CN117229148A - Method for preparing o-chloronitrotoluene mixture - Google Patents
Method for preparing o-chloronitrotoluene mixture Download PDFInfo
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- CN117229148A CN117229148A CN202311274830.9A CN202311274830A CN117229148A CN 117229148 A CN117229148 A CN 117229148A CN 202311274830 A CN202311274830 A CN 202311274830A CN 117229148 A CN117229148 A CN 117229148A
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- 239000000203 mixture Substances 0.000 title claims abstract description 86
- VDEXMYMRDWWWAE-UHFFFAOYSA-N 1-chloro-2-(nitromethyl)benzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1Cl VDEXMYMRDWWWAE-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 263
- 239000000376 reactant Substances 0.000 claims abstract description 125
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 claims abstract description 119
- 239000002253 acid Substances 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 58
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 120
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 65
- 229910017604 nitric acid Inorganic materials 0.000 claims description 65
- 239000012071 phase Substances 0.000 claims description 46
- 239000003921 oil Substances 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000005191 phase separation Methods 0.000 claims description 11
- 229910052715 tantalum Inorganic materials 0.000 claims description 11
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 11
- 239000008346 aqueous phase Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910000856 hastalloy Inorganic materials 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 34
- 239000000126 substance Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 238000005406 washing Methods 0.000 description 19
- 239000011593 sulfur Substances 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- 238000006396 nitration reaction Methods 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 239000003513 alkali Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 208000012839 conversion disease Diseases 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BGDCQZFFNFXYQC-UHFFFAOYSA-N 1-chloro-2-methyl-4-nitrobenzene Chemical compound CC1=CC([N+]([O-])=O)=CC=C1Cl BGDCQZFFNFXYQC-UHFFFAOYSA-N 0.000 description 1
- XTSGZXRUCAWXKY-UHFFFAOYSA-N 2-chloro-1-methyl-3-nitrobenzene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1Cl XTSGZXRUCAWXKY-UHFFFAOYSA-N 0.000 description 1
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- XCSNRORTQRKCHB-UHFFFAOYSA-N 2-chloro-6-nitrotoluene Chemical compound CC1=C(Cl)C=CC=C1[N+]([O-])=O XCSNRORTQRKCHB-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
Abstract
The invention relates to the technical field of preparation of o-chloronitrotoluene, in particular to a method for preparing an o-chloronitrotoluene mixture. Comprising the following steps: preparing n material flows; at least one stream comprises o-chlorotoluene and the remaining stream comprises an acid; transferring o-chlorotoluene to a reaction zone for reaction with an acid of one of the streams to generate a first reactant stream; transferring the acid of the first reactant stream to a reaction zone for reaction with the acid of the next stream to produce an n- (n-2) th reactant stream; repeating the foregoing process until an n-1 th reactant stream is produced; the n-1 th reactant stream comprises o-chlorotoluene, an o-chloronitrotoluene mixture, an acid. In the prior art, o-chlorotoluene can be effectively nitrified, but the substances are difficult to effectively separate in the reaction process, and finally become part of impurities. Compared with the prior art, the final product of the invention also comprises a plurality of different substances, but the separation among the substances is convenient, so that the amount of final impurities can be effectively reduced.
Description
Technical Field
The invention relates to the technical field of preparation of o-chloronitrotoluene, in particular to a method for preparing an o-chloronitrotoluene mixture.
Background
The o-chlorotoluene is used as a raw material for nitration, and the obtained product is o-chloronitrotoluene. Ortho-chloronitrotoluene contains mainly four isomers. O-chloronitrotoluene is an important intermediate or raw material in the fields of dyes, pesticides, medicines and the like. At present, common preparation means are as follows: beta zeolite is used as a catalyst to nitrify the o-chlorotoluene, so that the o-chloronitrotoluene is obtained.
Chinese patent discloses a method for catalyzing and nitrifying o-chlorotoluene by modified beta zeolite [ application number: cn201810605976.X, publication No.: CN108658775a includes: adding a solvent into a container under stirring, and then sequentially adding o-chlorotoluene, acetic anhydride, fuming nitric acid, a modified beta zeolite molecular sieve catalyst and silica supported perfluorinated sulfonic acid resin; and heating and refluxing for 1-9 h, and stopping the reaction.
Chinese patent discloses that direct nitration of o-chlorotoluene produces CLT acid [ application number: CN201010252894.5, publication No.: CN101906057a ]. In the technical scheme of the patent, the nitration process of the o-chlorotoluene is as follows: 1.0 to 1.1 mol of nitric acid, 10 to 30 g of acid beta zeolite are added into a reaction bottle, 1 to 1.3 mol of acetic anhydride is dripped into the reaction bottle at the temperature of 10 to 15 ℃ under stirring to react for half an hour, 1.0 mol of o-chlorotoluene is dripped into the reaction bottle at the temperature of 10 to 25 ℃ for 1 to 2 hours, the reaction is carried out for 30 minutes at the temperature of 25 ℃ after the dripping is finished, and the reaction is continued for 4 to 8 hours at the temperature of 30 to 45 ℃. Filtering while the zeolite is hot, and washing the acid beta zeolite with acetic acid for 2 to 3 times.
Although the technical proposal can effectively nitrify the o-chlorotoluene, the impurities are difficult to be effectively stripped by adopting the method, so that the product contains more impurities. The impurities comprise organic solvents added in the nitration process, including acetic anhydride and nitric acid ester. At the same time, such organic solvents are themselves corrosive and can easily introduce some other uncontrollable impurities during the production process. The impurities also contained added catalyst (zeolite beta). The catalyst is eventually separated for reuse. However, there is always a small portion of catalyst remaining during the separation process, and the remaining catalyst becomes part of the impurities.
In summary, the foregoing technical solutions are difficult to apply industrially on a large scale.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a method for preparing an o-chloronitrotoluene mixture.
