CN117024370A - Microchannel reaction process for oxidation chlorination in saccharin production - Google Patents
Microchannel reaction process for oxidation chlorination in saccharin production Download PDFInfo
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- CN117024370A CN117024370A CN202311072977.XA CN202311072977A CN117024370A CN 117024370 A CN117024370 A CN 117024370A CN 202311072977 A CN202311072977 A CN 202311072977A CN 117024370 A CN117024370 A CN 117024370A
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- reaction
- microchannel
- oxidation
- saccharin
- chlorination
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 66
- 229940081974 saccharin Drugs 0.000 title claims abstract description 38
- 235000019204 saccharin Nutrition 0.000 title claims abstract description 38
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 title claims abstract description 38
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 22
- 230000003647 oxidation Effects 0.000 title claims abstract description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 48
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 230000001590 oxidative effect Effects 0.000 claims abstract description 37
- 239000007800 oxidant agent Substances 0.000 claims abstract description 35
- 230000010718 Oxidation Activity Effects 0.000 claims abstract description 28
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 claims abstract description 25
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000012546 transfer Methods 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- 229910052952 pyrrhotite Inorganic materials 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 17
- 239000012498 ultrapure water Substances 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 9
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 9
- 229940099607 manganese chloride Drugs 0.000 claims description 9
- 235000002867 manganese chloride Nutrition 0.000 claims description 9
- 239000011565 manganese chloride Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052683 pyrite Inorganic materials 0.000 claims description 7
- 239000011028 pyrite Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- 238000007670 refining Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 206010007269 Carcinogenicity Diseases 0.000 description 2
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical class C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 2
- 231100000260 carcinogenicity Toxicity 0.000 description 2
- 230000007670 carcinogenicity Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000003599 food sweetener Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000003765 sweetening agent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- RIFBCJROYYDUNQ-UHFFFAOYSA-N 2-methoxycarbonylbenzenediazonium Chemical class COC(=O)C1=CC=CC=C1[N+]#N RIFBCJROYYDUNQ-UHFFFAOYSA-N 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000926 not very toxic Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 201000001474 proteinuria Diseases 0.000 description 1
- -1 saccharin anion Chemical class 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
- C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
- B01J2523/17—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/70—Constitutive chemical elements of heterogeneous catalysts of Group VII (VIIB) of the Periodic Table
- B01J2523/72—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/842—Iron
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of saccharin production, in particular to a microchannel reaction process for oxidation and chlorination in saccharin production, which comprises the steps of respectively introducing sulfinic acid, toluene, a composite oxidant and chlorine into a microchannel reactor for reaction; the microchannel reactor is an enhanced mass transfer type microchannel reactor and comprises a preheating module, a reaction module and a cooling module. According to the invention, the oxidation and chlorination reaction in saccharin production is carried out in the micro-channel, and the composite oxidant consisting of the oxidation activity promoter and hydrogen peroxide is added, so that not only can part of liquid chlorine be replaced to be used as the oxidant, but also potential safety hazards can be effectively reduced, and the composite oxidant has high oxidation activity, and can better promote sulfinic acid to generate toluenesulfonyl chloride through reaction, thereby improving the conversion rate of sulfinic acid, the yield and the purity of toluenesulfonyl chloride, further having promotion effect on improving the yield and the purity of saccharin, and being beneficial to industrialized mass production of saccharin.
Description
Technical Field
The invention relates to the technical field of saccharin production, in particular to a microchannel reaction process for oxidation chlorination in saccharin production.
Background
Saccharin is a commonly used synthetic sweetener in the food industry and has the longest history of use, but is also the most controversial synthetic sweetener. Saccharin is 300-500 times sweeter than sucrose, and is not decomposed in organism, and is discharged from the body through kidney. However, it is not very toxic and is mainly in its carcinogenicity. Recent studies have shown that saccharin carcinogenicity may not be caused by saccharin but is associated with sodium ions and high proteinuria in rats. The saccharin anion can act as a carrier for sodium ions resulting in a change in the physiological properties of urine.
