CN104387267B - A kind of preparation method of high base number hydrocarbyl salicylate calcium - Google Patents
A kind of preparation method of high base number hydrocarbyl salicylate calcium Download PDFInfo
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- CN104387267B CN104387267B CN201410675981.XA CN201410675981A CN104387267B CN 104387267 B CN104387267 B CN 104387267B CN 201410675981 A CN201410675981 A CN 201410675981A CN 104387267 B CN104387267 B CN 104387267B
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- hydrocarbyl salicylate
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- -1 hydrocarbyl salicylate calcium Chemical compound 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229960001860 salicylate Drugs 0.000 claims abstract description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 29
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 29
- 239000004571 lime Substances 0.000 claims abstract description 29
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000197 pyrolysis Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 239000002585 base Substances 0.000 claims description 65
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 26
- 239000003921 oil Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N malonic acid group Chemical group C(CC(=O)O)(=O)O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002199 base oil Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 238000001246 colloidal dispersion Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229960004889 salicylic acid Drugs 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 241000158728 Meliaceae Species 0.000 claims description 3
- 240000000203 Salix gracilistyla Species 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- VBIGULIJWJPALH-UHFFFAOYSA-L calcium;2-carboxyphenolate Chemical compound [Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O VBIGULIJWJPALH-UHFFFAOYSA-L 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000006386 neutralization reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 235000013399 edible fruits Nutrition 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 40
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 15
- 239000000920 calcium hydroxide Substances 0.000 description 15
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 150000004996 alkyl benzenes Chemical class 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- GTRHHOMIEMLBPC-UHFFFAOYSA-N 2-dodecoxybenzoic acid Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1C(O)=O GTRHHOMIEMLBPC-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 2
- JNGQJCLPTALFGM-UHFFFAOYSA-M C(C=1C(O)=CC=CC1)(=O)[O-].C(CCCCCCCCCCC)[Ca+] Chemical compound C(C=1C(O)=CC=CC1)(=O)[O-].C(CCCCCCCCCCC)[Ca+] JNGQJCLPTALFGM-UHFFFAOYSA-M 0.000 description 2
- SKZKKFZAGNVIMN-UHFFFAOYSA-N Salicilamide Chemical class NC(=O)C1=CC=CC=C1O SKZKKFZAGNVIMN-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical group 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229960004025 sodium salicylate Drugs 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 230000026676 system process Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 description 1
- MVQBFZXBLLMXGS-UHFFFAOYSA-N chembl331220 Chemical compound C1=CC=C2C(N=NC=3C4=CC=CC=C4C=C(C=3O)C(=O)O)=C(O)C=C(S(O)(=O)=O)C2=C1 MVQBFZXBLLMXGS-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010710 diesel engine oil Substances 0.000 description 1
- 239000013051 drainage agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to petrochemical industry, be particularly related to a kind of preparation method of high base number hydrocarbyl salicylate calcium, described method comprises: shell dry distillation liquid obtains hydrocarbyl salicylate through shallow degree Hydrogenation, under the effect of kicker, carry out neutralization reaction with lime with the hydrocarbyl salicylate making, then, pass into carbon dioxide and lime and carry out carbonation reaction, then obtain different base number hydrocarbyl salicylate calcium salt products through post processing. In preparation process of the present invention, selecting through the shell dry distillation liquid of shallow degree hydrogenation is raw material and high activity kicker, and the product biological degradability of producing is good, and having solved traditional product can not degrade and the problem of contaminated environment; Because alkyl side chain in product structure of the present invention is longer, improve the oil-soluble of product. In addition selected raw material fruit shell liquid wide material sources, green, nontoxic, renewable, is a kind of environmental friendliness raw materials for production.
Description
Technical field
The present invention relates to petrochemical industry, particularly a kind of high base number hydrocarbyl salicylate calciumPreparation method.
Background technology
High base number hydrocarbyl salicylate calcium is one of conventional detergent for lubricating oil, has goodAbility in high temperature detergency and fast acid also has certain low energy dispersion, antioxygen simultaneouslyVoltinism energy and corrosion resistance. This product has higher heat endurance, is particularly suitable asVarious diesel engine oils, railway machine oil and marine engine oil detersive.
About the preparation method of hydrocarbyl salicylate acid calcium, there are a lot of patents to disclose both at home and abroad.
Chinese patent, document 1: a kind of preparation method of calcium alkyl salicylate with high base number, public affairsThe number of opening: CN1144216A, open day: 1997.3.5, with dodecyl salicylic acid and oxidationCalcium is raw material, with certain material proportion and the charging sequence of regulation, has synthesized total base number largeIn the dodecyl calcium salicylate of 250mgKOH/g.
Document 2: a kind of alkyl salicylate as additive of lubricant oil, publication number:CN1199086A, discloses day: 1998.11.18, utilizes the consumption of adjustment form surface-active agent,Synthesize the dodecyl calcium salicylate with calcium sulfonate with high base number with favorable compatibility.
Document 3, the preparation method of alkaline alkyl sodium salicylate, publication number: CN1202479A,Open day: 1998.12.23 is taking dodecyl salicylic acid and lime as raw material, with different joiningMaterial ratio, by controlling the pH value of reactant liquor of carbonating, can synthesize respectively different base numbers12 alkyl sodium salicylates.
Document 4, a kind of preparation method of ultrahigh basicity alkyl salicylate, publication number:CN1345921A, open day, 2002.4.24, taking dodecyl salicylic acid as raw material, drewEnter organic carboxyl acid or alkyl benzene sulphonate as surfactant, use respectively alkaline earth oxideParticipate in reaction with hydroxide, and through twice carbonation reaction, obtain total base numberThe alkaline calcium salicylate of 400mgKOH/g.
Document 5, new method prepared by a kind of alkaline alkyl salicylate, publication number:CN1504451A, open day: 2004.6.16, utilizes the magnesium that adds organic carboxyl acid or sulfonic acidSalt, under methyl alcohol promoter exists, taking dodecyl salicylic acid and lime as raw material, can divideDo not synthesize different base number alkyl sodium salicylates, the pH of reactant liquor for the reaction end of carbonatingValue is controlled.
Document 6, the preparation method of lubricant detergents, publication number: CN1708471A, public affairsOpen day, 2005.12.14, discloses a kind of alkylated salicylamide that utilizes alkyl side chain to be greater than 14 carbonAcid is raw material, under the promoter such as methyl alcohol and surfactant exist, by carbon dioxide andLime generation carbonation reaction generates alkaline alkyl sodium salicylate; This patent also discloses simultaneouslyUtilize alkyl salicylate and sulfonate with high base number reactant salt to generate alkaline alkyl salicylate.
In foregoing invention, except document 6, its common feature is all to adopt numerous and diverse tradition rawProduce dodecyl salicylic acid technique, taking phenol as raw material by carrying out alkylation with lauryleneReaction makes dodecylphenol, then is reacted and carried out carboxylation reaction and obtain by Koble-SchmittTo dodecyl salicylic acid. The raw material phenol using in such technique has dirt to environment and water qualityDye, in product, also exist the ortho position dodecylphenol that 10%-25% activity is lower, and residualIn product, can not degrade, environment and animal body are also had to harmful effect.
Although adopt by alkene and salicylic acid synthesis of alkyl under the effect of catalyst in document 6Salicylic acid technique, but this technique shortcoming is catalyst divide unclean, the alkylated salicylamide newly synthesizingAcid is unstable, very easily resolves into a large amount of solid salicylic acids and alkene, has had a strong impact on productQuality and yield. In view of this, special proposition the present invention.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high base number hydrocarbyl salicylate calcium,Simplify relieving haperacidity flow process, also stopped phenol pollution problem in conventional procedure, prepared productProduct oil-soluble is good, thermal stability is good, base number can reach 450mgKOH/g.
In order to realize above-mentioned purpose of the present invention, spy by the following technical solutions:
A preparation method for high base number hydrocarbyl salicylate calcium, in accordance with the following methods preparation:
(1) obtain hydrocarbyl salicylate by shell dry distillation liquid through shallow degree hydrogenation technique, it is group mainlyBe divided into 15 carbon hydroxyl salicylic acids;
Wherein, described hydrocarbyl salicylate is obtained through shallow degree hydrogenation technique by shell dry distillation liquidProduct, its key component is 15 carbon hydroxyl salicylic acids, oil-soluble is good, is monohydroxy alkylSalicylic acid or two hydroxy alkylene salicylic acid, its concrete structure formula is as shown in the formula (1) and formula (2);
In formula (1) and formula (2), wherein R chain length is alkene or the alkane of 15 carbon,Any one in all the other four substituting groups on can substituted benzene ring.
(2) will be mixed by volatile solvent oil, base oil, lime, kickerMixture is warming up to 40-80 DEG C, then adds surfactant and described hydrocarbyl salicylate,Stirring reaction 30-40 minute at 60-80 DEG C, generates neutral alkyl calcium salicylate salt;
In this step, hydrocarbyl salicylate is on kicker and volatile solvent oil, basisUnder the effect of oil and surfactant, carry out neutralization reaction with lime, generate neutral alkyl bigcatkin willowAcid calcium salt.
Lime wherein, can be disposable a large amount of before generating neutral alkyl calcium salicylate saltAdd; Wherein generating when neutral alkyl calcium salicylate salt unreacted, lime can be shape completelyBecome and in stable colloidal dispersion system process, participate in reaction.
Also can before generating neutral alkyl calcium salicylate salt, add on a small quantity the lime addingOnly participate in this step reaction; And forming in stable colloidal dispersion system process from newly addingLime. In order to improve reaction efficiency, adding fashionable can adding several times.
