CN104163514B - A kind of ammonium chloride waste-water ammoniacal liquor, hydrochloric acid technique of zero discharge - Google Patents
A kind of ammonium chloride waste-water ammoniacal liquor, hydrochloric acid technique of zero discharge Download PDFInfo
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- CN104163514B CN104163514B CN201410403821.XA CN201410403821A CN104163514B CN 104163514 B CN104163514 B CN 104163514B CN 201410403821 A CN201410403821 A CN 201410403821A CN 104163514 B CN104163514 B CN 104163514B
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Abstract
The invention discloses a kind of ammonium chloride waste-water ammoniacal liquor, hydrochloric acid technique of zero discharge, comprise the steps: step 1: ammonium chloride waste-water is collected in equalizing tank, ammonium chloride waste-water in equalizing tank carries out micro-filtrate membrane filtration, obtain micro-filtration dialyzate and micro-filtration concentrated solution, micro-filtration concentrated solution is back to equalizing tank circular treatment; Step 2: micro-filtration dialyzate carries out high pressure reverse osmosis isolation, obtains high pressure reverse osmosis dialyzate and high pressure reverse osmosis concentrated liquid; Step 3: high pressure reverse osmosis concentrated liquid enters in Bipolar Membrane system and enters the process of Bipolar Membrane system, obtains hydrochloric acid and ammoniacal liquor; Step 4: high pressure reverse osmosis dialyzate carries out low pressure reverse osmosis separation, obtain low pressure reverse osmosis dialyzate and low pressure reverse osmosis concentrated solution, low pressure reverse osmosis concentrated solution enters circular treatment in high pressure reverse osmosis, and low pressure reverse osmosis dialyzate is back to production.Present invention process abandons the great number cost evaporating and bring, and the salt in waste water and moisture is recycled in process, and reaches the zero release of waste water.
Description
Technical field
The present invention relates to field of hydrometallurgy, particularly a kind of ammonium chloride waste-water ammoniacal liquor, hydrochloric acid zero release novel process.
Background technology
One of strategic mineral resources that the Gu Shi world is important, it has high temperature resistant, corrosion-resistant, the feature such as high strength and ferromagnetism, be widely used in Aeronautics and Astronautics, electrical equipment, machinofacture, Wimet, magneticsubstance, chemistry and the industry such as ceramic, acquire a special sense in national economy and social development.The synthesis of current cobalt chloride mostly is cobalt ore and hydrochloric acid after pre-treatment and synthesizes under the catalysts such as nitric acid, owing to containing the impurity such as nickel, iron, zinc, lead in cobalt ore, unavoidably needs to add ammoniacal liquor, hydrogen peroxide is removed.Therefore after filtration in filtrate containing ammonium sulfate.
Hydrometallurgy mainly comprises, as shown in Figure 1: ammonium chloride waste-water in processes, because ion content is high, and problems such as ammonium chloride low finished product cost, cannot direct outer row.The methods such as general employing multiple-effect evaporation process, and cause evaporation cost high, reclaim meaning lower, be a difficult point in ammonium chloride waste-water process always.
Summary of the invention
For deficiency of the prior art, the object of the present invention is to provide one can efficient recovery water resources, reclaim salinity and reduce enterprise's production cost, improve ammonium chloride waste-water ammoniacal liquor, the hydrochloric acid technique of zero discharge of the reuse of income water cycle.
For achieving the above object, the technical scheme that the present invention proposes is: a kind of ammonium chloride waste-water ammoniacal liquor, hydrochloric acid technique of zero discharge, is characterized in that, comprise the steps:
Step 1: ammonium chloride waste-water is collected in equalizing tank, the ammonium chloride waste-water in equalizing tank carries out micro-filtrate membrane filtration, and obtain micro-filtration dialyzate and micro-filtration concentrated solution, micro-filtration concentrated solution is back to equalizing tank circular treatment;
Step 2: micro-filtration dialyzate carries out high pressure reverse osmosis isolation, obtains high pressure reverse osmosis dialyzate and high pressure reverse osmosis concentrated liquid;
Step 3: high pressure reverse osmosis concentrated liquid enters in Bipolar Membrane system and enters the process of Bipolar Membrane system, obtains hydrochloric acid and ammoniacal liquor;
Step 4: high pressure reverse osmosis dialyzate carries out low pressure reverse osmosis separation, obtain low pressure reverse osmosis dialyzate and low pressure reverse osmosis concentrated solution, low pressure reverse osmosis concentrated solution enters circular treatment in high pressure reverse osmosis, and low pressure reverse osmosis dialyzate is back to production.
