CN115005497B - Degradable cigarette filter stick master batch and degradable cigarette filter stick - Google Patents
Degradable cigarette filter stick master batch and degradable cigarette filter stick Download PDFInfo
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- CN115005497B CN115005497B CN202210852089.9A CN202210852089A CN115005497B CN 115005497 B CN115005497 B CN 115005497B CN 202210852089 A CN202210852089 A CN 202210852089A CN 115005497 B CN115005497 B CN 115005497B
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- cigarette filter
- titanium dioxide
- haematococcus pluvialis
- degradable cigarette
- master batch
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- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 59
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 48
- 241000168517 Haematococcus lacustris Species 0.000 claims abstract description 42
- 238000001179 sorption measurement Methods 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 241000168525 Haematococcus Species 0.000 claims abstract description 20
- 229920006239 diacetate fiber Polymers 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 241000208125 Nicotiana Species 0.000 claims description 9
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000010257 thawing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims 1
- 150000001860 citric acid derivatives Chemical class 0.000 claims 1
- -1 epoxyesters Chemical class 0.000 claims 1
- 125000005498 phthalate group Chemical class 0.000 claims 1
- 238000001782 photodegradation Methods 0.000 abstract description 7
- 239000000779 smoke Substances 0.000 abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 102000004169 proteins and genes Human genes 0.000 abstract description 5
- 108090000623 proteins and genes Proteins 0.000 abstract description 5
- 206010070834 Sensitisation Diseases 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 4
- 230000008313 sensitization Effects 0.000 abstract description 4
- 229920001184 polypeptide Polymers 0.000 abstract description 3
- 102000004196 processed proteins & peptides Human genes 0.000 abstract description 3
- 108090000765 processed proteins & peptides Proteins 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 14
- 229920001747 Cellulose diacetate Polymers 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 208000017983 photosensitivity disease Diseases 0.000 description 3
- 231100000434 photosensitization Toxicity 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000000391 smoking effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 2
- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 description 2
- 239000004593 Epoxy Chemical class 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 150000001278 adipic acid derivatives Chemical class 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 235000013793 astaxanthin Nutrition 0.000 description 2
- 239000001168 astaxanthin Substances 0.000 description 2
- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 description 2
- 229940022405 astaxanthin Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229960002715 nicotine Drugs 0.000 description 2
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- 206010006458 Bronchitis chronic Diseases 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 206010014561 Emphysema Diseases 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 241000694540 Pluvialis Species 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 241001116459 Sequoia Species 0.000 description 1
- 206010042674 Swelling Diseases 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940035427 chromium oxide Drugs 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 208000007451 chronic bronchitis Diseases 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
- A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/04—Tobacco smoke filters characterised by their shape or structure
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides a degradable cigarette filter stick master batch which consists of a base material and a porous adsorption material, wherein the base material is diacetate fiber, and the porous adsorption material is haematococcus pluvialis-titanium dioxide composite material. The application also provides a degradable cigarette filter stick. The degradable cigarette filter stick master batch provided by the application utilizes haematococcus pluvialis to modify titanium dioxide, so that the surface sensitization of the titanium dioxide can be realized, and the absorption wavelength range is red shifted, thereby expanding the light absorption wavelength of the titanium dioxide to a visible light region and improving the visible light degradability of the titanium dioxide to diacetate fibers; meanwhile, haematococcus pluvialis contains rich proteins and polypeptides, and has high-efficiency adsorption capacity on smoke, tar, heavy metals and the like, so that the obtained degradable cigarette filter stick has excellent photodegradation and adsorptivity.
Description
Technical Field
The invention relates to the technical field of cigarette production, in particular to a degradable cigarette filter stick master batch and a degradable cigarette filter stick.
Background
With the development of the age, people pay more and more attention to the environment. Increasingly prominent white pollution of plastics is becoming a heavy burden for society development. Worldwide, there are restrictions on the use of non-degradable plastics. Therefore, the development of the degradable material is extremely complete in living aspects. China is the country with the largest smoking population in the world. In the past, people's harmful research on smoking is usually focused on health problems caused by the harmful research, such as chronic bronchitis, emphysema, lung cancer and the like, while the research on the environmental behaviors of cigarette butts which are by-products of smoking is not enough, and how to fully utilize or quickly decompose the cigarette butts by-products to reduce the pollution to the environment is a current urgent problem to be solved. The development of degradable mouthpiece materials has therefore become significant. In the past, the main material of the cigarette holder is nondegradable PP fiber yarn, and with increasing importance on degradable materials, cellulose diacetate slowly replaces PP to become a cigarette filter. Cellulose diacetate is degradable, but is weak in degradation capacity, and often requires certain auxiliary degradation.
The accelerated degradation of butts by light provides a valuable research concept. However, the band gap of current photoresponsive materials such as ruthenium-containing compounds, titanium dioxide, determine that they are responsive only to light in the ultraviolet region. Therefore, the light-responsive material is modified to form the visible light active photosensitive material, which is an effective way for improving the light utilization rate and accelerating the photodegradation.
Meanwhile, the cigarette smoke contains a large amount of harmful components such as nicotine, tar and carbon monoxide, which constitute the harm of the tobacco cigarette. With the development of the tobacco industry, the requirements for cigarette filters are continuously increasing in order to meet the health concept demands of consumers. It is necessary to have a trapping effect on more than 20 harmful components of the flue gas, such as acetaldehyde, formaldehyde, radioactive elements, heavy metal elements and the like. Develop the efficient removal of harmful substances in cigarettes, and can effectively improve the health performance of cigarettes. In view of the above, it is important to provide a cigarette filter rod material to achieve synergistic increase in light response and harmful substance adsorption.
Disclosure of Invention
The technical problem solved by the invention is to provide the degradable cigarette filter stick master batch which can realize degradation and efficient adsorption under visible light.
In view of this, the present application provides a degradable cigarette filter stick master batch, which is composed of a base material and a porous adsorption material, wherein the base material is diacetate fiber, and the porous adsorption material is haematococcus pluvialis-titanium dioxide composite material.
Preferably, the preparation method of the haematococcus pluvialis-titanium dioxide composite material specifically comprises the following steps:
performing wall breaking treatment on the haematococcus pluvialis to obtain haematococcus pluvialis slurry;
mixing the haematococcus pluvialis slurry with titanium dioxide powder, filtering and drying to obtain the haematococcus pluvialis-titanium dioxide composite material.
Preferably, the mass ratio of the haematococcus pluvialis slurry to the titanium dioxide powder is 5:1-1:5.
Preferably, the wall breaking treatment is selected from one or more of a freeze thawing method, a mechanical stirring method, a strong acid method and an ethanol method.
Preferably, the diameter of the haematococcus pluvialis-titanium dioxide composite material is 300-600 meshes, and the specific surface area is more than 1200m 2 /g。
Preferably, the mass ratio of the substrate to the porous adsorption material is 1:1 to 10:1.
preferably, the degradable cigarette filter stick master batch is obtained by melt extrusion of a base material and a porous adsorption material; the melting temperature is 50-100 ℃, and the shearing rate is 10-100 s -1 。
The application also provides a degradable cigarette filter stick, which comprises cut tobacco and master batch, wherein the master batch is the degradable cigarette filter stick master batch.
Preferably, the mass ratio of the tobacco shreds to the master batch is 5: 1-30: 1.
preferably, the degradable cigarette filter stick further comprises a plasticizer, wherein the plasticizer is one or more selected from phthalic acid esters, adipic acid esters, epoxy esters and citric acid esters.
The application provides a degradable cigarette filter stick master batch, which consists of a base material and a porous adsorption material, wherein the base material is diacetate fiber, and the porous adsorption material is haematococcus pluvialis-titanium dioxide composite material. The degradable cigarette filter stick master batch provided by the application can realize the surface sensitization of the photocatalyst by utilizing the haematococcus pluvialis-titanium dioxide composite material, the surface photosensitization enables the absorption wavelength range to be red shifted, and the light absorption wavelength is expanded to a visible light region; under the irradiation of visible light, electrons are excited to transition to TiO 2 Injecting a conduction band on the surface to induce visible light photocatalytic activity; meanwhile, haematococcus pluvialis contains rich proteins and polypeptides, and has high-efficiency adsorption capacity on smoke, tar, heavy metals and the like; therefore, the filter stick obtained by the application can accelerate photodegradation of cellulose diacetate, can efficiently adsorb harmful substances, and achieves the purposes of green, health and environmental friendliness.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
In view of the requirements of visible light degradation and harmful substance adsorption of the cigarette filter stick in the prior art, the application provides a visible light catalysis-adsorption coupled degradable cigarette filter stick master batch, which has the advantages of higher visible light degradation and high-efficiency harmful substance adsorption of the filter stick due to the introduction of haematococcus pluvialis-titanium dioxide composite material. Specifically, the embodiment of the invention discloses a degradable cigarette filter stick master batch, which consists of a base material and a porous adsorption material, wherein the base material is diacetate fiber, and the porous adsorption material is haematococcus pluvialis-titanium dioxide composite material.