In order to solve the technical problems, the invention provides the following technical scheme:
a process for preparing an o-chloronitrotoluene mixture comprising: preparing n material flows; at least one stream comprises o-chlorotoluene and the remaining stream comprises an acid; transferring o-chlorotoluene to a reaction zone for reaction with an acid of one of the streams to generate a first reactant stream; transferring the acid of the first reactant stream to a reaction zone for reaction with the acid of the next stream to produce an n- (n-2) th reactant stream; repeating the foregoing process until an n-1 th reactant stream is produced; the n-1 th reactant stream comprises o-chlorotoluene, an o-chloronitrotoluene mixture, an acid.
In actual implementation, the invention divides the nitration process of the o-chlorotoluene into a plurality of reaction sections which are spaced from each other, so that the whole reaction process is safer and more controllable, and the nitration process can be normally carried out even if no catalyst or organic solvent exists. Thus, the final resulting reactant comprises only o-chlorotoluene, o-chloronitrotoluene mixture, acid. Wherein, the mixture of the o-chlorotoluene and the o-chloronitrotoluene is organic matter and the acid is inorganic matter. The inorganic matters and the organic matters are not mutually dissolved and are easy to separate. The mixture of the o-chlorotoluene and the o-chloronitrotoluene can be separated by rectification. In summary, the final reactant, while still comprising a variety of different materials, is free of organic solvents and catalysts and is not susceptible to the introduction of some uncontrollable impurities due to corrosiveness and the like. On the other hand, the substances of different species are easier to separate. Thus, the invention can effectively reduce the residual impurities in the o-chloronitrotoluene mixture.
Further, the streams include a first stream, a second stream, a third stream; the first stream comprises o-chlorotoluene; the second stream, the third stream, comprises an acid; the reaction zone comprises a first reaction zone and a second reaction zone; the method also comprises the following steps: transferring the first stream to a first reaction zone for reaction with the second stream to produce a first reactant stream; transferring the first reactant stream to a second reaction zone for reaction with the third reactant stream to produce a second reactant stream; the second reactant stream comprises o-chlorotoluene, an o-chloronitrotoluene mixture, an acid.
Further, the method also comprises the following steps: subjecting the first reactant stream to phase separation; taking an oil phase of the first reactant stream; the oil phase is transferred to a second reaction zone for reaction with a third stream.
Further, the reaction temperature of the first reaction zone is: -10 ℃ to 50 ℃; the reaction temperature of the second reaction zone is: 0 ℃ to 80 ℃.
Further, the reaction residence time of the first reaction zone is 0-5min; the reaction residence time in the second reaction zone is from 0 to 5 minutes.
Further, the flow rate of the first material flow is 30-4000ml/min; the flow rate of the second material flow is 30-5000ml/min; the flow rate of the first reactant stream is in the range of 30 to 5000ml/min; the flow rate of the third stream is 10-2000ml/min; the flow rate of the second reactant stream is in the range of 30 to 10000ml/min.
Further, the acid comprises one or more of nitric acid, mixed acid and sulfuric acid.
Further, the molar ratio of o-chlorotoluene to acid is (1-2.5): (1-3.5).
Further, the reaction zone employs a microchannel reactor.
Further, the configuration of the microchannel reactor comprises V-shaped, heart-shaped, funnel-shaped and T-shaped; the micro-channel reactor is made of one or more of hastelloy, tweezer, tantalum, zirconium, glass, polytetrafluoroethylene and silicon carbide.
Compared with the prior art, the invention has the following advantages:
the invention divides the nitration process of the o-chlorotoluene into a plurality of reaction sections which are mutually spaced, thereby ensuring that the whole reaction process is safer and more controllable, and further ensuring that the nitration process can be normally carried out even without the participation of a catalyst and an organic solvent.
According to the invention, various parameters in the nitrification process are controlled, so that the whole nitrification process can be carried out according to requirements.
The invention can effectively reduce the residual impurities in the o-chloronitrotoluene mixture, thereby being more suitable for the current industrial production.
Drawings
Fig. 1: an overall flow chart.
Detailed Description
The following are specific embodiments of the present invention and the technical solutions of the present invention will be further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Embodiment one:
a process for preparing an ortho-chloronitrotoluene mixture comprising the steps of: n streams are prepared. At least one of the streams comprises o-chlorotoluene and the other stream comprises an acid. The stream comprising o-chlorotoluene is reacted with one of the streams comprising acid into a reaction zone to produce a first reactant stream. The acid of the first reactant stream and the next stream is transferred to a reaction zone for reaction to produce an n- (n-2) th reactant stream. The foregoing process is repeated until an n-1 th reactant stream is produced. The resulting n-1 th reactant stream comprises o-chlorotoluene, o-chloronitrotoluene mixture, acid. The reaction zone adopts a micro-channel reactor, and the configuration of the micro-channel reactor can be one of V type, heart type, funnel type and T type. The material of the microchannel reactor can be one or more of hastelloy, tweezer, tantalum, zirconium, glass, polytetrafluoroethylene and silicon carbide.
Specifically, n is more than or equal to 3. When n=3, the streams include a first stream, a second stream, and a third stream. The first stream comprises o-chlorotoluene. The second stream employs a mixed acid of nitro and sulfur. The third stream employs 98% sulfuric acid. Wherein, the molar ratio of the materials of the nitre-sulfur mixed acid is nitric acid: sulfuric acid: the water level is 1:2:0.5. Specifically, 95% nitric acid, 98% sulfuric acid, and water are introduced into a storage tank for formulation to obtain the above molar ratio of the nitric-sulfuric mixed acid and as a second stream. The micro-channel reactor adopts a tantalum reactor with a V-shaped structure.
