CN107266637B - A kind of preparation method of fuel thickener - Google Patents

A kind of preparation method of fuel thickener Download PDF

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Publication number
CN107266637B
CN107266637B CN201710510645.3A CN201710510645A CN107266637B CN 107266637 B CN107266637 B CN 107266637B CN 201710510645 A CN201710510645 A CN 201710510645A CN 107266637 B CN107266637 B CN 107266637B
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oil
added
starch
fuel thickener
reaction
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CN107266637A (en
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周文斌
陈春
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Liaoning Yongrun Petroleum Products Group Co., Ltd.
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Liaoning Yongrun Petroleum Products Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Public Health (AREA)
  • Materials Engineering (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention belongs to technical field of petrochemical industry, and in particular to a kind of preparation method of fuel thickener.The present invention mixes soluble starch and collagen, diatomite, obtains starch mixed liquor, then by starch mixed liquor and methyl methacrylate, maleation vegetable oil, it is reacted under the action of crosslinking agent and initiator, reaction solution is obtained after reaction, and is freeze-dried, and fuel thickener can be obtained, fuel thickener gelation rate produced by the present invention is fast, oil slick's pervasion can be prevented, oil spilling can be controlled in lesser range, be easy to salvage, in sea noresidue, secondary pollution not will cause.

Description

A kind of preparation method of fuel thickener
Technical field
The invention belongs to technical field of petrochemical industry, and in particular to a kind of preparation method of fuel thickener.
Background technique
As offshore oil development and sea transport industry rapidly develop, petroleum pollution in ocean is increasingly by countries in the world Greatly pay attention to.Marine oil overflow mainly from shipping work and marine incident, especially oil carrier accident and oil platform, oil storage and The sporadic accident such as oil transportation facility.China's Industry layout is made a general survey of, petrochemical industry is collected in the coastal region in east China, in coastal, riverine Along the river zonal distribution feature, once oil spill events occur, it is huge to the environmental pollution of water body.
Fuel thickener is that one kind can make spilled oil on water surface fast gelation, forms solid-state or semisolid block and floats on the water surface Chemical treatments.Fuel thickener utilizes the physically or chemically effect with oil, changes the viscosity of oily phase, is allowed to the shape in conjunction with fuel thickener At gel, reach and oil spilling is prevented to spread, convenient for salvaging the purpose of recycling.
In recent years, the raw material of fuel thickener have polyvinyl alcohol, sorbierite and leather fiber etc., but are not obtaining in practice To application, at present still in the experimental stage.At present using more fuel thickener because production technology is complicated, high expensive, price is held high It is expensive, it is unfavorable for promoting, coagulating oiliness can be lower, secondary pollution can be generated after use, and be difficult to be applied in practice.In future The main direction of studying of fuel thickener is to develop solidifying speed oil, low pollution, hypotoxicity, low dosage, be easily recycled, not vulnerable to ring around The novel fuel thickener that border influences.
Summary of the invention
Present invention mainly solves the technical issues of: produce work using more Yeast protein fuel thickener at present for existing Skill is complicated, and solidifying speed oil leads to the problem of secondary pollution slowly, after gel, provides a kind of preparation method of fuel thickener.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
(1) 1:10 in mass ratio weighs soluble starch and is added in deionized water, is stirred after heating, obtains starch fluid, Collagen and diatomite are added into starch fluid, obtains starch mixed liquor；
(2) according to parts by weight, 50~60 portions of starch mixed liquors, 20~40 parts of methyl methacrylates, 10 are chosen respectively ~15 parts of maleation vegetable oil, 1~3 part of initiator, 2~5 parts of crosslinking agents and 5~10 parts of emulsifiers；
(3) said components are pressed, first mix methyl methacrylate, maleation vegetable oil and emulsifier, stirring is mixed Emulsion is obtained after conjunction, then emulsion and starch mixed liquor are mixed, and is heated to 50~60 DEG C after initiator is added, is stirred to react 1 Crosslinking agent is added after reaction in~2h, continues to be stirred to react 2~4h, reaction solution is obtained after reaction, and be freeze-dried, obtains dried object, i.e., Fuel thickener can be obtained.
