CN104387267A - Preparation method of high-base-number hydrocarbyl calcium salicylate - Google Patents
Preparation method of high-base-number hydrocarbyl calcium salicylate Download PDFInfo
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- CN104387267A CN104387267A CN201410675981.XA CN201410675981A CN104387267A CN 104387267 A CN104387267 A CN 104387267A CN 201410675981 A CN201410675981 A CN 201410675981A CN 104387267 A CN104387267 A CN 104387267A
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- China
- Prior art keywords
- hydrocarbyl salicylate
- calcium
- base number
- hydrocarbyl
- salicylate
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- -1 hydrocarbyl calcium salicylate Chemical compound 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 33
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 31
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 31
- 239000004571 lime Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000000197 pyrolysis Methods 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- 230000007935 neutral effect Effects 0.000 claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 5
- 229960001860 salicylate Drugs 0.000 claims description 73
- 239000002585 base Substances 0.000 claims description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 239000003921 oil Substances 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 33
- 235000011089 carbon dioxide Nutrition 0.000 claims description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 15
- 230000003311 flocculating effect Effects 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- 239000002199 base oil Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 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
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001246 colloidal dispersion Methods 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
- 239000003513 alkali Substances 0.000 claims description 5
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000002075 main ingredient Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002674 ointment Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical group CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 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
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- 238000009835 boiling Methods 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
- 239000013078 crystal Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract description 3
- 229960004889 salicylic acid Drugs 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 24
- 239000000920 calcium hydroxide Substances 0.000 description 24
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 229960004025 sodium salicylate Drugs 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 3
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 150000003839 salts Chemical class 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
- 241000196324 Embryophyta Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect 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
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 238000006473 carboxylation reaction Methods 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
- 230000001143 conditioned effect Effects 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
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910021518 metal oxyhydroxide 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
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 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
- 239000004094 surface-active agent Substances 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
Abstract
The invention relates to the petrochemical industry field and in particular relates to a preparation method of high-base-number hydrocarbyl calcium salicylate. The method comprises the following steps: carrying out shallow hydrogenation on shell dry distillation liquid to prepare hydrocarbyl salicylic acid; carrying out neutral reaction with lime on prepared hydrocarbyl salicylic acid under the action of a kicker, then introducing carbon dioxide to perform carbonation reaction with the lime, and posttreating to obtain the hydrocarbyl salicylic acid calcium salt products with different base numbers. According to the preparation process, the shell dry distillation liquid with shallow hydrogenation is selected as a raw material and a high-activity kicker, the prepared product is good in biodegradability, and the problem that traditional products can not be degraded and pollute the environment is solved. Hydrocarbyl side chain is longer in the product structure so that the oil solubility of the product is improved. In addition, the selected raw material of the shell liquid is extensive in source, environmental friendly, nontoxic and renewable and is an environmentally friendly production raw material.
Description
Technical field
The present invention relates to petrochemical industry, particularly a kind of preparation method of high base number hydrocarbyl salicylate calcium.
Background technology
High base number hydrocarbyl salicylate calcium is one of conventional detergent for lubricating oil, has ability in good high temperature detergency and fast acid, also has certain low energy dispersion, antioxidant property and corrosion resistance simultaneously.This product has higher thermostability, is particularly suitable as various diesel engine oil, railway machine oil and marine engine oil purification agent.
About the preparation method of hydrocarbyl salicylate acid calcium, a lot of patent is had to disclose both at home and abroad.
Chinese patent, document 1: a kind of preparation method of calcium alkyl salicylate with high base number, publication number: CN1144216A, publication date: 1997.3.5, with dodecyl Whitfield's ointment and calcium oxide for raw material, with the order of addition(of ingredients) of certain material proportion and regulation, synthesize the dodecyl calcium salicylate that total basicnumber is greater than 250mgKOH/g.
Document 2: a kind of alkyl salicylate as additive of lubricant oil, publication number: CN1199086A, publication date: 1998.11.18, utilizes the consumption of adjustment sheet surface-active agent, synthesizes 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, publication date: 1998.12.23 with dodecyl Whitfield's ointment and lime for raw material, with different ratio of components, by controlling the pH value of the reaction solution of carbonating, different base number 12 alkyl sodium salicylate can be synthesized respectively.
