CN104355502B - A kind of ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde - Google Patents
A kind of ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde Download PDFInfo
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- CN104355502B CN104355502B CN201410659148.6A CN201410659148A CN104355502B CN 104355502 B CN104355502 B CN 104355502B CN 201410659148 A CN201410659148 A CN 201410659148A CN 104355502 B CN104355502 B CN 104355502B
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Abstract
The present invention discloses a kind of ethene oxidation step and prepares the wastewater produced treatment process of acetaldehyde, comprises the steps: (1) Wastewater Pretreatment: after pre-treatment, waste water active sludge oxygen-consuming rate inhibiting rate or anaerobic methane production inhibiting rate are down to less than 10%; (2) adding nutritive substance in described pretreated waste water, described nutritive substance is nitrogenous source nutritive substance, phosphorus source nutritive substance and trace nutrient; (3) by described add nutritive substance after waste water carry out Aerobic biological process or anaerobic biological treatment. Ethene oxidation step of the present invention prepares the advantage that the wastewater produced treatment process of acetaldehyde has processing load height, stable, processing cost is low.
Description
Technical field
The present invention relates to the treatment process of a kind of waste water, it is specifically related to a kind of ethene oxidation step and prepares the wastewater produced treatment process of acetaldehyde.
Background technology
Ethene oxidation step acetaldehyde technique is one of prevailing technology of current acetaldehyde production, it is taking ethene, oxygen as main raw material, taking Palladous chloride-cupric chloride-aqueous hydrochloric acid as catalyzer, through the obtained acetaldehyde of oxidation step reaction, its production process discharges a large amount of high density poisonous organic wastewater; Waste water COD reaches 2000��4000mg/L, although the acetic acid containing high density in this waste water, but due to containing a large amount of toxic substance, biological treatment toxicity is obvious, aerobic activated sludge and anaerobic methane production sludge activity all being shown obvious restraining effect, causes sludge acclimatization difficulty, this waste water shortage effectively processes technology at present, mainly through carrying out a biological disposal upon after dilution in a large number, processing cost height, investment are greatly.
Summary of the invention
It is an object of the invention to provide a kind of ethene oxidation step and prepare the wastewater produced treatment process of acetaldehyde, the advantage that the method has processing load height, stable, processing cost is low.
Ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde, comprises the steps:
(1) Wastewater Pretreatment: the pH value of waste water is adjusted to 12��13, reacts 0.5��10h under 30��90 DEG C of conditions, keeps pH value in reaction process more than 9.5, then with acid neutralization; After pre-treatment, waste water active sludge oxygen-consuming rate inhibiting rate or anaerobic methane production inhibiting rate are down to less than 10%;
(2) adding nutritive substance in described pretreated waste water, described nutritive substance is nitrogenous source nutritive substance, phosphorus source nutritive substance and trace nutrient;
(3) by described add nutritive substance after waste water carry out Aerobic biological process or anaerobic biological treatment or the two combines.
Ethene oxidation step of the present invention prepares the wastewater produced treatment process of acetaldehyde, wherein, the described method that the pH value of waste water is adjusted to 12��13 is add industrial mineral alkali or the waste water containing mineral alkali in described waste water, and in the described waste water containing mineral alkali, the massfraction of mineral alkali is 1%��30%;Active sludge oxygen-consuming rate inhibiting rate��10% or anaerobic methane production inhibiting rate��10% after described waste water containing mineral alkali and described waste water hybrid reaction.
Described neutralization acid used is industrial mineral acid or the waste water containing mineral acid, in the described waste water containing mineral acid, the massfraction of mineral acid is 1%��50%, active sludge oxygen-consuming rate inhibiting rate��10% or anaerobic methane production inhibiting rate��10% after described waste water containing mineral acid and described waste water neutralize.
Ethene oxidation step of the present invention prepares the wastewater produced treatment process of acetaldehyde, wherein, the method adding nutritive substance described in is: add the aqueous solution containing nitrogenous source nutritive substance, phosphorus source nutritive substance and trace nutrient respectively in described pretreated waste water.
