CN102464401A - COD (chemical oxygen demand) degradation agent for removing formaldehyde in industrial wastewater - Google Patents
COD (chemical oxygen demand) degradation agent for removing formaldehyde in industrial wastewater Download PDFInfo
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- CN102464401A CN102464401A CN2011103207594A CN201110320759A CN102464401A CN 102464401 A CN102464401 A CN 102464401A CN 2011103207594 A CN2011103207594 A CN 2011103207594A CN 201110320759 A CN201110320759 A CN 201110320759A CN 102464401 A CN102464401 A CN 102464401A
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- Prior art keywords
- formaldehyde
- wastewater
- cod
- removing formaldehyde
- enzyme
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 230000015556 catabolic process Effects 0.000 title claims abstract description 30
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 28
- 239000000126 substance Substances 0.000 title abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 3
- 239000001301 oxygen Substances 0.000 title abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 3
- 239000010842 industrial wastewater Substances 0.000 title abstract 2
- 241000894006 Bacteria Species 0.000 claims abstract description 12
- 102000004190 Enzymes Human genes 0.000 claims abstract description 11
- 108090000790 Enzymes Proteins 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims description 13
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 7
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 7
- 101000925662 Enterobacteria phage PRD1 Endolysin Proteins 0.000 claims description 6
- 102000004882 Lipase Human genes 0.000 claims description 6
- 108090001060 Lipase Proteins 0.000 claims description 6
- 239000004367 Lipase Substances 0.000 claims description 6
- 108091005804 Peptidases Proteins 0.000 claims description 6
- 102000035195 Peptidases Human genes 0.000 claims description 6
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 6
- 235000019421 lipase Nutrition 0.000 claims description 6
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 6
- 150000003950 cyclic amides Chemical class 0.000 claims description 5
- -1 glycase Proteins 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 28
- 239000010865 sewage Substances 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract 2
- 238000010353 genetic engineering Methods 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002156 adsorbate Substances 0.000 description 3
- 235000012745 brilliant blue FCF Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000009279 wet oxidation reaction Methods 0.000 description 3
- 101710188412 Cyclic amide hydrolase Proteins 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000003851 biochemical process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a COD (chemical oxygen demand) degrading agent for removing formaldehyde in industrial wastewater, belonging to the technical field of environmental sewage treatment. The degrading agent is prepared by compounding an inorganic strong oxidant, a catalyst and genetic engineering bacteria enzyme, wherein the mass content of the inorganic strong oxidant is 30-85%, the mass content of the catalyst is 1-5%, and the mass content of the genetic engineering bacteria enzyme is 10-30%. The degradation agent and the wastewater are added into the wastewater in a mass ratio of 1: 100-1: 500, the mixture is continuously stirred and then is statically separated, the concentration of formaldehyde in the wastewater is reduced from 10-1000 mg/L to below 0.5mg/L, and the removal rate of the formaldehyde is up to above 99.9%. The invention has the advantages of easily obtained raw materials, simple use, no sediment generation and no odor generation, can change the chromaticity of the wastewater, and does not cause secondary pollution.
Description
Technical field
The removal method of the formaldehyde hardly degraded organic substance that the present invention relates to contain in the trade effluents such as pharmacy, chemical industry belongs to technical field of sewage in the environment protection.
