CN103469664B - A kind of alkali collection workshop section green liquor flocculation silicon removing method - Google Patents

A kind of alkali collection workshop section green liquor flocculation silicon removing method Download PDF

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Publication number
CN103469664B
CN103469664B CN201310376672.8A CN201310376672A CN103469664B CN 103469664 B CN103469664 B CN 103469664B CN 201310376672 A CN201310376672 A CN 201310376672A CN 103469664 B CN103469664 B CN 103469664B
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green liquor
metal salt
trivalent metal
mud
modified alta
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CN103469664A (en
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林涛
李雪
徐永建
殷学风
章伟鹏
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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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

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  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

A kind of alkali collection workshop section disclosed by the invention green liquor flocculation silicon removing method, first trivalent metal salt modified alta-mud is prepared, causticization section green liquor after next gets clarification is poured in beaker, be heated to 90-100 DEG C, then be that 20-50g/L takes the trivalent metal salt modified alta-mud that step 1 obtains and joins in green liquor according to the quality-volumetric concentration of trivalent metal salt modified alta-mud, stirring reaction 10min, leave standstill and treat abundant reaction, be that the cationic polyacrylamide solution of 0.01%-1.0% joins in beaker according to the ratio that the volume ratio with green liquor is 1:20-1:200 by mass concentration, be that 10-30g/L adds quick lime according to the quality-volumetric concentration relative to green liquor again, leave standstill and treat complete sedimentation.The inventive method is simple to operate, and absorption element silicon performance is extremely strong, and silica removal is most effective reaches 99.9%, and green liquor pH changes very little, introduces other ions little.

