CN1018729B - Method for treating waste liquid from gourmet powder plant and products thereof - Google Patents
Method for treating waste liquid from gourmet powder plant and products thereofInfo
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- CN1018729B CN1018729B CN 91102317 CN91102317A CN1018729B CN 1018729 B CN1018729 B CN 1018729B CN 91102317 CN91102317 CN 91102317 CN 91102317 A CN91102317 A CN 91102317A CN 1018729 B CN1018729 B CN 1018729B
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- waste liquid
- add
- treating waste
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Abstract
The present invention relates to a method for wastewater treatment and a product obtained by wastewater treatment, which is suitable for treating waste liquid of monosodium glutamate factory factories and similar waste liquid and produces products of farm chemical composition, feed additive, etc. The present invention mainly provides a method for thoroughly removing waste liquid of glutamic acid monosodium glutamate, and simultaneously, produces a systemic farm chemical composition with high efficiency, low toxicity and broad spectrum. The method of the present invention is mainly formed by procedures of heating and pretreating, complex reaction for removing SO42-ion, neutralization reaction, etc.
Description
The present invention relates to method for treating waste liquid from gourmet powder plant.
There is tame Gourmet Powder Factory more than 200 in China at present, all is to be that raw material extracts L-glutamic acid with the rice after fermenting basically, again L-glutamic acid is made monosodium glutamate.Technology when waste liquid (being the said Gourmet Powder Factory of the present invention waste liquid) the composition basis behind the extraction L-glutamic acid is carried L-glutamic acid is different and slightly variant, but all similar substantially.Mainly be grouped into through sampling analysis: soluble protein (≤1.5%), L-glutamic acid (≤1.5%), reducing sugar (＜1.0%), other amino acid (about 0.5%), dry mycelium (0.9%), COD(8 * 10 by following one-tenth
4Mg/l), BOD(2.7 * 10
4Mg/l), also has NH
4, K
+, Na
+, Mg
2+, Ca
2+, Fe
2+, Cl
-, SO
4, PO
4(0.5-0.8% altogether), ° Be '≤5.0, pH=3.0-3.2.Every day is discharged three, 40 tons by little factory, big factory every day five, 600 tons, does not have a kind of effective ways to carry out the comprehensive regulation as yet, how directly to be discharged near the rivers and lakes, cause serious pollution, cause fish kills, crop growth bad, destroyed the eubiosis of this area.
The method of handling monosodium glutamate, terramycin, nystatin production composite waste with the anaerobic-aerobic two-stage biological process introduced in the article of the Feng Xishao that " chemical industry environmental protection " 1987 the 7th volumes 32-35 page or leaf is published " monosodium glutamate terramycin nystatin is produced the anaerobic-aerobic biological treatment of composite waste ".Its objective is and remove COD
ErAnd BOD
6Make after the processing water quality near or reach national industrial wastewater discharge standard substantially, the anaerobic sludge and the aerobic activated sludge of anti-high loading need be cultivated and tame to this method, three kinds of components in the composite waste are also required certain ratio, complex technical process, the maintenance of equipment is also very difficult, cost and energy consumption height.
" monosodium glutamate wastewater treatment with utilize technical progress " of the Zhang Changquan that publishes on " chemical industry environmental protection " nineteen ninety the 10th volume 43-45 page or leaf introduced the experience of Shenyang Gourmet Powder Factory according to Japan consonance Fang Fu workshop, the method of the improvement waste water of formulating in conjunction with China's particular case, this method is by reduction vaporization, the neutralization evaporation, mother liquid evaporation, hydrolysis, neutralization, steps such as separation and mixing granulation are formed, can solve waste water pollution problem substantially, but energy consumption is higher, and the fertilizer efficiency that obtains behind the improvement waste water is not high, be difficult to obtain economical effectiveness, so this method also is difficult to apply.
