CN102924957A - New tower type oxidation technology for indigo blue - Google Patents
New tower type oxidation technology for indigo blue Download PDFInfo
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- CN102924957A CN102924957A CN201110226836XA CN201110226836A CN102924957A CN 102924957 A CN102924957 A CN 102924957A CN 201110226836X A CN201110226836X A CN 201110226836XA CN 201110226836 A CN201110226836 A CN 201110226836A CN 102924957 A CN102924957 A CN 102924957A
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Abstract
The present invention relates to a new technology for direct oxidation of a 3-indoxyl salt into indigo blue in a novel efficient ultrasonic circulation type reactor by using air or oxygen-containing gas. According to the present invention, the new technology and the new equipment are combined, such that concentration of the existing oxide material can be substantially increased, yield and purity of the reaction can be ensured well, significant effects of energy saving and consumption reduction are provided, and indigo production with characteristics of large scale, continuality and automation can be achieved.
Description
Technical field
The present invention relates to a kind of new technology of utilizing the novel tower-type reactor to substitute indigo traditional tank reactor high-level efficiency synthesizing indigo under the high-alkalinity condition, this technology has significant energy-saving and cost-reducing, lifting quality effect, can realize maximization, serialization and the automatization of indigo production.
Background technology
Indigo is a kind of vat dyes, is widely used in the cellulose textiles such as cotton, fiber crops painted, the especially fine gauze of indigo jean goods dyeing.
Factory is many at present prepares indigo via the oxidation of 3-indoles phenates, comprising the mixed base reaction under 220～250 ℃ by anilino-acetate, sodium amide and sodium hydroxide and potassium hydroxide, obtain the alkali fusion thing of 24～30% 3-indoles phenates, this alkali fusion thing is put into water to be made into and to contain 3-indoles phenates 5%, the solution of indistinct alkali about 12% is at 30m
3The oxidation of blowing air bubbling is after 2 hours in the stills for air blowing, again through press filtration, washing, pickling, drying and granulation obtain content be about 95% indigo.The method is owing to can constantly have water-fast indigo being precipitated out in oxidising process, constantly absorption and encapsulation reaction raw material 3-indoles phenates, cause reacting not exclusively, the oxygen utilization rate low reaction not exclusively, when easily blue water, oven dry occurring when long reaction time, washing raw material 3-indolol salinity depolymerize, the problem such as the indigo yield of many impacts and quality such as how of the flocculent precipitate in the product reduced liquid.
To such gas-liquid-solid three-phase system, effectively mass transfer is the key of the indigo oxidizing reaction of impact.Existing still reaction model exists the gas distribution inequality, air utilization ratio is low, easy foaming long reaction time, react not thorough, product causes greatly washing loss large to the absorption parcel of raw material and alkali, the concentration of oxidation sig water can only reach about 12%, be condensed into solid caustic soda and need to consume a large amount of heats and the large evaporation equipment of configuration process amount, the concentration that improves alkali can cause reaction more incomplete, product yield and purity are poorer, solve the above-mentioned engineering problem of indigo oxidizing process, must consider novel efficient mass transfer apparatus, having developed of our success is efficient, the energy-conservation tower loop reactor (patent No.: 200810173635.6), this reactor is all to embody good effect at intermittent reaction or in continuous reaction, and the efficient mass transfer tower of this macroscopic view is strengthened the reactor that intermolecular disperse phase is combined on microcosmic be maximum bright spot of the present invention.200610086498.3) and the novel technique for preparing fine calcium carbonate (patent No.: obtained good effect 200710098833.6) in a kind of novel process of the preparing glyphosate by oxidizing N-Phosphonomethyl iminodiacetic acid in air (patent No.:, this novel tower-type circulating reactor has efficiently, energy-conservationly can effectively improve the mass-and heat-transfer effect, be particularly suitable for the gas-liquid-solid three-phase system, reactant gases can well contact with liquid material through the first distribution of gas distributor, greatly improved effective contact area of material, gas imports the difference in specific gravity that produces, and can drive whole feed liquid quick circulation in reactor.The dispersion that gas, solid have further been strengthened in ultrasonic introducing can effectively prevent from poly-ly also helping air to indigo middle absorption material diffusion, also is conducive to be adsorbed on the solubility 3-indoles phenates stripping in indigo, improves alternate mass-and heat-transfer.The novel tower-type conversion unit can better be realized the strong turbulence of gas-to-liquid contact and material, well solves the technical barrier that exists in the existing technique.It is higher than the mass-and heat-transfer efficient of the reactors such as fixed bed, fluidized-bed and bubble tower, be easy to amplify, power consumption is lacked.
