyrolactone from 1,4-butanediol and method for producing gamma-butyrolactone from 1,4-butanediol using the same
WO2022154048A1 (en) Production method for indan and hydrindane
CN108069830A (en) A kind of method that formaldehyde acetylene is combined to 1,4- butynediols coproduction propilolic alcohols

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination