CN113620456A - Solvent recovery and waste acid treatment system and method suitable for producing acesulfame potassium - Google Patents
Solvent recovery and waste acid treatment system and method suitable for producing acesulfame potassium Download PDFInfo
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- CN113620456A CN113620456A CN202110741599.4A CN202110741599A CN113620456A CN 113620456 A CN113620456 A CN 113620456A CN 202110741599 A CN202110741599 A CN 202110741599A CN 113620456 A CN113620456 A CN 113620456A
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- 239000002699 waste material Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000011084 recovery Methods 0.000 title claims abstract description 34
- WBZFUFAFFUEMEI-UHFFFAOYSA-M Acesulfame k Chemical compound [K+].CC1=CC(=O)[N-]S(=O)(=O)O1 WBZFUFAFFUEMEI-UHFFFAOYSA-M 0.000 title claims abstract description 31
- 229960004998 acesulfame potassium Drugs 0.000 title claims abstract description 23
- 235000010358 acesulfame potassium Nutrition 0.000 title claims abstract description 23
- 239000000619 acesulfame-K Substances 0.000 title claims abstract description 23
- 238000010306 acid treatment Methods 0.000 title claims abstract description 15
- 239000002904 solvent Substances 0.000 title claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 458
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 103
- 238000007670 refining Methods 0.000 claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims description 95
- 238000005336 cracking Methods 0.000 claims description 34
- 238000004891 communication Methods 0.000 claims description 26
- 238000004821 distillation Methods 0.000 claims description 26
- 239000012530 fluid Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000010521 absorption reaction Methods 0.000 claims description 14
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 238000007363 ring formation reaction Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- JNONJXMVMJSMTC-UHFFFAOYSA-N hydron;triethylazanium;sulfate Chemical compound OS(O)(=O)=O.CCN(CC)CC JNONJXMVMJSMTC-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000010933 acylation Effects 0.000 description 4
- 238000005917 acylation reaction Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000003599 food sweetener Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003765 sweetening agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NVKQKAZYUPPRJX-UHFFFAOYSA-N 1,3,5-tribromo-2-(2,5-dibromophenyl)benzene Chemical group BrC1=CC=C(Br)C(C=2C(=CC(Br)=CC=2Br)Br)=C1 NVKQKAZYUPPRJX-UHFFFAOYSA-N 0.000 description 1
- 206010013911 Dysgeusia Diseases 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229960005164 acesulfame Drugs 0.000 description 1
- YGCFIWIQZPHFLU-UHFFFAOYSA-N acesulfame Chemical compound CC1=CC(=O)NS(=O)(=O)O1 YGCFIWIQZPHFLU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium peroxide Inorganic materials [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 1
- 235000019605 sweet taste sensations Nutrition 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a solvent recovery and waste acid treatment method and system suitable for acesulfame potassium production3The raw materials are used for cyclization reaction in the acesulfame potassium production process; the by-produced sulfuric acid was partially used for purification of water-washed methylene chloride, and partially used as it was for sale. On the one hand, solves the problem of waste acidSO that SO is3Recycling is obtained; on the other hand, concentrated sulfuric acid has the effects of removing water and strong oxidizing property, and the byproduct sulfuric acid is used in a refining section of dichloromethane, so that the recycled dichloromethane with qualified quality is obtained. Simple process, low energy consumption, low cost and accordance with the national industrial policy.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a solvent recovery and waste acid treatment system and method suitable for producing acesulfame potassium.
Background
Acesulfame is the common name of AK sugar (Acesulfame-K), the Chinese cultural name is 6-Methyl-1,2,3-oxathiazin-4(3H) -ketone-2, 2-potassium dioxide, and the English chemical name is 6-Methyl-1,2,3-oxathiazin-4(3H) -one 2,2-dioxide potassium salt. Appearance properties: colorless crystals. Solubility: is easily dissolved in water, and the solubility is 270g/L at 20 ℃. CAS number: 55589-62-3. The molecular formula is as follows: c4H4O4KNS. Molecular weight: 201.24. melting Point (. degree. C.): 229-232. Relative density (water ═ 1): 1.81. pH value: the pH value is 5.5-7.5. Acesulfame potassium has the advantages of safety, no toxicity, stable property, sweet taste, no bad aftertaste, proper price and the like, is one of the sweeteners with the best stability in the world at present, and is used as a sweetener in the aspects of food, medicine and the like.
