CN111266105A - VOCs non-toxic catalyst and preparation method thereof - Google Patents
VOCs non-toxic catalyst and preparation method thereof Download PDFInfo
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- CN111266105A CN111266105A CN202010177873.5A CN202010177873A CN111266105A CN 111266105 A CN111266105 A CN 111266105A CN 202010177873 A CN202010177873 A CN 202010177873A CN 111266105 A CN111266105 A CN 111266105A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 61
- 231100000252 nontoxic Toxicity 0.000 title claims abstract description 47
- 230000003000 nontoxic effect Effects 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000002738 chelating agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 150000000703 Cerium Chemical class 0.000 claims abstract description 5
- 150000002696 manganese Chemical class 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- 239000013522 chelant Substances 0.000 claims abstract description 3
- 238000000605 extraction Methods 0.000 claims abstract description 3
- 239000012778 molding material Substances 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- -1 cerium ions Chemical class 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 19
- 239000008096 xylene Substances 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/617—
-
- B01J35/618—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- 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
Abstract
The invention discloses a VOCs non-toxic catalyst and a preparation method thereof, wherein the method comprises the following steps: step 1, preparing an aqueous solution containing cerium salt and manganese salt, then adding a precipitator and an oxidant into the aqueous solution, then adding a chelating agent (to chelate the generated oxide for convenient extraction) and stirring to obtain a solution containing primary precipitate; step 2, aging the solution containing the primary precipitate, filtering, drying the precipitate obtained after filtering, and roasting the dried precipitate to obtain MnOx‑CeO2(ii) a Step 3, the M is addednOx‑CeO2Mixing with activated carbon to obtain powder, and then extruding and molding to obtain a molding material; and drying and roasting the formed product in sequence to obtain a catalyst finished product. The invention adopts a new mode of combining the catalyst and the activated carbon carrier, adopts a mode of adhering and extruding and granulating by an extruder, and is more suitable for indoor purification product types such as an air purifier and the like.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a VOCs (volatile organic compounds) non-toxic catalyst and a preparation method thereof.
Background
In recent years, with the progress of research on the problem of indoor environmental pollution, researchers have come to have new recognitions on Volatile Organic Compounds (VOCs). In addition to the toxicity of VOCs, which may cause various health problems, such as cancer, more and more studies show that the formation of VOCs and secondary aerosol has a high correlation, and is one of the important pollution sources to be treated urgently in China at present or even in a future period of time.
The current treatment technologies for VOCs are mainly classified into two categories: non-destructive methods and catalytic oxidation methods. When the VOCs are adsorbed and absorbed by adopting a nondestructive method, the molecular structure of the VOCs is not changed by the method, such as activated carbon adsorption, but the problems of saturated adsorption, low adsorption rate, secondary pollution and the like are caused. When the catalytic oxidation method is used, the traditional VOCs catalyst, such as noble metal catalysts like Pt and Ru and transition metal oxide catalysts like manganese oxide, has certain effect on the catalytic degradation of VOCs; however, these catalysts suffer from severe deactivation and the formation of a variety of more toxic organic by-products during use.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a VOCs non-toxic catalyst.
The invention also aims to provide a VOCs non-toxic catalyst.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of a VOCs non-toxic catalyst comprises the following steps:
step 1, preparing an aqueous solution containing cerium salt and manganese salt, then adding a precipitator and an oxidant into the aqueous solution, then adding a chelating agent (to chelate the generated oxide for convenient extraction) and stirring to obtain a solution containing primary precipitate;
step 2, aging the solution containing the primary precipitate, filtering, drying the precipitate obtained after filtering, and roasting the dried precipitate to obtain MnOx-CeO2；
Step 3, MnO is addedx-CeO2Mixing with activated carbon to obtain powder, and then extruding and molding to obtain a molding material; and drying and roasting the formed product in sequence to obtain a catalyst finished product.
In the above method for preparing non-toxic VOCs catalyst, as a preferred embodiment, in the aqueous solution of step 1, the molar ratio of cerium ions to manganese ions is 2-5:1, preferably, the molar ratio of cerium ions to manganese ions is 5:2, 3:1, 4: 1; preferably, the cerium salt is at least one of cerous nitrate, cerous acetate, cerous sulfate and cerous nitrate; preferably, the manganese salt is manganese nitrate and/or manganese sulfate.
