CN107099359B - A kind of preparation method and its pour-point depressant of diesel pour inhibitor - Google Patents
A kind of preparation method and its pour-point depressant of diesel pour inhibitor Download PDFInfo
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- CN107099359B CN107099359B CN201710301274.8A CN201710301274A CN107099359B CN 107099359 B CN107099359 B CN 107099359B CN 201710301274 A CN201710301274 A CN 201710301274A CN 107099359 B CN107099359 B CN 107099359B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/24—Mixing, stirring of fuel components
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2300/00—Mixture of two or more additives covered by the same group of C10L1/00 - C10L1/308
- C10L2300/20—Mixture of two components
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a kind of preparation method of diesel pour inhibitor and its pour-point depressants, wherein described method includes following steps：1) it adds a solvent in reaction kettle, plastic of poly vinyl acetate and polymethacrylates are added in reaction kettle again, under stirring conditions, it carries out heating and reaches 60~120 DEG C, pressure control dissolves reaction 1~6 hour, after reaction in 0.01~0.02MPa, it waits for that pressure is down to 0MPa, obtains initial stage product；2) the initial stage product obtained carries out shear treatment repeatedly under heat-retaining condition by shearing equipment, until initial stage product, under the conditions of 100 DEG C, kinematic viscosity reaches 30~200mm2/ s stops shearing, obtains finished product；Above-mentioned preparation method only needs simply dissolving and shearing step, makes simply, of low cost, and has many advantages, such as that depression effeCt is good by pour-point depressant prepared by this method.
Description
Technical field
The present invention disclose the technical field for being related to petrochemical industry more particularly to a kind of diesel pour inhibitor preparation method and its
Pour-point depressant.
Background technology
When oil plant carries out diesel oil refining, the height of measuring change of diesel oil solidifying point can influence the final trade mark of diesel oil, and different boards
Number diesel-fuel price differ greatly, in refining process, the solidification point that often will appear diesel oil is hovered between two trades mark, this
When, the solidification point of diesel oil will be adjusted by the way of pour-point depressant is added, be required to touch the mark.
Currently, common diesel pour inhibitor has ten as many as several in the market, but most pour-point depressant is required for using high temperature
The mode of high pressure is processed preparation, and the requirement to processing is more harsh, there are processing difficulties, it is of high cost the problems such as.
Therefore, how to research and develop a kind of preparation method of novel diesel pour-point depressant becomes people urgently to solve the above problems
It solves the problems, such as.
Invention content
In consideration of it, the purpose of the present invention is to provide a kind of preparation method of diesel pour inhibitor and its pour-point depressants, at least
The preparation method of existing diesel pour inhibitor is solved there are processing difficulties, the problems such as high processing costs.
Technical solution provided by the invention, specifically, a kind of preparation method of diesel pour inhibitor, includes the following steps：
1) after adding a solvent in reaction kettle, then using plastic of poly vinyl acetate and polymethacrylates as solute
It is added in reaction kettle, under stirring conditions, heats up to the material in reaction kettle, until temperature reaches 60~120 DEG C,
By the pressure control of reaction kettle in 0.01~0.02MPa, dissolving reaction is carried out, the dissolving reaction time is 1~6 hour, and dissolving is anti-
After answering, waits for that pressure is down to 0MPa in reaction kettle, obtain initial stage product；
2) the initial stage product that will be obtained in step 1) carries out initial stage product by shearing equipment anti-under heat-retaining condition
Multiple shear treatment, until the initial stage product, under the conditions of 100 DEG C, kinematic viscosity reaches 30~200mm2/ s stops shearing, obtains
Obtain pour-point depressant finished product.
It is preferred that the solvent be toluene, dimethylbenzene, trimethylbenzene, durene, the isomer of toluene, dimethylbenzene it is same
One or more of isomer of enantiomers, the isomer of trimethylbenzene and durene mixes.
Further preferably, the solvent is under the conditions of 40 DEG C, and kinematic viscosity is 5~20mm2The cycloalkane of/s.
Further preferably, the mass ratio of the solvent and solute is (0.5~1.5)：1.
Further preferably, the mass ratio of the plastic of poly vinyl acetate and the polymethacrylates is 1：(0.1~
1)。
Further preferably, the molecular weight of the plastic of poly vinyl acetate is 2000~15000g/mol, vinylacetate
Content is 10~50%.
Further preferably, the molecular weight of the polymethacrylates is 1000~11000g/mol.
Further preferably, the polymethacrylates is that methyl esters, ethyl ester, the butyl ester of polymethylacrylic acid are one such
Or several mixing.
