CN103613228A - Method for treating vitamin K3 production wastewater - Google Patents
Method for treating vitamin K3 production wastewater Download PDFInfo
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- CN103613228A CN103613228A CN201310694760.2A CN201310694760A CN103613228A CN 103613228 A CN103613228 A CN 103613228A CN 201310694760 A CN201310694760 A CN 201310694760A CN 103613228 A CN103613228 A CN 103613228A
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Abstract
The invention relates to a method for treating vitamin K3 production wastewater. The method comprises the following steps: a) adding a flocculant into the vitamin K3 production wastewater to flocculate suspended solids and/or flotage in the wastewater and remove the suspended solids and/or flotage as filter residues; b) enabling the wastewater obtained by flocculation and residue removal in the step a) to come into contact with oxygen at 100-360 DEG C for 1-8 hours to carry out an oxidation reaction; and c) adding an adsorbent capable of decoloring and deodorizing the wastewater into the wastewater which has the oxidation reaction in the step b). The method can be used for removing a large amount of organic pollutants out of the vitamin K3 wastewater, the treated wastewater can not only reach the direct emission standard, but also can be recycled, even can be directly reused in a vitamin K3 production process, and the method is low in energy consumption, free of secondary pollution and capable of realizing zero wastewater emission, so that the method is a very clean and environmental-friendly wastewater treatment method.
Description
Technical field
The present invention relates to a kind of method of processing vitamin K3 factory effluent, relate in particular to a kind of method for cleaning of processing vitamin K3 factory effluent.
Background technology
At present, on market, vitamin K3 series products mainly contains sodium menadione sulfate (MSB), vitamin k3 mixture (MSBC), menadione dimethylpyrimidinol bisulfite (MPB), vitamin k4 niacinamide sulphite (MNB).Vitamin K3 has medicine effect, is the strongest class of biological activity in the VITAMIN ，Shi vitamin K family using the earliest.It is also a kind of important intermediate of hemorrhage medicine, clinically, spasmolysis hemorrhage for preventing and treating, town pain.Also can be used as fodder additives, plant-growth regulator, promotor, weedicide; Can also be for the coating of steamer, warship etc., purposes is very extensive, and market outlook are wide.
Vitamin K3 product MSB (sodium menadione sulfate) is to be reacted and form with sodium bisulfite, niacinamide by 2-MNQ with MNB (bisulfite niacinamide vitamin k4).And 2-MNQ is to be formed through oxygenant oxidations such as chromic acid, hydrogen peroxide by 2 – methylnaphthalenes, generate the by products such as 6 – methyl naphthoquinones, 2-naphthoic acid simultaneously.
In the building-up process of vitamin K3, need to use a large amount of solvents as butanols, water etc., through sulfonation reaction, generate MSB solution, then add a large amount of salting-out agent to separate out MSB product as sodium-chlor etc. carries out Crystallization Separation.Due to saltout can only separated approximately 30% MSB product, therefore by isolated mother liquor for refining MNB product, refiningly add salting-out agent after synthetic and isolate MNB product.In the building-up process of MSB and MNB, added a large amount of organic solvents (such as, at 2-methyl isophthalic acid, 4-naphthoquinones reacts preparation MSB process and uses a large amount of butanols solvents with sodium bisulfite) and salting-out agent, because solvent recuperation is incomplete, salting-out agent consumption is large, cause final waste water containing a large amount of salinities and organism.Meanwhile, in waste water, dissolve and remain a certain amount of naphthoquinones product and by product, make waste water complicated component, containing organism such as quinone, alcohol, niacinamide, naphthoquinone derivatives and high polymers, and colourity is high, is conventionally red-brown, has intense stimulus smell.
Because vitamin K3 factory effluent organic content is high, make the chemical oxygen demand (COD) (COD) of waste water higher, its value is generally in about 20000-300000mg/L, processes more difficultly, therefore cannot reach that waste water commercial recovery utilizes and direct emission request.Along with the continuous generation of factory effluent, if do not take effective Disposal Measures, will have a strong impact on environment, the normal development of restriction industry.
At present, the general treatment process adopting is " evaporation concentration+multistage rectification ", then adopts the mode of burning to process.In treatment method of phenol sodium salt waste water as disclosed in Chinese patent CN102126777B, with regard to having adopted, first add 70% dilute sulphuric acid and cause then evaporation concentration of layering, the method of the disclosed high-salt wastewater zero release of Chinese patent CN102616873A has just adopted high-efficiency evaporating to realize the zero release of high-salt wastewater, in the high salinity of processing of Chinese patent CN102351269A instruction, the method for high organic substance content wastewater, adopted extraction phase-splitting, water carries out evaporation process, and organic phase is carried out burning disposal.Yet for the waste water of the high organic content of high salinity, evaporation concentration not only energy consumption is large, and evaporation difficulty is large, and operation stability is not high.Meanwhile, burning disposal can be emitted smelly property gas, easily causes secondary pollution, and has increased processing cost.
In addition, also have the biochemical treatment process of the dilution of adopting, but for high-concentration waste water, dilution not only consumes large water gaging but also has increased total release.And under high salinity environment, biochemical treatment is difficult to realize, treatment effect is bad.And due to high salt content in waste water, microorganism is difficult to survival, make to adopt the active processing of biological process.
Therefore,, in view of above-mentioned prior art situation, wish to find a kind for the treatment of process of polluting little, environmental friendliness, vitamin K3 factory effluent that energy consumption is low.
Summary of the invention
In view of above-mentioned condition of the prior art, the present inventor has carried out extensive and deep research aspect vitamin K3 production wastewater treatment, to finding a kind of method of polluting little, environmental friendliness, processing vitamin K3 factory effluent that energy consumption is low.Found that, by vitamin K3 factory effluent is first flocculated with flocculation agent, then use dioxygen oxidation, finally, with sorbent material decolouring and taste removal, the method can be removed a large amount of organic pollutants in vitamin K3 waste water, the waste water of processing can not only reach direct emission standard, and can recycle, even can directly return to vitamin K3 technique and use, and the method energy consumption is low, can not cause secondary pollution, be a kind of method of wastewater treatment of extremely clean environment firendly.
Therefore, the object of this invention is to provide a kind of method of processing vitamin K3 factory effluent, the method can be removed a large amount of organic pollutants in vitamin K3 waste water, the waste water of processing can not only reach direct emission standard, and can recycle, and even can directly return to vitamin K3 technique and use, and the method energy consumption is low, can not cause secondary pollution, can realize wastewater zero discharge, be a kind of method of wastewater treatment of extremely clean environment firendly.
The technical scheme that realizes above-mentioned purpose of the present invention can be summarized as follows:
1. a method of processing vitamin K3 factory effluent, comprises the steps:
A) in vitamin K3 factory effluent, add flocculation agent, make suspended substance and/or the floating matter flocculation in waste water and remove as filter residue;
B) make step a) in the waste water that obtains of flocculation slagging-off with oxygen at 100-360 ℃, contact 1-8 hour to carry out oxidizing reaction at preferred 120-180 ℃; And
C) to step b) in carried out adding and can adsorbing the sorbent material of this waste water decoloring and taste removal in the waste water of oxidizing reaction.
2. according to the method for the 1st, the flocculation agent that wherein step is used in a) is polyacrylamide, potassium aluminium sulfate, polymeric aluminium ferrum silicate, iron trichloride or its mixture.
3. according to the 1st or the method for 2, wherein step a) in the addition of flocculation agent be that every liter of vitamin K3 factory effluent adds 1-10g, preferred 1-5g; The temperature that flocculation is carried out is 25-80 ℃, is preferably 30-50 ℃; And/or flocculation time is 0.5-24 hour, be preferably 0.5-1.5 hour.
4. the oxidizing reaction according to the method for any one in 1-3 item, step b wherein), at 0-12MPa, is preferably carried out under the gauge pressure pressure of 0.3-4MPa; And/or step b) oxidizing reaction in continues 1-8 hour, preferably continues 1-3 hour.
5. the oxygen using according to the method for any one in 1-4 item, step b wherein) is the oxygen-containing gas that oxygen content is at least 21 volume %, is preferably pure oxygen or air.
