CN102516817B - Method for preparing indigo white solution - Google Patents
Method for preparing indigo white solution Download PDFInfo
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- CN102516817B CN102516817B CN2011104462449A CN201110446244A CN102516817B CN 102516817 B CN102516817 B CN 102516817B CN 2011104462449 A CN2011104462449 A CN 2011104462449A CN 201110446244 A CN201110446244 A CN 201110446244A CN 102516817 B CN102516817 B CN 102516817B
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Abstract
The invention discloses an environment-friendly preparation method for an indigo white solution. The preparation method comprises the following steps of: 1, adding an indigo suspension which is not washed and acidified and is oxidized, an activated Raney nickel catalyst and sodium hydroxide into a high-pressure reaction kettle, replacing air in the reaction kettle with nitrogen, aerating hydrogen, adjusting the temperature and pressure of the system, and performing catalytic hydrogenation reaction; 2, continuing to aerate the hydrogen, raising the temperature and pressure of the system, and performing further hydrogenation reaction; and 3, stopping the reaction, adding a stabilizer, and removing the catalyst by a filtration method to obtain the indigo white solution. By the method, the disadvantages of environmental pollution, high reaction pressure, high temperature and large using amount of the catalyst in the prior art are overcome; and the method is high in yield.
Description
Technical field
The invention belongs to the indigo white category for preparing, be specifically related to shortening and prepare indigo white method.
Background technology
Indigo is a kind of common vat dyes, for the dyeing cellulosic textile material, in particular for the dyeing of blue jean product.Indigo own water insoluble, during use, must make it change into the water-soluble leuco body with cellulose affinity through the reduction processing indigo white, after being attached on material to be dyed, thereby then change into water-insoluble indigo colour developing through atmospheric oxygen.In traditional dye process, indigo reduction is to carry out in the alkaline medium in one container of dye bath upstream, adopts inorganic reducing agent, and for example vat powder and thiocarbamide oxide compound, also can adopt the organic reducing agents such as pyruvic alcohol.With above-mentioned reductive agent, come the shortcoming of indigotin to be, when adopting vat powder, contain high concentration sulfate in dyeing mill wastewater; When adopting pyruvic alcohol, contain the aerobic substance of high density in waste water.This reduction mode, cost for wastewater treatment is high, and environment is existed to detrimentally affect.
WO-A-94/23114 discloses a kind of indigo reduction method of environmental protection, adopts the mode of catalytic reduction, by indigo suspension, prepares the indigo white aqueous solution of causticity, and relative and conventional staining method, can reduce vitriol or the organism content in waste water.
Existing catalytic reduction prepares the indigo white mode of indigo leuco compound and need to be in advance by indigo, adds the hydrochloric acid that mass concentration is 10 ~ 15% to carry out acidifying after being washed to neutrality again, carry out hydrogenation reaction after being washed to again neutrality, indigo washing and acidization produce a large amount of waste liquids, environment is existed to detrimentally affect, lack at present a kind of without raw material being carried out to washing and acidification, temperature of reaction is low, pressure is low, catalyst levels the is few indigo white preparation method of environment-friendly type.
