CN114133090B - Method and equipment for recycling propionic acid and butyric acid secondary mother liquor water - Google Patents

Method and equipment for recycling propionic acid and butyric acid secondary mother liquor water Download PDF

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CN114133090B
CN114133090B CN202111535360.8A CN202111535360A CN114133090B CN 114133090 B CN114133090 B CN 114133090B CN 202111535360 A CN202111535360 A CN 202111535360A CN 114133090 B CN114133090 B CN 114133090B
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decoloring
distillation
water
negative pressure
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CN114133090A (en
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李先明
金爱军
沈楠
李晨
李洋
王国珍
沈井然
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Jiangxi Jiyu New Material 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
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • 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
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/02—Odour removal or prevention of malodour

Abstract

A propionic acid or butyric acid secondary mother liquor waste liquid pollution-free resource processing method, separate light component (aqueous) and heavy component of propionic acid or butyric acid secondary mother liquor water first; carrying out reduced pressure distillation cutting on the propionic acid or butyric acid light component again, and separating most of acidic water containing a small amount of light component from the light component; sending the acid water containing a small amount of light components to a factory sewage treatment system; respectively treating the light and heavy components by two methods of decoloring, deodorizing and neutralizing to obtain an intermediate with light color and nearly neutral pH value; and (3) carrying out amination or boronization treatment on the intermediate to obtain a substitute of the water-based industrial oil raw material for metal processing.

Description

Method and equipment for recycling propionic acid and butyric acid secondary mother liquor water
Technical Field
The invention provides a pollution-free and resource-recycling treatment process adopting reduced pressure distillation cutting, which is used for treating viscous secondary mother liquor waste liquid of propionic acid and butyric acid and obtaining a substitute raw material for producing water-based industrial oil.
Background
The propionic acid is named 2, 2-dimethylolpropionic acid and has a molecular formula C 5 H 10 O 4 The synthesis is firstly carried out in 1901, and a patent report is already made in 1965 abroad. Propionic acid is a multipurpose organic raw material, is a chain extender and a self-emulsifying agent of the waterborne polyurethane in the production of the waterborne polyurethane, can prepare the self-emulsifying agent waterborne polyurethane with excellent stability, and can be used in the production and the manufacture of various products.
The butyric acid is named 2, 2-dimethylolbutyric acid and has a molecular formula C 6 H 12 O 4 The 5-month-day-2000 cost chemical company realizes the industrial production of butyric acid. The comprehensive performance of the butyric acid is far better than that of the propionic acid, and the butyric acid is a renewal product of the propionic acid and has very wide application prospect. In recent years, the application reports of butyric acid at home and abroad are increasing, the product demand is expanding, and butyric acid is expected to become a demand hotspot of the international market in a plurality of future times.
The aldol condensation reaction of formaldehyde and butyraldehyde under the action of an alkaline catalyst is a common organic chemical reaction, but under the influence of multiple factors existing in the reaction process, a series of side reactions are inevitably generated in the production, some side reactions only influence the yield of products, and products generated by other side reactions cause serious environmental pollution if the side reactions are not properly treated, and even the whole production process of the products cannot be normally carried out. For example, various polymers and polycondensates generated in the production process are finally concentrated in the mother liquor after secondary crystallization, so that the viscosity of the mother liquor is greatly increased, and the mother liquor is difficult to recover and treat. As described by one skilled in the art, a foreign enterprise producing propionic acid is forced to stop production because there is no way to handle the mother liquor water.
There have been many units which could not make the work of treating the mother liquor after the second crystallization.
The prior art introduces the discussion that the components in an organic phase are complex, and a certain product is difficult to recover from the complex organic phase, so that the treatment of a large amount of high-content organic wastes is an important problem of normal production of propionic acid and butyric acid. Three treatments are described in this document.
1. Fenton reagent oxidation (Fenton reaction):
the oxidation system of hydrogen peroxide and ferrous ions attacks organic molecules by generating hydroxyl radicals (HO.) through catalytic decomposition and oxidizes the hydroxyl radicals into CO 2 、H 2 And O and the like. At least 10t (27.5%) of hydrogen peroxide is needed to be completely oxidized when 1t of products are produced.
2. The burning method comprises the following steps:
the waste water incineration means that in a combustion chamber of the incinerator, the molecular structures of various harmful substances in the waste water are destroyed through controllable high-temperature chemical reaction, and the waste water is oxidized into CO 2 And H 2 And O and other harmless substances.
3. A water-coal-slurry method:
the water for producing 1t of coal water slurry needs 0.372t of water, 0.62t of coal powder and 0.008t of additive, the mixture is ground and sieved in a ball mill, coarse materials are returned to be reground, and the product is qualified to be used.
As can be seen from the above wastewater treatment process, the preferred treatment process is the water-coal-slurry process. 4.4t of waste water can be produced when 1t of product (DM PA) is produced, and 11.6t of coal water slurry with the concentration of 62 percent can be produced if the product is used for the production of the coal water slurry. Therefore, the water-coal-slurry method is suitable for treating the production wastewater.
In recent years, the common methods for treating the secondary mother liquor of propionic acid and butyric acid are as follows: fenton reagent oxidation (Fenton reaction), incineration and water-coal-slurry methods, but the water-coal-slurry method is generally adopted by enterprises, and the basic idea is to convert carbon in organic waste liquid into carbon dioxide by any of the methods. This causes resource waste and increase of carbon emission, restricts the development of enterprises to a certain extent, influences the ecological environment, and increases the pressure of carbon peak reaching and carbon neutralization.
The application of the process and the equipment for recycling the secondary mother liquor water of the propionic acid and the butyric acid to the treatment of the secondary mother liquor water of the propionic acid and the butyric acid is undoubtedly an effective way for recycling the waste liquor and reducing the carbon emission. According to preliminary calculation, 220 tons of heavy components of propionic acid and 402 tons of heavy components of butyric acid can be recovered by treating 1000 tons of propionic acid and secondary mother liquor waste water of butyric acid by using the method (see the table below), and compared with the currently generally adopted combustion method, the method can reduce 1200 tons of carbon dioxide emission.
Figure GDA0003928771390000021
Figure GDA0003928771390000031
The technology has wide market prospect and application value in the conditions of relative scarcity of resources, strict ecological environment requirement and aggravated carbon emission pressure at present.
Disclosure of Invention
The invention aims to provide a thought and a method for comprehensively utilizing secondary mother liquor waste liquid generated in the production process of two products of propionic acid and butyric acid, so that the problems encountered in the production process of the two products of propionic acid and butyric acid are solved, the resource waste and the environmental pollution are avoided, and the carbon emission is increased. The secondary mother liquor waste liquid contains heavy components of propionic acid and butyric acid, and the heavy components are mainly some polycondensates and a small amount of impurities.
