CN108946955A - A kind of preparation method of degreaser - Google Patents
A kind of preparation method of degreaser Download PDFInfo
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- CN108946955A CN108946955A CN201810667597.3A CN201810667597A CN108946955A CN 108946955 A CN108946955 A CN 108946955A CN 201810667597 A CN201810667597 A CN 201810667597A CN 108946955 A CN108946955 A CN 108946955A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
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Abstract
The invention discloses a kind of preparation methods of degreaser, belong to water-treatment technology field.Graphene oxide is mixed with water 1:8~1:10 in mass ratio, ultrasonic disperse obtains graphene oxide solution, and graphene oxide solution is mixed with pre- modified polystyrene chitosan microball 5:1~8:1 in mass ratio, and 0.1~0.2 times of graphene oxide solution quality of modification sodium cellulose glycolate is added, after ultrasonic disperse, filters, obtain degreaser blank, degreaser blank is mixed into immersion with organic solvent 1:3~1:5 in mass ratio, filtering, washing, obtains degreaser.The degreaser of technical solution of the present invention preparation has the characteristics that excellent oil removing performance, has broad prospects in the development of water treatment technology industry.
Description
Technical field
The invention discloses a kind of preparation methods of degreaser, belong to water-treatment technology field.
Background technique
Metal in storage, carrying and process, inevitably polluted by extraneous some dirts by surface.Oil removing is
A kind for the treatment of process of water-oil separating and oil recovery is carried out to oily waste water.Oily waste water derives from oil field, oil plant, petroleum
Factory, meat, fish, birds processing factory, grease factory, the industrial and mining enterprises such as Leather Factory.The chemicals treatment of oily sludge is to utilize chemical drugs
The oil removings mechanism such as the rolling, emulsify, dissolving of agent, solubilising, to reach the method for oil removing purpose.It is summarized according to medicament kind the author
The present Research of recent domestic oily sludge chemicals treatment, including surfactant elution oil removing, demulsifier demulsification remove
Compounding oil removing between oil, soda lye wash oil removing, flocculant flocculation deoiling and medicament.Pollutant include factory be antirust, drawing and
Machine oil, lubricating oil, vegetable and animals oils used in machining or forming process etc., must be driven off oil pollution before carrying out coating
Object.Oil removing is one of surface treatment important procedure.Because greasy dirt can be such that the adhesive force of film reduces, other property of film are had an effect on
Can, so must clean up.Piece surface greasy dirt is removed by chemistry or other methods.Common method mainly has alkalinity at present
Oil removing, Solvent degreasing and metal cleaner oil removing etc..
Physical oil-removing method is that have solvent solvent using to greasy dirt (vegetable and animals oils or mineral oil), and greasy dirt is washed away
Method.This method processing speed is fast, but deoiling effect is not so good, and most solvents are inflammable and explosive, and there are also certain toxicity, make
It uses less safe.Workpiece and die casting of the method suitable for the stamping parts of steel material, casting, aluminium, copper and its alloy.
It is relatively applicable in cleared mineral oil and more serious grease is difficult to lye.Implement solvent oil removing technique have scouring method,
Vapor method and infusion process etc., because most of organic solvent burns with toxic with easy, in using and storing, it is contemplated that
Safety and ventilating problem.Chemistry goes out oil removing according to the type and property of grease, and degreaser includes two kinds of bulk compositions, and bases, which helps, to be washed
Agent and surfactant.Bases builder is commonly sodium hydroxide, soda ash, sodium metasilicate and sodium tripolyphosphate.Surfactant
It is the most crucial ingredient of degreaser, the degreaser of early stage is based on the emulsification with emulsifier, such as fatty alcohol polyoxyethylene ether
(AEO) series, alkyl phenol polyoxyethylene ether (TX, NP) series etc..
And traditional degreaser the problem of can not being further increased there is also oil removing performance, therefore, how to improve tradition and remove
The shortcomings that oil removing performance of finish can not further increase, in the hope of explore develop the degreaser with good comprehensive performance be to
It solves the problems, such as.