Methylene chloride is a common solvent in the production of acesulfame k. The recovery of dichloromethane is an important section in the acesulfame potassium synthesis process. According to the traditional dichloromethane recovery process in the acesulfame potassium production process, washed dichloromethane firstly enters a first distillation tower for rough distillation, then enters a second distillation tower for dehydration, and finally enters a rectifying tower for refining and high boiling removal to obtain a finished dichloromethane product. The process for recovering the dichloromethane has long time and low capacity, so the production cost is high; the process is complex, the quality of the recycled dichloromethane is unstable, and the reaction is influenced when the dichloromethane is reused. In addition, a large amount of wastewater is generated in the production process of the acesulfame potassium, and the wastewater mainly contains sulfuric acid, triethylamine, dichloromethane, a small amount of acesulfame potassium and organic matters. The general process is as follows: the generated wastewater reacts with calcium carbonate, and CaSO is generated in the process of recycling triethylamine4.2H2O, washed with water and then raisedAnhydrous CaSO generated by warm calcination treatment process4. The process has high energy consumption and is easy to cause environmental pollution.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a solvent recovery and spent acid treatment method and system suitable for producing acesulfame k, which solves the problems of the prior art.
In order to achieve the above objects and other related objects, the present invention adopts the following technical solutions:
in a first aspect of the present invention, there is provided a solvent recovery and spent acid treatment system suitable for use in the production of acesulfame k, comprising:
the lightness removing device is used for removing lightness of waste acid to be recovered to obtain condensed dichloromethane and pretreated waste acid;
the cracking device is used for mixing and reacting the pretreated waste acid with liquid sulfur and air to crack the waste acid to obtain cracked gas;
the conversion device is used for converting the pyrolysis gas to obtain SO3A gas;
an absorption device for absorbing the SO3Gas to obtain fuming sulfuric acid;
a distillation device for distilling the oleum to obtain SO3And concentrated sulfuric acid;
the dichloromethane refining device is used for refining dichloromethane to be recovered by concentrated sulfuric acid from the distillation device to obtain waste acid and finished dichloromethane in a dichloromethane refining stage;
the light component removal device is in fluid communication with a cracking device, the cracking device is in fluid communication with the conversion device, the conversion device is in fluid communication with the absorption device, the absorption device is in fluid communication with the distillation device, and the distillation device is in fluid communication with the dichloromethane refining device.
Preferably, the dichloromethane refining device is in fluid communication with the light ends removal device, and is further configured to receive condensed dichloromethane from the light ends removal device and treat the condensed dichloromethane with concentrated sulfuric acid from the distillation device to obtain waste acid in the dichloromethane refining stage and dichloromethane.
Preferably, the waste acid to be recovered in the light-off device is from the extracted waste acid. The extracted waste acid refers to an acid layer obtained after acylation, cyclization and hydrolysis reactions is extracted by adopting dichloromethane, and raffinate is the waste acid. The waste acid after extraction contains sulfuric acid, triethylamine sulfate, ACH, water, acetic acid, acetone, dichloromethane and other components.
More preferably, the light ends removal device is also used for receiving waste acid of the dichloromethane refining stage. The waste acid in the dichloromethane refining stage contains sulfuric acid, triethylamine sulfate, water, acetone, dichloromethane and other components.
Preferably, the system further comprises an SO3Recovery unit, said SO3A recovery unit is in fluid communication with the distillation unit.
Preferably, the system further comprises a concentrated sulfuric acid recovery unit in fluid communication with the distillation unit.
Preferably, the system further comprises a dichloromethane recovery unit in fluid communication with the dichloromethane refining unit.
In the invention, the light component removal refers to removing dichloromethane in waste acid according to the boiling point of dichloromethane.
The cracking of the waste acid refers to that the sulfuric acid in the waste acid is subjected to cracking reaction at high temperature to generate SO2A gas.
The cracking gas mainly contains SO2、O2、SO3And (3) components.
Preferably, concentrated sulfuric acid is provided in the absorption device 4 for absorbing SO3A gas.
Conversion refers to the SO in the cracking gas under the action of a catalyst2And O2Reaction takes place to form SO3。
The purification of dichloromethane is to remove water and organic impurities in dichloromethane, thereby improving the quality of dichloromethane.
