CN113244938A - P-Nb/Co for low-temperature vinyl chloride catalytic combustion3O4Catalyst, preparation method and application thereof - Google Patents

P-Nb/Co for low-temperature vinyl chloride catalytic combustion3O4Catalyst, preparation method and application thereof Download PDF

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Publication number
CN113244938A
CN113244938A CN202110555618.4A CN202110555618A CN113244938A CN 113244938 A CN113244938 A CN 113244938A CN 202110555618 A CN202110555618 A CN 202110555618A CN 113244938 A CN113244938 A CN 113244938A
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catalyst
vinyl chloride
hours
catalytic combustion
chloroethylene
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郭杨龙
刘浩
詹望成
郭耘
王丽
王筠松
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East China University of Science and Technology
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East China University of Science and Technology
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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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

The invention provides P-Nb/Co for low-temperature vinyl chloride catalytic combustion3O4A catalyst, a preparation method and application thereof. The catalyst adopts an impregnation method to mix phosphoric acid and Nb2O5By stepwise impregnation in Co3O4On a carrier. P-Nb/Co3O4The catalyst comprises the following components in percentage by weight: 0.5-5.0% of P, 0.5-3.0% of Nb and Co3O492.0% -99.0%. The invention can oxidize the chloroethylene waste gas into HCl/Cl and CO through catalytic reaction at lower temperature2And H2And O, wherein HCl/Cl can be completely absorbed by the alkali liquor, so that secondary pollution to the environment is avoided, and the aim of purifying the chloroethylene waste gas is achieved. The catalyst of the invention can be prepared by Nb2O5The B acid site generated by the species and the phosphate radical timely removes Cl species generated in the catalytic combustion process of the chloroethylene, so that the catalyst keeps excellent activity, selectivity and stability. 1000ppm of vinyl chloride can be completely eliminated at 300 ℃, no polychlorinated by-product is generated in the reaction process, and the conversion rate is kept stable for 120 hours continuously. The catalyst preparation method is simple and easy to implement, has a good chloroethylene purification effect, and is suitable for industrial production and application.

