CN116785779A - Preparation method of biomass carbonization amino demulsifier, demulsifier and application - Google Patents
Preparation method of biomass carbonization amino demulsifier, demulsifier and application Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 58
- 238000003763 carbonization Methods 0.000 title claims abstract description 47
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920002678 cellulose Polymers 0.000 claims abstract description 35
- 239000001913 cellulose Substances 0.000 claims abstract description 35
- 229920000742 Cotton Polymers 0.000 claims abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 4
- 239000000839 emulsion Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- -1 amino compound Chemical class 0.000 claims description 20
- 238000005576 amination reaction Methods 0.000 claims description 18
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 235000010288 sodium nitrite Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 26
- 238000002474 experimental method Methods 0.000 description 12
- 238000000926 separation method Methods 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 239000007764 o/w emulsion Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003922 charged colloid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 230000000368 destabilizing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method, a demulsifier and an application of a biomass carbonization amino demulsifier, which are characterized in that cotton is regenerated by phosphoric acid hydrolysis to obtain a cellulose oligomer, and then the cellulose oligomer is carbonized and reacted with an amino chemical to prepare the biomass carbonization amino demulsifier, wherein the application of the biomass carbonization amino demulsifier in oily wastewater is carried out under normal temperature for 30min, the water phase light transmittance after demulsification of the oily wastewater is more than 82%, and the oil removal rate is as high as 99.24%. The demulsifier provided by the invention has the characteristics of cheap and easily available raw materials, small dosage of the demulsifier, high demulsification efficiency, short time, recycling and reutilization of biomass waste, no pollution, easy degradation, simple preparation method and the like, has good adaptability, and has better application and popularization prospects.
Description
Technical Field
The invention relates to the technical field of demulsifiers in the petroleum and natural gas industry, in particular to a preparation method of a biomass carbonization amino demulsifier, a demulsifier and application thereof.
Background
The oily wastewater produced in the processes of drilling, completion, production and refining in the petroleum and natural gas industry contains fine clay suspended particles, oils, soluble treating agents and the like, and the treating agents are used as a glue protecting agent, and a polydisperse negatively charged colloid or emulsified solution formed by functional groups and clay particles has high stability and can last for a few minutes to a few years. Stable colloidal or emulsion solutions suffer from a number of disadvantages in the wastewater treatment process including equipment corrosion, increased difficulty in dewatering, increased transportation costs, etc., and therefore it is critical to demulsify the colloid or emulsion prior to treatment. The existing emulsion breaking methods mainly comprise chemical breaking, membrane breaking, electric field breaking, heating breaking, centrifugal breaking and the like. The chemical method has more demulsification application, namely, demulsifier is added into emulsified oil-containing drilling wastewater, and the purpose of destabilizing colloid or emulsion, demulsifiing and realizing oil-water separation is achieved by chemical action and other separation modes.
The chemical demulsifier is an amphiphilic compound with hydrophilicity and hydrophobicity and can be adsorbed on an oil-water interface. Generally, they can be classified into inorganic and organic types. Among them, organic demulsifiers have more advantages than inorganic demulsifiers. Such as: the method has the advantages of less dosage, strong demulsification capability, large formed floccules, difficult breaking, no increase of mud amount, no corrosiveness and small influence by salts, pH value and temperature. The device not only has the capability of adsorbing, bridging and flocculating to remove suspended matters, but also has the functions of electric neutralization, demulsification and oil removal, and the capability of removing pollutants through electrostatic adsorption and flocculation rolling among different molecules. Specifically, the method comprises the steps of synthesizing an organic polymeric flocculant and a natural organic polymeric flocculant. For example, ethylene oxide-propylene oxide (EO-PO) block copolymers, silicone polyethers, dendrimers, biodegradable polymeric surfactants, ionic liquids and nanoparticle-based demulsifiers have attracted increasing attention in the industry. However, these demulsifiers have some inherent problems such as complex and dangerous preparation process, high cost of raw materials, certain pollution to the environment, serious resource waste and the like.
