CN101974866B - Method for preparing flocculant for treating papermaking black liquor by using waste collagen - Google Patents
Method for preparing flocculant for treating papermaking black liquor by using waste collagen Download PDFInfo
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- CN101974866B CN101974866B CN2010102799167A CN201010279916A CN101974866B CN 101974866 B CN101974866 B CN 101974866B CN 2010102799167 A CN2010102799167 A CN 2010102799167A CN 201010279916 A CN201010279916 A CN 201010279916A CN 101974866 B CN101974866 B CN 101974866B
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Abstract
The invention discloses a method for preparing a flocculant for treating papermaking black liquor by using waste collagen. The method comprises the following steps of: soaking waste scurf in water at room temperature; adding protease and performing enzymolysis at the temperature of between 45 and 50 DEG C; performing stirring reaction under the condition of the pH of between 4.0 and 4.5 and the temperature of between 70 and 90 DEG C; cooling to the temperature of between 50 and 60 DEG C, adding a cationization agent for stirring reaction when the pH is between 8.0 and 8.5, and filtering, washing, drying, and crushing to prepare the flocculant. The flocculant prepared by the method of the invention achieves a larger adsorption ratio surface area, and can be more widely combined with hydroxyls, sulfo groups and the like of hemicellulose and lignin in the papermaking black liquor so as to promote soluble pollutants in the black liquor to be separated, adsorbed and precipitated, and thus, the overall treatment efficiency of the black liquor is improved and a treatment period of the black liquor is shortened greatly. In the invention, the price of raw materials is low, the preparation process is simple, the operability is high, the promotion is easy, the production cost is low, and thus, the method has a good market prospect.
Description
Technical field
The invention belongs to preparation and handle the technical field of waste water flocculant, be specifically related to a kind of with the former method of handling the black liquid flocculant for preparing of scrap rubber.
Background technology
China's paper-making industry extensively adopts soda pulping process, is about to raw material in sodium hydroxide lye, carry out boiling under 150 ℃ of conditions, and black liquor just is meant the raffinate of separating after the boiling from paper pulp.With 1 ton of paper pulp of the every production of this method, produce 10 tons of this black liquor approximately.Black liquor belongs to the high pollution organic liquid waste, wherein not only contain polyhydroxy organic matters such as hemicellulose, alkali lignin, and its chemical oxygen demand COD is often up to hundreds thousand of mg/litre.As with black liquor of pulp making not treated and directly the discharging, can cause severe contamination to environment undoubtedly, Just because of this, people make great efforts seeking the governance way of black liquor always for many years.
At present, though technology such as alkali recovery, acid out, biochemistry, film processing are adopted in the improvement for black liquor of report mostly both at home and abroad, but processing method real economic and that have industrial applications potentiality should be a chemical flocculation and the combining of Biochemical Engineering, and in this combination treatment method, be the key link (Lan Zequan very as the pretreated flocculation sediment of biochemistry, Ma Hanpeng. administration of papermaking black liquid utilizes the state of the art. Treatment of Industrial Water, 2008,28:9-13).Existing flocculant---polyaluminium salts and the polymeric ferric salt that is widely used in the sanitary wastewater processing, though can precipitate the suspended contaminant in the sanitary wastewater effectively, but medicament expense is with higher on the one hand, account for 50% of processing cost, on the other hand owing to most pollutants in the black liquid are to exist with dissolved state, so inorganic flocculating agents such as conventional aluminium salt and molysite are difficult to form floccule body with it,, can not effectively reduce the contaminated wastewater load so sedimentation effect is relatively poor.Just because of this, in the flocculation sediment of black liquid was handled, people were to efficient cheap flocculant, particularly to very interested based on the flocculant of organic polymer research and development.
Leather production can produce a large amount of scrap leather bits inevitably.According to statistics, this class scrap leather bits account for that process hides raw material skin total amount is nearly 30%, and promptly the world will produce more than 60 ten thousand tons of this type of materials every year, and wherein collagen content accounts for 80-90% greatly.At present these collagens remove seldom that a part is used for producing regenerated leather, and all the other great majority all are to handle as rubbish, and this both can cause environmental pollution, was again a kind of huge waste to resource.
Even so, the scrap rubber that does not also come from the tanning production generation at present prepared the report of flocculation material originally, did not more have this kind flocculation material is used for the precipitation process black liquid, effectively reduced the report of the processing load of later stage Biochemical Engineering.
