CN214299950U - Waste liquid treatment device in TPO production technology - Google Patents

Abstract

The utility model relates to a waste liquid treatment device in TPO production technology, which comprises an esterification reaction kettle for mixing synthetic waste liquid, sulfuric acid and water and carrying out esterification reaction and a synthetic reaction kettle for mixing and reacting material phase and hydrogen peroxide, wherein the bottom of the esterification reaction kettle is provided with a first discharge hole for discharging the material phase, and the first discharge hole is connected with a material addition material port of the synthetic reaction kettle; in the device, the synthetic waste liquid in the esterification reaction kettle is subjected to esterification reaction and liquid separation to obtain a material phase; the material phase enters a synthesis reaction kettle, is mixed with hydrogen peroxide for reaction, is subjected to liquid separation and alkali washing to obtain tert-butyl peroxide; adopt above-mentioned waste liquid treatment device to realize the utilization of synthetic waste liquid as a resource, the product contains TPO synthesis workshop section oxidant, greatly reduced TPO production technology's raw and other materials purchase and technology manufacturing cost, has obvious economic value.

Description

Waste liquid treatment device in TPO production technology

Technical Field

The utility model belongs to photoinitiator preparation field relates to a waste liquid treatment device in TPO production technology.

Background

2,4, 6-trimethylbenzoyldiphenylphosphine oxide (TPO) is a high-efficiency free radical (I) type photoinitiator, has a wide absorption range, has an effective absorption peak value of 350-400nm, can generate two free radicals of benzoyl and phosphoryl after illumination, and can initiate polymerization, so that the photoinitiator has the characteristic of high photocuring speed, is suitable for thick film deep layer curing, has a photobleaching function, has the characteristic of no yellowing of a coating, can be used for a transparent coating, and is particularly suitable for products with low odor requirements. It is used alone in unsaturated polyester containing styrene system and has high initiating effect. It is widely used in the fields of ultraviolet curing coatings, printing inks, ultraviolet curing adhesives, optical fiber coatings, photoresists, photopolymerization printing plates, stereolithography resins, composite materials, tooth fillers and the like.

At present, synthetic wastewater in domestic TPO production process generally directly enters sewage treatment, but the treatment difficulty is extremely high due to high COD concentration; in addition, the desolventizing solvent after the oxidation reaction can be directly used for rectification and forward distillation after rectification, but most factories for rectification before rectification adopt a waste mode for treatment, secondary rectification is not needed, and the factories for dangerous waste with high quality are used for treatment before rectification, so that the cost is higher.

CN106883265A discloses a method for efficiently and cyclically synthesizing 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, comprising the following steps: a) selecting a vanadium source and a molecular sieve as reaction raw materials to prepare a vanadium molecular sieve catalyst; b) adding 2,4, 6-trimethyl benzaldehyde and diphenylphosphine oxide into a three-necked bottle filled with dichloromethane, and stirring at normal temperature to react to obtain a TPO intermediate; c) after the reaction in the step b) is finished, putting the three-necked bottle into a low-temperature water bath, cooling to 8-10 ℃, then sequentially adding the vanadium molecular sieve catalyst and the oxidant tert-butyl peroxide prepared in the step a) into the three-necked bottle, stirring and reacting for 0.5 hour, and then placing the three-necked bottle at normal temperature and continuously stirring for 3-5 hours to obtain a reaction solution; wherein the molar ratio of the TPO intermediate to the tert-butyl peroxide is 1: 1.2; d) filtering the reaction liquid obtained in the step c), recovering the vanadium molecular sieve, treating the obtained filtrate with a sodium thiosulfate aqueous solution to remove unreacted oxides, and carrying out post-treatment to obtain a TPO product; in the scheme, the tert-butyl alcohol peroxide is used in a large amount, and the tert-butyl alcohol generated by the reaction is mostly dissolved in water and enters waste liquid, but a subsequent treatment method for synthetic waste liquid is not provided.

Therefore, the development of a waste liquid treatment device in the TPO production process with low cost and resource utilization still has important significance.

SUMMERY OF THE UTILITY MODEL

The utility model aims to provide a waste liquid treatment device in TPO production technology, which comprises an esterification reaction kettle for mixing synthetic waste liquid, sulfuric acid and water and carrying out esterification reaction and a synthetic reaction kettle for mixing and reacting material phase and hydrogen peroxide, wherein the bottom of the esterification reaction kettle is provided with a first discharge hole for discharging the material phase, and the first discharge hole is connected with a material addition material port of the synthetic reaction kettle; in the device, the synthetic waste liquid in the esterification reaction kettle is subjected to esterification reaction and liquid separation to obtain a material phase; the material phase enters a synthesis reaction kettle, is mixed with hydrogen peroxide for reaction, is subjected to liquid separation and alkali washing to obtain tert-butyl peroxide; adopt above-mentioned waste liquid treatment device to realize the utilization of synthetic waste liquid as a resource, the product contains TPO synthesis workshop section oxidant, greatly reduced TPO production technology's raw and other materials purchase and technology manufacturing cost, has obvious economic value.

In order to achieve the purpose of the utility model, the utility model adopts the following technical proposal:

the utility model provides a waste liquid treatment device in TPO production technology, waste liquid treatment device is including being used for synthetic waste liquid, sulphuric acid and water mixture, carrying out esterification reaction's esterification reaction cauldron and the synthetic reation kettle who is used for material looks and hydrogen peroxide solution mixing reaction, esterification reaction cauldron's bottom is provided with the first discharge gate that is used for discharging material looks, first discharge gate is connected synthetic reation kettle's material phase material addition material mouth.

The esterification reaction kettle in the device is used for mixing sulfuric acid, water and synthetic waste liquid, carrying out esterification reaction to obtain tert-butyl hydrogen sulfate, and discharging a material phase through a first discharge port after standing; the first discharge port is connected with a material phase feeding port of a synthesis reaction kettle, the material phase is fed into the synthesis reaction kettle, the synthesis reaction kettle is used for reacting tert-butyl hydrogen sulfate in the material phase with hydrogen peroxide to obtain tert-butyl peroxide, and the reaction liquid is stood for layering to obtain a tert-butyl peroxide phase and an acid liquid phase; and (3) carrying out alkali washing on the subsequent tert-butyl peroxy-alcohol phase to obtain tert-butyl peroxy-alcohol, which can be recycled as an oxidant.