Background technology
The technology of domestic and international application formaldehyde in removing trade effluent mainly contains method and technologies such as Fenton method, blow-off method, absorption method, wet oxidation process, dioxide peroxide oxidation style at present; The Fenton method is because H
2O
2Expense higher, Fe
2+The regeneration difficulty along with the reduction of both concentration, makes that speed of reaction is difficult to maintain on the higher level in reaction process.Particularly the degradation time of hardly degraded organic substance is longer to organism.Degradation effect is not ideal enough, and the water treatment expense is also very high.Therefore this method processing formaldehyde waste water efficient is not high.Blow-off method is to utilize the difference that exists between actual concentrations and the equilibrium concentration of materials such as formaldehyde contained in the waste water; Under alkaline condition, use air stripping; Volatile matter such as formaldehyde in the waste water are constantly transferred in the gas phase by liquid phase, thereby reached the purpose of from waste water, removing formaldehyde.But because there is the dissolution equilibrium relation in formaldehyde in water, when the formaldehyde of gas-liquid two-phase is in equilibrium state, the formaldehyde in the water can not be overflowed by stripping, so this technology is not suitable for high-concentration formaldehyde wastewater.And conventional filler formula stripping process also exists stripping efficient low, and stripping air quantity big (about vapour-liquid ratio 3000:1), time are long, shortcomings such as, filler easy fouling high to temperature requirement.Absorption method is influenced by character and the concentration of temperature, pressure, adsorbate etc., and suitably elevated temperature helps chemisorption, and low temperature helps physical adsorption, and temperature is big to the influence of the influence comparison liquid phase adsorption of Gas Phase Adsorption.For gas adsorption, the pressure increase helps absorption, and the pressure reduction helps desorb; For Gas Phase Adsorption, the critical diameter of adsorbate, relative molecular mass, boiling point, saturabilities etc. influence adsorptive capacity, for liquid phase adsorption, the molecular polarity of adsorbate, relative molecular mass, the solubleness in solvent etc. influences adsorptive capacity.Therefore this method processing formaldehyde waste water operational condition is had relatively high expectations, and is unfavorable for the industry popularization.Wet oxidation process is (under 0.5～20MPa) the operational condition, as oxygenant, the organism in the waste water to be converted into the process of carbonic acid gas and water with oxygen and air at high temperature (150～350 ℃) and high pressure.Wet oxidation process is because system device is complicated, and investment is big, former thereby not seen widespread use such as operational administrative difficulty and working cost height.The dioxide peroxide oxidation style is about 6.5 at the influent waste water pH value generally; Flow velocity is 250ml/L, and temperature is 25 ℃, and the volume ratio of dioxide peroxide and waste water is under 0.1 the condition; Clearance can reach the highest effect; The pH value that waste water gets into, oxygenant consumption, flow velocity etc. all clearance of PARA FORMALDEHYDE PRILLS(91,95) waste water have very big influence, so this method complex process, are unfavorable for the industry popularization.
Present domestic removal formaldehyde waste water technology mainly concentrates on refining of petroleum and wastewater treatment aspect.For example: Japanese Patent (openly speciallyying permit clear 54-3002) adopts the oxide catalyst through special activation treatment, makes formaldehyde under alkaline condition, carry out disproportionation reaction, is transformed into formaldehyde and sodium formate.Another patent of Japan (clear 49-087613) also is the method that adds alkaline purification formaldehyde, and these method alkali consumptions are big, still have secondary pollution; The method that Japanese Patent (clear 48-60454) provides biochemical process to handle cyanalcohol, high-concentration formaldehyde can be to production by biological toxigenicity restraining effect, so biochemical process can only be handled the waste water that contains below the aldehyde 800mg/l.Unsuitable treatment of high concentration aldehyde-containing sewage, and the volumetric loading of handling is lower, needs bigger volume of equipment.
Summary of the invention
A kind of COD (COD) degradation agents that is applicable to that formaldehyde is removed in the trade effluent that the present invention proposes, purpose is to improve existing aldehyde removal method, and is simple to obtain, efficient, low cost, blanket effect.
The technical scheme that the present invention adopted is: this degradation agents by inorganic strong oxidizer, catalyzer, genetically engineered bacteria enzyme three is composite forms; Wherein inorganic strong oxidizer mass content is 30%～85%; Catalyst quality content is 1%～5%, and genetically engineered bacteria enzyme mass content is 10%～30%.
Described inorganic strong oxidizer is one or both in potassium permanganate, Na2Fe04, sodium perchlorate, the potassium perchlorate.
Described catalyzer is one or both in chromic oxide, powder blue, the nickel oxide.
Described genetically engineered bacteria enzyme is one or both in cyclic amide lytic enzyme, proteolytic enzyme, glycase, lipase, the nucleicacidase.
The per-cent that each material accounts for composite back total mass is respectively: potassium permanganate 35%～85%, Na2Fe04 45%～85%, sodium perchlorate 30%～85%, potassium perchlorate 40%～85%, chromic oxide 1%～4%, powder blue 1%～5%, nickel oxide 1%～5%, cyclic amide hydrolase 10 %～30%, proteolytic enzyme 15%～30%, glycase 10%～30%, lipase 15%～30%, nucleicacidase 15%～30%.
The realization of the object of the invention is to contain in the organic trade effluent of difficult degradation formaldehyde through composite good COD degradation agents is added; The mass ratio of dosage and trade effluent is 1:100～1:500; Constantly stir to be not less than the 300r/min rotating speed; Churning time is 10～30min, and the concentration of formaldehyde in the waste water is dropped to below the 0.5mg/L from 10～1000mg/L, and the formaldehyde clearance is up to more than 99.9%.
