CN116196889A - Toluene adsorbent prepared from industrial vermiculite and method and application thereof - Google Patents
Toluene adsorbent prepared from industrial vermiculite and method and application thereof Download PDFInfo
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- CN116196889A CN116196889A CN202310224875.9A CN202310224875A CN116196889A CN 116196889 A CN116196889 A CN 116196889A CN 202310224875 A CN202310224875 A CN 202310224875A CN 116196889 A CN116196889 A CN 116196889A
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910052902 vermiculite Inorganic materials 0.000 title claims abstract description 128
- 239000010455 vermiculite Substances 0.000 title claims abstract description 128
- 235000019354 vermiculite Nutrition 0.000 title claims abstract description 128
- 239000003463 adsorbent Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 68
- 239000011230 binding agent Substances 0.000 claims abstract description 60
- 239000002245 particle Substances 0.000 claims abstract description 50
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005341 cation exchange Methods 0.000 claims abstract description 8
- 239000002689 soil Substances 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000010865 sewage Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 21
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 239000000440 bentonite Substances 0.000 claims description 13
- 229910000278 bentonite Inorganic materials 0.000 claims description 13
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 13
- 239000000428 dust Substances 0.000 claims description 13
- 239000004927 clay Substances 0.000 claims description 9
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000010413 gardening Methods 0.000 claims description 3
- 229910052900 illite Inorganic materials 0.000 claims description 3
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 150000004756 silanes Chemical class 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 238000005453 pelletization Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 61
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 24
- 239000007789 gas Substances 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 description 21
- 150000001555 benzenes Chemical class 0.000 description 16
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 description 12
- 239000011707 mineral Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002912 waste gas Substances 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052628 phlogopite Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000004965 Silica aerogel Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 210000005036 nerve Anatomy 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 208000028389 Nerve injury Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 208000032140 Sleepiness Diseases 0.000 description 1
- 206010041349 Somnolence Diseases 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008764 nerve damage Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- VYMDGNCVAMGZFE-UHFFFAOYSA-N phenylbutazonum Chemical compound O=C1C(CCCC)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 VYMDGNCVAMGZFE-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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
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- 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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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention provides a toluene adsorbent prepared from industrial vermiculite, and a method and application thereof. The method comprises the steps of: stripping and removing impurities from the raw industrial vermiculite ore to obtain refined industrial vermiculite slices; grinding the industrial vermiculite fine flakes to obtain industrial vermiculite powder; uniformly mixing industrial vermiculite powder with a binder, and granulating to obtain industrial vermiculite particles; and (3) carrying out post-treatment on the industrial vermiculite particles to obtain the adsorbent. The adsorbent can be prepared by the method. The applications may include purification of benzene-based gases such as toluene, sewage treatment, horticultural planting, soil improvement and agricultural carrier applications. The adsorbent has the advantages of high cation exchange capacity, large internal specific surface area, strong adsorption of toluene, light weight, multiple pores and the like, and the preparation method has the advantages of simple process, environment friendliness, low production cost and easiness in large-scale production.
Description
Technical Field
The invention relates to the field of preparing functional mineral materials from nonmetallic mineral raw materials, in particular to a toluene adsorbent prepared from industrial vermiculite, a method and application thereof.
Background
Benzene is a general term for benzene derivatives, and includes all aromatic compounds in a broad sense, and includes BTEX in a narrow sense, i.e., benzene (benzone), toluene (tolene), ethylbenzene (ethylbenzone), and xylene (xylene). Benzene series are widely detected in human living environment due to pollution in production and living, and have strong harm to human body and environment. Toluene, for example, is a commonly used organic aid in petroleum, pharmaceutical and chemical industries, and is one of the important causes of elevated ozone concentration, global warming and regional photochemical smog pollution due to its high volatility and ease of entering the atmosphere. Toluene has serious toxicity to human and animals, and various lesions such as nerve injury and cell canceration of human body can be caused by long-time exposure to toluene-containing environment. Deep toluene poisoning can have a severe effect on central nerves, manifested as strong excitation or inhibition of nerves, such as agitation, dullness, somnolence, etc.
