CN1762992A - Method for synthesizing p-nitrotoluene-ortho-sulfonic acid from p-nitrotoluene adopting mother liquid circulation style - Google Patents

Method for synthesizing p-nitrotoluene-ortho-sulfonic acid from p-nitrotoluene adopting mother liquid circulation style Download PDF

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Publication number
CN1762992A
CN1762992A CN 200510015326 CN200510015326A CN1762992A CN 1762992 A CN1762992 A CN 1762992A CN 200510015326 CN200510015326 CN 200510015326 CN 200510015326 A CN200510015326 A CN 200510015326A CN 1762992 A CN1762992 A CN 1762992A
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nitrotoluene
para
sulfuric acid
mother liquid
sulfonation
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CN 200510015326
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张凤宝
秦丽红
张国亮
王淑兰
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Tianjin University
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Tianjin University
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Abstract

The present invention discloses mother liquid circulating p-nitrotoluene sulfonating process of preparing p-nitrotoluene sulfonic acid. The process includes the following steps: adding fuming sulfuric acid in 20 % into molten p-nitrotoluene, sulfonation, and maintaining the temperature until completing reaction; cooling to crystallize, filtering to obtain sulfuric acid mother liquid; mixing molten p-nitrotoluene and sulfuric acid mother liquid, dropping fuming sulfuric acid in 50-65 %, sulfonation, and maintaining the temperature until completing reaction; cooling, crystallizing, filtering to obtain filter cake as NTS and filtrate as sulfuric acid mother liquid; reusing parital sulfuric acid mother liquid, adding water into residual filtrate to regulate sulfuric acid concentration, and filtering to obtain NTS crystal; and circulating so on. The present invention adopts fuming sulfuric acid as sulfonating agent, circulating partial sulfuric acid mother liquid, and has the advantages of reduced sulfuric acid consumption and decreased waste acid exhaust.