Numerous synthetic methods of saccharin are disclosed, for example, in the patent publication No. CN111269195A, which discloses a synthetic method for preparing saccharin, wherein 1, 2-benzisothiazolin-3-one compounds are subjected to oxidation reaction with an oxidizing agent, and the oxidizing agent oxidizes thioether of the 1, 2-benzisothiazolin-3-one compounds into sulfamide to obtain o-benzoyl sulfamide compounds. Also for example, a method for producing saccharin from an o-methoxycarbonyl benzene diazonium salt as an anthranilate derivative is well known. As other methods, a method of oxidizing and chlorinating sulfinic acid is widely used. However, in the method for oxidizing and chlorinating sulfinic acid, liquid chlorine is used as an oxidant, so that the method has extremely toxic effects, has great potential safety hazards in industrial production reaction, and has lower yield of tosyl chloride due to lower reaction rate in the whole synthesis process, thereby adversely affecting the yield and purity of subsequent saccharin.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a microchannel reaction process for oxidation chlorination in saccharin production.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a microchannel reaction process for oxidation chlorination in saccharin production comprises the steps of respectively introducing sulfinic acid, toluene, a compound oxidant and chlorine into a microchannel reactor for reaction;
the microchannel reactor is an enhanced mass transfer type microchannel reactor and comprises a preheating module, a reaction module and a cooling module.
As a further preferred embodiment of the invention, the hydraulic diameter of the microchannel reactor is 1-8mm;
the temperature of the reaction is 40-60 ℃ and the pressure is 0.8-1.5MPa.
As a further preferable scheme of the invention, the dosage proportion of sulfinic acid, toluene, composite oxidant and chlorine in the microchannel reactor is (12-20) g: (150-280) mL: (1.2-2.6) g: (0.1-0.3) m 3 。
As a further preferable mode of the invention, the reaction residence time of the mixture of sulfinic acid, toluene and the composite oxidant and chlorine in the reaction module is 10-20min.
As a further preferable mode of the present invention, after the reaction is completed, the toluene sulfonyl chloride is obtained by filtering, decoloring and then refining.
As a further preferable scheme of the invention, the composite oxidant consists of an oxidation activity promoter and hydrogen peroxide according to a solid-to-liquid ratio of 1g: (80-100) mL;
the concentration of the hydrogen peroxide is 20-25wt%;
the preparation method of the oxidation activity promoter comprises the following steps:
1) Adding copper acetate, deionized water, ethylene glycol and cetyltrimethylammonium bromide into a container, magnetically stirring and dissolving for 30-50min to obtain a mixed solution, and simultaneously dispersing the composite pyrrhotite into the mixed solution of the deionized water and the ethylene glycol, and carrying out ultrasonic dispersion for 2-5h to obtain a dispersion;
2) Mixing the mixed solution and the dispersion liquid with equal volume, stirring for 3-5h at 100-150r/min, centrifuging after the reaction is finished, washing the product with ethanol and deionized water repeatedly, and vacuum drying in a 50-60 ℃ oven for 3-6h to obtain the required oxidation activity promoter.
As a further preferable scheme of the invention, the dosage proportion of the copper acetate, the deionized water, the ethylene glycol and the hexadecyl trimethyl ammonium bromide in the mixed solution is (5-10) mg: (5-10) mL: (5-10) mL: (48-80) mg;
in the dispersion liquid, the dosage proportion of the composite pyrrhotite, deionized water and glycol is (20-30) mg: (5-10) mL: (5-10) mL.
As a further preferable scheme of the invention, the preparation method of the composite pyrrhotite comprises the following steps:
1) Grinding pyrite by superfine grinding, soaking in hydrochloric acid solution for 24-30h, centrifuging and leaching with ultrapure water, drying, placing into a tube furnace, heating to 620-650 ℃ under nitrogen atmosphere, calcining for 3-5h, controlling the flow rate of nitrogen to 10-20mL/min during calcining, taking out the product after calcining, and cooling to room temperature under nitrogen atmosphere to obtain pyrrhotite;
2) Uniformly dispersing pyrrhotite in ultrapure water, then rapidly adding tetramethyl ammonium hydroxide and hydrogen peroxide, fully mixing, then adding manganese chloride solution, stirring at 80-130r/min overnight, centrifuging, repeatedly cleaning precipitate with ultrapure water and methanol, and drying to obtain the composite pyrrhotite.