Industrial vermiculite is a kind of layered silicate mineral containing vermiculite crystal layer, an important nonmetallic mineral product. The industrial vermiculite has the characteristics of extremely large internal specific surface area, high cation exchange capacity, strong adsorptivity and the like, and can be used as a catalyst, an adsorbent, a soil heavy metal stabilizer and the like. At present, cr in industrial and domestic sewage is treated by utilizing adsorption performance of vermiculite 3+ 、Cu 2+ 、Pb 2+ 、Ag + 、Cd 2+ Many studies on the equivalent weight metal ions are reported, but the study on the adsorption of benzene compounds and other organic gaseous pollutants and the technology for preparing industrial vermiculite adsorbents have not been reported yet.
At present, benzene series pollution is most commonly usedThe method is an adsorption method, and common adsorbents comprise active carbon, active carbon fibers, molecular sieves and the like, and various adsorbents generally have uneven effects and have the problems of higher raw material cost, complex modification process, easiness in ageing and difficult recovery after the use of the adsorbents and the like. For example, conventional toluene adsorbents are activated carbon, zeolite molecular sieves, silica aerogel, and the like. The benzene series is a weak polar substance, the adsorption capacity of the activated carbon to toluene is large, but the benzene series has the problems of uneven pore size distribution, low content of surface functional groups, easy poisoning and the like, and most of the benzene series needs to be subjected to complicated modification treatment, so that the raw material cost is high; the zeolite molecular sieve has lower specific surface area and porosity, less adsorption quantity to benzene series, more complex synthesis and preparation process and higher raw material cost; the silica aerogel has the characteristics of low density, specific surface area and large surface energy, and the adsorption capacity of the p-toluene can reach 5-200 mg/m 3 However, the application as an adsorbent is limited due to the complicated preparation process due to the uneven pore size distribution.
Therefore, the development of the benzene series adsorbent with high efficiency and low cost has important significance.
Disclosure of Invention
The present invention aims to address at least one of the above-mentioned deficiencies of the prior art. For example, it is an object of the present invention to achieve efficient adsorption and purification of benzene series.
In order to achieve the above object, the present invention provides, in one aspect, a method for preparing a toluene adsorbent from industrial vermiculite.
The method may comprise the steps of: stripping and removing impurities from the raw industrial vermiculite ore to obtain refined industrial vermiculite slices; grinding the industrial vermiculite fine flakes to obtain industrial vermiculite powder; uniformly mixing industrial vermiculite powder with a binder, and granulating to obtain industrial vermiculite particles; and (3) carrying out post-treatment on the industrial vermiculite particles to obtain the industrial vermiculite benzene series adsorbent, namely the adsorbent.
Alternatively, the cation exchange capacity of the technical vermiculite fine powder may be 30-180 mmol/100g.
Alternatively, the particle size of the industrial vermiculite powder may be: -100 to-325 mesh.
Alternatively, the binder may comprise one or more of an inorganic binder and an organic binder; wherein the inorganic binder may include one or more of bentonite powder, kaolin powder, attapulgite clay powder, sepiolite clay powder and illite clay powder; the organic binder may include one or more of sodium carboxymethyl cellulose, polyacrylamide, polyvinyl alcohol, and MS-modified silane.
Alternatively, in the case of using only an inorganic binder, the mass ratio of the industrial vermiculite powder to the inorganic binder may be 1:0.2 to 0.8;
in the case of using only an organic binder, the mass ratio of the industrial vermiculite powder to the organic binder may be 1:0.02-0.08;
in the case of using both inorganic and organic binders, the mass ratio of the industrial vermiculite powder to the inorganic and organic binders may be 1 (0.15-0.6): 0.015-0.06.
Alternatively, the granulation may be extrusion granulation using an extruder, rotary disk granulation, or rotary disk granulation.
