CN114984906A - VOC (volatile organic compound) removing master batch with high adsorption and gas retention capacity and preparation method thereof - Google Patents
VOC (volatile organic compound) removing master batch with high adsorption and gas retention capacity and preparation method thereof Download PDFInfo
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- CN114984906A CN114984906A CN202110874426.XA CN202110874426A CN114984906A CN 114984906 A CN114984906 A CN 114984906A CN 202110874426 A CN202110874426 A CN 202110874426A CN 114984906 A CN114984906 A CN 114984906A
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 33
- 230000014759 maintenance of location Effects 0.000 title claims abstract description 30
- 239000012855 volatile organic compound Substances 0.000 title claims description 28
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 82
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 82
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000001354 calcination Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000007900 aqueous suspension Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000005909 Kieselgur Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 abstract description 6
- -1 polypropylene Polymers 0.000 abstract description 6
- 229920001155 polypropylene Polymers 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000001877 deodorizing effect Effects 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J20/02—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
- B01J20/14—Diatomaceous 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
- B01J20/02—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
-
- 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
- B01J20/16—Alumino-silicates
-
- 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
- B01D2253/106—Silica or silicates
-
- 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
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- 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
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the technical field of inorganic materials, in particular to B01J20/14, and more particularly relates to a VOC removing master batch with high adsorption and gas retention capacity and a preparation method thereof. According to the method, the aperture of the diatomite is modified and adjusted by adopting a calcination process, so that the adsorption capacity of the diatomite is further improved; and then the molecular sieve is synthesized or settled on the surface of the diatomite to further improve the gas retention capacity of the diatomite, and the VOC removing master batch is used in the preparation process of the modified polypropylene, so that the odor removing effect is obvious.
Description
Technical Field
The invention relates to the technical field of inorganic materials, in particular to B01J20/14, and more particularly relates to a VOC removing master batch with high adsorption and gas retention capacity and a preparation method thereof.
Background
CN201711343473 provides a VOC removing masterbatch by using a polymer, porous synthetic calcium silicate and diatomaceous earth, which can remove VOC gas generated during processing of materials, however, the VOC removing masterbatch provided by the invention contains a polymer, which causes the VOC removing masterbatch to easily affect the mechanical properties and the processability of polyolefin materials during processing and using of the polyolefin materials, and the VOC provided by the VOC removing masterbatch has poor gas retention. CN201910442455 provides a rubber material meeting the requirements of automotive interiors, and a deodorizing system of at least one of activated carbon, zeolite, molecular sieve and diatomite is added in the preparation process of the rubber material, so as to meet the requirements of automotive interiors on odor, however, the deodorizing system has poor deodorizing effect in the production and use processes of polypropylene or modified polypropylene.
Disclosure of Invention
In view of the problems in the prior art, the first aspect of the present invention provides a VOC removing masterbatch with high adsorption and gas retention capacity, which comprises diatomite with a molecular sieve adsorbed on the surface, wherein the molecular sieve is selected from one or more of sodium a type molecular sieve, calcium a type molecular sieve and all-silica molecular sieve.
In one embodiment, the molecular sieves are sodium a type molecular sieve and calcium a type molecular sieve in a weight ratio of 1: (8-15), more preferably 1: 12.
preferably, the particle size of the sodium A type molecular sieve is 2-6 μm.
The Na A type molecular sieve with the particle size of 2-6 mu m is purchased from Zhengzhou super-honor nano material Co Ltd, and the model is AT-3.
Preferably, the particle size D50 of the calcium A-type molecular sieve is 5-12 μm, and more preferably 7.5-9.5 μm.
Preferably, the calcium type a molecular sieve has an exchange degree of 75 to 90 wt%, more preferably 81 to 85 wt%.
The calcium A type molecular sieve with the particle size D50 of 7.5-9.5 mu m and the exchange degree of 81-85 wt% is purchased from Xinxin Innovation New Material science and technology Co., Ltd, Qingdao, and the model is 5A-D-83.
The degree of exchange in this application refers to exchanged Ca 2+ The content of (b).