In the degradable cigarette filter stick master batch, the diacetic acid fiber serving as a base material is prepared by taking natural wood pulp (early obtained from sequoia, high seed production rate, good processability, rich lignin and longer wood fiber) as a raw material, performing acetification (acetylation) to obtain a diacetic acid cellulose sheet, and performing processes such as dissolving, impurity filtering, spinning (spinning), curling, drying and the like. The cellulose diacetate has the characteristics of adsorptivity, weather resistance, oil resistance, processability and the like, and meanwhile, the cellulose diacetate also has degradability. The titanium dioxide has photosensitivity and can absorb photons, valence band electrons are excited to transit to a conduction band to generate electron-hole pairs, and the photoexcited electrons and holes migrate to the bulk phase or the surface of the composite material; titanium dioxide has the advantages of low cost, no toxicity, good photocatalytic performance, high stability and the like, but TiO 2 The photocatalyst is responsive only in the ultraviolet region; the titanium dioxide is modified by haematococcus pluvialis, so that the surface sensitization of the photocatalyst can be realized, the surface photosensitization enables the absorption wavelength range to be red shifted, and the light absorption wavelength is expanded to a visible light region; under the irradiation of visible light, electrons are excited to transition to TiO 2 And injecting a conduction band on the surface to induce visible light photocatalytic activity. Photocatalytic properties of titanium dioxide can be used to catalyze twoDegradation of cellulose acetate. The haematococcus pluvialis contains abundant active ingredients such as polysaccharide, protein, pigment, polyunsaturated fatty acid, terpenoid, vitamins, minerals and the like, and can absorb harmful ingredients in smoke.
In view of this, this application has adopted haematococcus pluvialis-titanium dioxide combined material as photodegradation catalyst and adsorbent, and its preparation method specifically is:
performing wall breaking treatment on the haematococcus pluvialis to obtain haematococcus pluvialis slurry;
mixing the haematococcus pluvialis slurry with titanium dioxide powder, filtering and drying to obtain the haematococcus pluvialis-titanium dioxide composite material.
In the present application, the wall breaking treatment is selected from treatment modes well known to those skilled in the art, and exemplified by one or more selected from a freeze thawing method, a mechanical stirring method, a strong acid method and an ethanol method. The mixing is carried out in a stirring mode, the stirring rotating speed is 1500-2500 rpm, and the mixing time is 1-3 h; the temperature of the filtration is 30-50 ℃. The mass ratio of the haematococcus pluvialis slurry to the titanium dioxide powder is 5:1-1:5, and more specifically, the mass ratio of the haematococcus pluvialis slurry to the titanium dioxide powder is 1:1-2:1.
The particle size of the haematococcus pluvialis-titanium dioxide composite material is 300-600 meshes, and the haematococcus pluvialis-titanium dioxide composite material has rich specific surface area of more than-1200 m 2 /g。
In the degradable cigarette filter rod master batch provided by the application, the mass ratio of the base material to the porous adsorption material is 1:1 to 10:1. the degradable cigarette filter stick master batch is obtained by melting and extruding a base material and a porous adsorption material, wherein the melting temperature is 50-100 ℃, and the shearing rate is 10-100 s -1 The method comprises the steps of carrying out a first treatment on the surface of the Specifically, the melting temperature is 60-80 ℃, and the shearing rate is 30-70 s -1 。
Further, the application also provides a degradable cigarette filter stick, which comprises cut tobacco and master batch, wherein the master batch is specifically the degradable cigarette filter stick master batch according to the scheme.
In the degradable cigarette filter stick, the mass ratio of the tobacco shreds to the master batch is 5: 1-30: 1. the degradable cigarette filter stick further comprises a plasticizer, which is well known to those skilled in the art, and exemplified by one or more selected from phthalate esters, adipic acid esters, epoxy esters, and citric acid esters.
