CN102337696A - Method for removing silicon in green liquid through cooperation of calcium oxide and aluminum salt - Google Patents
Method for removing silicon in green liquid through cooperation of calcium oxide and aluminum salt Download PDFInfo
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- CN102337696A CN102337696A CN2011103380278A CN201110338027A CN102337696A CN 102337696 A CN102337696 A CN 102337696A CN 2011103380278 A CN2011103380278 A CN 2011103380278A CN 201110338027 A CN201110338027 A CN 201110338027A CN 102337696 A CN102337696 A CN 102337696A
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- green liquor
- calcium oxide
- causticization
- aluminium salt
- green liquid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/40—Production or processing of lime, e.g. limestone regeneration of lime in pulp and sugar mills
Abstract
The invention relates to a method for reducing the silicon content in a green liquid of a non-wood fiber material pulping causticization section through the cooperation of calcium oxide and aluminum salt. In the method, calcium oxide and aluminum sulfate, aluminum oxide, aluminum hydroxide or sodium metaaluminate are sequentially added into the green liquid of the causticization section, the temperature is 90-100 DEG C in the reaction process, a stirrer is used for continuous stirring in the reaction process, the reaction time is 25-30 minutes, and insoluble precipitate is removed by filtration after the reaction is completed. The method is provided for the green liquid produced during non-wood fiber material pulping, and comprises the following steps: adding calcium oxide and aluminum salt into the green liquid of the pulping causticization section to react with silicate in the green liquid so as to generate insoluble precipitate, then filtering to remove the generated insoluble precipitate from the green liquid. The method can achieve a silicon removal rate higher than 87%, and ensures that white slime can be used for calcining and recycling lime after causticization.
Description
Technical field
The slurrying alkali that the invention belongs to paper industry reclaims the green liquor silicon removing process, is specifically related to a kind of with calcium oxide, the collaborative method that reduces the green liquor silicone content of aluminium salt.
Background technology
The non-wood-fiber paper making raw material is the resource of a kind of important renewable fiber of China; Particularly under the situation of current social enviroment protection consciousness and the reinforcement of energy crisis consciousness, correctly being familiar with non-wood material is very necessary in importance aspect China's pulping and paper-making and position.Because the cause specific of non-wood-fiber raw material self, hemicellulose level is higher than timber, and heteroproteose cell is many, and ash content is high, and silica accounts for ash content more than 60%, and the result causes alkali recovery process " silicon interference " problem." silicon interference " problem is mainly reflected in workshop sections such as evaporation, causticization and lime recovery.At evaporation section, when siliceous black liquor is concentrated into 30%～40% solid content, SiO in the black liquor
2Solubility reaches capacity, and separates out the silicon dirt and is deposited on the tube wall, influences evaporation efficiency, increases gas consumption.At caustic room, have CaSiO in the green liquor causticizing reaction
3Generate, reduced green liquor causticizing efficient.This external burning of lime sludge is produced lime and is back in the process of caustic room; Silicon in the white clay can reduce the lime activity, has a strong impact on the normal running in limekiln, and the silicon in the white clay can make in the white clay residual base number higher in addition; Because the fusing point of residual alkaloid substance is lower than lime; Fusing earlier before white clay carries out calcination reaction or in the process of reacting is formed block perhaps sticking to lime and is formed balling, ring formation and knot ring on the inwall of limekiln, and the result causes the as easy as rolling off a log production fault that occurs in limekiln.The researcher has proposed many solutions to non-wood material slurrying alkali recycle section " silicon interference " problem, has carried out useful exploration, and alleviating of " silicon interference " played positive role.The method that is adopted has: 1, in green liquor, feed carbon dioxide, soon green liquor is diluted to concentration and is roughly 80g/l (with Na
2The O meter), in green liquor, feed carbon dioxide, precipitated silicic acid then.Through filtration, silicic acid to be separated from green liquor, green liquor passes through multi-effect evaporation system behind the silica removal; Its concentration is brought up to the needs that adapt to the causticization operation; Be sent to dorr continuous recausticezing system again, but green liquor pH value is low behind the silica removal, need green liquor pH value be adjusted back to high alkalinity.2, in green liquor, add lime; Promptly two step causticizing processes remove silicon technology, and promptly the first step only adds 30% lime and carries out causticization, produces outside the white clay factory and discharges; Second step added 70% lime and carries out causticization; Be back to causticization after producing burning of lime sludge, the method silicon clearance is 56%, but still contains a large amount of silicon in the second step causticization gained white clay.The deposition fine size, the viscosity that generate in addition are big, are difficult for from green liquor, separating, and the residual base number of white clay is higher.Above method all unresolved " silicon interference " problem.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of silica removal rate to reach more than 87%, and white clay can be used for calcining the collaborative green liquor silicon removing method of calcium oxide, aluminium salt that reclaims lime after guaranteeing causticization.
For achieving the above object; The technical scheme that the present invention adopts is: in causticization section green liquor, add the calcium oxide reaction after 10～15 minutes that accounts for the calcareous amount total amount of the required oxidation of causticization 10%-30% at 90～100 ℃; The aluminium salt that adds the calcareous amount total amount 5% of the required oxidation of causticization again continues stirring reaction; React after 10～15 minutes, all insoluble matter depositions that filtration will generate are removed from green liquor.
