CN101746907B - Silicon-containing wastewater treatment method - Google Patents
Silicon-containing wastewater treatment method Download PDFInfo
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- CN101746907B CN101746907B CN2008102279131A CN200810227913A CN101746907B CN 101746907 B CN101746907 B CN 101746907B CN 2008102279131 A CN2008102279131 A CN 2008102279131A CN 200810227913 A CN200810227913 A CN 200810227913A CN 101746907 B CN101746907 B CN 101746907B
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Abstract
The invention relates to a silicon-containing wastewater treatment method. The silicon-containing wastewater treatment method provided by the invention comprises: adding a nucleation coagulant aid to silicon-containing wastewater and mixing the silicon-containing wastewater with the nucleation coagulant aid, wherein the nucleation coagulant aid is an insoluble solid which serves as a growing core capable of allowing granular micro-substances that are suspended in water and not easy to coagulate to aggregate, grow up and settle; and regulating the pH of the silicon-containing wastewater between 3.5 and 9. The treatment method provided by the invention has the advantages of applicability to silicate wastewater discharged in various processes, capability of thoroughly solving the problem that SiO2 in the silicon-containing wastewater is easy to gel, mild using conditions, simple operation process and capability of enabling treated wastewater to reach discharge standards.
Description
Technical field
The invention relates to a kind of silicon-containing wastewater treatment method.
Background technology
In petroleum chemical industry Catalyst Production process, in the silicon-containing wastewater of a large amount of high pH (the pH value is more than 11) of molecular sieve workshop generation, the silicate that wherein contains is with SiO at present
2Meter can be up to 2.0%～4.0%, and quite stable.These waste water generally show alkalescence, if directly be discharged in the natural water, and along with pH reduces, SiO
2Become gel or floss to settle out, form plain boiled water, polluted-water stops up water channel.If not with the solubility SiO in these waste water
2Thoroughly handle i.e. discharging, will cause pollution and the destruction that to estimate environment.
Processing to this type waste water does not have relevant report abroad.Domestic bigger manufacturer adopts neutralization earlier, and settled again method makes the SiO in the water
2Content reaches permissible value, again discharging.But adopt the settled again method of neutralization earlier; Be easy to generate a large amount of gelling materials, water cut is high, volume is big, be difficult to press filtration becomes cake, and slower, the residual turbidity of settling velocity is high; And the sedimentation colloid is difficult for filtering to be removed; If adopt existing in the market flocculation agent to handle, then expense is higher, increases production cost.
Normally used water conditioner is as gathering aluminium (PAC), SEPIGEL 305 (PAM) and ROHM etc. to the processing of above-mentioned silicon-containing wastewater to no effect or poor; If adopt neutralization earlier again with the method for water conditioner; Owing to can't solve the gel problem, so effect is also undesirable; Adopting dimethyl diallyl ammonium chloride homopolymerization or multipolymer to handle this type of waste water has certain effect, but dosing is very big, increases production cost, also can't use.
Summary of the invention
The object of the present invention is to provide a kind of method of effective processing silicon-containing wastewater.
The invention provides a kind of silicon-containing wastewater treatment method; This method is included in and adds the nucleation coagulant aids in the silicon-containing wastewater; And silicon-containing wastewater and nucleation coagulant aids are mixed, said nucleation coagulant aids is meant as the growth core minitype particle material aggregation of the difficult cohesion that suspends in the water is grown up and settled insoluble solid; With the pH regulator of silicon-containing wastewater to 3.5-9.
Treatment process provided by the invention is applicable to the silicate waste water that various technological process is discharged, and can thoroughly solve SiO in the silicon-containing wastewater
2Be prone to the gel problem, working conditions relaxes, and operating procedure is simple, and processed waste water can qualified discharge.
Embodiment
Silicon-containing wastewater treatment method provided by the invention comprises: in silicon-containing wastewater, add the nucleation coagulant aids; And silicon-containing wastewater and nucleation coagulant aids are mixed, said nucleation coagulant aids is meant as the growth core minitype particle material aggregation of the difficult cohesion that suspends in the water is grown up and settled insoluble solid; With the pH regulator of silicon-containing wastewater to 3.5-9.
At first, in pending said silicon-containing wastewater, add said nucleation coagulant aids, and silicon-containing wastewater and nucleation coagulant aids are mixed.
Method of mixing can be the method for routine, as stirring.Stirring can be carried out with the mode of routine, like modes such as various forms of stirring rakes, pneumatic blending or static mixers.
The purpose that adds said nucleation coagulant aids is that silicon-containing material can all be settled with filtrable sedimentary form after regulating pH, and no longer is gel form.The nucleation coagulant aids plays and changes SiO
2But gel form, make it be condensed into the effect of sedimentation suspended substance.
Said nucleation coagulant aids is to grow up and settled insoluble solid as the minitype particle material aggregation that the growth core can make dissolved in the water be difficult for cohesion, the standard of selection be through still can keep after the fragmentation its granularity not with water in the material that reacts of other materials and flocculation agent.In order to realize the object of the invention, under the preferable case, the average particulate diameter of nucleation coagulant aids is the 0.001-1 millimeter, further is preferably 0.005-0.5 millimeter.For example, said nucleation coagulant aids can be in zeyssatite, kaolin, boron-moisten soil, the recessed soil of high stick, barbital, fuller's earth, polynite, talcum powder, gac, the Sudan's soil, earth, sandy soil, magnesia, coal dust, cement dust, oil refining catalyst dust, molecular sieve dust, the mud one or more.Said nucleation-accelerant can obtain through commercial the purchase, and is complete works of or all can find on the net like the Chemicals handbook, is the routine article, specifically sees embodiment.
In this step, the amount ratio of waste water and nucleation coagulant aids can be very wide, and art technology can be done the coagulation stirring test arbitrarily and confirm that optimum quantity calculates, and confirms amount ratio according to the waste water situation.Under the preferable case, said silicon-containing wastewater is in silicon-dioxide, and when the silica concentration of said silicon-containing wastewater was 0.1-40g/L, the consumption of every liter of said nucleation coagulant aids was the 0.1-400 gram, more preferably the 5-380 gram.
Add the nucleation coagulant aids and do not limit, for example can before regulating pH, add said nucleation flocculation agent, also can in the process of regulating pH, add, preferably before regulating pH, add the nucleation flocculation agent with the order of regulating pH is special.
The pH that regulates silicon-containing wastewater is 3.5-9, is preferably 4-8.5.The add-on of acid is according to the control of pH value, and adding acid back silicon-dioxide and the absorption of nucleation coagulant aids form and precipitates.
The method of regulating the pH of silicon-containing wastewater comprises that working concentration is the aqueous acid of 200g/L-500g/L.Can be various mineral acids; Like sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, hypochlorous acid and perchloric acid; Also can make in the various spent acid solutions one or more; Also can be organic acid, like in Hydrocerol A, tartrate and the Glacial acetic acid min. 99.5 one or more, also can be one or more the solution that is combined to form in organic acid and the mineral acid.Be preferably in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, the Glacial acetic acid min. 99.5 one or more.
Under the preferable case, when regulating pH or after adding acid solution, stir.Churning time is 1-6 hour, stirs to help making the silicon-containing material in the silicon-containing wastewater to react completely, and all settles.
Under the preferable case, regulate after the pH, can also further add flocculation agent, thereby can further reduce turbidity.
Under the optimum condition, stir when adding flocculation agent.Can use conventional mode to stir modes such as for example various forms of stirring rakes, pneumatic blending or static mixer.
Said flocculation agent mainly is meant the group that has positive electricity (bearing) property; Neutralize and have negative (just) in some water and electrically be difficult to more isolating particles or particle; Reduce its electromotive force; It is played pendulum, and utilize its aggregation property to make these particles concentrate, and separate through physics or chemical process.Flocculation agent comprises inorganic flocculating agent, organic polymer coargulator and microbial flocculant etc.In order to realize the object of the invention, said flocculation agent can be for various conventional flocculation agents, like inorganic flocculating agent, like Tai-Ace S 150, iron trichloride, gather aluminium, gather iron; Organic polymer coargulator, like SEPIGEL 305, Poly Dimethyl Diallyl Ammonium Chloride and (little) biological flocculant, the flocculation agent kind of microorganisms is a lot, and structure, performance are different, mainly contain polysaccharide, gp, Mierocrystalline cellulose etc. at present.The kind that can produce the mikrobe of flocculation agent includes but not limited to AHU 7165 parasitic aspergillus, mud penicillium mould bacterium, AJ7002 soy sauce aspergillus etc.Said flocculation agent can be buied through commerce, all can and find on the net in the Chemicals complete works.Specifically see embodiment.Flocculation agent sweeps through electrostatic adhesion and volume mainly that particle is grown up its gathering in the action principle planar water, and formed flco is loose, frangible; And the effect of nucleation coagulant aids mainly is to play central role, makes in the water particle assemble gradually, grow up on its surface, the particle denser of formation.
Under the preferable case, said flocculation agent is Tai-Ace S 150, aluminum chloride, iron trichloride, gather aluminium, gather iron, in the polysilicate, Poly Dimethyl Diallyl Ammonium Chloride, SEPIGEL 305, acrylic amide-chlorination dimethyldiallylammonium multipolymer, ZX-I, polymine, tannin, starch-acrylamide grafted copolymer, guar gum, chitosan, carboxymethyl cellulose sodium one or more.According to the present invention, add flocculation agent and can make the thorough sedimentation of siliceous suspended substance, realize removing contamination separation, but the waste water qualified discharge.With respect to the minitype particle material of the difficult cohesion that suspends in the per 1000 milligrams of water in the said silicon-containing wastewater, said flocculation agent consumption can be the 0.1-50 milligram.
Under the preferable case, with the step that can also comprise solid-liquid separation afterwards, the method for solid-liquid separation can be ordinary method before adding flocculation agent, as filtering etc.
Through embodiment the present invention is described further below, but said embodiment should not be construed as limitation of the present invention.
Embodiment 1
Present embodiment is explained silicon-containing wastewater treatment method of the present invention.
Get silicon-dioxide quality concentration and be 1 liter of the silicon-containing wastewater of 38.9g/L; The oil refining FCC spent catalyst dust of taking from oil refining catalyst factory (average particulate diameter 150 μ m) that adds 360 grams; Under agitation condition, slowly adding concentration is the 250g/L sulphuric acid soln; Monitor pH value of solution to 8.2 simultaneously, get supernatant and survey its turbidity and filtration velocity, the result is as shown in table 1.
Add 5 milligrams of polyacrylamide flocculants (capital, Zhengzhou joins water-purifying material ltd, scape sun board), stir the back standing sedimentation.
Turbidity is a kind of method of investigating wadding slag gel degree, if filtration velocity explains that soon having solved silica dioxide gel is difficult for filtration problem, and with funnel (be conventional glass funnel, the chemical industry shop is on sale) mensuration filtration velocity.The result is as shown in table 1.
The monitoring method of pH is: pH meter (HACH company, pH10)
The measuring method of turbidity is: turbidometer (HACH company, 2100AN TURBIDIMETER)
Embodiment 2
Present embodiment is explained silicon-containing wastewater treatment method of the present invention.
Get silicon-dioxide quality concentration and be 1 liter of the silicon-containing wastewater of 20.4g/L; (Qingdao is opened up and is contained zeyssatite ltd to add 10 gram zeyssatite; DP1200), under agitation condition, slowly adding concentration is the 500g/L sulphuric acid soln, simultaneously according to monitoring pH value of solution to 4.7 with embodiment 1 identical method; Get supernatant according to surveying its turbidity and filtration velocity with embodiment 1 identical method, the result is as shown in table 1.
Embodiment 3
Present embodiment is explained silicon-containing wastewater treatment method of the present invention.
Get silicon-dioxide quality concentration and be 1 liter of the silicon-containing wastewater of (32.4g/L); Add the 270 gram talcum powder (North Sea, Liaoning Industrial Co., Ltd.s; AJ75-99.9GB), under agitation condition, slowly adding concentration is the 400g/L hydrochloric acid soln, simultaneously according to monitoring pH value of solution to 7.9 with embodiment 1 identical method; Get supernatant according to surveying its turbidity with embodiment 1 identical method, the result is as shown in table 1.
Comparative Examples 1
Handle the method for waste water according to prior art
According to handling waste water with embodiment 1 identical method, difference is not add the step of 360 gram oil refining FCC spent catalyst dust.According to the method monitoring pH identical with embodiment 1 and the turbidity and the filtration velocity of supernatant, the result is as shown in table 1.