O-chlorotoluene as a first stream was continuously pumped into the first reaction zone by a plunger pump through a feed inlet, the flow rate of the first stream being 60ml/min. Simultaneously, a second stream is pumped into the first reaction zone by a plunger pump through a feed frame via a feed port, the second stream having a flow rate of 100ml/min. Whereby the first stream reacts with the second stream in the first reaction zone. Wherein, in the first reaction zone, the molar ratio of the o-chlorotoluene to the nitric acid is 1:1.05, the reaction temperature is 15 ℃, and the reaction residence time is 1min. And after the reaction residence time is reached, discharging a reaction mixture obtained by the reaction of the o-chlorotoluene and the nitric acid out of the first reaction zone as a first reactant stream.
98% sulfuric acid was introduced into a tank, the temperature of which was controlled at 20 ℃. The sulfuric acid is pumped as a third stream from the feed inlet into the second reaction zone by a plunger pump through the feed frame. The flow rate of the third stream was 30ml/min. Simultaneously, the first reactant stream is pumped into the second reaction zone. The flow rate of the first reactant stream was 160ml/min. Whereby the first reactant stream reacts with the third reactant stream in the second reaction zone. Wherein, in the second reaction zone, the reaction temperature is 50 ℃ and the reaction residence time is 3min. After the reaction residence time is reached, the reactants are withdrawn from the second reaction zone as a second reactant stream.
The second reactant stream comprises mainly a mixture of ortho-chloronitrotoluene, and ortho-chlorotoluene, nitric acid, sulfuric acid that is not fully reacted. The second reactant stream is discharged into a knock-out pot for two-phase separation. Whereby the mixture of o-chloronitrotoluene and o-chlorotoluene in the second reactant stream is separated as an oil phase. The nitric acid and sulfuric acid in the second reactant stream are separated as an aqueous phase. The water phase is led into a batching tank for subsequent recycling. The oil phase is dried by anhydrous sodium sulfate after alkali washing and water washing. And (3) carrying out quantitative detection on the oil phase after drying in a gas chromatograph, and quantifying the concentration of the product according to the peak area. According to analysis, the conversion rate of raw material o-chlorotoluene is 98%, the content of the o-chloronitrotoluene mixture is 96%, and the content of other impurities is 1.5%. It can be seen that with the process of the invention the reaction conversion was 98% and the selectivity was 96%. Preferably, the o-chlorotoluene in the oil phase can be separated by rectification to further refine the o-chloronitrotoluene mixture.
Embodiment two:
when n=3, the streams include a first stream, a second stream, and a third stream. The first stream comprises o-chlorotoluene. The second stream employs a mixed acid of nitro and sulfur. The third stream employs sulfuric acid. Wherein, the molar ratio of the materials of the nitre-sulfur mixed acid is nitric acid: sulfuric acid: the water level is 1:2:0.5. Specifically, 95% nitric acid, 98% sulfuric acid, and water are introduced into a storage tank for formulation to obtain the above molar ratio of the nitric-sulfuric mixed acid and as a second stream. The microchannel reactor adopts a T-shaped tantalum reactor.
O-chlorotoluene as a first stream was continuously pumped into the first reaction zone via a feed inlet by a plunger pump, the flow rate of the first stream being 80ml/min. Simultaneously, a second stream is pumped into the first reaction zone by a plunger pump through a feed frame via a feed port, the second stream having a flow rate of 133ml/min. Whereby the first stream reacts with the second stream in the first reaction zone. Wherein, in the first reaction zone, the molar ratio of the o-chlorotoluene to the sulfuric acid to the nitric acid is 1:1.2, the reaction temperature is 10 ℃, and the reaction residence time is 45s. And after the reaction residence time is reached, discharging a reaction mixture obtained by the reaction of the o-chlorotoluene and the nitric acid out of the first reaction zone as a first reactant stream.
98% sulfuric acid was introduced into a tank, the temperature of which was controlled at 15 ℃. The sulfuric acid is pumped as a third stream from the feed inlet into the second reaction zone by a plunger pump through the feed frame. The flow rate of the third stream was 40ml/min. Simultaneously, the first reactant stream is pumped into the second reaction zone. The flow rate of the first reactant stream was 213ml/min. Whereby the first reactant stream reacts with the third reactant stream in the second reaction zone. Wherein, in the second reaction zone, the reaction temperature is 60 ℃ and the reaction residence time is 2.5min. After the reaction residence time is reached, the reactants are withdrawn from the second reaction zone as a second reactant stream.
The second reactant stream comprises mainly a mixture of ortho-chloronitrotoluene, and ortho-chlorotoluene, nitric acid, sulfuric acid that is not fully reacted. The second reactant stream is discharged into a knock-out pot for two-phase separation. Whereby the mixture of o-chloronitrotoluene and o-chlorotoluene in the second reactant stream is separated as an oil phase. The nitric acid and sulfuric acid in the second reactant stream are separated as an aqueous phase. The water phase is led into a batching tank for subsequent recycling. The oil phase is dried by anhydrous sodium sulfate after alkali washing and water washing. And (3) carrying out quantitative detection on the oil phase after drying in a gas chromatograph, and quantifying the concentration of the product according to the peak area. According to analysis, the conversion rate of raw material o-chlorotoluene is 98%, the content of the o-chloronitrotoluene mixture is 96.5%, and the content of other impurities is 1.2%. It can be seen that with the process of the invention the reaction conversion was 98% and the selectivity was 96.5%. Preferably, the o-chlorotoluene in the oil phase can be separated by rectification to further refine the o-chloronitrotoluene mixture.
Embodiment III:
when n=3, the streams include a first stream, a second stream, and a third stream. The first stream comprises o-chlorotoluene. The second stream employs a mixed acid of nitro and sulfur. The third stream employs sulfuric acid. Wherein, the molar ratio of the materials of the nitre-sulfur mixed acid is nitric acid: sulfuric acid: the water level is 1:1.5:1. Specifically, 95% nitric acid, 98% sulfuric acid, and water are introduced into a storage tank for formulation to obtain the above molar ratio of the nitric-sulfuric mixed acid and as a second stream. The microchannel reactor adopts a silicon carbide reactor with a heart-shaped structure.