Chinese patent publication No. CN105384927a, publication No. 2016, 3 and 9 discloses an oil-in-water emulsion breaker and a preparation method thereof, wherein bisamide is prepared sequentially, chlorinated polyether is prepared, and finally cationic polyether is prepared, namely the oil-in-water emulsion breaker; the preparation method comprises the following steps: 1) Under stirring, the organic amine and fatty acid were mixed according to 1: 2-1: 4 (molar ratio), controlling the temperature of the reaction system at 50-170 ℃ and the reaction time at 3-18 h to obtain bisamide; 2) Sequentially adding an organic solvent ethanol and bisamide into a four-mouth bottle with a thermometer, a stirrer and a condenser tube, beginning to drop the polyepichlorohydrin at 20-120 ℃, stirring for 5 hours, and cooling to obtain chlorinated polyether which is a brownish red viscous liquid; 3) Placing the synthesized chlorinated polyether and dimethylamine aqueous solution into a clean reaction kettle, introducing nitrogen to remove air, controlling the temperature to be 50-80 ℃, reacting for 5 hours, continuously heating to 120 ℃, and reacting for 6 hours to obtain the tan water-soluble cationic polyether which is the oil-in-water emulsion demulsifier. The organic demulsifier prepared by the method has the advantages of complex process and high raw material cost, and the demulsifier can be left in an oil phase or a water phase after demulsification, so that corresponding environmental problems are generated. Thus, there remains a major challenge to find a new demulsifier that is widely available, low cost and excellent in performance.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides a preparation method of a biomass carbonization amination demulsifier, and the method can effectively solve the technical problems of high raw material cost, narrow source selection range and poor performance of the demulsifier in the prior art.
The invention also aims at providing the demulsifier prepared by the preparation method.
It is a further object of the present invention to provide the use of the demulsifier prepared.
The invention is realized by adopting the following technical scheme:
a preparation method of a biomass carbonization amino demulsifier is characterized by comprising the following steps: and (3) regenerating cotton through phosphoric acid hydrolysis to obtain a cellulose oligomer, and then carbonizing the cellulose oligomer and reacting the carbonized cellulose oligomer with an amino compound to prepare the biomass carbonized amino demulsifier.
The preparation method specifically comprises the following steps: adding cotton into phosphoric acid, fully dissolving, heating to 40-70 ℃ and stirring for 1-3 hours, adding ethanol to regenerate dissolved cellulose and obtain cellulose oligomer, carbonizing the cellulose oligomer, uniformly dispersing the cellulose oligomer in an amino compound, adding sodium nitrite and stirring for 0.5-2 hours, adding concentrated sulfuric acid, stirring for 0.5-24 hours at 40-80 ℃, centrifuging and washing to neutrality, and freeze-drying the product to obtain the biomass carbonized amino demulsifier.
Further, the cotton is natural cotton.
Further, the cotton is a product taking cotton as a raw material.
Further, the mass ratio of the cotton to the phosphoric acid is 1-5:100.
further, the mass ratio of the carbonized cellulose oligomer to sodium nitrite to concentrated sulfuric acid is 1:10-30:35-60;
further, the mass ratio of the amino compound to the carbonized cellulose oligomer is 20-50:1.
further, the mass ratio of the carbonized cellulose oligomer to the amino compound aqueous solution is 2:40-50.
Further, the amino compound is at least one of ammonia water, urea, ammonium bicarbonate, ethylenediamine, propylenediamine, polyethylene polyamine and polyethyleneimine.
The biomass carbonization amino demulsifier prepared by the preparation method of the biomass carbonization amino demulsifier.
The application of the biomass carbonization amino demulsifier prepared by the preparation method of the biomass carbonization amino demulsifier in the oil-containing wastewater emulsion is provided.
Further, the application comprises the following steps: dispersing the biomass carbonization amino demulsifier in water to obtain a suspension, and then mixing the suspension and the oily wastewater emulsion at room temperature and standing for 10-30 min.
After demulsification is finished, most of the biomass carbonization and amination demulsifier adsorbs oil and floats on water together with the separated oil phase, and a small part of the oil phase is settled in the water, so that the separation is simpler through long-time settlement or centrifugal separation.
Further, the mass fraction of the suspension is 0.01-0.6 wt%.
Further, the volume ratio of the suspension to the oily wastewater emulsion is 1:10-20.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the preparation method, cotton is used as a precursor, and the biomass carbonization and amination demulsifier is prepared through the steps, and the surface of the biomass carbonization and amination demulsifier is provided with a large amount of active amino groups, and the biomass carbonization and amination demulsifier shows high interfacial activity, so that the interfacial tension can be quickly reduced, and demulsification is induced.