As a further preferable mode of the invention, the concentration of the hydrochloric acid solution is 1-3wt%;
in the tube furnace, the heating rate is 10-15 ℃/min.
As a further preferable scheme of the invention, the dosage proportion of the pyrrhotite, the ultrapure water, the tetramethyl ammonium hydroxide, the hydrogen peroxide and the manganese chloride solution is (1-3) g: (20-40) mL: (2.3-3.5) g: (3-5) mL: (12-16) mL;
the concentration of the hydrogen peroxide is 30-35wt%;
the concentration of the manganese chloride solution is 0.3-0.4mol/L.
Compared with the prior art, the invention has the beneficial effects that:
according to the method, pyrite is subjected to thermal decomposition after superfine grinding, so that pyrrhotite with highest activity is obtained, and the pyrrhotite is used as a heterogeneous catalyst, so that the oxidation activation capacity of hydrogen peroxide can be effectively enhanced, and the oxidation rate of double oxidation is improved; in addition, the manganese dioxide nano-sheets can be used as an excellent carrier and can be used as a carrier material of an organic catalyst, copper nano-particles are directly reduced on the surface of the composite pyrrhotite to form an oxidation activity promoter, and the surface of the carrier material contains rich oxygen-containing functional groups, so that the charges of copper can be offset after the copper nano-particles are compounded, higher catalytic activity is reflected, the oxidation effect is realized, the consumption of liquid chlorine in microchannel reaction can be effectively reduced, the potential safety hazard is reduced, and the oxidation activity promoter has high catalytic activity, can be used as an oxidant alone, can be used as an enhanced oxidation activity of hydrogen peroxide, can be used for effectively accelerating the oxidation reaction, can be used for accelerating the oxidation reaction, and has better oxidation activity and the oxidation activity of the hydrogen peroxide, and can be used for generating the oxidation activity of the composite toluene sulfonic acid with high purity.
According to the invention, the oxidation chlorination reaction in saccharin production is carried out in the micro-channel, and the composite oxidant consisting of the oxidation activity promoter and hydrogen peroxide is added, so that the composite oxidant can be used as an oxidant instead of partial liquid chlorine, can effectively reduce potential safety hazards, reduces the generation of highly toxic waste liquid, lightens the burden for subsequent waste liquid treatment, has high oxidation activity, and can better promote the sulfinic acid to generate tosyl chloride through the reaction, thereby improving the conversion rate of the sulfinic acid, the yield and the purity of the tosyl chloride, having a promotion effect on improving the yield and the purity of the saccharin, and being beneficial to the industrialized mass production of the saccharin.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A microchannel reaction process for oxidation chlorination in saccharin production comprises the steps of respectively introducing sulfinic acid, toluene, a compound oxidant and chlorine into a microchannel reactor for reaction;
the microchannel reactor is an enhanced mass transfer type microchannel reactor and comprises a preheating module, a reaction module and a cooling module;
wherein the hydraulic diameter of the microchannel reactor is 1mm;
the reaction temperature is 40 ℃ and the pressure is 0.8MPa;
in the microchannel reactor, the dosage ratio of sulfinic acid, toluene, composite oxidant and chlorine is 12g:150mL:1.2g:0.1m 3 ；
The reaction residence time of the mixed material of sulfinic acid, toluene, the composite oxidant and chlorine in the reaction module is 10min;
after the reaction is finished, the tosyl chloride is obtained by filtering and decoloring and then refining.
