CN102898535A - Preparation method and application of H-polysaccharide carboxymethyl oleoyl derivatives for oily sewage treatment - Google Patents
Preparation method and application of H-polysaccharide carboxymethyl oleoyl derivatives for oily sewage treatment Download PDFInfo
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Abstract
The invention discloses a preparation method and application of H-polysaccharide carboxymethyl oleoyl derivatives for oily sewage treatment. The preparation method comprises the following steps: (1) adding carboxymethyl polysaccharide and anhydrous acetone into a reaction vessel; (2) evenly mixing oleoyl chloride solution and anhydrous acetone in a volume ratio of 1:1; (3) dropwisely adding the mixed solution obtained in the step (2) into the reaction vessel in the step (1), and meanwhile, adding an NaOH solution with equal volume to the mixed solution in the step (2), thereby obtaining Na-carboxymethyl oleoyl polysaccharide; (4) respectively adding the Na-carboxymethyl oleoyl polysaccharide, an ethanol solution and concentrated hydrochloric acid into another reaction vessel; and after the reaction finishes, filtering, desalting, deacidifying, dehydrating, and drying to obtain the H-carboxymethyl oleoyl polysaccharide. The method has the advantages of simple preparation technique, wide raw material sources and favorable oily sewage treatment effect; the removal rate of residual oil in the sewage is higher than 90%, and the removal rate of suspended substances in the oily sewage system is up to 95%; and thus, the invention can be widely used in oily sewage treatment.
Description
Technical field
The present invention relates to the environmental protection product technical field, be specifically related to preparation method and the application of a kind of H type for oily water treatment-polyose carboxymethyl oleoyl derivative.
Background technology
Along with the development of petrochemical industry, water pollution problems is day by day serious, processes trade effluent extremely urgent, and particularly the processing of oily(waste)water is the difficulties of wastewater treatment.Oily(waste)water is mainly derived from the industrial sectors such as oil, petrochemical complex, iron and steel, coking, gas generating station, mechanical workout.Realize the oily(waste)water harmless treatment, various physics, chemistry and biological means have been used for removing being dispersed in the particles in solution material, colloid in the processing oily(waste)water and a kind of important means of particulate matter are used flocculation agent exactly, and flocculation agent is divided into inorganic flocculating agent, microbial flocculant and polymeric flocculant.
Inorganic water treatment flocculant (such as polymerize aluminum chloride, bodied ferric sulfate etc.), shortcoming: the flocculation scale of construction is large, and sedimentation speed is slow, the dehydration difficulty; The metal ion that remains in the water has potential harm to HUMAN HEALTH; The water treatment effect low to temperature, that turbidity is low is poor; Place to go weak effect to the organism micropollutant.
Polymeric flocculant is divided into two kinds of synthetic macromolecule and natural polymers, wherein synthetic polymeric flocculant mainly is poly-propionic acid amide and derivative thereof, although the poly-propionic acid amide of polymerization is environment-friendly property material fully, but its polymerization single polymerization monomer acrylamide has strong neurotoxicity, and be strong carcinogens, so the poly-application of propionic acid amide in oily water treatment of the residue problem of monomer restriction in the polymerization process.
Natural macromolecule flocculating agent is extensive because of raw material sources, and environmental friendliness is without potential safety hazard, cheap, nontoxic, be easy to the characteristics such as biological degradation, shown good application prospect, wherein the natural polysaecharides material is as natural polymer, because its abundant reserves become study hotspot day by day.Polysaccharose substance refers to and is widespread in nature, and is the general name of the polymer condenses of various monose.Common polysaccharose substance has Mierocrystalline cellulose and starch.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of H type for oily water treatment-polyose carboxymethyl oleoyl derivative.It is simple that the method has preparation technology, and cost is low, wide accommodation, the advantage such as raw material sources are wide, cheap.
Another object of the present invention provides a kind of H type-application of polyose carboxymethyl oleoyl derivative in oily water treatment.
For achieving the above object, the invention provides the preparation method of a kind of H type for oily water treatment-polyose carboxymethyl oleoyl derivative, its preparation process may further comprise the steps:
Step 1: the ratio of 1:15～20 adds carboxymethyl polysaccharide and anhydrous propanone in mass ratio in the reaction vessel, and wherein the carboxymethyl polysaccharide add-on is 10 g～15 g, and temperature of reaction system is 1 ℃～5 ℃, stirs swelling 2 hours;
Step 2: be that 1:1 evenly mixes with oleoyl chloride solution according to volume ratio with anhydrous propanone, oleoyl chloride solution and anhydrous propanone add-on are respectively 20 mL～25 mL;
Step 3: the mixed solution that step 2 is obtained is added drop-wise in the reaction vessel in the step 1, be 8.0 %～10.0 % NaOH solution to wherein adding the mass concentration that equates with the step 2 mixeding liquid volume simultaneously, temperature in the reaction vessel is controlled at 1 ℃～5 ℃, in 4 hours～6 hours reaction times, namely make Na type-carboxymethyl oleoyl polysaccharide;
Step 4: in another reaction vessel, add respectively the Na type that step 3 makes-carboxymethyl oleoyl polysaccharide 1 g, mass concentration is ethanolic soln 100 ml of 80.0 %, mass concentration is concentrated hydrochloric acid 10 ml of 37 %, temperature is controlled to be 50 ℃ in the reaction vessel, reaction times is 30 minutes, reaction is finished afterreaction liquid and is filtered, and filter cake is through desalination, depickling and processed, then dries to such an extent that namely make H type-carboxymethyl oleoyl polysaccharide.