6. the sorbent material using according to the method for any one in 1-5 item, step c wherein) is gac, diatomite, resin, silica gel or its mixture.
7. according to the method for any one in 1-6 item, wherein the addition of sorbent material is that every liter of waste water upon adsorption adds 10-100g, preferably adds 10-50g.
8. according to the method for any one in 1-7 item, step c wherein), be adsorbed on 25-80 ℃, preferably carry out at 25-50 ℃; And/or adsorption time is 5 minutes-24 hours, be preferably 6-120 minute.
9. according to the method for any one in 1-8 item, wherein the COD of vitamin K3 factory effluent is less than 300000mg/L, is preferably 10000-100000mg/L; Total salinity of this waste water is no more than 30 % by weight, is preferably 5-30 % by weight; And/or the pH of this waste water is 0.1-5.5, be preferably 0.5-3.0.
10. according to the method for any one in 1-9 item, wherein vitamin K3 factory effluent is for making 2-methyl isophthalic acid through oxygenant as chromic acid, hydrogen peroxide oxidation by 2 – methylnaphthalenes, 4-vitamin k4 is also subsequently by 2-methyl isophthalic acid, and 4-vitamin k4 is prepared the waste water that vitamin K3 produces.
11. according to the method for any one in 1-10 item, wherein by through step c) the waste water of adsorption cleaning after processing return to the production for vitamin K3.
Embodiment
According to an aspect of the present invention, provide a kind of method of processing vitamin K3 factory effluent, comprised the steps:
A) in vitamin K3 factory effluent, add flocculation agent, make suspended substance and/or the floating matter flocculation in waste water and remove as filter residue;
B) make step a) in the waste water that obtains of flocculation slagging-off with oxygen at 100-360 ℃, contact 1-8 hour to carry out oxidizing reaction at preferred 120-180 ℃; And
C) to step b) in carried out adding and can adsorbing the sorbent material of this waste water decoloring and taste removal in the waste water of oxidizing reaction.
Vitamin K3 factory effluent is because the cause of production technique can contain organism and salt, and wherein salt is mainly for liberating vitamin K3 product adds, and organism had both comprised and adding as solvent, also comprised production by product.
In a preferred embodiment of the invention, vitamin K3 factory effluent is for making 2-methyl isophthalic acid through oxygenant as chromic acid, hydrogen peroxide oxidation by 2 – methylnaphthalenes, 4-vitamin k4 subsequently by 2-methyl isophthalic acid, and 4-vitamin k4 is prepared the waste water that vitamin K3 produces.
In the present invention, the reducing substances in vitamin K3 factory effluent reduces required amount of oxygen completely and is called COD.COD represents chemical oxygen demand (COD), refers under certain condition, and the reducing substances in water is under the effect of additional strong oxidizer, and the quantity of oxidized decomposition time institute's oxygen consumed agent, represents with the mg/L of oxygen.Chemical oxygen demand (COD) has reflected the degree that polluted by reducing substances, these materials comprise organism and inorganics etc., but in general vitamin K3 factory effluent, the quantity of inorganic reduction material is relatively little, and be very general by Organic pollutants, therefore, COD can be used as a composite target of organic substance relative content.
Preferably, the main water quality characteristic of vitamin K3 factory effluent used according to the invention comprises: COD is less than 300000mg/L, is generally 10000-120000mg/L.The salt content of this waste water is very high, but is conventionally no more than 30 % by weight, is preferably 5-30 % by weight, more preferably 10-30 % by weight.It is acid that this waste water is conventionally, and its pH value typically is 0.1-5.5, is preferably 0.5-3.0.The colourity of this waste water is high, is conventionally red-brown, has intense stimulus smell, and under alkaline condition, it is darker that color becomes.The water-quality constituents of this waste water is complicated, mainly comprises quinone, alcohol, niacinamide and byproduct of reaction, salinity, moisture etc.
Vitamin K3 factory effluent, due to the cause of production technique, can contain suspended substance and/or floating matter, and these suspended substances and/or floating matter are mainly some organic oily substances.By add flocculation agent in waste water, thereby can, by the suspended substance in waste water and/or floating matter flocculation sedimentation together, by filtering, can remove these suspensions and/or floating substance subsequently.
