CN103509365A - Indigo blue oxidation filter cake post-treatment process - Google Patents
Indigo blue oxidation filter cake post-treatment process Download PDFInfo
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- CN103509365A CN103509365A CN201210211897.3A CN201210211897A CN103509365A CN 103509365 A CN103509365 A CN 103509365A CN 201210211897 A CN201210211897 A CN 201210211897A CN 103509365 A CN103509365 A CN 103509365A
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Abstract
The present invention relates to a new post-treatment process for an indigo blue oxidation filter cake obtained in an oxidation work section during an indigo blue dye production process. The process comprises that: an indigo blue oxidation filter cake in a plate frame with no washing or proper washing is taken out and placed into a stirring kettle; a proper amount of dilution water is poured; an acid substance is added while stirring to carry out a complete neutralization reaction, wherein the acid substance comprises four substances such as hydrogen chloride, sulfuric acid, phosphoric acid and carbon dioxide and concurrently comprises aqueous solutions of the four substances; and the neutralization reaction produces corresponding salts, and a filtration method is adopted to separate the salts and the indigo blue, wherein the indigo blue is slightly washed and is added to a finished product work section, the salts can be treated by adopting targeted methods according to the added different acids, hydroxides can be recovered from carbonates by adopting a causticization method, hydroxides can be recovered from chlorides by adopting an electrolysis method, and sulfates and phosphates can be sold after refinement. According to the invention, alkali consumption can be substantially reduced, an indigo blue yield can be increased, and the total amount of wastewater can be reduced.
Description
Technical field
The present invention relates to the indigo production technique of conventional dyes in fine chemistry industry.Be specifically related to the aftertreatment technology of indigo oxidation section gained filter cake.
Background technology
Indigo is a kind of traditional vat, molecular formula is C16H10O2N2, No. CAS is 482-89-3, is first with anilinoacetic acid potassium/sodium, potassium hydroxide, sodium amide reaction, to generate indolol potassium/sodium, then in dilute alkaline aqueous solution, uses air or oxygen oxidation to generate.Indigo oxidation filter cake described in the present invention just refers to that the indigo crude product that produces from the oxidation of indolol potassium/sodium obtains through press filtration.Because a large amount of potassium hydroxide and sodium hydroxide are contained in the indigo filter cake the inside of the sheet frame just having filtered the inside, these highly basic parts exist with unbound state, part is that the form with indigo title complex exists, the highly basic existing with free state is displacement and washing easily, and the highly basic existing with indigo title complex form is present in filter cake with solid phase form, in water, exist faint dissociation equilibrium, can only dissociate out gradually and then be dissolved in water, the result causing is exactly the very difficult neutrality of washing rapidly of alkalescence of indigo filter cake, the neutrality that approaches in order to ensure the finished product, need to add a large amount of fresh waters to wash, produced a large amount of alkaline waste waters simultaneously, one ton of indigo product of average production will produce 70 tons of alkaline waste waters, the title complex that contains a large amount of indigo and potassium hydroxide/sodium in these waste water.The waste water of discharge had both caused serious environmental pollution, had consumed again and had been worth very high potassium hydroxide/sodium, had reduced the yield of product simultaneously.The valuable material that annual domestic indigo industry emits, more than 200,000,000 yuan, is wasted extremely surprising.
For this incomplete traditional technology, need to form and a kind ofly can significantly reduce washing water consumption, can effectively reclaim or utilize the technique of the potassium hydroxide/sodium emitting simultaneously, author is through a large amount of experiment and theoretical investigation, adopt with the following method and achieve this end, directly with acidic substance, neutralize exactly the title complex of constitutionally stable indigo and potassium hydroxide/sodium, make indigoly can dissociate out, while potassium hydroxide/sodium changes into its corresponding potassium/sodium salt.After converting corresponding salt to, after filtering, obtain approaching neutral indigo filter cake, and the aqueous solution of corresponding salt, neutral indigo filter cake can directly go granulation, and the solution of relative salt can be processed targetedly for the sour difference of using.Wherein use carbonic acid gas can generate corresponding carbonate as the method for acidic substance, and we can use causticizing reaction, use exactly the reactant aqueous solution of calcium oxide and salt of wormwood/sodium, convert most of salt of wormwood/sodium wherein to potassium hydroxide/sodium, calcium oxide converts calcium carbonate to, and adjust as required extent of reaction, obtain needing containing the high highly basic of potassium, unnecessary sodium carbonate is because common-ion effcet can be by concentrated this solution, and first sodium carbonate can separate out and discharge system with the pattern of crystallization.Expensive potassium hydroxide can return to system.The calcination of calcium carbonate that causticizing reaction generates regenerates carbonic acid gas and calcium oxide cover and uses above in two-step reaction.Reasonably arrange reaction ratio and reaction conditions, can make whole energy consumption minimum, yield is the highest, just both can realize the recycled of most of potassium hydroxide/sodium, also can improve the yield of indigo product, and most waste water of system can have been removed, realize environmental protection and produced indigo object.The salt that reaction produces for other acidic substance also can be processed with diverse ways, some for example potassium/sodium just can make single salt of potassium/sodium or mixing salt for different client's direct marketings by ordinary method.Author is in the result of the literature survey to current, also do not find that associated class published like the document of content, and the understanding of domestic indigo enterprise is not seen to relevant implementation content yet.
