CN106478469B - A kind of method of the recycling of residual nitric acid in nitrification liquid of H acid - Google Patents
A kind of method of the recycling of residual nitric acid in nitrification liquid of H acid Download PDFInfo
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- CN106478469B CN106478469B CN201510557958.5A CN201510557958A CN106478469B CN 106478469 B CN106478469 B CN 106478469B CN 201510557958 A CN201510557958 A CN 201510557958A CN 106478469 B CN106478469 B CN 106478469B
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Abstract
The invention belongs to the technical field of organic chemical industry, it is related to the method for the recycling of residual nitric acid in the nitrification liquid of reactive dye intermediate H acid, more specifically, it is related to one kind using refined naphthalene as raw material, after sulfonated, nitrification, reaction in-situ occurs for the nitric acid remained using introducing in organic solvent, with nitrification liquid, can efficiently control nitric acid content and be less than 100ppm.The features of the present invention has that production environment safety and environmental protection, production cost are low and equipment investment is few.
Description
Technical field
The invention belongs to the technical field of organic chemical industry, is related to residual nitric acid in the nitrification liquid of reactive dye intermediate H acid
Recycling method, more particularly, to one kind using refined naphthalene as raw material, it is sulfonated, nitrification after, using introduce it is organic molten
Reaction in-situ occurs for the nitric acid remained in agent, with nitrification liquid, can efficiently control nitric acid content and be less than 100ppm.The present invention's
Feature has that production environment safety and environmental protection, production cost are low and equipment investment is few.
Background technology
H acid (1- amino-8-naphthol -3,6- disulfonate sodiums) is mainly produced as follows：(1) naphthalene sulfonation
Obtain 1,3,6- naphthalene sulfonic acids；(2) 1,3,6- naphthalene trisulfonic acids nitrification generation 1- nitros -3,6,8- naphthalene trisulfonic acids, and make nitrating mixture
Take off nitrogen dioxide；(3) nitrating mixture is neutralized with ammoniacal liquor；(4) ammonium salt of neutralized reaction product nitro naphthalene trisulfonic acid three reduces, and uses sulfuric acid
Reduction acidizing product amino T acid is separated out with salt；(5) amino T acid is transformed into sodium salt, alkali fusion, acid out, obtains H acid.Wherein,
The main process of 1- nitro -3,6,8- naphthalene trisulfonic acids reaction is represented by the chemical formula as follows：
Publication No. CN 103739524A Chinese patent, disclose remove nitrification liquid in remain nitric acid it is existing
Processing method, reaction system is flowed out after the buffered tank of material after nitrification, into denitration kettle, nitrification material is with water with 1:0.5 body
Product is mixed, and it is 90 DEG C to control temperature, and denitration, nitrogen oxide gas caused by denitration, condensed device cooling were completed in 2 hours
Alkali absorption is used after to 50 DEG C.However, this technique can produce substantial amounts of oxynitrides noxious material, larger safety collar be present
Hidden danger is protected, and needs long-time high-temperature heat treatment, energy consumption is big, and lectotype selection is difficult, using high temperature thermal decomposition nitric acid so as to reaching
Be present the problem of notable in the traditional handicraft to denitration purpose, have to be solved.
Therefore, patent of the present invention using refined naphthalene as raw material, after sulfonated, nitrification, is diluted with water to required dehydrating value of sulfuric acid
(DVS) organic solvent, is then introduced, reaction in-situ occurs with the nitric acid remained in nitrification liquid, so as to reach the mesh for removing nitric acid
, there is following advantage：
(1) nitric acid clearance is high.Reaction in-situ occurs for the nitric acid remained using introducing in organic solvent, with nitrification liquid, can
It is less than 100ppm to efficiently control nitric acid content；
(2) it is easy to operate simple.Nitrification liquid after nitration reaction is terminated, is added dropwise in solvent, continues stirring reaction number
After hour, layering；
(3) safety and environmental protection low energy consumption.Solvent in-situ method denitrification process, does not produce oxynitrides, without high-temperature heat treatment.
The content of the invention
The invention belongs to the technical field of organic chemical industry, is related to residual nitric acid in the nitrification liquid of reactive dye intermediate H acid
Recycling method, more particularly, to one kind using refined naphthalene as raw material, it is sulfonated, nitrification after, using introduce it is organic molten
Reaction in-situ occurs for the nitric acid remained in agent, with nitrification liquid, can efficiently control nitric acid content and be less than 100ppm.The present invention's
Feature has that production environment safety and environmental protection, production cost are low and equipment investment is few.
Brief description of the drawings
Fig. 1 is the flow chart of the recycling of residual nitric acid in the sour nitrification liquids of H.
The method of the recycling of residual nitric acid, comprises the following steps in a kind of nitrification liquid of H acid：
(1) organic solvent is thrown into reaction bulb, opens stirring；
(2) toward water is added in the nitrification liquid before denitration, required dehydrating value of sulfuric acid (DVS) is diluted to, then, is added to above-mentioned
In organic solvent, a few hours are reacted；
(3) after reaction terminates, layering, oil reservoir is the mixture of organic solvent and organic itrated compound, and water layer is the H after denitration
Sour itrated compound；
(4) oil reservoir distills, and Separation of Organic and organic itrated compound, the organic solvent of recovery are directly applied to step (1).
In above-mentioned steps (1), the organic solvent is benzene,toluene,xylene, chlorobenzene, methyl phenyl ethers anisole, benzamide, benzene first
One or more mixtures in sour methyl esters, DMA, its dosage are 1~500 times of residual nitric acid molal quantity.