Summary of the invention
The present invention solves the technical problem of: for traditional degreaser there is also oil removing performances can not be into one
The shortcomings that step improves, provides a kind of preparation method of degreaser.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of degreaser, specific preparation step are as follows:
(1) chitosan acetic acid solution is mixed with sodium hydroxide solution 1:3~1:4 in mass ratio, after being stirred, is stood, mistake
Filter, obtains filter cake, and filter cake is washed to cleaning solution as neutrality, chitosan microball blank is obtained, by chitosan microball blank and glutaraldehyde
The mixing of 1:5~1:8 in mass ratio, is filtered, and washing obtains chitosan microball, by chitosan microball and lipase 1:2 in mass ratio~
1:3 mixing, and 5~10 times of chitosan microball quality of water is added, it after being stirred, impregnates, filters, it is poly- to obtain modified shell for washing
Sugared microballoon；
(2) modification of chitosan microballoon is mixed with water 1:10~1:15 in mass ratio, and sequentially add modification of chitosan quality 1~
2 times of styrene, the divinylbenzene that 0.8~1.5 times of modification of chitosan quality, the mistake that 0.2~0.3 times of modification of chitosan quality
Benzoyl Oxide and 1~2 times of modification of chitosan quality of epoxy propane butyl ether obtain shell after being stirred under nitrogen atmosphere
Chitosan microball mixture is mixed with initiator 100:1 in mass ratio, is stirred to react by glycan mixture of microspheres, is filtered, is washed
It washs, it is dry, obtain polystyrene chitosan microball；
(3) sodium cellulose glycolate is mixed with normal heptane 1:2 in mass ratio, and is added 2~3 times of sodium cellulose glycolate quality
Fat acyl chloride, after being stirred to react, concentrated by rotary evaporation is washed, dry, obtains modified sodium cellulose glycolate；
(4) polystyrene chitosan microball is mixed with water 1:10~1:20 in mass ratio, and it is micro- that polystyrene chitosan is added
The mix acid liquor that 1~2 times of ball quality, after being stirred to react, filtering, washing to cleaning solution is neutrality, dry, must pre-process polyphenyl second
Alkene chitosan microball mixes pretreatment polystyrene chitosan microball with potassium hydroxide solution 1:5~1:8 in mass ratio, and
The sodium thiosulfate of 0.2~0.3 times of polystyrene chitosan microball quality of pretreatment is added, after being stirred to react, filtering, washing is extremely
Cleaning solution is neutrality, dry, obtains pre- modified polystyrene chitosan microball；
(5) graphene oxide is mixed with water 1:8~1:10 in mass ratio, ultrasonic disperse obtains graphene oxide solution, will aoxidize
Graphene solution is mixed with pre- modified polystyrene chitosan microball 5:1~8:1 in mass ratio, and graphene oxide solution is added
0.1~0.2 times of quality of modification sodium cellulose glycolate after ultrasonic disperse, filters, degreaser blank is obtained, by degreaser blank
Immersion is mixed with organic solvent 1:3~1:5 in mass ratio, is filtered, washing obtains degreaser.
Step (1) the chitosan acetic acid solution be 10 by the chitosan of deacetylation 60~80% and mass fraction~
12% acetic acid 1:50~1:60 in mass ratio mixing, obtains chitosan acetic acid solution.
Step (1) lipase is Adipose trigtyceride lipase, and hormone-sensitive lipase is appointed in monoester lipase
The composition for one or two of anticipating.
Step (2) initiator is potassium peroxydisulfate, any one in ammonium persulfate or sodium peroxydisulfate.
Step (3) fat acyl chloride is any one in hexadecanoyl chloride or 18 acyl chlorides.
Step (4) described mix acid liquor be 40~60% by mass fraction sulfuric acid and mass fraction be 30~50% nitre
Acid 3:1 in mass ratio mixing, obtains mix acid liquor.
Step (5) organic solvent is toluene, any one in dimethylbenzene or chloroform.
The beneficial effects of the present invention are:
The present invention pre- modified polystyrene chitosan microball when preparing degreaser, and modified sodium cellulose glycolate is added, it is first
It, can be after being added in product first containing the chitosan microball for having adsorbed lipase in pre- modified polystyrene chitosan microball
It is exposed in product preparation process with the immersion in organic solvent, to adsorb lipase in product use process
Chitosan microball can effectively improve the oil removal efficiency of product, secondly, the pre- modified polystyrene chitosan microball surface band being added
There are positive charge, adsorbable graphene oxide, to adsorb after organic solvent immersion in pre- modified polystyrene chitosan microball
One layer of porous graphene oxide can be coated on the outside of the chitosan microball of lipase, to make product in use can be equal
It is even to be distributed in water, and then further increase the deoiling effect of product, furthermore, the modification sodium cellulose glycolate of addition can be
It is fixed in porous oxidation graphene coated layer during filtering, so that the oil absorption efficiency of product be made to improve, and then makes product
Deoiling effect further increase.
Specific embodiment
Sodium hydroxide solution 1:3~1:4 in mass ratio that chitosan acetic acid solution is 10~12% with mass fraction is mixed
It closes, is 45~65 DEG C in temperature, after revolving speed is stirred 20~30min under conditions of being 200~300r/min, room temperature stands 1
~2h, filtering, obtains filter cake, and filter cake is washed with water to cleaning solution as neutrality, chitosan microball blank is obtained, by chitosan microball base
