CN102924956B - Recovery, balance adjustment and comprehensive utilization technology for mixing alkali in indigo blue production - Google Patents
Recovery, balance adjustment and comprehensive utilization technology for mixing alkali in indigo blue production Download PDFInfo
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- CN102924956B CN102924956B CN201110226829.XA CN201110226829A CN102924956B CN 102924956 B CN102924956 B CN 102924956B CN 201110226829 A CN201110226829 A CN 201110226829A CN 102924956 B CN102924956 B CN 102924956B
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- alkalinity
- mixed alkali
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- 239000003513 alkali Substances 0.000 title claims abstract description 42
- COHYTHOBJLSHDF-UHFFFAOYSA-N Indigo Chemical compound N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000011084 recovery Methods 0.000 title claims abstract description 9
- 238000002156 mixing Methods 0.000 title abstract description 4
- 238000005516 engineering process Methods 0.000 title description 5
- 239000011734 sodium Substances 0.000 claims abstract description 95
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 76
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 50
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 25
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 15
- 239000012141 concentrate Substances 0.000 claims abstract description 5
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 20
- 229940097275 indigo Drugs 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 239000012452 mother liquor Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims 3
- 229910001414 potassium ion Inorganic materials 0.000 claims 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims 2
- 239000001099 ammonium carbonate Substances 0.000 claims 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000009993 causticizing Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 239000003546 flue gas Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000005457 ice water Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 abstract description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 16
- 239000011591 potassium Substances 0.000 abstract description 16
- 238000005406 washing Methods 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 55
- 239000000706 filtrate Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- 239000000984 vat dye Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000565357 Fraxinus nigra Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BJKZXRGDVGYJTP-UHFFFAOYSA-N anilino acetate Chemical compound CC(=O)ONC1=CC=CC=C1 BJKZXRGDVGYJTP-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010850 salt effect Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Detergent Compositions (AREA)
Abstract
A purpose of the invention is to achieve sodium reduction, potassium retention, and no use or less use of potassium hydroxide based on recovery utilization of mixing alkali and potassium-sodium balance adjustment in an indigo blue production process. According to the present invention, waste alkali residue, washing alkali water and surplus sodium hydroxide in oxidation alkali in the existing production are utilized, bicarbonate or carbon dioxide, and a plurality of ways are applied and introduced to the concentrate, and difference between dissolubility of sodium carbonate and potassium carbonate and a common ion effect are delicately utilized to generate sodium carbonate precipitate and separate, such that removal of surplus sodium hydroxide in the liquid alkali is achieved without introduction of new impurities, the sodium carbonate product is co-produced, about 0.5 ton of the potassium hydroxide is saved and about 1 ton of the sodium carbonate is by-produced when per ton of the indigo blue product is produced, and a new process route with characteristics of alkali resource comprehensive utilization and delicate potassium and sodium balance is developed. With the present invention, characteristics of low investment, resource saving, cleaning, environmental protection, economy, novelty, strong practicality and wide generalization application value are provided, significant theory and application values are provided for the circular economy and sustainable development strategy, and wide social benefits, economic benefits and ecological benefits are provided.
Description
Technical field
The invention belongs to dye chemical industry raw material production field, for indigo, wait cleaning of vat dyes to produce and comprehensive utilization of resources technology.
Background technology
Indigo is a kind of environmental protection, time-honored primary colour dye, is widely used in the fabric colorings such as cotton, fiber crops and viscose glue, and especially aspect the warp dyeing of indigo jean, consumption is very large.
Current industrial production is all indigo via 3-indoles phenates oxidation preparation, wherein reaction process comprises a certain amount of anilino-acetate, sodium amide and sodium hydroxide is reacted at 220～250 ℃ with the mixed base of potassium hydroxide, obtain the alkali fusion thing of 20～30% 3-indoles phenates, this alkali fusion thing is dissolved in large water gaging, after blowing air oxidation, then obtain indigo through press filtration, washing, granulation.
