A kind of dimethyl sulfoxide preparation device and preparation method capable of removing anions

Abstract

The present invention discloses a dimethyl sulfoxide preparation device and preparation method capable of removing anions, the preparation device comprises a reaction unit and a distillation unit, and also comprises an ion exchange unit; the ion exchange unit comprises a crude sulfoxide buffer tank, and also comprises a plurality of groups of ion exchangers arranged in parallel; the feed port of the ion exchanger is connected to the crude sulfoxide buffer tank through a crude sulfoxide feeding pump, and the discharge port of the ion exchanger is connected to the distillation unit; and also comprises a regeneration liquid buffer tank for holding regeneration liquid. In this scheme, the crude sulfoxide prepared by the hydrogen peroxide method contains trace amounts of phosphoric acid, nitric acid and sulfate ions adsorbed by materials such as ion exchange resin, activated carbon and molecular sieve, thereby reducing corrosion to the distillation equipment, and at the same time, the by-product sulfone can be further purified in the subsequent distillation system, thereby reducing raw material consumption and energy consumption.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical industry, and in particular relates to a preparation device and a preparation method of dimethyl sulfoxide capable of removing anions. Background Art

[0002] Dimethyl sulfoxide is an important chemical product, widely used in fluorochloroaniline, acrylic, aromatic hydrocarbon extraction, external medicine, inositol nicotinate, antioxidant 1010, synthetic berberine, esterification accelerator, Chinese medicine extraction agent, water-based paint antifreeze, capacitors, tumor treatment, paint stripper, trifluoronitrobenzene, sucrose stearate, chlorofiber, paraffin refining, automobile antifreeze in high-cold areas, kettle cleaning agent, pesticide synergist, etc.

[0003] Hydrogen peroxide itself is chemically unstable and easily decomposed. Phosphoric acid can react with metal ions (such as iron, copper, manganese, etc.) in hydrogen peroxide to form complexes, thereby reducing the catalytic effect of these metal ions on the decomposition of hydrogen peroxide, allowing hydrogen peroxide to exist more stably and extend its shelf life.

[0004] Phosphoric acid can help control the pH value of the hydrogen peroxide system. The appropriate pH range helps hydrogen peroxide to perform its best and can further enhance the stability of hydrogen peroxide.

[0005] In order to improve the stability of hydrogen peroxide and prevent its decomposition, stabilizers containing phosphoric acid or its salts may be added during the production process. These stabilizers can combine with impurities such as metal ions in hydrogen peroxide to inhibit the decomposition of hydrogen peroxide, but they will also cause hydrogen peroxide to contain a certain amount of phosphoric acid, nitric acid and sulfate ions. In the production of dimethyl sulfoxide, these ionic groups will not only cause corrosion to the equipment during the distillation process, but the high boiling point of ionic compounds will also cause these substances to be enriched in the by-product dimethyl sulfone, making it difficult to purify the by-product and the raw material consumption remains high. Summary of the invention

[0006] The purpose of the present invention is to provide a dimethyl sulfoxide preparation device and application capable of removing anions, wherein the crude sulfoxide prepared by the hydrogen peroxide method contains trace amounts of phosphoric acid, nitric acid and sulfate ions adsorbed by materials such as ion exchange resin, activated carbon and molecular sieve, thereby reducing the corrosion of distillation equipment, and further purifying the by-product sulfone in the subsequent distillation system, thereby reducing raw material consumption and energy consumption.

[0007] The present invention is achieved through the following technical solutions: A preparation device for dimethyl sulfoxide capable of removing anions, comprising a reaction unit and a distillation unit, characterized in that: it also comprises an ion exchange unit; The ion exchange unit includes a crude sulfoxide buffer tank connected to the reaction unit or the distillation unit, and also includes a plurality of groups of ion exchangers arranged in parallel; the feed port of the ion exchanger is connected to the crude sulfoxide buffer tank through a crude sulfoxide feeding pump, and the discharge port of the ion exchanger is connected to the distillation unit; It also includes a regeneration liquid buffer tank for containing regeneration liquid. The regeneration liquid buffer tank is connected to the regeneration liquid feed port of the ion exchanger through a regeneration liquid feeding pump, and the regeneration liquid discharge port of the ion exchanger is connected to the sewage treatment system.

[0008] Further: the ion exchangers have two groups.

[0009] Furthermore: the ion exchanger is provided with a filler for adsorbing ions, and the filler is a mixture of one or more of ion exchange resin, activated carbon, molecular sieve, activated alumina, and silica gel.

[0010] Further: the regeneration liquid is sodium hydroxide solution or water.

[0011] Furthermore: the distillation unit includes two or more distillation towers 31.