Summary of the invention
The objective of the invention is the former utilization of scrap rubber at the deficiencies in the prior art and tanning production generation, and a kind of former method of handling the black liquid flocculant for preparing of scrap rubber of using that provides.
The inventor finds in the process of the organic polymer coargulator of research and development processing black liquid, the scrap leather bits that tanning production produces are to be entwined by the multiply collagenous fibres, and also contain on the collagen can with a large amount of active groups of a lot of material generation chemical actions, as carboxyl, amino, peptidyl etc., if can open and disperse these fibers by the physics and chemistry processing mode, just can obtain to have adsorbing huge specific area, a large amount of active groups of its existence perhaps can promote flocculation of solubilised state pollutant and precipitation in the water body.Also can carry out some chemical modifications to it in addition, make it obtain some characteristic,, make electric charge opposite on the collagen band, can efficiently pollutant adsorption-flocculation precipitation be removed by charge effect with pollutant in the water body as the electrophilic characteristic.Therefore, with the inexpensive flocculation material efficiently of the original preparation of the scrap rubber that comes from tanning production, analytically be practicable not only in theory, and through inventor's research and development, search out a kind of like this preparation method and can reach purpose of the present invention, the processing step and the condition of this method are as follows:
1) 50～100 parts of scrap leather bits is added in 200～300 parts of water, soak at room temperature 8～12 hours, adding 0.3～0.8 part of protease then, in 45～50 ℃ of stirring reactions of temperature 3～5 hours, is stirring reaction 2～3 hours under 4.0～4.5 and 70～90 ℃ of conditions at pH again;
2) be cooled to 50～60 ℃, behind adjust pH to 8.0～8.5, add 0.8～2.0 part of quaternary ammonium salt cation agent, stirring reaction 6～8 hours filters, and flushing with clean water is to the no obvious residue in collagen flocculant surface, drying is 6～8 hours under 50～60 ℃, is crushed to 0.1～0.15mm and gets final product
More than the umber of each material be weight portion.
Used protease is any in papain, 2709 protease, bromelain, 537 acid proteases, 1398 protease or the trypsase in the above method.Wherein preferred 2709 protease, 1398 protease or trypsase, more preferably 2709 protease.
Used quaternary ammonium salt cation agent is any in 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl triethyl ammonium chloride or the 3-chloro-2-hydroxypropyl trihydroxyethyl ammonium chloride in the above method.
Protease, quaternary ammonium salt cation agent used in the above method are industrialization reagent.
Prepared flocculant can use separately, also can act synergistically on absorption, flocculation, the precipitation process of black liquid with other flocculants (as polyaluminium chloride).
The present invention has following advantage:
1, because the inventive method has adopted technologies such as immersion, enzymolysis and pulverizing, collagenous fibres in the scrap leather bits have been carried out abundant dispersion, make it have bigger specific area, thereby when handling black liquid, provide big adsorption plane for absorb polluted matter, both be convenient to pollutant and adsorbed better, also be convenient to pollutant better with the flocculant reaction precipitation.
2, because the specific area of the macromolecule collagen flocculant of the present invention's preparation is big, its carboxyl that contains, amino, peptidyl isoreactivity group expose manyly, thereby make them more widely by modes such as ionic bond, hydrogen bond or hydrophobic bonds, combine with the hydroxyl of hemicellulose in the black liquid and lignin, sulfonic group etc., impel in the black liquor solubility pollutant to separate out, adsorb and be precipitated out.
3, because the specific area of the macromolecule collagen flocculant of the present invention's preparation is big, its carboxyl that contains, amino, peptidyl isoreactivity group expose manyly, also flocculant has been carried out cation modifying among the preparation technology in addition, thereby make flocculant have positive charge, in order to black liquid in many pollutants that exist with the anion state produce and interact, promote the precipitation of pollutant to remove.
4, because macromolecule collagen flocculant provided by the invention can effectively reduce the pollutional load of black liquid, thereby make the later stage Biochemical Engineering of black liquid be easy to processing up to standard, improve the overall process efficiency of black liquor, shorten its improvement cycle greatly.
5, because the used main raw material scrap leather of the present invention is considered to be worth doing cheap, other chemical reagent also is homemade, wide material sources, whole process of preparation is simple in addition, strong operability, thereby not only production cost is low, has very strong price competitiveness, and also be easy to promote, have good market prospects.