In the above method for preparing a nontoxic catalyst for VOCs, as a preferred embodiment, the total concentration of cerium ions and manganese ions in the aqueous solution is 0.9 to 1.2 mol/L.
In the above method for preparing a nontoxic catalyst for VOCs, as a preferred embodiment, in the step 1, the precipitant is at least one of ammonia water, ammonium carbonate and ammonium bicarbonate.
In the above method for preparing nontoxic catalysts for VOCs, as a preferred embodiment, in step 1, the oxidant is hydrogen peroxide and/or sodium chlorate.
Preparation of the nontoxic catalyst for the VOCsIn the method, as a preferred embodiment, in the step 1, the oxidizing agent is added in an amount such that the aqueous solution has a pH of 9 to 10, and the pH is too low or too high to be favorable for MnOx-CeO2And (4) generating.
In the above method for preparing a non-toxic catalyst for VOCs, as a preferred embodiment, in the step 1, the chelating agent is at least one of polyethylene glycol, tetrasodium ethylenediaminetetraacetate and EDTA, and the amount of the chelating agent added is 0.2-0.4% of the mass of the aqueous solution.
In the above method for preparing a nontoxic catalyst for VOCs, as a preferred embodiment, in the step 1, the stirring time is 30 to 40 minutes.
In the above method for preparing non-toxic catalysts for VOCs, as a preferred embodiment, in the step 2, the aging time is 6 to 8 hours (e.g., 6.5, 7, 7.5 hours); preferably, the aging refers to standing the solution containing the primary precipitate at normal temperature for 6-8 hours.
In the above preparation method of the non-toxic catalyst for VOCs, as a preferred embodiment, in the step 2, the drying temperature is 100-120 ℃.
In the above method for preparing non-toxic VOCs catalyst, as a preferred embodiment, in step 2, the water content of the dried precipitate is 20-30% (e.g., 22%, 24%, 26%, 28%); the method of the invention can use MnO having a relatively high water contentx-CeO2And higher temperature or extra long time is not needed for drying, so that the energy consumption is avoided being too large and the cost is higher.
In the above method for preparing nontoxic catalysts for VOCs, as a preferred embodiment, in the step 2, the MnOx-CeO2MnO of mediumxIs MnO and Mn2O3And MnO2Mixtures of the like manganese-containing compounds; preferably, X is 2-4. In the above method for preparing nontoxic catalysts for VOCs, as a preferred embodiment, in the step 2, the calcination temperature is 600-750 ℃ (such as 630 ℃, 650 ℃, 670 ℃, 700 ℃),720℃)。MnOx-CeO2in the preparation process of the catalyst, partial Mn replaces CeO along with the rise of the roasting temperature2Ce in the center of the crystal nucleus4+The specific surface area of the catalyst is increased, the activity of the catalyst is increased, but more CeO is added along with the further increase of the roasting temperature2Aggregation of the unit cell occurs, resulting in sintering of the sample, reducing the activity of the catalyst.
In the above preparation method of the non-toxic VOCs catalyst, as a preferred embodiment, in the step 3, the iodine value of the activated carbon is 1000-1200, and the CTC value is 70-85; when the iodine value is greater than 1200 and the CTC is greater than 85, the cost of the activated carbon is increased more, and the activated carbon has better adsorption performance and higher cost performance.
In the above preparation method of VOCs nontoxic catalyst, as a preferred embodiment, the MnOx-CeO2The mass ratio in the powder is 4 to 20% (for example, 5%, 8%, 11%, 14%, 17%, 19%), and more preferably 9 to 15%.
In the above preparation method of the non-toxic VOCs catalyst, as a preferred embodiment, in step 3, before the extrusion molding, an auxiliary agent and water are added to the powder to obtain a mixture, and then the extrusion molding is performed; preferably, the auxiliary agent is at least one of phosphoric acid, formic acid, ethanolamine and polyvinyl alcohol, and the auxiliary agent can bond materials, so that the forming pore structure and strength of the catalyst can be effectively improved; more preferably, the mass ratio of the auxiliary agent to the powder is 10-15%; preferably, the mass ratio of the water to the powder is 0.5-0.7: 1, the strength of the finished catalyst product can be improved by carrying out extrusion forming according to the water-powder ratio, and the radial strength of the finished catalyst product is the maximum and can reach 85N/cm.
