CN115772332A - Cottonseed protein intermediate and preparation method and application thereof - Google Patents
Cottonseed protein intermediate and preparation method and application thereof Download PDFInfo
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- CN115772332A CN115772332A CN202211455541.4A CN202211455541A CN115772332A CN 115772332 A CN115772332 A CN 115772332A CN 202211455541 A CN202211455541 A CN 202211455541A CN 115772332 A CN115772332 A CN 115772332A
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- 235000012343 cottonseed oil Nutrition 0.000 title claims abstract description 128
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 88
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920002770 condensed tannin Polymers 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 20
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- 235000012054 meals Nutrition 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 17
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- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 claims description 3
- 229920001864 tannin Polymers 0.000 claims description 3
- 239000001648 tannin Substances 0.000 claims description 3
- 235000018553 tannin Nutrition 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 description 32
- 239000000243 solution Substances 0.000 description 26
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- 239000005995 Aluminium silicate Substances 0.000 description 13
- 235000012211 aluminium silicate Nutrition 0.000 description 13
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000005189 flocculation Methods 0.000 description 10
- 230000016615 flocculation Effects 0.000 description 10
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- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 6
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- 239000000047 product Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 4
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- QBKSWRVVCFFDOT-UHFFFAOYSA-N gossypol Chemical compound CC(C)C1=C(O)C(O)=C(C=O)C2=C(O)C(C=3C(O)=C4C(C=O)=C(O)C(O)=C(C4=CC=3C)C(C)C)=C(C)C=C21 QBKSWRVVCFFDOT-UHFFFAOYSA-N 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- CHNLPLHJUPMEOI-UHFFFAOYSA-N oxolane;trifluoroborane Chemical compound FB(F)F.C1CCOC1 CHNLPLHJUPMEOI-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
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- 238000002834 transmittance Methods 0.000 description 4
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- 229920006158 high molecular weight polymer Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- QHOPXUFELLHKAS-UHFFFAOYSA-N Thespesin Natural products CC(C)c1c(O)c(O)c2C(O)Oc3c(c(C)cc1c23)-c1c2OC(O)c3c(O)c(O)c(C(C)C)c(cc1C)c23 QHOPXUFELLHKAS-UHFFFAOYSA-N 0.000 description 2
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- 238000010408 sweeping Methods 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 238000006068 polycondensation reaction Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
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Abstract
The invention discloses a cottonseed protein intermediate, a preparation method and application thereof, wherein the cottonseed protein intermediate is prepared from the following raw materials in parts by weight: 8-15 parts of cottonseed protein, 2-4 parts of 1,2, 3-glycerol triglycidyl ether, 5-10 parts of depolymerized condensed tannin and 45-55 parts of water. The depolymerized condensed tannin is prepared from the following raw materials in parts by weight: 5-10 parts of urea, 2-4 parts of 2-mercaptoethanol, 2-4 parts of NaOH,30-50 parts of condensed tannin and 90 parts of water. According to the invention, the condensed tannin is treated by utilizing green and environment-friendly urea and 2-mercaptoethanol, the steric hindrance of the condensed tannin is reduced, the reaction activity of the condensed tannin is increased, the condensed tannin solution after depolymerization is uniformly dispersed in cottonseed protein, and a net structure is added, so that the net capturing adsorption performance is enhanced.
Description
Technical Field
The invention relates to the technical field of cottonseed protein, and particularly relates to a cottonseed protein intermediate as well as a preparation method and application thereof.
Background
The cottonseed protein is a high protein product prepared by removing down and husks from cottonseeds, soaking in oil once at low temperature, draining, and then removing toxic substances (gossypol).
At present, the production process of the cottonseed protein needs detoxification treatment, and wet meal subjected to solvent detoxification treatment mostly adopts a heating evaporation process to dry the wet meal, so that the finished product protein is prepared. Patent application No. 200510124534.6 introduces a cottonseed protein production method, which comprises the following steps: the cottonseed protein extraction is completed in a leacher by using a mixed solvent of No. 6 solvent and methanol 1.5; and extruding the wet meal by an extruder, and drying by a disc dryer to obtain the finished cottonseed protein. The production process is simple, the loss is less, the energy consumption is low, the cost is low, high-quality cottonseed protein with the protein free gossypol content of less than 400ppm and the protein solubility of more than 55 percent can be obtained, and the continuous industrial production is easy to realize; however, the cottonseed protein in the prior art has the defect of poor net-catching adsorption performance, and the application range of the cottonseed protein is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a cottonseed protein intermediate and a preparation method and application thereof.
