CN116410115A - Preparation method of 2-nitro-4-methylsulfonyl benzoic acid - Google Patents
Preparation method of 2-nitro-4-methylsulfonyl benzoic acid Download PDFInfo
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- CN116410115A CN116410115A CN202111662987.XA CN202111662987A CN116410115A CN 116410115 A CN116410115 A CN 116410115A CN 202111662987 A CN202111662987 A CN 202111662987A CN 116410115 A CN116410115 A CN 116410115A
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- QNOUABMNRMROSL-UHFFFAOYSA-N 110964-79-9 Chemical compound CS(=O)(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QNOUABMNRMROSL-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000005086 pumping Methods 0.000 claims abstract description 22
- YYDNBUBMBZRNQQ-UHFFFAOYSA-N 1-methyl-4-methylsulfonylbenzene Chemical compound CC1=CC=C(S(C)(=O)=O)C=C1 YYDNBUBMBZRNQQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 21
- OXBDLEXAVKAJFD-UHFFFAOYSA-N 1-methyl-4-methylsulfonyl-2-nitrobenzene Chemical compound CC1=CC=C(S(C)(=O)=O)C=C1[N+]([O-])=O OXBDLEXAVKAJFD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006396 nitration reaction Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 9
- 239000000498 cooling water Substances 0.000 claims abstract description 8
- 238000010791 quenching Methods 0.000 claims abstract description 8
- 230000000171 quenching effect Effects 0.000 claims abstract description 8
- 239000011343 solid material Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- BEARMXYKACECDH-UHFFFAOYSA-N methylsulfonylmethylbenzene Chemical compound CS(=O)(=O)CC1=CC=CC=C1 BEARMXYKACECDH-UHFFFAOYSA-N 0.000 claims description 2
- -1 p-methylsulfonyl toluene sulfuric acid Chemical compound 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000001546 nitrifying effect Effects 0.000 claims 2
- 230000003647 oxidation Effects 0.000 claims 1
- 150000002826 nitrites Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 239000005578 Mesotrione Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KPUREKXXPHOJQT-UHFFFAOYSA-N mesotrione Chemical compound [O-][N+](=O)C1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O KPUREKXXPHOJQT-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VOYADQIFGGIKAT-UHFFFAOYSA-N 1,3-dibutyl-4-hydroxy-2,6-dioxopyrimidine-5-carboximidamide Chemical compound CCCCn1c(O)c(C(N)=N)c(=O)n(CCCC)c1=O VOYADQIFGGIKAT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 2-nitro-4-methylsulfonyl benzoic acid, which comprises the following steps: s1: pumping sulfuric acid into a batching kettle by using a metering pump, adding metered p-methylsulfonyl toluene solid materials into the batching kettle, and stirring; s2: conveying the p-methylsulfonyl toluene solution and nitric acid to a tubular reactor by a metering pump for continuous nitration reaction; s3: pumping cooling water into a receiving kettle in advance, starting stirring, allowing reaction liquid of a tubular reactor to enter the receiving kettle, and separating out a product after water quenching; s4: cooling the materials in the receiving kettle, and centrifuging and washing to obtain a wet product of the 2-nitro-4-methylsulfonyl toluene; s5: adding water, concentrated nitric acid and 2-nitro-4-methylsulfonyl toluene in the step S4 into a batching kettle in sequence; s6: the temperature of the reactor is set at 150-160 ℃, materials in the overhead tank are pumped into the reactor, the pressure in the reactor is stabilized at 1.3-1.5 MPa, and the materials in the reactor are conveyed into a receiving kettle; s7: and (3) distilling and recovering nitric acid in a receiving kettle under reduced pressure to obtain the target product 2-nitro-4-methylsulfonyl benzoic acid.
Description
Technical Field
The invention relates to a preparation method of 2-nitro-4-methylsulfonyl benzoic acid.
