CN101182057A - Method for preparing sewage water additive by intermediate product of diatomite purification - Google Patents
Method for preparing sewage water additive by intermediate product of diatomite purification Download PDFInfo
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- CN101182057A CN101182057A CNA2007100663620A CN200710066362A CN101182057A CN 101182057 A CN101182057 A CN 101182057A CN A2007100663620 A CNA2007100663620 A CN A2007100663620A CN 200710066362 A CN200710066362 A CN 200710066362A CN 101182057 A CN101182057 A CN 101182057A
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Abstract
A sewage treatment agent preparing method of using diatomite to purify intermediate products of essential earth relates to the preparation and the application of an urban sewage treatment agent. The invention uses low grade diatomite and waste acid liquid in associated SiO2 in a pickling essential diatom earth purifying process. The diatom earth is mixed in the waste acid liquid according to the solid quid volume ratio of 1 to 20-40. The mixture after the pulp mixing is heated at the temperature of 90-100 degree Celsius for 3-5 hours, impregnated and cooled. Cetyl trimethyl ammonium bromide is dissolved in water to prepare solution, the weight percent concentration of which is 1.35-2 percent. The pH value is adjusted to be 8-11. The solution is added in the refrigerant and is roasted after the stirring and the filtration. A resultant is collected. When used, the diatomite sewage treatment agent of 0.1-0.3g/L is put in the urban sewage to be stirred for thirty seconds and kept statically. Supernatant liquid is siphoned. Diatomite sewage sludge of lower layer is recycled. Making use of discarded raw materials, the invention has the advantages of less energy consumption, low cost, reduced environmental pollutions, short action time and obvious water body COD and SS lowering. The settled sludge is easy to be removed. And the invention has no pollution on the water body.
Description
Affiliated technical field
The present invention relates to the preparation and the application of the water conditioner of Treating Municipal Sewage.
Background technology
City domestic sewage unprocessed and directly the discharging, make the contamination level in waters substantially exceed the degree that water body self-purification ability can bear, water body is by severe contamination.In the sewage denitrification and dephosphorization method, shown good performance through purification, modification, activatory diatomite.Soak research (the Adsorption offluoride that silica gel adsorbs fluorine phosphorus arsenic as S.A.WaSSay with lanthanum chloride solution, phosphate and arsenate iron on lanthanum impregnated silicagel.Wat.Env.Res.1996,68 (3): 295-300); The peaceful equality of Chinese invention patent publication number 1803274 Kunming University of Science and Technology obtains the sewage denitrification and dephosphorization sorbent material by modified load with metal-salts such as lanthanum nitrate, cerous nitrates in diatomite, powdery zeolite.Denitrogenate, outside the inorganic pollution such as phosphorus, the pollutent that is colloid and suspension is big, the COD major reason for higher of the low visibility of sewage water body, turbidity, therefore, removing the pollution substance that is colloid and suspension in the sewage is to need the basic problem that solves in the sewage disposal.The general flocculation agent that adopts is polymerize aluminum chloride and polyacrylamide.Compression double electric layer, the electrically neutralization of the former effect by it or it hydrolysate, the winding net is caught and the effect of adsorbing four aspects of bridging is finished, causing the particulate matter of COD to precipitate oxidized dose of oxidation of energy filters out, thereby reduced COD, the precipitation of particulate matter has reduced suspended substance simultaneously; And the latter is an organic polymer coargulator, has the consequent huge surface adsorption effect of flco that formation is bigger between particle, thereby flocculation water-borne glue body and suspended substance reduce COD and suspended substance.The use flocculation agent is disposed of sewage, and the water quality condition after the processing obviously improves.But the flocculation agent price is more expensive, the flocculation sediment time is long, the formation of wadding flower is looser, and dispersion forms suspended substance once more easily under the situation of rocking.Organism in water all dissolves, and does not become colloid, and when also not existing with Granular forms, the nitrogen and the phosphorus that drop in the flocculation agent removal water then have little effect.Chinese invention patent application number 2006100440153 " method that drop liquid sewage is oozed in the compound diatomite treating refuse of a kind of usefulness ", comprise digestion, the sudden and violent gas of air blast, help reactions steps such as mixing with fixed attention, flocculation, precipitation, compound diatomite is that 70-95% diatomite mixes with aluminum oxide or the bauxitic clay of 5-30%, contains crystalline structure r-Al 450-550 ℃ of dry acquisition
2O
3Mixing material, as coagulant aids.But need coagulate mixed flocculation step and drop into coagulating agent again helping when using, particularly aluminum oxide is the powder that the utmost point is insoluble in water, also be insoluble to acid through strong burning, the aluminum oxide of high temperature sintering as the diamantine of high temperature material can wear and tear the pipeline of admitting water body, stop up soil, environment is caused negative consequence.