Described aluminium salt is aluminum sulfate, aluminium oxide, sodium metaaluminate or aluminium hydroxide.
Described calcium oxide and aluminium salt are added in the green liquor with the form of solid.
The silicone content of described reaction back green liquor is with SiO
2Meter is lower than 1.55g/l.
The residual base number of white clay that described causticization generates is lower than 4.35g/l in NaOH.
The present invention adds calcium oxide earlier in the causticization section; Make the silicate reaction in calcium oxide and the green liquor generate calcium silicates; Add aluminium salt again, when reducing the green liquor silicone content, with the big insoluble matter deposition of the relative calcium silicates of calcium silicates formation particle in the green liquor; From green liquor, remove by filter the insoluble matter deposition of generation then, carry out green liquor causticizing again.After experimental study was found to add calcium oxide earlier in the green liquor, the silicate in calcium oxide meeting and the green liquor generated precipitated calcium silicate, and when adding aluminium salt again, aluminium salt can play two aspect effects: aluminium salt plays the effect of silica removal on the one hand, and aluminium salt can make silicate become silicic acid.Play the effect of flocculant on the other hand, the calcium silicates that under the aluminium salt action, generates, silicic acid wadding are got together, thereby make the insoluble matter deposit seed of generation become big, are easy to from green liquor, separate out and filter out.
The specific embodiment
The used green liquor of the present invention is taken from green liquor clarification groove between soda pulping process factory alkali recovery vehicle, and the main component carbonate content is that 87.81g/l, sodium hydrate content are 35.26g/l in the green liquor, and silicone content 11.52g/l is (with SiO
2Meter).
Embodiment 1: get in green liquor 500ml to the 1000ml beaker after the clarification; Green liquor is heated to the calcium oxide reaction after 10 minutes account for the calcareous amount total amount 10% of the required oxidation of causticization 95 ℃ in causticization section green liquor, add with water-bath; The aluminum sulfate that adds the calcareous amount total amount 5% of the required oxidation of causticization again continues stirring reaction; React after 15 minutes, all insoluble matter depositions that filtration will generate are removed from green liquor.Silicone content 1.47g/l is (with SiO in the green liquor of reaction end back
2Count), residual base number 4.21g/l (in NaOH) in the white clay after the final causticization.
Embodiment 2: get in green liquor 500ml to the 1000ml beaker after the clarification; Green liquor is heated to the calcium oxide reaction after 15 minutes account for the calcareous amount total amount 20% of the required oxidation of causticization 90 ℃ in causticization section green liquor, add with water-bath; The aluminum sulfate that adds the calcareous amount total amount 5% of the required oxidation of causticization again continues stirring reaction; React after 15 minutes, all insoluble matter depositions that filtration will generate are removed from green liquor.Silicone content 1.34g/l is (with SiO in the green liquor of reaction end back
2Count), residual base number 3.92g/l (in NaOH) in the white clay after the final causticization.
Embodiment 3: get in green liquor 500ml to the 1000ml beaker after the clarification; Green liquor is heated to the calcium oxide reaction after 12 minutes account for the calcareous amount total amount 30% of the required oxidation of causticization 93 ℃ in causticization section green liquor, add with water-bath; The aluminum sulfate that adds the calcareous amount total amount 5% of the required oxidation of causticization again continues stirring reaction; React after 10 minutes, all insoluble matter depositions that filtration will generate are removed from green liquor.Silicone content 1.23g/l is (with SiO in the green liquor of reaction end back
2Count), residual base number 3.20g/l (in NaOH) in the white clay after the final causticization.
Embodiment 4: get in green liquor 500ml to the 1000ml beaker after the clarification; Green liquor is heated to the calcium oxide reaction after 11 minutes account for the calcareous amount total amount 25% of the required oxidation of causticization 100 ℃ in causticization section green liquor, add with water-bath; The aluminium hydroxide that adds the calcareous amount total amount 5% of the required oxidation of causticization again continues stirring reaction; React after 13 minutes, all insoluble matter depositions that filtration will generate are removed from green liquor.Silicone content 1.43g/l is (with SiO in the green liquor of reaction end back
2Count), residual base number 4.11g/l (in NaOH) in the white clay after the final causticization.
Embodiment 5: get in green liquor 500ml to the 1000ml beaker after the clarification; Green liquor is heated to the calcium oxide reaction after 14 minutes account for the calcareous amount total amount 15% of the required oxidation of causticization 98 ℃ in causticization section green liquor, add with water-bath; The aluminium oxide that adds the calcareous amount total amount 5% of the required oxidation of causticization again continues stirring reaction; React after 11 minutes, all insoluble matter depositions that filtration will generate are removed from green liquor.Silicone content 1.49g/l is (with SiO in the green liquor of reaction end back
2Count), residual base number 4.25g/l (in NaOH) in the white clay after the final causticization.
