CN115584301B - Method and system for recycling water-based spraying cleaning agent - Google Patents
Method and system for recycling water-based spraying cleaning agent Download PDFInfo
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- CN115584301B CN115584301B CN202211131778.7A CN202211131778A CN115584301B CN 115584301 B CN115584301 B CN 115584301B CN 202211131778 A CN202211131778 A CN 202211131778A CN 115584301 B CN115584301 B CN 115584301B
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- 238000004064 recycling Methods 0.000 title description 17
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
- B08B3/14—Removing waste, e.g. labels, from cleaning liquid; Regenerating cleaning liquids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/44—Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/48—Regeneration of cleaning solutions
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Landscapes
- Cleaning By Liquid Or Steam (AREA)
Abstract
The embodiment of the application discloses a method and a system for recovering a water-based spraying cleaning agent, wherein the method for recovering the water-based spraying cleaning agent comprises the following steps: collecting waste liquid of the spraying cleaning agent; evaporating or distilling the waste liquid of the spraying cleaning agent to obtain high-boiling point liquid and low-boiling point liquid; separating the oil phase liquid and the water phase liquid from the low boiling point liquid to obtain the oil phase liquid and the water phase liquid; and taking the aqueous phase liquid as a circulating cleaning agent. The recovery method of the aqueous spraying cleaning agent can reduce the waste liquid discharge by at least 80% -95% for automobiles and other similar spraying process manufacturers, reduce the use of aqueous cleaning agent concentrated solution, reduce the cleaning and waste liquid treatment cost of user manufacturers, and greatly reduce the environmental pollution.
Description
Technical Field
The application relates to the technical field of waste liquid treatment, in particular to a water-based spray cleaning agent recovery method and a spray cleaning agent recovery system.
Background
In industrial spraying processes, for example in the coating shop of a whole car, it is necessary to clean spraying equipment, such as needle valves, bell cups, spiral tubes, pumps, lines, etc., when changing the coating of the paint, in different stages of spraying, including spraying different colors and coatings. After a period of operation of the spray shop, the entire spray line also needs to be cleaned. With the importance of environmental protection and occupational health, aqueous cleaning agents are increasingly being used in cleaning processes. The aqueous cleaning agent concentrate is diluted with pure water at a certain ratio at the user side and then used as a working solution (i.e., a diluent). After cleaning, the mixture containing the paint and the cleaning liquid becomes hazardous waste. In the whole automobile factory, the consumption of the aqueous cleaning agent diluent can reach 1-10 kg/car. For a whole vehicle factory producing 100 ten thousand vehicles in a year, 1000-10000 tons/year of wastewater cleaning agent can be produced. At present, most of waste cleaning agents are treated as waste water and are discharged into the environment or burnt by fuel after reaching the discharge standard. Such a treatment method creates a large financial burden on the manufacturer and also creates a large burden and challenge for environmental protection.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art or related art.
To this end, the first aspect of the invention provides a method for recovering an aqueous spray cleaning agent.
In a second aspect of the invention, a spray cleaner recovery system is provided.
In view of this, according to a first aspect of the embodiments of the present application, there is provided a method for recovering an aqueous spray cleaning agent, including:
collecting waste liquid of the spraying cleaning agent;
evaporating or distilling the waste liquid of the spraying cleaning agent to obtain high-boiling point liquid and low-boiling point liquid containing paint solids;
Separating the oil phase liquid and the water phase liquid from the low boiling point liquid to obtain the oil phase liquid and the water phase liquid;
And taking the aqueous phase liquid as a circulating cleaning agent.
In a possible embodiment, the step of evaporating or distilling the waste liquid of the spray cleaning agent comprises:
Pretreating the spraying cleaning agent waste liquid to obtain liquid waste liquid and solid waste;
Evaporating or distilling the liquid waste liquid.
In a possible embodiment, the step of evaporating or distilling treatment comprises:
The evaporation or distillation treatment is carried out by one of thin film evaporation, wiped film evaporation, kettle type simple distillation, tray type distillation and packing type distillation.
In one possible embodiment, the working temperature of the evaporation or distillation treatment is from 10 ℃ to 150 ℃ and the temperature of the distillate cooling water is from 1 ℃ to 40 ℃.
In a possible embodiment, the step of pretreating the spray cleaning agent waste liquid includes:
The solid-liquid separation is performed by one of precipitation, screen filtration, ultrafiltration and centrifugal separation.
