CN102267849A - Reduction method of aromatic nitro-compound for replacing sodium sulfide - Google Patents
Reduction method of aromatic nitro-compound for replacing sodium sulfide Download PDFInfo
- Publication number
- CN102267849A CN102267849A CN2011102000375A CN201110200037A CN102267849A CN 102267849 A CN102267849 A CN 102267849A CN 2011102000375 A CN2011102000375 A CN 2011102000375A CN 201110200037 A CN201110200037 A CN 201110200037A CN 102267849 A CN102267849 A CN 102267849A
- Authority
- CN
- China
- Prior art keywords
- aromatic nitro
- reduction
- compound
- sodium
- sodium sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a reduction method of an aromatic nitro-compound. The method comprises the following steps of: dissolving sulfur powder into a sodium hydroxide solution of which the mass percent concentration is 15-45 percent at the temperature 60-100 DEG C for later use; and putting the aromatic nitro-compound into the prepared reduction liquid, and heating to 95-125 DEG C for undergoing a reduction reaction to obtain an aromatic amino-compound. The reduction method has the advantages that: (1) high-pollution and high-energy-consumption sodium sulfide can be replaced almost in all application fields of the sodium sulfide; and (2) the concentration of sodium thiosulfate in a reduction mother liquid is 2 times of that of a sodium sulfide method, so that recovery of the sodium thiosulfate in the mother liquid is facilitated, and clean production is realized.
Description
Technical field
The present invention relates to aromatic nitro compound and be reduced into amino method, specifically, is a kind of cleaning method of reducing of aromatic nitro compound of replacement sulfur choline.
Background technology
The amidized method of aromatic nitro compound has: reductive agent reduction, catalytic hydrogenating reduction, electrolytic reduction and high pressure ammonia are separated.Wherein the reductive agent reduction is traditional method, and reductive agent has: iron powder, zinc powder, tin grain, low price sulphide, hydrazine hydrate etc., and in general, the contaminated wastewater that the reductive agent reduction produces is serious, and difficulty of governance is big, the expense height.Hydrogenating reduction, electrochemical reduction, high pressure ammonia such as separate at cleaning procedure, still can not use in the chemical compound lot reduction reaction.Use low price sulphide, particularly the sodium sulfide reducing aromatic nitro compound is because cost is low, technology is simple, constant product quality is still generally used in chemical industry.
From the production process of Sodium Sulphide, Sodium Sulphide is the product of a high pollution, highly energy-consuming fully.Sodium Sulphide, is not produced because of seriously polluted already in developed country, has only a small amount of use.It is reported that China's Sodium Sulphide output is up to more than 700,000 tons/year, the production capacity that adds planned project is up to 1,200,000 tons.The Sodium Sulphide place of production concentrates on west areas such as Shanxi, Inner Mongol, Xinjiang, Sichuan, and the Sodium Sulphide more than 90% all uses coal dust reduction of mirabilite method to produce, and pollution is extremely serious, energy consumption is higher.The high pollution project of many use Sodium Sulphide is introduced in some Sodium Sulphide place of production even also plan the Sodium Sulphide industrial zone.Therefore research thoroughly replaces the method for Sodium Sulphide, is the task of top priority.
Summary of the invention
The present invention be directed to the deficiencies in the prior art, provide a kind of in cost and environmental protection the cleaning method of reducing of the aromatic nitro compound of all competitive replacement sulfur choline.
The technical scheme that realizes above-mentioned purpose is:
A kind of method of reducing of aromatic nitro compound is characterized in that comprising the steps:
The preparation of step 1 reduced liquid: sulfur flour is dissolved in mass percentage concentration under 60～100 ℃ of conditions be that SULPHUR POWDER is 0.8～2:1 with the ratio of the amount of substance of sodium hydroxide, and is standby in 15～45% the sodium hydroxide solution;
Step 2 reduction: aromatic nitro compound is put in the above-mentioned reduced liquid for preparing, be warmed up to 95～125 ℃ and carry out reduction reaction, make aromatic amino compound, SULPHUR POWDER is 1.5～4:1 with the ratio of the amount of substance of aromatic nitro compound.
The method of reducing of above-mentioned aromatic nitro compound, the described reaction of step 2 can be reacted under normal pressure or pressure.
Along with the reinforcement of China's sulfurous gas management, the resource of sulfur flour can be more and more abundant, and price is also cheap more than Sodium Sulphide, adopts method of the present invention to replace the Sodium Sulphide of high pollution, highly energy-consuming that tangible economic benefit is arranged with SULPHUR POWDER.
Adopt the advantage of method of the present invention to be:
(1) almost all can replace the Sodium Sulphide of high pollution, highly energy-consuming in the Application Areas of all Sodium Sulphide
(2) present method also in the original nut liquid concentration of Sulfothiorine be 2 times of sulfuration alkaline process, help the recovery of Sulfothiorine in the mother liquor, realize cleaner production.
