CN101746779B - Refining method of liquid ammonium sulfate for water treatment - Google Patents
Refining method of liquid ammonium sulfate for water treatment Download PDFInfo
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- CN101746779B CN101746779B CN2009102012360A CN200910201236A CN101746779B CN 101746779 B CN101746779 B CN 101746779B CN 2009102012360 A CN2009102012360 A CN 2009102012360A CN 200910201236 A CN200910201236 A CN 200910201236A CN 101746779 B CN101746779 B CN 101746779B
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Abstract
The invention relates to a refining method of liquid ammonium sulfate for water treatment, which comprises the following steps of step one, detecting various metal ion contents in ammonium sulfate; step two, pretreating: oxidation, sequentially adding ammonia water and an oxidant into water solution of the ammonium sulfate and continuously stirring for above 5min so as to enable low valence metalions in the ammonium sulfate solution to be oxidated to form high valence metal ions; step three, enabling the metal ions in the ammonium sulfate solution obtained in the step two to form precipitation by adding heavy metal ion remover; and step four, standing and separating: stirred precipitate is in standing before separating with water and then is separated by filtering, the PH value of a mother liquor after filtering is regulated, and the mother liquor enters a finished product pool. The refining method of the ammonium sulfate can enable contents of elements including iron, lead, mercury, chromium (hexavalent), cadmium and arsenic to achieve a national standard (GB535-1995) and enable the liquid ammonium sulfate after refining to be used for life drinking water treatment.
Description
Technical field
The present invention relates to a kind of fine-finishing method of ammonium sulfate, particularly, relate to a kind of process for purification that is used for the liquid ammonium sulfate of water treatment.
Background technology
Existing water factory directly under the jurisdiction of a municipal government generally all adopts chloramine disinfection to guarantee the chlorine content of pipe network end because the transmission pipeline network that dispatches from the factory is longer so filter the back.Chloramine disinfection (chloramine disinfection) refers to chlorine and ammonia react generation monochloro amine and dichlormaine to finish oxidation and disinfectant method, promptly when in the water that is sterilized during ammonia-nitrogen content 0.05mg/L, just first ammonification or ammonium salt before chlorination, chlorination makes it to generate the sterilization method of chemical combination chlorine again.But the liquid ammonia steel bottle that uses in tap water is produced has many unsafe factors.So, under the situation of the public safety of guaranteeing the city, seek surrogate, abolish the ammonia bottle, imperative.From security, the safety performance of ammonium sulfate has substantially exceeded liquefied ammonia, carries out chloramines disinfection if promote the use of the alternative liquefied ammonia of ammonium sulfate in water factory, can reduce the security risk of water factory, eliminates a big potential safety hazard of puzzlement water factory.But according to the related request of Drinking Water, ammonium sulfate also has a problem, mainly is that harmful elements such as the requirement iron that is used for water treatment liquid ammonium sulfate product, lead, mercury, chromium (sexavalence), cadmium, arsenic will reach requirement.And solid ammonium sulfate on the market, by GB (GB 535-1995) requirement, above-mentioned composition no requirement (NR), or be higher than the requirement of water treatment; So need make with extra care industrial ammonium sulfate, to be used for water treatment.
Summary of the invention
The invention provides a kind of industrial sulphuric acid ammonium is refined into and to be used for the drinking water treatment compositions and methods, harmful elements such as the iron in the liquid ammonium sulfate product that this method provides, lead, mercury, chromium (sexavalence), cadmium, arsenic reach the domestic water standard, can be used for Drinking Water and handle.
In order to achieve the above object, the invention provides a kind of process for purification that is used for the liquid ammonium sulfate of water treatment, comprise following concrete steps:
Step 1 detects the various metal ion contents in the ammonium sulfate;
Step 2, pre-treatment: oxidation step, in the aqueous solution of ammonium sulfate, add ammoniacal liquor, oxygenant successively under the stirring at normal temperature, continue to stir, make the metal ion of the low price in the ammoniumsulphate soln be oxidized to high volence metal ion;
Step 3 under condition of stirring, adds the removal of heavy metal ions agent, makes the metal ion in the ammoniumsulphate soln of gained in the step 2 form the insolubles precipitation;
Step 4, leave standstill, separate: leave standstill before throw out after the stirring and the water sepn, then with the throw out filtering separation, the mother liquor after the filtration is regulated pH value free acid extremely wherein with sulphur acid meter, after its weight content is not more than 0.015%, enters the finished product pond.