As flocculation agent, preferably use polyacrylamide, potassium aluminium sulfate, polymeric aluminium ferrum silicate, iron trichloride or its mixture.The addition of flocculation agent is how many depending on the suspended substance in vitamin K3 factory effluent and floating matter.Typically, the addition of flocculation agent should make every liter of vitamin K3 factory effluent add 1-10g, preferably 1-5g.Advantageously, flocculation agent adds in waste water flocculating effect better after dissolving.The temperature that flocculation is carried out has no particular limits, as long as can make suspended substance and floating matter flocculation in waste water cause sedimentation.Typically, flocculation, at 25-80 ℃, is preferably carried out at 30-50 ℃.Flocculation time is advantageously 0.5-24 hour, is preferably 0.5-1.5 hour.
After step flocculation treatment a), can remove a part of larger molecular organics, impurity, oils condensed matter, reduce the COD of waste water, reduce post-processed difficulty, make subsequent oxidation treating processes obtain higher oxidation removal rate.Flocculation agent after use can pass through recycling utilization.
Step b in the inventive method) in, make step a) in the waste water that obtains of flocculation slagging-off contact to carry out oxidizing reaction with oxygen.This oxidizing reaction becomes CO by the oxidation operation in waste water
2and H
2o, and release energy, heating energy consumption reduced.
For implementation step b) oxidation, the oxygen of use is advantageously the oxygen-containing gas that oxygen content is at least 21 volume %, is preferably pure oxygen or air.Step b) oxidizing reaction is advantageously 0-12MPa in gauge pressure, preferably under the pressure of 0.3-4MPa, carries out.Oxidization time is preferably 1-8 hour, preferably continues 1-3 hour.
By step b) processing, thereby utilize the oxidisability of oxygen and the organism in waste water to interact, remove organic pollutant, make COD at least reduce by 95%.After oxide treatment, waste liquid can produce some solid residues, at the step c carrying out subsequently) before, by this solid slag filtering.
Then, at step c subsequently) in, to step b) in carried out adding and can adsorbing the sorbent material of this waste water decoloring and taste removal in the waste water of oxidizing reaction.As specially suitable sorbent material used herein, can use gac, diatomite, resin, silica gel or its mixture.The consumption of sorbent material is generally every liter of waste water upon adsorption and adds 10-100g, preferably adds 10-50g sorbent material.Absorption is advantageously at 25-80 ℃, preferably carries out at 25-50 ℃.Adsorption time is 5 minutes-24 hours suitably, is preferably 5-120 minute.
Adsorption treatment be utilize sorbent material adsorption activity for waste water decoloring with de-taste, and remove the residual pollutent wherein of part by adsorption.Process step c) waste water of processing, its color is generally light green or faint yellow (trivalent chromium and a small amount of organism), and organic content is extremely low, and COD is generally below 200mg/L, can reach the requirement of direct discharge.
The organic content of the waste water of processing through the inventive method is few and contain a large amount of salinities, conventionally contain 1-30 % by weight, can advantageously return to the production for vitamin K3, and the waste liquid after this processing is directly returned and in production, makes salting-out agent and use and can not produce obvious impact to the quality of vitamin K3 product.Therefore, the inventive method has not only been processed waste liquid effectively, reduces and pollutes, and can also recycle a large amount of salinities contained in waste water, reduces factory effluent usage quantity, reduces production costs.
The beneficial effect that the present invention has: the present invention has adopted the treatment process clean environment firendly of " flocculation+oxidation+absorption ", process stabilizing, the low pollutants removal rate of working cost is high, non-secondary pollution.Meanwhile, in flocculation process, sorbent material, by regeneration, reduces processing cost greatly; In processed waste water COD reach national organic matter of sewage discharge secondary even primary standard (in GB/8978-1996-< < integrated wastewater discharge standard > >, " the highest permission emission concentration of Equations of The Second Kind pollutent " has specific requirement, pharmacy class waste water first discharge standard is COD≤100mg/L, secondary discharge standard is COD≤300mg/L, three grades of emission standards are COD≤1000mg/L), directly return in production and use and can not produce obvious impact to quality product.The about 1-30 % by weight of salts contg in while waste water, the usage quantity that can greatly reduce fresh salting-out agent and process water saves production cost, and improves resource circulation utilization rate.In addition the waste water that, the present invention processes is used and has been realized wastewater zero discharge by recovery.
