CN114180773A - Novel post-treatment process of working solution for producing hydrogen peroxide by anthraquinone method - Google Patents

Novel post-treatment process of working solution for producing hydrogen peroxide by anthraquinone method Download PDF

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CN114180773A
CN114180773A CN202111478887.1A CN202111478887A CN114180773A CN 114180773 A CN114180773 A CN 114180773A CN 202111478887 A CN202111478887 A CN 202111478887A CN 114180773 A CN114180773 A CN 114180773A
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alkali
tower
fiber membrane
working solution
solution
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庞飞
许颖睿
马俊
柴春玲
白立光
沈冲
赵晓东
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Liming Research Institute of Chemical Industry Co Ltd
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Liming Research Institute of Chemical Industry 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F2101/10—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32

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Abstract

The invention relates to a novel post-treatment process of working solution for producing hydrogen peroxide by an anthraquinone process, which comprises a fiber membrane alkali tower, an alkali settler, an alkali evaporator, a concentrated alkali solution storage tank, a clay bed and a working solution storage tank, wherein the working solution from an extraction process and the concentrated alkali solution from the concentrated alkali storage tank pass through the fiber membrane alkali tower together and fully react in the fiber membrane alkali tower; discharging the reacted working solution and dilute alkali solution from the fiber membrane alkali tower into an alkali settler; the dilute alkali liquor flows from the alkali settler to the alkali evaporator, the concentrated alkali liquor is formed again after the water is removed in the alkali evaporator, and the concentrated alkali liquor flows to the concentrated alkali liquor storage tank and then enters the fiber membrane alkali tower to continue to contact and react with the working solution; the working solution flows from the alkali settler to the clay bed, flows into the working solution storage tank after being treated by the clay bed, and then enters the hydrogenation process. The invention obviously improves the mass transfer efficiency of the working solution and the alkali liquor and reduces the liquid holdup of the existing alkali treatment unit.

Description

Novel post-treatment process of working solution for producing hydrogen peroxide by anthraquinone method
Technical Field
The invention relates to a novel post-treatment process of a working solution for producing hydrogen peroxide by an anthraquinone process.
Background
The hydrogen peroxide is a green oxidant and has wide application in the field of chemical industry. Currently, hydrogen peroxide is generally produced by an anthraquinone method in industry, wherein a working solution is formed by a carrier and a solvent according to a certain proportion in the anthraquinone method process, 2-ethyl anthraquinone, 2-butyl anthraquinone, 2-amyl anthraquinone or a mixture of the 2-ethyl anthraquinone, the 2-butyl anthraquinone and the 2-amyl anthraquinone is generally used as the carrier, and a mixture of heavy aromatic hydrocarbon, trioctyl phosphate, o-methylcyclohexyl acetate, tetrabutyl urea and the like is used as the solvent. The working solution circulates in the system according to the sequence of hydrogenation, oxidation, extraction and post-treatment, and hydrogen peroxide is produced. In the hydrogenation process, the working solution is subjected to hydrogenation reaction under the action of a catalyst to obtain a hydrogenation solution; in the oxidation process, reacting the hydrogenated liquid with oxygen to obtain an oxidized liquid; in the extraction process, hydrogen peroxide in the oxidation liquid is extracted by water to obtain a hydrogen peroxide crude product, and working liquid flowing out of the extraction process is called raffinate; in the post-treatment process, the raffinate enters a working solution storage tank after being dehydrated, subjected to hydrogen peroxide removal and degraded matter regeneration, so that one cycle is completed.
Wherein, too much hydrogen peroxide remained in the extracted working solution can influence the activity of the hydrogenation catalyst, and the hydrogen peroxide is easy to decompose, so that the oxygen generated by decomposition is gathered in the tower, thereby having potential safety hazard. Moisture can also adversely affect the activity of the palladium catalyst in the hydrogenation reaction. In addition, with the increase of the cycle number, the anthraquinone substances gradually form degradation products such as hydroxyl anthrone, octahydroanthraquinone, epoxy anthraquinone and the like, so that the composition of the working solution gradually changes, and the system stability is influenced. Therefore, the post-treatment of the extracted working solution is of great importance.
At present, the post-treatment process of the hydrogen peroxide process by the anthraquinone process in industry generally adopts the methods of coalescence separation, alkali liquor treatment, clay bed treatment filled with activated alumina, vacuum flash evaporation and the like to treat working solution, and two or more of the processes can also be combined. In the alkali liquor treatment process, aqueous solution of alkaline substances such as potassium carbonate, sodium hydroxide and the like is generally used as a treating agent, concentrated alkali liquor enters from top to bottom and fills a packing layer of an alkali tower, and working solution passes through the alkaline solution from bottom to top to complete the processes of hydrogen peroxide decomposition, working solution dehydration, regeneration and the like. The working solution flowing out from the top of the alkali tower enters an alkali settler to separate entrained alkali liquor (or enters a washing tower to wash and remove the entrained alkali liquor), and then enters a clay bed filled with activated alumina for further purification treatment. Along with the circulation of the working solution, the concentrated alkali solution is gradually diluted, and the dilute alkali solution is continuously or periodically discharged. When the alkali liquor is potassium carbonate aqueous solution, the dilute alkali liquor returns to the alkali tower for continuous use after the water in the dilute alkali liquor is removed by the alkali evaporator; when the alkali liquor is sodium hydroxide aqueous solution, the dilute alkali liquor is directly discharged out of the system. Fresh concentrated alkali liquor can be supplemented into the alkali tower according to the consumption condition of the alkali liquor.