Alternatively, the shape of the industrial vermiculite particles may include cylindrical and/or spherical; wherein, the diameter of the cylinder can be 1 mm-5 mm, and the length can be 2 mm-10 mm; the diameter of the spherical particles may be 1mm to 5mm.
Alternatively, the post-treatment of the industrial vermiculite particles may include drying and dust removal. Wherein, the drying can be air-dried or dried in a drying device with the temperature not exceeding 200 ℃; the dust removal can be to remove the dried industrial vermiculite particles by sieving or industrial vacuum dust collection equipment to remove the particles with the granularity less than 0.1 mm.
In another aspect, the invention provides an adsorbent.
The moisture content of the adsorbent can be less than 10%, and the dust content can be less than 1%.
The saturated adsorption capacity of the adsorbent for toluene can be 30 mg/g-200 mg/g, and the adsorption rate from the beginning of adsorption to 2 hours can be up to 67% -83%.
In yet another aspect, the invention provides the use of an adsorbent.
The applications may include the use of the adsorbent in gas purification, sewage treatment, horticultural planting, soil improvement and agricultural carriers.
Alternatively, the gas clean-up may include adsorption of benzene-based gases, such as organic gases like benzene, toluene, ethylbenzene, xylenes, etc. Further alternatively, the catalyst can be used for adsorbing toluene, and has good adsorption effect.
Compared with the prior art, the invention has the beneficial effects that at least one of the following contents is included:
(1) The industrial vermiculite adsorbent prepared by the invention belongs to a typical inorganic nonmetallic mineral material, and has high cation exchange capacity (up to about 180mmol/100 g) and large internal specific surface area (up to 750 m) 2 High adsorption rate to toluene (adsorption capacity of 30-200 mg/g for two hr) and light porous (volume weight of 50-200 kg/m) 3 ) Has the advantages of (a).
(2) The adsorbent prepared by using the industrial vermiculite is used for adsorbing and purifying gases containing benzene series in industrial production, such as benzene, ethylbenzene, xylene and the like, and is applied to the fields of gardening planting, soil improvement, agricultural carriers and the like.
(3) The raw materials and the auxiliary materials used in the production of the invention have low price and excellent performance, and have better economic and social benefits.
(4) The industrial vermiculite adsorbent prepared by the invention is short cylindrical or spherical, the crystal layer structure of the vermiculite is not destroyed in the preparation process, and the industrial vermiculite adsorbent still has diffraction characteristics of vermiculite, vermiculite-phlogopite interlayer minerals, phlogopite and the like on an XRD diffraction pattern.
(5) The preparation method of the adsorbent has the advantages of simple process, environment friendliness, low production cost, easiness in large-scale production, and difficulty in ageing and easiness in recovery.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate a further understanding of the invention and, together with the description, serve to explain the principles of the invention, the above and other objects and/or features of the invention, should become apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 shows a schematic flow diagram of a method for preparing toluene adsorbent from industrial vermiculite in example 1 of the present invention;
FIG. 2A shows a physical diagram of an industrial vermiculite fine flake of the present invention;
FIG. 2B shows the gray scale of FIG. 2A;
FIG. 3 shows XRD patterns of the adsorbents of the present invention;
fig. 4 shows an external profile of the adsorbent of the present invention.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to exemplary embodiments and drawings, but the following embodiments are only for the purpose of aiding in understanding the technology of the present invention, and are not to be construed as further limiting the scope of the present invention.
Example embodiment 1
The present exemplary embodiment provides a method for preparing toluene adsorbent from industrial vermiculite. FIG. 1 shows a flow chart of the adsorbent preparation process of the present invention, as shown in FIG. 1, which may include the steps of:
s01: stripping and removing impurities from the raw industrial vermiculite ore to obtain the industrial vermiculite fine tablet.