The invention provides a cottonseed protein intermediate, which is prepared from the following raw materials in parts by weight: 8-15 parts of cottonseed protein, 2-4 parts of 1,2, 3-glycerol triglycidyl ether, 5-10 parts of depolymerized condensed tannin and 45-55 parts of water.
In the invention, as a preferred embodiment, the cottonseed protein intermediate is prepared from the following raw materials in parts by weight: 8-15 parts of cottonseed protein, 3 parts of 1,2, 3-glycerol triglycidyl ether, 5-10 parts of depolymerized condensed tannin and 50 parts of water.
In the invention, as a preferred embodiment, the cottonseed protein intermediate is prepared from the following raw materials in parts by weight: 10 parts by weight of cottonseed protein, 3 parts by weight of 1,2, 3-glycerol triglycidyl ether, 8 parts by weight of depolymerized condensed tannin and 50 parts by weight of water.
In the present invention, as a preferred embodiment, the depolymerized condensed tannin is prepared from the following raw materials in parts by weight: 5-10 parts of urea, 2-4 parts of 2-mercaptoethanol, 2-4 parts of NaOH,30-50 parts of condensed tannin and 90 parts of water.
In the present invention, as a preferred embodiment, the depolymerized condensed tannin is prepared from the following raw materials in parts by weight: 8 parts of urea, 3 parts of 2-mercaptoethanol, 4 parts of NaOH,40 parts of condensed tannin and 90 parts of water.
The second aspect of the invention also provides a preparation method of the cottonseed protein intermediate, which comprises the following steps of modifying cottonseed protein by condensed tannin: mixing the cottonseed protein, the depolymerized condensed tannin, 1,2, 3-glycerol triglycidyl ether and water according to the formula ratio, and stirring for 6-8 hours at normal temperature to obtain a cottonseed protein intermediate.
In the present invention, as a preferred embodiment, the method further comprises a step of depolymerizing the condensed tannin: adding urea, 2-mercaptoethanol, naOH, condensed tannin and water in formula amounts into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in water bath, reacting for 2-4h, and continuously stirring the solution at normal temperature for a preset time to obtain the depolymerized condensed tannin.
In the present invention, as a preferable example, in the depolymerization step of the condensed tannin, the solution is stirred at normal temperature for 15 hours.
In the present invention, as a preferred embodiment, the method further comprises a pretreatment step: grinding oil-squeezed cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for several times, preparing a cottonseed meal solution with a concentration of 40%, preheating in a water bath at 80-85 deg.C for 30min, continuously stirring the cottonseed meal solution during the treatment process, cooling to normal temperature after preheating, and centrifuging; placing the centrifuged cottonseed meal in a drying oven, and drying at 60 ℃ to constant weight; and (3) grinding the dried cottonseed meal again and sieving the cottonseed meal with a 200-mesh sieve to obtain the cottonseed protein.
The third aspect of the invention also provides an application of the cottonseed protein intermediate, which is used as a raw material for preparing the flocculant.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the condensed tannin is treated by utilizing green and environment-friendly urea and 2-mercaptoethanol, the steric hindrance of the condensed tannin is reduced, the reaction activity of the condensed tannin is increased, the condensed tannin solution after depolymerization is uniformly dispersed in cottonseed protein, and a net structure is added, so that the net capturing adsorption performance is enhanced.
Drawings
FIG. 1 is a graph showing the effect of different dosages of bio-based waterborne polyetheramine high molecular weight polymer on the transmittance of kaolin solution in example 3;
FIG. 2 is a graph comparing the oil removing effect of bio-based aqueous polyetheramine high molecular weight polymer of example 3 and a market comparison sample on polymer-containing wastewater;
FIG. 3 is a graph comparing the flocculation effect of bio-based waterborne polyetheramine high molecular weight polymers of examples 1-4 on kaolin suspensions.
Detailed Description
The invention is further described with reference to the drawings and the detailed description, and it should be noted that, in the case of no conflict, any combination of the embodiments or technical features described below may form a new embodiment. Except as specifically noted, the materials and equipment used in this example are commercially available.