The types of caustic towers currently used in industry are generally packed towers, and these types of caustic towers have the following disadvantages:
firstly, an alkali tower and an alkali settler are large in size, and a large amount of working solution stays in an alkali treatment unit;
secondly, the working solution is easy to carry with alkali liquor, and the alkali settler cannot completely separate the alkali liquor, so that the consumption of active alumina is high in the subsequent clay bed treatment process, and potential safety hazards are caused;
and thirdly, the working solution cannot be fully mixed in the alkali liquor, so that the working solution is not fully contacted with the alkali liquor, and the effects of dehydration, hydrogen peroxide removal and degradation product regeneration are easy to fluctuate. After the contact between the working solution and the alkali liquor is enhanced by using the traditional means, the emulsification of the working solution and the alkali liquor is easily caused, the two phases are difficult to separate, and great difficulty is brought to the subsequent alkali sedimentation.
For this reason, researchers have made process improvements. Chinese patent CN101618859A discloses a drying tower with an alkali liquor distributor, which uses a liquid injection method to promote the contact between the alkali liquor and the working liquid, and improves the treatment capacity, but does not significantly reduce the volume of the alkali tower. Chinese patent CN206457253U discloses an alkali liquid separator for a process for preparing hydrogen peroxide by an anthraquinone process, wherein positive and negative staggered and superposed corrugated fillers are adopted to promote the aggregation of alkali liquid drops carried in a working solution, but the promotion effect on two-phase contact reaction is general.
The fiber filaments are filled at the contact part of the oil phase and the water phase, so that the contact and mass transfer of the oil phase and the water phase can be promoted, but the mass transfer of the oil phase and the water phase in a non-dispersive state is ensured, and the subsequent separation of the oil phase and the water phase is facilitated. For example, in the field of liquefied gas alkali washing desulfurization, fiber yarns are filled in a reactor, liquefied gas is attached to the fiber yarns to form a liquid film, so that the contact of oil and water phases is promoted, and the desulfurization efficiency is improved. The technology generally combines a fiber membrane reactor and an alkali separator for use, the fiber membrane reactor is arranged at the top of a horizontal alkali separator, and no gas is discharged in the whole process (Tongren can, application of a fiber membrane hydrogen sulfide removal process in liquefied gas hydrogen sulfide removal [ J ]. petrochemical technology and application, 2018,36(04): 255-257.). In the anthraquinone process hydrogen peroxide production technology, the working solution contains hydrogen peroxide, the hydrogen peroxide is decomposed in the alkali treatment process to generate oxygen, and the generation of gas causes the following problems: the oil-water two phases are prevented from forming a liquid film, and mass transfer is influenced; leading to the foaming of the working fluid and the entrainment in severe cases. The existing fiber membrane technology can not be directly used in the field of hydrogen peroxide production by an anthraquinone method.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a novel post-treatment process of working solution for producing hydrogen peroxide by an anthraquinone process, which comprises a fiber membrane alkali tower (1), an alkali settler (2), an alkali evaporator (3), a concentrated alkali solution storage tank (4), a clay bed (7) and a working solution storage tank (8), wherein the working solution from an extraction process and the concentrated alkali solution from the concentrated alkali storage tank (4) pass through the fiber membrane alkali tower (1) together and fully react in the fiber membrane alkali tower (1); discharging the reacted working solution and the dilute alkali solution from the fiber membrane alkali tower (1) to enter an alkali settler (2), and rapidly separating two phases in the alkali settler (2); the dilute alkali liquor flows to the alkali evaporator (3) from the alkali settler (2), the concentrated alkali liquor is formed again after the water is removed in the alkali evaporator (3), and the concentrated alkali liquor flows to the concentrated alkali liquor storage tank (4) and then enters the fiber membrane alkali tower (1) to continuously contact and react with the working solution; the working solution flows from the alkali settler (2) to the clay bed (7), flows into the working solution storage tank (8) after being treated by the clay bed (7), and then enters the hydrogenation process;
the fiber membrane alkali tower (1) comprises a fiber membrane alkali tower body (1-1) and a fiber membrane alkali tower head (1-2), and the bottom of the fiber membrane alkali tower head (1-1) is not higher than the liquid level in the alkali settling device (2).
Further, the flow direction of the working solution and the concentrated alkali solution in the fiber membrane alkali tower (1) is a two-phase down-flow from top to bottom or a two-phase down-flow from bottom to top; preferably, the flow direction of the working solution and the concentrated alkali solution in the fiber membrane alkali tower (1) is two-phase concurrent flow from top to bottom, the working solution is fed from the tower head (1-1) of the fiber membrane alkali tower, and the concentrated alkali solution is fed from the tower body (1-2) of the fiber membrane alkali tower; preferably, the working solution inlet of the fiber membrane alkali tower (1) is lower than the liquid level in the tower head (1-1) of the fiber membrane alkali tower, and the concentrated alkali solution inlet of the fiber membrane alkali tower (1) is positioned at the upper part of the tower body (1-2).