Document 4, a kind of preparation method of ultrahigh basicity alkyl salicylate, publication number: CN1345921A, publication date, 2002.4.24, with dodecyl Whitfield's ointment for raw material, introducing organic carboxyl acid or alkyl benzene sulphonate (ABS) are as tensio-active agent, participate in reaction with alkaline earth metal oxide and oxyhydroxide respectively, and through twice carbonation reaction, obtain the alkaline calcium salicylate of total basicnumber 400mgKOH/g.
Document 5, the novel method that a kind of alkaline alkyl salicylate is prepared, publication number: CN1504451A, publication date: 2004.6.16, utilize and add the magnesium salts of organic carboxyl acid or sulfonic acid, under methyl alcohol promotor exists, with dodecyl Whitfield's ointment and lime for raw material, can synthesize different base number alkyl sodium salicylate respectively, the pH value of the reaction end reaction solution of carbonating controls.
Document 6, the preparation method of lubricant detergents, publication number: CN1708471A, publication date, 2005.12.14, disclosing a kind of alkyl salicylate utilizing alkyl group side chain to be greater than 14 carbon is raw material, under the promotor such as methyl alcohol and tensio-active agent exist, generates alkaline alkyl sodium salicylate by carbonic acid gas and lime generation carbonation reaction; This patent also also discloses and utilizes 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 adopt numerous and diverse traditional mode of production dodecyl Whitfield's ointment technique, namely be raw material with phenol by and laurylene carry out alkylated reaction and obtain 4-dodecylphenol, then carry out carboxylation reaction by Koble-Schmitt reaction and obtain dodecyl Whitfield's ointment.The raw material phenol used in such technique has pollution to environment and water quality, also there is the active lower ortho position 4-dodecylphenol of 10%-25% in product, and residually can not degrade in the product, also has detrimentally affect to environment and animal body.
Although adopt by alkene and Whitfield's ointment synthesis of alkyl Whitfield's ointment technique under the effect of catalyzer in document 6, but this processing disadvantages is catalyzer divide unclean, the alkyl salicylate newly synthesized is unstable, very easily resolves into a large amount of solid Whitfield's ointment and alkene, has had a strong impact on quality and the yield of product.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 product 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, prepares in accordance with the following methods:
(1) obtain hydrocarbyl salicylate by shell dry distillation liquid through either shallow hydrogenation technique, its main ingredient is 15 carbon hydroxyl Whitfield's ointments;
Wherein, described hydrocarbyl salicylate is the product obtained through either shallow hydrogenation technique by shell dry distillation liquid, its main ingredient is 15 carbon hydroxyl Whitfield's ointments, oil soluble is good, for monohydroxy hydrocarbyl salicylate or two hydroxy alkylene Whitfield's ointment, 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, can any one in all the other four substituting groups on substituted benzene ring.
(2) mixture be mixed by volatile solvent oil, base oil, lime, secondary accelerator is warming up to 40-80 DEG C, add tensio-active agent and described hydrocarbyl salicylate again, stirring reaction 30-40 minute at 60-80 DEG C, generates neutral alkyl calcium salicylate salt;
In this step, hydrocarbyl salicylate carries out neutralization reaction with lime under the effect of secondary accelerator and volatile solvent oil, base oil and tensio-active agent, generates neutral alkyl calcium salicylate salt.
Lime wherein, can disposablely before the neutral alkyl calcium salicylate salt of generation add in a large number; Wherein when generating neutral alkyl calcium salicylate salt unreacted completely lime can participate in reaction being formed in stable colloidal dispersion system process.
Also can add on a small quantity before the neutral alkyl calcium salicylate salt of generation, this step reaction only participated in by the lime added; And formed in stable colloidal dispersion system process from newly adding lime.In order to improve reaction efficiency, adding fashionable can adding several times.
(3) when system temperature is down to 50-54 DEG C, add promotor or add promotor and lime in the described neutral alkyl calcium salicylate salt generated, and pass into carbon dioxide, form stable colloidal dispersion system, obtain the hydrocarbyl salicylate calcium first product of object base number;
In this step, the carbonic acid gas passed into carries out carbonation reaction together with the lime added in remaining lime in step (2) or step (3), obtains subcarbonate.The calcium carbonate of new life encases by the colloid being dissolved in oil, and form water-in-oil system, the calcium carbonate more voluminous thing total basicnumber of bag is higher.