The invention provides a cottonseed protein intermediate which is prepared from the following raw materials in parts by weight: 8-15 parts of cottonseed protein, 2-4 parts of 1,2, 3-glycerol triglycidyl ether, 5-10 parts of depolymerized condensed tannin and 45-55 parts of water.
As a preferred embodiment, the cottonseed protein intermediate is prepared from the following raw materials in parts by weight: 8-15 parts of cottonseed protein, 3 parts of 1,2, 3-glycerol triglycidyl ether, 5-10 parts of depolymerized condensed tannin and 50 parts of water.
As a preferred embodiment, the cottonseed protein intermediate is prepared from the following raw materials in parts by weight: 10 parts by weight of cottonseed protein, 3 parts by weight of 1,2, 3-glycerol triglycidyl ether, 8 parts by weight of depolymerized condensed tannin and 50 parts by weight of water.
As a preferred embodiment, the depolymerized condensed tannin is prepared from the following raw materials in parts by weight: 5-10 parts of urea, 2-4 parts of 2-mercaptoethanol, 2-4 parts of NaOH,30-50 parts of condensed tannin and 90 parts of water.
As a preferred embodiment, the depolymerized condensed tannin is prepared from the following raw materials in parts by weight: 8 parts of urea, 3 parts of 2-mercaptoethanol, 4 parts of NaOH,40 parts of condensed tannin and 90 parts of water.
The invention also provides a preparation method of the cottonseed protein intermediate, which comprises the following steps of modifying cottonseed protein by condensed tannin: mixing the cottonseed protein, the depolymerized condensed tannin, 1,2, 3-glycerol triglycidyl ether and water according to the formula ratio, and stirring for 6-8 hours at normal temperature to obtain a cottonseed protein intermediate.
As a preferred embodiment, it further comprises a step of depolymerisation of the condensed tannin: adding urea, 2-mercaptoethanol, naOH, condensed tannin and water in formula amounts into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in water bath, reacting for 2-4h, and continuously stirring the solution at normal temperature for a preset time to obtain the depolymerized condensed tannin.
As a preferred example, in the depolymerization step of the condensed tannin, the solution is stirred at room temperature for 15 hours.
As a preferred embodiment, the method further comprises the following pretreatment steps: grinding oil-squeezed cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for several times, preparing a cottonseed meal solution with a concentration of 40%, preheating in a water bath at 80-85 deg.C for 30min, continuously stirring the cottonseed meal solution during the treatment process, cooling to normal temperature after preheating, and centrifuging; placing the centrifuged cottonseed meal in an oven, and drying at 60 ℃ to constant weight; and (3) grinding the dried cottonseed meal again and sieving the cottonseed meal with a 200-mesh sieve to obtain the cottonseed protein.
The invention also provides application of the cottonseed protein intermediate, and the cottonseed protein intermediate is used as a raw material for preparing the flocculant.
The embodiments described below with reference to the accompanying drawings are exemplary only for explaining the present application and are not to be construed as limiting the present application.
Example 1:
the embodiment provides a preparation method of a cottonseed protein intermediate, which comprises the following steps:
1) Pretreatment of cottonseed meal: grinding oil-extracted cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for three times, preparing a 40% cottonseed meal solution, preheating in a 80-85 deg.C water bath for 30min, stirring the cottonseed meal solution continuously during the treatment process, cooling to normal temperature after preheating, and centrifuging. Placing the centrifuged cottonseed meal in an oven, and drying at 60 ℃ to constant weight. And grinding the dried cottonseed meal again through a 200-mesh screen to be used as an intermediate product base material.
2) Depolymerization of condensed tannins: adding 5 parts by weight of urea, 3 parts by weight of 2-mercaptoethanol, 2 parts by weight of NaOH,30 parts by weight of condensed tannin and 90 parts by weight of water into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in a water bath, reacting for 4 hours, and continuing to stir the solution at normal temperature for 15 hours to obtain depolymerized condensed tannin.
3) Condensed tannin modified cottonseed protein: weighing 8 parts by weight of pretreated cottonseed protein, 5 parts by weight of depolymerized condensed tannin, 3 parts by weight of 1,2, 3-glycerol triglycidyl ether and 50 parts by weight of water, and stirring at normal temperature for 6-8 hours to obtain a cottonseed protein intermediate.
