CN1133283A - Preparing nitro-chlorobenzene by catalytic nitration - Google Patents

Preparing nitro-chlorobenzene by catalytic nitration Download PDF

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Publication number
CN1133283A
CN1133283A CN95117038A CN95117038A CN1133283A CN 1133283 A CN1133283 A CN 1133283A CN 95117038 A CN95117038 A CN 95117038A CN 95117038 A CN95117038 A CN 95117038A CN 1133283 A CN1133283 A CN 1133283A
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liquid
acid
chlorobenzene
concentration
washed
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CN95117038A
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CN1056829C (en
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沙耀武
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Tsinghua University
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Tsinghua University
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06Preparation of nitro compounds
    • C07C201/08Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a method for preparing nitrochlorobenzene by catalytic nitrofication. Said preparation method is as follows: the chlorobenzene and carbon tetrachloride are mixed, and in said organic mixture liquid the mixed acid of sulfuric acid and nitric acid is added in drops under the condition of stirring, and then they are reacted for 30-50 min. under the condition of that its reaction temp. is higher than room temp., and then the stirring operation is stopped, and after the solution is layered, the acid phase is extracted by using carbon tetrachloride, and the organic phase is washed with water, and then the carbon tetrachloride is distilled out at normal pressure, and then the material which is remained in the distilling flask is the invented product.

