CN108840336A - A method of high performance active carbon is prepared using vanillic aldehyde production waste liquid - Google Patents
A method of high performance active carbon is prepared using vanillic aldehyde production waste liquid Download PDFInfo
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- CN108840336A CN108840336A CN201810916318.2A CN201810916318A CN108840336A CN 108840336 A CN108840336 A CN 108840336A CN 201810916318 A CN201810916318 A CN 201810916318A CN 108840336 A CN108840336 A CN 108840336A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/30—Regeneration or reactivation of catalysts comprising compounds of sulfur, selenium or tellurium
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
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- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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Abstract
The present invention relates to a kind of methods for preparing high performance active carbon using vanillic aldehyde production waste liquid, first vanillic aldehyde production waste liquor is reacted under alkaline condition with formaldehyde and generates thermosetting property methoxy substitution phenolic resin, it is dipped into the chemical activation agent solution prepared with dead catalyst again, mixes milling after dry.Carbonization-activation is kept the temperature at nitrogen protection and 550-600 DEG C, naturally cools to room temperature, dipping soluble chemistry activator is classified with dilute sulfuric acid, is separated by filtration to obtain active carbon.Chemical activation agent solution is concentrated by evaporation, and separates crystallization after cooling, is used as vanillic aldehyde and is produced oxidation catalyst.The present invention is used as Activated Carbon Production chemical activating agent using vanillic aldehyde production dead catalyst, not only reduces the cost of chemical activating agent, and it is resin activated during make catalyst regeneration again, realize catalyst circulation and use.
Description
Technical field
The present invention relates to a kind of methods for preparing high performance active carbon using vanillic aldehyde production waste liquid, belong to chemical industry and material
Field.
Background technique
Vanillic aldehyde be one of maximum synthetic perfume of output and pharmaceutical synthesis and Chemical Manufacture in the world it is important in
Mesosome, 2.5 ten thousand tons of Chinese vanillic aldehyde production capacity, it has also become the world's largest vanillic aldehyde producing country.Vanillic aldehyde is widely used in
In the various blending food for needing to increase milk breath, it may also be used in perfumed soap, toothpaste, perfume, rubber, plastics and pharmaceuticals.
There are many vanillic aldehyde industrial product route, generally use acetaldehyde acid system process route both at home and abroad at present.I.e. by guaiacol and acetaldehyde
Condensation generates 3-methoxy-4-hydroxyphenyle-thanol acid to acid under alkaline condition, further under alkaline condition, in copper or other mistakes
It crosses in the presence of metallic catalyst, homovanillin acid is generated by air catalytic oxidation, then in acid condition
Decarboxylize generates vanillic aldehyde, obtains vanillic aldehyde product with toluene extraction and crystallization.
Yield 78%-82%, oxidization-hydrogenation ratio 94%-98%, decarboxylation yield 90%- are condensed during acetaldehyde acid system synthesis of vanillin
95%, yield 92%-95% is refined, the total recovery in terms of raw material guaiacol is 61%-72%.A large amount of phenols in industrial production are useless
Gurry a part is the bottoms generated in subtractive process, in early days using landfill and burning disposal after solidification, as environmental protection is wanted
The cost of disposal of the continuous improvement asked, the waste residue containing phenol is higher and higher.It is organic that another part is dissolved in the phenols in reaction mother liquor
Object after generalling use macroporous absorbent resin absorption, then is further processed low concentration with chemical oxidization method and bioanalysis and gives up containing phenol
Water, to realize the qualified discharge of waste water.The problem is that being needed after macroporous absorbent resin adsorption saturation using organic solvent
Or phenol organic matter is desorbed in aqueous slkali, and it is high with the cost of oxidation processes residence using burning that the high-concentration phenol type organic to get off is desorbed
Under not, secondary pollution is serious, and there is an urgent need to vanillic aldehydes to produce phenolic waste liquor comprehensive utilization technique for relevant enterprise.