(3) in the time that system temperature is down to 50-54 DEG C, the described neutral alkyl bigcatkin willow generatingIn acid calcium salt, add promoter or add promoter and lime, and passing into carbon dioxide,Form stable colloidal dispersion system, obtain the hydrocarbyl salicylate calcium first product of object base number;
In this step, remaining lime or step in the carbon dioxide passing into and step (2)Suddenly the lime adding in (3) carries out carbonation reaction together, obtains subcarbonate. Be dissolved inThe colloid of oil encases newborn calcium carbonate, forms Water-In-Oil system, and the calcium carbonate of bag is moreProduct total base number is higher.
Wherein, the calcium hydroxide not being wrapped does not drop and and titanium dioxide at colloid surfaceCarbon reaction has generated calcium carbonate and has been attached to colloid surface nor can be filtered. So,This total base number comprises the base number of the calcium carbonate that the calcium hydroxide reaction that is not wrapped generates and is wrappedThe summation of the base number of the calcium carbonate of living.
In step (2) and (3), the lime adding can be also oxygen for calcium hydroxideChange calcium, it adds quality is 25-130g.
(4) the hydrocarbyl salicylate calcium first product distillation to the described object base number obtaining, removes bodySolvent, promoter and water in system, obtain containing unreacted lime, crystal form calcium carbonate andThe thick product of the hydrocarbyl salicylate calcium of the object base number of polarity thing impurity;
Preferably, the system temperature while removing solvent in system, promoter and water is controlled at130-150℃。
Wherein, the calcium carbonate being encased by colloid is amorphous calcium carbonate, remaining unreactedThe impurity such as lime, sizing calcium carbonate and other polarity thing to be impurity residual.
(5) in the described thick product obtaining, add filter aid to filter, obtain object base numberHydrocarbyl salicylate calcium product. Preferably, described filter aid is super-cell.
The preparation method of a kind of high base number hydrocarbyl salicylate calcium provided by the invention, selects by fruitIt is the salicylic alkyl of 15 carbon hydroxyl that shell dry distillation liquid obtains main component through shallow degree hydrogenation techniqueSalicylic acid, its preparation method, compared with traditional alkyl salicylate preparation method, is simplified greatlyRelieving haperacidity flow process, also stopped the phenol pollution problem producing in traditional mode of production process.
Shell dry distillation liquid belongs to natural plant kind, very easily degraded, and this has just solved traditional productThe pollution problem can not biodegradation causing.
In shell dry distillation liquid, contain C in addition15Side chain alkyl, segment is longer, and oil-soluble is good,Improve the solubility property of product in lubricating oil.
The present invention can be according to user's request in preparation process, by adjusting material proportion,Produce the hydrocarbyl salicylate calcium product of different size base number. The high base number of product can reach450mgKOH/g, and the existing hydrocarbyl salicylate calcium product base number of the industry can reach at presentPeak be only 250mgKOH/g.
Further, in step (1), prepare the shallow degree that described hydrocarbyl salicylate adopts and addHydrogen technique specifically comprises the following steps:
Normal temperature leads to after nitrogen replacement 8-12 minute in autoclave, adds shell dry distillation liquid, urgesAgent, is warmed up to 28-45 DEG C, within logical hydrogen 9-10 hour, reaches to pressure in autoclave1.8-2MPa, adds filter aid to filter and obtains hydrocarbyl salicylate.
Further, described catalyst is skeleton nickel or palladium charcoal; Hydrogenation temperature while passing into hydrogenDegree is not higher than 50 DEG C, and the pressure in described autoclave is not more than 2.0MPa.
Further, in step (2), described volatile solvent oil is boiling point 80-200 DEG CHydro carbons or aromatic hydrocarbon solvent oil, it adds quality is that described hydrocarbyl salicylate adds quality50-200％；
Preferably, described volatile solvent oil is: heptane, octane, 120# solvent naphtha, 200Any one in solvent naphtha, toluene, dimethylbenzene, trimethylbenzene or multiple combination.
Further, in step (2), described base oil be 75SN, 150SN, 200SN,The combination of any one or more in 2 centistokes(cst) hydrogenated oils, 5 centistokes(cst) hydrogenated oils, it adds qualityFor described hydrocarbyl salicylate adds the 10-100% of quality.
Preferably, it adds quality is the 30-80% that described hydrocarbyl salicylate adds quality, morePreferably, its to add quality be the 50-60% that described hydrocarbyl salicylate adds quality.
Further, in step (2), described kicker is C1-C4Organic carboxyl acid orDiacid, it adds quality is the 0.5%-4% that described hydrocarbyl salicylate adds quality. Preferably,It adds quality is the 2%-3% that described hydrocarbyl salicylate adds quality;
Preferably, C1-C4Organic carboxyl acid kicker be formic acid, acetic acid, propionic acid, butyric acidIn any one or multiple combination; Diacid kicker is malonic acid or succinic acid, orThe combination of the two.
The present invention selects above-mentioned efficient kicker, can simplify control procedure, accelerate high-alkaliChange the quality of reaction process, raising product.