O-chlorotoluene as a first stream was continuously pumped into the first reaction zone by a plunger pump through a feed inlet, the flow rate of the first stream being 300ml/min. Simultaneously, a second stream is pumped into the first reaction zone through the feed frame by a plunger pump, the second stream having a flow rate of 500ml/min. Whereby the first stream reacts with the second stream in the first reaction zone. Wherein, in the first reaction zone, the molar ratio of the o-chlorotoluene to the nitric acid is 1:1.5, the reaction temperature is 20 ℃, and the reaction residence time is 1min. And after the reaction residence time is reached, discharging a reaction mixture obtained by the reaction of the o-chlorotoluene and the nitric acid out of the first reaction zone as a first reactant stream.
98% sulfuric acid was introduced into a tank, the temperature of which was controlled at 20 ℃. The sulfuric acid is pumped as a third stream from the feed inlet into the second reaction zone by a plunger pump through the feed frame. The flow rate of the third stream was 150ml/min. Simultaneously, the first reactant stream is pumped into the second reaction zone. The flow rate of the first reactant stream was 800ml/min. Whereby the first reactant stream reacts with the third reactant stream in the second reaction zone. Wherein, in the second reaction zone, the reaction temperature is 40 ℃ and the reaction residence time is 4min. After the reaction residence time is reached, the reactants are withdrawn from the second reaction zone as a second reactant stream.
The second reactant stream comprises mainly a mixture of ortho-chloronitrotoluene, and ortho-chlorotoluene, nitric acid, sulfuric acid that is not fully reacted. The second reactant stream is discharged into a knock-out pot for two-phase separation. Whereby the mixture of o-chloronitrotoluene and o-chlorotoluene in the second reactant stream is separated as an oil phase. The nitric acid and sulfuric acid in the second reactant stream are separated as an aqueous phase. The water phase is led into a batching tank for subsequent recycling. The oil phase is dried by anhydrous sodium sulfate after alkali washing and water washing. And (3) carrying out quantitative detection on the oil phase after drying in a gas chromatograph, and quantifying the concentration of the product according to the peak area. According to analysis, the conversion rate of raw material o-chlorotoluene is 96%, the content of the o-chloronitrotoluene mixture is 94.5%, and the content of other impurities is 1.5%. It was found that the reaction conversion was 96% and the selectivity was 94.5% by the method of the present invention. Preferably, the o-chlorotoluene in the oil phase can be separated by rectification to further refine the o-chloronitrotoluene mixture.
Embodiment four:
when n=4, the streams include a first stream, a second stream, a third stream, a fourth stream. The first stream comprises o-chlorotoluene. The second stream employs a mixed acid of nitro and sulfur. The third stream employs a mixed acid of nitro and sulfur. The fourth stream is sulfuric acid. The specific material mole ratio of the nitric-sulfuric mixed acid is nitric acid: sulfuric acid: the water is 1:2:0.5. Specifically, 95% nitric acid, 98% sulfuric acid, and water are introduced into a storage tank and configured to obtain the above molar ratio of the nitric-sulfuric mixed acid as the second stream and the third stream. The selected microchannel reactor adopts a tantalum reactor with a V-shaped structure.
O-chlorotoluene as a first stream was continuously pumped into the first reaction zone by a plunger pump through a feed inlet, the flow rate of the first stream being 60ml/min. Simultaneously, a second stream was pumped into the first reaction zone by a plunger pump through a feed frame via a feed port, the second stream having a flow rate of 63ml/min. Whereby the first stream reacts with the second stream in the first reaction zone. Wherein, in the first reaction zone, the molar ratio of the o-chlorotoluene to the nitric acid is 1:0.63, the reaction temperature is 15 ℃, and the reaction residence time is 45s. And after the reaction residence time is reached, discharging a reaction mixture obtained by the reaction of the o-chlorotoluene and the nitric acid out of the first reaction zone as a first reactant stream.
The mixture as a first reactant stream was continuously pumped into the second reaction zone via the feed port by a plunger pump at a flow rate of 123ml/min. Simultaneously, a third stream was pumped into the second reaction zone through the feed frame by a plunger pump at a flow rate of 37ml/min. Whereby the first reactant stream reacts with the third reactant stream in the second reaction zone. Wherein, in the second reaction zone, the molar ratio of the o-chlorotoluene to the nitric acid is 1:0.42, the reaction temperature is 15 ℃, and the reaction residence time is 1min. And after the reaction residence time is reached, discharging a reaction mixture obtained by the reaction of the o-chlorotoluene and the nitric acid out of the second reaction zone as a second reaction stream.
98% sulfuric acid was introduced into a tank, the temperature of which was controlled at 20 ℃. The sulfuric acid is pumped as a fourth stream from the feed inlet into the third reaction zone by a plunger pump through the feed frame. The flow rate of the fourth stream was 30ml/min. At the same time, the second reactant stream is discharged into the third reaction zone. The flow rate of the second reactant stream was 160ml/min. Whereby the second reactant stream reacts with the fourth stream in the third reaction zone. Wherein, in the third reaction zone, the reaction temperature is 50 ℃ and the reaction residence time is 3min. After the reaction residence time is reached, the reactants are discharged as a third reactant stream from the third reaction zone.
