CN105524216B - A kind of environment-friendly type pour-point depressant and preparation method thereof - Google Patents
A kind of environment-friendly type pour-point depressant and preparation method thereof Download PDFInfo
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- CN105524216B CN105524216B CN201510740799.2A CN201510740799A CN105524216B CN 105524216 B CN105524216 B CN 105524216B CN 201510740799 A CN201510740799 A CN 201510740799A CN 105524216 B CN105524216 B CN 105524216B
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- friendly type
- point depressant
- esterification
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- 230000000994 depressogenic effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 70
- 150000002148 esters Chemical class 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 238000005886 esterification reaction Methods 0.000 claims abstract description 41
- 230000032050 esterification Effects 0.000 claims abstract description 40
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001530 fumaric acid Substances 0.000 claims abstract description 32
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 5
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 150000002191 fatty alcohols Chemical class 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002199 base oil Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000004411 aluminium Substances 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 230000009967 tasteless effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- -1 butene dioic acid ester Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
- C08F222/145—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates the ester chains containing seven or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
- C10M2209/062—Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a kind of preparation method of environment-friendly type pour-point depressant, specific reactions steps include successively：Step 1:Esterification prepares thick ester；Step 2：The refined purification of thick ester；Step 3：Monomer dehydration after refined, produces fumaric acid Arrcostab essence monome；Step 4：Monomer copolymerization；Finally obtain environment-friendly type pour-point depressant.Pollution-free, high income in the production process of the environment-friendly type pour-point depressant.Product of the present invention is tasteless, nontoxic, has good inoxidizability and heat endurance, corrosion-free to copper, aluminium and its alloy, not the active element such as sulfur-bearing, phosphorus, chlorine.
Description
Technical field
The present invention relates to the production field of pour depressant for lubricating oil, in particular it relates to a kind of environment-friendly type pour-point depressant and its preparation
Method.
Background technology
Phase late 1920s, having chanced on the condensation product of chlorinated paraffin and naphthalene has a pour-point depressing process, and with 1931
Year has applied for first pour-point depressant patent, trade name Paraflow.Occur in succession the thirties chlorinated paraffin and phenol condensation product,
The pour-point depressant of the commodity such as polymethacrylates, the forties is delivered polyacrylamide, alkyl polystyrene etc., the fifties delivers
Polyacrylate, maleate-long-chain alkyl methacrylates copolymer etc., has delivered olefin polymer the sixties, and 70
Age has delivered the pour-point depressant patent such as alpha olefin copolymer, maleic anhydride vinyl acetate copolymer.Deliver so far relevant
The existing hundreds of pieces of pour-point depressant patent, conventional has the class compound of alkylnaphthalene, polyesters and TPO etc. 3.
Expecting the lubricating oil of low pour point has two approach, first, carrying out depth dewaxing to base oil, can obtain low
The lubricating oil of pour point, the yield of such oil product is low, while takes off a large amount of useful normal hydrocarbons, also damages the quality of oil product；Second,
After the dewaxing for carrying out appropriateness, then the pour point for adding pour-point depressant to reach requirement, this is a kind of both economical feasible method, and now
The means generally used.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation method of environment-friendly type pour-point depressant.The environment-friendly type pour point depression
Pollution-free, high income in the production process of agent.Product of the present invention is tasteless, nontoxic, has good inoxidizability and heat endurance,
It is corrosion-free to copper, aluminium and its alloy, the not active element such as sulfur-bearing, phosphorus, chlorine.
