CN102312388A - Method of comprehensive utilization of black liquor from alkaline pulping - Google Patents
Method of comprehensive utilization of black liquor from alkaline pulping Download PDFInfo
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- CN102312388A CN102312388A CN201110267889A CN201110267889A CN102312388A CN 102312388 A CN102312388 A CN 102312388A CN 201110267889 A CN201110267889 A CN 201110267889A CN 201110267889 A CN201110267889 A CN 201110267889A CN 102312388 A CN102312388 A CN 102312388A
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- black liquor
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- alkaline pulping
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Abstract
The invention relates to a method of comprehensive utilization of black liquor from alkaline pulping, which reduces the cost of three-waste treatment, eliminates pollution, and also generates good economic benefit. According to the invention, black liquor is concentrated, oxidated and incinerated; posttreatment is performed by carbon dioxide-containing gas and a flocculant to obtain a bicarbonate product of alkali metal which can be calcined to obtain a carbonate product. The method has easily available raw materials, simple operations, and low energy consumption, not only eliminates pollution, but also obtains products with high added value, generates certain economic benefit, and is applicable to popularization and application in industry.
Description
Technical field
The present invention relates to the comprehensive utilization of alkaline pulping black liquor, especially the alkali in the black liquor is comprehensively utilized again.
Background technology
In the paper industry; Many employing alkaline solutions carry out boiling to plant fiber material and obtain the needed slurry of papermaking; Also can produce simultaneously a large amount of is master's black liquor with lignin, hemicellulose and alkaline matter, and wherein alkaline matter comprises alkali-metal hydroxide, alkali-metal sulfide, alkali-metal silicate and alkali-metal acylate.This black liquor becomes the maximum pollution sources of paper industry.Along with advocating of green economy, be one of important topic of environmental protection aspect research to the improvement of black liquid.At present, the improvement of black liquor is mainly started with from two aspects, and the one, wherein organic matters such as lignin are separated, as fertilizer, the alkali recycling; The 2nd, black liquor is concentrated the back burn, carry out causticization system alkali again.
Organic matters such as lignin in the black liquor are separated, and the alkali of recovery utilizes, and the method for employing has: electroosmose process, reverse osmosis method, counter-infiltration platen press, ultrafiltrationmembrane process etc.The problem that said method is deposited is that equipment investment is big, and operating condition is harsh, and processing cost is high, and what cause in suitability for industrialized production, using is few.Also having a kind of method is that black liquor is regulated the pH value with acid or sulfur dioxide gas, and when the pH value drops in the certain limit, lignin and hemicellulose are separated out; Salting liquid after the neutralization is used for inorganic fertilizer production; Perhaps process sulfate or sulphite, this method needs spent acid or sulfur dioxide gas in large quantities, and when filtering lignin, hemicellulose; Difficulty is big, filter plant is required high.
What employing was more in the industry is black liquor to be concentrated the back burn; Alkali lye that obtains and calcium oxide carry out causticization system alkali; But have a large amount of white claies to generate in this method, the content of calcium carbonate has only about 80% in the white clay, so the utilization again of white clay receives certain limitation; Cause a large amount of white claies to be piled up, again environment is caused secondary pollution.
Summary of the invention
In order to overcome above technological deficiency; The invention provides a kind of method that fully utilizes alkaline pulping black liquor; This method raw material is easy to get, simple to operate, energy consumption is low; In pollution abatement, can access the added value high product, produce certain economic benefits, help in industry, applying.
The technical scheme that the present invention mainly adopts is: after black liquor is burned through concentrated, oxidation, carry out post processing with carbonated gas and flocculant.
The carbon dioxide volumetric concentration is more than 40% in the carbonated gas of the present invention.The source of carbon dioxide can be the petroleum refining manufacture gas, the ammonia synthesizing industry manufacture gas, and fermentation industry manufacture gas or treated various combustion gas are like the carbon dioxide of substance combustions such as coal, natural gas, limekiln, coke generation.
The concrete steps that the present invention adopts are:
(1) black liquor of pulp making is carried out evaporation and concentration;
(2) concentrate being carried out oxidation burns;
(3) it is water-soluble products therefrom to be burned in oxidation, filters;
(4) will go up the carbonated gas of feeding in the step gained filtrating;
(5) will go up the step adds flocculant in the solution, filters;
(6) will go up the carbonated gas of step gained filtrating cooling back feeding, and cross and filter product.