On the other hand, utilize diatomite to produce diatomite related products such as diatomite flocculating aids, material of construction and in the purification diatomite process, low-grade diatomite does not obtain utilizing among association a large amount of; The a large amount of acid solutions of exhausted are discarded in vain in purification process.As be positioned at the diatomite in pioneer mining area, Xun Dianxian pioneer township, Yunnan Province, and to verify geologic reserve and reach 7,759 ten thousand tons, ore bed is thick, reserves are big.This diatomite ore bed directly is covered on the huge thick brown coal layer, is rich in organic matter, burns vector and reaches 15%~24%, ore shows brown-black, the fine and smooth homogeneous of quality, loose porous, hardness is little, unit weight is light, adsorptivity is strong, and specific surface area is big, and height contains aluminium, iron amount, thermal value 3.3~5.7MJ/kg is high fever vector type diatomite.But owing to described reason, pollution is threatening fragile ecology around the mining area potentially.
Summary of the invention
The present invention is directed to the shortcoming of above nonmetalliferous ore modified water treatment agent and flocculation agent, with the middle soil behind the purification diatomite, tail soil and spent acid solution is raw material, provide a kind of action time fast, can keep long-time and be adsorbed with the suspended substance of organic pollutants, sedimentation sewage expeditiously, the high fever vector type Purification of Diatomite intermediate product that utilizes of reduction water pollution prepares the method for sewage-treating agent.
Diatomite sewage-treating agent of the present invention prepares by following approach:
Comprise sulfuric acid washing purify to burn vector be the dioxide-containing silica of association in 15%~24% diatomite process be 50-60% in low-grade diatomite and spent acid solution, this sewage-treating agent preparation process is:
(1) this diatomite is sneaked in the spent acid solution by solid-liquid volume ratio 1: 20~40, stir pulping, under 90~100 ℃ of conditions, heated 3~5 hours, dipping cooling 3~5 hours;
(2) cetyl trimethylammonium bromide is soluble in water, be made into weight percent concentration and be 1.35~2% solution, regulating pH with sodium hydroxide again in this solution is 8~11;
(3) step (2) solution is added roasting after the agitation and filtration in step (1) refrigerant, and collect resultant.
Step (3) can further be step (2) solution to be poured in step (1) refrigerant stirred dipping 10~15 hours, filtration, obtain the diatomite filter cake, again filter cake is placed 150~250 ℃ of following roastings of temperature to collect resultant after 0.5~2 hour, pulverize, screening.
The using method of treatment agent of the present invention: described diatomite sewage-treating agent is dropped in the municipal effluent with 0.1~0.3g/L, evenly stirred 30 seconds, left standstill 10 minutes, the siphon supernatant liquid reclaims lower floor's diatomite mud.
The present invention utilizes diatomite loose porous, hardness is little, unit weight is light, adsorptivity is strong, advantages such as specific surface area is big, and utilize sulfuric acid acid to cook off except that the aluminium in the diatomite, iron, calcium, produce in the element purification process such as magnesium, contain a large amount of aluminium, iron, calcium, the discarded acid solution of vitriol such as magnesium, pass through sodium hydroxide, the cetyl trimethylammonium bromide chemical reaction, the modification pyrolysis obtains comparatively good diatomite sewage-treating agent, make the metal ion that is attached to diatomaceous salt generation generate the indissoluble throw out with suspension in the water and gelatinoid, and materials such as adsorption of nitrogen and phosphorus, thereby increase water quality, reduce the COD and the SS water-quality guideline of sewage.
Compared with prior art, the beneficial effect that this treatment agent produces is: the first, and the treatment agent that utilizes middle native tail soil behind the purification diatomite and spent acid solution to make for raw material, improved utilization ratio of raw materials, power consumption is few, and cost value is low, avoid the discharging alluvial of spent acid solution, alleviated environmental pollution; Secondly, the flocculation sediment time is short, can take effect in 10 minutes; The adsorption efficiency height, wadding flower forms closely knit, can remove nitrogen and phosphorus in the water, and therefore, suspended substance, colloidalmaterial, organic pollutant that it not only can the sedimentation municipal effluent can also reduce the nitrogen and the phosphorus eutrophication material of water body; The 3rd, be carried on aluminium salt on the diatomite, molysite, cetyl trimethylammonium bromide etc. by being doped in securely after the modification in the carrier, can not reveal, do not contain the aluminum oxide that is insoluble in water, more closely knit behind the sludge settling, remove easily, can not cause secondary pollution to water body.