The embodiment also provides a preparation method of the bio-based waterborne polyether amine high molecular polymer, which comprises the following preparation steps: adding 45 parts by weight of tetrahydrofuran solvent, adding 0.36 part by weight of ethylene glycol and 0.7 part by weight of boron trifluoride tetrahydrofuran complex into a flask with a thermometer, a stirrer, a water separator and a reflux condenser, cooling to below 10 ℃, slowly dropwise adding 90 parts by weight of epichlorohydrin diluted by 45 parts by weight of tetrahydrofuran, dropwise adding for 6 hours, reacting for 12 hours after dropwise adding to obtain polyepichlorohydrin, adding 50 parts by weight of cottonseed protein intermediate, 280 parts by weight of polyethylene polyamine and 150 parts by weight of methanol, stirring at 50 ℃ for reaction for 3 hours, subsequently heating to 90 ℃, reacting for 3 hours, cooling at room temperature to obtain a target product, and adding water for dilution according to the required solid content.
Example 2
This embodiment provides a method for preparing a cottonseed protein intermediate, including:
1) Pretreatment of cottonseed meal: grinding oil-extracted cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for three times, preparing a 40% cottonseed meal solution, preheating in a 80-85 deg.C water bath for 30min, stirring the cottonseed meal solution continuously during the treatment process, cooling to normal temperature after preheating, and centrifuging. Placing the centrifuged cottonseed meal in an oven, and drying at 60 ℃ to constant weight. The dried cottonseed meal is ground again through a 200-mesh screen to be used as an intermediate product base material.
2) Depolymerization of condensed tannins: adding 10 parts by weight of urea, 3 parts by weight of 2-mercaptoethanol, 4 parts by weight of NaOH, 50 parts by weight of condensed tannin and 90 parts by weight of water into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in a water bath, reacting for 4 hours, and continuing to stir the solution at normal temperature for 15 hours to obtain depolymerized condensed tannin.
3) Condensed tannin modified cottonseed protein: weighing 15 parts by weight of pretreated cottonseed protein, 10 parts by weight of depolymerized condensed tannin, 3 parts by weight of 1,2, 3-glycerol triglycidyl ether and 50 parts by weight of water, and stirring for 8 hours at normal temperature to obtain a cottonseed protein intermediate.
The embodiment also provides a preparation method of the bio-based waterborne polyether amine high molecular polymer, which comprises the following preparation steps: adding 40 parts by weight of tetrahydrofuran solvent into a flask with a thermometer, a stirrer, a water separator and a reflux condenser, then adding 0.5 part by weight of ethylene glycol and 1.2 parts by weight of boron trifluoride tetrahydrofuran complex, reducing the temperature to below 10 ℃, slowly adding 90 parts by weight of epoxy chloropropane diluted by 40 parts by weight of tetrahydrofuran dropwise for 6 hours, reacting for 12 hours after dropwise addition to obtain polyepichlorohydrin, then adding 80 parts by weight of cottonseed protein intermediate, 320 parts by weight of polyethylene polyamine and 280 parts by weight of methanol, stirring at 50 ℃ for reaction for 3 hours, subsequently heating to 90 ℃, reacting for 5 hours, cooling at room temperature to obtain a target product, and adding water for dilution according to the required solid content.
Example 3
This embodiment provides a method for preparing a cottonseed protein intermediate, including:
1) Pretreatment of cottonseed meal: grinding oil-squeezed cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for three times, preparing 40% cottonseed meal solution, preheating in a 80-85 deg.C water bath for 30min while stirring, cooling to room temperature, and centrifuging. Placing the centrifuged cottonseed meal in an oven, and drying at 60 ℃ to constant weight. And grinding the dried cottonseed meal again through a 200-mesh screen to be used as an intermediate product base material.
2) Depolymerization of condensed tannins: adding 8 parts by weight of urea, 3 parts by weight of 2-mercaptoethanol, 4 parts by weight of NaOH,40 parts by weight of condensed tannin and 90 parts by weight of water into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in a water bath, reacting for 3 hours, and continuing to stir the solution for 15 hours at normal temperature to obtain depolymerized condensed tannin.
3) Condensed tannin modified cottonseed protein: weighing 10 parts by weight of pretreated cottonseed protein, 8 parts by weight of depolymerized condensed tannin, 3 parts by weight of 1,2, 3-glycerol triglycidyl ether and 50 parts by weight of water, and stirring at normal temperature for 8 hours to obtain a cottonseed protein intermediate.