Technical scheme is used by the present invention solves above-mentioned technical problem：A kind of preparation method of environment-friendly type pour-point depressant,
Characterized in that, specific reactions steps include successively：
Step 1:Esterification prepares thick ester, comprises the following steps that：
1. according to carboxyl and hydroxyl mol ratio it is 1.15 by fumaric acid and a variety of normal fatty alcohols:1 ratio is (i.e. anti-
The mol ratio of butene dioic acid and fatty alcohol is 0.575:1) reaction kettle of the esterification is added；A variety of normal fatty alcohols are n-C14H29-
OH、n-C16H33- OH and n-C18H37-OH；
2. opening stirring, the concentrated sulfuric acid is added in the reaction kettle of the esterification；
3. opening the vacuum system of reaction kettle of the esterification, industrial naptha is pumped into reaction kettle of the esterification using vacuum；
4. closing vacuum system, and 105 DEG C -130 DEG C are warming up to reaction kettle of the esterification, carry out esterification；
5. esterification oozes now to anhydrous, terminate esterification, open the industrial naptha in vacuum system removing material,
The thick ester of product needed for producing；
Step 2：The refined purification of thick ester；
1. the thick ester in reaction kettle of the esterification described in step 1 is pumped to refining reaction kettle, with KOH buck neutralized crude esters
Excessive fumaric acid, acid sulfate, sulfuric acid, make the fumaric acid in thick ester, acid sulfate, the sulfuric acid conversion be
Water soluble salt, separated with thick ester monomer；
2. the water-soluble substances remained in thick ester monomer is washed with water, separation water-yielding stratum produces the monomer after refining；
Step 3：Monomer dehydration after refined, produces fumaric acid Arrcostab essence monome；
Step 4：Monomer copolymerization；
1. fumaric acid Arrcostab essence monome obtained by step 3 is pumped into polymeric kettle, stir, be heated up to 80-90 DEG C and in
It is incubated under the conditions of 80-90 DEG C, adds benzoyl peroxide；
2. Vinyl Acetate Monomer is added dropwise in the monomer of above-mentioned polymeric kettle and participates in polymerisation；The polymerisation point
Two periods are carried out, including first time period and second time period；
3. polymerisation after the first time period, adds base oil into polymeric kettle, continue polymerisation and pass through
The second time period, finally obtain environment-friendly type pour-point depressant.
As further technical scheme, in the step 1, it is described 1. in, the composition of a variety of normal fatty alcohols and
Corresponding mass ratio is：n-C14H29- OH 20-40%, n-C16H33- OH 25-45%, n-C18H37- OH 20-50%.
As further technical scheme, in the step 1, it is described 1. in, the composition of a variety of normal fatty alcohols and
Corresponding mass ratio is：n-C14H29- OH 34.8%, n-C16H33- OH 37%, n-C18H37- OH 28.2%.
As further technical scheme, in the step 1, it is described 2. in, the addition weight of the concentrated sulfuric acid is relative
In the 0.3% of fumaric acid and normal fatty alcohol gross weight；It is described 3. in, the suction amount of the industrial naptha is relative to anti-
The 30% of butene dioic acid and normal fatty alcohol gross weight, and the industrial naptha is 120# industrial napthas.
As further technical scheme, in the step 2, it is described 1. in, the KOH bucks are that mass fraction is 3-
The 5% KOH aqueous solution；It is described 2. in, the water for washing thick ester monomer is softened water, and the usage amount of the softened water is
Relative to the 15-20% of thick ester weight.
As further technical scheme, the concrete operations of the step 3 are：Monoblock pump after being refined described in step 2
Enter vacuum reaction kettle, at the vacuum that vacuum is 700mmHg, 65-75 DEG C of temperature, monomer reclaimed water is sloughed in the stirring of nitrogen air lift
Part, after material is transparent, produce fumaric acid Arrcostab essence monome.
As further technical scheme, the concrete operations of the step 3 are：Monoblock pump after being refined described in step 2
Enter vacuum reaction kettle, under the vacuum that vacuum is 700mmHg, temperature 70 C, moisture content in monomer is sloughed in the stirring of nitrogen air lift, is treated
After material is transparent, fumaric acid Arrcostab essence monome is produced.