The technical scheme of the invention is that the propionic acid or butyric acid secondary mother liquor waste liquid is subjected to pollution-free resource treatment after vacuum distillation and cutting, and the secondary mother liquor water is separated from light components (water content) and heavy components according to the preset requirements. The light component (water-containing) is subjected to distillation cutting under reduced pressure again, and most of the acidic water containing a small amount of light component is separated from the light component. The acid water containing a small amount of light components is sent to a factory sewage treatment system. The light and heavy components are respectively treated by two methods of decolorization, deodorization and neutralization to obtain an intermediate with light color and almost neutral pH value. And (3) carrying out amination (or boronization) treatment on the intermediate to obtain a substitute of the raw material of the aqueous industrial oil which is easy to further process and can be used for metal processing. Not only finds a way for mother liquor, but also finds a substitute for industrial oil production, thereby reducing environmental pollution and saving resources.
The method can be used for carrying out pollution-free resource treatment on the secondary mother liquor waste water of propionic acid or butyric acid by adopting reduced pressure distillation cutting.
The propionic acid or butyric acid secondary mother liquor waste water is subjected to pollution-free resource treatment after being mixed according to any arbitrary proportion and cut by reduced pressure distillation.
Further, the reduced pressure distillation cutting treatment process for separating the light component (water content) from the heavy component is as follows:
the materials enter a distillation still, and light and heavy components in the process wastewater are separated by simple distillation under the condition of high temperature and negative pressure. The process conditions are set according to the requirements of the product, namely the temperature is between normal temperature and 200 ℃; the pressure is-0.050 to-0.098 MPa. The whole process unit operation can be carried out in a batch mode or a continuous mode.
The method is briefly described as an intermittent distillation process, wherein secondary mother liquor is conveyed and metered by a conveying pump and enters a negative pressure distillation kettle for reduced pressure distillation to separate light components from heavy components. The negative pressure distillation kettle is heated by steam (electricity or other heat-conducting media). The negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser. The light components after heating and gasification enter a condenser to be condensed into liquid phase and then enter a light component storage kettle. And (3) removing entrained liquid phase light components from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump (if the environment protection has requirements, the tail gas can be washed by dilute alkali water and then discharged). And when the distillation temperature and pressure meet the process requirements, stabilizing the operation condition for 30min. The whole reduced pressure distillation operation is controlled within four hours. And (3) reducing the temperature of the kettle to between 60 and 80 ℃, recovering the pressure of the kettle to normal pressure, opening a direct emptying valve of the kettle, keeping a normal stirring state, discharging the recombined split material, or carrying out the next operation.
The continuous distillation process includes conveying and metering secondary mother liquor, and vacuum distillation in a negative pressure distillation kettle to separate light and heavy components. The negative pressure distillation kettle adopts steam for heating. The negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser. The light components after heating and gasification enter a condenser to be condensed into liquid phase and then enter a light component storage kettle. And (4) removing entrained liquid phase light components from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump (if the environment protection has requirements, the tail gas can be washed by dilute alkali water and then discharged). And after the distillation temperature and pressure meet the technological requirements, stabilizing the operation condition for 30min, and controlling the liquid level of the kettle to be not more than 1/2. Sampling and analyzing indexes such as viscosity, flash point, pH value and the like, and discharging to the heavy component storage kettle after meeting the requirements. The balance between the kettle feed and the discharge of light and heavy components is to be maintained.
Further, the treatment process for carrying out once more reduced pressure distillation and cutting on the light component (containing water) comprises the following steps:
the light component (containing water) material enters a distillation still, and most of organic matters in the light component (containing water) material are separated from water (containing a small amount of organic matters) through simple distillation under the condition of high temperature and negative pressure. The technological conditions are set according to the requirements of the product, namely the temperature is between normal temperature and 120 ℃; the pressure is-0.050 to-0.098 MPa. The whole process unit operation can be carried out in a batch mode or a continuous mode.
The intermittent distillation process includes conveying and metering light component material, vacuum distillation in a negative pressure distillation kettle to separate most of organic matter from water. The negative pressure distillation kettle adopts steam for heating. The negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser. The water (containing a small amount of organic matters) after heating and gasification enters a condenser to be condensed into a liquid phase and then enters a water phase collection and storage kettle. And (4) removing an entrained water phase (containing a small amount of organic matters) from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump (if the environment is required, the tail gas can be washed by dilute alkali water and then discharged). And when the distillation temperature and pressure meet the process requirements, stabilizing the operation condition for 30min. The whole reduced pressure distillation operation is controlled within three hours. And (3) reducing the temperature of the kettle to between 60 and 80 ℃, recovering the pressure of the kettle to normal pressure, opening a direct emptying valve of the kettle, keeping a normal stirring state, and discharging the light component organic phase material, or carrying out the next operation.
The water body containing a small amount of light component organic matters in the water phase collection and storage kettle is sent to a factory sewage treatment system for further treatment.
According to the continuous distillation process, the light component (containing water) material is conveyed and metered by a conveying pump, and continuously enters a negative pressure distillation kettle for reduced pressure distillation to separate most of organic matters from water (containing a small amount of organic matters). The negative pressure distillation kettle adopts steam for heating. The negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser. The water (containing a small amount of organic matters) after heating and gasification enters a condenser to be condensed into a liquid phase and then enters a water phase collection and storage kettle. And (4) removing an entrained water phase (containing a small amount of organic matters) from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump (if the environment is required, the tail gas can be washed by dilute alkali water and then discharged). And after the distillation temperature and pressure meet the process requirements, stabilizing the operation condition for 20min, and controlling the liquid level of the kettle to be not more than 1/2. Sampling and analyzing indexes such as viscosity, flash point, pH value and the like, and discharging to a light component organic phase storage kettle after meeting the requirements. The balance of the kettle feed and the discharge of the aqueous phase (containing a small amount of organic matter) and the light component organic phase is maintained.
The water body containing a small amount of light component organic matters in the water phase collection and storage kettle is sent to a factory sewage treatment system for further treatment.
The secondary mother liquor water waste liquid of propionic acid and butyric acid is a mixture consisting of carbon, hydrogen and oxygen elements, but the components in an organic phase are complex, and a certain product is difficult to recover from the organic phase. In order to find out the real situation of the water component of the crystallization mother liquor, the negative pressure distillation of two samples is attempted by a conventional reduced pressure distillation method, and the conditions are that the temperature is from normal temperature to 200 ℃; the pressure is from-0.050 to-0.098 MPa. And receiving distilled samples according to a plurality of pressure and temperature sections, and carrying out full-composition analysis by a professional detection mechanism.
From the analysis results, the secondary crystallization mother liquor has more complex components, which are shown in the table I and the table II.
TABLE I statistics of DMPA (propionic acid) analysis
Figure GDA0003928771390000051
Figure GDA0003928771390000061
TABLE II, DMBA (butyric acid) analysis data statistics
Figure GDA0003928771390000062
From the analysis results, it is found that the three main organic components in the mother liquor after the secondary crystallization of the two products are all fine chemical products with wide application in the state of single existence, but the complete separation of the three main organic components into the independent components in the mixture is difficult to realize, and the secondary utilization is completely feasible after the proper processing treatment of the mixed state.