Preferably, the esterification reaction kettle is provided with a water inlet, a sulfuric acid inlet and a synthetic waste liquid feeding port, and the synthetic reaction kettle is provided with a hydrogen peroxide inlet, a material addition port and an alkali liquor inlet.

The water inlet, the sulfuric acid inlet and the synthetic waste liquid inlet are respectively used for adding water, sulfuric acid and synthetic waste liquid into the esterification reaction kettle.

The hydrogen peroxide adding port, the material phase feeding port and the alkali liquor adding port are respectively used for adding hydrogen peroxide, the material phase and alkali liquor into the synthesis reaction kettle.

Preferably, the material phase feeding port is provided with a valve, and the valve is preferably in a dropwise adding mode.

Among the operation technology of waste liquid treatment device, preferred material adopts dropwise add mode and hydrogen peroxide solution to mix mutually, and the material is injectd here and the material adds material mouth valve and is dropwise add formula valve, and its synthetic reaction's of being convenient for control avoids the emergence of peroxy tertiary butanol formation process reaction out of control phenomenon.

Preferably, stirring paddles are arranged in the esterification reaction kettle and the synthesis reaction kettle.

The utility model discloses the esterification reaction of well synthetic waste liquid, sulphuric acid and water needs to go on under the stirring condition, and the reaction of material phase and hydrogen peroxide solution also needs to go on under the stirring condition, all is provided with the stirring rake in consequently esterification reaction cauldron and the synthetic reation kettle.

Preferably, a cooling sleeve is arranged outside the esterification reaction kettle, and a saline coil is arranged in the cooling sleeve.

Esterification reaction cauldron is to the exothermic condition of sulphuric acid and water mixing process violent exothermic and follow-up esterification reaction, adopts salt solution to cool down the accuse temperature, and then can guarantee that the esterification process goes on smoothly.

Preferably, the water feeding port, the sulfuric acid feeding port and the synthetic waste liquid feeding port are respectively and independently provided with a valve. The valve arrangement facilitates control of the addition rate.

Preferably, the valve of the sulfuric acid adding port is a dropping valve.

The process of adding the sulfuric acid into the water is accompanied with violent heat release, a dripping mode is required, a valve of a sulfuric acid adding port is limited to be a dripping valve, the temperature control in the sulfuric acid adding process is facilitated, the temperature runaway phenomenon is avoided, and the reaction controllability is improved.

Preferably, the valve of the synthetic waste liquid feeding port is a dropwise adding valve.

The utility model discloses synthetic waste liquid and sulfuric acid solution's mixed esterification reaction's in-process, the rate of adding that needs control synthetic waste liquid is the dropwise add, and the valve of the preferred synthetic waste liquid charge door of here adopts dropwise add formula valve.

Preferably, the bottom of the esterification reaction kettle is also provided with a second discharge hole for discharging an organic phase.

When the synthetic waste liquid is the mixed liquid of rectification or the synthetic waste water and rectification, standing and layering are further carried out after the esterification reaction is finished to obtain a material phase and an organic phase, and the organic phase is discharged from the second discharge hole.

Preferably, the second discharge port is connected with a solvent storage tank.

Here, a solvent storage tank is provided, wherein the stored solvent can be recycled to the TPO synthesis section.

Preferably, a diaphragm pump is arranged between the second discharge port and the solvent storage tank.

The diaphragm pump is arranged to be convenient for conveying the organic phase in the esterification reaction kettle to the solvent storage tank.

Preferably, the device also comprises a tert-butyl hydrogen sulfate dripping tank, the first discharge port is connected with an inlet of the tert-butyl hydrogen sulfate dripping tank, and a discharge port of the tert-butyl hydrogen sulfate dripping tank is connected with a material phase feeding port on the synthesis reaction kettle.

The tert-butyl sulfate dripping tank is used for storing a material phase output by a first discharge port of the esterification reaction kettle, and is convenient for controlling the material phase to be input into the synthesis reaction kettle in a dripping mode, so as to control the stable operation of the waste liquid treatment device.

Preferably, a heat-insulating sleeve is arranged outside the synthesis reaction kettle, and a steam coil pipe and a water coil pipe are arranged in the heat-insulating sleeve.

The steam coil pipe is filled with steam and used for heating the synthesis reaction kettle; cold water is introduced into the water coil pipe and is used for cooling the synthesis reaction kettle; thereby being convenient for controlling the stability of the temperature of the reaction of the material phase and the hydrogen peroxide and the alkali washing process in the synthesis reaction kettle.

Preferably, an acid liquid phase discharge port, an alkali liquor outlet and a tert-butyl alcohol peroxide discharge port are arranged at the bottom of the synthesis reaction kettle.

Preferably, the device further comprises an acid liquor storage tank, an alkaline wash storage tank and a tert-butyl peroxide storage tank; the acid liquid phase discharge port is connected with the acid liquid storage tank, and the alkali liquor outlet is connected with the alkali liquor storage tank; the discharge port of the tert-butyl peroxide is connected with the tert-butyl peroxide storage tank.

In the waste liquid treatment process, the obtained acid liquid phase also contains hydrogen peroxide which can be decomposed to generate oxygen, so that the acid liquid storage tank is in a non-sealed design.

The acid liquid phase discharge port is used for discharging the acid liquid phase after standing and layering, and the acid liquid phase enters an acid liquid storage tank for storage; the alkali liquor outlet is used for discharging alkali liquor phase which is subjected to alkali washing and standing layering, and the alkali liquor phase enters an alkali liquor storage tank for storage; the discharge hole of the tert-butyl peroxy alcohol is used for discharging the tert-butyl peroxy alcohol and allowing the tert-butyl peroxy alcohol to enter a tert-butyl peroxy alcohol storage tank.

Preferably, the device further comprises a mixing tank, and an outlet of the mixing tank is connected with a synthetic waste liquid feeding port of the esterification reaction kettle.