Embodiment
Below in conjunction with embodiment, technical solution of the present invention is carried out to exemplary illustration, so that those skilled in the art understand better, these embodiment should not be construed as limiting the scope of the invention.
Comparative example 1
By 5000ml, COD=25.56g/L and inorganic salt content are that the vitamin K3 factory effluent of 5 % by weight adds in autoclave, stir to be warming up to 180 ℃, and the industrial oxygen that passes into oxygen content and be 99.2 volume % is forced into 0.5MPa, reaction 1h, filter cleaner.In reacted filtrate, add 50g gac (granular size is 4 orders for analytical pure, purity 99%), at 40 ℃, adsorb 30min, then filtering sorbent material.Filtrate after filtering sorbent material is carried out to analyzing and testing, its COD=458.14mg/L.
Embodiment 1
To 5000ml, COD=25.56g/L and inorganic salt content are to add the solution of 40.11g potassium aluminium sulfate in 500ml water in the vitamin K3 factory effluent of 5 % by weight, mix the 1.5h that flocculates at 50 ℃, filter cleaner.Get the waste water filtrate that 1000ml obtains through aforementioned flocculation and add in autoclave, stir and be warming up to 180 ℃, the industrial oxygen that passes into oxygen content and be 99.2 volume % is forced into 0.5MPa, reaction 1h, filter cleaner.In gained filtrate, add 10g gac (granular size is 4 orders for analytical pure, purity 99%), at 40 ℃, adsorb 30min, then filtering sorbent material.The filtrate obtaining after filtering sorbent material is carried out to analyzing and testing, its COD=92.18mg/L, this has reached organism discharge primary standard in industrial wastewater discharge standard.This waste water is directly returned to vitamin K3 Workshop Production and use, after by this cycling utilization of wastewater 20 times, do not find that the quality of vitamin K3 product is because being used the waste water reclaiming to have a negative impact.
Comparative example 2
To 5000ml, COD=26.56g/L and inorganic salt content are to add the solution of 20.06g potassium aluminium sulfate in 250ml water in the vitamin K3 factory effluent of 5 % by weight, mix the 0.5h that flocculates at 50 ℃, filter cleaner.Get the waste water filtrate that 1000ml obtains through aforementioned flocculation and add in autoclave, stir and be warming up to 150 ℃, the industrial oxygen that passes into oxygen content and be 99.2 volume % is forced into 2.0MPa, reaction 1h, filter cleaner.Gained filtrate is carried out to analyzing and testing, its COD=276.18mg/L.
Embodiment 2
The waste water of getting the COD=276.18mg/L that 1000ml comparative example 2 finally obtains, adds 10g gac (granular size is 4 orders for analytical pure, purity 99%) wherein, adsorbs 5min, then filtering sorbent material at 50 ℃.The filtrate obtaining after filtering sorbent material is carried out to analyzing and testing, its COD=59.25mg/L, this has reached organism discharge primary standard in industrial wastewater discharge standard.This waste water is directly returned to vitamin K3 Workshop Production and use, after by this cycling utilization of wastewater 20 times, do not find that the quality of vitamin K3 product is because being used the waste water reclaiming to have a negative impact.
Embodiment 3
To 5000ml, COD=28.69g/L and inorganic salt content are in the vitamin K3 factory effluent of 5 % by weight, to add 3.125g polyacrylamide (number-average molecular weight is 5,000,000, anionic) solution in 125ml water and the solution of 3.125g potassium aluminium sulfate in 125ml water, mix, the 0.5h that flocculates at 30 ℃, filter cleaner.Get the waste water filtrate that 1000ml obtains through aforementioned flocculation and add in autoclave, stir and be warming up to 180 ℃, the industrial oxygen that passes into oxygen content and be 99.2 volume % is forced into 2MPa, reaction 3h, filter cleaner.In gained filtrate, add 50g gac (granular size is 4 orders for analytical pure, purity 99%), at 40 ℃, adsorb 10min, then filtering sorbent material.The filtrate obtaining after filtering sorbent material is carried out to analyzing and testing, its COD=36.28mg/L, this has reached organism discharge primary standard in industrial wastewater discharge standard.This waste water is directly returned to vitamin K3 Workshop Production and use, after by this cycling utilization of wastewater 20 times, do not find that the quality of vitamin K3 product is because being used the waste water reclaiming to have a negative impact.