In this embodiment, the main mineral composition of the industrial vermiculite may include vermiculite, regular and irregular interlayer minerals of vermiculite-gold mica crystal layer, regular and irregular interlayer minerals of vermiculite-black mica crystal layer, and regular and irregular interlayer minerals of vermiculite-chlorite crystal layer, and a small amount of impurity minerals phlogopite and/or biotite, etc.
In this example, the industrial vermiculite flakes, as shown in fig. 2A and 2B, may be brown or dark green with a greasy luster.
In this example, the cation exchange capacity of the technical vermiculite flakes may be 30 to 180mmol/100g, e.g. 40, 50, 70, 100, 120, 145, 160, 175mmol/100g etc.
S02: grinding the industrial vermiculite fine flakes to obtain industrial vermiculite powder.
In this embodiment, the particle size of the industrial vermiculite powder may be-100 mesh to-325 mesh (i.e. 100 mesh sieve mesh (coarsest sieve mesh) to 325 mesh (finest sieve mesh, also 200 mesh, 250 mesh and other different sieve meshes), i.e. < 0.15mm to < 0.044mm, such as-100, -150, -200, -250, -300, -325 mesh, wherein, -100 mesh means undersize powder capable of passing 100 mesh, i.e. 100 mesh, 325 mesh means undersize powder capable of passing 325 mesh, i.e. 325 mesh.
S03: and uniformly mixing the industrial vermiculite powder with a binder, and granulating to obtain the industrial vermiculite particles.
In this example, as one embodiment of the present invention, the binder may include an inorganic binder. The inorganic binder may include at least one of bentonite powder, kaolin powder, attapulgite clay powder, sepiolite clay powder and illite clay powder. The mass ratio of the industrial vermiculite powder to the inorganic binder may be 1:0.2 to 0.8, for example 1:0.25, 1:0.4, 1:0.5, 1:0.75, etc.
As another embodiment of the present invention, the binder may include an organic binder. The organic binder may include at least one of sodium carboxymethyl cellulose, polyacrylamide, polyvinyl alcohol, and MS-modified silane. The mass ratio of the industrial vermiculite powder to the organic binder may be 1:0.02-0.08, for example 1:0.03, 1:0.04, 1:0.05, 1:0.07, 1:0.075, etc.
As still another embodiment of the present invention, the binder used may include both the inorganic binder and the organic binder described above. In this case, the mass ratio of the industrial vermiculite powder, the inorganic binder and the organic binder may be 1:0.15 to 0.6 (e.g., values of 0.16, 0.2, 0.4, 0.5, 0.58, etc.) to 0.015 to 0.06 (e.g., values of 0.018, 0.02, 0.04, 0.05, 0.058, etc.).
The mass ratio of the industrial vermiculite powder to the binder is one of the important factors affecting the structure and performance of the industrial vermiculite particles. If the consumption of the binder is too small, the industrial vermiculite powder cannot be bonded, so that granulation failure can be caused, and inferior industrial vermiculite particles cannot be produced; and when the binder is used in an excessive amount, the produced industrial vermiculite particles have the defects of pore structure blockage and reduced specific surface area, so that the adsorption capacity of the industrial vermiculite toluene adsorbent is reduced.
In this embodiment, the granulation method used in the present invention may include an extruder extrusion granulation method or a rotary granulation method. The rotary granulation method may include a round pot rotary granulation method or a disk rotary granulation method.
In this embodiment, the morphology of the industrial vermiculite particles may include cylindrical and spherical.
Wherein the diameter of the cylindrical particles may be 1mm to 5mm, for example, 1.5, 2, 3, 4, 4.5mm, etc., and the length may be 2mm to 10mm, for example, 2.5, 3, 4, 5, 7, 8, 9, 9.5mm, etc.
The diameter of the spherical particles may be 1mm to 5mm, for example, 1.2, 2, 3, 4, 4.8mm, etc. By controlling the shape and the size of the particle bodies within the requirements, the adsorbent and benzene series molecules can be ensured to be fully contacted, and better adsorption performance is realized.
S04: and (5) carrying out post-treatment on the industrial vermiculite particles to obtain the adsorbent.