Description

Catalyst for low-temperature chloroethyleneChemical combustion of P-Nb/Co3O4Catalyst, preparation method and application thereof
Technical Field
The invention relates to the field of environmental catalysis and the field of air purification, and the catalytic oxidation of chloroethylene waste gas under low temperature condition. The catalyst can completely convert 1000ppm of vinyl chloride gas at 300 ℃, no polychlorinated by-product is generated in the reaction process, and the conversion rate is kept stable after 120 hours of continuous reaction.
Background
Vinyl chloride is an important chemical raw material, particularly, a large amount of low-concentration vinyl chloride waste gas is generated in the production of polyvinyl chloride, a large amount of vinyl chloride waste gas is also generated in the industries of medicine, fine chemistry and chlor-alkali, and the vinyl chloride waste gas can seriously pollute the environment and harm public health if being directly discharged into the atmosphere. With the strictness of environmental regulations and emission standards in China, how to treat vinyl chloride waste gas efficiently becomes a hot topic of attention of researchers. The catalytic combustion method has the advantages of low operation temperature, high purification efficiency, no secondary pollution and the like, and has wide application prospect, so that the design and preparation of the chloroethylene catalytic combustion catalyst with high activity, high selectivity and high stability are very important.
Catalysts for the catalytic combustion of vinyl chloride are generally perovskite catalysts, transition metal oxide catalysts and supported noble metal catalysts. The perovskite catalyst has the characteristics of stable structure, strong adjustable deformation and the like, and shows higher activity in the catalytic combustion reaction of vinyl chloride, such as La-Bi-La-Ce-La-Bi-La-Ce-La-Ce-La-Ce-La-Ce-La-Ce-La-Ce-La-Ce-La-Ce-La-Ce-Ca-Ce-Ca-La-Ce-La-Ce-La-Ce-La-Ce-La-Ce-La-Ce-La-Ce0.8Sr0.2MnO3The catalyst shows higher catalytic combustion activity of vinyl chloride, but generates more polychlorinated byproducts in the reaction process and is easily deactivated by chlorine poisoning. Transition metal oxide catalysts are of great interest due to their low cost and good activity, and Co-Ce catalysts reported in the literature (chem. eng. j., 2017, 315: 392-. The supported noble metal catalyst has high catalytic activityBut is expensive to produce, as in RuO reported in the literature (Environ. Sci. Technol., 2021, 6: 4007-x-CeO2The catalyst shows excellent activity for catalytic combustion of vinyl chloride, but generates a large amount of polychlorinated byproducts in the reaction process, and is easy to adsorb on the surface of the catalyst to reduce the activity of the catalyst.
The catalysts in the reports have the following defects although having advantages: polychlorinated byproducts are easily generated in the reaction process, so that secondary pollution to the environment is caused; catalyst centers are susceptible to deactivation by chlorine poisoning, resulting in a decrease in catalyst stability.
Disclosure of Invention
The invention aims to provide P-Nb/Co for catalytic combustion of vinyl chloride3O4The catalyst and the preparation method thereof overcome the defects of the prior catalyst. The catalyst has the characteristics of low P, Nb loading capacity, high catalytic activity, high stability and the like.
P-Nb/Co for vinyl chloride catalytic combustion as herein described in the invention3O4The catalyst comprises the following components in percentage by weight:
P 0.5%~5.0%，
Nb 0.5%~3.0%，
Co3O4 92.0%~99.0%。
the invention relates to P-Nb/Co for vinyl chloride catalytic combustion3O4Co in catalyst3O4The carrier is prepared by a reflux method, and the preparation method comprises the following specific steps: dissolving cobalt nitrate and PVP-30 in deionized water, heating the obtained solution to 85 ℃, violently stirring for 30 minutes, then dropwise adding ammonia water, adjusting the pH value to 8.5, then dropwise adding hydrogen peroxide, refluxing for 24 hours at 85 ℃, performing suction filtration, washing a filter cake for three times to be neutral by using the deionized water, drying the obtained precipitate in a drying oven at 110 ℃ for 24 hours, and then roasting for 3 hours in a muffle furnace at 500 ℃.
The invention relates to P-Nb/Co for vinyl chloride catalytic combustion3O4The catalyst is prepared by adopting an impregnation method, and the method comprises the following specific steps: co to be prepared3O4Adding the carrier into an ammonium niobate oxalic acid aqueous solution,ultrasonic treatment is carried out for 1 hour at normal temperature, aging is carried out for 24 hours, and then drying is carried out for 24 hours in an oven at 110 ℃ in sequence, and roasting is carried out for 3 hours in a muffle furnace at 500 ℃. Nb/Co to be prepared3O4Adding the carrier into trimethyl phosphate aqueous solution, carrying out ultrasonic treatment for 1 hour at normal temperature, aging for 24 hours, then sequentially drying in an oven at 110 ℃ for 24 hours, and roasting in a muffle furnace at 500-750 ℃ for 3 hours.
The P-Nb/Co of the invention3O4The catalyst is used in the catalytic combustion reaction of vinyl chloride, and the specific reaction conditions are as follows: the concentration of chloroethylene is 1000ppm, and the reaction space velocity is 15000-50000 mL-1•h-1。
One of the obvious advantages of the invention is that no polychlorinated by-product is generated in the reaction process, no secondary pollution is generated, the complete conversion of the chloroethylene waste gas can be completed at a lower temperature, and the standard discharge of the chloroethylene waste gas is realized.
The invention has the second significant advantage that a large amount of B acid centers are generated on the surface of the catalyst through co-modification of phosphoric acid and niobate, so that not only can C-Cl bonds in vinyl chloride molecules be easily broken, but also HCl generated by reaction with Cl species after dissociation and adsorption of vinyl chloride can be separated from the surface of the catalyst, thereby blocking the generation path of polychlorinated byproducts in the reaction process and improving the activity, selectivity and stability of the catalyst.