Background
The nitro-4-methylsulfonyl benzoic acid is an important fine chemical intermediate, and is widely used in the fields of medicines, pesticides, dyes and the like, in particular to synthesis of herbicide mesotrione. Mesotrione belongs to a trione herbicide, and has been successful in foreign countries with the characteristics of broad herbicide spectrum, high activity, strong miscibility, low toxicity, environmental friendliness, safety to succeeding crops, flexible use and the like. The potential safety hazard of the synthetic route of the nitration and oxidation reaction of the 2-nitro-4-methylsulfonyl benzoic acid is large, and the main problems of the original batch kettle type process of enterprises are as follows: the heat release amount in the nitration process is large, the adiabatic temperature rise reaches 132.8 ℃, the initial decomposition temperature of ARC test nitration reaction liquid is 140 ℃, and the runaway reaction and even explosion are easily caused by maintaining a higher temperature for a long time or continuously increasing the reaction temperature. The control difficulty of the oxidation reaction is high, the control of the dripping process is strict, and under a sulfuric acid system, once nitric acid is dripped too fast, dinitration byproducts are easy to generate, and the risk is high; the kettle type reaction has high temperature and long time, and is easy to generate tar impurities.
The present invention has been made in order to solve the above-described problems.
Disclosure of Invention
The invention aims to provide a preparation method of 2-nitro-4-methylsulfonyl benzoic acid.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of 2-nitro-4-methylsulfonyl benzoic acid comprises the steps of preparing 2-nitro-4-methylsulfonyl toluene by continuous tubular nitration reaction with methylsulfonyl toluene as raw material, sulfuric acid as solvent and catalyst and nitric acid as nitration reagent, and oxidizing with nitric acid to obtain 2-nitro-4-methylsulfonyl benzoic acid, wherein the synthesis reaction formula is as follows:
the method comprises the following specific steps:
s1: the preparation of the p-methylsulfonyl toluene sulfuric acid solution and nitric acid pumps sulfuric acid into a batching kettle by a metering pump, and the metered p-methylsulfonyl toluene solid material is added into the batching kettle, stirred and completely dissolved for standby; pumping fuming nitric acid into a high-level tank for standby;
s2: tubular nitration reaction operation
Delivering the p-methylsulfonyl toluene solution and nitric acid to a tubular reactor by a metering pump for continuous nitration, wherein the retention time of the reaction solution in the tubular reactor is 2-3min;
s3: water separation
Pumping cooling water into a receiving kettle in advance, starting stirring, allowing reaction liquid of a tubular reactor to enter the receiving kettle, and separating out a product after water quenching;
s4: centrifuging and washing
After the materials in the receiving kettle are cooled, obtaining a wet product of the 2-nitro-4-methylsulfonyl toluene through centrifugation and washing, and the nitrifier is directly used for oxidization without drying;
s5: proportioning materials
Adding water, concentrated nitric acid and 2-nitro-4-methylsulfonyl toluene in the step S4 into a batching kettle in sequence, stirring until the solid is dissolved, cooling to room temperature, filtering by a filter, and transferring to a high-level tank for standby;
s6: feeding material
The temperature of the reactor is set at 150-160 ℃, materials in the overhead tank are pumped into the reactor, the pressure in the reactor is stabilized at 1.3-1.5 MPa, and the materials in the reactor are conveyed into a receiving kettle;
s7: post-treatment
And (3) distilling under reduced pressure in a receiving kettle to recover nitric acid, regulating the pH of the obtained solid with NaOH solution, controlling the final pH of alkali dissolution to 7-8, filtering, recovering a filter cake as unreacted raw material, regulating the pH of the filtrate to strong acidity with hydrochloric acid, cooling to room temperature, fully crystallizing, filtering, leaching the filter cake with a small amount of water, and drying to obtain the target product 2-nitro-4-methylsulfonyl benzoic acid.
Preferably, in step S2, the reaction solution is held in the tubular reactor for a residence time of 2.5min.
Preferably, in step S6, the reactor temperature is set to 155 ℃ by the external circulation oil bath temperature.
Preferably, in step S7, the filtrate is made strongly acidic with hydrochloric acid, ph=1.
