CN1814670A - Method for producing idigo by cyclic utilization of non-reacted raw materials - Google Patents

Method for producing idigo by cyclic utilization of non-reacted raw materials Download PDF

Info

Publication number
CN1814670A
CN1814670A CN 200610049659 CN200610049659A CN1814670A CN 1814670 A CN1814670 A CN 1814670A CN 200610049659 CN200610049659 CN 200610049659 CN 200610049659 A CN200610049659 A CN 200610049659A CN 1814670 A CN1814670 A CN 1814670A
Authority
CN
China
Prior art keywords
reaction
water
condensation
hydrolysis
aniline
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
Application number
CN 200610049659
Other languages
Chinese (zh)
Other versions
CN100365071C (en
Inventor
赵国生
方标
叶尧亮
罗党生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Changzheng Chemical Industry Co., Ltd.
Original Assignee
Zhejiang Runtu Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang Runtu Co Ltd filed Critical Zhejiang Runtu Co Ltd
Priority to CNB2006100496591A priority Critical patent/CN100365071C/en
Publication of CN1814670A publication Critical patent/CN1814670A/en
Application granted granted Critical
Publication of CN100365071C publication Critical patent/CN100365071C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

This invention discloses a new method for producing indigo blue by utilizing un-reacted raw materials in circulation, which takes un-reacted raw materials as the substrate to prepare aniline acetonitrile, uses concentrated deposition as the hydrolyst and adjusts the ratio of NaOH higher in a mixed alkali to prepare indigo blue. This invention synthesizes and recovers waste water with un-reacted raw materials and slag containing waste water and filtered intermediate products and recovers discharged ammonia as industrial products to reduce cost and reduce the discharge of pollutant water and secondary infectants.