The invention has the third remarkable advantage that phosphoric acid and niobic acid are loaded on Co by adopting an immersion method3O4On the carrier, the preparation method is simple and feasible, and is suitable for industrial application.
Drawings
FIG. 1 shows P-Nb/Co3O4The influence of the calcination temperature of the catalyst on the catalytic activity of the catalyst;
FIG. 2 shows P-Nb/Co3O4The effect of the Nb loading of the catalyst on its catalytic activity;
FIG. 3 shows P-Nb/Co3O4The effect of the P loading of the catalyst on its (a) catalytic activity and (b) selectivity to polychlorinated by-products;
FIG. 4 is a graph of the effect of reaction space velocity on catalyst activity;
FIG. 5 shows P-Nb/Co3O4120 hours stability of the catalyst.
Detailed Description
The vinyl chloride catalytic combustion catalyst and the preparation method thereof according to the present invention are further described in detail by the following specific examples, it should be noted that the following examples are only for describing the contents of the present invention, and the scope of the present invention is not limited to these examples. It is within the scope of the present invention to make simple modifications or substitutions to the methods, procedures or conditions for preparing the catalyst of the present invention without departing from the spirit or essential attributes thereof; the basic operations used in the examples are conventional and well known to those skilled in the art, unless otherwise specified.
Example 1
Preparation of Co3O4 carrier: 2.9g of Co (NO)2•6H2O and 5g PVP-30 were dissolved in 100mL deionized water at 85 deg.C, stirred to dissolve completely, and then dissolved with NH3•H2O the pH of the solution was adjusted to 8.5 and 2mL of H was slowly injected into the solution under vigorous stirring2O2Refluxing the obtained solution at 85 ℃ for 24h, filtering the obtained solution, washing the solution with deionized water for three times during filtering until the pH value of the filtrate is neutral, drying the obtained precipitate in a 100 ℃ oven for 10h, and roasting in a 500 ℃ muffle furnace for 3h to obtain Co3O4And (3) a carrier.
0.5%P-0.5%Nb/Co3O4Preparation of the catalyst: 1.0g of prepared Co is added into 1mL of prepared ammonium niobate oxalic acid aqueous solution (containing 0.02g of ammonium niobate oxalate)3O4And (3) carrying out ultrasonic treatment on the powder for 1h, standing for 24h, putting the powder into a 110 ℃ oven for drying for 24h, and finally putting the sample into a muffle furnace for roasting at 500 ℃ for 3 h. 0.030g of trimethyl phosphate (TMP) was dissolved in 1.3g H2O, then 1.0g Nb/Co was added to the aqueous TMP solution3O4Aging the obtained solution for 24h, baking the solution in a 110 ℃ oven for 24h, and finally baking the solution in a muffle furnace at 500 ℃ for 3h to obtain P-Nb/Co3O4A catalyst.
P-Nb/Co3O4Of catalystsEvaluation conditions were as follows: the catalyst is subjected to tabletting and sieving procedures before activity evaluation, the sieving mesh number is 40-60 meshes, the obtained granular catalyst is placed in a fixed bed type quartz reaction tube, the inner diameter of the reaction tube is 6mm, and the catalyst is filled with 40-60 meshes of high-temperature roasted quartz sand up and down to ensure that the height of a bed layer is about 25 mm. The raw material gas used in the test is 2% C2H3Cl/N2And air, wherein the mixture is fully mixed and then is introduced into a reaction tube, the concentration of the chloroethylene is 1000ppm, and the mass space velocity (WHSV) is 30000 mL/(g.h). The concentration of raw material gas is detected at room temperature before each test as the concentration of imported chloroethylene, the test temperature range is from room temperature to 400 ℃, sampling detection is carried out after stabilization is carried out for 40 min at every 20 ℃, and the concentrations of chloroethylene and polychlorinated byproducts in the outlet gas are detected on line by a gas chromatography equipped with an FID detector.
Example 2
Changing P-Nb/Co3O4The roasting temperature of the catalyst is 500 ℃, 600 ℃, 650 ℃, 700 ℃ and 750 ℃, and the roasting temperature is 0.5 percent of P-0.5 percent of Nb/Co3O4Other preparation procedures and evaluation conditions of the catalyst were the same as those of example 1, P-Nb/Co3O4The effect of the calcination temperature of the catalyst on its catalytic activity is shown in FIG. 1.
Example 3
Changing P-Nb/Co3O4Nb loading of the catalyst is 0.5%, 1%, 2% and 3%, P-Nb/Co3O4Other preparation procedures and evaluation conditions of the catalyst were the same as those of example 1, P-Nb/Co3O4The effect of Nb loading of the catalyst on its catalytic activity is shown in fig. 2.
Example 4
Changing P-Nb/Co3O4The P loading of the catalyst is 0.5%, 2.0%, 3.0% and 5.0%, P-Nb/Co3O4Other preparation procedures and evaluation conditions of the catalyst were the same as those of example 1, P-Nb/Co3O4The effect of the P loading of the catalyst on its catalytic activity and the amount of polychlorinated by-products produced is shown in figure 3.
Example 5
The reaction space velocity of the catalyst was changed to 15000mL-1•h-1、30000mL•g-1•h-1、40000mL•g-1•h-1And 50000 mL.g-1•h-1。P-Nb/Co3O4The other preparation of the catalyst was the same as in example 1, and the effect of the reaction space velocity on the catalyst activity is shown in FIG. 4.
Example 6
0.24g of P-Nb/Co3O4The catalyst is put into a quartz tube fixed bed reactor, the concentration of chloroethylene is 1000ppm, air is balance gas, and the reaction space velocity is 30000mL-1•h-1And a reaction temperature of 280 ℃ for 120 hours, and the stability of the catalyst was examined by the catalytic combustion reaction of vinyl chloride, and the catalyst was prepared in the same manner as in example 1, and the results of the stability of the catalyst are shown in FIG. 5.

