CN102958894B - Method for producing formic acid - Google Patents
Method for producing formic acid Download PDFInfo
- Publication number
- CN102958894B CN102958894B CN201180031930.8A CN201180031930A CN102958894B CN 102958894 B CN102958894 B CN 102958894B CN 201180031930 A CN201180031930 A CN 201180031930A CN 102958894 B CN102958894 B CN 102958894B
- Authority
- CN
- China
- Prior art keywords
- formic acid
- stream
- tertiary amine
- amine
- 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
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 775
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 387
- 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 385
- 238000004519 manufacturing process Methods 0.000 title description 5
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 165
- 238000000034 method Methods 0.000 claims abstract description 101
- 239000007791 liquid phase Substances 0.000 claims abstract description 61
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 181
- 239000012071 phase Substances 0.000 claims description 58
- 150000001412 amines Chemical class 0.000 claims description 55
- 238000007599 discharging Methods 0.000 claims description 34
- 238000009835 boiling Methods 0.000 claims description 30
- 238000006460 hydrolysis reaction Methods 0.000 claims description 25
- 230000007062 hydrolysis Effects 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000006200 vaporizer Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 16
- 229910000765 intermetallic Inorganic materials 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000002015 acyclic group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 238000004821 distillation Methods 0.000 abstract description 52
- 239000000047 product Substances 0.000 description 57
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- 239000000203 mixture Substances 0.000 description 39
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 34
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 34
- -1 alkyl imidazole Chemical compound 0.000 description 33
- 150000001875 compounds Chemical class 0.000 description 28
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
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- NTWORZKWAKBVFS-UHFFFAOYSA-N 2-methyltridecan-2-amine Chemical compound CCCCCCCCCCCC(C)(C)N NTWORZKWAKBVFS-UHFFFAOYSA-N 0.000 description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 description 2
- YJLYANLCNIKXMG-UHFFFAOYSA-N N-Methyldioctylamine Chemical compound CCCCCCCCN(C)CCCCCCCC YJLYANLCNIKXMG-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- ATTZFSUZZUNHBP-UHFFFAOYSA-N Piperonyl sulfoxide Chemical compound CCCCCCCCS(=O)C(C)CC1=CC=C2OCOC2=C1 ATTZFSUZZUNHBP-UHFFFAOYSA-N 0.000 description 2
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- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 2
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- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- WBGPDYJIPNTOIB-UHFFFAOYSA-N n,n-dibenzylethanamine Chemical compound C=1C=CC=CC=1CN(CC)CC1=CC=CC=C1 WBGPDYJIPNTOIB-UHFFFAOYSA-N 0.000 description 1
- FZPXKEPZZOEPGX-UHFFFAOYSA-N n,n-dibutylaniline Chemical compound CCCCN(CCCC)C1=CC=CC=C1 FZPXKEPZZOEPGX-UHFFFAOYSA-N 0.000 description 1
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- MMFBQHXDINNBMW-UHFFFAOYSA-N n,n-dipropylaniline Chemical compound CCCN(CCC)C1=CC=CC=C1 MMFBQHXDINNBMW-UHFFFAOYSA-N 0.000 description 1
- GXFHZISVUPJOCI-UHFFFAOYSA-N n-(2-ethylhexyl)aniline Chemical compound CCCCC(CC)CNC1=CC=CC=C1 GXFHZISVUPJOCI-UHFFFAOYSA-N 0.000 description 1
- WYZDCUGWXKHESN-UHFFFAOYSA-N n-benzyl-n-methyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(C)CC1=CC=CC=C1 WYZDCUGWXKHESN-UHFFFAOYSA-N 0.000 description 1
- XRKQMIFKHDXFNQ-UHFFFAOYSA-N n-cyclohexyl-n-ethylcyclohexanamine Chemical compound C1CCCCC1N(CC)C1CCCCC1 XRKQMIFKHDXFNQ-UHFFFAOYSA-N 0.000 description 1
- POMGZMHIXYRARC-UHFFFAOYSA-N n-hexyl-n-methylhexan-1-amine Chemical compound CCCCCCN(C)CCCCCC POMGZMHIXYRARC-UHFFFAOYSA-N 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000012207 quantitative assay Methods 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- SLRCCWJSBJZJBV-AJNGGQMLSA-N sparteine Chemical compound C1N2CCCC[C@H]2[C@@H]2CN3CCCC[C@H]3[C@H]1C2 SLRCCWJSBJZJBV-AJNGGQMLSA-N 0.000 description 1
- 229960001945 sparteine Drugs 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- XLRPYZSEQKXZAA-OCAPTIKFSA-N tropane Chemical compound C1CC[C@H]2CC[C@@H]1N2C XLRPYZSEQKXZAA-OCAPTIKFSA-N 0.000 description 1
- 229930004006 tropane Natural products 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000010457 zeolite 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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/02—Formic acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for obtaining formic acid by the thermal separation of a flow containing formic acid and a tertiary amine (I), wherein a liquid flow which contains formic acid and a tertiary amine (I) in a molar ratio of 0.5 to 5 is produced by combining tertiary amine (I) and a source of formic acid, 10 to 100 wt % of the secondary components contained in said flow are separated, and formic acid is removed by distillation from the resulting liquid flow in a distillation device at a bottoms temperature of 100 to 300 DEG C and a pressure of 30 to 3000 hPa abs, wherein the bottoms product from the distillation device is separated into two liquid phases and the upper liquid phase is returned to the source of formic acid and the lower liquid phase is returned for separation of the secondary components and/or to the distillation device.
Description
The application is incorporated in the U.S. Provisional Patent Application 61/392062 and 61/359382 of on October 12nd, 2010 and submission on June 29th, 2010 by reference.
The present invention relates to and a kind of comprise the stream material of formic acid and tertiary amine (I) by thermal separation and obtain the method for formic acid, wherein by tertiary amine (I) and formic acid source being merged, generation comprises the liquid stream of formic acid that mol ratio is 0.5-5 and tertiary amine (I), isolate the 10-100 % by weight of wherein existing secondary component, and from gained liquid stream, take out formic acid by distilling under 100-300 DEG C of column bottom temperature and 30-3000hPa absolute pressure in water distilling apparatus.