6, because papermaking and process hides are two big pollution sources of light industry; the present invention is based on the principle of " treatment of wastes with processes of wastes against one another "; prepare the flocculant of handling black liquid with tanning waste; thereby the national environmental protection and the strategy of sustainable development had both been met; avoid the waste of environmental pollution and resource, sought a kind of new organic polymer coargulator for administering black liquid again.
Description of drawings
Fig. 1 is the infrared spectrum of the collagen base black liquid flocculant of the embodiment of the invention 1 preparation, 970cm among the figure
-1, 931cm
-1, 898cm
-1, 867cm
-1Be the characteristic peak of cationization, this explanation cationization effect is obvious, and this flocculant is cationic product.
Fig. 2 is the sem photograph of the collagen base black liquid flocculant of the embodiment of the invention 1 preparation, and the scale ratio is 10 μ m, disperses from the visible prepared flocculant structure of this figure, has bigger specific area.
Fig. 3 is the sem photograph of the collagen base black liquid flocculant of the embodiment of the invention 1 preparation, and the scale ratio is 2 μ m, as can be seen from this figure the particle characteristic on flocculant surface behind the cationization.
The specific embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
In addition, be worth this explanation be, below among each embodiment the umber of used material be weight portion; That the mensuration of the chemical oxygen demand of waste water COD of each application examples adopts is national standard method-potassium dichromate method (GB11914-1989), and its clearance is to calculate by the variation of waste water COD concentration before and after the precipitation.
Embodiment 1
50 parts of useless pigskins bits were added in 200 parts of water soak at room temperature 9 hours, change in the reactor that has agitator and thermometer, add 0.3 part of 2709 protease then, in 45 ℃ of stirring reactions of temperature 3.5 hours, stirring reaction 2～3 hours under pH 4.0 and 70～75 ℃ of conditions again; Be cooled to 55 ℃, behind the adjust pH to 8.0, add 0.8 part of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, stirring reaction 7 hours filters, and flushing with clean water is to the no obvious residue in collagen flocculant surface, and drying is 8 hours under 50 ℃, is crushed to 0.1～0.15mm and gets final product.
The infrared spectrum of prepared pig skin gelatin original hase black liquid flocculant as shown in Figure 1, its sem photograph is shown in Fig. 2,3.
60 parts of useless ox-hides bits were added in 250 parts of water soak at room temperature 12 hours, change in the reactor that has agitator and thermometer, add 0.6 part of 2709 protease then, in 50 ℃ of stirring reactions of temperature 4 hours, stirring reaction 2.5 hours under pH 4.5 and 80～85 ℃ of conditions again; Be cooled to 60 ℃, behind the adjust pH to 8.5, add 1.1 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, stirring reaction 8 hours filters, and flushing with clean water is to the no obvious residue in collagen flocculant surface, and drying is 8 hours under 50 ℃, is crushed to 0.1～0.15mm and gets final product.
Embodiment 3
70 parts of useless sheepskins bits were added in 250 parts of water soak at room temperature 8 hours, change in the reactor that has agitator and thermometer, add 0.5 part of 2709 protease then, in 47 ℃ of stirring reactions of temperature 3 hours, stirring reaction 2.5 hours under pH 4.0 and 75～80 ℃ of conditions again; Be cooled to 55 ℃, behind the adjust pH to 8.3, add 1.2 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, stirring reaction 6 hours filters, and flushing with clean water is to the no obvious residue in collagen flocculant surface, and drying is 7 hours under 55 ℃, is crushed to 0.1～0.15mm and gets final product.
Embodiment 4
80 parts of useless pigskins bits were added in 265 parts of water soak at room temperature 10 hours, change in the reactor that has agitator and thermometer, add 0.6 part of 1398 protease then, in 50 ℃ of stirring reactions of temperature 4 hours, stirring reaction 2 hours under pH 4.0 and 70～75 ℃ of conditions again; Be cooled to 52 ℃, behind the adjust pH to 8.0, add 1.5 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, stirring reaction 6 hours filters, and flushing with clean water is to the no obvious residue in collagen flocculant surface, and drying is 8 hours under 50 ℃, is crushed to 0.1～0.15mm and gets final product.