The embodiment also provides a preparation method of the bio-based waterborne polyether amine high molecular polymer, which comprises the following preparation steps: adding 45 parts by weight of tetrahydrofuran solvent, adding 0.6 part by weight of ethylene glycol and 1.4 parts by weight of boron trifluoride tetrahydrofuran complex into a flask with a thermometer, a stirrer, a water separator and a reflux condenser, cooling to below 10 ℃, slowly adding 45 parts by weight of tetrahydrofuran diluted epichlorohydrin 90 parts by weight, dropwise adding for 7 hours, reacting for 12 hours after dropwise adding to obtain polyepichlorohydrin, adding 70 parts by weight of cottonseed protein intermediate, 280 parts by weight of polyethylene polyamine and 300 parts by weight of methanol, stirring at 50 ℃ for reaction for 3 hours, subsequently heating to 90 ℃, reacting for 5 hours, cooling at room temperature to obtain a target product, and adding water for dilution according to the required solid content.
Example 4
This embodiment provides a method for preparing a cottonseed protein intermediate, including:
1) Pretreatment of cottonseed meal: grinding oil-extracted cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for three times, preparing a 40% cottonseed meal solution, preheating in a 80-85 deg.C water bath for 30min, stirring the cottonseed meal solution continuously during the treatment process, cooling to normal temperature after preheating, and centrifuging. Placing the centrifuged cottonseed meal in an oven, and drying at 60 ℃ to constant weight. The dried cottonseed meal is ground again through a 200-mesh screen to be used as an intermediate product base material.
2) Depolymerization of condensed tannins: adding 6 parts by weight of urea, 3 parts by weight of 2-mercaptoethanol, 3 parts by weight of NaOH, 45 parts by weight of condensed tannin and 90 parts by weight of water into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in a water bath, reacting for 2 hours, and continuing to stir the solution at normal temperature for 15 hours to obtain the depolymerized condensed tannin.
3) Condensed tannin modified cottonseed protein: weighing 12 parts by weight of pretreated cottonseed protein, 8 parts by weight of depolymerized condensed tannin, 3 parts by weight of 1,2, 3-glycerol triglycidyl ether and 50 parts by weight of water, and stirring for 8 hours at normal temperature to obtain a cottonseed protein intermediate.
The embodiment also provides a preparation method of the bio-based waterborne polyether amine high molecular polymer, which comprises the following preparation steps: adding 30 parts by weight of tetrahydrofuran solvent, then adding 0.4 part by weight of ethylene glycol and 1.0 part by weight of boron trifluoride tetrahydrofuran complex into a flask with a thermometer, a stirrer, a water separator and a reflux condenser, cooling to below 10 ℃, slowly adding 30 parts by weight of tetrahydrofuran diluted epichlorohydrin by 90 parts by weight, dropwise adding for 8 hours, reacting for 12 hours after dropwise adding to obtain polyepichlorohydrin, then adding 60 parts by weight of cottonseed protein intermediate, 260 parts by weight of polyethylene polyamine and 200 parts by weight of methanol, stirring at 50 ℃ for reaction for 2 hours, subsequently heating to 90 ℃, reacting for 3 hours, cooling at room temperature to obtain a target product, and adding water for dilution according to the required solid content.
In conclusion, the bio-based water-based polyether amine high molecular polymer prepared by using the cottonseed protein intermediate as a raw material can be used as a flocculating agent. On one hand, the method keeps the inherent excellent performances of innocuity, biocompatibility, degradability, macromolecular adsorption and the like of the condensed tannin and cottonseed protein, and simultaneously, because the tannin has certain steric hindrance and poor reaction activity with other molecules due to the large relative molecular weight, the tannin is treated by utilizing green environment-friendly urea and 2-mercaptoethanol, the steric hindrance of the condensed tannin is reduced, and the reaction activity of the condensed tannin is increased; on the other hand, the polyepichlorohydrin with the relative molecular weight is synthesized to be used as a cross-linking agent, not only the polyepichlorohydrin and the polyethylene polyamine are subjected to cross-linking polycondensation reaction, but also the catechol group on the condensed tannin and the NH of the cottonseed protein chain and the polyethylene polyamine are utilized 2 The groups react to form a double-cross-linked network structure to enhance the net catching and sweeping effect, so that the polymer molecular chain is longer, the branching degree is high, a more developed network structure is formed, the bridging effect and the electric neutralization effect on oil drops are stronger, the emulsified oil drops are easier to contact, some original natural surfactants on the surface of oil water are replaced, the oil drops are extruded to promote coalescence, and floating or sinking is promoted.