Description

A kind of alkali collection workshop section green liquor flocculation silicon removing method
Technical field
The invention belongs to paper industry technical field, be specifically related to a kind of alkali collection workshop section green liquor flocculation silicon removing method.
Background technology
Non-wood-fiber paper making raw material is the resource of a kind of important renewable fiber of China.Due to the restriction of resource, China's present stage adopts non-wood material slurrying mostly, such as bamboo, wheat straw etc.Due to the cause specific of non-wood fibrous 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 result causes alkali recovery process " silicon obstacle " problem.It is mainly reflected in evaporation, the workshop sections such as causticization and lime recovery.At caustic room, in green liquor causticizing reaction, have CaSiO 3generate, reduce the causticizing efficiency of green liquor, in addition, generate lime at burning of lime sludge and be back in the process of caustic room, silicon in white clay can reduce Activity of Lime, in addition, the silicon in white clay can make residual base number in white clay higher, because residual alkaloid substance fusing point is lower than lime, can first melt before white clay carries out calcination reaction or in course of reaction, form block with lime or stick on the inwall of limekiln and form balling, ring formation and knot ring, result causes that limekiln is as easy as rolling off a log breaks down.These problems not only can make alkali recovery efficiency reduce above, and it is serious that papermaking wastewater process workshop section is consumed energy, and do not reach national requirements.So, a lot of solution is had for alleviating " silicon obstacle " problem, as carbon dioxide process, aluminate method and soda lime method etc., but all have some limitations, while making to eliminate " silicon obstacle " problem, face other problems again, when the siliceous colloid particle passing into carbon dioxide/flue gas generation in black liquor is very tiny, and be suspended in solution, be difficult to precipitation, meanwhile, CO is worked as 2when method green liquor silica removal rate is 85%, the burning of lime sludge that green liquor causticizing produces reclaims lime still can not reuse, and green liquor pH value is low after silica removal, need supplementary NaOH that green liquor pH is adjusted back to high alkalinity, although aluminate method silica removal rate is higher, aluminum ions introduction volume increases along with the increase of silica removal rate, and aluminum ions a large amount of existence makes green liquor pH reduce, and the sodium silicoaluminate colloid formed is difficult to go out from system, causes other problems.Quick lime method silica removal rate is not high enough, still has the CaSiO of generation at lime calcining recovery stage 3be difficult to calcining.
Carbon dioxide seeding technique needs to adjust green liquor pH, adds desiliconizing agent in two steps and draws silicea.Two sections of lime technologies also need to add quick lime in two steps, and silica removal rate in factory is high not.So, the shortcomings such as above silicon removing process all exists complicated operation, and controllability is poor, and silica removal effect is good not, a kind of silica removal rate can be found high, introducing aluminium ion is few, and green liquor pH changes little, simple to operate, the silicon removing process that cost is low, to improve " silicon obstacle " problem of alkali collection workshop section, and alleviate facility load, be enterprise's improve effects.
Summary of the invention
The object of this invention is to provide a kind of alkali collection workshop section green liquor flocculation silicon removing method, solve existing silicon removing process and green liquor pH is reduced, silica removal rate is not high, and precipitation is slow, the problem of complicated operation.
The technical solution adopted in the present invention is, a kind of alkali collection workshop section green liquor flocculation silicon removing method, specifically implements according to following steps:
Step 1: prepare trivalent metal salt modified alta-mud;
Step 2: get the causticization section green liquor after clarification and pour in beaker, be heated to 90-100 DEG C, then be that 20-50g/L takes the trivalent metal salt modified alta-mud that step 1 obtains and joins in green liquor according to the quality-volumetric concentration of trivalent metal salt modified alta-mud, stirring reaction 10min, leave standstill and treat abundant reaction, be that the cationic polyacrylamide solution of 0.01%-1.0% joins in beaker according to the ratio that the volume ratio with green liquor is 1:20-1:200 by mass concentration, be that 10-30g/L adds quick lime according to the quality-volumetric concentration relative to green liquor again, leave standstill and treat complete sedimentation.
Feature of the present invention is also:
Step 1 wherein prepares trivalent metal salt modified alta-mud, specifically implement according to following steps: get sodium bentonite and be added to the water and be stirred to suspension, add trivalent metal salt, stir 2h, leave standstill 10-15h, remove supernatant, turbid for lower floor liquid is put into oven drying 24h, takes out, grinding, cross 200 mesh sieves, make trivalent metal salt modified alta-mud.
Sodium bentonite is wherein 15-50g/L relative to the quality-volumetric concentration of water.
Trivalent metal salt wherein and the mass ratio of sodium bentonite are 1:1-1:5.
Trivalent metal salt wherein adopts aluminium chloride, aluminum sulfate, ferric sulfate, the one in iron chloride or sodium metaaluminate.
The invention has the beneficial effects as follows, simple to operate, the expansion efficiency of silicon trapping agent is higher, absorption element silicon performance is extremely strong, and after adding flocculant flocculation reaction, sinking speed is fast, and silica removal is most effective reaches 99.9%, and green liquor pH changes very little, introduces other ions little.
Accompanying drawing explanation
Fig. 1 is technological process of the present invention;
Fig. 2 is green liquor element energy spectrogram before silica removal of the present invention;
Fig. 3 is green liquor element energy spectrogram after silica removal of the present invention.
Detailed description of the invention
The present invention's bamboo pulp green liquor used is from soda pulping process factory alkali collection workshop green liquor clarification groove, green liquor composition: total alkali 137.21g/l, active alkali 39.88g/l, Na 2cO 397.27g/l, Na 2s 31.94g/l, SiO 24.36g/l, the pH of green liquor is 12.94.The quality of flocculation silicon removing process is evaluated by the change of the silica removal rate in green liquor, sediment sedimentation time and green liquor pH.
Alkali collection workshop section of the present invention green liquor flocculation silicon removing method, as shown in Figure 1, specifically implement according to following steps:
