CN1321073C - Safety and ecological natural built-up flocculant, its production and use - Google Patents
Safety and ecological natural built-up flocculant, its production and use Download PDFInfo
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- CN1321073C CN1321073C CNB2005100458699A CN200510045869A CN1321073C CN 1321073 C CN1321073 C CN 1321073C CN B2005100458699 A CNB2005100458699 A CN B2005100458699A CN 200510045869 A CN200510045869 A CN 200510045869A CN 1321073 C CN1321073 C CN 1321073C
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Abstract
The present invention relates to an ecological safe natural compound flocculant. A natural material containing silicate is compounded with inorganic molysite according to certain proportion and order; monosodium glutamate waste water can be effectively flocculated. The natural material containing silicate, which relates to black soil, brown soil, red soil, slag, etc. which widely exist in nature, is a main ingredient of the compound flocculant, so the flocculant has the maximum ecological safety performance. On the other hand, the inorganic molysite of certain proportion, which serves as an auxiliary ingredient, is added to enhance the flocculating performance of the compound flocculant; alkaline substances are added to regulate the pH value. The using method comprises: (1) first, the alkaline substances are added to the monosodium glutamate waste water to regulate the pH value; (2) the natural material containing silicate is added to the monosodium glutamate waste water, and the monosodium glutamate waste water is quickly stirred to carry out flocculation and compounding; (3) after the monosodium glutamate waste water is quickly stirred, a proper amount of inorganic molysite is added to the monosodium glutamate waste water to carry out auxiliary flocculation. The present invention has the advantages of high efficiency, economy, high ecological safety performance and no secondary pollution to the environment.
Description
Technical field
The present invention relates to a kind of novel flocculation agent with maximum ecological safety performance and preparation method thereof, and the application in high density organic waste waters such as monosodium glutamate are administered; In addition, also can be applicable in the city water.
Background technology
Gourmet powder waste water is a kind of organic waste water of high density, and its COD is up to 10000-80000mgL
-1, and have characteristics such as high ammonium state nitrogen, high sulfate radical, low pH value, and never have a kind of good treatment method, be one of present water treatment difficult problem.China has 94 tame Gourmet Powder Factories now, and 1997 annual production reach 63.1284 ten thousand tons, has surpassed half of world wide production.Yet every production 1t monosodium glutamate will produce 25-30m
3High concentrated organic wastewater.According to statistics, will produce the above high concentrated organic wastewater of more than one hundred million tons every year.Because this kind wastewater treatment difficulty is big, the processing cost height causes having many Gourmet Powder Factories direct discharging of waste water, brings severe contamination for China's water surrounding.From the seventies in 20th century, China has carried out the research at the gourmet powder waste water purifying treatment already, but so far very quantum jump is not arranged as yet.It is big that its key issue is that gourmet powder waste water has a sewage quantity, is rich in NH
4 +-N, high COD, high SO
4 2-, characteristics such as multiple amino acids and organic acid, low pH value, make it be difficult to obtain degrade, be not easy to reach emission standard.
Current, the method for processing gourmet powder waste water commonly used mainly contains: physics method, chemical method, physico-chemical processes, biological process.
1, the physical method that mainly uses of physics method China monosodium glutamate wastewater treatment has evaporation concentration method and centrifugal separation.
2, the process object of chemical method chemical method mainly is inorganic and organic dissolved substance or a colloidalmaterial in the waste water.In monosodium glutamate wastewater treatment, commonly used mainly contains: flocculence, neutralization-chemical precipitation method etc.Wherein, flocculence is a kind of widely used water technology, is all bringing into play crucial effect in feedwater, wastewater treatment.The selection of flocculation agent is very important, and flocculation agent commonly used at present is divided into inorganic flocculating agent and organic floculant two big classes: 1) inorganic flocculating agent is used always molysite, aluminum salt flocculant.For example, department of chemistry of Shenzhen University adopts inorganic flocculating agents such as aluminium chlorohydroxide, ferrous sulfate, iron trichloride and calcium hydroxide that the flocculation of glutami acid fermentation liquor is studied, the result shows, simple inorganic flocculating agent, even cooperation coagulant aids, flocculating effect is also undesirable, is difficult to satisfy requirement of actual application.2) organic floculant is generally good than inorganic flocculating agent treatment effect, but different types of flocculation agent is to the requirement difference of operational condition, and flocculating effect is difference to some extent also.For example, environment system of Shanghai University adopts Xylo-Mucine, xylogen and sodium polyacrylate to carry out flocculating experiment, three kinds of flocculation agents flocculating effect under acidic conditions is better relatively, but pretreating effect is not good when using Xylo-Mucine or xylogen as flocculation agent separately, its COD clearance has only 18.4% and 23.5 respectively, does not almost have the possibility of using in production reality.Although the treatment effect of sodium polyacrylate is better relatively, the COD clearance also has only 36.0%.