The third reaction stream comprises an ortho-chloronitrotoluene mixture, and ortho-chlorotoluene, nitric acid, sulfuric acid that is not fully reacted. The second reactant stream is discharged into a knock-out pot for two-phase separation. Whereby the mixture of o-chloronitrotoluene and o-chlorotoluene in the third reaction stream is separated off as an oil phase. The nitric acid and sulfuric acid in the third reaction stream are separated in the form of an aqueous phase. The water phase is led into a batching tank for subsequent recycling. The oil phase is dried by anhydrous sodium sulfate after alkali washing and water washing. And (3) carrying out quantitative detection on the oil phase after drying in a gas chromatograph, and quantifying the concentration of the product according to the peak area. According to analysis, the conversion rate of raw material o-chlorotoluene is 98.1%, the content of the o-chloronitrotoluene mixture is 96.6%, and the content of other impurities is 1.2%. As can be seen, with the process of the present invention, the reaction conversion was 98.1% and the selectivity was 96.6%. Preferably, the o-chlorotoluene in the oil phase can be separated by rectification to further refine the o-chloronitrotoluene mixture.
Fifth embodiment:
compared with the first embodiment, the difference is that:
the flow rate of the first material flow is 60ml/min, the flow rate of the second material flow is 76ml/min, the molar ratio of the o-chlorotoluene to the nitric acid in the first reaction zone is 1:0.85, and the residence time of the first reaction zone is 1min. The third stream flow rate was 42ml/min and the second reaction zone reaction residence time was 4min.
According to this operating condition, the o-chlorotoluene conversion was finally obtained at 81.5%, the o-chloronitrotoluene mixture selectivity was 98.6%, and the impurity content was 0.5%.
Example six:
compared with the first embodiment, the difference is that:
the flow rate of the first material flow is 60ml/min, the flow rate of the second material flow is 91ml/min, the mol ratio of the o-chlorotoluene to the nitric acid in the first reaction zone is 1:0.95, the residence time in the first reaction zone is 1min, the flow rate of the third material flow is 36ml/min, and the residence time in the second reaction zone is 4min
According to this operating condition, the o-chlorotoluene conversion was finally obtained at 88.6%, the o-chloronitrotoluene mixture selectivity was 98.3%, and the impurity content was 0.7%.
Embodiment seven:
compared with the first embodiment, the difference is that:
the flow rate of the first material flow is 850ml/min, the flow rate of the second material flow is 1360ml/min, the residence time of the first reaction zone is 2.5min, the flow rate of the third material flow is 425ml/min, and the residence time of the second reaction zone is 4min
According to this operating condition, the o-chlorotoluene conversion was finally obtained at 95.8%, the o-chloronitrotoluene mixture selectivity was 97.6%, and the impurity content was 1.1%.
Example eight:
compared with the first embodiment, the difference is that:
the flow rate of the first material flow is 3000ml/min, the flow rate of the second material flow is 4800ml/min, the residence time of the first reaction zone is 3min, the flow rate of the third material flow is 1500ml/min, and the residence time of the second reaction zone is 5min
According to this operating condition, the o-chlorotoluene conversion was 94.6%, the o-chloronitrotoluene mixture selectivity was 97.1%, and the impurity content was 1.2%.
Example nine:
compared with the first embodiment, the difference is that:
the flow rate of the first material flow is 80ml/min, the flow rate of the second material flow is 86ml/min, the residence time of the first reaction zone is 2min, and the specific material mole ratio of the nitre-sulfur mixed acid in the second material flow is nitric acid: sulfuric acid: water is 1:2:0; the first reaction zone temperature was 40 ℃. The third stream was at a flow rate of 30ml/min and the second reaction zone was at a residence time of 3min and a temperature of 40 ℃.
According to this operating condition, the o-chlorotoluene conversion was 98%, the o-chloronitrotoluene mixture selectivity was 94%, and the impurity content was 4.5%.
Example ten:
compared with the first embodiment, the difference is that:
the flow rate of the first material flow is 80ml/min, the flow rate of the second material flow is 86ml/min, the residence time of the first reaction zone is 2min, and the specific material mole ratio of the nitre-sulfur mixed acid in the second material flow is nitric acid: sulfuric acid: water is 1:2:0; the first reaction zone temperature was 0 ℃. The third stream was at a flow rate of 30ml/min and the second reaction zone was at a residence time of 3min and a temperature of 40 ℃.
According to this operating condition, the o-chlorotoluene conversion was finally obtained at 82%, the o-chloronitrotoluene mixture selectivity was 98%, and the impurity content was 1.5%.
Example eleven:
compared with the first embodiment, the difference is that:
the specific material mole ratio of the nitre-sulfur mixed acid in the second material flow is nitric acid: sulfuric acid: water 1:2.5:0.5; the temperature of the first reaction zone was-10℃and the temperature of the second reaction zone was 30 ℃.
According to this operating condition, the o-chlorotoluene conversion was 79%, the o-chloronitrotoluene mixture selectivity was 95%, and the impurity content was 0.17%.
Embodiment twelve:
compared with the first embodiment, the difference is that:
the flow rate of the first material flow is 80ml/min, the flow rate of the second material flow is 68ml/min, and the specific material mole ratio of the nitre-sulfur mixed acid in the second material flow is nitric acid: sulfuric acid: water is 1:1:0; the first reaction zone temperature was 18℃and the second reaction zone temperature was 56 ℃.
According to this operating condition, the o-chlorotoluene conversion was finally obtained at 78%, the o-chloronitrotoluene mixture selectivity was 98%, and the impurity content was 0.5%.
Embodiment thirteen:
compared with the first embodiment, the difference is that:
the specific material mole ratio of the nitre-sulfur mixed acid in the second material flow is nitric acid: sulfuric acid: water is 1:1.5:0; the first reaction zone temperature was 50℃and the second reaction zone temperature was 80 ℃.
According to this operating condition, the o-chlorotoluene conversion was finally obtained at 95%, the o-chloronitrotoluene mixture selectivity was 94%, and the impurity content was 4.5%.
Fourteen examples:
compared with the first embodiment, the difference is that:
the specific material mole ratio of the nitre-sulfur mixed acid in the second material flow is nitric acid: sulfuric acid: water 1:2.5:0.5; the second material flow rate was 118ml/min and the third material flow rate was 18ml/min. The temperature of the first reaction zone was 5℃and the temperature of the second reaction zone was 45 ℃.