Step 1: prepare trivalent metal salt modified alta-mud, specifically implements according to following steps: get sodium bentonite and be added to the water and be stirred to suspension, sodium bentonite is 15-50g/L relative to the quality-volumetric concentration of water, add trivalent metal salt, the mass ratio of trivalent metal salt and sodium bentonite is 1:1-1:5, stirs 2h, leaves standstill 10-15h, remove supernatant, turbid for lower floor liquid is put into oven drying 24h, takes out, grinding, cross 200 mesh sieves, namely make trivalent metal salt modified alta-mud.Trivalent metal salt adopts aluminium chloride, aluminum sulfate, ferric sulfate, iron chloride, sodium metaaluminate etc.
Step 2: get the causticization section green liquor after clarification and pour in beaker, be heated to 90-100 DEG C, then be that 20-50g/L takes trivalent metal salt modified alta-mud and joins in green liquor according to the quality-volumetric concentration of trivalent metal salt modified alta-mud, stirring reaction 10min, leave standstill 1min, treat abundant reaction, be that the cationic polyacrylamide solution of 0.01%-1.0% adds according to the ratio that the volume ratio with green liquor is 1:20-1:200 by mass concentration, be that 10-30g/L adds flocculant aid quick lime according to quality-volumetric concentration again, leave standstill and treat its complete sedimentation, sedimentation time is 5min, getting supernatant, to survey its silica removal rate be 80.0%-99.9%.
By the green liquor after flocculation process process through pH value determination, known green liquor pH after clarification is 12.94, and the green liquor pH after flocculation process process is that 12.90, pH is substantially constant.
Following examples green liquor used takes from soda pulping process factory alkali collection workshop green liquor clarification groove, and the silicon content of green liquor is that 4.27g/L is (with SiO 2meter), green liquor pH is 13.21.
Embodiment 1: get the causticization section green liquor 100mL after clarification, be heated to 90 DEG C, add 2.0g trivalent metal salt modified alta-mud in green liquor, stirring reaction 10min, adds 2mL 0.04%CPAM, 2g quick lime, stir and leave standstill 5min, survey clear liquid silicone content is 0.663g/L, pH is 13.17.
Embodiment 2: get the causticization section green liquor 100mL after clarification, be heated to 90 DEG C, add 3.0g trivalent metal salt modified alta-mud in green liquor, stirring reaction 10min, adds 0.5mL 0.04%CPAM, 2g quick lime, stir and leave standstill 5min, survey clear liquid silicone content is 0.061g/L, pH is 13.07.
Embodiment 3: get the causticization section green liquor 100mL after clarification, be heated to 90 DEG C, add 5g trivalent metal salt modified alta-mud in green liquor, stirring reaction 10min, adds 2mL 0.04%CPAM, 2g quick lime, stir and leave standstill 5min, survey clear liquid silicone content is 0g/L, pH is 12.90.
Embodiment 4: get the causticization section green liquor 100mL after clarification, be heated to 90 DEG C, 1.6g trivalent metal salt modified alta-mud is added in green liquor, stirring reaction 10min, adds 0.5mL 0.04%CPAM, 2g quick lime, stir and leave standstill 5min, survey clear liquid silicone content is 1.61g/L, pH is 13.15, settling time 15min.
Embodiment 5: get the causticization section green liquor 100mL after clarification, be heated to 90 DEG C, 1.6g trivalent metal salt modified alta-mud is added in green liquor, stirring reaction 10min, adds 2mL 0.04%CPAM, 2g quick lime, stir and leave standstill 5min, survey clear liquid silicone content is 1.39g/L, pH is 13.09, settling time 5min.
Embodiment 6: get the causticization section green liquor 100mL after clarification, be heated to 90 DEG C, 1.6g trivalent metal salt modified alta-mud is added in green liquor, stirring reaction 10min, adds 5mL 0.04%CPAM, 2g quick lime, stir and leave standstill 5min, survey clear liquid silicone content is 1.44g/L, pH is 13.01, settling time 5min.
Embodiment 7: get the causticization section green liquor 100mL after clarification, be heated to 90 DEG C, add 1.6g trivalent metal salt modified alta-mud in green liquor, stirring reaction 10min, adds 2mL 0.04%CPAM, 0.1g quick lime, stir and leave standstill 5min, survey clear liquid silicone content is 1.61g/L, pH is 13.03.
Embodiment 8: get the causticization section green liquor 100mL after clarification, be heated to 90 DEG C, add 1.6g trivalent metal salt modified alta-mud in green liquor, stirring reaction 10min, adds 2mL 0.04%CPAM, 2g quick lime, stir and leave standstill 5min, survey clear liquid silicone content is 1.51g/L, pH is 13.16.
Embodiment 9: get the causticization section green liquor 100mL after clarification, be heated to 90 DEG C, add 1.6g trivalent metal salt modified alta-mud in green liquor, stirring reaction 10min, adds 2mL 0.04%CPAM, 3g quick lime, stir and leave standstill 5min, survey clear liquid silicone content is 1.55g/L, pH is 13.25.
Inventive point of the present invention is that trivalent metal salt modified alta-mud combines with cationic polyacrylamide (CPAM), CPAM adds the sinking speed after accelerating trivalent metal salt modified alta-mud absorption silicon, in addition, adding of quick lime, there is the effect helping flocculation and help silica removal, and the change of the green liquor pH that modified alta-mud causes can be alleviated, alleviate meeting of alkali collection workshop section.
This flocculation silicon removing process is characterised in that, first adds trivalent metal salt modified alta-mud 20g-50g/L, and add and green liquor pH decline too much can be caused too fast, silica removal rate at least of crossing does not reach requirement.Be that the cationic polyacrylamide solution of 0.01%-1.0% adds according to the ratio that the volume ratio with green liquor is 1:200-1:1000 subsequently by mass concentration, CPAM too much can be caused to adsorb OH -ion, green liquor pH declines, increase alkali collection load, CPAM crosses silica removal speed at least and declines, and time of repose lengthens, affect the continuity of technique, finally, adding quality-volumetric concentration is 10-30g/L quick lime, and quick lime is very few less to green liquor pH regulating action, help flocculating effect also not good, so select 10-30g/L to be advisable.After silica removal, the pH of green liquor controls between 12.90-13.30, and silica removal rate controls at 80.0%-99.9%.
This technological operation is simple, and continuity is strong, and silica removal rate is high and pH rate of change is little, alleviates meeting of alkali collection workshop section.
Fig. 2 is green liquor energy spectrogram before silica removal, obviously can see the element silicon in green liquor, Fig. 3 is the energy spectrogram of green liquor after 99.9% flocculation silica removal, can find out that element silicon disappears in the drawings, by the contrast of Fig. 2 Fig. 3, the effect before and after the flocculation silica removal that can visually see.