Wherein the composite oxidant consists of an oxidation activity promoter and hydrogen peroxide with the concentration of 20wt% according to the solid-to-liquid ratio of 1g:80 mL;
the preparation method of the oxidation activity promoter comprises the following steps:
1) Grinding pyrite by superfine grinding, soaking for 24 hours by using hydrochloric acid solution with the concentration of 1wt%, centrifugally leaching by using ultrapure water, drying, placing into a tube furnace, heating to 620 ℃ at the speed of 10 ℃ per minute under nitrogen atmosphere, calcining for 3 hours, controlling the flow rate of nitrogen at 10mL/min during calcining, taking out the product after calcining is finished, and cooling to room temperature under nitrogen atmosphere to obtain pyrrhotite;
2) Uniformly dispersing 1g of pyrrhotite in 20mL of ultrapure water, then rapidly adding 2.3g of tetramethylammonium hydroxide and 3mL of 30wt% hydrogen peroxide, fully mixing, then adding 12mL of 0.3mol/L manganese chloride solution, stirring at 80r/min for overnight, centrifuging, repeatedly cleaning the precipitate with ultrapure water and methanol, and drying to obtain the composite pyrrhotite;
3) Adding 5mg of copper acetate, 5mL of deionized water, 5mL of ethylene glycol and 48mg of cetyl trimethyl ammonium bromide into a container, magnetically stirring and dissolving for 30min to obtain a mixed solution, and simultaneously dispersing 20mg of composite pyrrhotite into a mixed solution of 5mL of deionized water and 5mL of ethylene glycol, and performing ultrasonic dispersion for 2h at 200W to obtain a dispersion;
4) Mixing the mixed solution and the dispersion liquid with equal volume, stirring for 3 hours at 100r/min, centrifuging after the reaction is finished, washing the product repeatedly with ethanol and deionized water in sequence, and then drying in a 50 ℃ oven for 3 hours in vacuum to obtain the required oxidation activity promoter.
Example 2
A microchannel reaction process for oxidation chlorination in saccharin production comprises the steps of respectively introducing sulfinic acid, toluene, a compound oxidant and chlorine into a microchannel reactor for reaction;
the microchannel reactor is an enhanced mass transfer type microchannel reactor and comprises a preheating module, a reaction module and a cooling module;
wherein the hydraulic diameter of the microchannel reactor is 5mm;
the reaction temperature is 50 ℃ and the pressure is 1.2MPa;
in the microchannel reactor, the dosage ratio of sulfinic acid, toluene, composite oxidant and chlorine is 18g:230mL:2g:0.2m 3 ；
The reaction residence time of the mixed material of sulfinic acid, toluene, the composite oxidant and chlorine in the reaction module is 15min;
after the reaction is finished, the tosyl chloride is obtained by filtering and decoloring and then refining.
Wherein the composite oxidant consists of an oxidation activity promoter and hydrogen peroxide with the concentration of 22wt percent according to the solid-to-liquid ratio of 1g:90 mL;
the preparation method of the oxidation activity promoter comprises the following steps:
1) Grinding pyrite by superfine grinding, soaking in hydrochloric acid solution with the concentration of 2wt% for 28 hours, centrifuging and leaching by ultrapure water, drying, placing into a tube furnace, heating to 640 ℃ at 12 ℃/min under nitrogen atmosphere, calcining for 4 hours, controlling the flow rate of nitrogen at 15mL/min during calcining, taking out the product after calcining is finished, and cooling to room temperature under nitrogen atmosphere to obtain pyrrhotite;
2) Uniformly dispersing 2g of pyrrhotite in 30mL of ultrapure water, then rapidly adding 3.2g of tetramethylammonium hydroxide and 4mL of hydrogen peroxide with the concentration of 32wt%, fully mixing, then adding 15mL of manganese chloride solution with the concentration of 0.4mol/L, stirring at 100r/min for overnight, centrifuging, repeatedly cleaning the precipitate with ultrapure water and methanol, and drying to obtain the composite pyrrhotite;
3) Adding 7mg of copper acetate, 7mL of deionized water, 7mL of ethylene glycol and 65mg of cetyl trimethyl ammonium bromide into a container, magnetically stirring and dissolving for 40min to obtain a mixed solution, and simultaneously dispersing 25mg of composite pyrrhotite into a mixed solution of 8mL of deionized water and 8mL of ethylene glycol, and performing ultrasonic dispersion for 3h at 300W to obtain a dispersion;
4) Mixing the mixed solution and the dispersion liquid with equal volume, stirring for 4 hours at 120r/min, centrifuging after the reaction is finished, washing the product repeatedly with ethanol and deionized water in sequence, and then drying in a 55 ℃ oven for 5 hours in vacuum to obtain the required oxidation activity promoter.