In a second aspect of the invention, there is provided the use of the aforementioned system for the recovery of dichloromethane and the treatment of spent acid generated during the production of acesulfame k.
In a third aspect of the invention, a solvent recovery and waste acid treatment method suitable for producing acesulfame potassium is provided, which comprises the following steps:
(1) removing light from waste acid to be recovered to obtain condensed dichloromethane and pretreated waste acid;
(2) mixing the pretreated waste acid obtained in the step (1) with liquid sulfur and air for reaction, and cracking the waste acid to obtain cracked gas;
(3) converting the pyrolysis gas obtained in the step (2) to obtain SO3A gas;
(4) absorbing SO obtained in step (3)3Gas to obtain fuming sulfuric acid;
(5) distilling the fuming sulfuric acid obtained in the step (4) to obtain SO3And concentrated sulfuric acid;
(6) and (4) treating dichloromethane to be recovered by using concentrated sulfuric acid obtained in the step (5) to obtain waste acid and dichloromethane in a dichloromethane refining stage.
Preferably, in the step (1), the waste acid to be recovered is waste acid after extraction. The extracted waste acid refers to an acid layer obtained after acylation, cyclization and hydrolysis reactions is extracted by adopting dichloromethane, and raffinate is the waste acid. The waste acid after extraction contains sulfuric acid, triethylamine sulfate, ACH, water, acetic acid, acetone, dichloromethane and other components.
Preferably, the waste acid to be recovered is also from the waste acid obtained in the dichloromethane refining stage in the step (6). The waste acid in the dichloromethane refining stage contains sulfuric acid, triethylamine sulfate, water, acetone, dichloromethane and other components.
Preferably, the dichloromethane to be recovered comes from washing dichloromethane with water. The washing of dichloromethane refers to the neutralization and layering of a dichloromethane layer after acylation, cyclization and hydrolysis reaction and a potassium hydroxide solution, the washing of the dichloromethane layer is carried out, and an organic layer after washing is the washing of dichloromethane. The washing dichloromethane contains AK, DCM, water, acetone, triethylamine and the like.
Preferably, the dichloromethane to be recovered also comprises condensed dichloromethane from step (1). The condensed dichloromethane contains dichloromethane and water components.
In the invention, the light component removal refers to removing dichloromethane in waste acid according to the boiling point of dichloromethane.
The cracking of the waste acid refers to that the sulfuric acid in the waste acid is subjected to cracking reaction under the high-temperature condition to generate SO2A gas.
The cracking gas mainly contains SO2、O2、SO3And (3) components.
Preferably, in step (4), concentrated sulfuric acid is used for absorbing SO3A gas.
Conversion means the SO in the cracked gas in the presence of a catalyst2And O2Reaction takes place to form SO3。
The purification of dichloromethane is to remove water and organic impurities in dichloromethane, thereby improving the quality of dichloromethane.
The solvent recovery and waste acid treatment system and method suitable for producing acesulfame potassium provided by the invention have the following beneficial effects:
the invention mainly aims at the problems of complex dichloromethane recovery process, long time, high production cost, unstable dichloromethane recovery quality and the like in the current acesulfame potassium synthesis process, and the problems of high energy consumption, easy environmental pollution and the like of a waste acid treatment process, and provides a system and a method integrating dichloromethane recovery and waste acid treatment. Waste acid generated in the production process of acesulfame potassium is pretreated to remove dichloromethane, and the pretreated waste acid is subjected to pyrolysis to prepare SO3The raw materials are used for cyclization reaction in the acesulfame potassium production process; the by-produced sulfuric acid is used for purification of a part for washing methylene chloride with water, and a part for use as it is sold. On the one hand, the treatment of waste acid is solved, SO that SO3Recycling is obtained; on the other hand, concentrated sulfuric acid has the effects of removing water and strong oxidizing property, and the byproduct sulfuric acid is used in a refining section of dichloromethane, so that the recycled dichloromethane with qualified quality is obtained. Simple process and low energy consumptionThe cost is reduced, and the method conforms to the national industrial policy.