Embodiment 4
To 5000ml, COD=236.72g/L and inorganic salt content are in the vitamin K3 factory effluent of 30 % by weight, to add 3.125g polyacrylamide (number-average molecular weight is 5,000,000, anionic) solution in 125ml water and the solution of 3.125g potassium aluminium sulfate in 125ml water, mix, the 10h that flocculates at 50 ℃, filter cleaner.Get the waste water filtrate that 1000ml obtains through aforementioned flocculation and add in autoclave, stir and be warming up to 280 ℃, the industrial oxygen that passes into oxygen content and be 99.2 volume % is forced into 4.0MPa, reaction 5h, filter cleaner.In gained filtrate, add 10g gac (granular size is 4 orders for analytical pure, purity 99%), at 30 ℃, adsorb 120min, then filtering sorbent material.The filtrate obtaining after filtering sorbent material is carried out to analyzing and testing, its COD=88.62mg/L, this has reached organism discharge primary standard in industrial wastewater discharge standard.This waste water is directly returned to vitamin K3 Workshop Production and use, after by this cycling utilization of wastewater 20 times, do not find that the quality of vitamin K3 product is because being used the waste water reclaiming to have a negative impact.
Comparative example 5
To 5000ml, COD=112.21g/L and inorganic salt content are to add 50g gac (granular size is 4 orders for analytical pure, purity 99%) in the vitamin K3 factory effluent of 10 % by weight, adsorb 5h, filter cleaner at 50 ℃.Gained filtrate is added in autoclave, stir and to be warming up to 200 ℃, the industrial oxygen that passes into oxygen content and be 90.26 volume % is forced into 2.0MPa, reaction 5h, filter cleaner.In gained filtrate, add the solution of 20.02g potassium aluminium sulfate in 250ml water, mix, the 10h that flocculates at 50 ℃, filter cleaner.Gained filtrate is carried out to analyzing and testing, its COD=208.36mg/L.
Embodiment 5
To 5000ml, COD=112.21g/L and inorganic salt content are to add the solution of 20.02g potassium aluminium sulfate in 250ml water in the vitamin K3 factory effluent of 10 % by weight, mix the 10h that flocculates at 50 ℃, filter cleaner.Get the waste water filtrate that 1000ml obtains through aforementioned flocculation and add in autoclave, stir and be warming up to 200 ℃, the industrial oxygen that passes into oxygen content and be 90.26 volume % is forced into 2.0MPa, reaction 5h, filter cleaner.In gained filtrate, add 10g gac (granular size is 4 orders for analytical pure, purity 99%), at 50 ℃, adsorb 5h, then filtering sorbent material.The filtrate obtaining after filtering sorbent material is carried out to analyzing and testing, its COD=55.87mg/L, this has reached organism discharge primary standard in industrial wastewater discharge standard.This waste water is directly returned to vitamin K3 Workshop Production and use, after by this cycling utilization of wastewater 20 times, do not find that the quality of vitamin K3 product is because being used the waste water reclaiming to have a negative impact.
Comparative example 6
To 5000ml, COD=112.21g/L and inorganic salt content are to add the solution of 20.10g potassium aluminium sulfate in 250ml water in the vitamin K3 factory effluent of 10 % by weight, mix the 10h that flocculates at 50 ℃, filter cleaner.In gained filtrate, add 50g gac (granular size is 4 orders for analytical pure, purity 99%), at 50 ℃, adsorb 5h, filter cleaner.Gained filtrate is carried out to analyzing and testing, and its COD=40g/L, has surpassed organism emission standard in industrial wastewater discharge standard.