Embodiment 5
90 parts of useless pigskins bits were added in 280 parts of water soak at room temperature 10 hours, change in the reactor that has agitator and thermometer, add 0.5 part of 537 acid protease then, in 50 ℃ of stirring reactions of temperature 5 hours, stirring reaction 2 hours under pH 4.5 and 80～85 ℃ of conditions again; Be cooled to 50 ℃, behind the adjust pH to 8.0, add 1.6 parts of 3-chloro-2-hydroxypropyl triethyl ammonium chlorides, stirring reaction 6.5 hours filters, and flushing with clean water is to the no obvious residue in collagen flocculant surface, drying is 6 hours under 60 ℃, is crushed to 0.1～0.15mm and gets final product.
Embodiment 6
100 parts of useless pigskins bits were added in 300 parts of water soak at room temperature 11 hours, change in the reactor that has agitator and thermometer, add 0.8 part of trypsase then, in 50 ℃ of stirring reactions of temperature 4.5 hours, stirring reaction 2.5 hours under pH 4.2 and 75～80 ℃ of conditions again; Be cooled to 50 ℃, behind the adjust pH to 8.0, add 2.0 parts of 3-chloro-2-hydroxypropyl trihydroxyethyl ammonium chlorides, stirring reaction 7 hours filters, and flushing with clean water is to the no obvious residue in collagen flocculant surface, drying is 6 hours under 60 ℃, is crushed to 0.1～0.15mm and gets final product.
Embodiment 7
With soak at room temperature in 80 parts of useless pigskins bits and 300 parts of water of 20 parts of useless ox-hide bits addings 12 hours, change in the reactor that has agitator and thermometer, add 0.7 part of 2709 protease then, in 48 ℃ of stirring reactions of temperature 5 hours, stirring reaction 3 hours under pH 4.5 and 85～90 ℃ of conditions again; Be cooled to 58 ℃, behind the adjust pH to 8.5, add 1.8 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, stirring reaction 6.5 hours filters, and flushing with clean water is to the no obvious residue in collagen flocculant surface, drying is 6 hours under 60 ℃, is crushed to 0.1～0.15mm and gets final product.
Embodiment 8
With soak at room temperature in 20 parts of useless pigskins bits and 300 parts of water of 80 parts of useless ox-hide bits addings 12 hours, change in the reactor that has agitator and thermometer, add 0.8 part of trypsase then, in 50 ℃ of stirring reactions of temperature 5 hours, stirring reaction 3 hours under pH 4.5 and 85～90 ℃ of conditions again; Be cooled to 60 ℃, behind the adjust pH to 8.0, add 2.0 parts of 3-chloro-2-hydroxypropyl triethyl ammonium chlorides, stirring reaction 7.5 hours filters, and flushing with clean water is to the no obvious residue in collagen flocculant surface, drying is 7 hours under 58 ℃, is crushed to 0.1～0.15mm and gets final product.
Embodiment 9
With soak at room temperature in 50 parts of useless pigskins bits and 300 parts of water of 50 parts of useless ox-hide bits addings 12 hours, change in the reactor that has agitator and thermometer, add 0.7 part of 1398 protease then, in 50 ℃ of stirring reactions of temperature 4.5 hours, stirring reaction 3 hours under pH 4.0 and 85～90 ℃ of conditions again; Be cooled to 60 ℃, behind the adjust pH to 8.5, add 1.8 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, stirring reaction 8 hours filters, and flushing with clean water is to the no obvious residue in collagen flocculant surface, and drying is 8 hours under 50 ℃, is crushed to 0.1～0.15mm and gets final product.
Application examples 1
(straw pulp black liquor pH 11.3, chemical oxygen demand COD 22600mg/L) puts into graduated cylinder with 500mL stalk black liquid, under slow stirring condition, drips 10% volumetric concentration salt acid for adjusting pH value to 5.0; The flocculant of 1.0g embodiment 1 preparation is disperseed with low amounts of water earlier, add then in the graduated cylinder, slowly stirred 1 minute, left standstill 1.5 hours, get supernatant and measure its chemical oxygen demand COD.The COD clearance is 53% as calculated.
Application examples 2
(pulp black liquor pH 11.0, chemical oxygen demand COD 8500mg/L) puts into graduated cylinder with 500mL wood pulp papermaking black liquor, under slow stirring condition, drips 10% volumetric concentration salt acid for adjusting pH value to 5.5; The flocculant of 1.0g embodiment 2 preparations is disperseed with low amounts of water earlier, add then in the graduated cylinder, slowly stirred 1 minute, left standstill 1.5 hours, get supernatant and measure its chemical oxygen demand COD.The COD clearance is 58% as calculated.