Example 3
A microchannel reaction process for oxidation chlorination in saccharin production comprises the steps of respectively introducing sulfinic acid, toluene, a compound oxidant and chlorine into a microchannel reactor for reaction;
the microchannel reactor is an enhanced mass transfer type microchannel reactor and comprises a preheating module, a reaction module and a cooling module;
wherein the hydraulic diameter of the microchannel reactor is 8mm;
the reaction temperature is 60 ℃ and the pressure is 1.5MPa;
in the microchannel reactor, the dosage proportion of sulfinic acid, toluene, composite oxidant and chlorine is 20g:280mL:2.6g:0.3m 3 ；
The reaction residence time of the mixed material of sulfinic acid, toluene, the composite oxidant and chlorine in the reaction module is 20min;
after the reaction is finished, the tosyl chloride is obtained by filtering and decoloring and then refining.
Wherein the composite oxidant consists of an oxidation activity promoter and 25wt% hydrogen peroxide according to a solid-to-liquid ratio of 1g:100 mL;
the preparation method of the oxidation activity promoter comprises the following steps:
1) Grinding pyrite by superfine grinding, soaking for 30 hours by using hydrochloric acid solution with the concentration of 3wt%, centrifugally leaching by using ultrapure water, drying, placing into a tube furnace, heating to 650 ℃ at 15 ℃/min under nitrogen atmosphere, calcining for 5 hours, controlling the flow rate of nitrogen at 20mL/min during calcining, taking out the product after calcining is finished, and cooling to room temperature under nitrogen atmosphere to obtain pyrrhotite;
2) Uniformly dispersing 3g of pyrrhotite in 40mL of ultrapure water, then rapidly adding 3.5g of tetramethylammonium hydroxide and 5mL of 35wt% hydrogen peroxide, fully mixing, then adding 16mL of 0.4mol/L manganese chloride solution, stirring at 130r/min for overnight, centrifuging, repeatedly cleaning the precipitate with ultrapure water and methanol, and drying to obtain the composite pyrrhotite;
3) Adding 10mg of copper acetate, 10mL of deionized water, 10mL of ethylene glycol and 80mg of cetyl trimethyl ammonium bromide into a container, magnetically stirring and dissolving for 50min to obtain a mixed solution, and simultaneously dispersing 30mg of composite pyrrhotite into a mixed solution of 10mL of deionized water and 10mL of ethylene glycol, and performing ultrasonic dispersion for 5h at 300W to obtain a dispersion;
4) Mixing the mixed solution and the dispersion liquid with equal volume, stirring for 5 hours at 150r/min, centrifuging after the reaction is finished, washing the product repeatedly with ethanol and deionized water in sequence, and then drying in a 60 ℃ oven for 6 hours in vacuum to obtain the required oxidation activity promoter.
Comparative example 1: this comparative example is essentially the same as example 1, except that no complex oxidant is added to the microchannel reactor.
Comparative example 2: this comparative example is substantially the same as example 1 except that the composite oxidizing agent does not contain an oxidizing activity promoter.
Comparative example 3: this comparative example is substantially the same as example 1, except that pyrite is used instead of the oxidation activity promoter in the formulation of the composite oxidizing agent.
Comparative example 4: this comparative example is substantially the same as example 1, except that a complex pyrrhotite was used instead of the oxidation activity promoter in the formulation of the complex oxidant.
Comparative example 5: this comparative example is substantially the same as example 1 except that step 2) is omitted in the preparation of the oxidation activity promoter.
Test experiment:
the chlorination oxidation reaction was carried out by using the microchannel reaction methods of examples 1 to 3 and comparative examples 1 to 5, wherein the conversion rate data of sulfinic acid in examples 1 to 3 and comparative examples 2 to 5 were compared with that of comparative example 1, and the improvement amounts of the conversion rates of sulfinic acid in examples 1 to 3 and comparative examples 2 to 5 were calculated, respectively, with comparative example 1 as a control group, and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the conversion rate of sulfinic acid can be effectively improved by the microchannel reaction in the invention, thereby being beneficial to the improvement of the yield and purity of subsequent saccharin and the industrialized mass production of saccharin.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. A microchannel reaction process for oxidation chlorination in saccharin production is characterized by comprising the steps of respectively introducing sulfinic acid, toluene, a compound oxidant and chlorine into a microchannel reactor for reaction;
the microchannel reactor is an enhanced mass transfer type microchannel reactor and comprises a preheating module, a reaction module and a cooling module.