Ethene oxidation step of the present invention prepares the wastewater produced treatment process of acetaldehyde, and wherein, described nitrogenous source nutritive substance is at least one in the vitriol of urea and ammonium, hydrochloride and phosphoric acid salt; Described phosphorus source nutritive substance is at least one in the phosphoric acid salt of ammonium, sodium, potassium; Described trace nutrient is iron, calcium, magnesium, cobalt, nickel, manganese, the vitriol of zinc or the molybdate of hydrochloride and basic metal, after adding, the concentration of iron, calcium, magnesium, cobalt, nickel, manganese, zinc, molybdenum is respectively 5��20mg/L, 2��20mg/L, 1��5mg/L, 0.1��5mg/L, 0.1��5mg/L, 0.1��0.5mg/L, 0.1��1mg/L, 0.2��1mg/L.
Ethene oxidation step of the present invention prepares the wastewater produced treatment process of acetaldehyde, and wherein, described mineral alkali is at least one in sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate; Described mineral acid is at least one in hydrochloric acid, sulfuric acid.
Ethene oxidation step of the present invention prepares the wastewater produced treatment process of acetaldehyde, wherein, described active sludge oxygen-consuming rate inhibiting rate measuring method as follows:
Measure containing described waste water when active sludge oxygen-consuming rate: according to volume ratio 5:2:(5��10) by beef extract-peptone nutrient solution, active sludge concentrated solution and described be neutralized to pH value be 6.5��7.5 waste water mix after, make described mixed solution dissolved oxygen rises to more than 7mg/L by aeration, then described for part mixed solution is transferred in the encloses container of band dissolved oxygen probe, with the air in the container of the emptying described band dissolved oxygen probe of described mixed solution; 25 DEG C of water-baths measure the oxygen consumption rate V of described mixed solution1;
Measure active sludge oxygen-consuming rate when non-toxic substance: beef extract-peptone nutrient solution and active sludge concentrated solution are mixed according to volume ratio 5:2, add deionized water more wherein, described deionized water with measure containing described waste water when active sludge oxygen-consuming rate described in be neutralized to pH value be 6.5��7.5 wastewater volume identical; Active sludge oxygen-consuming rate V when measuring non-toxic substance under the active sludge oxygen-consuming rate the same terms when containing described waste water with mensuration2;
The method of calculated activity mud oxygen consumption rate inhibiting rate is: active sludge oxygen-consuming rate inhibiting rate=(1-V1/V2) �� 100%.
Ethene oxidation step of the present invention prepares the wastewater produced treatment process of acetaldehyde, and wherein, described beef extract-peptone nutrient solution moiety is as follows: peptone 16.0g/L, extractum carnis 11.0g/L, sodium acetate 200mg/L, urea 3.0g/L, NaCl0.7g/L, CaCl2��2H2O0.4g/L, MgSO4��7H2O0.2g/L, K2HPO42.8g/L;Volatile suspended solid concentration >=the 10000mg/L of described active sludge concentrated solution.
