CN107244756A - A kind of post-processing approach of phenylenediamine hydrolyzate - Google Patents
A kind of post-processing approach of phenylenediamine hydrolyzate Download PDFInfo
- Publication number
- CN107244756A CN107244756A CN201710418475.6A CN201710418475A CN107244756A CN 107244756 A CN107244756 A CN 107244756A CN 201710418475 A CN201710418475 A CN 201710418475A CN 107244756 A CN107244756 A CN 107244756A
- Authority
- CN
- China
- Prior art keywords
- aqueous phase
- phenylenediamine
- hydrolyzate
- extraction
- post
- 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.)
- Granted
Links
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000012805 post-processing Methods 0.000 title claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 83
- 239000008346 aqueous phase Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000012545 processing Methods 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012071 phase Substances 0.000 claims abstract description 30
- 238000001556 precipitation Methods 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000003610 charcoal Substances 0.000 claims abstract description 18
- 230000007062 hydrolysis Effects 0.000 claims abstract description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 17
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000004042 decolorization Methods 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 16
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 10
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 6
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 5
- 244000060011 Cocos nucifera Species 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000010903 husk Substances 0.000 claims description 5
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 5
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 5
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 5
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 4
- 229940011051 isopropyl acetate Drugs 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- -1 pentyl ester Chemical class 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 150000002576 ketones Chemical class 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 26
- 229940018564 m-phenylenediamine Drugs 0.000 description 26
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 14
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 12
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 8
- 239000000284 extract Substances 0.000 description 7
- 229940018563 3-aminophenol Drugs 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/045—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen
- C07C37/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen by substitution of a NH2 group
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to phenylenediamine production technical field, a kind of post-processing approach of phenylenediamine hydrolyzate is particularly disclosed.The post-processing approach of the phenylenediamine hydrolyzate, it is characterized in that：Hydrolyzate is subjected to three sections of extractions, every section of 38 grades of extraction point is extracted, every grade of extraction oil phase and raffinate aqueous phase is through filtering and impurity removing, and extraction oil phase enters precipitation process rich in benzenediol, and raffinate aqueous phase enters next section and handled；Raffinate aqueous phase carries out charcoal absorption decolorization afterwards, and activated carbon is loaded using packed column, and raffinate aqueous phase flows in series through activated carbon packed column and adsorbed, and the aqueous phase after processing meets hydrolysis complex acid use requirement.Alcohol, acid, ketone, ether, esters content are less than 50ppm in aqueous phase after present invention processing, the aqueous phase is by a certain percentage with reusing p-phenylenediamine hydrolysis without influence after pure water mixing complex acid, processing is convenient, scientific in principle, improve the utilization rate of reaction material liquid, green economy.
Description
（One）Technical field
The present invention relates to phenylenediamine production technical field, more particularly to a kind of post-processing approach of phenylenediamine hydrolyzate.
（Two）Background technology
Benzenediol and amino-phenol are important fine Organic Chemicals, are widely used in agricultural, dyestuff, coating, medicine, modeling
The fields such as material, rubber, electronic chemical product.At present, the main preparation methods of benzenediol and amino-phenol have sulfonated alkali fusion method, it is two different
Propyl benzene oxidizing process and phenylenediamine Hydrolyze method.Compared to first two production method, phenylenediamine Hydrolyze method has benefited from raw material sources just
Profit, technological process succinct, technology maturation and of reduced contamination and be widely studied uses, the good application prospect of presentation.
In phenylenediamine hydrolysis prepares benzenediol and amino-phenol technique, it is related to benzenediol and amino-phenol from hydrolyzate
The process and raffinate aqueous phase of middle extraction are decolourized, the process of removal of impurities, because raffinate aqueous phase amount is big in technical process and contains salt, no
Can directly it discharge, it is necessary to which appropriately processed Posterior circle is used；And the extraction process of benzenediol and amino-phenol is used mostly at present
There is certain solubility in alcohols, ketone, ethers and esters extractant, the kind of extractants, and esters extractant is in acid in water
Property the aqueous solution in easily occur hydrolysis, generate corresponding alcohol and acid, experiments verify that, alcohol, acid, ketone, ether, esters p-phenylenediamine
Hydrolysis have considerable influence, can aggravate the generation of burnt oil impurities, reduce reaction yield, the processing for increasing hydrolyzate is difficult
Degree.Therefore, it will be unable to meet the requirement that complex acid is recycled again, gesture after in aqueous phase extracted containing alcohol, acid, ketone, ether, esters
Necessity carries out purified treatment to it.