Description

Catalytic nitration prepares the method for nitro-chlorobenzene
The present invention relates to the method that a kind of catalytic nitration prepares nitro-chlorobenzene, belong to chemical technology field.
Nitro-chlorobenzene is important basic chemical raw materials, is used to prepare dyestuff intermediates such as nitrophenol, amino phenol.About 80,000 tons of China's annual requirement.China produces the yield of nitro-chlorobenzene mostly about 97% at present.Have at least every year 2000 tons of nitro-chlorobenzenes to be difficult to recycle and emit, value is 1,600 ten thousand yuan, and nitro-chlorobenzene is a kind of huge compound that poisons, and environmental pollution is serious.Level and China of reported in literature are close at present, as Poland Patent Pol, PL154456 report yield is 97.4%, Japanese Patent JP8224331 is reported to 98.4%, preparation about nitro-chlorobenzene has a lot of documents and patent report, but yield and practicality differ too big, and is industrial in order to improve the method that yield adopts excessive chlorobenzene, productive rate can reach 97-98% level, but the chlorobenzene loss is bigger.
The objective of the invention is to design a kind of method for preparing nitro-chlorobenzene with catalytic nitration, under lower temperature, will react closely quantitatively and carry out, reaction times shortens one times at least than existing condition, the broadening of reaction allowable temperature scope, and do not detect dinitrochlorobenzene, reaction is closely quantitatively carried out, and has promptly improved yield and has obtained considerable economic, the pollution that has alleviated environment again significantly.Industrial in rectifying product process, the heavy corrosion problem of ubiquity equipment, the product that novel method is produced is not because the purity height through 2000 hours high temperature experiment, is found corrosion.
Catalytic nitration of the present invention prepares the method for nitro-chlorobenzene, comprises following each step:
(1) preparation A liquid is organic liquid mixture, be 95% chlorobenzene with 1 part of concentration with 0.7-1.5 parts of concentration is that 99.5% tetracol phenixin mixes mutually, and it is standby to make organic liquid mixture;
(2) preparation B liquid is mixed acid liquid, in concentration is 65-68% nitric acid, adds concentration and be 95-98% sulfuric acid, and nitric acid and vitriolic volume ratio are 1: 1-1.5, and liquid temp to be mixed is reduced to after the room temperature standby;
(3) 1 part of A liquid is added in the container, while stirring 1-1.4 parts of B liquid are added in the reactor, rate of addition maintains between 40-70 ℃ reacting liquid temperature, after nitration mixture finishes, keeps reaction 30-50 minutes under 60-70 ℃;
(4) stop to stir, make the reaction solution static layering, with separating funnel organic phase is separated mutually with acid, carbon tetrachloride extraction is used in acid mutually, extracting solution and former organic being harmonious also;
(5) under 30-50 ℃, above-mentioned organic phase is washed, be 5% sodium hydroxide solution washing again with concentration, be washed to neutrality at last;
(6) above-mentioned (5) step is washed to the neutral organic phase and under normal pressure, distills out tetracol phenixin, (25 mmhg) is distilled to 110-130 ℃ of former liquid temps under the water pump decompression again, underpressure distillation thing and tetracol phenixin merge stand-by, be p-Nitrophenyl chloride, m-nitrochlorobenzene and o-Nitrochlorobenzene mixture, product promptly of the present invention in the matrass;
Or at first above-mentioned (5) step is washed to the neutral organic phase solution and is cooled to 10 ℃, kept 1 hour, promptly there is p-Nitrophenyl chloride to separate out, it is filtered out, again with tetracol phenixin washing, drying, the same step process of remaining carbon tetrachloride solution.
Be embodiments of the invention below.
Embodiment 1:
With 213 gram chlorobenzenes, the 140ml tetracol phenixin adds in three mouthfuls of reaction flasks of 1000ml.After 200ml98% sulfuric acid and the mixing of 170ml 65-68% nitric acid, under agitation in reaction flask, drip.Add 1/5th of total amount earlier fast, temperature is raised to about 50 ℃.Holding temperature is no more than under 65 ℃, and rest part is added, and finishes in 30 minutes, keep 60-70 ℃ 30 minutes.Behind the stopped reaction standing demix 1 hour, organic layer and acid layer are separated, sour layer extracts three times with tetracol phenixin 30ml, and with the organic layer merging, organic layer washes twice with 30ml, and 30ml5% caustic wash(ing) twice is washed twice again.In the organic layer washing process, temperature will maintain more than 30 ℃.Tetracol phenixin product solution temperature is reduced to 10 ℃, has 80 gram p-Nitrophenyl chlorides to separate out after one hour, account for total amount 42%, detecting through TLC does not have other isomer.Fusing point is 83.5 degree, gets p-Nitrophenyl chloride after mother liquor concentrates, and m-nitrochlorobenzene and o-Nitrochlorobenzene mixture 236 grams in the mix products, do not detect dinitrochlorobenzene, total recovery 99.4%.
Embodiment 2:
With 213 gram chlorobenzenes, the 150ml tetracol phenixin adds in three mouthfuls of reaction flasks of 1000ml.After 190ml98% sulfuric acid and the mixing of 160ml 65-68% nitric acid, under agitation in reaction flask, drip.Add 1/5th of total amount earlier fast, temperature is raised to about 50 ℃.Holding temperature is no more than under 55 ℃, and rest part is added, and finishes in 30 minutes, keep 60 ℃ 40 minutes.Behind the stopped reaction standing demix 1 hour, organic layer and acid layer are separated, sour layer extracts three times with tetracol phenixin 30ml, and with the organic layer merging, organic layer washes twice with 30ml, and 30ml5% caustic wash(ing) twice is washed twice again.In the organic layer washing process, temperature will maintain more than 30 ℃, distill out tetracol phenixin under the normal pressure, change underpressure distillation into, receive 110-120 ℃/8 mmhg, get three kinds of isomer mixtures, 316.5 grams, yield 99.7%, p-Nitrophenyl chloride accounts for about 67%, and o-Nitrochlorobenzene accounts for about 32%, and m-nitrochlorobenzene is less than 1%.
Embodiment 3:
With 213 gram chlorobenzenes, the 160ml tetracol phenixin adds in three mouthfuls of reaction flasks of 1000ml.After 180ml98% sulfuric acid and the mixing of 155ml 65-68% nitric acid, under agitation in reaction flask, drip.Add 1/5th of total amount earlier fast, temperature is raised to about 50 ℃.Holding temperature is no more than between 60-70 ℃, and rest part is added, and finishes in 30 minutes, keeps about 65 ℃ 30 minutes.Behind the stopped reaction standing demix 1 hour, organic layer and acid layer are separated, sour layer extracts three times with tetracol phenixin 30ml, and with the organic layer merging, organic layer washes twice with 30ml, and 30ml5% caustic wash(ing) twice is washed twice again.In the organic layer washing process, temperature will maintain more than 30 degree, is reduced to 10 degree with tetracol phenixin product solution temperature, has 71 gram p-Nitrophenyl chlorides to separate out, and (total amount 37%) detects other isomer of nothing through TLC.After concentrating, mother liquor gets mix products 246 grams, tell the public carbon 220ml of tetrachloro, concentrated solution has 28 gram contraposition products to separate out again after cooling to 37 degree, excess weighs 217 grams, the total production rate of contraposition product is about 67%, and the ortho position is about 33%, and a position is less than 1%, total recovery is 99.7%, and no dinitrobenzene quality testing measures.
In the process of producing product of the present invention, as follows to the corrosion test result of equipment: selection: A-1 1Cr18Ni9Ti 77mm-15mm-1.5mm
Cut off in the middle of the A-11 1Cr18Ni9Ti 77mm-15m-1.5mm, connect with welding rod of the same race again
B-1 1C188Ni 53mm-15mm-1.8mm
Cut off in the middle of the B-11 1Cr18Ni 53mm-15mm-1.8mm, weld with 1Cr18Ni9Ti again
On bar connects, condition: 190 degree, three equality experiments are carried out simultaneously, totally 2000 hours action time, the result is as follows: material: A-X A-1-1 A-1-2 A-1-3 A-11-1 A-11-2 A-11-3 plays starting weight: mg 14919,15 13698,40 13991,60 13320,95 13740,15 13758,202000h, back: 14019,80 13699,80 13991,70 13320,70 13741,20 13758,80 materials: B-X B-1-1 B-1-2 B-1-3 B-11-l B-11-2 B-11-3 plays starting weight: mg11567,70 11448,90 11683,85 10856,08 11183,95 11344,252000h, back: 11568,70 11450,00 11684,00 10855,90 11184,70 11344,00