Formic acid is important and can the product of widespread use.Its such as the acidifying in fodder production, as sanitas, as sterilizing agent, the auxiliary agent be used as in weaving and leather industry, as the deicing being used for aircraft and airstrip with the mixture of salt and the synthon be used as in chemical industry.
Formic acid preparation method the most frequently used at present may be by methyl formate hydrolysis, and described methyl-formiate can such as be obtained by methyl alcohol and carbon monoxide.Subsequently the water-containing formic acid obtained by hydrolysis is concentrated, such as, by using extraction agent as dialkylformamide (DE2545658A1).
In addition, known formic acid also by formic acid and tertiary nitrogen alkali compound thermo-cracking and obtain.These compounds are generally the formic acid ammonium acid salt of tertiary nitrogen alkali, and wherein formic acid and tertiary nitrogen alkali react until exceed typical salt-forming stage, thus obtain the stable addition compound via hydrogen bridge band bridge joint.The addition compound of formic acid and tertiary nitrogen alkali is by merging tertiary nitrogen alkali and formic acid source and formed.Therefore, such as WO2006/021,411 disclose usual pass through (i) makes tertiary nitrogen alkali and formic acid direct reaction, (ii) under the existence of tertiary nitrogen alkali transition metal-catalyzed hydrogenation carbonic acid gas to obtain formic acid, (iii) make methyl-formiate and water react the formic acid also extracting gained subsequently with tertiary nitrogen alkali, and (iv) make methyl-formiate and water react under the existence of tertiary nitrogen alkali and prepare this kind of addition compound.
The addition compound of formic acid and tertiary nitrogen alkali is used to be with the general advantage obtaining formic acid: first, described addition compound is first enough strong with the combination of formic acid, to such an extent as to can from medium, such as, remove formic acid in free formic acid form (wherein said formic acid first by chemosynthesis or such as formed by dilute formic acid solution) in reaction medium, and formic acid can be made thus more easily to isolate with the form of its addition compound; Secondly, described addition compound is enough weak, to such an extent as to again discharges described formic acid to be concentrated and to obtain formic acid with the free form through purifying by thermo-cracking subsequently.
EP0001432A discloses a kind of method obtaining formic acid, is included in tertiary amine, is hydrolyzed methyl-formiate under the existence of particularly alkyl imidazole, wherein forms the addition compound of formic acid and described tertiary amine.The gained hydrolysed mix comprising unreacted methyl-formiate, water, methyl alcohol, addition compound and tertiary amine is removed low-boiler methyl-formiate and methyl alcohol in the first distillation tower.In the second tower, bottom product dehydration will be remained.Then the dehydration tower bottom product still comprising the second tower of addition compound and tertiary amine is fed in the 3rd tower, described addition compound is thermally cracked to formic acid and described tertiary amine wherein.The formic acid discharged takes out as overhead product.Described tertiary amine to be collected at the bottom of tower and to be recirculated in hydrolysis reaction.
DE3428319A discloses a kind of method being obtained formic acid by hydrolysis by methyl-formiate.The gained hydrolysed mix comprising unreacted methyl-formiate, water, methyl alcohol and formic acid is removed low-boiler methyl-formiate and methyl alcohol in the first distillation tower.Then at extra hydrophobic solvent, under especially aliphatic, alicyclic or aromatic hydrocarbon exists, with more high boiling amine, the especially more hydrophobic C of long-chain
6-C
14the water-containing formic acid that trialkylamine extraction obtains at the bottom of tower, and change into the moisture addition compound of formic acid and described amine thus.It is dewatered in second column.Then the uppermost tower tray (being labeled as in FIG " K4 ") feeding described distillation tower through dehydration addition compound will obtained at the bottom of tower, and according to DE3428319A thermo-cracking.All hydrophobic solvent is there is at the top of described tower and bottom.Gaseous top stream, except described hydrophobic solvent, especially comprises discharged formic acid.This stream is liquefied within the condenser again.Form two-phase, i.e. polarity formic acid phase and hydrophobic solvent phase.Described formic acid is taken out as product, and described solvent phase is recycled in tower as backflow.According to the instruction of this DE-A, owing to there is hydrophobic solvent, the complete cracking of described adducts can be realized, and claim that this cracking is not causing formic acid to divide taking off carrying out.(almost) described hydrophobic amine and hydrophobic solvent is not comprised containing the bottom product of formic acid.Described bottom product is recycled to extraction stages.
EP0181078A and EP0126524A describes and obtains the method for formic acid, is included in transition-metal catalyst and tertiary amine as C
1-C
10under trialkylamine exists, hydrogenation is carried out to carbonic acid gas, thus form the addition compound of formic acid and described tertiary amine, aftertreatment is carried out to be separated described catalyzer and low-boiler to described hydrogenation discharging, with more weak and the tertiary amine (especially alkyl imidazole) that boiling point is higher replaces described addition alkali, thus be separated the first tertiary amine, the addition compound thermo-cracking in a distillation column will newly formed subsequently.For this reason, according to Fig. 1 of EP0181078A, the stream comprising formic acid and amine is fed in the region intermediate of tower " 30 ".The formic acid discharged in thermo-cracking takes out as overhead product.Described more weak and boiling point is higher tertiary amine to be collected at the bottom of tower and to be recirculated in described alkali exchange step.
WO2008/116,799 disclose a kind of method obtaining formic acid, be included in transition-metal catalyst, high bp polar solvent (as alcohol, ether, tetramethylene sulfone, methyl-sulphoxide or acid amides) and with at least one hydroxyl polarity amine exist under, to hydrogenation of carbon dioxide to form the addition compound of formic acid and described amine.According to WO2008/116, the instruction of 799, directly can feed hydrogenation discharging in water distilling apparatus to make described addition compound thermo-cracking.If described water distilling apparatus can comprise distillation tower and wish the film that the residence time is short or falling-film evaporator.The formic acid discharged takes out as overhead product.Be not separated the described polarity amine of removing, polar solvent and any catalyst collection at the bottom of tower, and can be recirculated in hydrotreating stage.