According to this operating condition, the o-chlorotoluene conversion was 98%, the o-chloronitrotoluene mixture selectivity was 94%, and the impurity content was 3.5%.
Example fifteen:
compared with the first embodiment, the difference is that:
the third material flow rate was 15ml/min. The residence time in the second reaction zone was 4min and the temperature in the second reaction zone was 65 ℃.
According to this operating condition, the o-chlorotoluene conversion was finally obtained at 84%, the o-chloronitrotoluene mixture selectivity was 98%, and the impurity content was 0.8%.
Example sixteen:
the third material flow rate was 45ml/min. The residence time in the second reaction zone was 2.5min and the temperature in the second reaction zone was 35 ℃.
According to the operation conditions, the o-chlorotoluene conversion rate is 98%, the o-chloronitrotoluene mixture selectivity is 95%, and the impurity content is 3.6%.
Comparative example one:
when n=2, the streams include a first stream, a second stream, the first stream including o-chlorotoluene. The second stream is a nitrated sulfuric acid mixture. The specific material mole ratio of the nitric-sulfuric mixed acid is nitric acid: sulfuric acid: the water is 1:3.5:1. Specifically, 95% nitric acid, 98% sulfuric acid, and water are introduced into a storage tank for formulation to obtain the above molar ratio of the nitric-sulfuric mixed acid and as a second stream. The selected microchannel reactor adopts a tantalum reactor with a V-shaped structure.
O-chlorotoluene as a first stream was continuously pumped into the first reaction zone by a plunger pump through a feed inlet, the flow rate of the first stream being 60ml/min. Simultaneously, a second stream was pumped into the first reaction zone through the feed frame by a plunger pump, the second stream having a flow rate of 135ml/min. Whereby the first stream reacts with the second stream in the first reaction zone. Wherein, in the first reaction zone, the molar ratio of the o-chlorotoluene to the nitric acid is 1:1.2, the reaction temperature is 20 ℃, and the reaction residence time is 2.5min. And after the reaction residence time is reached, discharging a reaction mixture obtained by the reaction of the o-chlorotoluene and the nitric acid out of the first reaction zone as a first reactant stream.
The first reactant stream comprises mainly a mixture of ortho-chloronitrotoluene, and ortho-chlorotoluene, nitric acid, sulfuric acid that is not fully reacted. The first reactant stream is discharged into a knock-out pot for two-phase separation. Whereby the mixture of o-chloronitrotoluene and o-chlorotoluene in the first reactant stream is separated as an oil phase. Nitric acid and sulfuric acid in the first reactant stream are separated as an aqueous phase. The water phase is led into a batching tank for subsequent recycling. The oil phase is dried by anhydrous sodium sulfate after alkali washing and water washing. And (3) carrying out quantitative detection on the oil phase after drying in a gas chromatograph, and quantifying the concentration of the product according to the peak area. According to analysis, the conversion rate of raw material o-chlorotoluene is 94.6%, the content of the o-chloronitrotoluene mixture is 92%, and the content of other impurities is 3.5%.
Comparative example two:
when n=3, the streams include a first stream, a second stream, the first stream including o-chlorotoluene. The second stream is a nitrated sulfuric acid mixture. The specific material mole ratio of the nitric-sulfuric mixed acid is nitric acid: sulfuric acid: water was 1:4.5:2. Specifically, 95% nitric acid, 98% sulfuric acid, and water are introduced into a storage tank for formulation to obtain the above molar ratio of the nitric-sulfuric mixed acid and as a second stream. Selected microchannel reactor adopts V-shaped tantalum reactor
O-chlorotoluene as a first stream was continuously pumped into the first reaction zone by a plunger pump through a feed inlet, the flow rate of the first stream being 60ml/min. Simultaneously, a second stream is pumped into the first reaction zone by a plunger pump through a feed frame via a feed port, the second stream having a flow rate of 220ml/min. Whereby the first stream reacts with the second stream in the first reaction zone. Wherein, in the first reaction zone, the molar ratio of the o-chlorotoluene to the nitric acid is 1:1.05, the reaction temperature is 10 ℃, and the reaction residence time is 1min. And after the reaction residence time is reached, discharging a reaction mixture obtained by the reaction of the o-chlorotoluene and the nitric acid out of the first reaction zone as a first reactant stream.
98% sulfuric acid was introduced into a tank, the temperature of which was controlled at 20 ℃. The sulfuric acid is pumped as a third stream from the feed inlet into the second reaction zone by a plunger pump through the feed frame. The flow rate of the third stream was 45ml/min. Simultaneously, the first reactant stream is flowed into the second reaction zone. The flow rate of the first reactant stream was 280ml/min. Whereby the first reactant stream reacts with the third reactant stream in the second reaction zone. Wherein, in the second reaction zone, the reaction temperature is 15 ℃, and the reaction residence time is 2min. After the reaction residence time is reached, the reactants are withdrawn from the second reaction zone as a second reactant stream.
The second reactant stream comprises mainly a mixture of ortho-chloronitrotoluene, and ortho-chlorotoluene, nitric acid, sulfuric acid that is not fully reacted. The first reactant stream is discharged into a knock-out pot for two-phase separation. Whereby the mixture of o-chloronitrotoluene and o-chlorotoluene in the second reactant stream is separated as an oil phase. The nitric acid and sulfuric acid in the second reactant stream are separated as an aqueous phase. The water phase is led into a batching tank for subsequent recycling. The oil phase is dried by anhydrous sodium sulfate after alkali washing and water washing. And (3) carrying out quantitative detection on the oil phase after drying in a gas chromatograph, and quantifying the concentration of the product according to the peak area. According to analysis, the conversion rate of raw material o-chlorotoluene is 96%, the content of o-chloronitrotoluene mixture is 91%, and the content of other impurities is 7.5%.
