CN212769872U - Regenerating unit of working solution for producing hydrogen peroxide by anthraquinone process - Google Patents
Regenerating unit of working solution for producing hydrogen peroxide by anthraquinone process Download PDFInfo
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Abstract
The utility model discloses a regeneration device of working solution for producing hydrogen peroxide by anthraquinone process, which is characterized in that the regeneration device comprises a raffinate separator (2), a drying tower (3), an alkali separator (4) and a carclazyte bed (5); the feed end of the raffinate separator (2) is connected with the extraction tower (1), the discharge end is divided into a line 1 and a line 2, and the line 1 is sequentially connected with a drying tower (3), an alkali separator (4) and a carclazyte bed (5); the line 2 is divided into two branches of a line 3 and a line 4, the line 4 is connected with the bottom of the clay bed (5), and an outlet pipeline at the top of the clay bed (5) is combined with the line 3 and then connected with a hydrogenation process; the connecting lines 1, 2, 3 and 4 are pipelines. The regeneration device has good regeneration effect, low equipment investment and low raw material consumption.
Description
Technical Field
The utility model relates to a regenerating unit of working solution for preparing hydrogen peroxide by an anthraquinone process.
Background
The hydrogen peroxide is an important fine chemical raw material and has wide application. The hydrogen peroxide generates water and oxygen after decomposition, has no secondary pollution to the environment and is green and environment-friendly.
In the prior art, hydrogen peroxide is generally prepared by the anthraquinone process. The anthraquinone process for preparing hydrogen peroxide uses 2-alkyl anthraquinone (such as 2-ethyl anthraquinone and 2-tert-amyl anthraquinone) as carrier, and two or three of heavy aromatic hydrocarbon, trioctyl phosphate, tetrabutyl urea, methyl cyclohexyl acetate and diisobutyl methanol as mixed solvent to prepare solution (hereinafter referred to as "working solution") with certain composition. The working solution and hydrogen gas are fed into hydrogenation tower with palladium catalyst, and hydrogenation reaction is carried out under a certain pressure and temperature, so as to obtain corresponding alkyl anthrahydroquinone solution (called 'hydrogenation solution' for short). The hydrogenated liquid is oxidized by air in the oxidation tower, and the alkyl anthrahydroquinone in the solution is restored to the original alkyl anthraquinone, and hydrogen peroxide is generated at the same time. The difference in solubility of hydrogen peroxide in water and working fluid and the difference in density between the working fluid and water are used to extract the working fluid containing hydrogen peroxide (simply referred to as "oxidizing fluid") with pure water in an extraction column to obtain an aqueous hydrogen peroxide solution of a certain concentration. The hydrogen peroxide aqueous solution is purified by aromatic hydrocarbon to obtain the hydrogen peroxide product with the concentration of 27.5 w% -35 w%. The working solution (raffinate for short) after pure water extraction is returned to the hydrogenation process after regeneration treatment, and a cycle of circulation is completed.
Degradation products such as anthrone, hydroxyl anthrone, epoxy anthraquinone and octahydro anthraquinone can be generated in the circulating process of the working solution, the degradation products can be increased along with the operation of the device, if the degradation products are not treated in time, the quality of the working solution can be influenced, the extraction process and the product quality of hydrogen peroxide can be influenced, and potential safety hazards can also be generated. Therefore, the working fluid circulating in the production process must be regenerated to reduce degradation products and ensure the normal operation of the device. Patent document CN205973795 discloses a working fluid regeneration method, which regenerates the working fluid by combining alkali solution treatment and flash evaporation, and has a complex process, and because the flash evaporation process only plays a role in dehydration, the flash evaporation process does not play a role in regeneration of anthraquinone. The main components of the raffinate are organic solvents such as aromatic hydrocarbon and the like, and the raffinate also contains substances such as hydrogen peroxide and the like which are easy to decompose by heating, so that the risk of forming a gas-phase explosive mixture exists in the flash evaporation process, and potential safety hazards exist in the technical process.
SUMMERY OF THE UTILITY MODEL
The to-be-solved technical problem of the utility model is to provide a regenerating unit of working solution for anthraquinone process production hydrogen peroxide, this regenerating unit regeneration is effectual, and equipment investment is low, and raw and other materials consume fewly.
The technical proposal of the utility model is that a regeneration device of the working solution for producing hydrogen peroxide by the anthraquinone method comprises a raffinate separator 2, a drying tower 3, an alkali separator 4 and a carclazyte bed 5; the feed end of the raffinate separator 2 is connected with the extraction tower 1, the discharge end is divided into a line 1 and a line 2, and the line 1 is sequentially connected with a drying tower 3, an alkali separator 4 and a carclazyte bed 5; the line 2 is divided into two branches of a line 3 and a line 4, the line 4 is connected with the bottom of the clay bed 5, and an outlet pipeline at the top of the clay bed 5 is combined with the line 3 and then connected to the hydrogenation process. The working solution inlet of the raffinate separator is arranged at the lower part of the raffinate separator, the outlet of the raffinate separator is arranged at the upper part of the raffinate separator, and the bottom of the raffinate separator is provided with a discharge hole. The working solution inlet of the drying tower is arranged at the lower part of the drying tower, the outlet is arranged at the upper part of the drying tower, and the bottom of the drying tower is provided with a discharge hole. The line 1, the line 2, the line 3 and the line 4 are pipelines. The raffinate separator is preferably packed with polytetrafluoroethylene packing or stainless steel packing.