After the secondary crystallization, the mother liquor is flowable brown viscous acidic liquid and emits pungent odor. Aiming at the mother liquor after secondary crystallization with complex composition, a corresponding disposal scheme is established, the mother liquor is subjected to reduced pressure distillation and cutting, mixed light components which cannot be reused are removed, mixed heavy components are reserved and are processed, and the mother liquor can be used as substitute raw materials of other industrial products.
The heavy component of propionic acid is brown and is in a semi-solid state at normal temperature. The liquid can flow when heated to 60 ℃, has heavy peculiar smell and has different pH values of 3-5. After heating, the water can be dissolved in water. The lubricating oil has certain corrosivity on metals when not treated, has general lubricating performance, and is a water-soluble substance but has poor emulsibility. The direct utilization value is not great. Mainly comprises 2, 2-dimethylolpropionic acid polycondensate, 2-methacrylic acid polycondensate and trimethylolethane, and also comprises a certain amount of sodium sulfate and sodium formate.
The heavy component of butyric acid is brown, and is in a soft wax paste state at normal temperature. The mixture can flow when heated to 40 ℃, has heavy peculiar smell and has different pH values of 3-5. After heating, the water can be dissolved in water. Has a certain viscosity in a flowing state. The lubricating oil has certain corrosivity on metal when not treated, poor lubricating property and favorable emulsibility. Mainly comprises 2, 2-dimethylolbutyric acid polycondensate, 2-ethacrylic acid polycondensate, trimethylolpropane monoacetate and a certain amount of sodium sulfate.
Secondary mother liquor waste liquid and heavy components: the method comprises the following steps of (1) propionic acid secondary mother liquor, propionic acid heavy components (dark color), butyric acid secondary mother liquor and butyric acid heavy components (dark brown color), wherein the heavy components can be reasonably utilized and need to be subjected to a series of treatments. The composition or proportion of the treated heavy components of the C and the butyric acid can be changed along with the change of the production condition because the heavy components of the C and the butyric acid are random mixtures, and the yield of the heavy components of the C and the butyric acid is also limited by the yield of main products. These characteristics determine that the heavy components of the propane and the butyric acid obtained after the treatment cannot become a complete industrial product, and can only be used as a substitute to meet the requirements of some aspects of industrial products.
At present, the heavy components of the treated propane and butyric acid are used as auxiliary materials and blended into an industrial coating for utilization.
Has the advantages that: the invention determines a reasonable process route through a plurality of tests. The heavy component is put into a kettle, the temperature of the kettle is raised to 90 ℃, and a decoloring agent is slowly dripped under the stirring state, so that the brown material can be decolored to yellow, and the peculiar smell of the material can be greatly reduced. After the decoloring operation is finished, adding a proper amount of liquid alkali to allow the materials to carry out sodium (potassium) reaction at a certain temperature. After a period of time, adding a certain amount of alcohol amine for amination. Through the series of operations, the viscous liquid which is yellow, has light peculiar smell, has the pH value of about 7.5, can flow at normal temperature and has better water solubility is obtained. The decoloring of the heavy component of the propionic acid and the decoloring of the heavy component of the butyric acid are obviously light in color.
Drawings
FIG. 1 is a schematic diagram of a batch principle process;
FIG. 2 is a schematic diagram of a continuous principle process;
FIG. 3, heating structure in tower kettle;
fig. 4 shows a reboiler heating structure.
Detailed description of the preferred embodiments
The invention is further illustrated by the following examples.
Example (b):
in the present embodiment, the mixture of the secondary mother liquor of propane and butyric acid in the ratio of 1. The whole treatment process is divided into four operation units.
1. Separating light components and heavy components of the secondary mother liquor wastewater of the third and fourth acids:
the materials enter a distillation still, and light and heavy components in the process wastewater are separated by simple distillation under the condition of high temperature and negative pressure. The process conditions are 160-170 ℃; the pressure is-0.090 to-0.095 MPa. The whole process unit operation is carried out in a batch mode.
Conveying and metering the secondary mother liquor water by a conveying pump, and carrying out reduced pressure distillation in a negative pressure distillation kettle to separate light components from heavy components. The negative pressure distillation kettle adopts steam for heating. The negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser. The light components after heating and gasification enter a condenser to be condensed into liquid phase and then enter a light component storage kettle. And (3) removing entrained liquid phase light components from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump (if the environment protection has requirements, the tail gas can be washed by dilute alkali water and then discharged). And when the distillation temperature and pressure meet the process requirements, stabilizing the operation condition for 30min. The whole reduced pressure distillation operation is controlled within four hours. And (3) reducing the temperature of the kettle to 60-80 ℃, recovering the kettle pressure to normal pressure, opening a direct emptying valve of the kettle, keeping a normal stirring state, discharging the recombined material, or carrying out the next operation.
2. Decoloring, neutralizing and aminating heavy components:
the unit operation is still carried out in a still pot and related equipment. Firstly, decoloring, then carrying out sodium treatment and neutralization to neutrality by adopting inorganic alkali substances, and then adding organic amine for amination. Qualified by analysis and sold as a factory byproduct.
And (4) reducing the temperature of the kettle to 60-80 ℃, recovering the kettle pressure to normal pressure, keeping a normal stirring state, and carrying out the next operation. And (4) pumping the decolorizing agent from the charging bucket into a decolorizing agent metering kettle for later use. When the decoloring operation is started, nitrogen is firstly used for purging a decoloring agent feeding pipeline to ensure smoothness. And opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle part of the kettle after the decoloring agent is limited and metered by a flow limiting orifice plate so as to perform chemical decoloring on the material. The decoloring operation is timed from the decolorant entering the kettle and controlled within one hour. Can remove the peculiar smell in the materials while decoloring.
And after the decoloring operation is finished, pumping the liquefied inorganic base into a kettle according to the process dosage, carrying out sodium treatment and neutralization on the material to neutrality, and stirring for 30min. Then pumping organic amine (boronizing agent) to make amination (boronizing) treatment. And (5) after the operation is finished, analyzing related data, and discharging after the data are qualified.
3. Light component
The light component (containing water) material enters a distillation still, and most of organic matters and water (containing a small amount of organic matters) in the light component (containing water) material are separated by simple distillation under the condition of high temperature and negative pressure. The process conditions are set according to the requirements of the product, namely the temperature is between normal temperature and 120 ℃; the pressure is-0.050 to-0.098 Mpa.
The light component (containing water) material is conveyed and metered by a conveying pump, enters a negative pressure distillation kettle for reduced pressure distillation, and separates most organic matters from water (containing a small amount of organic matters). The negative pressure distillation kettle adopts steam for heating. The negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser. The gasified water (containing a small amount of organic matters) is condensed into a liquid phase in a condenser and then enters a water phase collection and storage kettle. And (4) removing an entrained water phase (containing a small amount of organic matters) from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump (if the environment is required, the tail gas can be washed by dilute alkali water and then discharged). And when the distillation temperature and pressure meet the process requirements, stabilizing the operation condition for 30min. The whole reduced pressure distillation operation is controlled within three hours. And (3) reducing the temperature of the kettle to 60-80 ℃, recovering the kettle pressure to normal pressure, opening a direct emptying valve of the kettle, keeping a normal stirring state, and discharging the light-component organic phase material, or performing the next operation.