2. The raw materials can be directly obtained from natural cotton or obtained from waste cotton fabrics, can interact with asphaltene after modification, and can carry out electrostatic neutralization between positively charged oil drops and negatively charged oil drops in emulsion after modification to promote demulsification. The invention fully utilizes natural biomass, reduces the use of fossil raw materials, can be degraded in natural environment, and has better application prospect.
3. The biomass carbonization amination demulsifier provided by the invention can realize normal-temperature demulsification of oil-containing emulsion, realizes effective oil-water separation, has the characteristics of small dosage and high demulsification efficiency, and the oil removal rate of 25mg/L of the demulsifier under the normal-temperature condition for 30min can reach 99.24%.
Drawings
FIG. 1 is a scanning electron microscope image of a biomass carbonization and amination demulsifier described in example 1.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The cotton used in the examples is natural cotton. The concentrated sulfuric acid described in the examples is commercially available 98wt% concentrated sulfuric acid.
Example 1
As a preferred embodiment of the invention, a preparation method of a biomass carbonization and amination demulsifier is disclosed, cotton is regenerated by phosphoric acid hydrolysis to obtain a cellulose oligomer, and then the cellulose oligomer is carbonized and reacted with an amino compound to prepare the biomass carbonization and amination demulsifier.
Example 2
As another preferred embodiment of the invention, a preparation method of a biomass carbonization amino demulsifier is disclosed, which specifically comprises the following steps: adding cotton into phosphoric acid, fully dissolving, heating to 40-70 ℃ and stirring for 1-3 hours, adding ethanol to regenerate dissolved cellulose and obtain cellulose oligomer, carbonizing the cellulose oligomer, uniformly dispersing the cellulose oligomer in an amino compound, adding sodium nitrite and stirring for 0.5-2 hours, adding concentrated sulfuric acid, stirring for 0.5-24 hours at 40-80 ℃, centrifuging and washing to neutrality, and freeze-drying the product to obtain the biomass carbonized amino demulsifier. The cotton is natural cotton. The mass ratio of cotton to phosphoric acid is 3:100. the mass ratio of the carbonized cellulose oligomer to the sodium nitrite to the concentrated sulfuric acid is 1:20:50; the mass ratio of the amino compound to the carbonized cellulose oligomer is 35:1. the mass ratio of the carbonized cellulose oligomer to the amino compound aqueous solution is 2:45. The amino compound is at least one of ammonia water, urea, ammonium bicarbonate, ethylenediamine, propylenediamine, polyethylene polyamine and polyethyleneimine.
Example 3
The biomass carbonization amino demulsifier prepared in the embodiment 1 or 2 is applied to an oil-containing wastewater emulsion, and comprises the following steps: dispersing the biomass carbonization amino demulsifier in water to obtain a suspension, and then mixing the suspension and the oily wastewater emulsion at room temperature and standing for 10-30 min.
After demulsification is finished, most of the biomass carbonization and amination demulsifier adsorbs oil and floats on water together with the separated oil phase, and a small part of the oil phase is settled in the water, so that the separation is simpler through long-time settlement or centrifugal separation. The mass fraction of the suspension was 0.03wt%. The volume ratio of the suspension to the oily wastewater emulsion is 1:15.
example 4
The embodiment provides a biomass carbonization and amination demulsifier, which is obtained by the following steps:
2g of cotton is added into 100ml of phosphoric acid, after being fully dissolved, the temperature is raised to 50 ℃ and the mixture is stirred for 2 hours, then 50ml of ethanol is added and the mixture is stirred for 20 minutes to regenerate cellulose oligomer, and then the product is freeze-dried by centrifugal washing to be neutral.
2g of cellulose oligomer is carbonized at 400 ℃, then 1g of carbonized product is evenly dispersed into 22.5ml of amino compound, 23g of sodium nitrite is added and stirred for 10min, then 21ml of concentrated sulfuric acid is added dropwise, then the pasty sample is stirred for 1 h at 60 ℃, after the reaction is finished, the product is centrifugally washed to be neutral, and the biomass carbonized amino demulsifier is obtained by freeze drying.