Furthermore, the inlet of the drying tower, the inlet of the carclazyte bed and the line 3 are all provided with flow meters; the line 1, the line 2 and the line 3 are provided with pneumatic valves.
The drying tower is filled with alkali liquor, wherein the alkali liquor is 20-50% of potassium carbonate aqueous solution, 20-50% of potassium carbonate and potassium bicarbonate mixed aqueous solution or 1-10% of potassium hydroxide and calcium hydroxide mixed aqueous solution. By optimizing the concentration and the type of the alkali, the regeneration efficiency of the drying tower can be improved, the residual hydrogen peroxide in the working solution is decomposed more thoroughly, the alkalinity of the working solution is improved, and the regeneration conversion rate of the clay bed on anthraquinone degradation products in the working solution is favorably improved.
The utility model discloses the device is through setting up the raffinate separator, has reduced moisture and hydrogen peroxide content in the working solution, can maintain the activity of hydrogenation tower catalyst well, guarantees the safety of hydrogenation tower.
The utility model discloses a set up the drying tower, further reduced hydrogen peroxide content in the working solution, for the clay bed regeneration provides alkaline environment, more be favorable to the hydrogenation efficiency that remains stable, extension catalyst life guarantees the safety of hydrogenation tower simultaneously.
Anthraquinone process production working solution's for hydrogen peroxide regenerating unit, the clay bed generally is parallelly connected for 1 ~ 4, preferably 3.
The method for regenerating the working solution by using the device of the utility model is that the working solution coming out of the extraction tower in the technical process of producing hydrogen peroxide by the anthraquinone method is separated into two paths by the raffinate separator, the working solution in the line 1 is sent into the drying tower for drying and then flows into the clay bed after passing through the alkali separator; part of the working solution in the line 2 enters the clay bed through the line 4, and the other part of the working solution is combined with the working solution treated by the clay bed through the line 3 and then enters the hydrogen peroxide production process flow for circulation.
Further, after the working solution from the extraction tower is separated by the raffinate separator, 5-60% of the working solution in volume percentage flows through a line 1, and 40-95% of the working solution in volume percentage flows through a line 2. The working fluid flowing through the line 2 respectively enters the line 3 and the line 4, wherein 5-50% of the working fluid in volume percentage flows through the line 3.
The working solution in equipment such as drying tower, alkali separator, clay bed and circuits such as circuit 1, circuit 2, circuit 3, circuit 4 all flows through gravity mode, need not additionally to increase power equipment.
Further, the regeneration treatment method of the working solution for producing hydrogen peroxide by the anthraquinone process is divided into two paths according to the content of degradation products in the working solution after separation by the raffinate separator according to the following principle:
when the content of the degradation products is less than 10g/l, the working solution flowing through the line 1 is less than 10 percent of the total volume of the working solution separated by the raffinate separator;
when the content of the degradation products is 10-20g/l, the working solution flowing through the line 1 is 10-30% of the total volume of the working solution separated by the raffinate separator;
when the content of the degradation products is 20-35g/l, the working solution flowing through the line 1 is 30-60% of the total volume of the working solution separated by the raffinate separator.
The working solution comprises a nonpolar aromatic hydrocarbon solvent, a polar solvent and anthraquinone, wherein the nonpolar aromatic hydrocarbon solvent refers to alkyl-substituted aromatic hydrocarbon or a mixture thereof, and the polar solvent is tetrabutyl urea, trioctyl phosphate, methyl cyclohexyl acetate or a mixture thereof; the anthraquinone in the working solution refers to 2-ethyl anthraquinone, 2-amyl anthraquinone or mixture thereof, and corresponding tetrahydroanthraquinone or mixture thereof.
Device, through setting up surplus separator, drying tower, alkali separator, carclazyte bed bypass (circuit 3) etc. of extraction, simplified process flow, reduced the equipment investment to through the concentration and the kind of optimizing the alkali solution, working solution flow has improved regeneration efficiency in the adjustment different circuits, has reduced raw and other materials and has consumed, has prolonged carclazyte bed life, has improved technological stability, security.
