CN102070287B - Process for reducing chloride ions in white mud from ammonia soda plants - Google Patents
Process for reducing chloride ions in white mud from ammonia soda plants Download PDFInfo
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- CN102070287B CN102070287B CN 201010572644 CN201010572644A CN102070287B CN 102070287 B CN102070287 B CN 102070287B CN 201010572644 CN201010572644 CN 201010572644 CN 201010572644 A CN201010572644 A CN 201010572644A CN 102070287 B CN102070287 B CN 102070287B
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Abstract
The invention discloses a process for reducing chloride ions in white mud from ammonia soda plants, which comprises the following steps: adding a white mud raw material and flocculant into a primary solid-liquid separation device for fully dehydration; adding the white mud slag dewatered in the previous step into a dispersing mixer, adding water at the same time to prepare white mud slurry at a mass concentration of 5 to 40 percent, and fully dispersing and mixing; and delivering white mud slurry into a middle tank, and delivering the slurry to a secondary solid and liquid separation device from the middle tank to fully dehydrate to obtain white mud with reduced chloride ions. The process of the invention can reduce the chloride ion content in the white mud, which is difficult to treat in industry, from the ammonia soda plants to below 15 percent; when the white mud with reduced chloride ions is used as a desulfurizer, the desulfurization rate can reach 95 to 99 percent; and thus, the process reaches the standards for waste recycling, and is environmentally-friendly and low in cost and in accordance with the sustained development strategy of China.
Description
Technical field
The present invention relates to a kind of technology that reduces chlorion in the ammonia alkali factory white clay.
Background technology
Soda ash is widely used in industries such as chemical industry, building materials, metallurgy as important basic chemical industry raw material.As maximum in the world soda ash producing country, the present soda ash annual production of China is up to 2,170 ten thousand tons, and wherein ammonia-soda process soda ash accounts for more than 55% of total output.Produce a large amount of waste mud of distillation (being commonly called as white clay) and first and second salt slurries of by-product in the soda ash process in ammonia-soda process, in general every production 1t soda ash can produce 300 ~ 350kg white clay, the butt annual production of white clay is all more than 3,000,000 tons, these white claies are owing to can not get handling fully and utilizing, overwhelming majority air storage, perhaps directly row is extra large.The long-term white clay of stacking has not only taken a large amount of land resource, and as the high alkalinity material, a large amount of stackings of white clay finally can be killed the microorganism in the soil, destroys the original structure of soil, finally becomes the salt-soda soil, and its surperficial weathering simultaneously also can produce dust pollution; The destruction that white clay row Hai Ze causes the marine ecology balance, harm aquaculture, and also may the crisis navigation channel after the deposition.
At present, white clay has all been obtained certain progress in the application aspect engineering construction, chemical industry environmental protection and the agricultural fishery, but because some physico-chemical properties of white clay self are restricted the road of white clay integrated application.On the one hand, the particle of white clay is very thin, and wherein the granularity of 95% above solid phase is less than 25 μ m, specific area is big, and is electronegative, thereby has colloidal sol character, participate in Activity of Chemical Reaction (as desulfurization) though be conducive to improve it, also can cause the white clay sinking speed slow simultaneously, the dehydration difficulty.On the other hand, a large amount of muriatic existence in the white clay make its very easily moisture absorption deliquescence, thereby cause it in industrial recycling, and particularly the utilization in building materials industry is very limited.No matter be used as the asphalt filler, still make landfill soil and handle soluble chloride (CaCl in the white clay
2, NaCl) all be maximum obstacle.Therefore, the emphasis of exploitation white clay comprehensive utilization technique and difficult point are exactly the chlorion that utilizes in the various technology removal white claies.
At present the dechlorination technology comprises following several means: 1. the high temperature dechlorination process of Tianjin Caustic Soda Plant's exploitation in 1970, this technology can be divided into four steps: the first step is by the river previous cleaning, the second step admixture rubble, the 3rd step press filtration, high-temperature calcination more at last, this fresh water (FW) consumption, energy consumption is huge, the production cost height, finally fail industrialization and industrialization, 2.. the physical method of mechanical dehydration reduces chlorion, especially adopt large-scale filtering equipment by the chlorion in the Separation of Solid and Liquid reduction white clay, as the PF full automatic pressure filter of Tianjin Caustic Soda Plant from the introduction of Finland LAROX company, but import equipment is simple to operate, and disposal ability is big, cake moisture≤46%, though this measure can remove the chlorion of a part by the dewatering efficiency height, invests hugely, can not use on a large scale and promote, and the filter cake after the dehydration is chloride still can be difficult to reach the standard of changing rejected material to useful resource recycling up to about 8%.
