CN101475487B - Recycling use method of nitration acid - Google Patents
Recycling use method of nitration acid Download PDFInfo
- Publication number
- CN101475487B CN101475487B CN2008102428954A CN200810242895A CN101475487B CN 101475487 B CN101475487 B CN 101475487B CN 2008102428954 A CN2008102428954 A CN 2008102428954A CN 200810242895 A CN200810242895 A CN 200810242895A CN 101475487 B CN101475487 B CN 101475487B
- Authority
- CN
- China
- Prior art keywords
- acid
- phenoxy
- mother liquor
- anthraquinones
- nitric acid
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing 1,5(1,8)-hexa-nitride by reclaiming and recycling nitric acid, which comprises: feeding 1,5(1,8)-di-phenoxyl anthraquinone into the nitric acid at a temperature of between 15 and 50 DEG C, wherein the mass ratio of materials, namely the nitric acid to sulfuric acid to the 1,5(1,8)-di-phenoxyl anthraquinone is 6.4-7.8:15-30:1; performing reaction for 6 to 8 hours at a temperature of between 30 and 65 DEG C after the feeding is over, cooling the mixture to the room temperature, filtrating the mixture, collecting mother liquor acid and filter cakes, feeding the filter cakes into cold water for pulping, filtrating the filter cakes, using water to wash the filter cakes to be neutral, and obtaining 1,5(1,8)-hexa-nitride; and taking a fixed quantity of the collected mother liquor acid, supplementing fuming sulfuric acid or introducing sulphur trioxide and concentrated sulfuric acid, restoring the mother liquor acid to the prior nitric acid, namely the ratio of the nitric acid to the sulfuric acid is 6.40-7.8:15-30, and using the mother liquor acid for next nitration. The consumption of the sulfuric acid for preparing one ton of the 1,5(1,8)-hexa-nitride by the method is less than 1,000 kilograms, and is only 20 percent of that of the prior art, so that the method greatly reduces emission of waste acid water, and has obvious environmental benefit and economic benefit.
Description
Technical field
The present invention relates to 1,5 (1,8)-two phenoxy anthraquinone nitration reaction is used in dyestuff DISPERSE BLUE 2BLN (C.I. Disperse Blue-56) production process nitration acid recovery, recycle.The chemical structural formula of this nitration product 1,5 (1,8)-six itrated compound is following:
Background technology
DISPERSE BLUE 2BLN (C.I. Disperse Blue-56) is one of blue kind of output maximum in the ahthraquinone disperse dye, is widely used in the dyeing of terylene and mixed fibre thereof, has good colorant match consistency.China existing four more than ten years production history, adopt phenoxy method production technique basically, i.e. 1,5 (1,8)-dinitroanthraquinone and phenol reactant generation, 1,5 (1,8)-two phenoxy anthraquinone (DPA) gets the dyestuff filter cake through nitrated, hydrolysis, reduction, bromination again.This product obviously exists technology long, the problem that the acid waste water quantity discharged is big.
The nitration reaction of above-mentioned 1,5 (1,8)-two phenoxy anthraquinone (DPA) is being total to six nitros on anthraquinone ring and the phenyl ring; Get 1,5 (1,8)-six itrated compound; Generate a large amount of water in the reaction, sulfuric acid and nitric acid proportioning are big, thereby nitrating acid (nitration mixture of promptly being prepared by sulfuric acid and nitric acid) consumption is very big.After nitration reaction was accomplished, itrated compound dilute in big water gaging separated out, refilter, wash six itrated compounds, drop into post use down.In the dilute filtration process, produce a large amount of acid waste waters, thereby this operation is the maximum operation of spent acid quantity discharged during DISPERSE BLUE 2BLN is produced.
Summary of the invention:
The object of the invention is intended to realize above-mentioned nitration acid recycling, thereby reduces the nitrating acid consumption, reduces the raw materials cost of product, reduces discharged waste water simultaneously again significantly.