Further, in step (2), described surfactant is mahogany acid, synthetic heavyAny one in alkyl benzene sulphonate, low alkali value sulfoacid calcium, alkenyl succinic anhydride or multipleCombination, it adds quality is the 0-50% that described hydrocarbyl salicylate adds quality. Preferably,It adds quality is the 10-40% that described hydrocarbyl salicylate adds quality, more preferably20-30％。
Further, in step (3), described promoter is methyl alcohol, and it adds quality for instituteState the 40-60% of hydrocarbyl salicylate quality. Preferably, its to add quality be described alkyl waterThe 45-55% of poplar acid quality.
Further, in step (3), described carbon dioxide intake is the lime that addsThe 60-100% of molal quantity, the speed that passes into of described carbon dioxide is 100-140mL/min;Temperature of reaction system is 40-55 DEG C, and the reaction time is 0.5-6 hour. Preferably, described twoCarbonoxide intake is the 70-80% of the molal quantity of the lime that wherein adds, the temperature of reaction systemDegree is 45-50 DEG C, and the reaction time is 2-4 hour.
Further, in step (5), the quality that adds of described filter aid is described thick productThe 6-15% of quality. Preferably, the quality that adds of described filter aid is described thick product quality8-12%.
Compared with prior art, the present invention has the following advantages:
(1) hydrocarbyl salicylate using is to be obtained through shallow degree hydrogenation technique by shell dry distillation liquid,This preparation method, compared with traditional alkyl salicylate preparation method, has simplified relieving haperacidity stream greatlyJourney, has also stopped the phenol pollution problem producing in traditional mode of production process.
(2) biodegradation of product energy, is beneficial to environmental protection.
(3) solubility property of product in lubricating oil is good.
(4) product base number can reach 450mgKOH/g.
(5) high, the good stability of product purity, quality and yield are all relatively high.
Brief description of the drawings
Fig. 1 is high base number hydrocarbyl salicylate calred external structure spectrogram provided by the invention.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but thisThose skilled in the art will be understood that, the following example is only for the present invention is described, and should not lookFor limiting the scope of the invention. Unreceipted actual conditions person in embodiment, according to normal conditionOr the condition of manufacturer's suggestion is carried out. The unreceipted person of production firm of agents useful for same or instrument, allFor the conventional products that can obtain by commercially available purchase.
A preparation method for high base number hydrocarbyl salicylate calcium, in accordance with the following methods preparation:
(1) obtain hydrocarbyl salicylate by shell dry distillation liquid through shallow degree hydrogenation technique, it is group mainlyBe divided into 15 carbon hydroxyl salicylic acids;
Wherein, described hydrocarbyl salicylate is obtained through shallow degree hydrogenation technique by shell dry distillation liquidProduct, its key component is 15 carbon hydroxyl salicylic acids, can be monohydroxy hydrocarbyl salicylateOr two hydroxy alkylene salicylic acids, its concrete structure formula is as shown in the formula (1) and formula (2);
In formula (1) and formula (2), wherein R chain length is alkene or the alkane of 15 carbon,Any one in all the other four substituting groups on can substituted benzene ring, the segment of hydrocarbon chain is longer,Can improve energetically the solubility property of product in lubricating oil.
Preferably, preparing the shallow degree hydrogenation technique that described hydrocarbyl salicylate adopts specifically comprisesFollowing steps:
Normal temperature leads to after nitrogen replacement 8-12 minute in autoclave, adds shell dry distillation liquid, urgesAgent, is warmed up to 28-45 DEG C, within logical hydrogen 9-10 hour, reaches to pressure in autoclave1.8-2MPa, adds filter aid to filter and obtains hydrocarbyl salicylate.
Wherein, preferably, in 1000mL autoclave, add the quality of shell dry distillation liquid to be400-410g, the quality that adds of catalyst is 4-8g, the intake of hydrogen is 39-40L.
Selecting and obtaining main component by shell dry distillation liquid through shallow degree hydrogenation technique is 15 carbon hydroxylsSalicylic hydrocarbyl salicylate, the alkyl salicylate using in its preparation method and conventional methodPreparation method compare, prepare the preparation flow of hydrocarbyl salicylate and more simplify, reduced workThe complexity of skill, has also stopped in traditional mode of production process to produce phenol and the pollution that causesProblem.
Preferably, described catalyst is skeleton nickel or palladium charcoal; The amounts of hydrogen wherein passing into is preferredFor 38-42L, the hydrogenation temperature while passing into hydrogen is higher than 50 DEG C, the pressure in described autoclavePower is not more than 2.0MPa.
(2) will be mixed by volatile solvent oil, base oil, lime, kickerMixture is warming up to 40-80 DEG C, then adds surfactant and described hydrocarbyl salicylate,Stirring reaction 30-40 minute at 60-80 DEG C, generates neutral alkyl calcium salicylate salt;
Preferably, first add surfactant to add again hydrocarbyl salicylate, add alkyl bigcatkin willowWhen acid, adopt the mode dripping to add.