3, physico-chemical processes consists predominantly of absorption method, extraction process, film and analyses method, distillation, crystallization etc.Wherein, handle gourmet powder waste water sorbent material commonly used gac, unslaked lime, chitosan and modified alta-mud etc. are arranged.Adopt absorption method to handle gourmet powder waste water, sorbent material costs an arm and a leg, and high to the pre-treatment requirement of water inlet, maintenance difficulties is big, and the regeneration of sorbent material also is a more scabrous problem.For example, people such as Wang Yongjie adopt the treatment with chitosan gourmet powder waste water, and the result shows that the only pH value of treatment with chitosan gourmet powder waste water is between 7-11; Chitosan is insensitive to temperature variation, stable in properties, and in 5-35 ℃ of temperature range, the flocculate with chitosan settling property changes little; The flocculating effect of chitosan improves with the increase of concentration.But fail to obtain fine popularization because of the price of flocculation agent own is higher.Therefore, this method generally is mainly used to remove the micropollutant in the waste water, reaches the purpose of deep purifying.
4, the biological process main biological treatment that is used for gourmet powder waste water at present has anaerobic biological treatment method and aerobic biological treatment.Wherein, the anaerobic biological treatment method is under the situation of anaerobic, effect by facultative anaerobe and obligatory anaerobic bacteria, the biological treatment that organism in the waste water is decomposed, its advantage is: energy consumption is low, recyclable bioenergy (biogas), microorganism (mud) amount that every removal unit weight substrate produces is few, has the potentiality of higher organic loading; And main shortcoming comprises: the COD value of handling the back water outlet is higher, handles the SO of back water outlet
4 2-Be worth higherly, hydraulic detention time is longer, produces foul smell, causes secondary pollution.The aerobe facture is not generally directly handled fermented waste fluid, just as the subsequent disposal means of entire treatment flow process, makes waste water finally reach emission standard, and commonly used at present have a SBR method.
From monosodium glutamate wastewater treatment on the whole, be not difficult to find that monosodium glutamate wastewater treatment is just by single physics, chemistry and biological process, to several different methods comprehensive treating process development, as physical-chemical-biological process, physics-biological process, chemical-biological method etc.Flocculation agent used in chemical method is just developed, is developed to compound or Compositional type by single type to polymer by low molecule-type.At present the research focus is at monosodium glutamate cost of sewage disposal height, easily brings secondary pollution, considers ecological security and applicability, needs a kind of efficient, economy of development, flocculation agent that the ecological safety performance is good.
Summary of the invention
The object of the present invention is to provide a kind of novel ecological safety built-up flocculant and preparation method and using method in gourmet powder waste water and the processing of similar high concentrated organic wastewater.
Technical scheme of the present invention is:
A kind of ecological safety type natural built-up flocculant, it contains one or more of silicates natural materials, based on the above-mentioned silicates natural materials that contains, be ancillary component with the inorganic molysite material that accounts for the 1%-5% that contains silicates natural materials weight.
The described natural materials that contains silicates comprises in black earth, brown earth, red soil and the scoriae that nature extensively distributes one or more.
Described inorganic molysite material is one or more in poly-ferric chloride, the bodied ferric sulfate.
Described ecological safety type natural built-up flocculant also comprises the alkaline matter of the 10-20% that accounts for the natural materials weight that contains silicates.
