CN102516817A - Method for preparing indigo white solution - Google Patents
Method for preparing indigo white solution Download PDFInfo
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- CN102516817A CN102516817A CN2011104462449A CN201110446244A CN102516817A CN 102516817 A CN102516817 A CN 102516817A CN 2011104462449 A CN2011104462449 A CN 2011104462449A CN 201110446244 A CN201110446244 A CN 201110446244A CN 102516817 A CN102516817 A CN 102516817A
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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 indigo white preparation category, be specifically related to shortening and prepare indigo white method.
Background technology
Indigo is a kind of common vat dyes, is used for the dyeing cellulosic textile material, in particular for the dyeing of blue jean product.Indigo own water insoluble, it is indigo white to make it change into the water-soluble leuco body with fiber affinity through the reduction processing during use, after waiting to dye on the material, thereby changes into water-insoluble indigo colour developing through atmospheric oxygen again.In the traditional dyeing process, indigo reduction is to carry out in the alkaline medium in one container of the dye bath upper reaches, adopts inorganic reducing agent, and for example vat powder and thiocarbamide oxide compound also can adopt organic reducing agents such as pyruvic alcohol.Come the shortcoming of indigotin to be with above-mentioned reductive agent, when adopting vat powder, contain high concentration sulfate in the dyeing mill wastewater; When adopting pyruvic alcohol, contain the aerobic substance of high density in the waste water.This reduction mode, cost for wastewater treatment is high, and there is detrimentally affect in environment.
WO-A-94/23114 discloses a kind of indigo reduction method of environmental protection, adopts the mode of catalytic reduction, obtains the indigo white aqueous solution of causticity by indigo suspension preparation, with conventional staining method, can reduce vitriol or the organism content in waste water relatively.
It is that 10 ~ 15% hydrochloric acid carries out acidifying with adding mass concentration after indigo washing to the neutrality more in advance that existing catalytic reduction prepares the indigo white mode needs of indigo leuco compound; Wash again to neutrality and carry out hydrogenation reaction; Indigo washing and acidization produce a large amount of waste liquids; There is detrimentally affect in environment, lacks a kind of need not at present raw material is washed 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 that the present invention will solve provides the leucoindigo solutions preparation method that a kind of reaction yield is high, pressure is low, temperature is low, catalyst levels is few, and this method can be avoided the 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 scheme that the present invention adopted is:
The environment-friendly preparation method of leucoindigo solutions is made up 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 the autoclave, earlier with the air in the nitrogen replacement reaction kettle; Charge into the hydrogen of 0.1 ~ 1MPa again; Closed reactor is warmed up to 80 ~ 110 ℃, and the pressure that continues to charge in hydrogen to the reaction kettle is 1.5 ~ 3MPa; Reaction 2.5 ~ 3.5h; In the reaction process, when the pressure drop-out value in the reaction kettle during greater than 0.5 MPa, hydrogen make-up is recovered the pressure in the reaction kettle;
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 the step 1 is warming up to 115 ~ 145 ℃ with reaction kettle after finishing, and the pressure that continues to charge in hydrogen to the reaction kettle is 3.5 ~ 5.5MPa; Reaction 0.5 ~ 1h; In the reaction process, when the pressure drop-out value in the reaction kettle during greater than 0.5 MPa, hydrogen make-up is recovered the pressure in the reaction kettle;
Step 3: after the reaction in the step 2 finishes, the cooling of question response still, the hydrogen with in the nitrogen replacement reaction kettle adds stablizer in the reaction kettle, adopts filtering method to remove Raney's nickel, obtains leucoindigo solutions.
Stablizer according to the invention is a bisphosphite anti-oxidant.
Improvement of the present invention is: the temperature of reaction in the step 1 is 105 ℃, and the pressure in the reaction kettle is 2.5MPa, and the temperature of reaction in the said step 2 is 130 ℃, and the pressure in the reaction kettle is 4.5 MPa; The proportioning of said 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 adopted technique scheme, institute of the present invention acquisition of technology progress is:
Among the 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 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 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, because the indigo white concentration of product raises; Temperature and pressure through the reaction system of 2 ~ 3h raising in the short period of time promotes reaction to carry out, and improves indigo white productive rate.Because the above-mentioned preparation method that adopts, the present invention can be to raw material under the indigo condition of washing with acidification, and reaction obtains yield height, leucoindigo solutions that 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 that obtains 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 can make indigo white productive rate reach 85 ~ 90% in 5 ~ 8 hours; Again with 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 reduce side reaction ground effectively and take place, the product purity that obtains is high, solvability is good.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explain.
Embodiment 1
The indigo raw material of 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 oven dry seal, charge into the nitrogen of 0.8MP, keep 30min, pressure is good like the explanation reaction kettle stopping property that significantly do not descend, and carries out subsequent operations; Take by weighing the indigo solid of a certain amount of raw material, be dispersed in the water, be mixed with suspension liquid.This suspension liquid, Raney's nickel catalyst, sodium hydroxide are added in the reaction kettle, 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 reaction kettle uses the air 3 times in the nitrogen replacement reaction kettle then, uses hydrogen exchange again instead 3 times; Making the hydrogen pressure in the reaction kettle is 0.5MPa, and closed reactor is warmed up to 80 ℃; The pressure that charges in hydrogen to the reaction kettle is 1.5MPa, and reaction 2.5h is in the reaction process; When the pressure drop-out value in the reaction kettle during greater than 0.5 MPa, hydrogen make-up is recovered the pressure in the reaction kettle.