Summary of the invention
The technical problem to be solved in the present invention is to provide the leucoindigo solutions preparation method that a kind of reaction yield is high, pressure is low, temperature is low, catalyst levels is few, and the method can be avoided washing and the acidification technique of raw material, has the characteristics of energy-conserving and environment-protective.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is:
The environment-friendly preparation method of leucoindigo solutions, be comprised of following following steps,
Step 1: get without the indigo suspension liquid after the oxidation of washing and acidification, above-mentioned suspension liquid and Raney's nickel catalyst, sodium hydroxide are added in autoclave, first use the air in the nitrogen replacement reactor, be filled with again the hydrogen of 0.1 ~ 1MPa, closed reactor, be warmed up to 80 ~ 110 ℃, continuing to be filled with hydrogen to the pressure in reactor is 1.5 ~ 3MPa, reaction 2.5 ~ 3.5h, in reaction process, when the pressure drop value in reactor is greater than 0.5 MPa, hydrogen make-up is recovered the pressure in reactor;
The proportioning of reaction mass is:
Solid is indigo: Raney's nickel ratio of quality and the number of copies=1: 0.03 ~ 0.15;
Solid is indigo: sodium hydroxide ratio of quality and the number of copies=1: 0.075 ~ 0.35;
Solid is indigo: water=1: 0.5 ~ 3;
Step 2: the reaction in step 1 is warming up to 115 ~ 145 ℃ by reactor after finishing, and continuing to be filled with hydrogen to the pressure in reactor is 3.5 ~ 5.5MPa, reaction 0.5 ~ 1h, in reaction process, when the pressure drop value in reactor is greater than 0.5 MPa, hydrogen make-up is recovered the pressure in reactor;
Step 3: after the reaction in step 2 finishes, the question response still is cooling, and the hydrogen with in the nitrogen replacement reactor, add stablizer in reactor, adopts the method for filtering to remove Raney's nickel, obtains leucoindigo solutions.
Stablizer of the present invention is bisphosphite anti-oxidant.
Improvement of the present invention is: the temperature of reaction in step 1 is 105 ℃, and the pressure in reactor is 2.5MPa, and the temperature of reaction in described step 2 is 130 ℃, and the pressure in reactor is 4.5 MPa; The proportioning of described reaction mass is:
Solid is indigo: Raney's nickel ratio of quality and the number of copies=1: 0.1;
Solid is indigo: sodium hydroxide ratio of quality and the number of copies=1: 0.2;
Solid is indigo: water=1: 1.
Owing to having adopted technique scheme, the invention technological progress is:
In indigo white preparation method of the present invention, at first under 80 ~ 110 ℃ of lower temperature of reaction and pressure 1.5 ~ 3MPa, indigo suspension liquid is carried out to catalytic hydroprocessing, and then 115 ~ 145 ℃ of the temperature of reaction of rising system and pressure 3.5 ~ 5.5MPa, carry out carrying out further hydrotreatment to indigo.When lower temperature of reaction and pressure carry out hydrogenation reaction, in the katalysis of giving full play to catalyzer, reduce the generation of side reaction, after 5 ~ 8h is carried out in reaction, the concentration indigo white due to product raises, temperature and pressure by the reaction system of 2 ~ 3h raising in the short period of time promotes reaction to carry out, and improves indigo white productive rate.Due to the above-mentioned preparation method adopted, the present invention can not to raw material indigo wash and the condition of acidification under, reaction obtains the leucoindigo solutions that yield is high, by product is few, has avoided the detrimentally affect of the waste water of washing and acidification technique generation to environment.
In the suspension liquid obtained after the indigo water with 1 mass parts of the raw material solid of 1 mass parts mixes, add the Raney's nickel catalyst of 0.1 mass parts and the sodium hydroxide of 0.2 mass parts, at 110 ℃, react under the condition of 2.5MPa and within 5 ~ 8 hours, can make indigo white productive rate reach 85 ~ 90%; Again by above-mentioned reaction solution at 130 ℃, react 2 ~ 3h under the condition of 4.5 MPa, can make indigo white productive rate reach 95 ~ 98%, adopt above-mentioned conditional parameter, can effectively reduce side reaction ground and occur, the product purity obtained is high, solvability is good.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
The indigo raw material of the present embodiment is that oxidation style obtains, without the indigo solid of washing and acidification.Prepare leucoindigo solutions according to following steps,
Step 1: carry out the leak detection of autoclave, autoclave is cleaned to dry and seal, be filled with the nitrogen of 0.8MP, keep 30min, pressure is as good as the explanation reactor stopping property that significantly do not descend, and carries out subsequent operations; Take the indigo solid of a certain amount of raw material, be dispersed in water, be mixed with suspension liquid.This suspension liquid, Raney's nickel catalyst, sodium hydroxide are added in reactor, and wherein, the mass ratio of each component is indigo solid: Raney's nickel: sodium hydroxide: water=1: 0.15: 0.35: 3.Airtight good reactor, then use air in the nitrogen replacement reactor 3 times, use hydrogen exchange instead 3 times, making the hydrogen pressure in reactor is 0.5MPa, closed reactor again, be warmed up to 80 ℃, being filled with hydrogen to the pressure in reactor is 1.5MPa, and reaction 2.5h, in reaction process, when the pressure drop value in reactor is greater than 0.5 MPa, hydrogen make-up is recovered the pressure in reactor.