In oxidation sig water, the mol ratio of KOH and NaOH is 0.6: 1 left and right, ratio far below 1: 1 left and right of production requirement, potassium sodium compares serious unbalance, for this reason, existing indigo production technique is all the method adopting to adding potassium hydroxide in mixed base, regulate potassium sodium ratio, due to per ton, indigoly need to add 440～450kg metal sodium production sodium amide, finally be converted into sodium hydroxide, cause sodium hydroxide excessive, the potassium hydroxide of having to again add about 500kg is adjusted potassium sodium ratio simultaneously, causes alkali number more more than needed.A part for alkali more than needed is by airborne carbonic acid gas and form alkaline residue, a part is washed after indigo carrying secretly forms diluted alkaline water in water, finally by sulfuric acid and rear discharge, oxidation diluted alkaline more than needed there is no good outlet, alkali is arbitrarily processed or is sold at a bargain, and wherein valuable potassium is failed fine utilization.Current mixed base Cycling And Utilizing Patterns has not only caused the huge waste of potassium resource, and there is no the fine potassium that utilizes shortage of resources, and the indigo mixed base that has 6000 yuan of left and right per ton is worth and could not realizes, and has greatly increased indigo production cost.
Visible, existing indigo production technique is also undesirable aspect the recycling of mixed base, particularly potassium hydroxide consumption is high starting material, alkaline residue, buck, mixed base more than needed are failed the problems such as fine utilization, production cost height, not only can cause impact, the waste of resource and increasing of processing costs on environment, and it's a pity a large amount of consumption and wasted the potassium resource of rare preciousness most, the profit of enterprise self is not high yet.
Due to indigo, wait in vat dyes production process, capital usually utilizes mixed base as the solvent in alkali fusion condensation reaction, in recovery process, exist " the few potassium of rich sodium ", need additional potassium hydroxide, with balance potassium sodium ratio, cause mixed base more than needed, exist diluted alkaline water and alkaline residue to fail the Universal Problems of recycling simultaneously.
Reducing the charging capacity of potassium hydroxide, fully utilize mixed base, rationally regulate the potassium-sodium balance in mixed base, is emphasis and a difficult problem of tackling key problems for many years in the product lines such as indigotin, there is no so far good solution.
For potassium sodium in existing production, compare serious unbalance, potassium resource is not fully used, this situation of serious waste of resources, therefore, the mode that excessive sodium hydroxide in mixed base is precipitated by salify is separated and is used, reclaim as far as possible the mixed base in washing water and alkaline residue, allowing valuable potassium hydroxide preserve as far as possible and to get back in alkali systems is our main direction.
The present invention is directed to the problems referred to above, we have adopted the opposition thinking of " fall sodium and stay potassium ", by technique and engineering, guarantee as far as possible the recycling of diluted alkaline water and alkaline residue, utilized cleverly the significant difference of sodium carbonate and salt of wormwood solubleness, by making the way of sodium carbonate Precipitation, reach easy, the low-cost potassium-sodium balance that regulates, realized and recycle alkali more than needed, used no or little the object of potassium hydroxide.
Summary of the invention
The inventor, by the comparative analysis to the dissolubility data of each potassium, sodium salt, finds Na
2cO
3solubleness compare K
2cO
3much smaller, while spending in 0 degree～30, Na
2cO
3the K that only has of solubleness
2cO
31/15～1/5, by further test, also find that the common-ion effcet of sodium can also further reduce Na
2cO
3solubleness, temperature is little on its impact.If pass into CO in shortage toward mixing in buck
2or stack gas should preferentially form with the NaOH mixing in buck the Na that solubleness is lower
2cO
3, by temperature, regulate and common-ion effcet, can be easily early stage direct crystallization separate out sodium carbonate, a small amount of carbonate can further be separated out in later stage concentrated.Can form the mixed base that meets production requirement completely by existing processing requirement acquisition potassium, sodium, realize the easy adjusting of potassium sodium ratio.
Based on above-mentioned thinking, the inventor is through repeatedly the groping of lab scale, and completed a separate part NaOH from be rich in the mixed alkali liquor of NaOH and KOH, thereby reached the invention that regulates the simple and easy to do method of potassium sodium ratio in alkali lye.Its flow process is in alkali lye, to add supercarbonate (as bicarbonate of ammonia, sodium bicarbonate), CO
2or stack gas, utilizes Na
2cO
3with K
2cO
3in water, the remarkable difference of solubleness and common-ion effcet and salt effect, make Na
2cO
3preferential precipitation is separated, thereby reaches the object that regulates potassium sodium ratio.
The inventor, by experimental exploring and condition optimizing repeatedly, has proved economy, novelty, the practicality of this method.This method can be well combined with filter progress except alkaline residue, washing with existing, and not increase, does not introduce new impurity, is the new technology route of a best adjusting potassium sodium ratio.