[0012] The present invention also discloses a method for preparing dimethyl sulfoxide, comprising a reaction step, a deionization step and a distillation step; wherein: The reaction steps: S11, the raw materials hydrogen peroxide and sulfide are pumped to a pressure of 0.1~3Mpa.G and then injected into the sulfoxide reaction unit, the reaction pressure is 0.1~3Mpa.G, and the temperature is 10~100℃; The ion exchange step: S21: The crude sulfoxide enters the crude sulfoxide buffer tank, and enters the ion exchanger after being pressurized by the crude sulfoxide feeding pump; S22: the crude sulfoxide is subjected to ion exchange with a filler in the ion exchanger in an ion exchanger, and the deionized crude sulfoxide after the ion exchange is sent to a subsequent process section; S23: When the crude sulfoxide after passing through the ion exchanger is detected to still contain anions such as phosphate, nitrate and sulfate exceeding the specified value, it is proved that the filler in the ion exchanger needs to be regenerated. At this time, the regeneration liquid in the regeneration liquid buffer tank is pressurized by the regeneration liquid feeding pump and then pumped into the ion exchanger to regenerate the ion exchanger; The distillation step: S31: the crude sulfoxide is distilled in a sulfoxide removal tower, and the recovered sulfide obtained at the top of the tower is dehydrated in a thioether three-stage dehydration tank, and the organic phase returns to the refined sulfide buffer tank and then re-enters the reactor to participate in the reaction, and the aqueous phase enters the sulfoxide wastewater removal tower; the concentrated sulfoxide removal sulfoxide dehydration tower at the bottom of the tower continues to distill; S32: The sulfoxide distillation wastewater at the top of the sulfoxide dehydration tower is sent to the external pipe network, and the concentrated sulfoxide at the bottom of the tower enters the sulfoxide distillation tower for further distillation; S33: sulfoxide distillation tower top sulfoxide removal finished product storage tank, tower bottom containing sulfoxide sulfone removal sulfone crystallization kettle; S34: The sulfoxide wastewater tower top recovers sulfide to go to the sulfide buffer tank, and the sulfoxide distillation wastewater at the bottom of the tower goes to the external pipe network.

[0013] Furthermore: the operating temperature of the ion exchanger is 10-150°C; the operating pressure is 0.1-2MpaG.

[0014] Further: it also includes step S35: the sulfoxide-containing sulfoxide solution from the bottom of the sulfoxide distillation tower is cooled in the sulfone crystallization kettle to precipitate crystals and then enters the sulfone centrifuge, the dimethyl sulfone centrifuged is bagged, and the centrifuged mother liquor is sent to the centrifuged mother liquor storage tank and then pumped to the crude sulfoxide buffer tank.

[0015] Further: the reaction unit includes multiple groups of reactors, and the reactor is one of a tubular reactor, a kettle reactor, and a microchannel reactor.

[0016] The advantages of the present invention are: 1. Remove trace amounts of phosphoric acid, nitric acid and sulfate ions contained in the raw hydrogen peroxide before distillation to reduce corrosion to the distillation equipment.

[0017] 2. Remove trace phosphoric acid, nitric acid and sulfate ions contained in the raw material hydrogen peroxide, further purify the by-product sulfone, reduce raw material consumption and reduce energy consumption.

[0018] 3. Use ion exchange resins, activated carbon, molecular sieves and other materials to adsorb phosphoric acid, nitric acid and sulfate ions without introducing other substances, thereby reducing the difficulty of purification and reducing waste emissions. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a schematic diagram of the overall structure of the device of the present invention; Figure 2 It is a schematic diagram of the structure of the deionization device in the distillation unit; Figure 3 It is a process flow chart of the present invention. DETAILED DESCRIPTION

[0020] As attached Figure 1-3 As shown, the present invention discloses a preparation device for dimethyl sulfoxide capable of removing anions, comprising a reaction unit 1 and a distillation unit 3, and also comprising an ion exchange unit 1; The ion exchange unit 2 includes a crude sulfoxide buffer tank 21 connected to the reaction unit or the distillation unit, and also includes a plurality of groups of ion exchangers 23 arranged in parallel; the feed port of the ion exchanger is connected to the crude sulfoxide buffer tank through a crude sulfoxide feeding pump 22, and the discharge port of the ion exchanger is connected to the distillation unit; It also includes a regeneration liquid buffer tank 24 for containing regeneration liquid. The regeneration liquid buffer tank is connected to the regeneration liquid feed port of the ion exchanger through a regeneration liquid feeding pump 25, and the regeneration liquid discharge port of the ion exchanger is connected to the sewage treatment system.

[0021] Preferably, the ion exchangers are provided in two or three groups, so that when one group is in use, at least one of the remaining groups is in a regenerating or regenerated state, so as to ensure that the ion exchangers can be replaced at any time.