As further technical scheme, in the step 4, it is described 1. in, the addition of the benzoyl peroxide is
Relative to the 0.3% of fumaric acid Arrcostab essence monome weight；It is described 2. in, the addition of the Vinyl Acetate Monomer is
Relative to the 20% of fumaric acid Arrcostab essence monome weight；It is described 3. in, the addition of the base oil is relative to anti-
The 45% of butene dioic acid ester and Vinyl Acetate Monomer gross weight, and the base oil is 150N base oils.
As further technical scheme, in the step 4, it is described 1. in, 0.4-1h is incubated under the conditions of 80-90 DEG C；Institute
In stating 3., the second time period is the 0.4~0.8 of first time period.
As further technical scheme, in the step 4, it is described 1. in, soaking time 0.5h；It is described 3. in, gather
After closing reaction 5h, base oil is added into polymeric kettle, continues polymerisation 3h.
Present invention also offers the environment-friendly type pour-point depressant that above-mentioned preparation method is prepared.
The present invention compared with prior art, has the following advantages that：
(1) chemical industry synthesis method is used, produces the environment-friendly type pour point depression with excellent heat endurance and oxidation stability
Agent.Product shearing rate of descent is small, and good mechanical property, molecular weight is controlled between 50000-70000, and heat decomposition temperature reaches 200-
250℃.(there is non-polyester without influence in any polymerization product on acid number after oil low-temperature kinematic viscosity and oxidation in product
A certain amount of non-polyester), it is excellent to middle based lubricating oil base oil depression effeCt.
(2) the good biological degradability of product.This project uses the carboxylic acid long-chain fat alcohol ester of chemical industry synthesis method production
Analog copolymer, belong to chemical synthesis esters, compared with common mineral oil, this Project Product has excellent environment compatibility,
These esters 21d biodegradability is 70%-100%.Advanced profit for engine oil, machinery oil or Metalworking fluid etc.
Lubricating oil and additive, it is desirable to the water pollution soil pollution such as river and lake, underground water will not be caused after natural environment,
And this item purpose product can then meet these requirements well.
(3) it is of the invention compared with existing fumaric acid esters monomer polymerization reactions, polymerization is have adjusted in polymerization technique
Initiation temperature, the addition number and time-temperature of initiator are controlled, and combine polymerization to control molecular weight, reduce non-polyester
Content improves active principle, user is reduced dosage in actual use, reduces cost.
(4) production technology of environment-friendly type pour-point depressant of the present invention adds the yield of monomer, reduces in final products and does not gather
Ester content, active princlple is improved, plus C14-C18 higher alcohols compared with single carbon alcohol, price is relatively low.So product is in cost performance
On compared with other products have obvious advantage.
Embodiment
Content for a better understanding of the present invention, is described further with reference to specific embodiment.It should be understood that these
Embodiment is only used for that the present invention is further described, rather than limitation the scope of the present invention.In addition, it is to be understood that reading this
After the described content of invention, person skilled in art makes some nonessential changes or adjustment to the present invention, still falls within this
The protection domain of invention.
A kind of preparation method of environment-friendly type pour-point depressant of the present invention, specific reactions steps include successively：
Step 1:Esterification prepares thick ester, comprises the following steps that：
1. according to carboxyl and hydroxyl mol ratio it is 1.15 by fumaric acid and a variety of normal fatty alcohols:1 ratio adds
Reaction kettle of the esterification；The composition and corresponding mass ratio of a variety of normal fatty alcohols be：n-C14H29- OH 34.8%, n-C16H33-
OH 37%, n-C18H37- OH 28.2%；
2. opening stirring, relative fumaric acid and normal fatty alcohol gross weight are added in the reaction kettle of the esterification
0.3% concentrated sulfuric acid；
3. the vacuum system of reaction kettle of the esterification is opened, will relative fumaric acid and normal fatty alcohol gross weight using vacuum
30% 120# industrial napthas are pumped into reaction kettle of the esterification；
4. closing vacuum system, and 105 DEG C -130 DEG C are warming up to reaction kettle of the esterification, carry out esterification；
5. esterification oozes now to anhydrous, terminate esterification, open the 120# solvents in vacuum system removing material
Gasoline, produce the thick ester of required product；
Step 2：The refined purification of thick ester；
1. the thick ester in reaction kettle of the esterification described in step 1 is pumped to refining reaction kettle, with the KOH water prepared in advance
Slightly excessive fumaric acid, acid sulfate, sulfuric acid in solution neutralized crude esters, make fumaric acid in thick ester, acidity
Sulfuric ester, sulfuric acid conversion are water soluble salt, are separated with thick ester monomer；The KOH bucks are the KOH that mass fraction is 3-5%
The aqueous solution；
2. the water-soluble substances remained in thick ester monomer is washed away into the softened water of the 15-20% relative to thick ester weight
Property, separation water-yielding stratum produces the monomer after refining；
Step 3：The dehydration of monomer after refined；
Monomer described in step 2 is pumped into vacuum reaction kettle, under the vacuum that vacuum is 700mmHg, temperature 70 C, nitrogen
Moisture content in monomer is sloughed in the stirring of gas air lift, after material is transparent, produces fumaric acid Arrcostab essence monome.
