CN112044403A - Preparation method and application of sepiolite-based formaldehyde adsorbent - Google Patents
Preparation method and application of sepiolite-based formaldehyde adsorbent Download PDFInfo
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- 239000004113 Sepiolite Substances 0.000 title claims abstract description 152
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 152
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 152
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003463 adsorbent Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 55
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 29
- 239000000725 suspension Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 238000010306 acid treatment Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 238000002715 modification method Methods 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 210000001508 eye Anatomy 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 206010003497 Asphyxia Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 210000001331 nose Anatomy 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 210000003800 pharynx Anatomy 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01J20/02—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
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
Abstract
The invention discloses a preparation method and application of a sepiolite-based formaldehyde adsorbent. The preparation method comprises the steps of raw sepiolite purification, acid activation and graft modification, namely, the raw sepiolite is purified by a physical sedimentation method, the purified raw sepiolite is activated by acid, and the sepiolite subjected to acid treatment is subjected to appropriate graft modification by adopting amino silane. The sepiolite-based formaldehyde adsorbent prepared by the modification method can effectively and stably adsorb formaldehyde, has better formaldehyde adsorption performance compared with the natural mineral adsorbents of the same type, and is particularly suitable for removing formaldehyde gas; the preparation process is simple, the preparation cost is low, and the method is more favorable for industrial production.
Description
Technical Field
The invention belongs to the field of adsorbent material preparation, and particularly relates to a method for preparing a sepiolite adsorbent by utilizing acid and aminosilane composite modification and application of the sepiolite adsorbent in formaldehyde adsorption and purification.
Background
VOCs means that the saturated vapor pressure is more than 7 at normal temperatureThe organic compound with the boiling point of 50-260 ℃ under the normal pressure and 0Pa comprises saturated hydrocarbon, olefin, alkyne, aromatic hydrocarbon, alcohol, aldehyde, ketone, acid, ester, halogenated hydrocarbon and the like. VOCs have adverse effects on human bodies and the environment, most of VOCs have toxicity and can generate harmful effects on the central nervous systems of the skin, eyes, nose, throat, liver and kidney of people, and the VOCs can generate atmospheric chemical reaction with other pollutants such as nitric oxides, sulfur oxides and the like to generate secondary pollutants such as ozone, secondary organic aerosol, acidic substances and the like, so that non-negligible effects are generated. VOCs are the formation of fine Particulate Matter (PM)2.5) And ozone (O)3) Compared with pollution control of particulate matters, sulfur dioxide and nitrogen oxides, the important precursor in the method is weak in VOCs management basis in China and becomes a short atmospheric environment management board.
At room temperature, formaldehyde is a transparent gas with pungent odor, and is widely used in chemical production in industrial production. The paint and plywood used in the indoor decoration process are the main sources of indoor formaldehyde.
The quality condition of indoor air is closely related to the health of human bodies, formaldehyde is the most typical one of the current indoor air pollutants, the occurrence frequency of formaldehyde is high, the sources are wide, the formaldehyde has great harm to human bodies, suffocation can be caused, strong pungent smell is generated, and the formaldehyde obviously has a stimulating effect on eyes and mucous membranes of people.
In recent years, many researchers have studied formaldehyde pollution treatment methods, including a series of methods such as absorption, adsorption, photocatalysis, plasma, biological methods, etc., but various treatment methods have various problems (such as high cost, limited effect, secondary pollution, etc.) when being popularized and applied. At present, an adsorption method is one of the methods with good treatment effect and wide application, but the method has problems in the aspects of material cost and recycling, and the development of an environment-friendly and low-cost VOC adsorption material is urgently needed.
Disclosure of Invention
The invention aims to provide a method for preparing an adsorbent by using sepiolite and an application technology in formaldehyde adsorption aiming at the defects of the prior art. The sepiolite raw ore is purified and subjected to acid treatment, and then aminosilane and sepiolite in a certain proportion are subjected to graft modification, so that the sepiolite adsorbing material with specific groups is prepared. The adsorbent has the advantages of low price, high selective adsorption capacity and the like due to the self pore volume and pore channel structure and the group function.
In order to solve the technical problems, the preparation method of the sepiolite-based formaldehyde adsorbent comprises the following steps:
(1) purification of raw ore sepiolite
a. Adding raw sepiolite ore and water into a stirring tank, starting a stirrer, and continuously stirring at normal temperature to obtain sepiolite ore slurry;
b. b, adding a dispersing agent into the sepiolite ore slurry obtained in the step a, stirring, and then sending into a settling tank for settling to obtain suspension slurry of the sepiolite and impurity precipitates;
c. and c, dehydrating and drying the sepiolite suspension slurry obtained in the step b, and grinding to obtain the purified sepiolite.