The invention provides a novel post-treatment process of working solution for producing hydrogen peroxide by an anthraquinone process, which comprises a fiber membrane alkali tower (1), an alkali settler (2), an alkali evaporator (3), a concentrated alkali solution storage tank (4), a clay bed (7) and a working solution storage tank (8), wherein the working solution from an extraction process and the concentrated alkali solution from the concentrated alkali storage tank (4) pass through the fiber membrane alkali tower (1) together to fully react in the fiber membrane alkali tower (1); discharging the reacted working solution from the fiber membrane alkali tower (1) to enter an alkali settler (2), rapidly separating two phases in the alkali settler (2), allowing a dilute alkali solution carried by the working solution to flow out of the alkali settler (2) to an alkali evaporator (3), discharging the dilute alkali solution from the fiber membrane alkali tower (1) to enter the alkali evaporator (3), removing water in the alkali evaporator (3) by the dilute alkali solution to form a concentrated alkali solution again, allowing the concentrated alkali solution to flow to a concentrated alkali solution storage tank (4), and allowing the concentrated alkali solution to enter the fiber membrane alkali tower (1) to continuously contact and react with the working solution; the working solution flows from the alkali settler (2) to the clay bed (7), flows into the working solution storage tank (8) after being treated by the clay bed (7), and then enters the hydrogenation process;
the fiber membrane alkali tower (1) comprises a fiber membrane alkali tower body (1-1) and a fiber membrane alkali tower head (1-2), and the bottom of the fiber membrane alkali tower head (1-1) is not higher than the liquid level in the alkali settling device (2).
Further, working liquid in the fiber membrane alkali tower (1) flows back from top to bottom and concentrated alkali liquid flows back from bottom to top or working liquid flows back from bottom to top and concentrated alkali liquid flows back from top to bottom.
Furthermore, the fiber membrane alkali tower head (1-1) is positioned at the top of the fiber membrane alkali tower body (1-2), the ratio of the diameter of the fiber membrane alkali tower head (1-1) to the diameter of the fiber membrane alkali tower body (1-2) is 1.5-5, and the liquid level of the fiber membrane alkali tower (1) is positioned in the fiber membrane alkali tower head (1-1).
Furthermore, a bent fiber yarn is arranged in the fiber membrane alkali tower body (1-2), the bent fiber yarn is subjected to surface hydrophilic and alkali corrosion resistant treatment, the diameter of the fiber yarn is 0.01-0.2mm, the fiber yarn is made of at least one of stainless steel, polytetrafluoroethylene, modified polypropylene, polyurethane, polyvinyl chloride and polyester, and preferably stainless steel is selected.
Further, a fiber membrane alkali tower vent pipe (9) is arranged above the top of the fiber membrane alkali tower head (1-1), and an alkali settler vent pipe (10) is arranged above the top of the alkali settler (2); concentrated alkali liquor in the concentrated alkali liquor storage tank (4) is sent to a concentrated alkali head tank (6) through a concentrated alkali liquor pump (5), and then enters the fiber membrane alkali tower (1) through a level difference.
Furthermore, the volume flow ratio of the concentrated alkali liquor and the working solution which jointly pass through the fiber membrane alkali tower (1) is 1/500-1/2.
Further, the alkali liquor is one or more aqueous solutions of potassium carbonate, sodium hydroxide and potassium hydroxide, the density of the concentrated alkali liquor is 1.3-1.5g/mL, and the density of the dilute alkali liquor is 1.2-1.4 g/mL.
Further, the structure of the tower head (1-1) of the fiber membrane alkali tower is a hollow structure or a structure filled with a demister, and the structure (2) of the alkali settler is a hollow structure or a structure filled with coalescence-separation filler.
In the invention, the alkali liquor is adsorbed on the surface of the fiber yarn and is pulled by gravity to form a film, and the working solution is attached to the outer side of the alkali liquor film. When the two phases flow downwards along the fiber yarns, the friction force between the oil phase and the alkali phase further changes the shapes of the alkali liquor and the working liquid, and finally two layers of parallel flowing liquid films are formed to generate a larger contact area; and because the two phases have different flow speeds, the two phases always keep higher concentration driving force. Thus, as the flow, the contact area increases and a higher concentration driving force is maintained, the mass transfer rate increases greatly. In the fiber membrane alkali tower, the working solution is contacted with the alkali liquor but not mixed, mass transfer is carried out between the two phases in a non-dispersive state, the interface between the two phases is always clear, the phenomena of interphase mixing and emulsification are greatly reduced, and the subsequent separation speed of the two phases is accelerated.
The beneficial effects of the invention are as follows:
firstly, the fiber membrane alkali tower promotes the mass transfer between the working solution and the alkali liquor, the water content and the hydrogen peroxide content in the treated working solution are lower than those of the prior alkali tower process, and the regeneration of degradation products is more sufficient;
the fiber membrane alkali tower promotes the mass transfer between the working solution and the alkali liquor, the mass transfer resistance is reduced, the moisture removal, the hydrogen peroxide decomposition and the degradation product regeneration in the working solution are more stable and rapid, and the volume of the fiber membrane alkali tower is greatly reduced compared with the conventional alkali tower;
the mixing and emulsification of the working solution and the alkali liquor are avoided, the two-phase separation speed is high, and the volume of the alkali settler is greatly reduced;
fourthly, the liquid holdup of the fiber membrane alkali tower and the alkali tower is far less than that of the prior art, and the occupied working liquid amount is greatly reduced;
the fiber membrane alkali tower is provided with a tower head to slow down the escape speed of generated gas, and the fiber membrane alkali tower has one of hollow structures and structures filled with demister, so that the difficult gas-liquid separation caused by oxygen generation and even entrainment are avoided;
sixthly, the bottom of the tower head of the fiber membrane alkali tower is not higher than the liquid level in the alkali settler, so that the liquid phase in the fiber membrane alkali tower is ensured to be a continuous phase, and the contact effect of oil and water phases in the fiber membrane alkali tower is ensured.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Description of reference numerals: the device comprises a fiber membrane contactor 1, a fiber membrane alkali tower body 1-1, a fiber membrane alkali tower head 1-2, an alkali settler 2, an alkali evaporator 3, a concentrated alkali liquor storage tank 4, a concentrated alkali liquor pump 5, a concentrated alkali head tank 6, a carclazyte bed 7, a working solution storage tank 8, a fiber membrane alkali tower vent pipe 9 and an alkali settler vent pipe 10.
