CN100591664C - H acid continuous nitration and denitration, extraction, hydrogenation reduction production process - Google Patents
H acid continuous nitration and denitration, extraction, hydrogenation reduction production process Download PDFInfo
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- CN100591664C CN100591664C CN200810169724A CN200810169724A CN100591664C CN 100591664 C CN100591664 C CN 100591664C CN 200810169724 A CN200810169724 A CN 200810169724A CN 200810169724 A CN200810169724 A CN 200810169724A CN 100591664 C CN100591664 C CN 100591664C
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Abstract
The present invention relates to a novel technology of continuous nitration and denitration, extraction, hydrogenation and reduction of H acid, and belongs to the technical field of H acid production.In the novel technology, H acid is prepared with liquid naphthalene through sulfonation, continuous nitration and denitration, extraction, hydrogenation and reduction, concentration, alkali fusion and separation of the H acid. The present invention not only solves the problems in the traditional technological process that the steps are more, the process is complex, the labor intensity of workersis high, the yield rate of the H acid is low and the pollution of wastewater is serious, but also eliminates the factors that the slightly inaccurate control over the reaction temperature and time ofnitration and denitration can easily cause explosive polynitro compounds and thus hidden danger of security. The present invention has the advantages that the process is shortened, the byproducts arefewer, and the labor intensity is reduced. The continuous nitration and denitration has the advantages that the occupied area is small, the production capacity is high, the energy consumption is low,the yield rate is improved by 8 percent compared with the traditional process, about 1 ton of sulphuric acid is saves in production of one ton of the product, and the wastewater discharge is reduced.No iron ions are contained in the materials, the product quality of the H acid is improved, and the workshop production environment is obviously better.
Description
Technical field:
The present invention relates to a kind of continuous nitrification denitrating, extraction, hydrogenating reduction new process of production of H acid, belong to H acid production technical field.
Background technology:
H acid is a kind of special-purpose intermediate of making dyestuff, is widely used in industries such as printing and dyeing, weaving, chemical industry.Existing manufacturing technique is: with refined naphthalene sulfonation → nitrated → denitration → neutralization → iron powder reducing → iron mud press filtration → T acid segregation → T acid filtration → dehydration → low pressure alkali fusion → H acid segregation.This technological process of production is long, step is many, technology is numerous and diverse, labor strength is big, ubiquity H acid yield is low, iron mud and the serious problem of various contaminated wastewater, and the temperature of reaction of nitrated, denitration and time control the inaccurate explosive many nitro-compounds that also easily generate a little, have major safety risks.
Summary of the invention:
Problems such as the objective of the invention is to: provide a kind of solution traditional technology Production Flow Chart step many, technology is numerous and diverse, and labor strength is big, and H acid yield is low, and contaminated wastewater is serious; Employing is produced the novel process of H acid with refined naphthalene through sulfonation → continuous nitrification denitrating → extraction → hydrogenating reduction → alkali fusion → H acid segregation; Shortened process avoids by product many, reduces continuous nitrification denitrating, extraction, the hydrogenating reduction new process of production of the H acid of labour intensity.
The present invention realizes above-mentioned purpose by following technical solution:
A kind of continuous nitrification denitrating of H acid, extraction, hydrogenating reduction new process of production is characterized in that it comprises following steps;
(1), sulfonation:
The liquid naphthalene is dropped into sulfidation pan, adds 100% sulfuric acid and 65% oleum again, heat up through 4～8 hours, be warming up to 155 ℃ of reactions after, logical cooling water temperature to 100～130 ℃, sampling analysis 1,3,6-three naphthene sulfonic acid HPLC content are qualified greater than 78%.
(2), continuous nitrification denitrating:
The ratio of sulfonated liquid and nitric acid 1: 1.0 in molar ratio～1.3 is successively entered recirculation reactor simultaneously, and temperature of reaction is 32～70 ℃; When temperature surpassed 35 ℃, the charging valve of nitric acid and material was closed automatically, with material pump circulation in the recirculation reactor; When temperature superelevation during to 80 ℃ of limit numerical value, the baiting valve of recirculation reactor bottom is opened automatically, and nitrated material is all put to emergency tank; Enter denitrator by nitrated material and water with 1: 0.2～0.5 volume again and enter denitration reaction, the control temperature of charge was finished denitration at 50～100 ℃ in 2 hours, and the nitrogen oxide gas that denitration produces absorbs with alkali after condenser is cooled to 50 ℃.