Step 2: the reaction in step 1 is warming up to 115 ℃ by reactor after finishing, and continuing to be filled with hydrogen to the pressure in reactor is 3.5MPa, reaction 0.5h, in reaction process, when the pressure drop value in reactor is greater than 0.5 MPa, hydrogen make-up is recovered the pressure in reactor.
Step 3: after the reaction in step 2 finishes, temperature in reaction system is fallen and put room temperature, release the hydrogen in reactor, then use nitrogen replacement 3 minutes, bisphosphite anti-oxidant 626 is added in reactor, guarantee reaction solution in the situation that ingress of air is difficult for oxidized rotten.Then the elimination Raney's nickel, obtain leucoindigo solutions.Wherein, oxidation inhibitor 626 chemical names are two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, purchased from Jinhai-Yabao Chemical Co., Ltd., Ningbo.
The yield of leucoindigo solutions prepared by the calculating aforesaid method, result is 95.3%.
Embodiment 2
The leucoindigo solutions preparation method of the present embodiment and the difference of embodiment 1 are:
In step 1, the mass ratio of each component is indigo solid: Raney's nickel: sodium hydroxide: water=1: 0.1: 0.2: 1, and temperature of reaction is 105 ℃, and reactor pressure is 2.5MPa, and the time is 3h;
In step 2, temperature of reaction is 130 ℃, and reactor pressure is 4.5 MPa, and the time is 0.8h.
The yield of gained leucoindigo solutions is 98.5%.
Embodiment 3
The leucoindigo solutions preparation method of the present embodiment and the difference of embodiment 1 are:
In step 1, the mass ratio of each component is indigo solid: Raney's nickel: sodium hydroxide: water=1: 0.03: 0..075: 0.5, and temperature of reaction is 110 ℃, and reactor pressure is 3 MPa, and the time is 3.5h;
In step 2, temperature of reaction is 145 ℃, and reactor pressure is 5.5MPa, and the time is 1h.
The yield of gained leucoindigo solutions is 95.7%.
Embodiment 4
The leucoindigo solutions preparation method of the present embodiment and the difference of embodiment 1 are:
In step 1, the mass ratio of each component is indigo solid: Raney's nickel: sodium hydroxide: water=1: 0.12: 0.22: 1.5, and temperature of reaction is 110 ℃, and reactor pressure is 3 MPa, and the time is 2.8h;
In step 2, temperature of reaction is 135 ℃, and reactor pressure is 4MPa, and the time is 0.6h.
The yield of gained leucoindigo solutions is 96.3%.
Claims (3)
1. the environment-friendly preparation method of leucoindigo solutions, is characterized in that being comprised of following steps,
Step 1: get without the indigo suspension liquid after the oxidation of washing and acidification, above-mentioned suspension liquid and Raney's nickel catalyst, sodium hydroxide are added in autoclave, first use the air in the nitrogen replacement reactor, use again hydrogen exchange instead 3 times, be filled with again the hydrogen of 0.1～1MPa, closed reactor, be warmed up to 80～110 ℃, continuing to be filled with hydrogen to the pressure in reactor is 1.5～3MPa, reaction 2.5～3.5h, in reaction process, when the pressure drop value in reactor is greater than 0.5MPa, hydrogen make-up is recovered the pressure in reactor;
The proportioning of reaction mass is:
Solid is indigo: Raney's nickel ratio of quality and the number of copies=1: 0.03～0.15;
Solid is indigo: sodium hydroxide ratio of quality and the number of copies=1: 0.075～0.35;
Solid is indigo: water=1: 0.5～3;
Step 2: after the reaction in step 1 finishes, reactor is warming up to 115～145 ℃, continuing to be filled with hydrogen to the pressure in reactor is 3.5～5.5MPa, reaction 0.5～1h, in reaction process, when the pressure drop value in reactor is greater than 0.5MPa, hydrogen make-up is recovered the pressure in reactor;
Step 3: after the reaction in step 2 finishes, the question response still is cooling, and the hydrogen with in the nitrogen replacement reactor, add stablizer in reactor, adopts the method for filtering to remove Raney's nickel, obtains leucoindigo solutions.