Embodiment 6
To 5000ml, COD=112.21g/L and inorganic salt content are to add the solution of 20.10g potassium aluminium sulfate in 250ml water in the vitamin K3 factory effluent of 10 % by weight, mix the 10h that flocculates at 50 ℃, filter cleaner.Get the waste water filtrate that 1000ml obtains through aforementioned flocculation and add in autoclave, stir and be warming up to 110 ℃, the industrial oxygen that passes into oxygen content and be 99.2 volume % is forced into 2.0MPa, reaction 5h, filter cleaner.In gained filtrate, add 10g gac (granular size is 4 orders for analytical pure, purity 99%), at 50 ℃, adsorb 5 hours, then filtering sorbent material.The filtrate obtaining after filtering sorbent material is carried out to analyzing and testing, its COD=91.22mg/L, this has reached organism discharge primary standard in industrial wastewater discharge standard.This waste water is directly returned to vitamin K3 Workshop Production and use, after by this cycling utilization of wastewater 20 times, do not find that the quality of vitamin K3 product is because being used the waste water reclaiming to have a negative impact.
The foregoing is only preferred embodiment of the present invention, be not limited to the present invention, all any modifications of doing within principle of the present invention and spirit, be equal to and replace and improvement etc., within being all just included in protection scope of the present invention.
Claims (11)
1. a method of processing vitamin K3 factory effluent, comprises the steps:
A) in vitamin K3 factory effluent, add flocculation agent, make suspended substance and/or the floating matter flocculation in waste water and remove as filter residue;
B) make step a) in the waste water that obtains of flocculation slagging-off with oxygen at 100-360 ℃, contact 1-8 hour to carry out oxidizing reaction at preferred 120-180 ℃; And
C) to step b) in carried out adding and can adsorbing the sorbent material of this waste water decoloring and taste removal in the waste water of oxidizing reaction.
2. according to the process of claim 1 wherein that the flocculation agent using during step a) is polyacrylamide, potassium aluminium sulfate, polymeric aluminium ferrum silicate, iron trichloride or its mixture.
3. according to the method for claim 1 or 2, wherein step a) in the addition of flocculation agent be that every liter of vitamin K3 factory effluent adds 1-10g, preferred 1-5g; The temperature that flocculation is carried out is 25-80 ℃, is preferably 30-50 ℃; And/or flocculation time is 0.5-24 hour, be preferably 0.5-1.5 hour.
4. according to the method for any one in claim 1-3, wherein step b) in oxidizing reaction at 0-12MPa, preferably under the gauge pressure pressure of 0.3-4MPa, carry out; And/or step b) oxidizing reaction in continues 1-8 hour, preferably continues 1-3 hour.
5. according to the method for any one in claim 1-4, wherein step b) in the oxygen that uses be the oxygen-containing gas that oxygen content is at least 21 volume %, be preferably pure oxygen or air.
6. according to the method for any one in claim 1-5, wherein step c) in the sorbent material that uses be gac, diatomite, resin, silica gel or its mixture.
7. according to the method for any one in claim 1-6, wherein the addition of sorbent material is that every liter of waste water upon adsorption adds 10-100g, preferably adds 10-50g.
8. according to the method for any one in claim 1-7, wherein step c) in be adsorbed on 25-80 ℃, preferably carry out at 25-50 ℃; And/or adsorption time is 5 minutes-24 hours, be preferably 6-120 minute.
9. according to the method for any one in claim 1-8, wherein the COD of vitamin K3 factory effluent is less than 300000mg/L, is preferably 10000-100000mg/L; Total salinity of this waste water is no more than 30 % by weight, is preferably 5-30 % by weight; And/or the pH of this waste water is 0.1-5.5, be preferably 0.5-3.0.
10. according to the method for any one in claim 1-9, wherein vitamin K3 factory effluent is for making 2-methyl isophthalic acid through oxygenant as chromic acid, hydrogen peroxide oxidation by 2 – methylnaphthalenes, 4-vitamin k4 is also subsequently by 2-methyl isophthalic acid, and 4-vitamin k4 is prepared the waste water that vitamin K3 produces.
