CN1116475C - Method for bleaching waste water of paper making - Google Patents
Method for bleaching waste water of paper making Download PDFInfo
- Publication number
- CN1116475C CN1116475C CN00131006A CN00131006A CN1116475C CN 1116475 C CN1116475 C CN 1116475C CN 00131006 A CN00131006 A CN 00131006A CN 00131006 A CN00131006 A CN 00131006A CN 1116475 C CN1116475 C CN 1116475C
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- China
- Prior art keywords
- waste water
- anode
- lignin
- bleaching
- electrode
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002351 wastewater Substances 0.000 title claims abstract description 21
- 238000004061 bleaching Methods 0.000 title claims abstract description 16
- 229920005610 lignin Polymers 0.000 claims abstract description 18
- 239000010893 paper waste Substances 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 9
- 238000006056 electrooxidation reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000007747 plating Methods 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 229910000464 lead oxide Inorganic materials 0.000 claims description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000005684 electric field Effects 0.000 abstract description 3
- 238000011282 treatment Methods 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract 1
- 239000012982 microporous membrane Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000004042 decolorization Methods 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000002175 menstrual effect Effects 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 235000011609 Pinus massoniana Nutrition 0.000 description 1
- 241000018650 Pinus massoniana Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000185 dioxinlike effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The present invention relates to a method for bleaching waste water produced in a paper making process. An electric oxidation bleaching technique is utilized, a cathode and an anode are inserted into waste water for paper making, and an insulating filter screen is used for isolating the cathode and the anode, and then DC current with the voltage of 2 to 8 V is switched on; pH values are regulated to 2 to 14 at the temperature of 10 to 50 DEG C, the quantity of electricity Q consumed by unit mass lignin at a certain power is controlled, and the value of Q is from 15 to 30 kilo microcoulombs/g; microporous membrane electrodes can be particularly used for the electric oxidation treatment of the waste water for paper making, the lignin can be effectively oxidized and degraded under the action of an electric field with no pollution and high current efficiency.
Description
The invention belongs to the method for electroxidation bleaching paper waste.
Paper waste comprises the waste water of pulping process and bleaching process.Paper waste mainly is made up of lignin, polysaccharide and inorganic salts, and wherein lignin is the main matter that causes chroma in waste water.At present, China's paper industry adopts the chlorine bleaching process mostly, introduces the chlorine atom in the residual lignin structure, to remove the residual lignin that remains in the paper pulp.In the bleaching process, produce the chlorophenols and the dioxin-like compound of many poisonous, carcinogenic and difficult degradations, these direct discharging of waste water become harm greatly to environment.
In order to reduce or eliminate the pollution of paper waste to environment, present treatment technology is divided into chemical method substantially, physical method and bioanalysis, and chemical method need consume more chemicals, and some can cause secondary pollution; Bioanalysis generally can only be removed carbohydrate, and it is extremely limited that chloride lignin is removed ability, and whiterot fungi is considered to the most effective lignin degrading, at present that is that all right is ripe and degradation rate is very slow for technology, human Ganodetma Lacidum bacterial strains such as Wang remove the colourity of bleaching effluent, 6 days percent of decolourization ability 90% (Wang shuhom etal Holzforschung, 1992,46 (3): 219-223).Physical method is considered to a kind of secondary pollution method fast and effectively that do not produce.CN1153843A discloses a kind of improvement method of soda pulping black liquor, and it takes acidifying to remove delignification, under 3-6 volt DC voltage, carries out electrolytic treatments then.This method inconvenience is to remove delignification earlier.
The method that the purpose of this invention is to provide a kind of bleaching waste water of paper making, it adopts the electroxidation bleaching technology, and energy the efficient oxidation lignin degrading is pollution-free under electric field action, and the current efficiency height.
The method of employing electroxidation bleaching paper waste provided by the invention, electro-oxidation process is to insert anode and negative electrode in paper waste, and described anode and negative electrode are the microporous barrier electrode, isolates with the insulation filter screen in the middle of the electrode, passing to direct current carries out, voltage 2-8 volt, the pH value transfers to 8-14, temperature 10-50 ℃, the electric weight Q value of control unit mass lignin consumption reaches 15-30 kil. ocoulomb human relations/gram under certain voltage, wherein, Q=It/1000G (kil. ocoulomb human relations/gram)
In the formula: I is current strength (ampere), and t is reaction time (second), and G is a lignin quality (gram) in the waste water.
When carrying out electroxidation, voltage is the 2-8 volt, preferred 5-6 volt.
Anode and negative electrode are the microporous barrier electrode among the present invention, can be through chemical plating and electroplate the plastic filter screen or the titanium net electrode of brown lead oxide film as anode, or on nonmetal or metal screen the membrane electrode of gold-plated or platinum; Negative electrode can be 300 orders or the above stainless (steel) wire of 300 orders.