Description

Mother liquid circulation is by the method for the synthetic sodium p-nitrotoluene-2-sulfonic acid of para-nitrotoluene
Technical field
The present invention relates to the method for a kind of mother liquid circulation, belong to the synthetic technology of sodium p-nitrotoluene-2-sulfonic acid by the synthetic sodium p-nitrotoluene-2-sulfonic acid of para-nitrotoluene.
Background technology
Sodium p-nitrotoluene-2-sulfonic acid (NTS) is a synthetic dyestuff intermediate 4,4 '-diaminobenzil-2, the raw material of 2 '-disulfonic acid (DSD acid).The white dyes of making based on DSD acid has kind more than 100, kind surplus the reactive dyestuffs 50, kind surplus the substantive dyestuff 70.With the substitute of DSD acid synthetic dyestuff as the diphenyl amine dyestuff, there are not characteristics such as accumulation owing to nontoxicity, in human body, be subjected to extensive attention in recent years, its industrial scale development is very fast.
Industrial, NTS normally at high temperature carries out sulfonation with the fused para-nitrotoluene and makes.Sulphonating agent is the gaseous sulfur trioxide of 20% oleum, liquid sulphur trioxide and all kinds of SOLVENTS dilution.Because sulfonation reaction is a strong exothermal reaction, thereby when using sulphur trioxide as sulphonating agent, even adopt rare gas element, air, sulfurous gas or organic solvent that it is diluted, still can the growing amount of byproduct of reaction be increased greatly, so traditional para-nitrotoluene process for sulfonation mostly adopts 20% oleum as sulphonating agent.This processing method maturation, yield higher (can reach 95-96%).Shortcoming be must in reaction residual liquor, add after sulfonation reaction is finished water adjust sulfuric acid concentration to 55-60% with separated product NTS, thereby the sulfur waste acid that produces a large amount of 55-60% is produced NTS per ton usually and is produced 2 tons of spent acid approximately; This spent acid COD and colourity are all very high, are difficult to be for recycling and reuse.Therefore from economy and environmental, do not met modern cleaner production requirement.
Summary of the invention
The object of the present invention is to provide the method for a kind of mother liquid circulation by the synthetic sodium p-nitrotoluene-2-sulfonic acid of para-nitrotoluene, this method technology is simple, and the spent acid quantity discharged is few, and production cost is low.
The present invention is realized by following technical proposals, a kind of mother liquid circulation is by the method for the synthetic sodium p-nitrotoluene-2-sulfonic acid of para-nitrotoluene, its feature may further comprise the steps: the oleum that adds mass concentration 20% in the fusion para-nitrotoluene, the mol ratio of contained sulphur trioxide and para-nitrotoluene is 1.0-1.5 in the oleum: 1.0, under 80-120 ℃, carry out sulfonation 0.5-1h.After sulfonation reaction finishes, be incubated 0.5-1h down at 80-130 ℃.After reacting completely,, filter at 0-20 ℃ of following crystallisation by cooling.Gained filtrate is sulfate liquor, and NTS quality percentage composition is 5-15% in this sulfate liquor.Then under 55-70 ℃, press mass ratio 1.0: 0.6-2.5 with fused para-nitrotoluene and sulfate liquor thorough mixing after, be heated to 70-90 ℃.Dripping mass concentration in this reaction solution is the oleum of 50-65%, sulfonation reaction 0.5-1h, and sulphur trioxide and para-nitrotoluene mol ratio are 1.5-1.0 in the oleum that is dripped: 1.0, temperature is controlled at 80-120 ℃.The aging 0.5-1h of insulation makes the para-nitrotoluene complete reaction, and temperature is controlled between 80-130 ℃.After reaction finishes liquid is finished in sulfonation and be cooled to 5-25 ℃, crystallization is filtered, and filter cake is NTS, and filtrate is sulfate liquor.This sulfate liquor part cyclically utilizing, adding less water in remaining filtrate, to adjust sulfuric acid concentration be 55-60%, filter the NTS crystal.So circulation repeatedly.
Compare with existing technology, the invention has the advantages that: the oleum that adopts 50-65% recycles the part of sulfuric acid mother liquor as sulphonating agent, has both reduced the sulfuric acid consumption as solvent, has also reduced useless vitriolic quantity discharged simultaneously.
Embodiment
Example one:
1. the 137g para-nitrotoluene is added in the glass four-hole bottle of 1L heating and melting; Regulate 500 rev/mins of stir speed (S.S.)s, add 440g 20% oleum in 1h, temperature of reaction is controlled within 90-95 ℃ all the time in the dropping process.After oleum dropwised, insulation reacted completely para-nitrotoluene, and temperature is controlled at 100-105 ℃.After reacting completely, be cooled to 10 ℃, crystallization, suction filtration gets NTS and sulfate liquor.
2. the 137g para-nitrotoluene is added in the glass four-hole bottle of 1L heating and melting; Regulate 500 rev/mins of stir speed (S.S.)s, in 0.5h, add the 127.3g sulfate liquor.After treating para-nitrotoluene and sulfate liquor thorough mixing, be heated to 90 ℃.Drip the 176g50% oleum then in 1h, sulfonation temperature is controlled at 90-95 ℃.After oleum dropwised, insulation 1h transformed para-nitrotoluene fully, and temperature is controlled at 100-105 ℃ in the insulating process.After treating that para-nitrotoluene transforms fully, be cooled to 10 ℃, crystallization, suction filtration gets 210.5gNTS and 229.8g sulfate liquor.
3. getting 127.3g sulfonation next time from the gained sulfate liquor uses.Remaining 99.5g spent acid adds the dilution of 73.2g water, and suction filtration, filter cake are the 6.6gNTS crystal, and filtrate is the acid of 166.1g sulfur waste, and concentration is 56%.
As stated above middle step 2,3 circulating reactions three times, reaction yield (with respect to the Theoretical Mass of the para-nitrotoluene that adds, down together) is respectively 98.9%, 99.2% and 98.8%.With respect to existing 20% oleum method of sulfonation (down together), spent acid reduces 75%.
Example two:
Preparing sulfate liquor with the method for step 1 in the example one recycles.
The 68.5g para-nitrotoluene is added in the glass four-hole bottle of 1L heating and melting.Regulate 500 rev/mins of stir speed (S.S.)s, add the 102.8g sulfate liquor in 0.5h, as thinner, temperature of reaction is controlled at 100-105 ℃ in the process.Splash into the 88g50% oleum then within 0.5h, temperature of reaction is controlled within 100-105 ℃ all the time in the dropping process.After oleum dropwised, insulation 0.75h transformed para-nitrotoluene fully, and temperature is controlled at 110-115 ℃ in the insulating process.After treating that para-nitrotoluene transforms fully, be cooled to 10 ℃, crystallization, suction filtration gets NTS103.5 and 155.5 sulfate liquors.
Getting 102.8g sulfonation next time from the gained sulfate liquor uses.Remaining spent acid adds the dilution of 40g water, and suction filtration, filter cake are the 4.1gNTS crystal, and filtrate is the acid of 88.9g sulfur waste, and concentration is 55%.
Circulating reaction is three times as stated above, and reaction yield is respectively 98.2%, 98.7% and 98.5%.Spent acid reduces 75%.
Example three:
Preparing sulfate liquor with the method for step 1 in the example one recycles.
The 137g para-nitrotoluene is added in the glass four-hole bottle of 1L heating and melting; Regulate 500 rev/mins of stir speed (S.S.)s, add the 133.3g sulfate liquor in 0.5h, as thinner, controlled temperature is at 80-85 ℃ in the process.Splash into the 160g55% oleum then within 0.75h, temperature of reaction is controlled within 100-105 ℃ all the time in the dropping process.After oleum dropwised, insulation 0.5h transformed para-nitrotoluene fully, and temperature is controlled at 110-115 ℃ in the insulating process.After treating that para-nitrotoluene transforms fully, be cooled to 10 ℃, crystallization, suction filtration gets 209.8gNTS and 220.5g sulfate liquor.
Getting 133.3g sulfonation next time from the gained sulfate liquor uses.Remaining 87.2g spent acid adds the dilution of 64.8g water, and suction filtration, filter cake are the 5.7gNTS crystal, and filtrate is the acid of 146.3g sulfur waste, and concentration is 56%.
Circulating reaction is three times as stated above, and reaction yield is respectively 98.9%, 98.2% and 98.8%, and spent acid reduces 74%.
Example four:
Preparing sulfate liquor with the method for step 1 in the example one recycles.
The 137g para-nitrotoluene is added in the glass four-hole bottle of 1L heating and melting.Regulate suitable stir speed (S.S.), add the 135.4g sulfate liquor in 0.5h, as thinner, temperature of reaction is controlled at 90-95 ℃ in the process.Splash into the 158g65% oleum then within 1h, temperature of reaction is controlled within 90-95 ℃ all the time in the dropping process.After oleum dropwised, insulation transformed para-nitrotoluene fully, and temperature is controlled at 100-105 ℃ in the insulating process.After treating that para-nitrotoluene transforms fully, be cooled to 10 ℃, crystallization, suction filtration gets 209.8gNTS and 220.6g sulfate liquor.
Getting 135.4g sulfonation next time from the gained sulfate liquor uses.Remaining 85.2g spent acid adds the dilution of 64.8g water, and suction filtration, filter cake are the 4.5gNTS crystal, and filtrate is the acid of 145.5g sulfur waste, and concentration is 56%.
Circulating reaction is three times as stated above, and reaction yield is respectively 98.3%, 98.7% and 98.8%.Spent acid reduces 70%.