Claims (1)

1, a kind of catalytic nitration prepares the method for nitro-chlorobenzene, it is characterized in that this preparation method comprises following each step:
(1) preparation A liquid is organic liquid mixture, is that 95% chlorobenzene and 0.7-1.5 parts of concentration are that 99,5% tetracol phenixin mixes mutually with 1 part of concentration, and it is standby to make organic liquid mixture;
(2) preparation B liquid is mixed acid liquid, in concentration is 65-68% nitric acid, adds concentration and be 95-98% sulfuric acid, and nitric acid and vitriolic volume ratio are 1: 1-1.5, and liquid temp to be mixed is reduced to after the room temperature standby;
(3) 1 part of A liquid is added in the container, while stirring 1-1.4 parts of B liquid are added in the reactor, rate of addition maintains between 40-70 ℃ reacting liquid temperature, after nitration mixture finishes, keeps reaction 30-50 minutes under 60-70 ℃;
(4) stop to stir, make the reaction solution static layering, with separating funnel organic phase is separated mutually with acid, carbon tetrachloride extraction is used in acid mutually, extracting solution and former organic being harmonious also;
(5) under 30-50 ℃, above-mentioned organic phase is washed, be 5% sodium hydroxide solution washing again with concentration, be washed to neutrality at last;
(6) above-mentioned (5) step is washed to the neutral organic phase and under normal pressure, distills out tetracol phenixin, (25 mmhg) is distilled to 110-130 ℃ of former liquid temps under the water pump decompression again, underpressure distillation thing and tetracol phenixin merge stand-by, are p-Nitrophenyl chloride, m-nitrochlorobenzene and o-Nitrochlorobenzene mixture in the matrass;
Or at first above-mentioned (5) step is washed to the neutral organic phase solution and is cooled to 10 ℃, kept 1 hour, promptly there is p-Nitrophenyl chloride to separate out, it is filtered out, again with tetracol phenixin washing, drying, remaining the same step process of carbon tetrachloride solution.
CN95117038A 1995-10-20 1995-10-20 Preparing nitro-chlorobenzene by catalytic nitration Expired - Fee Related CN1056829C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100368377C (en) * 2006-06-19 2008-02-13 常州市佳森化工有限公司 Tech. of producing ortho nitro methyl-phenoxide para nitro methyl-phenoxide and meta nitro chlorobenzene from chlorobenzene
CN101607909B (en) * 2009-07-07 2012-05-30 扬州大学 Rapid material cooling and waste acid recycling process after chlorobenzene thermal insulation nitration
CN101607911B (en) * 2009-07-07 2012-08-22 扬州大学 Washing impurity-removing technology of crude nitrochlorobenzene products after chlorobenzene thermal insulation nitration
CN101607910B (en) * 2009-07-07 2012-10-17 扬州大学 Removal technology of nitrogen oxides generated in chlorobenzene thermal insulation nitration
CN114621095A (en) * 2022-03-03 2022-06-14 安徽东至广信农化有限公司 Clean nitrochlorobenzene production process

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5724331A (en) * 1980-07-17 1982-02-08 Nippon Kayaku Co Ltd Nitration of chlorobenzene
JPS606644A (en) * 1983-06-27 1985-01-14 Mitsui Toatsu Chem Inc Nitration of monochlorobenzene
JP4046140B1 (en) * 2006-11-29 2008-02-13 住友電気工業株式会社 Method for manufacturing silicon carbide semiconductor device

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100368377C (en) * 2006-06-19 2008-02-13 常州市佳森化工有限公司 Tech. of producing ortho nitro methyl-phenoxide para nitro methyl-phenoxide and meta nitro chlorobenzene from chlorobenzene
CN101607909B (en) * 2009-07-07 2012-05-30 扬州大学 Rapid material cooling and waste acid recycling process after chlorobenzene thermal insulation nitration
CN101607911B (en) * 2009-07-07 2012-08-22 扬州大学 Washing impurity-removing technology of crude nitrochlorobenzene products after chlorobenzene thermal insulation nitration
CN101607910B (en) * 2009-07-07 2012-10-17 扬州大学 Removal technology of nitrogen oxides generated in chlorobenzene thermal insulation nitration
CN114621095A (en) * 2022-03-03 2022-06-14 安徽东至广信农化有限公司 Clean nitrochlorobenzene production process

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