The invention utilizes the marine algae processing byproduct-haematococcus pluvialis, and the obtained cigarette holder filter stick adsorption material contains rich natural polysaccharide and protein, and the polarity of the adsorption material is favorable for adsorbing harmful components in smoke; natural haematococcus pluvialis contains abundant astaxanthin; the titanium dioxide is modified by haematococcus pluvialis, so that the surface sensitization of the photocatalyst can be realized, the surface photosensitization enables the absorption wavelength range to be red shifted, and the light absorption wavelength is expanded to a visible light region; the photosensitive substance is excited to transition to TiO under the irradiation of visible light 2 Injecting a conduction band on the surface to induce visible light photocatalytic activity; the prepared cigarette filter stick contains rich proteins and polypeptides in haematococcus pluvialis, and has high-efficiency adsorption capacity on smoke, tar, heavy metals and the like; the used cigarette holder can accelerate photodegradation of cellulose diacetate due to the existence of the photocatalyst, so that the purposes of green health and environmental friendliness are realized.
For a further understanding of the present invention, the degradable cigarette filter rod master batch and the degradable cigarette filter rod provided by the present invention are described in detail below with reference to examples, and the scope of the present invention is not limited by the following examples.
Example 1
In an embodiment of a visible light catalytic-adsorption coupling degradable cigarette filter stick master batch, the preparation and production process comprises the following steps:
in the first step, titanium dioxide nanoparticles prepared by a sol-gel process:
tetraethyl titanate is used as a functional monomer, water is used as a solvent, glacial acetic acid is used as a catalyst, stirring is carried out for 2 hours, heat treatment is carried out for 6 hours at 160 ℃, and drying is carried out, thus obtaining titanium dioxide nano particles;
secondly, the haematococcus pluvialis is directly crushed and treated by a freeze thawing method, so that vitamin A, astaxanthin and the like in the material are exposed:
after cleaning haematococcus pluvialis, freezing and crushing the haematococcus pluvialis within the range of-20 ℃ and 40 ℃ to cause cell rupture due to cell wall osmotic pressure change of the haematococcus pluvialis, and then settling and concentrating the haematococcus pluvialis by a centrifugal method;
thirdly, haematococcus pluvialis and titanium dioxide are mixed according to the following ratio of 1:1, stirring, centrifuging and drying to form the photoactive adsorption coupling material:
adding titanium dioxide powder into haematococcus pluvialis slurry, stirring at 2000rpm to thoroughly mix nano titanium dioxide and wall-broken haematococcus pluvialis for 2 hours, filtering, and drying at 40deg.C to form load-type TiO 2 Composite photocatalytic material of haematococcus pluvialis;
fourthly, the prepared haematococcus pluvialis-titanium dioxide composite material is used as a porous adsorption material of a cigarette filter stick, cellulose diacetate filaments are used as a base material, and the materials are mixed, melted and extruded according to the mass ratio of 10 percent, the processing temperature is 100 ℃, and the shearing rate is 100s -1. 。
Example 2
In an embodiment of a visible light catalytic-adsorption coupling degradable cigarette filter stick master batch, the preparation and production process comprises the following steps:
in the first step, titanium dioxide nanoparticles prepared by a sol-gel process:
tetraethyl titanate is used as a functional monomer, water is used as a solvent, glacial acetic acid is used as a catalyst, stirring is carried out for 2 hours, heat treatment is carried out for 6 hours at 160 ℃, and drying is carried out, thus obtaining titanium dioxide nano particles;
secondly, directly crushing haematococcus pluvialis, and carrying out ethanol swelling treatment:
after cleaning haematococcus pluvialis, adding ethanol to cause cell rupture caused by cell wall osmotic pressure change of haematococcus pluvialis, and then settling and concentrating haematococcus pluvialis by a centrifugal method;
thirdly, haematococcus pluvialis and titanium dioxide are mixed according to the following ratio of 2:1, stirring, centrifuging and drying to form the photoactive adsorption coupling material:
adding titanium dioxide powder into haematococcus pluvialis slurry, stirring at 2000rpm to thoroughly mix nano titanium dioxide and wall-broken haematococcus pluvialis for 2 hours, filtering, and drying at 40deg.C to form load-type TiO 2 Composite photocatalytic material of haematococcus pluvialis;
fourthly, the prepared haematococcus pluvialis-titanium dioxide composite material is used as a porous adsorption material of a cigarette filter stick, cellulose diacetate filaments are used as a base material, and the materials are mixed, melted and extruded according to the mass ratio of 10 percent, the processing temperature is 100 ℃, and the shearing rate is 100s -1 。
The adsorption materials prepared in the above examples were evaluated for their overall properties, and the results are shown in Table 1. Target adsorbate in flue gas at 10g adsorbate: the adsorption level of nicotine, tar, heavy metal chromium and carbon monoxide is used as the investigation and characterization. Quantitative analysis was performed by gas mass spectrometry.