The water body containing a small amount of light component organic matters in the water phase collection and storage kettle is sent to a factory sewage treatment system for further treatment.
4. Decoloring, neutralizing and aminating a light component organic phase:
the unit operation is still carried out in a distillation still and relevant equipment. Firstly, decoloring, then carrying out sodium treatment and neutralization to neutrality by adopting inorganic alkali substances, and then adding organic amine for amination. Qualified by analysis and sold as a factory byproduct.
And (4) pumping the decolorizing agent from the charging bucket into a decolorizing agent metering kettle for later use. When the decoloring operation is started, nitrogen is firstly used for purging the decoloring agent feeding pipeline so as to ensure smoothness. Opening the discharge valve of the metering kettle, and allowing the decoloring agent to enter the material layer from the middle of the kettle after being limited and metered by the flow limiting orifice plate to chemically decolor the material. The decoloring operation is timed from the decolorant entering the kettle and controlled within one hour. The material can be decolorized and simultaneously the peculiar smell in the material can be removed.
And after the decoloring operation is finished, pumping the liquefied inorganic base into a kettle according to the process dosage, carrying out sodium treatment and neutralization on the material to neutrality, and stirring for 30min. When the temperature of the materials in the kettle is reduced to 60 ℃, organic amine (a boronizing agent) is pumped in for amination (boronization). And (5) after the operation is finished, analyzing related data, and discharging after the data are qualified.
The light and heavy components are respectively treated by two methods of decoloring, deodorizing and neutralizing to obtain an intermediate with light color and almost neutral pH value, and the treatment process comprises the following steps:
(1) Two methods of chemical decolorization, deodorization and neutralization are adopted to treat the components:
the batch distillation can be carried out in the original still. And (4) reducing the temperature of the kettle to 60-80 ℃, recovering the kettle pressure to normal pressure, keeping a normal stirring state, and carrying out the next operation. The decolorant is pumped into a decolorant metering kettle from a charging basket for standby. When the decoloring operation is started, nitrogen is firstly used for purging the decoloring agent feeding pipeline so as to ensure smoothness. Opening the discharge valve of the metering kettle, and allowing the decoloring agent to enter the material layer from the middle of the kettle after being limited and metered by the flow limiting orifice plate to chemically decolor the material. The decoloring operation is timed from the time when the decoloring agent enters the kettle, and is controlled within one hour. Can remove the peculiar smell in the materials while decoloring. Chemical decoloration and deodorization are oxidants;
and after the decoloring operation is finished, pumping the liquefied inorganic base into a kettle according to the process amount, neutralizing the material to be neutral, and stirring for 30min. The material can be discharged or subjected to further processing.
And (3) continuous distillation, namely pumping and metering the materials in the heavy component storage kettle and feeding the materials into a heavy component refining kettle. Starting stirring, and heating the kettle to 60-80 ℃. The decolorant is pumped into a decolorant metering kettle from a charging basket for standby. When the decoloring operation is started, nitrogen is firstly used for purging the decoloring agent feeding pipeline so as to ensure smoothness. And opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle part of the kettle after the decoloring agent is limited and metered by a flow limiting orifice plate so as to perform chemical decoloring on the material. The decoloring operation is timed from the decolorant entering the kettle and controlled within one hour. The material can be decolorized and simultaneously the peculiar smell in the material can be removed.
And (3) after the decoloring operation is finished, pumping the liquefied inorganic base into the kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min. The material can be discharged or subjected to the next operation.
The decolorizing agent can be selected from hydrogen peroxide and other substances.
The neutralizer is selected from potassium hydroxide, sodium hydroxide, etc.
(2) Two methods of decolorization, deodorization and neutralization are adopted to treat the light component organic phase:
batch distillation can be carried out in the original still. And (4) reducing the temperature of the kettle to 60-80 ℃, recovering the kettle pressure to normal pressure, keeping a normal stirring state, and carrying out the next operation. The decolorant is pumped into a decolorant metering kettle from a charging basket for standby. When the decoloring operation is started, nitrogen is firstly used for purging a decoloring agent feeding pipeline to ensure smoothness. Opening the discharge valve of the metering kettle, and allowing the decoloring agent to enter the material layer from the middle of the kettle after being limited and metered by the flow limiting orifice plate to chemically decolor the material. The decoloring operation is timed from the time when the decoloring agent enters the kettle, and is controlled within one hour. The material can be decolorized and simultaneously the peculiar smell in the material can be removed.
And (3) after the decoloring operation is finished, pumping the liquefied inorganic base into the kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min. The material can be discharged or subjected to further processing.
And (3) continuous distillation, namely pumping and metering the materials in the light component organic phase storage kettle, and feeding the materials into a light component organic phase refining kettle. Starting stirring, and heating the kettle to 60-80 ℃. The decolorant is pumped into a decolorant metering kettle from a charging basket for standby. When the decoloring operation is started, nitrogen is firstly used for purging the decoloring agent feeding pipeline so as to ensure smoothness. Opening the discharge valve of the metering kettle, and allowing the decoloring agent to enter the material layer from the middle of the kettle after being limited and metered by the flow limiting orifice plate to chemically decolor the material. The decoloring operation is timed from the time when the decoloring agent enters the kettle, and is controlled within one hour. The material can be decolorized and simultaneously the peculiar smell in the material can be removed.
And (3) after the decoloring operation is finished, pumping the liquefied inorganic base into the kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min. The material can be discharged or subjected to the next operation.
The decolorizing agent can be selected from hydrogen peroxide, etc.
The neutralizer is selected from potassium hydroxide, sodium hydroxide, etc.
The amination (or boronization) treatment process of the intermediate comprises the following steps:
and (3) intermittent distillation, namely keeping the normal stirring state, and pumping organic amine (or a boronizing agent) for amination (boronization) treatment after the temperature of materials in the kettle is reduced to 60 ℃. And (5) after the operation is finished, analyzing related data, and discharging after the data are qualified.
And (3) continuous distillation, namely keeping the normal stirring state, and pumping organic amine (a boronizing agent) for amination (boronization) treatment after the temperature of the materials in the kettle is reduced to 60 ℃. And (5) after the operation is finished, analyzing related data, and discharging after the data are qualified.
The aminating agent can be selected from monoethanolamine, diethanolamine, triethanolamine, etc.
The borating agent can be selected from borax, boric acid, etc.
The basic process of pollution-free resource treatment after the whole intermittent reduced pressure distillation and cutting comprises the steps of adopting two reduced pressure distillation kettles and simultaneously using the reduced pressure distillation kettles as a material refining kettle.