High efficiency reactor is applied to oxidation production indigo, in conjunction with indigo process characteristic, the indigo synthetic technology of exploitation in new equipment may be the effective ways that effectively solve variety of issue in the existing autoclave oxidizing process technology.The present invention just is being based on this working foundation and thinking, and we have developed indigo new synthesis technology, and details is as follows:
Summary of the invention
The purpose of this invention is to provide a kind of highly effective reaction device that effectively is combined to form that utilizes sonic generator and loop reactor air or oxygen-containing gas and the oxidation of 3-indoles phenates are produced indigo method.
Specifically, its key step of preparation method of the present invention is:
The mixing solutions of 3-indoles phenates and water reacts under ul-trasonic irradiation at a certain temperature, utilize observation to ooze the oxidation situation of circle color and the method tracking 3-indoles phenates of changing minute analysis indigo filter, when treating that filter paper oozes circle outside color water white transparency, stop oxidation, the analysis of indigo filter is carried out in sampling, analyze up to standard after, reaction mass is filtered, isolate product indigo.
The present invention a kind ofly prepares indigo method with air or oxygen-containing gas direct oxidation 3-indoles phenates, and feature is to prepare indigo with ultrasonic wave and circulation tower reactor co-oxidation 3-indoles phenates.The present invention equips the tower reactor of built-in gas distributor, guide shell, ultrasonic generator and plug-in condenser that refers to have the liquid circulation feature of the circulation tower reactor of ultrasonic generator.The outer circulation of reactor can be active cycle and passive circulation among the present invention, and preferred active cycle is namely used the pump pump circulation.Active cycle is conducive to utilize external heat exchanger to carry out heat exchange, also helps liquid circulation, has strengthened liquid mass transfer and heat transfer.See accompanying drawing 1 for details.
The ultrasonic wave of using in the reaction can be caused by the hyperacoustic equipment of initiation by any, and ultrasonic wave is delivered to reaction system by the solid-liquid medium, and its general frequency is greater than 15KHz.
This novel tower-type reactor can be fit to the material of very wide alkali concn scope, production test shows in the situation of 3 times of traditional reaction base concentration raisings, the yield of product, quality reach or are better than the traditional technology level, reaction efficiency improves, can reduce required time of oxidation and temperature, the alkali concn that oxidation generates after indigo can reach about 40%, can reduce in the buck concentration process steam consumption more than 2/3.Concrete processing condition are as follows: the add-on of water or buck is about 4 times of 3-indoles phenates weight, and the alkali concn in the reaction mass is the highest can to reach 60%, is preferably 30%-50%; Temperature in the oxidising process is 40～90 ℃, and the degree in the indigo oxidising process is 40～90 ℃, is preferably 55～65 ℃, also can make 60～65 ℃ of temperature of reaction in early stage, and latter temperature is 55～60 ℃; Oxidization time is 40～250min, and oxidative pressure is 0～1.0Mp, is preferably 0～0.5Mp.Oxidizing reaction mode among the present invention can be for also can be intermittent reaction continuously.
Figure of description
Accompanying drawing 1 is the circulation tower reactor figure of equipment ultrasonic generator, and it comprises the parts such as tower body 1, diversing bucket 2, interchanger 3, gas distributor 4 and ultrasonic generator 5, and tower body is provided with discharge port 6, inlet mouth 7, drain 8 and opening for feed 9.
Embodiment
Control experiment
The 2T alkali fusion material put into be added with 8m
3Tap water is done in the oxidation tank of end water after the dissolving (alkali concn is 10%, and temperature is 71.6 ℃), passes into air in oxidation tank, keeping the interior temperature of charge of reactor is 68～70 ℃, behind the reaction 120min, arrives reaction end, after reaction mass filtration, washing, obtain indigo product.Indigo filter value is 4.3g/L in the filtrate, and carbonate content is 15.36g/L, and basicity is 21%, and content is 95.5% after the indigo oven dry, and moisture is 0.42%, and iron ion is 88ppm.
Embodiment 1
This tests employed ultrasonic generator frequency is 25KHz, and power is 100W.