WO2006/021,411 describe a kind of method by addition compound (formic acid quaternary ammonium salt) thermo-cracking of formic acid and tertiary amine being obtained formic acid, and wherein said tertiary amine has the boiling point of 105-175 DEG C.As preferred tertiary amine, be referred to alkyl pyridine.The colour stability of gained formic acid is improved due to the specific boiling range of described tertiary amine.Addition compound used can be obtained by tertiary amine and formic acid source usually.Advantageously, first make the discharging of synthesizing available from this addition remove volatile component, then feed in thermo-cracking.Thermo-cracking is carried out usually in a distillation column, wherein according to Fig. 1, the stream comprising formic acid and amine is introduced the region intermediate of tower (C).The formic acid discharged takes out as overhead product.The tertiary amine that still optionally can comprise formic acid resistates is collected at the bottom of tower, and can be recirculated in formic acid source.
EP0563831A is referred to the addition compound (formic acid quaternary ammonium salt) of a kind of thermo-cracking formic acid and tertiary amine to obtain improving one's methods of formic acid.Addition compound used can be obtained by tertiary amine and formic acid source usually.Advantageously, first make the discharging available from described synthesis remove volatile component, then fed in the thermo-cracking that portion carries out in a distillation column.Described improvement is essentially the thermo-cracking implementing addition compound under the secondary methane amide that can improve gained formic acid colour stability exists.The formic acid discharged takes out as overhead product.Described tertiary amine and secondary methane amide are collected at the bottom of tower, and can be recirculated in described formic acid source.
The object of this invention is to provide and a kind ofly comprise the stream of formic acid and tertiary amine by thermal separation and obtain the method for formic acid, it has some advantages relative to prior art and can reclaim formic acid with high yield, high density and high purity.In addition, described method also should be able to be implemented in energetically favourable as far as possible mode, especially should have economic advantages compared with the preparation method of the methyl formate hydrolysis of current industrial enforcement.Low colour and high color value stability also have primary importance.In addition, described method certainly should be able to easily and should reliably implement.
Therefore, found a kind ofly comprise the stream of formic acid and tertiary amine (I) by thermal separation and obtain the method for formic acid, wherein:
A () generation comprises the liquid stream of formic acid that mol ratio is 0.5-5 and tertiary amine (I) by tertiary amine (I) and formic acid source being merged;
B () is from the secondary component being present in the 10-100 % by weight in described liquid stream available from separation the liquid stream of step (a); With
C () takes out formic acid by distilling under the absolute pressure of the column bottom temperature of 100-300 DEG C and 30-3000hPa in water distilling apparatus from available from the liquid stream of step (b);
And wherein:
Tertiary amine (I) used is the amine of the boiling point had under 1013hPa absolute pressure than high at least 5 DEG C of formic acid; In addition, select for the separation rate in water distilling apparatus described in the tertiary amine (I) in step (a) and step (c), to make to form two liquid phases in discharging at the bottom of the tower of water distilling apparatus described in step (c) under the prevailing conditions in step (d);
D discharging at the bottom of tower available from water distilling apparatus described in step (c) is separated into two liquid phases by (), wherein upper phase has formic acid and tertiary amine (I) mol ratio of 0-0.5, and lower floor's liquid phase has formic acid and tertiary amine (I) mol ratio of 0.5-5;
E the upper phase be separated is recycled in step (a) by step (d) by (); With
F the lower floor's liquid phase be separated is recycled in step (b) and/or (c) by step (d) by ().
Formic acid source is interpreted as meaning comprising in dilution, pollute and/or the streams of formic acid of chemical bonding form, or comprises the streams of the precursor being prepared formic acid by chemical reaction by it.Dilution and/or the formic acid polluted can such as derive from various preparation method or application.It can such as with water or organic solvent diluting and by various other with Substances Pollution.As its specific examples, can mention such as available from the pollution formic acid of the dilution of the fermentation of renewable raw materials, and by methyl formate hydrolysis and after removing methyl alcohol and residual methyl-formiate the water-containing formic acid that obtains.Addition in chemical bonding form such as can be carried out with the form of the title complex between formic acid and the amine being different from tertiary amine (I), salt or addition compound.Suitable chemical reaction is in principle for wherein producing all chemical reactions of formic acid.But, when present patent application industrial particularly importantly prepare formic acid by methyl formate hydrolysis and by the transition metal-catalyzed Hydrogenation of carbonic acid gas for formic acid.Described two kinds of possible building-up reactionss are well-known to those skilled in the art, and are previously described with different modification and embodiment.The relevant possibility of another industry preparing formic acid by chemical reaction is also such as the direct reaction of carbon monoxide and water.
When methyl formate hydrolysis, usually methyl-formiate, water are introduced together with tertiary amine (I) or successively in hydrolysis reactor, thus absorb the formic acid being hydrolyzed and being formed with the form of addition compound with tertiary amine (I), and thus it is removed from hydrolysising balance.Therefore, high methyl-formiate transformation efficiency can be obtained and particularly advantageously realize the separation of unreacted water by distillation subsequently.
When the transition metal-catalyzed hydrogenation of carbonic acid gas, usually tertiary amine (I) is introduced in hydrogenator, thus in hydrogenation itself, form the stream comprising formic acid and tertiary amine (I).
Prepare by being hydrolyzed methyl-formiate under the existence of water and tertiary amine (I) stream comprising formic acid and tertiary amine (I) preferably to carry out in step (a).Preferred in step (a) further, prepared by concentrating under tertiary amine (I) existence the stream comprising formic acid and tertiary amine (I) by dilute formic acid.But, prepare by hydrolysis methyl-formiate under water and tertiary amine (I) existence the stream comprising formic acid and tertiary amine (I) particularly preferably in step (a).