Carboxymethyl polysaccharide is the carboxymethyl derivant of natural polysaccharide in the described step 2, and degree of substitution by carboxymethyl is 30 % ~ 70 %.
Oleoyl chloride solution is prepared from by phosphorus trichloride and oleic acid in the described step 2, its preparation process is: be that phosphorus trichloride solution more than 99.0% slowly is added drop-wise in the oleic acid with mass percent, the volume ratio of phosphorus trichloride solution and oleic acid is 1:3 ~ 6, temperature of reaction is 50 ℃ ~ 65 ℃, in 1 hour ~ 2 hours reaction times, obtain oleoyl chloride solution after the reaction.
Rate of addition is 1 drops/sec ~ 3 drops/secs in the described step 3, and should dropwise in 0.5 hour.
Desalination and depickling in the described step 4 refer to mass concentration to be 70.0% ethanolic soln desalination, depickling.
Dewater in the described step 4, refer to mass concentration to be the ethanolic soln dehydration of 95.0 %.
Another aspect of the present invention also provides a kind of H type-polyose carboxymethyl oleoyl derivative treatment process in oily(waste)water, and the method may further comprise the steps:
(1) oily(waste)water is added agitated pool, oleaginousness is lower than 200.0 mg/L in the waste water, wastewater pH＜8.0;
(2) the preparation mass concentration is 0.1 g/L ~ 0.3 g/L H type-carboxymethyl oleoyl polysaccharide soln, add in the agitated pool that adds oily(waste)water and prepare H type-carboxymethyl oleoyl polysaccharide soln, H type-carboxymethyl oleoyl polysaccharide soln and oily(waste)water volume ratio are 1:9 ~ 10, and churning time is more than 15 minutes.
Compared with prior art, the present invention has following advantage and beneficial effect:
(1) desired raw material wide material sources, environmental friendliness, without potential safety hazard, cheap;
(2) product belongs to the natural polysaccharide product, and is biodegradable, nontoxic, harmless, can not cause environmental pollution;
(3) oily water treatment is effective, and remaining the oil removal efficiency is higher than 90 % in the sewage, and oily(waste)water system removal efficiency can reach 95 %.
Embodiment
The present invention will be described in detail below in conjunction with specific embodiment.
Embodiment 1
(1) preparation of H type-polyose carboxymethyl oleoyl derivative
At first in the there-necked flask with 500 ml of agitator, drop into 10 g carboxymethyl celluloses and 150 g anhydrous propanones, temperature stirred swellings 2 hours under 5 ℃, secondly, drip the oleoyl chloride of 20ml and the mixed solution solution of 20 ml anhydrous propanones according to 2 drops/secs speed, the mass concentration that adds 40 ml is the NaOH solution of 8.0 %, the system temperature of reaction is 5 ℃, 5 hours reaction times, obtain the Na type of solid powdery-carboxymethyl oleoyl polysaccharide, then, in another there-necked flask, the Na type of adding solid powdery-carboxymethyl oleoyl polysaccharide 1 g, mass concentration is 80 % ethanolic solns, 100 ml, and mass concentration is 37 % concentrated hydrochloric acids, 10 ml, 50 ℃ of temperature of reaction, 0.5 hour reaction times, reaction times with reacted solution filter, is the ethanolic soln desalination of 70.0 % with mass concentration after finishing, depickling, ethanolic soln dehydration with 95.0 % namely makes H type-carboxymethyl oleoyl polysaccharide after the oven dry.
(2) flocculating experiment
Get Gudao area of Shengli Oilfield oil recovery factory oily(waste)water 1000 ml, oleaginousness is 131.2 mg/L in the sewage after testing, suspension content is 96.8 mg/L, pH 7.5, add mass concentration and be 0.3 % volume and be 100ml according to the H type of above-mentioned steps preparation-carboxymethyl oleoyl polysaccharide soln, churning time 0.5 hour, oleaginousness 10.2 mg/L in the oily(waste)water after processing after measured, crude oil removal reaches 92.3 %, and suspension content is 4.2 mg/L, and removal efficiency is 95.7 %.