Comparative Examples 2
Handle the method for waste water according to prior art
According to handling waste water with embodiment 2 identical methods, difference is not add the diatomaceous step of 10 grams.According to the method monitoring pH identical with embodiment 1 and the turbidity and the filtration velocity of supernatant, the result is as shown in table 1.
Comparative Examples 3
Handle the method for waste water according to prior art
According to handling waste water with embodiment 3 identical methods, difference is not add the talcous step of 270 grams.According to the method monitoring pH identical with embodiment 1 and the turbidity and the filtration velocity of supernatant, the result is as shown in table 1
Comparative Examples 4
Get silicon-dioxide quality concentration and be 1 liter of the silicon-containing wastewater of 38.9g/L, under the situation of not regulating the pH value, add 5 milligrams of polyacrylamide flocculants, other treatment processs are with embodiment 1
Table 1
| The embodiment numbering | Nucleation coagulant aids/consumption amount | The initial turbidity of solution/processing back turbidity (NTU) | Filtration velocity |
| Embodiment 1 | Spent catalyst dust/360 weight parts | 132/9.6 | Comparatively fast |
| Embodiment 2 | Zeyssatite/10 weight parts | 87/8.1 | Comparatively fast |
| Embodiment 3 | Talcum powder/270 weight parts | 96/7.3 | Comparatively fast |
| Comparative Examples 1 | —— | 132/25 | SiO 2Form gel, sad filter |
| Comparative Examples 2 | —— | 87/33 ? | SiO 2Form gel, sad filter |
| Comparative Examples 3 | —— | 96/32 ? | SiO 2Form gel, sad filter |
| Comparative Examples 4 | 132/23 | SiO 2Form gel, sad filter |
Can find out that from the result of table 1 turbidity after silicon-containing wastewater is handled according to the method for the invention reduces significantly, filtration velocity obviously accelerates, and operation is more prone to.
Claims (8)
1. silicon-containing wastewater treatment method; It is characterized in that; This method is included in and adds the nucleation coagulant aids in the silicon-containing wastewater; Said nucleation coagulant aids is meant as the growth core minitype particle material aggregation of the difficult cohesion that suspends in the water is grown up and settled insoluble solid; The average particulate diameter of said nucleation coagulant aids is the 0.001-1 millimeter, and said nucleation coagulant aids is one or more in zeyssatite, kaolin, boron-moisten soil, the recessed soil of high stick, barbital, fuller's earth, polynite, talcum powder, gac, the Sudan's soil, earth, sandy soil, magnesia, coal dust, cement dust, oil refining catalyst dust, molecular sieve dust and the mud; With the pH regulator of silicon-containing wastewater to 3.5-9.
2. method according to claim 1, wherein, in silicon-dioxide, when the silica concentration of said silicon-containing wastewater was 0.1-40g/L, the amount of the said nucleation coagulant aids that every liter of silicon-containing wastewater is used was the 0.1-400 gram.
3. method according to claim 1 and 2, wherein, said nucleation coagulant aids added before regulating pH.
4. method according to claim 1, wherein, with the pH regulator of silicon-containing wastewater to 4-8.5.
5. according to claim 1 or 4 described methods; Wherein, The method of regulating the pH of silicon-containing wastewater comprises that working concentration is the aqueous acid of 200g/L-500g/L, and said acid is one or more in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, hypochlorous acid, perchloric acid, Hydrocerol A, tartrate, the Glacial acetic acid min. 99.5.
6. according to claim 1 or 4 described methods, wherein, after regulating pH, also add flocculation agent.
7. method according to claim 6; Wherein, said flocculation agent be Tai-Ace S 150, aluminum chloride, iron trichloride, gather aluminium, gather iron, in the polysilicate, Poly Dimethyl Diallyl Ammonium Chloride, SEPIGEL 305, acrylic amide-chlorination dimethyldiallylammonium multipolymer, ZX-I, polymine, tannin, starch-acrylamide grafted copolymer, guar gum, chitosan, carboxymethyl cellulose sodium one or more.
8. method according to claim 6, wherein, with respect to the minitype particle material of the difficult cohesion that suspends in the per 1000 milligrams of water in the said silicon-containing wastewater, said flocculation agent consumption is the 0.1-50 milligram.
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