The microporous barrier electrode has thin and the structure of porous, usually can take on cancellated matrix the plating conductive materials to make, preparation existing introduction in Chinese patent 98113390.8 (publication number CN 1221046A, open day on June 30th, 1999) about the microporous barrier electrode.Adopt the microporous barrier electrode, with respect to excellent type and flat pole, increased the effective area of electroxidation, and the microporous barrier electrode also is convenient to mass transfer in liquid phase in the electro-oxidation process, current efficiency is higher more than 30% than traditional electrolysis.
Method provided by the invention both can be used for the wastewater treatment of papermaking digestion process, also can be used for the wastewater treatment of bleaching process.
Electro-oxidation process of the present invention can carry out in wastewater disposal basin or in waste water flows by process.
Electroxidation bleaching technology provided by the invention belongs to physical-chemical process, and lignin oxidation is degraded to colourless, innocuous substance under electric field action,
Decolorization rate of wastewater is to represent with the absorbance of otoelectric spectrophotometer measurement waste water, select the 710nm wavelength during measurement, with distilled water is reference, and the absorbance A o of unreacted paper waste is adjusted to 1.0, solution absorbency At after surveying electroxidation under the same wavelength.Percent of decolourization D=(Ao-At)/Ao * 100%.
Method provided by the invention is compared with traditional electrolysis, owing to adopted the microporous barrier electrode, increased effective area, simultaneously again because microporous barrier is convenient to mass transfer in liquid phase in the electro-oxidation process, therefore, current efficiency of the present invention is higher more than 30% than traditional electrolysis.
Embodiment 1:
Masson pine sulphite boiling waste water filters through 400 mesh filter screens, and lignin sulfonic acid calcium content 8% transfers to 12 with the solution pH value, puts into gross area 182cm in 100 ml solns
2Is negative electrode through the polypropylene plastics filter screen electrode of plating brown lead oxide film as anode and the 300 order stainless (steel) wires that equate with annode area, plastic film with porous between anode and the negative electrode is separated by, stimulate the menstrual flow 4 volts in the direct current of voltage stabilizing, the percent of decolourization of solution is 92.5% when power consumption reaches 20.5 kil. ocoulombs human relations/gram lignin.And under similarity condition, adopting the plate electrode percent of decolourization only is 61%.
Embodiment 2:
Wheat straw sulphate cook waste water, alkali lignin concentration are 7%, filter through 400 mesh filter screens, and the pH value of solution is transferred to 13, put into gross area 219cm in 120 ml solns
2The titanium net electrode of plating brown lead oxide film is as anode, the 300 order stainless (steel) wires that equate with annode area are negative electrode, plastic film with porous between anode and the negative electrode is separated by, 3.5 volts of the DC voltages of the voltage stabilizing of stimulating the menstrual flow, and the percent of decolourization of solution is 98% when power consumption reaches 22 kil. ocoulombs human relations/gram lignin.And adopt the plate electrode percent of decolourization under similarity condition only is 65%.
Claims (5)
1, a kind of method for bleaching of paper waste, adopt the electroxidation technology, electro-oxidation process is to insert anode and negative electrode in paper waste, described anode and negative electrode are the microporous barrier electrode, middle with the isolation of insulation filter screen, pass to direct current and carry out, voltage 2-8 volt, the pH value transfers to 8-14, temperature 10-50 ℃, the electric weight Q that control unit mass lignin consumes under certain voltage, the Q value is 15-30 kil. ocoulomb human relations/gram, wherein, Q=It/1000G (kil. ocoulomb human relations/gram), in the formula: I is current strength (ampere), and t is reaction time (second), and G is a lignin quality (gram) in the waste water.
2,, it is characterized in that described voltage is the 5-6 volt according to the method described in the claim 1.
3, according to the method described in claim 1 or 2, it is characterized in that described anode is through chemical plating and electroplates the plastic filter screen or the titanium net electrode of brown lead oxide film, or on nonmetal or metal screen the membrane electrode of gold-plated or platinum; Negative electrode is 300 orders or the above stainless (steel) wire of 300 orders.
4,, it is characterized in that described paper waste is the waste water of papermaking digesting process generation or the waste water of papermaking bleaching process generation according to the method described in claim 1 or 2.
5,, it is characterized in that described electro-oxidation process carries out in wastewater disposal basin or in waste water flows by process according to the method described in claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00131006A CN1116475C (en) | 2000-12-27 | 2000-12-27 | Method for bleaching waste water of paper making |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00131006A CN1116475C (en) | 2000-12-27 | 2000-12-27 | Method for bleaching waste water of paper making |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1296100A CN1296100A (en) | 2001-05-23 |
| CN1116475C true CN1116475C (en) | 2003-07-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00131006A Expired - Fee Related CN1116475C (en) | 2000-12-27 | 2000-12-27 | Method for bleaching waste water of paper making |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1116475C (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153843A (en) * | 1996-09-10 | 1997-07-09 | 刘友会 | Alkali process for treating black liquor |
-
2000
- 2000-12-27 CN CN00131006A patent/CN1116475C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153843A (en) * | 1996-09-10 | 1997-07-09 | 刘友会 | Alkali process for treating black liquor |
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| Publication number | Publication date |
|---|---|
| CN1296100A (en) | 2001-05-23 |
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