Ethene oxidation step of the present invention prepares the wastewater produced treatment process of acetaldehyde, and wherein, the mensuration of described anaerobic methane production inhibiting rate is taking sodium acetate nutrient solution as methane phase substrate; Described sodium acetate nutrient solution is composed as follows: sodium acetate 5.32g/L, resazurin 0.9mg/L, (NH4)2HPO472.1mg/L��CaCl2��2H2O225mg/L��NH4Cl359mg/L��MgCl2��4H2O1620mg/L��KCl1170mg/L��MnCl2��4H2O18.0mg/L��CoCl2��6H2O27mg/L��H3BO35.13mg/L�� CuCl2��2H2O2.43mg/L��Na2MoO4��2H2O2.30mg/L��ZnCl21.89mg/L��FeCl2��4H2O333mg/L��Na2S��9H2O450mg/L, vitamin H 0.018mg/L, folic acid 0.018mg/L, vitamins B60.09mg/L, vitamins B20.045mg/L, vitamins B10.045mg/L, nicotinic acid 0.045mg/L, calcium pantothenate 0.045mg/L, vitamins B120.0009mg/L, para-amino benzoic acid 0.045mg/L, alpha-lipoic acid 0.045mg/L;
Measure containing described waste water when methane produce speed: according to volume ratio 1:1:8 by described sodium acetate nutrient solution, methane phase granule sludge and described be neutralized to pH value be 6.5��7.5 waste water mixing, measure mixed solution methane production under 35 DEG C of conditions, calculate methane and produce speed V3; Described methane phase granule sludge VSS=40g/L;
Methane when measuring non-toxic substance produces speed: according to volume ratio 1:1:8 by described sodium acetate nutrient solution, methane phase granule sludge and the mixing of described deionized water, methane when measuring methane production and calculate non-toxic substance under 35 DEG C of conditions produces speed V4;
The method calculating described anaerobic methane production inhibiting rate is: anaerobic methane production inhibiting rate=(1-V3/V4) �� 100%.
Ethene oxidation step of the present invention prepares the wastewater produced treatment process of acetaldehyde, and wherein, described bioremediation, when waste water active sludge oxygen-consuming rate inhibiting rate is down to below 10% after pre-treatment, adopts aerobic biological process for treating; When anaerobic waste water methane phase inhibiting rate is down to below 10% after pre-treatment, anaerobic biological treatment method or anaerobic-aerobic combined treatment method can be adopted.
Ethene oxidation step of the present invention prepares the wastewater produced treatment process of acetaldehyde, wherein, in described Aerobic biological process process, reaction zone temperature maintains 20��35 DEG C, hydraulic detention time 12��48h, active sludge or microbial film volatile suspended solid concentration maintain 2500��8000mg/L, and reaction zone end dissolved oxygen maintains more than 2mg/L; Described anaerobic biological treatment, reaction zone temperature maintains 35��55 DEG C, hydraulic detention time 12��48h, and biological sludge volatile suspended solid concentration maintains more than 10000mg/L, up-flow speed 0.1��1m/h.
The process that the present invention is used for acetaldehyde production waste water has the following advantages:
Acetaldehyde is wastewater produced carries out pre-treatment to adopt the method for the present invention to be prepared by ethene oxidation step, can effectively reduce wastewater toxicity, is conducive to improving processing load and the stable water outlet of subsequent biological treatment, reduces floor space.
Waste water alkali adjust ph to 12��13, after reacting the corresponding time at 30��90 DEG C, the toxic action of active sludge and anaerobic methane production sludge microbe is significantly declined by waste water; Before adopting pretreatment process of the present invention to process, waste water need to dilute 150 times just can not produce restraining effect to methane phase process, and after waste water adopts pretreatment process of the present invention to process, do not need dilution methane phase process can not be produced restraining effect yet, acetaldehyde production waste water adopt pretreatment process of the present invention process after with process before compared with, the retarding effect of sodium acetate methane phase is significantly declined. Acetaldehyde production waste water adopt pretreatment process of the present invention to process after compared with before process, the retarding effect of the aerobic breathing of active sludge by substrate of beef extract-peptone nutrient solution is significantly declined.
The method of the invention can significantly reduce acetaldehyde wastewater biological treatment toxicity, is convenient to improve operation stability and the processing load of subsequent biological treatment unit, reduces scale and the occupation of land of waste water disposal facility, reduces initial cost, saves processing cost.
The medicament wanted required for the present invention is simple, can make full use of in other production processes the waste lye and spent acid solution that produce, while realizing wastewater toxicity reduction, it is achieved the recycling treatment of waste lye is disposed.
Treatment facility required for the present invention is simple, can utilize the wastewater neutralizer of the usual auxiliary construction of acetaldehyde production device, is convenient to reconstruction project and implements, and saves capital cost.
Below in conjunction with accompanying drawing, the treatment process that ethene oxidation step of the present invention prepares acetaldehyde wastewater produced is described further.
