CN105964133A - Method for eliminating formaldehyde with biological protease - Google Patents

Method for eliminating formaldehyde with biological protease Download PDF

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Publication number
CN105964133A
CN105964133A CN201610421388.1A CN201610421388A CN105964133A CN 105964133 A CN105964133 A CN 105964133A CN 201610421388 A CN201610421388 A CN 201610421388A CN 105964133 A CN105964133 A CN 105964133A
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formaldehyde
enzyme
zein
kilogram
kilograms
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张园
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Priority to CN201610421388.1A priority Critical patent/CN105964133A/en
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Priority to CN201710391661.5A priority patent/CN107158927A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/804—Enzymatic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention relates to a method for treating of indoor formaldehyde pollution caused by decorating. According to a method for eliminating formaldehyde with the biological protease method, corn protein, protein activation enzymed, hydrolytic enzymed, oxidase, tea polyphenol, triethanolamine, surfactant and the like are mainly adopted. A formaldehyde eliminating agent for treating indoor decorating pollution is produced, and formaldehyde in decorating materials or formaldehyde in indoor air is eliminated, adsorbed and decomposed.

Description

Utilize the method that bio protease removes formaldehyde
Technical field:
A kind of method that the present invention relates to Treatment of Indoor Formaldehyde Pollution caused due to decorations.
Background technology:
1, the harm of formaldehyde, source:
In recent years, along with the raising of living standards of the people, people are more and more higher to the requirement of interior decoration standard, household Decoration modernizes increasingly, but the room air chemical contamination problem caused due to material and finishing is following.This It is healthy that a little chemicals have had a strong impact on resident, has caused countries in the world and the great attention of domestic relevant department.Crowd In multiple pollutant sources, formaldehyde is big with amount, strong toxicity, absorption is strong, scope is wide, has been classified as No.1 pollutant.
Formaldehyde is a kind of volatile organic matter with bigger toxicity.(chemical molecular formula HCHO, molecular weight: 30.03 are A kind of colourless, there is the gas of intense stimulus abnormal smells from the patient.Soluble in water, alcohol ether.Formaldehyde is gaseous state at normal temperatures, generally with water Solution form occurs.Its aqueous solution of 40% is referred to as formalin, and this solution boiling point is 19 DEG C.Therefore easily wave when room temperature Send out, along with the rising evaporation rate of temperature is accelerated.
Formaldehyde is more highly toxic material, is defined as carcinogenic by World Health Organization (WHO) and causes deformed material, being well recognized as Allergen, is also one of potential strong mutagen.Research shows: formaldehyde has strong carcinogenic and tumor promotion. Lot of documents record, formaldehyde the impact of health is mainly manifested in heterosmia, stimulation, allergy, abnormal pulmonary function, The aspect such as abnormal liver function and immunologic dysfunction.When its concentration reaches 0.06-0.07mg/m3 in every cubic metres of air, Child will occur slightly to pant.When formaldehyde content in indoor air is 0.1mg/m3, just there are abnormal flavour and sense of discomfort；Reach During to 0.5mg/m3, eyes can be stimulated, cause and shed tears；Reach 0.6mg/m3, throat discomfort or pain can be caused.Dense When spending higher, nausea and vomiting can be caused, cough uncomfortable in chest, even pulmonary edema of panting；When reaching 30mg/m3, can cause immediately People is dead.Long Term Contact low dosage formaldehyde can cause chronic respiratory tract disease, causes nasopharyngeal carcinoma, colon cancer, cerebroma, the moon Through gene mutation disorderly, nuclear, commissure and DNA and protein commissure and suppression DNA damage in DNA strand Reparation, pregnancy syndrome, cause neonatal chromosome disorder, leukemia, cause teenager memory and intelligence to decline. In all contactees, child and anemia of pregnant woman's PARA FORMALDEHYDE PRILLS(91,95) are particularly sensitive, and harm is bigger, is because the dirt of finishing and furniture Dye is caused, and its release phase, heat and wet will evaporate from material deep layer, serious environment pollution up to 3-15, Become insoluble global problem.