In one possible embodiment, the aqueous liquid is a mixture of water, ethylene glycol hexyl ether, ethanolamine, and spray coating.
According to a second aspect of the embodiments of the present application, a spray cleaning agent recovery system is provided, for implementing the method for recovering an aqueous spray cleaning agent according to any one of the above technical solutions, where the spray cleaning agent recovery system includes:
the evaporation or distillation treatment unit is communicated with the pretreatment unit and is used for evaporating or distilling the liquid waste liquid after pretreatment;
The high-solid-content waste liquid storage unit is communicated with the pretreatment unit and the evaporation or distillation treatment unit and is used for storing high-boiling-point liquid and solid waste;
the water-oil separation unit is communicated with the evaporation or distillation treatment unit and is used for separating the oil phase liquid and the water phase liquid from the low-boiling point liquid to obtain the oil phase liquid and the water phase liquid;
the water phase storage unit is communicated with the water-oil separation unit and is used for storing the water phase liquid;
and the oil phase storage unit is communicated with the water-oil separation unit and is used for storing the oil phase liquid.
In a possible embodiment, the evaporation or distillation treatment unit comprises:
The distillation unit is communicated with the collecting unit, the demister and the cooler are sequentially communicated with each other, and the cooler is communicated with the water-oil separation unit.
In one possible embodiment, the spray rinse recovery system further comprises:
the collecting unit is used for collecting waste liquid of the spraying cleaning agent generated in the production workshop;
The pretreatment unit is connected with the collection unit and used for pretreating the waste liquid of the spraying cleaning agent, and the evaporation or distillation treatment unit is communicated with the pretreatment unit; ;
The tail gas treatment unit is communicated with the water-oil separation unit;
A first filter is disposed between the water-oil separation unit and the aqueous phase storage unit.
In one possible embodiment, the spray rinse recovery system further comprises: a reprocessing unit, the reprocessing unit comprising:
A second filter;
The mixing tank is communicated with the water phase storage unit, and the second filter is arranged between the mixing tank and the water phase storage unit;
and the conveying unit is communicated with the blending tank and used for conveying the circulating cleaning agent in the blending tank to a production workshop.
Compared with the prior art, the application at least comprises the following beneficial effects: the application provides a method for recovering an aqueous spray cleaning agent and a system for recovering the spray cleaning agent, which can collect the aqueous waste cleaning agent, carry out physical separation processing on the aqueous waste cleaning agent through evaporation or distillation treatment, further carry out separation of oil phase liquid and aqueous phase liquid, and keep effective cleaning components in the aqueous phase, wherein the aqueous phase liquid has a certain cleaning force, and the cleaning capability of fresh diluent can be completely recovered after a certain amount of fresh cleaning agent components or concentrated solution is added into the circulating cleaning agent, so that the aqueous spray cleaning agent can be used as the cleaning agent in a spray workshop, thereby forming a recycling process of the closed-loop aqueous cleaning agent. Therefore, the waste liquid discharge of at least 80% -95% can be reduced for manufacturers of automobiles and other similar spraying processes, the use of aqueous cleaning agent concentrated solution is reduced, the cleaning and waste liquid treatment cost of the manufacturers is reduced, and the environmental pollution is greatly reduced.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Also, like reference numerals are used to designate like parts throughout the figures. In the drawings:
FIG. 1 is a schematic step flow diagram of an aqueous spray cleaner recovery method according to one embodiment of the present application;
FIG. 2 is a block diagram of another embodiment of a spray rinse recovery system provided by the present application;
FIG. 3 is a GC spectrum of the circulating cleaning agent of example 1 provided by the present application.
The correspondence between the reference numerals and the component names in fig. 2 is:
The device comprises a collecting unit 1, a pretreatment unit 2, an evaporation or distillation treatment unit 3, a high-solid-content waste liquid storage unit 4, a water-oil separation unit 5, a water phase storage unit 6, an oil phase storage unit 7, a distillation unit 8, a demister 9, a cooler 10, an exhaust gas treatment unit 11, a first filter 12, a second filter 13, a blending tank 14, a conveying unit 15 and a production workshop 16.
Detailed Description
In order to better understand the above technical solutions, the following detailed description of the technical solutions of the embodiments of the present application is made by using the accompanying drawings and the specific embodiments, and it should be understood that the specific features of the embodiments of the present application are detailed descriptions of the technical solutions of the embodiments of the present application, and not limit the technical solutions of the present application, and the technical features of the embodiments of the present application may be combined with each other without conflict.