Summary of the invention
The purpose of this invention is to provide a kind of technology that reduces chlorion in the ammonia alkali factory white clay.
The technical solution used in the present invention is:
A kind of technology that reduces chlorion in the ammonia alkali factory white clay, it is characterized in that: it may further comprise the steps:
1) white clay raw material, flocculant being added the one-level equipment for separating liquid from solid fully dewaters;
2) clay-slag that will go up after the step dewaters adds in the dispersion mixer, adds water simultaneously, is mixed with the white clay slurries of 5-40% mass concentration, fully disperses mixing;
3) the white clay slurries are sent into intermediate storage tank, then slurries are sent into the secondary equipment for separating liquid from solid from middle storage tank and fully dewater, obtain falling the chlorine white clay.
The white clay raw material is the waste liquid settling tank underflow of ammonia alkali factory.
Flocculant is polyacrylamide.
In the step 1), flocculant is the solid adding or is configured to the flocculant solution adding that concentration is 2-5 ‰.
The flocculant solid masses: the white clay solid in the waste liquid settling tank underflow divides quality=(0.5-1kg): 1t perhaps is the flocculant solution volume: waste liquid settling tank underflow volume=(10-15ml): 1L.
Equipment for separating liquid from solid comprises plate and frame filter press, horizontal type screw settling centrifuge.
Equipment for separating liquid from solid comprises barrier film plate and frame filter press, horizontal type screw settling centrifuge.
The invention has the beneficial effects as follows: technology of the present invention can be reduced to the chloride ion content in the industrial reluctant ammonia alkali factory white clay below 1.5%, in the time of will falling the chlorine white clay as desulfurizing agent, desulfurization degree can reach 95-99%, reached the standard of changing rejected material to useful resource recycling, the technology environmental protection, cost is low, meets the strategy of national sustainable development.
The specific embodiment
A kind of technology that reduces chlorion in the ammonia alkali factory white clay, it is characterized in that: it may further comprise the steps:
1) white clay raw material, flocculant being added the one-level equipment for separating liquid from solid fully dewaters;
2) clay-slag that will go up after the step dewaters adds in the dispersion mixer, adds water simultaneously, is mixed with the white clay slurries of 5-40% mass concentration, fully disperses mixing;
3) the white clay slurries are sent into intermediate storage tank, then slurries are sent into the secondary equipment for separating liquid from solid from middle storage tank and fully dewater, obtain falling the chlorine white clay.
Wherein, the white clay raw material is the waste liquid settling tank underflow of ammonia alkali factory, flocculant is polyacrylamide, in the step 1), flocculant is the solid adding or is configured to the flocculant solution adding that concentration is 2-5 ‰, the flocculant solid masses: the white clay solid in the white clay underflow divides quality=(0.5-1kg): 1t, perhaps be the flocculant solution volume: white clay underflow volume=(10-15ml): 1L, equipment for separating liquid from solid comprises plate and frame filter press, horizontal type screw settling centrifuge, as further preferred version, equipment for separating liquid from solid comprises the barrier film plate and frame filter press, horizontal type screw settling centrifuge.
The present invention is described further below in conjunction with specific embodiment:
Embodiment 1:
1) drawing flow from ammonia alkali factory settling tank is 20m
3The white clay underflow slurries of/h, recording its chloride ion content is 96.57g/L, with its barrier film plate and frame filter press that adds the flushing of a band filter cake, adds flocculant---the polyacrylamide (PAM) of 2-5 ‰ simultaneously, the amount of splashing into is (10-15ml) PAM solution/1L white clay underflow, fully dehydration;
2) clay-slag that will go up after the step dewaters adds in the dispersion mixer, adds water simultaneously, is mixed with the white clay slurries of 13% mass concentration, fully disperses mixing;
3) the white clay slurries are sent into intermediate storage tank, then slurries are sent into plate and frame filter press from middle storage tank and fully dewater, obtain falling the chlorine white clay, the solid content in the final white clay is 48.1%, chloride ion content only 1.07%.