[0022] Preferably, a filler for adsorbing ions is arranged inside the ion exchanger, and the filler is a mixture of one or more of ion exchange resin, activated carbon, molecular sieve, activated alumina, and silica gel.

[0023] Preferably, the regeneration liquid is a sodium hydroxide solution or water, which can neutralize the anions adsorbed by the filler to achieve the regeneration effect.

[0024] Preferably, the distillation unit comprises two or more distillation towers, and the distillation towers are connected in series to separate the by-products in the product step by step.

[0025] The present invention also discloses a method for preparing dimethyl sulfoxide, which comprises a reaction step, a deionization step and a distillation step; The reaction steps are carried out in the reaction unit, as follows: S11, the raw materials hydrogen peroxide and sulfide are pumped to a pressure of 0.1~3Mpa.G and then injected into the sulfoxide reaction unit, the reaction pressure is 0.1~3Mpa.G, and the temperature is 10~100℃; The ion exchange step: S21: The crude sulfoxide enters the crude sulfoxide buffer tank, and enters the ion exchanger after being pressurized by the crude sulfoxide feeding pump; S22: the crude sulfoxide is subjected to ion exchange with a filler in the ion exchanger in an ion exchanger, and the deionized crude sulfoxide after the ion exchange is sent to a subsequent process section; S23: When the crude sulfoxide after passing through the ion exchanger is detected to still contain anions such as phosphate, nitrate and sulfate exceeding the specified value, it is proved that the filler in the ion exchanger needs to be regenerated. At this time, the regeneration liquid in the regeneration liquid buffer tank is pressurized by the regeneration liquid feeding pump and then pumped into the ion exchanger to regenerate the ion exchanger; The distillation step: S31: the crude sulfoxide is distilled in a sulfoxide removal tower, and the recovered sulfide obtained at the top of the tower is dehydrated in a thioether three-stage dehydration tank, and the organic phase returns to the refined sulfide buffer tank and then re-enters the reactor to participate in the reaction, and the aqueous phase enters the sulfoxide wastewater removal tower; the concentrated sulfoxide removal sulfoxide dehydration tower at the bottom of the tower continues to distill; S32: The sulfoxide distillation wastewater at the top of the sulfoxide dehydration tower is sent to the external pipe network, and the concentrated sulfoxide at the bottom of the tower enters the sulfoxide distillation tower for further distillation; S33: sulfoxide distillation tower top sulfoxide removal finished product storage tank, tower bottom containing sulfoxide sulfone removal sulfone crystallization kettle; S34: The sulfoxide wastewater tower top recovers sulfide to go to the sulfide buffer tank, and the sulfoxide distillation wastewater at the bottom of the tower goes to the external pipe network.

[0026] Preferably, the operating temperature of the ion exchanger is 10-150° C. and the operating pressure is 0.1-2 MpaG.

[0027] Preferably, the method further comprises step S35: the sulfoxide-containing sulfoxide solution from the bottom of the sulfoxide distillation tower is cooled in the sulfone crystallization kettle to precipitate crystals and then enters a sulfone centrifuge, the dimethyl sulfone centrifuged is bagged, and the centrifuged mother liquor is sent to the centrifuged mother liquor storage tank and then pumped to the crude sulfoxide buffer tank. The sulfoxide-containing sulfoxide solution from the bottom of the sulfoxide distillation tower can be centrifuged or directly used as a byproduct without centrifugation.

[0028] Preferably, the reaction unit comprises a plurality of groups of reactors, and the reactor is one of a tubular reactor, a kettle reactor, a microchannel reactor and other types of reactors.

[0029] In this scheme, a deionization device is arranged behind the reactor. Specifically, the deionization device can be installed before distillation (after the reaction unit), between distillation (between two adjacent distillation towers), after distillation, and before centrifugation and after centrifugation (in front of or behind the centrifuge, the centrifuge is arranged behind the distillation tower of the distillation unit) as needed. The crude sulfoxide can effectively remove the trace phosphoric acid, nitric acid and sulfate ions brought by the raw material hydrogen peroxide before or during distillation, thereby effectively reducing the corrosion of the distillation equipment during the reaction process, reducing the anti-corrosion requirements of the distillation equipment, and improving the service life of the equipment, while reducing the impurity content in the product. The deionization device can remove the trace phosphoric acid, nitric acid and sulfate ions contained in the reaction product, further purify the by-product sulfone, reduce the raw material consumption in the distillation process, reduce energy consumption, and greatly reduce the difficulty of the distillation process. At the same time, the fillers used in the deionization device are ion exchange resins, activated carbon and molecular sieves, etc., which adsorb phosphoric acid, nitric acid and sulfate ions without introducing other substances, reducing the difficulty of purification and reducing waste emissions.