Described alkaline matter is one or more in calcium hydroxide, calcium chloride, sodium hydroxide, Wingdale and the gypsum.
A kind of preparation method of ecological safety type natural built-up flocculant may further comprise the steps:
1) selecting to contain silicates is that one or more of natural materials of main body mix;
2) will contain silicates be the natural materials of main body screen, dry, be milled into granularity and be 1-200 purpose particle, standby;
3) one or more in the selection inorganic molysite mix;
4) one or more in the selection alkaline matter mix.
A kind of using method of ecological safety type natural built-up flocculant, adding earlier adds inorganic molysite again and assists flocculation sediment after containing the flocculation of silicates natural materials vigorous stirring, comprises the steps:
1) regulates the pH value of monosodium glutamate sewage between 4-7 with selected alkaline matter earlier;
2) according to different quality, will contain silicates natural materials quantity in accordance with regulations with Powdered direct interpolation, the standard addition is a benchmark with the 10-30% that is equivalent to chemical oxygen demand (COD) in the sewage;
3) be 80-140 rev/min at rotating speed and stir 1min-5min down fast;
4) according to different quality, add selected inorganic molysite material, its standard addition is a benchmark to account for the 1%-5% that contains silicates natural materials weight;
5) be 80-140 rev/min at rotating speed earlier and stir 1min-10min down fast that the back is that 40-80 rev/min of following middling speed stirs 5min-10min at rotating speed, is to stir 10min-30min under 10-40 rev/min at a slow speed at rotating speed again, back standing sedimentation 15min-2h;
6) waste water after the processing enters biochemistry pool, realizes the solid-liquid separation of built-up flocculant and water.
Among the present invention, to contain the natural materials of silicates, wherein contain the organic matter and the mineral substance of some amount, all effectively play a role in the sewage in pH is the 4-7 scope, the pollutent in purifying waste water by Reaction Separation such as exchange, absorption, aggegation, fixing curing.Be present in other trace elements that contain in the natural materials that silicates is a main body, As time goes on can in sewage, separate out, and under dissolved oxygen, acid ion acting in conjunction, make solubility pollutent generation chemical reaction in the sewage, generation is insoluble in the congealed solid of water, and water quality is purified.Based on natural materials that silicates is arranged can be black earth, brown earth, red soil and scoriae etc., can be used alone or as a mixture.
The inorganic molysite material that adds among the present invention can make organism in the monosodium glutamate sewage by bringing into play its net and catch and characteristic such as bridge formation, quickens the aggegation, fixing and transform of pollutent, makes that molecule and pollutent aggegation form flocs unit in the water body.
The alkaline matter that adds among the present invention, as calcium hydroxide, calcium chloride, sodium hydroxide, Wingdale, gypsum etc. one or more, main purpose is the free acidic substance that can play in neutralization, the aggegation sewage, regulates the purpose of pH value, also plays the effect of flocculant aid simultaneously.
In sum, the feature of this built-up flocculant is to be that main body, inorganic polymer molysite material and a certain amount of alkaline matter are allocated the Compositional type flocculation agent that forms according to a certain percentage by containing the silicates natural materials, is used for the improvement of monosodium glutamate sewage and similar high concentration organic sewage.
The invention has the beneficial effects as follows:
After adding this class built-up flocculant in gourmet powder waste water and the similar high concentration organic sewage, aggegation rapidly, separation sewage middle and high concentration organic substance, COD is effectively removed, and significantly reduces cost of sewage disposal, reduce secondary pollution, obtain neutral treating water.Technology of preparing among employing the present invention has reduced the consumption of inorganic polymer molysite flocculation agent, has reduced the toxicity of inorganic polymer molysite flocculation agent to treating water, has significantly reduced the corrodibility to water treating equipment simultaneously.Sewage treatment process is stable, simple and direct, and non-secondary pollution in sewage treatment process has improved the ecological security of handling back water quality.The novel built flocculation agent that the present invention is a kind of efficient, economy, ecological security is good will play important effect in sewage disposals such as monosodium glutamate.