Investigation finds, causing the main path of Formaldehyde Pollution of Indoor Air is a large amount of ornament materials of using of household and furniture etc., Mainly include the artificial boards such as indoor decoration plywood, core-board, particieboard.Made owing to producing decorative panel at present Adhesive many based on Lauxite, therefore in sheet material residual formaldehyde components can gradually in air discharge, become The main source that in indoor gas, formaldehyde gas pollutes, and the formaldehyde gas discharged also can be gradually on wall, floor, very Gather to toy for children, human body especially teenager is caused bigger harm.Additionally, other kinds ornament materials such as wall Cloth, wallpaper, chemical fibre carpet, paint and coating etc. also contain formaldehyde components thus cause indoor formaldehyde gas content to increase. And artificial floor, furniture such as employ underproof sheet material or adhesives employs glue inferior and also can produce substantial amounts of Formaldehyde emissions.Be noted that especially formaldehyde be also from cosmetics, cleaning agent, insecticide, disinfectant, preservative, Printing, ink, paper etc., even also contain substantial amounts of formaldehyde in some medicated clothing.
Above-mentioned analysis shows: formaldehyde has the features such as multipath, disguise, characteristic of concentration in indoor pollution.It distributes way Footpath includes building materials, ornament materials and articles for daily use etc., simultaneously because the slow release characteristics of formaldehyde is toward being difficult to be examined by people Feeling, and itself will not quickly decompose, this extent of injury allowing for formaldehyde is even more serious compared with other polluters.Institute Extremely important with a kind of medicament that can the most thoroughly remove formaldehyde of invention！
2, prior art:
At present formaldehyde eliminating agent (formaldehyde catching agent) is basically divided into 4 classes:
The first kind is sealer, such as blocking absorbent of formaldehyde and preparation method thereof and the user of Application No. 01138098.5 invention Method, is mainly made up of chitosan, acetic acid and water, is formed transparent membrane sealed formaldehyde.
Equations of The Second Kind is the oxidant of energy oxidation of formaldehyde, and the formaldehyde scavenger such as Application No. 200510090754.1 invention is with carbonic acid Hydrogen sodium, hydrogen peroxide and the mixed solution of water composition, play the effect eliminating formaldehyde pollution by oxidation free formaldehyde molecule；
3rd class is the derivant of ammonia, and the derivant utilizing ammonia such as Application No. 02100765.9 invention is raw material, with carbamide in Carry out reaction under the conditions of property and manufacture formaldehyde catching removing formaldehyde.
4th class is amino acids, such as a kind of amino acid type formol release agent and the system thereof of Application No. 200610017363.1 invention Preparation Method, is reacted by aminoacid and formaldehyde and generates methylol acid removing formaldehyde.
For from principle, sealer has blocked the source of Form aldehyde release, it should can thoroughly eliminate the pollution channel of formaldehyde, be A kind of relatively good way, but, in actual use, owing to furniture is the most inevitably worn, The sealer smeared the most originally will lose original effect.And use formaldehyde eliminating agent, agent for capturing The problem that there is eradicating efficacy etc. method, although pollution can be reduced to a certain extent, but due to the dirt of indoor environment Contaminate the impact of the factors such as contaminated degree, temperature, air rate of filtration, eliminate reaction and be often difficult to thoroughly, because of This also is difficult to the effect reaching preferably to eliminate formaldehyde.The most also should remind consumer alert especially is that some formaldehyde disappears Except agent itself is with low quality, not only eradicating efficacy is inconspicuous, does not even have an effect eliminating formaldehyde, contrary it is also possible to Cause the secondary pollution of room air.Amino acids formaldehyde scavenger reacts mainly by aminoacid and formaldehyde and generates high score Sub-compound, but there is the drawback that reaction is insufficient, formaldehyde removing rate is low in it！
3, summary of the invention