Active carbon is widely used in as a kind of environmentally friendly solid absorbent cheap and easy to get in daily production and living
It is adsorbed and removed harmful substance, is usually used in decoloration, deodorization, purification, catalyst and electronic material of product etc. in the industry.It is living
Property the natural materials manufacture such as charcoal conventionally employed timber, plant, shell, petroleum, coal, often residual ash impurity in product；With
Science and technology progress, the requirement to Properties of Activated Carbon is higher and higher, product quality main indicator do not require nothing more than specific surface area and
Adsorption capacity is big, and requires the other performances such as content of ashes and surface texture, with the performance of the active carbon of natural material production
Needs cannot be fully met.Since synthetic polymer has determining macromolecular structure, the active carbon of preparation has pore structure
Controllably, the stable advantage low with impurity content of performance is increasingly subject to weight by precursor preparation activated carbon process of synthetic polymer
Depending on.With the fast development of attention and battery new energy industry to environmental protection, the active carbon market demand is pushed quickly to increase
Long, China produces active carbon per year up to 600,000 tons or more, and hair will be become by seeking cheap raw material and waste production high performance active carbon
Exhibition trend.
The type of carbonaceous material and source are very big on the performance of active carbon and yield influence, with synthesizing polymeric material
For, if producing active carbon using waste plastics, the inorganic filler and fire retardant in waste plastics often contain the ash content of active carbon
It measures excessively high；If active carbon is produced using polyester, Lauxite or epoxy resin, since there are a large amount of C-O or C-N in polymer
Key, unstable chemical bond rupture, is cracked into volatile small molecule, carbonization yield often only has during high temperature carbonization
0.5%-10%, obtained activated carbon structure defective tightness, mechanical strength are also bad；If using phenolic resin, polymer molecule
In mainly stable C-C key connection, the volatile small molecule for cracking formation is fewer, and carbonization yield is up to 60%-75%, charcoal
The carbon backbone structure for changing post-consumer polymer is not destroyed, and active carbon mechanical strength is relatively high, so, high performance active carbon generally selects
Phenolic resin is selected as raw material preparation.If selecting low-volatile fortified phenol as phenolic resin starting material, the activity prepared with it
Charcoal mechanical strength and regenerability will more preferably, and carbonization rate also will be higher.
Summary of the invention
The purpose of the present invention is separating the phenol organic matter in vanillic aldehyde synthesis mother liquid, high-performance is prepared using it
Active carbon, to reduce treating phenolic waste water pressure and the cost of disposal of waste residue containing phenol in vanillic aldehyde production.
Vanillic aldehyde production mother liquor composition is extremely complex, and the waste liquid quality group after concentration becomes：Phenol organic matter 20%-25%,
Inorganic salts 2%-8%, remaining is water.Wherein, phenol organic matter group becomes：Ortho vanillin 20%-30%, dystopy vanillic aldehyde 10%-
15%, vanillic aldehyde 10%-15%, dimerization vanillic aldehyde 10%-15%, vanillic aldehyde acid 15%-20%, methoxv mandelic acid 5%-10%, dimerization are flat
Peach acid 5%-10% is convenience of calculation phenol organic matter average molecular weight with vanillic aldehyde Molecular weights；Inorganic salts therein are mainly
Sodium sulphate and transition metal sulfate.