In this embodiment, the post-treatment may include drying. The adsorbent obtained after drying has better adsorption performance.
Wherein, the drying can be by adopting a drying or baking mode. The drying can be performed in drying equipment with the temperature not exceeding 200 ℃, the drying temperature is controlled between 50 ℃ and 200 ℃, industrial vermiculite particles are not easy to dry when the temperature is lower than 50 ℃, the dehydration efficiency is low, and vermiculite in the industrial vermiculite particles expands due to heating when the temperature is higher than 200 ℃, so that the vermiculite particles are broken, and the granulating effect is poor or fails.
Further, after drying, the post-treatment stage may also include dust removal.
The dust removal can remove the powder particles with the granularity smaller than 0.1mm in the dried industrial vermiculite particles, because the powder particles with the granularity smaller than the prior art are easy to block pores among the particles, influence the flow of gas among the particles, further influence the adsorption rate and the adsorption effect of the adsorbent, and cause dust to fly easily. The powder particles with the particle diameter smaller than 0.1mm after dust removal can be used as raw materials to be added into the granulating process for re-granulating. The dust removal may be by screening or industrial vacuum equipment.
The adsorbent prepared by the invention can be used for adsorbing and purifying benzene series gases, such as benzene, toluene, ethylbenzene, xylene and other organic gases. The adsorbent prepared by the invention can also be used for treating wastewater. The adsorbent prepared by the invention can also be used in the fields of gardening planting, soil improvement, agricultural carriers and the like.
Example embodiment 2
The present exemplary embodiment provides an adsorbent. The adsorbent may be prepared by the method of example 1.
Figure 3 shows the XRD pattern of the adsorbent of the present invention. Wherein, the XRD patterns of the adsorbents prepared from industrial vermiculite powder with different granularity (-300 meshes, -200 meshes and-100 meshes) are respectively from top to bottom in the figure. FIG. 4 shows an external appearance map of the industrial vermiculite particles (i.e. adsorbents) prepared by the invention, wherein the average particle size of the particles is 1mm + -0.2 mm.
The adsorbent can be in a short cylindrical shape or a spherical shape, the crystal layer structure of vermiculite is not destroyed in the preparation process, and as shown in figure 3, the adsorbent still has diffraction characteristics of vermiculite, vermiculite-phlogopite interlayer minerals, phlogopite and the like on an XRD diffraction pattern.
The industrial vermiculite adsorbent prepared by the invention belongs to a typical inorganic nonmetallic mineral material, and has the advantages of high cation exchange capacity, large internal specific surface area, strong adsorptivity to benzene series, light weight, multiple pores and the like. Wherein the cation exchange capacity is up to about 180mmol/100g and the internal specific surface area is up to 750m 2 Per gram, the light porous volume weight is only 50-200 kg/m 3 。
The saturated adsorption capacity of the adsorbent of the invention for toluene can be 30mg/g to 200mg/g, for example 31, 40, 50, 80, 100, 120, 150, 180, 198mg/g. The adsorption rate of the adsorbent is high, and the adsorption capacity of the adsorbent can reach 67-83% of the saturated adsorption capacity from the beginning to 2 hours.
The moisture content of the adsorbent of the present invention is <10%, for example 9%, 8%, etc., and the dust content is <1%, for example 0.8%, 0.7%, 0.5%, etc.
Example embodiment 3
The present exemplary embodiment provides for the use of an adsorbent.
The application can be applied to the adsorption purification of benzene series gas, such as the adsorption purification of toluene gas in industrial production, and the adsorption of benzene, ethylbenzene, xylene and other organic gases in tail gas.
The application may also include application in wastewater treatment for the adsorption of heavy metal ions in industrial or domestic sewage. For example, the heavy metal ion Cr in the water body is adsorbed 3+ 、Cu 2+ 、Pb 2+ 、Ag + 、Cd 2+ Etc., wherein, for Cd 2+ And Pb 2+ The maximum adsorption capacities of (2) are 60mg/g and 167mg/g, respectively, which are related to the hydrated cation layer with exchangeable property in the interlayer domain of vermiculite, and the exchangeable cations such as Ca of heavy metal pollutants and vermiculite in the water body during the adsorption process 2+ 、Na + 、Mg 2+ The plasma produces ion exchange adsorption.