The applicant unexpectedly found that the calcium A type molecular sieve and the sodium A type molecular sieve in specific proportions and types can avoid the agglomeration of the molecular sieves to a certain extent when the molecular sieves are adsorbed on the surface of the diatomite.
When the molecular sieve comprises a calcium A type molecular sieve and a sodium A type molecular sieve, the weight ratio of the molecular sieve to the diatomite is 3: 2.
when the molecular sieve includes a calcium a type molecular sieve and a sodium a type molecular sieve, the method of surface adsorption of the molecular sieve by the diatomaceous earth is not particularly limited in the present application, and may be selected conventionally by those skilled in the art.
In one embodiment, the molecular sieve is an all-silica molecular sieve.
Preferably, the all-silicon molecular sieve is a Silicalite-1 molecular sieve and/or a Silicalite-2 molecular sieve.
In one embodiment, the diatomaceous earth has a particle size ranging from 40 to 60 nm.
The applicant finds that when the conventional 3A type, 4A type and 5A type molecular sieves are used for adsorption on the surface of diatomite, the molecular sieve membrane layer has defects such as pinholes, and the like, and the applicant finds that when the molecular sieve is an all-silica molecular sieve, particularly a Silicalite-1 molecular sieve, and the particle size of the diatomite is 40-60nm, the molecular sieve can form a continuous and compact molecular sieve membrane layer on the surface of the diatomite without defects such as pinholes, and the applicant thinks that the probable reason is that the special Z-shaped pore channel and straight pore channel of the Silicalite-1 molecular sieve with ten-membered ring pore channels cause fast nucleation rate and certain thickness in the growth process of the molecular sieve in the application, and the Silicalite-1 molecular sieve with the ten-membered ring pore channels can fill the large pore defects on the surface of the diatomite.
In one embodiment, the method for preparing the VOC-removing masterbatch with high adsorption and gas retention capacity comprises the following steps:
(1) mixing tetrapropylammonium hydroxide, tetraethoxysilane, ethanol and water, stirring, carrying out reflux reaction at 90-120 ℃ for 10-48h, carrying out centrifugal separation on a product, washing with water, and adding water to prepare 0.3-0.8 wt% of water suspension;
(2) calcining the diatomite at 250-1200 ℃ for 50-80min, cooling to room temperature, and grinding to obtain particles with the particle size of 40-60 nm;
(3) adding the diatomite obtained in the step (2) into the water suspension obtained in the step (1), adsorbing for 15-30min, filtering, washing with ammonia water for multiple times, and drying;
(4) and (2) mixing tetrapropylammonium hydroxide, tetraethoxysilane and water to obtain a mixed solution, adding the solid obtained in the step (3) into the mixed solution, reacting at the temperature of 160-200 ℃ for 12-36h, repeatedly washing, drying at the temperature of 50 ℃ for 1-5h, and calcining at the temperature of 550 ℃ for 6-8 h.
In one embodiment, the molar ratio of tetrapropylammonium hydroxide, ethyl orthosilicate, ethanol and water in step (1) is (6-12): (20-30): (90-110): (460) 490), preferably 10: 25: 98: 480.
in one embodiment, the step (1) comprises: tetrapropylammonium hydroxide, tetraethoxysilane, ethanol and water are mixed and stirred, reflux reaction is carried out for 36h at 100 ℃, the product is centrifugally separated and washed, and water is added to prepare 0.6 wt% aqueous suspension.
In one embodiment, the step (2) comprises: calcining at 250-350 deg.C for 15-25 min; then heating to 650-750 ℃ at the speed of 10-15 ℃/min, and carrying out heat preservation and calcination for 20-35 min; then raising the temperature to 1150-1250 ℃ at the speed of 5-10 ℃/min, carrying out heat preservation calcination for 20-30min, then cooling to room temperature, and grinding and sieving to obtain the diatomite with the particle size of 40-60 nm.
In a preferred embodiment, the step (2) comprises: calcining at 300 deg.C for 20 min; then heating to 700 ℃ at the speed of 12 ℃/min, and carrying out heat preservation and calcination for 30 min; then heating to 1200 ℃ at the speed of 7 ℃/min, carrying out heat preservation and calcination for 25min, then cooling to room temperature, grinding and sieving to obtain the diatomite with the particle size of 40-60 nm.
