CN102295337B - Printing and dyeing wastewater processing technology by quaternary ammonium salt cationic flocculant prepared by the use of straws - Google Patents
Printing and dyeing wastewater processing technology by quaternary ammonium salt cationic flocculant prepared by the use of straws Download PDFInfo
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- CN102295337B CN102295337B CN 201110161944 CN201110161944A CN102295337B CN 102295337 B CN102295337 B CN 102295337B CN 201110161944 CN201110161944 CN 201110161944 CN 201110161944 A CN201110161944 A CN 201110161944A CN 102295337 B CN102295337 B CN 102295337B
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Abstract
A technology for preparing a quaternary ammonium salt cationic flocculant by the use of straws and processing printing and dyeing wastewater belongs to the technical field of biomass resource comprehensive utilization and dyeing wastewater processing. According to the invention, rice straws are crushed and then the crushed rice straws directly react with 2,3-epoxypropyltrimethylammonium chloride (GTMAc). A cationic polymeric flocculant with good water-solubility is prepared. The synthesized flocculant is used for the flocculation treatment of simulated printing and dyeing wastewater active orange K-GN and active blue; when the concentration of a dye liquor reaches 100mg/L, the flocculant has high decolouring effect and COD clearance at any pH values. The flocculant has an extensive source of raw materials, requires low preparation cost, is ecological and environmentally friendly, and has advantages of less dispensing amount during the printing and dyeing wastewater processing, simple process, high efficiency and wide pH application range and the like.
Description
Technical field
The invention belongs to the backbone waste material and utilize the field, particularly a kind of technology of utilizing cation quaternary ammonium salt to prepare full rice straw flocculation agent treatment of dyeing and printing.
Background technology
China's stalk ultimate production occupies first place in the world, and it is many that real ultimate production reaches 800,000,000 t, and wherein rice straw accounts for 25%.Carry out the formed byproduct of photosynthesis as farm crop, stalk contains the multiple useful component that is utilized, day by day exhausted and ecotope is constantly under the situation of deterioration at petroleum resources, biomass energy becomes current more and more important development field, makes straw resource utilization be subject to the unprecedented attention in countries in the world.
With discarded agricultural byproducts rice straw for example, wheat stalk, sesame stalk, the pre-treatment such as bagasse obtain Mierocrystalline cellulose, then it is carried out etherificate, esterification, and the modifications such as acidylate or cationization are used for industrial production, and chemical material or wastewater treatment have been reported.Although can improve the reactive behavior of rice straw through pre-treatment, not only make the xylogen in rice straw, hemicelluloses etc. run off serious, and the black liquor of its generation has brought burden to a certain degree to environmental purification.
China is textile industry big country, and the dyeing and printing products total amount ranks first in the world.Dyeing waste water is very serious to the pollution of water body, and its processing is become more and more important.Utilize the flocculation agent treatment of dyeing and printing than additive method, cheapness to be arranged, easy to use, low power consuming and do not damage the advantage of dyestuff, therefore adopting flocculation decoloration technical finesse trade effluent is one of focus of research both at home and abroad at present, wherein quaternary cation flocculant has obtained people's very big concern.Product after the salinization of Mierocrystalline cellulose quaternary ammonium has good flocculating property, can be effectively applied to the processing of dyeing waste water.
The year unboiled water rice straw that the present invention is Mierocrystalline cellulose, lignin and hemicellulose to main component has carried out quaternised modified research, obtained water-soluble good cation-modified straw, be applied to the processing of active dye printing waste water, shown high percent of decolourization and COD clearance.The agent of modified straw flocculation agent is compared with other flocculation agent and is not only saved cost and resource, and provides an approach for the higher value application of discarded rice straw.
Summary of the invention
The purpose of this invention is to provide a kind of method of rice straw complete utilization modification synthetic organic polymer cationic flocculant and be applied to the technique for the treatment of of dyeing and printing, the method can make this " misplaced local " resource of rice straw be utilized, and it is low to have production cost, and dosage is few, technique is simple, the efficient advantages of higher.Reach more than 93% at any pH value scope percent of decolourization, the COD clearance surpasses 86%.
A kind of method of utilizing full rice straw to prepare quaternary cation flocculant and using its treatment of dyeing and printing provided by the invention comprises the following steps:
1. the synthetic method of full rice straw flocculation agent
Mass ratio by research straw quaterisation time, catalyst levels and modifying agent and straw is on the impact of the quaternized degree of modified product, and the modified-reaction condition that obtains optimization is as follows:
Catalyzer: NaOH, mass concentration is 1%; The mass ratio of rice straw powder and etherifying agent (glycidyl ester is abbreviated as GTMAc): 1: 9; Temperature of reaction: 85 ℃; Reaction times: 6h.