In step (a), tertiary amine (I) and formic acid source are merged and the liquid stream that produces has formic acid and tertiary amine (I) mol ratio of 0.5-5.This mol ratio preferably >=1 and preferably≤4, particularly preferably≤3.Described mol ratio is based on total liquid stream, no matter it is with single-phase or heterogeneous form existence.
Comprise formic acid and tertiary amine (I) and the formic acid that the liquid stream produced in step (a) has 1-99 % by weight usually adds tertiary amine (I) concentration, based on the total amount of this stream.Preferred described stream has >=and 5 % by weight, particularly preferably >=15 % by weight, and preferably≤95 weight, the formic acid of particularly preferably≤90 % by weight adds tertiary amine (I) concentration.
From available from the secondary component be present in described liquid stream being separated 10-100 % by weight liquid stream of step (a).The secondary component concentration that described numerical range has based on the liquid stream produced in step (a).This concentration can be described as " c hereinafter
secondary component(stream available from step (a)) ".The liquid stream of this poor secondary component is corresponding to the stream fed according to step (c) in water distilling apparatus.This concentration can be described as " c hereinafter
secondary component(feeding the stream of step (c)) ".Therefore, the above-mentioned separation of secondary component is based on following business:
Preferably >=20 % by weight, particularly preferably >=30 % by weight, and the secondary component of preferably≤99.99 % by weight, particularly preferably≤99.9 % by weight is separated removing in step (b).
Term " secondary component " to be interpreted as meaning to be present in the liquid stream available from step (a) and not to be all components of formic acid or tertiary amine (I).Can mention as an example water, methyl alcohol (particularly in methyl formate hydrolysis), dissolve be not hydrolyzed methyl-formiate (particularly in methyl formate hydrolysis), possible tertiary amine (I) degradation production, the rare gas element of dissolving, homogeneous catalyst (particularly in hydrogenation of carbon dioxide), the hydrogen (particularly in hydrogenation of carbon dioxide) of the carbonic acid gas dissolved or dissolving, solvent and other components.
The mode being separated removing secondary component is unimportant for method of the present invention.Therefore, the routine for separating of the liquid mixture of each material and currently known methods can such as be used.First and foremost, fractionation by distillation can be mentioned herein.In fractionation by distillation, the liquid mixture of each material is separated in water distilling apparatus.Therefore, such as or can get as side and isolate lower boiling secondary component as methyl alcohol, methyl-formiate or water via tower top.But, also can via isolating high boiling point secondary component at the bottom of tower and isolating the mixture comprising formic acid and tertiary amine (I) as side stream or overhead product.But, except fractionation by distillation, also can use film, absorption and sorption, crystallization, filtration, precipitation or extracting process.Rare water-containing formic acid concentrated in preferably use extracting process, and to use with water immiscibility or only with the tertiary amine (I) of little degree miscible.
Certainly also can will also can combine based on multiple separating steps of different methods in addition.The design of separating step can use routine techniques knowledge to carry out.
In the method for the invention, other processing steps except step (b) certainly can be implemented between step (a) and (c).
Formic acid is removed from available from the liquid stream of step (b) by distilling under the absolute pressure of the column bottom temperature of 100-300 DEG C and 30-3000hPa in water distilling apparatus.
Described water distilling apparatus, except the actual tower body with internals, especially comprises vaporizer at the bottom of overhead condenser and tower.In addition, it also can optionally comprise other peripheral units or internals, and flash chamber in such as charging (such as separating of the gas fed in the charging of tower body and liquid), central evaporator (heat such as improving described method is integrated) or the internals (such as can the tower tray of constant temperature, scum dredger, coalescer or thick bed diffusional filter) for avoiding or reduce aerosol to be formed.Described tower body such as can be equipped with structuring filling, random packing or tower tray.Required separation progression especially depends on formic acid in the charging of the type of tertiary amine (I), the water distilling apparatus of step (c) and the concentration of tertiary amine (I) and the desired concn of formic acid or required purity, and can be determined in a usual manner by those skilled in the art.Required separation progression usually >=3, preferably >=6, particularly preferably >=7.There is not the upper limit in principle.But, for actual cause, usually can use usually≤50, optional≤30 separation levels.
Can will comprise formic acid and tertiary amine (I) and stream available from step (b) feeds in water distilling apparatus, such as, feed in tower body as side stream.
Described interpolation optionally also can such as carried out in the upstream of flasher.In order to keep the thermal load in water distilling apparatus on feed stream low as far as possible, usually advantageously fed the lower region of described water distilling apparatus.Therefore, preferably be separated in the region of level by comprising formic acid with the 4th, the stream infeed bottom of tertiary amine (I) is available in step (c), the preferred bottom the 5th that feeds is separated in the region of level, particularly preferably feeding the bottom 6th is separated in the region of level, now certainly also comprises and directly feeding at the bottom of tower.
But, alternately, also preferred in (c), the described stream comprising formic acid and tertiary amine (I) available from step (b) is fed in vaporizer at the bottom of the tower of described water distilling apparatus.
Described water distilling apparatus runs under the absolute pressure of the column bottom temperature of 100-300 DEG C and 30-3000hPa.Preferred described water distilling apparatus, at >=120 DEG C, particularly preferably >=140 DEG C, and preferably≤220 DEG C, runs under the column bottom temperature of particularly preferably≤200 DEG C.Pressure preferably >=30hPa (definitely), particularly preferably >=60hPa (definitely), and preferably≤1500hPa (definitely), particularly preferably≤500hPa (definitely).
Depend on the composition comprising the charging of tertiary amine (I) in formic acid and the described water distilling apparatus of infeed and source, formic acid can be used as overhead product and/or side product is obtained by described water distilling apparatus.When described charging comprises the composition of boiling point lower than formic acid, these compositions of removing can be separated advantageous by distillation as overhead product, and take out formic acid in side is got.But, when gas (such as carbon monoxide or carbonic acid gas) may be dissolved with in described charging, also formic acid can be isolated as overhead product together with these compositions in principle.If described charging comprises the composition of boiling point higher than formic acid, then formic acid is separated as overhead product preferably by distillation, but optional replace these or be aided with side get in the second stream form.In this case, boiling point is then preferred via extra side stream taking-up higher than the composition of formic acid.The side stream this with secondary component is optionally back in step (b) to remove described secondary component.