The applicant has found unexpectedly in experiments that by adopting a sectional calcination mode, the calcination temperature and time of each stage are controlled, and the specific temperature rise rate is controlled, particularly the calcination is carried out at 300 ℃ for 20 min; then heating to 700 ℃ at the speed of 12 ℃/min, and carrying out heat preservation and calcination for 30 min; the applicant believes that the possible reason is that through the specific hierarchical calcination mode in the application, the porous structure distributed on the surface of the diatomite molecules causes uneven surface of the diatomite, even after subsequent grinding, the diatomite surface still presents a rough surface, possibly the porous distribution in the diatomite is different, the pore size is different, and under the action of external force, the molecular sieve distributed on the valley of the diatomite surface avoids influencing the adsorption of other VOC molecules due to the space resistance among adsorbed VOC molecules.
In one embodiment, the step (3) comprises: adding the diatomite obtained in the step (2) into the water suspension obtained in the step (1), adsorbing for 22min, filtering, washing with ammonia water for multiple times, and drying at 50 ℃.
Preferably, the content of the diatomaceous earth and the aqueous suspension in the step (3) is measured by adding 1g of diatomaceous earth per 50mL of the aqueous suspension.
In one embodiment, the step (4) comprises: and (4) mixing tetrapropylammonium hydroxide, tetraethoxysilane and water to obtain a mixed solution, adding the solid obtained in the step (3) into the mixed solution, reacting at 200 ℃ for 20 hours, repeatedly washing, drying at 50 ℃ for 3 hours, and calcining at 550 ℃ for 7 hours.
Preferably, the molar ratio of tetrapropylammonium hydroxide, ethyl orthosilicate and water in the step (4) is 1: 16: 1200.
preferably, in the step (4), the solid obtained in the step (3) is added to the mixed solution in an amount of 0.1g per 1mL of the mixed solution.
The applicant found that after the molecular sieve is adsorbed on the surface of the diatomite with a specific particle size and a specific calcining mode of the diatomite in the application, the thickness of the molecular sieve film is extremely uneven, and the applicant found that in a series of researches and improvement processes, when the molar ratio of the tetrapropylammonium hydroxide, the tetraethoxysilane, the ethanol and the water in the step (1) is (6-12): (20-30): (90-110): (460) 490), wherein the molar ratio of the tetrapropylammonium hydroxide to the ethyl orthosilicate to the water in the step (4) is 1: 16: 1200, at this time, after the molecular sieve is adsorbed on the surface of the diatomite with a specific diatomite calcining mode and a specific particle size, the thickness of the molecular sieve membrane layer is uniform, and the applicant thinks that the possible reason is that after the adsorption of the water suspension with the specific particle size in the step (1) in the application, the particle size of the seed crystal is relatively uniform, and the appearance of mixed crystals is avoided, and when the molecular sieve membrane layer is adsorbed later, the nucleation active sites are the same, so that the film thickness differentiation caused by the too fast nucleation rate of the Silicalite-1 molecular sieve is avoided.
The third aspect of the invention provides an application of the VOC removing master batch with high adsorption and gas retention capacity in polypropylene or modified polypropylene.
Compared with the prior art, the invention has the following beneficial effects:
(1) the calcium A type molecular sieve and the sodium A type molecular sieve in a specific proportion and type avoid the agglomeration of the molecular sieves to a certain extent when the molecular sieves are adsorbed on the surface of the diatomite.
(2) According to the method, the aperture of the diatomite is modified and adjusted by adopting a calcination process, so that the adsorption capacity of the diatomite is further improved; and then the molecular sieve is synthesized or settled on the surface of the diatomite to further improve the gas retention capacity of the diatomite, and the VOC removing master batch is used in the preparation process of the modified polypropylene, so that the odor removing effect is obvious.
(3) According to the method, a specific all-silicon molecular sieve and diatomite with a specific particle size are adopted, and at the moment, the molecular sieve can form a continuous and compact molecular sieve film layer on the surface of the diatomite.
(4) The method adopts a sectional calcination mode, controls the calcination temperature and time of each stage, and controls the specific heating rate to have a good gas-retaining effect after the molecular sieve is grown on the surface of the diatomite.