In the operation process of the utility model, firstly preparing sulfuric acid solution in an esterification reaction kettle, then dripping synthetic waste liquid, and when the synthetic waste liquid is mixed liquid of synthetic waste water and rectification foredistillation, adding a mixing tank in front of the esterification reaction kettle for mixing the synthetic waste water and the rectification foredistillation, which has important significance for the stable operation of the operation process; and when the synthetic waste liquid only contains rectification front-end distillation or synthetic waste water, a material mixing tank is not needed.

Preferably, a stirring paddle is arranged in the mixing tank and is used for stirring and mixing the synthetic wastewater and the rectification front-end.

Preferably, the device further comprises a dripping tank, wherein an inlet of the dripping tank is connected with an outlet of the mixing tank, and an outlet of the dripping tank is connected with a synthetic waste liquid feed inlet of the esterification reaction kettle.

Because of the synthetic waste liquid and the sulphuric acid reaction in-process need control synthetic waste liquid's rate of addition, the setting is dripped the jar here and is regarded as the buffer tank, and it is to control synthetic waste liquid dropwise add rate, keeps the device steady operation to have an important role.

Preferably, the device further comprises a sulfuric acid storage tank, and an outlet of the sulfuric acid storage tank is connected with a sulfuric acid adding port of the esterification reaction kettle.

The sulfuric acid storage tank is used for storing sulfuric acid, and the outlet of the sulfuric acid storage tank is connected with the sulfuric acid adding port on the esterification reaction kettle, so that the adding speed of the sulfuric acid is convenient to control, and the stable operation of the device is ensured.

The operation process of the waste liquid treatment device comprises the following steps:

(1) mixing the synthetic waste liquid with sulfuric acid and water in an esterification reaction kettle, and carrying out esterification reaction to obtain a material phase; the synthetic waste liquid comprises rectification front-end and/or synthetic waste water;

(2) feeding the material phase obtained in the step (1) into a synthesis reaction kettle through a first discharge hole of the esterification reaction kettle and a material phase feeding hole of the synthesis reaction kettle, mixing the material phase with hydrogen peroxide, reacting, separating liquid to obtain an acid liquid phase and a tert-butyl peroxide phase, and discharging the acid liquid phase;

(3) and (3) in a synthesis reaction kettle, carrying out alkaline washing on the tert-butyl peroxide phase in the step (2), and separating liquid to obtain tert-butyl peroxide.

In the utility model, the 'rectification fore-run' refers to the fore-run part generated after the rectification of the solvent generated by the desolventizing unit after the oxidation reaction is finished in the TPO production process, and can not be directly used, and the 'synthetic wastewater' refers to the wastewater phase (containing water, salt, water-soluble impurities and water-soluble organic matters) generated by the washing unit after the oxidation reaction is finished in the TPO production process and is a mixed phase containing water and tert-butyl alcohol obtained after the distillation; the distillation step is aimed at obtaining a mixed phase containing water and tert-butanol, removing salt components contained in the raw water phase, and concentrating tert-butanol to facilitate the treatment by the wastewater treatment device; the analysis of the utility model shows that the tertiary butanol in the rectification and synthesis wastewater is the main component; in rectification, the content of the tertiary butanol can reach 25 wt% -35 wt%, the content of a solvent in a TPO synthesis section can reach 35 wt% -50 wt%, the balance is water, the content of the tertiary butanol in a wastewater phase can reach 10 wt% -20 wt%, the content of the tertiary butanol in the synthetic wastewater obtained after rectification can reach 80 wt% -90 wt%, and the balance is water; for the synthetic waste liquid, the treatment method of the waste water phase generally directly enters sewage treatment, but the treatment difficulty is high due to high COD concentration; for rectification, the further rectification cost is higher, so that secondary rectification is not generally performed, and the hazardous waste is selected to be treated by qualified hazardous waste treatment factories, so that the cost is higher; in order to solve the above-mentioned problem, and further reduce the manufacturing cost of raw and other materials purchase and TPO technology, realize TPO's green production, the utility model discloses based on above-mentioned analysis discovery has developed a TPO production technology in based on the waste liquid treatment device of oxidant cyclic utilization, it contains and is used for synthetic waste liquid (including rectification prefractionation and/or synthetic waste water), sulphuric acid and water mixture, carry out esterification reaction's esterification reaction cauldron, wherein, sulphuric acid reacts with tert-butyl alcohol in the synthetic waste liquid in the esterification reaction cauldron and generates tert-butyl hydrogen sulfate and dissolve in aqueous phase, after the reaction liquid stood, obtain layered material phase and organic phase (if contain in the synthetic waste liquid when rectification prefractionation, contain the organic phase, if only synthetic waste water, then do not include the organic phase); wherein the material phase contains acid liquor and tert-butyl hydrogen sulfate, which can be discharged from a first discharge port of the esterification reaction kettle and enter the synthesis reaction kettle, and the organic phase is a TPO synthesis section solvent (i.e. an oxidation section solvent) and can be discharged from a second discharge port of the esterification reaction kettle; in a synthesis reaction kettle, mixing the material phase with hydrogen peroxide, and reacting to obtain a tert-butyl peroxide phase; standing the reaction liquid, and then layering the reaction liquid into a tert-butyl peroxide phase and an acid liquid phase, wherein the acid liquid phase contains unreacted hydrogen peroxide, discharging after liquid separation, then performing alkali washing on the tert-butyl peroxide phase to obtain a mixed phase of alkali washing liquid and tert-butyl peroxide, and performing liquid separation to obtain tert-butyl peroxide; the obtained tert-butyl peroxide has high purity and can be recycled to a TPO production process to be used as an oxidant, so that the raw material purchase cost of the TPO production process is reduced, and the process cost is reduced.

Waste liquid treatment device has realized rectifying the utilization of forerunner and synthetic waste water among the TPO production technology, and the treatment cost is obviously reduced than further rectification, has realized the green production of TPO production technology, has reduced the useless production of danger, has reduced the useless treatment cost of danger, has practiced thrift the treatment cost, has further reduced TPO product cost.