Description

A kind of recycle unreacting material is produced indigo method
Technical field
The present invention relates to a kind of production method of chemical dyestuff, specifically a kind of recycle unreacting material is produced indigo novel method.
Background technology
The indigo synthetic middle industrial goods liquefied ammonia that uses of tradition, make the condensing agent sodium amide with the sodium Metal 99.5 reaction, use for alkali fusion, the mixed base that alkali fusion uses is solid industrial goods sodium hydroxide and the potassium hydroxide that market is bought, in 1: 1.5 ratio solvent as alkali fusion after melting, anilinoacetic acid sylvite generates indolol potassium after the alkali fusion cyclization, again through oxidation, press filtration, drying and make indigo product.The synthetic of intermediate anilinoacetic acid sylvite is raw material with aniline, Mono Chloro Acetic Acid, the ferrous sulfate crystal is dissolved the back makes ferrous sulfate, liquid caustic soda, aniline, chloroacetate reaction make the anilinoacetic acid molysite in synthesis tank, to make the anilinoacetic acid potassium salt soln with the liquid nak response then, again through press filtration, the concentrated and dry dry powder anilinoacetic acid sylvite that gets.Because a large amount of ferrous sulfate, aniline etc. of using in the manufacturing processed, not only the manufacturing cycle long, and molysite filter cake treatment capacity is big, pollution problem is difficult to solution.
Publication number is that the application for a patent for invention of CN1465625A discloses a kind of indigo production method, is 1 with aniline and hydroxyacetonitrile with mol ratio: 0.9-1: after condensation reaction is carried out in 1.2 metering, reaction product is carried out layer oily matter after the static layering and is carried out the aniline acetonitrile that crystallization obtains and be hydrolyzed, hydrolysis is in the presence of liquid potassium, seethe with excitement and have under the backflow and carry out, the anilinoacetic acid sylvite that obtains carries out the alkali fusion oxidation and produces indigo.
Notification number is that to disclose a kind of be that main raw material prepares indigo method with the aniline-acetonitrile to the patent of invention of CN1191307C, at a certain temperature, make solvent to reclaim the anhydrous mixed base of potassium sodium, sodium amide is made condensing agent, the gap adds a collection of anilinoacetic acid k-na salt, under high temperature, hyperbaric environment, the cyclization of anilinoacetic acid k-na salt is become the indolol k-na salt, make indigo through oxidation, press filtration, drying again.
Above-mentioned two kinds of production method intermediate steps can produce a large amount of by products, and wastewater discharge is big, and the production cost height is seriously polluted.
Summary of the invention
Be workout cost and pollution problem, the present invention proposes the raw material that unreacted produces in the reacted processing product of a kind of abundant reuse and produce indigo method, make wastewater discharge significantly reduce, reduce and pollute, reduce production costs greatly.
A kind of recycle unreacting material is produced indigo method, comprises condensation reaction, hydrolysis reaction and alkali fusion oxidizing reaction successively, and reactions steps is:
(1) condensation reaction: raw material aniline is dropped into condensation reactor, with the mother liquor water of deviating from after the last consignment of condensation reaction is end water, temperature is 30-95 ℃, aniline and hydroxyacetonitrile add-on are 1: 1.0~1.5, drip or directly add hydroxyacetonitrile and carry out condensation reaction to the reaction end, reaction mass is warmed up to 100-105 ℃, carries out the vacuum concentration dehydration, and the mother liquor water reuse of deviating from is to condensation reactor; The aniline-acetonitrile that makes enters next flow process;
(2) hydrolysis reaction: aniline-acetonitrile is added hydrolysis reactor, and the concentrated precipitate after concentrating with the oxidation mother liquor water after the last consignment of alkali fusion oxidizing reaction is an end water, carries out the vacuum heat-preserving hydrolysis under 35-99 ℃; The ammonia that produces absorbs by water under the sealing and circulating vacuum environment, makes industrial ammonia; After cooling to 90~95 ℃ of adjustment basicity to 7~15g/l after hydrolysis finishes, filtration drying gets the anilinoacetic acid k-na salt;
(3) sodium Metal 99.5 and liquefied ammonia are reacted, generate sodium amide, add in the alkali fusion reactor, then the dry thing of oxidation mother liquor after the last consignment of alkali fusion oxidizing reaction of adding recovery, add an amount of fresh solid potassium hydroxide again, make sodium hydroxide: potassium hydroxide=76~85: 24~15; The gap adds the anilinoacetic acid k-na salt, under high temperature, high pressure the cyclization of anilinoacetic acid k-na salt is become the indolol k-na salt, makes indigo through oxidation, press filtration, drying again; The ammonia that produces absorbs by water under the sealing and circulating vacuum environment, makes industrial ammonia; Oxidizing reaction is filtered the oxidation mother liquor water warp that produces and is concentrated, filters, and concentrates the end water of precipitate as hydrolysis reaction, and concentrated oxidizing water drops into the reuse of alkali fusion reactor after drying.
Adjusting basicity in the described hydrolysis reaction adopts 80% sulfuric acid that reclaims to regulate.
In the prior art, unreacted aniline and hydroxyacetonitrile are generally as discharge of wastewater in the condensation reaction, and the present invention's employing is an end water with the mother liquor water of deviating from after the last consignment of condensation reaction, the directly vacuum concentration dehydration of reaction back, reduced facility investment, as filtration unit, centrifugal device and intermediate transportation process etc.; Can make full use of aniline and hydroxyacetonitrile in the water, reduce raw materials cost and improve product yield; Can reduce the pollution of aniline and hydroxyacetonitrile, also reduce labour intensity, improve Working environment, thoroughly solve the governing problem of aniline waste water environment.