Embodiment 2:
1) drawing flow from ammonia alkali factory settling tank is 50m
3The white clay underflow slurries of/h, recording its chloride ion content is 102.85g/L, it is added in the decaner, add polyacrylamide (PAM) solid simultaneously, addition is the flocculant solid masses: the white clay solid branch quality in the white clay underflow=(0.5-1kg): 1t, fully dehydration;
2) clay-slag that will go up after the step dewaters adds in the dispersion mixer, adds water simultaneously, is mixed with the white clay slurries of 13% mass concentration, fully disperses mixing;
3) the white clay slurries are sent into intermediate storage tank, then slurries are sent into the barrier film plate and frame filter press from middle storage tank and fully dewater, obtain falling the chlorine white clay, the solid content in the final white clay is 53.8%, chloride ion content 0.81%.
Embodiment 3:
1) drawing flow from ammonia alkali factory settling tank is 400m
3The white clay underflow slurries of/h, recording its chloride ion content is 105g/L, and it is added a platen frame filter press, adds polyacrylamide (PAM) solid simultaneously, addition is the flocculant solid masses: the white clay solid branch quality in the white clay underflow=(0.5-1kg): 1t, fully dehydration;
2) clay-slag that will go up after the step dewaters adds in the dispersion mixer, adds water simultaneously, is mixed with the white clay slurries of 16% mass concentration, fully disperses mixing;
3) the white clay slurries are sent into intermediate storage tank, then slurries are sent into decaner from middle storage tank and fully dewater, obtain falling the chlorine white clay, the solid content in the final white clay is 53.8%, chloride ion content 0.85%.
Embodiment 4:
1) drawing flow from ammonia alkali factory settling tank is 100m
3The white clay underflow slurries of/h, recording its chloride ion content is 113.41g/L, it is added a horizontal type screw settling centrifuge, add polyacrylamide (PAM) solid simultaneously, addition is the flocculant solid masses: the white clay solid branch quality in the white clay underflow=(0.5-1kg): 1t, fully dehydration;
2) clay-slag that will go up after the step dewaters adds in the dispersion mixer, adds water simultaneously, is mixed with the white clay slurries of 5% mass concentration, fully disperses mixing;
3) the white clay slurries are sent into intermediate storage tank, then slurries are sent into plate and frame filter press from middle storage tank and fully dewater, obtain falling the chlorine white clay, the solid content in the final white clay is 52%, chloride ion content 0.5%.
Embodiment 5:
1) drawing flow from ammonia alkali factory settling tank is 400m
3The white clay underflow slurries of/h, recording its chloride ion content is 46.7g/L, it is added a horizontal type screw settling centrifuge, add polyacrylamide (PAM) solid simultaneously, addition is the flocculant solid masses: the white clay solid branch quality in the white clay underflow=(0.5-1kg): 1t, fully dehydration;
2) clay-slag that will go up after the step dewaters adds in the dispersion mixer, adds water simultaneously, is mixed with the white clay slurries of 40% mass concentration, fully disperses mixing;
3) the white clay slurries are sent into intermediate storage tank, then slurries are sent into the barrier film plate and frame filter press from middle storage tank and fully dewater, obtain falling the chlorine white clay, the solid content in the final white clay is 51.7%, chloride ion content 1.47%.
Embodiment 6:
1) drawing flow from ammonia alkali factory settling tank is 50m
3The white clay underflow slurries of/h, recording its chloride ion content is 90g/L, it is added in the decaner, add polyacrylamide (PAM) solid simultaneously, addition is the flocculant solid masses: the white clay solid branch quality in the white clay underflow=(0.5-1kg): 1t, fully dehydration;
2) clay-slag that will go up after the step dewaters adds in the dispersion mixer, adds water simultaneously, is mixed with the white clay slurries of 20% mass concentration, fully disperses mixing;
3) the white clay slurries are sent into intermediate storage tank, then slurries are sent into plate and frame filter press from middle storage tank and fully dewater, obtain falling the chlorine white clay, the solid content in the final white clay is 51%, chloride ion content 1.5%.
The chlorine white clay that falls among the embodiment 1-6 is sent into the white clay slurries of making mass concentration 20-25% in power plant's slurries case, and deliver to the desulphurization system desulfurization.The result shows, adopts the white clay of handling to make desulfurizing agent, and desulfurization degree is respectively 95.2%, 97%, 99%, 98%, 96.8%, 97.5%, and the chloride ion content in the white clay slurries that are mixed with simultaneously is respectively 0.42%, 0.32%, 0.34%, 0.2%, 0.58%, 0.6%.
As can be seen, through the processing of this technology, the chloride ion content in the discarded white clay among the embodiment 1-6 is all below 1.5%, during as desulfurizing agent, desulfurization degree has reached the standard of changing rejected material to useful resource recycling all more than 95%, environmental protection meets the strategy of national sustainable development.