Claims (1)

1. a mother liquid circulation is by the method for the synthetic sodium p-nitrotoluene-2-sulfonic acid of para-nitrotoluene, its feature may further comprise the steps: the oleum that adds mass concentration 20% in the fusion para-nitrotoluene, the mol ratio of contained sulphur trioxide and para-nitrotoluene is 1.0-1.5 in the oleum: 1.0, under 80-120 ℃, carry out sulfonation 0.5-1h; After sulfonation reaction finishes, be incubated 0.5-1h down at 80-130 ℃; After reacting completely,, filter at 0-20 ℃ of following crystallisation by cooling; Gained filtrate is sulfate liquor, and NTS quality percentage composition is 5-15% in this sulfate liquor; Then under 55-70 ℃, press mass ratio 1.0: 0.6-2.5 with fused para-nitrotoluene and sulfate liquor thorough mixing after, be heated to 70-90 ℃; Dripping mass concentration in this reaction solution is the oleum of 50-65%, sulfonation reaction 0.5-1h, and sulphur trioxide and para-nitrotoluene mol ratio are 1.5-1.0 in the oleum that is dripped: 1.0, temperature is controlled at 80-120 ℃; The aging 0.5-1h of insulation makes the para-nitrotoluene complete reaction, and temperature is controlled between 80-130 ℃; After reaction finishes liquid is finished in sulfonation and be cooled to 5-25 ℃, crystallization is filtered, and filter cake is NTS, and filtrate is sulfate liquor; This sulfate liquor part cyclically utilizing, adding less water in remaining filtrate, to adjust sulfuric acid concentration be 55-60%, filter the NTS crystal; So circulation repeatedly.
CN 200510015326 2005-10-08 2005-10-08 Method for synthesizing p-nitrotoluene-ortho-sulfonic acid from p-nitrotoluene adopting mother liquid circulation style Pending CN1762992A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102786445A (en) * 2011-05-19 2012-11-21 中国科学院大连化学物理研究所 Method and device for producing m-nitrobenzenesulphonic acid
CN106146356A (en) * 2016-07-01 2016-11-23 宁夏紫光川庆化工有限公司 Produce the method for 1 naphthalene sulfonic acids continuously
CN106748900A (en) * 2017-02-17 2017-05-31 四川省中明环境治理有限公司 A kind of Waste Sulfuric Acid prepares the environment-protection production method of paratoluenesulfonic acid sodium salt
CN112159325A (en) * 2020-10-10 2021-01-01 浙江工业大学 Method for synthesizing 2-amino-3-nitrotoluene

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102786445A (en) * 2011-05-19 2012-11-21 中国科学院大连化学物理研究所 Method and device for producing m-nitrobenzenesulphonic acid
CN102786445B (en) * 2011-05-19 2014-07-02 中国科学院大连化学物理研究所 Method and device for producing m-nitrobenzenesulphonic acid
CN106146356A (en) * 2016-07-01 2016-11-23 宁夏紫光川庆化工有限公司 Produce the method for 1 naphthalene sulfonic acids continuously
CN106146356B (en) * 2016-07-01 2018-07-20 宁夏紫光川庆化工有限公司 The method of continuous production 1-naphthalene sulfonic aicd
CN106748900A (en) * 2017-02-17 2017-05-31 四川省中明环境治理有限公司 A kind of Waste Sulfuric Acid prepares the environment-protection production method of paratoluenesulfonic acid sodium salt
CN106748900B (en) * 2017-02-17 2018-10-23 四川省中明环境治理有限公司 A kind of Waste Sulfuric Acid prepares the environment-protection production method of paratoluenesulfonic acid sodium salt
CN112159325A (en) * 2020-10-10 2021-01-01 浙江工业大学 Method for synthesizing 2-amino-3-nitrotoluene

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