And conveying and metering the secondary mother liquor water by a conveying pump, and feeding the secondary mother liquor water into a negative pressure distillation kettle for reduced pressure distillation to separate light components from heavy components. The negative pressure distillation kettle adopts steam for heating. The negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser. The light component after heating and gasifying enters a condenser to be condensed into a liquid phase and then enters a light component storage kettle. And (4) removing entrained liquid phase light components from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump (if the environment protection has requirements, the tail gas can be washed by dilute alkali water and then discharged). And when the distillation temperature and pressure meet the process requirements, stabilizing the operation condition for 30min. The whole reduced pressure distillation operation is controlled within four hours. And (3) reducing the temperature of the kettle to 60-80 ℃, recovering the kettle pressure to normal pressure, opening a direct emptying valve of the kettle, and keeping the normal stirring state. The decolorant is pumped into a decolorant metering kettle from a charging basket for standby. When the decoloring operation is started, nitrogen is firstly used for purging the decoloring agent feeding pipeline so as to ensure smoothness. And opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle part of the kettle after the decoloring agent is limited and metered by a flow limiting orifice plate so as to perform chemical decoloring on the material. The decoloring operation is timed from the time when the decoloring agent enters the kettle, and is controlled within one hour. Can remove the peculiar smell in the materials while decoloring. And (3) after the decoloring operation is finished, pumping the liquefied inorganic base into the kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min. The material can be discharged or subjected to the next operation. Keeping normal stirring state, when the temperature of the materials in the kettle is reduced to 60 ℃, pumping organic amine (boronizing agent) for amination (boronizing). And (5) after the operation is finished, analyzing related data, and discharging after the data are qualified.
The light component (containing water) material is conveyed and metered by a conveying pump, enters a negative pressure distillation kettle for reduced pressure distillation, and separates most organic matters from water (containing a small amount of organic matters). The negative pressure distillation kettle adopts steam for heating. The negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser. The water (containing a small amount of organic matters) after heating and gasification enters a condenser to be condensed into a liquid phase and then enters a water phase collection and storage kettle. And (4) removing an entrained water phase (containing a small amount of organic matters) from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump (if the environment is required, the tail gas can be washed by dilute alkali water and then discharged). And when the distillation temperature and pressure meet the process requirements, stabilizing the operation condition for 30min. The whole reduced pressure distillation operation is controlled within three hours. The temperature of the kettle is reduced to 60-80 ℃, the pressure of the kettle is recovered to normal pressure, and the normal stirring state is maintained. And (4) pumping the decolorizing agent from the charging bucket into a decolorizing agent metering kettle for later use. When the decoloring operation is started, nitrogen is firstly used for purging a decoloring agent feeding pipeline to ensure smoothness. And opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle part of the kettle after the decoloring agent is limited and metered by a flow limiting orifice plate so as to perform chemical decoloring on the material. The decoloring operation is timed from the time when the decoloring agent enters the kettle, and is controlled within one hour. Can remove the peculiar smell in the materials while decoloring. And (3) after the decoloring operation is finished, pumping the liquefied inorganic base into the kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min. The material can be discharged or subjected to further processing. Keeping normal stirring state, pumping organic amine (boronizing agent) to make amination (boronization) treatment when the material in the kettle is reduced to 60 deg.C. And (5) after the operation is finished, analyzing related data, and discharging after the data are qualified.
The water body containing a small amount of light component organic matters in the water phase collection and storage kettle is sent to a factory sewage treatment system for further treatment.
The applicant has compiled enterprise standards for products processed by the secondary mother liquor of the propionic acid and the butyric acid. And reports to relevant government departments.
FIG. 1 is a schematic diagram of a batch-type principle process, in which the reference numerals indicate:
1. storing the secondary mother solution in a kettle; 2. a delivery pump; 3. a negative pressure distillation kettle; 4. a condenser; 5. a buffer kettle; 6. a vacuum pump; 7. storing the light component in a kettle; 8. a decolorant charging basket; 9. a decolorizing agent delivery pump; 10. a decolorant metering kettle; 11. packaging barrels for organic alkali; 12. an organic base delivery pump; 13. packaging the heavy component into a barrel; 14. a light component delivery pump; 15. neutralizing the light component in a distillation kettle; 16. a condenser; 17. a buffer kettle; 18. a vacuum pump; 19. a water phase collection kettle; 20. alkaline substance packaging barrel; 21. a delivery pump; 22. a metering kettle; 23. catalyst packing barrel; 24. a catalyst transfer pump; 25. and a water phase conveying pump.
The basic process of pollution-free resource treatment after the whole continuous reduced pressure distillation cutting comprises the steps of adopting four kettles, using two kettles as reduced pressure distillation kettles and using two kettles as material refining kettles. The vacuum distillation part is operated continuously, and the material refining part is operated intermittently.
And conveying and metering the secondary mother liquor water by a conveying pump, and continuously feeding the secondary mother liquor water into a negative pressure distillation kettle for reduced pressure distillation to separate light components from heavy components. The negative pressure distillation kettle adopts steam for heating. The negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser. The light component after heating and gasifying enters a condenser to be condensed into a liquid phase and then enters a light component storage kettle. And (3) removing entrained liquid phase light components from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump (if the environment protection has requirements, the tail gas can be washed by dilute alkali water and then discharged). And after the distillation temperature and pressure meet the process requirements, stabilizing the operation condition for 30min, and controlling the liquid level of the kettle to be not more than 1/2. Sampling and analyzing indexes such as viscosity, flash point, pH value and the like, and discharging to the heavy component storage kettle after meeting the requirements. The balance between the kettle feed and the discharge of light and heavy components is to be maintained.
And (4) pumping and metering the materials in the heavy component storage kettle, and feeding the materials into a heavy component refining kettle. Starting stirring, and heating the kettle to 60-80 ℃. And (4) pumping the decolorizing agent from the charging bucket into a decolorizing agent metering kettle for later use. When the decoloring operation is started, nitrogen is firstly used for purging the decoloring agent feeding pipeline so as to ensure smoothness. Opening the discharge valve of the metering kettle, and allowing the decoloring agent to enter the material layer from the middle of the kettle after being limited and metered by the flow limiting orifice plate to chemically decolor the material. The decoloring operation is timed from the decolorant entering the kettle and controlled within one hour. The material can be decolorized and simultaneously the peculiar smell in the material can be removed. And (3) after the decoloring operation is finished, pumping the liquefied inorganic base into the kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min. The material can be discharged or subjected to further processing. Keeping normal stirring state, when the temperature of the materials in the kettle is reduced to 60 ℃, pumping organic amine (boronizing agent) for amination (boronizing). And (5) after the operation is finished, analyzing related data, and discharging after the data are qualified.
The light component (containing water) material is conveyed and metered by a conveying pump, and continuously enters a negative pressure distillation kettle for reduced pressure distillation to separate most of organic matters from water (containing a small amount of organic matters). The negative pressure distillation kettle adopts steam for heating. The negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser. The gasified water (containing a small amount of organic matters) is condensed into a liquid phase in a condenser and then enters a water phase collection and storage kettle. And (3) removing the entrained water phase (containing a small amount of organic matters) from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump (if the environment protection has requirements, the tail gas can be washed by dilute alkali water and then discharged). And after the distillation temperature and pressure meet the process requirements, stabilizing the operation condition for 20min, and controlling the liquid level of the kettle to be not more than 1/2. Sampling and analyzing indexes such as viscosity, flash point, pH value and the like, and discharging to a light component organic phase storage kettle after meeting the requirements. The balance between the kettle feed and the discharge of the aqueous phase (containing a small amount of organic matter) and the light organic phase is maintained.