Step 4：Monomer copolymerization；
1. fumaric acid Arrcostab essence monome obtained by step 3 is pumped into polymeric kettle, stir, be heated up to 80-90 DEG C, protect
Warm 0.5h, add the benzoyl peroxide of relative monomer weight 0.3%；
2. the Vinyl Acetate Monomer for accounting for above-mentioned monomer weight 20% is added dropwise to above-mentioned polymerization in a manner of nitrogen pressurizes
Polymerisation is participated in the monomer of kettle；
3. after polymerisation 5h, added into polymeric kettle and preprepared account for fumarate and vinylacetate list
The 150N base oils of body gross weight 45%, continue polymerisation 3h, finally obtain environment-friendly type pour-point depressant.
Product of the present invention has an excellent environment compatibility, and esters 21d biodegradability is 70%- in product
100%.
The production of the environment-friendly type pour-point depressant of embodiment 1
Step A：Esterification prepares thick ester.
1. by 66.7kg fumaric acid and n-C14H29-OH 82.87kg、n-C16H33-OH 88.10kg、n-C18H37-OH
67.15kg add reaction kettle of the esterification；2. opening stirring, the 0.914kg concentrated sulfuric acid is added in the reaction kettle of the esterification；3. open
The vacuum system of reaction kettle of the esterification, 91.45kg 120# industrial napthas are pumped into reaction kettle of the esterification using vacuum；4. close vacuum
System, and 105 DEG C -130 DEG C are warming up to reaction kettle of the esterification, carry out esterification；5. esterification oozes existing, end to anhydrous
Esterification, the 120# industrial napthas in vacuum system removing material are opened, produce the thick ester of required product.
Step B：The refined purification of thick ester.
1. the thick ester in reaction kettle of the esterification described in step A is pumped to refining reaction kettle, with the quality prepared in advance point
Number is the slightly excessive fumaric acid in 3% KOH aqueous solution neutralized crude esters, acid sulfate, sulfuric acid, is made anti-in thick ester
Butene dioic acid, acid sulfate, sulfuric acid conversion are water soluble salt, are separated with thick ester monomer；2. washed away with 45kg softened water
The water-soluble substances remained in thick ester monomer to neutrality, separation water-yielding stratum produces the monomer about 282kg after refining.
Step C：The dehydration of monomer after refined.
Monomer described in step B is pumped into vacuum reaction kettle, under the vacuum that vacuum is 700mmHg, temperature 70 C, nitrogen
Moisture content in monomer is sloughed in air lift stirring, after material is transparent, produces fumaric acid Arrcostab essence monome about 280kg.
Step D：Monomer copolymerization.
1. 280kg monomers described in step C are pumped into polymeric kettle, stir, be heated up to 80-90 DEG C, be incubated 0.5h, add
0.84kg benzoyl peroxide；2. 56kg Vinyl Acetate Monomer is added dropwise to above-mentioned polymeric kettle in a manner of nitrogen pressurizes
Monomer in participate in polymerisation；3. after polymerisation 5h, 151.2kg 150N base oils are added into polymeric kettle, continue to gather
Reaction 3h is closed, finally obtains environment-friendly type pour-point depressant.
