CN102312388B - 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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- CN102312388B CN102312388B CN 201110267889 CN201110267889A CN102312388B CN 102312388 B CN102312388 B CN 102312388B CN 201110267889 CN201110267889 CN 201110267889 CN 201110267889 A CN201110267889 A CN 201110267889A CN 102312388 B CN102312388 B CN 102312388B
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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 bicarbonateproduct 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 recycled.
Background technology
In the paper industry, many employing alkaline solutions carry out boiling to plant fiber material and obtain the needed slurry of papermaking, while also can produce a large amount of take lignin, hemicellulose and alkaline matter as main black liquor, and wherein alkaline matter comprises alkali-metal hydroxide, alkali-metal sulfide, alkali-metal silicate and alkali-metal acylate.This black liquor becomes the pollution sources of paper industry maximum.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 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 rear the burning, carry out again the causticization alkaline.
The 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 large, and operating condition is harsh, and processing cost is high, and what cause using in suitability for industrialized production is few.Also having a kind of method is that black liquor is regulated the pH value with acid or sulfur dioxide gas, 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 make sulfate or sulphite, the method need to have in large quantities spent acid or sulfur dioxide gas, and when filtering lignin, hemicellulose, difficulty is large, requires high to filter plant.
What industrial employing was more is to burn behind the Black Liquor Concentration, the alkali lye that obtains and calcium oxide carry out the causticization alkaline, but there is a large amount of white claies to generate in the method, the content of calcium carbonate only has about 80% in the white clay, so the recycling of white clay is subject to 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 of comprehensive utilization of black liquor from alkaline pulping, this method raw material is easy to get, simple to operate, energy consumption is low, in pollution abatement, can access the higher product of added value, produce certain economic benefit, be conducive to apply industrial.
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 carbonated carbon dioxide in gas volumetric concentration of the present invention is more than 40%.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 such as the carbon dioxide of the 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) products therefrom is burned in oxidation water-soluble, filter;
(4) will pass into carbonated gas in the gained filtrate of upper step;
(5) will add flocculant in the solution of upper step, filter;
(6) with passing into carbonated gas after the gained filtrate cooling of upper step, filter to get product.
Main component is the 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 total solid content wherein is 30-65%, makes its not only easy oxidized burning but also be conducive to the conveying that black liquor enters incinerator in subsequent processes.
Black liquor after concentrated is sent into the high temperature oxidation furnace oxidation 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 passed in the water, most of also had insoluble matter in a small amount of water by water-soluble solution, and this insoluble matter is mainly sand, mechanical admixture (iron rust) by analysis, 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 be to environment.Because the relatively alkali-metal salt mass percent of insoluble substance is 0.05～0.2%, on not impact of later reaction, so in the present invention, the quality of insoluble substance is disregarded.
When the oxidation incineration ashes is water-soluble, preferably control the mass fraction of alkali metal salt in the aqueous solution in 13%～35% scope, because concentration is lower than 13%, the utilization rate to equipment in the production reduces; Concentration is higher than 35%, have to salt out, and later stage flocculation is during except silicic acid impurity, and silicic acid can be indivisible, affects the quality of product.
Pass into carbonated gas after the aqueous solution filtration with above-mentioned formation, the silicate reaction in carbon dioxide and the solution generates silicic acid.Owing to this step reaction belongs to strong acid weak acid reaction processed, can under arbitrary temp, carry out, but the as far as possible shortening 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, because alkali-metal silicate do not reacted, thereby affect the quality of product; If the pH value is lower than 8, then have alkali-metal bicarbonate and separate out, affect the yield of final products.