Preferably, the Bipolar Membrane in described Bipolar Membrane system is polyether-ether-ketone material, and service temperature less than 300 DEG C, selective penetrated property is more than 96%.
Preferably, use titanium platinum plating as anodic-cathodic in described Bipolar Membrane system, diaphragm is homogeneous membrane, and control voltage is 20V, and feed liquid room and sour room, alkali room volume ratio are 1:5.
Preferably, the factory effluent of described ammonium chloride waste-water for producing in cobalt chloride smelting industry.
Adopt technique scheme, ammonium chloride waste-water ammoniacal liquor of the present invention, hydrochloric acid technique of zero discharge, feed liquid after concentrated made hydrochloric acid and ammoniacal liquor reuse in technique by Bipolar Membrane, obtain reuse water by the advanced treatment of low pressure reverse osmosis system to product water; The innovative point of whole technique is to make ammonium chloride waste-water reach the object of reuse, abandons the great number cost evaporating and bring, the salt in waste water and moisture is recycled in process, and reaches the zero release of waste water.
Accompanying drawing explanation
Fig. 1 is hydrometallurgical processes schema;
Fig. 2 is ammonium chloride waste-water ammoniacal liquor of the present invention, hydrochloric acid technique of zero discharge schema.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment:
The present embodiment use the factory effluent of waste water for producing in cobalt chloride smelting industry, concrete technology flow process as shown in Figure 2:
Step 1: use microfiltration systems to process ammonium chloride waste-water, suspended substance, floss and particle in removing feed liquid, ensure the steady running of follow-up reverse osmosis, and micro-filtration is dense, and to carry out circulation concentrated, carries out three batches of experiments:
From experimental data, the pressure that microfiltration systems has, high yield water rate, etc. feature, simultaneously because flux during process feed liquid all reaches very high level, cost of investment is also relatively low.
Step 2: use high pressure reverse osmosis to process micro-filtration dialyzate, micro-filtration dialyzate contains a large amount of chlorion, ammonium ion and a small amount of cobalt ion; General chlorion >25g/L, ammonium ion >10g/L, cobalt ion <0.04g/L, control temperature at 40 DEG C, pressure 60Bar; Carry out three batches of experiments:
From experimental data, by high pressure reverse osmosis, feed liquid intermediate ion is concentrated, there is cycles of concentration, producing water ratio comparatively high.
Step 3: use Bipolar Membrane system against high voltage reverse osmosis concentrated liquid to process, uses titanium platinum plating as anodic-cathodic, and use diaphragm to be homogeneous membrane, control voltage is 20V, and feed liquid room and sour room, alkali room volume ratio are 1:5, carry out three batches of experiments:
From experimental data, use homogeneous membrane as diaphragm, titanium platinum plating has the features such as current efficiency is high, energy consumption is lower as pole plate when handle high voltages reverse osmosis concentrated liquid, and product acid, alkali directly can return in former technique and use.
Step 4: use low pressure reverse osmosis system process electric osmose high pressure reverse osmosis dialyzate, make dialyzate directly can carry out reuse, reach the zero release of ammonium chloride waste-water, control into film pressure be 20Bar, temperature less than 40 DEG C, carry out three batches of experiments:
From experimental data, the reverse osmosis system features such as tool producing water ratio is high when handle high voltages reverse osmosis dialyzate, average flux is high, cost of investment is lower, and product water reaches reuse rank completely.
In the above-described embodiments, only to invention has been exemplary description, but those skilled in the art can carry out various amendment to the present invention without departing from the spirit and scope of the present invention after reading present patent application.