The applications may also include use in horticultural planting, soil improvement, and agricultural vehicles. The specific application mode can be applied in the processes of seeding, fertilizing and soil cultivation.
In order to better understand the above-described exemplary embodiments, they are further described below in connection with specific examples.
Example 1
And respectively grinding the obtained industrial vermiculite fine flakes to-100 meshes to obtain industrial vermiculite powder.
Uniformly mixing the obtained industrial vermiculite powder and the inorganic binder bentonite powder according to the mass percentages of 1:0.2, 1:0.3, 1:0.4, 1:0.5 and 1:0.8 respectively, granulating by adopting a disc rotary granulating method, wherein the granulating appearance is a sphere shape with the diameter of 3mm, and obtaining the industrial vermiculite powder and the inorganic binder bentonite under different proportions.
And drying the industrial vermiculite particles obtained under different proportions at 50 ℃, and sieving to remove particles with the granularity smaller than 0.1mm to obtain 5 adsorbents, wherein the water content of the adsorbents is smaller than 10%.
For 5 adsorbents, 100g of each was added to 5 closed containers containing the same toluene waste gas, and the 5 adsorbents were fully contacted with toluene, and the adsorption amounts of toluene for 5 adsorbents were 68%, 78%, 85%, 83% and 62% of the saturated adsorption amounts, respectively, when the test was performed from the start of adsorption to 2 hours. At 6h, the adsorption capacity of each adsorbent was substantially saturated, and the saturated adsorption capacities were 89, 122, 136, 123 and 79mg/g, respectively.
Example 2
And respectively grinding the obtained industrial vermiculite fine flakes to-150 meshes to obtain industrial vermiculite powder.
Uniformly mixing the obtained industrial vermiculite powder and the inorganic binder bentonite powder according to the mass percentages of 1:0.2, 1:0.3, 1:0.4, 1:0.5 and 1:0.8 respectively, granulating by adopting a disc rotary granulating method, wherein the granulating appearance is a sphere shape with the diameter of 1mm, and obtaining the industrial vermiculite powder and the inorganic binder bentonite under different proportions.
And drying the industrial vermiculite particles obtained under different proportions at the temperature of 70 ℃, and sieving to remove particles with the granularity of less than 0.1mm to obtain 5 adsorbents, wherein the water content of the adsorbents is less than 10%.
For 5 adsorbents, 100g of each was added to 5 closed containers containing the same toluene waste gas, and the 5 adsorbents were fully contacted with toluene, and the adsorption amounts of toluene for the 5 adsorbents were 73%, 79%, 88%, 85% and 71% of the saturated adsorption amounts, respectively, when the test was performed from the start of adsorption to 2 hours. At 6 hours, the adsorption capacity of each adsorbent is basically saturated, and the saturated adsorption capacity is 92mg/g, 128 mg/g, 141 mg/g, 124 mg/g and 86mg/g respectively.
Example 3
And respectively grinding the obtained industrial vermiculite fine flakes to-200 meshes to obtain industrial vermiculite powder.
Uniformly mixing the obtained industrial vermiculite powder and the inorganic binder kaolin powder according to the mass percentages of 1:0.2, 1:0.3, 1:0.4, 1:0.5 and 1:0.8 respectively, granulating by adopting a disc rotary granulating method, wherein the granulating appearance is a sphere shape with the diameter of 1mm, and obtaining the industrial vermiculite powder and the inorganic binder bentonite under different proportions.
And drying the industrial vermiculite particles obtained under different proportions at the temperature of 105 ℃, and sieving to remove particles with the granularity smaller than 0.1mm to obtain 5 adsorbents, wherein the water content of the adsorbents is smaller than 10%.