Accompanying drawing explanation
Fig. 1 be in treatment process of the present invention before and after acetaldehyde production Wastewater Pretreatment on the impact of sodium acetate nutrient solution methane phase;
Fig. 2 be in treatment process of the present invention before and after acetaldehyde production Wastewater Pretreatment on the impact of active sludge taking beef extract-peptone nutrient solution as substrate oxygen consumption rate.
Embodiment
Embodiment 1:
Ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde, comprises the steps:
(1) Wastewater Pretreatment: the pH value of waste water is adjusted to 12��13, reacts 0.5��10h under 30��90 DEG C of conditions, keeps pH value in reaction process more than 9.5, then with acid neutralization; After pre-treatment, waste water active sludge oxygen-consuming rate inhibiting rate or anaerobic methane production inhibiting rate are down to less than 10%;
(2) adding nutritive substance in described pretreated waste water, described nutritive substance is nitrogenous source nutritive substance, phosphorus source nutritive substance and trace nutrient;
(3) by described add nutritive substance after waste water carry out Aerobic biological process or anaerobic biological treatment or the two combines.
Above scheme can complete ethene oxidation step and prepare the wastewater produced process of acetaldehyde, provides preferred version on this basis:
The described method that the pH value of waste water is adjusted to 12��13 is add industrial mineral alkali or the waste water containing mineral alkali in described waste water, in the described waste water containing mineral alkali, the massfraction of mineral alkali is 1%��30%, active sludge oxygen-consuming rate inhibiting rate��10% or anaerobic methane production inhibiting rate��10% after described waste water containing mineral alkali and described waste water hybrid reaction; Neutralizing acid used is industrial mineral acid or the waste water containing mineral acid, in the described waste water containing mineral acid, the massfraction of mineral acid is 1%��50%, active sludge oxygen-consuming rate inhibiting rate��10% or anaerobic methane production inhibiting rate��10% after described waste water containing mineral acid and described waste water neutralize;
The method adding nutritive substance is: add the aqueous solution containing nitrogenous source nutritive substance, phosphorus source nutritive substance and trace nutrient respectively in described pretreated waste water; Nitrogenous source nutritive substance is at least one in the vitriol of urea and ammonium, hydrochloride and phosphoric acid salt; Described phosphorus source nutritive substance is at least one in the phosphoric acid salt of ammonium, sodium, potassium; Described trace nutrient is iron, calcium, magnesium, cobalt, nickel, manganese, the vitriol of zinc or the molybdate of hydrochloride and basic metal, after adding, the concentration of iron, calcium, magnesium, cobalt, nickel, manganese, zinc, molybdenum is respectively 5��20mg/L, 2��20mg/L, 1��5mg/L, 0.1��5mg/L, 0.1��5mg/L, 0.1��0.5mg/L, 0.1��1mg/L, 0.2��1mg/L;
Mineral alkali is at least one in sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate; Described mineral acid is at least one in hydrochloric acid, sulfuric acid;
Active sludge oxygen-consuming rate inhibiting rate measuring method as follows:
Measure containing described waste water when active sludge oxygen-consuming rate: according to volume ratio 5:2:(5��10) by beef extract-peptone nutrient solution, active sludge concentrated solution and described be neutralized to pH value be 6.5��7.5 waste water mix after, make described mixed solution dissolved oxygen rises to more than 7mg/L by aeration, then described for part mixed solution is transferred in the encloses container of band dissolved oxygen probe, with the air in the container of the emptying described band dissolved oxygen probe of described mixed solution; 25 DEG C of water-baths measure the oxygen consumption rate V of described mixed solution1;
Measure active sludge oxygen-consuming rate when non-toxic substance: beef extract-peptone nutrient solution and active sludge concentrated solution are mixed according to volume ratio 5:2, add deionized water more wherein, described deionized water with measure containing described waste water when active sludge oxygen-consuming rate described in be neutralized to pH value be 6.5��7.5 wastewater volume identical; Active sludge oxygen-consuming rate V when measuring non-toxic substance under the active sludge oxygen-consuming rate the same terms when containing described waste water with mensuration2;
The method of calculated activity mud oxygen consumption rate inhibiting rate is: active sludge oxygen-consuming rate inhibiting rate=(1-V1/V2) �� 100%.