Taking 10 ten thousand tons/a 27.5 w% hydrogen peroxide production apparatus as an example:
the utility model discloses a reduce the flash distillation system, the working solution regeneration facility investment has reduced more than 20%, reduces consumption of power 5% to the security of equipment operation has been improved. By optimizing the concentration and the type of the alkali, the regeneration efficiency of the drying tower and the clay bed is improved, the residual hydrogen peroxide in the working solution is decomposed more completely, the alkali consumption is reduced, and the alkali rated consumption for producing 1t 27.5 percent hydrogen peroxide is reduced from 1kg to below 0.9 kg; the alumina consumption is reduced, and the rated consumption of the alumina for producing 1t 27.5 percent of hydrogen peroxide is reduced from 5.0kg to below 4.0 kg.
The flow of the drying tower is adjusted according to the content and acidity of total degradation products in the working solution, the flow of the line 3 is adjusted, so that the acidic solution of the line 4 and the alkaline working solution of the line 1 pass through the drying tower to be neutralized, the working solution entering the clay bed is alkalescent, the capacity of regenerating anthraquinone by alumina is enhanced, the replacement cycle of the clay bed is prolonged, the service life of the clay bed can be prolonged by more than 20%, and the replacement cycle of 45 days is prolonged to more than 55 days; the flow of the line 3 and the flow of the line 1 are regulated, so that the working solution from the clay bed is neutral or weakly acidic, the neutral or weakly acidic working solution and the acidic working solution of the line 3 are combined to be weakly acidic, only few salt substances are generated, excessive accumulation of acidic substances in the working solution is avoided, the activity of a catalyst in a hydrogenation tower in a subsequent process is not influenced, the consumption of phosphoric acid of a system is reduced, and the quantitative consumption of phosphoric acid for producing 1t 27.5 percent hydrogen peroxide is reduced from 0.9kg to below 0.8 kg; the inlet of the drying tower, the inlet of each clay bed and the line 3 are all provided with a working fluid flowmeter, the line 1 and the line 3 adopt pneumatic valves to control the flow, and the line 2 adopts pneumatic valves to control the liquid level of the raffinate separator, so that the flow stability of the drying tower can be ensured, and the alkali formation caused by flow fluctuation can be avoided; finally, the content of degradation products in the working solution can be stably maintained below 30g/l, and the safe and stable operation of the device is ensured.
Drawings
FIG. 1 is a schematic view of the working fluid regenerating device comprising three clay beds
In the figure: 1. an extraction tower 2, a raffinate separator 3, a drying tower 4, an alkali separator 5, a clay bed 6, a pneumatic valve 7 and a flowmeter.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
As shown in fig. 1, a regeneration device of a working solution for producing hydrogen peroxide by an anthraquinone process comprises a raffinate separator 2, a drying tower 3, an alkali separator 4 and a clay bed 5; the feed end of the raffinate separator 2 is connected with the extraction tower 1, the discharge end is divided into a line 1 and a line 2, and the line 1 is sequentially connected with a drying tower 3, an alkali separator 4 and a carclazyte bed 5; the line 2 is divided into two branches of a line 3 and a line 4, the line 4 is connected with the bottom of the clay bed 5, and an outlet pipeline at the top of the clay bed 5 is combined with the line 3 and then connected with the hydrogenation process. The working solution inlet of the raffinate separator is arranged at the lower part of the raffinate separator, the outlet of the raffinate separator is arranged at the upper part of the raffinate separator, and the bottom of the raffinate separator is provided with a discharge hole. The working solution inlet of the drying tower is arranged at the lower part of the drying tower, the outlet is arranged at the upper part of the drying tower, and the bottom of the drying tower is provided with a discharge hole. The connecting lines 1, 2, 3 and 4 are pipelines. The white soil bed is connected in parallel. The alkali liquor in the drying tower is potassium carbonate water solution with the mass percentage concentration of 48%. The raffinate separator is filled with polytetrafluoroethylene filler.
The drying tower inlet, the carclazyte bed inlet and the line 3 are all provided with flowmeters, and the line 1, the line 2 and the line 3 are all provided with pneumatic valves. The working liquids in the drying tower, the alkali separator, the clay bed and other equipment and the lines 1, 2, 3, 4 and other lines all flow automatically in a gravity mode without additionally adding power equipment.
The regeneration method of the working solution for producing hydrogen peroxide by the anthraquinone method comprises the following steps: in the technological process of producing hydrogen peroxide by anthraquinone method, the working solution coming out from the extraction tower is separated by a raffinate separator and then divided into two paths, the working solution in the line 1 is sent into a drying tower for treatment, then flows into a clay bed after passing through an alkali separator, part of the working solution in the line 2 directly enters the clay bed, and the other part of the working solution is combined with the working solution treated by the clay bed through the line 3 and then enters the technological process of producing hydrogen peroxide for circulation.
Distributing the line 1 and the line 2 according to the content of the degradation products in the working solution separated by the raffinate separator;
when the content of the degradation products is less than 10g/l, the volume percentage of the working solution which is separated by the raffinate separator and sent into the drying tower through the line 1 is 8 percent of the total volume of the raffinate working solution;
when the content of the degradation products is 10-20g/l, the volume percentage of the working solution which is separated by the raffinate separator and sent into the drying tower through the line 1 is 26 percent of the total volume of the raffinate working solution;
when the content of the degradation products is 20-35g/l, the volume percentage of the working solution which is sent into the drying tower through the line 1 after the raffinate working solution is separated by the raffinate separator is 57 percent of the total volume of the raffinate working solution.