The quaternized degree of straw flocculation agent is determined with the silver nitrate solution potentiometric titration, regards straw as holocellulose in calculating.
Get 0.2g product 100mL deionized water dissolving, stir, with the AgNO of 0.01mol/L
3Solution is surveyed Cl by potentiometric titration
-Concentration, its quaternized degree (D) are pressed equation (1) and are calculated.
C:AgNO
3The concentration of solution, mo1/L
V:AgNO
3The volume of solution, mL
163: the molar mass of glucose unit, mol/g
M
1, M
2: be the quality of the straw before and after reaction, g
M: the quality of sample, g
Specific embodiments:
Embodiment 1
Be in the solution of 1%NaOH in the 50mL mass concentration, add rice straw powder 5.00g, etherifying agent 45.0g, react 6h under 85 ℃ of conditions, be cooled to room temperature, dropwise add HCl solution to neutral in mixed solution, add the 200mL dehydrated alcohol, product (quaternized straw) is separated out, suction filtration, and solid cleans four times with a small amount of dehydrated alcohol.Final product is stored in moisture eliminator with the rear sealing of vacuum drying oven oven dry.The quaternized degree of product is 97.1%.
Embodiment 2
Be in the solution of 1%NaOH in the 25mL mass concentration, add rice straw powder 2.50g, etherifying agent 22.5g, react 6h under 85 ℃ of conditions, be cooled to room temperature, dropwise add HCl solution to neutral in mixed solution, add the 100mL dehydrated alcohol, product (quaternized straw) is separated out, suction filtration, and solid cleans four times with a small amount of dehydrated alcohol.Final product is stored in moisture eliminator with the rear sealing of vacuum drying oven oven dry.The quaternized degree of product is 97.0%.
The synthetic straw quaternary ammonium salt that obtains all has good solvability in the aqueous solution of any pH value.FT-IR(KBr，cm
-1)：3400，2908，1636，1481，1110，1040，607.
2 full straw quaternary ammonium salt flocculants are processed active dye printing waste water:
(1) preparation of simulation printing and dyeing waste liquid: get reactive orange K-GN or the Reactive blue KN-R solution of 100mg/L, regulate dye liquor pH to analog value with rare HCl solution or NaOH solution.
(2) flocculation decoloration is processed: add a certain amount of straw quaternary ammonium salt flocculant in waste liquid, stir the mixture with the S212 constant speed stirrer.First stir soon 5min with the speed of 150rpm, slowly stir 10min with the speed of 50rpm again, after standing 3h, get supernatant liquid with syringe, use ultraviolet-visible pectrophotometer to measure supernatant liquid at the absorbancy at the maximum absorption wavelength 462nm place of reactive orange K-GN, by formula (2) calculating percent of decolourization.
A
0, the absorbancy of dye liquor before and after A represents respectively to decolour,
V
0, the volume of solution before and after V represents respectively to decolour.
Adopt National Standard Method (GB/T11914-1989) to measure the COD clearance of the rear water of dye liquor decolouring.
When 30mL concentration is in the reactive orange K-GN solution of 100mg/L, add 4mg straw quaternary ammonium salt flocculant, solution colour obviously changes after stir finishing, and in 20 minutes flocculation sediment fully.Percent of decolourization almost reaches 100% greater than 98%, COD clearance.The Reactive blue KN-R of same concentration under the same conditions also can rapid flocculation, percent of decolourization greater than 94%, COD clearance greater than 86%.
Specific embodiments
Embodiment 1
Get the dye liquor of 30mL preparation in Erlenmeyer flask, pH=7.Drop into synthetic flocculation agent 4mg, the speed of 150rpm stirs 5min, continues to stir 10min with the speed of 50rpm, after standing 3h, gets supernatant liquid, surveys its percent of decolourization and COD clearance.Reactive orange is respectively 98.01% and 99.4%; Reactive blue is respectively 94.1% and 86.3%.
Embodiment 2
Get the dye liquor of 30mL preparation in Erlenmeyer flask, pH=7.Drop into synthetic flocculation agent 3.2mg, the speed of 150rpm stirs 5min, continues to stir 10min with the speed of 50rpm, after standing 3h, gets supernatant liquid, records the reactive orange decolorization rate of wastewater and the COD clearance is respectively 92.23% and 98.6%.
Embodiment 3
Get the dye liquor of 30mL preparation in Erlenmeyer flask, pH=1.7.Drop into synthetic flocculation agent 4mg, the speed of 150rpm stirs 5min, continues to stir 10min with the speed of 50rpm, after standing 3h, gets supernatant liquid, records the reactive orange percent of decolourization and the COD clearance is respectively 98.81% and 99.9%.