(2) Acid modification of sepiolite
i. Mixing sepiolite powder with a certain volume of acid solution, and standing at normal temperature;
after standing, pouring out the upper layer of acid liquor, repeatedly washing the sepiolite suspension of the lower layer of acid liquor by using deionized water, and adjusting the pH to 6-8;
and iii, carrying out centrifugal separation, drying and grinding on the acid-treated sepiolite obtained in the step b to obtain the acid-treated sepiolite.
(3) Acid-treated sepiolite grafting modification
A. Adding the acid-treated sepiolite obtained in the step (2) into an organic solvent, stirring to obtain a mixed solution, then adding aminosilane, and continuously stirring to react;
B. and D, washing the suspension obtained in the step A with an organic solution to remove the organic solvent and the ungrafted silane, drying and grinding to obtain solid powder, namely the sepiolite modified by the acid-amino silane composite.
Further, the mass ratio (short for solid-to-liquid ratio) of the sepiolite raw ore and water in the step a is preferably 1: 5-20, and more preferably 1: 15-20; the stirring rate is preferably 50 to 900rmp, more preferably 600 to 900 rmp.
Furthermore, the dispersant in the step b is one or the combination of more than two of polyphosphate, and the adding amount of the dispersant is 0.1 to 1 percent of the mass of the sepiolite raw ore, and more preferably 0.2 to 0.4 percent; the settling time is preferably 30min or more, more preferably 180min or more, and further preferably 180 to 1200 min.
Further, a vacuum filter is adopted for dehydration in the step c.
Further, the acid in the step i is one or more of hydrochloric acid, sulfuric acid or nitric acid, and hydrochloric acid is more preferable; the concentration (by hydrogen ion concentration) of the acid solution is 0.01-12 mol/L; the mass ratio (solid-liquid ratio) of the purified sepiolite to the acid solution is 1: 5-15, preferably 1: 5-10; the standing time is 3-48 h, and more preferably 3-12 h.
And further, the deionized water is used for washing away the acid liquid in the step ii, specifically, the suspension is separated by using a centrifuge, the upper layer of acid liquid is poured into a waste liquid pool, the solid is transferred into a container, water is added, stirring is carried out until no solid particles exist at the bottom of the container, the suspension is obtained, then the centrifuge is used for separating, and the operation is repeated for 3-5 times.
Further, in the step iii, the drying temperature is 90-120 ℃, and the drying time is 12-48 h.
Further, the organic solvent in the step A is toluene, and the mass ratio (solid-to-liquid ratio) of the acid-treated sepiolite to the organic solvent is 1: 20-50, and more preferably 1: 25-50; the stirring time is 30min to 3h, preferably 30min to 2 h.
Further, the aminosilane in the step A is preferably 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane;
the addition amount of the amino silane is preferably 5 to 100 percent of the mass of the acid-treated sepiolite, and the stirring time is 4 to 24 hours.
Further, the organic solution used in the step B is methanol, the drying temperature is 50-80 ℃, and the drying time is 30 min-2 h.
The invention further provides the aminosilane modified sepiolite adsorbent prepared by the method.
The invention further provides application of the aminosilane modified sepiolite adsorbent in adsorbing formaldehyde gas.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention compounds amino silane with sepiolite by purifying, acid treating and grafting amino silane to improve the surface and pore structure of sepiolite, which combines the advantages of amino silane adsorbent and solid adsorbent effectively to improve the adsorption property of sepiolite-base adsorbent to formaldehyde.
(2) The preparation method of the aminosilane modified sepiolite adsorbent has the advantages of low cost of the used immobilized material, simple and feasible process and contribution to large-scale and industrial development. The prepared aminosilane modified sepiolite adsorbent is low in price, high in adsorption efficiency and convenient to use. The advantages of the components of the sepiolite solid adsorbent and the aminosilane can be effectively exerted, and the adsorption performance and the practical application capability of the sepiolite solid adsorbent and the aminosilane are improved.
(3) The invention realizes the precedent of preparing the sepiolite grafted aminosilane adsorbent and applying the sepiolite grafted aminosilane adsorbent to formaldehyde adsorption, and the prepared adsorbent has low price and convenient and effective use. The invention solves the problems of complex preparation, high price and high requirements on equipment and environment of the traditional formaldehyde solid adsorbent.
