CN105293657A - Further treatment method of papermaking method reproduced tobacco leaf waste water - Google Patents
Further treatment method of papermaking method reproduced tobacco leaf waste water Download PDFInfo
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- CN105293657A CN105293657A CN201510659692.5A CN201510659692A CN105293657A CN 105293657 A CN105293657 A CN 105293657A CN 201510659692 A CN201510659692 A CN 201510659692A CN 105293657 A CN105293657 A CN 105293657A
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- papermaking
- reconstituted tobaccos
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Abstract
The invention relates to a further treatment method of papermaking method reproduced tobacco leaf waste water. The method comprises the following steps: first dissolving ferrous sulfate hydrate, acidifying by adding sulfuric acid, adding a phosphate stabilizer during stirring at 40 to 60 DEG C, then adding the sodium chlorate oxidant, and continuously stirring and reacting for about 2h to obtain a high-efficiency phosphoric polyferric sulfate coagulant. The preparation process is simple in process, the reaction condition is moderate, the reaction rate is high, the control is easy, and the prepared coagulant product is good in stability. The prepared high-efficiency phosphoric polyferric sulfate coagulant is used for further treatment of the papermaking method reproduced tobacco leaf production waste water, during a coagulation process, by controlling the pH value, the waste water CODcr can be reduced from around 400mg/L to less than 150mg/L, the chromaticity is reduced from 800CU to about 80CU, the content of ammonia nitrogen is reduced from 18mg/L to about 5mg/L, the content of phosphate (counted as P) is reduced from 8mg/L to less than 1mg/L, the national sewage comprehensive discharging secondary standard can be basically reached, and the treatment effect is very good.
Description
Technical field
The invention belongs to the utilization of resources and environmental protection technical field, particularly relate to a kind of papermaking-method reconstituted tobaccos advanced waste treatment method.
Background technology
Coagulation (flocculation) process is by adding some chemical agents (being commonly referred to coagulating agent and coagulant aids) in water, changes the surface property of colloidal solid, the colloidal solid being difficult to precipitate can be polymerized mutually, grow up to the degree of energy natural sedimentation in water.The mechanism of action of coagulation generally includes electrostatic double layer compression mechanism, the absorption charge neutrality mechanism of action, the adsorption bridging mechanism of action and throw out net and catches mechanism etc.Coagulation (flocculation) is the important operating unit of water treatment field one, is all used widely in feedwater, industry/sanitary sewage disposal etc.The principal element affecting coagulation effect comprises the time etc. of coagulating agent kind, water quality, pH value, water temperature, HYDRODYNAMIC CONDITION RELATING TO and coagulating, and wherein the kind of coagulating agent is the most important factor affecting coagulation effect and processing cost.Therefore, developing Be very effective, processing cheap, that suitability is wide coagulating agent is the key realizing coagulating treatment.
When selecting for certain specific waste water of process the coagulating agent adapted to, usually determined by the consideration of comprehensive following several respects.One is that treatment effect is good, has higher clearance, can meet design requirement to the pollutent that hope is removed.In order to reach this target, sometimes need two or more coagulating agent and coagulant aids simultaneously with the use of.Two is that the price of coagulating agent and coagulant aids should be suitably cheap, and the dosage of needs should be moderate, to prevent because the expensive process working cost that causes is too high.Three is that the source of coagulating agent should be reliable, and product performance are more stable, and should be suitable for and store and add conveniently.Four is that all coagulating agent should not produce secondary pollution to process water outlet.When processing water outlet and having a reuse requirement, the impact such as the residual volume of coagulating agent or the slight colourity that causes in due regard to water outlet.At present, flocculation agent is broadly divided into the three major types such as inorganic coagulant, organic coagulants and microorganism coagulating agent.Wherein, inorganic coagulant is divided into again low-molecular inorganic coagulating agent and inorganic polymer coagulant.Inorganic polymer coagulant (poly-aluminium, Polyferric Sulfate, compound Polyaluminium iron etc.) has more excellent usefulness than traditional low-molecular inorganic coagulating agent (as alum, Tai-Ace S 150, ferric sulfate, iron(ic) chloride etc.), lower than organic coagulants cost again, become the main flow coagulating agent of current water treatment field gradually, be used widely in feedwater, industry/sanitary sewage disposal.But in embody rule process, also there is the problems such as quality instability, facile hydrolysis, universality difference in single inorganic polymer coagulant.Found by research, composite type inorganic polymer coagulating agent can overcome these deficiencies of single inorganic polymer coagulant, while reduction cost of water treatment, can improve flocculating property.Wherein PPFS is exactly a kind of composite type inorganic polymer flocculation agent, it introduces phosphate anion on the basis of bodied ferric sulfate, increasing by phosphate radical gathers effect, improve the basicity of product, its hydrolysis property is improved, significantly improve the stability of product, there is the outstanding advantage such as temperature/pH value wide accommodation, COD clearance height simultaneously.