The utility model discloses in the above-mentioned waste liquid treatment device use, if contain rectification fore-run in the synthetic waste liquid, can obtain the organic phase in step (1), it is TPO synthesis workshop section solvent, through waste liquid treatment device handles, and the purity of gained solvent is high, can reach more than 90%, and then can circulate and use, reduces solvent purchasing cost, and the purity of gained tert-butyl alcohol can reach more than 70%, can regard as TPO production workshop section oxidant circulation to use.

Preferably, the synthetic waste liquid is a mixed liquid of synthetic waste water and rectification before rectification.

The utility model discloses well preferred mixed liquid that adopts synthetic waste water and rectification prefraction is as the technology raw materials, and tert-butyl alcohol, TPO synthesis workshop section solvent and synthetic waste water in tert-butyl alcohol, TPO's recovery in the rectification prefraction in it can realize, and solvent recovery purity is high, can circulate to TPO synthesis workshop section and use, and the purity of gained tert-butyl alcohol peroxide is high, has further reduced the purchasing cost of raw and other materials.

Preferably, when the synthetic waste liquid is a mixed liquid of rectification or synthetic waste water and rectification, the step (1) further comprises liquid separation after the reaction is finished, so as to obtain a material phase and an organic phase.

Preferably, the synthetic waste liquid is obtained by rectification and mixing of synthetic waste water.

Synthetic waste liquid includes rectification forerun and/or synthetic waste water, all contains a large amount of tert-butyl alcohol in rectifying forerun and rectification for rectification forerun and synthetic waste water can mix and not layering, and then the utility model discloses an effect of handling in the lump with rectification forerun and synthetic waste water mixture. When the synthetic waste liquid is a mixed liquid of synthetic waste water and pre-rectification, it is preferable that the pre-rectification and the synthetic waste water are mixed before the synthetic waste liquid is mixed with sulfuric acid and water for esterification, and then mixed with sulfuric acid and water for esterification.

Before synthetic waste liquid mixes with sulphuric acid, water among the operation technology, still including testing its component content, including water and tert-butyl alcohol's content promptly, and then confirm the addition of each material.

The solvent for TPO synthesis section is selected from non-polar solvent, preferably at least one of dichloroethane, dichloromethane, toluene, cyclohexane, n-hexane and chlorobenzene.

The reaction equation in the operation process of the waste liquid treatment device is as follows:

in the above formula, sulfuric acid reacts with tert-butyl alcohol to generate tert-butyl hydrogen sulfate, and then reacts with hydrogen peroxide to generate tert-butyl peroxy-alcohol, thereby realizing resource utilization of the synthetic waste liquid.

Recycling the tert-butyl peroxide obtained in the step (3) as an oxidant to prepare TPO.

Preferably, the organic phase comprises at least one of dichloroethane, dichloromethane, toluene, cyclohexane, n-hexane, and chlorobenzene.

Preferably, the content of tert-butanol in the synthetic waste liquid of step (1) is 40 wt% to 90 wt%, such as 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt% or 85 wt%, etc., preferably 40 wt% to 50 wt%.

Preferably, the mass ratio of the tert-butanol to the sulfuric acid in the synthetic waste liquid in the step (1) is 0.4 to 0.5, for example, 0.42, 0.45, or 0.48, preferably 0.43 to 0.46.

The quality of injecing tert-butyl alcohol in waste liquid treatment device's the operation technology and the ratio of the addition of sulphuric acid are in above-mentioned within range, and it is favorable to sulphuric acid and tert-butyl alcohol's esterification reaction to fully go on, and then make tert-butyl alcohol turn into tert-butyl hydrogen sulfate completely to dissolve in the acidizing fluid, obtain the material phase, realize the maximum recovery rate of tert-butyl alcohol.

Preferably, the ratio of the mass of the water added in the step (1) to the mass of the sulfuric acid to the sum of the mass of the water in the synthesis waste liquid is 0.39 to 0.45, such as 0.4, 0.41, 0.42, 0.425, 0.43 or 0.44, and preferably 0.42 to 0.43.

The utility model discloses the source of operation technology normal water includes the water that contains in the water and the synthetic waste liquid by outside addition, waste liquid treatment technology injects water content in above-mentioned within range, and it is favorable to guaranteeing going on of esterification reaction to make gained tert-butyl hydrogen sulfate dissolve in the acidizing fluid, realize that the high purity of organic phase solvent is retrieved, and the separation obtains the material phase that is rich in tert-butyl hydrogen sulfate. In the step (1), if the amount of water in the synthesis waste liquid and the amount of sulfuric acid added satisfy the above conditions, water may not be externally added.

Preferably, the method for mixing the synthetic waste liquid with sulfuric acid and water in an esterification reaction kettle to carry out esterification reaction comprises the following steps:

(a) adding water into an esterification reaction kettle, and then adding sulfuric acid into the water to obtain a sulfuric acid solution;

(b) and (b) adding synthetic waste liquid into the sulfuric acid solution in the step (a) for reaction.

Among the operation technology of waste liquid treatment device, before carrying out esterification reaction, mix sulphuric acid and water in synthetic reation kettle, obtain sulphuric acid solution, later add synthetic waste liquid wherein and carry out esterification reaction, it is favorable to the high-efficient abundant going on of esterification reaction.

Preferably, the stirring paddle in the esterification reaction kettle is started during the addition of the sulfuric acid in the step (a), so that the addition of the sulfuric acid is accompanied by stirring.

Preferably, before adding the sulfuric acid in the step (a), the temperature reduction sleeve of the esterification reaction kettle is opened, and the temperature of the water is reduced to 5-15 ℃, such as 6 ℃, 8 ℃, 10 ℃, 12 ℃ or 14 ℃.

Preferably, the sulfuric acid in step (a) is added dropwise.

Preferably, the temperature during the addition of sulphuric acid in step (a) is controlled to be ≦ 40 deg.C, such as 25 deg.C, 30 deg.C or 35 deg.C.

Preferably, the temperature is reduced to 20-30 ℃, for example 22 ℃, 25 ℃ or 28 ℃ after the sulfuric acid is added in the step (a).

Because the process of adding sulphuric acid into water is accompanied with violent heat release, the utility model discloses a dropwise add mode to along with the cooling, the utility model discloses preferred adoption salt solution cooling.