Realize nitration acid recycled; After nitration reaction; The nitration reaction thing can not dilute in big water gaging as existing technology that kind separates out; And will itrated compound be filtered out earlier, in the mother liquor acid that leaches, add oleum or sulphur trioxide and nitric acid and regulate nitration acid composition, be reused for nitrated.But the nitration product crystal formation of current technology is superfine, is difficult to filter, and makes the mother liquor acid amount that contains in the filter cake very big, is difficult to reach recovery set and uses purpose.In addition; Nitrating acid after mother liquor acid is added new sulfuric acid or fed sulphur trioxide and nitric acid is formed should be consistent with the nitrating acid composition of beginning; It is very stable that reacted mother liquor acid is formed, and nitration reaction can normally be carried out, and could realize nitration acid recovery set usefulness smoothly like this.
The technology that the present invention adopts has solved the problems referred to above well.
Technical scheme of the present invention is following:
The method that the nitrating acid that a kind of 1,5 (1,8)-two phenoxy anthraquinone nitration reaction is used reclaims and recycles, it comprises the steps:
Step 1. is with 1; 5 (1,8)-two phenoxy anthraquinones are put in the nitrating acid at 15～50 ℃, and the ratio of the amount of substance of material is: nitric acid: sulfuric acid: 1; 5 (1; 8) phenoxy anthraquinone=6.4～7.8-two: 15～30: 1, the nitration product crystal formation that under such conditions of mixture ratios, obtains is thick, easy filtration;
Step 2. feeds intake complete, 30～65 ℃ of reactions 6～8 hours, is cooled to room temperature, filters, and collects mother liquor acid and filter cake;
Step 3. drops into 30 minutes after-filtration of making beating in the cold water with step 2 gained filter cake, and the filter cake washing gets 1,5 (1,8)-six itrated compound to neutral after drying;
The mother liquor acid that step 4. is collected step 2 is got fixed amount, after replenishing oleum or feeding sulphur trioxide and concentrated nitric acid, makes mother liquor acid return to former nitration acid composition: nitric acid: sulfuric acid=6.4～7.8: 15～30, be used for nitrated next time.
The method of above-mentioned production 1,5 (1,8)-six itrated compound, the ratio of the amount of substance of the described material of step 1 be preferably: nitric acid: sulfuric acid: 1,5 (1,8)-two phenoxy anthraquinone=6.8～7.5: 20～25: 1.
The method of above-mentioned production 1,5 (1,8)-six itrated compound, preferably 25～40 ℃ of the described feed temperatures of step 1.
The method of above-mentioned production 1,5 (1,8)-six itrated compound, step 2 are preferably 40～55 ℃ of reactions 6～8 hours.
Six itrated compounds that working method of the present invention is produced are used high effective liquid chromatography for measuring, and the total content of 1,5 (1,8)-six itrated compound reaches 92～95%, and unreacted 1,5 (1,8)-DPA is less than 0.5%, and yield reaches 99～101%.
It is thick to obtain six itrated compound crystallizations under the working condition of the present invention, and dry back product is loose.Itrated compound can adopt straining installation commonly used in the Chemical Manufacture when filtering, as: plate-and-frame filter press, van-type (barrier film) pressure filter, vacuum suction filter groove, pressure filter, belt vacuum (squeezing) continuous filter etc.
Working method of the present invention is to use as nitrating acid again after in the mother liquor acid that filtration six itrated compounds obtain, replenishing oleum or feeding sulphur trioxide and nitric acid, and nitration acid composition is same as described above.The HNO that uses in the nitrating acid
3Concentration is 96～98%, SO in the oleum of adding
3Concentration is between 20～65%.
Nitrating acid after working method of the present invention, mother liquor acid are added new oleum or fed sulphur trioxide and nitric acid is formed and the nitrating acid of beginning is formed consistently, makes reacted mother liquor acid composition very stable, and nitration reaction can normally be carried out.
Consuming sulfuric acid less than 1000kg according to one ton of 1,5 (1,8)-six of explained hereafter of the present invention itrated compound, only is that existing technology consumes 20% of sulfuric acid amount, has reduced the discharging of waste acid water significantly, has tangible environmental benefit and economic benefit.A small amount of waste acid water of discharging is recycled, and makes this operation realize " zero " discharging basically.