The present invention, with zein as primary raw material, uses biological enzyme, oxidation, technology for hydrolyzing, and adds compound enzyme Preparation makes a kind of transparent, colourless, tasteless, nontoxic zein formaldehyde scavenger through special process.During use, adopt Using potent barrier formulations so that it is through material deep layer, the formaldehyde utilizing infiltration to neutralize in reaction principle, with material is carried out instead Should, thoroughly eradicate formaldehyde, generate a kind of colourless material nontoxic, Undec after reaction, do not result in secondary pollution.Spray Brush just can take effect after 20 minutes, and after 24, hour effect is more preferable, and the clearance rate of PARA FORMALDEHYDE PRILLS(91,95) is up to more than 90%.
Therefore, zein formaldehyde scavenger of the present invention, the Organic substance (first that both can effectively degrade harmful are used Aldehyde, benzene etc.), antibacterial effect can be played again, also do not result in secondary pollution.So, this product can effectively be dispelled The new home, because decorating harmful gas and the stinks such as the benzene of generation, formaldehyde, solves air pollution problem inside rooms well.Simultaneously Can also be used for cleaning the public places such as hospital, hotel, restaurant, school.
Due to biological product have pure environmental protection, subject range is extensive, treatment cost is low, easy to use and dirty without secondary The features such as dye.At present, have application to all over the world and all trades and professions.In China, also will be for contribution one of curbing environmental pollution Part strength.
Disclosure of the invention:
The present invention, with zein as primary raw material, uses biological enzyme, oxidation, technology for hydrolyzing, and adds compound enzyme Preparation makes a kind of transparent, colourless, tasteless, nontoxic zein formaldehyde scavenger through special process.
The manufacturing enterprise the most much producing wood-based plate finds, adds the zein of 10%～30% in Lauxite Powder, the artificial board formaldehyde burst size produced can reduce by more than 30% the highest, utilize this phenomenon, and we utilize Biological enzyme, scientific and reasonable multiple interpolation composite chemical auxiliary agent, stabilizer, develop a kind of novel corn albumen formaldehyde clear Except agent.
Zein formaldehyde scavenger of the present invention, the principle absorbing formaldehyde relies primarily on bioenzyme activity, actively absorption, absorb, Catch formaldehyde, then react with formaldehyde.
Being connected in central carbon atom it is known that aminoacid formula is H2N-CH (R)-COOH, R, formaldehyde is HCHO, Reaction expression is: HCHO+H2N-CH (R)-COOH=H2O+H2C=N-CH (R)-COOH.
Formaldehyde and aminoacid water generation reaction and gel-like albumen (carboxyl micel)
Owing to bioprotein formaldehyde scavenger of the present invention is compound formulation, not only contain aminoacid, possibly together with bioactive enzyme, Synergistic enzyme, adsorptive enzyme, its reaction and product are the most complicated, and equation above is main body reaction, does not include enzyme Activation adsorption reaction because enzyme activation absorb very difficult equation represent！
Detailed description of the invention:
The present invention uses raw material: zein, acid protease, As3.350 produce, and enzyme is lived 11520u/ G, hydrolytic enzyme (hydrolysis auxiliary agent, Ph value regulator) citric acid, tea polyphenols, triethanolamine (Ph value regulator, table Face activating agent, synergist)
Specific embodiment
The first step: zein-hydrolytic enzyme-tune pH-adds enzyme hydrolysis-enzyme denaturing-filtration-cooling
Second step: oxidation-decolorizing with activated carbon-filtration-cooling-crystallization-dehydration separates-dry-drying
3rd step: secondary dissolves-add organized enzyme-citric acid-tea polyphenols, edible ethanol, Oleum menthae or eucalyptus oil-three second Hydramine-filter-detect qualified-packaging
Concrete technology:
1, feed intake.Zein 100 kilograms, pure water 400 kilograms, add hydrolytic enzyme 3.5 kilograms, adjust Ph value=3.0, heating It is warming up to 90 DEG C, acid hydrolysis 3.5h.
2, enzymolysis.It is cooled to 50 DEG C, is 4000u/g by enzyme concentration, add acid protease, at 50 DEG C of enzymolysis 3h.
3, oxidation.After enzymolysis 3h, measure enzymolysis degree, as reached requirement, then 2% divided by corn separation protein, amount quality Add sodium hypochlorite (content 10%), aoxidize, note suitably being cooled to about 75 DEG C, time about 4h.
4, decolorizing with activated carbon.After becoming pure color to oxidation solution, 0.12-0.2% in an amount, add activity and carry out carbon decolouring, Temperature can be warming up to keep more than 95 DEG C, about 1.5h-2.5h.