Material mix with glutaraldehyde 1:5~1:8 in mass ratio, in temperature be 30~50 DEG C, revolving speed under conditions of 200~300r/min,
After being stirred 30~60min, filtering obtains filter residue, filter residue is washed with water 8~10 times, chitosan microball is obtained, and chitosan is micro-
Ball is mixed with lipase 1:2~1:3 in mass ratio, and chitosan microball is added into the mixture of chitosan microball and lipase
The water that 5~10 times of quality is 30~50 DEG C in temperature, under conditions of revolving speed is 200~300r/min, it is stirred 30~
After 50min, after impregnating 12~15h under room temperature, filtering obtains modification of chitosan microballoon, by modification of chitosan microballoon water
Washing 5~8 times, obtains modification of chitosan microballoon；Modification of chitosan microballoon and water 1:10~1:15 in mass ratio are mixed in three mouthfuls
In flask, and 1~2 times of modification of chitosan quality of styrene is successively added into three-necked flask, modification of chitosan quality 0.8~
1.5 times of divinylbenzene, the benzoyl peroxide and modification of chitosan quality 1~2 that 0.2~0.3 times of modification of chitosan quality
Times epoxy propane butyl ether, nitrogen is passed through with the rate of 5~15mL/min into three-necked flask, in temperature be 65~70 DEG C,
After revolving speed is stirred under conditions of being 200~350r/min after 5~6h, chitosan microball mixture is obtained, by chitosan microball
Mixture is mixed with initiator 100:1 in mass ratio, continue in nitrogen atmosphere, in temperature be 65~70 DEG C, revolving speed be 200~
After being stirred to react 2~3h under conditions of 350r/min, filters, obtain polystyrene chitosan microball blank, polystyrene shell is gathered
After sugared microballoon blank is washed with water 2~3 times, dry 1~2h under conditions of being 50~60 DEG C in temperature obtains polystyrene chitosan
Microballoon；Sodium cellulose glycolate and normal heptane 1:2 in mass ratio are mixed in beaker, and hydroxylmethyl cellulose is added into beaker
The fat acyl chloride of 2~3 times of plain sodium quality is 45~55 DEG C in temperature, and revolving speed is stirred to react under conditions of being 200~300r/min
It is 50~70 DEG C in temperature after 1~2h, revolving speed is 120~150r/min, is rotated under conditions of 500~600kPa of pressure position dense
It contracts after 3~5h, obtains concentrate, after concentrate is washed 2~3 times with normal heptane, dry 2 under conditions of being 60~70 DEG C in temperature
~3h obtains modified sodium cellulose glycolate；Polystyrene chitosan microball is mixed with water 1:10~1:20 in mass ratio, and to
The mix acid liquor of 1~2 times of polystyrene chitosan microball quality is added in the mixture of polystyrene chitosan microball and water, in
Temperature is 55~60 DEG C, and after revolving speed is stirred to react 1~2h under conditions of being 200~300r/min, filtering must pre-process polyphenyl second
Pretreatment polystyrene chitosan microball blank is washed with water to cleaning solution as neutrality by alkene chitosan microball blank, and in temperature
Degree after dry 1~2h, must pre-process polystyrene chitosan microball under conditions of being 50~60 DEG C, will pre-process polystyrene shell
Potassium hydroxide solution 1:5~1:8 in mass ratio that glycan microballoon and mass fraction are 15~18% mix, and to pre-processing polyphenyl
In the mixture of ethylene chitosan microball and sodium hydroxide solution be added pretreatment polystyrene chitosan microball quality 0.2~
0.3 times of sodium thiosulfate is 65~70 DEG C in temperature, revolving speed is stirred to react 30 under conditions of being 200~350r/min~
After 40min, filtering obtains pre- modified polystyrene chitosan microball blank, and pre- modified polystyrene chitosan microball blank is used
Water washing to cleaning solution is neutrality, and obtains pre- modified polyphenyl second after dry 30~40min under conditions of being 50~65 DEG C in temperature
Alkene chitosan microball；Graphene oxide is mixed with water 1:8~1:10 in mass ratio, under conditions of frequency is 55~60kHz
After 20~30min of ultrasonic disperse, graphene oxide solution is obtained, graphene oxide solution and pre- modified polystyrene chitosan is micro-
Ball 5:1~8:1 in mass ratio is mixed in conical flask, and 0.1~0.2 times of graphene oxide solution quality is added into conical flask
Modification sodium cellulose glycolate, after 20~30min of ultrasonic disperse, filter under conditions of frequency is 55~60kHz, obtain oil removing
Agent blank mixes degreaser blank with organic solvent 1:3~1:5 in mass ratio, and in 30~40min of immersion under room temperature
Afterwards, it filters, obtains pretreatment degreaser, pretreatment degreaser is washed with water 8~15 times, degreaser is obtained.The chitosan acetic acid
Solution is that the acetic acid 1:50~1:60 in mass ratio for being 10~12% with mass fraction by the chitosan of deacetylation 60~80% is mixed
It closes, obtains chitosan acetic acid solution.The lipase is Adipose trigtyceride lipase, hormone-sensitive lipase, monoester fat
Any one in enzyme or two kinds of composition.The initiator is potassium peroxydisulfate, any one in ammonium persulfate or sodium peroxydisulfate.
The fat acyl chloride is any one in hexadecanoyl chloride or 18 acyl chlorides.It is 40~60% that the mix acid liquor, which is by mass fraction,
Sulfuric acid and mass fraction be 30~50% nitric acid 3:1 in mass ratio mix, obtain mix acid liquor.The organic solvent is toluene,
Any one in dimethylbenzene or chloroform.