Described beef extract-peptone nutrient solution moiety is as follows: peptone 16.0g/L, extractum carnis 11.0g/L, sodium acetate 200mg/L, urea 3.0g/L, NaCl0.7g/L, CaCl2��2H2O0.4g/L, MgSO4��7H2O0.2g/L, K2HPO42.8g/L; Volatile suspended solid concentration >=the 10000mg/L of described active sludge concentrated solution.
The mensuration of described anaerobic methane production inhibiting rate is taking sodium acetate nutrient solution as methane phase substrate; Described sodium acetate nutrient solution is composed as follows: sodium acetate 5.32g/L, resazurin 0.9mg/L, (NH4)2HPO472.1mg/L��CaCl2��2H2O225mg/L��NH4Cl359mg/L��MgCl2��4H2O1620mg/L��KCl1170mg/L��MnCl2��4H2O18.0mg/L��CoCl2��6H2O27mg/L��H3BO35.13mg/L��CuCl2��2H2O2.43mg/L��Na2MoO4��2H2O2.30mg/L��ZnCl21.89mg/L��FeCl2��4H2O333mg/L��Na2S��9H2O450mg/L, vitamin H 0.018mg/L, folic acid 0.018mg/L, vitamins B60.09mg/L, vitamins B20.045mg/L, vitamins B10.045mg/L, nicotinic acid 0.045mg/L, calcium pantothenate 0.045mg/L, vitamins B120.0009mg/L, para-amino benzoic acid 0.045mg/L, alpha-lipoic acid 0.045mg/L;
Measure containing described waste water when methane produce speed: according to volume ratio 1:1:8 by described sodium acetate nutrient solution, methane phase granule sludge (VSS40g/L) and described be neutralized to pH value be 6.5��7.5 waste water mix, measure mixed solution methane production under 35 DEG C of conditions, calculate methane and produce speed V3;
Methane when measuring non-toxic substance produces speed: according to volume ratio 1:1:8 by described sodium acetate nutrient solution, methane phase granule sludge (VSS40g/L) and the mixing of described deionized water, methane when measuring methane production and calculate non-toxic substance under 35 DEG C of conditions produces speed V4;
The method calculating described anaerobic methane production inhibiting rate is: anaerobic methane production inhibiting rate=(1-V3/V4) �� 100%.
Bioremediation: when waste water active sludge oxygen-consuming rate inhibiting rate is down to below 10% after pre-treatment, adopts aerobic biological process for treating; When anaerobic waste water methane phase inhibiting rate is down to below 10% after pre-treatment, anaerobic biological treatment method or anaerobic-aerobic combined treatment method can be adopted.
In Aerobic biological process process, reaction zone temperature maintains 20��35 DEG C, hydraulic detention time 12��48h, and active sludge or microbial film volatile suspended solid concentration maintain 2500��8000mg/L, and reaction zone end dissolved oxygen maintains more than 2mg/L;Described anaerobic biological treatment, reaction zone temperature maintains 35��55 DEG C, hydraulic detention time 12��48h, and biological sludge volatile suspended solid concentration maintains more than 10000mg/L, up-flow speed 0.1��1m/h.
Embodiment 2
Ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde, comprises the steps:
(1) Wastewater Pretreatment: with the pH regulator to 12 of NaOH by waste water, react 10h under 30 DEG C of conditions, keep pH in reaction process more than 9.5, be then neutralized to pH=7 with acid; After pre-treatment, waste water active sludge oxygen-consuming rate inhibiting rate drops to 2% by 63%, before and after acetaldehyde production Wastewater Pretreatment on the impact of sodium acetate nutrient solution methane phase as shown in Figure 1;
(2) adding nutritive substance in described pretreated waste water, described nutritive substance is nitrogenous source nutritive substance, phosphorus source nutritive substance and trace nutrient;
(3) by described add nutritive substance after waste water carry out Aerobic biological process or anaerobic biological treatment; After supplementing nitrogen phosphorus and trace nutrient, adopting aerobic activated sludge reactor to process, operating temperature 25 DEG C, when reactor hydraulic detention time 36h, recording influent COD is 2500mg/L, and water outlet COD is mg/L.