Preferably, the batching kettle and the receiving kettle are glass lining open stirring containers.
Preferably, in step S6, the transfer pump is a magnetic pump.
The beneficial technical effects are as follows:
according to the preparation method of the 2-nitro-4-methylsulfonyl benzoic acid, the concentration of sulfuric acid is within the range of 85-87%, the tubular nitrification temperature is between 60-80 ℃, the content of dinitrate is qualified, and the reaction yield and purity meet the requirements.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, 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
The preparation method of 2-nitro-4-methylsulfonyl benzoic acid comprises the following steps of:
s1: pumping sulfuric acid into a batching kettle by using a metering pump, adding metered p-methylsulfonyl toluene solid materials into the batching kettle, stirring, and completely dissolving for later use; pumping fuming nitric acid into a high-level tank for standby; 87% of sulfuric acid, 307kg/h of mass flow rate, 130kg/h of p-methylsulfonyl toluene, 98% of nitric acid and 54kg/h of mass flow rate; the temperature of the batching kettle is controlled at 30 ℃ and normal pressure.
S2: delivering the p-methylsulfonyl toluene solution and nitric acid to a tubular reactor by a metering pump for continuous nitration, wherein the retention time of the reaction solution in the tubular reactor is 2min; the tubular reactor was 60 ℃.
S3: pumping cooling water into a receiving kettle in advance, starting stirring, feeding reaction liquid into the receiving kettle through a pipe-type reactor, and separating out a product after water quenching; the temperature range of the receiving tank was 20 ℃.
S4: and cooling the materials in the receiving kettle, centrifuging and washing to obtain a wet product of the 2-nitro-4-methylsulfonyl toluene, wherein the wet product is directly used for oxidization of the nitrites without drying.
S5: adding water, concentrated nitric acid and 2-nitro-4-methylsulfonyl toluene in the step S4 into a batching kettle in sequence, stirring until the solid is dissolved, cooling to room temperature, filtering by a filter, and transferring to a high-level tank for standby.
S6: the temperature of the reactor is set at 150 ℃, materials in the overhead tank are pumped into the reactor, the pressure in the reactor is stabilized at 1.3MPa, and the materials in the reactor are conveyed into a receiving kettle.
S7: and (3) distilling under reduced pressure in a receiving kettle to recover nitric acid, regulating the pH of the obtained solid by using a NaOH solution, controlling the final pH of the alkali solution to 7, filtering, recovering a filter cake which is an unreacted raw material, regulating the filtrate to be strongly acidic by using hydrochloric acid, cooling to room temperature, fully crystallizing, filtering, leaching the filter cake by using a small amount of water, and drying to obtain the target product 2-nitro-4-methylsulfonyl benzoic acid.
Example 2
The preparation method of 2-nitro-4-methylsulfonyl benzoic acid comprises the following steps of:
s1: pumping sulfuric acid into a batching kettle by using a metering pump, adding metered p-methylsulfonyl toluene solid materials into the batching kettle, stirring, and completely dissolving for later use; pumping fuming nitric acid into a high-level tank for standby; 87% of sulfuric acid, 307kg/h of mass flow rate, 130kg/h of p-methylsulfonyl toluene, 98% of nitric acid and 54kg/h of mass flow rate; the temperature of the batching kettle is controlled at 40 ℃.
S2: and (3) conveying the p-methylsulfonyl toluene solution and nitric acid to a tubular reactor by a metering pump for continuous nitration, wherein the retention time of the reaction solution in the tubular reactor is 3min, and the temperature of the tubular reactor is 80 ℃.
S3: pumping cooling water into a receiving kettle in advance, starting stirring, feeding reaction liquid into the receiving kettle through a pipe-type reactor, and separating out a product after water quenching; the temperature range of the receiving tank was 80 ℃.
S4: and cooling the materials in the receiving kettle, centrifuging and washing to obtain a wet product of the 2-nitro-4-methylsulfonyl toluene, wherein the wet product is directly used for oxidization of the nitrites without drying.