Under the control of the process conditions, the whole hydrogen peroxide device can run stably.
In the working solution, the nonpolar solvent is an aromatic hydrocarbon mixture, the polar solvent is a mixture of tetrabutyl urea, trioctyl phosphate and methylcyclohexyl acetate, and the anthraquinone is a mixture of 2-ethylanthraquinone and 2-ethyltetrahydroanthraquinone.
After the working solution from the extraction tower is separated by the raffinate separator, 10-58% of the working solution flows through a line 1, and 42-90% of the working solution flows through a line 2. The working fluid in line 2 flows through line 3 in a volume percentage of 5% to 48%.
This example is applied to a 10 ten thousand ton/a 27.5 w% hydrogen peroxide production apparatus as an example:
compared with the post-treatment equipment with a flash evaporation system, the investment of the working fluid regeneration equipment is reduced by 25%, the power consumption is reduced by 5%, and the running safety of the equipment is improved.
By optimizing the concentration and the type of the alkali, the regeneration efficiency of the drying tower and the clay bed is improved, the residual hydrogen peroxide in the working solution is decomposed more thoroughly, the alkali consumption is reduced, and the quantitative consumption of the alkali for producing 1t 27.5 percent hydrogen peroxide is reduced from 1kg to 0.7 kg; the alumina consumption is reduced, and the rated consumption of the alumina for producing 1t 27.5 percent of hydrogen peroxide is reduced from 5.0kg to 3.8 kg.
The flow of the drying tower is adjusted according to the content and acidity of total degradation products in the working solution, the flow of the line 3 is adjusted, so that the acidic solution of the line 4 and the alkaline working solution of the line 1 pass through the drying tower to be neutralized, the working solution entering the clay bed is alkalescent, the capacity of regenerating anthraquinone by alumina is enhanced, the replacement cycle of the clay bed is prolonged, the service life of the clay bed can be prolonged by more than 30%, and the replacement cycle of 45 days is prolonged to 68 days; the flow of the line 3 and the flow of the line 1 are adjusted, so that the working solution from the clay bed is neutral or weakly acidic, the neutral or weakly acidic working solution and the acidic working solution of the line 3 are combined to be weakly acidic, only a few salt substances are generated, excessive accumulation of acidic substances in the working solution is avoided, the activity of a catalyst in a hydrogenation tower in a subsequent process is not influenced, the consumption of phosphoric acid of a system is reduced, and the quantitative consumption of phosphoric acid for producing 1t 27.5% hydrogen peroxide is reduced from 0.9kg to 0.6 kg; working solution flow meters are arranged at the inlet of the drying tower, the inlet of each clay bed and the line 3, the flow of the lines 1 and 3 is controlled by adopting a pneumatic valve, the liquid level of the raffinate separator is controlled by adopting a pneumatic valve in the line 2, the flow of the drying tower can be ensured to be stable, and alkali can not be generated due to flow fluctuation; finally, the content of degradation products in the working solution can be stably maintained below 30g/l, and the safe and stable operation of the device is ensured.
Example 2
The utility model provides a regenerating unit of anthraquinone method production working solution for hydrogen peroxide, the white soil bed is two side by side, alkali lye is 45% by mass concentration's potassium carbonate and potassium bicarbonate mixed solution (wherein potassium carbonate mass fraction is 40%, potassium bicarbonate potassium carbonate mass fraction is 5%) in the drying tower, is filled with stainless steel filler in the raffinate separator, other the same example 1. The regeneration method was the same as in example 1.
After the raffinate working solution is separated by the raffinate separator, distributing the raffinate working solution according to the content of degradation products in the working solution;
when the content of the degradation products is less than 10g/l, the volume percentage of the working solution which is separated by the raffinate separator and sent into the drying tower through the line 1 is 3 percent of the total volume of the raffinate working solution;
when the content of the degradation products is 10-20g/l, the volume percentage of the working solution which is separated by the raffinate separator and sent into the drying tower through the line 1 is 13 percent of the total volume of the raffinate working solution;
when the content of the degradation products is 20-35g/l, the volume percentage of the working solution which is sent into the drying tower through the line 1 after the raffinate working solution is separated by the raffinate separator is 34% of the total volume of the raffinate working solution.
Under the control of the process conditions, the whole hydrogen peroxide device can run stably.
The nonpolar solvent in the working solution is an aromatic hydrocarbon mixture, the polar solvent is a mixture of tetrabutyl urea and trioctyl phosphate, and the anthraquinone is a mixture of 2-ethyl anthraquinone and 2-ethyl tetrahydro anthraquinone.