When concrete operations, keep environment temperature at normal temperature, the hydrocarbyl salicylate adding and promotionAgent generation neutralization reaction, prepares hydrocarbyl salicylate calcium neutral salt.
Preferably, described volatile solvent oil is that hydro carbons or the aromatic hydrocarbons of boiling point 80-200 DEG C is moltenAgent oil, it adds quality is the 50-200% that described hydrocarbyl salicylate adds quality. More preferablyGround, described volatile solvent oil is: heptane, octane, 120# solvent naphtha, 200# solvent naphtha,Any one in toluene, dimethylbenzene, trimethylbenzene or multiple combination.
Preferably, described base oil be 75SN, 150SN, 200SN, 2 centistokes(cst) hydrogenated oils,The combination of any one or more in 5 centistokes(cst) hydrogenated oils, it adds quality is described alkyl waterPoplar acid adds the 10-100% of quality. More preferably, its to add quality be described alkyl bigcatkin willowAcid adds the 30-80% of quality, and most preferably, it adds quality is that described hydrocarbyl salicylate addsEnter the 50-60% of quality.
Preferably, described kicker is C1-C4Organic carboxyl acid or diacid, it adds matterAmount is the 0.5%-4% that described hydrocarbyl salicylate adds quality. Preferably, it adds quality to beDescribed hydrocarbyl salicylate adds the 2%-3% of quality. More preferably, C1-C4Organic carboxyl acidKicker is any one or the multiple combination in formic acid, acetic acid, propionic acid, butyric acid;Diacid kicker is malonic acid or succinic acid, or the combination of the two.
The present invention selects above-mentioned efficient kicker, can simplify control procedure, accelerate high-alkaliChange the quality of reaction process, raising product.
Preferably, described surfactant is mahogany acid, synthesized heavy alkyl benzene sulfonic acid, lowAny one in base number sulfoacid calcium, alkenyl succinic anhydride or multiple combination, it adds matterAmount is the 0-50% that described hydrocarbyl salicylate adds quality. Preferably, it adds quality for instituteState the 10-40% that hydrocarbyl salicylate adds quality, more preferably 20-30%.
(3) in the time that system temperature is down to 50-54 DEG C, the described neutral alkyl bigcatkin willow generatingIn acid calcium salt, add promoter or add promoter and lime, and passing into carbon dioxide,Form stable colloidal dispersion system, obtain the hydrocarbyl salicylate calcium first product of object base number. ?In this step, remaining lime or step (3) in the carbon dioxide passing into and step (2)In the lime that rejoins carry out together carbonation reaction and obtain subcarbonate and form stableColloidal dispersion system. Be dissolved in oily colloid Speleothem encased, form Water-In-Oil system,The more voluminous thing total base number of calcium carbonate of bag is higher. And then obtain the hydrocarbyl salicylate of object base numberCalcium first product.
In step (2) and (3), the lime adding can be also oxygen for calcium hydroxideChange calcium, it adds quality is 25-130g.
Preferably, described promoter is methyl alcohol, and it adds quality is described hydrocarbyl salicylate matterThe 40-60% of amount. Preferably, its to add quality be described hydrocarbyl salicylate quality45-55％。
Preferably, described carbon dioxide intake is the 60-of the molal quantity of the lime that adds100%, the speed that passes into of described carbon dioxide is 100-140mL/min; Temperature of reaction systemFor 40-55 DEG C, the reaction time is 0.5-6 hour. Preferably, described carbon dioxide intakeFor the 70-80% of the molal quantity of the lime that wherein adds, the temperature of reaction system is 45-50 DEG C,Reaction time is 2-4 hour.
(4) the hydrocarbyl salicylate calcium first product distillation to the described object base number obtaining, removes bodySolvent, promoter and water in system, obtain containing unreacted lime, crystal form calcium carbonate andThe thick product of the hydrocarbyl salicylate calcium of the object base number of polarity thing impurity;
(5) in the described thick product obtaining, add filter aid to filter, obtain object base numberHydrocarbyl salicylate calcium product. Preferably, described filter aid is super-cell.
Preferably, the quality that adds of described filter aid is the 6-15% of described thick product quality.More preferably, the quality that adds of described filter aid is the 8-12% of described thick product quality.
The present invention can be according to user's request in preparation process, by adjusting material proportion,Produce the hydrocarbyl salicylate calcium product of different size base number. Product total base number can reach450mgKOH/g, and the existing hydrocarbyl salicylate calcium product total base number of the industry can reach at presentThe peak arriving is only 250mgKOH/g.
Embodiment 1: the shallow degree Hydrogenation of shell dry distillation liquid is for the method for hydrocarbyl salicylate.
Normal temperature leads to nitrogen replacement 10 minutes in 1000mL autoclave, adds shell dry distillation liquid400g, skeleton nickel 8g, is warmed up to 45 DEG C, logical hydrogen 40L, the logical 10 hours hydrogen time,Pressure 1.8MPa, reacts complete, adds the filtration of 20g super-cell and obtains 365.4g hydrocarbonBase salicylic acid, acid number is 110.56mgKOH/g.