Claims (4)

1. an alkali collection workshop section green liquor flocculation silicon removing method, is characterized in that, specifically implement according to following steps:
Step 1: prepare trivalent metal salt modified alta-mud;
Step 2: get the causticization section green liquor after clarification and pour in beaker, be heated to 90-100 DEG C, then be that 20-50g/L takes the trivalent metal salt modified alta-mud that step 1 obtains and joins in green liquor according to the quality-volumetric concentration of trivalent metal salt modified alta-mud, stirring reaction 10min, leave standstill and treat abundant reaction, be that the cationic polyacrylamide solution of 0.01%-1.0% joins in beaker according to the ratio that the volume ratio with green liquor is 1:20-1:200 by mass concentration, be that 10-30g/L adds quick lime according to the quality-volumetric concentration relative to green liquor again, leave standstill and treat complete sedimentation,
Described trivalent metal salt adopts aluminium chloride, aluminum sulfate, ferric sulfate, the one in iron chloride or sodium metaaluminate.
2. alkali collection workshop section according to claim 1 green liquor flocculation silicon removing method, it is characterized in that, described step 1 prepares trivalent metal salt modified alta-mud, specifically implement according to following steps: get sodium bentonite and be added to the water and be stirred to suspension, add trivalent metal salt, stir 2h, leave standstill 10-15h, remove supernatant, turbid for lower floor liquid is put into oven drying 24h, takes out, grinding, cross 200 mesh sieves, make trivalent metal salt modified alta-mud.
3. alkali collection workshop section according to claim 2 green liquor flocculation silicon removing method, it is characterized in that, described sodium bentonite is 15-50g/L relative to the quality-volumetric concentration of water.
4. alkali collection workshop section according to claim 2 green liquor flocculation silicon removing method, it is characterized in that, described trivalent metal salt and the mass ratio of sodium bentonite are 1:1-1:5.
CN201310376672.8A 2013-08-26 2013-08-26 A kind of alkali collection workshop section green liquor flocculation silicon removing method Expired - Fee Related CN103469664B (en)

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CN108840361B (en) * 2018-08-02 2019-07-19 广东鼎丰纸业有限公司 A method of high-purity calcium carbonate is refined using green liquor causticizing
JP6901032B1 (en) * 2020-07-02 2021-07-14 栗田工業株式会社 Green liquid treatment agent
CN115434178B (en) * 2022-08-23 2023-09-01 天津科技大学 Chemical alkali recovery treatment process for chemical mechanical pulp waste liquid

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