After the working solution from the extraction tower is separated by the raffinate separator, 15-50% of the working solution in volume percentage flows through a line 1, 50-85% of the working solution in volume percentage flows through a line 2, and 6-40% of the working solution in volume percentage flows through a line 3.
This example is applied to the manufacture of a 10 ten thousand ton/a 27.5 w% hydrogen peroxide device as an example:
compared with the post-treatment equipment with a flash evaporation system, the investment of the working fluid regeneration equipment is reduced by 28%, the power consumption is reduced by 5%, and the operation safety of the equipment is improved.
By optimizing the concentration and the type of the alkali, the regeneration efficiency of the drying tower and the clay bed is improved, the residual hydrogen peroxide in the working solution is decomposed more thoroughly, the alkali consumption is reduced, and the quantitative consumption of the alkali for producing 1t 27.5 percent hydrogen peroxide is reduced from 1kg to 0.8 kg; the alumina consumption is reduced, and the rated consumption of the alumina for producing 1t 27.5 percent of hydrogen peroxide is reduced from 5.0kg to 3.9 kg.
The flow of the drying tower is adjusted according to the content and acidity of total degradation products in the working solution, the flow of the line 3 is adjusted, so that the acidic solution of the line 4 and the alkaline working solution of the line 1 pass through the drying tower to be neutralized, the working solution entering the clay bed is alkalescent, the capacity of regenerating anthraquinone by alumina is enhanced, the replacement cycle of the clay bed is prolonged, the service life of the clay bed can be prolonged by more than 20%, and the replacement cycle of 45 days is prolonged to 60 days; the flow of the line 3 and the flow of the line 1 are adjusted, so that the working solution from the clay bed is neutral or weakly acidic, the neutral or weakly acidic working solution and the acidic working solution of the line 3 are combined to be weakly acidic, only a few salt substances are generated, excessive accumulation of acidic substances in the working solution is avoided, the activity of a catalyst in a hydrogenation tower in a subsequent process is not influenced, the consumption of phosphoric acid of a system is reduced, and the quantitative consumption of phosphoric acid for producing 1t 27.5% hydrogen peroxide is reduced from 0.9kg to 0.8 kg; working solution flow meters are arranged at the inlet of the drying tower, the inlet of each clay bed and the line 3, the flow of the lines 1 and 3 is controlled by adopting a pneumatic valve, the liquid level of the raffinate separator is controlled by adopting a pneumatic valve in the line 2, the flow of the drying tower can be ensured to be stable, and alkali can not be generated due to flow fluctuation; finally, the content of degradation products in the working solution can be stably maintained below 30g/l, and the safe and stable operation of the device is ensured.
Example 3
The regeneration device of the working solution for producing hydrogen peroxide by the anthraquinone process is characterized in that four clay beds are arranged in parallel, the alkali liquor in the drying tower is a mixed solution of potassium hydroxide and calcium hydroxide with the mass percentage concentration of 8% (wherein the mass fraction of the potassium hydroxide is 7.85%, and the mass fraction of the calcium hydroxide is 0.15%), the raffinate separator is filled with stainless steel filler, and the other steps are the same as those in example 1. The regeneration method was the same as in example 1.
After the raffinate working solution is separated by the raffinate separator, distributing the raffinate working solution according to the content of degradation products in the working solution;
according to the method for post-treating the working solution for producing the hydrogen peroxide by the anthraquinone method, the raffinate working solution is separated by the raffinate separator and then distributed according to the content of degradation products in the working solution;
when the content of the degradation products is less than 10g/l, the volume percentage of the working solution which is separated by the raffinate separator and sent into the drying tower through the line 1 is 7 percent of the total volume of the raffinate working solution;
when the content of the degradation products is 10-20g/l, the volume percentage of the working solution which is separated by the raffinate separator and sent into the drying tower through the line 1 is 28% of the total volume of the raffinate working solution;
when the content of the degradation products is 20-35g/l, the volume percentage of the working solution which is sent into the drying tower through the line 1 after the raffinate working solution is separated by the raffinate separator is 46 percent of the total volume of the raffinate working solution.
Under the control of the process conditions, the whole hydrogen peroxide device can run stably.
In the working solution, a nonpolar solvent aromatic hydrocarbon mixture and a polar solvent are tetrabutyl urea and trioctyl phosphate, and anthraquinone is a mixture of 2-ethyl anthraquinone, 2-ethyl tetrahydro anthraquinone, 2-amyl anthraquinone and 2-amyl tetrahydro anthraquinone.
After the working solution from the extraction tower is separated by the raffinate separator, 18-52% of the working solution in volume percentage flows through a line 1, 48-82% of the working solution in volume percentage flows through a line 2, and 8-50% of the working solution in volume percentage flows through a line 3.
This example is applied to the manufacture of a 10 ten thousand ton/a 27.5 w% hydrogen peroxide device as an example:
compared with the post-treatment equipment with a flash system, the investment of the working fluid regeneration equipment is reduced by 21%, the power consumption is reduced by 5% by canceling the flash system, and the running safety of the equipment is improved.