For 5 adsorbents, 100g of each was added to 5 closed containers containing the same toluene waste gas, and the 5 adsorbents were fully contacted with toluene, and the adsorption amounts of toluene for the 5 adsorbents were 72%, 79%, 85%, 83% and 70% of the saturated adsorption amounts, respectively, when the test was performed from the start of adsorption to 2 hours. At 6 hours, the adsorption capacity of each adsorbent was substantially saturated, and the saturated adsorption capacities were 88, 122, 128, 109, 82mg/g, respectively.
Example 4
Grinding the obtained industrial vermiculite fine flakes to-250 meshes respectively to obtain industrial vermiculite powder.
Uniformly mixing the obtained industrial vermiculite powder and organic binder sodium carboxymethyl cellulose according to the mass percentages of 1:0.02, 1:0.04, 1:0.05, 1:0.06 and 1:0.08 respectively, granulating by adopting a disc rotary granulating method, wherein the granulating appearance is in a sphere shape with the diameter of 1mm, and obtaining the industrial vermiculite powder and inorganic binder bentonite under different proportions.
And drying the industrial vermiculite particles obtained under different proportions at the temperature of 120 ℃, and sieving to remove particles with the granularity smaller than 0.1mm to obtain 5 adsorbents, wherein the water content of the adsorbents is smaller than 10%.
For 5 adsorbents, 100g of each was added to 5 closed containers containing the same toluene waste gas, and the 5 adsorbents were fully contacted with toluene, and the adsorption amounts of toluene for 5 adsorbents were 75%, 82%, 93%, 84% and 80% of the saturated adsorption amounts, respectively, when the test was performed from the start of adsorption to 2 hours. At 6 hours, the adsorption amounts of the adsorbents were substantially saturated, and the saturated adsorption amounts were 100, 156, 167, 149 and 102mg/g, respectively.
Example 5
Grinding the obtained industrial vermiculite fine flakes to minus 325 meshes respectively to obtain industrial vermiculite powder.
Uniformly mixing the obtained industrial vermiculite powder, the inorganic binder bentonite powder and the organic binder sodium carboxymethyl cellulose according to the mass percentages of 1:0.15:0.06, 1:0.2:0.04, 1:0.25:0.02, 1:0.45:0.02 and 1:0.55:0.015 respectively, granulating by adopting a disc rotary granulating method, and obtaining the industrial vermiculite powder and the industrial vermiculite powder under different proportions of the inorganic binder bentonite in a spherical shape with the diameter of 1 mm.
And drying the industrial vermiculite particles obtained under different proportions at the temperature of 150 ℃, and sieving to remove particles with the granularity of less than 0.1mm to obtain 5 adsorbents, wherein the water content of the adsorbents is less than 10%.
For 5 adsorbents, 100g of each was added to 5 closed containers containing the same toluene waste gas, and the 5 adsorbents were fully contacted with toluene, and the adsorption amounts of toluene for the 5 adsorbents were 74%, 85%, 89%, 86% and 81% of the saturated adsorption amounts, respectively, when the test was performed from the start of adsorption to 2 hours. At 6 hours, the adsorption amounts of the adsorbents were substantially saturated, and the saturated adsorption amounts were 98, 127, 131, 113 and 92mg/g, respectively.
Example 6
Grinding the obtained industrial vermiculite fine flakes to minus 325 meshes respectively to obtain industrial vermiculite powder.
Uniformly mixing the obtained industrial vermiculite powder and the inorganic binder bentonite powder according to the mass percentages of 1:0.2, 1:0.3, 1:0.4, 1:0.5 and 1:0.8 respectively, granulating by adopting a disc rotary granulating method, wherein the granulating appearance is a sphere shape with the diameter of 1mm, and obtaining the industrial vermiculite powder and the inorganic binder bentonite under different proportions.