In the prior art, need be concentrated to 48% when oxidation mother liquor water is used alkali fusion and can produce a large amount of precipitates, contain 75~85% mixed alkali in the precipitate, 10~15% pseudo-indole phenol natrium potassium salt, 5~10% anilinoacetic acid k-na salt, concentrated precipitate behind the oxidation mother liquor water thickening filtration generally is to be used as waste residue to handle, and in the inventive method, hydrolysis reaction utilizes oxidation mother liquor water to concentrate precipitate and makes raw material, make full use of mixed alkali and effective constituent anilinoacetic acid k-na salt in the precipitate, can improve yield, reduce production costs; Reduced oxidation mother liquor water simultaneously and concentrated the pollution of precipitate environment; The ammonia water that hydrolysis produces absorbs, and makes industrial ammonia, has both reduced the influence of ammonia to environment, has accomplished the second stage employ of waste gas again.
When alkali fusion reacts in the inventive method, optimized and revised the ratio of sodium hydroxide and potassium hydroxide, can reduce raw materials cost, reduced its fusing point, reduced facility investment and improve working condition; The pseudo-indole phenol k-na salt that utilizes the oxidation mother liquor water that adds to concentrate in the precipitate stops the more pseudo-indole phenol k-na salt of generation, improves the yield in this step of oxidation.
Adjust basicity in the inventive method hydrolysis reaction and adopt 80% sulfuric acid that reclaims to regulate, regulate than the dilute sulphuric acid of former employing about 20%, follow-up drying process power consumption is little, shortens the operating time, cuts the waste.
The inventive method appropriate design reaction process shortens reaction process, fully efficiently utilizes unreacted raw material in each process flow, reduces facility investment, significantly reduces discharged waste water, reduces pollutent, and easy to operate, cost reduces greatly.
Description of drawings
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
Embodiment 1:
(1) condensation reaction: raw material aniline is dropped into condensation reactor, with the mother liquor water of deviating from after the last consignment of condensation reaction is end water, temperature is 30-95 ℃, drip or directly add hydroxyacetonitrile (pH value of hydroxyacetonitrile is controlled at 2.0~3.0) and carry out condensation reaction to the reaction end, the add-on of aniline and hydroxyacetonitrile is: 1: 1.1, reaction mass was warmed up to 100-105 ℃, carries out vacuum concentration, dehydration, the mother liquor water reuse of deviating from is to condensation reactor; Make aniline-acetonitrile simultaneously, the purity of aniline-acetonitrile is more than 97.5% behind the recycle mother liquor water, and yield is more than 98%;
(2) hydrolysis reaction: with a collection of adding hydrolysis reactor of aniline-acetonitrile, concentrated precipitate after concentrating with the oxidation mother liquor water after the last consignment of alkali fusion oxidizing reaction is an end water, 35~39 ℃ of insulations 9~10 hours, slowly be warmed up to 55~59 ℃ of insulations 2~3 hours then, be warmed up to 76~79 ℃ of insulations 2~3 hours again, be warmed up to 97~99 ℃ of insulations 2~3 hours again, finish up to terminal point, wherein the insulation beginning just keeps vacuum, so that fast reaction speed and carry out ammonia and reclaim is made industrial ammonia; After terminal point arrives, cool to 90~95 ℃ and adjust basicity to 7~15g/l, the sulfuric acid of wherein transferring alkali to use is transferred alkali with 80% sulfuric acid that reclaims, and carries out the dry anilinoacetic acid k-na salt that gets at last; The yield of anilinoacetic acid k-na salt (not indistinct alkali) is more than 98%;
(3) sodium Metal 99.5 and liquefied ammonia are reacted, generate sodium amide, add in the alkali fusion reactor, then the dry thing of oxidation mother liquor after the last consignment of alkali fusion oxidizing reaction of adding recovery, add an amount of fresh solid potassium hydroxide again, make sodium hydroxide: potassium hydroxide=76: 24; The gap adds the anilinoacetic acid k-na salt, under high temperature, high pressure the cyclization of anilinoacetic acid k-na salt is become indolol potassium sodium, makes indigo through oxidation, press filtration, drying again; The ammoniacal liquor that produces absorbs by sealing and circulating vacuum environment water, makes industrial ammonia; Oxidizing reaction is filtered the oxidation mother liquor water warp that produces and is concentrated, filters, and concentrates the end water of precipitate as hydrolysis reaction, and concentrated oxidizing water drops into the reuse of alkali fusion reactor after drying; Indigo yield (in the anilinoacetic acid k-na salt) is greater than 95%.
Embodiment 2
(1) condensation reaction: the mother liquor water of deviating from after the last consignment of condensation reaction is joined condensation reactor for end water, then aniline is dropped into condensation reactor, temperature is 30-95 ℃, drip hydroxyacetonitrile (pH value of hydroxyacetonitrile is controlled at 2.0~3.0) and carry out condensation reaction to the reaction end, the add-on of aniline and hydroxyacetonitrile is: 1: 1.5, cool to 30 ℃ then, carrying out crystallization separates out, filtration washing and aniline-acetonitrile, the purity of aniline-acetonitrile is more than 98%, yield is more than 93%;
(2) hydrolysis reaction: with a collection of adding hydrolysis reactor of aniline-acetonitrile, with the oxidation mother liquor water after the last consignment of alkali fusion oxidizing reaction is end water, 35~39 ℃ of insulations 9~10 hours, slowly be warmed up to 55~59 ℃ of insulations 2~3 hours then, be warmed up to 76~79 ℃ of insulations 2~3 hours again, be warmed up to 97~99 ℃ of insulations 2~3 hours again, finish up to terminal point, wherein insulation beginning just keeps vacuum, so that fast reaction speed and carry out ammonia and reclaim is made industrial ammonia; After terminal point arrives, cool to 90~95 ℃ and adjust basicity to 7~15g/l, the sulfuric acid of wherein transferring alkali to use is transferred alkali with 80% sulfuric acid that reclaims, and carries out the dry anilinoacetic acid k-na salt that gets at last; The yield of anilinoacetic acid k-na salt (not indistinct alkali) is more than 92%;
(3) sodium Metal 99.5 and liquefied ammonia are reacted, generate sodium amide, add in the alkali fusion reactor, the dry thing of mother liquor water after oxidation mother liquor water after the last consignment of alkali fusion oxidizing reaction of adding recovery concentrates then, add an amount of fresh solid potassium hydroxide again, make sodium hydroxide: potassium hydroxide=85: 15; The gap adds the anilinoacetic acid k-na salt, under high temperature, high pressure the cyclization of anilinoacetic acid k-na salt is become the indolol k-na salt, makes indigo through oxidation, press filtration, drying again; The ammoniacal liquor that produces absorbs by sealing and circulating vacuum environment water, makes industrial ammonia; Concentrated oxidizing water drops into the reuse of alkali fusion reactor after drying; Indigo yield (in the anilinoacetic acid k-na salt) is greater than 90%.