（Three）The content of the invention
There is provided a kind of extraction yield is high, raffinate aqueous phase utilization rate is high, processing cost in order to make up the deficiencies in the prior art by the present invention
The post-processing approach of low phenylenediamine hydrolyzate.
The present invention is achieved through the following technical solutions：
A kind of post-processing approach of phenylenediamine hydrolyzate, the hydrolyzate of benzenediol or amino-phenol is prepared as place using phenylenediamine hydrolysis
Object is managed, is comprised the following steps：
（1）Hydrolyzate is subjected to first paragraph extraction, point 3-8 grades of extractions, every grade of Solvent quantity is the 15-35% of hydrolyzate quality,
Extraction temperature filters out solid impurity for 15-40 DEG C, every grade of extraction oil phase and raffinate aqueous phase process, and extraction oil phase is rich in benzene two
Phenol enters precipitation process, and raffinate aqueous phase enters next section of processing；
（2）By step（1）Gained raffinate aqueous phase uses liquefied ammonia or mass concentration to adjust pH to 6.5-7.5 for 15-35% ammoniacal liquor,
Precipitation solid impurity is filtered to remove, filtrate carries out second segment extraction, the same step of extraction step（1）, obtained extraction oil phase is rich in
Amino-phenol enters precipitation process, and raffinate aqueous phase enters next section of processing；
（3）By step（2）Gained raffinate aqueous phase carries out the 3rd section of extraction, the same step of extraction step（1）, obtained extraction oil phase enters
Enter precipitation process and reclaim extractant, raffinate aqueous phase enters next section of processing；
（4）By step（3）Gained raffinate aqueous phase carries out charcoal absorption decolorization, and activated carbon is loaded using packed column, raffinate
Aqueous phase flows in series through activated carbon packed column and adsorbed, flow velocity 1-50BV/hr, and the liquid after absorption meets hydrolysis will
Ask, progress complex acid, the hydrolysis for phenylenediamine are mixed with pure water.
The hydrolyzate that phenylenediamine hydrolysis prepares benzenediol or amino-phenol is carried out stage extraction and activated carbon suction by the present invention
Attached processing, every section of extraction processing is operated using fractional extraction, and the raffinate aqueous phase after processing meets the requirement of complex acid reuse, changed
The defect of existing process method is entered, while high extraction yield is ensured, has met the demand of raffinate aqueous phase recycling, reduce
Side reaction, improves yield, has saved cost.
The present invention more excellent technical scheme be：
In the hydrolyzate, benzenediol weight ratio is 1-10%, and amino-phenol weight ratio is 1-10%, and phenylenediamine weight ratio is less than
0.5%, pH are less than 1.
Step（1）In, 4-6 grades of extractions of first paragraph extraction point, every grade of Solvent quantity is the 20-30% of hydrolyzate quality, extraction
It is 20-30 DEG C of to take temperature
Step（2）In, use liquefied ammonia or mass concentration to adjust the pH to 6.5-7.0 of raffinate aqueous phase for 25-30% ammoniacal liquor.
Step（1）With（2）In, extractant is hexone, n-butanol, n-propyl acetate, isopropyl acetate, second
One or more in sour N-butyl, isobutyl acetate, pentyl acetate and Di Iso Propyl Ether；It is preferred that hexone, second
One or more in sour N-butyl, isobutyl acetate and pentyl acetate.
Step（3）In, extractant is alkane derivative, one kind in such as pentane, hexane, heptane and octane, preferably penta
One kind in alkane, hexane and heptane.
Step（4）In, the activated carbon for adsorption bleaching is one kind in coconut husk charcoal, fruit shell carbon, carbo lignius or ature of coal charcoal,
It is preferred that coconut husk charcoal or ature of coal charcoal；Upper prop flow velocity is 10-30BV/hr.