The application contemplates that the aqueous automotive cleaner is used to clean a spray shop of an automotive refinish plant, or other (e.g., vessel, furniture, metal working) similar spray line. After a period of use of the spray line, and when switching between different coatings, the formulated aqueous cleaning agent dilution may be used to clean pipelines, plumbing, robotic nozzles, and/or manually sprayed surfaces, etc. After cleaning, the aqueous cleaning agent mixture waste liquid containing the paint is usually treated as waste water, and the treatment mode generates a large financial burden on manufacturers and also generates a large burden and challenge on environmental protection.
As shown in fig. 1, according to a first aspect of the embodiment of the present application, a method for recovering an aqueous spray cleaning agent is provided, including:
step 101: collecting waste liquid of the spraying cleaning agent;
step 102: evaporating or distilling the waste liquid of the spray cleaning agent to obtain high-boiling point liquid and low-boiling point liquid containing paint solids;
Step 103: separating the oil phase liquid and the water phase liquid from the low boiling point liquid to obtain the oil phase liquid and the water phase liquid;
step 104: the aqueous phase liquid is used as a circulating cleaning agent.
The embodiment of the application provides a method and a system for recycling an aqueous spray cleaning agent, which can collect the aqueous waste cleaning agent, carry out physical separation processing on the aqueous waste cleaning agent through evaporation or distillation treatment, further separate oil phase liquid and aqueous phase liquid, and then keep effective cleaning components in the aqueous phase, wherein the aqueous phase liquid has a certain cleaning force, and the cleaning capability of fresh diluent can be completely recovered after a certain amount of fresh cleaning agent components or concentrated solution is added into the recycled cleaning agent, so that the aqueous spray cleaning agent can be used as the cleaning agent in a spray workshop, thereby forming a recycling process of the closed-loop aqueous cleaning agent. Sometimes this part of the aqueous liquid can be used directly as a cleaning agent in a workshop. Therefore, the waste liquid discharge of at least 80% -95% can be reduced for manufacturers of automobiles and other similar spraying processes, the use of aqueous cleaning agent concentrated solution is reduced, the cleaning and waste liquid treatment cost of the manufacturers is reduced, and the environmental pollution is greatly reduced.
According to the recovery method of the water-based spray cleaning agent, provided by the embodiment of the application, water is evaporated by using an evaporation and/or distillation method, and simultaneously, part or all of organic matters in the water are azeotroped with water or are carried out by water vapor (stripping). This operation may be a continuous or batch evaporation/distillation process. The recovered aqueous phase can be used as a cleaning agent directly or as a diluent, and can be used as a cleaning agent after adding the active ingredients. The application is characterized in that the solid in the waste solvent is separated from the liquid, and the water phase in the liquid is separated from the organic oil phase without cleaning effect, thereby recycling the aqueous cleaning agent or the diluent of the aqueous cleaning agent, and forming closed-loop recycling of the aqueous cleaning agent. The technology can greatly reduce the discharge of polluted waste liquid, reduce the cost and increase the income for users and manufacturers of the water-based cleaning agent, and has great environmental benefit.
It will be appreciated that the recovery method of the aqueous spray cleaning agent provided by the embodiment of the application comprises, but is not limited to, cleaning agent waste liquid used in the whole automobile and parts thereof, metal parts and product spray production lines, plastic parts and product spray production lines, ships, aircrafts and other spray processes.
It will be appreciated that the aqueous cleaning agent concentrate contains a plurality of organic components, wherein the surfactant causes the water and the organic components to form a single homogeneous or emulsified mixture. The concentrate is further diluted with water at the user end and then stirred to form a diluted solution (or working solution) of the cleaning agent. The working fluid is used for cleaning all links and the whole system in the spraying working line. The cleaned mixture contains various components in the cleaning agent and the coating, and the mixture becomes dangerous chemical waste solvent and is delivered to qualified dangerous waste processors for treatment because of containing solids and high organic components. When used as chemical wastewater treatment, the high COD and solid content make the bacterial purification treatment difficult. Even so, the high-value chemical components therein lose the utility value due to the discharge by wastewater treatment, and the burden of environmental protection is increased. Some factories can treat the wastewater as industrial wastewater by themselves, so that the effective components in the wastewater are wasted, and the treatment cost is high. Some hazardous waste processors burn the waste liquid, but because the water content is too high, the heat value is low, the cost of burning treatment is also high, and carbon emission which can be avoided is brought. The invention utilizes the characteristic that organic components in the aqueous cleaning agent and water form a low-boiling-point azeotrope, and the effective organic components in the aqueous cleaning agent are evaporated together when water is evaporated during distillation (or evaporation). The aqueous liquid thus recovered is colorless and has a certain detergency, which is restored to the level of fresh detergent after addition of a small amount of detergent concentrate or of some concentrate ingredients. The addition amount of the concentrated solution or the active ingredient is much less than that of pure water, so that the cleaning cost of users can be greatly reduced. The technology for recycling the water-based cleaning agent waste liquid in a closed loop can greatly reduce the dangerous waste discharge, save the cost of users, reduce the carbon discharge and have great economic and environmental benefits.