Preferably, the temperature is controlled to 20-30 ℃, for example, 22 ℃, 25 ℃ or 28 ℃ during the process of adding the synthetic waste liquid in the step (b).

Preferably, the synthetic waste liquid is added in step (b) in a dropwise manner.

Preferably, the addition of the synthesis waste liquid in step (b) is accompanied by stirring.

Preferably, after the synthetic waste liquid is added in the step (b), the stirring is continued; preferably, the stirring is continued for a period of time of 0.2 to 1 hour, e.g., 0.5 hour, 0.8 hour, etc.

Preferably, the temperature of the continuous stirring is 20-30 ℃, such as 22 ℃, 25 ℃ or 28 ℃.

Preferably, after the esterification reaction in step (1) is finished, still standing and heat preservation are further included before liquid separation.

Preferably, the standing and heat preservation time is 0.2-2 h, such as 0.5h, 1h or 1.5 h.

Preferably, the temperature of the standing heat preservation is 20-30 ℃, such as 22 ℃, 25 ℃ or 28 ℃ and the like.

Preferably, in the step (2), the method for reacting the material phase obtained in the step (1) by entering the synthesis reaction kettle through the first discharge port of the esterification reaction kettle and the material phase feeding port of the synthesis reaction kettle and mixing the material phase with hydrogen peroxide comprises the following steps: adding the material phase into hydrogen peroxide, and carrying out heat preservation reaction.

Preferably, the temperature of the heat preservation reaction is 39-41 ℃, for example 40 ℃ and the like.

In the operation process of the device, the temperature of the thermal insulation reaction between the hydrogen peroxide and the material is controlled within the range, which is beneficial to the full reaction and reduces the operation risk; the temperature of the peroxidation reaction is not suitable to be too high, the reaction is not controllable easily due to the too high temperature, the temperature rises suddenly, the material washing occurs, the hydrogen peroxide is decomposed, and the process risk is increased.

Preferably, the manner of adding the material phase is dropwise.

Preferably, the concentration of the hydrogen peroxide in the step (2) is 20 wt% to 30 wt%, such as 22 wt%, 25 wt% or 28 wt%, etc., preferably 24 wt% to 28 wt%.

Preferably, the ratio of the mass of the hydrogen peroxide in the step (2) to the mass of the tertiary butanol in the synthetic waste liquid in the step (1) is 3 to 3.5, for example, 3.1, 3.2, 3.3 or 3.4, and preferably 3.2 to 3.3.

Among the operation technology of waste liquid treatment device, the concentration and the addition of control hydrogen peroxide solution are in above-mentioned within range, and it is favorable to going on fully of reaction, and avoids hydrogen peroxide solution addition to lead to the fact follow-up potential safety hazard excessively.

Preferably, before the material phase in the step (1) is added into hydrogen peroxide, a heat-insulating sleeve of a synthesis reaction kettle is opened to heat the hydrogen peroxide to 36-39 ℃, for example, 37 ℃ or 38 ℃.

Preferably, the heat preservation reaction is continued after the material phase is added, the temperature of the heat preservation reaction is preferably 39-41 ℃, for example 40 ℃, and the time of the heat preservation reaction is preferably 1-2 h, for example 1.5 h.

Preferably, the reaction in step (2) is carried out with stirring.

Preferably, after the reaction in step (2), still standing is further included before liquid separation.

Preferably, the standing time is 30-60min, such as 35min, 40min, 45min, 50min or 55min, etc.

Preferably, the alkali washing method in the step (3) comprises adding alkali liquor into the tert-butyl peroxy-alcohol phase and keeping the temperature for reaction.

Preferably, the lye comprises an aqueous sodium carbonate solution and/or an aqueous sodium bicarbonate solution.

The utility model adopts the weak base to carry out alkaline cleaning, and can effectively remove acidic materials in the product.

Preferably, the concentration of the lye is 8-12 wt%, such as 9 wt%, 10 wt% or 11 wt% etc.

Preferably, the ratio of the mass of the lye to the mass of the sulfuric acid is 0.18 to 0.22, such as 0.19, 0.2 or 0.21.

Concentration and the addition of alkali lye satisfy above-mentioned condition, it is favorable to realizing fully washing with alkaline, and then obtains high-purity tert-butyl alcohol peroxide.

Preferably, the temperature of the incubation reaction is 20 to 28 ℃, for example, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃ or 27 ℃, and the like.

Alkali wash process control temperature among waste liquid treatment device's the operation technology is in above-mentioned within range, and it is favorable to guaranteeing the stability of tert-butyl alcohol peroxide in alkali wash process, promotes the technological process controllability, reduces the operation risk.

Preferably, the time of the heat preservation reaction is 0.2-1h, such as 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h or 0.9 h.

Preferably, the alkali wash is accompanied by agitation.

Preferably, after the alkaline washing, still standing is further included before liquid separation, and the still standing time is preferably 1 to 1.5 hours, such as 1.1 hour, 1.2 hours, 1.3 hours or 1.4 hours.

As an operation process of the preferable waste liquid treatment apparatus of the present invention, the operation process comprises the following steps:

adding water into an esterification reaction kettle, cooling to 5-15 ℃, then starting a stirring paddle, dropwise adding sulfuric acid under the stirring condition, controlling the temperature to be less than or equal to 40 ℃, and after the dropwise adding of the sulfuric acid is finished, cooling to 20-30 ℃ to obtain a sulfuric acid solution;

(II) dripping synthetic waste liquid with the tert-butyl alcohol content of 40-90 wt% into the sulfuric acid solution obtained in the step (I) in the esterification reaction kettle under the stirring condition, controlling the temperature to be 20-30 ℃, continuing to stir for 0.2-1h under heat preservation after dripping is finished, then closing stirring, and standing and preserving heat for 0.2-2 h; opening a material discharging valve of the esterification reaction kettle, and discharging a material phase in the esterification reaction kettle;

(III) adding hydrogen peroxide into a synthesis reaction kettle, starting a heat-insulating sleeve of the synthesis reaction kettle, heating the hydrogen peroxide in the kettle to 36-39 ℃, dropwise adding the material phase obtained in the step (II) into the synthesis reaction kettle under the condition of stirring, controlling the temperature to be 39-41 ℃ in the dropwise adding process, continuing stirring for 1-2 hours under heat insulation after dropwise adding is finished, stopping stirring, and standing for 30-60 minutes; then opening a discharge valve of the synthesis reaction kettle, and discharging the acid liquid phase to obtain a tert-butyl peroxide phase;

(IV) dropwise adding alkali liquor into the tert-butyl peroxy alcohol phase in the step (III), after dropwise adding, keeping the temperature at 20-28 ℃, stirring for 0.2-1h, turning off stirring, standing for 1-1.5 h, and discharging the alkali liquor phase to obtain the tert-butyl peroxy alcohol.