(5) According to the preparation method, the thickness of the obtained molecular sieve membrane layer is uniform by controlling the proportion of the raw material components in the preparation process of the VOC-removing master batch.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
Examples
Example 1
The embodiment 1 of the invention provides a VOC removing master batch with high adsorption and gas retention capacity, and specifically provides diatomite with a molecular sieve adsorbed on the surface.
The molecular sieve is a Silicalite-1 molecular sieve, and the particle size of the diatomite is 40-60 nm.
The preparation method of the VOC removing master batch with high adsorption and gas retention capacity comprises the following steps:
(1) mixing a mixture of 6: 20: 90: 460 tetrapropylammonium hydroxide, tetraethoxysilane, ethanol and water are mixed and stirred, reflux reaction is carried out for 48 hours at 90 ℃, the product is centrifugally separated and washed, and water is added to prepare 0.3 weight percent aqueous suspension;
(2) calcining at 250 deg.C for 25 min; then heating to 650 ℃ at the speed of 10 ℃/min, and carrying out heat preservation and calcination for 35 min; then heating to 1150 ℃ at the speed of 5 ℃/min, carrying out heat preservation and calcination for 30min, then cooling to room temperature, grinding and sieving to obtain diatomite with the particle size of 40-60 nm;
(3) adding the diatomite obtained in the step (2) into the water suspension obtained in the step (1), adsorbing for 15min, filtering, washing with ammonia water for multiple times, and drying at 50 ℃;
(4) mixing the components in a molar ratio of 1: 16: 1200, mixing tetrapropylammonium hydroxide, tetraethoxysilane and water to obtain a mixed solution, adding the solid obtained in the step (3) into the mixed solution, reacting at 160 ℃ for 36 hours, repeatedly washing, drying at 50 ℃ for 2 hours, and calcining at 550 ℃ for 6 hours.
The content of the diatomaceous earth and the aqueous suspension in the step (3) is measured by adding 1g of diatomaceous earth per 50mL of the aqueous suspension.
In the step (4), the content of the solid obtained in the step (3) added to the mixed solution is determined by adding 0.1g of the solid obtained in the step (3) to 1mL of the mixed solution.
Example 2
Embodiment 2 of the invention provides a VOC-removing master batch with high adsorption and gas retention capacity, and specifically relates to diatomite with a molecular sieve adsorbed on the surface.
The molecular sieve is a Silicalite-1 molecular sieve, and the particle size of the diatomite is 40-60 nm.
The preparation method of the VOC removing master batch with high adsorption and gas retention capacity comprises the following steps:
(1) mixing a mixture of a molar ratio of 12: 30: 110: 490 of tetrapropylammonium hydroxide, tetraethoxysilane, ethanol and water are mixed and stirred, reflux reaction is carried out for 10 hours at 120 ℃, the product is centrifugally separated and washed, and water is added to prepare 0.8 wt% aqueous suspension;
(2) calcining at 350 deg.C for 15 min; then heating to 750 ℃ at the speed of 15 ℃/min, and carrying out heat preservation and calcination for 20 min; then heating to 1250 ℃ at the speed of 10 ℃/min, carrying out heat preservation and calcination for 20min, then cooling to room temperature, and grinding and sieving to obtain diatomite with the particle size of 40-60 nm;
(3) adding the diatomite obtained in the step (2) into the water suspension obtained in the step (1), adsorbing for 30min, filtering, washing with ammonia water for multiple times, and drying at 50 ℃;
(4) mixing a mixture of 1: 16: 1200, mixing tetrapropylammonium hydroxide, tetraethoxysilane and water to obtain a mixed solution, adding the solid obtained in the step (3) into the mixed solution, reacting at 200 ℃ for 12 hours, repeatedly washing, drying at 50 ℃ for 5 hours, and calcining at 550 ℃ for 8 hours.
The content of the diatomaceous earth and the aqueous suspension in the step (3) is measured by adding 1g of diatomaceous earth per 50mL of the aqueous suspension.
In the step (4), the content of the solid obtained in the step (3) added to the mixed solution is determined by adding 0.1g of the solid obtained in the step (3) to 1mL of the mixed solution.