In one possible embodiment, the step of spraying the cleaning agent waste liquid for evaporation or distillation treatment comprises: pretreating spraying cleaning agent waste liquid to obtain liquid waste liquid and waste material with high solid content; evaporating or distilling the liquid waste liquid.
In the technical scheme, the specific steps of evaporation or distillation treatment are further provided, and the pretreatment is carried out firstly, and then the evaporation or distillation treatment is carried out, so that the solid components and the solid adsorbed liquid components in the waste liquid of the spraying cleaning agent are mainly removed. After separating the liquid, the oil layer liquid can be separated from the water phase by a centrifuge or a sedimentation layering method. When the water-based waste liquid is colorless, the filtrate can be directly used as a recovery liquid, and the water phase can be recycled. Sedimentation methods can also be used to separate solid and liquid phases, the principle being similar to that of a centrifuge, but requiring a longer time.
In one possible embodiment, the step of evaporating or distilling treatment comprises: the evaporation or distillation treatment is performed by one of thin film evaporation, wiped film evaporation, kettle distillation and tray distillation.
In the technical scheme, a specific mode of evaporation or distillation treatment is further provided, and the water-based waste cleaning agent can be collected by performing evaporation or distillation treatment through one of thin film evaporation, wiped film evaporation, kettle distillation, tower plate distillation and packed distillation.
In one possible embodiment, the working temperature of the evaporation or distillation treatment is from 10 ℃ to 150 ℃ and the temperature of the distillate cooling water is from 1 ℃ to 40 ℃.
In the technical scheme, the operation parameters of the evaporation or distillation treatment are further provided, and the collection of the aqueous waste cleaning agent can be realized through the operation temperature of the evaporation or distillation treatment is 10 ℃ to 150 ℃ and the temperature of the fraction cooling water is 10 ℃ to 40 ℃.
In one possible embodiment, the step of pre-treating the spray rinse waste stream comprises: pretreatment is performed by one of precipitation, screen filtration, ultrafiltration and centrifugation. The arrangement is convenient for realizing the removal of solid components and solid adsorbed liquid components in the waste liquid of the cleaning agent.
In one possible embodiment, the aqueous liquid is a mixture of water, ethylene glycol hexyl ether, ethanolamine, and spray coating. The aqueous phase liquid is a mixture of water, glycol hexyl ether, ethanolamine and water-soluble components in the spray coating, and the cleaning capability of the fresh diluent can be completely recovered after a certain amount of fresh cleaning agent components or concentrated solution is added into the recycled cleaning agent, so that the aqueous phase liquid can be used as the cleaning agent in a spray coating workshop, and a recycling process of the closed-loop aqueous cleaning agent is formed.
As shown in fig. 2, a second aspect of the embodiment of the present application provides a spray cleaning agent recovery system for implementing the method for recovering an aqueous spray cleaning agent according to any one of the above-mentioned aspects, where the spray cleaning agent recovery system includes: the collecting unit 1, the collecting unit 1 is used for collecting the waste liquid of the spraying cleaning agent generated in the production workshop 16; the pretreatment unit 2 is connected with the collection unit 1 and is used for pretreating the waste liquid of the spraying cleaning agent; an evaporation or distillation treatment unit 3, which is communicated with the pretreatment unit 2 and is used for evaporating or distilling the liquid waste liquid after pretreatment; the high-solid-content waste liquid storage unit 4 is communicated with the pretreatment unit 2 and the evaporation or distillation treatment unit 3 and is used for storing high-boiling-point liquid and solid waste; the water-oil separation unit 5 is communicated with the evaporation or distillation treatment unit 3 and is used for separating oil phase liquid and water phase liquid from low boiling point liquid to obtain the oil phase liquid and the water phase liquid; an aqueous phase storage unit 6, which is communicated with the water-oil separation unit 5 and is used for storing aqueous phase liquid; and the oil phase storage unit 7 is communicated with the water-oil separation unit 5 and is used for storing oil phase liquid.