Wherein, the calcium hydroxide be not wrapped does not drop at colloid surface and generates calcium carbonate with carbon dioxide reaction and is attached to colloid surface nor can be filtered.So this total basicnumber comprises the base number of calcium carbonate of the calcium hydroxide reaction generation be not wrapped and the summation of the base number of the calcium carbonate be wrapped.
In step (2) and (3), the lime added can be also calcium oxide for calcium hydroxide, and it adds quality is 25-130g.
(4) distill the hydrocarbyl salicylate calcium first product of the described object base number obtained, the solvent in removing system, promotor and water, obtain the thick product of the hydrocarbyl salicylate calcium of the object base number containing unreacted lime, crystal form calcium carbonate and polarity thing impurity;
Preferably, the solvent in removing system, promotor and water time system temperature control at 130-150 DEG C.
Wherein, be amorphous calcium carbonate by the calcium carbonate that colloid encases, remaining unreacted lime, impurity such as sizing calcium carbonate and other polarity thing etc. are impurities left.
(5) in the described thick product obtained, add filter aid, obtain the hydrocarbyl salicylate calcium product of object base number.Preferably, described flocculating aids is super-cell.
The preparation method of a kind of high base number hydrocarbyl salicylate calcium provided by the invention, selecting and obtaining main component by shell dry distillation liquid through either shallow hydrogenation technique is the salicylic hydrocarbyl salicylate of 15 carbon hydroxyl, its preparation method is compared with traditional alkyl salicylate preparation method, enormously simplify relieving haperacidity flow process, also stop the phenol pollution problem produced in Conventional process.
Shell dry distillation liquid belongs to natural plant kind, very easily degrades, and which solves traditional product can not the pollution problem that causes of biological degradation.
C is contained in addition in shell dry distillation liquid
15side chain alkyl, segment is longer, and oil soluble is good, improves the solubility property of product in lubricating oil.
The present invention according to customer need, by adjustment material proportion, can produce the hydrocarbyl salicylate calcium product of different size base number in preparation process.The most high base number of product can reach 450mgKOH/g, and the maximum that the hydrocarbyl salicylate calcium product base number that the industry is existing at present can reach is only 250mgKOH/g.
Further, in step (1), prepare the either shallow hydrogenation technique that described hydrocarbyl salicylate adopts and specifically comprise the following steps:
Normal temperature is logical in autoclave to add shell dry distillation liquid, catalyzer, is warmed up to 28-45 DEG C after nitrogen replacement 8-12 minute, led to and reached 1.8-2MPa to pressure in autoclave in hydrogen 9-10 hour, add filter aid and obtain hydrocarbyl salicylate.
Further, described catalyzer is skeleton nickel or palladium charcoal; Hydrogenation temperature when passing into hydrogen 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 hydro carbons or the aromatic hydrocarbon solvent oil of boiling point 80-200 DEG C, and it adds quality is the 50-200% that described hydrocarbyl salicylate adds quality;
Preferably, described volatile solvent oil is: any one or multiple combination in heptane, octane, 120# solvent oil, 200# solvent oil, toluene, dimethylbenzene, trimethylbenzene.
Further, in step (2), described base oil is the combination of any one or more in 75SN, 150SN, 200SN, 2 centistokes(cst) hydrogenated oils, 5 centistokes(cst) hydrogenated oils, and it adds quality is the 10-100% that described hydrocarbyl salicylate adds quality.
Preferably, it adds quality is the 30-80% that described hydrocarbyl salicylate adds quality, and more preferably, it adds quality is the 50-60% that described hydrocarbyl salicylate adds quality.
Further, in step (2), described secondary accelerator is C
1-C
4organic carboxyl acid or diacid, 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, C
1-C
4organic carboxyl acid secondary accelerator be any one or multiple combination in formic acid, acetic acid, propionic acid, butyric acid; Diacid secondary accelerator is propanedioic acid or succinic acid, or the combination of the two.
The present invention selects above-mentioned efficient secondary accelerator, the quality that can simplify control process, accelerate high alkalization reaction process, improve product.
Further, in step (2), described tensio-active agent is any one or multiple combination in mahogany acid, synthesized heavy alkyl benzene sulfonic acid, low alkali value calcium sulphonate, alkenyl succinic anhydride, and 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, is more preferably 20-30%.
Further, in step (3), described promotor is methyl alcohol, and it adds the 40-60% that quality is described hydrocarbyl salicylate quality.Preferably, it adds the 45-55% that quality is described hydrocarbyl salicylate quality.