Chitosan acetic acid solution is mixed with the sodium hydroxide solution 1:4 in mass ratio that mass fraction is 12%, is in temperature
65 DEG C, after revolving speed is stirred 30min under conditions of being 300r/min, room temperature stands 2h, and filtering obtains filter cake, by filter cake water
Washing to cleaning solution is neutrality, obtains chitosan microball blank, chitosan microball blank is mixed with glutaraldehyde 1:8 in mass ratio,
It is 50 DEG C in temperature, under conditions of revolving speed is 300r/min, after being stirred 60min, filtering obtains filter residue, filter residue is washed with water
Wash 10 times, obtain chitosan microball, chitosan microball is mixed with lipase 1:3 in mass ratio, and to chitosan microball and fat
10 times of chitosan microball quality of water is added in the mixture of enzyme, is 50 DEG C in temperature, under conditions of revolving speed is 300r/min, stirs
After mixing mixing 50min, after impregnating 15h under room temperature, filtering obtains modification of chitosan microballoon, modification of chitosan microballoon is used
Water washing 8 times, obtain modification of chitosan microballoon；Modification of chitosan microballoon and water 1:1:15 in mass ratio are mixed in three-necked flask
In, and 2 times of modification of chitosan quality of styrene, the diethyl that 1.5 times of modification of chitosan quality are successively added into three-necked flask
Alkenyl benzene, the benzoyl peroxide and 2 times of modification of chitosan quality of epoxy propane butyl ether that 0.3 times of modification of chitosan quality,
Nitrogen is passed through with the rate of 15mL/min into three-necked flask, is 70 DEG C in temperature, revolving speed stirs under conditions of being 350r/min
After mixing after 6h, chitosan microball mixture is obtained, chitosan microball mixture is mixed with initiator 100:1 in mass ratio, after
Continue in nitrogen atmosphere, is 70 DEG C in temperature, after revolving speed is stirred to react 3h under conditions of being 350r/min, filters, obtain polyphenyl second
Alkene chitosan microball blank after polystyrene chitosan microball blank is washed with water 3 times, is done under conditions of being 60 DEG C in temperature
Dry 2h obtains polystyrene chitosan microball；Sodium cellulose glycolate and normal heptane 1:2 in mass ratio are mixed in beaker, and
3 times of sodium cellulose glycolate quality of fat acyl chloride is added into beaker, is 55 DEG C in temperature, revolving speed is the condition of 300r/min
Under be stirred to react 2h after, in temperature be 70 DEG C, revolving speed 150r/min, under conditions of the 600kPa of pressure position after concentrated by rotary evaporation 5h,
Concentrate is obtained, after concentrate is washed 3 times with normal heptane, it is fine to obtain modified methylol by dry 3h under conditions of being 70 DEG C in temperature
Tie up plain sodium；Polystyrene chitosan microball is mixed with water 1:20 in mass ratio, and to polystyrene chitosan microball and water
The mix acid liquor of 2 times of polystyrene chitosan microball quality is added in mixture, is 60 DEG C in temperature, revolving speed is 300r/min's
Under the conditions of be stirred to react 2h after, filtering, must pre-process polystyrene chitosan microball blank, will pretreatment polystyrene chitosan
Microballoon blank is washed with water to cleaning solution as neutrality, and must pre-process polyphenyl second after dry 2h under conditions of being 60 DEG C in temperature
Alkene chitosan microball will pre-process potassium hydroxide solution that polystyrene chitosan microball and mass fraction are 18% in mass ratio
1:8 mixing, and pretreatment polyphenyl second is added into the mixture of pretreatment polystyrene chitosan microball and sodium hydroxide solution
The sodium thiosulfate of 0.3 times of alkene chitosan microball quality is 70 DEG C in temperature, and revolving speed is stirred to react under conditions of being 350r/min
After 40min, filtering obtains pre- modified polystyrene chitosan microball blank, and pre- modified polystyrene chitosan microball blank is used
Water washing to cleaning solution is neutrality, and obtains pre- modified polystyrene chitosan after dry 40min under conditions of being 65 DEG C in temperature
Microballoon；Graphene oxide is mixed with water 1:10 in mass ratio, under conditions of frequency is 60kHz after ultrasonic disperse 30min, is obtained
Graphene oxide solution and pre- modified polystyrene chitosan microball 8:1 in mass ratio are mixed in cone by graphene oxide solution
In shape bottle, and 0.2 times of graphene oxide solution quality of modification sodium cellulose glycolate is added into conical flask, is in frequency
It under conditions of 60kHz after ultrasonic disperse 30min, filters, obtains degreaser blank, in mass ratio with organic solvent by degreaser blank
1:5 mixing, and after impregnating 40min under room temperature, filtering obtains pretreatment degreaser, and pretreatment degreaser is washed with water
15 times, obtain degreaser.The chitosan acetic acid solution is the acetic acid for being 12% by the chitosan of deacetylation 80% and mass fraction
The mixing of 1:60 in mass ratio, obtains chitosan acetic acid solution.The lipase is Adipose trigtyceride lipase.The initiator is
Potassium peroxydisulfate.The mix acid liquor be 60% by mass fraction sulfuric acid and mass fraction be 50% nitric acid 3:1 in mass ratio
Mixing, obtains mix acid liquor.The organic solvent is toluene.