(3), extraction:
With nitrated material and with the mol ratio of nitrated material be that 1: 1.1～1.5 extraction agent injects extractor, the extractor temperature is controlled at 30～45 ℃, nitrated material and extraction agent mix under stirring action, in layering equipment, produce oil phase and water, regulate water and flow out control valve opening, control water take-off rate guarantees stably manufactured to keep the phase interface balance; Material after the extraction adds alkali in 1: 0.1～0.2 ratio and mixes and carry out back extraction, and extraction agent is separated with nitro T acid.
(4), hydrogenating reduction:
Draw Buddhist nun's nickel catalyzator suspension and the back extraction thing of content 3～15% enter autoclave in 1: 1～1.5 ratio, under 22～25MPa hydrogen pressure, 170～190 ℃ of temperature, react, residence time of material is 1～3 hour, and the transformation efficiency that online sampling detects material reaches more than 99.5% after interchanger enters knockout drum after being cooled to 100～120 ℃; Material is decompressed to 0.5～1.0MPa through the release of pressure jar and enters strainer, and catalyzer is separated with T acid.
(5) alkali fusion:
The hydrogenating reduction product is joined in the alkal melting pan, add 75% sodium hydroxide solvent simultaneously, airtight alkal melting pan is warming up to 150～180 ℃, keep-ups pressure under 2.0～3.0MPa condition, reacts 1～2 hour, slowly deviates from solvent.
(6) H acid segregation:
In alkali fusion liquid, add 20% dilute sulphuric acid and neutralize, add acid during controlled temperature between 60～85 ℃, when pH value reaches after 3～6, stop to add acid, stirred 1-2 hour, fully deviate from SO
2After filter, dry, pulverize after, the single sodium salt finished product of H acid.
The present invention's beneficial effect compared with prior art is:
The present invention adopts technique scheme, has shortened technical process, has avoided by product many, has reduced labour intensity.In addition also have the following advantages:
1, continuous nitrification, denitration, occupation area of equipment is little, and throughput is big, and energy consumption is low, and old relatively process recovery ratio has improved 8%.Material and nitric acid is access arrangement simultaneously, and it is inhomogeneous to have avoided material to mix with nitric acid, reacts the problem of easy overtemperature, has improved safety coefficient.
2, after the employing extraction extracted sour water, product per ton was saved sulfuric acid (amounting to into 98% sulfuric acid) 1 ton, had cut T acid segregation technology, had reduced labour intensity, reduced wastewater discharge.
3, hydrogenation reduction process adopts clean energy hydrogen as raw material, and reacted by product is a water, has thoroughly eliminated the pollution of iron mud waste residue to environment, reduce three waste discharge, do not contain iron ion in the material, improved H acid product quality, significantly improved the Workshop Production environment.
Embodiment:
(is example with the sulfonation of 650L liquid naphthalene)
The first step: sulfonation:
650L liquid naphthalene is dropped into sulfidation pan, add 100% sulfuric acid 520L and 65% oleum 900L again, heat up through 4～8 hours, be warming up to 155 ℃ of reactions after, logical cooling water temperature to 100 ℃, sampling analysis 1,3,6-three naphthene sulfonic acid HPLC content, greater than 78% is qualified, make content and be 78% 1,3, the sulfonation material of 6-three naphthene sulfonic acid.
Second step: continuous nitrification denitrating:
The present invention adopts the circulating reaction still to replace traditional nitrating pot, to contain 78%1,3, the sulfonation material of 6-three naphthene sulfonic acid and 1: 1.18 in molar ratio ratio of nitric acid continuously join in the recirculation reactor through pump, control 1,3, the flow of 6-three naphthene sulfonic acid is that the flow of 1000L/h, nitric acid is 135L/h, and 32～70 ℃ of control reaction temperature are when temperature surpasses 35 ℃, the charging valve of nitric acid and material is closed automatically, with material pump circulation in the recirculation reactor; When temperature superelevation during to 80 ℃ of limit numerical value, the baiting valve of recirculation reactor bottom is opened automatically, and nitrated material is all put to emergency tank; Enter to denitrator in proportion by nitrated material and water again, nitrated material is with the 15001/h charging, and adding water speed simultaneously is 800L/h.The control temperature of charge was finished denitration at 70 ℃ in 2 hours, the nitrogen oxide gas that denitration produces absorbs with alkali after condenser is cooled to 50 ℃.