Add flocculant with having led in the solution of carbon dioxide.Flocculant can be inorganic flocculating agent, such as 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 single cationic flocculant of process modification, such as poly-sial (iron), poly-phosphorus aluminium (iron); Or the polycation flocculant of process modification, such as the polyaluminum sulfate aluminium chloride ferrum.Flocculant can be the organic polymer class also, comprising: the nonionic organic polymer coargulator, such as polyacrylamide; The anionic organic polymer coargulator such as the basic hydrolysis thing of polyacrylic acid, Sodium Polyacrylate, calcium polyacrylate (CPA) and polyacrylamide, also has the series copolymer of acrylamide.Wherein, find by test of many times, more outstanding with aluminum sulfate, polyaluminium sulfate and polyaluminum sulfate aluminium chloride effect in the inorganic flocculating agent, 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 silicic acid, can be with reference to " method for making thick in the inorganic chemicals industry handbook (Chemical Industry Press), Kiselgel A is prepared silica gel, as by-product sale.
Leach the filtrate behind the silicic acid, again pass into carbonated gas, 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 carry out under arbitrary temp.But when temperature is higher than 40 ℃, be unfavorable for that carbon dioxide participates in reaction, temperature is lower than 0 ℃, can cause again the increase of energy consumption, determines preferred 10～35 ℃ of reaction temperature through long term test.When pH 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 benefit.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 oar black liquor processed is effectively processed, belongs to real environment-friendly clean process.
2, the present invention has fully utilized the carbon dioxide in factory's emission gases when oar black liquor processed is effectively processed, has reduced the carbon emission to environment.
3, the treatment process to oar black liquor processed involved in the present invention, suitability for industrialized production equipment is simple, and easy operating is easilier applied in industry.
4, the present invention is to oar black liquor processing method processed, and cost is low, and the bicarbonate that generates or carbonate is minimum satisfies industrial goods product condition, so there is good market to use, can create good economic benefit.
The specific embodiment
The specific embodiment of form is described in further detail foregoing of the present invention by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
The reed grass when black liquor that obtains reaches 56% through evaporation and concentration total solid content extremely wherein, enters high temperature oxidation furnace and burns in 900 ℃ of oxidations after the sodium hydroxide lye boiling.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 filtrate, and analyzing wherein, the mass fraction of alkali metal salt is 30%.
Get above-mentioned filtrate 1000Kg, in 20 ℃ to the resolution gas that wherein passes into from coking workshop, refinery, the carbon dioxide volume content is 40% in the resolution gas, other is hydrogen, alkane gas, carbon monoxide.Duration of ventilation was at 5 hours, and pH reaches at 9 o'clock, stopped to pass into resolution gas.In the complete solution of ventilation, 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 made silica gel.
Be cooled to 10 ℃, in the filtrate of removing behind the silicic acid, continue to pass into resolution gas, reach at 6 o'clock to pH, stop general solution and enter gassing, stirred 1 hour, filter, get sodium bicarbonate.After the drying, sodium bicarbonate content is 99%.
Embodiment 2
Wheat straw when the black liquor that obtains reaches 65% through evaporation and concentration total solid content extremely wherein, enters high temperature oxidation furnace and burns in 1000 ℃ of oxidations after the boiling of potassium hydroxide alkali lye.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 filtrate, and analyzing wherein, the mass fraction amount of alkali metal salt is 35%.
Get above-mentioned filtrate 1000Kg, in 60 ℃ to wherein passing into 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, pH reaches at 8 o'clock, stops to pass into the low sudden strain of a muscle gas in the decarbonization device.Add the Sodium Polyacrylate of 0.7Kg in the complete solution of ventilation, 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 made silica gel.
Be cooled to 35 ℃, continue to pass into the low sudden strain of a muscle gas in the decarbonization device in the filtrate of removing behind the silicic acid, reach at 7 o'clock to pH, stop to pass into the low sudden strain of a muscle gas in the decarbonization device, stirred 0.5 hour, filter, get the saleratus product.After the drying, saleratus content 98.8%.
Embodiment 3
Take the pulp black liquor of NaOH boiling gained, when evaporation and concentration total solid content extremely wherein reaches 30%, enter high temperature oxidation furnace and burn in 925 ℃ 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 filtrate, and analyzing wherein, the mass fraction of alkali metal salt is 20%.