Introduced the method for several system compounded amino acids agricultural chemicals in the article " amino acids antiseptic-germicide " of " Shaanxi chemical industry " 1988 the 6th interim Yang Zhe people, Hou Lu, wherein a kind of method is to be raw material with the cotton cake dregs, with the protein in the sulfuric acid solution grouts, its weak point is to expend a large amount of sulfuric acid and hydrated barta, and contain a kind of very deleterious material-gossypol in the cotton cake dregs, in the process of system agricultural chemicals, it is not removed, after the applications of pesticide, once people and animals eat by mistake, can cause poisoning, and this method cost height.
Introduced a kind of method of making agricultural chemicals in " Harbin Science and Technology Univ.'s journal " the 1st phase in 1988 the 124th page of last Lee intelligent " comprehensive utilization of animal ceratin " literary composition of a specified duration, this method is to make the aminoacids complex mantoquita with animal hair, angle, hoof, clot etc. after acidolysis, as agricultural antibiotic, sterilant, its weak point is that raw material is expensive and rare, need expend a large amount of sulfuric acid and hydrated barta, cost is very high.
The method that the objective of the invention is to avoid above-mentioned the deficiencies in the prior art part and a kind of comprehensive regulation L-glutamic acid monosodium glutamate waste liquid that can effectively promote is provided, thoroughly remove the pollution that Gourmet Powder Factory's waste liquid causes, utilize effective constituent in the waste liquid with the materials such as high protein of synthetic a kind of efficient, the low toxicity of lower cost, wide spectrum, interior absorption amino acids pesticide composition and additive capable of using as feed simultaneously, turn waste into wealth.
Purpose of the present invention can reach by following measure: monosodium glutamate waste liquid is introduced carried out heat pre-treatment in the well heater, heating and temperature control makes soluble protein and some suspended substances in the waste liquid solidify sedimentation 95-100 ℃ (available saturation steam heating).If temperature is lower than 95 ℃, then protein can not solidify fully, if temperature is higher than 100 ℃, then can destroy proteinic effective constituent, and the effect of isolated solid protein matter is reduced, and energy consumption increases simultaneously.Separated liquid supernatant can enter reactor after the pre-treatment after concentrating, neutralizing, and adds copper sulfate then in reactor, as CuSO
45H
2O, and heated and stirred carry out complex reaction, and the amount that adds copper sulfate accounts for the 1-10% of mixture total weight amount in the reactor.In addition, yet can add MnSO simultaneously
4Or NiCl
2Wait at least a in other soluble heavy metal salt to carry out complex reaction, if add MnSO
4, its add-on is counted 0.1-1.2% with mixed solution weight, and temperature of reaction is controlled at 90-100 ℃ (available saturation steam heating), stirs more than 0.8 hour, is advisable with 0.8-1.2 hour, and reaction formula is as follows:
Wherein: R represents " CH
3-", " HOOC-CH
2-", " HOOC-CH
2-CH
2-" wait the atomic radical in each seed amino acid,
Represent each seed amino acid
It in the heavy metal elements such as Cu, Mn, Ni is the Cu element at least that Me represents.
When for example L-glutamic acid and metal copper ion reacted, reaction formula (1) was exactly:
In above-mentioned reaction, CuSO
45H
2O(also can also have MnSO
4Or NiCl
2Deng) with waste liquid in the kilnitamin complexing, form aminoacids complex mantoquita (also can also have other aminoacids complex heavy metallic salt), a large amount of free ammonias and ammonium radical ion and cupric ion reaction generate cupric ammine complex in the waste liquid in addition, constitute the main component of the said pesticide composition of the present invention.In this reaction, the amount that adds copper sulfate is lower than 1% makes DeGrain antibiotic, sterilant, if be higher than 10%, causes unnecessary waste again.Speed of response was too slow when temperature of reaction was lower than 90 ℃, was higher than 100 ℃, and energy consumption increases, and might destroy the effective constituent in the mixed solution.Churning time is less than 0.8 hour, and complex reaction is incomplete, surpasses 1.2 hours, then increases unnecessary energy consumption.Mixed solution after the complex reaction can pump in another reactor, and hydro-oxidation barium is as Ba(OH)
28H
2O, and stir more than 0.8 hour to remove SO
2- 4, add Ba(OH)
28H
2The amount of O is according to the SO in the concentrated solution
2- 4What and decide, just to remove SO
2- 4Be as the criterion.Hydrated barta is a highly toxic substance, and it is excessive to add, and has lacked and can not remove SO fully if add
2- 4, churning time was advisable with 0.8-1.2 hour.Through removing SO
2- 4After, upper clear supernate to be separated handle, isolated liquid is used alkali and is neutralized, and makes pH=7-7.5.