Main component is materials such as lignin, hemicellulose and alkali-metal hydroxide, alkali-metal sulfide, alkali-metal silicate and alkali-metal acylate in the soda pulping process gained black liquor; At first it being carried out evaporation and concentration to solid quality mark wherein is 30-65%, makes its not only easy oxidized burning but also help the conveying that black liquor gets into incinerator in subsequent processes.
Black liquor after concentrating is sent into the oxidation of high-temperature oxydation stove burn, remove fully in order to guarantee lignin, hemicellulose and alkali-metal acylate in the black liquor, and the product that generates is molten condition, incineration temperature is 900～1000 ℃.In the burning process, the lignin in the black liquor, hemicellulose all generate carbon dioxide, can generate alkali-metal carbonate with the alkali-metal hydroxide reaction of part; Alkali-metal acylate generates alkali-metal carbonate and carbon dioxide in the black liquor in the oxidation burning process.Main component is alkali-metal carbonate, silicate, alkali-metal oxide and sulfide in the products therefrom so burn at last.
The fused mass that gained is burned in oxidation has very high heat energy value, so with in this smelt flow entry, produce a large amount of water vapours, introduces workshop through pipeline, as the industrial steam energy.After fused mass fed in the water, most of also had insoluble matter in a spot of water by water-soluble, and this insoluble matter is mainly sand, mechanical admixture (iron rust) through analyzing, and also has the insoluble molysite of trace.Iron itself is one of indispensable element in the soil, so the insoluble matter that filters out can not pollute environment.Because the alkali-metal relatively salt mass percent of insoluble substance is 0.05～0.2%,, so in the present invention, the quality of insoluble substance is disregarded not influence of later reaction.
When the oxidation incineration ashes was water-soluble, the mass fraction of preferably controlling alkali metal salt in the aqueous solution because concentration is lower than 13%, reduced usage ratio of equipment in the production in 13%～35% scope; Concentration is higher than 35%, have to salt out, and later stage flocculation is when removing silicic acid impurity, and silicic acid can be indivisible, influences the quality of product.
The aqueous solution of above-mentioned formation is filtered the carbonated gas of back feeding, and the silicate reaction in carbon dioxide and the solution generates silicic acid.Owing to this step reaction belongs to the reaction of strong acid system weak acid, can under arbitrary temp, carry out, but the shortening as far as possible of the cycle of consideration suitability for industrialized production, optimum temperature is at 20～60 ℃.
When the pH of solution value reaches 8～10, stop logical carbonated gas.At this moment, the silicate in the alkali lye has all generated silicic acid and has separated out.If the pH value is higher than 10,, thereby influence the quality of product owing to alkali-metal silicate has reacted; If the pH value is lower than 8, then have alkali-metal bicarbonate and separate out, influence the yield of final products.
With adding flocculant in the solution that has led to carbon dioxide.Flocculant can be an inorganic flocculating agent, like aluminum sulfate, aluminium chloride, ferric sulfate, iron chloride, and the flocculant that exists of their polymer form such as polyaluminium sulfate (iron), polymerization aluminum chloride (iron); Or through single cationic flocculant of modification, as gather sial (iron), gather phosphorus aluminium (iron); Or the polycation flocculant of process modification, like the polyaluminum sulfate aluminium chloride ferrum.Flocculant can be the organic polymer class also, comprising: the nonionic organic polymer coargulator, like polyacrylamide; The anionic organic polymer coargulator like the basic hydrolysis thing of polyacrylic acid, Sodium Polyacrylate, calcium polyacrylate (CPA) and polyacrylamide, also has the series copolymer of acrylamide.Wherein, find through test of many times, more outstanding in the inorganic flocculating agent with aluminum sulfate, polyaluminium sulfate and polyaluminum sulfate aluminium chloride effect, and organic polymer coargulator is relatively good with polyacrylamide and Sodium Polyacrylate effect.The addition of flocculant be in the solution alkali metal salt gross mass 0.2%～4%, when the amount of flocculant is lower than 0.2%, can not effectively silicic acid be flocculated out; And the amount of flocculant is higher than 4%, can cause filtration difficulty and wastage of material again, so, preferred 0.2～4% scope of the amount of flocculant.