Claims

1. A preparation device for dimethyl sulfoxide capable of removing anions, comprising a reaction unit and a distillation unit, characterized in that: Also included is an ion exchange unit; The ion exchange unit includes a crude sulfoxide buffer tank connected to the reaction unit or the distillation unit, and also includes a plurality of groups of ion exchangers arranged in parallel; the feed port of the ion exchanger is connected to the crude sulfoxide buffer tank through a crude sulfoxide feeding pump, and the discharge port of the ion exchanger is connected to the distillation unit; It also includes a regeneration liquid buffer tank for containing regeneration liquid. The regeneration liquid buffer tank is connected to the regeneration liquid feed port of the ion exchanger through a regeneration liquid feeding pump, and the regeneration liquid discharge port of the ion exchanger is connected to the sewage treatment system.

2. The device for preparing dimethyl sulfoxide capable of removing anions according to claim 1, characterized in that: The ion exchangers have two groups.

3. The device for preparing dimethyl sulfoxide capable of removing anions according to claim 1, characterized in that: The ion exchanger is provided with a filler for adsorbing ions, and the filler is a mixture of one or more of ion exchange resin, activated carbon, molecular sieve, activated alumina, and silica gel.

4. The device for preparing dimethyl sulfoxide capable of removing anions according to claim 1, characterized in that: The regeneration liquid is sodium hydroxide solution or water.

5. The device for preparing dimethyl sulfoxide capable of removing anions according to claim 1, characterized in that: The distillation unit includes two or more distillation towers.

6. A method for preparing dimethyl sulfoxide, using the device as described in any one of claims 1 to 5, characterized in that: It includes a reaction step, a deionization step and a distillation step; The reaction steps: S11, the raw materials hydrogen peroxide and thioether are pumped to a pressure of 0.1-3 Mpa.G and then pumped into a sulfoxide reaction unit to prepare crude sulfoxide, the reaction pressure is 0.1-3 Mpa.G, and the temperature is 10-100°C; The ion exchange step: S21: The crude sulfoxide enters the crude sulfoxide buffer tank, and enters the ion exchanger after being pressurized by the crude sulfoxide feeding pump; S22: the crude sulfoxide is subjected to ion exchange with a filler in the ion exchanger in an ion exchanger, and the deionized crude sulfoxide after the ion exchange is sent to a subsequent process section; S23: When the crude sulfoxide after passing through the ion exchanger is detected to still contain anions such as phosphate, nitrate and sulfate exceeding the specified value, it is proved that the filler in the ion exchanger needs to be regenerated. At this time, the regeneration liquid in the regeneration liquid buffer tank is pressurized by the regeneration liquid feeding pump and then pumped into the ion exchanger to regenerate the ion exchanger; The distillation step is carried out in a distillation unit, as follows: S31: the crude sulfoxide is distilled in a sulfoxide removal tower, and the recovered sulfide obtained at the top of the tower is dehydrated in a thioether three-stage dehydration tank, and the organic phase returns to the refined sulfide buffer tank and then re-enters the reactor to participate in the reaction, and the aqueous phase enters the sulfoxide wastewater removal tower; the concentrated sulfoxide removal sulfoxide dehydration tower at the bottom of the tower continues to distill; S32: The sulfoxide distillation wastewater at the top of the sulfoxide dehydration tower is sent to the external pipe network, and the concentrated sulfoxide at the bottom of the tower enters the sulfoxide distillation tower for further distillation; S33: sulfoxide distillation tower top sulfoxide removal finished product storage tank, tower bottom containing sulfoxide sulfone removal sulfone crystallization kettle; S34: The sulfoxide wastewater tower top recovers sulfide to go to the sulfide buffer tank, and the sulfoxide distillation wastewater at the bottom of the tower goes to the external pipe network.

7. A method for preparing dimethyl sulfoxide according to claim 6, characterized in that: The operating temperature of the ion exchanger is 10-150°C; the operating pressure is 0.1-2MpaG.

8. The method for preparing dimethyl sulfoxide according to claim 6, characterized in that: The step S35 is also included: the sulfoxide-containing sulfoxide solution from the bottom of the sulfoxide distillation tower is cooled in the sulfone crystallization kettle to precipitate crystals and then enters the sulfone centrifuge, the dimethyl sulfone centrifuged is bagged, and the centrifuged mother liquor is sent to the centrifuged mother liquor storage tank and then pumped to the crude sulfoxide buffer tank.

9. The method for preparing dimethyl sulfoxide according to claim 6, characterized in that: The reaction unit comprises a plurality of groups of reactors, and the reactor is one of a tubular reactor, a kettle reactor and a microchannel reactor.

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