CN115367912B - Recycling method and reuse method of plasticizer-containing waste liquid - Google Patents

Recycling method and reuse method of plasticizer-containing waste liquid Download PDF

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Publication number
CN115367912B
CN115367912B CN202210954410.4A CN202210954410A CN115367912B CN 115367912 B CN115367912 B CN 115367912B CN 202210954410 A CN202210954410 A CN 202210954410A CN 115367912 B CN115367912 B CN 115367912B
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plasticizer
waste liquid
containing waste
production
wallpaper
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CN115367912A (en
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张海雄
龙有恩
陆勇新
王亚浩
叶国明
袁铸洋
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Guangdong Yulan Group Co ltd
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Guangdong Yulan Group Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The application discloses a method for recycling and treating plasticizer-containing waste liquid and multiplexing the plasticizer-containing waste liquid, wherein the pH value of the treated plasticizer-containing waste liquid is neutral, and the treatment efficiency is high. The application condenses and recovers the flue gas in the production to obtain plasticizer-containing waste liquid; placing the plasticizer-containing waste liquid in a container, adding the treatment liquid into the plasticizer-containing waste liquid while stirring, and continuing stirring after the treatment liquid is added until stirring is uniform to obtain a mixed liquid; standing the mixed solution for 24-48 h until layering occurs in the mixed solution; filtering the mixed solution by a filter, and obtaining the secondary plasticizer-containing raw material after filtering. The application can save the liquid treatment cost of plasticizer-containing waste liquid, and uses secondary plasticizer-containing raw materials to produce PVC wallpaper, thereby saving the production cost of PVC wallpaper, effectively reducing the output of waste liquid and waste residue, reducing the resource waste, reducing the environmental pollution, utilizing the recycling of resources, improving the utilization of renewable resources, reducing the environmental pollution and achieving the purposes of green production and environment-friendly production.

Description

Recycling method and reuse method of plasticizer-containing waste liquid
Technical Field
The application belongs to the technical field of waste liquid recycling, and particularly relates to a method for recycling plasticizer-containing waste liquid and recycling the plasticizer-containing waste liquid, which aims at recycling the waste liquid after PVC wallpaper production and reusing the waste liquid, so that resource waste and environmental pollution are reduced.
Background
Wallpaper is an interior decoration material pasted on a wall surface, is widely applied to interior decoration of houses, offices, hotels and hotels, and is loved by people due to rich colors. At present, the most common wallpaper is PVC wallpaper, which has strong three-dimensional sense and can be manufactured into various vivid texture effects, such as simulated wood grain, simulated brocade, simulated ceramic tile and the like, and in addition, the PVC wallpaper has strong texture and good air permeability, and is suitable for being used in household places and business places.
The production process of the existing PVC wallpaper mainly comprises the following four steps:
(1) Coating a layer of PVC sizing agent on the surface of a base material such as pure paper, non-woven fabric and woven fabric;
the PVC slurry mainly comprises the following components:
PVC paste resin, finished plasticizer, filler, foaming agent, stabilizer and solvent;
(2) After drying, printing patterns with aqueous ink (pigment);
(3) Foaming at 150-200 deg.c;
(4) Hot embossing.
According to the production flow of the PVC wallpaper, partial volatile matters exist in the printing, drying, high-temperature foaming and embossing processes, smoke (main components of smoke are the mixture of water, pigment in water-based ink, plasticizer, solvent, stabilizer and other auxiliary agents) is formed by volatilization at high temperature, the smoke is condensed and recycled into waste liquid in production, and a large amount of waste liquid is accumulated along with the continuous production process, and the waste liquid contains a large amount of plasticizer components. However, the recycled waste liquid has low plasticizing efficiency due to deep color (the waste liquid is brownish black); in addition, the printing of wallpaper has high requirement on color expression, and the recovered waste liquid is difficult to directly reuse and is generally treated as liquid waste, so that great resource waste and environmental pollution are caused.
Therefore, the development of a treatment method of plasticizer-containing waste liquid, which can recycle the plasticizer-containing waste liquid, has great significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the application aims at providing a method for recycling and treating waste liquid containing plasticizer, wherein the color of the treated waste liquid containing plasticizer becomes light and the pH value is neutral; the processing steps are optimized, and the processing efficiency is high.