In the above method for preparing a non-toxic catalyst for VOCs, as a preferred embodiment, in the step 3, the molded object is a granular object or a columnar object; preferably, the granules or pillars have a particle size of 1.5-4.0 mm. When the shaped article is a pillar, the particle size refers to the diameter of the horizontal cross section of the pillar.
In the above preparation method of the non-toxic catalyst for VOCs, as a preferred embodiment, in the step 3, the drying temperature is 100-120 ℃ and the drying time is 8-10 hours.
In the above method for preparing nontoxic catalysts for VOCs, as a preferred embodiment, in the step 3, the calcination temperature is 600-750 ℃ (e.g. 620 ℃, 640 ℃, 660 ℃, 680 ℃, 700 ℃, 720 ℃, 740 ℃) for 2-4 hours (e.g. 2.5 hours, 3 hours, 3.5 hours); more preferably, the calcination temperature is 650-700 ℃. The calcination temperature may affect the structure and activity of the catalyst, and specifically, the calcination temperature may affect the decomposition state of the catalyst precursor component, affect the valence, physicochemical structure and dispersity of the active component on the surface of the catalyst, and also affect the pore structure of the carrier, which are important factors for the activity of the catalyst. When the temperature is higher than 750 ℃, the crystal grain size of the catalyst is rapidly increased, which shows that Mn ions are separated from CeO2In crystal lattice migration to CeO2Surface of CeO2The unit cells aggregate, causing the catalyst to sinter, the pore channels to collapse, and the catalytic efficiency to decrease.
In the above method for preparing non-toxic VOCs catalyst, as a preferred embodiment, the molar ratio of Mn: Ce: C in the final catalyst is (0.01-0.02): (0.04-0.06):1, preferably, Mn: Ce: C is 0.02:0.05:1, 0.02:0.06:1, 0.01:0.04: 1.
The VOCs non-toxic catalyst is prepared by adopting the preparation method of the VOCs non-toxic catalyst.
A non-toxic catalyst for VOCs comprises activated carbon and MnOx-CeO2 composite oxide loaded on the activated carbon.
In the above VOC non-toxic catalyst, as a preferred embodiment, the Mn: Ce: C ═ 0.01 to 0.02 (0.04 to 0.06):1, preferably, the Mn: Ce: C ═ 0.02:0.05:1, 0.02:0.06:1, 0.01:0.04:1, in the final catalyst product, in a molar ratio.
Among the above-mentioned VOC non-toxic catalysts, as a preferred embodiment, the VOC non-toxic catalyst has a specific surface area of 1200-1500m2/g。
Among the above-mentioned VOC non-toxic catalysts, as a preferred embodiment, the strength of the VOC non-toxic catalyst is 75 to 88N/cm.
Compared with the prior art, the invention has the following positive effects:
(1) the invention adopts active carbon as a carrier and synthesizes MnOx-CeO2The composite oxide catalyst is loaded on the active carbon powder, and a cylindrical catalyst finished product is obtained by kneading, extrusion molding, drying and roasting. The catalyst prepared by the method has long service life (50% longer than that of the common catalyst of the same type), and high efficiency.
(2) MnO obtained in the preparation process of the catalyst does not need to be preparedx-CeO2The contained water is completely removed, the energy consumption is low, and the prepared catalyst has good economical efficiency and practicability.
(3) The catalyst prepared by the invention is nontoxic and friendly to human body and environment.
(4) The invention adopts the active carbon as the carrier of the catalyst, so that the catalyst can be better dispersed on the surface of the active carbon, and in addition, the active carbon has developed specific porosity and large surface area, can more quickly adsorb VOCs, and increases the catalytic efficiency of the catalyst.
(5) The invention adopts a new mode of combining the catalyst and the activated carbon carrier, adopts a mode of adhering and extruding and granulating by an extruder, and is more suitable for indoor purification product types such as an air purifier and the like. The activated carbon has the function of absorbing VOCs and MnOx-CeO2The catalyst is well dispersed in the activated carbon, so that the adsorbed VOCs can be easily catalyzed and oxidized, and the removal efficiency and the removal total amount of the VOCs are greatly improved.