The formic acid of content up to 100 % by weight content can be obtained in this way.Usually the formic acid content of 75-99.995 % by weight can be obtained without any problems.Residue content to 100 % by weight is mainly water, and other components as solvent, or also can be possible degradation production certainly according to each material introduced in described water distilling apparatus except formic acid and tertiary amine (I).Therefore, such as water can be present in the charging of described water distilling apparatus, but also can optionally only be formed on a small quantity due to formic acid decompose themselves in thermal separation process.
At the bottom of as tower or side product to reclaim content be in the concentrated formic acid of 95-100 % by weight, water is discharged together with a part of formic acid removed in the stream of side.The formic acid content of this side stream is generally 75-95 % by weight.But, the formic acid of water and removing also can be discharged in same tower top or side stream.Now, the formic acid content of thus obtained product is generally 85-95 % by weight.Water-containing formic acid available from side stream can optionally be back in step (b) to remove water.
In addition; should know according to the present invention; the oxygenolysis of tertiary amine (I) can be there is owing to there is oxygen; therefore particularly advantageously (when especially running described water distilling apparatus under lower than the absolute pressure of 0.1MPa) is avoided or is at least kept the oxygen introduced extremely low, and this is by the least possible joint, nozzle and flange quantity, by taking special care to install, by using tight especially Flange joint (such as have cavity molded line (chamber profile) sealing or welding flange sealing those) or being realized by the Flange joint of nitrogen protection.Suitable Flange joint is such as disclosed in DE102009046310A1.
The formic acid obtained by the inventive method has low colour and high color value stability.Usually≤20APHA can be obtained without any problems, especially even≤10APHA, the colour of optionally even≤5APHA.Even if after stored for several weeks, colour still keeps substantially constant or only increases to non-significant.
In addition, although secondary component can be formed as aldehyde, carboxylic acid, alcohol, alkyl formate or methane amide by the cracking of tertiary amine (I) in theory, content≤100 weight the ppm of this kind of secondary component in obtainable formic acid, preferably≤50 weight ppm, very particularly preferably≤25 weight ppm.
Be determined on a case-by-case basis, also advantageously multiple water distilling apparatus can be used in step (c), especially, if except containing free formic acid and containing amine (I) bottom product except, also reclaim other fractions, such as comprise the formic acid fraction with material, byproduct of reaction, impurity and/or different purity and concentration, then also can use multiple water distilling apparatus in step (c).
Water distilling apparatus for separating of formic acid also can be designed to distillation tower or the next door tower of thermal coupling certainly.
The tertiary amine (I) be ready to use in the inventive method has the boiling point than high at least 5 DEG C of formic acid under 1013hPa absolute pressure.Tertiary amine (I) preferably used has the boiling point than high at least 10 DEG C of formic acid, the particularly preferably boiling point of high at least 50 DEG C, the very particularly preferably boiling point of high at least 100 DEG C.Do not need to limit the upper limit of this boiling point, because alap tertiary amine (I) vapour pressure is favourable to the inventive method in principle.Tertiary amine (I) is by currently known methods, by vacuum, the boiling point be extrapolated under 1013hPa absolute pressure is usually less than 500 DEG C.
In addition, select for the tertiary amine (I) in step (a) and the separation rate in water distilling apparatus described in step (c), to make under the prevailing conditions of step (d), in discharging at the bottom of the tower of water distilling apparatus described in step (c), form two liquid phases.
The formation of two liquid phases determines primarily of the chemistry of described two-phase and physical properties.These can be subject to again the selection of tertiary amine used (I), the separation rate in described water distilling apparatus and the existence of any other component as solvent and the impact of concentration thereof.
Described separation rate is interpreted as following business:
" m
formic acid(feeding the stream of step (c)) " feed the amount of formic acid in water distilling apparatus, " m corresponding to the unit time
formic acid(at the bottom of tower discharging) " amount of formic acid that removes via discharging at the bottom of tower corresponding to the unit time.In the method for the invention, select usually >=10%, preferably >=25%, particularly preferably >=40%, and usually≤99.9%, the separation rate of preferably≤99.5%, particularly preferably≤99.0%.Separation rate can such as only by the temperature and pressure condition in water distilling apparatus and the impact of the residence time in water distilling apparatus.It is by simple experiment, optionally also measures between the inventive method effective date.
The suitability of the solvent of tertiary amine (I) or any extra needs can such as measure in simple experiment, and wherein phase performance measures under anticipated conditions.
In step (d), two liquid phases are separated into available from discharging at the bottom of the tower in described water distilling apparatus by step (c), wherein upper phase has formic acid and tertiary amine (I) mol ratio of 0-0.5, and lower floor's liquid phase has formic acid and tertiary amine (I) mol ratio of 0.5-5.
Be separated and can such as carry out at the independent phase separator being arranged in described water distilling apparatus downstream.But, also phase separator can be integrated in the region of circulating evaporator at the bottom of condenser zone at the bottom of the bottom section of described water distilling apparatus or tower or tower.Such as, also can use centrifuge separator or optional now or even favourable.
Because the formation of two liquid phases is not only by the chemistry of two-phase and the impact of physical properties, and be subject to the impact of temperature, therefore miscibility improves along with temperature usually, and this optionally advantageously can improve and is separated, thus runs this separator at the temperature lower than selected column bottom temperature in advance.For this reason, usually discharging at the bottom of tower is cooled to the temperature of 30-180 DEG C in intermediate heat.Be separated and preferably carry out at the temperature of the temperature of >=50 DEG C or≤160 DEG C.