And drying the industrial vermiculite particles obtained under different proportions at 180 ℃, and sieving to remove particles with the granularity smaller than 0.1mm to obtain 5 adsorbents, wherein the water content of the adsorbents is smaller than 10%.
For 5 adsorbents, 100g of each adsorbent was added to 5 closed containers containing the same ethylbenzene waste gas, and the 5 adsorbents were tested from the start of adsorption to 2 hours by fully contacting the 5 closed containers with ethylbenzene, and the adsorption amounts of the 5 adsorbents to toluene reached 72%, 82%, 90%, 86% and 80% of the saturated adsorption amounts, respectively. At 6 hours, the adsorption capacity of each adsorbent was substantially saturated, and the saturated adsorption capacities were 95, 132, 138, 113 and 94mg/g, respectively.
Although the present invention has been described above by way of the combination of the exemplary embodiments, it should be apparent to those skilled in the art that various modifications and changes can be made to the exemplary embodiments of the present invention without departing from the spirit and scope defined in the appended claims.
Claims (10)
1. A method for preparing toluene adsorbent by using industrial vermiculite, comprising the following steps:
stripping and removing impurities from the raw industrial vermiculite ore to obtain refined industrial vermiculite slices;
grinding the industrial vermiculite fine flakes to obtain industrial vermiculite powder;
uniformly mixing industrial vermiculite powder with a binder, and granulating to obtain industrial vermiculite particles;
and (3) carrying out post-treatment on the industrial vermiculite particles to obtain the adsorbent.
2. The method for preparing toluene adsorbent by using industrial vermiculite according to claim 1, wherein the cation exchange capacity of the fine piece of industrial vermiculite is 30-180 mmol/100g.
3. The method of preparing toluene adsorbent from industrial vermiculite according to claim 1, wherein the industrial vermiculite powder has a particle size of: -100 to-325 mesh.
4. The method of preparing toluene adsorbent with industrial vermiculite according to claim 1, wherein the binder includes at least one of an inorganic binder and an organic binder, wherein,
the inorganic binder comprises one or more of bentonite powder, kaolin powder, attapulgite clay powder, sepiolite clay powder and illite clay powder;
the organic binder includes one or more of sodium carboxymethyl cellulose, polyacrylamide, polyvinyl alcohol, and MS-modified silane.
5. The method for producing a toluene adsorbent by using an industrial vermiculite according to claim 4, wherein in the case where the binder includes only an inorganic binder, a mass ratio of the industrial vermiculite powder to the inorganic binder is 1:0.2 to 0.8;
in the case that the binder only comprises an organic binder, the mass ratio of the industrial vermiculite powder to the organic binder is 1:0.02-0.08;
in the case that the binder comprises an inorganic binder and an organic binder, the mass ratio of the industrial vermiculite powder to the inorganic binder to the organic binder is 1 (0.15-0.6) (0.015-0.06).
6. The method of preparing toluene adsorbent from industrial vermiculite according to claim 1, wherein the pelletization method comprises: extrusion granulation by an extruder, rotary granulation by a circular pot or rotary granulation by a circular disk.
7. The method of preparing toluene adsorbent by industrial vermiculite according to claim 1, wherein the shape of the industrial vermiculite particles comprises cylindrical and/or spherical, wherein,
the diameter of the cylindrical particle body is 1 mm-5 mm, and the length is 2 mm-10 mm;
the diameter of the spherical particle body is 1 mm-5 mm.
8. The method for preparing a toluene adsorbent by using industrial vermiculite according to claim 1, wherein the post-treatment includes drying or includes drying and dust removal, wherein,
drying means including air-drying or oven-drying in a drying device at a temperature not exceeding 200deg.C;
dust removal can remove particles with a particle size of less than 0.1 mm.
9. An adsorbent, characterized in that it is produced by the method of any one of claims 1 to 8, the moisture content of the adsorbent being <10% and the dust content being <1%.
10. The use of the adsorbent of claim 9 in the fields of gas purification, sewage treatment, gardening, soil improvement, agricultural carriers and the like.
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