Compared with the prior art, the utility model discloses following beneficial effect has:

(1) the waste liquid treatment device realizes the recovery of the tert-butyl alcohol in the synthetic waste liquid of the TPO synthetic section, converts the tert-butyl alcohol into the peroxy-tert-butyl alcohol, and circularly uses the peroxy-tert-butyl alcohol-peroxy-tert-butyl alcohol as the oxidant of the TPO synthetic section, thereby realizing the recycling of the peroxy-tert-butyl alcohol-peroxy-tert-butyl alcohol oxidant in the TPO production process and further reducing the purchase cost of raw materials;

(2) when the synthetic waste liquid adopted by the waste liquid treatment device of the utility model is the mixed liquid of rectification front-end distillation or synthetic waste water and rectification front-end distillation, the recovery of TPO synthetic workshop section solvent is realized, the solvent purchasing cost is further reduced, and the waste liquid treatment cost is reduced;

(3) waste liquid treatment device has not only saved the treatment cost of synthetic waste water and rectification prefractionation, has more practiced thrift the purchasing cost of part raw materials to greatly reduced manufacturing cost, promoted the competitiveness of enterprise's product.

Drawings

FIG. 1 is a schematic view of a waste liquid treatment apparatus according to an embodiment of the present invention;

FIG. 2 is a schematic representation of a portion of the synthesis section of TPO;

1-esterification reaction kettle, 2-synthesis reaction kettle, 3-first discharge port, 4-second discharge port, 5-water inlet, 6-sulfuric acid inlet, 7-synthetic waste liquid inlet, 8-solvent storage tank, 9-material addition port, 10-tert-butyl hydrogen sulfate dropping tank, 11-sulfuric acid storage tank, 12-mixing tank, 13-dropping tank, 14-hydrogen peroxide inlet, 15-alkali liquid inlet, 16-acid liquid phase discharge port, 17-alkali liquid outlet, 18-tert-butyl peroxide discharge port, 19-acid liquid storage tank, 20-alkaline washing liquid storage tank, 21-tert-butyl peroxide storage tank, 22-stirring paddle, 23-cooling sleeve and 24-heat preservation sleeve.

Detailed Description

The technical solution of the present invention will be further explained by the following embodiments. It should be understood by those skilled in the art that the described embodiments are merely provided to assist in understanding the present invention and should not be construed as specifically limiting the present invention.

As one of the implementation modes, the schematic diagram of the device of the waste liquid treatment process of the present invention is shown in fig. 1, the device includes an esterification reaction kettle 1 and a synthesis reaction kettle 2, the bottom of the esterification reaction kettle 1 is provided with a first discharge port 3 and a second discharge port 4, the first discharge port 3 is connected to a material addition port 9 of the synthesis reaction kettle, and the esterification reaction kettle 1 is further provided with a water addition port 5, a sulfuric acid addition port 6 and a synthesis waste liquid addition port 7;

the second discharge port 4 is used for discharging an organic phase obtained by standing and layering, the second discharge port 4 is connected with a solvent storage tank 8, the solvent storage tank is used for storing the organic phase, and a diaphragm pump is arranged between the second discharge port 4 and the solvent storage tank 8; the first discharge hole 3 is connected with a material phase feeding hole 9 on the synthesis reaction kettle 2 and is used for feeding a material phase into the synthesis reaction kettle; the device also comprises a tert-butyl hydrogen sulfate dripping tank 10, wherein the inlet of the tert-butyl hydrogen sulfate dripping tank 10 is connected with the first discharge port 3, and the outlet of the tert-butyl hydrogen sulfate dripping tank 10 is connected with the material addition material port 9;

the device also comprises a sulfuric acid storage tank 11, wherein an outlet of the sulfuric acid storage tank 11 is connected with a sulfuric acid adding port 6 of the esterification reaction kettle 1;

the device also comprises a mixing tank 12 and a dripping tank 13, wherein the mixing tank is used for mixing and rectifying the prefractionation and the synthetic wastewater, an outlet of the mixing tank is connected with an inlet of the dripping tank 13, and an outlet of the dripping tank 13 is connected with a synthetic wastewater feed inlet 7 of the esterification reaction kettle 1;

the synthesis reaction kettle 2 is provided with a material addition port 9, a hydrogen peroxide addition port 14 and an alkali liquor addition port 15; respectively adding a material phase, hydrogen peroxide and alkali liquor into the synthesis reaction kettle; the bottom of the synthesis reaction kettle 2 is provided with an acid liquid phase discharge port 16, an alkali liquid outlet 17 and a tert-butyl peroxide discharge port 18 which are respectively used for discharging acid liquid phase, alkali liquid phase and tert-butyl peroxide products.

The acid liquor phase discharge port 16, the alkali liquor outlet 17 and the tert-butyl peroxide discharge port 18 are respectively connected with an acid liquor storage tank 19, an alkali liquor storage tank 20 and a tert-butyl peroxide storage tank 21.

Stirring paddles 22 are arranged in the esterification reaction kettle, the synthesis reaction kettle and the material mixing tank;

a cooling sleeve 23 is arranged outside the esterification reaction kettle, and a brine coil is arranged in the cooling sleeve 23;

the synthesis reaction kettle is externally provided with a heat insulation sleeve 24, and a steam coil pipe and a water coil pipe are arranged in the heat insulation sleeve 24.