Comparative example three:
when n=3, the streams include a first stream, a second stream, the first stream including o-chlorotoluene. The second stream was 95% nitric acid. Selected microchannel reactor adopts V-shaped tantalum reactor
O-chlorotoluene as a first material stream is continuously pumped into the first reaction zone through a feed inlet by a plunger pump, and the flow rate of the first material stream is 100ml/min. Simultaneously, a second stream was pumped into the first reaction zone through the feed frame by a plunger pump, the flow rate of the second stream being 65ml/min. Whereby the first stream reacts with the second stream in the first reaction zone. Wherein, in the first reaction zone, the molar ratio of the o-chlorotoluene to the nitric acid is 1:1.5, the reaction temperature is 60 ℃, and the reaction residence time is 5min. And after the reaction residence time is reached, discharging a reaction mixture obtained by the reaction of the o-chlorotoluene and the nitric acid out of the first reaction zone as a first reactant stream.
98% sulfuric acid was introduced into a tank, the temperature of which was controlled at 20 ℃. The sulfuric acid is pumped as a third stream from the feed inlet into the second reaction zone by a plunger pump through the feed frame. The flow rate of the third stream was 200ml/min. Simultaneously, the first reactant stream was flowed into the second reaction zone through a cooling module at a temperature of 20℃and a flow rate of 165ml/min. Whereby the first reactant stream reacts with the third reactant stream in the second reaction zone. Wherein, in the second reaction zone, the reaction temperature is 30 ℃ and the reaction residence time is 2min. After the reaction residence time is reached, the reactants are withdrawn from the second reaction zone as a second reactant stream.
The second reactant stream comprises mainly a mixture of ortho-chloronitrotoluene, and ortho-chlorotoluene, nitric acid, sulfuric acid that is not fully reacted. The second reactant stream is discharged into a knock-out pot for two-phase separation. Whereby the mixture of o-chloronitrotoluene and o-chlorotoluene in the second reactant stream is separated as an oil phase. The nitric acid and sulfuric acid in the second reactant stream are separated as an aqueous phase. The water phase is led into a batching tank for subsequent recycling. The oil phase is dried by anhydrous sodium sulfate after alkali washing and water washing. And (3) carrying out quantitative detection on the oil phase after drying in a gas chromatograph, and quantifying the concentration of the product according to the peak area. According to analysis, the conversion rate of raw material o-chlorotoluene is 97%, the content of the o-chloronitrotoluene mixture is 87%, and the content of other impurities is 10.5%.
Comparative example four:
when n=3, the streams include a first stream, a second stream, the first stream including o-chlorotoluene. The second stream is a nitrated sulfuric acid mixture. The specific material mole ratio of the nitric-sulfuric mixed acid is nitric acid: sulfuric acid: water was 1:2.5:0.5. Specifically, 95% nitric acid, 98% sulfuric acid, and water are introduced into a storage tank for formulation to obtain the above molar ratio of the nitric-sulfuric mixed acid and as a second stream. Selected microchannel reactor adopts V-shaped tantalum reactor
O-chlorotoluene as a first stream was continuously pumped into the first reaction zone by a plunger pump through a feed inlet, the flow rate of the first stream being 60ml/min. Simultaneously, a second stream is pumped into the first reaction zone by a plunger pump through a feed frame via a feed port, the second stream having a flow rate of 60ml/min. Whereby the first stream reacts with the second stream in the first reaction zone. Wherein, in the first reaction zone, the molar ratio of the o-chlorotoluene to the nitric acid is 1:0.6, the reaction temperature is 40 ℃, and the reaction residence time is 2min. And after the reaction residence time is reached, discharging a reaction mixture obtained by the reaction of the o-chlorotoluene and the nitric acid out of the first reaction zone as a first reactant stream.
98% sulfuric acid was introduced into a tank, the temperature of which was controlled at 20 ℃. The sulfuric acid is pumped as a third stream from the feed inlet into the second reaction zone by a plunger pump through the feed frame. The flow rate of the third stream was 48ml/min. Simultaneously, the first reactant stream was flowed into the second reaction zone through a cooling module at a temperature of 20℃and a flow rate of the first reactant stream of 120ml/min. Whereby the first reactant stream reacts with the third reactant stream in the second reaction zone. Wherein, in the second reaction zone, the reaction temperature is 60 ℃ and the reaction residence time is 3min. After the reaction residence time is reached, the reactants are withdrawn from the second reaction zone as a second reactant stream.
The second reactant stream comprises mainly a mixture of ortho-chloronitrotoluene, and ortho-chlorotoluene, nitric acid, sulfuric acid that is not fully reacted. The second reactant stream is discharged into a knock-out pot for two-phase separation. Whereby the mixture of o-chloronitrotoluene and o-chlorotoluene in the second reactant stream is separated as an oil phase. The nitric acid and sulfuric acid in the second reactant stream are separated as an aqueous phase. The water phase is led into a batching tank for subsequent recycling. The oil phase is dried by anhydrous sodium sulfate after alkali washing and water washing. And (3) carrying out quantitative detection on the oil phase after drying in a gas chromatograph, and quantifying the concentration of the product according to the peak area. According to analysis, the conversion rate of raw material o-chlorotoluene is 45%, the content of the o-chloronitrotoluene mixture is 44.6%, and the content of other impurities is 0.14%.
Comparative example five:
when n=2, the streams include a first stream, a second stream, the first stream including o-chlorotoluene. The second stream was 95% nitric acid. Selected microchannel reactor adopts V-shaped tantalum reactor
O-chlorotoluene as a first material stream is continuously pumped into the first reaction zone through a feed inlet by a plunger pump, and the flow rate of the first material stream is 100ml/min. Simultaneously, a second stream is pumped into the first reaction zone by a plunger pump through a feed frame via a feed port, the second stream having a flow rate of 230ml/min. Whereby the first stream reacts with the second stream in the first reaction zone. Wherein, in the first reaction zone, the molar ratio of the o-chlorotoluene to the nitric acid is 1:6, the reaction temperature is 70 ℃, and the reaction residence time is 5min.