Detailed Description
In order to highlight the objects, technical solutions and advantages of the present invention, the present invention is further illustrated by the following examples, which are presented by way of illustration of the present invention and are not intended to limit the present invention. The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
Example 1
The preparation method of the VOC non-toxic catalyst of the embodiment is as follows:
(1) preparing a cerous nitrate and manganese nitrate aqueous solution with the total concentration of cerium and manganese being 1mol/L, wherein the molar ratio of cerium to manganese is 5:2, adding excessive ammonia water serving as a precipitator, adding hydrogen peroxide (serving as an oxidant) until the pH of the solution is 9, adding 0.3% mass fraction of polyethylene glycol [ namely, the addition amount of the polyethylene glycol is 0.3% of the total mass of the aqueous solution ], and stirring for 30 minutes to perform a chelation reaction. Aging the solution containing precipitate at room temperature for 6 hr, filtering, drying the filtered precipitate at 100 deg.C to obtain catalyst precipitate with water content of 20%, pulverizing, and calcining at 650 deg.C for 4 hr to obtain MnOx-CeO2(specific surface area of 112 m)2/g)。
(2) MnO to be preparedx-CeO2Mixing the powder with activated carbon powder according to a mass ratio of 1:10 (the iodine value of the activated carbon is 1100, the CTC value is 80) to obtain mixed powder, adding auxiliary agent phosphoric acid and water into the mixed powder, wherein the addition amount of the auxiliary agent accounts for 10% of the mass of the powder, the mass ratio of the water powder is 1:2, extruding and molding the mixture by an extruder, forming the formed product into columnar granules (the particle size is 1.5mm, namely the cross section diameter of the columnar granules is 1.5mm), drying the columnar granules for 10 hours at the temperature of 100 ℃, and roasting the columnar granules for 2 hours at the roasting temperature of 650 ℃ to obtain a columnar catalyst finished product, wherein the Mn: Ce: C in the catalyst finished product is 0.02:0.05:1 (molar ratio), and the specific surface area of the catalyst finished product is 1300m2In terms of/g, the strength was 88N/cm.
Test of xylene degradation Performance:
the experiment was carried out in two completely closed 3 cubic meters laboratory chambers with identical conditions, into both of which xylene (representative of VOC) gas was introduced to bring the xylene concentration in the laboratory chamber to 1 ppm. Then 100 g of the finished catalyst prepared in example 1 was placed in one of the chambers, the other chamber was used as a blank control, a fan was started to stir air, and under the same conditions of temperature and humidity (room temperature and humidity of about 30%), the xylene content in the chamber into which the catalyst was placed after 24 hours was 5% of the xylene content in the blank chamber, i.e., the catalyst was prepared with a xylene removal rate of 95% after 24 hours.
Example 2:
the preparation method of the VOC non-toxic catalyst of the embodiment is as follows:
(1) preparing an aqueous solution of cerous nitrate and manganese nitrate with the total concentration of cerium and manganese being 1mol/L, wherein the molar ratio of cerium to manganese is 4:1, adding excessive ammonia water serving as a precipitator, adding hydrogen peroxide (serving as an oxidant) until the pH of the solution is 9, adding polyethylene glycol accounting for 0.3% of the mass of the aqueous solution, and stirring for 30 minutes to carry out the chelating reaction. Aging the solution containing precipitate at room temperature for 8 hr, filtering, drying the precipitate at 120 deg.C, pulverizing, and calcining at 600 deg.C for 4 hr to obtain 30% water catalyst MnOx-CeO2(specific surface area 82.5 m)2/g)。
(2) MnO to be preparedx-CeO2Mixing the powder with activated carbon powder (iodine value 1200, CTC value 85) according to the mass ratio of 1:10 to obtain mixed powder, adding auxiliary agent phosphoric acid and water into the mixed powder, wherein the addition amount of the auxiliary agent accounts for 10% of the mass of the powder, the mass ratio of the water powder is 1:1, then extruding and molding the powder by an extruder, and obtaining a molded product which is columnar granules (the particle size is 2.0mm), then drying the molded product for 10 hours at 120 ℃, and roasting the molded product for 4 hours at 700 ℃ to obtain a columnar catalyst finished product. Wherein the molar ratio of Mn to Ce to C in the finished catalyst is 0.01:0.04:1, and the specific surface area of the finished catalyst is 1500m2G, strength 80N/cm.