Chitosan acetic acid solution is mixed with the sodium hydroxide solution 1:4 in mass ratio that mass fraction is 12%, is in temperature
65 DEG C, after revolving speed is stirred 30min under conditions of being 300r/min, room temperature stands 2h, and filtering obtains filter cake, by filter cake water
Washing to cleaning solution is neutrality, obtains chitosan microball blank, chitosan microball blank is mixed with glutaraldehyde 1:8 in mass ratio,
It is 50 DEG C in temperature, under conditions of revolving speed is 300r/min, after being stirred 60min, filtering obtains filter residue, filter residue is washed with water
It washs 10 times, obtains chitosan microball, chitosan microball and water 1:1:15 in mass ratio are mixed in three-necked flask, and successively to three
2 times of modification of chitosan quality of styrene, the divinylbenzene that 1.5 times of chitosan mass, chitosan mass are added in mouth flask
0.3 times of benzoyl peroxide and 2 times of chitosan mass of epoxy propane butyl ether, into three-necked flask with the speed of 15mL/min
Rate is passed through nitrogen, is 70 DEG C in temperature, after revolving speed is stirred rear 6h under conditions of being 350r/min, obtains chitosan microball mixing
Object mixes chitosan microball mixture with initiator 100:1 in mass ratio, continue in nitrogen atmosphere, in temperature be 70 DEG C,
After revolving speed is stirred to react 3h under conditions of being 350r/min, filters, polystyrene chitosan microball blank is obtained, by polystyrene shell
After glycan microballoon blank is washed with water 3 times, dry 2h under conditions of being 60 DEG C in temperature obtains polystyrene chitosan microball；It will
Sodium cellulose glycolate and normal heptane 1:2 in mass ratio are mixed in beaker, and sodium cellulose glycolate matter is added into beaker
3 times of fat acyl chloride of amount, in temperature be 55 DEG C, after revolving speed is stirred to react 2h under conditions of being 300r/min, in temperature be 70 DEG C,
Revolving speed is that 150r/min obtains concentrate under conditions of the 600kPa of pressure position after concentrated by rotary evaporation 5h, and concentrate is washed with normal heptane
After 3 times, dry 3h under conditions of being 70 DEG C in temperature obtains modified sodium cellulose glycolate；By polystyrene chitosan microball with
Water 1:20 in mass ratio mixing, and polystyrene chitosan microball is added into the mixture of polystyrene chitosan microball and water
The mix acid liquor that 2 times of quality is 60 DEG C in temperature, and after revolving speed is stirred to react 2h under conditions of being 300r/min, filtering obtains pre- place
Polystyrene chitosan microball blank is managed, pretreatment polystyrene chitosan microball blank is washed with water to during cleaning solution is
Property, and must pre-process polystyrene chitosan microball after dry 2h, polystyrene will be pre-processed under conditions of being 60 DEG C in temperature
Chitosan microball is mixed with the potassium hydroxide solution 1:8 in mass ratio that mass fraction is 18%, and poly- to pretreatment polystyrene shell
The thiosulfuric acid of 0.3 times of polystyrene chitosan microball quality of pretreatment is added in the mixture of sugared microballoon and sodium hydroxide solution
Sodium is 70 DEG C in temperature, and after revolving speed is stirred to react 40min under conditions of being 350r/min, filtering obtains pre- modified polystyrene shell
Pre- modified polystyrene chitosan microball blank is washed with water to cleaning solution as neutrality, and is in temperature by glycan microballoon blank
Under conditions of 65 DEG C after dry 40min, pre- modified polystyrene chitosan microball is obtained；By graphene oxide and water in mass ratio 1:
10 mixing obtain graphene oxide solution, by graphene oxide solution under conditions of frequency is 60kHz after ultrasonic disperse 30min
It is mixed in conical flask with pre- modified polystyrene chitosan microball 8:1 in mass ratio, and graphite oxide is added into conical flask
0.2 times of alkene solution quality of modification sodium cellulose glycolate is taken out under conditions of frequency is 60kHz after ultrasonic disperse 30min
Filter, obtains degreaser blank, degreaser blank is mixed with organic solvent 1:5 in mass ratio, and in impregnating 40min under room temperature
Afterwards, it filters, obtains pretreatment degreaser, pretreatment degreaser is washed with water 15 times, degreaser is obtained.The chitosan acetic acid solution
To mix the chitosan of deacetylation 80% with the acetic acid 1:60 in mass ratio that mass fraction is 12%, it is molten to obtain chitosan acetic acid
Liquid.The initiator is potassium peroxydisulfate.The mix acid liquor be 60% by mass fraction sulfuric acid and mass fraction be 50%
Nitric acid 3:1 in mass ratio mixing, obtains mix acid liquor.The organic solvent is toluene.
Chitosan acetic acid solution is mixed with the sodium hydroxide solution 1:4 in mass ratio that mass fraction is 12%, is in temperature
65 DEG C, after revolving speed is stirred 30min under conditions of being 300r/min, room temperature stands 2h, and filtering obtains filter cake, by filter cake water
Washing to cleaning solution is neutrality, obtains chitosan microball blank, chitosan microball blank is mixed with glutaraldehyde 1:8 in mass ratio,
It is 50 DEG C in temperature, under conditions of revolving speed is 300r/min, after being stirred 60min, filtering obtains filter residue, filter residue is washed with water