Papermaking-method reconstituted tobaccos is for raw material with the tobacco waste such as offal, offal, adopt modern extraction and separation technology and the one " artificial tobacco leaf " that processes of paper technology after improving, reconstituted tobacco so that its incendivity is good, Filling power is high, releasing content of coke tar is low, physical and chemical index is adjustable the remarkable advantage such as controlled be used widely in cigarette industry.Papermaking-method reconstituted tobaccos can produce a large amount of waste water in process of manufacture, and waste water has the features such as high COD, high chroma and high suspended matter.Along with society is to the pay attention to day by day of environmental protection, the waste water generated during paper-making process reconstituted-tobacco production how processing high density becomes a key factor of industry development.Through theoretical investigation and the practical exploration of more than 10 years, current domestic papermaking-method reconstituted tobaccos manufacturing enterprise has begun to take shape the tupe of " pre-treatment+anaerobism+aerobic+advanced treatment " to the process of waste water, substantially can meet the secondary discharge standard of " GB8978-1996 integrated wastewater discharge standard ".
The pay attention to day by day to environmental protection along with country and society, sewage disposal emission standard improves constantly.Meanwhile, also the high request being strict in national standard is proposed to papermaking-method reconstituted tobaccos sewage discharge in tobacco industry.In this case, adopt coagulation technology, develop the new and effective retardant being suitable for papermaking-method reconstituted tobaccos sewage disposal just very necessary; One is the emission request that better can reach country and industry, and two is can provide a kind of important Means of Ensuring for sewage works operation.
Open (bulletin) number is the synthetic method disclosing a kind of waste water generated during paper-making process reconstituted-tobacco production advanced treatment coagulating agent in the patent of CN101898820A.Although the advanced treatment of the coagulating agent that the method obtains to reforged tobacco wastewater has reasonable effect (having higher COD and chroma removal rate), but because preparation process needs the processing condition such as high-temperature calcination, ebuillition of heated, the slightly aobvious complexity of all preparation process, energy consumption are also higher, also do not introduce the clearance of other pollutents (ammonia nitrogen, total phosphorus etc.) in waste water.
Summary of the invention
The present invention, in order to solve weak point of the prior art, provides that a kind of preparation process is simple, good stability, easy to use, the convenient papermaking-method reconstituted tobaccos advanced waste treatment method controlled.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: papermaking-method reconstituted tobaccos advanced waste treatment method, comprises the steps:
(1) get a certain amount of reductive agent ferrous salt and put into container, under the water bath condition that 40-60 DEG C is carried out to container, in container, add suitable quantity of water stirring and dissolving, and add the appropriate vitriol oil and carry out acidifying, Keep agitation solubilize;
(2), after ferrous sulfate dissolves completely, while Keep agitation, Fe is pressed
2+/ P mol ratio is an alkali metal salt stablizer that 0.07-0.12 adds phosphate radical;
(3) while Keep agitation, slowly add oxygenant, continue the temperature of control to container water-bath at 40-60 DEG C, after reaction 2h, namely obtain the PPFS coagulating agent of high stability;
(4) the biochemical stage water outlet of papermaking-method reconstituted tobaccos wastewater treatment is got from sewage plant, high-speed mixing stirs and slowly adds PPFS coagulating agent, the change of monitoring waste water ph, when pH value drops to 4.0-4.3, stop stirring, staticly settle, get supernatant liquor and detect COD, ammonia nitrogen, total phosphorus and chromaticity index.