Further, the oxygenant in the described step 2 is a hydrogen peroxide, the low valence metal ion valency is raise, so that remove; For example with Fe
2+Be oxidized to Fe
3+, Fe
3+Be easy to form that precipitation is separated falls; As Fe
2+Content is not high, can not add.
Add ammoniacal liquor in the described step 2, make that the pH value in the solution raises, can make tentatively that the part metals ion in the solution forms precipitation of hydroxide, reach the purpose of initial gross separation.
Further, described removal of heavy metal ions agent is sulfide-based heavy metal ion trapping agent, include machine sulfide and inorganic sulphide, can make metal ion iron, lead, mercury, chromium (sexavalence), cadmium, arsenic and sulfonium ion form the sulfide precipitation of indissoluble entry, remove the foreign metal ion further.
Described organic sulfide is a TMT series heavy metal ion trapping agent, and it comprises any one or more than one the mixture of TMT-15 and TMT-18 series organic sulfide; TMT-18 series organic sulfide comprises organic sulfides such as TMT-18B, TMT-18C, TMT-18D, TMT-18E, TMT-18F.
Below, with Cd
2+And Hg
2+Be example, TMT-18 precipitin reaction principle of work be described:
3Cd
2++2(TMT-18)
3-→Cd
3(TMT-18)
2
3Hg
2++2(TMT-18)
3-→Hg
3(TMT-18)
2
Reaction formula is as follows in detail:
TMT class heavy metal ion trapping agent can react rapidly with various heavy metal ions in waste water (mercury, lead, copper, cadmium, nickel, manganese, zinc, chromium etc.) at normal temperatures, generate water insoluble, and have the inner complex of good chemical stability, catch the purpose of removing heavy metal thereby reach.
Described inorganic sulphide is any one in sodium sulphite, potassium sulphide or the calcium polysulfide.
Further, after described step 3, also comprise: step 3.1, add flocculation agent, continue to stir 5～10 minutes; Described flocculation agent can produce synergistic effect with the metal ion remover, and performance absorption, bridge formation, net are caught effect, just throw the net as one, the trickle throw out that separates out is linked to be one, forms bigger precipitation, sedimentation rapidly, be convenient to filter and remove, improve strainability.
Particularly, described flocculation agent is the polyacrylamide (PAM) of non-ionic type.
Described ammoniacal liquor and sulfuric acid are used to regulate pH value and the auxiliary heavy metal of removing.
Further, also comprise after described step 3.1: step 3.2 adds flocculating aids, to improve strainability; Described flocculating aids is diatomite or gac, and wherein, gac can also play the effect of decolouring taste removal further.
The present invention passes through initial oxidation, adding the heavy metal remover then makes metal ion form the insolubles precipitation to carry out the method for separation and purification, metal ion in the industrial sulphuric acid ammonium is removed, and nitrogen is kept here, make the content of elements such as iron in the ammoniumsulphate soln, lead, mercury, chromium (sexavalence), cadmium, arsenic reach GB (GB535-1995), make liquid ammonium sulfate after refining can be used for Drinking Water and handle.
Embodiment
Below in conjunction with embodiment embodiments of the present invention are described further.
Embodiment
Step 1 detects the various metal ion contents in the ammonium sulfate;
Step 2, pre-treatment, oxidation step in the reactor of 10000L, is added to the ammonium sulfate solids of 4000kg in the 6000L water, is stirred to dissolving fully; Under the stirring at normal temperature, in above-mentioned ammoniumsulphate soln, add 30kg ammoniacal liquor, 0.08kg hydrogen peroxide, make the metal ion of the low price in the ammoniumsulphate soln be oxidized to high volence metal ion, continue to stir more than 5 minutes, treat color burn after, carry out next step;
Step 3, add the removal of heavy metal ions agent, make the metal ion in the ammoniumsulphate soln of gained in the step 2 form the insolubles precipitation, under condition of stirring, add 120g heavy metal remover---sulfide, adopting code name in the present embodiment is the heavy metal ion trapping agent of TMT-18, continue to stir more than 10 minutes, make the heavy metal ion complete precipitate and separate of trying one's best come out; Determine total input on the same day according to the needs that produce every day, before throwing in the medicament (TMT-18) of measuring is diluted to 1～2% concentration in the medicine system of special use, need be diluted to 12 kilograms～24 kilograms as 120 gram TMT-18 in the present embodiment;
Step 3.1 adds 25g flocculation agent non-ionic polyacrylamide (PAM) (being diluted to 0.05% concentration in the medicine system of special use) again, continues to stir (should not be strong excessively) 5～10 minutes, stops to stir;
Step 3.2 adds flocculating aids diatomite, continues to stir;
Step 4, filtration, separation obtain the purified ammoniumsulphate soln: leave standstill as throw out after the stirring and water sepn are last more than 10 minutes, then throw out is separated through filter (bag type filtering machine), the filter cake that contains heavy metal is as there not being the buried processing of the toxic refuse of leaching; Mother liquor after the filtration is the purified ammoniumsulphate soln, and it treats free acid with sulphur acid meter by after adding the allotment of 6～10kg sulfuric acid, and its weight content is not more than 0.015%, enters the finished product pond.
The finished product ammoniumsulphate soln that aforesaid method is obtained carries out the ion content check and analysis, sees Table 1, unless otherwise indicated, and equal operational analysis pure reagent; Employed water should meet three grades of water (only measuring pH value scope and specific conductivity) specification among the GB/T 6682-2008; All titrimetries are pressed GB/T 601 preparations with standardized solution and are demarcated; All impurity analysis are pressed GB/T 602 preparations with standardized solution; Used preparation and goods are pressed GB/T 603 preparations in all test methods.
The measuring method of described nitrogen content is: take by weighing the about 4g of liquid sample (being accurate to 0.0001g), add water 30mL, add neutral formalin solution 30mL, shake up, place 5min, (C (NaOH)=1.0000mol/L) is titrated to the solution pinkiness with standard solution of sodium hydroxide, keeps 1min not disappear and is terminal point.
Nitrogen (N) content X (in mass percent, %) calculate by following formula:
In the formula:
V---test consumes the volume of standard solution of sodium hydroxide, mL;
C---the test volumetric molar concentration of standard solution of sodium hydroxide, mol/L;
M---sample mass, g;
0.01401---the quality of suitable with 1.00mL standard solution of sodium hydroxide (C (NaOH)=1.0000mol/L) nitrogen with the gram expression.
Table 1 is by the content analysis of the refining front and back of embodiment ammoniumsulphate soln intermediate ion
As shown in table 1, iron, lead, mercury, chromium (sexavalence), cadmium, arsenic metal ion and free acid content in the refining liquid sulfuric acid ammonium product that obtains of the process for purification of employing present embodiment all are up to state standards, meet the processing requirement of handling Drinking Water.
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute all will be conspicuous.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (7)
1. a process for purification that is used for the liquid ammonium sulfate of water treatment is characterized in that, comprises following concrete steps:
Step 1 detects the various metal ion contents in the ammonium sulfate;
Step 2, pre-treatment: oxidation step, in the aqueous solution of ammonium sulfate, add ammoniacal liquor, oxygenant successively under the stirring at normal temperature, continue to stir, make the metal ion of the low price in the ammoniumsulphate soln be oxidized to high volence metal ion;
Step 3 under condition of stirring, adds the removal of heavy metal ions agent, makes the metal ion in the ammoniumsulphate soln of gained in the step 2 form the insolubles precipitation;
Step 4, leave standstill, separate: leave standstill before throw out after the stirring and the water sepn, then with the throw out filtering separation, the mother liquor after the filtration is regulated pH value free acid extremely wherein with sulphur acid meter, after its weight content is not more than 0.015%, enters the finished product pond;
Oxygenant in the described step 2 is a hydrogen peroxide;
Removal of heavy metal ions agent in the described step 3 is a sulfide, includes machine sulfide and inorganic sulphide.