Wash 10 times, obtain chitosan microball, chitosan microball is mixed with lipase 1:3 in mass ratio, and to chitosan microball and fat
10 times of chitosan microball quality of water is added in the mixture of enzyme, is 50 DEG C in temperature, under conditions of revolving speed is 300r/min, stirs
After mixing mixing 50min, after impregnating 15h under room temperature, filtering obtains modification of chitosan microballoon, modification of chitosan microballoon is used
Water washing 8 times, obtain modification of chitosan microballoon；Modification of chitosan microballoon and water 1:1:15 in mass ratio are mixed in three-necked flask
In, and 2 times of modification of chitosan quality of styrene, the diethyl that 1.5 times of modification of chitosan quality are successively added into three-necked flask
Alkenyl benzene, the benzoyl peroxide and 2 times of modification of chitosan quality of epoxy propane butyl ether that 0.3 times of modification of chitosan quality,
Nitrogen is passed through with the rate of 15mL/min into three-necked flask, is 70 DEG C in temperature, revolving speed stirs under conditions of being 350r/min
After mixing after 6h, chitosan microball mixture is obtained, chitosan microball mixture is mixed with initiator 100:1 in mass ratio, after
Continue in nitrogen atmosphere, is 70 DEG C in temperature, after revolving speed is stirred to react 3h under conditions of being 350r/min, filters, obtain polyphenyl second
Alkene chitosan microball blank after polystyrene chitosan microball blank is washed with water 3 times, is done under conditions of being 60 DEG C in temperature
Dry 2h obtains polystyrene chitosan microball；Sodium cellulose glycolate and normal heptane 1:2 in mass ratio are mixed in beaker, and
3 times of sodium cellulose glycolate quality of fat acyl chloride is added into beaker, is 55 DEG C in temperature, revolving speed is the condition of 300r/min
Under be stirred to react 2h after, in temperature be 70 DEG C, revolving speed 150r/min, under conditions of the 600kPa of pressure position after concentrated by rotary evaporation 5h,
Concentrate is obtained, after concentrate is washed 3 times with normal heptane, it is fine to obtain modified methylol by dry 3h under conditions of being 70 DEG C in temperature
Tie up plain sodium；Polystyrene chitosan microball is mixed with water 1:20 in mass ratio, and to polystyrene chitosan microball and water
The mix acid liquor of 2 times of polystyrene chitosan microball quality is added in mixture, is 60 DEG C in temperature, revolving speed is 300r/min's
Under the conditions of be stirred to react 2h after, filtering, must pre-process polystyrene chitosan microball blank, will pretreatment polystyrene chitosan
Microballoon blank is washed with water to cleaning solution as neutrality, and must pre-process polyphenyl second after dry 2h under conditions of being 60 DEG C in temperature
Alkene chitosan microball will pre-process potassium hydroxide solution that polystyrene chitosan microball and mass fraction are 18% in mass ratio
1:8 mixing, and pretreatment polyphenyl second is added into the mixture of pretreatment polystyrene chitosan microball and sodium hydroxide solution
The sodium thiosulfate of 0.3 times of alkene chitosan microball quality is 70 DEG C in temperature, and revolving speed is stirred to react under conditions of being 350r/min
After 40min, filtering obtains pre- modified polystyrene chitosan microball blank, and pre- modified polystyrene chitosan microball blank is used
Water washing to cleaning solution is neutrality, and obtains pre- modified polystyrene chitosan after dry 40min under conditions of being 65 DEG C in temperature
Microballoon；Pre- modified polystyrene chitosan microball and modified sodium cellulose glycolate 1:1.6 in mass ratio are mixed in conical flask
In, after ultrasonic disperse 30min, filter under conditions of frequency is 60kHz, obtain degreaser blank, by degreaser blank with it is organic
Solvent 1:5 in mass ratio mixing, and after impregnating 40min under room temperature, filtering obtains pretreatment degreaser, pretreatment is removed
Finish is washed with water 15 times, obtains degreaser.The chitosan acetic acid solution is by the chitosan and mass fraction of deacetylation 80%
It is mixed for 12% acetic acid 1:60 in mass ratio, obtains chitosan acetic acid solution.The lipase is Adipose trigtyceride lipase.
The initiator is potassium peroxydisulfate.The mix acid liquor be 60% by mass fraction sulfuric acid and mass fraction be 50% nitric acid
The mixing of 3:1 in mass ratio, obtains mix acid liquor.The organic solvent is toluene.
Chitosan acetic acid solution is mixed with the sodium hydroxide solution 1:4 in mass ratio that mass fraction is 12%, is in temperature
65 DEG C, after revolving speed is stirred 30min under conditions of being 300r/min, room temperature stands 2h, and filtering obtains filter cake, by filter cake water
Washing to cleaning solution is neutrality, obtains chitosan microball blank, chitosan microball blank is mixed with glutaraldehyde 1:8 in mass ratio,
It is 50 DEG C in temperature, under conditions of revolving speed is 300r/min, after being stirred 60min, filtering obtains filter residue, filter residue is washed with water
Wash 10 times, obtain chitosan microball, chitosan microball is mixed with lipase 1:3 in mass ratio, and to chitosan microball and fat
10 times of chitosan microball quality of water is added in the mixture of enzyme, is 50 DEG C in temperature, under conditions of revolving speed is 300r/min, stirs