Detailed Description
The following further describes the embodiments of the present invention with reference to the drawings and examples.
The following examples and comparative examples are all exemplified by a device applied to a production of 27.5wt% hydrogen peroxide of 30 ten thousand tons/year. The working solution flow of the alkali treatment unit is 750m3The water content in the working solution from the extraction process is 0.3wt%, the hydrogen peroxide content is 0.3g/L, and the effective anthraquinone content is 158 g/L.
Example 1
Working solution from the extraction process and concentrated alkali solution from the concentrated alkali head tank 6 flow downwards and flow through the fiber membrane alkali tower 1, and fully react in the fiber membrane alkali tower 1; discharging the reacted working solution and diluted alkali liquor from the bottom of the fiber membrane alkali tower 1 into an alkali settler 2, and rapidly separating two phases in the alkali settler 2; the dilute alkali solution flows out from the lower part of the alkali settler 2 to the alkali evaporator 3, the concentrated alkali solution is formed again after the water is removed in the alkali evaporator 3, the concentrated alkali solution flows to the concentrated alkali solution storage tank 4, then is sent to the concentrated alkali head tank 6 by the concentrated alkali solution pump 5, and then enters the fiber membrane alkali tower 1 through the position difference to continuously contact and react with the working solution; the working solution overflows from the upper part of the alkali settler 2 to the clay bed 7, flows into the working solution storage tank 8 after being treated by the clay bed 7, and then enters the hydrogenation process.
The tower head 1-1 of the fiber membrane alkali tower is positioned at the top of the tower body 1-2, the ratio of the diameter of the tower head 1-1 to the diameter of the tower body 1-2 is 2, the liquid level of the fiber membrane alkali tower 1 is positioned in the tower head 1-1, and the bottom of the tower head 1-1 of the fiber membrane alkali tower is not higher than the liquid level in the alkali settler 2.
The working solution inlet of the fiber membrane alkali tower 1 extends to the position below the liquid level in the tower head 1-1 of the fiber membrane alkali tower, and the concentrated alkali solution inlet of the fiber membrane alkali tower 1 is positioned at the upper part of the tower body 1-2.
The fiber membrane alkaline tower 1 contains bent stainless steel fiber wires, and the stainless steel fiber wires are subjected to surface hydrophilic and alkaline corrosion resistant treatment, wherein the diameter of each stainless steel fiber wire is 0.1 mm.
And a fiber membrane alkali tower vent pipe 9 is arranged above the top of the fiber membrane alkali tower 1, and an alkali settler vent pipe 10 is arranged above the top of the alkali settler 2.
The volume flow ratio of the concentrated alkali liquor to the working solution is 1/50.
The alkali liquor is a potassium carbonate aqueous solution, the density of the concentrated alkali liquor is 1.4g/mL, and the density of the dilute alkali liquor is 1.36 g/mL.
The structure of the tower head 1-1 of the fiber membrane alkali tower is a filling demister structure, and the structure of the alkali settler 2 is a filling coalescence-separation filler structure.
The operational effect is shown in table 1.
Example 2
Working solution from the extraction process and concentrated alkali solution from the concentrated alkali head tank 6 flow downstream from bottom to top through the fiber membrane alkali tower 1 and fully react in the fiber membrane alkali tower 1; discharging the reacted working solution and diluted alkali liquor from the top of the fiber membrane alkali tower 1 into an alkali settler 2, and rapidly separating two phases in the alkali settler 2; the dilute alkali solution flows out from the lower part of the alkali settler 2 to the alkali evaporator 3, the concentrated alkali solution is formed again after the water is removed in the alkali evaporator 3, the concentrated alkali solution flows to the concentrated alkali solution storage tank 4, then is sent to the concentrated alkali head tank 6 by the concentrated alkali solution pump 5, and then enters the fiber membrane alkali tower 1 through the position difference to continuously contact and react with the working solution; the working solution overflows from the upper part of the alkali settler 2 to the clay bed 7, flows into the working solution storage tank 8 after being treated by the clay bed 7, and then enters the hydrogenation process.
The tower head 1-1 of the fiber membrane alkali tower is positioned at the top of the tower body 1-2, the ratio of the diameter of the tower head 1-1 to the diameter of the tower body 1-2 is 1.5, the liquid level of the fiber membrane alkali tower 1 is positioned in the tower head 1-1, and the bottom of the tower head 1-1 of the fiber membrane alkali tower is not higher than the liquid level in the alkali settler 2.
The working solution inlet of the fiber membrane alkali tower 1 is positioned at the lower part of the fiber membrane alkali tower body 1-2, and the concentrated alkali liquor inlet of the fiber membrane alkali tower 1 is positioned at the lower part of the tower body 1-2.