The vegetable oil is soybean oil, castor oil, sesame oil, tea oil, one or more in peanut oil.
The maleic anhydride quality is plant oil quality 5~10%.
The vegetable oil can also be modified using maleic anhydride, method of modifying are as follows: weigh vegetable oil and reaction is added In kettle, and 60~80 DEG C are warming up to, then to 5~10% maleic anhydride of plant oil quality is added in reaction kettle, it is warming up to 100~ 105 DEG C, insulated and stirred reacts 3~5h, and 8~10% maleic anhydride of plant oil quality is added after reaction, is warming up to 180~190 DEG C, insulated and stirred reacts 1~3h, is cooled to room temperature after reaction, obtains maleation vegetable oil.
The collagen is starch fluid quality 3~5%, and diatomite quality is starch fluid quality 1~3%.
The initiator is one of ammonium persulfate, azodiisobutyronitrile, potassium peroxydisulfate.
The crosslinking agent is one of divinylbenzene, cumyl peroxide and trimethylolpropane.
The emulsifier is sorbitan monostearate, polyoxyethylene oleic acid ester, octyl phenol polyoxyethylene ether, coconut palm One of oleamide propyl betaine is a variety of.
The beneficial effects of the present invention are:
(1) present invention uses the substances such as soluble starch, collagen, diatomite and methyl methacrylate,
Cross-linking reaction is carried out under the action of initiator, the fuel thickener gelation rate obtained after reaction is fast, can prevent oil film from expanding It dissipates, oil spilling can be controlled in lesser range, improve recovery efficiency；
(2) fuel thickener that the present invention is prepared is easily recycled, and is easy to salvage, will not in sea noresidue
Cause secondary pollution；
(3) present invention reacts the substances such as starch mixture and methyl methacrylate, reacts latter two or more
The copolymer that the cross-linked polymer that is intertwined is formed, the winding between network can improve system dispersibility, interface Compatibility and stability, due to the infiltration that intersects between polymer network, mechanical interlocking is played to force and be dissolved each other and synergistic effect Effect.
Specific embodiment
It weighs vegetable oil to be added in reaction kettle, and is warming up to 60~80 DEG C, then to addition plant oil quality 5 in reaction kettle ~10% maleic anhydride is warming up to 100~105 DEG C, and insulated and stirred reacts 3~5h, and plant oil quality 8~10% is added after reaction Maleic anhydride is warming up to 180~190 DEG C, and insulated and stirred reacts 1~3h, is cooled to room temperature after reaction, obtains maleation plant Oil；1:10 in mass ratio weighs soluble starch and is added in deionized water, is heated to 60~70 DEG C, is stirred 30~50min, Starch fluid is obtained, 3~5% collagen of starch fluid quality and 1~3% diatomite of starch fluid quality are added into starch fluid, stirring is mixed Starch mixed liquor is obtained after conjunction；According to parts by weight, 50~60 portions of starch mixed liquors, 20~40 parts of methyl methacrylates are chosen respectively Ester, 10~15 parts of maleation vegetable oil, 1~3 part of initiator, 2~5 parts of crosslinking agents and 5~10 parts of emulsifiers；By above-mentioned group Point, first methyl methacrylate, maleation vegetable oil and emulsifier are mixed, with the stirring of 2000~3000r/min revolving speed 20~30min is mixed, emulsion is obtained, then emulsion and starch mixed liquor are mixed, is heated to 50~60 DEG C after initiator is added After be stirred to react 1~2h, crosslinking agent is added after reaction, continues to be stirred to react 2~4h, after reaction reaction solution, and be freeze-dried, Dried object is obtained, fuel thickener can be obtained.
The vegetable oil is soybean oil, castor oil, sesame oil, tea oil, one or more in peanut oil.
The initiator is one of ammonium persulfate, azodiisobutyronitrile, potassium peroxydisulfate.
The crosslinking agent is one of divinylbenzene, cumyl peroxide and trimethylolpropane.
The emulsifier is sorbitan monostearate, polyoxyethylene oleic acid ester, octyl phenol polyoxyethylene ether, coconut palm One of oleamide propyl betaine is a variety of.
Example 1
It weighs vegetable oil to be added in reaction kettle, and is warming up to 60 DEG C, then to addition 5% horse of plant oil quality in reaction kettle Carry out acid anhydrides, be warming up to 100 DEG C, insulated and stirred reacts 3h, and 8% maleic anhydride of plant oil quality is added after reaction, is warming up to 180 DEG C, insulated and stirred reacts 1h, is cooled to room temperature after reaction, obtains maleation vegetable oil；1:10 weighs solubility in mass ratio Starch is added in deionized water, is heated to 60 DEG C, is stirred 30min, obtains starch fluid, and starch fluid quality is added into starch fluid 1% diatomite of 3% collagen and starch fluid quality obtains starch mixed liquor after being stirred；According to parts by weight, 50 are chosen respectively Part starch mixed liquor, 20 parts of methyl methacrylates, 10 parts of maleation vegetable oil, 1 part of ammonium persulfate, 2 parts of divinyl Benzene and 5 parts of emulsifiers；By said components, first methyl methacrylate, maleation vegetable oil and emulsifier are mixed, with 2000r/min revolving speed is stirred 20min, obtains emulsion, then emulsion and starch mixed liquor are mixed, adds after initiator is added Heat is added after being stirred to react 1h to 50 DEG C, continues to be stirred to react 2h, reaction solution is obtained after reaction, and be freeze-dried, obtains dried object, Fuel thickener can be obtained.
The vegetable oil is soybean oil, castor oil, the mixing of 1:5 in mass ratio.
The emulsifier is sorbitan monostearate and polyoxyethylene oleic acid ester, the mixing of 2:1 in mass ratio.
Example 2
It weighs vegetable oil to be added in reaction kettle, and is warming up to 70 DEG C, then to addition 8% horse of plant oil quality in reaction kettle Carry out acid anhydrides, be warming up to 103 DEG C, insulated and stirred reacts 4h, and 9% maleic anhydride of plant oil quality is added after reaction, is warming up to 185 DEG C, insulated and stirred reacts 2h, is cooled to room temperature after reaction, obtains maleation vegetable oil；1:10 weighs solubility in mass ratio Starch is added in deionized water, is heated to 65 DEG C, is stirred 40min, obtains starch fluid, and starch fluid quality is added into starch fluid 2% diatomite of 4% collagen and starch fluid quality obtains starch mixed liquor after being stirred；According to parts by weight, 55 are chosen respectively Part starch mixed liquor, 30 parts of methyl methacrylates, 13 parts of maleation vegetable oil, 2 parts of azodiisobutyronitriles, 3 parts of peroxides Change diisopropylbenzene (DIPB) and 8 parts of emulsifiers；By said components, first by methyl methacrylate, maleation vegetable oil and emulsifier Mixing, is stirred 25min with 2500r/min revolving speed, obtains emulsion, then emulsion and starch mixed liquor are mixed, addition is drawn It is stirred to react 1.5h after being heated to 55 DEG C after hair agent, cumyl peroxide is added after reaction, continues to be stirred to react 3h, after reaction Reaction solution is obtained, and is freeze-dried, dried object is obtained, fuel thickener can be obtained.
The vegetable oil is sesame oil and tea oil, the mixing of 2:1 in mass ratio.
The emulsifier is polyoxyethylene oleic acid ester and octyl phenol polyoxyethylene ether, the mixing of 1:1 in mass ratio.
Example 3
1:10 in mass ratio weighs soluble starch and is added in deionized water, is heated to 70 DEG C, is stirred 50min, obtains 5% collagen of starch fluid quality and 3% diatomite of starch fluid quality are added into starch fluid, must form sediment after being stirred for starch fluid Powder mixed liquor；According to parts by weight, 60 portions of starch mixed liquors, 40 parts of methyl methacrylates, 15 parts of vegetable oil, 3 are chosen respectively Part potassium peroxydisulfate, 5 parts of trimethylolpropanes and 10 parts of emulsifiers；By said components, first by methyl methacrylate, maleic anhydride Change vegetable oil and emulsifier mixing, 30min is stirred with 3000r/min revolving speed, obtains emulsion, then emulsion and starch are mixed Liquid mixing is closed, 2h is stirred to react after being heated to 60 DEG C after addition initiator, trimethylolpropane is added after reaction, it is anti-to continue stirring 4h is answered, reaction solution is obtained after reaction, and be freeze-dried, obtains dried object, fuel thickener can be obtained.
The vegetable oil is tea oil, peanut oil, the mixing of 3:1 in mass ratio.
The emulsifier is octyl phenol polyoxyethylene ether, Cocoamidopropyl betaine, the mixing of 1:4 in mass ratio.
Comparative example: commercially available aluminum stearate fuel thickener.
The fuel thickener of the obtained fuel thickener of example 1~3 and comparative example is subjected to solidifying oily performance test, operating procedure are as follows: take glass Glass bottle is added 100 g water and 50g crude oil, fuel thickener is added after stratification, is added and starts timing, stand after shaking, work as gel It can be just solidifying oil success at gel upper layer by hydropexis, stop timing, record time, fuel thickener dosage and gelling used Situation.
Its testing result is as shown in Table 1 and Table 2:
Table 1
Detection project Example 1 Example 2 Example 3 Comparative example
Oleogel intensity (Pas) 201.6 235.8 22.9 81.8
Oil/fuel thickener (g/g) 2.5 2.3 2.0 1.5
Oleogel situation It can pick up, water body is limpid It can pick up, water body is limpid It can pick up, water body is limpid In flexible glue, water body is muddy
Table 2 detects the gel time of different oil products:
Gasoline (s) Diesel oil (s) Light crude oil (s)
Example 1 25 400 80
Example 2 20 392 75
Example 3 28 410 80
Comparative example 30 600 100
It coagulates fast speed oil in conclusion fuel thickener is made in the present invention, low dosage, be easily recycled.

Claims (6)

1. a kind of preparation method of fuel thickener, it is characterised in that it is specific the preparation method comprises the following steps:
(1) 1:10 in mass ratio weighs soluble starch and is added in deionized water, is stirred after heating, obtains starch fluid, to shallow lake Collagen and diatomite are added in powder liquid, obtains starch mixed liquor；
(2) according to parts by weight, 50~60 portions of starch mixed liquors, 20~40 parts of methyl methacrylates, 10~15 are chosen respectively Part maleation vegetable oil, 1~3 part of initiator, 2~5 parts of crosslinking agents and 5~10 parts of emulsifiers；The maleation is planted Object oil is to weigh vegetable oil to be added in reaction kettle, and is warming up to 60~80 DEG C, then to be added in reaction kettle plant oil quality 5~ 10% maleic anhydride is warming up to 100~105 DEG C, and insulated and stirred reacts 3~5h, and 8~10% horse of plant oil quality is added after reaction Carry out acid anhydrides, be warming up to 180~190 DEG C, insulated and stirred reacts 1~3h, is cooled to room temperature after reaction, obtains maleation plant Oil；
(3) said components are pressed, are first mixed methyl methacrylate, maleation vegetable oil and emulsifier, after being stirred Emulsion is obtained, then emulsion and starch mixed liquor are mixed, 50~60 DEG C is heated to after initiator is added, is stirred to react 1~2h, Crosslinking agent is added after reaction, continues to be stirred to react 2~4h, reaction solution is obtained after reaction, and be freeze-dried, obtains dried object, can obtain To fuel thickener.
2. a kind of preparation method of fuel thickener according to claim 1, it is characterised in that: the vegetable oil is soybean It is oil, castor oil, sesame oil, tea oil, one or more in peanut oil.
3. a kind of preparation method of fuel thickener according to claim 1, it is characterised in that: the collagen is starch Liquid quality 3~5%, diatomite quality are starch fluid quality 1~3%.
4. a kind of preparation method of fuel thickener according to claim 1, it is characterised in that: the initiator is persulfuric acid One of ammonium, azodiisobutyronitrile, potassium peroxydisulfate.
5. a kind of preparation method of fuel thickener according to claim 1, it is characterised in that: the crosslinking agent is divinyl One of base benzene, cumyl peroxide and trimethylolpropane.
6. a kind of preparation method of fuel thickener according to claim 1, it is characterised in that: the emulsifier is dehydration mountain One of pears alcohol monostearate, polyoxyethylene oleic acid ester, octyl phenol polyoxyethylene ether, Cocoamidopropyl betaine are more Kind.
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CN110358446A (en) * 2019-08-14 2019-10-22 杭州易贝环保科技有限公司 A kind of solid wood maintenance wax and preparation method thereof

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CN106746685A (en) * 2016-12-21 2017-05-31 浙江慈航海洋环保科技发展有限公司 A kind of fuel thickener for processing marine floating oil

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