The reductive agent ferrous salt adopted is titanium dioxide industry by product iron vitriol.
An alkali metal salt stablizer added is SODIUM PHOSPHATE, MONOBASIC, disodium-hydrogen, sodium phosphate, potassium primary phosphate, potassium phosphate,monobasic or potassiumphosphate.
Oxygenant used is Potcrate or sodium chlorate.
The bath temperature of preparation process controls 50
oc, the reaction times total in container is 2-3h.
In coagulation process, the addition of phosphorus ferric sulfate coagulating agent drops to 4.2 with the pH value in waste water and is as the criterion.
Adopt technique scheme, compared to existing technology, the present invention has following outstanding effect:
1, the present invention is with titanium dioxide industry by-product ferrous sulfate during and sulfuric acid for main raw material, and raw material sources are extensive, with low cost, better can realize the recycling of trade waste; Preparation process, without the need to adding catalyzer, introduces impurity few in product, avoid the pollution to atmospheric environment (adding of nitrite catalyzer causes) occurred when oxidation style prepares bodied ferric sulfate simultaneously.
2, preparation process technical process is simple, reaction conditions is gentle, speed of reaction is fast, be suitable for control, the transformation efficiency of ferrous ion is higher, has saved production cost greatly, has been applicable to large-scale commercial production.
3, the phosphate stabilizers such as SODIUM PHOSPHATE, MONOBASIC are added in preparation process, PO
4-with Fe
3+complexing can delay to be hydrolyzed and stop generate crystallized product, PO
4-existence make Fe formant rest on the dimer stage, hydrolytic polymerization is hindered, and morphological structure trend is linear and open, and these are all conducive to the raising of flocculation agent stability, significantly improve the product stability of PPFS coagulating agent.
4, the phosphoric polyferric sulfate flocculant prepared of the present invention has extraordinary effect for the process of papermaking-method reconstituted tobaccos wastewater treatment mesophytization water outlet, flocculation efficiency is high, settling velocity is fast, sludge quantity is few, has higher clearance to the COD of bio-chemical effluent, colourity, ammonia nitrogen, total phosphorus.
5, the present invention is that papermaking-method reconstituted tobaccos Sewage advanced treatment provides one and efficiently, easily processes means, has the outstanding advantages such as less investment, successful, operation be convenient.
Embodiment
The content of the application of the invention prepares a kind of new and effective PPFS coagulating agent, then carries out advanced treatment with the novel coagulant prepared to the bio-chemical effluent of papermaking-method reconstituted tobaccos wastewater treatment.After the pre-treatment, aerobic/anaerobic biochemical treatment of leading portion, reforged tobacco wastewater outward appearance is generally in faint yellow, and CODcr is generally between 300-600, and colourity 600-1000C.U, pH value is about 7.5, ammonia nitrogen 10-25mg/L, total phosphorus 5-10mg/L.
Embodiment 1
Papermaking-method reconstituted tobaccos advanced waste treatment method: get iron vitriol (FeSO
47H
2o) 50g, 50
ounder the water bath condition of C, add 50mL water stirring and dissolving; The 4mL vitriol oil (H is added in ferrous sulfate aqueous solution
2sO
4) carrying out acidifying, Keep agitation dissolves; By n(Fe)/n(P) mol ratio 0.07 adds 3.5g SODIUM PHOSPHATE, MONOBASIC (NaH
2pO
4) stablizer; 3g sodium chlorate is used 30mL hot water dissolving, is made into sodium chlorate aqueous solution; While Keep agitation, sodium chlorate aqueous solution is slowly added in copperas solution, control bath temperature 50
oc, obtains PPFS (PPFS) coagulating agent of high stability, color reddish-brown, pH value 0.45 after reaction 2h.