In above method, waste liquid left standstill 3-5 hour after heat pre-treatment, upper clear supernate can be pumped into vaporizer and concentrate, preferably adopt the decompression low-temperature evaporation, to reduce or to avoid the volatilization and the destruction of useful component, and the concentrated solution ratio after control clear liquid and the evaporation is 3-7: 1 is advisable, if less than 3: 1, fully do not play spissated effect, increased the burden and the cost of subsequent disposal, if greater than 7: 1, then concentrated solution is dried partially, makes pipe-line transportation inconvenience, and complex reaction is difficult to carry out.COD in the former waste liquid, BOD can remove substantially through evaporation concentration, and the overwhelming majority that steams during evaporation is a water vapor, has only the NH of minute quantity
3Concentrated solution can neutralize with multiple water soluble alkalis such as NaOH, KOH, ammoniacal liquor, makes pH=6-8, is convenient to the complex reaction of back.
Mixed solution after the complex reaction is after adding an amount of hydrated barta and stir, leaving standstill 10-13 hour then, and the pH value can reach 5-6, isolate upper liquid this moment, can add CaO and carry out aftertreatment, and add-on is counted 0.05-0.13% with the weight of mixture, and stirred 0.8-1.2 hour, make it thorough mixing.The purpose that adds CaO is a neutralization solution, makes pH=7-7.5, and makes in the prepared pesticide composition and increase Ca
2+Ion.
By the pesticide composition that above-mentioned liquid waste disposal makes, mainly form by following two compounds:
(1) aminoacids complex heavy metallic salt:
(2) cupric ammine complex:
[Cu(NH
3)
4]
2+Account for the 15-20% of composition weight.
In addition, in this pesticide composition Mg can also be arranged
2+, Fe
2+, Ca
2+, K
+, NH
+ 4, PO
3- 4Etc. different kinds of ions, account for the 5-10% of composition weight altogether.
Add copper sulfate in the waste liquid through the aminoacids complex mantoquita that the complexing reaction forms, in the plant suction body, cause the accumulation of cupric ion, to precipitate viral endobacillary protein, enzyme is lost activity, thereby reach the purpose of antibiotic and sterilizing.In addition, cupric ammine complex itself also has the antibiotic and sterilizing effect.If in reactor, added MnSO
4Or NiCl
2Carry out complex reaction, then can generate aminoacids complex manganese salt or nickel salt, its effect and aminoacids complex copper salt kind seemingly in addition, after manganese element is added, still can promote plant germination, promote plant-growth, increase grain yield.If preceding method has carried out aftertreatment through adding CaO, then increased Ca in this pesticide composition
2+Ion after the plant materials absorption, can strengthen plant ability resistant to lodging.Contain a large amount of nitrogen elements in this pesticide composition, be a kind of good nitrogenous fertilizer, the chemical element such as potassium, calcium, magnesium, phosphorus that has also kept the some amount that itself contains in the waste liquid in this pesticide composition, can serve as a kind of good inorganic composite fertilizer again, therefore this pesticide composition has the dual function of antibiotic bactericide and fertilizer.
In the method for the present invention, waste liquid left standstill after heat pre-treatment 3-5 hour, sedimentary protein in bottom and suspended substance can be separated, under 80-100 ℃, carry out spraying drying with in the alkali and back and obtain pulverous material, after measured, this flour contains the protein of 55-70%, with this flour with sulfuric acid solution after, 835 type automatic analyzer for amino acidss are tested through Hitachi, obtain each amino acid that 16 kinds of content do not wait.The solid matter of spraying drying gained can be made following purposes: (1) as the high-grade animal feedstuff additive, (2) can be made into compounded amino acid metal salt antibiotic bactericide after acidolysis, and (3) can therefrom isolate expensive simple amino acid.