The inventive method can adopt following specific embodiments:
1. a short-cut method that regulates potassium sodium ratio in mixed alkali liquor, it comprises the steps:
In the certain density mixed base aqueous solution, add bicarbonate of ammonia, the sodium bicarbonate of proportional quantity or pass into appropriate CO
2or stack gas reacts, NaOH is changed into Na
2cO
3, limit coronite stirs, and temperature of reaction is at 15～100 ℃, and preferably reaction (70 ℃ of left and right) at the temperature of factory's two effect evaporated liquors, has reacted rear cooling, stirring, crystallization, and then filtered while hot, obtains Na
2cO
3crude product and process after mother liquor, mother liquor is got back to the original vapo(u)rization system of factory and is directly condensed into mixed base and applies mechanically, Na
2cO
3crude product is prepared NaOH through saturated aqueous sodium carbonate washing through causticization and is reclaimed alkali, also can be directly as commodity Na
2cO
3take out; Saturated sodium carbonate solution after washing, mainly contains potassium hydroxide and sodium hydroxide and salt of wormwood, can time use wash, until sodium carbonate non-conformity of quality closes while requiring, can concentrate separately or be inserted in mixed base, carries out potassium-sodium balance adjusting.
In preferred specific embodiments, technique of the present invention comprises the steps:
In the certain density mixed base aqueous solution, add bicarbonate of ammonia or the sodium bicarbonate of proportional quantity or pass into appropriate CO
2or stack gas reacts, limit coronite stirs, and temperature of reaction is at 15～100 ℃, preferably reaction (70 ℃ of left and right) at the temperature of factory's two effect evaporated liquors, has reacted rear stirred crystallization, and Tc is 0～80 ℃, preferably, at 0～10 ℃, then filtered while hot, obtains Na
2cO
3crude product and process after mother liquor, mother liquor is got back to the original vapo(u)rization system of factory and is directly condensed into mixed base and applies mechanically, Na
2cO
3crude product, through saturated aqueous sodium carbonate washing, is prepared NaOH through causticization and is reclaimed alkali, also can be directly as commodity Na
2cO
3take out.Saturated sodium carbonate solution after washing can concentrate separately or be inserted in mixed base, carries out potassium-sodium balance adjusting.
Adopt the Na in the separated alkali lye of the inventive method
2cO
3, the potassium sodium ratio in regulator solution, has investment very little, substantially can utilize existing most facilities, with " giving up ", control the feature of " giving up ", Benefit, not only can make potassium substantially realize complete recovery, and can also be formed with the sodium product of value.Can realize and substantially not consume potassium hydroxide, can also the coproduction huge market demand, the good sodium carbonate of profit or the target of sodium hydroxide product.
Technique of the present invention has the feature of less investment, instant effect, energy-efficient, clean environment firendly, economy, novelty, practical, this method can be well combined with filter progress except alkaline residue, washing with existing, and not increasing, do not introduce new impurity, is the new technology route of a best adjustment potassium sodium ratio.There is extensively huge application value, for indigo and other vat produce in sodium carbonate or the sodium hydroxide of rationally the applying mechanically of mixed base, coproduction high added value, few with or without potassium hydroxide, founded new method.
Embodiment
The present invention can be further described with indefiniteness embodiment hereinafter.
1 70 ℃ of crystallization experiments of embodiment
Take triple effect concentrated solution (mixed base) 200.00g (K/Na=0.62: 1, CO
3 2-=15.54g/L, basicity (mixed base)=692.41g/L), in mixed base, pass into 15.00g CO
2, the Na of adularescent at once
2cO
3generate, and heat release is obvious, along with CO
2constantly pass into, crystallization increases, when being reacted to CO
2after the amount of the appointment passing into, temperature of reaction has reached 62 ℃ of left and right, stops CO
2pass into, 70 ℃ of insulations, continue to stir 2 hours, sufficient crystallising and cooling after, heat filtering, obtains mother liquor 154.00g (K/Na=1.08, CO
3 2-=41.45g/L, basicity (mixed base)=446.99g/L, potassium content 3.82%) and crude product Na
2cO
338.79g (K/Na=0, CO
3 2-=51.03g/L, basicity (mixed base)=7.53%).
(20 ℃) crystallization experiment under embodiment 2 room temperatures
Take triple effect concentrated solution 200.00g (K/Na=0.62: 1, CO
3 2-=15.54g/L, basicity (mixed base)=692.41g/L), in mixed base, pass into 15.00g CO
2, the Na of adularescent at once
2cO
3generate, and heat release is obvious, along with CO
2constantly pass into, crystallization increases, when being reacted to CO
2after the amount of the appointment passing into, temperature of reaction has reached 62 ℃ of left and right, stops CO
2pass into, be cooled to room temperature, stir 2 hours sufficient crystallisings, filter, obtain mother liquor 155.00g (K/Na=1.08: 1, CO
3 2-=41.93g/L, basicity (mixed base)=442.59g/L, potassium content 3.82%) and crude product Na
2cO
336.40g (K/Na=0, CO
3 2-=51.63g/L, basicity (mixed base)=6.51%).