Further preferably, the shearing equipment is gear pump or colloid mill.
The present invention also provides a kind of diesel pour inhibitor, which is to be prepared using any one of the above method.
The preparation method of diesel pour inhibitor provided by the invention, due to plastic of poly vinyl acetate and polymethacrylates
All with electric nuclear repulsion characteristic between molecule, it can effectively prevent wax molecule from assembling, can reach the purpose for reducing measuring change of diesel oil solidifying point, because
This selects plastic of poly vinyl acetate and polymethacrylates is solute, after above-mentioned solute and solvent are carried out mixed dissolution,
It is sheared by shearing equipment, plastic of poly vinyl acetate and polymethacrylates is cut into small-molecular-weight, Jin Ersheng
At more nucleus, after being mixed with diesel oil as pour-point depressant, plastic of poly vinyl acetate and polymethacrylates are by cutting
The numerous nucleus generated after cutting can attract the wax to dissociate in diesel oil, so that free wax is separated from each other, prevent free wax from condensing upon
Net is formed together, and then avoids the solidification of diesel oil.
The preparation method of diesel pour inhibitor provided by the invention, it is only necessary to which simply dissolving and shearing step make letter
It is single, it is of low cost, and have many advantages, such as that depression effeCt is good by pour-point depressant prepared by this method.
Specific implementation mode
Explanation is further explained to the present invention with specific embodiment below, but is not limited to this hair
Bright protection domain.
The problems such as there are processing difficulties, high processing costs for the preparation method that solves previous diesel pour inhibitor, the present invention
A kind of preparation method of novel diesel pour-point depressant is provided, which specifically comprises the following steps：
1) after adding a solvent in reaction kettle, then using plastic of poly vinyl acetate and polymethacrylates as solute
It is added in reaction kettle, under stirring conditions, heats up to the material in reaction kettle, until temperature reaches 60~120 DEG C,
By the pressure control of reaction kettle in 0.01~0.02MPa, dissolving reaction is carried out, the dissolving reaction time is 1~6 hour, and dissolving is anti-
After answering, waits for that pressure is down to 0MPa in reaction kettle, obtain initial stage product；
2) the initial stage product that will be obtained in step 1) carries out initial stage product by shearing equipment anti-under heat-retaining condition
Multiple shear treatment, until the initial stage product, under the conditions of 100 DEG C, kinematic viscosity reaches 30~200mm2/ s stops shearing, obtains
Obtain pour-point depressant finished product.
In the preparation method, since plastic of poly vinyl acetate and polymethacrylates are all arranged with electric core between molecule
Denounce characteristic, wax molecule can effectively be prevented to assemble, achievees the purpose that reduce measuring change of diesel oil solidifying point, therefore select both as solute,
In, it is 60~120 DEG C by temperature setting, is 0.01~0.02MPa by pressure control, main reason is that：If temperature is less than
60 DEG C, the solution rate of solute is slow, and manufacturing cycle is caused to extend, and temperature is higher than 120 DEG C, and solvent volatilization can be caused more,
Pressure is larger in dissolving tank, and there are security risks.After plastic of poly vinyl acetate and polymethacrylates are dissolved in solvent,
Initial stage product；Under heat-retaining condition, shear treatment repeatedly is carried out to initial stage product by shearing equipment, until at 100 DEG C
Under the conditions of, kinematic viscosity reaches 30~200mm2/ s, by the requirement to product viscosity after shearing, main purpose, which is to control, cuts
The molecular weight of plastic of poly vinyl acetate and polymethacrylates after cutting so that exist in the pour-point depressant of preparation a large amount of brilliant
Core, after the pour-point depressant is mixed with diesel oil, numerous nucleus in pour-point depressant can attract in diesel oil dissociate wax, make free wax that
This separation, prevents free wax formation net agglomerated together, and then avoid the solidification of diesel oil.
The isomer of the optional toluene of solvent, dimethylbenzene, trimethylbenzene, durene, toluene in the embodiment above,
One or more of isomer of the isomer of dimethylbenzene, the isomer of trimethylbenzene and durene is mixed
It closes, selects above-mentioned benzene class to make solvent, main reason is that its solvability is strong, the intersolubility between solute can be improved.
In addition, the solvent in the embodiment above can also be selected under the conditions of 40 DEG C, kinematic viscosity is 5~20mm2/s
Cycloalkane, its intersolubility with solute is considered not only using cycloalkane, and since the flash-point of cycloalkane is higher than aromatic hydrocarbons, have
Have the advantages that safety is good.