Drawings
FIG. 1: the invention provides a schematic diagram of a solvent recovery and waste acid treatment system suitable for producing acesulfame potassium.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art. Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
A solvent recovery and spent acid treatment system suitable for use in the production of acesulfame k, as shown in figure 1, comprising:
the lightness-removing device 1 is used for removing lightness of waste acid to be recovered to obtain condensed dichloromethane and pretreated waste acid;
the cracking device 2 is used for mixing and reacting the pretreated waste acid with liquid sulfur and air to crack the waste acid to obtain cracked gas;
a conversion device 3 for converting the cracking gas to obtain SO3A gas;
an absorption device 4 for absorbing the SO3Gas to obtain fuming sulfuric acid;
a distillation device 5 for distilling the oleum to obtain SO3And concentrated sulfuric acid;
the dichloromethane refining device 6 is used for refining dichloromethane to be recovered by concentrated sulfuric acid from the distillation device 5 to obtain waste acid and dichloromethane in a dichloromethane refining stage;
the light component removal device 1 is in fluid communication with a cracking device 2, the cracking device 2 is in fluid communication with the conversion device, the conversion device 3 is in fluid communication with the absorption device 4, the absorption device 4 is in fluid communication with the distillation device 5, and the distillation device 5 is in fluid communication with the dichloromethane refining device 6.
In a preferred embodiment, the dichloromethane refining device 6 is in fluid communication with the light component removal device 1, and the dichloromethane refining device 6 is further configured to receive condensed dichloromethane from the light component removal device 1 and treat the condensed dichloromethane with concentrated sulfuric acid from the distillation device 5 to obtain waste acid from the dichloromethane refining stage and dichloromethane.
In a preferred embodiment, the waste acid to be recovered in the lightness-removing device 1 is derived from waste acid after extraction. The extracted waste acid refers to an acid layer obtained after acylation, cyclization and hydrolysis reactions is extracted by adopting dichloromethane, and raffinate is the waste acid. The waste acid after extraction contains sulfuric acid, triethylamine sulfate, ACH, water, acetic acid, acetone, dichloromethane and other components.
In another preferred embodiment, the light ends removal device 1 is also used for receiving waste acid from the dichloromethane refining stage. The waste acid in the dichloromethane refining stage contains sulfuric acid, triethylamine sulfate, water, acetone, dichloromethane and other components.
In a preferred embodiment, the system further comprises an SO3Recovery unit, said SO3The recovery means is in fluid communication with said distillation means 5.
In a preferred embodiment, the system further comprises a methylene dichloride recovery unit in fluid communication with the methylene dichloride refining unit 6.
The light component removal refers to removing the dichloromethane in the waste acid according to the boiling point of the dichloromethane.
The cracking of the waste acid refers to that the sulfuric acid in the waste acid is subjected to cracking reaction at high temperature to generate SO2A gas.
The cracking gas mainly contains SO2、O2、SO3And (3) components.
The conversion is SO in the cracking gas in the presence of a catalyst2And O2Reaction takes place to form SO3。
Concentrated sulfuric acid is provided in the absorption device 4 for absorbing SO3A gas.
The purification of dichloromethane is to remove water and organic impurities in dichloromethane, thereby improving the quality of dichloromethane.
Example 1
10.2kg of extracted waste acid (the sulfuric acid content is 55%) and 0.75kg of waste acid (the sulfuric acid content is 90%) from a dichloromethane refining section enter a light component removal device 1 for light component removal, namely dichloromethane in the waste acid is removed according to the boiling point of dichloromethane, 0.2kg of condensed dichloromethane and 10.75kg of pretreated waste acid are generated, the condensed dichloromethane enters a dichloromethane refining device 6, and the pretreated waste acid enters a cracking device 2. 1.5kg of liquid sulfur, 38.3kg of air and 10kg of pretreated waste acid react in a cracking device 2, so that the waste sulfuric acid is completely cracked at high temperature to generate cracked gas. The cracking gas enters a conversion device 3 to generate SO3A gas. SO (SO)3The gas enters the absorption device 4 and is absorbed by the concentrated sulfuric acid to generate fuming sulfuric acid. The fuming sulfuric acid enters a distillation device 5 to respectively obtain 4kgSO3And 6.2kg 98% sulfuric acid, the SO3The recovered raw material can be used as the raw material of the cyclization reaction in the production of acesulfame potassium, wherein 5.5kg of 98% sulfuric acid can be sold as a byproduct of concentrated sulfuric acid, and 0.7kg of 98% sulfuric acidThe obtained product is fed into a dichloromethane refining device 6. In the dichloromethane refining device 6, 0.2kg of condensed dichloromethane obtained by light component removal and 35.5kg of water-washed dichloromethane are treated by 0.7kg of concentrated sulfuric acid to obtain 35.4kg of qualified recovered dichloromethane, and 0.75kg of waste sulfuric acid enters the light component removal device 1. Recovery of SO3And the quality of the recycled dichloromethane meets the requirements of superior products.