The present invention compared with prior art, using three sections of extractions plus the technique of one section of adsorption treatment, makes benzenediol extraction yield
Higher than 99%, amino-phenol extraction yield is higher than 98.5%, and alcohol, acid, ketone, esters content are less than 50ppm, the aqueous phase in aqueous phase after processing
By a certain percentage with reusing p-phenylenediamine hydrolysis after pure water mixing complex acid without influence, processing is convenient, and scientific in principle is carried
The high utilization rate of reaction material liquid, green economy.
（Four）Embodiment
Embodiment 1：A kind of post-processing approach of m-phenylene diamine (MPD) hydrolyzate, concrete processing procedure is：
（1）Resorcinol content 5%, m-aminophenol content 1%, m-phenylene diamine (MPD) content about 0.2%, pH in m-phenylene diamine (MPD) hydrolyzate
About 0.3, the hydrolyzate is subjected to first paragraph extraction：Divide 4 grades of extractions；Every grade of Solvent quantity is the 20% of hydrolyzate quality, extraction
Agent is hexone；20 DEG C of extraction temperature；Every grade of extraction oil phase and raffinate aqueous phase is through filtering and impurity removing；By first
Oil phase after section extraction is rich in resorcinol precipitation process to be entered, and raffinate aqueous phase is waited to enter next section of processing.
（2）Through step（1）Obtained raffinate aqueous phase uses mass concentration to adjust pH to 6.5 for 25% ammoniacal liquor, is filtered to remove
Impurity is separated out, filtrate carries out second segment extraction, extracting operation similar step（1）, extractant is n-butanol；Extracted by second segment
Oil phase afterwards is rich in m-aminophenol precipitation process to be entered, and raffinate aqueous phase is waited to enter next section of processing.
（3）Through step（2）Obtained raffinate aqueous phase adopts the 3rd section of extraction of progress, extracting operation similar step（1）And step
（2）, extractant is pentane；Oil phase after the 3rd section extracts enters precipitation process and reclaims extractant, and raffinate aqueous phase is waited to enter
Next section of processing.
（4）Through step（3）Obtained raffinate aqueous phase flows in series through activated carbon packed column and adsorbed, and activated carbon uses coconut husk
Charcoal, upper prop flow velocity 10BV/hr, the aqueous phase after processing through chromatogram ration analysis, wherein hexone content about
21ppm, levels of n-butanol about 20ppm, isopentane content are less than 8ppm, can meet hydrolysis complex acid use demand.
Confirmatory experiment A：
Learning from else's experience, (through analysis, 12.25%) wherein ammonium sulphate content is mixes to the aqueous phase 100g after above-mentioned processing with 200g deionized waters
Close, the 38g concentrated sulfuric acids are dissolved in above-mentioned 300g aqueous phases, 21.6g m-phenylene diamine (MPD)s is weighed and is completely dissolved in above-mentioned dilution heat of sulfuric acid, shift
Into 500mL autoclaves, air 6 times in displacement kettle are repeated using nitrogen, starts stirring to 200rpm, is heated to 220 DEG C
Maintain 8hr.Cool to room temperature pressure release, and hydrolyzate is through efficient liquid phase chromatographic analysis：M-phenylene diamine (MPD) conversion ratio 99.7%,
Benzenediol yield is about 95.2%.
Confirmatory experiment B：
The 38g concentrated sulfuric acids are dissolved in 300g deionized waters, 21.6g m-phenylene diamine (MPD)s is weighed and is completely dissolved in above-mentioned dilution heat of sulfuric acid, are turned
Move in 500mL autoclaves, air 6 times in displacement kettle are repeated using nitrogen, starts stirring to 200rpm, is heated to 220
DEG C maintain 8hr.Cool to room temperature pressure release, and hydrolyzate is through efficient liquid phase chromatographic analysis：M-phenylene diamine (MPD) conversion ratio is about
99.8%, resorcinol yield is about 95.4%.
Embodiment 2：A kind of post-processing approach of m-phenylene diamine (MPD) hydrolyzate, concrete processing procedure is：
（1）Resorcinol content 7%, m-aminophenol content 2%, m-phenylene diamine (MPD) content about 0.1%, pH in m-phenylene diamine (MPD) hydrolyzate
About 0.5, the hydrolyzate is subjected to first paragraph extraction：Divide 6 grades of extractions；Every grade of Solvent quantity is the 30% of hydrolyzate quality, extraction
Agent is n-butanol；30 DEG C of extraction temperature；Every grade of extraction oil phase and raffinate aqueous phase is through filtering and impurity removing；After first paragraph is extracted
Oil phase be rich in resorcinol precipitation process to be entered, raffinate aqueous phase wait enter next section handle.