Embodiment
Below with specific embodiment technical scheme of the present invention is described, protection scope of the present invention is not limited to this.
Embodiment 1
200 gram 32 % liquid caustic soda (1.60 mol) and 50 are restrained sulfur flours (1.58 mol) join in the beaker, be warming up to 60 ℃, insulated and stirred was clarified to solution more than 30 minutes.In there-necked flask, add 600 parts of water, add 100 gram 1-nitroanthraquinone (0.395 mol) making beating.Add the above-mentioned reduced liquid for preparing, be warming up to 95 ℃, 95～100 ℃ of insulation reduction 3 hours, sampling analysis, the 1-nitroanthraquinone all is converted into the 1-aminoanthraquinone.
Embodiment 2
191 gram 45 % liquid caustic soda (2.15 mol) and 55 are restrained sulfur flours (1.72 mol) join in the beaker, be warming up to 85 ℃, insulated and stirred was clarified to solution more than 30 minutes.Reduced liquid is moved in the autoclave, again 75 gram o-Nitrophenyl methyl ethers (0.49 mol) are put into autoclave about 2 hours, airtight, be warming up to 120 ℃, insulation reaction 2 hours, the sampling analysis o-Nitrophenyl methyl ether all is converted into Ortho Anisidine.
Embodiment 3
200 gram 15 % liquid caustic soda (0.75 mol) and 48 gram sulfur flours (1.50 mol) are joined in the reactor, be warming up to 100 ℃, insulated and stirred got sodium polysulfide solution to feed clarification in 30 minutes; Restrain 2 with 100 in addition, the liquid caustic soda and 100 that 4-dinitrochlorobenzene (0.99 mol) is put into 100 grams, 30 % restrain in the alkaline solution of water composition, are heated to 100 ℃ under stirring, and get 2, the 2, 4-dinitrophenol sodium solution.Above-mentioned 100 ℃ of sodium polysulfide solutions that prepare are joined under boiling state in 100 ℃ the above-mentioned phenol sodium solution, finish, move into autoclave pressure and proceed reduction and vulcanization reaction.Be warming up to 125 ℃ of insulation reaction 6 hours, 2,2, 4-dinitrophenol sodium Restore All becomes 2, and 4-diaminophenol sodium continues to be warming up to 135 ℃ of insulations 2 hours, and vulcanization reaction finishes.Pressure release adds water and regulates concentration, 85 ℃ of left and right sides blowing air oxidations in reactor; The oxidation material is filtered, press dry.Filter cake is sized mixing at 80 ℃ of reduced liquids that are made into 6.5 gram sulfur flours and 20 grams, 42 % liquid caustic soda, and oven dry gets double sulphur black.
Embodiment 4
With giving money as a gift is 1 of 330 grams, and 5-dinitrobenzene-4,8-dihydroxyanthraquinone and 1,8-dinitrobenzene-4, the mixture filter cake of 5-dihydroxyanthraquinone (2.00 mol) are put in the 2000 gram water, making beating; Add the people and restrain 32 % liquid caustic soda (8.0 mol) at 80 ℃ of reduced liquids that are mixed with, be warming up to 96～98 ℃ of reactions 3 hours by 255 gram SULPHUR POWDER (7.96 mol) and 1000.Sampling analysis, above-mentioned dinitrobenzene dihydroxyanthraquinone mixture all change diamino dihydroxyanthraquinone (that is: Disperse Blue-56 reduzate) into.
Claims (2)
1. the method for reducing of an aromatic nitro compound is characterized in that comprising the steps:
The preparation of step 1 reduced liquid: sulfur flour is dissolved in mass percentage concentration under 60～100 ℃ of conditions be that SULPHUR POWDER is 0.8～2:1 with the ratio of the amount of substance of sodium hydroxide, and is standby in 15～45% the sodium hydroxide solution;
Step 2 reduction: aromatic nitro compound is put in the above-mentioned reduced liquid for preparing, be warmed up to 95～125 ℃ and carry out reduction reaction, make aromatic amino compound, SULPHUR POWDER is 1.5～4:1 with the ratio of the amount of substance of aromatic nitro compound.