The spray cleaning agent recovery system provided by the embodiment of the application has all the beneficial effects of the water-based spray cleaning agent recovery method of the technical scheme because the spray cleaning agent recovery system is used for realizing the water-based spray cleaning agent recovery method of the technical scheme.
In the use process, the collecting unit 1 is used for collecting the waste liquid of the spraying cleaning agent generated in the production workshop 16; then the pretreatment unit 2 is used for pretreating the waste liquid sprayed with the cleaning agent; then evaporating or distilling the pretreated liquid waste liquid by an evaporating or distilling treatment unit 3; storing the high boiling point liquid and the solid waste material by the high solid waste liquid storage unit 4; separating the oil phase liquid and the water phase liquid from the low boiling point liquid by the water-oil separation unit 5; storing the aqueous phase liquid by the aqueous phase storage unit 6; by storing the oil phase liquid by the oil phase storage unit 7, it is possible to realize evaporation of water using evaporation and/or distillation methods while the organic matter therein is partly or entirely azeotroped with water or entrained (stripped) by water vapor. This operation may be a continuous or batch evaporation/distillation process. The recovered aqueous phase can be used as a cleaning agent directly or as a diluent, and can be used as a cleaning agent after adding the active ingredients. The invention is characterized in that the solid in the waste solvent is separated from the liquid, and the water phase in the liquid is separated from the organic oil phase without cleaning effect, thereby recycling the aqueous cleaning agent or the diluent of the aqueous cleaning agent, and forming closed-loop recycling of the aqueous cleaning agent. The technology can greatly reduce the discharge of polluted waste liquid, reduce the cost and increase the income for users and manufacturers of the water-based cleaning agent, and has great environmental benefit.
In a possible embodiment, the evaporation or distillation treatment unit 3 comprises: the distillation unit 8, the demister 9 and the cooler 10 are communicated in sequence, the distillation unit 8 is communicated with the collecting unit 1, and the cooler 10 is communicated with the water-oil separating unit 5. The arrangement is convenient for recycling the effective cleaning matters in the waste liquid.
In one possible embodiment, the spray rinse recovery system further comprises: a tail gas treatment unit 11 which is communicated with the water-oil separation unit 5; the first filter 12 is provided between the water-oil separation unit 5 and the aqueous phase storage unit 6.
In this technical scheme, spraying cleaner recovery system can also include tail gas treatment unit 11 and first filter 12, can handle tail gas through tail gas treatment unit 11, reduces harm to the environment, through the setting of first filter 12, can avoid solid-state granule to enter into among the aqueous phase storage unit 6.
In one possible embodiment, the spray rinse recovery system further comprises: a reprocessing unit including: a second filter 13; a tempering tank 14 communicated with the aqueous phase storage unit 6, and a second filter 13 provided between the tempering tank 14 and the aqueous phase storage unit 6; and a conveying unit 15, which is communicated with the blending tank 14 and is used for conveying the circulating cleaning agent in the blending tank 14 to a production workshop 16.
In this solution, the spray cleaning agent recovery system may further comprise a reprocessing unit, and the reprocessing unit comprises a second filter 13, a blending tank 14 and a conveying unit 15, wherein the second filter 13 may be used for filtering, and a certain amount of fresh cleaning agent component or concentrate may be added to the circulated cleaning agent by the setting of the blending tank 14 to form a cleaning agent with cleaning ability, and the cleaning agent with cleaning ability may be conveyed to the production shop 16 through the conveying unit 15 for reuse.
Example 1
A2000 ml three-necked flask (still) was charged with 1500 ml of the waste liquid of the spray cleaning agent produced from a certain factory, and a condenser and a fraction collector were installed above the still. Atmospheric evaporation was carried out in an evaporator with stirring. The temperature of the distillation still (which may also be referred to as an evaporator) was 102℃and the temperature of the distillate cooling water was 25 ℃. Because of the lack of a fractionation column, this distillation experiment should be practically referred to as an evaporation experiment (i.e., theoretical plate number of 1). The experimental results are shown in table 1. The results of the raw waste liquid and the separated aqueous phase are shown in tables 2 and 3.
In subsequent experiments, it was found that when the aqueous phase and the oil layer in the evaporated liquid were mixed, the detergency was inferior to that of the aqueous phase alone. So at the relevant pilot and pilot trials only the aqueous phase was collected for reuse, while the properties of the oil phase are not discussed.