After mixing mixing 50min, after impregnating 15h under room temperature, filtering obtains modification of chitosan microballoon, modification of chitosan microballoon is used
Water washing 8 times, obtain modification of chitosan microballoon；Modification of chitosan microballoon and water 1:1:15 in mass ratio are mixed in three-necked flask
In, and 2 times of modification of chitosan quality of styrene, the diethyl that 1.5 times of modification of chitosan quality are successively added into three-necked flask
Alkenyl benzene, the benzoyl peroxide and 2 times of modification of chitosan quality of epoxy propane butyl ether that 0.3 times of modification of chitosan quality,
Nitrogen is passed through with the rate of 15mL/min into three-necked flask, is 70 DEG C in temperature, revolving speed stirs under conditions of being 350r/min
After mixing after 6h, chitosan microball mixture is obtained, chitosan microball mixture is mixed with initiator 100:1 in mass ratio, after
Continue in nitrogen atmosphere, is 70 DEG C in temperature, after revolving speed is stirred to react 3h under conditions of being 350r/min, filters, obtain polyphenyl second
Alkene chitosan microball blank after polystyrene chitosan microball blank is washed with water 3 times, is done under conditions of being 60 DEG C in temperature
Dry 2h obtains polystyrene chitosan microball；Polystyrene chitosan microball is mixed with water 1:20 in mass ratio, and to polyphenyl second
In the mixture of alkene chitosan microball and water be added 2 times of polystyrene chitosan microball quality mix acid liquor, in temperature be 60
DEG C, after revolving speed is stirred to react 2h under conditions of being 300r/min, filtering must pre-process polystyrene chitosan microball blank, will
Pretreatment polystyrene chitosan microball blank is washed with water to cleaning solution as neutrality, and in temperature be under conditions of 60 DEG C it is dry
After 2h, polystyrene chitosan microball must be pre-processed, the hydrogen that polystyrene chitosan microball and mass fraction are 18% will be pre-processed
Potassium oxide solution 1:8 in mass ratio mixing, and to pretreatment polystyrene chitosan microball and sodium hydroxide solution mixture
It is middle be added pretreatment 0.3 times of polystyrene chitosan microball quality sodium thiosulfate, in temperature be 70 DEG C, revolving speed 350r/
After being stirred to react 40min under conditions of min, filtering obtains pre- modified polystyrene chitosan microball blank, by pre- modified polyphenyl second
Alkene chitosan microball blank is washed with water to cleaning solution as neutrality, and is obtained pre- under conditions of being 65 DEG C in temperature after dry 40min
Modified polystyrene chitosan microball；Graphene oxide is mixed with water 1:10 in mass ratio, under conditions of frequency is 60kHz
After ultrasonic disperse 30min, graphene oxide solution is obtained, graphene oxide solution and pre- modified polystyrene chitosan microball are pressed
Mass ratio 8:1 is mixed in conical flask, under conditions of frequency is 60kHz after ultrasonic disperse 30min, is filtered, is obtained degreaser base
Material, degreaser blank is mixed with organic solvent 1:5 in mass ratio, and after impregnating 40min under room temperature, and filtering obtains pre-
Degreaser is handled, pretreatment degreaser is washed with water 15 times, degreaser is obtained.The chitosan acetic acid solution is by deacetylation
80% chitosan is mixed with the acetic acid 1:60 in mass ratio that mass fraction is 12%, obtains chitosan acetic acid solution.The lipase
For Adipose trigtyceride lipase.The initiator is potassium peroxydisulfate.The mix acid liquor is the sulfuric acid for being 60% by mass fraction
The nitric acid 3:1 in mass ratio for being 50% with mass fraction is mixed, and obtains mix acid liquor.The organic solvent is toluene.
Comparative example: the degreaser of Wuxi Science and Technology Ltd. production.
Example 1 to the resulting degreaser of example 4 and comparative example product are subjected to performance detection, the specific detection method is as follows:
Oil content presses petroleum gas standard " clastic rock reservoir water water quality fertilizer index and analysis method " (SY/ in sewage
T5329-1994 regulation), the absorbance by petroleum ether extraction liquid in 430nm are found out.
Using general bottle test method.Take mining site Produced Liquid, stratification, be packed into 150mL trial jar l00mL lower layer without
Oil slick water sample, is placed in water bath with thermostatic control and is heated to predetermined temperature；It accurately measures a certain amount of 0.1% test specimen to be added in trial jar, vibration examination
Bottle 50~200 times, observes and records the variation of water-oil separating immediately；A certain amount of water sample is taken after trial jar stands 10min~15min
Oil removal rate is calculated using remaining oil mass in 721 spectrophotometric colos measurement water with petroleum ether extraction.
Specific testing result is as shown in table 1:
1 degreaser performance test results of table
| Detection project | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Oil removal rate/% | 96.3 | 93.6 | 91.8 | 90.2 | 86.4 |
By 1 testing result of table it is found that the degreaser of technical solution of the present invention preparation has the characteristics that excellent oil removing performance, in water
It has broad prospects in the development of processing technique industry.