2. the method for reducing of aromatic nitro compound according to claim 1 is characterized in that: step 2 is described to be reflected at normal pressure or pressure reaction down.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102000375A CN102267849A (en) | 2011-07-18 | 2011-07-18 | Reduction method of aromatic nitro-compound for replacing sodium sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102000375A CN102267849A (en) | 2011-07-18 | 2011-07-18 | Reduction method of aromatic nitro-compound for replacing sodium sulfide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102267849A true CN102267849A (en) | 2011-12-07 |
Family
ID=45050332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102000375A Pending CN102267849A (en) | 2011-07-18 | 2011-07-18 | Reduction method of aromatic nitro-compound for replacing sodium sulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102267849A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497116A (en) * | 2013-09-26 | 2014-01-08 | 江苏亚邦染料股份有限公司 | Synthetic method of 1-amino-anthraquinone |
| CN105085286A (en) * | 2015-08-05 | 2015-11-25 | 盐城市瓯华化学工业有限公司 | Method for synthesizing 1-aminoanthraquinone |
| CN106478426A (en) * | 2015-08-26 | 2017-03-08 | 盐城市瓯华化学工业有限公司 | A kind of method that nicotinic acid method prepares the aromatic nitro compound of akali sulphide |
| CN108395381A (en) * | 2018-04-10 | 2018-08-14 | 大连傲视化学有限公司 | The synthetic method of 1,4- diamino-anthraquinone leuco compounds |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157591A (en) * | 2007-10-16 | 2008-04-09 | 中国医学科学院生物医学工程研究所 | Method for amido deoxidization from nitryl of compound containing nitryl phenyl |
-
2011
- 2011-07-18 CN CN2011102000375A patent/CN102267849A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157591A (en) * | 2007-10-16 | 2008-04-09 | 中国医学科学院生物医学工程研究所 | Method for amido deoxidization from nitryl of compound containing nitryl phenyl |
Non-Patent Citations (1)
| Title |
|---|
| 王树清等: "由对硝基苯甲醚制备对氨基苯甲醚的工艺研究", 《应用化工》, vol. 32, no. 6, 31 December 2003 (2003-12-31) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497116A (en) * | 2013-09-26 | 2014-01-08 | 江苏亚邦染料股份有限公司 | Synthetic method of 1-amino-anthraquinone |
| CN103497116B (en) * | 2013-09-26 | 2016-04-20 | 江苏亚邦染料股份有限公司 | The synthetic method of 1-aminoanthraquinone |
| CN105085286A (en) * | 2015-08-05 | 2015-11-25 | 盐城市瓯华化学工业有限公司 | Method for synthesizing 1-aminoanthraquinone |
| CN106478426A (en) * | 2015-08-26 | 2017-03-08 | 盐城市瓯华化学工业有限公司 | A kind of method that nicotinic acid method prepares the aromatic nitro compound of akali sulphide |
| CN108395381A (en) * | 2018-04-10 | 2018-08-14 | 大连傲视化学有限公司 | The synthetic method of 1,4- diamino-anthraquinone leuco compounds |
| CN108395381B (en) * | 2018-04-10 | 2020-09-22 | 大连傲视化学有限公司 | Synthesis method of 1, 4-diamino anthraquinone leuco body |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100591664C (en) | H acid continuous nitration and denitration, extraction, hydrogenation reduction production process | |
| CN104592063B (en) | A kind of environment-friendly production process of H acid | |
| CN102267849A (en) | Reduction method of aromatic nitro-compound for replacing sodium sulfide | |
| CN102516195B (en) | Production method of 6-nitro-1,2,4-sulfonic acid | |
| CN105017028B (en) | The improvement synthetic method of o-phenylenediamine is prepared in a kind of ortho-nitraniline reduction | |
| CN102584596B (en) | Method for preparing age inhibitor 3100 | |
| CN104774165A (en) | Green and industrial preparation method of rubber peptizer DBD | |
| CN102320635A (en) | Comprehensive utilization method of waste sulfuric acid of sulfonated products | |
| CN101531596A (en) | Preparation method for dinitrotoluene | |
| CN105837391A (en) | Application of metal-free hydrogenation catalyst to catalysis of benzene hydrogenation | |
| CN108250085A (en) | The method that paraphenetidine is prepared with the device catalytic hydrogenation of industrially scalable | |
| CN103113269B (en) | 1,8-dinitro-3,6-naphthalene disulfonate hydrogenation reduction method | |
| CN107744833A (en) | A kind of preparation method of MOF catalyst for catalytic eliminating organic sulfur | |
| CN107597173A (en) | A kind of catalyst of phenol hydroxylation synthesizing benzene diphenol and preparation method thereof | |
| CN104276928B (en) | The preparation method of two [1-(4-hydroxy phenyl)-1-the methylethyl]-Resorcinol of a kind of 4,6- | |
| CN102614921B (en) | Preparation method of liquid-state sulfonated cobalt phthalocyanine of catalyst for sweetening | |
| CN108675946A (en) | A method of preparing 2,4- diamino benzene sulfonic acids | |
| CN102701915B (en) | Method for preparing anti-aging agent SP (styrenated phenol) | |
| CN102391163A (en) | Preparation method of sulfonated para-ester serving as dye intermediate | |
| CN111349015A (en) | Clean production process of monoamino anthraquinone | |
| CN106145187A (en) | A kind of use vanadium titano-magnetite or technique that titanium chats is raw material production titanium dioxide | |
| CN101607917B (en) | Production method of high-quality p-aminophenol | |
| CN110590702B (en) | Novel method for preparing 2-mercaptobenzothiazole | |
| CN103450047A (en) | Preparation method of 1, 5-naphthalene diisocyanate | |
| CN100365071C (en) | Method for producing indigo by recycling unreacted raw materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111207 |