In the present embodiment, technique raw material and proportioning such as following table：
The product quality indicator measurement result of environment-friendly type pour-point depressant prepared by embodiment is as follows：
After adding same ratio product of the present invention in different base oils, by actual measurement as can be seen that this product tool
There is excellent depression effeCt, it is as shown in the table：
It is described above, be only presently preferred embodiments of the present invention, any formal limitation not done to the present invention, it is every according to
Any simply modification, the equivalent variations made according to the technical spirit of the present invention to above example, each fall within the protection of the present invention
Within the scope of.
Claims (10)
1. a kind of preparation method of environment-friendly type pour-point depressant, it is characterised in that specific reactions steps include successively：Step 1:Esterification
Reaction prepares thick ester, comprises the following steps that：
1. according to carboxyl and hydroxyl mol ratio it is 1.15 by fumaric acid and a variety of normal fatty alcohols:1 ratio adds esterification
Reactor；A variety of normal fatty alcohols are n-C14H29-OH、n-C16H33- OH and n-C18H37-OH；
2. opening stirring, the concentrated sulfuric acid is added in the reaction kettle of the esterification；
3. opening the vacuum system of reaction kettle of the esterification, industrial naptha is pumped into reaction kettle of the esterification using vacuum；
4. closing vacuum system, and 105 DEG C -130 DEG C are warming up to reaction kettle of the esterification, carry out esterification；
5. esterification produces to the anhydrous industrial naptha for oozing existing, end esterification, opening in vacuum system removing material
The required thick ester of product；
Step 2：The refined purification of thick ester；
1. the thick ester in reaction kettle of the esterification described in step 1 is pumped to refining reaction kettle, with the mistake in KOH buck neutralized crude esters
Fumaric acid, acid sulfate, the sulfuric acid of amount, it is water-soluble to make the fumaric acid in thick ester, acid sulfate, sulfuric acid conversion
Property salt, is separated with thick ester monomer；
2. the water-soluble substances remained in thick ester monomer is washed with water, separation water-yielding stratum produces the monomer after refining；
Step 3：Monomer dehydration after refined, produces fumaric acid Arrcostab essence monome；
Step 4：Monomer copolymerization；
1. fumaric acid Arrcostab essence monome obtained by step 3 is pumped into polymeric kettle, stirs, be heated up to 80-90 DEG C and in 80-
It is incubated under the conditions of 90 DEG C, adds benzoyl peroxide；
2. Vinyl Acetate Monomer is added dropwise in the monomer of above-mentioned polymeric kettle and participates in polymerisation；The polymerisation is divided to two
Period is carried out, including first time period and second time period；
3. polymerisation after the first time period, adds base oil into polymeric kettle, continue described in polymerisation process
Second time period, finally obtain environment-friendly type pour-point depressant.
A kind of 2. preparation method of environment-friendly type pour-point depressant according to claim 1, it is characterised in that in the step 1,
It is described 1. in, the composition and corresponding mass ratio of a variety of normal fatty alcohols are：n-C14H29- OH 20-40%, n-C16H33-
OH 25-45%, n-C18H37- OH 20-50%.
A kind of 3. preparation method of environment-friendly type pour-point depressant according to claim 1, it is characterised in that in the step 1,
It is described 1. in, the composition and corresponding mass ratio of a variety of normal fatty alcohols are：n-C14H29- OH 34.8%, n-C16H33-OH
37%th, n-C18H37- OH 28.2%.
A kind of 4. preparation method of environment-friendly type pour-point depressant according to claim 3, it is characterised in that in the step 1,
It is described 2. in, the addition weight of the concentrated sulfuric acid is 0.3% relative to fumaric acid and normal fatty alcohol gross weight；
It is described 3. in, the suction amount of the industrial naptha is 30% relative to fumaric acid and normal fatty alcohol gross weight,
And the industrial naptha is 120# industrial napthas.