Meanwhile, the filter stick made of the haematococcus pluvialis-titanium dioxide composite material is used as a control group.
Table 1 table for evaluation of adsorption comprehensive properties of filter rods prepared in examples and control groups
As shown in Table 1, the adsorption performance of titanium dioxide is obviously improved by introducing haematococcus pluvialis. As the proportion of haematococcus pluvialis increases, the adsorption effect on harmful components in the smoke increases.
In addition, the degradation performance of the prepared cut tobacco is detected in a material aging box; wherein the addition amount of the titanium dioxide is 10 percent, and the tensile modulus of the cellulose diacetate filaments is taken as a degradation index. The xenon lamp simulates and strengthens sunlight, and the irradiation time is 2 weeks; see table 2 in detail;
TABLE 2 degradation evaluation Table of examples
As shown in Table 2, the introduction of haematococcus pluvialis significantly improves the photodegradation performance of titanium dioxide; with the increase of the proportion of haematococcus pluvialis, the photodegradation performance of cellulose filaments is improved.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A degradable cigarette filter stick master batch consists of a base material and a porous adsorption material, wherein the base material is diacetate fiber, and the porous adsorption material is haematococcus pluvialis-titanium dioxide composite material;
the preparation method of the haematococcus pluvialis-titanium dioxide composite material specifically comprises the following steps:
performing wall breaking treatment on the haematococcus pluvialis to obtain haematococcus pluvialis slurry;
mixing the haematococcus pluvialis slurry with titanium dioxide powder, filtering and drying to obtain the haematococcus pluvialis-titanium dioxide composite material.
2. The degradable cigarette filter rod masterbatch according to claim 1, characterized in that the mass ratio of haematococcus pluvialis slurry to the titanium dioxide powder is 5:1-1:5.
3. The degradable cigarette filter rod masterbatch of claim 1 wherein the wall breaking treatment is selected from one or more of freeze thawing, mechanical stirring, strong acid and ethanol.
4. The degradable cigarette filter stick master batch according to claim 1, wherein the haematococcus pluvialis-titanium dioxide composite material has a diameter of 300-600 meshes and a specific surface area of more than 1200m 2 /g。
5. The degradable cigarette filter rod masterbatch of claim 1 wherein the mass ratio of the substrate to the porous adsorbent material is 1:1 to 10:1.
6. the degradable cigarette filter masterbatch of claim 1, wherein the degradable cigarette filter masterbatch is melt extruded from a substrate and a porous adsorbent material; the melting temperature is 50-100 ℃, and the shearing rate is 10-100 s -1 。
7. A degradable cigarette filter rod comprising cut tobacco and a master batch, characterized in that the master batch is the degradable cigarette filter rod master batch according to any one of claims 1 to 6.
8. The degradable cigarette filter rod of claim 7 wherein the mass ratio of tobacco to masterbatch is 5: 1-30: 1.
9. the degradable cigarette filter rod of claim 7 further comprising a plasticizer therein, the plasticizer selected from one or more of phthalates, adipates, epoxyesters, and citrates.
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| US5491024A (en) * | 1995-03-14 | 1996-02-13 | Hoechst Celanese Corporation | Photodegradable cellulose ester tow |
| US8697213B2 (en) * | 2008-08-14 | 2014-04-15 | Solvay Acetow Gmbh | Photodegradable plastics material and its use |
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| US20120325231A1 (en) * | 2011-06-23 | 2012-12-27 | Eastman Chemical Company | Filters having improved degradation and methods of making them |
| US20120325233A1 (en) * | 2011-06-23 | 2012-12-27 | Eastman Chemical Company | Cellulose esters having mixed-phase titanium dioxide particles for improved degradation |
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| CN106434352A (en) * | 2016-09-28 | 2017-02-22 | 山东金晶生物技术有限公司 | Method for controlling haematococcus pluvialis pests and diseases by using photocatalyst |
| CN106984293A (en) * | 2017-05-06 | 2017-07-28 | 山西兰花华明纳米材料股份有限公司 | TiO 2 visible light catalyst of doping vario-property and preparation method thereof |
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