It can be seen from the aqueous phase analysis that, although the boiling point of the organic substances in the cleaning agent via the cleaning ability is high, they are vaporized together with water by azeotropy with water, which is also the principle of the present invention.
TABLE 1 Experimental data for recovery of aqueous spent solvent
| Water-based hazardous waste raw material, gram | 1500 |
| Recovery of liquid fraction, gram | 1392 |
| Oil layer in fraction, g | 21 |
| Water layer in fraction, g | 1369 |
| Residue at bottom of still pot, g | 108 |
| Loss, g | 2 |
| Raw material solid content, wt% | 2.2％ |
| Evaporator bottom solids content, wt% | 30.0％ |
| The recovered liquid accounts for the weight percent of the raw materials | 92.8％ |
| The oil phase accounts for fraction, wt% | 1.5％ |
| The water phase accounts for fraction, wt% | 98.5％ |
| Effective water phase recovery rate, wt% | 91.4％ |
| The bottom residue accounts for the proportion of the raw materials, wt% | 7.2％ |
TABLE 2 composition of aqueous hazardous waste raw materials (wt% after solids removal)
| Water and its preparation method | 94.5％ |
| Ethylene glycol hexyl ether | 2.74％ |
| Ethanolamine | 0.53％ |
| Other organic component combinations | 2.23％ |
| All components are combined | 100.00％ |
TABLE 3 composition of the recovered water separated aqueous phase (wt%)
| Water and its preparation method | 96.9％ |
| Ethylene glycol hexyl ether | 1.80％ |
| Ethanolamine | 0.35％ |
| Other organic component combinations | 0.95％ |
| All components are combined | 100.00％ |
As can be seen from fig. 3, the circulating cleaning agent contains water and organic substances having cleaning ability, and the circulating cleaning agent has cleaning ability.
Example 2
And filling 6875.5 kg of barreled waste liquid of spraying cleaning agent into a raw material tank. The original tank is provided with a stirrer for continuous stirring so as to keep the raw materials at a constant quality. The waste solvent is pumped into a thin film evaporator by a centrifugal pump, and the waste liquid of the spray cleaning agent directly enters the evaporator for continuous evaporation operation. The evaporator was subjected to reduced pressure evaporation under an absolute pressure of 80kpa using 7kg of saturated steam as a heating medium. The material balance after evaporation treatment is as follows:
TABLE 4 Experimental data for recovery of aqueous spent solvent
Comparing tables 1 and 4, the results of example 1 are very similar to those of example 2, with the same starting materials. The analysis of the components of the aqueous phase is also very similar and will not be further listed or discussed herein.
Test example 1
The test method comprises the following steps: according to the standard method of the main automobile host factory in China, the method comprises the steps of dripping and weighing.
Test adjustment: the room temperature was 23℃and the humidity was 64%, and the detergency test temperature was 35 ℃.
1) The standard cleaning agent for comparison reference was the aqueous cleaning agent P (reference sample) being used by the user, i.e., the aqueous cleaning agent P contained in the raw waste liquid in examples 1 and 2.
1520G of pure water of example 2 and 80g of standard cleaning agent concentrated solution are added into a beaker, and the aqueous cleaning agent reference standard cleaning agent is obtained after uniform stirring. The dilution ratio was 1:19
2) Test using pure water and aqueous concentrate of Kagaku (Chongqing) science and technology company
Into a beaker, 80g of an aqueous concentrate from Kagaku (Chongqing) technology company, reference numeralThen 1520g of pure water is added, and the mixture is stirred uniformly to obtain the water-based cleaning agent/>36613 (Pure water dilution). The dilution ratio was 1:19
3) Test using recovered aqueous phase with aqueous concentrate of Kagaku (Chongqing) science and technology company
1560G of the circulating cleaning agent of example 2 and 40g of the concentrated solution were added to a beaker36613, Stirring uniformly to obtain the water-based cleaning agent/>36613R (recovered water dilution). The dilution ratio was 1:39
Test conclusion:
1) The dilutions of 3 above were used in different colour paints. The results obtained from the drip test are that, with the same dilution ratio, the dilution is 20 times 36613 And dilution 40 times/>36613R all showed better detergency than the 20-fold dilution of the P-test solution.
2) While when recycled water is used, half of the aqueous cleaner concentrate can be saved and the same or better detergency can be obtained.
The same conclusion is reached when a weighing method is used.