The invention has the beneficial effects as follows:
(1) according to the molecular structure of formaldehyde material; Selecting to select appropriate catalyst again on the suitable oxygenant basis; And composite corresponding engineering bacterium lytic enzyme; Concentration of formaldehyde in the waste water is dropped to below the 0.5mg/L from 1000mg/L, and the formaldehyde clearance is up to more than 99.9%;
(2) the Degradation Formaldehyde agent that adds does not have deposition and generates in waste water, and also odorlessness produces, and can also change the colourity in the waste water, to the environment non-secondary pollution.
Embodiment
COD degradation agents of the present invention by inorganic strong oxidizer, catalyzer, genetically engineered bacteria enzyme three is composite forms, wherein inorganic strong oxidizer mass content is 30%～85%, catalyst quality content is 1%～5%, genetically engineered bacteria enzyme mass content is 10%～30%;
Described inorganic strong oxidizer is one or both in potassium permanganate, Na2Fe04, sodium perchlorate, the potassium perchlorate;
Described catalyzer is one or both in chromic oxide, powder blue, the nickel oxide;
Described genetically engineered bacteria enzyme is one or both in cyclic amide lytic enzyme, proteolytic enzyme, glycase, lipase, the nucleicacidase.
The per-cent that each material proportioning of above-mentioned COD degradation agents accounts for the COD total mass is specially: potassium permanganate 35%～85%, Na2Fe04 45%～85%, sodium perchlorate 30%～85%, potassium perchlorate 40%～85%, chromic oxide 1%～4%, powder blue 1%～5%, nickel oxide 1%～5%, cyclic amide hydrolase 10 %～30%, proteolytic enzyme 15%～30%, glycase 10%～30%, lipase 15%～30%, nucleicacidase 15%～30%.
The realization of the object of the invention is to contain in the organic trade effluent of difficult degradation formaldehyde through composite good COD degradation agents is added; The mass ratio of dosage and trade effluent is 1:100～1:500; Constantly stir to be not less than the 300r/min rotating speed; Churning time is 10～30min, and the concentration of formaldehyde in the waste water is dropped to below the 0.5mg/L from 10～1000mg/L, and the formaldehyde clearance is up to more than 99.9%.
Embodiment 1
With mass percent be: potassium permanganate 85%, nickel oxide 1%, cyclic amide lytic enzyme 14% are made into formaldehyde COD degradation agents; Add composite good COD degradation agents in the trade effluent; The quality that adds is 3%; Churning time is 20min, can make the concentration of formaldehyde in the waste water drop to 0.4mg/L from 1000mg/L, and the formaldehyde clearance is up to 99.9%.
Embodiment 2
With mass percent be: Na2Fe04 82%, powder blue 1%, glycase 17% are made into formaldehyde COD degradation agents; Add composite good COD degradation agents in the trade effluent; The quality that adds is 2%; Churning time is 15min, can make the concentration of formaldehyde 800mg/L in the waste water drop to 0.2mg/L, and the formaldehyde clearance is up to 99.9%.
Embodiment 3
With mass percent be: potassium perchlorate 80%, powder blue 5%, proteolytic enzyme 15% are made into formaldehyde COD degradation agents; Add composite good COD degradation agents in the trade effluent; The quality that adds is 2%; Churning time is 10min, can make the concentration of formaldehyde in the waste water drop to 0.2mg/L from 500mg/L, and the formaldehyde clearance is up to 99.9%.
Embodiment 4
With mass percent be: sodium perchlorate 66%, chromic oxide 4%, nucleicacidase 30% are made into formaldehyde COD degradation agents; Add composite good COD degradation agents in the trade effluent; The quality that adds is 2%; Churning time is 10min, can make the concentration of formaldehyde in the waste water drop to 0.1mg/L from 300mg/L, and the formaldehyde clearance is up to 99.9%.
Embodiment 5
With mass percent be: potassium permanganate 75%, nickel oxide 3%, lipase 22% are made into formaldehyde COD degradation agents; Add composite good COD degradation agents in the trade effluent; The quality that adds is 1%; Churning time is 10min, can make the concentration of formaldehyde in the waste water drop to 0.1mg/L from 200mg/L, and the formaldehyde clearance is up to 99.9%.