(0 ℃) crystallization experiment under embodiment 3 room temperatures
Take triple effect concentrated solution 200.00g (K/Na=0.62: 1, CO
3 2-=15.54g/L, basicity (mixed base)=692.41g/L), in mixed base, pass into 15.00g CO
2, the Na of adularescent at once
2cO
3generate, and heat release is obvious, along with CO
2constantly pass into, crystallization increases, when being reacted to CO
2after the amount of the appointment passing into, temperature of reaction has reached 62 ℃ of left and right, stops CO
2pass into, place in frozen water coolingly, stirs 2 hours sufficient crystallisings, filtration, obtains mother liquor 154.00g (K/Na=1.08: 1, CO
3 2-=43.22g/L, basicity (mixed base)=444.76g/L, potassium content 3.81%) and crude product Na
2cO
335.40g (K/Na=0, CO
3 2-=50.76g/L, basicity (mixed base)=49.50%).
Implementation column 4
Take triple effect concentrated solution 200.00g (K/Na=0.62: 1, CO
3 2-=15.54g/L, basicity (mixed base)=692.41g/L), in mixed base, pass into 11.25g CO
2, the Na of adularescent at once
2cO
3generate, and heat release is obvious, along with CO
2constantly pass into, crystallization increases, when being reacted to CO
2after the amount of the appointment passing into, temperature of reaction has reached 62 ℃ of left and right, stops CO
2pass into, 70 ℃ of insulations, continue to stir 2 hours, sufficient crystallising and cooling after, heat filtering, obtains mother liquor 162.00g (K/Na=0.96: 1, CO
3 2-=23.96g/L, basicity (mixed base)=511.75g/L, potassium content 4.37%) and crude product Na
2cO
329.49g (K/Na=0, CO
3 2-=50.42g/L, basicity (mixed base)=6.51%).
Embodiment 5
Take triple effect concentrated solution 400.00g (K/Na=0.62: 1, CO
3 2-=15.54g/L, basicity (mixed base)=692.41g/L), in mixed base, pass into 70.00g CO
2, the Na of adularescent at once
2cO
3generate, and heat release is obvious, along with CO
2constantly pass into, crystallization increases, when being reacted to CO
2after the amount of the appointment passing into, temperature of reaction has reached 64 ℃ of left and right, stops CO
2pass into, filtered while hot, obtains mother liquor 255.00g (K/Na=1.22: 1, CO
3 2-=154.21g/L, basicity (mixed base)=209.15g/L) and crude product Na
2cO
392.58g (K/Na=0, CO
3 2-=52.91g/L, basicity (mixed base)=6.72%).
Embodiment 6
Get 100g unwashed indigo after filter press in producing, add the washing of pulling an oar of 500g water, obtain 510g washing water (K/Na=0.85, CO
3 2-=0.22%, basicity (mixed base)=4.36%).Get the above-mentioned wash water of 150g, in wash water, add 210g alkaline residue (K/Na=0.68, CO
3 2-=13.29%, basicity (mixed base)=33.65%), be stirred to alkaline residue and dissolve completely, allow solution naturally be down to room temperature and filter, obtain 305g filtrate (K/Na=0.71, CO
3 2-=6.52%L, basicity (mixed base)=22.00%) and 60g solid (K/Na=0.42, CO
3 2-=18.81%, basicity (mixed base)=11.38%), solid and filtrate are washed respectively and are concentrated.The saturated Na of 100ml for a
2cO
3in washing, step solid, obtains 8.59g over dry Na
2cO
3g solid, analyzes Na
2cO
3content is 99.07%.
B is concentrated by upper step filtrate heating, is condensed into 52% alkali (K/Na=0.97, CO
3 2-=0.83%, basicity (mixed base)=52.35%), the saturated Na of 100ml for the solid obtaining
2cO
3washing, obtains 18.9g content and is 99.20% Na
2cO
3finished product.