Detailed Description
The present invention will be further described with reference to specific examples.
Example 1
The embodiment provides a preparation method of an aminosilane modified sepiolite adsorbent, which is characterized by purifying raw ore sepiolite, treating the raw ore sepiolite with an acid solution with a certain concentration for a period of time, and combining a certain proportion of aminosilane and sepiolite by using a grafting method on the basis to prepare a hydrophobic acid-ammonia composite modified sepiolite adsorption material; the method specifically comprises the following steps:
(1) purification of raw ore sepiolite (refer to patent publication No. CN106745014A)
a. Weighing 20g of raw ore sepiolite powder, adding water to 400ml, and stirring at room temperature for 3 h; after stirring, pouring into a separating funnel, standing for layering, taking the sepiolite turbid liquid at the lower layer, continuously adding water to 400ml, stirring for 1h, pouring into the separating funnel again for standing for layering, and repeating the steps until no layering occurs to obtain sepiolite ore slurry;
b. adding 0.48g of sodium hexametaphosphate, continuously stirring for 3h, and standing for 48h to obtain suspension slurry of sepiolite and impurity precipitate;
c. and (3) taking the sepiolite suspension slurry on the upper layer for centrifugal separation, drying for 24 hours in a drying oven at 110 ℃, and grinding to obtain the purified sepiolite.
(2) Acid modification of purified sepiolite
i. Weighing 5g of purified sepiolite, adding 100ml of hydrochloric acid with the mass fraction of 1.25 wt%, and standing for 12 hours;
after standing, pouring out the upper-layer acid solution, repeatedly washing the lower-layer acid with deionized water for 3 times, adjusting the pH value to be neutral with NaOH, and repeatedly washing with the deionized water for 3 times;
and iii, carrying out centrifugal separation on the washed acid-treated sepiolite suspension to obtain sepiolite precipitate, drying for 24 hours at 108 ℃, and grinding to obtain the acid-treated sepiolite.
(3) Acid-treated sepiolite grafting modification
A. Adding 2g of acid-modified sepiolite into 50ml of toluene solution, stirring for 30min until the sepiolite is uniformly dispersed, then adding 0.4g of 3-aminopropyltriethoxysilane, and continuously stirring at 90 ℃ to react;
B. and D, washing the suspension obtained in the step A with an organic solution to remove the organic solvent and the ungrafted silane, drying and grinding to obtain solid powder, namely the sepiolite modified by the acid-amino silane composite.
Example 2
(1) Purification of raw ore sepiolite (refer to patent publication No. CN106745014A)
a. Weighing 20g of raw ore sepiolite powder, adding water to 400ml, and stirring at room temperature for 3 h; after stirring, pouring into a separating funnel, standing for layering, taking the sepiolite turbid liquid at the lower layer, continuously adding water to 400ml, stirring for 1h, pouring into the separating funnel again for standing for layering, and repeating the steps until no layering occurs to obtain sepiolite ore slurry;
b. adding 0.48g of sodium hexametaphosphate, continuously stirring for 3h, and standing for 48h to obtain suspension slurry of sepiolite and impurity precipitate;
c. and (3) taking the sepiolite suspension slurry on the upper layer for centrifugal separation, drying for 24 hours in a drying oven at 110 ℃, and grinding to obtain the purified sepiolite.
(2) Acid modification of purified sepiolite
i. Weighing 5g of purified sepiolite, adding 100ml of hydrochloric acid with the mass fraction of 1.25 wt%, and standing for 12 hours;
after standing, pouring out the upper-layer acid solution, repeatedly washing the lower-layer acid with deionized water for 3 times, adjusting the pH value to be neutral with NaOH, and repeatedly washing with the deionized water for 3 times;
and iii, centrifugally separating the washed sepiolite suspension subjected to acid treatment to obtain sepiolite precipitate at 108 DEG C
Drying for 24h, and grinding to obtain the acid-treated sepiolite.
(3) Acid-treated sepiolite grafting modification
A. Adding 2g of acid-modified sepiolite into 100ml of toluene solution, stirring for 30min until the sepiolite is uniformly dispersed, then adding 0.24g of 3-aminopropyltriethoxysilane, and continuously stirring at 90 ℃ to react;
B. and D, washing the suspension obtained in the step A with an organic solution to remove the organic solvent and the ungrafted silane, drying and grinding to obtain solid powder, namely the sepiolite modified by the acid-amino silane composite.