Further, in step (3), described carbonic acid gas intake is the 60-100% of the mole number of the lime added, and the speed that passes into of described carbonic acid gas is 100-140mL/min; Temperature of reaction system is 40-55 DEG C, and the reaction times is 0.5-6 hour.Preferably, described carbonic acid gas intake is the 70-80% of the mole number of the lime wherein added, and the temperature of reaction system is 45-50 DEG C, and the reaction times is 2-4 hour.
Further, in step (5), described flocculating aids add the 6-15% that quality is described thick quality product.Preferably, described flocculating aids add the 8-12% that quality is described thick quality product.
Compared with prior art, the present invention has the following advantages:
(1) hydrocarbyl salicylate used is obtained through either shallow hydrogenation technique by shell dry distillation liquid, this preparation method is compared with traditional alkyl salicylate preparation method, enormously simplify relieving haperacidity flow process, also stop the phenol pollution problem produced in Conventional process.
(2) biological degradation 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.
Accompanying drawing explanation
Fig. 1 is high base number hydrocarbyl salicylate calred outer structure spectrogram provided by the invention.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting the scope of the invention.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturers suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, be and can buy by commercially available the conventional products obtained.
A preparation method for high base number hydrocarbyl salicylate calcium, prepares in accordance with the following methods:
(1) obtain hydrocarbyl salicylate by shell dry distillation liquid through either shallow hydrogenation technique, its main ingredient is 15 carbon hydroxyl Whitfield's ointments;
Wherein, described hydrocarbyl salicylate is the product obtained through either shallow hydrogenation technique by shell dry distillation liquid, its main ingredient is 15 carbon hydroxyl Whitfield's ointments, and can be monohydroxy hydrocarbyl salicylate or two hydroxy alkylene Whitfield's ointment, its concrete structure formula be 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, can any one in all the other four substituting groups on substituted benzene ring, and the segment of hydrocarbon chain is longer, can improve the solubility property of product in lubricating oil energetically.
Preferably, prepare the either shallow hydrogenation technique that described hydrocarbyl salicylate adopts specifically to comprise the following steps:
Normal temperature is logical in autoclave to add shell dry distillation liquid, catalyzer, is warmed up to 28-45 DEG C after nitrogen replacement 8-12 minute, led to and reached 1.8-2MPa to pressure in autoclave in hydrogen 9-10 hour, add filter aid and obtain hydrocarbyl salicylate.
Wherein, preferably, the quality adding shell dry distillation liquid in 1000mL autoclave is 400-410g, and the quality that adds of catalyzer is 4-8g, and the intake of hydrogen is 39-40L.
Selecting and obtaining main component by shell dry distillation liquid through either shallow hydrogenation technique is the salicylic hydrocarbyl salicylate of 15 carbon hydroxyl, its preparation method is compared with the method for preparing alkyl salicylic acid used in traditional method, the preparation flow preparing hydrocarbyl salicylate simplifies more, reduce the complexity of technique, also stopped produce phenol in Conventional process and the pollution problem caused.
Preferably, described catalyzer is skeleton nickel or palladium charcoal; The amounts of hydrogen wherein passed into is preferably 38-42L, and hydrogenation temperature when passing into hydrogen is not higher than 50 DEG C, and the pressure in described autoclave is not more than 2.0MPa.
(2) mixture be mixed by volatile solvent oil, base oil, lime, secondary accelerator is warming up to 40-80 DEG C, add tensio-active agent and described hydrocarbyl salicylate again, stirring reaction 30-40 minute at 60-80 DEG C, generates neutral alkyl calcium salicylate salt;
Preferably, first add tensio-active agent and add hydrocarbyl salicylate again, when adding hydrocarbyl salicylate, adopt the mode dripped to add.
During concrete operations, keep envrionment temperature at normal temperature, there is neutralization reaction in the hydrocarbyl salicylate added and promotor, prepares hydrocarbyl salicylate calcium neutral salt.
Preferably, described volatile solvent oil is hydro carbons or the aromatic hydrocarbon solvent oil of boiling point 80-200 DEG C, and it adds quality is the 50-200% that described hydrocarbyl salicylate adds quality.More preferably, described volatile solvent oil is: any one or multiple combination in heptane, octane, 120# solvent oil, 200# solvent oil, toluene, dimethylbenzene, trimethylbenzene.
Preferably, described base oil is the combination of any one or more in 75SN, 150SN, 200SN, 2 centistokes(cst) hydrogenated oils, 5 centistokes(cst) hydrogenated oils, and it adds quality is the 10-100% that described hydrocarbyl salicylate adds quality.More preferably, it adds quality is the 30-80% that described hydrocarbyl salicylate adds quality, and most preferably, it adds quality is the 50-60% that described hydrocarbyl salicylate adds quality.
Preferably, described secondary accelerator is C
1-C
4organic carboxyl acid or diacid, 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.More preferably, C
1-C
4organic carboxyl acid secondary accelerator be any one or multiple combination in formic acid, acetic acid, propionic acid, butyric acid; Diacid secondary accelerator is propanedioic acid or succinic acid, or the combination of the two.
The present invention selects above-mentioned efficient secondary accelerator, the quality that can simplify control process, accelerate high alkalization reaction process, improve product.
Preferably, described tensio-active agent is any one or multiple combination in mahogany acid, synthesized heavy alkyl benzene sulfonic acid, low alkali value calcium sulphonate, alkenyl succinic anhydride, and 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, is more preferably 20-30%.
(3) when system temperature is down to 50-54 DEG C, add promotor or add promotor and lime in the described neutral alkyl calcium salicylate salt generated, and pass into carbon dioxide, form stable colloidal dispersion system, obtain the hydrocarbyl salicylate calcium first product of object base number.In this step, the carbonic acid gas passed into carries out carbonation reaction and obtains the stable colloidal dispersion system of basic carbonate salt formation together with the lime rejoined in remaining lime in step (2) or step (3).Speleothem encases by the colloid being dissolved in oil, and form water-in-oil system, the calcium carbonate more voluminous thing total basicnumber of bag is higher.And then obtain the hydrocarbyl salicylate calcium first product of object base number.
In step (2) and (3), the lime added can be also calcium oxide for calcium hydroxide, and it adds quality is 25-130g.
Preferably, described promotor is methyl alcohol, and it adds the 40-60% that quality is described hydrocarbyl salicylate quality.Preferably, it adds the 45-55% that quality is described hydrocarbyl salicylate quality.
Preferably, described carbonic acid gas intake is the 60-100% of the mole number of the lime added, and the speed that passes into of described carbonic acid gas is 100-140mL/min; Temperature of reaction system is 40-55 DEG C, and the reaction times is 0.5-6 hour.Preferably, described carbonic acid gas intake is the 70-80% of the mole number of the lime wherein added, and the temperature of reaction system is 45-50 DEG C, and the reaction times is 2-4 hour.
(4) distill the hydrocarbyl salicylate calcium first product of the described object base number obtained, the solvent in removing system, promotor and water, obtain the thick product of the hydrocarbyl salicylate calcium of the object base number containing unreacted lime, crystal form calcium carbonate and polarity thing impurity;
(5) in the described thick product obtained, add filter aid, obtain the hydrocarbyl salicylate calcium product of object base number.Preferably, described flocculating aids is super-cell.
Preferably, described flocculating aids add the 6-15% that quality is described thick quality product.More preferably, described flocculating aids add the 8-12% that quality is described thick quality product.
The present invention according to customer need, by adjustment material proportion, can produce the hydrocarbyl salicylate calcium product of different size base number in preparation process.Product total basicnumber can reach 450mgKOH/g, and the maximum that the hydrocarbyl salicylate calcium product total basicnumber that the industry is existing at present can reach is only 250mgKOH/g.
Embodiment 1: shell dry distillation liquid either shallow Hydrogenation is for the method for hydrocarbyl salicylate.
Normal temperature leads to nitrogen replacement 10 minutes in 1000mL autoclave, add shell dry distillation liquid 400g, skeleton nickel 8g, be warmed up to 45 DEG C, logical hydrogen 40L, the logical 10 hours hydrogen time, pressure 1.8MPa, react complete, add the filtration of 20g super-cell and obtain 365.4g hydrocarbyl salicylate, acid number is 110.56mgKOH/g.
Embodiment 2: shell dry distillation liquid either shallow Hydrogenation is for the method for hydrocarbyl salicylate.
Normal temperature leads to nitrogen replacement 10 minutes in 1000mL autoclave, add shell dry distillation liquid 400g, palladium charcoal 4g, be warmed up to 28 DEG C, logical hydrogen 39L, the logical 10 hours hydrogen time, pressure 1.8MPa, react complete, add the filtration of 20g super-cell and obtain 362.3g hydrocarbyl salicylate, acid number is 112.14mgKOH/g.
Embodiment 3: the synthesis of high base number hydrocarbyl salicylate calcium
Normal temperature adds 120# solvent oil 60g in 1000mL flask, 150SN 23g, calcium hydroxide 25g, Glacial acetic acid 0.5g, stirs and is warmed up to 60 DEG C, adds low alkali value calcium sulphonate 10g, then drip the hydrocarbyl salicylate 117g in embodiment 1, holding temperature 60-80 DEG C 30 minutes.System cools to 54 DEG C, adds methyl alcohol 10g, regulates temperature between 40-50 DEG C, passes into carbonic acid gas 7L with 140mL/min speed, controls carbonation temperature between 40-55 DEG C.Be warmed up to 150 DEG C of distillations methanol removal, water and solvents gradually, add flocculating aids 14g, use Büchner funnel suction filtration, the base number of the product obtained is 201mgKOH/g, viscosity (100 DEG C) 26.3mm
2/ s, turbidity 12JTU.
Embodiment 4: the synthesis of high base number hydrocarbyl salicylate calcium
Normal temperature adds octane 91g in 1000mL flask, 200SN 21g, calcium hydroxide 30.2g, and propionic acid 1.5g stirs and is warmed up to 60 DEG C, adds heavy alkylbenzene sulfonic acid 12g, then drips 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, passes into carbonic acid gas 8L with 140mL/min speed, controls carbonation temperature at 40-50 DEG C.Be warmed up to 150 DEG C of distillations methanol removal, water and solvents gradually.Add flocculating aids 10g, use Büchner funnel suction filtration, obtaining product base number is 258mgKOH/g, viscosity (100 DEG C) 34.12mm
2/ s, turbidity 11.6JTU.
Embodiment 5: the synthesis of high base number hydrocarbyl salicylate calcium
Normal temperature adds dimethylbenzene 120g in 1000mL flask, 5 centistokes(cst) hydrogenated oil 75g, calcium oxide 8.9, propanedioic acid 6g, stirs and is warmed up to 60 DEG C, adds oil alkyl benzene sulphonate (ABS) 37.5g, then drip the hydrocarbyl salicylate 75g in embodiment 1, holding temperature 60-80 DEG C 30 minutes.System cools to 54 DEG C, adds methyl alcohol 45g.Add 22g calcium hydroxide (or adding before neutralization) to system, adjust the temperature to 48-50 DEG C, pass into carbonic acid gas 10L with 100mL/min speed, control carbonation temperature is 48-52 DEG C.Add 15g calcium hydroxide to system, regulate temperature at 48-50 DEG C, pass into carbonic acid gas 5L with 100mL/min speed, control carbonation temperature at 48-52 DEG C.Methanol removal, water and solvent, add flocculating aids 12g, uses Büchner funnel suction filtration, and the base number obtaining product is 320mgKOH/g, viscosity (100 DEG C) 60.54mm
2/ s, turbidity 17.6JTU.
Embodiment 6: the synthesis of high-base-number calcium alkyl salicylate detergent
Normal temperature adds unsym-trimethyl benzene 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, adds low alkali value calcium sulphonate 21g, then drip the hydrocarbyl salicylate 100g in embodiment 2, holding temperature 60-80 DEG C 30 minutes.System cools to 54 DEG C, adds methyl alcohol 30g.Add 24g calcium hydroxide (or adding before neutralization) to system, regulate temperature between 50-55 DEG C, pass into carbonic acid gas 9.2L with 100mL/min speed, control carbonation temperature at 50-55 DEG C.Add 16g calcium hydroxide to system, regulate temperature between 50-55 DEG C, pass into carbonic acid gas 5L with 100mL/min speed, control carbonation temperature at 48-52 DEG C.Methanol removal, water and solvent.Add flocculating aids 25g, use Büchner funnel suction filtration, the base number obtaining product is 326mgKOH/g, viscosity (100 DEG C) 65.04mm
2/ s, turbidity 19.2JTU.
Embodiment 7: the synthesis of high base number hydrocarbyl salicylate calcium
Normal temperature adds 200# solvent oil 101g in 1000mL flask, 75SN52g, calcium hydroxide 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 30g calcium hydroxide (or adding before neutralization) to system, adjustment temperature is 48-50 DEG C, passes into carbonic acid gas 7L with 100mL/min speed, controls carbonation temperature between 48-52 DEG C.Add 22g calcium hydroxide to system, regulate temperature at 48-50 DEG C, pass into carbonic acid gas with 100mL/min speed and be about 5.1L, control carbonation temperature is 48-52 DEG C.Methanol removal, water and solvent.Add flocculating aids 30g, use Büchner funnel suction filtration, the base number obtaining product is 312mgKOH/g, viscosity (100 DEG C) 68.07mm
2/ s, turbidity 13.1JTU.
Embodiment 8: the synthesis of high base number hydrocarbyl salicylate calcium
Normal temperature adds 120# solvent oil 150g in 1000mL flask, 2 centistokes(cst) hydrogenated oil 61g, calcium hydroxide 11.7g, calcium oxide 4.7g, formic acid 6g, stir and be warmed up to 60 DEG C, add heavy alkylbenzene sulfonic acid 30g, then drip the hydrocarbyl salicylate 99g in embodiment 2, 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 carbonic acid gas 7L with 100mL/min speed, control carbonation temperature between 48-52 DEG C.Add 22g calcium hydroxide to system, regulate temperature between 48-50 DEG C, pass into carbonic acid gas 5.1L with 100mL/min speed, control carbonation temperature between 48-52 DEG C.Add 17g calcium hydroxide to system, regulate temperature between 48-50 DEG C, pass into carbonic acid gas with 100mL/min speed and be about 5.2L, control carbonation temperature between 48-52 DEG C.Add 15g calcium hydroxide to system, regulate temperature between 48-50 DEG C, pass into carbonic acid gas with 100mL/min speed and be about 4.8L, control carbonation temperature between 48-52 DEG C.Methanol removal, water and solvent.Add flocculating aids 40g, use Büchner funnel suction filtration, the base number obtaining product is 402mgKOH/g, viscosity (100 DEG C) 125.02mm
2/ s, turbidity 23.4JTU.
Embodiment 9: high base number hydrocarbyl salicylate calcium synthesizes
Normal temperature adds heptane 200g in 1000mL flask, 2 centistokes(cst) hydrogenated oil 63g, calcium hydroxide 17.9, formic acid 6g, stirs and is warmed up to 60 DEG C, adds heavy alkylbenzene sulfonic acid 25g, then drip the hydrocarbyl salicylate 102g in embodiment 1, holding temperature 60-80 DEG C 30 minutes.System cools to 54 DEG C, adds methyl alcohol 59g.Add 29g calcium hydroxide (or adding before neutralization) to system, regulate temperature between 48-50 DEG C, pass into carbonic acid gas 8.4L with 100mL/min speed, control carbonation temperature at 48-52 DEG C.Add 27g calcium hydroxide to system, regulate temperature between 48-50 DEG C, pass into carbonic acid gas with 100mL/min speed and be about 8.5L, control carbonation temperature at 48-52 DEG C.Add 25g calcium hydroxide to system, regulate temperature between 48-50 DEG C, pass into carbonic acid gas with 100mL/min speed and be about 6.5L, control carbonation temperature at 48-52 DEG C.Add 23g calcium hydroxide to system, regulate temperature between 48-50 DEG C, pass into carbonic acid gas with 100mL/min speed and be about 6L, control carbonation temperature at 48-52 DEG C.Methanol removal, water and solvent, add flocculating aids 40g, uses Büchner funnel suction filtration, and the base number obtaining product is 452mgKOH/g, viscosity (100 DEG C) 171.41mm
2/ s, turbidity 44.1JTU.
The infrared structure spectrogram that Fig. 1 makes for the high base number hydrocarbyl salicylate calcium provided according to the embodiment of the present invention 9, can be clear that according to spectrogram, the characteristic peaks of the amorphous calcium carbonate in the present embodiment product is 861.0.
Although illustrate and describe the present invention with specific embodiment, however it will be appreciated that can to make when not deviating from the spirit and scope of the present invention many other change and amendment.Therefore, this means to comprise all such changes and modifications belonged in the scope of the invention in the following claims.
Claims (10)
1. a preparation method for high base number hydrocarbyl salicylate calcium, is characterized in that, prepares in accordance with the following methods:
(1) obtain hydrocarbyl salicylate by shell dry distillation liquid through either shallow hydrogenation technique, its main ingredient is 15 carbon hydroxyl Whitfield's ointments;
(2) mixture be mixed by volatile solvent oil, base oil, lime, secondary accelerator is warming up to 40-80 DEG C, add tensio-active agent and described hydrocarbyl salicylate again, stirring reaction 30-40 minute at 60-80 DEG C, generates neutral alkyl calcium salicylate salt;
(3) when system temperature is down to 50-54 DEG C, add promotor or add promotor and lime in the described neutral alkyl calcium salicylate salt generated, and pass into carbon dioxide, form stable colloidal dispersion system, obtain the hydrocarbyl salicylate calcium first product of object base number;
(4) distill the hydrocarbyl salicylate calcium first product of the described object base number obtained, the solvent in removing system, promotor and water, obtain the thick product of the hydrocarbyl salicylate calcium of the object base number containing unreacted lime, crystal form calcium carbonate and polarity thing impurity;
(5) in the described thick product obtained, add filter aid, obtain the hydrocarbyl salicylate calcium product of object base number.
2. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, is characterized in that, in step (1), prepares the either shallow hydrogenation technique that described hydrocarbyl salicylate adopts and specifically comprises the following steps:
Normal temperature is logical in autoclave to add shell dry distillation liquid, catalyzer, is warmed up to 28-45 DEG C after nitrogen replacement 8-12 minute, led to and reached 1.8-2MPa to pressure in autoclave in hydrogen 9-10 hour, add filter aid and obtain hydrocarbyl salicylate.
3. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 2, is characterized in that,
Described catalyzer is skeleton nickel or palladium charcoal; Hydrogenation temperature when passing into hydrogen is less than or equal to 50 DEG C, and the pressure in described autoclave is less than or equal to 2.0MPa.
4. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, is characterized in that,
In step (2), described volatile solvent oil for boiling point be that the hydro carbons of 80-200 DEG C or aromatic hydrocarbon solvent are oily, it adds quality is the 50-200% that described hydrocarbyl salicylate adds quality;
Preferably, described volatile solvent oil is: any one or multiple combination in heptane, octane, 120# solvent oil, 200# solvent oil, toluene, dimethylbenzene, trimethylbenzene.
5. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, is characterized in that,
In step (2), described base oil is the combination of any one or more in 75SN, 150SN, 200SN, 2 centistokes(cst) hydrogenated oils, 5 centistokes(cst) hydrogenated oils, and it adds quality is the 10-100% that described hydrocarbyl salicylate adds quality.
6. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, is characterized in that, in step (2), described secondary accelerator is C
1-C
4organic carboxyl acid or diacid, it adds quality is the 0.5%-4% that described hydrocarbyl salicylate adds quality;
Preferably, C
1-C
4organic carboxyl acid secondary accelerator be any one or multiple combination in formic acid, acetic acid, propionic acid, butyric acid; Diacid secondary accelerator is propanedioic acid or succinic acid, or the combination of the two.
7. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, it is characterized in that, in step (2), described tensio-active agent is any one or multiple combination in mahogany acid, synthesized heavy alkyl benzene sulfonic acid, low alkali value calcium sulphonate, alkenyl succinic anhydride, and it adds quality is the 0-50% that described hydrocarbyl salicylate adds quality.
8. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, is characterized in that, in step (3), described promotor is methyl alcohol, and it adds the 40-60% that quality is described hydrocarbyl salicylate quality.
9. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, it is characterized in that, in step (3), described carbonic acid gas intake is the 60-100% of the lime total amount added, and the speed that passes into of described carbonic acid gas is 100-140mL/min; Temperature of reaction system is 40-55 DEG C, and the reaction times is 0.5-6 hour.
10. the preparation method of high base number hydrocarbyl salicylate calcium according to claim 1, is characterized in that, in step (5), described flocculating aids add the 6-15% that quality is described thick quality product.
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| CN105646187A (en) * | 2016-03-01 | 2016-06-08 | 锦州康泰润滑油添加剂股份有限公司 | Preparation method of super-basic-value alkyl aryl salicylic acid calcium salt |
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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 |
| CN111995515A (en) * | 2019-05-27 | 2020-11-27 | 浙江工业大学 | Method for preparing nano-grade calcium malate by compounding shell raw material with surfactant |
| 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 |
| CN113549481A (en) * | 2021-07-29 | 2021-10-26 | 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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