Embodiment 7
Toward triple effect concentrated solution 5T (K/Na=0.97: 1, CO is housed
3 2-=30g/L, basicity (mixed base)=562.41g/L) in still, pass into stack gas CO
2, the Na of adularescent at once
2cO
3generate, and heat release is obvious, along with CO
2constantly pass into, crystallization increases, when potassium sodium stops passing into of stack gas than after reaching required standard, filter press, K/Na=1.06 in filtrate: 1, CO
3 2-=35.23g/L, basicity (mixed base)=555.37g/L, obtains crude product Na
2cO
3(K/Na=0.83, CO
3 2-=9.31%, basicity (mixed base)=33.66%), filtrate heating being concentrated into over dry and becoming dehydration alkali, (zero pour is 199 ℃ to this dehydration alkali, K/Na=1.09: 1, CO
3 2-=2.76%, basicity (mixed base)=96.21%) and plant produced dehydration alkali (zero pour=197 ℃, K/Na=1.12: 1, CO
3 2-=2.07%, basicity (mixed base)=96.21%) every analytical data all approaches, and indigo quality is not affected after applying mechanically back indigo production system.
Embodiment 8
Toward triple effect concentrated solution 5T (K/Na=0.97: 1, CO is housed
3 2-=30g/L, adds NH in the still of basicity (mixed base=562.41g/L)
4hCO
3, the Na of adularescent at once
2cO
3generate, and emit a large amount of ammonias, along with NH
4hCO
3constantly add, crystallization increases, and after potassium sodium ratio reaches required standard, stops adding NH
4hCO
3, filter press, K/Na=1.08 in filtrate: 1, CO
3 2-=33.23g/L, basicity (mixed base)=560.22g/L, obtains crude product Na
2cO
3(K/Na=0.46, CO
3 2-=31.71%, basicity (OH
-)=5.25%, moisture=20.77%), filtrate heating being concentrated into over dry and becoming dehydration alkali, this dehydration alkali zero pour is 197 ℃, K/Na=1.12: 1, CO
3 2-=2.10%, basicity (mixed base)=96.21%.
Embodiment 9
By black ash solid obtained above 68.50 grams of (K/Na=0.46, CO
3 2-=31.71%, basicity (OH
-)=5.25%, moisture=20.77%), with the saturated Na of 100g
2cO
3washing (CO
3 2-=16.08%) filter, obtain 54.46g sodium carbonate solid (K/Na=0, CO
3 2-=40.65%, basicity (OH
-)=0, moisture=27.68%) and 114g washings (K/Na=0.53, CO
3 2-=16.10%, basicity (OH
-)=2.73%), can fully wash out potassium hydroxide and sodium hydroxide and the salt of wormwood carried secretly, the Na obtaining after sodium carbonate is dry
2cO
3finished product content is 99.72%.
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| CN103556420B (en) * | 2013-10-30 | 2015-11-18 | 江苏泰丰化工有限公司 | A kind of method reclaiming mixed alkali liquor from indigo aftertreatment washing process |
| CN103554995A (en) * | 2013-10-30 | 2014-02-05 | 江苏泰丰化工有限公司 | Method for recycling mixed alkali liquor in indigo production |
| CN103554952B (en) * | 2013-11-06 | 2015-06-17 | 江苏泰丰化工有限公司 | Device for recycling mixed alkali from indigo-dyed product |
| CN104761483A (en) * | 2015-02-13 | 2015-07-08 | 内蒙古泰兴泰丰化工有限公司 | Mixed alkaline residue treatment method during indigo production |
| CN104624617B (en) * | 2015-02-13 | 2017-04-05 | 内蒙古泰兴泰丰化工有限公司 | A kind of method of mixed base Slag treatment in indigo production |
| CN104624615B (en) * | 2015-02-13 | 2016-05-18 | 内蒙古泰兴泰丰化工有限公司 | In a kind of indigo production, mix its Future about Alkaline Residue Treatment Unit |
| CN104624616B (en) * | 2015-02-13 | 2016-08-17 | 内蒙古泰兴泰丰化工有限公司 | A kind of indigo production mixes its Future about Alkaline Residue Treatment Unit and processing method |
| CN104692422B (en) * | 2015-02-13 | 2016-03-30 | 内蒙古泰兴泰丰化工有限公司 | Its Future about Alkaline Residue Treatment Unit and treatment process is mixed in indigo production |
| CN104876247B (en) * | 2015-04-30 | 2016-10-05 | 浙江奇彩环境科技股份有限公司 | A kind of method of indigo alkaline residue resource recycling |
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| JPS606374B2 (en) * | 1977-08-08 | 1985-02-18 | 倉敷紡績株式会社 | How to recover indigo dye |
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