After adding flocculant, stirred 0.5～2 hour, filter precipitate.This precipitate mainly is a silicic acid, can be with reference to " method for making thick in the inorganic chemicals industry handbook (Chemical Industry Press), Kiselgel A prepares silica gel, as by-product sale.
Leach the filtrating behind the silicic acid, feed carbonated gas once more, at this moment, carbon dioxide is main to react with alkali-metal carbonate and alkali-metal sulfide, and this step reacts and belongs to acid-base reaction, can under arbitrary temp, carry out.But when temperature is higher than 40 ℃, be unfavorable for carbon dioxide participation reaction, temperature is lower than 0 ℃, can cause the increase of energy consumption again, confirms preferred 10～35 ℃ of reaction temperature through long term test.When the pH value of solution value is 6～7; Alkali metal in the solution all exists with bicarbonate, stops logical carbon dioxide, stirs 0.5～1 hour; Filtration obtains alkali-metal bicarbonate product, and this bicarbonate product can carry out high-temperature calcination again and obtain carbonate products.No matter be bicarbonate or carbonate, content all reaches more than 98%, can sell as industrial goods, obtains good economic benefits.Mainly contain bicarbonate in the filter liquor, can recycle fully.
In sum, the present invention has the following advantages:
1, the present invention does not have the three wastes fully when system oar black liquor is effectively handled, belongs to real environment-friendly clean process.
2, the present invention has fully utilized the carbon dioxide in factory's emission gases when system oar black liquor is effectively handled, has reduced the carbon emission to environment.
3, treatment process involved in the present invention to system oar black liquor, suitability for industrialized production equipment is simple, and easy operating is applied in industry more easily.
4, the present invention is to system oar black liquor processing method, and cost is low, and the bicarbonate that generates or carbonate is minimum satisfies industrial goods product condition, so good application market is arranged, can create good economic benefits.
The specific embodiment
Below, foregoing of the present invention is done further detailed description, but should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following instance through the specific embodiment of embodiment form.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
The reed grass is after the sodium hydroxide lye boiling, and the black liquor that obtains reaches at 56% o'clock through evaporation and concentration solid quality mark extremely wherein, gets into the high-temperature oxydation stove and burns in 900 ℃ of oxidations.Oxidation is burned in the smelt flow entry that obtains, and a large amount of water vapours of generation are introduced workshop as the industrial steam energy through pipeline, remove by filter insoluble matter, obtain filtrating, and analyzing wherein, the mass fraction of alkali metal salt is 30%.
Get above-mentioned filtrating 1000Kg, in 20 ℃ to the gassing of separating that wherein feeds from coking workshop, refinery, separate that the carbon dioxide volume content is 40% in the gassing, other is hydrogen, alkane gas, carbon monoxide.Duration of ventilation was at 5 hours, and the pH value of solution value reaches at 9 o'clock, stopped to feed separating gassing.In the solution that ventilation finishes, add the 3Kg polyaluminium sulfate, stirred 2 hours, remove by filter silicic acid.Silicic acid is with reference to " method described in the inorganic chemicals industry handbook (Chemical Industry Press) is processed silica gel.
Be cooled to 10 ℃, continue feed in the filtrating after removing silicic acid and separate gassing, reach at 6 o'clock to the pH value of solution value, stop general solution and go into gassing, stirred 1 hour, filter, must sodium acid carbonate.After the drying, sodium acid carbonate content is 99%.
Embodiment 2
Wheat straw is after the boiling of potassium hydroxide alkali lye, and the black liquor that obtains reaches at 65% o'clock through evaporation and concentration solid quality mark extremely wherein, gets into the high-temperature oxydation stove and burns in 1000 ℃ of oxidations.Oxidation is burned in the smelt flow entry that obtains, and a large amount of water vapours of generation are introduced workshop as the industrial steam energy through pipeline, remove by filter insoluble matter, obtain filtrating, and analyzing wherein, the mass fraction amount of alkali metal salt is 35%.