In the method for the present invention, add Ba(OH)
2Remove SO
2- 4Reaction finish after, left standstill 10-13 hour, when making upper liquid pH=5-6, bottom BaSO
4Precipitate and separate is come out, and again through centrifugal or filtering separation, isolated liquid turns back in the upper liquid, carries out aftertreatment, solid BaSO
4Can be used as industrial chemicals after treatment.
The present invention has following advantage compared to existing technology:
1. method for treating waste liquid from gourmet powder plant provided by the invention, technology is simpler, and is not high to equipment requirements, and cost and energy consumption are all lower, and no three wastes material discharging in the entire treatment process, can not cause secondary pollution, have thoroughly cleared up the waste liquid that Gourmet Powder Factory discharges.And can produce multiple useful matteies such as agricultural chemicals, high protein, and turn waste into wealth, can bring good social benefit and economic benefit, very advantageous conditions is provided for applying of this method.
2, the pesticide composition that makes with method of the present invention is a kind of efficient, low toxicity, wide spectrum, systemic pesticide, has excellent antibiotic sterilization and fertilizer efficiency double effects, and is lower, effective than existing like product cost.This agricultural chemicals is measured through the indoor cultivation ware, and phytophthora root rot and Radix Panacis Quinquefolii root-rot disease to the blight of the head blight of wheat, cotton, anthrax, tomato suppress effect at 60-70%; Through the big area field test, to damping-off, the samping off of vegetables, prevention effect is at 83-100%, to the effect of increasing production of vegetables at 10-16%.Protect and the street virus center to be measured by the animal acute toxicity of this agricultural chemicals work through Chinese bacterium, mice lavage test Lethal Dose 50 LD
50Be 1250mg/kg, and the agricultural chemicals virulence standard code LD of China
50＞500mg/kg just belongs to low-toxin farm chemicals.
3, the powdery high protein material that obtains with method of the present invention is the high-grade feed additive, and can make other purposes.
Accompanying drawing is the process flow sheet of the method for the invention.
The present invention is described in further detail below in conjunction with drawings and Examples:
With 5 tons of L-glutamic acid monosodium glutamate waste liquids (pH=3.0-3.2,
0Be '=5) squeeze into (pretreater can be used stainless material, also can apply impregnating material at inwall) in the pretreater 1 with acid proof pump, and with Boiler Steam by heating coil 2 indirect heating to 95 ℃, left standstill 5 hours.Then supernatant liquor is introduced storage tank 4; The bottom flocculent precipitate is introduced storage tank 3, with in the alkali lye and after can send into Highspeedcentrifugingandsprayingdrier and carry out drying, must the canescence bacterium protein.Supernatant liquor in the storage tank 4 is squeezed into header tank 6 with acid proof pump 5, introduce concentration tank 7 then, the cryoconcentration that reduces pressure, temperature is 50-55 ℃, gets 1 ton of concentrated solution.Introduce storage tank 8, with acid proof pump 9 concentrated solution is squeezed in the neutralizing well 10 again, be neutralized to pH=7 with strong aqua.Concentrated solution after the neutralization is squeezed in the enamel reaction still 12 of strap clamp cover with impeller pump 11, adds 40kg industrial sulphuric acid copper, and the 5kg manganous sulfate carries out indirect heating with Boiler Steam, and homo(io)thermism stirred 1 hour at 95-100 ℃, carried out complex reaction.Put into storage tank 13 afterwards, squeeze in the reactor 15 with ionic pump 14 again, add the 60kg hydrated barta, stirred 1 hour, left standstill then 10 hours.Enter storage tank 18 with siphon method sucking-off supernatant liquor.Remaining barium sulfate precipitate is pressed into flame filter press 17 with high-pressure pump 16 and filters, and filter residue is a barium sulfate, can be used as industrial chemicals after treatment and sells, and filtrate merges in the supernatant liquor in the above-mentioned storage tank 18, at this moment supernatant liquor pH=5-6.Add 1kg unslaked lime and stirred 1 hour, be neutralized to pH=7-7.5.Carry out commercialization at last and handle, brown,
01.07 tons in the mixture that Be ' is 23, mainly be made up of aminoacids complex heavy metallic salt and cupric ammine complex is the said pesticide composition of the present invention.