The fiber membrane alkaline tower 1 contains bent stainless steel fiber wires, and the stainless steel fiber wires are subjected to surface hydrophilic and alkaline corrosion resistant treatment, wherein the diameter of each stainless steel fiber wire is 0.2 mm.
And a fiber membrane alkali tower vent pipe 9 is arranged above the top of the fiber membrane alkali tower 1, and an alkali settler vent pipe 10 is arranged above the top of the alkali settler 2.
The volume flow ratio of the concentrated alkali liquor to the working solution is 1/20.
The alkali liquor is a potassium carbonate aqueous solution, the density of the concentrated alkali liquor is 1.43g/mL, and the density of the dilute alkali liquor is 1.4 g/mL.
The structure of the tower head 1-1 of the fiber membrane alkali tower is a filling demister structure, and the structure of the alkali settler 2 is a filling coalescence-separation filler structure.
The operational effect is shown in table 1.
Example 3
Working solution from the extraction process and concentrated alkali solution from the concentrated alkali head tank 6 flow downwards and flow through the fiber membrane alkali tower 1, and fully react in the fiber membrane alkali tower 1; discharging the reacted working solution and diluted alkali liquor from the bottom of the fiber membrane alkali tower 1 into an alkali settler 2, and rapidly separating two phases in the alkali settler 2; the dilute alkali solution flows out from the lower part of the alkali settler 2 to the alkali evaporator 3, the concentrated alkali solution is formed again after the water is removed in the alkali evaporator 3, the concentrated alkali solution flows to the concentrated alkali solution storage tank 4, then is sent to the concentrated alkali head tank 6 by the concentrated alkali solution pump 5, and then enters the fiber membrane alkali tower 1 through the position difference to continuously contact and react with the working solution; the working solution overflows from the upper part of the alkali settler 2 to the clay bed 7, flows into the working solution storage tank 8 after being treated by the clay bed 7, and then enters the hydrogenation process.
The tower head 1-1 of the fiber membrane alkali tower is positioned at the top of the tower body 1-2, the ratio of the diameter of the tower head 1-1 to the diameter of the tower body 1-2 is 2, the liquid level of the fiber membrane alkali tower 1 is positioned in the tower head 1-1, and the bottom of the tower head 1-1 of the fiber membrane alkali tower is not higher than the liquid level in the alkali settler 2.
The working solution inlet of the fiber membrane alkali tower 1 extends to the position below the liquid level in the tower head 1-1 of the fiber membrane alkali tower, and the concentrated alkali solution inlet of the fiber membrane alkali tower 1 is positioned at the upper part of the tower body 1-2.
The fiber membrane alkaline tower 1 contains bent stainless steel fiber wires, and the stainless steel fiber wires are subjected to surface hydrophilic and alkaline corrosion resistant treatment, wherein the diameter of each stainless steel fiber wire is 0.1 mm.
And a fiber membrane alkali tower vent pipe 9 is arranged above the top of the fiber membrane alkali tower 1, and an alkali settler vent pipe 10 is arranged above the top of the alkali settler 2.
The volume flow ratio of the concentrated alkali liquor to the working solution is 1/2.
The alkali liquor is a potassium carbonate aqueous solution, the density of the concentrated alkali liquor is 1.4g/mL, and the density of the dilute alkali liquor is 1.39 g/mL.
The structure of the tower head 1-1 of the fiber membrane alkali tower is a filling demister structure, and the structure of the alkali settling device 2 is a hollow structure.
The operational effect is shown in table 1.
Example 4
Working solution from the extraction process and concentrated alkali solution from the concentrated alkali head tank 6 flow downwards and flow through the fiber membrane alkali tower 1, and fully react in the fiber membrane alkali tower 1; discharging the reacted working solution and diluted alkali liquor from the bottom of the fiber membrane alkali tower 1 into an alkali settler 2, and rapidly separating two phases in the alkali settler 2; the dilute alkali solution flows out from the lower part of the alkali settler 2 to the alkali evaporator 3, the concentrated alkali solution is formed again after the water is removed in the alkali evaporator 3, the concentrated alkali solution flows to the concentrated alkali solution storage tank 4, then is sent to the concentrated alkali head tank 6 by the concentrated alkali solution pump 5, and then enters the fiber membrane alkali tower 1 through the position difference to continuously contact and react with the working solution; the working solution overflows from the upper part of the alkali settler 2 to the clay bed 7, flows into the working solution storage tank 8 after being treated by the clay bed 7, and then enters the hydrogenation process.
The tower head 1-1 of the fiber membrane alkali tower is positioned at the top of the tower body 1-2, the ratio of the diameter of the tower head 1-1 to the diameter of the tower body 1-2 is 5, the liquid level of the fiber membrane alkali tower 1 is positioned in the tower head 1-1, and the bottom of the tower head 1-1 of the fiber membrane alkali tower is not higher than the liquid level in the alkali settler 2.
The working solution inlet of the fiber membrane alkali tower 1 extends to the position below the liquid level in the tower head 1-1 of the fiber membrane alkali tower, and the concentrated alkali solution inlet of the fiber membrane alkali tower 1 is positioned at the upper part of the tower body 1-2.
The fiber membrane alkali tower 1 contains bent modified polypropylene fiber yarns, and the modified polypropylene fiber yarns are subjected to surface hydrophilic and alkali-resistant corrosion treatment, wherein the diameter of each modified polypropylene fiber yarn is 0.01 mm.
And a fiber membrane alkali tower vent pipe 9 is arranged above the top of the fiber membrane alkali tower 1, and an alkali settler vent pipe 10 is arranged above the top of the alkali settler 2.