The 3rd step: extraction:
Material enters denitration thing basin after condensation, liquid level reaches at 60% o'clock and pumps to extractor with pump, with nitrated material and with the mol ratio of nitrated material be that 1: 1.5 extraction agent injects extractor, the extractor temperature is controlled at 35～45 ℃, nitrated material and extraction agent mix under stirring action, produce oil phase and water in layering equipment, regulate water and flow out control valve opening, control water take-off rate guarantees stably manufactured to keep the phase interface balance; Material after the extraction adds alkali in 1: 0.15 ratio and mixes and carry out back extraction, and 35～50 ℃ of controlled temperature make extraction agent separate with nitro T acid.Extraction agent is got back to the basin recycled, and nitro T acid enters basin.
The 4th step: hydrogenating reduction:
Draw Buddhist nun's nickel catalyzator suspension and the back extraction thing of content 10% enter autoclave in 1: 1.5 ratio, adding pressure simultaneously is the hydrogen of 22～25Mpa, content 99.9%, under 170～180 ℃ of temperature, react, residence time of material was at 1～3 hour, and qualified material enters knockout drum after interchanger is cooled to 100～120 ℃; Separated hydrogen enters systemic circulation and applies mechanically after the recycle compressor compression.Material is decompressed to 0.5～1.0MPa through the release of pressure jar and enters strainer, and catalyzer is separated with T acid.The material of T acid after filtering advances basin, and catalyst recirculation is applied mechanically.
The 5th step: alkali fusion:
The hydrogenating reduction product is joined in the alkal melting pan, add 75% sodium hydroxide, solvent simultaneously, airtight alkal melting pan is warming up to 150～180 ℃, keep-ups pressure under the 2.8MPa condition, reacts 1 hour, slowly deviates from solvent.
The 6th step: H acid segregation:
In alkali fusion liquid, add 20% dilute sulphuric acid and neutralize, add acid during controlled temperature at 60～85 ℃, when pH value reaches after 3～6, stop to add acid, stirred 2 hours, fully deviate from SO
2After filter, dry, pulverize after, promptly get the sour single sodium salt finished product of H.
Claims (1)
1, a kind of continuous nitrification denitrating of H acid, extraction, hydrogenating reduction new process of production is characterized in that it comprises following steps;
(1), sulfonation:
The liquid naphthalene is dropped into sulfidation pan, adds 100% sulfuric acid and 65% oleum again, heat up through 4～8 hours, be warming up to 155 ℃ of reactions after, logical cooling water temperature to 100～130 ℃, sampling analysis 1,3,6-three naphthene sulfonic acid HPLC content are qualified greater than 78%;
(2), continuous nitrification denitrating:
The ratio of sulfonated liquid and nitric acid 1: 1.0 in molar ratio～1.3 is successively entered recirculation reactor simultaneously, and temperature of reaction is 32～70 ℃; When temperature surpassed 35 ℃, the charging valve of nitric acid and material was closed automatically, with material pump circulation in the recirculation reactor; When temperature superelevation during to 80 ℃ of limit numerical value, the baiting valve of recirculation reactor bottom is opened automatically, and nitrated material is all put to emergency tank; Enter denitrator by nitrated material and water with 1: 0.2～0.5 volume again and enter denitration reaction, the control temperature of charge was finished denitration at 50～100 ℃ in 2 hours, and the nitrogen oxide gas that denitration produces absorbs with alkali after condenser is cooled to 50 ℃;
(3), extraction:
With nitrated material and with the mol ratio of nitrated material be that 1: 1.1～1.5 extraction agent injects extractor, the extractor temperature is controlled at 30～45 ℃, nitrated material and extraction agent mix under stirring action, in layering equipment, produce oil phase and water, regulate water and flow out control valve opening, control water take-off rate guarantees stably manufactured to keep the phase interface balance; Material after the extraction adds alkali in 1: 0.1～0.2 ratio and mixes and carry out back extraction, and extraction agent is separated with nitro T acid;
(4), hydrogenating reduction:
Draw Buddhist nun's nickel catalyzator suspension and the back extraction thing of content 3～15% enter autoclave in 1: 1～1.5 ratio, under 22～25MPa hydrogen pressure, 170～190 ℃ of temperature, react, residence time of material is 1～3 hour, and the transformation efficiency that online sampling detects material reaches more than 99.5% after interchanger enters knockout drum after being cooled to 100～120 ℃; Material is decompressed to 0.5～1.0MPa through the release of pressure jar and enters strainer, and catalyzer with after T acid separates, is entered the isolating subsequent process steps of alkali fusion and H acid.