Test of xylene degradation Performance:
experiments are carried out in two completely closed 3 cubic meters experiment chambers with completely identical conditions, xylene (representative of VOC) gas is introduced into the two chambers, the concentration of the xylene in the experiment chambers reaches 1ppm, then 100 g of the finished catalyst prepared in the example 2 is placed into one chamber, the other experiment chamber is used as a blank control, a fan is started for air stirring, under the condition that all conditions such as temperature and humidity (room temperature and humidity are about 30 percent) are identical, the xylene content in the experiment chamber in which the catalyst is placed after 24 hours is 15 percent of that in the blank experiment chamber, and the xylene clearance rate of the prepared catalyst after 24 hours reaches 85 percent.
Example 3
In this example 3, the mass ratio of the water powder was 1:1, and the other conditions were the same as in example 1.
The results were: the ratio of Mn to Ce to C in the finished catalyst is 0.02 to 0.05 to 1, and the specific surface area of the finished catalyst is 1300m2G, strength 80N/cm.
Example 4
In this example 4, the mass ratio of the water powder was 1:3, and the other conditions were the same as in example 1.
The results were: the ratio of Mn to Ce to C in the finished catalyst is 0.02 to 0.05 to 1, and the specific surface area of the finished catalyst is 1300m2G, strength 75N/cm.
Comparative example 1
In this comparative example, MnO was prepared in step (1)x-CeO2The calcination temperature was 800 ℃ and the other conditions were the same as in example 1, and the results were: MnOx-CeO2The specific surface area is 55m2The xylene removal efficiency was 60% per g.
Comparative example 2
In this comparative example 2, MnO was prepared in the step (1)x-CeO2The calcination temperature was 550 ℃ and the other conditions were the same as in example 1, with the results that: MnOx-CeO2The specific surface area is 70m2The xylene removal efficiency was 75% per g.
Example 5
In this example, MnO in step (2)x-CeO2The mass ratio of the activated carbon powder to the activated carbon powder was 1:5, and the other conditions were the same as in example 1, and the results were: the xylene removal efficiency was 92%.
Example 6
In this example, MnO in step (2)x-CeO2The mass ratio of the activated carbon powder to the activated carbon powder was 1:15, and the other conditions were the same as in example 1, and the results were: the xylene removal efficiency was 80%.
Example 7
In this example, MnO in step (2)x-CeO2The mass ratio of the activated carbon powder to the activated carbon powder was 1:20, and the other conditions were the same as in example 1, and the results were: the xylene removal efficiency was 65%.
Example 8
In this example, the molar ratio of cerium to manganese in step (1) was 3:1, and the rest of the conditions were the same as in example 1, resulting in MnOx-CeO2The specific surface area is 100m2The xylene removal efficiency of the finished catalyst is 90 percent.
Example 9
In this example, the calcination temperature in step (2) was 400 ℃ and the other conditions were the same as in example 1, and the specific surface area of the final catalyst product was 900m2The xylene removal efficiency of the finished catalyst is 70%.
Example 10
In this example, the calcination temperature in step (2) was 800 ℃ and the other conditions were the same as in example 1, and the specific surface area of the final catalyst product was 1200m2The xylene removal efficiency of the finished catalyst is 60 percent.
Claims (10)
1. A preparation method of a VOCs non-toxic catalyst is characterized by comprising the following steps:
step 1, preparing an aqueous solution containing cerium salt and manganese salt, then adding a precipitator and an oxidant into the aqueous solution, then adding a chelating agent (to chelate the generated oxide for convenient extraction) and stirring to obtain a solution containing primary precipitate;
step 2, aging the solution containing the primary precipitate, filtering, drying the precipitate obtained after filtering, and roasting the dried precipitate to obtain MnOx-CeO2；
Step 3, MnO is addedx-CeO2Mixing with activated carbon to obtain powder, and then extruding and molding to obtain a molding material; and drying and roasting the formed product in sequence to obtain a catalyst finished product.