Embodiment
The invention provides a kind of novel ecological safety built-up flocculant, contain the natural materials of silicates, relate generally in extensive black earth, brown earth, red soil and the scoriae etc. that distribute of nature one or more.
The invention provides a kind of novel ecological safety built-up flocculant, the auxiliary flocculation of one or more conducts of 1%-5% (weight percentage) inorganic molysite that the above-mentioned natural materials that contains silicates is main body component, according to the water quality difference of treatment sewage, adopt different ratios and different components to add the prescription of order.The alkaline matter of the 10-20% (weight percentage) that the above-mentioned natural materials that contains silicates is a main body, as calcium hydroxide, calcium chloride, sodium hydroxide, Wingdale and gypsum etc. one or more.
The invention provides the preparation method of novel ecological safety built-up flocculant, may further comprise the steps:
1, selecting the above-mentioned silicates that contains is that one or more of natural materials of main body mix.
2, will contain silicates be the natural materials of main body screen, dry, be milled into granularity and be 1-200 purpose particle, standby.
3, one or more in the inorganic molysites such as selective polymerization iron(ic) chloride and bodied ferric sulfate mix.
4, select alkaline matter: one or more mix calcium hydroxide, calcium chloride, sodium hydroxide, Wingdale, gypsum etc.
Using method:
(1) regulates the pH value of monosodium glutamate sewage between 4-7 with selected alkaline matter earlier.
(2) according to different quality, natural materials quantity in accordance with regulations is with Powdered direct interpolation.The standard addition is a benchmark with the 10-30% (weight percentage) that is equivalent to chemical oxygen demand (COD) in the sewage (COD).
(3) stir (80-140 rev/min) 1min-5min fast.
(4) according to different quality, add selected inorganic molysite material, its standard addition is a benchmark to account for the 1%-5% that contains silicates natural materials weight.
(5) stir (80-140 rev/min) 1min-10min earlier fast, back middling speed stirs (40-80 rev/min) 5min-10min, stirs (10-40 rev/min) 10min-30min, back standing sedimentation 15min-2h more at a slow speed.
(6) waste water after the processing enters biochemistry pool, realizes the solid-liquid separation of built-up flocculant and water.
Embodiment 1
The present invention is a raw material with black earth, bodied ferric sulfate, calcium chloride.Wherein black earth is main component, and bodied ferric sulfate is auxiliary flocculation agent, and calcium chloride is the conditioning agent and the flocculant aid of pH value.The mass ratio of black earth and bodied ferric sulfate is 20: 1.
Its preparation method is:
(1) regulates about monosodium glutamate sewage pH value to 6.0 with calcium chloride.
(2) black earth that will prepare is that benchmark joins in the sewage with 30% of sewage chemical oxygen demand (COD), stirs fast (80-140 rev/min) about 5min.
(3) bodied ferric sulfate is added.
(4) stir (80-140 rev/min) 3min earlier fast, back middling speed stirs (40-80 rev/min) 10min, stirs (10-40 rev/min) 15min, back standing sedimentation 45min more at a slow speed.
(5) behind the quiet heavy 45min, get its supernatant liquor and measure turbidity.
Adopt the embodiment of the invention 1 to handle monosodium glutamate sewage, its turbidity removal rate is 95.12%.Under the same conditions, the polymeric ferric sulfate flocculant that adds same dose is separately handled monosodium glutamate sewage, and its turbidity removal rate only is 84.39%.From above comparative experiments as can be seen, adopt the present invention to handle monosodium glutamate sewage, the turbidity removal rate height, the flocculation agent consumption is few, and cost of sewage disposal reduces greatly, and treatment effect is better than existing various commercially available flocculation agents.
Embodiment 2
Be with example 1 difference: raw material is main component with brown earth, replaces bodied ferric sulfate with poly-ferric chloride.
Its preparation method is:
(1) regulates about monosodium glutamate sewage pH value to 4.0 with calcium chloride.
(2) brown earth that will prepare is that benchmark joins in the sewage with 25% of sewage chemical oxygen demand (COD), stirs (about 5min) fast.
(3) poly-ferric chloride is added.