Claims (3)
1. ammonium chloride waste-water ammoniacal liquor, a hydrochloric acid technique of zero discharge, is characterized in that, comprise the steps:
Step 1: ammonium chloride waste-water is collected in equalizing tank, the ammonium chloride waste-water in equalizing tank carries out micro-filtrate membrane filtration, and obtain micro-filtration dialyzate and micro-filtration concentrated solution, micro-filtration concentrated solution is back to equalizing tank circular treatment;
Step 2: micro-filtration dialyzate carries out high pressure reverse osmosis isolation, obtains high pressure reverse osmosis dialyzate and high pressure reverse osmosis concentrated liquid;
Step 3: high pressure reverse osmosis concentrated liquid enters in Bipolar Membrane system and enters the process of Bipolar Membrane system, obtains hydrochloric acid and ammoniacal liquor; Use titanium platinum plating as anodic-cathodic in described Bipolar Membrane system, diaphragm is homogeneous membrane, and control voltage is 20V, and feed liquid room and sour room, alkali room volume ratio are 1:5;
Step 4: high pressure reverse osmosis dialyzate carries out low pressure reverse osmosis separation, obtain low pressure reverse osmosis dialyzate and low pressure reverse osmosis concentrated solution, low pressure reverse osmosis concentrated solution enters circular treatment in high pressure reverse osmosis, and low pressure reverse osmosis dialyzate is back to production.
2. a kind of ammonium chloride waste-water ammoniacal liquor according to claim 1, hydrochloric acid technique of zero discharge, is characterized in that, the Bipolar Membrane in described Bipolar Membrane system is polyether-ether-ketone material, and service temperature less than 300 DEG C, selective penetrated property is more than 96%.
3. a kind of ammonium chloride waste-water ammoniacal liquor according to claim 1, hydrochloric acid technique of zero discharge, is characterized in that, the factory effluent of described ammonium chloride waste-water for producing in cobalt chloride smelting industry.
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| CN201410403821.XA CN104163514B (en) | 2014-08-16 | 2014-08-16 | A kind of ammonium chloride waste-water ammoniacal liquor, hydrochloric acid technique of zero discharge |
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| CN104163514B true CN104163514B (en) | 2016-03-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105060405A (en) * | 2015-08-10 | 2015-11-18 | 厦门世达膜科技有限公司 | Process for preparing strong acid and strong alkali by separating cobalt smelting wastewater |
| CN107487874A (en) * | 2017-07-28 | 2017-12-19 | 盐城市龙强机械制造有限公司 | Sewage treatment technology on a kind of hang plating production line |
| CN115557574A (en) * | 2022-10-20 | 2023-01-03 | 徐州水处理研究所 | Process for recycling ammonium sulfate and ammonium chloride wastewater by full membrane method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491900A (en) * | 2003-08-27 | 2004-04-28 | 兖矿鲁南化工科技发展有限公司 | Method for treating waste water containing low concentration ammonium chloride |
| CN102153168A (en) * | 2010-12-01 | 2011-08-17 | 杭州水处理技术研究开发中心有限公司 | Method for adjusting quality of water produced by desalting sea water by reverse osmosis method by using bipolar membrane |
| JP2013017951A (en) * | 2011-07-12 | 2013-01-31 | Jfe Steel Corp | Method and apparatus for treatment of pickling waste liquid |
| CN103508521A (en) * | 2013-09-18 | 2014-01-15 | 中国海洋大学 | Recycling treatment method for salt-containing wastewater |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491900A (en) * | 2003-08-27 | 2004-04-28 | 兖矿鲁南化工科技发展有限公司 | Method for treating waste water containing low concentration ammonium chloride |
| CN102153168A (en) * | 2010-12-01 | 2011-08-17 | 杭州水处理技术研究开发中心有限公司 | Method for adjusting quality of water produced by desalting sea water by reverse osmosis method by using bipolar membrane |
| JP2013017951A (en) * | 2011-07-12 | 2013-01-31 | Jfe Steel Corp | Method and apparatus for treatment of pickling waste liquid |
| CN103508521A (en) * | 2013-09-18 | 2014-01-15 | 中国海洋大学 | Recycling treatment method for salt-containing wastewater |
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Application publication date: 20141126 Assignee: Xiamen Shida membrane Engineering Co.,Ltd. Assignor: XIAMEN STARMEM TECHNOLOGY CO.,LTD. Contract record no.: X2021980014823 Denomination of invention: A zero discharge process for ammonia and hydrochloric acid from ammonium chloride wastewater Granted publication date: 20160316 License type: Exclusive License Record date: 20211221 |