By optimizing the concentration and the type of the alkali, the regeneration efficiency of the drying tower and the clay bed is improved, the residual hydrogen peroxide in the working solution is decomposed more thoroughly, the alkali consumption is reduced, and the quantitative consumption of the alkali for producing 1t 27.5 percent hydrogen peroxide is reduced from 1kg to 0.8 kg; the alumina consumption is reduced and the alumina quota consumption for the production of 1t 27.5% hydrogen peroxide is reduced from 5.0kg to 4.0 kg.
The flow of the drying tower is adjusted according to the content and acidity of total degradation products in the working solution, the flow of the line 3 is adjusted, so that the acidic solution of the line 4 and the alkaline working solution of the line 1 pass through the drying tower to be neutralized, the working solution entering the clay bed is alkalescent, the capacity of regenerating anthraquinone by alumina is enhanced, the replacement cycle of the clay bed is prolonged, the service life of the clay bed can be prolonged by more than 20%, and the replacement cycle of 45 days is prolonged to 56 days; the flow of the line 3 and the flow of the line 1 are adjusted, so that the working solution from the clay bed is neutral or weakly acidic, the neutral or weakly acidic working solution and the acidic working solution of the line 3 are combined to be weakly acidic, only a few salt substances are generated, excessive accumulation of acidic substances in the working solution is avoided, the activity of a catalyst in a hydrogenation tower in a subsequent process is not influenced, the consumption of phosphoric acid of a system is reduced, and the quantitative consumption of phosphoric acid for producing 1t 27.5% hydrogen peroxide is reduced from 0.9kg to 0.8 kg; working solution flow meters are arranged at the inlet of the drying tower, the inlet of each clay bed and the line 3, the flow of the lines 1 and 3 is controlled by adopting a pneumatic valve, the liquid level of the raffinate separator is controlled by adopting a pneumatic valve in the line 2, the flow of the drying tower can be ensured to be stable, and alkali can not be generated due to flow fluctuation; finally, the content of degradation products in the working solution can be stably maintained below 30g/l, and the safe and stable operation of the device is ensured.
Example 4
The regeneration device of the working solution for producing the hydrogen peroxide by the anthraquinone method is characterized in that three clay beds are arranged in parallel, the alkali liquor in the drying tower is potassium carbonate solution with the mass percentage concentration of 30 percent, a raffinate separator is filled with stainless steel filler, and the other steps are the same as those in example 1. The regeneration method was the same as in example 1.
After the raffinate working solution is separated by the raffinate separator, distributing the raffinate working solution according to the content of degradation products in the working solution; when the content of the degradation products is less than 10g/l, the volume percentage of the working solution which is separated by the raffinate separator and sent into the drying tower through the line 1 is 3 percent of the total volume of the raffinate working solution;
when the content of the degradation products is 10-20g/l, the volume percentage of the working solution which is separated by the raffinate separator and sent into the drying tower through the line 1 is 12 percent of the total volume of the raffinate working solution;
when the content of the degradation products is 20-35g/l, the volume percentage of the working solution which is sent into the drying tower through the line 1 after the raffinate working solution is separated by the raffinate separator is 33 percent of the total volume of the raffinate working solution.
Under the control of the process conditions, the whole hydrogen peroxide device can run stably.
The non-polar solvent in the working solution is an aromatic hydrocarbon mixture, the polar solvent is a mixture of tetrabutyl urea and trioctyl phosphate, and the anthraquinone is a mixture of 2-ethyl anthraquinone and 2-ethyl tetrahydro anthraquinone.
After the working solution from the extraction tower is separated by the raffinate separator, 14-50% of the working solution in volume percentage flows through a line 1, 50-86% of the working solution in volume percentage flows through a line 2, and 5-45% of the working solution in volume percentage flows through a line 3.
This example is applied to the manufacture of a 10 ten thousand ton/a 27.5 w% hydrogen peroxide device as an example:
by reducing the drying tower and the clay bed system, the investment of the working solution regeneration equipment is reduced by 25 percent, by canceling the flash evaporation system, the power consumption is reduced by 5 percent, and the running safety of the equipment is improved.
By optimizing the concentration and the type of the alkali, the regeneration efficiency of the drying tower and the clay bed is improved, the residual hydrogen peroxide in the working solution is decomposed more thoroughly, the alkali consumption is reduced, and the quantitative consumption of the alkali for producing 1t 27.5 percent hydrogen peroxide is reduced from 1kg to 0.9 kg; the alumina consumption is reduced, and the rated consumption of the alumina for producing 1t 27.5 percent of hydrogen peroxide is reduced from 5.0kg to 3.9 kg.