Embodiment 6
With mass percent be: sodium perchlorate 65%, chromic oxide 4%, cyclic amide lytic enzyme 31% are made into formaldehyde COD degradation agents; Add composite good COD degradation agents in the trade effluent; The quality that adds is 1%; Churning time is 10min, can make the concentration of formaldehyde in the waste water drop to 0.1mg/L from 100mg/L, and the formaldehyde clearance is up to 99.9%.
Claims (4)
1. COD degradation agents of removing formaldehyde in the trade effluent; By inorganic strong oxidizer, catalyzer, genetically engineered bacteria enzyme three is composite forms; It is characterized in that: wherein inorganic strong oxidizer mass content is 30%～85%; Catalyst quality content is 1%～5%, and genetically engineered bacteria enzyme mass content is 10%～30%.
2. a kind of COD degradation agents of removing formaldehyde in the trade effluent according to claim 1 is characterized in that: described inorganic strong oxidizer is one or both in potassium permanganate, Na2Fe04, sodium perchlorate, the potassium perchlorate.
3. a kind of COD degradation agents of removing formaldehyde in the trade effluent according to claim 1, it is characterized in that: described catalyzer is one or both in chromic oxide, powder blue, the nickel oxide.
4. a kind of COD degradation agents of removing formaldehyde in the trade effluent according to claim 1 is characterized in that: described genetically engineered bacteria enzyme is one or both in cyclic amide lytic enzyme, proteolytic enzyme, glycase, lipase, the nucleicacidase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103207594A CN102464401A (en) | 2011-10-20 | 2011-10-20 | COD (chemical oxygen demand) degradation agent for removing formaldehyde in industrial wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103207594A CN102464401A (en) | 2011-10-20 | 2011-10-20 | COD (chemical oxygen demand) degradation agent for removing formaldehyde in industrial wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102464401A true CN102464401A (en) | 2012-05-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103207594A Pending CN102464401A (en) | 2011-10-20 | 2011-10-20 | COD (chemical oxygen demand) degradation agent for removing formaldehyde in industrial wastewater |
Country Status (1)
| Country | Link |
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| CN (1) | CN102464401A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011529A (en) * | 2012-12-07 | 2013-04-03 | 常州大学 | Industrial wastewater treatment technology |
| CN104628119A (en) * | 2015-01-04 | 2015-05-20 | 河海大学 | Method for removing trace polluting organic substances from water through catalyzing potassium permanganate by cobalt oxide |
| CN106865716A (en) * | 2017-04-13 | 2017-06-20 | 曹恩惠 | A kind of novel C OD degradation agents |
| CN111362424A (en) * | 2020-04-10 | 2020-07-03 | 浙江龙奇印染有限公司 | Efficient composite oxidant for treating COD (chemical oxygen demand) of printing and dyeing wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4623465A (en) * | 1981-04-20 | 1986-11-18 | Massachusetts Institute Of Technology | Removal of combined organic substances from aqueous solutions |
| WO1991013036A1 (en) * | 1990-02-27 | 1991-09-05 | Oy Keskuslaboratorio - Centrallaboratorium Ab | Process for purification of waste water |
| CN102070237A (en) * | 2010-11-26 | 2011-05-25 | 常州大学 | COD degradation agent for removing sulfamide from industrial wastewater |
-
2011
- 2011-10-20 CN CN2011103207594A patent/CN102464401A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4623465A (en) * | 1981-04-20 | 1986-11-18 | Massachusetts Institute Of Technology | Removal of combined organic substances from aqueous solutions |
| WO1991013036A1 (en) * | 1990-02-27 | 1991-09-05 | Oy Keskuslaboratorio - Centrallaboratorium Ab | Process for purification of waste water |
| CN102070237A (en) * | 2010-11-26 | 2011-05-25 | 常州大学 | COD degradation agent for removing sulfamide from industrial wastewater |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011529A (en) * | 2012-12-07 | 2013-04-03 | 常州大学 | Industrial wastewater treatment technology |
| CN104628119A (en) * | 2015-01-04 | 2015-05-20 | 河海大学 | Method for removing trace polluting organic substances from water through catalyzing potassium permanganate by cobalt oxide |
| CN106865716A (en) * | 2017-04-13 | 2017-06-20 | 曹恩惠 | A kind of novel C OD degradation agents |
| CN111362424A (en) * | 2020-04-10 | 2020-07-03 | 浙江龙奇印染有限公司 | Efficient composite oxidant for treating COD (chemical oxygen demand) of printing and dyeing wastewater |
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Application publication date: 20120523 |