11. according to the method for any one in claim 1-10, wherein by through step c) the waste water of adsorption cleaning after processing return to the production for vitamin K3.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506668A (en) * | 2015-12-23 | 2016-04-20 | 四川省银河化学股份有限公司 | Electrolytic comprehensive utilization method of naphthoquinone raffinate |
| CN107572587A (en) * | 2017-09-30 | 2018-01-12 | 重庆民丰化工有限责任公司 | A kind of K3 raffinates ammonium method prepares chrome green technique |
| CN108841911A (en) * | 2018-07-21 | 2018-11-20 | 宁夏泰瑞制药股份有限公司 | Vitamin B12The method for producing wastewater fraction substitution Ferment of DM industrial water |
| CN108866129A (en) * | 2018-07-21 | 2018-11-23 | 宁夏泰瑞制药股份有限公司 | Vitamin B12Produce the method that wastewater fraction substitutes safe ten thousand rhzomorph fermenting and producing water |
| CN108913740A (en) * | 2018-07-21 | 2018-11-30 | 宁夏泰瑞制药股份有限公司 | Vitamin B12The method for producing wastewater fraction substitution tylosin fermenting and producing water |
| CN108913728A (en) * | 2018-07-21 | 2018-11-30 | 宁夏泰瑞制药股份有限公司 | Vitamin B12The method for producing wastewater fraction substitution pleuromutilin fermenting and producing water |
| CN114314994A (en) * | 2022-02-17 | 2022-04-12 | 上海师范大学 | Device system and method for treating vitamin B6 production wastewater through membrane separation |
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| CN105506668A (en) * | 2015-12-23 | 2016-04-20 | 四川省银河化学股份有限公司 | Electrolytic comprehensive utilization method of naphthoquinone raffinate |
| CN107572587A (en) * | 2017-09-30 | 2018-01-12 | 重庆民丰化工有限责任公司 | A kind of K3 raffinates ammonium method prepares chrome green technique |
| CN108841911B (en) * | 2018-07-21 | 2021-10-01 | 宁夏金维制药股份有限公司 | Vitamin B12Method for partially replacing aureomycin fermentation production water with production wastewater |
| CN108866129A (en) * | 2018-07-21 | 2018-11-23 | 宁夏泰瑞制药股份有限公司 | Vitamin B12Produce the method that wastewater fraction substitutes safe ten thousand rhzomorph fermenting and producing water |
| CN108913740A (en) * | 2018-07-21 | 2018-11-30 | 宁夏泰瑞制药股份有限公司 | Vitamin B12The method for producing wastewater fraction substitution tylosin fermenting and producing water |
| CN108913728A (en) * | 2018-07-21 | 2018-11-30 | 宁夏泰瑞制药股份有限公司 | Vitamin B12The method for producing wastewater fraction substitution pleuromutilin fermenting and producing water |
| CN108841911A (en) * | 2018-07-21 | 2018-11-20 | 宁夏泰瑞制药股份有限公司 | Vitamin B12The method for producing wastewater fraction substitution Ferment of DM industrial water |
| CN108866129B (en) * | 2018-07-21 | 2021-11-16 | 黑龙江联顺生物科技有限公司 | Vitamin B12Method for partially replacing production water for fermentation of tulathromycin by production wastewater |
| CN108913728B (en) * | 2018-07-21 | 2021-12-31 | 黑龙江联顺生物科技有限公司 | Vitamin B12Method for partially replacing pleuromutilin fermentation production water with production wastewater |
| CN108913740B (en) * | 2018-07-21 | 2022-03-18 | 宁夏泰益欣生物科技有限公司 | Vitamin B12Method for partially replacing tylosin fermentation production water with production wastewater |
| CN115246768A (en) * | 2021-04-28 | 2022-10-28 | 四川飞楼环保科技有限公司 | Method for extracting menadione from wastewater generated in vitamin K3 production |
| CN115246768B (en) * | 2021-04-28 | 2023-08-22 | 四川飞楼环保科技有限公司 | Method for extracting menaquinone from wastewater from vitamin K3 production |
| CN114314994A (en) * | 2022-02-17 | 2022-04-12 | 上海师范大学 | Device system and method for treating vitamin B6 production wastewater through membrane separation |
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