Advanced treatment coagulation experiment: get papermaking-method reconstituted tobaccos sewage plant biological section water outlet 200mL, prepared coagulating agent is slowly dripped under violent stirring (300rpm), stop dripping after pH value drops to about 4.2, leave standstill 20min, the volume carrying out COD, colourity, ammonia nitrogen and total phosphorus by national standard measures, and the results are shown in following table.
Embodiment 2
Papermaking-method reconstituted tobaccos advanced waste treatment method: get ferrous sulfate (FeSO
47H
2o) 50g, 60
ounder the water bath condition of C, add 50mL water stirring and dissolving; The 4mL vitriol oil (H is added in ferrous sulfate aqueous solution
2sO
4) carrying out acidifying, Keep agitation dissolves; By n(Fe)/n(P) mol ratio 0.05 adds 2.5g SODIUM PHOSPHATE, MONOBASIC (KaH
2pO
4) stablizer; 3g Potcrate is used 30mL hot water dissolving, is made into sodium chlorate aqueous solution; While Keep agitation, sodium chlorate aqueous solution is slowly added in copperas solution, control bath temperature 60
oc, obtains PPFS (PPFS) coagulating agent of high stability, color reddish-brown, pH value 0.38 after reaction 2h.
Advanced treatment coagulation experiment: get papermaking-method reconstituted tobaccos sewage plant biological section water outlet 200mL, prepared coagulating agent is slowly dripped under violent stirring (300rpm), stop dripping after pH value drops to about 4.0, leave standstill 20min, the volume carrying out COD, colourity, ammonia nitrogen and total phosphorus by national standard measures, and the results are shown in following table.
| CODcr | Colourity | Ammonia nitrogen | Phosphoric acid salt (in P) | |
| Former water | 390 | 730 | 18 | 5.8 |
| Coagulating agent process of the present invention | 125 | 73 | 5.4 | 0.98 |
| Clearance | 68％ | 90％ | 70％ | 83％ |
Embodiment 3
Papermaking-method reconstituted tobaccos advanced waste treatment method: get ferrous sulfate (FeSO
47H
2o) 50g, 50
ounder the water bath condition of C, add 50mL water stirring and dissolving; The 4mL vitriol oil (H is added in ferrous sulfate aqueous solution
2sO
4) carrying out acidifying, Keep agitation dissolves; By n(Fe)/n(P) mol ratio 0.08 adds 4.0g SODIUM PHOSPHATE, MONOBASIC (NaH
2pO
4) stablizer; 3.2g sodium chlorate is used 30mL hot water dissolving, is made into sodium chlorate aqueous solution; While Keep agitation, sodium chlorate aqueous solution is slowly added in copperas solution, control bath temperature 50
oc, obtains PPFS (PPFS) coagulating agent of high stability, color reddish-brown, pH value 0.46 after reaction 2.5h.
Advanced treatment coagulation experiment: get papermaking-method reconstituted tobaccos sewage plant biological section water outlet 200mL, prepared coagulating agent is slowly dripped under violent stirring (300rpm), stop dripping after pH value drops to about 4.1, leave standstill 20min, the volume carrying out COD, colourity, ammonia nitrogen and total phosphorus by national standard measures, and the results are shown in following table.