Application examples 3
(pulp black liquor pH 11.0, chemical oxygen demand COD 8500mg/L) puts into graduated cylinder with 500mL wood pulp papermaking black liquor, under slow stirring condition, drips 10% volumetric concentration salt acid for adjusting pH value to 5.0; The flocculant of 1.2g embodiment 3 preparations is disperseed with low amounts of water earlier, add then in the graduated cylinder, slowly stirred 1 minute, left standstill 1.5 hours, get supernatant and measure its chemical oxygen demand COD.The COD clearance is 64% as calculated.
Application examples 4
(straw pulp black liquor pH 11.3, chemical oxygen demand COD 22600mg/L) puts into graduated cylinder with 500mL stalk black liquid, under slow stirring condition, drips 10% volumetric concentration salt acid for adjusting pH value to 7.8; Dripping concentration again is the polyaluminium chloride solution 15mL of 15g/L, slowly stirs 30 seconds; The flocculant of 1.2g embodiment 1 preparation is disperseed with low amounts of water earlier, add then in the graduated cylinder, slowly stirred 1 minute, left standstill 1.5 hours, get supernatant and measure its chemical oxygen demand COD.The COD clearance is 71% as calculated.
Claims (2)
1. one kind with the former method of handling the black liquid flocculant for preparing of scrap rubber, and the processing step and the condition of this method are as follows:
1) 50～100 parts of scrap leather bits is added in 200～300 parts of water, soak at room temperature 8～12 hours, adding 0.3～0.8 part of protease then, in 45～50 ℃ of stirring reactions of temperature 3～5 hours, is stirring reaction 2～3 hours under 4.0～4.5 and 70～90 ℃ of conditions at pH again;
2) be cooled to 50～60 ℃, behind adjust pH to 8.0～8.5, add 0.8～2.0 part of quaternary ammonium salt cation agent, stirring reaction 6～8 hours filters, and flushing with clean water is to the no obvious residue in collagen flocculant surface, drying is 6～8 hours under 50～60 ℃, is crushed to 0.1～0.15mm and gets final product
More than the umber of each material be weight portion, wherein used quaternary ammonium salt cation agent is any in 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl triethyl ammonium chloride or the 3-chloro-2-hydroxypropyl trihydroxyethyl ammonium chloride.
2. according to claim 1 with the former method of handling the black liquid flocculant for preparing of scrap rubber, used protease is any in 2709 protease, 1398 protease or the trypsase in this method.
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| CN104356317B (en) * | 2014-10-17 | 2019-05-24 | 武汉纺织大学 | Utilize the sewage treating material and its preparation method and application of leather leftover preparation |
| CN114426655B (en) * | 2020-10-10 | 2023-11-14 | 中国石油化工股份有限公司 | Lignin-based water-in-oil emulsion demulsifier, preparation method thereof and treatment method of crude oil water-in-oil emulsion |
| CN117110198B (en) * | 2023-08-28 | 2024-04-12 | 石家庄市长安育才建材有限公司 | Method for rapidly detecting type and content of flocculant in machine-made sand |
Citations (2)
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|---|---|---|---|---|
| CN1101954A (en) * | 1993-10-22 | 1995-04-26 | 席炳炬 | Flocculant for treating paper-making black liquor |
| CN101362816A (en) * | 2008-09-19 | 2009-02-11 | 大连工业大学 | Method for preparing high polymer coagulant from pulp and paper waste liquor recovery material |
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| JP4655862B2 (en) * | 2004-09-07 | 2011-03-23 | 株式会社 ケイ・アイシステム | Black liquor processing method |
| EP2130802A1 (en) * | 2007-03-07 | 2009-12-09 | Nihon Cellulose Co., Ltd. | Method for treatment of black liquor containing no sulfide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101954A (en) * | 1993-10-22 | 1995-04-26 | 席炳炬 | Flocculant for treating paper-making black liquor |
| CN101362816A (en) * | 2008-09-19 | 2009-02-11 | 大连工业大学 | Method for preparing high polymer coagulant from pulp and paper waste liquor recovery material |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2006-102743A 2006.04.20 |
| 孙彦珍等.絮凝沉淀法处理制浆造纸废水.《黑龙江造纸》.1999,(第3期),第24-26页. * |
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