The nitrating acid of the inventive method reclaims and recycles method and also can be applied in the production of similar nitrated product.
Embodiment
Umber in following examples and percentage are all by quality.
Embodiment 1
At 93%H
2SO
4In 645 parts, add 98%HNO
3100 parts, become nitrating acid after mixing.Under 15～20 ℃ of conditions, in nitrating acid, drop into 80 parts of (DPA content: 92.5%), added of exsiccant DPA at 2 hours.It was complete to feed intake, and slowly is warming up to 60 ℃ with 2 hours, 60～65 ℃ of insulation reaction 6 hours.Insulation is finished, and is cooled to room temperature, filters, and collection mother liquor confession batch reaction is down applied mechanically.Filter cake drops in the cold water and pulled an oar 30 minutes, filters, and washing gets 136 parts of six itrated compounds (giving money as a gift) to neutral, and the total content of 1,5 (1,8)-six itrated compound is 92.3%, unreacted DPA 0.39%, yield 100.4%.
Embodiment 2
At 100%H
2SO
4In 400 parts, add 96%HNO
388 parts, mixing becomes nitrating acid.Under 35～40 ℃ of conditions, in nitrating acid, drop into 90 parts of (DPA content: 95.4%), added of DPA of moisture 11% at 2 hours.It is complete to feed intake, and continues 35～40 ℃ of insulation reaction 8 hours.Below press instance 1 operation, get 135 parts of six itrated compounds (giving money as a gift), the total content of 1,5 (1,8)-six itrated compound is 95.0%, unreacted DPA 0.48%, yield 99.4%.
Embodiment 3
In the mother liquor acid that embodiment 2 obtains, get 355 parts, add 98%HNO
390 parts, 132 parts of the oleums of adding 65% after mixing, under 30～35 ℃ condition, drop into 84 parts of (DPA content: 93.8%), added at 1 hour of DPA of moisture 5% in this nitrating acid.It was complete to feed intake, and is warming up to 45 ℃, 45～50 ℃ of insulation reaction 6 hours.Below press instance 1 operation, get 135.8 parts of hexanitro-things (giving money as a gift), the total content 94.2% of 1,5 (1,8)-six itrated compound, unreacted DPA 0.28%, yield 100.2%.
Embodiment 4
In the mother liquor acid that embodiment 1 obtains, get 520 parts, add 98%HNO
3150 parts, slowly add 350 parts of 20% oleums, mix.Under 25～30 ℃ condition, in this nitrating acid, add 142 parts of (DPA content: 94.5%), added of exsiccant DPA at 1.5 hours.It was complete to feed intake, and slowly is warming up to 50 ℃ with 1 hour, 50～55 ℃ of insulation reaction 7 hours.Below press instance 1 operation, get 242 parts of six itrated compounds (giving money as a gift), the total content of 1,5 (1,8)-six itrated compound is 94.5%, unreacted DPA 0.33%, yield 100.9%.
Embodiment 5
In the mother liquor acid that embodiment 4 obtains, get 650 parts, add 96%HNO
3150 parts, slowly add 250 parts of 50% oleums, mix.Under 40～45 ℃ condition, add 142 parts of (DPA content: 93.5%), added of exsiccant DPA at 1.5 hours.It was complete to feed intake, 45～50 ℃ of insulation reaction 6 hours.Below press instance 1 operation, the mother liquor acid of recovery is applied mechanically 20 times by the present embodiment proportioning continuously, average 240.8 parts of six itrated compounds (giving money as a gift) that get; The average total content of 1,5 (1,8)-six itrated compound is 93.2%; Unreacted DPA average out to 0.31%, average yield are 100.1%.