| CODcr | Colourity | Ammonia nitrogen | Phosphoric acid salt (in P) | |
| Former water | 520 | 710 | 17.8 | 7.0 |
| Coagulating agent process of the present invention | 146 | 71 | 5.7 | 0.63 |
| Clearance | 72％ | 90％ | 68％ | 91％ |
Embodiment 4
Papermaking-method reconstituted tobaccos advanced waste treatment method: get ferrous sulfate (FeSO
47H
2o) 50g, 40
ounder the water bath condition of C, add 50mL water stirring and dissolving; The 4mL vitriol oil (H is added in ferrous sulfate aqueous solution
2sO
4) carrying out acidifying, Keep agitation dissolves; By n(Fe)/n(P) mol ratio 0.07 adds 3.5g SODIUM PHOSPHATE, MONOBASIC (NaH
2pO
4) stablizer; 3.2g Potcrate is used 30mL hot water dissolving, is made into sodium chlorate aqueous solution; While Keep agitation, sodium chlorate aqueous solution is slowly added in copperas solution, control bath temperature 40
oc, obtains PPFS (PPFS) coagulating agent of high stability, color reddish-brown, pH value 0.50 after reaction 2h.
Advanced treatment coagulation experiment: get papermaking-method reconstituted tobaccos sewage plant biological section water outlet 200mL, prepared coagulating agent is slowly dripped under violent stirring (300rpm), stop dripping after pH value drops to about 4.3, leave standstill 20min, the volume carrying out COD, colourity, ammonia nitrogen and total phosphorus by national standard measures, and the results are shown in following table.
| CODcr | Colourity | Ammonia nitrogen | Phosphoric acid salt (in P) | |
| Former water | 390 | 620 | 15.2 | 5.2 |
| Coagulating agent process of the present invention | 125 | 81 | 4.4 | 0.87 |
| Clearance | 68％ | 87％ | 71％ | 86％ |
Embodiment 5
Papermaking-method reconstituted tobaccos advanced waste treatment method: get ferrous sulfate (FeSO
47H
2o) 50g, 40
ounder the water bath condition of C, add 50mL water stirring and dissolving; The 4mL vitriol oil (H is added in ferrous sulfate aqueous solution
2sO
4) carrying out acidifying, Keep agitation dissolves; By n(Fe)/n(P) mol ratio 0.07 adds 3.0g dipotassium hydrogen phosphate (K
2hPO
4) stablizer; 3.2g sodium chlorate is used 30mL hot water dissolving, is made into sodium chlorate aqueous solution; While Keep agitation, sodium chlorate aqueous solution is slowly added in copperas solution, control bath temperature 40
oc, obtains PPFS (PPFS) coagulating agent of high stability, color reddish-brown, pH value 0.50 after reaction 2h.
Advanced treatment coagulation experiment: get papermaking-method reconstituted tobaccos sewage plant biological section water outlet 200mL, prepared coagulating agent is slowly dripped under violent stirring (300rpm), stop dripping after pH value drops to about 4.3, leave standstill 20min, the volume carrying out COD, colourity, ammonia nitrogen and total phosphorus by national standard measures, and the results are shown in following table.
| CODcr | Colourity | Ammonia nitrogen | Phosphoric acid salt (in P) | |
| Former water | 398 | 650 | 16.5 | 6.0 |
| Coagulating agent process of the present invention | 123 | 78 | 4.6 | 0.9 |
| Clearance | 69％ | 88％ | 72％ | 85％ |
The present embodiment not does any pro forma restriction to shape of the present invention, material, structure etc.; every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all belong to the protection domain of technical solution of the present invention.
Claims (6)
1. papermaking-method reconstituted tobaccos advanced waste treatment method, is characterized in that: comprise the steps:
(1) get a certain amount of reductive agent ferrous salt and put into container, under the water bath condition that 40-60 DEG C is carried out to container, in container, add suitable quantity of water stirring and dissolving, and add the appropriate vitriol oil and carry out acidifying, Keep agitation solubilize;
(2), after ferrous sulfate dissolves completely, while Keep agitation, Fe is pressed
2+/ P mol ratio is an alkali metal salt stablizer that 0.07-0.12 adds phosphate radical;
(3) while Keep agitation, slowly add oxygenant, continue the temperature of control to container water-bath at 40-60 DEG C, after reaction 2h, namely obtain the PPFS coagulating agent of high stability;
(4) the biochemical stage water outlet of papermaking-method reconstituted tobaccos wastewater treatment is got from sewage plant, high-speed mixing stirs and slowly adds PPFS coagulating agent, the change of monitoring waste water ph, when pH value drops to 4.0-4.3, stop stirring, staticly settle, get supernatant liquor and detect COD, ammonia nitrogen, total phosphorus and chromaticity index.