Embodiment 6: get in green liquor 500ml to the 1000ml beaker after the clarification; Green liquor is heated to the calcium oxide reaction after 13 minutes account for the calcareous amount total amount 10% of the required oxidation of causticization 96 ℃ in causticization section green liquor, add with water-bath; The sodium metaaluminate that adds the calcareous amount total amount 5% of the required oxidation of causticization again continues stirring reaction; React after 12 minutes, all insoluble matter depositions that filtration will generate are removed from green liquor.Silicone content 1.54g/l is (with SiO in the green liquor of reaction end back
2Count), residual base number 4.32g/l (in NaOH) in the white clay after the final causticization.
Claims (5)
1. calcium oxide, aluminium salt are worked in coordination with the green liquor silicon removing method; It is characterized in that: in causticization section green liquor, add the calcium oxide reaction after 10～15 minutes account for the calcareous amount total amount of the required oxidation of causticization 10%-30% at 90～100 ℃; The aluminium salt that adds the calcareous amount total amount 5% of the required oxidation of causticization again continues stirring reaction; React after 10～15 minutes, all insoluble matter depositions that filtration will generate are removed from green liquor.
2. calcium oxide according to claim 1, the collaborative green liquor silicon removing method of aluminium salt, it is characterized in that: described aluminium salt is aluminum sulfate, aluminium oxide, sodium metaaluminate or aluminium hydroxide.
3. calcium oxide according to claim 1, the collaborative green liquor silicon removing method of aluminium salt, it is characterized in that: described calcium oxide and aluminium salt are added in the green liquor with the form of solid.
4. calcium oxide according to claim 1, the collaborative green liquor silicon removing method of aluminium salt is characterized in that: the silicone content of described reaction back green liquor is with SiO
2Meter is lower than 1.55g/l.
5. calcium oxide according to claim 1, the collaborative green liquor silicon removing method of aluminium salt, it is characterized in that: the residual base number of white clay that described causticization generates is lower than 4.35g/l in NaOH.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102619123A (en) * | 2012-03-16 | 2012-08-01 | 陕西科技大学 | Method for removing silicon from green liquor through synergism of calcium oxide, carbon dioxide and aluminum-containing compound |
| CN103061187A (en) * | 2012-12-17 | 2013-04-24 | 陕西科技大学 | Technology of recycling white slime to refine pearl filler with sulfate process |
| CN103334329A (en) * | 2013-06-28 | 2013-10-02 | 陕西科技大学 | Bamboo pulp green liquor silica pre-removing method through utilizing sodium bentonite and application of method |
| CN103498377A (en) * | 2013-10-16 | 2014-01-08 | 陕西科技大学 | Method for removing silica in multinuclear polymeric hydroxy-aluminum green liquor |
| CN103708522A (en) * | 2014-01-03 | 2014-04-09 | 三三环保科技（北京）有限公司 | Causticization method for producing high-quality calcium carbonate by recycling green liquor by alkali |
| CN104928482A (en) * | 2015-05-25 | 2015-09-23 | 云南驰宏锌锗股份有限公司 | Method for improving filtration performance of zinc oxide leaching liquid |
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| JPS6045692A (en) * | 1983-08-18 | 1985-03-12 | 石川島播磨重工業株式会社 | Removal of silica from pulp black liquor and green liquor |
| JPS645692A (en) * | 1987-06-26 | 1989-01-10 | Mitsubishi Electric Corp | Laser cutting method |
| JPH0645692A (en) * | 1992-07-27 | 1994-02-18 | Sanyo Electric Co Ltd | Semiconductor laser |
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2011
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| JPS6045692A (en) * | 1983-08-18 | 1985-03-12 | 石川島播磨重工業株式会社 | Removal of silica from pulp black liquor and green liquor |
| JPS645692A (en) * | 1987-06-26 | 1989-01-10 | Mitsubishi Electric Corp | Laser cutting method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102619123A (en) * | 2012-03-16 | 2012-08-01 | 陕西科技大学 | Method for removing silicon from green liquor through synergism of calcium oxide, carbon dioxide and aluminum-containing compound |
| CN103061187A (en) * | 2012-12-17 | 2013-04-24 | 陕西科技大学 | Technology of recycling white slime to refine pearl filler with sulfate process |
| CN103334329A (en) * | 2013-06-28 | 2013-10-02 | 陕西科技大学 | Bamboo pulp green liquor silica pre-removing method through utilizing sodium bentonite and application of method |
| CN103498377A (en) * | 2013-10-16 | 2014-01-08 | 陕西科技大学 | Method for removing silica in multinuclear polymeric hydroxy-aluminum green liquor |
| CN103708522A (en) * | 2014-01-03 | 2014-04-09 | 三三环保科技（北京）有限公司 | Causticization method for producing high-quality calcium carbonate by recycling green liquor by alkali |
| CN104928482A (en) * | 2015-05-25 | 2015-09-23 | 云南驰宏锌锗股份有限公司 | Method for improving filtration performance of zinc oxide leaching liquid |
| CN104928482B (en) * | 2015-05-25 | 2018-03-09 | 云南驰宏锌锗股份有限公司 | A kind of method for improving oxidation zinc lixiviating solution strainability |
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Application publication date: 20120201 |