Embodiment
(1) preparation of treatment agent of the present invention
Embodiment 1: the dioxide-containing silica of getting association in the sulfuric acid washing purification high fever vector type diatomite process is 60% diatomite and spent acid solution, according to solid-liquid volume ratio 1: 20 diatomite is sneaked in the spent acid solution, stir pulping, heating is 4 hours under 90 ℃ of conditions, dipping cooling 3 hours; Cetyl trimethylammonium bromide is soluble in water, be made into the solution that weight percent concentration is 1.35wt%, be 9 with sodium hydrate regulator solution pH; This solution poured in diatomite and the spent acid solution refrigerant stirred dipping 10 hours, obtain the diatomite filter cake after the filtration, again filter cake is placed the retort furnace roasting of 150 ℃ of temperature to pulverize after 1 hour, screening collection resultant.
Embodiment 2: the dioxide-containing silica of getting association in the sulfuric acid washing purification high fever vector type diatomite process is 50% diatomite and spent acid solution, according to solid-liquid volume ratio 1: 30 diatomite is sneaked in the spent acid solution, stir pulping, heating is 3 hours under 100 ℃ of conditions, dipping cooling 4 hours; Cetyl trimethylammonium bromide is soluble in water, be made into the solution that weight percent concentration is 1.55wt%, be 11 with sodium hydrate regulator solution pH; This solution poured in diatomite and the spent acid solution refrigerant stirred dipping 12 hours, obtain the diatomite filter cake after the filtration, again filter cake is placed the retort furnace roasting of 200 ℃ of temperature to pulverize after 2 hours, screening collection resultant.
Embodiment 3: the dioxide-containing silica of getting association in the sulfuric acid washing purification high fever vector type diatomite process is 60% diatomite and spent acid solution, according to solid-liquid volume ratio 1: 40 diatomite is sneaked in the spent acid solution, stir pulping, heating is 5 hours under 100 ℃ of conditions, dipping cooling 5 hours; Cetyl trimethylammonium bromide is soluble in water, be made into the solution that weight percent concentration is 1.8wt%, be 9 with sodium hydrate regulator solution pH; This solution poured in diatomite and the spent acid solution refrigerant stirred dipping 15 hours, obtain the diatomite filter cake after the filtration, again filter cake is placed the retort furnace roasting of 250 ℃ of temperature to pulverize after 0.5 hour, screening collection resultant.
(2) treatment agent of the present invention is used for municipal sewage treatment using method and effect
Relate to term among the following result:
Chemical oxygen demand COD refers to use oxygenant K
2CrO
7Organism in the oxygenolysis sewage is used and the organic amount of amount secondary indication that consumes suitable oxygen.
Ss suspended solid in the water, referring to can not be by the solid matter in the water of aperture 6-7 micron filter membrane.
As table 1, get Kunming respectively and return in triumph the municipal effluent of river, sharp ship room upstream and downstream as process object, former water COD in upstream and SS are through being measured as 145.08mg/L and 32.4mg/L, and former water COD in downstream and SS are through being measured as 200.88mg/L and 25.2mg/L.
Get six kinds of various dose of embodiment 2 diatomite water conditioner 0.1g-0.35g and put in the 1L municipal effluent, evenly stirred 30 seconds fast, left standstill 10 minutes, get supernatant liquid, measure its COD and SS, calculate each COD clearance and SS clearance.
Get commercial polymerize aluminum chloride (PAC) 0.3g and put in the 1L municipal effluent, evenly stirred 30 seconds fast, left standstill 10 minutes, get supernatant liquid, measure its COD and SS, calculate the COD clearance, the SS clearance.
Table 1 the present invention and river, PAC ship room upstream and downstream municipal sewage treatment data are relatively
The water conditioner type | Consumption (g) | Ship Fang He upstream sewage (COD145.08mg/L, SS32.4mg/L) | Ship Fang He downstream sewage (COD 200.88mg/L, SS25.2mg/L) | ||
COD clearance % | SS clearance % | COD clearance % | SS clearance % | ||
Treatment agent of the present invention treatment agent of the present invention treatment agent of the present invention treatment agent of the present invention treatment agent of the present invention treatment agent polymerize aluminum chloride of the present invention | 0.10 0.15 0.20 0.25 0.30 0.35 0.30 | 30.8 34.9 47.4 58.6 67.4 68.1 65.5 | 73.8 75.4 80.6 83.8 84.5 84.2 76.8 | 27.1 42.1 55.1 63.9 65.0 64.9 56.4 | 59.4 67.0 68.7 72.1 83.0 82.5 75.2 |
As table 2, get the precious cultural city of Kunming good fortune and go into the sewage of Dian Chi mouth as process object, its former water COD and SS are through being measured as 245.4mg/L and 75.8mg/L, get embodiment 3 diatomite water conditioner 0.3g and put in the sewage of the precious cultural city of 1L good fortune, evenly stirred 30 seconds fast, left standstill 10 minutes, get supernatant liquid, measuring its COD and SS is 85.4 mg/L and 7.12mg/L, and its COD clearance is: 65.2%, and the SS clearance is: 90.6%.