Claims (6)

1. A catalyst for the catalytic combustion of vinyl chloride at low temperatures, the catalyst comprising a support and an active component, characterized in that:
said Co3O4The alloy is prepared by a reflux method and has a cubic structure, the load capacity of P is 0.5-5.0 wt.%, and the load capacity of Nb is 0.5-3.0 wt.%.
2. The catalyst for catalytic combustion of vinyl chloride as claimed in claim 1, wherein the Co in the carrier3O4The particle size of the nanoparticles is 10-50 nm.
3. The catalyst for catalytic combustion of vinyl chloride as claimed in claim 1, wherein said Co is selected from the group consisting of3O4The carrier is obtained by the following method: dissolving cobalt nitrate and PVP-30 in deionized water, heating the obtained solution to 85 ℃, violently stirring for 30 minutes, then dropwise adding ammonia water, adjusting the pH value to 8.5, then dropwise adding hydrogen peroxide, refluxing for 24 hours at 85 ℃, performing suction filtration, washing a filter cake for three times to be neutral by using the deionized water, drying the obtained precipitate in a drying oven at 110 ℃ for 24 hours, and then roasting for 3 hours in a muffle furnace at 500 ℃.
4. A catalyst for catalytic combustion of vinyl chloride according to claim 1 and claim 3, characterized in that the preparation process is an impregnation process, and the specific process is as follows: co to be prepared3O4Adding the carrier into an ammonium niobate oxalic acid aqueous solution, carrying out ultrasonic treatment for 1 hour at normal temperature, aging for 24 hours, then sequentially drying in an oven at 110 ℃ for 24 hours, and roasting in a muffle furnace at 500 ℃ for 3 hours.
5. A catalyst for the catalytic combustion of vinyl chloride according to claim 1 and claim 4, characterized in that the preparation process is an impregnation process, the specific process being as follows: Nb/Co to be prepared3O4Adding the catalyst into trimethyl phosphate aqueous solution, carrying out ultrasonic treatment for 1 hour at normal temperature, aging for 24 hours, then sequentially drying in an oven at 110 ℃ for 24 hours, and roasting in a muffle furnace at 500 ℃ for 3 hours.
6. P-Nb/Co for vinyl chloride catalytic combustion according to claim 13O4The application of the catalyst is characterized in that the catalytic reaction conditions are as follows: the concentration of chloroethylene is 1000ppm, and the reaction space velocity is 15000-60000 mL-g-1·h-1The gas flow rate is 120mL/min, and the balance gas is dried air.
CN202110555618.4A 2021-05-21 2021-05-21 P-Nb/Co for low-temperature vinyl chloride catalytic combustion3O4Catalyst, preparation method and application thereof Pending CN113244938A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5238656A (en) * 1990-10-26 1993-08-24 Tosoh Corporation Treatment equipment of exhaust gas containing organic halogen compounds
CN1962462A (en) * 2006-11-23 2007-05-16 南京大学 Process for preparing nanometer cobalt oxide
CN105251476A (en) * 2015-10-10 2016-01-20 浙江大学 Preparation method of CeO2-Cr2O3-Nb2O5 compound oxide catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5238656A (en) * 1990-10-26 1993-08-24 Tosoh Corporation Treatment equipment of exhaust gas containing organic halogen compounds
CN1962462A (en) * 2006-11-23 2007-05-16 南京大学 Process for preparing nanometer cobalt oxide
CN105251476A (en) * 2015-10-10 2016-01-20 浙江大学 Preparation method of CeO2-Cr2O3-Nb2O5 compound oxide catalyst

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHAO WANG ET AL.: ""Insights into the Morphological Effect of Co3O4 Crystallite on Catalytic Oxidation of Vinyl Chloride"", 《CATALYSTS》, vol. 9, 30 April 2019 (2019-04-30), pages 5 - 8 *
QIGUANG DAI ET AL.: ""Comparative studies of P/CeO2 and Ru/CeO2 catalysts for catalytic combustion of dichloromethane:From effects of H2O to distribution of chlorinated by-products"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》, vol. 249, 23 February 2019 (2019-02-23), pages 2 *
戴启广等: ""含氯挥发性有机物废气在CeO2基催化剂上的低温催化燃烧净化：从高活性到高稳定性再到高选择性"", 《工业催化》, vol. 28, no. 4, 30 April 2020 (2020-04-30), pages 2 *
王新喜等: ""湿法制备纳米晶Co3O4及其微观结构研究"", 《化学学报》, vol. 61, no. 11, 31 December 2003 (2003-12-31), pages 1849 - 1850 *

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Application publication date: 20210813