S5: adding water, concentrated nitric acid and 2-nitro-4-methylsulfonyl toluene in the step S4 into a batching kettle in sequence, stirring until the solid is dissolved, cooling to room temperature, filtering by a filter, and transferring to a high-level tank for standby.
S6: the temperature of the reactor is set at 160 ℃, materials in the overhead tank are pumped into the reactor, the pressure in the reactor is stabilized at 1.5MPa, and the materials in the reactor are conveyed into a receiving kettle.
S7: and (3) distilling under reduced pressure in a receiving kettle to recover nitric acid, regulating the pH of the obtained solid with NaOH solution, controlling the final pH of alkali solution to 7-8, filtering, recovering a filter cake as unreacted raw material, regulating the filtrate to strong acidity with hydrochloric acid, cooling to room temperature, fully crystallizing, filtering, leaching the filter cake with a small amount of water, and drying to obtain the target product 2-nitro-4-methylsulfonyl benzoic acid.
Example 3
The preparation method of 2-nitro-4-methylsulfonyl benzoic acid comprises the following steps of:
s1: pumping sulfuric acid into a batching kettle by using a metering pump, adding metered p-methylsulfonyl toluene solid materials into the batching kettle, stirring, and completely dissolving for later use; pumping fuming nitric acid into a high-level tank for standby; 85% of sulfuric acid is adopted, the mass flow rate is controlled to be 307kg/h, the flow rate of p-methylsulfonyl toluene is controlled to be 130kg/h, 98% of nitric acid is adopted, and the mass flow rate is controlled to be 54kg/h; the temperature of the batching kettle is controlled at 30 ℃, the normal pressure is controlled, and the pressure of the metering pump is 0.6MPa.
S2: and (3) conveying the p-methylsulfonyl toluene solution and nitric acid to a tubular reactor by a metering pump for continuous nitration, wherein the retention time of the reaction solution in the tubular reactor is 2.5min, and the temperature of the tubular reactor is 60 ℃.
S3: pumping cooling water into a receiving kettle in advance, starting stirring, feeding reaction liquid into the receiving kettle through a pipe-type reactor, and separating out a product after water quenching; the temperature range of the receiving tank was 40 ℃.
S4: and cooling the materials in the receiving kettle, centrifuging and washing to obtain a wet product of the 2-nitro-4-methylsulfonyl toluene, wherein the wet product is directly used for oxidization of the nitrites without drying.
S5: adding water, concentrated nitric acid and 2-nitro-4-methylsulfonyl toluene in the step S4 into a batching kettle in sequence, stirring until the solid is dissolved, cooling to room temperature, filtering by a filter, and transferring to a high-level tank for standby.
S6: the temperature of the reactor is set at 155 ℃, materials in the overhead tank are pumped into the reactor, the pressure in the reactor is stabilized at 1.4MPa, and the materials in the reactor are conveyed into a receiving kettle.
S7: and (3) distilling under reduced pressure in a receiving kettle to recover nitric acid, regulating the pH of the obtained solid by using a NaOH solution, controlling the final pH of the alkali solution to 7.5, filtering, recovering a filter cake as unreacted raw materials, regulating the filtrate to be strong acid by using hydrochloric acid, cooling to room temperature, fully crystallizing, filtering, leaching the filter cake by using a small amount of water, and drying to obtain the target product 2-nitro-4-methylsulfonyl benzoic acid.
Example 4
The preparation method of 2-nitro-4-methylsulfonyl benzoic acid comprises the following steps of:
s1: pumping sulfuric acid into a batching kettle by using a metering pump, adding metered p-methylsulfonyl toluene solid materials into the batching kettle, stirring, and completely dissolving for later use; pumping fuming nitric acid into a high-level tank for standby; 85% of sulfuric acid is adopted, the mass flow rate is controlled to be 307kg/h, the flow rate of p-methylsulfonyl toluene is controlled to be 130kg/h, 98% of nitric acid is adopted, and the mass flow rate is controlled to be 54kg/h; the temperature of the batching kettle is controlled at 30 ℃, the normal pressure is controlled, and the pressure of the metering pump is 0.6MPa.
