CN1086377C - Method for preparing high-concentration formic acid - Google Patents
Method for preparing high-concentration formic acid Download PDFInfo
- Publication number
- CN1086377C CN1086377C CN99119352A CN99119352A CN1086377C CN 1086377 C CN1086377 C CN 1086377C CN 99119352 A CN99119352 A CN 99119352A CN 99119352 A CN99119352 A CN 99119352A CN 1086377 C CN1086377 C CN 1086377C
- Authority
- CN
- China
- Prior art keywords
- formic acid
- entrainer
- water
- concentration
- tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 127
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 9
- 238000010533 azeotropic distillation Methods 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 18
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 12
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 241000282326 Felis catus Species 0.000 claims description 7
- -1 octane-iso Chemical compound 0.000 claims description 7
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 6
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 claims description 6
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 claims description 6
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 claims description 6
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 claims description 6
- CHBAWFGIXDBEBT-UHFFFAOYSA-N 4-methylheptane Chemical compound CCCC(C)CCC CHBAWFGIXDBEBT-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isononane Chemical compound CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 claims description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 claims description 3
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004914 cyclooctane Substances 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 7
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 description 5
- WGECXQBGLLYSFP-UHFFFAOYSA-N 2,3-dimethylpentane Chemical compound CCC(C)C(C)C WGECXQBGLLYSFP-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BZHMBWZPUJHVEE-UHFFFAOYSA-N 2,3-dimethylpentane Natural products CC(C)CC(C)C BZHMBWZPUJHVEE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- QWHNJUXXYKPLQM-UHFFFAOYSA-N 1,1-dimethylcyclopentane Chemical compound CC1(C)CCCC1 QWHNJUXXYKPLQM-UHFFFAOYSA-N 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- FLTJDUOFAQWHDF-UHFFFAOYSA-N 2,2-dimethylhexane Chemical compound CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 2
- CXOWYJMDMMMMJO-UHFFFAOYSA-N 2,2-dimethylpentane Chemical compound CCCC(C)(C)C CXOWYJMDMMMMJO-UHFFFAOYSA-N 0.000 description 2
- KUMXLFIBWFCMOJ-UHFFFAOYSA-N 3,3-dimethylhexane Chemical compound CCCC(C)(C)CC KUMXLFIBWFCMOJ-UHFFFAOYSA-N 0.000 description 2
- AEXMKKGTQYQZCS-UHFFFAOYSA-N 3,3-dimethylpentane Chemical compound CCC(C)(C)CC AEXMKKGTQYQZCS-UHFFFAOYSA-N 0.000 description 2
- RNTWWGNZUXGTAX-UHFFFAOYSA-N 3,4-dimethylhexane Chemical compound CCC(C)C(C)CC RNTWWGNZUXGTAX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- JXPOLSKBTUYKJB-UHFFFAOYSA-N xi-2,3-Dimethylhexane Chemical compound CCCC(C)C(C)C JXPOLSKBTUYKJB-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- RMMXTBMQSGEXHJ-UHFFFAOYSA-N Aminophenazone Chemical compound O=C1C(N(C)C)=C(C)N(C)N1C1=CC=CC=C1 RMMXTBMQSGEXHJ-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- VWINVIKDWACGAB-UHFFFAOYSA-N acetyl acetate;benzoic acid Chemical compound CC(=O)OC(C)=O.OC(=O)C1=CC=CC=C1 VWINVIKDWACGAB-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229960000212 aminophenazone Drugs 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229940120889 dipyrone Drugs 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005454 flavour additive Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- OFEVLLPPRKRSAN-UHFFFAOYSA-N formic acid;hexane Chemical compound OC=O.CCCCCC OFEVLLPPRKRSAN-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- DJGAAPFSPWAYTJ-UHFFFAOYSA-M metamizole sodium Chemical compound [Na+].O=C1C(N(CS([O-])(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 DJGAAPFSPWAYTJ-UHFFFAOYSA-M 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention relates to an azeotropic distillation method for separating a formic acid product with the concentration of more than 95 weight percent from an aqueous solution containing 80 to 85 weight percent of formic acid. The azeotropic distillation method of the invention uses an entrainer which is not miscible with water and formic acid, and the entrainer is C5-C10An alkane.
Description
The present invention relates to a kind of separation method of azeotropic mixture.Specifically, relate to a kind of employing azeotropic distillation process, from the formic acid water azeotropic mixture of 80-85 weight % concentration, preparation purity is greater than the method for 95% formic acid product.
Formic acid is one of basic Organic Chemicals, is widely used in industry such as agricultural chemicals, leather, dyestuff, medicine and rubber.Aspect medicine industry, can be used for producing medicines such as borneol, aminopyrin, caffeine, VITMAIN B1 and Sulpyrine; Aspect tanning industry, can be used for making leather and tan soft dose; Aspect rubber industry, can be used as the rubber flocculation agent; Formic acid also can be used as the printing and dyeing mordant, the staining agent of fiber and paper and treatment agent, and softening agent and animal flavoring additive are made mould inhibitor etc. with formic acid in the foodstuffs industry.
Domestic formic acid product purity is 80-85 weight % at present, water-content is 15-20 weight %, the formic acid product of 90-95 weight % seldom, and both prices differ also bigger, this is because the boiling point of formic acid is 100.5 ℃, the boiling point of water is 100 ℃, both very approaching and easy generation azeotropic mixtures; And formic acid and water are two materials that polarity is very strong, make separating and refining very difficult cause of formic acid and water mixture.Therefore how will be a job highly significant for 80-85% formic acid is purified to more than the 95 weight % industrial concentration commonly used at present.
Chinese patent CN85104491A discloses the preparation method of anhydrous methanol, and this method is in the presence of methane amide, hydrolyzing methyl manthanoate, distilled water hydrolysis products then.
Chinese patent CN1063483 discloses the method for preparing high purity formic acid.This method has adopted the additive thionyl chloride, makes itself and aqueous formic acid react dehydration, vacuum distilling then.But because technology is complicated, and needs to consume big quantity of material or reagent, so seldom adopt.
Chinese patent CN1069261A discloses a kind of method for preparing high purity formic acid.This method is that the aqueous formic acid of 80-90 weight % is refrigerated to solid, is warming up to 0-7 ℃ then, ice thaw is removed anhydrate.U.S. Pat-A4877490 and US-A4909907 etc. have introduced the method that reclaims formic acid from aqueous mixture.This method obtains by the extractive distillation with other high boiling point organic compound of carboxylic acid a great deal of, be that formic acid and extraction agent reclaim from distillation kettle liquid, water obtains from distillate, and the extraction agent that distillation is used is ethyl benzoate or glycol ether dimethyl ester or phenylformic acid diacetyl oxide etc.
Adopt expensive extraction agent to carry out extracting rectifying, produce the rectificating method of concentration formic acid and high, cost is very high.Add these extraction agents and be high boiling substance, make its recovery and reuse very difficult.And effect of extracting is also not ideal enough, so these methods are in industrial difficult realization.
Adopt the component distillation of entrainers such as propyl formate, butyl formate, make the tower still can obtain the formic acid product of 96% concentration, but these entrainers are easy to hydrolysis, promptly be subjected to thermal hydrolysis to generate formic acid and propyl alcohol or butyl ester in still-process, thereby separation can not be proceeded.
In order to overcome the above-mentioned defective of prior art, the inventor compares and repetitious experimental study multiple entrainer through long term studies, has proposed to adopt a kind of inexpensive entrainer one alkane, improve the method for formic acid concn, this method has its important practical sense industrial.
Therefore, the purpose of this invention is to provide a kind of production method of concentration formic acid and high, from the aqueous formic acid of 80-85 weight %, remove and anhydrate the formic acid product of production high density.
Above-mentioned Azotropic distillation method may further comprise the steps:
With C
5-C
10Alkane entrainer and concentration are the aqueous formic acid raw material of 80-85 weight %, add in the distillation tower together in the distillation tower center, in tower top temperature is 50-65 ℃, tower still temperature is 69-100 ℃, pressure is that entrainer concentration is to distill under the 50-70 weight % condition in normal pressure and the tower still, formed formic acid-water-entrainer ternary minimum boiling point azcotrope at cat head, its steam in condenser after condensation, layering forms oil reservoir and water layer in quantizer, oil reservoir is back in the distillation tower, water layer extraction, the water layer of extraction are concentration 〉=95% formic acid product.
The number of theoretical plate of above-mentioned azeotropic distillation column can be the 20-40 piece.
The amount of the entrainer in the above-mentioned tower still is a steady state value.
The material of the above-mentioned continuous extraction of tower still can adopt layered approach.
The mol ratio of formic acid and water can be selected (0.5-1.4) for use in the above-mentioned extraction material: 1.Above-mentioned entrainer can be selected C for use
5-C
10Alkane or C
5-C
10The mixture of alkane; Wherein preferred C
5-C
10Normal paraffin, C
5-C
10Isoparaffin, C
5-C
10The C of naphthenic hydrocarbon, replacement
5-C
10The C of branched paraffin or replacement
5-C
10At least a in the naphthenic hydrocarbon; Wherein preferred especially Skellysolve A, normal hexane, normal heptane, octane, positive nonane, n-decane, iso-pentane, isohexane, isoheptane, octane-iso, isononane, isodecane, pentamethylene, hexanaphthene, suberane, cyclooctane, cyclononane, cyclodecane, the 2-methylbutane, the 2-methyl hexane, the 2-methylpentane, the 2-methylheptane, the 3-methylpentane, the 3-methyl hexane, the 3-methylheptane, 2, the 2-dimethylbutane, 2, the 2-dimethylpentane, the 4-methylheptane, 2, the 3-dimethylpentane, 2, the 2-dimethylhexane, 2, the 4-dimethylpentane, 2, the 3-dimethylhexane, 3, the 3-dimethylpentane, 3, the 3-dimethylhexane, 3, the 4-dimethylhexane, methylcyclohexane, methylcyclopentane, the methyl suberane, 1, at least a in 1-dimethylcyclopentane or their combination.
The boiling point of formic acid is 100.5 ℃, and is very approaching with the boiling point of water, and forms azeotropic mixture, so can not separate by general distillating method.Anhydrate in order to remove from the aqueous formic acid of 80-85 weight %, the applicant finds, add C in the aqueous formic acid of 80-85 weight %
5-C
10A kind of alkane after, distill again, just water wherein can be removed, obtain the formic acid product of high density.
After alkane added stock liquid to be separated, because alkane and water and formic acid form the mixture of the minimum boiling point with same nature respectively, the boiling point of these mixtures and formic acid boiling point differed bigger, and layering after the condensation helps separating.Moreover formic acid and water all are insoluble to alkane, and it is effective especially therefore to make entrainer with it.
Employed alkane in the Azotropic distillation method of the present invention is C
5-C
10Alkane or its mixture, preferred C
7-C
9Alkane or its mixture.They can be normal paraffin such as Skellysolve A, normal hexane, normal heptane, octane, positive nonane or n-decane; Can be isoparaffin such as iso-pentane, isohexane, isoheptane, octane-iso, isononane or isodecane; They also can be naphthenic hydrocarbon such as pentamethylene, hexanaphthene, suberane, cyclooctane, cyclononane or cyclodecane etc.; They also can be the branched paraffin that replaces such as 2-methylbutane, 2-methyl hexane, 2-methylpentane, 2-methylheptane, 3-methylpentane, 3-methyl hexane, 3-methylheptane, 2,2-dimethylbutane, 2,2-dimethylpentane, 4-methylheptane, 2,3-dimethylpentane, 2,2-dimethylhexane, 2,4-dimethylpentane, 2,3-dimethylhexane, 3,3-dimethylpentane, 3,3-dimethylhexane or 3,4-dimethylhexane; Or the naphthenic hydrocarbon that replaces such as methylcyclohexane, methylcyclopentane, methyl suberane or 1,1-dimethylcyclopentane or the like.
Normal hexane and water and formic acid form binary azeotrope respectively and form boiling point and the composition that tertiary blending closes the thing that boils, and list in table one.
The azeotropic mixture that table 1 normal hexane and water, formic acid form
Title | The azeotropic mixture boiling point (℃) | Azeotropic mixture is formed (weight %) | ||
Normal hexane | Formic acid | Water | ||
Hexane-water | 61.55 | 98.77 | - | 1.23 |
Hexane-formic acid | 60.6 | 72.00 | 28.00 | - |
Hexane-formic acid-water | 55-57 | 85-86 | 13-14 | 0.4-0.6 |
When distillation, be divided into two layers of oil reservoir and water layers behind the ternary azeotrope vapor condensation, oil reservoir is the hexane layer of insoluble formic acid and water, and water layer is formic acid and water, and wherein formic acid content is higher than 95 weight %.
Owing to have entrainer in the still, form so the material in the still is formed the azeotropic that is lower than formic acid and water.Therefore the vapor-liquid equilibrium according to this two-component system concerns, up can produce more moisture from the tower still along stripping section, therefore only in the tower still, have under the situation of entrainer existence, the formic acid concn that makes progress along tower is constantly increased, so just help obtaining the formic acid product of high density at cat head.The obvious operation with general component distillation of this component distillation operation has obvious different, because general component distillation operation is at cat head the water in the raw material to be discharged from the top quantizer, and method of the present invention is that water is discharged from the tower still.Because entrainer and formic acid and water do not dissolve each other, therefore, the discharge material for the treatment of column still can make entrainer stay in the still, and lower concentration formic acid and water are then discharged from the tower still.
Fig. 1 represents the block diagram of formic acid-entrainer (normal hexane)-water component distillation.In the drawings, I represents distillation tower, and II represents condenser, and III represents the top quantizer.
Raw material 1 and additional entrainer 2 are added in the tower by the middle part together, the entrainer that replenishes also can add from top quantizer III, the tower still adopts electrically heated, formic acid in the charging and water are gone into top layer quantizer III at formation ternary azeotrope steam under the entrainer effect and are divided into two layers after condenser II condensation, oil reservoir 3 refluxes, and water layer 4 extraction obtain the formic acid product.Water in the charging and part formic acid down in the still in the presence of entrainer, be divided into two-layerly, with water layer 5 extraction, the mol ratio of formic acid and water is (0.5-1.4) in the extraction material: 1, thus reach the purpose that removes water in the formic acid water mixture.
Compared with prior art, the present invention has the following advantages:
1. the present invention is different from general component distillation and effective according to the working method that entrainer need be arranged in the formic acid steam liquid equilibrium relationship proposition tower still.
2. the present invention adopts azeotropic distillation process, utilizes the formic acid water formation ternary minimum azeotropic mixture of entrainer to produce concentration formic acid and high from cat head, has reduced general azeotropic dehydration obtains product from the tower still method.Because the product that the tower still obtains must also will and remove high boiling impurity through the decolouring of product purification tower, thereby has saved equipment and reduced energy consumption.
3. the component distillation device that adopts of the present invention, simple in structure, technology is reasonable, is fit to very much continuous operation.
4. the entrainer price that adopts of the present invention is low, aboundresources, and it is convenient to reclaim, and is that general formic acid water component distillation institute is incomparable.
Embodiment: example 1: raw material consists of H
2O16.71% (Wt), formic acid 83.92%.Add raw material 150ml, add entrainer normal hexane 140ml, at a φ 18mm * 1500mm, the reason stage number is in the glass distillation tower at intermittence of about 30, is 55 ℃ in tower top temperature, and tower still temperature is 69 ℃; Pressure is under the normal pressure, carries out component distillation, and cat head obtains formic acid purity average out to 96.24%, and the product of 87.3ml, product yield are~70%.Example 2: raw material consists of H
2O17.53% (Wt), formic acid 82.29%.Add raw material 150ml, add entrainer normal heptane 150ml, carry out component distillation under said apparatus identical with embodiment 1 and identical condition, cat head obtains formic acid purity average out to 95.23%, and the product of 86.2ml, product yield are~70%.Example 3. raw materials consist of H
2O17.53% (Wt), formic acid 82.29%.Raw materials 20ml/h adds the entrainer hexane, and under the device and condition identical with embodiment 1, component distillation is carried out in operate continuously.Total charging capacity is 245ml, and obtaining to eject formic acid purity is 96.24%, the product of 120.6ml.Product yield is~60%.
Claims (8)
1. isolate the Azotropic distillation method of concentration for 〉=95 weight % formic acid products for one kind from concentration is the aqueous formic acid of 80-85 weight %, described Azotropic distillation method may further comprise the steps:
With C
5-C
10Alkane entrainer and concentration are the aqueous formic acid raw material of 80-85 weight %, add in the distillation tower together in the distillation tower center, in tower top temperature is 50-65 ℃, tower still temperature is 69-100 ℃, pressure is that entrainer concentration is to distill under the 50-70 weight % condition in normal pressure and the tower still, formed formic acid-water-entrainer ternary minimum boiling point azcotrope at cat head, its steam in condenser after condensation, layering forms oil reservoir and water layer in quantizer, oil reservoir is back in the distillation tower, water layer extraction, the water layer of extraction are concentration 〉=95% formic acid product.
2. method according to claim 1 is characterized in that, the number of theoretical plate of described azeotropic distillation column is the 20-40 piece.
3. method according to claim 1, the amount that it is characterized in that the entrainer in the tower still is a steady state value.
4. method according to claim 1 is characterized in that, the material of the continuous extraction of tower still adopts layered approach, and the mol ratio of formic acid and water is (0.5-1.4) in the extraction material: 1.
5. method according to claim 1 is characterized in that entrainer is C
5-C
10Alkane or C
5-C
10The mixture of alkane.
6. method according to claim 5 is characterized in that entrainer is selected from C
5-C
10Normal paraffin, C
5-C
10Isoparaffin, C
5-C
10The C of naphthenic hydrocarbon, replacement
5-C
10The C of branched paraffin or replacement
5-C
10At least a in the naphthenic hydrocarbon.
7. according to claim 5 or 6 described methods, it is characterized in that entrainer is selected from Skellysolve A, normal hexane, normal heptane, octane, positive nonane, n-decane, iso-pentane, isohexane, isoheptane, octane-iso, isononane, isodecane, pentamethylene, hexanaphthene, suberane, cyclooctane, cyclononane, cyclodecane, the 2-methylbutane, the 2-methyl hexane, the 2-methylpentane, the 2-methylheptane, the 3-methylpentane, the 3-methyl hexane, the 3-methylheptane, 2, the 2-dimethylbutane, 2, the 2-dimethylpentane, the 4-methylheptane, 2, the 3-dimethylpentane, 2, the 2-dimethylhexane, 2, the 4-dimethylpentane, 2, the 3-dimethylhexane, 3, the 3-dimethylpentane, 3, the 3-dimethylhexane, 3, the 4-dimethylhexane, methylcyclohexane, methylcyclopentane, the methyl suberane, 1, at least a in 1-dimethylcyclopentane or their combination.