In order to improve the performance using the pour-point depressant prepared in the embodiment above, the improvement as scheme, it is preferable that
The mass ratio of above-mentioned solvent and solute is (0.5~1.5)：1；More preferably, plastic of poly vinyl acetate and polymethylacrylic acid
The mass ratio of ester is 1：(0.1~1).
Wherein, the plastic of poly vinyl acetate preferred molecular weight in solute is 2000~15000g/mol, vinylacetate
Content is 10~50%, test proves that the molecular weight ranges, and vinyl acetate content is in the polyethylene vinegar of this range
The depression effeCt of vinyl acetate, manufactured pour-point depressant is best；And in solute polymethacrylates preferred molecular weight be 1000~
11000g/mol, if polymethacrylates of the molecular weight less than 1000g/mol is without depression effeCt, molecular weight is higher than
The polymethacrylates of 11000g/mol is in solid state, also improper for producing pour-point depressant.
Above-mentioned polymethacrylates can be that methyl esters, ethyl ester, the butyl ester of polymethylacrylic acid are one such or several
Mixing.
The equipment that plastic of poly vinyl acetate and polymethacrylates shearing are carried out in the step 2) of above-mentioned preparation method
Gear pump or colloid mill can be selected, it is not limited to above two equipment.
The present invention is further illustrated with specific embodiment below.
Embodiment 1
After taking 4 parts by weight pseudocumenes to be added in reaction kettle, then by 4 weight account polyethylene vinylacetates and 4 weight
Part polymethacrylates is added to as solute in reaction kettle, under stirring conditions, is risen to the material in reaction kettle
The pressure of reaction kettle is controlled in 0.01~0.02MPa until temperature reaches 60~120 DEG C, carries out dissolving reaction by temperature, is dissolved
Reaction time is 1~6 hour, and dissolving after reaction, waits for that pressure is down to 0MPa in reaction kettle, obtains initial stage product；It will obtain
Initial stage product shear treatment 10 hours repeatedly are carried out to initial stage product by gear pump, stop shearing under heat-retaining condition,
Obtain pour-point depressant finished product.
For pour-point depressant finished product under the conditions of temperature is 100 DEG C, detection kinematic viscosity is 120.38mm2/s。
It is -9 DEG C to take solidification point, and the diesel oil that cold filter plugging point is -3.5 DEG C is added above-mentioned pour-point depressant 300ppm, measures addition pour point depression
The solidification point of diesel oil is -21 DEG C after agent, and cold filter plugging point is -12 DEG C.
Embodiment 2
After taking 1.1 parts by weight of toluene and 2.2 parts by weight ortho-xylenes to be added in reaction kettle, then by 2 weight account polyethylenes
Vinylacetate and 0.2 parts by weight polymethacrylates are added to as solute in reaction kettle, under stirring conditions, to anti-
It answers the material in kettle to heat up, until temperature reaches 60~120 DEG C, the pressure of reaction kettle is controlled in 0.01~0.02MPa,
Dissolving reaction is carried out, the dissolving reaction time is 1~6 hour, and dissolving after reaction, waits for that pressure is down to 0MPa in reaction kettle, obtains
To initial stage product；The initial stage product that will be obtained carries out shear treatment repeatedly by colloid mill under heat-retaining condition to initial stage product
16 hours, stop shearing, obtains pour-point depressant finished product.
For pour-point depressant finished product under the conditions of temperature is 100 DEG C, detection kinematic viscosity is 109.73mm2/s。
It is -9 DEG C to take solidification point, and the diesel oil that cold filter plugging point is -3.5 DEG C is added above-mentioned pour-point depressant 300ppm, measures addition pour point depression
The solidification point of diesel oil is -20 DEG C after agent.Cold filter plugging point is -10.5 DEG C.
Embodiment 3
Take 6 parts by weight under the conditions of 40 DEG C, kinematic viscosity is 5~20mm2After the cycloalkane of/s is added in reaction kettle, then
4 weight account polyethylene vinylacetates and 2 parts by weight polymethacrylates are added to as solute in reaction kettle, are being stirred
Under conditions of, it heats up to the material in reaction kettle, until temperature reaches 60~120 DEG C, the pressure control of reaction kettle is existed
0.01~0.02MPa carries out dissolving reaction, and the dissolving reaction time is 1~6 hour, and dissolving after reaction, waits for reaction kettle internal pressure
It is down to 0MPa by force, obtains initial stage product；The initial stage product that will be obtained, under heat-retaining condition, by gear pump to initial stage product into
Shear treatment 12 hours, stopping shearing obtaining pour-point depressant finished product to row repeatedly.