S2: and (3) conveying the p-methylsulfonyl toluene solution and nitric acid to a tubular reactor by a metering pump for continuous nitration, wherein the retention time of the reaction solution in the tubular reactor is 2.5min, and the temperature of the tubular reactor is 70 ℃.
S3: pumping cooling water into a receiving kettle in advance, starting stirring, feeding reaction liquid into the receiving kettle through a pipe-type reactor, and separating out a product after water quenching; the temperature range of the receiving tank was 60 ℃.
S4: and cooling the materials in the receiving kettle, centrifuging and washing to obtain a wet product of the 2-nitro-4-methylsulfonyl toluene, wherein the wet product is directly used for oxidization of the nitrites without drying.
S5: adding water, concentrated nitric acid and 2-nitro-4-methylsulfonyl toluene in the step S4 into a batching kettle in sequence, stirring until the solid is dissolved, cooling to room temperature, filtering by a filter, and transferring to a high-level tank for standby.
S6: the temperature of the reactor is set at 155 ℃, materials in the overhead tank are pumped into the reactor, the pressure in the reactor is stabilized at 1.4MPa, and the materials in the reactor are conveyed into a receiving kettle.
S7: and (3) distilling under reduced pressure in a receiving kettle to recover nitric acid, regulating the pH of the obtained solid by using a NaOH solution, controlling the final pH of the alkali solution to 7.5, filtering, recovering a filter cake as unreacted raw materials, regulating the filtrate to be strong acid by using hydrochloric acid, cooling to room temperature, fully crystallizing, filtering, leaching the filter cake by using a small amount of water, and drying to obtain the target product 2-nitro-4-methylsulfonyl benzoic acid.
Example 5
The preparation method of 2-nitro-4-methylsulfonyl benzoic acid comprises the following steps of:
s1: pumping sulfuric acid into a batching kettle by using a metering pump, adding metered p-methylsulfonyl toluene solid materials into the batching kettle, stirring, and completely dissolving for later use; pumping fuming nitric acid into a high-level tank for standby; 85% of sulfuric acid is adopted, the mass flow rate is controlled to be 307kg/h, the flow rate of p-methylsulfonyl toluene is controlled to be 130kg/h, 98% of nitric acid is adopted, and the mass flow rate is controlled to be 54kg/h; the temperature of the batching kettle is controlled at 30 ℃, the normal pressure is controlled, and the pressure of the metering pump is 0.6MPa.
S2: and (3) conveying the p-methylsulfonyl toluene solution and nitric acid to a tubular reactor by a metering pump for continuous nitration, wherein the retention time of the reaction solution in the tubular reactor is 2.5min, and the temperature of the tubular reactor is 80 ℃.
S3: pumping cooling water into a receiving kettle in advance, starting stirring, feeding reaction liquid into the receiving kettle through a pipe-type reactor, and separating out a product after water quenching; the temperature range of the receiving tank was 50 ℃.
S4: and cooling the materials in the receiving kettle, centrifuging and washing to obtain a wet product of the 2-nitro-4-methylsulfonyl toluene, wherein the wet product is directly used for oxidization of the nitrites without drying.
S5: adding water, concentrated nitric acid and 2-nitro-4-methylsulfonyl toluene in the step S4 into a batching kettle in sequence, stirring until the solid is dissolved, cooling to room temperature, filtering by a filter, and transferring to a high-level tank for standby.
S6: the temperature of the reactor is set at 155 ℃, materials in the overhead tank are pumped into the reactor, the pressure in the reactor is stabilized at 1.4MPa, and the materials in the reactor are conveyed into a receiving kettle.
S7: and (3) distilling under reduced pressure in a receiving kettle to recover nitric acid, regulating the pH of the obtained solid by using a NaOH solution, controlling the final pH of the alkali solution to 7.5, filtering, recovering a filter cake as unreacted raw materials, regulating the filtrate to be strong acid by using hydrochloric acid, cooling to room temperature, fully crystallizing, filtering, leaching the filter cake by using a small amount of water, and drying to obtain the target product 2-nitro-4-methylsulfonyl benzoic acid.