Claims (5)
1. technology that reduces chlorion in the ammonia alkali factory white clay, it is characterized in that: it may further comprise the steps:
1) white clay raw material, flocculant being added the one-level equipment for separating liquid from solid fully dewaters;
2) clay-slag that will go up after the step dewaters adds in the dispersion mixer, adds water simultaneously, is mixed with the white clay slurries of 5-40% mass concentration, fully disperses mixing;
3) the white clay slurries are sent into intermediate storage tank, then slurries are sent into the secondary equipment for separating liquid from solid from middle storage tank and fully dewater, obtain falling the chlorine white clay;
Wherein, described equipment for separating liquid from solid is plate and frame filter press or horizontal type screw settling centrifuge.
2. a kind of technology that reduces chlorion in the ammonia alkali factory white clay according to claim 1, it is characterized in that: the white clay raw material is the waste liquid settling tank underflow of ammonia alkali factory.
3. a kind of technology that reduces chlorion in the ammonia alkali factory white clay according to claim 1, it is characterized in that: flocculant is polyacrylamide.
4. a kind of technology that reduces chlorion in the ammonia alkali factory white clay according to claim 1 is characterized in that: in the step 1), flocculant is that solid adds or be configured to concentration is that the flocculant solution of 2-5 ‰ adds.
5. according to any described a kind of technology that reduces chlorion in the ammonia alkali factory white clay in the claim 1 to 4, it is characterized in that: the flocculant solid masses: the white clay solid branch quality in the waste liquid settling tank underflow=(0.5-1kg): 1t perhaps is the flocculant solution volume: waste liquid settling tank underflow volume=(10-15m1): 1L.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102557364B (en) * | 2011-12-30 | 2013-06-12 | 青岛碱业股份有限公司 | Method for reducing chloride ions in white mud of ammonia-alkali factory |
| CN104190690B (en) * | 2014-08-06 | 2016-05-04 | 华南理工大学 | A kind of method and application that utilizes ammonia-soda process alkaline residue to prepare dechlorination alkaline residue mixture |
| CN105879632A (en) * | 2014-12-16 | 2016-08-24 | 华北电力大学（保定） | Method and system for removing mercury of circulating fluidized bed coal-fired boiler by utilizing white mud |
| CN104857831B (en) * | 2015-05-29 | 2017-07-11 | 唐山三友化工股份有限公司 | Alkaline residue liquid apparatus for preparing desulphurizing agent and method |
| CN105032903B (en) * | 2015-09-08 | 2017-04-12 | 华北理工大学 | Method for removing chloride ions in waste alkaline residues |
| CN113813660A (en) * | 2021-09-30 | 2021-12-21 | 天津渤化永利化工股份有限公司 | System and method for comprehensively treating ammonia II mud of combined alkali production device |
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| CN101417870A (en) * | 2008-11-16 | 2009-04-29 | 青岛春风化工有限公司 | Method for producing architectural materials by using white slime |
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| CN101780464A (en) * | 2010-02-02 | 2010-07-21 | 山东海化集团有限公司 | Method for removing ammoniasoda process calcined soda waste residue chloride ion |
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| CN101417870A (en) * | 2008-11-16 | 2009-04-29 | 青岛春风化工有限公司 | Method for producing architectural materials by using white slime |
| CN101705025A (en) * | 2009-10-21 | 2010-05-12 | 江涛 | Method for producing building materials by red mud and lime mud |
| CN101780464A (en) * | 2010-02-02 | 2010-07-21 | 山东海化集团有限公司 | Method for removing ammoniasoda process calcined soda waste residue chloride ion |
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Owner name: ZHANG SHAOXUN GUANGDONG NANFANG SODA ASH INDUSTRY Free format text: FORMER OWNER: ZHANG SHAOXUN Effective date: 20120209 |
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Effective date of registration: 20120209 Address after: 301 Wen Sheng business building, No. 722, Whampoa East Road, Whampoa District, Guangdong, Guangzhou 510725 Applicant after: Guangzhou Tianyi Sanhe Energy & Environmental Co.,Ltd. Co-applicant after: Zhang Shaoxun Co-applicant after: Guangdong Nanfang Soda ASH Industrial Co.,Ltd. Address before: 301 Wen Sheng business building, No. 722, Whampoa East Road, Whampoa District, Guangdong, Guangzhou 510725 Applicant before: Guangzhou Tianyi Sanhe Energy & Environmental Co.,Ltd. Co-applicant before: Zhang Shaoxun |
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