The volume flow ratio of the concentrated alkali liquor to the working solution is 1/500.
The alkali liquor is a potassium carbonate aqueous solution, the density of the concentrated alkali liquor is 1.5g/mL, and the density of the dilute alkali liquor is 1.2 g/mL.
The structure of the tower head 1-1 of the fiber membrane alkali tower is a hollow structure, and the structure of the alkali settler 2 is a structure filled with coalescence-separation filler.
The operational effect is shown in table 1.
Example 5
Working solution from the extraction process and concentrated alkali solution from the concentrated alkali head tank 6 flow downwards and flow through the fiber membrane alkali tower 1, and fully react in the fiber membrane alkali tower 1; discharging the reacted working solution and diluted alkali liquor from the bottom of the fiber membrane alkali tower 1 into an alkali settler 2, and rapidly separating two phases in the alkali settler 2; the dilute alkali solution flows out from the lower part of the alkali settler 2 to the alkali evaporator 3, the concentrated alkali solution is formed again after the water is removed in the alkali evaporator 3, the concentrated alkali solution flows to the concentrated alkali solution storage tank 4, then is sent to the concentrated alkali head tank 6 by the concentrated alkali solution pump 5, and then enters the fiber membrane alkali tower 1 through the position difference to continuously contact and react with the working solution; the working solution overflows from the upper part of the alkali settler 2 to the clay bed 7, flows into the working solution storage tank 8 after being treated by the clay bed 7, and then enters the hydrogenation process.
The tower head 1-1 of the fiber membrane alkali tower is positioned at the top of the tower body 1-2, the ratio of the diameter of the tower head 1-1 to the diameter of the tower body 1-2 is 4, the liquid level of the fiber membrane alkali tower 1 is positioned in the tower head 1-1, and the bottom of the tower head 1-1 of the fiber membrane alkali tower is not higher than the liquid level in the alkali settler 2.
The working solution inlet of the fiber membrane alkali tower 1 extends to the position below the liquid level in the tower head 1-1 of the fiber membrane alkali tower, and the concentrated alkali solution inlet of the fiber membrane alkali tower 1 is positioned at the upper part of the tower body 1-2.
The fiber membrane alkali tower 1 contains bent polyester fiber yarns, and the polyester fiber yarns are subjected to surface hydrophilic and alkali corrosion resistant treatment, wherein the diameter of each polyester fiber yarn is 0.05 mm.
And a fiber membrane alkali tower vent pipe 9 is arranged above the top of the fiber membrane alkali tower 1, and an alkali settler vent pipe 10 is arranged above the top of the alkali settler 2.
The volume flow ratio of the concentrated alkali liquor to the working solution is 1/100.
The alkali liquor is a potassium carbonate aqueous solution, the density of the concentrated alkali liquor is 1.4g/mL, and the density of the dilute alkali liquor is 1.31 g/mL.
The structure of the tower head 1-1 of the fiber membrane alkali tower is a hollow structure, and the structure of the alkali settler 2 is a hollow structure.
The operational effect is shown in table 1.
Example 6
Working solution from the extraction process flows from bottom to top, concentrated alkali solution from a concentrated alkali head tank 6 flows from top to bottom, two phases flow in a fiber membrane alkali tower 1 in a countercurrent manner, and the two phases fully react in the fiber membrane alkali tower 1; discharging the reacted working solution from the top of the fiber film alkali tower 1 into an alkali settler 2, rapidly separating two phases in the alkali settler 2, and allowing the dilute alkali solution carried by the working solution to flow out of the lower part of the alkali settler 2 to an alkali evaporator 3; the dilute alkali liquor flowing out of the bottom of the fiber membrane alkali tower 1 flows to an alkali evaporator 3, the concentrated alkali liquor is formed again after moisture is removed in the alkali evaporator 3, the concentrated alkali liquor flows to a concentrated alkali liquor storage tank 4, then is conveyed to a concentrated alkali head tank 6 through a concentrated alkali liquor pump 5, and then enters the fiber membrane alkali tower 1 through a level difference to continuously contact and react with the working solution; the working solution overflows from the upper part of the alkali settler 2 to the clay bed 7, flows into the working solution storage tank 8 after being treated by the clay bed 7, and then enters the hydrogenation process.
The tower head 1-1 of the fiber membrane alkali tower is positioned at the top of the tower body 1-2, the ratio of the diameter of the tower head 1-1 to the diameter of the tower body 1-2 is 3, the liquid level of the fiber membrane alkali tower 1 is positioned in the tower head 1-1, and the bottom of the tower head 1-1 of the fiber membrane alkali tower is not higher than the liquid level in the alkali settler 2.
The working solution inlet of the fiber membrane alkali tower 1 is positioned at the lower part of the fiber membrane alkali tower body 1-2, and the concentrated alkali liquor inlet of the fiber membrane alkali tower 1 is positioned at the upper part of the tower body 1-2.
The fiber membrane alkali tower 1 contains bent polytetrafluoroethylene fiber yarns, and the fiber membrane alkali tower is subjected to surface hydrophilic and alkali-resistant corrosion treatment, wherein the diameter of each polytetrafluoroethylene fiber yarn is 0.1 mm.
And a fiber membrane alkali tower vent pipe 9 is arranged above the top of the fiber membrane alkali tower 1, and an alkali settler vent pipe 10 is arranged above the top of the alkali settler 2.