And after the reaction residence time is reached, discharging a reaction mixed solution obtained by the reaction of the o-chlorotoluene and the nitric acid into a separation tank for two-phase separation. Whereby the mixture of o-chloronitrotoluene and o-chlorotoluene in the first reactant stream is separated as an oil phase. The aqueous nitric acid phase in the second reactant stream is separated. The water phase is led into a batching tank for subsequent recycling. The oil phase is dried by anhydrous sodium sulfate after alkali washing and water washing. And (3) carrying out quantitative detection on the oil phase after drying in a gas chromatograph, and quantifying the concentration of the product according to the peak area. According to analysis, the conversion rate of raw material o-chlorotoluene is 53%, the content of the o-chloronitrotoluene mixture is 52.5%, and the content of other impurities is 0.42%.
Notably, the ortho-chloro nitrotoluene mixture includes 2 chloro 3 nitrotoluene, 2 chloro 5 nitrotoluene, 2 chloro 4 nitrotoluene, 2 chloro 6 nitrotoluene.
In summary, the invention divides the nitration process of the o-chlorotoluene into a plurality of reaction sections which are spaced from each other, thereby ensuring that the whole reaction process is safer and more controllable, and further ensuring that the nitration process can be normally carried out even if no catalyst or organic solvent exists. On the premise, various parameters in the nitrification process are controlled, so that the whole nitrification process can be carried out according to requirements. Thus, the final resulting reactant comprises only o-chlorotoluene, o-chloronitrotoluene mixture, acid. Wherein, the mixture of the o-chlorotoluene and the o-chloronitrotoluene is organic matter and the acid is inorganic matter. The inorganic matters and the organic matters are not mutually dissolved and are easy to separate. The mixture of the o-chlorotoluene and the o-chloronitrotoluene can be separated by rectification. In summary, the final reactant, while still comprising a variety of different materials, is free of organic solvents and catalysts and is not susceptible to the introduction of some uncontrollable impurities due to corrosiveness and the like. On the other hand, the substances of different species are easier to separate. Therefore, the invention can effectively reduce the residual impurities in the o-chloronitrotoluene mixture, thereby being more suitable for the current industrial production.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (10)
1. A process for preparing an ortho-chloronitrotoluene mixture, characterized by: comprising the following steps: preparing n material flows;
at least one of said streams comprises o-chlorotoluene, the remainder of said streams comprising acids;
transferring said o-chlorotoluene to a reaction zone for reaction with an acid of one of the streams to produce a first reactant stream;
transferring the first reactant stream to a reaction zone for reaction with the acid of the next stream to produce an n- (n-2) th reactant stream;
repeating the foregoing process until an n-1 th reactant stream is produced;
the n-1 th reactant stream comprises o-chlorotoluene, an o-chloronitrotoluene mixture, and an acid.
2. A process for preparing an o-chloronitrotoluene mixture according to claim 1, characterized in that: the streams include a first stream, a second stream, a third stream;
the first stream comprises o-chlorotoluene;
the second stream, third stream, comprises an acid;
the reaction zone comprises a first reaction zone and a second reaction zone;
the method also comprises the following steps:
transferring said first stream to said first reaction zone for reaction with said second stream to produce said first reactant stream;
transferring said first reactant stream to said second reaction zone for reaction with said third reactant stream to produce a second reactant stream;
the second reactant stream comprises the ortho-chlorotoluene, the ortho-chloronitrotoluene mixture, the acid.
3. A process for preparing an o-chloronitrotoluene mixture according to claim 2, characterized in that: the method also comprises the following steps:
performing phase separation treatment on the second reactant stream to obtain an oil phase and an aqueous phase of the second reactant stream;
taking an oil phase of the second reactant stream;
the aqueous phase comprises the acid;
the oil phase comprises the o-chlorotoluene and the o-chloronitrotoluene mixture.
4. A process for preparing an o-chloronitrotoluene mixture according to claim 2, characterized in that: the reaction temperature of the first reaction zone is as follows: -10 ℃ to 50 ℃;
the reaction temperature of the second reaction zone is as follows: 0 ℃ to 80 ℃.
5. A process for preparing an o-chloronitrotoluene mixture according to claim 2, characterized in that: the reaction residence time of the first reaction zone is 0-5min;
the reaction residence time of the second reaction zone is 0-5min.
6. A process for preparing an o-chloronitrotoluene mixture according to claim 2, characterized in that: the flow rate of the first material flow is 30-4000ml/min;
the flow rate of the second material flow is 30-5000ml/min;
the flow rate of the first reactant stream is 30-5000ml/min;
the flow rate of the third material flow is 10-2000ml/min;
the flow rate of the second reactant stream is 30-10000ml/min.
7. A process for preparing an ortho-chloronitrotoluene mixture according to any one of claims 1 to 4, characterized in that: the acid comprises one or more of nitric acid, mixed acid and sulfuric acid.
8. A process for preparing an ortho-chloronitrotoluene mixture according to any one of claims 1 to 4, characterized in that: the molar ratio of the o-chlorotoluene to the acid is (1-2.5):
(1-3.5)。
9. a process for preparing an ortho-chloronitrotoluene mixture according to any one of claims 1 to 4, characterized in that: the reaction zone adopts a micro-channel reactor.
10. A process for preparing an o-chloronitrotoluene mixture according to claim 9, wherein: the configuration of the microchannel reactor comprises a V shape, a heart shape, a funnel shape and a T shape;
the microchannel reactor is made of one or more of hastelloy, a forceps material, a tantalum material, a zirconium material, glass, polytetrafluoroethylene and silicon carbide.
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