Example 5
The embodiment provides a biomass carbonization amino demulsifier, which is obtained by the following steps:
2g of cotton is added into 100ml of phosphoric acid, after being fully dissolved, the temperature is raised to 60 ℃ and the mixture is stirred for 2 hours, then 50ml of ethanol is added and the mixture is stirred for 20 minutes to regenerate cellulose oligomer, and then the product is freeze-dried by centrifugal washing to be neutral.
2g of cellulose oligomer is carbonized at 400 ℃, 1g of carbonized product is uniformly dispersed into 22.5ml of amino compound, 11.5g of sodium nitrite is added and stirred for 10min, 30ml of concentrated sulfuric acid is then added dropwise, a pasty sample is stirred at 80 ℃ for 1 h, centrifugal washing is carried out to neutrality after the reaction is finished, and the product is freeze-dried to obtain the biomass carbonized amino demulsifier.
Example 6
Suspensions of different concentrations were formulated based on the biomass carbonization amino demulsifier prepared in example 4 to characterize the demulsification performance of the different concentrations of amino demulsifiers in oil-containing wastewater emulsions.
5 parts by weight of crude oil was added to 495 parts by weight of deionized water, stirred and mixed, heated to 60℃and then stirred at 11000r/min for 20 minutes, to obtain a stable oily wastewater emulsion (oil-in-water emulsion).
Adding different parts by weight of the amino demulsifier prepared in the example 4 into water to prepare amino demulsifier suspensions with mass fractions of 0.06%,0.05%,0.04%,0.03%,0.02% and 0.01%, and marking the obtained samples as experimental groups 1-6 respectively; the blank is water and the sample is designated as experimental group 7.
1 part by volume of the above experimental groups 1 to 6 was added to 20 parts by volume of the oily wastewater emulsion, and then mixed well by shaking, and then left at normal temperature for 30 minutes, and the light transmittance and oil removal rate thereof were measured, and the results are shown in Table 1.
Table 1 demulsification results for Experimental groups 1-7
| Group of | CN1（mg/L） | Transmittance (%) | Oil removal Rate (%) |
| Experiment group 1 | 30 | 81.70 | 99.02 |
| Experiment group 2 | 25 | 82.0 | 99.24 |
| Experiment group 3 | 20 | 57.7 | 98.26 |
| Experiment group 4 | 15 | 31.1 | 97.30 |
| Experiment group 5 | 10 | 23.4 | 97.16 |
| Experiment group 6 | 5 | 0.3 | 91.60 |
| Experiment group 7 | 0 | 0 | 0.5 |
Note that: the "amino demulsifier (mg/L)" in the table refers to the concentration of the amino demulsifier in the oil-containing wastewater emulsion.
As shown in Table 1, the biomass carbonization amination demulsifier provided by the invention has good demulsification performance, and the light transmittance of the oil-containing wastewater emulsion can reach 82.0% and the oil removal rate can reach 99.24% after sedimentation for 30min at normal temperature under the concentration of 25 mg/L.
Example 7
Based on the biomass carbonization amino demulsifier prepared in example 4, experimental groups 8-12 were sequentially established for characterizing the demulsification performance of the amino demulsifier at different pH values.
5 parts by weight of crude oil was added to 495 parts by weight of deionized water, stirred and mixed, the pH was adjusted by adding hydrochloric acid or sodium hydroxide, heated to 60℃and then stirred at 11000r/min for 20 minutes to obtain a stable oily wastewater emulsion (oil-in-water emulsion).
Adding the amino demulsifier prepared in the example 4 into water to prepare amino demulsifier suspensions with mass fractions of 0.05%, 0.1% and 0.15%, and respectively marking the samples as experimental groups 8-12;
1 part by volume of the above-mentioned aminated demulsifier suspension was added to 20 parts by volume of oil-containing wastewater emulsions having different pH values, and then mixed by sufficient shaking, and left at normal temperature for 30 minutes, and the light transmittance and oil removal rate thereof were measured, and the results are shown in Table 2.