200g alkali fusion thing is joined dissolving rear (temperature is 71.6 ℃) in the 800g water, material is transferred in the airlift reactor, open ultrasonic, in reactor, pass into air, keeping the interior temperature of charge of reactor is 68～72 ℃, reacts 3 hours, arrives reaction end, after reaction mass filtration, washing, obtain indigo product.Indigo filter value is 3.0g/L in the filtrate, and carbonate content is 13.2g/L, and basicity is 15%, and content is 95.6% after the indigo oven dry, and moisture is 0.40%, and iron ion is 86ppm.
Embodiment 2
This tests employed ultrasonic generator frequency is 25KHz, and power is 100W.
200g alkali fusion thing is joined (alkali concn is 25% after the dissolving in the buck (alkali concn is 15%) of 800g experiment one, temperature is 75.6 ℃), material is transferred in the airlift reactor, opened ultrasonicly, in reactor, pass into air, keeping the interior temperature of charge of reactor is 68～72 ℃, pressure is 0.15Mp, reacts 5 hours, arrives reaction end, after reaction mass filtration, washing, obtain indigo product.Indigo filter value is 5.4g/L in the filtrate, and carbonate content is 21.3g/L, and basicity is 36%, and content is 95.1% after the indigo oven dry, and moisture is 0.38%, and iron ion is 114ppm.
Embodiment 3
This tests employed ultrasonic generator frequency is 25KHz, and power is 100W.
(alkali concn was 25% after 400g alkali fusion thing joined in the 800g water dissolving, temperature is 80.6 ℃), material is transferred in the airlift reactor, opened ultrasonicly, in reactor, pass into air, keeping the interior temperature of charge of reactor is 68～72 ℃, pressure is 0.15Mp, reacts 6 hours, arrives reaction end, after reaction mass filtration, washing, obtain indigo product.Indigo filter value is 4.8g/L in the filtrate, and carbonate content is 18.2g/L, and basicity is 38%, and content is 95.3% after the indigo oven dry, and moisture is 0.42%, and iron ion is 109ppm.
Embodiment 4
This tests employed ultrasonic generator frequency is 25KHz, and power is 100W.
The 2T alkali fusion material put into be added with 8m
3Tap water does that (alkali concn is 15% after the dissolving in the oxidation tank of end water, temperature is 70.6 ℃), to air lift type reflux oxidation tower, open ultrasonicly material pumping, in reactor, pass into air, keeping the interior temperature of charge of reactor is 68～70 ℃, pressure is 0.2Mp, behind the reaction 110min, arrives reaction end, after reaction mass filtration, washing, obtain indigo product.Indigo filter value is 4.6g/L in the filtrate, and carbonate content is 14.76g/L, and basicity is 24%, and content is 96.0% after the indigo oven dry, and moisture is 0.40%, and iron ion is for detecting.
Embodiment 5
This tests employed ultrasonic generator frequency is 25KHz, and power is 100W.
The 2T alkali fusion material put into be added with 8m
3Buck (alkali concn is 15%) does that (alkali concn is 25% after the dissolving in the oxidation tank of end water, temperature is 84.1 ℃), with material pumping to air lift type reflux oxidation tower, open ultrasonic, in reactor, pass into air, reacting the front 1 hour interior temperature of charge of maintenance reactor is 60～65 ℃, pressure is 0.15Mp, react after 1 hour, keeping the interior temperature of charge of reactor is 55～60 ℃, and pressure is 0.15Mp, arrives reaction end behind the 30min, after reaction mass filtration, washing, obtain indigo product.Indigo filter value is 6.8g/L in the filtrate, and carbonate content is 20.38g/L, and basicity is 32%, and content is 96.58% after the indigo oven dry, and moisture is 0.60%, and iron ion is 79ppm.
This tests employed ultrasonic generator frequency is 25KHz, and power is 100W.
The 2T alkali fusion material put into be added with 8m
3Buck (alkali concn is 32%) does that (alkali concn is 45% after the dissolving in the oxidation tank of end water, temperature is 94.1 ℃), with material pumping to air lift type reflux oxidation tower, open ultrasonic, in reactor, pass into air, reacting the front 1 hour interior temperature of charge of maintenance reactor is 60～65 ℃, pressure is 0.25Mp, react after 1 hour, keeping the interior temperature of charge of reactor is 55～60 ℃, and pressure is 0.15Mp, arrives reaction end behind the 30min, after reaction mass filtration, washing, obtain indigo product.Indigo filter value is 7.5g/L in the filtrate, and carbonate content is 27.84g/L, and basicity is 50%, and content is 95.56% after the indigo oven dry, and moisture is 0.90%, and iron ion is 114ppm, and particle diameter is 0.43 μ m.