In above-mentioned steps (1), the consumption of organic solvent is 0.5~2 times of organic itrated compound molal quantity.
In above-mentioned steps (2), the dehydrating value of sulfuric acid (DVS) is 0.5~8.
In above-mentioned steps (2), the reaction temperature is -20~80 DEG C, and the reaction time is 0.5~20h.
In above-mentioned steps (4), the distillation vacuum is 0.1~101kPa.
In above-mentioned steps (4), organic itrated compound weight content 0~20% in the organic solvent of the recovery.
The present invention is solved the problems, such as in the presence of existing H acid high temperature denitrification process, it is proposed that a kind of easy to operate, safety
The method of the nitric acid recycling of environmental protection, it possesses advantages below：(1) use to introduce in organic solvent, with nitrification liquid and remain
Nitric acid nitration reaction in situ occurs, nitric acid content can be efficiently controlled and be less than 100ppm；(2) after nitration reaction is terminated
Nitrification liquid, it is added dropwise in solvent, and after continuing stirring reaction a few hours, layering, operation is very easy；(3) solvent is in situ
Method denitrification process, does not produce oxynitrides, without high-temperature heat treatment, safety and environmental protection low energy consumption, meets the requirement of clean manufacturing.
Embodiment
The following examples are illustrated the present invention in more detail, rather than limitation of the invention further.Unless
It is otherwise noted, " % " therein is " quality % ".
Embodiment 1
47.21g toluene is added in 250mL four-hole boiling flasks, is sufficiently stirred, and is warming up to 40 DEG C.Nitrification liquid before denitration
123.37g, DVS value are 6.10, nitric acid content 2.62%, are added dropwise in four-hole boiling flask, quiet after 40 DEG C are reacted 1 hour
Put layering, gained water layer 120.26g, nitric acid content 65ppm.Oil reservoir 43.32g, ortho-methylnitrobenzene yield 63.38%, to nitro
Toluene yield 36.62%.
Embodiment 2-4
On the basis of embodiment 1, using 57.76g chlorobenzenes to replace toluene, other conditions are constant for solvent.Acquired results
As shown in table 1.
The chlorobenzene of table 1 is solvent, influence of the differential responses time to denitration
Embodiment 5
40.08g benzene is added in 250mL four-hole boiling flasks, is sufficiently stirred, and is warming up to 40 DEG C.Nitrification liquid 123.37g before denitration,
DVS values are 6.10, nitric acid content 2.62%, are added dropwise in four-hole boiling flask, after 40 DEG C are reacted 1 hour, stratification, and institute
Obtain water layer 120.32g, nitric acid content 83ppm.Oil reservoir 43.07g, nitrobenzene yield 99.86%.
Embodiment 6-8
On the basis of embodiment 1, different DVS values are investigated, other conditions are constant.Acquired results are as shown in table 2.
The toluene of table 2 is solvent, influence of the different DVS values to denitration
Embodiment 9-11
On the basis of embodiment 1, differential responses temperature is investigated, other conditions are constant.Acquired results are as shown in table 3.
The toluene of table 3 is solvent, influence of the different DVS values to denitration
Embodiment 14-17
On the basis of embodiment 1, the toluene solvant of recovery is applied mechanically, the molal quantity that fresh toluene is added is to nitro first
1.1 times of benzene and ortho-methylnitrobenzene summation, other conditions are constant.Acquired results are as shown in table 4.
The difference of table 4 applies mechanically influence of the number to denitration
Claims (1)
1. a kind of method of the recycling of residual nitric acid in nitrification liquid of H acid, it is characterised in that comprise the following steps：
(1) organic solvent is thrown into reaction bulb, opens stirring；
(2) toward water is added in the nitrification liquid before denitration, required dehydrating value of sulfuric acid (DVS) is diluted to, then, is added to above-mentioned organic
In solvent, a few hours are reacted；
(3) after reaction terminates, layering, oil reservoir is the mixture of organic solvent and organic itrated compound, and water layer is the H acid nitre after denitration
Compound；
(4) oil reservoir distills, and Separation of Organic and organic itrated compound, the organic solvent of recovery are directly applied to step (1)；
In above-mentioned steps (1), the organic solvent is benzene, toluene or chlorobenzene, and its dosage is the 1~500 of residual nitric acid molal quantity
Times；Consumption of organic solvent is 0.5~2 times of organic itrated compound molal quantity；In above-mentioned steps (2), the dehydrating value of sulfuric acid (DVS)
For 0.5~8；In above-mentioned steps (2), the reaction temperature is -20~80 DEG C, and the reaction time is 0.5~20h；Above-mentioned steps (4)
In, the distillation vacuum is 0.1~101kPa；In above-mentioned steps (4), organic itrated compound weight in the organic solvent of the recovery
Measure content 0~20%.
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| CN201510557958.5A CN106478469B (en) | 2015-09-02 | 2015-09-02 | A kind of method of the recycling of residual nitric acid in nitrification liquid of H acid |
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| CN106478469B true CN106478469B (en) | 2017-12-29 |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3243840A1 (en) * | 1982-11-26 | 1984-05-30 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | METHOD FOR DENITITATING AQUEOUS, NITRIC ACID, SALTY WASTE SOLUTIONS |
| DE3243841C2 (en) * | 1982-11-26 | 1986-02-06 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | Process for the denitration of nitric acid, actinide-containing waste solutions with simultaneous separation of the actinides |
| CN100591664C (en) * | 2008-10-15 | 2010-02-24 | 湖北楚源高新科技股份有限公司 | H acid continuous nitration and denitration, extraction, hydrogenation reduction production process |
| 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 |
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