（2）Through step（1）Obtained raffinate aqueous phase uses mass concentration to adjust pH to 7.0 for 30% ammoniacal liquor, is filtered to remove
Impurity is separated out, filtrate carries out second segment extraction, extracting operation similar step（1）, extractant is n-propyl acetate；By second segment
Oil phase after extraction is rich in m-aminophenol precipitation process to be entered, and raffinate aqueous phase is waited to enter next section of processing.
（3）Through step（2）Obtained raffinate aqueous phase carries out the 3rd section of extraction, extracting operation similar step（1）And step
（2）, extractant is hexane；Oil phase after the 3rd section extracts enters precipitation process and reclaims extractant, and raffinate aqueous phase is waited to enter
Next section of processing.
（4）Through step（3）Obtained raffinate aqueous phase flows in series through activated carbon packed column and adsorbed, and activated carbon uses ature of coal
Charcoal, upper prop flow velocity 30BV/hr, the aqueous phase after processing is through chromatogram ration analysis, wherein levels of n-butanol about 25ppm, second
Sour n-propyl content about 10ppm, hexane content is less than 5ppm, can meet hydrolysis complex acid and use.
Embodiment 3：A kind of post-processing approach of m-phenylene diamine (MPD) hydrolyzate, concrete processing procedure is：
（1）In m-phenylene diamine (MPD) hydrolyzate resorcinol content 8%, m-aminophenol content 4%, m-phenylene diamine (MPD) content less than 0.3%,
PH is less than 0.6, and the hydrolyzate is carried out into first paragraph extraction：Divide 5 grades of extractions；Every grade of Solvent quantity is the 25% of hydrolyzate quality,
Extractant is n-propyl acetate；25 DEG C of extraction temperature；Every grade of extraction oil phase and raffinate aqueous phase is through filtering and impurity removing；By first paragraph
Oil phase after extraction is rich in resorcinol precipitation process to be entered, and raffinate aqueous phase is waited to enter next section of processing.
（2）Through step（1）Obtained raffinate aqueous phase uses mass concentration to adjust pH to 6.7 for 28% ammoniacal liquor, is filtered to remove
Impurity is separated out, filtrate carries out second segment extraction, extracting operation similar step（1）, extractant is isopropyl acetate；By second segment
Oil phase after extraction is rich in m-aminophenol precipitation process to be entered, and raffinate aqueous phase is waited to enter next section of processing.
（3）Through step（2）Obtained raffinate aqueous phase adopts the 3rd section of extraction of progress, extracting operation similar step（1）And step
（2）, extractant is heptane；Oil phase after the 3rd section extracts enters precipitation process and reclaims extractant, and raffinate aqueous phase is waited to enter
Next section of processing.
（4）Through step（3）Obtained raffinate aqueous phase flows in series through activated carbon packed column and adsorbed, and activated carbon uses ature of coal
Charcoal, upper prop flow velocity 20BV/hr, the aqueous phase after processing through chromatogram ration analysis, wherein n-propyl acetate content about
22ppm, isopropyl acetate ester content about 10ppm, heptane content are less than 10ppm, can meet hydrolysis complex acid and use.
Embodiment 4：A kind of post-processing approach of p-phenylenediamine hydrolyzate, concrete processing procedure is：
（1）Hydroquinones content 6%, para-aminophenol content 5%, p-phenylenediamine content about 0.4%, pH in p-phenylenediamine hydrolyzate
About 0.2, the hydrolyzate is subjected to first paragraph extraction：Divide 3 grades of extractions；Every grade of Solvent quantity is the 15% of hydrolyzate quality, extraction
Agent is isobutyl acetate；15 DEG C of extraction temperature；Every grade of extraction oil phase and raffinate aqueous phase is through filtering and impurity removing；Extract by first paragraph
Oil phase after taking is rich in hydroquinones precipitation process to be entered, and raffinate aqueous phase is waited to enter next section of processing.