Embodiment 2: the shallow degree Hydrogenation of shell dry distillation liquid is for the method for hydrocarbyl salicylate.
Normal temperature leads to nitrogen replacement 10 minutes in 1000mL autoclave, adds shell dry distillation liquid400g, palladium charcoal 4g, is warmed up to 28 DEG C, logical hydrogen 39L, the logical 10 hours hydrogen time,Pressure 1.8MPa, reacts complete, adds the filtration of 20g super-cell and obtains 362.3g hydrocarbonBase salicylic acid, acid number is 112.14mgKOH/g.
Embodiment 3: high base number hydrocarbyl salicylate calcium synthetic
Normal temperature adds 120# solvent naphtha 60g, 150SN23g, hydrogen in 1000mL flaskCalcium oxide 25g, glacial acetic acid 0.5g, stirs and is warmed up to 60 DEG C, adds low alkali value sulfonic acidCalcium 10g, then drips the hydrocarbyl salicylate 117g in embodiment 1, holding temperature60-80 DEG C 30 minutes. System cools to 54 DEG C, adds methyl alcohol 10g, regulates temperature to existBetween 40-50 DEG C, pass into carbon dioxide 7L with 140mL/min speed, control carbonating temperatureBetween 40-55 DEG C. Be warmed up to gradually 150 DEG C of distillations methanol removal, water and solvents, add and helpFiltering agent 14g, uses Buchner funnel suction filtration, and the base number of the product obtaining is 201mgKOH/g,Viscosity (100 DEG C) 26.3mm2/ s, turbidity 12JTU.
Embodiment 4: high base number hydrocarbyl salicylate calcium synthetic
Normal temperature adds octane 91g in 1000mL flask, 200SN21g, calcium hydroxide30.2g, propionic acid 1.5g, stirs and is warmed up to 60 DEG C, adds heavy alkylbenzene sulfonic acid 12g,Then drip the hydrocarbyl salicylate 119g in embodiment 2, holding temperature 60-80 DEG C 30 minutes.System cools to 54 DEG C, adds methyl alcohol 15g, regulates temperature at 40-50 DEG C, with 140mL/minSpeed passes into carbon dioxide 8L, controls carbonating temperature at 40-50 DEG C. Be warmed up to gradually150 DEG C of distillations methanol removal, water and solvents. Add filter aid 10g, use Buchner funnel suction filtration,Obtaining product base number is 258mgKOH/g, viscosity (100 DEG C) 34.12mm2/ s, turbidity11.6JTU。
Embodiment 5: high base number hydrocarbyl salicylate calcium synthetic
Normal temperature adds dimethylbenzene 120g in 1000mL flask, 5 centistokes(cst) hydrogenated oil 75g,Calcium oxide 8.9, malonic acid 6g, stirs and is warmed up to 60 DEG C, adds oil benzene sulfonamideAcid 37.5g, then drips the hydrocarbyl salicylate 75g in embodiment 1, holding temperature60-80 DEG C 30 minutes. System cools to 54 DEG C, adds methyl alcohol 45g. Add 22g to systemCalcium hydroxide (or adding before neutralization), adjusts the temperature to 48-50 DEG C, with 100mL/min speedPass into carbon dioxide 10L, controlling carbonating temperature is 48-52 DEG C. Add 15g to systemCalcium hydroxide, regulates temperature at 48-50 DEG C, passes into carbon dioxide with 100mL/min speed5L, controls carbonating temperature at 48-52 DEG C. Methanol removal, water and solvent, add drainageAgent 12g, uses Buchner funnel suction filtration, and the base number that obtains product is 320mgKOH/g, viscosity(100℃)60.54mm2/ s, turbidity 17.6JTU.
Embodiment 6: high-base-number calcium alkyl salicylate detergent synthetic
Normal temperature adds pseudocumene 150g in 1000mL flask, 2 centistokes(cst) hydrogenated oil 50g,Calcium hydroxide 4.3 and calcium oxide 5.6, succinic acid 6g, stirs and is warmed up to 60 DEG C, addsEnter low alkali value sulfoacid calcium 21g, then drip the hydrocarbyl salicylate 100g in embodiment 2, dimensionHold temperature 60-80 DEG C 30 minutes. System cools to 54 DEG C, adds methyl alcohol 30g. To systemAdd 24g calcium hydroxide (or adding before neutralization), regulate temperature between 50-55 DEG C, with 100mL/min speed passes into carbon dioxide 9.2L, controls carbonating temperature at 50-55 DEG C. Xiang TiSystem adds 16g calcium hydroxide, regulates temperature between 50-55 DEG C, with 100mL/min speedPass into carbon dioxide 5L, control carbonating temperature at 48-52 DEG C. Methanol removal, water and moltenAgent. Add filter aid 25g, use Buchner funnel suction filtration, the base number that obtains product is326mgKOH/g, viscosity (100 DEG C) 65.04mm2/ s, turbidity 19.2JTU.