Claims (8)
1. one kind is utilized air or oxygen-containing gas that 3-indoles phenates is direct oxidation into indigo method in new and effective ultrasonic recirculating-type reactor, it is characterized in that utilizing Efficient Ring streaming reactor, under certain material concentration, temperature, pressure and time conditions, utilize air or oxygen-containing gas that 3-indoles phenates is direct oxidation into indigo, the oxidizing reaction mode can be for also can be intermittent reaction continuously.
2. method according to claim 1, wherein, reactor be built-in ultra-sonic generator tank reactor, have the external ultrasonic producer of cycle specificity tubular type or tower reactor, have the built-in of cycle specificity or external ultrasonic reactor.
3. method according to claim 1, wherein, ultrasonic can be external also can be built-in, can be according to circumstances few with or need not.
4. method according to claim 1, wherein, the gas distribution mode can be that gas distribution makes therefrom mind-set cylinder outside circulation of reaction mass in guide shell, also can make reaction mass from the export-oriented guide shell internal recycle of cylinder by gas distribution outside guide shell, but also dual mode alternately adopts.
5. method according to claim 1, wherein, reaction system adds water or the buck amount can be adjusted as required, and minimum can be 1/4 of existing technique, alkali concn in the reaction mass is the highest can be reached for 60%, and material concentration is the highest can be reached more than 10%.
6. method according to claim 1, wherein, the temperature in the indigo oxidising process is 40～90 ℃, also can make 60～65 ℃ of temperature of reaction in early stage, latter temperature is 55～60 ℃.
7. method according to claim 1, wherein, pressure is 0～1.0Mp in the oxidising process.
8. method according to claim 1, wherein, reactive mode is continuously or intermittent reaction.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB190109774A (en) * | 1901-05-10 | 1902-04-17 | James Yate Johnson | The Manufacture and Production of Acylated Derivatives belonging to the Indigo Group. |
| US4283198A (en) * | 1980-01-11 | 1981-08-11 | Fletcher John M | Inert atmosphere indigo dyeing |
| US6767448B1 (en) * | 1999-04-29 | 2004-07-27 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Method for producing aqueous alkaline solutions or reduced indigoid dyes |
| ES2244310A1 (en) * | 2004-02-03 | 2005-12-01 | Universidad De Oviedo | Oxidised phosphate based substrate of peroxidases comprsies a generator of indigo blue based on indoxyl phosphate |
| JP2009197353A (en) * | 2008-02-20 | 2009-09-03 | Asahi Breweries Ltd | Enhancer for indigo dyeing and enhancing method |
| CN101590385A (en) * | 2008-05-28 | 2009-12-02 | 北京紫光英力化工技术有限公司 | A kind of efficient ultrasonic recirculating-type reaction device |
| CN101591476A (en) * | 2009-04-23 | 2009-12-02 | 江苏泰丰化工有限公司 | A kind of preparation method of continuous oxidation synthesizing indigo |
-
2011
- 2011-08-09 CN CN201110226836.XA patent/CN102924957B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB190109774A (en) * | 1901-05-10 | 1902-04-17 | James Yate Johnson | The Manufacture and Production of Acylated Derivatives belonging to the Indigo Group. |
| US4283198A (en) * | 1980-01-11 | 1981-08-11 | Fletcher John M | Inert atmosphere indigo dyeing |
| US6767448B1 (en) * | 1999-04-29 | 2004-07-27 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Method for producing aqueous alkaline solutions or reduced indigoid dyes |
| ES2244310A1 (en) * | 2004-02-03 | 2005-12-01 | Universidad De Oviedo | Oxidised phosphate based substrate of peroxidases comprsies a generator of indigo blue based on indoxyl phosphate |
| JP2009197353A (en) * | 2008-02-20 | 2009-09-03 | Asahi Breweries Ltd | Enhancer for indigo dyeing and enhancing method |
| CN101590385A (en) * | 2008-05-28 | 2009-12-02 | 北京紫光英力化工技术有限公司 | A kind of efficient ultrasonic recirculating-type reaction device |
| CN101591476A (en) * | 2009-04-23 | 2009-12-02 | 江苏泰丰化工有限公司 | A kind of preparation method of continuous oxidation synthesizing indigo |
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