（2）Through step（1）Obtained raffinate aqueous phase uses mass concentration to adjust pH to 6.5 for 15% ammoniacal liquor, is filtered to remove
Impurity is separated out, filtrate carries out second segment extraction, extracting operation similar step（1）, extractant is hexone；By
Oil phase after two-stage extraction is rich in para-aminophenol precipitation process to be entered, and raffinate aqueous phase is waited to enter next section of processing.
（3）Through step（2）Obtained raffinate aqueous phase carries out the 3rd section of extraction, extracting operation similar step（1）And step
（2）, extractant is octane；Oil phase after the 3rd section extracts enters precipitation process and reclaims extractant, and raffinate aqueous phase is waited to enter
Next section of processing.
（4）Through step（3）Obtained raffinate aqueous phase flows in series through activated carbon packed column and adsorbed, and activated carbon uses shell
Charcoal, upper prop flow velocity 48BV/hr, the aqueous phase after processing through chromatogram ration analysis, wherein Sucrose Acetate ester content about
12ppm, hexone content about 32ppm, isooctane content are less than 4ppm, can meet hydrolysis complex acid and use.
Embodiment 5：A kind of post-processing approach of p-phenylenediamine hydrolyzate, concrete processing procedure is：
（1）In p-phenylenediamine hydrolyzate hydroquinones content 3%, para-aminophenol content 8%, p-phenylenediamine content less than 0.4%,
PH about 0.5, first paragraph extraction is carried out by the hydrolyzate：Divide 8 grades of extractions；Every grade of Solvent quantity is the 35% of hydrolyzate quality, extraction
It is pentyl acetate to take agent；40 DEG C of extraction temperature；Every grade of extraction oil phase and raffinate aqueous phase is through filtering and impurity removing；Extract by first paragraph
Oil phase after taking is rich in hydroquinones precipitation process to be entered, and raffinate aqueous phase is waited to enter next section of processing.
（2）Through step（1）Obtained raffinate aqueous phase uses mass concentration to adjust pH to 7.5 for 35% ammoniacal liquor, is filtered to remove
Impurity is separated out, filtrate carries out second segment extraction, extracting operation similar step（1）, extractant is n-butyl acetate；By second segment
Oil phase after extraction is rich in para-aminophenol precipitation process to be entered, and raffinate aqueous phase is waited to enter next section of processing.
（3）Through step（2）Obtained raffinate aqueous phase carries out the 3rd section of extraction, extracting operation similar step（1）And step
（2）, extractant is heptane；Oil phase after the 3rd section extracts enters precipitation process and reclaims extractant, and raffinate aqueous phase is waited to enter
Next section of processing.
（4）Through step（3）Obtained raffinate aqueous phase flows in series through activated carbon packed column and adsorbed, and activated carbon is using wooden
Charcoal, upper prop flow velocity 2BV/hr, the aqueous phase after processing is through chromatogram ration analysis, wherein pentyl acetate content about 11ppm, second
Sour N-butyl content about 22ppm, heptane content is less than 7ppm, can meet hydrolysis complex acid and use.
Claims (10)
1. a kind of post-processing approach of phenylenediamine hydrolyzate, using phenylenediamine hydrolysis prepare the hydrolyzate of benzenediol or amino-phenol as
Process object, it is characterized in that, comprise the following steps：（1）Hydrolyzate is subjected to first paragraph extraction, point 3-8 grades of extractions, every grade of extraction
Agent consumption be hydrolyzate quality 15-35%, extraction temperature for 15-40 DEG C, every grade extraction oil phase and raffinate aqueous phase through filtering
Except solid impurity, extraction oil phase enters precipitation process rich in benzenediol, and raffinate aqueous phase enters next section of processing；（2）By step（1）
Gained raffinate aqueous phase uses liquefied ammonia or mass concentration to adjust pH to 6.5-7.5 for 15-35% ammoniacal liquor, is filtered to remove precipitation solid
Impurity, filtrate carries out second segment extraction, the same step of extraction step（1）, obtained extraction oil phase enters precipitation rich in amino-phenol
Process, raffinate aqueous phase enters next section of processing；（3）By step（2）Gained raffinate aqueous phase carries out the 3rd section of extraction, and extraction step is same
Step（1）, obtained extraction oil phase is into precipitation process recovery extractant, and raffinate aqueous phase enters next section and handled；（4）By step
（3）Gained raffinate aqueous phase carries out charcoal absorption decolorization, and activated carbon is loaded using packed column, and raffinate aqueous phase flows in series through work
Property charcoal packed column is adsorbed, and flow velocity 1-50BV/hr, the liquid after absorption meets hydrolysis requirement, is mixed with pure water
Carry out complex acid, the hydrolysis for phenylenediamine.