For pour-point depressant finished product under the conditions of temperature is 100 DEG C, detection kinematic viscosity is 163.96mm2/s。
It is -9 DEG C to take solidification point, and the diesel oil that cold filter plugging point is -3.5 DEG C is added above-mentioned pour-point depressant 300ppm, measures addition pour point depression
The solidification point of diesel oil is -25 DEG C after agent, and cold filter plugging point is -14 DEG C.
Embodiment 4
Two groups of effect experiments are carried out respectively, it is specific as follows：
First group：The pour-point depressant prepared in Example 3 be added separately to light diesel, heavy diesel, modification diesel oil with
And in mixed diesel, and measures the forward and backward corresponding freezing point temperature of pour-point depressant is added respectively；
Second group：Take market available diesel oil pour-point depressant T1804 be added separately to light diesel, heavy diesel, modification diesel oil and
In mixed diesel, and measures the forward and backward corresponding freezing point temperature of pour-point depressant is added respectively.
By the experimental data of above-mentioned two groups of experiments, it is shown in Table 1：
Table 1
From the pour point depression date comprision of two groups of experiments in table 1 it is found that diesel pour inhibitor in embodiment 3, depression effeCt
It is good, and wide adaptability.
Those skilled in the art after considering the specification and implementing the invention disclosed here, will readily occur to its of the present invention
Its embodiment.This application is intended to cover the present invention any variations, uses, or adaptations, these modifications, purposes or
Person's adaptive change follows the general principle of the present invention and includes undocumented common knowledge in the art of the invention
Or conventional techniques.The description and examples are only to be considered as illustrative, and true scope and spirit of the invention are by following
Claim is pointed out.
It should be understood that the invention is not limited in the precision architectures being described above, and can not depart from
Its range carry out various modifications and changes.The scope of the present invention is limited only by the attached claims.
Claims (8)
1. a kind of preparation method of diesel pour inhibitor, which is characterized in that include the following steps：
1) after adding a solvent in reaction kettle, then using plastic of poly vinyl acetate and polymethacrylates as solute addition
Into reaction kettle, under stirring conditions, heat up to the material in reaction kettle, until temperature reaches 60~120 DEG C, it will be anti-
It answers the pressure of kettle to control in 0.01~0.02MPa, carries out dissolving reaction, the dissolving reaction time is 1~6 hour, dissolving reaction knot
Shu Hou waits for that pressure is down to 0MPa in reaction kettle, obtains initial stage product；
2) the initial stage product that will be obtained in step 1) cuts initial stage product by shearing equipment under heat-retaining condition repeatedly
Processing is cut, until the initial stage product, under the conditions of 100 DEG C, kinematic viscosity reaches 30~200mm2/ s stops shearing, is dropped
Solidifying agent finished product；
The solvent is toluene, dimethylbenzene and its isomer, trimethylbenzene and its isomer and durene and its same
One or more of enantiomers mix；
Or the solvent is under the conditions of 40 DEG C, kinematic viscosity is 5~20mm2The cycloalkane of/s.
2. the preparation method of diesel pour inhibitor according to claim 1, which is characterized in that the mass ratio of the solvent and solute
For (0.5~1.5)：1.
3. the preparation method of diesel pour inhibitor according to claim 1, which is characterized in that the plastic of poly vinyl acetate with
The mass ratio of the polymethacrylates is 1：(0.1~1).
4. the preparation method of diesel pour inhibitor according to claim 1, which is characterized in that the plastic of poly vinyl acetate
Molecular weight is 2000~15000g/mol, and vinyl acetate content is 10~50%.
5. the preparation method of diesel pour inhibitor according to claim 1, which is characterized in that point of the polymethacrylates
Son amount is 1000~11000g/mol.
6. the preparation method of diesel pour inhibitor according to claim 1, which is characterized in that the polymethacrylates is poly-
Methyl esters, ethyl ester, the butyl ester of methacrylic acid be one such or several mixing.
7. the preparation method of diesel pour inhibitor according to claim 1, which is characterized in that the shearing equipment be gear pump or
Colloid mill.
8. a kind of diesel pour inhibitor, which is characterized in that the pour-point depressant is using any one method system in claim 1~7
It is standby to obtain.
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| CN113201372B (en) * | 2021-04-27 | 2023-05-30 | 上海应用技术大学 | Naphthalene-containing diesel pour point depressant composition and preparation and application thereof |
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