TABLE 1
TABLE 2
Example 2
25kg of extracted waste acid (the sulfuric acid content is 60%) and 2.0kg of waste acid (the sulfuric acid content is 91%) from a dichloromethane refining section enter a light component removal device 1 for light component removal, namely dichloromethane in the waste acid is removed according to the boiling point of dichloromethane, 0.6kg of condensed dichloromethane and 26.4kg of pretreated waste acid are generated, the condensed dichloromethane enters a dichloromethane refining device 6, and the pretreated waste acid enters a cracking device 2. 2.5kg of liquid sulfur, 65kg of air and 26kg of pretreated waste acid react in the cracking device 2, so that the waste sulfuric acid is completely cracked at high temperature to generate cracking gas. The cracking gas enters a conversion device 3 to generate SO3A gas. SO (SO)3The gas enters the absorption device 4 and is absorbed by the concentrated sulfuric acid to generate fuming sulfuric acid. The fuming sulfuric acid enters a distillation device 5 to respectively obtain 12.2kgSO3And 9.7kg 98% sulfuric acid, the SO3The recovered raw materials can be used as raw materials for cyclization reaction in production of acesulfame potassium, wherein 7.9kg of 98% sulfuric acid can be sold as a byproduct of concentrated sulfuric acid, and in addition, 1.8kg of 98% sulfuric acid enters a dichloromethane refining device 6. In the dichloromethane refining device 6, 0.6kg of condensed dichloromethane and 88.5kg of water-washed dichloromethane obtained by light component removal are treated by 1.8kg of concentrated sulfuric acid to obtain 88.9kg of qualified recovered dichloromethane, and 2.0kg of waste sulfuric acid enters the light component removal device 1. Recovery of SO3And the quality of the recycled dichloromethane meets the requirements of superior products.
TABLE 3
TABLE 4
Example 3
25kg of extracted waste acid (the sulfuric acid content is 65%) and 2.5kg of waste acid (the sulfuric acid content is 92%) from a dichloromethane refining section enter a light component removal device 1 for light component removal, namely dichloromethane in the waste acid is removed according to the boiling point of dichloromethane, 0.5kg of condensed dichloromethane and 27kg of pretreated waste acid are generated, the condensed dichloromethane enters a dichloromethane refining device 6, and the pretreated waste acid enters a cracking device 2. 2.5kg of liquid sulfur, 65kg of air and 26kg of pretreated waste acid react in the cracking device 2, so that the waste sulfuric acid is completely cracked at high temperature to generate cracking gas. The cracking gas enters a conversion device 3 to generate SO3A gas. SO (SO)3The gas enters the absorption device 4 and is absorbed by the concentrated sulfuric acid to generate fuming sulfuric acid. The fuming sulfuric acid enters a distillation device 5 to respectively obtain 10kgSO3And 14.2kg 98% sulfuric acid, the SO3The recovered raw materials can be used as raw materials for cyclization reaction in production of acesulfame potassium, wherein 11.9kg of 98% sulfuric acid can be sold as a byproduct of concentrated sulfuric acid, and in addition, 2.3kg of 98% sulfuric acid enters a dichloromethane refining device 6. In the dichloromethane refining device 6, 0.5kg of condensed dichloromethane and 88.5kg of water-washed dichloromethane obtained by light component removal are treated by 2.3kg of concentrated sulfuric acid to obtain 88kg of recycled dichloromethane with qualified quality, and 2.5kg of waste sulfuric acid enters the light component removal device 1. Recovery of SO3And the quality of the recycled dichloromethane meets the requirements of superior products.
TABLE 5
TABLE 6
The waste acid generated in the production process of acesulfame potassium is pretreated to remove dichloromethane, and the pretreated waste acid is subjected to pyrolysis to prepare SO3The raw materials are used for cyclization reaction in the acesulfame potassium production process; the by-produced sulfuric acid was partially used for purification of water-washed methylene chloride, and partially used as it was for sale. On the one hand, the treatment of waste acid is solved, SO that SO3Recycling is obtained; on the other hand, concentrated sulfuric acid has the effects of removing water and strong oxidizing property, and the byproduct sulfuric acid is used in a refining section of dichloromethane, so that the recycled dichloromethane with qualified quality is obtained. Simple process, low energy consumption, low cost and accordance with the national industrial policy. Specifically, compared with the conventional process, the treatment cost of waste acid generated in the production process of acesulfame potassium can be reduced by 30%, and the recovery cost of dichloromethane can be reduced by 60%.