2. the post-processing approach of phenylenediamine hydrolyzate according to claim 1, it is characterised in that：In the hydrolyzate, benzene
Diphenol weight ratio is 1-10%, and amino-phenol weight ratio is 1-10%, and phenylenediamine weight ratio is less than 1 less than 0.5%, pH.
3. the post-processing approach of phenylenediamine hydrolyzate according to claim 1, it is characterised in that：Step（1）In, first paragraph
4-6 grades of extractions of extraction point, every grade of Solvent quantity is the 20-30% of hydrolyzate quality, and extraction temperature is 20-30 DEG C.
4. the post-processing approach of phenylenediamine hydrolyzate according to claim 1, it is characterised in that：Step（2）In, using liquid
Ammonia or mass concentration adjust the pH to 6.5-7.0 of raffinate aqueous phase for 25-30% ammoniacal liquor.
5. the post-processing approach of phenylenediamine hydrolyzate according to claim 1, it is characterised in that：Step（1）With（2）In,
Extractant is hexone, n-butanol, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second
One or more in sour pentyl ester and Di Iso Propyl Ether.
6. the post-processing approach of phenylenediamine hydrolyzate according to claim 1, it is characterised in that：Step（3）In, extractant
For one kind in pentane, hexane, heptane and octane.
7. the post-processing approach of phenylenediamine hydrolyzate according to claim 1, it is characterised in that：Step（4）In, activated carbon
For one kind in coconut husk charcoal, fruit shell carbon, carbo lignius or ature of coal charcoal；Upper prop flow velocity is 10-30BV/hr.
8. the post-processing approach of phenylenediamine hydrolyzate according to claim 5, it is characterised in that：Step（1）With（2）In,
Extractant is the one or more in hexone, n-butyl acetate, isobutyl acetate and pentyl acetate.
9. the post-processing approach of phenylenediamine hydrolyzate according to claim 6, it is characterised in that：Step（3）In, extractant
For one kind in pentane, hexane and heptane.
10. the post-processing approach of phenylenediamine hydrolyzate according to claim 7, it is characterised in that：Step（4）In, activity
Charcoal is coconut husk charcoal or ature of coal charcoal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710418475.6A CN107244756B (en) | 2017-06-06 | 2017-06-06 | A kind of post-processing approach of phenylenediamine hydrolyzate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710418475.6A CN107244756B (en) | 2017-06-06 | 2017-06-06 | A kind of post-processing approach of phenylenediamine hydrolyzate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107244756A true CN107244756A (en) | 2017-10-13 |
| CN107244756B CN107244756B (en) | 2018-07-20 |
Family
ID=60019023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710418475.6A Active CN107244756B (en) | 2017-06-06 | 2017-06-06 | A kind of post-processing approach of phenylenediamine hydrolyzate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107244756B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997088A (en) * | 2018-09-06 | 2018-12-14 | 青岛科技大学 | A method of resorcinol is recycled from m-phenylene diamine (MPD) hydrolysis waste residue |
| CN114940643A (en) * | 2022-03-14 | 2022-08-26 | 大邦(湖南)生物制药有限公司 | Synthetic method and system of hydroquinone for medical and aesthetic purposes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862245A (en) * | 1970-03-10 | 1975-01-21 | Koppers Co Inc | Resorcinol preparation |
| CN101486628A (en) * | 2009-02-24 | 2009-07-22 | 江苏扬农化工集团有限公司 | Method for extracting resorcin from resorcin-containing salt water solution |
| CN102826961A (en) * | 2012-08-14 | 2012-12-19 | 江苏扬农化工集团有限公司 | Cycling treatment method for waste acid produced in production of hydroquinone |
| CN102911018A (en) * | 2011-08-04 | 2013-02-06 | 浙江龙盛化工研究有限公司 | Method for separating phenol-containing organic substances from m-phenylenediamine acidic hydrolysate |
-
2017