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| CN102936214B (en) * | 2011-08-15 | 2014-04-09 | 中国中化股份有限公司 | Method for clean preparation H acid |
| CN102992433B (en) * | 2012-11-28 | 2014-08-20 | 中国科学院南京土壤研究所 | Extraction recovery method of waste water produced by naphthalene-series dye intermediate |
| CN103113269B (en) * | 2013-01-23 | 2015-07-22 | 绍兴奇彩化工有限公司 | 1,8-dinitro-3,6-naphthalene disulfonate hydrogenation reduction method |
| CN105272863B (en) * | 2014-06-11 | 2017-12-19 | 宁夏明盛染化有限公司 | The preparation method of paraphenetidine |
| CN104086464B (en) * | 2014-06-13 | 2016-03-23 | 通辽市龙盛化工有限公司 | A kind of method that H acid denitration exhaust-gas resource utilizes |
| CN106316895B (en) * | 2015-06-16 | 2018-01-02 | 江苏扬农化工集团有限公司 | A kind of resource utilization method of H soda acids liquation |
| CN106478469B (en) * | 2015-09-02 | 2017-12-29 | 江苏扬农化工集团有限公司 | A kind of method of the recycling of residual nitric acid in nitrification liquid of H acid |
| CN105348153A (en) * | 2015-11-06 | 2016-02-24 | 南京师范大学 | Technology for two-stage cross-flow extraction separation of mixed liquid of nitro T-acid, sulfuric acid and water |
| CN105693560A (en) * | 2016-02-29 | 2016-06-22 | 江苏吉华化工有限公司 | Method for preparing energy-efficient H-acid |
| CN105753744B (en) * | 2016-02-29 | 2017-06-16 | 江苏吉华化工有限公司 | A kind of H acid preparation facilities with energy-saving effect |
| CN105566171B (en) * | 2016-02-29 | 2017-06-16 | 江苏吉华化工有限公司 | A kind of device for preparing H acid |
| CN105669500A (en) * | 2016-02-29 | 2016-06-15 | 江苏吉华化工有限公司 | Method adopting clean process for preparing H-acid |
| CN105712907B (en) * | 2016-03-11 | 2017-10-27 | 楚源高新科技集团股份有限公司 | A kind of cleaning process for sulfonation in the sour production processes of H |
| CN106698744B (en) * | 2016-12-06 | 2019-10-18 | 浙江力禾集团有限公司 | A method of hydrazine hydrate in removal H acid waste water |
| CN106587494A (en) * | 2016-12-06 | 2017-04-26 | 浙江力禾集团有限公司 | Method for improving ammonia-nitrogen content of H acid wastewater |
| CN107162939A (en) * | 2017-06-15 | 2017-09-15 | 江苏力禾颜料有限公司 | A kind of sour restoring method of environment-friendly type H |
| CN108191717A (en) * | 2017-11-27 | 2018-06-22 | 江苏力禾颜料有限公司 | H acid isolates preparation process |
| CN108129361A (en) * | 2017-12-05 | 2018-06-08 | 江苏力禾颜料有限公司 | H acid monosodium salt continuously hydrogen adding reducing process |
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Owner name: CHUYUAN HIGH-NEW TECHNOLOGY GROUP CO., LTD. Free format text: FORMER OWNER: HUBEI CHUYUAN CHEMICAL CO., LTD. Effective date: 20120828 |
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Effective date of registration: 20120828 Address after: 434400 Hubei province Shishou City High-tech Park Patentee after: Chuyuan High-New Technology Group Co., Ltd. Address before: 434400 Hubei province Shishou City Zhang Huan high tech Park Patentee before: Hubei Chuyuan Chemical Co., Ltd. |