The flow of the drying tower is adjusted according to the content and acidity of total degradation products in the working solution, the flow of the line 3 is adjusted, so that the acidic solution of the line 4 and the alkaline working solution of the line 1 pass through the drying tower to be neutralized, the working solution entering the clay bed is alkalescent, the capacity of regenerating anthraquinone by alumina is enhanced, the replacement cycle of the clay bed is prolonged, the service life of the clay bed can be prolonged by more than 20%, and the replacement cycle of 45 days is prolonged to 58 days; the flow of the line 3 and the flow of the line 1 are adjusted, so that the working solution from the clay bed is neutral or weakly acidic, the neutral or weakly acidic working solution and the acidic working solution of the line 3 are combined to be weakly acidic, only a few salt substances are generated, excessive accumulation of acidic substances in the working solution is avoided, the activity of a catalyst in a hydrogenation tower in a subsequent process is not influenced, the consumption of phosphoric acid of a system is reduced, and the quantitative consumption of phosphoric acid for producing 1t 27.5% hydrogen peroxide is reduced from 0.9kg to 0.7 kg; working solution flow meters are arranged at the inlet of the drying tower, the inlet of each clay bed and the line 3, the flow of the lines 1 and 3 is controlled by adopting a pneumatic valve, the liquid level of the raffinate separator is controlled by adopting a pneumatic valve in the line 2, the flow of the drying tower can be ensured to be stable, and alkali can not be generated due to flow fluctuation; finally, the content of degradation products in the working solution can be stably maintained below 30g/l, and the safe and stable operation of the device is ensured.
Example 5
The regeneration device of the working solution for producing the hydrogen peroxide by the anthraquinone method is characterized in that two clay beds are arranged in parallel, the alkali liquor in the drying tower is potassium carbonate solution with the mass percentage concentration of 45 percent, a raffinate separator is filled with polytetrafluoroethylene filler, and the rest is the same as that in example 1. The regeneration method was the same as in example 1.
After the raffinate working solution is separated by the raffinate separator, distributing the raffinate working solution according to the content of degradation products in the working solution; when the content of the degradation products is less than 10g/l, the volume percentage of the working solution which is separated by the raffinate separator and sent into the drying tower through the line 1 is 6 percent of the total volume of the raffinate working solution;
when the content of the degradation products is 10-20g/l, the volume percentage of the working solution which is separated by the raffinate separator and sent into the drying tower through the line 1 is 12 percent of the total volume of the raffinate working solution;
when the content of the degradation products is 20-35g/l, the volume percentage of the working solution which is sent into the drying tower through the line 1 after the raffinate working solution is separated by the raffinate separator is 35% of the total volume of the raffinate working solution.
Under the control of the process conditions, the whole hydrogen peroxide device can run stably.
In the working solution, a nonpolar solvent aromatic hydrocarbon mixture and a polar solvent are tetrabutyl urea and trioctyl phosphate, and anthraquinone is a mixture of 2-amylanthraquinone and 2-amyltetrahydroanthraquinone.
After the working solution from the extraction tower is separated by the raffinate separator, 18-50% of the working solution in volume percentage flows through a line 1, 50-82% of the working solution in volume percentage flows through a line 2, and 6-45% of the working solution in volume percentage flows through a line 3.
This example is applied to the manufacture of a 33 ten thousand ton/a 27.5 w% hydrogen peroxide device as an example:
by reducing the drying tower and the clay bed system, the investment of the working solution regeneration equipment is reduced by 28 percent, by canceling the flash evaporation system, the power consumption is reduced by 5 percent, and the running safety of the equipment is improved.
By optimizing the concentration and the type of the alkali, the regeneration efficiency of the drying tower and the clay bed is improved, the residual hydrogen peroxide in the working solution is decomposed more thoroughly, the alkali consumption is reduced, and the quantitative consumption of the alkali for producing 1t 27.5 percent hydrogen peroxide is reduced from 1kg to 0.8 kg; the alumina consumption is reduced and the alumina quota consumption for the production of 1t 27.5% hydrogen peroxide is reduced from 5.0kg to 4.0 kg.
The flow of the drying tower is adjusted according to the content and acidity of total degradation products in the working solution, the flow of the line 3 is adjusted, so that the acidic solution of the line 4 and the alkaline working solution of the line 1 pass through the drying tower to be neutralized, the working solution entering the clay bed is alkalescent, the capacity of regenerating anthraquinone by alumina is enhanced, the replacement cycle of the clay bed is prolonged, the service life of the clay bed can be prolonged by more than 20%, and the replacement cycle of 45 days is prolonged to 56 days; the flow of the line 3 and the flow of the line 1 are adjusted, so that the working solution from the clay bed is neutral or weakly acidic, the neutral or weakly acidic working solution and the acidic working solution of the line 3 are combined to be weakly acidic, only a few salt substances are generated, excessive accumulation of acidic substances in the working solution is avoided, the activity of a catalyst in a hydrogenation tower in a subsequent process is not influenced, the consumption of phosphoric acid of a system is reduced, and the quantitative consumption of phosphoric acid for producing 1t 27.5% hydrogen peroxide is reduced from 0.9kg to 0.7 kg; working solution flow meters are arranged at the inlet of the drying tower, the inlet of each clay bed and the line 3, the flow of the lines 1 and 3 is controlled by adopting a pneumatic valve, the liquid level of the raffinate separator is controlled by adopting a pneumatic valve in the line 2, the flow of the drying tower can be ensured to be stable, and alkali can not be generated due to flow fluctuation; finally, the content of degradation products in the working solution can be stably maintained below 30g/l, and the safe and stable operation of the device is ensured.