The second purpose is to provide a reuse of the plasticizer-containing waste liquid after treatment, and the PVC wallpaper is produced by using the secondary plasticizer-containing raw material, the quality of which is the same as that of the common PVC wallpaper, and the physical and chemical properties of which meet the requirements of GB/T34844-2017 wallpaper and GB 18585-2001 limit the harmful substances in indoor decoration wallpaper.
In order to solve the problems in the prior art, the application adopts the following technical scheme:
a method for recycling plasticizer-containing waste liquid comprises the following steps:
condensing and recycling smoke in PVC wallpaper production to obtain plasticizer-containing waste liquid after PVC wallpaper production;
the main components of the plasticizer-containing waste liquid after the production of the PVC wallpaper are plasticizer, ferric chloride and other substances, wherein the other substances comprise water in water-based ink, partial high-temperature volatilized pigment, stabilizer in PVC slurry, dearomatization solvent oil and other volatile substances; wherein, the main components in the plasticizer-containing waste liquid after PVC wallpaper production are 55 to 75 percent of plasticizer components and 25 to 45 percent of other substances according to mass ratio;
2, placing the plasticizer-containing waste liquid after the production of the PVC wallpaper into a container, adding the treatment liquid into the plasticizer-containing waste liquid after the production of the PVC wallpaper while stirring, wherein the mass ratio of the plasticizer-containing waste liquid to the treatment liquid after the production of the PVC wallpaper is 1:0.05 to 0.3;
the treatment fluid comprises: comprises alkaline solution with mass fraction of 20-50%;
3, providing a mixed solution: continuing stirring after the treatment liquid is added, and waiting until stirring is uniform to obtain a mixed liquid;
4, standing the mixed solution for 24-48 h to settle until layering of the mixed solution occurs, wherein the lower layer solution is a flocculent solid-liquid mixture containing particles;
5, filtering the mixed solution subjected to standing settlement in the step 4 by using a filter;
and 6, filtering the filtrate through micropores to obtain a secondary plasticizer-containing raw material.
Further, in some embodiments, the alkaline solution in step ≡2 is: one or more of aqueous sodium hydroxide, aqueous potassium hydroxide, aqueous sodium carbonate, aqueous potassium carbonate, aqueous sodium bicarbonate or aqueous potassium bicarbonate.
Further, in some embodiments, the stirring time in step ≡3 is 10-30 min, and stirring is performed at a medium speed and then at a low speed;
specifically, stirring at a speed of 300-600 r/min for 5-15 min at medium speed; stirring at a low speed of 50-200 r/min for 5-15 min.
Further, in some embodiments, the filter in step ≡5 is a filter press, and the filtering is a filter press.
Further, in some embodiments, the filter cartridge of the filter: a metal filter screen with the aperture of 7-15 micrometers is selected.
Further, in some embodiments, in the step ≡5, the lower solid-liquid mixture is discharged (drained) and then filtered by a micro-porous filter.
The reuse method of the plasticizer-containing waste liquid after the production of the PVC wallpaper adopts the secondary plasticizer-containing raw material obtained after the treatment of the plasticizer-containing waste liquid after the production of the PVC wallpaper, and the secondary plasticizer-containing raw material is used for producing wallpaper by partially replacing solvent and finished plasticizer: the mass ratio of the finished plasticizer to the solvent is 0.05-0.2: 1, used in wallpaper production.
The application reduces resource waste, reduces environmental pollution, utilizes resource recovery multiplexing, improves the utilization of renewable resources and reduces the pollution to the environment. The application has the beneficial effects that:
1. the plasticizer-containing waste liquid after the production of the PVC wallpaper treated by the alkaline solution is used for obtaining a secondary plasticizer-containing raw material, so that impurities are effectively reduced, the color is lightened, the pH is neutral, and the PVC wallpaper can be used for production;
2. the waste liquid treatment step containing plasticizer components is simple and convenient, and the waste liquid treatment efficiency is high;
3. the secondary plasticizer-containing raw material can be applied to PVC wallpaper production, and the secondary plasticizer-containing raw material comprises the following components: the mass ratio of the finished plasticizer to the solvent is (0.05-0.2): 1 for production;
4. the produced wallpaper has the same appearance as the common PVC wallpaper, and the physical and chemical properties meet the requirements of GB/T34844-2017 wallpaper and GB 18585-2001 limit on harmful substances in indoor decorative wallpaper.