5, filter.Use filter press, filter in the case of temperature keeps more than 90 DEG C, the settled solution filtered out It is well-oxygenated hydrolysed corn protein solution, cools down immediately, crystallization.
6, the saturated solution after crystallizing goes back to mother solution pond and recycles and reuses, and crystal dries to be dried into drying tower after filtering and (so far gives birth to The well-oxygenated hydrolysed corn albumen produced, moisture Control, within 1%, can be directly used for producing after carrying out the regulation of Ph value The formaldehyde scavenger used for wood-based panel).
7., with the well-oxygenated hydrolysed corn protein 20 0 kilogram of the above content about more than 98% produced, add pure water 53.5-56.5 kilogram, citric acid 1 kilogram, acid protease 1.5-3 kilogram, tea polyphenols 0.2 kilogram, Oleum menthae or Folium eucalypti globueli (Eucalyptus globulus Labill.) Oil 0.05 kilogram adds after dissolving with 1.75 kilograms of edible ethanols, is sufficiently stirred for dissolving.
8. with triethanolamine adjust ph value=7.0, then filter, detect qualified after pack！
Zein formaldehyde scavenger of the present invention uses QB/T2761-2006 " indoor air purification product clean-up effect mensuration side Method " detect the concentration of formaldehyde in air sample, remove Formaldehyde Test.
QB/T2761-2006 formaldehyde scavenger goes removing and harmful gas test method:
Experiment condition:
Test temperature: (23.0 ± 3) DEG C, humidity: (50.0 ± 5) %RH；
Simulation laboratory: 1.5m3Air test cabin；
1.2, remove testing program:
1.2.1, in climate box, analytically pure formalin 2.0ml is placed in surface plate, volatilizees and carry out for 24 hours Sampling is designated as initial concentration.
1.2.2,300g formaldehyde scavenger is sprayed on uniformly three 1m2Base paper on, dry rear-mounted in experimental cabin Position, centre, air sample in 24 hours gather experimental cabin again, it is designated as 24 hour concentrations.
1.2.3, to the sample gathered according to QB/T2761-2006 " indoor air purification product clean-up effect assay method " inspection Survey the concentration of formaldehyde in air sample.According to the concentration detected in sample, calculate the removal of formaldehyde scavenger PARA FORMALDEHYDE PRILLS(91,95) Efficiency.
1.3, test explanation:
According to QB/T2761-2006 " indoor air purification product clean-up effect assay method " requirement, having of its examined project Pest matter Limited Doses is: concentration of formaldehyde≤0.10mg/m3.The initial concentration of EXPERIMENTAL DESIGN is 10 times of standard-required limitation Left and right.
1.4 removal efficiency calculates:
Removal efficiency=× 100%
Zein formaldehyde scavenger of the present invention is through the above method inspection of national environmental protection product quality supervision and inspection central laboratory Testing, zein formaldehyde scavenger of the present invention reaches 91% to formaldehyde in air elimination efficiency.(survey report is numbered: GHB2013HZ00459) according to the introduction of this laboratory worker, up to now, formaldehyde is removed with this experimental technique little Find to reach the product of this horizontal formaldehyde removing.
Zein formaldehyde scavenger of the present invention is identified through country Administration of Work Safety Supervision's hazardous chemical evaluating center, zein first Aldehyde scavenger is not belonging to hazardous chemical (survey report is numbered: 2013090308-C inquiry coding 3ME3L3E3P-I)
Zein formaldehyde scavenger of the present invention is through China Preventive Medicial Science Institute, country's disease prevention and control center's Institute for Toxicology Carrying out white mice Ld50 detection, result is actual nontoxic level.(survey report is numbered :)
Zein formaldehyde scavenger of the present invention is applied in Langfang in Hebei Province of Wood-based Panel Production enterprise Dong Sheng wood industry company limited multilamellar Plate workshop, the multi-layer sheet burst size of methanal of production is reduced to 0.2mg/L by original 4.6mg/L, and particieboard was by originally 27.6mg/100g be reduced to 3.8mg/100g, complete this F of Dagri (≤0.3mg/L) is without aldehyde level wood-based plate Burst size of methanal standard, and the bonding strength of wood-based plate, MOR, water proofing property etc. have raising in various degree, produce Workshop distributes almost without pungent formaldehyde odor, by enterprise's approval consistent with plant operations workman.