(4) stir (80-140 rev/min) 3min earlier fast, back middling speed stirs (40-80 rev/min) 10min, stirs (10-40 rev/min) 15min, back standing sedimentation 45min more at a slow speed.
(5) behind the quiet heavy 45min, get its supernatant liquor and measure turbidity.
Adopt the embodiment of the invention 2 to handle monosodium glutamate sewage, its turbidity removal rate is 92.13%.Under the same conditions, the poly ferric chloride flocculant agent that adds same dose is separately handled monosodium glutamate sewage, and its turbidity removal rate only is 80.09%.
Embodiment 3
Be with example 1 difference: raw material is main component with the scoriae, and the mass ratio of scoriae and bodied ferric sulfate is 25: 1.
Its preparation method is:
(1) regulates about monosodium glutamate sewage pH value to 7.0 with calcium chloride.
(2) scoriae that will prepare is that benchmark joins in the sewage with 25% of sewage chemical oxygen demand (COD), stirs (about 5min) fast.
(3) bodied ferric sulfate is added.
(4) stir (80-140 rev/min) 3min earlier fast, back middling speed stirs (40-80 rev/min) 10min, stirs (10-40 rev/min) 15min, back standing sedimentation 45min more at a slow speed.
(5) behind the quiet heavy 45min, get its supernatant liquor and measure turbidity.
Adopt the embodiment of the invention 3 to handle monosodium glutamate sewage, its turbidity removal rate is 85.14%.Under the same conditions, the polymeric ferric sulfate flocculant that adds same dose is separately handled monosodium glutamate sewage, and its turbidity removal rate only is 78.21%.
Embodiment 4
Be with example 1 difference: the mass ratio of black earth and bodied ferric sulfate is 30: 1.
Its preparation method is:
(1) regulates about monosodium glutamate sewage pH value to 6.0 with calcium chloride.
(2) scoriae that will prepare is that benchmark joins in the sewage with 30% of sewage chemical oxygen demand (COD), stirs (about 5min) fast.
(3) bodied ferric sulfate is added.
(4) stir (80-140 rev/min) 3min earlier fast, back middling speed stirs (40-80 rev/min) 10min, stirs (10-40 rev/min) 15min, back standing sedimentation 45min more at a slow speed.
(5) behind the quiet heavy 45min, get its supernatant liquor and measure turbidity.
Adopt the embodiment of the invention 4 to handle monosodium glutamate sewage, its turbidity removal rate is 90.65%.Under the same conditions, the polymeric ferric sulfate flocculant that adds same dose is separately handled monosodium glutamate sewage, and its turbidity removal rate only is 78.21%.
Utilization of the present invention contains the natural materials of silicates, by a certain percentage with a graded, carries out compositely with inorganic molysite, can reach gourmet powder waste water is carried out effective flocculation treatment.Wherein, the natural materials that contains silicates relates to black earth, brown earth, red soil and the scoriae etc. that nature extensively exists, and is the main component of this built-up flocculant, thereby makes it have maximum ecological safety performance.On the other hand, in order to strengthen the flocculating property of built-up flocculant, adding a certain proportion of inorganic molysite is ancillary component, and alkaline matters such as adding calcium hydroxide, calcium chloride, sodium hydroxide, Wingdale and gypsum carry out acid-alkali accommodation.After adding this built-up flocculant in the monosodium glutamate sewage, sewage middle and high concentration organism can compile separation rapidly, obtains neutral water.Employing the present invention dispose of sewage, and cost of sewage disposal is reduced greatly, and sludge quantity is few, do not have foul smell to produce.Meanwhile, also significantly having reduced the inorganic molysite flocculation agent gives birth to the corrosion of water treating equipment.Mud after the processing can carry out drying and carry mycoprotein, recycles.This kind novel ecological safety built-up flocculant is efficient, economy, ecological security are good, to the environment non-secondary pollution.
Claims (6)
1, a kind of ecological safety type natural built-up flocculant, it is characterized in that: it contains one or more of silicates natural materials, based on the above-mentioned silicates natural materials that contains, be ancillary component with the inorganic molysite material that accounts for the 1%-5% that contains silicates natural materials weight; The described silicates natural materials that contains comprises in black earth, brown earth, red soil and the scoriae that nature extensively distributes one or more.