Claims (6)
1, a kind of method for treating waste liquid from gourmet powder plant comprises steps such as evaporation concentration, neutralization, complexing, displacement, separation, carries out heat pre-treatment when it is characterized in that disposing waste liquid earlier to isolate protein, and heating and temperature control is at 95-100 ℃; Adding copper sulfate in the concentrated solution after evaporation and the neutralization, heated and stirred is carried out complex reaction, and add-on is counted 1-10% with mixed solution weight, and temperature of reaction is 90-100 ℃, stirs 0.8-1.2 hour; Add hydrated barta after the complex reaction, and stirred 0.8-1.2 hour, add-on is can remove SO fully
2- 4Be as the criterion; Last isolated liquid neutralizes with alkali, makes its pH=7-7.5.
2, method for treating waste liquid according to claim 1 is characterized in that adding in the in the end isolated liquid CaO and carries out aftertreatment, and add-on is counted 0.05-0.13% with mixed solution weight, and stirs 0.8-1.2 hour.
3, method for treating waste liquid according to claim 1 is to add CuSO in the concentrated solution after it is characterized in that neutralizing
45H
2O carries out complex reaction, adds MnSO simultaneously
4, NiCl
2Wait at least a complex reaction, the wherein MnSo of carrying out in other soluble heavy metal salt
4Add-on is counted 0.1-1.2% with mixed solution weight, and the reaction churning time is 0.8-1.2 hour.
4, method for treating waste liquid according to claim 1 when it is characterized in that the clear liquid that waste liquid is obtained carries out evaporation concentration after pre-treatment, adopts the decompression low-temperature evaporation, and the concentrated solution ratio after making clear liquid and evaporating is 3-7: 1.
5, method for treating waste liquid according to claim 1 is characterized in that with in the multiple water soluble alkalis such as NaOH, KOH, ammoniacal liquor and the concentrated solution after the evaporation, makes the concentrated solution pH=6-8 after the neutralization.
6, method for treating waste liquid according to claim 1 is characterized in that adding Ba(OH)
28H
2Behind the O stirring reaction, left standstill 10-13 hour, separate when making upper liquid pH=5-6, and the BaSO that the bottom is generated
4Precipitation is carried out centrifugal or filtering separation, and isolated liquid turns back in the upper liquid, carries out aftertreatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91102317 CN1018729B (en) | 1991-04-16 | 1991-04-16 | Method for treating waste liquid from gourmet powder plant and products thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91102317 CN1018729B (en) | 1991-04-16 | 1991-04-16 | Method for treating waste liquid from gourmet powder plant and products thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1054405A CN1054405A (en) | 1991-09-11 |
| CN1018729B true CN1018729B (en) | 1992-10-21 |
Family
ID=4905533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91102317 Expired CN1018729B (en) | 1991-04-16 | 1991-04-16 | Method for treating waste liquid from gourmet powder plant and products thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1018729B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11047841B2 (en) | 2017-10-17 | 2021-06-29 | Pierre Desjardins | Interconnecting detector |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106106571A (en) * | 2016-06-23 | 2016-11-16 | 袁春华 | A kind of method utilizing Gourmet Powder Factory's waste liquid compound botanical oil to prepare disinfectant use in agriculture |
| CN106904791A (en) * | 2017-03-06 | 2017-06-30 | 常州大学 | A kind of monosodium glutamate wastewater treatment apparatus and method |
| CN114538650A (en) * | 2021-12-31 | 2022-05-27 | 石家庄循环化工研究院 | Method for removing pollutants in wastewater generated in production of fermentation antibiotics |
-
1991
- 1991-04-16 CN CN 91102317 patent/CN1018729B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11047841B2 (en) | 2017-10-17 | 2021-06-29 | Pierre Desjardins | Interconnecting detector |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1054405A (en) | 1991-09-11 |
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