Summary of the invention
Problem to be solved by this invention is to overcome the weak point of the indigo oxidation filter cake of traditional technology aftertreatment, and the step that adopts three cores designs the novel process of a kind of indigo oxidation filter cake aftertreatment, the potassium hydroxide slatterning in traditional technology/sodium is recycled, and significantly reduced discharge of wastewater.
The invention provides the novel process of a kind of indigo oxidation filter cake aftertreatment, indigo oxidation filter cake refers to the indigo oxidation filter cake that the outstanding mixed liquid that completes oxidizing reaction of oxidation section in the indigo production process of tradition is obtained by the direct press filtration of plate-and-frame filter press, also comprises and uses a small amount of water washing indigo oxidation filter cake later.
Novel process provided by the invention comprises: the first step first adopts ordinary method to take out from filter indigo oxidation filter cake, be placed in stirred autoclave, the dilution water that adds certain mass, under certain temperature and pressure condition, add appropriate acidic substance carry out neutralization reaction neutralization remaining free potassium hydroxide/sodium and the potassium hydroxide/sodium existing with title complex pattern wherein and generate corresponding salt.Second step finishes the rear use pressure filter solidliquid mixture in press filtration reactor again by neutralization reaction, the filtrate of the salt that obtains approaching neutral indigo filter cake and contain potassium/sodium, and use cover water to wash to filter cake, remaining salinity in filter cake is removed in washing, the washing water that concentration is low can be used as dilution water and apply mechanically next times, and filtrate is to next step processing.The 3rd step is sent to finished product workshop section by indigo filter cake and is removed drying-granulating, and the filtrate of containing salt can adopt diverse ways to carry out respectively aftertreatment according to the difference of the acidic substance that add.
The acidic substance that use in this technique comprise hydrogenchloride, sulfuric acid, phosphoric acid, these four kinds of materials of carbonic acid gas, also comprise this four kinds of material aqueous solution simultaneously.The salt generating by neutralization reaction comprises Repone K/sodium, potassium/sodium, sal enixum/sodium, potassiumphosphate/sodium, potassium hydrogen phosphate/sodium, potassium primary phosphate/sodium, salt of wormwood/sodium, saleratus/sodium.
For the technique of using carbonic acid gas, can Formed hydrochlorate, the present invention uses unslaked lime to carry out causticizing reaction by salt of wormwood/sodium for raw material, the reaction of saleratus/sodium obtains potassium hydroxide and sodium hydroxide solution reuse, then by the carbonic acid gas and the unslaked lime that obtain applying mechanically after the calcium carbonate solid calcining of causticizing reaction.
For the acidic substance that use, be the technique of hydrogenchloride or its aqueous solution, can generate Repone K/sodium, the present invention uses the method reaction of electrolysis that the solution of Repone K/sodium is prepared into potassium hydroxide/sodium, chlorine, hydrogen, after chlorine and hydrogen reaction, generate hydrogenchloride and apply mechanically, potassium hydroxide/sodium can directly be applied mechanically.
For the acidic substance that use, be the technique of sulfuric acid, phosphoric acid and the aqueous solution thereof, can generate potassium/sodium, sal enixum/sodium, potassiumphosphate/sodium, potassium hydrogen phosphate/sodium, potassium primary phosphate/sodium, post-treating method of the present invention is to use conventional method by potassium/sodium, sal enixum/sodium, potassiumphosphate/sodium, potassium hydrogen phosphate/sodium, potassium primary phosphate/sodium water solution is processed and is made single salt or mixing salt product.
Embodiment
Mode below by embodiment further illustrates this Technology, but present technique can not be limited in the scope of described embodiment.
Embodiment 1: get 1.86 kilograms of indigo oxidation filter cakes, add the dilution of 2000g water, under whipped state, the form with bubbling passes into 220 grams of carbonic acid gas gradually, and most of carbonic acid gas is absorbed, and discharges on a small quantity system.Again filter this reaction solution obtain in and filter cake and neutralization filtrate, get in 1000g water washing and filter cake, in obtaining and washings, in and washings preparation do dilution water next time and apply mechanically, after washing in and filter cake directly go to dry and granulation workshop section to process.In neutralization filtrate, add 340 grams of finely powdered unslaked limes, under reflux conditions abundant stirring reaction is 36 hours, filters and obtains causticization filter cake and causticization filtrate after completion of the reaction.Potassium hydroxide recovery per pass reaches more than 60%.The content of each component is listed in following table.