Embodiment 7: high base number hydrocarbyl salicylate calcium synthetic
Normal temperature adds 200# solvent naphtha 101g, 75SN52g, hydrogen-oxygen in 1000mL flaskChange calcium 11.7, formic acid 3g, stirs and is warmed up to 60 DEG C, adds heavy alkylbenzene sulfonic acid 14g,Then drip the hydrocarbyl salicylate 98g in embodiment 1, holding temperature 60-80 DEG C 30 minutes.System cools to 54 DEG C, adds methyl alcohol 30g. Add (or the neutralization of 30g calcium hydroxide to systemBefore add), adjusting temperature is 48-50 DEG C, passes into carbon dioxide 7L with 100mL/min speed,Control carbonating temperature between 48-52 DEG C. Add 22g calcium hydroxide to system, regulate temperatureDegree, at 48-50 DEG C, passes into the about 5.1L of carbon dioxide with 100mL/min speed, controls carbonic acidChange temperature is 48-52 DEG C. Methanol removal, water and solvent. Add filter aid 30g, use Bu ShiFunnel suction filtration, the base number that obtains product is 312mgKOH/g, viscosity (100 DEG C)68.07mm2/ s, turbidity 13.1JTU.
Embodiment 8: high base number hydrocarbyl salicylate calcium synthetic
Normal temperature adds 120# solvent naphtha 150g in 1000mL flask, 2 centistokes(cst) hydrogenationOil 61g, calcium hydroxide 11.7g, calcium oxide 4.7g, formic acid 6g, stirs and is warmed up to60 DEG C, add heavy alkylbenzene sulfonic acid 30g, then drip the hydrocarbyl salicylate in embodiment 299g, holding temperature 60-80 DEG C 30 minutes. System cools to 54 DEG C, adds methyl alcohol 59g.Add 30g calcium hydroxide (or adding before neutralization) to system, regulate temperature between 48-50 DEG C,Pass into carbon dioxide 7L with 100mL/min speed, control carbonating temperature between 48-52 DEG C.Add 22g calcium hydroxide to system, regulate temperature between 48-50 DEG C, with 100mL/minSpeed passes into carbon dioxide 5.1L, controls carbonating temperature between 48-52 DEG C. Add to systemEnter 17g calcium hydroxide, regulate temperature between 48-50 DEG C, pass into 100mL/min speedThe about 5.2L of carbon dioxide, controls carbonating temperature between 48-52 DEG C. Add 15g to systemCalcium hydroxide, regulates temperature between 48-50 DEG C, passes into titanium dioxide with 100mL/min speedThe about 4.8L of carbon, controls carbonating temperature between 48-52 DEG C. Methanol removal, water and solvent.Add filter aid 40g, use Buchner funnel suction filtration, the base number that obtains product is 402mgKOH/g,Viscosity (100 DEG C) 125.02mm2/ s, turbidity 23.4JTU.
Embodiment 9: high base number hydrocarbyl salicylate calcium is synthetic
Normal temperature adds heptane 200g in 1000mL flask, 2 centistokes(cst) hydrogenated oil 63g, hydrogenCalcium oxide 17.9, formic acid 6g, stirs and is warmed up to 60 DEG C, adds heavy alkylbenzene sulfonic acid25g, then drips the hydrocarbyl salicylate 102g in embodiment 1, holding temperature 60-80 DEG C 30Minute. System cools to 54 DEG C, adds methyl alcohol 59g. To system add 29g calcium hydroxide (orBefore neutralization, add), regulate temperature between 48-50 DEG C, pass into dioxy with 100mL/min speedChange carbon 8.4L, control carbonating temperature at 48-52 DEG C. Add 27g calcium hydroxide to system,Regulate temperature between 48-50 DEG C, pass into the about 8.5L of carbon dioxide with 100mL/min speed,Control carbonating temperature at 48-52 DEG C. Add 25g calcium hydroxide to system, regulate temperatureBetween 48-50 DEG C, pass into the about 6.5L of carbon dioxide with 100mL/min speed, control carbonic acidChange temperature at 48-52 DEG C. Add 23g calcium hydroxide to system, regulate temperature at 48-50 DEG CBetween, pass into the about 6L of carbon dioxide with 100mL/min speed, control carbonating temperature and exist48-52 DEG C. Methanol removal, water and solvent, add filter aid 40g, uses Buchner funnel suction filtration,The base number that obtains product is 452mgKOH/g, viscosity (100 DEG C) 171.41mm2/ s is turbidDegree 44.1JTU.
Fig. 1 makes for the high base number hydrocarbyl salicylate calcium providing according to the embodiment of the present invention 9Infrared structure spectrogram, can be clear that according to spectrogram, in the present embodiment product without fixedThe characteristic peaks of shape calcium carbonate is 861.0.