Embodiment 4
Get the dye liquor of 30mL preparation in Erlenmeyer flask, pH=10.1.Drop into synthetic flocculation agent 4mg, the speed of 150rpm stirs 5min, continues to stir 10min with the speed of 50rpm, after standing 3h, gets supernatant liquid, records the reactive orange percent of decolourization and the COD clearance is respectively 98.21% and 99.7%.
Claims (2)
1. the preparation method of a straw quaternary cation flocculant, is characterized by: whole strain rice straw is crushed to 80 purpose straw powder; Be in the solution of 1%NaOH in the 25mL mass concentration, add straw powder 2.50g, etherifying agent glycidyl ester 22.5g, react 6h under 85 ℃ of conditions, be cooled to room temperature, dropwise add HCl solution to neutral in mixed solution, add the 100mL dehydrated alcohol, straw quaternary ammonium salt product is separated out, suction filtration, solid cleans four times with a small amount of dehydrated alcohol; Final product is stored in moisture eliminator with the rear sealing of vacuum drying oven oven dry; The quaternized degree that records straw quaternary ammonium salt product is 97%.
2. the treatment process of straw quaternary cation flocculant as claimed in claim 1 to active dye wastewater, it is characterized in that: dyestuff waste liquid is reactive orange K-GN or Reactive blue KN-R solution, its concentration is 100mg/L, the pH value of processing dyestuff waste liquid is 7, when processing dyestuff waste liquid amount is 30mL, dropping into straw quaternary cation flocculant amount is 4mg, the speed of 150 rev/mins stirs 5min, continuation is stirred 10min with the speed of 50 rev/mins, after standing 3h, get supernatant liquid, the percent of decolourization and the COD clearance that record reactive orange K-GN are respectively 98.01% and 99.4%, or the percent of decolourization of Reactive blue KN-R and COD clearance are respectively 94.1% and 86.3%.
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| CN102807275B (en) * | 2012-07-16 | 2013-08-14 | 三明学院 | Modified cellulose wastewater treatment flocculating agent and preparation method thereof |
| CN104310559B (en) * | 2014-11-10 | 2016-05-04 | 四川农业大学 | A kind of method of utilizing modified straw dye wastewater treatment using |
| CN105668738A (en) * | 2016-02-29 | 2016-06-15 | 济南大学 | Biomass coupling coagulant synthesized by vinegar residue |
| CN105731621A (en) * | 2016-02-29 | 2016-07-06 | 济南大学 | Biomass coupling coagulant aid synthesized by fungus chaffs and plantasan |
| CN107570122A (en) * | 2017-10-12 | 2018-01-12 | 南京信息工程大学 | A kind of difunctional hybrid material of biomass and preparation method and application |
| CN115957724B (en) * | 2023-03-17 | 2023-06-06 | 农业农村部环境保护科研监测所 | Preparation method and application of quaternary ammonium modified straw |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146999A (en) * | 1996-07-12 | 1997-04-09 | 清华大学 | Process for synthesis of lignin quaternary cation flocculant |
| CN101215033A (en) * | 2008-01-17 | 2008-07-09 | 南开大学 | Method for preparing ecological type composite flocculant by using straw |
| CN101342485A (en) * | 2008-07-03 | 2009-01-14 | 山东大学 | Method for preparing quaternary amines salt cationic adsorption agent with plant of high cellulose content |
-
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- 2011-06-04 CN CN 201110161944 patent/CN102295337B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146999A (en) * | 1996-07-12 | 1997-04-09 | 清华大学 | Process for synthesis of lignin quaternary cation flocculant |
| CN101215033A (en) * | 2008-01-17 | 2008-07-09 | 南开大学 | Method for preparing ecological type composite flocculant by using straw |
| CN101342485A (en) * | 2008-07-03 | 2009-01-14 | 山东大学 | Method for preparing quaternary amines salt cationic adsorption agent with plant of high cellulose content |
Non-Patent Citations (6)
| Title |
|---|
| Lifeng Yan etal.Synthesis and Flocculation Behavior of Cationic Cellulose Prepared in a NaOH/Urea Aqueous Solution.《clean》.2009,第37卷(第1期),第39-44页. |
| Synthesis and Flocculation Behavior of Cationic Cellulose Prepared in a NaOH/Urea Aqueous Solution;Lifeng Yan etal;《clean》;20090131;第37卷(第1期);第39-44页 * |
| 利用秸秆木质素制备阳离子絮凝剂的研究;罗渊;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20100215(第02期);第B027-193页 * |
| 叶健等.秸秆制备絮凝剂的研究.《皮革化工》.2006,第23卷(第5期),第42-44页. |
| 秸秆制备絮凝剂的研究;叶健等;《皮革化工》;20061031;第23卷(第5期);第42-44页 * |
| 罗渊.利用秸秆木质素制备阳离子絮凝剂的研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2010,(第02期),第B027-193页. |
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