Embodiment 2: get 1.86 kilograms of indigo oxidation filter cakes, add the dilution of 2000g water, pass into gradually 280 grams of hydrogenchloride under whipped state.Again filter obtain in and filter cake and neutralization filtrate, get in 1000g water washing and filter cake, in obtaining and washings.The content of each component is listed in following table.Filtrate goes electrolysis to produce potassium hydroxide after can refining, recovery per pass is more than 80%.
Claims (7)
1. an indigo oxidation filter cake post-treating method, is characterized in that the method comprises the steps:
(1) adopt ordinary method to take out from filter indigo oxidation filter cake, be placed in stirred autoclave, the dilution water that adds certain mass, under certain temperature and pressure condition, add appropriate acidic substance to carry out wherein free potassium hydroxide/sodium and the potassium hydroxide/sodium existing with title complex pattern generate corresponding salt of neutralization reaction neutralization;
(2) neutralization reaction finishes the solidliquid mixture in rear use pressure filter press filtration reactor, the filtrate of the salt that obtains approaching neutral indigo filter cake and contain potassium/sodium, and use cover water to wash to filter cake, remaining salinity in filter cake is removed in washing, the washing water that concentration is low can be used as dilution water and apply mechanically next times, and filtrate is to next step processing;
(3) indigo filter cake is sent to finished product workshop section and remove drying-granulating, and the aqueous solution that contains salt can adopt diverse ways to carry out respectively aftertreatment according to the difference of the acidic substance that add.
2. in accordance with the method for claim 1, it is characterized in that described indigo oxidation filter cake refers to the indigo oxidation filter cake that the outstanding mixed liquid that completes oxidizing reaction of oxidation section in the indigo production process of tradition is obtained by the direct press filtration of plate-and-frame filter press, also comprises and uses a small amount of water washing indigo oxidation filter cake later.
3. in accordance with the method for claim 1, it is characterized in that described acidic substance comprise hydrogenchloride, sulfuric acid, phosphoric acid, these four kinds of materials of carbonic acid gas, also comprise this four kinds of material aqueous solution simultaneously.
4. in accordance with the method for claim 1, it is characterized in that the salt that neutralization reaction generates comprises Repone K/sodium, potassium/sodium, sal enixum/sodium, potassiumphosphate/sodium, potassium hydrogen phosphate/sodium, potassium primary phosphate/sodium, salt of wormwood/sodium, saleratus/sodium.
5. in accordance with the method for claim 1, its special card is that the recovery method of described salt and the aqueous solution thereof comprises and uses unslaked lime to carry out causticizing reaction by salt of wormwood/sodium for raw material, the reaction of saleratus/sodium obtains potassium hydroxide and sodium hydroxide solution reuse, then by the carbonic acid gas and the unslaked lime that obtain applying mechanically after the calcium carbonate solid calcining of causticizing reaction.
6. in accordance with the method for claim 1, salt described in its special card is and the recovery method of the aqueous solution thereof comprise uses the method reaction of electrolysis that the solution of Repone K/sodium is prepared into potassium hydroxide/sodium, chlorine, hydrogen, after chlorine and hydrogen reaction, generate hydrogenchloride and apply mechanically, potassium hydroxide/sodium can directly be applied mechanically.
7. in accordance with the method for claim 1, its special card is that the post-treating method of described salts solution comprises potassium/sodium, sal enixum/sodium, potassiumphosphate/sodium, potassium hydrogen phosphate/sodium, potassium primary phosphate/sodium water solution is processed and is made single salt or mixing salt product by ordinary method.
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| CN201210211897.3A CN103509365A (en) | 2012-06-21 | 2012-06-21 | Indigo blue oxidation filter cake post-treatment process |
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| CN201210211897.3A CN103509365A (en) | 2012-06-21 | 2012-06-21 | Indigo blue oxidation filter cake post-treatment process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106975483A (en) * | 2017-05-05 | 2017-07-25 | 南京工业大学 | A kind of indigo hydrogenation synthesis hydrogenates indigo catalyst, its preparation method and application |
| CN109735863A (en) * | 2019-01-29 | 2019-05-10 | 陕西华秦新能源科技有限责任公司 | A kind of water electrolysis hydrogen producing electrolytic cell and design method |
-
2012
- 2012-06-21 CN CN201210211897.3A patent/CN103509365A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106975483A (en) * | 2017-05-05 | 2017-07-25 | 南京工业大学 | A kind of indigo hydrogenation synthesis hydrogenates indigo catalyst, its preparation method and application |
| CN109735863A (en) * | 2019-01-29 | 2019-05-10 | 陕西华秦新能源科技有限责任公司 | A kind of water electrolysis hydrogen producing electrolytic cell and design method |
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Application publication date: 20140115 |