Claims (7)
1. a kind of preparation method of degreaser, which is characterized in that specific preparation step are as follows:
(1) chitosan acetic acid solution is mixed with sodium hydroxide solution 1:3~1:4 in mass ratio, after being stirred, is stood, mistake
Filter, obtains filter cake, and filter cake is washed to cleaning solution as neutrality, chitosan microball blank is obtained, by chitosan microball blank and glutaraldehyde
The mixing of 1:5~1:8 in mass ratio, is filtered, and washing obtains chitosan microball, by chitosan microball and lipase 1:2 in mass ratio~
1:3 mixing, and 5~10 times of chitosan microball quality of water is added, it after being stirred, impregnates, filters, it is poly- to obtain modified shell for washing
Sugared microballoon；
(2) modification of chitosan microballoon is mixed with water 1:10~1:15 in mass ratio, and sequentially add modification of chitosan quality 1~
2 times of styrene, the divinylbenzene that 0.8~1.5 times of modification of chitosan quality, the mistake that 0.2~0.3 times of modification of chitosan quality
Benzoyl Oxide and 1~2 times of modification of chitosan quality of epoxy propane butyl ether obtain shell after being stirred under nitrogen atmosphere
Chitosan microball mixture is mixed with initiator 100:1 in mass ratio, is stirred to react by glycan mixture of microspheres, is filtered, is washed
It washs, it is dry, obtain polystyrene chitosan microball；
(3) sodium cellulose glycolate is mixed with normal heptane 1:2 in mass ratio, and is added 2~3 times of sodium cellulose glycolate quality
Fat acyl chloride, after being stirred to react, concentrated by rotary evaporation is washed, dry, obtains modified sodium cellulose glycolate；
(4) polystyrene chitosan microball is mixed with water 1:10~1:20 in mass ratio, and it is micro- that polystyrene chitosan is added
The mix acid liquor that 1~2 times of ball quality, after being stirred to react, filtering, washing to cleaning solution is neutrality, dry, must pre-process polyphenyl second
Alkene chitosan microball mixes pretreatment polystyrene chitosan microball with potassium hydroxide solution 1:5~1:8 in mass ratio, and
The sodium thiosulfate of 0.2~0.3 times of polystyrene chitosan microball quality of pretreatment is added, after being stirred to react, filtering, washing is extremely
Cleaning solution is neutrality, dry, obtains pre- modified polystyrene chitosan microball；
(5) graphene oxide is mixed with water 1:8~1:10 in mass ratio, ultrasonic disperse obtains graphene oxide solution, will aoxidize
Graphene solution is mixed with pre- modified polystyrene chitosan microball 5:1~8:1 in mass ratio, and graphene oxide solution is added
0.1~0.2 times of quality of modification sodium cellulose glycolate after ultrasonic disperse, filters, degreaser blank is obtained, by degreaser blank
Immersion is mixed with organic solvent 1:3~1:5 in mass ratio, is filtered, washing obtains degreaser.
2. a kind of preparation method of degreaser according to claim 1, it is characterised in that: step (1) the chitosan second
Acid solution is the acetic acid 1:50~1:60 in mass ratio for being 10~12% by the chitosan of deacetylation 60~80% and mass fraction
Mixing, obtains chitosan acetic acid solution.
3. a kind of preparation method of degreaser according to claim 1, it is characterised in that: step (1) described lipase is
Adipose trigtyceride lipase, hormone-sensitive lipase, any one in monoester lipase or two kinds of composition.
4. a kind of preparation method of degreaser according to claim 1, it is characterised in that: step (2) described initiator is
Any one in potassium peroxydisulfate, ammonium persulfate or sodium peroxydisulfate.
5. a kind of preparation method of degreaser according to claim 1, it is characterised in that: step (3) described fat acyl chloride
For any one in hexadecanoyl chloride or 18 acyl chlorides.
6. a kind of preparation method of degreaser according to claim 1, it is characterised in that: step (4) described mix acid liquor
For be 40~60% by mass fraction sulfuric acid mixed with the nitric acid 3:1 in mass ratio that mass fraction is 30~50%, obtain mixed acid
Liquid.
7. a kind of preparation method of degreaser according to claim 1, it is characterised in that: step (5) described organic solvent
For toluene, any one in dimethylbenzene or chloroform.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109825331A (en) * | 2019-03-12 | 2019-05-31 | 吉林化工学院 | The preparation and application of emulsified crude oil solid demulsifier in microwave field |
| CN111826191A (en) * | 2019-04-19 | 2020-10-27 | 宁波锋成先进能源材料研究院 | Graphene oxide amphiphilic nano oil-removing dispersion liquid and preparation method and application thereof |
| CN116986588A (en) * | 2023-07-26 | 2023-11-03 | 南方石墨新材料有限公司 | High-strength graphite ball and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113433A (en) * | 2007-06-29 | 2008-01-30 | 浙江工业大学 | Process for preparing chitosan microsphere immobilized lipolytic enzyme |
| CN103497476A (en) * | 2013-10-16 | 2014-01-08 | 苏州大学 | Composite material based on amphoteric cellulose and application thereof |
| CN105854836A (en) * | 2016-04-11 | 2016-08-17 | 华北水利水电大学 | Preparation method of oil absorption material for wastewater treatment |
-
2018
- 2018-06-26 CN CN201810667597.3A patent/CN108946955A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113433A (en) * | 2007-06-29 | 2008-01-30 | 浙江工业大学 | Process for preparing chitosan microsphere immobilized lipolytic enzyme |
| CN103497476A (en) * | 2013-10-16 | 2014-01-08 | 苏州大学 | Composite material based on amphoteric cellulose and application thereof |
| CN105854836A (en) * | 2016-04-11 | 2016-08-17 | 华北水利水电大学 | Preparation method of oil absorption material for wastewater treatment |
Non-Patent Citations (3)
| Title |
|---|
| 卞国庆等主编: "《综合化学实验》", 31 March 2007, 苏州大学出版社 * |
| 李进军等编著: "《绿色化学导论》", 31 August 2015, 武汉大学出版社 * |
| 邓一民主编: "《天然纺织纤维加工化学》", 30 September 2010, 西南师范大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109825331A (en) * | 2019-03-12 | 2019-05-31 | 吉林化工学院 | The preparation and application of emulsified crude oil solid demulsifier in microwave field |
| CN111826191A (en) * | 2019-04-19 | 2020-10-27 | 宁波锋成先进能源材料研究院 | Graphene oxide amphiphilic nano oil-removing dispersion liquid and preparation method and application thereof |
| CN116986588A (en) * | 2023-07-26 | 2023-11-03 | 南方石墨新材料有限公司 | High-strength graphite ball and preparation method thereof |
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Application publication date: 20181207 |