2. The microchannel reaction process for oxidative chlorination of saccharin production of claim 1, wherein the hydraulic diameter of the microchannel reactor is 1-8mm;
the temperature of the reaction is 40-60 ℃ and the pressure is 0.8-1.5MPa.
3. The microchannel reaction process for oxidation and chlorination in saccharin production according to claim 1, wherein the amount ratio of sulfinic acid, toluene, composite oxidant and chlorine in the microchannel reactor is (12-20) g: (150-280) mL: (1.2-2.6) g: (0.1-0.3) m 3 。
4. The microchannel process for oxidative chlorination of saccharin according to claim 1, wherein the reaction residence time of the sulfinic acid, toluene, and the mixture of the compound oxidant and chlorine in the reaction module is 10-20min.
5. The microchannel reaction process for oxidation and chlorination in saccharin production according to claim 1, wherein after the reaction is finished, the process is refined after filtration and decoloration to obtain tosyl chloride.
6. The microchannel reaction process for oxidation and chlorination in saccharin production according to claim 1, wherein the composite oxidant comprises an oxidation activity promoter and hydrogen peroxide in a solid-to-liquid ratio of 1g: (80-100) mL;
the concentration of the hydrogen peroxide is 20-25wt%;
the preparation method of the oxidation activity promoter comprises the following steps:
1) Adding copper acetate, deionized water, ethylene glycol and cetyltrimethylammonium bromide into a container, magnetically stirring and dissolving for 30-50min to obtain a mixed solution, and simultaneously dispersing the composite pyrrhotite into the mixed solution of the deionized water and the ethylene glycol, and carrying out ultrasonic dispersion for 2-5h to obtain a dispersion;
2) Mixing the mixed solution and the dispersion liquid with equal volume, stirring for 3-5h at 100-150r/min, centrifuging after the reaction is finished, washing the product with ethanol and deionized water repeatedly, and vacuum drying in a 50-60 ℃ oven for 3-6h to obtain the required oxidation activity promoter.
7. The microchannel reaction process for oxidation and chlorination in saccharin production according to claim 6, wherein the mixed solution comprises copper acetate, deionized water, ethylene glycol and cetyltrimethylammonium bromide in an amount of (5-10) mg: (5-10) mL: (5-10) mL: (48-80) mg;
in the dispersion liquid, the dosage proportion of the composite pyrrhotite, deionized water and glycol is (20-30) mg: (5-10) mL: (5-10) mL.
8. The microchannel reaction process for oxidation and chlorination in saccharin production according to claim 6, wherein the preparation method of the composite pyrrhotite is as follows:
1) Grinding pyrite by superfine grinding, soaking in hydrochloric acid solution for 24-30h, centrifuging and leaching with ultrapure water, drying, placing into a tube furnace, heating to 620-650 ℃ under nitrogen atmosphere, calcining for 3-5h, controlling the flow rate of nitrogen to 10-20mL/min during calcining, taking out the product after calcining, and cooling to room temperature under nitrogen atmosphere to obtain pyrrhotite;
2) Uniformly dispersing pyrrhotite in ultrapure water, then rapidly adding tetramethyl ammonium hydroxide and hydrogen peroxide, fully mixing, then adding manganese chloride solution, stirring at 80-130r/min overnight, centrifuging, repeatedly cleaning precipitate with ultrapure water and methanol, and drying to obtain the composite pyrrhotite.
9. The microchannel process for oxidative chlorination of saccharin production of claim 8, wherein the concentration of the hydrochloric acid solution is 1-3wt%;
in the tube furnace, the heating rate is 10-15 ℃/min.
10. The microchannel reaction process for oxidation and chlorination in saccharin production according to claim 8, wherein the dosage ratio of pyrrhotite, ultrapure water, tetramethyl ammonium hydroxide, hydrogen peroxide and manganese chloride solution is (1-3) g: (20-40) mL: (2.3-3.5) g: (3-5) mL: (12-16) mL;
the concentration of the hydrogen peroxide is 30-35wt%;
the concentration of the manganese chloride solution is 0.3-0.4mol/L.
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