Upper phase in step (d) has preferably >=0.005, and particularly preferably >=0.015 and the formic acid of preferably≤0.25, particularly preferably≤0.125 and tertiary amine (I) mol ratio.Lower floor's liquid phase of step (d) has preferably >=0.75, and particularly preferably >=1 and the formic acid of preferably≤3.5, particularly preferably≤3 and tertiary amine (I) mol ratio.
In addition, in the method for the invention, advantageously the separation rate in water distilling apparatus described in step (c) is selected, to make formic acid in discharging at the bottom of tower and tertiary amine (I) mol ratio for 0.1-2.0.Discharging at the bottom of tower is interpreted as meaning to leave described water distilling apparatus and being separated into condensation product at the bottom of the whole liquid tower of two liquid phases according to step (d).The bottom or such as unimportant available from the two of the such as vaporizer at the bottom of the direct bottom available from water distilling apparatus itself, tower of condensation product at the bottom of tower.Preferably, the separation rate in water distilling apparatus described in step (c) is selected, to make formic acid in discharging at the bottom of tower and tertiary amine (I) mol ratio≤1.5.
In the method for the invention, according to step (e), the upper phase be separated is recycled in step (a) by step (d).Therefore, use by merging with formic acid source and be present in tertiary amine (I) in upper phase to produce the stream comprising formic acid and tertiary amine (I) further.Usually by 10-100%, preferred 50-100%, particularly preferably 80-100%, very particularly preferably 90-100%, the upper phase being in particular 95-100% is recycled in step (a).
When methyl formate hydrolysis, preferably upper phase is directly recycled to hydrolysis stage.
Certainly other processing steps in the recirculation of upper phase can also be integrated.As limiting examples, such as can mention purify upper phase to be recycled or be present in tertiary amine (I) wherein undesirable with material, byproduct of reaction or impurity to remove.In principle, the type of intervening process steps is not also limited.Also a part of upper phase can be taken out especially as so-called purge stream.Certainly lacking or loss amount of tertiary amine (I) is supplemented by newly adding tertiary amine (I), can by it such as via recycle stream or directly feed in step (a).
In the method for the invention, according to step (f), the lower floor's liquid phase be separated is recycled in step (b) and/or (c) by step (d).Therefore, existing in lower floor's liquid phase formic acid can be used for obtaining formic acid by fractionation by distillation equally.Depend on required embodiment, can be recycled in step (b) by lower floor's liquid phase (i) thus in the method for the invention, (ii) shunts between step (b) and (c) or (iii) is recycled in step (c).But, usually be preferably recycled in step (c), this is because the charge capacity comprising lower floor's liquid phase of formic acid and tertiary amine (I) usually therefrom speech be minimum and streams in step (b) does not roll up, otherwise this will cause corresponding larger size.Usually by 10-100%, preferred 50-100%, particularly preferably 80-100%, very particularly preferably 90-100%, the lower floor's liquid phase being in particular 95-100% is recycled in step (b) and/or (c).
But, in the present invention, except described, lower floor's liquid phase is recycled to except step (b) and/or (c), also other parts can be recycled in step (a).This is favourable (such as when preparing formic acid by transition metal-catalyzed hydrogenation carbonic acid gas), because this carries out can be rich in equally in lower floor's liquid phase and therefore can be recycled under polar solvent in step (a) exists usually.
Also other processing steps can be integrated in the recirculation of certain lower floor liquid phase.Herein as limiting examples, also can mention purify lower floor's liquid phase to be recycled or the tertiary amine (I) be present in wherein and/or the formic acid that is present in wherein undesirable with material, byproduct of reaction or impurity to remove.In principle, the type of intervening process steps is not also limited.Also a part of lower floor liquid phase can be taken out in a targeted way as so-called purge stream, to remove undesirable by product or impurity thus.
According to the present invention, should know comprising the stream of formic acid and amine by thermal separation and reclaim in formic acid, metal and metallic compound are due to the inevitably minor surface corrosion and dissolve and enter in liquid material stream substantially when conventional material.The metal of described dissolving and/metallic compound can be distributed in the process stream in whole device, and concentrate and when exceeding solubility limit, understand with such as under meter, control valve, pump, heat exchanger surface and inner surface of container (bottom section of the such as water distilling apparatus) accumulation at each point place of uncontrolled mode.This can cause serious problems for a long time in plant running.Except affected apparatus parts being caused to directly infringement, frequently described device is stopped and also can cause the loss of throughput with clean affected device.In order to avoid this problem from the beginning, described device can be made up of more expensive material certainly.But this will be very complicated and expensive.
Should know in the method for the invention, the metal dissolved and metallic compound, at polar liquid phase, are accumulated especially in the lower floor's liquid phase formed according to step (d).In addition, should know and advantageously from the lower floor's liquid phase formed according to step (d), remove metal and metallic compound.According to step (d) formed and the upper phase be recycled in step (a) is substantially free of metal and metallic compound.This prevent dissolved metal and metallic compound to be distributed in via recirculating process stream in whole device and to cause the problems referred to above.In principle the mode of removing metal and metallic compound is not limited.Such as can remove these via so-called purge stream.The simplest removing method is that concentrated described metallic compound also to discharge in solid form higher than solubility limit from the phase separation container such as step (d).In order to the formic acid and tertiary amine (I) that are present in wherein can be reclaimed and by its recirculation, can advantageously make the purge stream of discharge evaporate, preferred vapourisation under reduced pressure.Evaporation is gone out by formic acid and tertiary amine (I), then reclaims by condensation.During evaporation, metal and metallic compound stay as residue.Such as part evaporation formic acid is to reduce solubleness, and leaches the metal of precipitation subsequently and metallic compound is also possible.Other possibilities removing metal and metallic compound from lower floor's liquid phase such as being removed from the purge stream of discharging, such as, are passed through with neutralizing treatment, by absorption on suitable adsorbent or by using ion-exchanger process.As suitable sorbent material, such as commercially available gac, silica gel, zeolite, molecular sieve, aluminum oxide can be mentioned and there is various functional group as-SO
3h ,-CO
2h ,-NR
1r
2(R
1, R
2be such as H, alkyl ,-CH
2cO
2h ,-CH
2pO
3h
2,-C (SH) NH) ,-PO
3h
2,-SH) ion exchange resin.In principle, described measure not only can use the purge stream of discharging certainly, and available whole liquid stream carries out together.But because liquid stream becomes more, then this will become much complicated, therefore usually preferably to remove from purge stream.
The tertiary amine (I) be preferred in the inventive method has general formula (Ia):
NR
1R
2R
3(Ia)，
Wherein R
1-R
3group is identical or different and independently of one another for have 1-16 carbon atom in each case, the aliphatic series of the straight or branched of a preferred 1-12 carbon atom, acyclic or ring-type, araliphatic or aromatic group, the assorted group that each carbon atom also can be selected from-O-and >N-independently of one another replaces; And two or all three groups also can link to be formed the chain comprising at least four atoms in each case each other.
Such as, as suitable amine, can mention as follows:
● Tri-n-Propylamine (boiling point
1013hPa=156 DEG C), tri-n-butylamine, tri-n-amyl amine, three normal hexyl Amines, three positive heptyl amices, tri-n-octyl amine, tri-n-nonylamine, three n-Decylamines, three n-undecane base amine, three dodecyl amine, three n-tridecane base amine, three n-tetradecane base amine, three Pentadecane base amine, three n-hexadecyl amine, tris-(2-ethylhexyl)amine.
● dimethyldodecyl amide, dimethyl dodecylamine, dimethyl tetradecyl amine, ethyl two (2-propyl group) amine (boiling point
1013hPa=127 DEG C), dioctylmethylamine, dihexyl methylamine.
● three cyclopentamine, tricyclohexyltin amine, three cycloheptylamines, three cyclooctylamines and the derivative replaced by one or more methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl or 2-methyl-2-propyl thereof.
● dimethylcyclohexylamine, methyldicyclohexylamine, diethyl cyclohexylamine, ethyl dicyclohexyl amine, dimethyl cyclopentamine, methyl bicyclic amylamine.
● triphenylamine, methyldiphenylamine, ethyl pentanoic, propyl group pentanoic, butyl pentanoic, 2-ethylhexyl pentanoic, xylidine, Diethyl Aniline, dipropyl aniline, dibutyl aniline, two (2-ethylhexyl) aniline, tribenzylamine, methyl dibenzylamine, ethyl dibenzylamine and the derivative replaced by one or more methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl or 2-methyl-2-propyl thereof.
● N-C
1-C
12piperidines, N, N-bis--C
1-C
12alkylpiperazine, N-C
1-C
12alkyl pyrrolidine, N-C
1-C
12alkyl imidazole and the derivative replaced by one or more methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl or 2-methyl-2-propyl thereof.
● 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (" DBU "), 1,4-diazabicylo [2.2.2] octane, N-methyl-8-azabicyclic [3.2.1] octane (" tropane "), N-methyl-9-azabicyclic [3.3.1] nonane (" granatane "), 1-azabicyclic [2.2.2] octane (" quinoline ring "), 7,15-diaza Fourth Ring [7.7.1.0
2,7.0
10,15] heptadecane (" sparteine ").
In the method for the invention, the mixture of different tertiary amine (I) can certainly also be used.Certainly, now all tertiary amines used (I) all preferably have the boiling point than high at least 5 DEG C of formic acid under 1013hPa absolute pressure.
In the above-mentioned tertiary amine of general formula (Ia), preferred wherein R again
1-R
3group is identical or different and independently of one another for have 1-16 carbon atom in each case, those of the straight or branched of a preferred 1-12 carbon atom acyclic or cyclic aliphatic, araliphatic or aromatic group; Wherein each carbon atom also can be selected from the assorted group replacement of-O-and >N-independently of one another, and two or all three groups also can link each other thus form the saturated chain comprising at least four atoms in each case.
Preferably, at least one group on alpha-carbon atom is with two hydrogen atoms.
In the method for the invention, particularly preferably wherein R is incited somebody to action
1-R
3group is independently from each other C
1-C
12alkyl, C
5-C
8the amine of the general formula (Ia) of cycloalkyl, benzyl and phenyl is used as tertiary amine (I).
In the method for the invention, particularly preferably the saturated amine of general formula (Ia) is used as tertiary amine (I).
In the method for the invention, very particularly preferably wherein R is incited somebody to action
1-R
3group is independently from each other C
5-C
8the amine, particularly tri-n-amyl amine of the general formula (Ia) of alkyl, three normal hexyl Amines, three positive heptyl amice, tri-n-octyl amine, dimethylcyclohexylamine, methyldicyclohexylamine, dioctylmethylamine and dimethyldodecyl amide are used as tertiary amine (I).
Except in the free formic acid of form of mixtures with except free uncle amine (I), formed in the inventive method and the stream comprising formic acid and tertiary amine (I) also can comprise in various other forms of formic acid and tertiary amine (I).Various forms of type and amount can be different, and this depends on prevailing conditions as the existence of the comparing of formic acid and tertiary amine (I), other components (as water, solvent, by product, impurity) and therefore final concentration, the temperature and pressure also depending on formic acid and tertiary amine (I).Therefore, following possible form is mentioned by way of example :-ammonium formiate (formic acid and tertiary amine (I) mol ratio are 1) or the adducts (formic acid being rich in formic acid with tertiary amine (I)
With the mol ratio >1 of tertiary amine (I)).
-ionic liquid.
Various forms of type is unimportant for enforcement the inventive method with amount.
Except formic acid and tertiary amine (I), the liquid stream be recycled in step (c) by step (b) also can comprise other components certainly, as not being separated the secondary component removing or be not separated completely removing in step (b).Except formic acid and tertiary amine (I), preferably only should by also can be no problem be separated from formic acid by distillation in step (c) or at least can easily such as by distillation subsequently, extraction, absorb or be adsorbed on those components be separated from gained formic acid in downstream procedures and be recycled to step (c).