Claims (3)

1. the first step: zein-albumen intensify enzyme-hydrolytic enzyme (adjust pH, add enzyme hydrolysis)-enzyme denaturing-filtration- Cooling.
2. second step: oxidation-decolorizing with activated carbon-filtration-cooling-crystallization-dehydration separates-dry-drying.
3. the 3rd step: secondary dissolve-add organized enzyme-citric acid-tea polyphenols, edible ethanol, Oleum menthae or eucalyptus oil- Triethanolamine-filter-detect qualified-packaging.
Concrete technology:
A, feed intake.Zein 100 kilograms, albumen intensifies enzyme 3.6 kilograms, pure water 400 kilograms, adds hydrolytic enzyme 3.5 public Jin, adjusts Ph value=3.0, is heated to 90 DEG C, acid hydrolysis 3.5h.
B, enzymolysis.It is cooled to 50 DEG C, is 4000u/g by adding hydrolysis enzyme amount, adds acid protease, at 50 DEG C of enzymolysis 3h.
C, oxidation.After enzymolysis 3h, measure enzymolysis degree, as reached requirement, then 2% addition time divided by zein amount quality Sodium chlorate (content 10%), aoxidizes, and notes suitably being cooled to about 75 DEG C, time about 4h.
D, decolorizing with activated carbon.After becoming pure color to oxidation solution, 0.12-0.2% in an amount, add activity and decolour, temperature Degree can be warming up to keep more than 95 DEG C, about 1.5h-2.5h.
E, filtration.Use filter press, filter in the case of temperature keeps more than 90 DEG C, the settled solution filtered out It is zein formaldehyde removing agent solution, cools down immediately, crystallization.
Saturated solution after f, crystallization goes back to mother solution pond and recycles and reuses, and crystal dries to be dried into drying tower after filtering and (so far gives birth to The solid formaldehyde scavenger produced, moisture Control, within 1%, can be directly used for producing wood-based plate after carrying out the regulation of Ph value and uses Formaldehyde catching agent).
G. with above content about more than the 98% zein formaldehyde scavenger 20 kilograms produced, pure water 53.5-56.5 is added Kilogram, citric acid 1 kilogram, acid protease 1.5-3 kilogram, tea polyphenols 0.2 kilogram, Oleum menthae or eucalyptus oil 0.05 Add after kilogram dissolving with 1.75 kilograms of edible ethanols, be sufficiently stirred for dissolving.
H. with triethanolamine adjust ph value=7.0, then filter, detect qualified after pack.
CN201610421388.1A 2016-06-15 2016-06-15 Method for eliminating formaldehyde with biological protease Pending CN105964133A (en)

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CN201710391661.5A CN107158927A (en) 2016-06-15 2017-05-27 A kind of zein formaldehyde scavenger and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
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CN107497286A (en) * 2017-09-15 2017-12-22 安徽中弘科技发展有限公司 A kind of biology enzyme formaldehyde scavenger
CN107670493A (en) * 2017-10-31 2018-02-09 山东德慧环境科技有限公司 A kind of animal protein formaldehyde scavenger, its preparation method and application
CN107774105A (en) * 2017-10-27 2018-03-09 于建伟 A kind of compound protein formaldehyde scavenger, its preparation method and application
CN108671714A (en) * 2018-01-25 2018-10-19 蔡进 It is a kind of to remove formaldehyde while have both the bio protease to eliminate the unusual smell
CN110945086A (en) * 2017-06-30 2020-03-31 陶氏环球技术有限责任公司 Coating for removing aldehydes and preparation method thereof

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CN107802978A (en) * 2017-10-31 2018-03-16 山东德慧环境科技有限公司 A kind of soybean protein formaldehyde scavenger and its production technology

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CN101195037A (en) * 2007-12-10 2008-06-11 诸城市良丰化学有限公司 Biological aldehydrase preparation prescription and its preparation technique
CN103272461A (en) * 2013-05-21 2013-09-04 赵杰 Technology for producing formaldehyde scavenging agent by using vegetable proteins
CN104645819A (en) * 2013-11-21 2015-05-27 马啸天 Production process of soybean protein formaldehyde removing agent
CN105126602A (en) * 2015-08-17 2015-12-09 王平 Manufacturing method of controlled natural biological odor-removal formaldehyde-removal product

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CN110945086A (en) * 2017-06-30 2020-03-31 陶氏环球技术有限责任公司 Coating for removing aldehydes and preparation method thereof
CN110945086B (en) * 2017-06-30 2022-09-16 陶氏环球技术有限责任公司 Coating for removing aldehydes and preparation method thereof
US11597845B2 (en) 2017-06-30 2023-03-07 Dow Global Technologies Llc Coating for aldehyde remediation and method of making
CN107497286A (en) * 2017-09-15 2017-12-22 安徽中弘科技发展有限公司 A kind of biology enzyme formaldehyde scavenger
CN107774105A (en) * 2017-10-27 2018-03-09 于建伟 A kind of compound protein formaldehyde scavenger, its preparation method and application
CN107670493A (en) * 2017-10-31 2018-02-09 山东德慧环境科技有限公司 A kind of animal protein formaldehyde scavenger, its preparation method and application
CN108671714A (en) * 2018-01-25 2018-10-19 蔡进 It is a kind of to remove formaldehyde while have both the bio protease to eliminate the unusual smell

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Application publication date: 20160928