And (3) performance testing:
1. the high molecular polymer of the embodiment 3 is prepared into a diluent with 20 percent of solid content, a certain amount of flocculant mother liquor is slowly added into 1g/L kaolin suspension under the continuous stirring of a cantilever stirrer, the timing is started, firstly, the solution is stirred for a certain time at a high rotating speed of 200r/min, then, the rotating speed is reduced to 100r/min, the stirring is carried out for 5min, after the stirring is finished, the stirrer is closed, the solution is allowed to stand for 5min, a certain amount of clear liquid below 1cm away from the liquid level is absorbed by a rubber head dropper, and the light transmittance (T percent) of the solution is measured at the wavelength of 550nm by using an ultraviolet UV-4802 type spectrophotometer. The effect of the polymer addition on the flocculation effect was examined and the results are shown in FIG. 1.
As can be seen from FIG. 1, before the addition amount of the high molecular polymer in example 3 is 20mg/L, the light transmittance (T%) and the addition amount are in positive correlation, when the addition amount is small, the positive charges generated by the self-made polymer molecules are not enough to neutralize the negative charges carried by the kaolin particles, the electric neutralization effect is weak, and most of the particles are removed by forming flocs through the net-flapping sweeping and adsorption-bridging mechanisms. However, with the continuous addition of the self-made polymer molecules, the surfaces of the particles are wrapped by the self-made polymer molecules, so that the steric hindrance is increased, the colloid protection is generated, the self-made polymer molecules cannot play the role, and the particles cannot be removed in a large amount, so that the light transmittance T% of the solution is greatly reduced, and the optimal addition of the polymer to the kaolin solution is 20mg/L in combination with the above description.
2. In order to compare the difference of the oil removing effect of the polymer-containing wastewater between the home-made polymer and the commercially available comparative sample, the final treatment effect of the polymer-containing wastewater was compared with the oil removing rate of the polymer-containing wastewater after adding the high molecular polymer of example 3 at a temperature of 60 ℃ under other conditions, as shown in fig. 2.
As can be seen from FIG. 2, after the polymer-containing wastewater added with the high molecular polymer in example 3 is treated, the oil removal rate increases and then decreases with the increase of the added amount, the optimal added amount is 15mg/L, and the removal rate reaches 86.2%. Compared with the prior art, the market comparison sample can be further improved when the adding amount is increased, the maximum removal rate can only reach 58.1 percent, the adding amount is 25mg/L, and is more than half of that of the high molecular polymer in the embodiment 3, so that the effect superior to that of the market comparison sample can be obtained due to the optimization of the developed double-net structure such as high branching degree, long molecular chain and the like and the high molecular weight and the like of the high molecular polymer in the embodiment 3 under the condition of low dosage, and the market comparison sample has better economical efficiency.
3. Under certain conditions (room temperature), taking several equal parts of 100m L kaolin suspension (1 g/L), respectively taking 0.5mg, 1.0mg, 1.5mg, 2.0mg, 2.5mg and 3.0mg of each self-made polymer (such as example 1, example 2, example 3 and example 4) to treat the kaolin suspension in a beaker, wherein the pH is 7-8, the kaolin suspension is rapidly stirred at the speed of 200 rad.min < -1 > for 1min, then the kaolin suspension is slowly stirred at the speed of 100 rad.min < -1 > for 5min, the stirring is stopped, the kaolin suspension is kept still for settling for a while, and the residual turbidity of the sample is measured. The influence of different contents of different self-made polymers in kaolin suspension on the flocculation performance is respectively inspected, and the index for evaluating the flocculation performance is the flocculation rate. The calculation formula of the flocculation rate is shown as follows:
in the formula:
e% is the flocculation rate;
N 0 is the turbidity of kaolin suspension before adding the medicament;
N 1 the turbidity of the high-collar soil turbid liquid after the medicament is added is shown.
As can be seen from FIG. 3, with the increase of the added amount, the flocculation effect of the four self-made polymers on the kaolin suspension is increased; when the optimal dosage is 15mg/L, the flocculation rate of the self-made polymer in example 3 reaches 95.3 percent, which is higher than that of other self-made polymers with the same quantity and is also higher than the highest flocculation rate of other self-made polymers with different dosages. Because in the self-made polymer structure, not only the inherent properties of macromolecular adsorption and the like of condensed tannin and cottonseed protein are kept, but also a double-crosslinked network structure formed by functional groups on the molecular structure and polyamine has more grafted positive charges, and the self-made polymer has strong electric neutralization capacity with colloidal particles, thereby being more beneficial to catching the bridged suspended particles.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. The cottonseed protein intermediate is characterized by being prepared from the following raw materials in parts by weight: 8-15 parts of cottonseed protein, 2-4 parts of 1,2, 3-glycerol triglycidyl ether, 5-10 parts of depolymerized condensed tannin and 45-55 parts of water.
2. The cottonseed protein intermediate of claim 1 wherein the cottonseed protein intermediate is prepared from the following raw materials in parts by weight: 8-15 parts of cottonseed protein, 3 parts of 1,2, 3-glycerol triglycidyl ether, 5-10 parts of depolymerized condensed tannin and 50 parts of water.
3. The cottonseed protein intermediate of claim 2 wherein the cottonseed protein intermediate is prepared from the following raw materials in parts by weight: 10 parts by weight of cottonseed protein, 3 parts by weight of 1,2, 3-glycerol triglycidyl ether, 8 parts by weight of depolymerized condensed tannin and 50 parts by weight of water.
4. The cottonseed protein intermediate of claim 1 wherein the depolymerized condensed tannin is prepared from the following raw materials in parts by weight: 5-10 parts of urea, 2-4 parts of 2-mercaptoethanol, 2-4 parts of NaOH,30-50 parts of condensed tannin and 90 parts of water.
5. The cottonseed protein intermediate of claim 4 wherein the depolymerized condensed tannin is prepared from the following raw materials in parts by weight: 8 parts by weight of urea, 3 parts by weight of 2-mercaptoethanol, 4 parts by weight of NaOH,40 parts by weight of condensed tannin and 90 parts by weight of water.
6. A method for preparing the cottonseed protein intermediate as claimed in any one of claims 1 to 5 comprising the step of condensing tannin to modify cottonseed protein: mixing the cottonseed protein, the depolymerized condensed tannin, 1,2, 3-glycerol triglycidyl ether and water according to the formula ratio, and stirring for 6-8 hours at normal temperature to obtain a cottonseed protein intermediate.
7. The method of producing the cottonseed protein intermediate of claim 6 further comprising the step of depolymerizing the condensed tannin: adding urea, 2-mercaptoethanol, naOH, condensed tannin and water in formula amounts into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in water bath, reacting for 2-4h, and continuously stirring the solution at normal temperature for a preset time to obtain the depolymerized condensed tannin.
8. The method for producing the cottonseed protein intermediate as claimed in claim 7, wherein in the step of depolymerising the condensed tannin, the solution is stirred at room temperature for 15 hours.
9. The method for preparing the cottonseed protein intermediate as claimed in claim 6, further comprising the step of pretreating: grinding oil-extracted cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for multiple times, preparing a 40% cottonseed meal solution, preheating in a 80-85 deg.C water bath for 30min, stirring the cottonseed meal solution continuously during the treatment process, cooling to normal temperature after preheating, and centrifuging; placing the centrifuged cottonseed meal in an oven, and drying at 60 ℃ to constant weight; and (4) grinding the dried cottonseed meal again and then sieving the cottonseed meal with a 200-mesh sieve to obtain the cottonseed protein.
10. Use of the cottonseed protein intermediate as claimed in any one of claims 1 to 5 as a feedstock for the preparation of a flocculant.
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| CN1382787A (en) * | 2001-04-25 | 2002-12-04 | 马连清 | Composition containing dannin and its appication |
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| CN1382787A (en) * | 2001-04-25 | 2002-12-04 | 马连清 | Composition containing dannin and its appication |
| CN109095579A (en) * | 2018-08-01 | 2018-12-28 | 广州振清环保技术有限公司 | A kind of biochemical modified soybean protein-carboxymethyl chitosan composite flocculation agent and its preparation method and application |
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