The water body containing a small amount of light component organic matters in the water phase collection and storage kettle is further treated by a factory sewage treatment system.
And (3) pumping and metering the materials in the light component organic phase storage kettle, and feeding the materials into a light component organic phase refining kettle. Starting stirring, and heating the kettle to 60-80 ℃. The decolorant is pumped into a decolorant metering kettle from a charging basket for standby. When the decoloring operation is started, nitrogen is firstly used for purging a decoloring agent feeding pipeline to ensure smoothness. And opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle part of the kettle after the decoloring agent is limited and metered by a flow limiting orifice plate so as to perform chemical decoloring on the material. The decoloring operation is timed from the time when the decoloring agent enters the kettle, and is controlled within one hour. Can remove the peculiar smell in the materials while decoloring. And (3) after the decoloring operation is finished, pumping the liquefied inorganic base into the kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min. The material can be discharged or subjected to further processing. Keeping normal stirring state, when the temperature of the materials in the kettle is reduced to 60 ℃, pumping organic amine (boronizing agent) for amination (boronizing). And (5) after the operation is finished, analyzing related data, and discharging after the data are qualified.
FIG. 2 is a schematic diagram of a continuous principle process, which is indicated by numeral notation, 1, a secondary mother liquid water storage kettle; 2. a delivery pump; 3. a negative pressure distillation kettle; 4. a condenser; 5. a buffer kettle; 6. a vacuum pump; 7. storing the light component in a kettle; 8. a recombination separate storage kettle; 9. a heavy component delivery pump; 10 heavy component refining kettle; 11. a decolorant charging basket; 12. a decolorant delivery pump 13 and a decolorant metering kettle; 14. packaging barrels for organic alkali; 15. an organic base delivery pump; 16. packaging the heavy component into a barrel; 17. a light component delivery pump; 18. the light component neutralizes the stills; 19. a condenser; 20. a buffer kettle; 21. a vacuum pump; 22. a water phase collection kettle; 23. alkaline substance packaging barrel; 24 light component organic delivery pumps, 25 light component refining kettles and 26 decolorant charging buckets; 27. a decolorizing agent delivery pump; 28. a decolorant metering kettle and a 29 alkaline substance packaging barrel; 31, packaging the light component organic phase into a barrel; 30 a delivery pump; 32. and a water phase conveying pump.
The reduced pressure distillation can adopt kettle type distillation or tower type distillation. The tower distillation is performed by selecting a packed tower, and the key point is on the mode of material heating. The heating part can be arranged in the tower kettle, or a reboiler can be arranged to circularly heat outside the tower. (see diagram 3 and figure 4.) the reduced pressure distillation can be heated by steam, superheated steam, heat transfer oil or electricity.

Claims (8)

1. A pollution-free resource treatment method for propionic acid or butyric acid secondary mother liquor waste water is characterized in that the propionic acid is 2, 2-dimethylolpropionic acid, and the butyric acid is 2, 2-dimethylolbutyric acid;
firstly, separating the light component containing water from the heavy component by propionic acid or butyric acid secondary mother liquor; carrying out one more reduced pressure distillation cutting on the propionic acid or butyric acid light component, and separating most of the acidic water containing a small amount of light component from the light component; sending the acid water containing a small amount of light components to a factory sewage treatment system; respectively treating the light and heavy components by two methods of decoloring, deodorizing and neutralizing to obtain an intermediate with light color and almost neutral pH value; carrying out amination or boronization treatment on the intermediate to obtain a substitute of the water-based industrial oil raw material for metal processing; the reduced pressure distillation cutting treatment process for separating the light components from the heavy components comprises the following steps:
feeding the material into a distillation still, and separating light and heavy components in the process wastewater by simple distillation under the condition of high temperature and negative pressure; the process conditions are set according to the requirements of the product, namely the temperature is normal temperature to 200 ℃, and the pressure is-0.050 to-0.098 MPa; the whole process unit operation is carried out in a batch mode or a continuous mode;
the batch distillation process is briefly described as follows: conveying and metering secondary mother liquor water of propionic acid or butyric acid by a conveying pump, and carrying out reduced pressure distillation in a negative pressure distillation kettle to separate light components from heavy components; the negative pressure distillation kettle adopts a heating mode, and a negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser; condensing the heated and gasified light components into a liquid phase in a condenser, and then feeding the liquid phase into a light component storage kettle; removing entrained liquid phase light components from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump; stabilizing the operation condition for 30min when the distillation temperature and pressure meet the process requirements; the whole reduced pressure distillation operation is controlled within four hours; reducing the temperature of the kettle to 60-80 ℃, recovering the pressure of the kettle to normal pressure, opening a direct emptying valve of the kettle, keeping a normal stirring state, discharging the recombined materials or carrying out the next operation;
the continuous distillation process is briefly described as follows: conveying and metering propionic acid or butyric acid secondary mother liquor water by a conveying pump, continuously feeding into a negative pressure distillation kettle for reduced pressure distillation, and separating light components from heavy components; the negative pressure distillation kettle adopts a heating mode, and a negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser; condensing the heated and gasified light components into a liquid phase in a condenser, and then feeding the liquid phase into a light component storage kettle; removing entrained liquid phase light components from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump; after the distillation temperature and pressure reach the technological requirements, stabilizing the operation condition for 30min, and controlling the liquid level of the kettle not to exceed 1/2; sampling and analyzing the viscosity, flash point and pH value indexes, and discharging to the heavy component storage kettle after meeting the requirements.
2. The method as set forth in claim 1, wherein the propionic acid or butyric acid secondary mother liquor waste liquid is subjected to pollution-free resource treatment after being cut by reduced pressure distillation.
3. The method as set forth in claim 1, wherein the propionic acid and butyric acid secondary mother liquor waste water is subjected to pollution-free resource treatment after being mixed in any proportion and cut by reduced pressure distillation.