Embodiment 6
In the mother liquor acid that embodiment 3 obtains, get 370 parts, add 98%HNO
379 parts, more under agitation with at the uniform velocity adding 120 parts of 65% oleums in 1～1.5 hour.Under 20～25 ℃ condition, in this nitrating acid, drop into 84 parts of (DPA content: 94.6%) of DPA of moisture 5%.It was complete to feed intake, and is warming up to 40 ℃, 40～45 ℃ of insulation reaction 7 hours.Below press instance 1 operation, the mother liquor acid of recovery is applied mechanically 30 times by the present embodiment proportioning continuously, average 135.5 parts of six itrated compounds (giving money as a gift) that get; The average total content of 1,5 (1,8)-six itrated compound is 94.8%; Unreacted DPA average out to 0.30%, average yield are 99.7%.
Embodiment 7
In the mother liquor acid that embodiment 2 obtains, get 370 parts, cooling feeds 100 parts of sulfur trioxide gas down, adds 96%HNO
382 parts, mix.Under 35～40 ℃ of conditions, in nitrating acid, drop into 90 parts of (DPA content: 95.4%), added of DPA of moisture 11% at 2 hours.It is complete to feed intake, and continues 35～40 ℃ of insulation reaction 8 hours.Below press instance 1 operation, get 136.3 parts of hexanitro-things (giving money as a gift), the total content of 1,5 (1,8)-six itrated compound is 95.0%, unreacted DPA 0.28%, yield 100.4%.The mother liquor acid that filtration obtains recycles by the operation of present embodiment proportioning.
Claims (4)
- A nitrating acid reclaim and recycle 1,5-or 1, the nitrated production hexanitro-1 of 8-two phenoxy anthraquinones, 5-or 1, the method for 8-two phenoxy anthraquinones is characterized in that it comprises the steps:Step 1. is 1,5-or 1, and 8-two phenoxy anthraquinones are put in the nitrating acid at 15～50 ℃, and the ratio of the amount of substance of material is: nitric acid: sulfuric acid: 1,5-or 1,8-two phenoxy anthraquinone=6.4～7.8: 15～30: 1;Step 2. feeds intake complete, 30～65 ℃ of reactions 6～8 hours, is cooled to room temperature, filters, and collects mother liquor acid and filter cake;Step 3. is with 30 minutes after-filtration of making beating in the step 2 gained filter cake input cold water, and the filter cake washing gets hexanitro-1,5-or 1,8-two phenoxy anthraquinones to neutral;The mother liquor acid that step 4. is collected step 2 is got fixed amount, after replenishing oleum or feeding sulphur trioxide and concentrated nitric acid, makes mother liquor acid return to former nitration acid composition: nitric acid: sulfuric acid=6.4～7.8: 15～30, be used for nitrated next time.
- 2. production hexanitro-1 according to claim 1; 5-or 1, the method for 8-two phenoxy anthraquinones is characterized in that: the ratio of the amount of substance of the described material of step 1 is: nitric acid: sulfuric acid: 1; 5-or 1,8-two phenoxy anthraquinone=6.8～7.5: 20～25: 1.
- 3. production hexanitro-1 according to claim 1,5-or 1, the method for 8-two phenoxy anthraquinones is characterized in that: the described feed temperature of step 1 is 25～40 ℃.
- 4. production hexanitro-1 according to claim 1,5-or 1, the method for 8-two phenoxy anthraquinones is characterized in that: step 2 is 40～55 ℃ of reactions 6～8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102428954A CN101475487B (en) | 2008-12-30 | 2008-12-30 | Recycling use method of nitration acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102428954A CN101475487B (en) | 2008-12-30 | 2008-12-30 | Recycling use method of nitration acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101475487A CN101475487A (en) | 2009-07-08 |
| CN101475487B true CN101475487B (en) | 2012-07-18 |
Family
ID=40836278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102428954A Active CN101475487B (en) | 2008-12-30 | 2008-12-30 | Recycling use method of nitration acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101475487B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276438A (en) * | 2011-07-08 | 2011-12-14 | 江苏吉华化工有限公司 | Production method of 1,5(1,8)-diphenoxy anthraquinone |
| CN102390820A (en) * | 2011-08-17 | 2012-03-28 | 中国石油化工股份有限公司 | Method for reclaiming nitric acid from nitrified waste acid |
| CN105541901B (en) * | 2015-12-21 | 2018-08-28 | 合肥星宇化学有限责任公司 | A kind of preparation method of bis- chloro- three esters of 5- nitrophenylphosphates of 2,4- |
| CN107446381A (en) * | 2017-07-13 | 2017-12-08 | 青岛海湾集团有限公司 | The method that nitrating wasting acid of Disperse Blue-56 recycles |
| CN110835301A (en) * | 2018-08-15 | 2020-02-25 | 青岛海湾精细化工有限公司 | Dinitration method of disperse blue 2BLN |
| CN111039798A (en) * | 2019-12-23 | 2020-04-21 | 浙江闰土研究院有限公司 | Environment-friendly preparation method of 2-chloro-4-nitro-6-bromo-aniline |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552692A (en) * | 2003-12-18 | 2004-12-08 | 姜日善 | Preparation of 1-Cl-4,8-dinitronaphthalene and 4-cl-1,8-dinitronaphthalene |
| CN1944393A (en) * | 2006-06-05 | 2007-04-11 | 甘肃银光化学工业集团有限公司 | Process for continuously preparing nitro-xylene isomer monomer |
-
2008
- 2008-12-30 CN CN2008102428954A patent/CN101475487B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552692A (en) * | 2003-12-18 | 2004-12-08 | 姜日善 | Preparation of 1-Cl-4,8-dinitronaphthalene and 4-cl-1,8-dinitronaphthalene |
| CN1944393A (en) * | 2006-06-05 | 2007-04-11 | 甘肃银光化学工业集团有限公司 | Process for continuously preparing nitro-xylene isomer monomer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101475487A (en) | 2009-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101475487B (en) | Recycling use method of nitration acid | |
| CN104649910B (en) | Method capable of recycling acids for preparing 2,5-dichloronitrobenzene (DCNB) through continuous nitration | |
| CN102070457B (en) | Method for continuously preparing dinitrochlorobenzene | |
| CN101423477B (en) | Method for producing 1,5(1,8)-dinitro-anthraquinones | |
| CN103146221B (en) | Method and device for continuously producing dyes | |
| CN101497579B (en) | Green process for producing nitroguanidine | |
| CN102516195B (en) | Production method of 6-nitro-1,2,4-sulfonic acid | |
| CN102399153B (en) | Method for preparing alpha,alpha'-dinitroanthraquinone refined substance by using waste residue generated during production of 1-nitroanthraquinone through solvent method | |
| CN102838489B (en) | Clean production method and device of dinitrotoluene | |
| CN108128826B (en) | Nitric acid-containing wastewater treatment device and treatment method | |
| CN101591249A (en) | " waste residue " of producing the 1-aminoanthraquinone is processed into the method for producing 1,5 (1,8)-dinitroanthraquinone raw material | |
| CN101391759B (en) | Sulfamic acid production process | |
| CN108218810A (en) | A kind of micro- reaction method for synthesizing 2,2 '-dithio-bis-benzothiazole | |
| CN105693560A (en) | Method for preparing energy-efficient H-acid | |
| CN101838204B (en) | Novel process for controlling waste residue and recycling resources in 1-anthraquinone production | |
| CN105130853B (en) | A kind of diamine method industry is combined to the nitration processes of H acid | |
| CN111253773A (en) | Method for producing disperse blue by using 1-aminoanthraquinone DMF residue | |
| CN107473943A (en) | A kind of preparation method of 2,6 orcin | |
| CN101633495A (en) | Method for preparing sulphur black dye and sodium thiosulfate from sulphur dye waste water | |
| CN106349733A (en) | Technique for compounding disperse red FB and device thereof | |
| CN109608354A (en) | A kind of refining methd of aniline dyes intermediate | |
| CN102786076B (en) | Method for preparing high-purity copper sulfate by means of waste liquid of copper-contained circuit boards | |
| CN113694858B (en) | Continuous nitration reaction device and method for benzene ring nitration | |
| CN101716261B (en) | Method for preparing hecogenin | |
| CN103696014A (en) | Method for producing calcium sulfate whisker and calcium sulfate by using wastes produced during production of nitroguanidine and dicyandiamide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |