CN106278875B - A kind of production method of isooctyl acid - Google Patents
A kind of production method of isooctyl acid Download PDFInfo
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- CN106278875B CN106278875B CN201510324617.3A CN201510324617A CN106278875B CN 106278875 B CN106278875 B CN 106278875B CN 201510324617 A CN201510324617 A CN 201510324617A CN 106278875 B CN106278875 B CN 106278875B
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- acid
- isooctanol
- isooctyl acid
- zinc
- reaction
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- 239000002253 acid Substances 0.000 title claims abstract description 69
- -1 isooctyl Chemical group 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000020477 pH reduction Effects 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 239000012071 phase Substances 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- 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 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 235000021050 feed intake Nutrition 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000009938 salting Methods 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 25
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- 239000004280 Sodium formate Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 4
- 235000019254 sodium formate Nutrition 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 3
- 229940106681 chloroacetic acid Drugs 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical class CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- KPFSGNRRZMYZPH-UHFFFAOYSA-M potassium;2-chloroacetate Chemical compound [K+].[O-]C(=O)CCl KPFSGNRRZMYZPH-UHFFFAOYSA-M 0.000 description 1
- 230000036584 pressor response Effects 0.000 description 1
- 239000006077 pvc stabilizer Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/295—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with inorganic bases, e.g. by alkali fusion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of production methods of isooctyl acid, using isooctanol and highly basic in 180 ~ 290 DEG C of reaction 1.5-16h of temperature, then with, up to thick isooctyl acid, isooctyl acid is made in purified handle after sour acidification reaction object；Isooctyl acid is prepared in this way, is carried out acidification using non-sulfuric acid and is replaced sulfuric acid in the prior art, the by-product species of acquisition are abundant, have a wide range of application, and added value is high.
Description
Technical field
The present invention relates to organic synthesis fields, are related to a kind of production method of isooctyl acid.
Background technique
Isooctyl acid can be used as the intermediate, alkyd resin modifying agent, production peroxide of paint and terebine to make
For the catalyst of polymerization reaction and for lubricating grease and PVC stabilizer etc., market is widely used, and produces isooctyl acid at present
Technique can substantially be divided into two kinds: one is using butyraldehyde as raw material, isooctene aldehyde or different octanal is made in substep, further oxidation life
At isooctyl acid, but since butyraldehyde is as a kind of important industrial chemicals, for producing butanol generally in octyl alconyl combined production device
Or octanol, this method are suitble to scale chemical company according to market adjustment product category, yield, are not appropriate for normalization production
It needs, and since butyraldehyde is as raw material, causes isooctyl acid production cost higher；Second is to mix isooctanol and sodium hydroxide
Generate sodium iso-octoate by high pressure dehydrogenation oxidation method or normal pressure dehydrogenation oxidation method, then neutralize with sulfuric acid sodium iso-octoate obtain it is thick different
Octanoic acid further refines available sterling isooctyl acid.
Domestic at present and Japan main manufacturer is all the raw material being primarily due in this method using second method
Isooctanol abundance is easy storage, transport.But it is sulfuric acid that this method, which neutralizes acid used, at present, is obtained after neutralization a large amount of
Metabisulfite solution (produce isooctyl acid per ton and will generate and contain 1.5 tons of solution or so of 30~50% sodium sulphate) or by plus
Work becomes market acceptable byproduct sulfite or falls as liquid waste processing.But metabisulfite solution is processed as
Market acceptable commodity sodium sulphate, value of goods is also less than the costs such as the energy consumption in process, therefore there is no again
The value of processing；And if as liquid waste processing because waste liquid salt content is high, and yield is too big, gives subsequent environmental protection treatment band
Very big problem is carried out.
Summary of the invention
The present invention is in view of the above-mentioned problems, provide a kind of production method of isooctyl acid, by isooctanol and highly basic in temperature
Then 180~290 DEG C of reactions are acidified at ethylhexanoate salt with non-sulfuric acid up to thick isooctyl acid, then purified handle to obtain isooctyl acid.It adopts
Prepare isooctyl acid in this way, using non-sulfuric acid acid replace sulfuric acid in the prior art, the corresponding hydrochlorate byproduct of acquisition,
Have a wide range of application, added value is high, does not have any influence simultaneously for environment, can widely replace existing isooctyl acid producer
Method.
The most important improvement of the present invention is to be acidified ethylhexanoate salt instead of sulfuric acid using the acid of Waste Sulfuric Acid, is acidified
The hydrochlorate of the high added value obtained afterwards, can be used for multiple fields, for example, formates can be used for oil exploitation drilling fluid,
The fields such as Road Snow Agent；Chloracetate can be used for the fields such as pharmacy, petrochemical industry, intermetallic composite coating.
The specific technical solution of the present invention is: a kind of production method of isooctyl acid, mainly using isooctanol and highly basic in temperature
180~290 DEG C of reaction 1.5-16h are spent, then with, up to thick isooctyl acid, purified processing is made different pungent after sour acidification reaction object
Acid；
Wherein the highly basic is selected from or mixtures thereof potassium hydroxide or sodium hydroxide；
The acid that the acidification uses is the acid that pKa is 0.5-5.0, especially can be selected from formic acid or acetic acid or monoxone；
The molar ratio that the highly basic and isooctanol feed intake is 0.7~1.3:1；Mole of acid dosage and highly basic when the acidification
Than for 1.3~1:1.
More specifically reaction step are as follows:
Isooctanol and highly basic are put into reactor according to aforementioned proportion, are added isooctanol and are fed intake the 0.5~3% of quality
Zinc compound be sufficiently mixed, under conditions of 180~290 DEG C of temperature react 1.5-16h after, continue keep the temperature 20-90min；It
After be cooled to 160 DEG C hereinafter, reaction product is substantially soluble in water under normal pressure, can be obtained at 40~80 DEG C with acid acidification later
Thick isooctyl acid is salting liquid in water phase after aqueous phase separation, and oil is mutually thick isooctyl acid, and handling through conventional rectification and purification can make
Isooctyl acid must be refined；
The salting liquid can be sold directly as product, change when can also produce after common process refines as other
Work raw material uses；
The molar ratio that highly basic and isooctanol feed intake in reaction process is 0.9-1.1:1, more preferably 1.1:1；
The compound of the zinc can be selected from zinc oxide or zinc formate or zinc acetate or zinc carbonate or zinc oxalate, but be not limited to
The compound of these zinc.
Time preferred 50min when insulation reaction.
Technology in the technical program in addition to foregoing description is all made of prior art inventor and repeats no more；
Due to there is hydrogen generation in reaction process, this reaction belongs to pressor response, can carry out with reaction
Pressure discharge operations make less than 30 atmospheric pressure of pressure in reactor i.e. and can guarantee the safe and smooth progress of reaction；In addition to this
The mode that excessive ethylhexanol reflux can be used carries out above-mentioned reaction under normal pressure.
After adopting the above technical scheme, inventor utilizes above-mentioned alternative acid instead of sulfuric acid in the prior art, simultaneously will
Highly basic is no longer limited as sodium hydroxide, but can further select or mixtures thereof potassium hydroxide, and it is former to extend reaction
The source of material, at the same can according to downstream product or manufacturing enterprise need organically to deploy above-mentioned bronsted lowry acids and bases bronsted lowry it is whole
It closes, to obtain the higher byproduct of added value, improves the efficiency of production and the benefit of enterprise, can get after specific allotment integration
Product such as sodium formate, potassium formate, sodium chloroacetate, potassium chloroacetate, in which:
Byproduct potassium formate or sodium formate will be obtained by being acidified with formic acid, and wherein formic acid acid group is easy by the bacterium in soil
Metabolism, and potassium is element required for plant growth, so potassium formate is environmental-friendly salt, in addition to this, potassium formate is in oil
Field exploitation aspect is used as drilling fluid, while can be used as deicing salt, has wide range of applications；They have preferable commercial value simultaneously:
If potassium formate (75% aqueous solution) price is generally 7500 yuan/ton, sodium formate price is generally 2400 yuan/ton；And ten water sulphur
Sour sodium price is less than 200 yuan/ton, and anhydrous sodium sulfate price is generally at 400 yuan/ton or so.
The sulphuric acid cost needed when being acidified to obtain isooctyl acid for isooctyl acid potassium is saved for isooctyl acid, to potassium formate
For then saved required potassium hydroxide cost, while avoiding the generation of a large amount of low value-added sodium sulphate, it is seen that use
Above-mentioned alternative acid obtains preferable market efficiency instead of sulfuric acid in the prior art, and byproduct obtained is exactly in the market
Required chemical products achieve unexpected effect compared with the prior art.And if neutralized with monoxone, chlorine will be obtained
Acetate: wherein sodium chloroacetate is a kind of important fine chemical product, is widely used in petrochemical industry, organic chemical industry, synthesis system
The industrial productions such as medicine, pesticide, dyestuff chemical industry, intermetallic composite coating, the price of sodium chloroacetate are generally 9000 yuan/ton, and above-mentioned
Potassium formate and sodium formate also belong to widely used industrial chemicals, the market value having be also sodium sulphate or potassium sulfate institute not
It can compare, therefore this technical solution that inventor provides has great progress compared with the prior art and achieves commercially
Success, for isooctyl acid production provide a completely new approach.
In conclusion the present invention carries out the system of isooctyl acid using the acid of non-sulfuric acid instead of sulfuric acid in the prior art
It is standby, while reaction highly basic used has been expanded into potassium hydroxide, although seeming simple, but achieve unexpected technology
Effect achieves commercial howling success, and the by-product species of acquisition are abundant, have a wide range of application, and added value is high, while right
There is no any influence in environment, can replace existing isooctyl acid production method.
Specific embodiment
The present invention is further illustrated below with reference to embodiment, can make those skilled in the art that this hair be more completely understood
It is bright, but do not limit the invention in any way.
Embodiment 1
The isooctanol of 500g, 258g potassium hydroxide, 10g zinc formate, reaction are sequentially added in 2000ml autoclave
Kettle is replaced 2 times with nitrogen and air in system is discharged, and at 230 DEG C after sealing, is reacted under the conditions of 2Mpa, and reaction carries out 6h
Afterwards, continue to keep the temperature 50min, be cooled to 160 DEG C later hereinafter, pressure in kettle is then down to normal pressure, the distillation of 400ml is added
Water stirs 30min, obtains isooctyl acid aqueous solutions of potassium.
Isooctyl acid aqueous solutions of potassium is transferred in flask, the formic acid solution 212g of 94wt% is slowly added under stirring, is controlled
Reaction temperature is 60 DEG C, reacts 30min, moves to separatory funnel, stands 30min, multi_layer extraction water phase, and water phase is simply concentrated to give
To potassium formate solutions (solution can directly as merchandise sales or be condensed into a certain concentration such as 74% sell)；Oil mutually uses 60g
Distilled water washing twice thick isooctyl acid, the unreacted alcohol of vacuum distillation removing, rectifying obtains isooctyl acid finished product 542g, with isooctanol
Collecting weight rate is 108.4%, molar yield 97.92%.
Embodiment 2
Sequentially add the isooctanol of 700g in 2000mL there-necked flask, 215g potassium hydroxide, 10g zinc oxide, under stirring by
It is gradually warming up to reflux, is carried out with reflux, temperature gradually rises in bottle.Obviously there is hydrogen releasing when reaching 180 DEG C, continues to heat
It maintains the reflux for steadily releasing with hydrogen, after 9-12h, temperature continues to keep the temperature 60min to 230 DEG C, it is cooled to 150 DEG C later
Hereinafter, the distilled water of 400mL is added, 30min is stirred, isooctyl acid aqueous solutions of potassium is obtained.
Isooctyl acid aqueous solutions of potassium is transferred in flask, the formic acid solution 207g of 94wt% is slowly added under stirring, is controlled
Reaction temperature is 60 DEG C, reacts 30min, moves to separatory funnel, stands 30min, multi_layer extraction water phase, and water phase is simply concentrated to give
To potassium formate solutions；It is oily mutually with the washing of 60g distilled water twice thick isooctyl acid, the unreacted alcohol of vacuum distillation removing, rectifying obtain
Isooctyl acid finished product 531g, molar yield is 96.03% in terms of potassium hydroxide.
Embodiment 3
The isooctanol of 500g, 169g sodium hydroxide, 10g zinc formate, reaction are sequentially added in 2000ml autoclave
Kettle is replaced 2 times with nitrogen and air in system is discharged, and at 240 DEG C after sealing, is reacted under the conditions of 3Mpa, and reaction carries out 4-
After 10h, continues to keep the temperature 50min, be cooled to 150 DEG C later hereinafter, pressure in kettle is then down to normal pressure, the steaming of 400ml is added
Distilled water stirs 30min, obtains sodium iso-octoate aqueous solution.
Sodium iso-octoate aqueous solution is transferred in flask, the chloroacetic acid solution 872g of 50wt% is slowly added under stirring, is controlled
Reaction temperature processed is 40 DEG C, reacts 30min, moves to separatory funnel, stands 30min, multi_layer extraction water phase, water phase is sodium chloroacetate
Solution；It is oily mutually with the washing of 60g distilled water twice thick isooctyl acid, the unreacted alcohol of vacuum distillation removing, rectifying obtain isooctyl acid at
Product 535g, weight yield is 107% in terms of isooctanol, molar yield 96.7%.
Embodiment 4
Sequentially add the isooctanol of 700g in 2000mL there-necked flask, 154g sodium hydroxide, 15g zinc oxide, under stirring by
It is gradually warming up to reflux, is carried out with reflux, temperature gradually rises in bottle.Obviously there is hydrogen releasing when reaching 180 DEG C, continues to heat
It maintains the reflux for steadily releasing with hydrogen, after 9-12h, temperature continues to keep the temperature 60min, be cooled to 150 DEG C later to 220 DEG C
Hereinafter, the distilled water of 400mL is then added, 30min is stirred, sodium iso-octoate aqueous solution is obtained.
Sodium iso-octoate aqueous solution is transferred in flask, the chloroacetic acid solution 793g of 50wt% is slowly added under stirring, is controlled
Reaction temperature processed is 40 DEG C, reacts 30min, moves to separatory funnel, stands 30min, multi_layer extraction water phase, water phase is sodium chloroacetate
Solution；It is oily mutually with the washing of 60g distilled water twice thick isooctyl acid, the unreacted alcohol of vacuum distillation removing (make for lower secondary response
With), rectifying obtains isooctyl acid finished product 536g, and molar yield is 96.7% in terms of sodium hydroxide.
Embodiment 5
Sequentially add the isooctanol of 600g in 2000mL there-necked flask, 154g sodium hydroxide, 15g zinc oxide, under stirring by
It is gradually warming up to reflux, is carried out with reflux, temperature gradually rises in bottle.Obviously there is hydrogen releasing when reaching 180 DEG C, continues to heat
It maintains the reflux for steadily releasing with hydrogen, after 9-12h, temperature continues to keep the temperature 60min, be cooled to 150 DEG C later to 240 DEG C
Hereinafter, the distilled water of 400mL is then added, 30min is stirred, sodium iso-octoate aqueous solution is obtained.
Sodium iso-octoate aqueous solution is transferred in flask, the sulfurous acid solution 630g of 50wt% is slowly added under stirring, is controlled
Reaction temperature processed is 50 DEG C, reacts 30min, moves to separatory funnel, stands 30min, multi_layer extraction water phase, water phase is sodium sulfite
Solution；It is oily mutually with the washing of 60g distilled water twice thick isooctyl acid, the unreacted alcohol of vacuum distillation removing, rectifying obtain isooctyl acid at
Product 532g, molar yield is 96.1% in terms of sodium hydroxide.
Embodiment 6
The isooctanol of 5000kg, 2000kg sodium hydroxide, 150kg zinc oxide, reaction are sequentially added in 8000L reaction kettle
Kettle is replaced 2 times with nitrogen and air in system is discharged, and at 240 DEG C after sealing, is reacted under the conditions of 3Mpa, and reaction carries out 4-
After 10h, continues to keep the temperature 50min, be cooled to 150 DEG C later hereinafter, then pressure is down to normal pressure in kettle, the distillation of 4000L is added
Water stirs 30min, obtains sodium iso-octoate aqueous solution.
Sodium iso-octoate aqueous solution is transferred to and is neutralized in kettle, the chloroacetic acid solution of 50wt% is slowly added under stirring
10300kg, control reaction temperature are 40 DEG C, react 30min, move to liquid separation kettle, stand 30min, multi_layer extraction water phase, and water phase is
Sodium chloroacetate solution；It is oily mutually with the washing of 600kg distilled water twice thick isooctyl acid, the unreacted alcohol of vacuum distillation removing, rectifying
Isooctyl acid finished product 5432kg is obtained, weight yield is 108.64% in terms of isooctanol, molar yield 98.14%.
Embodiment 7
The isooctanol of 5000kg, 2370kg potassium hydroxide, 100kg zinc oxide, reaction are sequentially added in 8000L reaction kettle
Kettle is replaced 2 times with nitrogen and air in system is discharged, and at 240 DEG C after sealing, is reacted under the conditions of 2.7Mpa, and reaction carries out 6-
After 10h, continues to keep the temperature 50min, be cooled to 150 DEG C later hereinafter, then pressure is down to normal pressure in kettle, the distillation of 4000L is added
Water stirs 30min, obtains isooctyl acid aqueous solutions of potassium.
Isooctyl acid aqueous solutions of potassium is transferred to and is neutralized in kettle, the formic acid solution 2070kg of 94wt% is slowly added under stirring,
Controlling reaction temperature is 40 DEG C, reacts 30min, moves to liquid separation kettle, stands 30min, multi_layer extraction water phase, and water phase is that potassium formate is molten
Liquid；It is oily mutually with the washing of 600kg distilled water twice thick isooctyl acid, the unreacted alcohol of vacuum distillation removing, rectifying obtain isooctyl acid at
Product 5428kg, weight yield is 108.56% in terms of isooctanol, molar yield 98.1%.
Claims (1)
1. a kind of production method of isooctyl acid, it is characterised in that: using isooctanol and highly basic in 180 ~ 290 DEG C of reaction 1.5- of temperature
16h, then with, up to thick isooctyl acid, isooctyl acid is made in purified handle after sour acidification reaction object；
Wherein the highly basic is selected from or mixtures thereof potassium hydroxide or sodium hydroxide；
The molar ratio that the highly basic and isooctanol feed intake is 0.7 ~ 1.3:1；Acid dosage and the molar ratio of highly basic are when the acidification
1.3~1:1；
The acid that the acidification uses is selected from formic acid or acetic acid；
Specific reaction step are as follows:
Isooctanol and highly basic are put into reactor according to aforementioned proportion, are added isooctanol and are fed intake 0.5 ~ 3% zinc impregnation of quality
It closes object to be sufficiently mixed, after reacting 1.5-16h under conditions of 180 ~ 290 DEG C of temperature, continues to keep the temperature 20-90min；It is cooled to later
160 DEG C hereinafter, reaction product is substantially soluble in water under normal pressure, can obtain thick isooctyl acid with acid acidification at 40 ~ 80 DEG C later,
It is salting liquid in water phase after aqueous phase separation, oil is mutually thick isooctyl acid, can be prepared by refining through the processing of conventional rectification and purification different
Octanoic acid；
The molar ratio that highly basic and isooctanol feed intake in reaction process is 0.7 ~ 1.3:1；
The compound of the zinc can be selected from zinc oxide or zinc formate or zinc acetate or zinc carbonate or zinc oxalate.
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| CN106748746B (en) * | 2017-02-23 | 2024-04-02 | 江西金泰化工股份有限公司 | Isooctanoic acid production system |
| CN108503530B (en) * | 2017-02-28 | 2021-04-13 | 中国石油化工股份有限公司 | Process for preparing isooctanoic acid |
| WO2020249691A1 (en) | 2019-06-12 | 2020-12-17 | Nouryon Chemicals International B.V. | Process for the production of diacyl peroxides |
| JP7336541B2 (en) | 2019-06-12 | 2023-08-31 | ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップ | Process for producing diacyl peroxide |
| US20240018083A1 (en) | 2020-12-01 | 2024-01-18 | Nouryon Chemicals International B.V. | Method for isolating carboxylic acid from an aqueous side stream with co-production of alkali metal salt |
| CN114516791A (en) * | 2022-01-24 | 2022-05-20 | 李建阁 | Method and system for recovering solid salt in production of isooctanoic acid |
| CN114874089A (en) * | 2022-01-31 | 2022-08-09 | 盘锦洪鼎化工有限公司 | Preparation method of high-performance isononanoic acid |
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| US3365476A (en) * | 1963-12-23 | 1968-01-23 | Gulf Research Development Co | Process for the preparation of carboxylic acid salts |
| CN1318047A (en) * | 1998-09-14 | 2001-10-17 | 道农业科学公司 | Process for preparing carboxylic acids |
| CN101125810A (en) * | 2007-09-26 | 2008-02-20 | 河南庆安化工高科技股份有限公司 | Method for preparing isooctanoic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3365476A (en) * | 1963-12-23 | 1968-01-23 | Gulf Research Development Co | Process for the preparation of carboxylic acid salts |
| CN1318047A (en) * | 1998-09-14 | 2001-10-17 | 道农业科学公司 | Process for preparing carboxylic acids |
| CN101125810A (en) * | 2007-09-26 | 2008-02-20 | 河南庆安化工高科技股份有限公司 | Method for preparing isooctanoic acid |
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