2. papermaking-method reconstituted tobaccos advanced waste treatment method according to claim 1, is characterized in that: the reductive agent ferrous salt adopted is titanium dioxide industry by product iron vitriol.
3. papermaking-method reconstituted tobaccos advanced waste treatment method according to claim 1, is characterized in that: an alkali metal salt stablizer added is SODIUM PHOSPHATE, MONOBASIC, disodium-hydrogen, sodium phosphate, potassium primary phosphate, potassium phosphate,monobasic or potassiumphosphate.
4. papermaking-method reconstituted tobaccos advanced waste treatment method according to claim 1, is characterized in that: oxygenant used is Potcrate or sodium chlorate.
5. papermaking-method reconstituted tobaccos advanced waste treatment method according to claim 1, is characterized in that: the bath temperature of preparation process controls 50
oc, the reaction times total in container is 2-3h.
6. papermaking-method reconstituted tobaccos advanced waste treatment method according to claim 1, is characterized in that: in coagulation process, the addition of phosphorus ferric sulfate coagulating agent drops to 4.2 with the pH value in waste water and is as the criterion.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966526A (en) * | 2017-05-03 | 2017-07-21 | 昆明理工大学 | The processing method of papermaking-method reconstituted tobaccos waste water |
| CN107467706A (en) * | 2017-01-17 | 2017-12-15 | 云南中烟再造烟叶有限责任公司 | The method for reducing water-soluble chemical oxygen demand in papermaking-method reconstituted tobaccos production plain boiled water |
| CN108083400A (en) * | 2017-12-21 | 2018-05-29 | 上海万狮环保科技有限公司 | A kind of preparation method of phosphorous polyiron sulfate and its application for handling coking wastewater |
| CN109650506A (en) * | 2019-02-25 | 2019-04-19 | 江苏兰鲸环保科技有限公司 | A kind of heavy metal ion flocculant and preparation method thereof |
| CN109777425A (en) * | 2019-01-22 | 2019-05-21 | 袁艺宁 | A kind of preparation method and applications of phosphorus ferric sulfate polymer |
| CN113716665A (en) * | 2021-09-22 | 2021-11-30 | 浙江吉泰新材料股份有限公司 | Method for preparing flocculating agent by utilizing strong-acid wastewater containing phosphorus and sulfur |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107467706A (en) * | 2017-01-17 | 2017-12-15 | 云南中烟再造烟叶有限责任公司 | The method for reducing water-soluble chemical oxygen demand in papermaking-method reconstituted tobaccos production plain boiled water |
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| CN108083400A (en) * | 2017-12-21 | 2018-05-29 | 上海万狮环保科技有限公司 | A kind of preparation method of phosphorous polyiron sulfate and its application for handling coking wastewater |
| CN109777425A (en) * | 2019-01-22 | 2019-05-21 | 袁艺宁 | A kind of preparation method and applications of phosphorus ferric sulfate polymer |
| CN109777425B (en) * | 2019-01-22 | 2021-06-04 | 袁艺宁 | Preparation method and application of iron phosphosulfate polymer |
| CN109650506A (en) * | 2019-02-25 | 2019-04-19 | 江苏兰鲸环保科技有限公司 | A kind of heavy metal ion flocculant and preparation method thereof |
| CN113716665A (en) * | 2021-09-22 | 2021-11-30 | 浙江吉泰新材料股份有限公司 | Method for preparing flocculating agent by utilizing strong-acid wastewater containing phosphorus and sulfur |
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Application publication date: 20160203 |
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