Embodiment 2
(1) preparation of H type-polyose carboxymethyl oleoyl derivative
At first in the there-necked flask with 500 ml of agitator, drop into 12g carboxymethyl cellulose and 240 g anhydrous propanones, temperature stirred swelling 2 hours under 1 ℃, secondly, drip the oleoyl chloride of 25 ml and the mixed solution solution of 25 ml anhydrous propanones according to 1 drops/sec speed, the mass concentration that adds 50 ml is the NaOH solution of 9.0 %, the system temperature of reaction is 2 ℃, 4 hours reaction times, obtain the Na type of solid powdery-carboxymethyl oleoyl polysaccharide, then, in another there-necked flask, the Na type of adding solid powdery-carboxymethyl oleoyl polysaccharide 1g, mass concentration is 80% ethanolic soln, 100 ml, and mass concentration is 37 % concentrated hydrochloric acids, 10 ml, 50 ℃ of temperature of reaction, 0.5 hour reaction times, reaction times with reacted solution filter, is the ethanolic soln desalination of 70.0 % with mass concentration after finishing, depickling, ethanolic soln dehydration with 95.0 % namely makes H type-carboxymethyl oleoyl polysaccharide after the oven dry.
(2) flocculating experiment
Get Gudao area of Shengli Oilfield oil recovery factory oily(waste)water 1000 ml, oleaginousness is 168.2 mg/L in the sewage after testing, suspension content is 192.8 mg/L, pH 7.2, add mass concentration and be 0.1% volume and be 110 ml according to the H type of above-mentioned steps preparation-carboxymethyl oleoyl polysaccharide soln, churning time 1.5 hours, oleaginousness 12.6 mg/L in the oily(waste)water after processing after measured, clearance reaches 92.5 %, and suspension content is 9.5 mg/L, and clearance is 95.1 %.
Embodiment 3
(1) preparation of H type-polyose carboxymethyl oleoyl derivative
At first in the there-necked flask with 500 ml of agitator, drop into 15g carboxymethyl cellulose and 250g anhydrous propanone, temperature stirred swellings 2 hours under 2 ℃, secondly, drip the oleoyl chloride of 23 ml and the mixed solution solution of 23 ml anhydrous propanones according to 3 drops/secs speed, the mass concentration that adds 46 ml is the NaOH solution of 10.0 %, the system temperature of reaction is 1 ℃, 6 hours reaction times, obtain the Na type of solid powdery-carboxymethyl oleoyl polysaccharide, then, in another there-necked flask, the Na type of adding solid powdery-carboxymethyl oleoyl polysaccharide 1 g, mass concentration is 80 % ethanolic solns, 100 ml, and mass concentration is 37 % concentrated hydrochloric acids, 10 ml, 50 ℃ of temperature of reaction, reaction times 0.5 h, after reaction times finishes, with reacted solution filter, be 70.0% ethanolic soln desalination with mass concentration, depickling, ethanolic soln dehydration with 95.0% namely makes H type-carboxymethyl oleoyl polysaccharide after the oven dry.
(2) flocculating experiment
Get Gudao area of Shengli Oilfield oil recovery factory oily(waste)water 1000 ml, oleaginousness is 131.2 mg/L in the sewage after testing, suspension content is 156.3 mg/L, pH 7.6, add mass concentration and be 0.2% volume and be 100ml according to the H type of above-mentioned steps preparation-carboxymethyl oleoyl polysaccharide soln, churning time 2.5h, oleaginousness 4.7 mg/L in the oily(waste)water after processing after measured, clearance reaches 96.4 %, and suspension content is 7.3 mg/L, and clearance is 95.3 %.
Claims (7)
1. the preparation method of the H type that is used for oily water treatment-polyose carboxymethyl oleoyl derivative, its preparation process may further comprise the steps:
(1), the ratio of 1:15～20 adds carboxymethyl polysaccharide and anhydrous propanone in mass ratio in the reaction vessel, wherein the carboxymethyl polysaccharide add-on is 10g～15g, and temperature of reaction system is 1 ℃～5 ℃, stirs swelling 2 hours;
(2), be that 1:1 evenly mixes with oleoyl chloride solution according to volume ratio with anhydrous propanone, oleoyl chloride solution and anhydrous propanone add-on are respectively 20 mL～25mL;
(3), the mixed solution that step (2) is obtained is added drop-wise in the reaction vessel in the step (1), be 8.0%～10.0 % NaOH solution to wherein adding the mass concentration that equates with step (2) mixeding liquid volume simultaneously, temperature in the reaction vessel is controlled at 1～5 ℃, in 4 hours～6 hours reaction times, namely make Na type-carboxymethyl oleoyl polysaccharide;
(4), in another reaction vessel, add respectively the Na type that step (3) makes-carboxymethyl oleoyl polysaccharide 1 g, mass concentration is ethanolic soln 100 ml of 80.0 %, mass concentration is 37% concentrated hydrochloric acid 10 ml, temperature is controlled to be 50 ℃ in the reaction vessel, reaction times is 30 minutes, reaction is finished afterreaction liquid and is filtered, and filter cake is through desalination, depickling and processed, then dries to such an extent that namely make H type-carboxymethyl oleoyl polysaccharide.