As can be seen from FIG. 3, the organic matter contained in the recovered water has a number of organic molecules which are not shown, in addition to the 4 effective cleaning agent components which are commonly used. These unidentified organic molecules were detected as organic components contained in the coating, and dissolved in water; according to the principle of similar miscibility, the organic molecules which are dissolved in water and volatilize due to azeotropy in distillation (evaporation) and exist in the water phase have obvious synergistic effect on the cleaning operation, so that a large amount of concentrated cleaning agent can be saved when the recovered water is used for preparing the diluent.
In industrial production, after the aqueous phase is washed when it is recovered for dilution, the waste liquid produced is reused for recovery of water and is always recycled as such, carrying out the closed loop recovery system described in the patent. Whether the detergency of such reclaimed water will maintain the same superior detergency will be critical for closed loop process applications.
Test example 2
A) Design of experiment
Based on test example 1, will36613 Mixing the stock solution and the water phase fraction uniformly according to the mass ratio of 1:79 to prepare a diluent, testing the cleaning power of the diluent by a dripping method, adding 1/10 great wall water paint into the diluent to prepare a water-based waste solvent, distilling the water-based waste solvent at normal pressure, collecting the fraction, and measuring the component content of the water phase fraction by GC; and then will be36613 The stock solution and the water phase fraction are uniformly mixed according to the mass ratio of 1:79 to prepare a diluent, and the water phase fraction is recycled for 20 times by repeating the experimental steps so as to grasp the cleaning power and the change condition of the component content of the fraction after repeated recycling.
B) Experimental procedure
1. Weighing 36613 raw solution 8.12g and water phase fraction 641.88g by using a beaker, uniformly mixing to prepare a diluent, weighing 50g of the diluent for testing the detergency, adding 60g of water-based paint into the rest 600g of the diluent to prepare a water-based waste solvent, measuring the solid content, transferring the water-based waste solvent into the flask, and recording the quality of the water-based waste solvent;
2. The aqueous waste solvent was evaporated at normal pressure, the temperature of the evaporated steam was 99 ℃, and the temperature of the bottom of the evaporator was about 105 ℃. Measuring the solid content of the residue after evaporation, recording the quality of the recovered fraction, calculating the fraction yield, adding pure water into the fraction to ensure that the quality reaches 660g, mixing uniformly, transferring the fraction into a separating funnel, standing for 0.5h, separating out the water phase, measuring the component content of the water phase fraction by GC, and recording the total peak area;
3. 8.12g of 36613 stock solution and 641.88g of water phase fraction are weighed by a beaker, uniformly mixed to prepare a diluent, the operation of the steps 1-2 is repeated, and the water phase fraction is used as the diluent for recycling for 20 times.
C) Experimental record
Table 5 records the test data for 20 reuse-recoveries. After 20 times, the conclusion showed that no further experiments were needed to make the conclusion: the long-term effect of closed loop recovery-reuse is unchanged. The closed loop process can be used industrially.
D) And (5) testing the cleaning power of the diluent. And comparing with a cleaning result photo of a standard cleaning agent.
1. BASF maltese red (35 ℃,10 drops).
2. The same method and procedure was used in the other color paint used by the host factory.
E) Experimental results and discussion
After the water-based waste solvent fraction is recycled for 15 times, the content of the effective component A is stabilized between 1.55 and 1.65 percent,
The sum of GC peak areas is stabilized between 1.85 multiplied by 106 and 1.95 multiplied by 106, the cleaning ability is also more stable (stronger than that of a reference product P), the shrinkage test result is qualified, and the experiment shows that the repeated recycling of the water-based waste solvent fraction generated by an automobile host factory is feasible, and the method has obvious economic benefit and environmental protection benefit.
TABLE 5 data relating to distillation of aqueous spent solvent
As can be seen from the above examples and test examples, the recovery method of the aqueous spray cleaning agent provided by the embodiment of the application can evaporate water by using an evaporation and/or distillation method, and simultaneously, part or all of organic matters in the aqueous spray cleaning agent are azeotroped with water or are entrained (stripped) by water vapor. This operation may be a continuous or batch evaporation/distillation process. The recovered aqueous phase can be used as a cleaning agent directly or as a diluent, and can be used as a cleaning agent after adding the active ingredients. The application is characterized in that the solid in the waste solvent is separated from the liquid, and the water phase in the liquid is separated from the organic oil phase without cleaning effect, thereby recycling the aqueous cleaning agent or the diluent of the aqueous cleaning agent, and forming closed-loop recycling of the aqueous cleaning agent. The technology can greatly reduce the discharge of polluted waste liquid, reduce the cost and increase the income for users and manufacturers of the water-based cleaning agent, and has great environmental benefit.