Example 3
Embodiment 3 of the invention provides a VOC removing master batch with high adsorption and gas retention capacity, and specifically provides diatomite with a molecular sieve adsorbed on the surface.
The molecular sieve is a Silicalite-1 molecular sieve, and the particle size of the diatomite is 40-60 nm.
The preparation method of the VOC removing master batch with high adsorption and gas retention capacity comprises the following steps:
(1) mixing the components in a molar ratio of 10: 25: 98: 480, mixing and stirring tetrapropylammonium hydroxide, tetraethoxysilane, ethanol and water, carrying out reflux reaction at 100 ℃ for 36 hours, carrying out centrifugal separation on the product, washing with water, and adding water to prepare 0.6 wt% of water suspension;
(2) calcining at 300 deg.C for 20 min; then heating to 700 ℃ at the speed of 12 ℃/min, and carrying out heat preservation and calcination for 30 min; then heating to 1200 ℃ at the speed of 7 ℃/min, carrying out heat preservation and calcination for 25min, then cooling to room temperature, and grinding and sieving to obtain diatomite with the particle size of 40-60 nm;
(3) adding the diatomite obtained in the step (2) into the water suspension obtained in the step (1), adsorbing for 22min, filtering, washing with ammonia water for multiple times, and drying at 50 ℃;
(4) mixing a mixture of 1: 16: 1200, mixing tetrapropylammonium hydroxide, tetraethoxysilane and water to obtain a mixed solution, adding the solid obtained in the step (3) into the mixed solution, reacting for 20 hours at 200 ℃, repeatedly washing, drying for 3 hours at 50 ℃, and calcining for 7 hours at 550 ℃.
The content of the diatomaceous earth and the aqueous suspension in the step (3) is measured by adding 1g of diatomaceous earth per 50mL of the aqueous suspension.
In the step (4), the content of the solid obtained in the step (3) added to the mixed solution is determined by adding 0.1g of the solid obtained in the step (3) to 1mL of the mixed solution.
Example 4
Embodiment 4 of the present invention provides a VOC-removing masterbatch with high adsorption and gas retention capabilities, and the specific implementation manner thereof is the same as that in embodiment 3.
The specific implementation manner of the preparation method of the VOC-removing masterbatch with high adsorption and gas retention capacity is the same as that in example 3, except that in the step (2), the diatomite is calcined at 1200 ℃ for 75min, then cooled to room temperature, and ground until the particle size is 40-60 nm.
Example 5
Embodiment 5 of the present invention provides a VOC-removing masterbatch with high adsorption and gas retention capabilities, and the specific implementation manner thereof is the same as that in embodiment 3, except that the particle size of the diatomaceous earth is 60 to 80 nm.
The specific implementation manner of the preparation method of the VOC removing master batch with high adsorption and gas retention capacity is the same as that in example 3, except that the diatomite with the particle size of 60-80nm is obtained by grinding and sieving in the step (2).
Performance evaluation
1. The appearance is as follows: the VOC-removed master batches obtained in examples 1 to 5 were observed with a scanning electron microscope, and the presence or absence of defects such as pinholes and the like, and whether the molecular sieves adsorbed on the surface were dense or not was recorded.
2. The bonding force of the diatomite, the seed crystal layer and the molecular sieve film layer is as follows: the cross section of the VOC-removed masterbatch of examples 1-5 was observed using a scanning electron microscope, and the bonding between the diatomaceous earth, the seed layer and the molecular sieve layer was recorded, and the absence of a gap between the three indicates tight bonding, and the result is recorded as pass, otherwise the result is fail.
TABLE 1
Claims (10)
1. The VOC removing master batch with high adsorption and gas retention capacity is characterized by comprising diatomite with a molecular sieve adsorbed on the surface, wherein the molecular sieve is selected from one or more of a sodium A type molecular sieve, a calcium A type molecular sieve and an all-silicon molecular sieve.
2. The VOC removal master batch with high adsorption and gas retention capacity of claim 1, wherein the all-silica molecular sieve is a Silicalite-1 molecular sieve and/or a Silicalite-2 molecular sieve.