Embodiment 3:
Ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde, comprises the steps:
(1) Wastewater Pretreatment: with containing Na2CO3Waste water and NaOH the pH value of waste water is adjusted to 12, under 60 DEG C of condition, react 0.5h, reaction process keep pH value more than 9.5, be then neutralized to pH value=7 with acid; After pre-treatment, waste water active sludge oxygen-consuming rate inhibiting rate drops to 3% by 63%;
(2) adding nutritive substance in described pretreated waste water, described nutritive substance is nitrogenous source nutritive substance, phosphorus source nutritive substance and trace nutrient;
(3) by described add nutritive substance after waste water adopt aerobic biological fluid-bed-aerobic activated sludge combination of reactors technique process, operating temperature 30 DEG C, aerobic biological fluid-bed hydraulic detention time is 12h, when aerobic activated sludge reactor hydraulic detention time is 12h, recording influent COD is 2400mg/L, and water outlet COD is 50mg/L.
Embodiment 4:
Ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde, comprises the steps:
(1) Wastewater Pretreatment: the pH value of waste water is adjusted to 13 with NaOH, reacts 6h under 70 DEG C of conditions, keeps pH value in reaction process more than 9.5, is then neutralized to pH value=7 with acid; After pre-treatment, anaerobic waste water methane phase inhibiting rate drops to 5% by 100%;
(2) adding nutritive substance in described pretreated waste water, described nutritive substance is nitrogenous source nutritive substance, phosphorus source nutritive substance and trace nutrient;
(3) by described add nutritive substance after waste water adopt EGSB (expanded granular sludge bed) (EGSB) reactor process, operating temperature 35 DEG C, hydraulic detention time is 24h, when effluent recycling is than 4:1, recording influent COD is 4000mg/L, and water outlet COD is 340mg/L.
Embodiment 5:
Ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde, comprises the steps:
(1) Wastewater Pretreatment: the pH value of waste water is adjusted to 12.6 with NaOH, reacts 1h under 90 DEG C of conditions, keeps pH value in reaction process more than 9.5, is then neutralized to pH value=7 with acid; After pre-treatment, anaerobic waste water methane phase inhibiting rate drops to 4% by 100%;
(2) adding nutritive substance in described pretreated waste water, described nutritive substance is nitrogenous source nutritive substance, phosphorus source nutritive substance and trace nutrient;
(3) by described add nutritive substance after waste water adopt EGSB (expanded granular sludge bed) (EGSB) oxygen activity sewage sludge reactor combination process of becoming reconciled to process, EGSB operating temperature 35 DEG C, hydraulic detention time is 24h, effluent recycling compares 4:1, aerobic activated sludge reactor hydraulic detention time 12h, recording influent COD is 3800mg/L, and water outlet COD is 85mg/L.
Embodiment 6:
Ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde, comprises the steps:
(1) Wastewater Pretreatment: with the pH regulator to 12.7 of NaOH by waste water, react 10h under 60 DEG C of conditions, keep pH in reaction process more than 9.5, be then neutralized to pH=7 with acid; After pre-treatment, anaerobic waste water methane phase inhibiting rate drops to 1% by 100%, before and after acetaldehyde production Wastewater Pretreatment on active sludge taking beef extract-peptone nutrient solution as the impact of substrate oxygen consumption rate as shown in Figure 2;
(2) adding nutritive substance in described pretreated waste water, described nutritive substance is nitrogenous source nutritive substance, phosphorus source nutritive substance and trace nutrient;
(3) by described add nutritive substance after waste water adopt upflow anaerobic sludge blanket process (UASB) and plug-flow type active sludge combination of reactors technique process, UASB operating temperature 55 DEG C, hydraulic detention time is 24h, activated sludge process hydraulic detention time 12h, recording influent COD is 3000mg/L, and water outlet COD is 45mg/L.