Get above-mentioned filtrating 1000Kg, in 60 ℃ to wherein feeding from the low sudden strain of a muscle gas in the synthesis ammonia plant decarbonization device, wherein the volume content of carbon dioxide is 96%, other is oxygen, alkane gas, hydrogen, carbon monoxide.Duration of ventilation 3 hours, the pH value of solution value reaches at 8 o'clock, stops to feed the low sudden strain of a muscle gas in the decarbonization device.In the solution that ventilation finishes, add the Sodium Polyacrylate of 0.7Kg, stirred 1 hour, remove by filter silicic acid.Silicic acid is with reference to " method described in the inorganic chemicals industry handbook (Chemical Industry Press) is processed silica gel.
Be cooled to 35 ℃, continue feed the low sudden strain of a muscle gas in the decarbonization device in the filtrating after removing silicic acid, reach at 7 o'clock to the pH value of solution value, stop to feed the low sudden strain of a muscle gas in the decarbonization device, stirred 0.5 hour, filter, must the saleratus product.After the drying, saleratus content 98.8%.
Embodiment 3
Take the pulp black liquor of NaOH boiling gained, reach at 30% o'clock, get into the high-temperature oxydation stove and burn in 925 ℃ of oxidations through evaporation and concentration solid quality mark extremely wherein.Oxidation is burned in the smelt flow entry that obtains, and a large amount of water vapours of generation are introduced workshop as the industrial steam energy through pipeline, remove by filter insoluble matter, obtain filtrating, and analyzing wherein, the mass fraction of alkali metal salt is 20%.
Get above-mentioned filtrating 1000Kg, in 30 ℃ to the carbon dioxide that wherein feeds from beer fermentation factory, its volume content is 95.8%, other component is ethanol, oxygen, nitrogen, lower member ester class.Duration of ventilation 2 hours, the pH value of solution value reaches at 10 o'clock, stops to feed fermentation gas.In the solution that ventilation finishes, add the polyaluminum sulfate aluminium chloride of 9Kg, stirred 0.5 hour, remove by filter silicic acid.Silicic acid is with reference to " method described in the inorganic chemicals industry handbook (Chemical Industry Press) is processed silica gel.
Be cooled to 15 ℃, continue feed fermentation gas in the filtrating after removing silicic acid, reach at 6.2 o'clock to the pH value of solution value; Stop to feed fermentation gas, stirred 0.8 hour, filter; Obtain the sodium acid carbonate product, this sodium acid carbonate is delivered to calcining furnace, in 270 ℃ calcining furnace, calcine; Obtain the monohydrated sodium carbonate product, carbonate content 98.5%.
Embodiment 4
After wheat straw, the mixed base boiling of reed grass with NaOH and vulcanized sodium, the black liquor that obtains reaches at 47% o'clock through evaporation and concentration solid quality mark extremely wherein, gets into the high-temperature oxydation stove and burns in 950 ℃ of oxidations.Oxidation is burned in the smelt flow entry that obtains, and a large amount of water vapours of generation are introduced workshop as the industrial steam energy through pipeline, remove by filter insoluble matter, obtain filtrating, and analyzing wherein, the mass fraction of alkali metal salt is 15%.
Get above-mentioned filtrating 1000Kg, in 50 ℃ to wherein feeding thermoelectric flue gas, the carbon dioxide volume content is 90%, other is nitrogen, carbon monoxide, oxygen.Duration of ventilation 2 hours, the pH value of solution value reaches at 8.5 o'clock, stops to feed flue gas.In the solution that ventilation finishes, add the aluminum sulfate of 6Kg, stirred 0.8 hour, remove by filter silicic acid.Silicic acid is with reference to " method described in the inorganic chemicals industry handbook (Chemical Industry Press) is processed silica gel.
Be cooled to 30 ℃, continue feed flue gas in the filtrating after removing silicic acid, reach at 6.5 o'clock to the pH value of solution value, stop to feed flue gas, stirred 0.7 hour, filtration obtains the sodium acid carbonate product.After the drying, sodium acid carbonate content 98.6%.