The present invention provides a kind of method for preparing high performance active carbon using vanillic aldehyde production waste liquid, it is characterized in that including first
The synthesis of oxygroup substituted phenolic resin, dead catalyst prepare chemical activating agent, the charing of resin and activation, the recycling of regenerated catalyst
Four parts, the technical solution taken and the specific steps are：
（1）Quality group is become：Phenol organic matter 20%-25%, inorganic salts 2%-8%, remaining produces waste liquid for the vanillic aldehyde of water, uses
It is 9-10 that sodium hydroxide solution, which adjusts pH value of solution, is heated to 60-80 DEG C, is added slowly with stirring the first that mass concentration is 37%
Aldehyde solution, control molar ratio are：Phenol organic matter：Formaldehyde=1:1.5-2.0, insulation reaction 1-2h, cold after the completion of charging
But 10-20 DEG C is arrived, the thermosetting property methoxy substitution phenolic resin precipitating of generation is separated by filtration；
（2）By vanillic aldehyde produce in dead catalyst heating and refluxing to dissolve generated in the sulfuric acid solution that mass concentration is 10% it is multiple
Sulfate liquor is closed, the crystallization for separating generation after room temperature is cooled to, the chemical composition of drying crystalline is CuxFeyZn2-x-y(SO4)2,
Wherein, x=0.05-0.95, y=0.05-0.95, the chemical activating agent as active carbon preparation；
（3）Heat cured methoxy substitution phenolic resin precipitating is impregnated into the chemical activation agent solution prepared with dead catalyst
In, evaporation water mixes milling after dry, and the mass ratio for controlling methoxy substitution phenolic resin and chemical activating agent is 1:0.2-
0.4；
（4）The crucible for filling resin and chemical activating agent mixed material is put into the high temperature furnace of logical nitrogen protection, high temperature furnace is made
It is warming up to 550-600 DEG C, carbonization-activation 1-2h is kept the temperature, oxygen and hydrogen atom in material resin molecule is made to be cracked into small point of volatility
Son；
（5）Stop high temperature stove heating and nitrogen to be passed through, material naturally cools to room temperature in air, make to carbonize material air into
The activation of one step, is oxidized the chemical activating agent being reduced；
（6）Activated material is transferred in accumulator tank, the sulfuric acid solution classification dipping soluble chemistry activator for being 10% with mass concentration,
It is separated by filtration active carbon, is 4-6 with deionized water cleaning active charcoal to pH, is dried at 120 DEG C, high performance active carbon powder is obtained
75g, specific surface area 1200-1500m2/ g, ash content 0.2%-0.5%, iodine absorption number are 1000-1500 mg/g, methylene blue
Decolorizing ability 120-150 mg/g, active carbon prepare yield 45%-50%；
（7）The chemical activation agent solution of recycling is concentrated by evaporation, separates crystallization, chemical composition Cu after coolingxFeyZn2-x-y
(SO4)2, wherein x=0.05-0.95, y=0.05-0.95 are recycled as vanillic aldehyde production oxidation catalyst.
If not using the method for being converted into phenolic resin, the further high temperature evaporation of waste liquid is concentrated, is difficult to locate with regard to being formed
The tar shaped polymer of reason.If its direct charing is prepared active carbon, these polymer are cracked to form greatly in carbonization process
Volatile small molecule is measured, than more serious, charcoal residual rate or carbonization yield are very low for secondary pollution.
The phenol organic matter in waste liquid that the present invention uses can react to be formed with formaldehyde because of the ring structure containing phenol
Methoxy-substituted phenolic resin, but its work of activity than phenol and formaldehyde progress polymerization reaction that polymerization reaction is carried out with formaldehyde
Property is much lower, and main cause is that methoxyl group occupies an active sites of phenol, while the chemical reaction to other active sites
There is space steric effect.For example, the ortho vanillin and vanillic aldehyde in waste liquid can react generation with formaldehyde under alkaline condition
Methoxy-substituted linear phenolic resin, this is because the aldehyde radical in ortho vanillin and vanillic aldehyde molecule under alkaline condition may be used
Methylol is disproportionated by formaldehyde reduction, and the reactive hydrogen on the phenolic hydroxyl group ortho position or contraposition in ortho vanillin and vanillic aldehyde molecule
Another methylol is generated with formaldehyde condensation, 2 active methylol functional groups have to form linear phenolic resin in a molecule
Condition.There are 2 reactive hydrogens that can restore disproportionation with formaldehyde condensation, aldehyde radical in dystopy vanillic aldehyde molecule in waste liquid to generate easily
The vanillic aldehyde alcohol of polymerization, 2 active function groups have the condition to form figure phenolic resin in a molecule.
Active sites are less than 2 in other phenol organic matter molecules in the waste liquid that the present invention uses, itself cannot be with formaldehyde
Reaction forms phenolic resin, but can react chain extension with the methylol in phenolic resin.Due to containing hydroxyl simultaneously in their molecules
Base and carboxyl-reactive functional group can occur step-reaction polymerization and generate alkyd resin.
It requires to primarily form methoxy substitution phenolic resin in Polymer supported catalyst in the present invention, makes polymer molecule master
Body skeleton is C-C key connection, and cannot be C-O key connection, and volatile small molecule is reduced in carbonization process and is generated, and makes to generate and live
The thermal stability of property charcoal is good, and improves carbonization-activation total recovery.
Addition excess formaldehyde is taken in technical solution of the present invention, it is made to restore the fragrant aldehyde radical of disproportionation under alkaline condition
Methylol, so that C-C is keyed in polymer molecule；Take simultaneously by resin precipitated and the small molecule that is dissolved in mother liquor and
Excess formaldehyde separation, to prevent from forming the secondary pollution of volatile small molecule in carbonization process.
The carbon content height of methoxy substitution phenolic resin and structure are closely knit in the present invention, the charing that toner surface is formed
Film will hinder resin deep charring and activation, so, selection uses chemical activation method rather than physical activation method.
It is generally added in alkaline oxygenated liquid using by soluble transition metal salt solution in vanillic aldehyde industrial production, with original
The transition metal hydroxide that position generates is as oxidation catalyst, especially with Kocide SD as the main of oxidation catalyst
Component, catalyst exist in the form of hydroxide colloid in oxidation solution, due to colloid quilt when catalyst separates after the reaction was completed
It destroys and loses activity, oxidation catalyst can not be recycled, and largely be regenerated by the useless oxidation catalyst of organic pollution
It is a technical problem.Vanillic aldehyde is selected to produce useless oxidation catalyst as chemical activating agent, not only reducing in the present invention
The cost of activator is learned, and regenerates oxidation catalyst again in process for preparing active carbon.
To reduce Activated Carbon Production consumption of raw materials and production cost, chemical activating agent additional proportion only has conventional in the present invention
/ 10th of method, the activation that may cause charing material is incomplete, using being passed through the further object of air in temperature-fall period
Reason activation not only prevents charing material activating not thorough, but also prevents the overactivity problem being easy to appear under high temperature.
The chemical activating agent mechanism of action is similar to the conventional mechanism of action of zinc chloride activation agent in the present invention, difference
It is that transition metal copper and iron are easier to react generation with carbon molecules than zinc atom with stronger oxidisability, copper oxide and iron oxide
Carbon dioxide makes carbonaceous material be etched, and the metal copper atom and iron atom for restoring generation are easier to capture in carbonaceous material molecule
Oxygen generate copper oxide and iron oxide, circulation carries out carbonization-activation to carbonaceous material.Experiment discovery copper and iron zinc multicomponent chemical is living
Agent has stronger activation effect than single component chemical activator, it may be possible to which composition fused salt has lower fusing point and higher
Boiling point, preferably constitute and the vanillic aldehyde oxidation catalyst of chemical activating agent preferably constitute identical, and oxidation operation is anti-in solution
Place should be communicated with the oxidation reaction under hot conditions.
Vanillic aldehyde production waste liquid and dead catalyst are from acetaldehyde acid system synthesis of vanillin mother liquor in laboratory in the present invention
Concentrate and dead catalyst, with Jilin Chemical group of domestic vanillic aldehyde industrial production enterprise early stage provide vanillic aldehyde production waste liquid and
Dead catalyst composition is identical；Other chemical raw material formaldehyde, sulfuric acid, sodium hydroxide, copper sulphate, ferrous sulfate and zinc sulfate are commercially available
Chemical reagent.The technical indicators reference such as specific surface area, ash content, iodine absorption number, Methylene blue adsorption of high performance active carbon powder
Water purification is measured with active carbon standard GB/T 13803.2-1999 and GB/T7701.2-2008 method.
The advantages of the present invention are embodied in：
（1）Vanillic aldehyde is produced phenol organic matter in waste liquid to separate, reduces treating phenolic waste water pressure in vanillic aldehyde production
Power and the cost of disposal of waste residue containing phenol；
（2）High performance active carbon is prepared with vanillic aldehyde production waste liquid, has both been opened for low cost production high performance active carbon new
Raw material sources channel, and realize the comprehensive utilization of chemical pharmaceutical waste；
（3）Useless oxidation catalyst is produced as Activated Carbon Production chemical activating agent using vanillic aldehyde, not only reduces chemical activation
The cost of agent, and oxidation catalyst is regenerated again in production process of activated carbon, realize the recycling of oxidation catalyst.
Specific embodiment
The purpose of the present invention is what is realized in the following ways, is described in detail below with reference to embodiment：
Embodiment 1
Vanillic aldehyde is added in beaker and produces waste liquid 760g（Equivalent 1.0mol phenol organic matter）, the hydrogen for being 10% with mass concentration
It is 9-10 that sodium hydroxide solution, which adjusts pH value of solution, is heated to 80 DEG C, is added slowly with stirring the formalin that mass concentration is 37%
121.6g（Equivalent 1.5mol formaldehyde）, insulation reaction 1h after the completion of charging is cooled to 20 DEG C, is separated by filtration the thermosetting property first of generation
Oxygroup substituted phenolic resin precipitates 150g.
By vanillic aldehyde produce in dead catalyst 30g heating and refluxing to dissolve 300g mass concentration be 10% sulfuric acid solution
In, sulfate composite salting liquid is generated, the crystallization for separating generation after room temperature is cooled to, the quality of drying crystalline is 45g, chemical composition
For Cu0.9Fe0.7Zn0.4(SO4)2, the chemical activating agent as active carbon preparation.
Chemical activating agent 45g is dissolved by heating in 100mL deionized water, by 150g thermosetting property methoxyl group made above
Substituted phenolic resin precipitating is impregnated into chemical activation agent solution, evaporation water, mixes milling after dry.Mixture will be filled
Crucible is put into the high temperature furnace of logical nitrogen protection, and high temperature furnace is made to be warming up to 550-600 DEG C, keeps the temperature carbonization-activation 2h；Stop high temperature
Stove heating and nitrogen are passed through, and activation material naturally cools to room temperature in air.
Activated material is transferred in accumulator tank, the sulfuric acid classification dipping soluble chemistry activator for being 10% with mass concentration, filtering
Isolating active charcoal is 4-6 with deionized water cleaning active charcoal to pH, is dried at 120 DEG C, and high performance active carbon powder is obtained
67.5g, specific surface area 1500m2/ g, ash content 0.2%, iodine absorption number are 1500 mg/g, 150 mg/ of Methylene blue adsorption
G, active carbon prepare yield 45%.The chemical activation agent solution of recycling is concentrated by evaporation, separates crystallization, chemical composition after cooling
For Cu0.9Fe0.7Zn0.4(SO4)2, it is used as vanillic aldehyde and produces oxidation catalyst.
Embodiment 2
Vanillic aldehyde is added in beaker and produces waste liquid 760g（Equivalent 1.0mol phenol organic matter）, the hydrogen for being 10% with mass concentration
It is 9-10 that sodium hydroxide solution, which adjusts pH value of solution, is heated to 80 DEG C, is added slowly with stirring the formalin that mass concentration is 37%
162.2g（Equivalent 2.0mol formaldehyde）, insulation reaction 1h after the completion of charging is cooled to 10 DEG C, is separated by filtration the thermosetting property first of generation
Oxygroup substituted phenolic resin precipitates 170g.
The chemical activating agent 34g that 1 method of embodiment is obtained is dissolved by heating in 100mL deionized water, will be made above
170g thermosetting property methoxy substitution phenolic resin precipitating be impregnated into chemical activation agent solution, evaporation water mixes after dry
Milling.The crucible for filling mixture is put into the high temperature furnace of logical nitrogen protection, so that high temperature furnace is warming up to 550-600 DEG C, heat preservation
Carbonization-activation 2h；Stop high temperature stove heating and nitrogen is passed through, activation material naturally cools to room temperature in air.
Activated material is transferred in accumulator tank, the sulfuric acid classification dipping soluble chemistry activator for being 10% with mass concentration, filtering
Isolating active charcoal is 4-6 with deionized water cleaning active charcoal to pH, is dried at 120 DEG C, and high performance active carbon powder 85g is obtained,
Specific surface area is 1200m2/ g, ash content 0.3%, iodine absorption number are 1000 mg/g, 120 mg/g of Methylene blue adsorption, activity
Charcoal prepares yield 50%.The chemical activation agent solution of recycling is concentrated by evaporation, separates crystallization after cooling, chemical composition is
Cu0.9Fe0.8Zn0.3(SO4)2, it is used as vanillic aldehyde and produces oxidation catalyst.
Claims (1)
1. a kind of method for preparing high performance active carbon using vanillic aldehyde production waste liquid, it is characterized in that including methoxy substitution phenolic aldehyde
Resins synthesis, dead catalyst prepare chemical activating agent, the charing of resin and activation, four part of the recycling of regenerated catalyst, take
Technical solution and the specific steps are：
（1）Quality group is become：Phenol organic matter 20%-25%, inorganic salts 2%-8%, remaining produces waste liquid for the vanillic aldehyde of water, uses
It is 9-10 that sodium hydroxide solution, which adjusts pH value of solution, is heated to 60-80 DEG C, is added slowly with stirring the first that mass concentration is 37%
Aldehyde solution, control molar ratio are：Phenol organic matter：Formaldehyde=1:1.5-2.0, insulation reaction 1-2h, cold after the completion of charging
But 10-20 DEG C is arrived, the thermosetting property methoxy substitution phenolic resin precipitating of generation is separated by filtration；
（2）By vanillic aldehyde produce in dead catalyst heating and refluxing to dissolve generated in the sulfuric acid solution that mass concentration is 10% it is multiple
Sulfate liquor is closed, the crystallization for separating generation after room temperature is cooled to, the chemical composition of drying crystalline is CuxFeyZn2-x-y(SO4)2,
Wherein, x=0.05-0.95, y=0.05-0.95, the chemical activating agent as active carbon preparation；
（3）Heat cured methoxy substitution phenolic resin precipitating is impregnated into the chemical activation agent solution prepared with dead catalyst
In, evaporation water mixes milling after dry, and the mass ratio for controlling methoxy substitution phenolic resin and chemical activating agent is 1:0.2-
0.4；
（4）The crucible for filling resin and chemical activating agent mixed material is put into the high temperature furnace of logical nitrogen protection, high temperature furnace is made
It is warming up to 550-600 DEG C, carbonization-activation 1-2h is kept the temperature, oxygen and hydrogen atom in material resin molecule is made to be cracked into small point of volatility
Son；
（5）Stop high temperature stove heating and nitrogen to be passed through, material naturally cools to room temperature in air, make to carbonize material air into
The activation of one step, is oxidized the chemical activating agent being reduced；
（6）Activated material is transferred in accumulator tank, the sulfuric acid solution classification dipping soluble chemistry activator for being 10% with mass concentration,
It is separated by filtration active carbon, is 4-6 with deionized water cleaning active charcoal to pH, is dried at 120 DEG C, high performance active carbon powder is obtained
75g, specific surface area 1200-1500m2/ g, ash content 0.2%-0.5%, iodine absorption number are 1000-1500 mg/g, methylene blue
Decolorizing ability 120-150 mg/g, active carbon prepare yield 45%-50%；
（7）The chemical activation agent solution of recycling is concentrated by evaporation, separates crystallization, chemical composition Cu after coolingxFeyZn2-x-y
(SO4)2, wherein x=0.05-0.95, y=0.05-0.95 are recycled as vanillic aldehyde production oxidation catalyst.
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| CN109813624A (en) * | 2019-01-04 | 2019-05-28 | 通标标准技术服务（天津）有限公司 | The detection method of the content of formaldehyde and benzene in paint |
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