In conclusion, the present invention effectively overcomes various disadvantages of the prior art and has high industrial utilization value.
The above examples are intended to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.
Claims (11)
1. A solvent recovery and spent acid treatment system suitable for use in the production of acesulfame k, comprising:
the lightness removing device is used for removing lightness of waste acid to be recovered to obtain condensed dichloromethane and pretreated waste acid;
the cracking device is used for mixing and reacting the pretreated waste acid with liquid sulfur and air to crack the waste acid to obtain cracked gas;
the conversion device is used for converting the pyrolysis gas to obtain SO3A gas;
an absorption device for absorbing the SO3Gas to obtain fuming sulfuric acid;
a distillation device for distilling the oleum to obtain SO3And concentrated sulfuric acid;
the dichloromethane refining device is used for refining dichloromethane to be recovered by concentrated sulfuric acid from the distillation device to obtain waste acid and finished dichloromethane in a dichloromethane refining stage;
the light component removal device is in fluid communication with a cracking device, the cracking device is in fluid communication with the conversion device, the conversion device is in fluid communication with the absorption device, the absorption device is in fluid communication with the distillation device, and the distillation device is in fluid communication with the dichloromethane refining device.
2. The system of claim 1, wherein the methylene dichloride refining unit is in fluid communication with the light ends removal unit, the methylene dichloride refining unit further configured to receive condensed methylene dichloride from the light ends removal unit and treat it with concentrated sulfuric acid from the distillation unit to obtain spent acid from the methylene dichloride refining stage and methylene dichloride.
3. The system according to claim 1 or 2, wherein the spent acid to be recovered in the lightener comes from the spent acid after extraction.
4. The system of claim 3, wherein the light ends removal device is further configured to receive spent acid from the dichloromethane refining stage.
5.The system of any one of claims 1-4, further comprising any one or more of the following features: (1) the system further comprises a SO3Recovery unit, said SO3A recovery unit in fluid communication with the distillation unit; (2) the system further comprises a concentrated sulfuric acid recovery unit in fluid communication with the distillation unit; (3) the system also includes a methylene dichloride recovery unit in fluid communication with the methylene dichloride refining unit.
6. Use of a system according to any one of claims 1 to 5 for the recovery of dichloromethane and waste acid treatment generated during the production of acesulfame k.
7. A solvent recovery and waste acid treatment method suitable for producing acesulfame potassium comprises the following steps: (1) removing light from waste acid to be recovered to obtain condensed dichloromethane and pretreated waste acid; (2) mixing the pretreated waste acid obtained in the step (1) with liquid sulfur and air for reaction, and cracking the waste acid to obtain cracked gas; (3) converting the pyrolysis gas obtained in the step (2) to obtain SO3A gas; (4) absorbing SO obtained in step (3)3Gas to obtain fuming sulfuric acid; (5) distilling the fuming sulfuric acid obtained in the step (4) to obtain SO3And concentrated sulfuric acid; (6) and (4) treating dichloromethane to be recovered by using concentrated sulfuric acid obtained in the step (5) to obtain waste acid and dichloromethane in a dichloromethane refining stage.
8. A method according to claim 7, characterized in that the spent acid to be recovered is derived from the spent acid after extraction.
9. The process according to claim 8, wherein the waste acid to be recovered also comes from the waste acid of the dichloromethane refining stage obtained in step (6).
10. The process according to claim 7, wherein the dichloromethane to be recovered further comprises condensed dichloromethane from step (1).
11. The process according to any one of claims 7 to 10, wherein in step (4) SO is absorbed by concentrated sulfuric acid3A gas.
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| CN113666342A (en) * | 2021-07-13 | 2021-11-19 | 南通醋酸化工股份有限公司 | Waste acid treatment method and system for producing acesulfame potassium |
| WO2023123405A1 (en) * | 2021-12-31 | 2023-07-06 | 安徽金禾实业股份有限公司 | Method and apparatus for processing hydrolysis reaction product containing acesulfame |
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