Table 1 (sulfuric acid and nitric acid in step S1):
as shown in Table 1, the concentration of sulfuric acid is 85-87%, the tubular nitrification temperature is 60-80 ℃ in the step S2, the content of dinitrate is qualified, and the reaction yield and purity meet the requirements.
While the fundamental and principal features of the invention and advantages of the invention have been shown and described, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a single embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to specific embodiments, and that the embodiments may be combined appropriately to form other embodiments that will be understood by those skilled in the art.
Claims (6)
1. The preparation method of the 2-nitro-4-methylsulfonyl benzoic acid is characterized in that methylsulfonyl toluene is used as a raw material, sulfuric acid is used as a solvent and a catalyst, nitric acid is used as a nitrifying reagent, the 2-nitro-4-methylsulfonyl toluene is prepared through continuous tubular nitrifying reaction, and then the 2-nitro-4-methylsulfonyl benzoic acid is obtained through nitric acid oxidation, and the preparation method comprises the following specific steps:
s1: preparation of p-methylsulfonyl toluene sulfuric acid solution and nitric acid
Pumping sulfuric acid into a batching kettle by using a metering pump, adding metered p-methylsulfonyl toluene solid material into the batching kettle, stirring, and completely dissolving for later use; pumping fuming nitric acid into a high-level tank for standby;
s2: tubular nitration reaction operation
Delivering the p-methylsulfonyl toluene solution and nitric acid to a tubular reactor by a metering pump for continuous nitration, wherein the retention time of the reaction solution in the tubular reactor is 2-3min;
s3: water separation
Pumping cooling water into a receiving kettle in advance, starting stirring, allowing reaction liquid of a tubular reactor to enter the receiving kettle, and separating out a product after water quenching;
s4: centrifuging and washing
Cooling the materials in the receiving kettle, and centrifuging and washing to obtain a wet product of the 2-nitro-4-methylsulfonyl toluene;
s5: proportioning materials
Adding water, concentrated nitric acid and 2-nitro-4-methylsulfonyl toluene in the step S4 into a batching kettle in sequence, stirring until the solid is dissolved, cooling to room temperature, filtering by a filter, and transferring to a high-level tank for standby;
s6: feeding material
The temperature of the reactor is set at 150-160 ℃, materials in the overhead tank are pumped into the reactor, the pressure in the reactor is stabilized at 1.3-1.5 MPa, and the materials in the reactor are conveyed into a receiving kettle;
s7: post-treatment
And (3) distilling under reduced pressure in a receiving kettle to recover nitric acid, regulating the pH of the obtained solid with NaOH solution, controlling the final pH of alkali dissolution to 7-8, filtering, recovering a filter cake as unreacted raw material, regulating the filtrate to strong acidity with hydrochloric acid, cooling to room temperature, fully crystallizing, filtering, leaching the filter cake with a small amount of water, and drying to obtain the target product 2-nitro-4-methylsulfonyl benzoic acid.
2. The method for producing 2-nitro-4-methylsulfonyl benzoic acid according to claim 1 wherein in step S2, the residence time of the reaction solution in the tubular reactor is 2.5min.
3. The method for producing 2-nitro-4-methylsulfonyl benzoic acid according to claim 1 wherein in step S6 the reactor temperature is set to 155 ℃ by the external circulation oil bath temperature.
4. The method for producing 2-nitro-4-methylsulfonyl benzoic acid according to claim 1 wherein in step S7 the filtrate is made strongly acidic with hydrochloric acid, ph=1.
5. The method for preparing 2-nitro-4-methylsulfonyl benzoic acid according to claim 1 wherein the batching kettle and the receiving kettle are glass lining open stirring vessels.
6. The method for preparing 2-nitro-4-methylsulfonyl benzoic acid according to claim 1, wherein in step S6, the transfer pump is a magnetic pump.
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