The use method of the device is as follows:

(a) adding water into the esterification reaction kettle from a water adding port of the esterification reaction kettle, wherein the water can be added by adopting a diaphragm pump or vacuum feeding; then starting a stirring paddle for stirring, introducing saline water into the cooling sleeve to cool to 5-15 ℃, slowly opening a sulfuric acid dropping valve, and adding sulfuric acid into the esterification reaction kettle from a sulfuric acid adding port; controlling the temperature below 40 ℃, closing a sulfuric acid dripping valve after dripping is finished, and cooling to 20-30 ℃;

(b) opening a dropping valve of a synthetic waste liquid feeding port, releasing heat in the dropping process, and controlling the temperature to be 20-30 ℃ through a cooling sleeve; after the dripping is finished, closing the dripping valve, continuing to keep the temperature and stir, then closing the stirring, standing, keeping the temperature and layering;

(c) respectively opening a valve of a second discharge port and a valve of a first discharge port of the esterification reaction kettle, opening a diaphragm pump, discharging an organic phase, feeding the organic phase into a solvent storage tank, discharging a material phase in the esterification reaction kettle, and feeding the material phase into a tert-butyl hydrogen sulfate dropping tank;

(d) adding hydrogen peroxide into the synthesis reaction kettle from a hydrogen peroxide adding port of the synthesis reaction kettle, starting a heat insulation sleeve for heating, heating the hydrogen peroxide in the kettle to 36-39 ℃, and closing the heating; opening a tert-butyl hydrogen sulfate dropping tank valve, and dropping a material phase containing tert-butyl hydrogen sulfate; the heat release is slow in the dropping process, but the duration is long; starting circulating water of a heat-insulating sleeve, cooling, controlling the temperature to be 39-41 ℃ in the dripping process, keeping the temperature and stirring after dripping is finished, then closing the stirring, standing, layering, wherein the lower layer is an acid liquid phase, and the upper layer is a tert-butyl peroxide phase;

(e) opening a valve of an acid liquid phase discharge port of the synthesis reaction kettle, separating the lower layer of acid liquid phase into an acid liquid storage tank, wherein the acid liquid storage tank cannot be sealed because unreacted hydrogen peroxide is contained in the acid liquid phase and oxygen is generated by decomposition of the hydrogen peroxide, and closing the valve of the acid liquid phase discharge port after the liquid separation is finished;

(f) starting a stirring paddle of the synthesis reaction kettle for stirring, adding alkali liquor into the synthesis reaction kettle from an alkali liquor adding port, keeping the temperature at 20-28 ℃ for stirring after the addition is finished, then closing the stirring, standing for layering, separating the alkali liquor into an alkali liquor storage tank, then closing the alkali liquor outlet valve, starting a discharge port valve of the tert-butyl peroxide, enabling the tert-butyl peroxide to enter the tert-butyl peroxide storage tank, and then closing the discharge port valve of the tert-butyl peroxide.

When the synthetic waste liquid is rectification waste water or synthetic waste water, the material mixing operation is not required to be carried out through a material mixing tank; when the synthetic waste liquid is a mixed liquid of synthetic waste water and pre-rectification, the pre-rectification and the synthetic waste water are firstly added into a mixing tank, stirred and mixed, and then injected into an esterification reaction kettle through a dropping tank.

The following examples all adopt the above waste liquid treatment process;

as shown in fig. 2, the TPO production process flow is exemplary, the TPO synthesis section includes an addition section and an oxidation section which are sequentially arranged, after the oxidation section, a mixed phase containing a product TPO and a solvent is obtained, then the mixed phase is washed and separated to obtain a waste water phase and an organic phase, the organic phase is desolventized, crystallized and dried to obtain a product TPO, and meanwhile, the desolventized solvent is rectified by a rectifying tower to obtain a rectification front-end and a solvent front-end, the solvent front-end can be directly recycled, and the rectification front-end (containing tert-butyl alcohol and the solvent of the TPO oxidation section) can be used as a raw material of the synthetic waste liquid treatment process of the present invention; in addition, the above-mentioned waste water phase that obtains after the distillation the utility model discloses synthetic waste water, it contains water and tert-butyl alcohol.

Example 1

In the embodiment, the synthetic waste liquid is a mixed liquid of synthetic waste water and rectification before rectification, and the synthetic waste liquid comprises 45 wt% of tert-butyl alcohol, 26 wt% of water and the balance of dichloroethane (TPO oxidation reaction section solvent) based on 100% of the synthetic waste liquid.

The composition of the synthetic waste liquid is obtained by testing through a gas chromatography method;

the embodiment provides a waste liquid treatment process of a TPO production process, which comprises the following steps:

adding 133.44kg of water into an esterification reaction kettle, cooling to 10 ℃, then dropwise adding 770kg of anhydrous sulfuric acid under the stirring condition, controlling the temperature to be less than or equal to 40 ℃, and cooling to 25 ℃ after the dropwise adding of the sulfuric acid is finished to obtain a sulfuric acid solution;

(II) dropwise adding 756kg of the synthetic waste liquid into the sulfuric acid solution obtained in the step (I) under the stirring condition, controlling the temperature to be 25 ℃, continuing to keep the temperature and stir for 0.5h after dropwise adding, then closing stirring, and standing and keeping the temperature for 0.5 h; opening a discharge valve of the esterification reaction kettle, discharging an organic phase and a material phase in the esterification reaction kettle, and separating the material phase into tert-butyl hydrogen sulfate dripping tanks;

(III) adding 1100kg of hydrogen peroxide with the concentration of 26 wt% into a synthesis reaction kettle, starting the synthesis reaction kettle for heating, heating the hydrogen peroxide in the kettle to 38 ℃, dropwise adding the material phase obtained in the step (II) into the synthesis reaction kettle under the condition of stirring, controlling the temperature at 40 ℃ in the dropwise adding process, continuing stirring for 1.5 hours under heat preservation after dropwise adding is finished, stopping stirring, and standing for 40 minutes; then opening a discharge valve of the synthesis reaction kettle, and discharging the lower acid liquid phase to obtain an upper tert-butyl peroxide phase;

(IV) dropwise adding 150kg of sodium carbonate solution with the concentration of 10 wt% into the tert-butyl peroxy alcohol phase in the step (III), keeping the temperature at 26 ℃ and stirring for 0.5h after dropwise adding, closing stirring, standing for 1.5h, and discharging the lower alkali liquor phase to obtain the tert-butyl peroxy alcohol.