2. the environment-friendly preparation method of leucoindigo solutions according to claim 1, it is characterized in that: described stablizer is bisphosphite anti-oxidant.
3. the environment-friendly preparation method of leucoindigo solutions according to claim 2, it is characterized in that: the temperature of reaction in step 1 is 105 ℃, and the pressure in reactor is 2.5MPa, and the temperature of reaction in described step 2 is 130 ℃, and the pressure in reactor is 4.5MPa; The proportioning of described reaction mass is:
Solid is indigo: Raney's nickel ratio of quality and the number of copies=1: 0.1;
Solid is indigo: sodium hydroxide ratio of quality and the number of copies=1: 0.2;
Solid is indigo: water=1: 1.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105566949B (en) * | 2016-02-04 | 2017-07-07 | 浙江长征化工有限公司 | A kind of environment-friendly preparation method of sulfur dye solution |
| CN106975483A (en) * | 2017-05-05 | 2017-07-25 | 南京工业大学 | Catalyst for synthesizing hydrogenated indigo through indigo hydrogenation, and preparation method and application thereof |
| CN110016816A (en) * | 2019-03-13 | 2019-07-16 | 广东前进牛仔布有限公司 | A kind of indigo dyeing method |
| CN110423492B (en) * | 2019-08-26 | 2021-04-06 | 约克夏(浙江)染化有限公司 | Process for the preparation of a leucoindigo salt solution and process for the continuous production of a leucoindigo salt solution |
| JP2023018161A (en) * | 2019-12-17 | 2023-02-08 | 岩谷産業株式会社 | Method for producing dyed fiber article and method of producing dye solution |
| CN114644585B (en) * | 2020-12-18 | 2023-10-27 | 沈阳化工研究院有限公司 | Method for preparing indigo white by fluidized bed catalytic hydrogenation |
| WO2024083795A1 (en) * | 2022-10-17 | 2024-04-25 | Archroma Ip Gmbh | Leucoindigo salt mixture from non-synthetic sources for dyeing processes |
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|---|---|---|---|---|
| CN1035521A (en) * | 1988-02-23 | 1989-09-13 | 三井东圧化学株式会社 | The preparation method of indigo compound |
| CN1120357A (en) * | 1993-03-30 | 1996-04-10 | Basf公司 | Method of dyeing cellulose-containing textile material with hydrogenated indigo |
| CN1129008A (en) * | 1993-08-13 | 1996-08-14 | Basf公司 | Granular indigo white prepn. |
| US6428581B1 (en) * | 1998-07-13 | 2002-08-06 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Concentrated leucoindigo solutions |
| CN101376747A (en) * | 2008-10-10 | 2009-03-04 | 江苏工业学院 | Method for recycling bipseudoindoxyl dye from indigo dyeing waste water |
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- 2011-12-28 CN CN2011104462449A patent/CN102516817B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035521A (en) * | 1988-02-23 | 1989-09-13 | 三井东圧化学株式会社 | The preparation method of indigo compound |
| CN1120357A (en) * | 1993-03-30 | 1996-04-10 | Basf公司 | Method of dyeing cellulose-containing textile material with hydrogenated indigo |
| CN1129008A (en) * | 1993-08-13 | 1996-08-14 | Basf公司 | Granular indigo white prepn. |
| US6428581B1 (en) * | 1998-07-13 | 2002-08-06 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Concentrated leucoindigo solutions |
| CN101376747A (en) * | 2008-10-10 | 2009-03-04 | 江苏工业学院 | Method for recycling bipseudoindoxyl dye from indigo dyeing waste water |
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