2, ecological safety type natural built-up flocculant according to claim 1 is characterized in that: described inorganic molysite material is one or more in poly-ferric chloride, the bodied ferric sulfate.
3, ecological safety type natural built-up flocculant according to claim 1 is characterized in that: the alkaline matter that also comprises the 10-20% that accounts for the natural materials weight that contains silicates.
4, ecological safety type natural built-up flocculant according to claim 3 is characterized in that: described alkaline matter is one or more in calcium hydroxide, calcium chloride, sodium hydroxide, Wingdale and the gypsum.
5, a kind of preparation method of ecological safety type natural built-up flocculant is characterized in that may further comprise the steps:
1) selecting to contain silicates is that one or more of natural materials of main body mix, and describedly contains the natural materials that silicates is a main body, comprises in black earth, brown earth, red soil and the scoriae that nature extensively distributes one or more;
2) will contain silicates be the natural materials of main body screen, dry, be milled into granularity and be 1-200 purpose particle, standby;
3) one or more in the selection inorganic molysite mix;
4) one or more in the selection alkaline matter mix.
6, a kind of using method of ecological safety type natural built-up flocculant, after it is characterized in that adding earlier contains the flocculation of silicates natural materials vigorous stirring, add inorganic molysite again and assist flocculation sediment, the described silicates natural materials that contains, comprise and comprise the steps: in black earth, brown earth, red soil and the scoriae that nature extensively distributes one or more
1) regulates the pH value of monosodium glutamate sewage between 4-7 with selected alkaline matter earlier;
2) according to different quality, will contain silicates natural materials quantity in accordance with regulations with Powdered direct interpolation, the standard addition is a benchmark with the 10-30% that is equivalent to chemical oxygen demand (COD) in the sewage;
3) be 80-140 rev/min at rotating speed and stir 1min-5min down fast;
4) according to different quality, add selected inorganic molysite material, its standard addition is a benchmark to account for the 1%-5% that contains silicates natural materials weight;
5) be 80-140 rev/min at rotating speed earlier and stir 1min-10min down fast that the back is that 40-80 rev/min of following middling speed stirs 5min-10min at rotating speed, is to stir 10min-30min under 10-40 rev/min at a slow speed at rotating speed again, back standing sedimentation 15min-2h;
6) waste water after the processing enters biochemistry pool, realizes the solid-liquid separation of built-up flocculant and water.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100532287C (en) * | 2006-08-25 | 2009-08-26 | 中国科学院沈阳应用生态研究所 | Natural compound flocculant of chitosan, producing method and uses of the same |
| CN101851026B (en) * | 2010-03-31 | 2012-05-23 | 吉林大学 | Ecological safety type natural permeable reactive barrier medium and preparation method thereof |
| CN101811764B (en) * | 2010-04-29 | 2012-07-04 | 南京神克隆科技有限公司 | Efficient ecological type sewage and sludge treating agent and preparation method thereof |
| CN103241819B (en) * | 2013-06-06 | 2015-04-01 | 玉溪师范学院 | Modified red earth flocculant and method for preparing same |
| CN103787475B (en) * | 2014-01-16 | 2015-08-12 | 刘洪军 | A kind of high efficiency sewage treating agent |
| CN114315096B (en) * | 2021-11-23 | 2023-01-03 | 河海大学 | Sludge soil additive and preparation method and application thereof |
| CN116253410A (en) * | 2023-02-28 | 2023-06-13 | 内蒙古农业大学 | Treating agent for reducing COD and ammonia nitrogen concentration in monosodium glutamate wastewater and preparation method and application thereof |
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| JPH1190112A (en) * | 1997-09-18 | 1999-04-06 | Kazuo Saito | Flocculation and sedimentation agent for sewage clarification |
| CN1227192A (en) * | 1998-02-24 | 1999-09-01 | 曾兆祥 | Compound coagulant for waste water treatment and its usage |
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