2. the process for purification that is used for the liquid ammonium sulfate of water treatment as claimed in claim 1, it is characterized in that, the described organic sulfide metal ion capturing agent of attaching most importance to, it comprises any one or more than one the mixture in TMT-15 and the TMT-18 series organic sulfide.
3. the process for purification that is used for the liquid ammonium sulfate of water treatment as claimed in claim 1 is characterized in that, described inorganic sulphide is any one or more than one the mixture in sodium sulphite, potassium sulphide or the calcium polysulfide.
4. the process for purification that is used for the liquid ammonium sulfate of water treatment as claimed in claim 1 is characterized in that, describedly also comprises after step 3:
Step 3.1 adds flocculation agent, continues to stir 5～10 minutes.
5. the process for purification that is used for the liquid ammonium sulfate of water treatment as claimed in claim 4 is characterized in that, the flocculation agent in the described step 3.1 is the polyacrylamide of non-ionic type.
6. the process for purification that is used for the liquid ammonium sulfate of water treatment as claimed in claim 4 is characterized in that, also comprises after described step 3.1:
Step 3.2 adds flocculating aids, continues to stir.
7. the process for purification that is used for the liquid ammonium sulfate of water treatment as claimed in claim 6 is characterized in that, described flocculating aids is diatomite or gac.
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| CN2009102012360A CN101746779B (en) | 2009-12-16 | 2009-12-16 | Refining method of liquid ammonium sulfate for water treatment |
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| CN101746779B true CN101746779B (en) | 2011-05-18 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708502B (en) * | 2014-01-03 | 2015-12-30 | 武汉科技大学 | A kind of method of desulfuration byproduct ammonium sulfate purifying |
| CN104787780B (en) * | 2015-04-21 | 2017-03-01 | 云南驰宏锌锗股份有限公司 | A kind of method of ammonium sulfate imurity-removal |
| CN107140763A (en) * | 2017-05-26 | 2017-09-08 | 佛山柯维光电股份有限公司 | A kind of processing method of the good mercury-containing waste water of applicability |
| CN111908487A (en) * | 2019-12-27 | 2020-11-10 | 深圳市宝安东江环保技术有限公司 | Method for preparing ammonium sulfate by microetching solution and automatic solution pH value adjusting system |
| CN113371734A (en) * | 2021-05-31 | 2021-09-10 | 武汉钢铁有限公司 | Method for removing iron, calcium, silicon and magnesium from ammonium sulfate clear liquid in ammonia desulphurization process |
| CN114656064A (en) * | 2022-04-11 | 2022-06-24 | 河北中科同创科技发展有限公司 | Method for removing ferric ions and ferrous ions in ammonium sulfate solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000021886A1 (en) * | 1998-10-13 | 2000-04-20 | Airborne Industrial Minerals Inc. | Method of ammonium sulfate purification |
| CN100999326A (en) * | 2006-12-29 | 2007-07-18 | 中国天辰化学工程公司 | Production method of ammonium sulphate |
-
2009
- 2009-12-16 CN CN2009102012360A patent/CN101746779B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000021886A1 (en) * | 1998-10-13 | 2000-04-20 | Airborne Industrial Minerals Inc. | Method of ammonium sulfate purification |
| CN1491890A (en) * | 1998-10-13 | 2004-04-28 | �Ҵ���˾ | Process for purifying ammonium sulfate |
| CN100999326A (en) * | 2006-12-29 | 2007-07-18 | 中国天辰化学工程公司 | Production method of ammonium sulphate |
Non-Patent Citations (1)
| Title |
|---|
| 刘静等.组合氯化消毒工艺的卤代消毒副产物生成特性.《环境科学》.2009,第30卷(第9期),2538-2542. * |
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