4. The method as set forth in claim 1, wherein the process of further performing the distillation and cutting under reduced pressure on the light component containing water comprises the following steps:
the water-containing light component material enters a distillation still, and most of organic matters in the water-containing light component material are separated from water containing a small amount of organic matters by simple distillation under the condition of high temperature and negative pressure; the process conditions are set according to the requirements of the product, namely the temperature is normal temperature to 120 ℃, and the pressure is-0.050 to-0.098 MPa; the whole process unit operation is carried out in a batch mode or a continuous mode;
according to the brief description of the intermittent distillation process, the material containing light components is conveyed and metered by a conveying pump and enters a negative pressure distillation kettle for reduced pressure distillation to separate most of organic matters from water; heating the negative pressure distillation kettle by adopting steam; the negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser; the heated and gasified water enters a condenser to be condensed into a liquid phase and then enters a water phase collection and storage kettle; removing entrained water phase from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump; controlling the whole reduced pressure distillation operation within three hours, reducing the temperature of the kettle to between 60 and 80 ℃, recovering the pressure of the kettle to normal pressure, opening a direct emptying valve of the kettle, keeping a normal stirring state, discharging a light component organic phase material, or performing the next operation;
a water phase collection and storage kettle contains a small amount of light component organic matter, and the water phase collection and storage kettle is sent to a factory sewage treatment system for further treatment;
the continuous distillation process is briefly described as follows: conveying and metering the water-containing light component material by a conveying pump, continuously feeding the material into a negative pressure distillation kettle for reduced pressure distillation, and separating most organic matters from water containing a small amount of organic matters; the negative pressure distillation kettle is heated by steam; the negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser; the water containing a small amount of organic matter after heating and gasification enters a condenser to be condensed into a liquid phase and then enters a water phase collection and storage kettle; the condensed tail gas is discharged after a vacuum pump after a negative pressure buffer kettle removes a small amount of organic matter-containing water phase, and is discharged after being washed by dilute alkali water when the requirement of environmental protection is met; after the distillation temperature and pressure meet the process requirements, stabilizing the operation condition for 20min, and controlling the liquid level of the kettle to be not more than 1/2; sampling and analyzing viscosity, flash point and pH value indexes, and discharging to a light component organic phase storage kettle after meeting the requirements; keeping the balance of the kettle feeding and the discharging of the water phase containing a small amount of organic matters and the organic phase containing light components;
the water body containing a small amount of light component organic matters in the water phase collection and storage kettle is sent to a factory sewage treatment system for further treatment.
5. The method as claimed in claim 1, wherein the light and heavy components are treated by two methods of decolorization, deodorization and neutralization to obtain intermediate with light color and nearly neutral pH value, and the treatment process comprises:
(1) Two methods of chemical decolorization, deodorization and neutralization are adopted to treat the components:
the batch distillation is carried out in the original distillation kettle; reducing the temperature of the kettle to 60-80 ℃, recovering the pressure of the kettle to normal pressure, keeping a normal stirring state, and carrying out the next operation; pumping the decolorizing agent from the charging bucket into a decolorizing agent metering kettle for later use; when the decoloring operation is started, firstly, purging a decoloring agent feeding pipeline by using nitrogen to ensure smoothness; opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle part of the kettle after the decoloring agent is limited and metered by a flow limiting orifice plate to perform chemical decoloring on the material; the decoloring operation is timed from the time when a decoloring agent enters a kettle, and is controlled within one hour; removing the peculiar smell in the materials while decoloring; chemically decolorizing and deodorizing to obtain oxidant;
after the decoloring operation is finished, pumping the liquefied inorganic base into a kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min; discharging the materials or carrying out the next operation;
continuous distillation, namely pumping and metering materials in a heavy component storage kettle, and feeding the materials into a heavy component refining kettle; starting stirring, and heating the kettle to 60-80 ℃; pumping the decolorizing agent from the charging basket into a decolorizing agent metering kettle for later use; when the decoloring operation is started, firstly, purging a decoloring agent feeding pipeline by using nitrogen to ensure smoothness; opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle of the kettle after the decoloring agent is limited and metered by a limiting orifice plate, so as to perform chemical decoloring on the material; the decoloring operation is timed from the time when the decoloring agent enters the kettle, and is controlled within one hour; removing the peculiar smell in the materials while decoloring;
after the decoloring operation is finished, pumping the liquefied inorganic base into a kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min; discharging the materials or carrying out the next operation;
the decolorizing agent is hydrogen peroxide;
the neutralizer is potassium hydroxide or sodium hydroxide;
(2) Two methods of decolorization, deodorization and neutralization are adopted to treat the light component organic phase:
the batch distillation is carried out in the original distillation kettle; reducing the temperature of the kettle to 60-80 ℃, recovering the pressure of the kettle to normal pressure, keeping a normal stirring state, and carrying out the next operation; pumping the decolorizing agent from the charging bucket into a decolorizing agent metering kettle for later use; when the decoloring operation is started, firstly, purging a decoloring agent feeding pipeline by using nitrogen to ensure smoothness; opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle part of the kettle after the decoloring agent is limited and metered by a flow limiting orifice plate to perform chemical decoloring on the material; the decoloring operation is timed from the time when the decoloring agent enters the kettle, and is controlled within one hour; removing the peculiar smell in the materials while decoloring;
after the decoloring operation is finished, pumping the liquefied inorganic base into a kettle according to the process amount, neutralizing the material to be neutral, and stirring for 30min; discharging the materials or carrying out the next operation;
continuous distillation: pumping and metering the materials in the light component organic phase storage kettle, and feeding the materials into a light component organic phase refining kettle; starting stirring, and heating the kettle to 60-80 ℃; pumping the decolorizing agent from the charging bucket into a decolorizing agent metering kettle for later use; when the decoloring operation is started, firstly, nitrogen is used for purging a decoloring agent inlet pipeline to ensure smoothness; opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle part of the kettle after the decoloring agent is limited and metered by a flow limiting orifice plate to perform chemical decoloring on the material; the decoloring operation is timed from the time when the decoloring agent enters the kettle, and is controlled within one hour; removing the peculiar smell in the materials while decoloring;
after the decoloring operation is finished, pumping the liquefied inorganic base into a kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min; discharging the materials and carrying out the next operation;
the decolorant is hydrogen peroxide; the neutralizer is potassium hydroxide or sodium hydroxide.
6. The method as claimed in claim 1, wherein the amination or boronization process of the intermediate comprises:
batch distillation: keeping a normal stirring state, and pumping organic amine or a boronizing agent for amination or boronization after the temperature of materials in the kettle is reduced to 60 ℃; after the operation is finished, analyzing relevant data, and discharging after the data are qualified;
continuous distillation: keeping a normal stirring state, and pumping organic amine or a boronizing agent for amination or boronization after the temperature of materials in the kettle is reduced to 60 ℃; after the operation is finished, analyzing relevant data, and discharging after the data are qualified;
the aminating agent is selected from monoethanolamine, diethanolamine and triethanolamine;
the borating agent is borax or boric acid.