By the treatment method and the application, the liquid treatment cost of the plasticizer-containing waste liquid after the production of the PVC wallpaper can be saved, and the consumption of the finished plasticizer (namely the common raw material plasticizer) during the production of the wallpaper can be saved, so that the production cost of the PVC wallpaper can be further saved.
Through this technical embodiment, the effectual promotion of the utilization ratio of raw materials in the PVC wall paper production, the effectual reduction of output of waste liquid and waste residue has reached green production, environmental protection production's purpose.
Drawings
FIG. 1 is a schematic flow chart of a method for recycling plasticizer-containing waste liquid according to an embodiment of the present application.
Detailed Description
The application will be further described in detail with reference to the drawings and the detailed description below, in order to further understand the features and technical means of the application and the specific objects and functions achieved. The following embodiments of the present application are described in terms of specific embodiments, so that those skilled in the art can easily understand the advantages and effects of the present application from the disclosure herein. The application may be practiced or carried out in other embodiments and details within the scope of the description, which may be modified or varied from various points of view and applications without departing from the spirit of the application.
The application relates to a method for recycling plasticizer-containing waste liquid, which comprises the following steps:
condensing and recycling smoke in PVC wallpaper production to obtain plasticizer-containing waste liquid after PVC wallpaper production;
the main components of the plasticizer-containing waste liquid after the production of the PVC wallpaper are plasticizer, ferric chloride and other substances, wherein the other substances comprise water in water-based ink, partial high-temperature volatilized pigment, stabilizer in PVC slurry, dearomatization solvent oil and other volatile substances; wherein, the main components in the plasticizer-containing waste liquid after PVC wallpaper production are 55 to 75 percent of plasticizer components and 25 to 45 percent of other substances according to mass ratio;
2, placing the plasticizer-containing waste liquid after the production of the PVC wallpaper into a container, adding the treatment liquid into the plasticizer-containing waste liquid after the production of the PVC wallpaper while stirring, wherein the mass ratio of the plasticizer-containing waste liquid to the treatment liquid after the production of the PVC wallpaper is 1:0.05 to 0.3;
the treatment fluid comprises: comprises alkaline solution with mass fraction of 20-50%;
3, providing a mixed solution: continuously stirring for 10-30 min after the treatment liquid is added, and uniformly stirring to obtain a mixed liquid;
4, standing the mixed solution for 24-48 h, and standing until layering of the mixed solution occurs after settlement, wherein the lower layer solution is a flocculent solid-liquid mixture containing particles;
5, filtering the mixed solution subjected to standing settlement in the step 4 by using a filter;
6, filtering the filtrate through micropores, wherein the filter element of the microporous filter is in a micron order; and filtering to obtain the secondary plasticizer-containing raw material.
The alkaline solution in step ≡2 is: one or more of aqueous sodium hydroxide, aqueous potassium hydroxide, aqueous sodium carbonate, aqueous potassium carbonate, aqueous sodium bicarbonate or aqueous potassium bicarbonate.
Stirring in the step 3 for 10-30 min, wherein stirring is performed at a medium speed and then at a low speed;
specifically, stirring for 5-15 min at a speed of 300-600 r/min (medium-speed stirring); then stirring at a speed of 50-200 r/min for 5-15 min (stirring at a low speed).
The filter in the step 5 is a filter press, and the filter is a filter press;
filter element of microporous filter: a metal filter screen with the aperture of 7-15 micrometers is selected.
In step (5), the solid-liquid mixture at the lower layer is discharged (drained) and filtered by a microporous filter.