Claims (3)

1. a recycle unreacting material is produced indigo method, comprises condensation reaction, hydrolysis reaction and alkali fusion oxidizing reaction successively, and reactions steps is:
(1) condensation reaction: raw material aniline is dropped into condensation reactor, with the mother liquor water of deviating from after the last consignment of condensation reaction is end water, temperature is 30-95 ℃, aniline and hydroxyacetonitrile add-on are 1: 1.0~1.5, drip or directly add hydroxyacetonitrile and carry out condensation reaction to the reaction end, reaction mass is warmed up to 100-105 ℃, carries out the vacuum concentration dehydration, and the mother liquor water reuse of deviating from is to condensation reactor; The aniline-acetonitrile that makes enters next flow process;
(2) hydrolysis reaction: aniline-acetonitrile is added hydrolysis reactor, and the concentrated precipitate after concentrating with the oxidation mother liquor water after the last consignment of alkali fusion oxidizing reaction is an end water, carries out the vacuum heat-preserving hydrolysis under 35-99 ℃; The ammonia that produces absorbs by water, makes industrial ammonia; After cooling to 90~95 ℃ of adjustment basicity to 7~15g/l after hydrolysis finishes, filtration drying gets the anilinoacetic acid k-na salt;
(3) sodium Metal 99.5 and liquefied ammonia are reacted, generate sodium amide, add in the alkali fusion reactor, then the dry thing of oxidation mother liquor after the last consignment of alkali fusion oxidizing reaction of adding recovery, add an amount of fresh solid potassium hydroxide again, make sodium hydroxide: potassium hydroxide=76~85: 24~15; The gap adds the anilinoacetic acid k-na salt; Under high temperature, high pressure, the cyclization of anilinoacetic acid k-na salt is become indolol potassium sodium, again through oxidation, press filtration, drying and make indigo; The ammonia that produces absorbs by water, makes industrial ammonia; Oxidizing reaction is filtered the oxidation mother liquor water warp that produces and is concentrated, filters, and concentrates the end water of precipitate as hydrolysis reaction, and concentrated oxidizing water drops into the reuse of alkali fusion reactor after drying.
2. method according to claim 1 is characterized in that: adjust basicity in the described hydrolysis reaction and adopt 80% sulfuric acid that reclaims to regulate.
3. method according to claim 1 is characterized in that: the ammonia water that produces in the described reaction is absorbed under the sealing and circulating vacuum environment and carries out.
CNB2006100496591A 2006-03-01 2006-03-01 Method for producing idigo by cyclic utilization of non-reacted raw materials Active CN100365071C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2006100496591A CN100365071C (en) 2006-03-01 2006-03-01 Method for producing idigo by cyclic utilization of non-reacted raw materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2006100496591A CN100365071C (en) 2006-03-01 2006-03-01 Method for producing idigo by cyclic utilization of non-reacted raw materials

Publications (2)

Publication Number Publication Date
CN1814670A true CN1814670A (en) 2006-08-09
CN100365071C CN100365071C (en) 2008-01-30

Family

ID=36907038

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006100496591A Active CN100365071C (en) 2006-03-01 2006-03-01 Method for producing idigo by cyclic utilization of non-reacted raw materials

Country Status (1)

Country Link
CN (1) CN100365071C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102627581A (en) * 2012-03-20 2012-08-08 河北诚信有限责任公司 Preparation technology of N-phenylglycinonitrile
CN104910032A (en) * 2015-03-20 2015-09-16 重庆紫光化工股份有限公司 Preparation method of anilino-acetate