The sepiolite obtained in the above example 1-2 is used for formaldehyde adsorption treatment, and the specific method is as follows:
preparing mixed gas (nitrogen or helium is used as balance gas) with the formaldehyde concentration of 140ppm, and taking the mixed gas as working gas. The fixed bed is filled with sepiolite, the sepiolite is measured by a Gas Chromatograph (GC) provided with a Flame Ionization Detector (FID), and the adsorption quantity of the modified sepiolite on formaldehyde is calculated according to an adsorption penetration curve. The adsorption capacity of the solid adsorbent obtained in example 1 on formaldehyde can reach 4.86mmol/g, and the adsorption capacity of the solid adsorbent obtained in example 2 on formaldehyde can reach 4.43 mmol/g.
Example 3
(1) Purification of raw ore sepiolite (refer to patent publication No. CN106745014A)
a. Weighing 20g of raw ore sepiolite powder, adding water to 400ml, and stirring at room temperature for 3 h; after stirring, pouring into a separating funnel, standing for layering, taking the sepiolite turbid liquid at the lower layer, continuously adding water to 400ml, stirring for 1h, pouring into the separating funnel again for standing for layering, and repeating the steps until no layering occurs to obtain sepiolite ore slurry;
b. adding 0.48g of sodium hexametaphosphate, continuously stirring for 3h, and standing for 48h to obtain suspension slurry of sepiolite and impurity precipitate;
c. and (3) taking the sepiolite suspension slurry on the upper layer for centrifugal separation, drying for 24 hours in a drying oven at 110 ℃, and grinding to obtain the purified sepiolite.
(2) Purified sepiolite grafting modification
A. Adding 10g of purified sepiolite into 300ml of toluene solution, stirring for 30min until the sepiolite is uniformly dispersed, then adding 2g of 3-aminopropyltriethoxysilane, and continuously stirring at 90 ℃ to react;
B. and D, washing the suspension obtained in the step A by using an organic solution to remove the organic solvent and the ungrafted silane, and drying and grinding to obtain solid powder, namely the silane modified sepiolite.
Example 4
(1) Purification of raw ore sepiolite (refer to patent publication No. CN106745014A)
a. Weighing 20g of raw ore sepiolite powder, adding water to 400ml, and stirring at room temperature for 3 h; after stirring, pouring into a separating funnel, standing for layering, taking the sepiolite turbid liquid at the lower layer, continuously adding water to 400ml, stirring for 1h, pouring into the separating funnel again for standing for layering, and repeating the steps until no layering occurs to obtain sepiolite ore slurry;
b. adding 0.48g of sodium hexametaphosphate, continuously stirring for 3h, and standing for 48h to obtain suspension slurry of sepiolite and impurity precipitate;
c. and (3) taking the sepiolite suspension slurry on the upper layer for centrifugal separation, drying for 24 hours in a drying oven at 110 ℃, and grinding to obtain the purified sepiolite.
(2) Acid modification of purified sepiolite
i. Weighing 10g of purified sepiolite, adding 100ml of sulfuric acid solution with the concentration of 2mol/l, and standing for 12 hours;
after standing, pouring out the upper-layer acid solution, repeatedly washing the lower-layer acid with deionized water for 3 times, adjusting the pH value to be neutral with NaOH, and repeatedly washing with the deionized water for 3 times;
and iii, carrying out centrifugal separation on the washed acid-treated sepiolite suspension to obtain sepiolite precipitate, drying for 24 hours at 108 ℃, and grinding to obtain the acid-treated sepiolite.
(3) Acid-treated sepiolite grafting modification
A. Adding 10g of acid-treated sepiolite into 300ml of toluene solution, stirring for 30min until the sepiolite is uniformly dispersed, then adding 2g of 3-aminopropyltriethoxysilane, and continuously stirring at 90 ℃ to react;
B. and D, washing the suspension obtained in the step A by using an organic solution to remove the organic solvent and the ungrafted silane, and drying and grinding to obtain solid powder, namely the silane modified sepiolite.
Examples 3 to 4 all studied the aminosilane-modified sepiolite, and found that the aminosilane-modified sepiolite adsorbent obtained by the above preparation method completely achieved the object of the present invention. The formaldehyde purification efficiency of sepiolite is determined in a formaldehyde experiment chamber with the relative humidity of 50%, the formaldehyde purification efficiency is determined according to the standard QBT 2761 plus 2006 method for determining the purification effect of indoor air purification products, and the initial concentration of formaldehyde in the experiment chamber is 1.12 mg/m3. When the adsorption time is 4.5h, the formaldehyde purification efficiency of example 3 reaches 63.13%, the formaldehyde purification efficiency of example 4 reaches 86.16%, which is far higher than the formaldehyde purification efficiency of sepiolite raw ore by 13.13%; when 24 hours of adsorption is carried out, the formaldehyde purification efficiency of example 3 reaches 94.38%, the formaldehyde purification efficiency of example 4 reaches 95.45%, and the formaldehyde purification efficiency is much higher than the formaldehyde purification efficiency of sepiolite raw ore by 19.11%.
