CN108276459A - A kind of NAPG-SiO2Nano material and its application as oil-spill dispersant - Google Patents
A kind of NAPG-SiO2Nano material and its application as oil-spill dispersant Download PDFInfo
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- CN108276459A CN108276459A CN201810018408.XA CN201810018408A CN108276459A CN 108276459 A CN108276459 A CN 108276459A CN 201810018408 A CN201810018408 A CN 201810018408A CN 108276459 A CN108276459 A CN 108276459A
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
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- C—CHEMISTRY; METALLURGY
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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- C09K3/00—Materials not provided for elsewhere
- C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
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Abstract
The present invention relates to a kind of NAPG SiO2Nano material and its application as environment-friendly type oil-spill dispersant, NAPG SiO of the invention2Nano material toxicity is low, safe, to brachionus plicatilis young acute toxicity LC for 24 hours50More than 30000mg/L；The NAPG SiO of the present invention2Nano material can be used for handling ocean, harbour, rivers the water surface on oil pollution, dosage is only 2% the 10% of crude quality.
Description
Technical field
The invention belongs to oil-spill dispersant fields, and in particular to a kind of NAPG-SiO2Nano material and its as environment-friendly type
The application of oil-spill dispersant.
Background technology
In oil exploration ＆ development, transportational process, due to misoperation or accident leakage etc., it is excessive often to have oil
Or discharge, oil spill accident occurs, serious environmental pollution can be caused.Petroleum pollution in ocean is difficult to the destruction of marine ecosystems
With what is retrieved.Oil floats across the sea, diffuses to form oil film rapidly.Oil film forms the reoxygenation effect for hindering water body, influences sea
Foreign planktonic organism growth, destroys marine ecology balance.The data shows that fish and shellfish are in the seawater that oil-containing is 0.01mg/L
Life can be stained with oily taste in 24 hours；If concentration rises to 0.1mg/L, there can be peculiar smell within 2-3 hours.In order to drop in a short time
Low oil spill uses oil-spill dispersant after physical method removes marine oil spill.Currently, when oil-spill dispersant handles oil spilling, it is main
If using surfactant it is amphipathic by marine oil spill emulsion dispersion at tiny suspension oil droplet, drift about with wave, diffusion,
To make oil spilling be easier, by oxygen in water oxidation or microbial degradation, to reduce the influence to ocean aquatic animals and plants, avoid
Seabird is stain and oil spilling disembarkation, reduces the influence to environment.Dispersant is mainly with the organic table of chemical synthesis class used at present
Based on the activating agent of face, but since its biological toxicity test is abundant not enough, the stability of emulsified oil droplet is by original after dispersant dispersion
The influence of the environmental factors such as oil type and ocean temperature, salinity, and cost is higher.Therefore, a kind of less toxic, high there is an urgent need to research and develop
The marine oil overflow dispersant of effect.
Polyethers amido alkyl glycosides (NPAG) includes alkyl, multiple hydrophilic hydroxyls, the 1-3 connected Portugal of 1 oleophylic
Grape saccharide ring, 1 hydrophilic polyether group and 1 polyamine group adsorbed by force, are chiefly used in drilling fluid (Chinese invention patent Shen at present
Please number：201510423557.0、201510486562.6、201510500893.0).
The present invention provides a kind of silicon dioxide carried polyethers amido alkyl glycosides type (NAPG-SiO2) nanoscale oil spilling point
Dispersant material.
Invention content
The present invention provides a kind of NAPG-SiO2Nano material, it is characterised in that the NAPG-SiO2The preparation of nano material
Method includes the following steps：
(1) at room temperature, it after polyethers amido alkyl glycosides being dissolved in the ethanol solution that volume fraction is 40%-60%, is added
Ammonium hydroxide obtains mixed liquor after stirring 0.5-1h；
(2) ethyl orthosilicate is added dropwise in the mixed liquor obtained to step (1), after continuing stirring until there is precipitation, heating
To 70-80 DEG C, continues after stirring 8-10h, be filtered, washed, dry to obtain solid；
(3) after the solid abrasive for obtaining step (2) is at powder, roasting 6-8h obtains white powder at 500-600 DEG C；
(4) white powder for obtaining step (3) is added in sulfuric acid solution, stirs evenly, and is heated to 70-80 DEG C of processing 8-
It after 10h, is filtered, washed, dries to obtain beige solid；
(5) beige solid that step (4) obtains is pulverized last, 3-5h is roasted at 700-800 DEG C and obtains black
Powder, the as NAPG-SiO2Nano material.
Polyethers amido alkyl glycosides described in step (1) has structure shown in Formulas I：
Wherein m is 1-16, n 1-3, o 0-4, R1For C1-C10 alkyl, R2For CH2Or CH2CH2；
The further preferred m of Formulas I structure is 1, n 1-3, o 0, R1For Me, R2For CH2；Or m is 9-10, n 1-3, o
It is 1, R1For Et, R2For CH2CH2。
The quality of ethanol solution is 3-4 times of polyethers amido alkyl glycosides in step (1), and the quality of ammonium hydroxide is polyethers amido
0.8-1.2 times of alkyl glycosides quality, a concentration of 1-2mol/L of ammonium hydroxide；
The quality of ethyl orthosilicate is 2.0-2.5 times of polyethers amido alkyl glycosides quality in step (2)；
The quality of sulfuric acid solution described in step (4) is 5-6 times of white powder quality, a concentration of 2- of sulfuric acid solution
4mol/L。
Another embodiment of the present invention provides a kind of NAPG-SiO2The preparation method of nano material, it is characterised in that packet
Include following steps：
(1) at room temperature, it after polyethers amido alkyl glycosides being dissolved in the ethanol solution that volume fraction is 40%-60%, is added
Ammonium hydroxide obtains mixed liquor after stirring 0.5-1h；
(2) ethyl orthosilicate is added dropwise in the mixed liquor obtained to step (1), after continuing stirring until there is precipitation, heating
To 70-80 DEG C, continues after stirring 8-10h, be filtered, washed, dry to obtain solid；
(3) after the solid abrasive for obtaining step (2) is at powder, roasting 6-8h obtains white powder at 500-600 DEG C；
(4) white powder for obtaining step (3) is added in sulfuric acid solution, stirs evenly, and is heated to 70-80 DEG C of processing 8-
It after 10h, is filtered, washed, dries to obtain beige solid；
(5) beige solid that step (4) obtains is pulverized last, 3-5h is roasted at 700-800 DEG C and obtains black
Powder, the as NAPG-SiO2Nano material.
Polyethers amido alkyl glycosides described in step (1) has structure shown in Formulas I：
Wherein m is 1-16, n 1-3, o 0-4, R1For C1-C10 alkyl, R2For CH2Or CH2CH2；
The further preferred m of Formulas I structure is 1, n 1-3, o 0, R1For Me, R2For CH2；Or m is 9-10, n 1-3, o
It is 1, R1For Et, R2For CH2CH2。
The quality of ethanol solution is 3-4 times of polyethers amido alkyl glycosides in step (1), and the quality of ammonium hydroxide is polyethers amido
0.8-1.2 times of alkyl glycosides quality, a concentration of 1-2mol/L of ammonium hydroxide；
The quality of ethyl orthosilicate is 2.0-2.5 times of polyethers amido alkyl glycosides quality in step (2)；
The quality of sulfuric acid solution described in step (4) is 5-6 times of white powder quality, a concentration of 2- of sulfuric acid solution
4mol/L。
Another embodiment of the present invention provides above-mentioned NAPG-SiO2Application of the nano material as oil-spill dispersant.
Another embodiment of the present invention provides above-mentioned NAPG-SiO2Application of the nano material as oil-spill dispersant,
The oil pollution being characterized in that on the water surface for handling ocean, harbour, rivers.
Another embodiment of the present invention provides above-mentioned NAPG-SiO2Application of the nano material as oil-spill dispersant,
It is characterized in that NAPG-SiO2The dosage of nano material is preferably the 2%-10% of crude quality.
Polyethers amido alkyl glycosides Formulas I of the present invention, can be according to Chinese Patent Application No.：In 201510486562.6
It is prepared by the method for record.
Compared with the prior art, the advantages of the present invention are as follows：(1) NAPG-SiO of the invention2Nano material toxicity is low, pacifies
Quan Xinggao, to brachionus plicatilis young acute toxicity LC for 24 hours50More than 30000mg/L；(2) NAPG-SiO of the invention2It receives
Rice material is few as oil-spill dispersant dosage and dispersion effect is good.
Description of the drawings
The TEM of Fig. 1 products A schemes
The TEM of Fig. 2 products B schemes
Specific implementation mode
For the ease of a further understanding of the present invention, examples provided below has done more detailed description to it.But
It is that these embodiments are only not supposed to be a limitation to the present invention or implementation principle for being better understood from invention, reality of the invention
The mode of applying is not limited to the following contents.
Embodiment 1
(1) at room temperature, polyethers amido alkyl glycosides (abbreviation NAPG-1) 100g is dissolved in the ethyl alcohol that volume fraction is 40%
After solution 300g, the ammonium hydroxide 120g of 1mol/L is added, after stirring 1h, obtains mixed liquor；
(2) ethyl orthosilicate 200g is added dropwise in the mixed liquor obtained to step (1), after continuing stirring until there is precipitation,
70 DEG C are warming up to, is continued after stirring 10h, is filtered, washed, dries to obtain solid；
(3) after the solid abrasive for obtaining step (2) is at powder, roasting 8h obtains white powder 210g at 500 DEG C；
(4) white powder for obtaining step (3) is added in 4mol/L sulfuric acid solutions 1050g, stirs evenly, is heated to 80
DEG C processing 8h after, be filtered, washed, dry to obtain beige solid；
(5) beige solid that step (4) obtains is pulverized last, 5h is roasted at 700 DEG C and obtains black powder
198g, the as NAPG-SiO2Nano material (hereinafter referred to as product A).
The NAPG-1 structures used in the present embodiment are following (according to Chinese Patent Application No.：201510486562.6 middle reality
Prepared by the method for applying the record of example 1)：
Wherein m is 1, n 1-3, o 0, R1For Me, R2For CH2。
Embodiment 2
(1) at room temperature, polyethers amido alkyl glycosides (abbreviation NAPG-2) 100g is dissolved in the ethyl alcohol that volume fraction is 60%
After solution 400g, the ammonium hydroxide 80g of 2mol/L is added, after stirring 0.5h, obtains mixed liquor；
(2) ethyl orthosilicate 250g is added dropwise in the mixed liquor obtained to step (1), after continuing stirring until there is precipitation,
80 DEG C are warming up to, is continued after stirring 8h, is filtered, washed, dries to obtain solid；
(3) after the solid abrasive for obtaining step (2) is at powder, roasting 6h obtains white powder 225g at 600 DEG C；
(4) white powder for obtaining step (3) is added in the sulfuric acid solution 1350g of 2mol/L, stirs evenly, is heated to
After 70 DEG C of processing 10h, it is filtered, washed, dries to obtain beige solid；
(5) beige solid that step (4) obtains is pulverized last, 3h is roasted at 800 DEG C and obtains black powder
211g, the as NAPG-SiO2Nano material (hereinafter referred to as product B).
The structure of the NAPG-2 used in the present embodiment is following (according to Chinese Patent Application No.：In 201510486562.6
Prepared by the method that embodiment 2 is recorded)：
Wherein m is 9-10, n 1-3, o 1, R1For Et, R2For CH2CH2。
3 acute toxicity test of embodiment
According to document (《Crude oil and 4 kinds of oil-spill dispersants are to brachionus plicatilis (Brachionus plicatili) toxicity
The research of effect》, Chen Yue, master thesis, 2014) described in method, test product A, B of the present invention, NAPG-1,
NAPG-2 and Chinese Patent Application No.：201510014913.3 environment-friendly type marine oil spill emulsifying dispersant prepared by middle embodiment 1
The acute toxicity test of (hereinafter referred to as patented product) to the brachionus plicatilis young, the experimental results showed that product A, B of the present invention,
The LC of NAPG-1, NAPG-250More than 30000mg/L, and the LC of patented product50Less than 1500mg/L, i.e., product and base of the present invention
Material biological safety is high.
The measurement of 4 oil-spill dispersant emulsification rate of embodiment (environment temperature is controlled at 20-25 DEG C when experiment)
After by a certain percentage mixing product A, B, NAPG-1, NAPG-2 of the present invention and patented product with crude oil, it is added 9 times
In the artificial seawater of volume, its emulsion dispersion ability to crude oil in the seawater is tested after carrying out acutely concussion emulsification 3min, is tied
Fruit is shown in Table 1.
Table 1
| Test sample | The mass ratio of sample and crude oil | Stand emulsification rate when 30s | Stand emulsification rate when 10min |
| Product A | 0.02 | 60.6% | 32.5% |
| Product A | 0.05 | 74.4% | 43.9% |
| Product A | 0.1 | 80.2% | 51.3% |
| Product B | 0.02 | 61.8% | 30.2% |
| Product B | 0.1 | 79.4% | 48.2% |
| NAPG-1 | 0.1 | 36.7% | 5.2% |
| NAPG-2 | 0.1 | 37.2% | 4.3% |
| Patented product | 0.1 | 58.3% | 28.7% |
| Patented product | 0.2 | 64.8% | 32.5% |
All references mentioned in the present invention is incorporated herein by reference document, just as each document quilt
It is individually recited as reference.In addition, it should also be understood that, after the above for having read the present invention, those skilled in the art
The present invention can be made various changes or modifications, such equivalent forms are equally fallen within defined by the application the appended claims
Range.
Claims (9)
1. a kind of NAPG-SiO2Nano material, it is characterised in that the NAPG-SiO2The preparation method of nano material includes as follows
Step：
(1) at room temperature, after polyethers amido alkyl glycosides being dissolved in the ethanol solution that volume fraction is 40%-60%, ammonium hydroxide is added,
After stirring 0.5-1h, mixed liquor is obtained；
(2) ethyl orthosilicate is added dropwise in the mixed liquor obtained to step (1), after continuing stirring until there is precipitation, is warming up to 70-
80 DEG C, continues after stirring 8-10h, be filtered, washed, dry to obtain solid；
(3) after the solid abrasive for obtaining step (2) is at powder, roasting 6-8h obtains white powder at 500-600 DEG C；
(4) white powder for obtaining step (3) is added in sulfuric acid solution, stirs evenly, and is heated to 70-80 DEG C of processing 8-10h
Afterwards, it is filtered, washed, dries to obtain beige solid；
(5) beige solid that step (4) obtains is pulverized last, 3-5h is roasted at 700-800 DEG C and obtains black powder,
The as NAPG-SiO2Nano material.
2. NAPG-SiO described in claim 12Nano material, it is characterised in that polyethers amido alkyl glycosides described in step (1)
With structure shown in Formulas I：
Wherein m is 1-16, n 1-3, o 0-4, R1For C1-C10 alkyl, R2For CH2Or CH2CH2；
The further preferred m of Formulas I structure is 1, n 1-3, o 0, R1For Me, R2For CH2；Or m is 9-10, n 1-3, o 1, R1
For Et, R2For CH2CH2。
3. claim 1-2 any one of them NAPG-SiO2Nano material, it is characterised in that the matter of ethanol solution in step (1)
Amount is 3-4 times of polyethers amido alkyl glycosides, and the quality of ammonium hydroxide is 0.8-1.2 times of polyethers amido alkyl glycosides quality, ammonium hydroxide
A concentration of 1-2mol/L.
4. claim 1-3 any one of them NAPG-SiO2Nano material, it is characterised in that ethyl orthosilicate in step (2)
Quality is 2.0-2.5 times of polyethers amido alkyl glycosides quality.
5. claim 1-4 any one of them NAPG-SiO2Nano material, it is characterised in that sulfuric acid solution described in step (4)
Quality be 5-6 times of white powder quality, a concentration of 2-4mol/L of sulfuric acid solution.
6. claim 1-5 any one of them NAPG-SiO2Application of the nano material as oil-spill dispersant.
7. the application described in claim 6, it is characterised in that for handle ocean, harbour, rivers the water surface on oil pollution.
8. claim 6-7 any one of them applications, it is characterised in that NAPG-SiO2The dosage of nano material is preferably crude oil
The 2%-10% of quality.
9. claim 1-5 any one of them NAPG-SiO2The preparation method of nano material.
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|---|---|---|---|---|
| CN1907852A (en) * | 2006-08-04 | 2007-02-07 | 华东师范大学 | Method of synthesizing ordered mesoporous silica dioxide using cation alkyl glycoside as template agent |
| CN103447003A (en) * | 2013-08-16 | 2013-12-18 | 中国科学院上海硅酸盐研究所 | Application of multistage hole carbon block body as material for absorbing/recovering oily organic substance |
| CN104962239A (en) * | 2015-06-01 | 2015-10-07 | 交通运输部水运科学研究所 | Eco-friendly oil spill dispersant and preparation method thereof |
| CN105601314A (en) * | 2015-12-29 | 2016-05-25 | 中国石油化工股份有限公司 | Preparation method of hydrophobic carbon-fiber aerogel for reclaiming oil spillage |
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2018
- 2018-01-08 CN CN201810018408.XA patent/CN108276459A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1907852A (en) * | 2006-08-04 | 2007-02-07 | 华东师范大学 | Method of synthesizing ordered mesoporous silica dioxide using cation alkyl glycoside as template agent |
| CN103447003A (en) * | 2013-08-16 | 2013-12-18 | 中国科学院上海硅酸盐研究所 | Application of multistage hole carbon block body as material for absorbing/recovering oily organic substance |
| CN104962239A (en) * | 2015-06-01 | 2015-10-07 | 交通运输部水运科学研究所 | Eco-friendly oil spill dispersant and preparation method thereof |
| CN105601314A (en) * | 2015-12-29 | 2016-05-25 | 中国石油化工股份有限公司 | Preparation method of hydrophobic carbon-fiber aerogel for reclaiming oil spillage |
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Application publication date: 20180713 |