A kind of 5. preparation method of environment-friendly type pour-point depressant according to claim 4, it is characterised in that in the step 2,
It is described 1. in, the KOH bucks are the KOH aqueous solution that mass fraction is 3-5%；
It is described 2. in, the water for washing thick ester monomer is softened water, and the usage amount of the softened water is relative to thick ester
The 15-20% of weight.
A kind of 6. preparation method of environment-friendly type pour-point depressant according to claim 5, it is characterised in that the tool of the step 3
Gymnastics is made：Monomer is pumped into vacuum reaction kettle after being refined described in step 2, in the vacuum that vacuum is 700mmHg, temperature 65-
At 75 DEG C, moisture content in monomer is sloughed in the stirring of nitrogen air lift, after material is transparent, produces fumaric acid Arrcostab essence monome.
A kind of 7. preparation method of environment-friendly type pour-point depressant according to claim 5, it is characterised in that the tool of the step 3
Gymnastics is made：Monomer is pumped into vacuum reaction kettle after being refined described in step 2, in the vacuum that vacuum is 700mmHg, temperature 70
At DEG C, moisture content in monomer is sloughed in the stirring of nitrogen air lift, after material is transparent, produces fumaric acid Arrcostab essence monome.
A kind of 8. preparation method of environment-friendly type pour-point depressant according to claim 6 or 7, it is characterised in that the step 4
In,
It is described 1. in, the addition of the benzoyl peroxide is relative to fumaric acid Arrcostab essence monome weight
0.3%；
It is described 2. in, the addition of the Vinyl Acetate Monomer is relative to fumaric acid Arrcostab essence monome weight
20%；
It is described 3. in, the addition of the base oil is relative to fumarate and Vinyl Acetate Monomer gross weight
45%, and the base oil is 150N base oils.
A kind of 9. preparation method of environment-friendly type pour-point depressant according to claim 8, it is characterised in that in the step 4,
It is described 1. in, 0.4-1h is incubated under the conditions of 80-90 DEG C；It is described 3. in, the second time period be first time period 0.4~
0.8。
10. environment-friendly type pour-point depressant, it is prepared according to preparation method described in claim 1-9 any one.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175614A (en) * | 1996-09-04 | 1998-03-11 | 中国科学院大连化学物理研究所 | Pour point reducer for high pour point crude oil |
| CN102311843A (en) * | 2010-07-01 | 2012-01-11 | 华东理工大学 | Low temperature flow property improver of lubricating oil basic oil |
| CN103772574A (en) * | 2013-12-25 | 2014-05-07 | 济南开发区星火科学技术研究院 | Preparation method of diesel oil pour point depressant containing styrene-fumaric acid copolymer |
| CN104818060A (en) * | 2015-05-20 | 2015-08-05 | 中国科学院长春应用化学研究所 | Diesel low-temperature flow improver |
-
2015
- 2015-11-04 CN CN201510740799.2A patent/CN105524216B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175614A (en) * | 1996-09-04 | 1998-03-11 | 中国科学院大连化学物理研究所 | Pour point reducer for high pour point crude oil |
| CN102311843A (en) * | 2010-07-01 | 2012-01-11 | 华东理工大学 | Low temperature flow property improver of lubricating oil basic oil |
| CN103772574A (en) * | 2013-12-25 | 2014-05-07 | 济南开发区星火科学技术研究院 | Preparation method of diesel oil pour point depressant containing styrene-fumaric acid copolymer |
| CN104818060A (en) * | 2015-05-20 | 2015-08-05 | 中国科学院长春应用化学研究所 | Diesel low-temperature flow improver |
Non-Patent Citations (1)
| Title |
|---|
| "两种润滑油降凝剂的合成及降凝机理研究";邹佩良;《中国优秀硕士学位论文全文数据库》;20080415;第3.3节 * |
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