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1465624A (en) * 2002-06-03 2004-01-07 上海蓝建染化有限公司 Method for producing indigo
CN1465625A (en) * 2002-06-03 2004-01-07 上海蓝建染化有限公司 Method for producing indigo
CN1191307C (en) * 2002-07-26 2005-03-02 江苏泰丰化工有限公司 Process for preparing indigo and its intermediate

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102627581A (en) * 2012-03-20 2012-08-08 河北诚信有限责任公司 Preparation technology of N-phenylglycinonitrile
CN104910032A (en) * 2015-03-20 2015-09-16 重庆紫光化工股份有限公司 Preparation method of anilino-acetate
CN104910032B (en) * 2015-03-20 2017-06-23 重庆紫光化工股份有限公司 A kind of preparation method of anilino-acetate

Also Published As

Publication number Publication date
CN100365071C (en) 2008-01-30

Similar Documents

Publication Publication Date Title
CN104592063B (en) A kind of environment-friendly production process of H acid
CN106745246B (en) A kind of method for preparing vanadic sulfate
CN103773972B (en) A kind of processing method of raw material containing lead
CN102432478B (en) Preparation process of glycine
CN103937286B (en) A kind of clean preparation method of disperse dyes
CN1990460B (en) Comprehensive treatment of glycine crystallization mother liquid
CN104119243B (en) A kind of energy-saving clean production method of iminodiethanoic acid
CN102531055B (en) The preparation method of sodium metavanadate/potassium metavanadate
CN1803660A (en) High-efficiency environment-friendly acid-mixed plating removal liquor
CN103663516A (en) Method for preparing aluminum hydroxide by utilizing high-alumina coal ash
CN103482695A (en) Method for low-temperature production of titanium dioxide by mixed alkali of sodium hydroxide and potassium hydroxide
CN1814670A (en) Method for producing idigo by cyclic utilization of non-reacted raw materials
CN101103800A (en) Green making technology for monosodium glutanmate
CN103043823A (en) Method for recycling waste water containing ammonium chloride
CN101012165B (en) Process of preparing oxalic acid by calcium sulfate cycle method
CN108569812B (en) Treatment system and treatment method for wastewater containing low-concentration sulfuric acid
CN103496722B (en) Method for preparing high-purity sodium sulfite through supercritical hydrothermal reduction
CN208883749U (en) A kind of hydroxyacetonitrile serialization prepares the coiled reaction unit of glycine
CN102992469B (en) Method for treating sodium sulfide waste water
CN102040225A (en) Process for preparing precipitated white carbon black by adopting carbon dioxide for decomposition
CN102502715B (en) Method for reclaiming reagent-grade anhydrous sodium sulfate from basic nickel carbonate production waste liquor
CN101693656A (en) High-conversion and high-yield process for producing oxalic acid by calcifying method
CN102336416B (en) Method for cleanly producing high-purity cyanate at low temperature
CN1191307C (en) Process for preparing indigo and its intermediate
CN101062772A (en) Improved borax ore deposition refinement method for preparing boracic acid

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
C14 Grant of patent or utility model
EE01 Entry into force of recordation of patent licensing contract

Assignee: Zhejiang Changzheng Chemical Industry Co., Ltd.

Assignor: Zhejiang Runtu Co., Ltd.

Contract fulfillment period: 2008.10.8 to 2015.10.8 contract change

Contract record no.: 2008330001718

Denomination of invention: Method for producing idigo by cyclic utilization of non-reacted raw materials

Granted publication date: 20080130

License type: Exclusive license

Record date: 2008.11.5

LIC Patent licence contract for exploitation submitted for record

Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.10.8 TO 2015.10.8; CHANGE OF CONTRACT

Name of requester: ZHEJIANG PROVINCE CHANGZHENG CHEMICAL CO., LTD.

Effective date: 20081105

C41 Transfer of patent application or patent right or utility model
ASS Succession or assignment of patent right

Owner name: LONG MARCH CHEMICAL CO., LTD.;ZHEJIANG PROVINCE

Free format text: FORMER OWNER: RUNTU CO., LTD., ZHEJIANG

Effective date: 20130322

TR01 Transfer of patent right

Effective date of registration: 20130322

Address after: 312369, No. five, No. 5, Shangyu Industrial Park, Hangzhou Bay, Zhejiang, Shaoxing

Patentee after: Zhejiang Changzheng Chemical Industry Co., Ltd.

Address before: 312368 Zhejiang city of Shangyu Province town

Patentee before: Zhejiang Runtu Co., Ltd.

COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 312368 SHAOXING, ZHEJIANG PROVINCE TO: 312369 SHAOXING, ZHEJIANG PROVINCE