- 2017-06-06 CN CN201710418475.6A patent/CN107244756B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862245A (en) * | 1970-03-10 | 1975-01-21 | Koppers Co Inc | Resorcinol preparation |
| CN101486628A (en) * | 2009-02-24 | 2009-07-22 | 江苏扬农化工集团有限公司 | Method for extracting resorcin from resorcin-containing salt water solution |
| CN102911018A (en) * | 2011-08-04 | 2013-02-06 | 浙江龙盛化工研究有限公司 | Method for separating phenol-containing organic substances from m-phenylenediamine acidic hydrolysate |
| CN102826961A (en) * | 2012-08-14 | 2012-12-19 | 江苏扬农化工集团有限公司 | Cycling treatment method for waste acid produced in production of hydroquinone |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997088A (en) * | 2018-09-06 | 2018-12-14 | 青岛科技大学 | A method of resorcinol is recycled from m-phenylene diamine (MPD) hydrolysis waste residue |
| CN108997088B (en) * | 2018-09-06 | 2021-08-03 | 青岛科技大学 | Method for recovering resorcinol from m-phenylenediamine hydrolysis waste residue |
| CN114940643A (en) * | 2022-03-14 | 2022-08-26 | 大邦(湖南)生物制药有限公司 | Synthetic method and system of hydroquinone for medical and aesthetic purposes |
| CN114940643B (en) * | 2022-03-14 | 2024-06-07 | 大邦(湖南)生物制药有限公司 | Synthesis method of medical hydroquinone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107244756B (en) | 2018-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2524452C (en) | Process for producing 1, 3-propanediol | |
| JPH041147A (en) | Separation of impurities in aqueous solution of crude ethanol | |
| JPH0699341B2 (en) | Purification method of crude ethanol aqueous solution | |
| CN107056876A (en) | A kind of method that high-purity tea saponin is extracted from camellia seed meal | |
| WO2017121343A1 (en) | Process for recovering lithium from industrial wastewater | |
| CN108659061B (en) | Purification treatment method of sucralose crystallization mother liquor | |
| CN107244756B (en) | A kind of post-processing approach of phenylenediamine hydrolyzate | |
| CN107337593B (en) | Preparation method of coenzyme Q10 pure product | |
| CN110015945B (en) | Separation and purification method of sugar alcohol chelated calcium in organic fertilizer | |
| CN106117011B (en) | A kind of refining methd of discrimination method production crude sodium formate byproduct from neopentyl glycol production | |
| CN107573248A (en) | The recovery method of resolving agent R phenyl ethylamines in prepared by R-DHLA | |
| CN105985315A (en) | Method for extracting nicotine from tobacco waste | |
| CN105037473B (en) | A kind of method of the purification sterol from tall oil | |
| NO168874B (en) | PROCEDURE AND APPARATUS FOR PREPARATION OF PIPE CONNECTIONS | |
| CN113548651A (en) | Method for purifying wet-process phosphoric acid by solvent extraction | |
| CN113354658A (en) | Method for purifying and producing high-content ginkgolide B | |
| CN102464898B (en) | Method for recovering yellow ginger pigment from yellow ginger hydrolysate saponin extraction waste liquid | |
| CN102648296B (en) | Method for producing white sugar, light brown sugar and dark brown sugar using direct recovery process | |
| CN100595193C (en) | Industrial method for producing natural capsicine | |
| CN109573975A (en) | A kind of extracting process of hydrochloric acid method phosphoric acid by wet process preparation high-quality phosphoric acid | |
| CN112094184B (en) | Method for extracting shikimic acid from ginkgo leaf extract chromatographic wastewater | |
| CN113801003B (en) | Industrial extraction method of cannabidiol | |
| CN101747657A (en) | Industrial method for improving quality of capsicum red pigment | |
| CN220656435U (en) | Device for recycling pyridine or pyridine derivative in hexachlorocyclo-triphosphazene synthetic waste residues | |
| CN109627157A (en) | The method of alpha-linolenic acid is purified in a kind of linseed oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |