CN105080501A - Preparation method for degradable oil-absorbing material by using natural sawdust - Google Patents
Preparation method for degradable oil-absorbing material by using natural sawdust Download PDFInfo
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- CN105080501A CN105080501A CN201510431990.9A CN201510431990A CN105080501A CN 105080501 A CN105080501 A CN 105080501A CN 201510431990 A CN201510431990 A CN 201510431990A CN 105080501 A CN105080501 A CN 105080501A
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Abstract
The invention relates to the technical field of new materials, and provides a preparation method for a degradable oil-absorbing material by using natural sawdust. The method is characterized by comprising the following steps: (1) subjecting sawdust to washing and drying and then carrying out sieving with a 30-mesh sieve, subjecting the sawdust to soaking pretreatment with concentrated alkali with a soaking time of 18 to 24 h, adjusting a pH value to be neutral, and carrying out filtering, washing and drying so as to obtain pretreated sawdust; (2) adding fatty acid with n-hexane added with concentrated sulfuric acid into the pretreated sawdust, allowing a mass ratio of the fatty acid and the sawdust to be 1: 2.5-5, wherein the n-hexane added with the concentrated sulfuric acid has a usage amount submerging the sawdust, and usage amount of the concentrated sulfuric acid accounts for 5% to 10% of the mass of the fatty acid, and carrying out reaction at 60 to 70 DEG C for 6 to 12 h; and (3) carrying out cooling and filtering, then successively carrying out washing with acetone and distilled water for a plurality of times, and carrying out drying so as to obtain the degradable oil-absorbing material. The preparation method for the degradable oil-absorbing material by using the natural sawdust provided by the invention has simple preparation process, mild reaction and easy operation, can recover a part of oil products by extrusion after oil absorption, wherein the recovered oil products can also be directly used as fuels; meanwhile, the material is easy to be degraded and does not produce secondary pollution to the environment.
Description
Technical field
The present invention relates to new material technology field, specifically refer to a kind of method using natural sawdust to prepare degradable oil absorption material.
Background technology
In recent years, along with industrial expansion, the environmental pollution that the discharge of factory's oily waste water, waste gas and oil carrier, the increase of tank leakage accident cause is day by day serious, according to statistics, the petroleum hydrocarbon every year entering ocean via various approach reaches 600 ~ 1,000 ten thousand tons, enter annual more than about 100,000 tons of the petroleum hydrocarbon of coastal area of china, oil pollution causes threat to the life of people and marine environment.
At present, oil absorption material is mainly divided into 3 classes: inorganic mineral material, organic synthesis material and natural biomass materials.Inorganic mineral material as mica, vermiculite, the inexpensive amounts such as perlite calcium carbonate are wide, but its oil absorbency is low, and after oil suction, recycling rate is also low, is unfavorable for widely using; Organic synthesis material is as polyethylene, and polypropylene, although the oil absorbencies such as polyacrylic resin are high, due to organic synthesis material degradation difficulty, can cause the secondary pollution to environment; Natural biomass materials is as not only widely distributed in stalk, sawdust, bagasse, peat etc., itself has good oil absorption, and is easy to recycling after oil suction, degradable, environmental friendliness.Prepare high oil-absorbent material with natural biologic material to be applied in oiliness sewage treatment.Chinese patent " water body oil spilling adsorbent prepared by a kind of modification agricultural stalk and method for making and application " thereof (application number 201210271903.4 date of publication on 01 16th, 2013) adopts agricultural stalk, after Alkaline pretreatment, with cellulase to stalk modification, through going out mould, filter, washing, obtain water body oil spilling adsorbent after drying, this adsorbent is 16.5g/g to the adsorbance of oil spilling.Sun Runcang, the Sun Xiaofeng of South China Science & Engineering University take agricultural stalk as raw material, at 100 ~ 135 DEG C, carry out acetylation modification to it, obtain a kind of efficient oil absorption material.By further Optimizing Technical, acetylization reaction temperature has been reduced to 50 ~ 80 DEG C under adding the condition of catalyst again by them.The people such as Chen Yuan [Chen Yuan; Luo Zhihui; Wei Qingmin; Yang Jiatian, thanks to autumn, cogongrass Yue Lei] disclose a kind of method that wood chip prepares high oil-absorbent material; with fast-growing Eucalyptus bits for raw material; after adopting Ball-stirring mill to carry out activation process to wood fiber, make catalyst with toluene sulfonic acide, obtain wood chip high oil-absorbent material by acetylation technique.
Masson pine distributed pole is wide, and north, from Henan and Southern Shandong Province, reaches Guangdong and Guangxi Provinces, Hunan (Cili County), Taiwan in the south, and east, from coastal, to central Sichuan and Guizhou, is dispersed throughout various places, south China, Central China.General at THE LOWER YANGTZE VALLEY height above sea level 600 ~ below 700m, middle reaches are about more than 1200m, and upstream is about below 1500m all has distribution, are that seeds used by the main material of SOUTHERN CHINA.Masson pine resin road is many greatly, there is obvious grease circle in cross section, inherently there is good oil absorption, but because its fiber content is also very high, the hydroxyl on cellulose has hydrophily, so pinus massoniana sawdust oil absorption is also fine, by the modification to hydroxyl on sawdust cellulose, its lipophile is increased, and hydrophily reduces, and becomes efficient oil absorbent.
Summary of the invention
The object of this invention is to provide a kind of method using natural sawdust to prepare degradable oil absorption material, to solve water body oil spill problem.
In order to realize above object, present invention employs following technical proposal: a kind of method using natural sawdust to prepare degradable oil absorption material, is adopt the biological sawdust of aliphatic acid modified natural under sulphuric acid catalysis effect; It is characterized in that comprising the following steps:
(1) sawdust is washed, dry after cross 30 mesh sieves, carry out dipping pretreatment with concentrated base to sawdust, soak time is 18-24h, regulate pH to filtering after neutral, washing, dry (oven dry), obtain pretreated sawdust;
(2) by aliphatic acid, the n-hexane being added with the concentrated sulfuric acid, join in the pretreated sawdust that step (1) obtains, aliphatic acid and sawdust mass ratio is made to be 1:2.5 ~ 5, the consumption being added with the n-hexane of the concentrated sulfuric acid is for flooding sawdust (sawdust is 1:3 ~ 5 with the n-hexane volume ratio being added with the concentrated sulfuric acid), concentrated sulfuric acid consumption is the 5%-10% of aliphatic acid quality, at 60 ~ 70 DEG C, react 6-12h;
(3) cool, filter, successively repeatedly wash (being repeatedly each 2-3 washing) with acetone, distilled water, after oven dry, namely obtain degradable oil absorption material.
Step (1) described sawdust is that masson pine sawdust obtains after pulverizer is pulverized.
The described concentrated base preferred concentration of step (1) is the NaOH solution of 2-3mol/L; Soak time is 24h.
What be used for adjust ph described in step (1) is the hydrochloric acid solution of 1mol/L.
The preferred suction filtration of step (1) described filter type, cleaning solution is distilled water; Baking temperature preferably 80 DEG C, the time is 24h.
Step (2) described concentrated sulfuric acid preferred mass mark is the concentrated sulfuric acid of 98%.
Step (2) described aliphatic acid is oleic acid, stearic acid or n-capric acid, the preferred oleic acid of aliphatic acid.
The preferred 1:2.5 of mass ratio of step (2) described aliphatic acid and sawdust, reaction temperature preferably 67 DEG C, reaction time preferred 8-10h.
The main component of sawdust is cellulose, hemicellulose and lignin, and lignin has certain lipophile, and cellulose is because itself is with many hydroxyls, has certain hydrophily; Sawdust is after one deck colloid that surface is removed in concentrated base pretreatment, present loose structure, have good suction-operated, then by modification, the hydrophilic hydroxyl groups on sawdust cellulose is converted to other lipophilic groups, the sawdust of such modification just becomes a kind of good oil absorption material.The present invention is that (tree families of use is masson pine to raw material with pinus massoniana sawdust, masson pine has in China and distributes widely, cheap and easy to get), after adopting concentrated base to carry out pretreatment to sawdust, take the concentrated sulfuric acid as catalyst, with aliphatic acid, modification is carried out to obtain oil absorption material to sawdust.After measured, modified sawdust has good adsorptivity to oil products, and have that oil suction efficiency is high, speed is fast, protect the features such as high, the reusable and environmental friendliness of oily rate.
the present invention has the following advantages:
(1) the present invention adopts natural biological sawdust to be modified feedstock, and wide material sources are with low cost.
(2) preparation technology of the present invention is simple, reaction temperature and, convenient operation.
(3) the water body oil spilling adsorbent prepared of the present invention, by extruding recovery section oil product after oil suction, can also directly be used as fuel, material is easy to degrade, and can not cause secondary pollution to environment.
(4) the present invention can be widely used in seawater pollution process, river and industrial oily waste water treatment.
Detailed description of the invention
embodiment 1:
Use natural sawdust to prepare a method for degradable oil absorption material, comprise the following steps:
(1) by the cleaning, drying of masson pine sawdust to constant weight, pulverize after cross 30 eye mesh screens, obtain pinus massoniana sawdust;
At room temperature soak sawdust by the NaOH solution of 2mol/L, soak time is 24h, then regulates pH to neutral with the hydrochloric acid solution of 1mol/L, cleans, dry to constant weight, obtain pretreated sawdust after filtration with distilled water;
(2) reactor will be placed in through pretreated sawdust, according to quality than aliphatic acid (employing oleic acid): sawdust is that 1:2.5 adds oleic acid in reactor, add the n-hexane dripping and have the concentrated sulfuric acid again, adding to drip has the amount of the n-hexane of the concentrated sulfuric acid to flood sawdust for making it, (mass fraction is the concentrated sulfuric acid of 98% to the concentrated sulfuric acid, identical below) consumption is 8% of aliphatic acid quality, mixture reacts 8h at temperature is 67 DEG C;
(3) reacted rear cooling, filtered, successively with acetone, distilled water washing (each washing 2 times), dried to constant weight and namely obtain degradable oil absorption material (or claim water body oil spilling adsorbent, or claim to change oil absorbent).Degradable oil absorption material is 12.5g/g to oil spilling adsorbance, and excellent adsorption is described.
embodiment 2
Use natural sawdust to prepare a method for degradable oil absorption material, comprise the following steps:
(1) by the cleaning, drying of masson pine sawdust to constant weight, pulverize after cross 30 eye mesh screens, obtain pinus massoniana sawdust;
At room temperature soak sawdust by the NaOH solution of 2mol/L, soak time is 24h, then regulates pH to neutral with the hydrochloric acid solution of 1mol/L, cleans, dry to constant weight, obtain pretreated sawdust after filtration with distilled water;
(2) reactor will be placed in through pretreated sawdust, according to quality than aliphatic acid (employing stearic acid): sawdust is that 1:2.5 adds stearic acid in reactor, add the n-hexane dripping and have the concentrated sulfuric acid again, adding to drip has the amount of the n-hexane of the concentrated sulfuric acid to flood sawdust for making it, concentrated sulfuric acid consumption is 5% of aliphatic acid quality, and mixture reacts 8h at temperature is 67 DEG C;
(3) rear cooling has been reacted, filter, successively with acetone, distilled water washing (each washing 3 times), dry to constant weight and namely obtain degradable oil absorption material (or claiming water body oil spilling adsorbent), degradable oil absorption material is 10.9g/g to oil spilling adsorbance, and excellent adsorption is described.
embodiment 3
Use natural sawdust to prepare a method for degradable oil absorption material, comprise the following steps:
(1) by the cleaning, drying of masson pine sawdust to constant weight, pulverize after cross 30 eye mesh screens, obtain pinus massoniana sawdust;
At room temperature soak sawdust by the NaOH solution of 2mol/L, soak time is 24h, then regulates pH to neutral with the hydrochloric acid solution of 1mol/L, cleans, dry to constant weight, obtain pretreated sawdust after filtration with distilled water;
(2) reactor will be placed in through pretreated sawdust, according to quality than aliphatic acid (employing n-capric acid): sawdust is that 1:2.5 adds n-capric acid in reactor, add the n-hexane dripping and have the concentrated sulfuric acid again, adding to drip has the amount of the n-hexane of the concentrated sulfuric acid to flood sawdust for making it, concentrated sulfuric acid consumption is 7% of aliphatic acid quality, and mixture reacts 8h at temperature is 67 DEG C;
(3) reacted rear filtration, successively with acetone, distilled water washing (each washing 3 times), dry and namely obtain degradable oil absorption material (or claiming water body oil spilling adsorbent) to constant weight, degradable oil absorption material is 11.2g/g to oil spilling adsorbance, and excellent adsorption is described.
embodiment 4
Use natural sawdust to prepare a method for degradable oil absorption material, comprise the following steps:
(1) by the cleaning, drying of masson pine sawdust to constant weight, pulverize after cross 30 eye mesh screens, obtain pinus massoniana sawdust;
At room temperature soak sawdust by the NaOH solution of 2mol/L, soak time is 24h, then regulates pH to neutral with the hydrochloric acid solution of 1mol/L, cleans, dry to constant weight, obtain pretreated sawdust after filtration with distilled water;
(2) reactor will be placed in through pretreated sawdust, according to quality than aliphatic acid: sawdust is that 1:5 adds oleic acid in reactor, add the n-hexane dripping and have the concentrated sulfuric acid again, adding to drip has the amount of the n-hexane of the concentrated sulfuric acid to flood sawdust for making it, concentrated sulfuric acid consumption is 10% of aliphatic acid quality, and mixture reacts 10h at temperature is 67 DEG C;
(3) reacted rear filtration, successively with acetone, distilled water washing (each washing 2 times), dry and namely obtain degradable oil absorption material (or claiming water body oil spilling adsorbent) to constant weight, degradable oil absorption material is 10.7g/g to oil spilling adsorbance, and excellent adsorption is described.
embodiment 5
Use natural sawdust to prepare a method for degradable oil absorption material, comprise the following steps:
(1) by the cleaning, drying of masson pine sawdust to constant weight, pulverize after cross 30 eye mesh screens, obtain pinus massoniana sawdust;
At room temperature soak sawdust by the NaOH solution of 3mol/L, soak time is 18h, then regulates pH to neutral with the hydrochloric acid solution of 1mol/L, cleans, dry to constant weight, obtain pretreated sawdust after filtration with distilled water;
(2) reactor will be placed in through pretreated sawdust, according to quality than aliphatic acid: sawdust is that 1:3.5 adds oleic acid in reactor, add the n-hexane dripping and have the concentrated sulfuric acid again, adding to drip has the amount of the n-hexane of the concentrated sulfuric acid to flood sawdust for making it, concentrated sulfuric acid consumption is 7% of aliphatic acid quality, and mixture reacts 12h at temperature is 60 DEG C;
(3) reacted rear filtration, successively with acetone, distilled water washing (each washing 3 times), dry and namely obtain degradable oil absorption material (or claiming water body oil spilling adsorbent) to constant weight, degradable oil absorption material is 11.3g/g to oil spilling adsorbance, and excellent adsorption is described.
Claims (10)
1. use natural sawdust to prepare a method for degradable oil absorption material, it is characterized in that comprising the following steps:
(1) sawdust is washed, dry after cross 30 mesh sieves, carry out dipping pretreatment with concentrated base to sawdust, soak time is 18-24h, regulates pH to filtering after neutral, washing, dry, obtains pretreated sawdust;
(2) by aliphatic acid, the n-hexane being added with the concentrated sulfuric acid, joining in pretreated sawdust, make aliphatic acid and sawdust mass ratio be 1:2.5 ~ 5, being added with the consumption of the n-hexane of the concentrated sulfuric acid for flooding sawdust, concentrated sulfuric acid consumption is the 5%-10% of aliphatic acid quality, at 60 ~ 70 DEG C, react 6-12h;
(3) cool, filter, successively repeatedly wash with acetone, distilled water, after oven dry, namely obtain degradable oil absorption material.
2. a kind of method using natural sawdust to prepare degradable oil absorption material according to claim 1, is characterized in that, step (1) described sawdust is that masson pine sawdust obtains after pulverizer is pulverized.
3. a kind of method using natural sawdust to prepare degradable oil absorption material according to claim 1, it is characterized in that, the described concentrated base preferred concentration of step (1) is the NaOH solution of 2-3mol/L.
4. a kind of method using natural sawdust to prepare degradable oil absorption material according to claim 1, it is characterized in that, step (1) described soak time is 24h.
5. a kind of method using natural sawdust to prepare degradable oil absorption material according to claim 1, is characterized in that, what be used for adjust ph described in step (1) is the hydrochloric acid solution of 1mol/L.
6. a kind of method using natural sawdust to prepare degradable oil absorption material according to claim 1, it is characterized in that, the preferred suction filtration of step (1) described filter type, cleaning solution is distilled water.
7. a kind of method using natural sawdust to prepare degradable oil absorption material according to claim 1, it is characterized in that, step (1) described baking temperature preferably 80 DEG C, the time is 24h.
8. a kind of method using natural sawdust to prepare degradable oil absorption material according to claim 1, it is characterized in that, step (2) described concentrated sulfuric acid preferred mass mark is the concentrated sulfuric acid of 98%.
9. a kind of method using natural sawdust to prepare degradable oil absorption material according to claim 1, it is characterized in that, step (2) described aliphatic acid is oleic acid, stearic acid or n-capric acid.
10. a kind of method using natural sawdust to prepare degradable oil absorption material according to claim 1, is characterized in that, the preferred 1:2.5 of mass ratio of step (2) described aliphatic acid and sawdust, reaction temperature preferably 67 DEG C, reaction time preferred 8-10h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076266A (en) * | 2016-06-07 | 2016-11-09 | 北京林业大学 | Oil absorption material and its production and use |
| CN116237012A (en) * | 2022-11-21 | 2023-06-09 | 浙江工商大学 | Modified sawdust adsorbent for thermal desorption wastewater and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5858191A (en) * | 1981-10-02 | 1983-04-06 | Yonemi Tanaka | Biological deodorization of organic waste matter |
| CN101565488A (en) * | 2009-06-01 | 2009-10-28 | 新疆大学 | Preparation method of cellulose-based oil-absorption material |
| CN102344531A (en) * | 2011-07-08 | 2012-02-08 | 大连工业大学 | Method for preparing oil absorption material by adopting straws as base materials |
| CN103145921A (en) * | 2013-03-28 | 2013-06-12 | 东华大学 | Preparation method of high oil-absorption material based on invasive plant |
| CN104624162A (en) * | 2013-11-08 | 2015-05-20 | 中国石油天然气集团公司 | Preparation method of oil absorbing material by taking palm fiber as basic material |
-
2015
- 2015-07-22 CN CN201510431990.9A patent/CN105080501A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5858191A (en) * | 1981-10-02 | 1983-04-06 | Yonemi Tanaka | Biological deodorization of organic waste matter |
| CN101565488A (en) * | 2009-06-01 | 2009-10-28 | 新疆大学 | Preparation method of cellulose-based oil-absorption material |
| CN102344531A (en) * | 2011-07-08 | 2012-02-08 | 大连工业大学 | Method for preparing oil absorption material by adopting straws as base materials |
| CN103145921A (en) * | 2013-03-28 | 2013-06-12 | 东华大学 | Preparation method of high oil-absorption material based on invasive plant |
| CN104624162A (en) * | 2013-11-08 | 2015-05-20 | 中国石油天然气集团公司 | Preparation method of oil absorbing material by taking palm fiber as basic material |
Non-Patent Citations (1)
| Title |
|---|
| SHASHWAT S. BANERJEE ET AL: ""Treatment of oil spill by sorption technique using fatty acid grafted sawdust"", 《CHEMOSPHERE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076266A (en) * | 2016-06-07 | 2016-11-09 | 北京林业大学 | Oil absorption material and its production and use |
| CN106076266B (en) * | 2016-06-07 | 2018-11-02 | 北京林业大学 | Oil absorption material and its preparation method and application |
| CN116237012A (en) * | 2022-11-21 | 2023-06-09 | 浙江工商大学 | Modified sawdust adsorbent for thermal desorption wastewater and preparation method and application thereof |
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Application publication date: 20151125 |