In this example, an alkaline solution is used, first: the pH value of the plasticizer-containing waste liquid after PVC wallpaper production can be adjusted; second,: the content of ferric chloride in the plasticizer-containing waste liquid after PVC wallpaper production (reddish brown ferric hydroxide is generated) can be reduced, so that the color of the waste liquid is reduced, and the waste liquid can be used. By adopting the stirring mode, the waste liquid and the alkaline solution can be fully contacted, so that part of water-soluble impurities are dissolved in the alkaline solution.
By adopting the stirring speed and the stirring time of the embodiment, a better flocculation effect can be achieved; when the stirring speed is too small, the full contact of the treatment fluid and the particulate matters is not facilitated, when the stirring strength is too high, the large-particle solids are easily crushed into small particles, the formation of precipitable particles is not facilitated, and the use effect of the treatment fluid is reduced.
The reuse of the plasticizer-containing waste liquid after the production of the PVC wallpaper adopts the treated plasticizer-containing waste liquid after the production of the PVC wallpaper as a secondary plasticizer-containing raw material, and the secondary plasticizer-containing raw material is used for the production of the wallpaper by partially replacing solvent (dearomatization solvent oil) and finished plasticizer: the mass ratio of the finished plasticizer to the solvent is 0.05-0.2: 1, used in wallpaper production.
The secondary plasticizer-containing raw material, the duty ratio and the same wallpaper production flow are adopted, and the produced wallpaper and the common wallpaper can meet the technical requirements of GB/T34844-2017 on appearance, physical properties and chemical properties.
The PVC wallpaper production method in the case comprises the following process flows:
(1) Coating PVC slurry on the substrate layer;
(2) The PVC sizing agent is dried and then the surface of the PVC sizing agent is printed with patterns by adopting water-based ink;
(3) Foaming at 150-200 deg.c;
(4) Hot embossing to form PVC wallpaper.
The PVC slurry comprises the following components in parts by mass:
specifically, the finished plasticizer (namely, common raw material plasticizer) is one or more of dioctyl terephthalate, 2, 4-trimethyl-1, 3-pentanediol diisobutyrate and diisononyl phthalate.
The filler is one or more of light calcium carbonate, heavy calcium carbonate, titanium pigment and talcum powder.
The foaming agent is one of microsphere foaming agent or AC foaming agent.
The stabilizer is one or more of calcium-zinc stabilizer, potassium-zinc stabilizer, barium-zinc stabilizer and organotin stabilizer.
The solvent adopts dearomatization solvent oil, and the dearomatization solvent oil is as follows: d80, D110 or D130 solvent oil.
In the steps (2) to (4) of the production of the PVC wallpaper, all the exhaust gas collecting devices are arranged. Wherein the collecting device is condensation recovery equipment, and waste gas is condensed and recovered to obtain waste liquid with brown black color. The main component of the waste liquid is plasticizer and other substances. Wherein, other substances comprise water in the water-based ink, partial high-temperature volatile pigment and other volatile substances, and stabilizer in PVC slurry, dearomatization solvent oil and other volatile substances. Wherein, the main components in the plasticizer-containing waste liquid after PVC wallpaper production are 55-75% by mass, and the other substances are 25-45% by mass.
PVC wallpaper is usually processed and molded at 150-200 ℃, and the polyvinyl chloride can start dehydrochlorination at 100-120 ℃ and the dehydrochlorination speed can be accelerated at about 200 ℃; in addition, free hydrogen chloride has a catalytic effect on dehydrochlorination of polyvinyl chloride.
In actual production, although auxiliaries such as a stabilizer are added, the dehydrogenation reaction of the polyvinyl chloride is reduced; however, the dehydrogenation reaction of the polyvinyl chloride cannot be completely avoided, and when the hydrogen chloride removed at high temperature is in contact with iron equipment and an iron pipeline during recovery, ferric chloride is generated by the action of the hydrogen chloride, and the color of the recovered waste liquid is dark after standing. In the aqueous ink, part of the pigment volatilized at high temperature is dispersed in the waste liquid to make the color of the waste liquid dark.
The application relates to a recycling method of plasticizer-containing waste liquid after PVC wallpaper production, which comprises the following steps:
condensing and recycling flue gas in PVC wallpaper production to obtain waste liquid containing plasticizer after PVC wallpaper production;
adding treatment fluid into the plasticizer-containing waste liquid after PVC wallpaper production, wherein the plasticizer-containing waste liquid after PVC wallpaper production: the treating fluid is prepared from the following components in percentage by mass (0.05-0.3): 1, stirring;
standing for 24-48 h, layering, and filtering to obtain the secondary plasticizer-containing raw material.
Wherein the treatment liquid comprises an alkaline solution with the mass fraction of 20-50%; the alkaline solution is one or more of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium bicarbonate aqueous solution or potassium bicarbonate aqueous solution. Stirring for 10-30 min, wherein stirring is performed at a medium speed and then at a low speed; specifically, stirring for 5-15 min at a speed of 300-600 min/r; stirring for 5-15 min at the speed of 50-200 min/r; among them, filter pressing is preferable for filtration.
In the application, alkaline solution is adopted, and the first: the pH value of the waste liquid containing the plasticizer after the PVC wallpaper is produced can be adjusted to be neutral; second,: the content of ferric chloride in the waste liquid (reddish brown ferric hydroxide is generated) can be reduced, so that the color of the waste liquid can be reduced, and the waste liquid can be reused.
By adopting the stirring mode, the waste liquid and the alkaline solution can be fully contacted.
By adopting the stirring speed and the stirring time, the better flocculation effect can be achieved; when the stirring speed is too small, the full contact of the treatment fluid and the particulate matters is not facilitated, when the stirring strength is too high, the large-particle solids are easily crushed into small particles, the formation of precipitable particles is not facilitated, and the use effect of the treatment fluid is reduced.
A reuse method of plasticizer-containing waste liquid after PVC wallpaper production comprises the steps that a secondary plasticizer-containing raw material partially replaces solvent (dearomatized solvent oil) and a finished plasticizer (namely common plasticizer) is used for wallpaper production, and the secondary plasticizer-containing raw material is used for wallpaper production: the mass ratio of the finished plasticizer to the solvent is 0.05-0.2: 1 is used in the production of wallpaper.
The wallpaper produced by using the secondary plasticizer-containing raw material, the duty ratio and adopting the same wallpaper production flow can meet the technical requirements of GB/T34844-2017 wallpaper in appearance, physical properties and chemical properties.
Example 1:
a production method of PVC wallpaper, wherein the finished plasticizer adopted in PVC slurry is TXIB, and waste liquid containing plasticizer (TXIB) components is obtained by condensation and recovery after production.
The method for treating the plasticizer-containing waste liquid after PVC wallpaper production comprises the following steps:
in this embodiment, the treatment liquid is added to the waste liquid containing plasticizer (TXIB) in the container, and the mass ratio of the waste liquid containing plasticizer (TXIB) to the treatment liquid is 1:0.05, wherein the treatment liquid is a 50% sodium hydroxide aqueous solution; stirring; wherein the stirring time is 20min, and the stirring is performed at a medium speed and then at a low speed; specifically, stirring for 10min at a speed of 600 min/r; stirring at a speed of 100min/r for 10min;
standing for 48h, layering, discharging a lower layer solution which is a flocculent solid-liquid mixture containing particles, filtering by a microporous filter, and filtering the filtrate to obtain a secondary plasticizer-containing raw material (TXIB component), wherein the TXIB content is 60-70%.
Example 2:
a production method of PVC wallpaper, wherein the finished plasticizer adopted in PVC slurry is DINP, and waste liquid containing plasticizer (DINP) is obtained by condensation recovery after production.
The method for treating the plasticizer-containing waste liquid after PVC wallpaper production comprises the following steps:
adding a treatment liquid into a waste liquid containing a plasticizer (DINP), wherein the mass ratio of the waste liquid containing the plasticizer (DINP) to the treatment liquid is (1): 0.3, adding a treatment solution which is a sodium carbonate aqueous solution with the mass fraction of 20%; stirring; wherein the stirring time is 30min, stirring is carried out at a medium speed and then at a low speed, and specifically, stirring is carried out at a speed of 300min/r for 15min; stirring at a speed of 50min/r for 15min;
standing for 24h until the mixed solution is layered, wherein the lower layer solution is a flocculent solid-liquid mixture containing particles; filtering by a filter, filtering the filtrate by a microporous filter, filtering out particles in the solid-liquid mixture, and filtering to obtain a secondary plasticizer-containing raw material (DINP), wherein the DINP content is 60-70%.
Example 3:
the secondary plasticizer-containing raw material (TXIB component) reclaimed materials are obtained by treating plasticizer-containing waste liquid after PVC wallpaper production in example 1.
The PVC wallpaper comprises the following components in parts by mass:
100 parts of PVC paste resin, 5 parts of secondary plasticizer-containing raw materials (TXIB components), 75 parts of finished plasticizer (finished TXIB), 5 parts of dearomatization solvent oil (D130 solvent oil) and 120 parts of filler (mixture of light calcium carbonate and titanium pigment according to a mass ratio of 5:1); 2 parts of a foaming agent (AC foaming agent); 1 part of stabilizer (calcium-zinc stabilizer).
Example 4:
according to example 2, a secondary plasticizer-containing raw material (DINP component) was obtained by treating a plasticizer-containing waste liquid after production of PVC wallpaper.
The PVC wallpaper comprises the following components in parts by mass:
taking 100 parts by mass of PVC as an example, 10 parts by mass of secondary plasticizer-containing raw material (DINP), 60 parts by mass of finished plasticizer (DINP), 1 part by mass of dearomatization solvent oil (D110 solvent oil), and 140 parts by mass of filler (mixture of heavy calcium carbonate and talcum powder according to the mass ratio of 10:1); 4 parts of a foaming agent (microsphere foaming agent); 3 parts of stabilizer (potassium zinc stabilizer).
Comparative example 1:
in the PVC wallpaper, the PVC slurry comprises the following components in parts by mass: 100 parts of PVC paste resin, 80 parts of finished plasticizer (DOTP), 130 parts of filler (light calcium carbonate), 4 parts of foaming agent (AC foaming agent), 3 parts of stabilizer (potassium zinc stabilizer) and 5 parts of dearomatization solvent oil (D130 solvent oil). Comparative example 2:
comparative example 2 is different from comparative example 1 in that the PVC layer slurry component of PVC wallpaper, PVC paste resin 100 parts, was replaced with 32 parts by mass of secondary plasticizer-containing raw material (TXIB) for 27 parts by mass of finished plasticizer and 5 parts by mass of dearomatization solvent oil (i.e., all dearomatization solvent oil).
The PVC wallpaper of example 3, example 4 and comparative example 1, comparative example 2 was tested for physical properties (rub fastness; fade; hiding; wet tensile strength); the PVC wallpaper of example 2 and comparative example 1 was tested for chemical properties (heavy metals; vinyl chloride monomer; formaldehyde).
(1) PVC wallpaper physical properties are tested according to the paper-based wallpaper in the method of GB/T34844-2017 wallpaper; the appearance quality and touch condition of the PVC wallpaper are carried out in a visual and finger touch mode;
(2) The chemical property of PVC wallpaper is tested according to the method of GB 18585-2001 'limit of harmful substances in indoor decorative wallpaper'.
Table 1: PVC wallpaper physical property test
In the case of the PVC wallpaper obtained in the embodiment 3 and the embodiment 4 of the application, each performance can reach the same technical level as that of the comparative example 1.
The multiplexing method is simple, can effectively reduce the stock quantity of waste liquid and reduce the production cost of PVC wallpaper.
Through the wall paper of comparative example 2, when the secondary plasticizer-containing raw material is used for replacing 27 parts by mass of finished plasticizer (common plasticizer) for PVC wall paper production, the prepared PVC wall paper has obvious color difference in appearance compared with common PVC wall paper, the same production flow, scratches are easily left on the surface of the PVC wall paper, the surface of the prepared wall paper is relatively rough, and the phenomenon of powder falling easily occurs to touch.
Table 2: PVC wallpaper chemical property test
Table 2 shows that the chemical properties of the PVC wallpaper according to GB 18585-2001 test of example 3 and the common PVC wallpaper (comparative example 1) are basically the same as the PVC wallpaper according to comparative example 1, and the quality of the wallpaper obtained by multiplexing the waste liquid treatment method according to the application is equivalent.