Above-described embodiment is only the preferred embodiment of the present invention be described; not the scope of the present invention is limited; under the prerequisite not departing from inventive design spirit; the various distortion that the technical scheme of the present invention is made by those of ordinary skill in the art and improvement, all should fall in the protection domain that claims of the present invention is determined.
Claims (10)
1. an ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde, it is characterised in that, comprise the steps:
(1) Wastewater Pretreatment: the pH value of waste water is adjusted to 12��13, reacts 0.5��10h under 30��90 DEG C of conditions, keeps pH value in reaction process more than 9.5, and being then neutralized to pH value with acid is 6.5��7.5; After pre-treatment, waste water active sludge oxygen-consuming rate inhibiting rate or anaerobic methane production inhibiting rate are down to less than 10%;
(2) adding nutritive substance in described pretreated waste water, described nutritive substance is nitrogenous source nutritive substance, phosphorus source nutritive substance and trace nutrient;
(3) by described add nutritive substance after waste water carry out Aerobic biological process or anaerobic biological treatment or the two combines.
2. ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde according to claim 1, it is characterized in that, the described method that the pH value of waste water is adjusted to 12��13 is add industrial mineral alkali or the waste water containing mineral alkali in described waste water, and in the described waste water containing mineral alkali, the massfraction of mineral alkali is 1%��30%; Active sludge oxygen-consuming rate inhibiting rate��10% or anaerobic methane production inhibiting rate��10% after described waste water containing mineral alkali and described waste water hybrid reaction;
Described neutralization acid used is industrial mineral acid or the waste water containing mineral acid, in the described waste water containing mineral acid, the massfraction of mineral acid is 1%��50%, active sludge oxygen-consuming rate inhibiting rate��10% or anaerobic methane production inhibiting rate��10% after described waste water containing mineral acid and described waste water neutralize.
3. ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde according to claim 1, it is characterized in that, described in add nutritive substance method be: in described pretreated waste water, add the aqueous solution containing nitrogenous source nutritive substance, phosphorus source nutritive substance and trace nutrient respectively.
4. ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde according to claim 3, it is characterised in that, described nitrogenous source nutritive substance is at least one in the vitriol of urea and ammonium, hydrochloride and phosphoric acid salt; Described phosphorus source nutritive substance is at least one in the phosphoric acid salt of ammonium, sodium, potassium; Described trace nutrient is iron, calcium, magnesium, cobalt, nickel, manganese, the vitriol of zinc or the molybdate of hydrochloride and basic metal, after adding, the concentration of iron, calcium, magnesium, cobalt, nickel, manganese, zinc, molybdenum is respectively 5��20mg/L, 2��20mg/L, 1��5mg/L, 0.1��5mg/L, 0.1��5mg/L, 0.1��0.5mg/L, 0.1��1mg/L, 0.2��1mg/L.
5. ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde according to claim 2, it is characterised in that, described mineral alkali is at least one in sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate; Described mineral acid is at least one in hydrochloric acid, sulfuric acid.
6. ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde according to claim 1, it is characterised in that, described active sludge oxygen-consuming rate inhibiting rate measuring method as follows:
Measure containing described waste water when active sludge oxygen-consuming rate: according to volume ratio 5:2:(5��10) by beef extract-peptone nutrient solution, active sludge concentrated solution and described be neutralized to pH value be 6.5��7.5 waste water mix after, make described mixed solution dissolved oxygen rises to more than 7mg/L by aeration, then described for part mixed solution is transferred in the encloses container of band dissolved oxygen probe, with the air in the container of the emptying described band dissolved oxygen probe of described mixed solution; 25 DEG C of water-baths measure the oxygen consumption rate V of described mixed solution1;
Measure active sludge oxygen-consuming rate when non-toxic substance: beef extract-peptone nutrient solution and active sludge concentrated solution are mixed according to volume ratio 5:2, add deionized water more wherein, described deionized water with measure containing described waste water when active sludge oxygen-consuming rate described in be neutralized to pH value be 6.5��7.5 wastewater volume identical; Active sludge oxygen-consuming rate V when measuring non-toxic substance under the active sludge oxygen-consuming rate the same terms when containing described waste water with mensuration2;
The method of calculated activity mud oxygen consumption rate inhibiting rate is: active sludge oxygen-consuming rate inhibiting rate=(1-V1/V2) �� 100%.
7. ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde according to claim 6, it is characterised in that, described beef extract-peptone nutrient solution moiety is as follows: peptone 16.0g/L, extractum carnis 11.0g/L, sodium acetate 200mg/L, urea 3.0g/L, NaCl0.7g/L, CaCl2��2H2O0.4g/L, MgSO4��7H2O0.2g/L, K2HPO42.8g/L; Volatile suspended solid concentration >=the 10000mg/L of described active sludge concentrated solution.
8. ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde according to claim 7, it is characterised in that, the mensuration of described anaerobic methane production inhibiting rate is taking sodium acetate nutrient solution as methane phase substrate; Described sodium acetate nutrient solution is composed as follows: sodium acetate 5.32g/L, resazurin 0.9mg/L, (NH4)2HPO472.1mg/L��CaCl2��2H2O225mg/L��NH4Cl359mg/L��MgCl2��4H2O1620mg/L��KCl1170mg/L��MnCl2��4H2O18.0mg/L��CoCl2��6H2O27mg/L��H3BO35.13mg/L��CuCl2��2H2O2.43mg/L��Na2MoO4��2H2O2.30mg/L��ZnCl21.89mg/L��FeCl2��4H2O333mg/L��Na2S��9H2O450mg/L, vitamin H 0.018mg/L, folic acid 0.018mg/L, vitamins B60.09mg/L, vitamins B20.045mg/L, vitamins B10.045mg/L, nicotinic acid 0.045mg/L, calcium pantothenate 0.045mg/L, vitamins B120.0009mg/L, para-amino benzoic acid 0.045mg/L, alpha-lipoic acid 0.045mg/L;
Measure containing described waste water when methane produce speed: according to volume ratio 1:1:8 by described sodium acetate nutrient solution, methane phase granule sludge and described be neutralized to pH value be 6.5��7.5 waste water mixing, measure mixed solution methane production under 35 DEG C of conditions, calculate methane and produce speed V3; Described methane phase granule sludge VSS=40g/L;
Methane when measuring non-toxic substance produces speed: according to volume ratio 1:1:8 by described sodium acetate nutrient solution, methane phase granule sludge and the mixing of described deionized water, methane when measuring methane production and calculate non-toxic substance under 35 DEG C of conditions produces speed V4;
The method calculating described anaerobic methane production inhibiting rate is: anaerobic methane production inhibiting rate=(1-V3/V4) �� 100%.
9. ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde according to claim 1, it is characterized in that, described bioremediation, when waste water active sludge oxygen-consuming rate inhibiting rate is down to below 10% after pre-treatment, adopts aerobic biological process for treating; When anaerobic waste water methane phase inhibiting rate is down to below 10% after pre-treatment, anaerobic biological treatment method or anaerobic-aerobic combined treatment method can be adopted.
10. ethene oxidation step prepares the wastewater produced treatment process of acetaldehyde according to claim 9, it is characterized in that, in described Aerobic biological process process, reaction zone temperature maintains 20��35 DEG C, hydraulic detention time 12��48h, active sludge or microbial film volatile suspended solid concentration maintain 2500��8000mg/L, and reaction zone end dissolved oxygen maintains more than 2mg/L; Described anaerobic biological treatment, reaction zone temperature maintains 35��55 DEG C, hydraulic detention time 12��48h, and biological sludge volatile suspended solid concentration maintains more than 10000mg/L, up-flow speed 0.1��1m/h.
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