Get commercial polymerize aluminum chloride (PAC) 0.3g and put in the sewage of the precious cultural city of 1L good fortune, evenly stirred 30 seconds fast, left standstill 10 minutes, get supernatant liquid, measuring its COD and SS is 88.2mg/L and 7.11mg/L, and its COD clearance is: 64.1%, and the SS clearance is: 90%.
Get polymerization ferrous sulfate 0.3g and be dissolved in wiring solution-forming in the 20mL water, anion-polyacrylamide 0.05g is dissolved in wiring solution-forming in the 20mL water, put into together in the sewage of the precious cultural city of 1L good fortune, evenly stirred 30 seconds fast, left standstill 10 minutes, and got supernatant liquid, measuring its COD and SS is 111.5mg/L and 9.24mg/L, its COD clearance is: 54.6%, and the SS clearance is: 87.8%.
The precious cultural city sewage disposal data of table 2 Kunming good fortune
The water conditioner type | Consumption (g) | The precious cultural city sewage (COD, SS are respectively 245.4mg/L, 75.8mg/L) of good fortune | |
COD clearance % | SS clearance % | ||
Treatment agent polymerize aluminum chloride polymerization ferrous sulfate 0.3g+ polyacrylamide 0.05g of the present invention | 0.30 0.30 - | 65.2 64.1 54.6 | 90.6 90 87.8 |
Claims (3)
1. utilize high fever vector type Purification of Diatomite intermediate product to prepare the method for sewage-treating agent, comprise sulfuric acid washing purify burn vector be the dioxide-containing silica of association in 15%~24% diatomite process be 50-60% in low-grade diatomite and spent acid solution,
It is characterized in that preparing this sewage-treating agent step is:
(1) this diatomite is mixed by solid-liquid volume ratio 1: 20~40 with spent acid solution, stir pulping, under 90~100 ℃ of conditions, heated 3~5 hours, dipping cooling 3~5 hours;
(2) cetyl trimethylammonium bromide is soluble in water, be made into the solution that weight percent concentration is 1.35~2wt%, regulating pH with sodium hydroxide again in this solution is 8~11;
(3) step (2) solution is added roasting after the agitation and filtration in step (1) refrigerant, and collect resultant.
2. the method for utilizing high fever vector type Purification of Diatomite intermediate product to prepare sewage-treating agent according to claim 1, it is characterized in that in step (3), step (2) solution poured in step (1) refrigerant stirred dipping 10~15 hours, filter, obtain the diatomite filter cake, filter cake is placed 150~250 ℃ of following roastings of temperature to pulverize after 0.5~2 hour, resultant is collected in screening again.
3. the using method of utilizing high fever vector type Purification of Diatomite intermediate product to prepare sewage-treating agent as claimed in claim 1 or 2, it is characterized in that described diatomite sewage-treating agent is dropped in the municipal effluent with 0.1~0.3g/L, evenly stirred 30 seconds, left standstill 10 minutes, the siphon supernatant liquid reclaims lower floor's diatomite mud.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101781025B (en) * | 2010-02-09 | 2013-03-13 | 集美大学 | Nano microecological modulator of aquatic product and production method thereof |
CN105016454A (en) * | 2015-07-15 | 2015-11-04 | 江苏振宇环保科技有限公司 | Purifying agent for COD in explosive waste water |
CN107970887A (en) * | 2017-11-22 | 2018-05-01 | 大连智讯科技有限公司 | A kind of preparation method of konilite |
-
2007
- 2007-11-07 CN CNB2007100663620A patent/CN100537442C/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101781025B (en) * | 2010-02-09 | 2013-03-13 | 集美大学 | Nano microecological modulator of aquatic product and production method thereof |
CN105016454A (en) * | 2015-07-15 | 2015-11-04 | 江苏振宇环保科技有限公司 | Purifying agent for COD in explosive waste water |
CN107970887A (en) * | 2017-11-22 | 2018-05-01 | 大连智讯科技有限公司 | A kind of preparation method of konilite |
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