Table 2 demulsification results for Experimental groups 8-12
| Group of | pH | Transmittance% | Oil removal rate% |
| Experiment group 8 | 4 | 5.2 | 95.81 |
| Experiment group 9 | 6 | 59.7 | 98.35 |
| Experiment group 10 | 7 | 82.0 | 99.24 |
| Experiment group 11 | 8 | 62 | 98. 47 |
| Experiment group 12 | 10 | 2.6 | 97.78 |
As can be seen from table 2: the biomass carbonization amination demulsifier provided by the invention can obtain higher demulsification efficiency near neutrality.
The invention provides a biomass carbonization amination demulsifier which is suitable for demulsification of oil-containing wastewater emulsion, and has the characteristics of simple preparation method, wide raw material sources, no pollution, easy degradation, excellent demulsification performance and the like.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (14)
1. A preparation method of a biomass carbonization amino demulsifier is characterized by comprising the following steps: and (3) regenerating cotton through phosphoric acid hydrolysis to obtain a cellulose oligomer, and then carbonizing the cellulose oligomer and reacting the carbonized cellulose oligomer with an amino compound to prepare the biomass carbonized amino demulsifier.
2. The method for preparing the biomass carbonization and amination demulsifier according to claim 1, which is characterized in that: the preparation method specifically comprises the following steps: adding cotton into phosphoric acid, fully dissolving, heating to 40-70 ℃ and stirring for 1-3 hours, adding ethanol to regenerate dissolved cellulose and obtain cellulose oligomer, carbonizing the cellulose oligomer, uniformly dispersing the cellulose oligomer in an amino compound, adding sodium nitrite and stirring for 0.5-2 hours, adding concentrated sulfuric acid, stirring for 0.5-24 hours at 40-80 ℃, centrifuging and washing to neutrality, and freeze-drying the product to obtain the biomass carbonized amino demulsifier.
3. The method for preparing the biomass carbonization amino demulsifier as claimed in claim 1 or 2, wherein the method comprises the following steps: the cotton is natural cotton.
4. The method for preparing the biomass carbonization amino demulsifier as claimed in claim 1 or 2, wherein the method comprises the following steps: the cotton is a product taking cotton as a raw material.
5. The method for preparing the biomass carbonization amino demulsifier as claimed in claim 1 or 2, wherein the method comprises the following steps: the mass ratio of the cotton to the phosphoric acid is 1-5:100.
6. the method for preparing the biomass carbonization amino demulsifier as claimed in claim 1 or 2, wherein the method comprises the following steps: the mass ratio of the carbonized cellulose oligomer to the sodium nitrite to the concentrated sulfuric acid is 1:10-30:35-60.
7. The method for preparing the biomass carbonization amino demulsifier as claimed in claim 1 or 2, wherein the method comprises the following steps: the mass ratio of the amino compound to the carbonized cellulose oligomer is 20-50:1.
8. the method for preparing the biomass carbonization amino demulsifier as claimed in claim 1 or 2, wherein the method comprises the following steps: the mass ratio of the carbonized cellulose oligomer to the amino compound aqueous solution is 2:40-50.
9. The method for preparing the biomass carbonization amino demulsifier as claimed in claim 1 or 2, wherein the method comprises the following steps: the amino compound is at least one of ammonia water, urea, ammonium bicarbonate, ethylenediamine, propylenediamine, polyethylene polyamine and polyethyleneimine.
10. A biomass carbonization-amination demulsifier prepared by the preparation method of the biomass carbonization-amination demulsifier according to claim 1 or 2.
11. Use of a biomass carbonization amino demulsifier prepared by the preparation method of the biomass carbonization amino demulsifier according to claim 1 or 2 in an oil-containing wastewater emulsion.
12. The use of the biomass carbonization amino demulsifier as claimed in claim 11 in oil-containing wastewater emulsion, characterized in that: the method comprises the following steps: dispersing the biomass carbonization amino demulsifier in water to obtain a suspension, and then mixing the suspension and the oily wastewater emulsion at room temperature and standing for 10-30 min.
13. The use of the biomass carbonization amino demulsifier as claimed in claim 12 in oil-containing wastewater emulsion, characterized in that: the mass fraction of the suspension is 0.01-0.6 wt%.
14. Use of the biomass carbonization amination demulsifier as described in claim 12 or 13 in oil-containing wastewater emulsion, characterized in that: the volume ratio of the suspension to the oily wastewater emulsion is 1:10-20.
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