The foregoing description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to understand and apply the present technology, and represents only one embodiment of the present application, and is described in detail and is not to be construed as limiting the scope of the present application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.

Claims (8)

1. The method for recycling the plasticizer-containing waste liquid is characterized by comprising the following steps:
condensing and recycling smoke in PVC wallpaper production to obtain plasticizer-containing waste liquid after PVC wallpaper production;
the main components of the plasticizer-containing waste liquid after the production of the PVC wallpaper are plasticizer, ferric chloride and other substances, wherein the other substances comprise water in water-based ink, partial high-temperature volatilized pigment, stabilizer in PVC slurry, dearomatization solvent oil and other volatile substances; wherein, the main components in the plasticizer-containing waste liquid after PVC wallpaper production are 55 to 75 percent of plasticizer components and 25 to 45 percent of other substances according to mass ratio;
2, placing the plasticizer-containing waste liquid after the production of the PVC wallpaper into a container, adding the treatment liquid into the plasticizer-containing waste liquid after the production of the PVC wallpaper while stirring, wherein the mass ratio of the plasticizer-containing waste liquid to the treatment liquid after the production of the PVC wallpaper is 1:0.05 to 0.3;
the treatment fluid comprises: comprises alkaline solution with mass fraction of 20-50%;
3, providing a mixed solution: continuing stirring after the treatment liquid is added, and waiting until stirring is uniform to obtain a mixed liquid;
4, standing the mixed solution for 24-48 h to settle until layering of the mixed solution occurs, wherein the lower layer solution is a flocculent solid-liquid mixture containing particles;
5, filtering the mixed solution subjected to standing settlement in the step 4 by using a filter;
and 6, filtering the filtrate through micropores to obtain a secondary plasticizer-containing raw material.
2. The method for recycling plasticizer-containing waste liquid according to claim 1, wherein the alkaline solution in the step ≡2 is: one or more of aqueous sodium hydroxide, aqueous potassium hydroxide, aqueous sodium carbonate, aqueous potassium carbonate, aqueous sodium bicarbonate or aqueous potassium bicarbonate.
3. The method for recycling plasticizer-containing waste liquid according to claim 1, wherein in the step ≡3, stirring is performed at a medium speed followed by a low speed for 10-30 min.
4. The method for recycling plasticizer-containing waste liquid according to claim 3, wherein the medium speed stirring in the step ≡3 is 300-600 r/min for 5-15 min; stirring at a low speed of 50-200 r/min for 5-15 min.
5. The method for recycling plasticizer-containing waste liquid according to claim 1, wherein the filter in step ≡5 is a filter press.
6. The method for recycling plasticizer-containing waste liquid according to claim 5, wherein the filter element of the filter comprises: a metal filter screen with the aperture of 7-15 micrometers is selected.
7. The method for recycling plasticizer-containing waste liquid according to claim 1, wherein in step ≡5, the lower solid-liquid mixture is discharged first and then filtered by a filter.
8. Reuse of plasticizer-containing waste liquid, characterized in that the secondary plasticizer-containing raw material obtained after treatment of plasticizer-containing waste liquid after production of PVC wallpaper according to any one of claims 1-7 is used for production of wallpaper by partially replacing solvent and finished plasticizer, and the secondary plasticizer-containing raw material: the mass ratio of the finished plasticizer to the solvent is 0.05-0.2: 1, used in wallpaper production.
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CN111847751A (en) * 2020-08-29 2020-10-30 江苏美能膜材料科技有限公司 Zero-emission recovery process for waste liquid generated by preparing polyvinylidene fluoride porous membrane

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066835A (en) * 1974-05-31 1978-01-03 Ruhrchemie Ag Process for purifying the waste water produced in the process of producing ester plasticizers
CN202898178U (en) * 2012-11-20 2013-04-24 上海蓓奕化工有限公司 Pre-treatment system of PTA (Pure Terephthalic Acid) waste
CN106032299A (en) * 2015-03-14 2016-10-19 骆阿明 Process for recycling and purification of PTA from printing and dyeing alkali decrement wastewater
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Denomination of invention: A method for recycling and reusing waste liquid containing plasticizers

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