7. The method as claimed in claim 1, wherein the basic process for pollution-free resource treatment after the batch-type vacuum distillation and cutting comprises using two vacuum distillation kettles and simultaneously using the vacuum distillation kettles as a refining kettle for the material;
conveying and metering the secondary mother liquor water by a conveying pump, and performing reduced pressure distillation in a negative pressure distillation kettle to separate light components from heavy components; the negative pressure distillation kettle is heated by steam; the negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser; condensing the heated and gasified light components into a liquid phase in a condenser, and then feeding the liquid phase into a light component storage kettle; removing entrained liquid phase light components from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump; when the environment is required, the waste water is washed by dilute alkali water and then discharged; stabilizing the operation condition for 30min when the distillation temperature and pressure meet the process requirements; the whole reduced pressure distillation operation is controlled within four hours; reducing the temperature of the kettle to between 60 and 80 ℃, recovering the pressure of the kettle to normal pressure, opening a direct emptying valve of the kettle, and keeping a normal stirring state; pumping the decolorizing agent from the charging bucket into a decolorizing agent metering kettle for later use; when the decoloring operation is started, firstly, purging a decoloring agent feeding pipeline by using nitrogen to ensure smoothness; opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle part of the kettle after the decoloring agent is limited and metered by a flow limiting orifice plate to perform chemical decoloring on the material; the decoloring operation is timed from the time when a decoloring agent enters a kettle, and is controlled within one hour; removing the peculiar smell in the materials while decoloring; after the decoloring operation is finished, pumping the liquefied inorganic base into a kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min; discharging the materials or carrying out the next operation; keeping normal stirring state, and pumping organic amine or a boronizing agent for amination or boronization after the temperature of the materials in the kettle is reduced to 60 ℃; after the operation is finished, analyzing relevant data, and discharging after the data are qualified;
conveying and metering the water-containing light component material by a conveying pump, and feeding the material into a negative pressure distillation kettle for reduced pressure distillation to separate most of organic matters from water containing a small amount of organic matters; the negative pressure distillation kettle is heated by steam; the negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser; the water containing a small amount of organic matters after heating and gasification enters a condenser to be condensed into a liquid phase and then enters a water phase collection and storage kettle; removing a small amount of organic matter-containing water phase carried by the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump; when the environment protection is required, the waste water is washed by dilute alkali water and then discharged; stabilizing the operation condition for 30min when the distillation temperature and pressure meet the process requirements; the whole reduced pressure distillation operation is controlled within three hours; reducing the temperature of the kettle to between 60 and 80 ℃, recovering the pressure of the kettle to normal pressure, and keeping a normal stirring state; pumping the decolorizing agent from the charging bucket into a decolorizing agent metering kettle for later use; when the decoloring operation is started, firstly, purging a decoloring agent feeding pipeline by using nitrogen to ensure smoothness; opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle part of the kettle after the decoloring agent is limited and metered by a flow limiting orifice plate to perform chemical decoloring on the material; the decoloring operation is timed from the time when the decoloring agent enters the kettle, and is controlled within one hour; removing the peculiar smell in the materials while decoloring; after the decoloring operation is finished, pumping the liquefied inorganic base into a kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min; discharging the materials or carrying out the next operation; keeping normal stirring state, and pumping organic amine or a boronizing agent for amination or boronization after the temperature of the materials in the kettle is reduced to 60 ℃; after the operation is finished, analyzing relevant data, and discharging after the data are qualified;
the water body containing a small amount of light component organic matters in the water phase collection and storage kettle is sent to a factory sewage treatment system for further treatment.
8. The method as claimed in claim 1, wherein the basic process of pollution-free resource treatment after the whole continuous vacuum distillation and cutting comprises the following steps:
four kettles are adopted, two of the kettles are used as reduced pressure distillation kettles, and two of the kettles are used as refining kettles of materials; the vacuum distillation part is operated continuously, and the material refining part is operated intermittently;
conveying and metering the secondary mother liquor water by a conveying pump, continuously feeding the secondary mother liquor water into a negative pressure distillation kettle for reduced pressure distillation, and separating light components from heavy components; the negative pressure distillation kettle is heated by steam; the negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser; condensing the heated and gasified light components into a liquid phase in a condenser, and then feeding the liquid phase into a light component storage kettle; removing entrained liquid phase light components from the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump; after the distillation temperature and pressure meet the process requirements, stabilizing the operation condition for 30min, and controlling the liquid level of the kettle not to exceed 1/2; sampling and analyzing indexes of viscosity, flash point and pH value, and discharging to a heavy component storage kettle after meeting the requirement; the balance between the kettle feeding and the discharging of the light and heavy components is kept;
the materials in the heavy component storage kettle are pumped and metered and sent into a heavy component refining kettle; starting stirring, and heating the kettle to 60-80 ℃; pumping the decolorizing agent from the charging bucket into a decolorizing agent metering kettle for later use; when the decoloring operation is started, firstly, nitrogen is used for purging a decoloring agent inlet pipeline to ensure smoothness; opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle part of the kettle after the decoloring agent is limited and metered by a flow limiting orifice plate to perform chemical decoloring on the material; the decoloring operation is timed from the time when a decoloring agent enters a kettle, and is controlled within one hour; removing the peculiar smell in the materials while decoloring; after the decoloring operation is finished, pumping the liquefied inorganic base into a kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min; discharging the materials or carrying out the next operation; keeping a normal stirring state, and pumping organic amine or a boronizing agent for amination or boronization after the temperature of materials in the kettle is reduced to 60 ℃; after the operation is finished, analyzing relevant data, and discharging after the data are qualified;
conveying and metering the water-containing light component material by a conveying pump, continuously feeding the material into a negative pressure distillation kettle for reduced pressure distillation, and separating most of organic matters from water containing a small amount of organic matters; heating the negative pressure distillation kettle by adopting steam; the negative pressure system consists of a vacuum pump, a negative pressure buffer kettle and a condenser; the water containing a small amount of organic matters after heating and gasification enters a condenser to be condensed into a liquid phase and then enters a water phase collection and storage kettle; removing a small amount of organic matter-containing water phase carried by the condensed tail gas through a negative pressure buffer kettle, and then discharging the tail gas through a vacuum pump; when the environment is required, the waste water is washed by dilute alkali water and then discharged; after the distillation temperature and pressure reach the technological requirements, stabilizing the operation condition for 20min, and controlling the liquid level of the kettle to be not more than 1/2; sampling and analyzing indexes of viscosity, flash point and pH value, and discharging to a light component organic phase storage kettle after meeting the requirement; keeping the balance of the feeding of the kettle and the discharging of the water phase containing a small amount of organic matters and the organic phase containing light components;
the water body containing a small amount of light component organic matters in the water phase collection and storage kettle is further treated by a factory sewage treatment system;
pumping and metering the materials in the light component organic phase storage kettle, and feeding the materials into a light component organic phase refining kettle; starting stirring, and heating the kettle to 60-80 ℃; pumping the decolorizing agent from the charging bucket into a decolorizing agent metering kettle for later use; when the decoloring operation is started, firstly, nitrogen is used for purging a decoloring agent inlet pipeline to ensure smoothness; opening a discharge valve of the metering kettle, and allowing a decoloring agent to enter a material layer from the middle part of the kettle after the decoloring agent is limited and metered by a flow limiting orifice plate to perform chemical decoloring on the material; the decoloring operation is timed from the time when the decoloring agent enters the kettle, and is controlled within one hour; removing the peculiar smell in the materials while decoloring; after the decoloring operation is finished, pumping the liquefied inorganic base into a kettle according to the process dosage, neutralizing the material to be neutral, and stirring for 30min; discharging materials or carrying out the next operation; keeping normal stirring state, and pumping organic amine or a boronizing agent for amination or boronization after the temperature of the materials in the kettle is reduced to 60 ℃; and (5) after the operation is finished, analyzing related data, and discharging after the data are qualified.
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