3. The VOC removal master batch with high adsorption and gas retention capacity as claimed in claim 2, wherein the particle size of said diatomaceous earth is 40-60 nm.
4. The VOC-removed master batch with high adsorption and gas retention capacity as claimed in claim 1, wherein the particle size of said Na A-type molecular sieve is 2-6 μm.
5. A VOC-removed master batch with high adsorption and gas retention capacity as claimed in claim 4, wherein the exchange degree of said Ca-A type molecular sieve is 75-90 wt%.
6. The VOC-removed master batch with high adsorption and gas retention capacity as claimed in claim 5, wherein the particle size D50 of said Ca type A molecular sieve is 5-12 μm.
7. A method for preparing a VOC removal master batch with high adsorption and gas retention capacity according to any one of claims 1-6, which comprises the following steps:
(1) mixing tetrapropylammonium hydroxide, tetraethoxysilane, ethanol and water, stirring, carrying out reflux reaction at 90-120 ℃ for 10-48h, carrying out centrifugal separation on a product, washing with water, and adding water to prepare 0.3-0.8 wt% of water suspension;
(2) calcining the diatomite at 250-1200 ℃ for 50-80min, cooling to room temperature, and grinding to obtain particles with the particle size of 40-60 nm;
(3) adding the diatomite obtained in the step (2) into the water suspension obtained in the step (1), adsorbing for 15-30min, filtering, washing with ammonia water for multiple times, and drying;
(4) and (2) mixing tetrapropylammonium hydroxide, tetraethoxysilane and water to obtain a mixed solution, adding the solid obtained in the step (3) into the mixed solution, reacting at the temperature of 160-200 ℃ for 12-36h, repeatedly washing, drying at the temperature of 50 ℃ for 1-5h, and calcining at the temperature of 550 ℃ for 6-8 h.
8. The method for preparing a VOC-removed masterbatch with high adsorption and gas retention ability according to claim 7, wherein the step (2) comprises: calcining at 250-350 deg.C for 15-25 min; then heating to 650-750 ℃ at the speed of 10-15 ℃/min, and carrying out heat preservation and calcination for 20-35 min; then raising the temperature to 1150-1250 ℃ at the speed of 5-10 ℃/min, carrying out heat preservation and calcination for 20-30min, then cooling to room temperature, and grinding and sieving to obtain the diatomite with the particle size of 40-60 nm.
9. The method for preparing a master batch with high adsorption and gas retention capacity for removing VOC (volatile organic Compounds) as claimed in claim 8, wherein the molar ratio of tetrapropylammonium hydroxide, tetraethoxysilane, ethanol and water in the step (1) is (6-12): (20-30): (90-110): (460-490).
10. The method for preparing a VOC-removing masterbatch with high adsorption and gas retention ability according to claim 9, wherein the molar ratio of tetrapropylammonium hydroxide, tetraethoxysilane and water in the step (4) is 1: 16: 1200.
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| CN103084144A (en) * | 2013-02-06 | 2013-05-08 | 中国科学院广州地球化学研究所 | Diatomite-based porous composite material for adsorbing volatile organic pollutants and preparation method thereof |
| CN106268629A (en) * | 2016-08-17 | 2017-01-04 | 吉林大学 | A kind of preparation method and applications of the micro-mesopore molecular sieve diatomite composite material for adsorption process |
| CN109304141A (en) * | 2018-12-13 | 2019-02-05 | 吉林大学 | It is a kind of for adsorbing diatomite/molecular sieves compound material preparation method of volatile organic contaminant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103084144A (en) * | 2013-02-06 | 2013-05-08 | 中国科学院广州地球化学研究所 | Diatomite-based porous composite material for adsorbing volatile organic pollutants and preparation method thereof |
| CN106268629A (en) * | 2016-08-17 | 2017-01-04 | 吉林大学 | A kind of preparation method and applications of the micro-mesopore molecular sieve diatomite composite material for adsorption process |
| CN109304141A (en) * | 2018-12-13 | 2019-02-05 | 吉林大学 | It is a kind of for adsorbing diatomite/molecular sieves compound material preparation method of volatile organic contaminant |
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