2. The method of claim 1, wherein in the aqueous solution of step 1, the molar ratio of cerium ions to manganese ions is 2-5:1, preferably the molar ratio of cerium ions to manganese ions is 5:2, 3:1, 4: 1; preferably, the cerium salt is at least one of cerous nitrate, cerous acetate, cerous sulfate and cerous nitrate; preferably, the manganese salt is manganese nitrate and/or manganese sulfate;
preferably, the total concentration of the cerium ions and the manganese ions in the aqueous solution is 0.9 to 1.2 mol/L.
3. The method of claim 1 for preparing nontoxic catalysts for VOCs,
in the step 1, the precipitant is at least one of ammonia water, ammonium carbonate and ammonium bicarbonate;
preferably, in the step 1, the oxidant is hydrogen peroxide and/or sodium chlorate; more preferably, the oxidizing agent is added in an amount such that the pH of the aqueous solution is 9 to 10;
preferably, in the step 1, the chelating agent is at least one of polyethylene glycol, ethylene diamine tetraacetic acid tetrasodium salt and EDTA, and the addition amount of the chelating agent is 0.2-0.4% of the mass of the aqueous solution;
preferably, in the step 1, the stirring time is 30 to 40 minutes.
4. The method of claim 1, wherein in step 2, the aging time is 6-8 hours; preferably, the aging refers to standing the solution containing the primary precipitate at normal temperature for 6-8 hours;
preferably, in the step 2, the temperature of the drying is 100-120 ℃;
preferably, in the step 2, the water content of the dried precipitate is 20-30%; preferably, in the step 2, the MnOx-CeO2MnO of mediumxIs MnO and Mn2O3And MnO2Mixtures of the like manganese-containing compounds; more preferably, X ═ 2-4; more preferably, in the step 2, the temperature of the calcination is 600-750 ℃.
5. The method as claimed in claim 1, wherein in step 3, the iodine value of the activated carbon is 1000-1200, the CTC value is 70-85;
preferably, the MnOx-CeO2The mass ratio of the powder is 4-20%, and the preferable mass ratio is 9-15%;
preferably, before the extrusion molding, an auxiliary agent and water are added into the powder to obtain a mixture, and then the extrusion molding is performed;
preferably, the auxiliary agent is at least one of phosphoric acid, formic acid, ethanolamine and polyvinyl alcohol; more preferably, the mass ratio of the auxiliary agent to the powder is 10-15%; preferably, the mass ratio of the water to the powder is 0.5-0.7: 1; preferably, the molding is a granular object or a columnar object; preferably, the granules or pillars have a particle size of 1.5-4.0 mm.
6. The method as claimed in claim 1, wherein in step 3, the drying temperature is 100-120 ℃ and the drying time is 8-10 hours;
preferably, in the step 3, the roasting temperature is 600-750 ℃ and the roasting time is 2-4 hours; more preferably, the roasting temperature is 650-700 ℃;
preferably, the molar ratio of Mn to Ce to C in the finished catalyst is (0.01-0.02): (0.04-0.06):1, and preferably, the molar ratio of Mn to Ce to C is 0.02:0.05:1, 0.02:0.06:1, 0.01:0.04: 1.
7. A non-toxic catalyst for VOCs, wherein the non-toxic catalyst for VOCs is prepared by the method for preparing the non-toxic catalyst for VOCs according to any one of claims 1 to 6.
8. The non-toxic catalyst for VOCs is characterized by comprising activated carbon and MnOx-CeO2 composite oxide loaded on the activated carbon.
9. A non-toxic catalyst for VOCs according to claim 8, wherein the molar ratio of Mn to Ce to C in the final catalyst is 0.01-0.02 to 0.04-0.06 to 1, preferably 0.02 to 0.05 to 1, 0.02 to 0.06 to 1, 0.01 to 0.04 to 1.
10. The VOCs non-toxic catalyst of claim 8, wherein the VOC non-toxic catalyst has a specific surface area of 1200-1500m2The strength of the VOC non-toxic catalyst is 75-88N/cm.
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