8. method according to claim 1 is characterized in that the entrainer that replenishes is to add at quantizer top, top.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN99119352A CN1086377C (en) | 1999-09-10 | 1999-09-10 | Method for preparing high-concentration formic acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN99119352A CN1086377C (en) | 1999-09-10 | 1999-09-10 | Method for preparing high-concentration formic acid |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1287995A CN1287995A (en) | 2001-03-21 |
CN1086377C true CN1086377C (en) | 2002-06-19 |
Family
ID=5280847
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN99119352A Expired - Fee Related CN1086377C (en) | 1999-09-10 | 1999-09-10 | Method for preparing high-concentration formic acid |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1086377C (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102225326B (en) * | 2011-04-29 | 2012-09-05 | 张明 | Apparatus and method for formic acid production |
CN103159629B (en) * | 2011-12-09 | 2014-09-03 | 中国科学院大连化学物理研究所 | Separation method for azeotrope of ethylene diamine and water |
CN105339339B (en) * | 2013-05-16 | 2018-09-14 | 帝斯曼知识产权资产管理有限公司 | Method for detaching formic acid with methyltetrahydrofuran |
CN106748737A (en) * | 2016-11-16 | 2017-05-31 | 南京师范大学 | A kind of method of formic acid in azeotropic extraction rectifying concentration aqueous formic acid |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3718547A (en) * | 1970-11-16 | 1973-02-27 | Alcan Res & Dev | Continuous electrolytic treatment for cleaning and conditioning aluminum surfaces |
CN1063483A (en) * | 1991-01-25 | 1992-08-12 | 北京农业大学 | The novel process of preparation anhydrous formic acid |
-
1999
- 1999-09-10 CN CN99119352A patent/CN1086377C/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3718547A (en) * | 1970-11-16 | 1973-02-27 | Alcan Res & Dev | Continuous electrolytic treatment for cleaning and conditioning aluminum surfaces |
CN1063483A (en) * | 1991-01-25 | 1992-08-12 | 北京农业大学 | The novel process of preparation anhydrous formic acid |
Also Published As
Publication number | Publication date |
---|---|
CN1287995A (en) | 2001-03-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20130284584A1 (en) | Process for separating ethylene glycol and 1, 2-butanediol | |
CN85109000A (en) | From brine waste, reclaim glycerine | |
CN101397260B (en) | Technology for recovering dimethylformamide from waste water by combination of saline extraction and rectification method | |
CA2314402C (en) | Process of recovering methyl ethyl ketone from an aqueous mixture of methyl ethyl ketone and ethanol | |
CN1058700C (en) | Process for purifying acetic acid | |
CN112225650B (en) | Refining method for obtaining high-purity methylal by purifying industrial-grade methylal | |
JPH09508384A (en) | Method for recovering glycol from dimethyl terephthalate | |
JP2022503653A (en) | How to Purify Non-Petroleum Ethylene Glycol | |
CN203923057U (en) | Improved Butanol Recycling device | |
CN111377802B (en) | Preparation method and system of sec-butyl alcohol | |
CN1086377C (en) | Method for preparing high-concentration formic acid | |
CN102633597A (en) | Process of recovering ethanol, propyl alcohol and isobutyl alcohol from polyalcohol-water mixture | |
CN103242121A (en) | Normal hexane and benzene extractive distillation operating method | |
CN101289363A (en) | Process for preparing 1-amylene by separating C5 distillate of petroleum | |
CN1331070A (en) | Process for separating methylisobutanone synthesized from acetone | |
EP0038668B1 (en) | Dehydration of alcohols | |
CN109704907B (en) | Method for preparing hexane from raffinate oil | |
CN205528519U (en) | A recovery, refining plant that is used for toluene - methyl alcohol / ethanol | |
CN101289362A (en) | Process for preparing 1-amylene by separating C5 distillate of petroleum | |
CN1880290A (en) | Method for separating and refining 1, 3-propylene glycol in fermentation liquor | |
US4229261A (en) | Process for separating water from organic multiple component mixtures by distillation | |
CN101289360A (en) | Process for preparing 2-amylene by separating C5 distillate of petroleum | |
CN101289361A (en) | Process for preparing 2-amylene by separating C5 distillate of petroleum | |
CN107848938A (en) | Organic acid is separated from the mixture comprising ammonium salt organic acid | |
EP0832885B1 (en) | Process for producing 3-methyltetrahydrofuran |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20020619 Termination date: 20100910 |