Embodiment 5
Wheat straw is after the boiling of potassium hydroxide alkali lye, and the black liquor that obtains reaches at 38% o'clock through evaporation and concentration solid quality mark extremely wherein, gets into the high-temperature oxydation stove and burns in 975 ℃ of oxidations.Oxidation is burned in the smelt flow entry that obtains, and a large amount of water vapours of generation are introduced workshop as the industrial steam energy through pipeline, remove by filter insoluble matter, obtain filtrating, and analyzing wherein, the mass fraction of alkali metal salt is 25%.
Get above-mentioned filtrating 1000Kg, in 40 ℃ to the gassing of separating that wherein feeds from coking workshop, refinery, separate that the carbon dioxide volume content is 55% in the gassing, other is hydrogen, alkane gas, carbon monoxide.Duration of ventilation 4 hours, the pH value of solution value reaches at 9.5 o'clock, stops to feed separating gassing.In the solution that ventilation finishes, add the polyacrylamide of 12Kg, stirred 1.6 hours, remove by filter silicic acid.Silicic acid is with reference to " method described in the inorganic chemicals industry handbook (Chemical Industry Press) is processed silica gel.
Be cooled to 20 ℃, continue feed in the filtrating after removing silicic acid and separate gassing, reach at 6.7 o'clock to the pH value of solution value, stop to feed and separate gassing, stirred 0.6 hour, filter, get the saleratus product.After the drying, saleratus content 98.5%.
Claims (10)
1. a method that fully utilizes alkaline pulping black liquor comprises evaporation and concentration, oxidation burning, it is characterized in that: after black liquor is burned through concentrated, oxidation, carry out post processing with carbonated gas and flocculant.
2. the method for comprehensive utilization alkaline pulping black liquor according to claim 1 is characterized in that: the carbon dioxide volumetric concentration is more than 40% in the carbonated gas.
3. the method for comprehensive utilization alkaline pulping black liquor according to claim 1 and 2 is characterized in that: its concrete steps are:
(1) black liquor of pulp making is carried out evaporation and concentration;
(2) concentrate being carried out oxidation burns;
(3) it is water-soluble products therefrom to be burned in oxidation, filters;
(4) will go up the carbonated gas of feeding in the step gained filtrating;
(5) will go up the step adds flocculant in the solution, filters;
(6) will go up the carbonated gas of step gained filtrating cooling back feeding, and cross and filter product.
4. the method for comprehensive utilization alkaline pulping black liquor according to claim 3 is characterized in that: step (1) black liquor of pulp making is 30-65% through solid quality mark after the evaporation and concentration.
5. the method for comprehensive utilization alkaline pulping black liquor according to claim 3 is characterized in that: step (2) oxidation incineration temperature is 900～1000 ℃.
6. the method for comprehensive utilization alkaline pulping black liquor according to claim 3 is characterized in that: in step (3) the gained filtrating, the mass fraction of alkali metal salt is 13-35%.
7. the method for comprehensive utilization alkaline pulping black liquor according to claim 3 is characterized in that: reaction temperature is preferred 20～60 ℃ in the step (4), and reaction back pH value of solution value is 8-10.
8. the method for comprehensive utilization alkaline pulping black liquor according to claim 3 is characterized in that: described flocculant preferably sulfuric acid aluminium or polyaluminium sulfate or polyaluminum sulfate aluminium chloride or polyacrylamide or Sodium Polyacrylate.
9. the method for comprehensive utilization alkaline pulping black liquor according to claim 3 is characterized in that: described flocculant addition is the 0.2%-4% of alkali metal salt gross mass in the solution.
10. the method for comprehensive utilization alkaline pulping black liquor according to claim 3 is characterized in that: reaction temperature is preferred 10～35 ℃ in the step (6), and reaction back pH value of solution value is 6-7.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217403A (en) * | 1997-10-13 | 1999-05-26 | 加科普里公司 | Process for recovering alkali and energy from black liquor containing silicate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217403A (en) * | 1997-10-13 | 1999-05-26 | 加科普里公司 | Process for recovering alkali and energy from black liquor containing silicate |
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Effective date of registration: 20180914 Address after: 256500 Boxing County Economic Development Zone, Binzhou, Shandong Patentee after: Yellow River Delta Jingbo Chemical Research Institute Co., Ltd. Address before: 256500 Jingbo Industrial Park, Boxing Economic Development Zone, Binzhou, Shandong, China Patentee before: Shandong Chambroad Holding Co., Ltd. |