Comparative example 1
Taking a current 10 ten thousand tons/a 27.5 w% hydrogen peroxide production device as an example:
the consumption of 1kg of alkali, 5.0kg of alumina, 0.9kg of phosphoric acid and 45 days of clay bed replacement were rated for 1t of 27.5% hydrogen peroxide.
TABLE 1 Radded consumption of raw materials for 1t 27.5% hydrogen peroxide production versus cycle time for clay bed replacement
| Rated consumption of raw material | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Alkali, kg | 0.7 | 0.8 | 0.8 | 0.9 | 0.8 | 1.0 |
| Alumina, kg | 3.8 | 3.9 | 4.0 | 3.9 | 4.0 | 5.0 |
| Phosphoric acid, kg | 0.6 | 0.8 | 0.8 | 0.7 | 0.7 | 0.9 |
| Change period of clay bed | 68 | 60 | 56 | 58 | 56 | 45 |
Claims (9)
1. A regeneration device of working solution for producing hydrogen peroxide by an anthraquinone process is characterized by comprising a raffinate separator (2), a drying tower (3), an alkali separator (4) and a clay bed (5); the feed end of the raffinate separator (2) is connected with the extraction tower (1), the discharge end is divided into a line 1 and a line 2, and the line 1 is sequentially connected with a drying tower (3), an alkali separator (4) and a carclazyte bed (5); the line 2 is divided into two branches of a line 3 and a line 4, the line 4 is connected with the bottom of the clay bed (5), and an outlet pipeline at the top of the clay bed (5) is combined with the line 3 and then connected to the hydrogenation process; the line 1, the line 2, the line 3 and the line 4 are pipelines.
2. The regeneration device of claim 1, wherein the working fluid inlet of the raffinate separator is arranged at the lower part of the raffinate separator, the working fluid outlet is arranged at the upper part of the raffinate separator, and the bottom of the raffinate separator is provided with a discharge port; the raffinate separator is filled with polytetrafluoroethylene filler or stainless steel filler.
3. The regeneration apparatus as claimed in claim 1, wherein the inlet of the working fluid of the drying tower is disposed at the lower portion of the drying tower, the outlet is disposed at the upper portion of the drying tower, and the bottom portion is provided with a discharge port.
4. The regeneration apparatus as claimed in claim 1, wherein the inlet of the drying tower, the inlet of the clay bed and the line 3 are provided with flow meters; the lines 1, 2 and 3 are all provided with pneumatic valves.
5. The regeneration apparatus as claimed in claim 1, wherein the number of the clay beds is 1 to 4 and arranged in parallel.
6. The regeneration apparatus as claimed in claim 1, wherein the drying tower is filled with a lye.
7. The regeneration device of claim 1, wherein the working fluid from the extraction tower is separated by a raffinate separator and then divided into two paths, and the working fluid in the line 1 is sent to a drying tower for drying, then flows into a clay bed after passing through an alkali separator; part of the working solution in the line 2 enters the clay bed through the line 4, and the other part of the working solution is combined with the working solution treated by the clay bed through the line 3 and then enters the hydrogen peroxide production process flow for circulation.
8. The regeneration apparatus as claimed in claim 1, wherein after the separation of the working fluid from the extraction column by the raffinate separator, 5 to 60% by volume of the working fluid flows through the line 1, and 40 to 95% by volume of the working fluid flows through the line 2; the working fluid flowing through the line 2 respectively enters a line 3 and a line 4, wherein 5-50% of the working fluid in volume percentage flows through the line 3; the working liquids in the drying tower, the alkali separator, the clay bed, the line 1, the line 2, the line 3 and the line 4 all automatically flow in a gravity mode.
9. The regeneration device of claim 1, wherein the content of the degradation products in the working solution after the separation by the raffinate separator is divided into two paths according to the following principle:
when the content of the degradation products is less than 10g/l, the working solution flowing through the line 1 is less than 10 percent of the total volume of the working solution separated by the raffinate separator;
when the content of the degradation products is 10-20g/l, the working solution flowing through the line 1 is 10-30% of the total volume of the working solution separated by the raffinate separator;
when the content of the degradation products is 20-35g/l, the working solution flowing through the line 1 is 30-60% of the total volume of the working solution separated by the raffinate separator.
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| CN111620309B (en) * | 2020-06-24 | 2024-02-27 | 黎明化工研究设计院有限责任公司 | Regeneration method and regeneration device for working solution for producing hydrogen peroxide by anthraquinone process |
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