Therefore, after the sepiolite subjected to acid activation is loaded with the aminosilane, the adsorption performance of the sepiolite on formaldehyde is greatly improved, the sepiolite has a good formaldehyde removal effect, and the cost is low.
Claims (11)
1. A preparation method of a sepiolite-based formaldehyde adsorbent is characterized by comprising the following steps:
(1) purification of raw ore sepiolite
a. Adding raw sepiolite ore and water into a stirring tank, starting a stirrer, and continuously stirring at normal temperature to obtain sepiolite ore slurry;
b. b, adding a dispersing agent into the sepiolite ore slurry obtained in the step a, stirring, and then sending into a settling tank for settling to obtain suspension slurry of the sepiolite and impurity precipitates;
c. b, dehydrating and drying the sepiolite suspension slurry obtained in the step b, and grinding to obtain purified sepiolite;
(2) acid modification of sepiolite
i. Mixing sepiolite powder with a certain volume of acid solution, and standing at normal temperature;
after standing, pouring out the upper layer of acid liquor, repeatedly washing the sepiolite suspension of the lower layer of acid liquor by using deionized water, and adjusting the pH to 6-8;
iii, carrying out centrifugal separation, drying and grinding on the acid-treated sepiolite obtained in the step ii to obtain the acid-treated sepiolite;
(3) acid-treated sepiolite grafting modification
A. Adding the acid-treated sepiolite obtained in the step (2) into an organic solvent, stirring to obtain a mixed solution, then adding aminosilane, and continuously stirring to react;
B. and D, washing the suspension obtained in the step A with an organic solution to remove the organic solvent and the ungrafted silane, drying and grinding to obtain solid powder, namely the sepiolite modified by the acid-amino silane composite.
2. The preparation method of the sepiolite-based adsorbent according to claim 1, wherein the mass ratio of the raw sepiolite ore to the water in the step a is 1: 5-20, and the stirring speed is 50-900 rpm.
3. The method for preparing the sepiolite-based adsorbent according to claim 1, wherein the dispersant in the step b is one or a combination of two or more of polyphosphate, the addition amount of the dispersant is 0.1-1% of the raw ore mass of the sepiolite, and the settling time is 30min or more.
4. The process for preparing sepiolite-based adsorbent according to claim 1, wherein the dehydration in step c is performed by a vacuum filter.
5. The preparation method of the sepiolite-based adsorbent according to claim 1, wherein the acid in step i is one or more of hydrochloric acid, sulfuric acid or nitric acid; the concentration of the acid solution is 0.01-12 mol/L; the mass ratio of the purified sepiolite to the acid solution is 1: 5-15, and the standing time is 3-48 h.
6. The preparation method of the sepiolite-based adsorbent according to claim 1, wherein the deionized water is used to wash away the acid solution in step ii, and the method comprises separating the suspension by using a centrifuge, pouring the upper layer acid solution into a waste solution pool, transferring the solid into a container, adding water, stirring until no solid particles exist at the bottom of the container to obtain the suspension, separating by using the centrifuge, and repeating the above operation for 3-5 times.
7. The preparation method of the sepiolite-based adsorbent according to claim 1, wherein the drying temperature in step iii is 90-120 ℃ and the drying time is 12-48 h.
8. The preparation method of the sepiolite-based adsorbent according to claim 1, wherein the organic solvent in the step a is toluene, the mass ratio of the acid-treated sepiolite to the organic solvent is 1: 20-50, and the stirring time is 30 min-3 h.
9. The preparation method of the sepiolite-based adsorbent according to claim 1, wherein the addition amount of the aminosilane in the step a is 2-100% of the mass of the acid-treated sepiolite, and the stirring time is 4-24 hours.
10. The preparation method of the sepiolite-based adsorbent according to claim 1, wherein the organic solvent in the step B is methanol, the drying temperature is 50 to 80 ℃, and the drying time is 30min to 2 h.
11. Use of the sepiolite-based adsorbent obtained by the preparation method according to any one of claims 1 to 10 for adsorbing formaldehyde in a gas.
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