In the present invention, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; the term "plurality" means two or more, unless expressly defined otherwise. The terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; "coupled" may be directly coupled or indirectly coupled through intermediaries. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the description of the present invention, it should be understood that the directions or positional relationships indicated by the terms "upper", "lower", "left", "right", "front", "rear", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or units referred to must have a specific direction, be constructed and operated in a specific direction, and thus should not be construed as limiting the present invention.
In the description of the present specification, the terms "one embodiment," "some embodiments," "particular embodiments," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The recovery method of the aqueous spraying cleaning agent is characterized by comprising the following steps of:
collecting waste liquid of the spraying cleaning agent;
Evaporating or distilling the waste liquid of the spraying cleaning agent to obtain high-boiling point liquid and low-boiling point liquid containing solids;
Separating the oil phase liquid and the water phase liquid from the low boiling point liquid to obtain the oil phase liquid and the water phase liquid;
Taking the aqueous phase liquid as a circulating cleaning agent;
The step of evaporating or distilling the waste liquid of the spraying cleaning agent comprises the following steps:
Pretreating the spraying cleaning agent waste liquid to obtain liquid waste liquid and solid waste;
evaporating or distilling the liquid waste liquid;
the step of evaporating or distilling treatment comprises:
Evaporating or distilling by one of thin film evaporation, wiped film evaporation, kettle type simple distillation, tray type distillation and packed type distillation;
the operation temperature of evaporation or distillation treatment is 10 ℃ to 150 ℃, and the temperature of fraction cooling water is 1 ℃ to 40 ℃;
and adding fresh cleaning agent into the circulating cleaning agent to obtain the cleaning agent with cleaning capability so as to reduce the discharge of waste liquid.
2. The method for recovering an aqueous spray cleaning agent according to claim 1, wherein the step of pretreating the spray cleaning agent waste liquid comprises:
The solid-liquid separation is performed by one of precipitation, screen filtration, ultrafiltration and centrifugal separation.
3. The method for recovering an aqueous spray cleaning agent according to claim 1 or 2, characterized in that,
The aqueous phase liquid is a mixture of water, ethylene glycol hexyl ether, ethanolamine and spray coating.
4. A spray cleaning agent recovery system for implementing the aqueous spray cleaning agent recovery method according to any one of claims 1 to 3, the spray cleaning agent recovery system comprising:
an evaporation or distillation treatment unit for evaporating or distilling the pretreated liquid waste liquid;
The high-solid-content waste liquid storage unit is communicated with the pretreatment unit and the evaporation or distillation treatment unit and is used for storing high-boiling-point liquid and solid waste;
the water-oil separation unit is communicated with the evaporation or distillation treatment unit and is used for separating the oil phase liquid and the water phase liquid from the low-boiling point liquid to obtain the oil phase liquid and the water phase liquid;
the water phase storage unit is communicated with the water-oil separation unit and is used for storing the water phase liquid;
and the oil phase storage unit is communicated with the water-oil separation unit and is used for storing the oil phase liquid.
5. The spray rinse recovery system of claim 4, wherein the evaporation or distillation treatment unit comprises:
the distillation unit, defroster and the cooler that communicate in proper order, distillation unit communicates in the collection unit, the cooler communicate in the water oil separation unit.
6. The spray rinse recovery system of claim 5, further comprising:
the collecting unit is used for collecting waste liquid of the spraying cleaning agent generated in the production workshop;
The pretreatment unit is connected with the collection unit and used for pretreating the waste liquid of the spraying cleaning agent, and the evaporation or distillation treatment unit is communicated with the pretreatment unit;
The tail gas treatment unit is communicated with the water-oil separation unit;
A first filter is disposed between the water-oil separation unit and the aqueous phase storage unit.
7. The spray rinse recovery system of claim 6, further comprising: a reprocessing unit, the reprocessing unit comprising:
A second filter;
The mixing tank is communicated with the water phase storage unit, and the second filter is arranged between the mixing tank and the water phase storage unit;
and the conveying unit is communicated with the blending tank and used for conveying the circulating cleaning agent in the blending tank to a production workshop.
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| CN104230086A (en) * | 2014-09-25 | 2014-12-24 | 成都源永科技发展有限公司 | Method for recycling water-based paint detergent waste liquid |
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