Example 2

This example differs from example 1 in that the mass of sulfuric acid was replaced with 680kg, i.e. the mass ratio of tert-butanol to sulfuric acid was 0.5, the amount of water added was replaced with 95kg, and the other parameters and conditions were exactly the same as in example 1.

Example 3

This example differs from example 1 in that the mass of sulfuric acid was replaced with 850kg, i.e. the mass ratio of tert-butanol to sulfuric acid was 0.4, the amount of water added was replaced with 168kg, and the other parameters and conditions were exactly the same as in example 1.

Example 4

The difference between the embodiment and the embodiment 1 is that the synthetic waste liquid is synthetic waste water, the mass of the synthetic waste liquid is 100%, the tertiary butanol is 85 wt%, and the rest is water;

replacing the adding amount of water in the step (I) with 270 kg; the amount of synthetic waste liquid added in step (II) was replaced with 400kg, and other parameters and conditions were exactly the same as those in example 1.

Example 5

This example differs from example 1 in that the temperature controlled in step (II) was replaced by 40 ℃ and the other parameters and conditions were exactly the same as in example 1.

Example 6

This example differs from example 1 in that the temperature during the addition of the material phase in step (III) is controlled at 50 ℃ and the other parameters and conditions are exactly the same as those in example 1.

Example 7

The difference between the embodiment and the embodiment 1 is that the synthetic waste liquid adopts rectification front distillation, based on the mass of the synthetic waste liquid as 100%, the tertiary butanol is 30 wt%, the dichloroethane is 40 wt%, and the balance is water;

in the step (I), water is not added; the amount of synthetic waste liquid added in step (II) was replaced with 1133kg, and other parameters and conditions were exactly the same as those in example 1.

And (3) performance testing:

taking the organic phase (dichloroethane) in the step (II) in the embodiment, and carrying out purity test;

taking the tert-butyl peroxy alcohol obtained in the step (IV) in the embodiment for purity test;

the method adopted by the test is gas chromatography; the above test results are shown in table 1;

TABLE 1

In the above table, "-" indicates that the content is empty;

as can be seen from the above table 1, the waste liquid treatment process of the present invention realizes the resource utilization of waste liquid in the TPO production process, the product contains TPO synthesis section solvent and oxidant, and the obtained product has high purity and can be recycled; thereby realizing the green TPO production process.

It can be seen from comparative examples 1 and 2-3 that, in the waste liquid treatment process, when the mass ratio of tert-butyl alcohol to sulfuric acid in the synthetic wastewater is 0.4-0.5, the purity of the obtained product is higher, and the further preferred mass ratio is 0.43-0.46.

Comparative examples 1 and 4 can be seen that the waste liquid treatment process is suitable for the treatment of synthetic wastewater, and the purity of the obtained product is higher. The recovery of the tertiary butanol and the solvent in the rectification can not be realized by only adopting the synthetic wastewater.

It can be seen from comparative examples 1 and 5 that, in the waste liquid treatment process, the temperature of the esterification reaction in the step (II) is controlled at 20-30 ℃, and the treatment effect is more excellent.

It can be seen from comparative examples 1 and 6 that, in the waste liquid treatment process, the reaction temperature is controlled at 39-41 ℃ in the step (III), and the treatment effect is better.

It can be seen from comparative examples 1 and 7 that the waste liquid treatment process is suitable for the treatment of rectification and the purity of the obtained product is higher.

The applicant states that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and those skilled in the art should understand that any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure scope of the present invention.

Claims (10)

1. The utility model provides a waste liquid treatment device in TPO production technology, its characterized in that, waste liquid treatment device is provided with the first discharge gate that is used for discharging material looks including esterification reaction cauldron and synthetic reation kettle, esterification reaction cauldron's bottom, first discharge gate is connected synthetic reation kettle's material phase material addition mouth.

2. The waste liquid treatment apparatus according to claim 1, wherein the esterification reaction vessel is provided with a water inlet, a sulfuric acid inlet, and a synthetic waste liquid inlet, and the synthetic reaction vessel is provided with a hydrogen peroxide inlet, a material addition port, and an alkali liquid inlet.

3. The apparatus of claim 1, wherein stirring paddles are disposed in both the esterification reaction vessel and the synthesis reaction vessel.

4. The waste liquid treatment device of claim 1, wherein a cooling jacket is arranged outside the esterification reaction kettle, and a saline water coil is arranged in the cooling jacket.

5. The waste liquid treatment device of claim 1, further comprising a tert-butyl hydrogen sulfate dropping tank, wherein the first discharge port is connected with an inlet of the tert-butyl hydrogen sulfate dropping tank, and a discharge port of the tert-butyl hydrogen sulfate dropping tank is connected with a material addition material port on the synthesis reaction kettle.

6. The waste liquid treatment apparatus according to claim 1, wherein a thermal insulation jacket is provided outside the synthesis reaction vessel, and a steam coil and a water coil are provided inside the thermal insulation jacket.

7. The waste liquid treatment apparatus according to claim 1, wherein an acid liquid phase outlet, an alkali liquid outlet and a tert-butyl peroxide outlet are provided at the bottom of the synthesis reaction kettle.

8. The apparatus for treating waste liquid according to claim 7, further comprising an acid storage tank, an alkaline washing liquid storage tank, and a tert-butyl peroxy-alcohol storage tank; the acid liquid phase discharge port is connected with the acid liquid storage tank, and the alkali liquor outlet is connected with the alkali liquor storage tank; the discharge port of the tert-butyl peroxide is connected with the tert-butyl peroxide storage tank.

9. The waste liquid treatment apparatus according to claim 1, further comprising a mixing tank, wherein an outlet of the mixing tank is connected to a synthetic waste liquid feed port of the esterification reaction vessel.

10. The waste liquid treatment apparatus according to claim 9, further comprising a dripping tank, wherein an inlet of the dripping tank is connected with an outlet of the mixing tank, and an outlet of the dripping tank is connected with a synthetic waste liquid feed inlet of the esterification reaction kettle.

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