Step 2: the reaction in the step 1 is warming up to 115 ℃ with reaction kettle after finishing, and the pressure that continues to charge in hydrogen to the reaction kettle is 3.5MPa; Reaction 0.5h; In the reaction process, when the pressure drop-out value in the reaction kettle during greater than 0.5 MPa, hydrogen make-up is recovered the pressure in the reaction kettle.
Step 3: after the reaction in the step 2 finishes; Temperature in the reaction system fallen put room temperature, release the hydrogen in the reaction kettle, used nitrogen replacement again 3 minutes; Bisphosphite anti-oxidant 626 is added in the reaction kettle, and it is oxidized rotten to guarantee that reaction solution is difficult under the situation of ingress of air.The elimination Raney's nickel gets leucoindigo solutions then.Wherein, oxidation inhibitor 626 chemical names are two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, available from Jinhai-Yabao Chemical Co., Ltd., Ningbo.
Calculate the yield of the leucoindigo solutions of method for preparing, the result is 95.3%.
Embodiment 2
The leucoindigo solutions preparation method of present embodiment and the difference of embodiment 1 are:
The mass ratio of each component is indigo solid in the step 1: Raney's nickel: sodium hydroxide: water=1: 0.1: 0.2: 1, and temperature of reaction is 105 ℃, and reaction kettle pressure is 2.5MPa, and the time is 3h;
Temperature of reaction is 130 ℃ in the step 2, and reaction kettle 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 present embodiment and the difference of embodiment 1 are:
The mass ratio of each component is indigo solid in the step 1: Raney's nickel: sodium hydroxide: water=1: 0.03: 0..075: 0.5, and temperature of reaction is 110 ℃, and reaction kettle pressure is 3 MPa, and the time is 3.5h;
Temperature of reaction is 145 ℃ in the step 2, and reaction kettle 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 present embodiment and the difference of embodiment 1 are:
The mass ratio of each component is indigo solid in the step 1: Raney's nickel: sodium hydroxide: water=1: 0.12: 0.22: 1.5, and temperature of reaction is 110 ℃, and reaction kettle pressure is 3 MPa, and the time is 2.8h;
Temperature of reaction is 135 ℃ in the step 2, and reaction kettle 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 made up 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 the autoclave, earlier with the air in the nitrogen replacement reaction kettle; Charge into the hydrogen of 0.1 ~ 1MPa again; Closed reactor is warmed up to 80 ~ 110 ℃, and the pressure that continues to charge in hydrogen to the reaction kettle is 1.5 ~ 3MPa; Reaction 2.5 ~ 3.5h; In the reaction process, when the pressure drop-out value in the reaction kettle during greater than 0.5 MPa, hydrogen make-up is recovered the pressure in the reaction kettle;
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 the step 1 is warming up to 115 ~ 145 ℃ with reaction kettle after finishing, and the pressure that continues to charge in hydrogen to the reaction kettle is 3.5 ~ 5.5MPa; Reaction 0.5 ~ 1h; In the reaction process, when the pressure drop-out value in the reaction kettle during greater than 0.5 MPa, hydrogen make-up is recovered the pressure in the reaction kettle;
Step 3: after the reaction in the step 2 finishes, the cooling of question response still, the hydrogen with in the nitrogen replacement reaction kettle adds stablizer in the reaction kettle, adopts filtering method 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: said stablizer is a 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 the step 1 is 105 ℃, and the pressure in the reaction kettle is 2.5MPa, and the temperature of reaction in the said step 2 is 130 ℃, and the pressure in the reaction kettle is 4.5 MPa; The proportioning of said 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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566949A (en) * | 2016-02-04 | 2016-05-11 | 浙江长征化工有限公司 | Environment-friendly preparation method of sulphur 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 |
| CN110423492A (en) * | 2019-08-26 | 2019-11-08 | 约克夏(浙江)染化有限公司 | The method of the indigo white salting liquid of preparation method and continuous production of indigo white salting liquid |
| WO2021125226A1 (en) * | 2019-12-17 | 2021-06-24 | 岩谷産業株式会社 | Method for producing dyed fiber article and method of producing dye solution |
| CN114644585A (en) * | 2020-12-18 | 2022-06-21 | 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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| 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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| 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. |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566949A (en) * | 2016-02-04 | 2016-05-11 | 浙江长征化工有限公司 | Environment-friendly preparation method of sulphur 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 |
| CN110423492A (en) * | 2019-08-26 | 2019-11-08 | 约克夏(浙江)染化有限公司 | The method of the indigo white salting liquid of preparation method and continuous production of indigo white salting liquid |
| 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 |
| WO2021125226A1 (en) * | 2019-12-17 | 2021-06-24 | 岩谷産業株式会社 | Method for producing dyed fiber article and method of producing dye solution |
| CN114644585A (en) * | 2020-12-18 | 2022-06-21 | 沈阳化工研究院有限公司 | Method for preparing indigo white by fluidized bed catalytic hydrogenation |
| 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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| CN102516817B (en) | 2013-12-11 |
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