The volume flow ratio of the concentrated alkali liquor to the working solution is 1/200.
The alkali liquor is a potassium carbonate aqueous solution, the density of the concentrated alkali liquor is 1.3g/mL, and the density of the dilute alkali liquor is 1.23 g/mL.
The structure of the tower head 1-1 of the fiber membrane alkali tower is a filling demister structure, and the structure of the alkali settler 2 is a filling coalescence-separation filler structure.
The operational effect is shown in table 1.
Comparative example
This comparative example is a packed caustic tower process commonly used in the industry today. The concentrated alkali filled in the alkali tower is potassium carbonate aqueous solution with the density of 1.4g/mL, the concentrated alkali liquor enters from the middle upper part of the alkali tower, the dilute alkali liquor is discharged from the bottom of the alkali tower, the density of the dilute alkali liquor is 1.3g/mL, and the volume flow ratio of the concentrated alkali liquor to the working solution is 1/200. Working solution from an extraction process passes through an alkali tower from bottom to top, the reacted working solution is discharged from the upper part of the alkali tower and enters an alkali settler with a hollow structure, and entrained alkali liquor is separated in the alkali settler; and the working solution overflows from the upper part of the alkali settling vessel to a clay bed, flows into a working solution storage tank after being treated by the clay bed, and then enters a hydrogenation process. And (3) discharging the dilute alkali liquor from the bottom of the alkali tower to a working liquid separator, separating the entrained working liquid, allowing the dilute alkali liquor to flow to an alkali evaporator, removing water in the alkali evaporator to form concentrated alkali liquor again, allowing the concentrated alkali liquor to flow to a concentrated alkali liquor storage tank, pumping the concentrated alkali liquor to a concentrated alkali head tank, and allowing the concentrated alkali liquor to enter the alkali tower through a level difference to continuously react with the working liquid.
The operational effect is shown in table 1.
Table 1 each example is compared to the comparative example run.
Figure 907421DEST_PATH_IMAGE002
As can be seen from the data in Table 1, the fiber membrane caustic tower can be reduced in volume by about 340m as compared to the conventional packed caustic tower3Meanwhile, the volume of the used alkali settler is obviously reduced, and the working solution liquid holdup of the alkali treatment unit can be reduced by about 400m3And the investment of the device is obviously reduced. Meanwhile, when the fiber membrane alkali tower is used, the effects of dehydration, hydrogen peroxide decomposition and degradation product regeneration of the working solution are superior to those of the traditional packed alkali tower.

Claims (10)

1. A new post-treatment process of working solution for producing hydrogen peroxide by an anthraquinone process comprises a fiber membrane alkali tower (1), an alkali settler (2), an alkali evaporator (3), a concentrated alkali solution storage tank (4), a clay bed (7) and a working solution storage tank (8), wherein the working solution from an extraction process and the concentrated alkali solution from the concentrated alkali storage tank (4) pass through the fiber membrane alkali tower (1) together to fully react in the fiber membrane alkali tower (1); discharging the reacted working solution and the dilute alkali solution from the fiber membrane alkali tower (1) to enter an alkali settler (2), and rapidly separating two phases in the alkali settler (2); the dilute alkali liquor flows to the alkali evaporator (3) from the alkali settler (2), the concentrated alkali liquor is formed again after the water is removed in the alkali evaporator (3), and the concentrated alkali liquor flows to the concentrated alkali liquor storage tank (4) and then enters the fiber membrane alkali tower (1) to continuously contact and react with the working solution; the working solution flows from the alkali settler (2) to the clay bed (7), flows into the working solution storage tank (8) after being treated by the clay bed (7), and then enters the hydrogenation process;
the fiber membrane alkali tower (1) comprises a fiber membrane alkali tower body (1-1) and a fiber membrane alkali tower head (1-2), and the bottom of the fiber membrane alkali tower head (1-1) is not higher than the liquid level in the alkali settling device (2).
2. The novel post-treatment process of the working solution for producing hydrogen peroxide by the anthraquinone process comprises a fiber membrane alkali tower (1), an alkali settler (2), an alkali evaporator (3), a concentrated alkali solution storage tank (4), a clay bed (7) and a working solution storage tank (8), wherein the working solution from an extraction process and the concentrated alkali solution from the concentrated alkali storage tank (4) pass through the fiber membrane alkali tower (1) together to fully react in the fiber membrane alkali tower (1); discharging the reacted working solution from the fiber membrane alkali tower (1) to enter an alkali settler (2), rapidly separating two phases in the alkali settler (2), allowing a dilute alkali solution carried by the working solution to flow out of the alkali settler (2) to an alkali evaporator (3), discharging the dilute alkali solution from the fiber membrane alkali tower (1) to enter the alkali evaporator (3), removing water in the alkali evaporator (3) by the dilute alkali solution to form a concentrated alkali solution again, allowing the concentrated alkali solution to flow to a concentrated alkali solution storage tank (4), and allowing the concentrated alkali solution to enter the fiber membrane alkali tower (1) to continuously contact and react with the working solution; the working solution flows from the alkali settler (2) to the clay bed (7), flows into the working solution storage tank (8) after being treated by the clay bed (7), and then enters the hydrogenation process;
the fiber membrane alkali tower (1) comprises a fiber membrane alkali tower body (1-1) and a fiber membrane alkali tower head (1-2), and the bottom of the fiber membrane alkali tower head (1-1) is not higher than the liquid level in the alkali settling device (2).