Get above-mentioned filtrate 1000Kg, in 30 ℃ to the carbon dioxide that wherein passes into 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, pH reaches at 10 o'clock, stops to pass into fermentation gas.Add the polyaluminum sulfate aluminium chloride of 9Kg in the complete solution of ventilation, 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 made silica gel.
Be cooled to 15 ℃, in the filtrate of removing behind the silicic acid, continue to pass into fermentation gas, reach at 6.2 o'clock to pH, stop to pass into fermentation gas, stirred 0.8 hour, filter, obtain the sodium bicarbonate product, this sodium bicarbonate 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, when the black liquor that obtains reaches 47% through evaporation and concentration total solid content extremely wherein, enter high temperature oxidation furnace and burn 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 filtrate, and analyzing wherein, the mass fraction of alkali metal salt is 15%.
Get above-mentioned filtrate 1000Kg, in 50 ℃ to wherein passing into thermoelectric flue gas, the carbon dioxide volume content is 90%, other is nitrogen, carbon monoxide, oxygen.Duration of ventilation 2 hours, pH reaches at 8.5 o'clock, stops to pass into flue gas.Add the aluminum sulfate of 6Kg in the complete solution of ventilation, 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 made silica gel.
Be cooled to 30 ℃, in the filtrate of removing behind the silicic acid, continue to pass into flue gas, reach at 6.5 o'clock to pH, stop to pass into flue gas, stirred 0.7 hour, filter, obtain the sodium bicarbonate product.After the drying, sodium bicarbonate content 98.6%.
Embodiment 5
Wheat straw when the black liquor that obtains reaches 38% through evaporation and concentration total solid content extremely wherein, enters high temperature oxidation furnace and burns in 975 ℃ of oxidations after the boiling of potassium hydroxide alkali lye.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 filtrate, and analyzing wherein, the mass fraction of alkali metal salt is 25%.
Get above-mentioned filtrate 1000Kg, in 40 ℃ to the resolution gas that wherein passes into from coking workshop, refinery, the carbon dioxide volume content is 55% in the resolution gas, other is hydrogen, alkane gas, carbon monoxide.Duration of ventilation 4 hours, pH reaches at 9.5 o'clock, stops to pass into resolution gas.Add the polyacrylamide of 12Kg in the complete solution of ventilation, 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 made silica gel.
Be cooled to 20 ℃, in the filtrate of removing behind the silicic acid, continue to pass into resolution gas, reach at 6.7 o'clock to pH, stop to pass into resolution gas, stirred 0.6 hour, filter, get the saleratus product.After the drying, saleratus content 98.5%.
Claims (3)
1. the method for a comprehensive utilization of black liquor from alkaline pulping, it is characterized in that: its concrete steps are:
(1) black liquor of pulp making is carried out evaporation and concentration;
(2) concentrate is carried out oxidation and burn, the oxidation incineration temperature is 900 ~ 1000 ℃;
(3) products therefrom is burned in oxidation water-soluble, filter;
(4) will pass into carbonated gas in the gained filtrate of upper step, reaction temperature is 20 ~ 60 ℃, and pH is 8-10 after the reaction;
(5) will add flocculant in the solution of upper step, filter; Wherein, described flocculant is aluminum sulfate or polyaluminium sulfate or polyaluminum sulfate aluminium chloride or polyacrylamide or Sodium Polyacrylate; Described flocculant addition is the 0.2%-4% of alkali metal salt gross mass in the solution;
(6) with passing into carbonated gas after the gained filtrate cooling of upper step, filter to get product; Wherein, reaction temperature is 10 ~ 35 ℃, and pH is 6-7 after the reaction;
Carbonated carbon dioxide in gas volumetric concentration is more than 40% in described step (4) and (6).
2. the method for comprehensive utilization of black liquor from alkaline pulping according to claim 1 is characterized in that: step (1) black liquor of pulp making is 30-65% through total solid content after the evaporation and concentration.
3. the method for comprehensive utilization of black liquor from alkaline pulping according to claim 1, it is characterized in that: in step (3) the gained filtrate, the mass fraction of alkali metal salt is 13-35%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 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. |
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