2. preparation method according to claim 1 is characterized in that carboxymethyl polysaccharide is the carboxymethyl derivant of natural polysaccharide in the described step (2), and degree of substitution by carboxymethyl is 30 % ~ 70 %.
3. preparation method according to claim 1 and 2, it is characterized in that oleoyl chloride solution is prepared from by phosphorus trichloride and oleic acid in the described step (2), its preparation process is: be that phosphorus trichloride solution more than 99.0 % slowly is added drop-wise in the oleic acid with mass percent, the volume ratio of phosphorus trichloride solution and oleic acid is 1:3 ~ 6, temperature of reaction is 50 ℃ ~ 65 ℃, in 1 ~ 2 hour reaction times, obtain oleoyl chloride solution after the reaction.
4. preparation method according to claim 1 is characterized in that rate of addition is 1 drops/sec ~ 3 drops/secs in the described step (3), and should dropwise in 0.5 hour.
5. preparation method according to claim 1 is characterized in that the middle desalination of described step (4) and depickling refer to mass concentration to be ethanolic soln desalination, the depickling of 70.0 %.
6. preparation method according to claim 1 or 5, its feature is dewatered in described step (4) refers to mass concentration to be the ethanolic soln dehydration of 95.0 %.
7.1-6 the H type of arbitrary claim preparation-polyose carboxymethyl oleoyl derivative treatment process in oily(waste)water, the method may further comprise the steps:
(1), oily(waste)water is added agitated pool, oleaginousness is lower than 200.0 mg/L in the waste water, wastewater pH＜8.0;
(2), the preparation mass concentration is 0.1 g/L ~ 0.3 g/L H type-carboxymethyl oleoyl polysaccharide soln, add in the agitated pool that adds oily(waste)water and prepare H type-carboxymethyl oleoyl polysaccharide soln, H type-carboxymethyl oleoyl polysaccharide soln and oily(waste)water volume ratio are 1:9 ~ 10, and churning time is more than 15 minutes.
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| CN107879447A (en) * | 2017-12-25 | 2018-04-06 | 宁波科邦华诚技术转移服务有限公司 | A kind of preparation method for being used to handle oil-polluted water flocculant |
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| CN1594366A (en) * | 2004-07-12 | 2005-03-16 | 天津大学 | Oil soluble O-chitosan derivatives and their preparation and use |
| EP2033934A1 (en) * | 2006-06-14 | 2009-03-11 | National Institute Of Advanced Industrial Science and Technology | Hollow-fiber-like organic nanotube and process for production thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107879447A (en) * | 2017-12-25 | 2018-04-06 | 宁波科邦华诚技术转移服务有限公司 | A kind of preparation method for being used to handle oil-polluted water flocculant |
| CN107879447B (en) * | 2017-12-25 | 2020-09-08 | 菏泽衡巽环保科技有限公司 | Preparation method of flocculant for treating oily sewage |
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Inventor after: Sun Gangzheng Inventor after: Guan Mengmeng Inventor after: Zhang Shouxian Inventor after: Song Xin Inventor after: Ba Yan Inventor after: Wang Jing Inventor after: Pan Yongqiang Inventor after: Cao Gongze Inventor after: Wu Xiaoling Inventor after: Duan Chuanhui Inventor after: Xu Dengting Inventor before: Sun Gangzheng Inventor before: Duan Chuanhui Inventor before: Chen Xiguang Inventor before: Guan Mengmeng Inventor before: Guo Shengxue Inventor before: Guo Liaoyuan Inventor before: Song Zhiyong Inventor before: Li Caifeng Inventor before: Hao Bin Inventor before: Wu Xiaoling |
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Free format text: CORRECT: INVENTOR; FROM: SUN GANGZHENG CHEN XIGUANG GUAN MENGMENG GUO SHENGXUE GUO LIAOYUAN SONG ZHIYONG LI CAIFENG HAO BIN WU XIAOLING DUAN CHUANHUI TO: SUN GANGZHENG SONG XIN BA YAN WANG JING PAN YONGQIANG CAO GONGZE WU XIAOLING DUAN CHUANHUI XU DENGTING GUAN MENGMENG ZHANG SHOUXIAN |
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