3. The novel post-treatment process for the working solution used for producing hydrogen peroxide by the anthraquinone process as claimed in claim 1, wherein the flow direction of the working solution and the concentrated alkali solution in the fiber membrane alkali tower (1) is a top-down two-phase concurrent flow or a bottom-up two-phase concurrent flow;
preferably, the flow direction of the working solution and the concentrated alkali solution in the fiber membrane alkali tower (1) is two-phase concurrent flow from top to bottom, the working solution is fed from the tower head (1-1) of the fiber membrane alkali tower, and the concentrated alkali solution is fed from the tower body (1-2) of the fiber membrane alkali tower; preferably, the working solution inlet of the fiber membrane alkali tower (1) is lower than the liquid level in the tower head (1-1) of the fiber membrane alkali tower, and the concentrated alkali solution inlet of the fiber membrane alkali tower (1) is positioned at the upper part of the tower body (1-2).
4. The novel post-treatment process for the working solution used in the production of hydrogen peroxide by the anthraquinone process as claimed in claim 2, wherein the working solution in the fiber membrane alkali tower (1) flows in a counter-current manner from top to bottom with the concentrated alkali solution from bottom to top or from bottom to top with the concentrated alkali solution from top to bottom.
5. The novel post-treatment process of the working solution for producing hydrogen peroxide by the anthraquinone process according to claim 1 or 2, wherein the tower head (1-1) of the fiber membrane alkali tower is positioned at the top of the tower body (1-2) of the fiber membrane alkali tower, the ratio of the diameter of the tower head (1-1) of the fiber membrane alkali tower to the diameter of the tower body (1-2) of the fiber membrane alkali tower is 1.5-5, and the liquid level of the fiber membrane alkali tower (1) is positioned in the tower head (1-1) of the fiber membrane alkali tower.
6. The novel post-treatment process of the working solution for producing hydrogen peroxide by the anthraquinone process according to claim 1 or 2, wherein the fiber membrane alkali tower body (1-2) is internally provided with bent fiber filaments, the bent fiber filaments are subjected to surface hydrophilic and alkali corrosion resistant treatment, the diameter of the fiber filaments is 0.01-0.2mm, and the fiber filaments are made of at least one of stainless steel, polytetrafluoroethylene, modified polypropylene, polyurethane, polyvinyl chloride and polyester, preferably stainless steel.
7. The novel process for post-treating the working solution for producing hydrogen peroxide by the anthraquinone process according to claim 1 or 2, wherein a fiber membrane alkaline tower vent pipe (9) is arranged above the top of the tower head (1-1) of the fiber membrane alkaline tower, and an alkaline settler vent pipe (10) is arranged above the top of the alkaline settler (2); concentrated alkali liquor in the concentrated alkali liquor storage tank (4) is sent to a concentrated alkali head tank (6) through a concentrated alkali liquor pump (5), and then enters the fiber membrane alkali tower (1) through a level difference.
8. The new process for post-treating the working solution for producing hydrogen peroxide by the anthraquinone process according to claim 1 or 2, wherein the volume flow ratio of the concentrated alkali liquor and the working solution which are jointly passed through the fiber membrane alkali tower (1) is 1/500-1/2.
9. The novel process for post-treating the working solution for producing hydrogen peroxide by the anthraquinone process according to claim 1 or 2, wherein the alkali solution is an aqueous solution of one or more of potassium carbonate, sodium hydroxide and potassium hydroxide, the density of the concentrated alkali solution is 1.3-1.5g/mL, and the density of the dilute alkali solution is 1.2-1.4 g/mL.
10. The new process for post-treating the working solution for producing hydrogen peroxide by the anthraquinone process according to claim 1 or 2, wherein the structure of the tower head (1-1) of the fiber membrane alkali tower is a hollow structure or a structure filled with a demister, and the structure (2) of the alkali settler is a hollow structure or a structure filled with a coalescence-separation filler.
CN202111478887.1A 2021-12-07 2021-12-07 Novel post-treatment process of working solution for producing hydrogen peroxide by anthraquinone method Pending CN114180773A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2657758Y (en) * 2003-10-20 2004-11-24 北京欣博通创新能源技术开发有限公司 High-efficient contact fiber type filler tower
CN204237558U (en) * 2014-11-27 2015-04-01 山东晋煤明水化工集团有限公司 The after-treatment device of hydrogen peroxide obtained by anthraquinone process production technique
CN108675265A (en) * 2018-07-05 2018-10-19 浙江工程设计有限公司 A kind of after-treatment device of process for prepairng hydrogen peroxide by anthraquinone technique
CN110482764A (en) * 2019-09-23 2019-11-22 扬州荣祥科技发展有限公司 The regenerative system of raffinate in hydrogen dioxide solution production by anthraquinone process technique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2657758Y (en) * 2003-10-20 2004-11-24 北京欣博通创新能源技术开发有限公司 High-efficient contact fiber type filler tower
CN204237558U (en) * 2014-11-27 2015-04-01 山东晋煤明水化工集团有限公司 The after-treatment device of hydrogen peroxide obtained by anthraquinone process production technique
CN108675265A (en) * 2018-07-05 2018-10-19 浙江工程设计有限公司 A kind of after-treatment device of process for prepairng hydrogen peroxide by anthraquinone technique
CN110482764A (en) * 2019-09-23 2019-11-22 扬州荣祥科技发展有限公司 The regenerative system of raffinate in hydrogen dioxide solution production by anthraquinone process technique

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