Although illustrated and described the present invention with specific embodiment, but it will be appreciated thatIn the situation that not deviating from the spirit and scope of the present invention, can make many other change andAmendment. Therefore, this means in claims and comprise and belonging in the scope of the inventionAll such changes and modifications.
Claims (8)
1. a preparation method for high base number hydrocarbyl salicylate calcium, is characterized in that, according toBelow legal system is standby:
(1) obtain hydrocarbyl salicylate by shell dry distillation liquid through shallow degree hydrogenation technique, it is group mainlyBe divided into hydrocarbyl salicylate, wherein, described hydrocarbyl salicylate be monohydroxy hydrocarbyl salicylate orTwo hydroxy alkylene salicylic acids, its structure is with following formula I or formula II:
Wherein, RFor chain length is alkene or the alkane of 15 carbon;
(2) will be mixed by volatile solvent oil, base oil, lime, kickerMixture is warming up to 40-80 DEG C, then adds surfactant and described hydrocarbyl salicylate,Stirring reaction 30-40 minute at 60-80 DEG C, generates neutral alkyl calcium salicylate salt;
(3) in the time that system temperature is down to 50-54 DEG C, the described neutral alkyl bigcatkin willow generatingIn acid calcium salt, add promoter or add promoter and lime, and passing into carbon dioxide,Form stable colloidal dispersion system, obtain the hydrocarbyl salicylate calcium first product of object base number;
(4) the hydrocarbyl salicylate calcium first product distillation to the described object base number obtaining, removes bodySolvent, promoter and water in system, obtain containing unreacted lime, crystal form calcium carbonate andThe thick product of the hydrocarbyl salicylate calcium of the object base number of polarity thing impurity;
(5) in the described thick product obtaining, add filter aid to filter, obtain object base numberHydrocarbyl salicylate calcium product;
Wherein, in step (1), prepare the shallow degree hydrogenation work that described hydrocarbyl salicylate adoptsSkill specifically comprises the following steps:
Normal temperature leads to after nitrogen replacement 8-12 minute in autoclave, adds shell dry distillation liquid, urgesAgent, is warmed up to 28-45 DEG C, within logical hydrogen 9-10 hour, reaches to pressure in autoclave1.8-2MPa, adds filter aid to filter and obtains hydrocarbyl salicylate; Described catalyst is skeleton nickelOr palladium charcoal;
Kicker in described step (2) is C1-C4Organic carboxyl acid or diacid, it addsEntering quality is the 0.5%-4% that described hydrocarbyl salicylate adds quality; C1-C4Organic carboxyl acidKicker is any one or the multiple combination in formic acid, acetic acid, propionic acid, butyric acid.
2. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, itsBe characterised in that,
In step (2), described volatile solvent oil is: heptane, octane, 120# solvent naphtha,Any one in 200# solvent naphtha, toluene, dimethylbenzene, trimethylbenzene or multiple combination.
3. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, itsBe characterised in that,
In step (2), described base oil is 75SN, 150SN, 200SN, 2 centistokes(cst)sThe combination of any one or more in hydrogenated oil, 5 centistokes(cst) hydrogenated oils, it adds quality for instituteState the 10-100% that hydrocarbyl salicylate adds quality.
4. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, itsBe characterised in that described diacid kicker is malonic acid or succinic acid, or the combination of the two.
5. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, itsBe characterised in that, in step (2), described surfactant is mahogany acid, synthetic heavy alkylAny one in benzene sulfonic acid, low alkali value sulfoacid calcium, alkenyl succinic anhydride or multiple combination,It adds quality is the 10-50% that described hydrocarbyl salicylate adds quality.
6. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, itsBe characterised in that, in step (3), described promoter is methyl alcohol, and it adds quality is described hydrocarbonThe 40-60% of base salicylic acid quality.
7. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, itsBe characterised in that, in step (3), described carbon dioxide intake is the lime total amount that adds60-100%, the speed that passes into of described carbon dioxide is 100-140mL/min; Reaction system temperatureDegree is 40-55 DEG C, and the reaction time is 0.5-6 hour.
8. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, itsBe characterised in that, in step (5), the quality that adds of described filter aid is described thick product quality6-15%.
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| CN107118137B (en) * | 2017-06-26 | 2021-10-29 | 锦州康泰润滑油添加剂股份有限公司 | Heavy alkyl benzene zinc sulfonate as oil product antirust agent and preparation method thereof |
| CN111995515B (en) * | 2019-05-27 | 2022-07-08 | 浙江工业大学 | Method for preparing nano-grade calcium malate by compounding shell raw material with surfactant |
| CN113549481B (en) * | 2021-07-29 | 2023-03-31 | 新乡市瑞丰新材料股份有限公司 | Preparation process of ultrahigh-base-number calcium alkyl salicylate |
| CN116478747A (en) * | 2022-01-13 | 2023-07-25 | 中国石油天然气股份有限公司 | Preparation method of high-base-number magnesium salicylate detergent |
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