Except formic acid and tertiary amine (I), the content of the concentration to other possibility components in the liquid stream in step (c) to be recycled and the formic acid be present in described stream and tertiary amine (I) is unimportant for enforcement the inventive method in principle.But, due to the efficiency of the inventive method, advantageously the formic acid too diluted and tertiary amine (I) are not recycled in step (c), this is because dilute the size and design and energy expenditure thereof that usually certainly also can affect water distilling apparatus.Therefore, recirculation formic acid and tertiary amine (I) total content are at least 10 % by weight, and preferably at least 50 % by weight, particularly preferably the stream of at least 80 % by weight is normally desirable.
The liquid stream be recycled in step (c) by step (b) also can optionally comprise so-called solvent.
If use solvent, then its usually advantageously can not with tertiary amine (I) miscible or only miscible a little, but to be easy to and formic acid miscible, and to be therefore present in lower floor's liquid phase of step (d).For this reason, preferably>=200 × 10 have been confirmed
-30the electrostatic considerations (being also abbreviated as EF) of Cm is a metric.Electrostatic considerations EF is defined as the relative permittivity ε of solvent
rwith the product of dipolemomentμ (see such as C.Reichardt, " Solvents and Solvent Effects in Organic Chemistry ", 3rd edition, Wiley-VCHVerlag GmbH & Co KGaA, Weinheim2003, Chapter3.2, the 67th page of bottom is to the 68th page of top).This preferred value ensure that described optional solvent there is specific least polar and with the subnatant phase miscible in step (d).
Use solvent such as can improve the separation of two liquid phases, this depends on corresponding system (such as the type, concentration, temperature, pressure etc. of tertiary amine (I)).
The material classification being particularly suitable for optionally solvent is in particular glycol and manthanoate, polyvalent alcohol and manthanoate thereof, sulfone, sulfoxide, open chain or cyclic amide and other mixture of described material type.
As suitable glycol and polyvalent alcohol, such as ethylene glycol (EF=290.3 × 10 can be mentioned
-30cm), glycol ether (EF=244.0 × 10
-30cm), triglycol, polyoxyethylene glycol, 1,3-PD (EF=285.6 × 10
-30cm), 2-methyl isophthalic acid, ammediol, BDO (EF=262.7 × 10
-30cm), dipropylene glycol, 1,5-PD (EF=212.5 × 10
-30cm), 1,6-hexylene glycol and glycerine.Due to its OH base, glycol and polyvalent alcohol can esterifications under the existence of formic acid.In the method for the invention, this comprises in the stream of formic acid and tertiary amine (I) in thermal separation especially and carries out in step (c) in described water distilling apparatus.Because gained manthanoate demonstrates closely similar phase behavior, therefore they are also suitable for usually as solvent.The water generated during esterification is also harmless to thermal separation.Be separated removing because these a small amount of water can be taken in described water distilling apparatus via side, therefore in the continuous operational process of the inventive method, the water yield can not increase.
As suitable sulfoxide, such as dialkyl sulphoxide can be mentioned, preferred C
1-C
6dialkyl sulphoxide, is in particular methyl-sulphoxide (EF=627.1 × 10
-30cm).
As suitable open chain or cyclic amide, such as methane amide (EF=1243.2 × 10 can be mentioned
-30cm), N-METHYLFORMAMIDE (EF=2352.9 × 10
-30cm), DMF (EF=396.5 × 10
-30cm), N-Methyl pyrrolidone (EF=437.9 × 10
-30cm), ethanamide and N-methyl caprolactam.
But, be determined on a case-by-case basis, also can advantageously only preferably use one to have <200 × 10
-30the non-polar solvent of Cm.Non-polar solvent optionally can reduce the formic acid concn in upper phase.
But the inventive method is preferably carried out when not adding solvent.
Fig. 1 a shows the simplified block diagram of the general embodiment of the inventive method.Herein, each letter has following implication:
A=is for generation of the device of stream comprising formic acid and tertiary amine (I)
B=is for separating of the device of removing secondary component
C=water distilling apparatus
D=phase separation container
By formic acid source via stream (1) and by tertiary amine (I) via the stream comprising formic acid and tertiary amine (I) in stream (8) infeed device A with generation.As explaining further above, formic acid source to be fed can such as comprise in dilution, pollute and/or the formic acid of chemical bonding form, or can comprise the precursor being prepared formic acid by chemical reaction by it.Take out comprising the stream of formic acid with tertiary amine (I) (2) from device A and feed in device B to be separated removing secondary component.Described device B such as can be wherein by the water distilling apparatus of distillation removing lower boiling secondary component.The secondary component be separated removes via stream (3).The stream that will concentrate with regard to formic acid and tertiary amine (I) feeds in water distilling apparatus C via stream (4).Formic acid is isolated with stream (5) by distillation.The bottom product of water distilling apparatus C is fed in the phase separation container D for being separated as stream (6).Upper phase is recycled in device A as stream (8).Lower floor's liquid phase is recycled in device C as stream (7).
Fig. 1 b shows another simplified block diagram of the general embodiment of the inventive method.Herein, each letter has following implication:
A=is for generation of the device of stream comprising formic acid and tertiary amine (I)
B=is for separating of the device of removing secondary component
C=is integrated with the water distilling apparatus be separated
The method of Fig. 1 b corresponds essentially to the method for Fig. 1 a, and difference is to be integrated into being separated in water distilling apparatus C.Formic acid is separated from water distilling apparatus C as stream (5) equally.Upper phase is recycled in device A as stream (8).Lower floor's liquid phase is recycled in device C as stream (7).
In the method for the invention, water distilling apparatus C and the various structures be separated in the region of D are possible.They not only exist different being separated to carry out in independently container or be integrated in bottom distillation tower, and also there is difference in the point of draw being added into discharging at the bottom of stream at the bottom of position in described water distilling apparatus and tower container and tower between vaporizer and tower of the stream by comprising formic acid and tertiary amine (I).
Fig. 2 shows the simplified block diagram that the inventive method preferably constructs in water distilling apparatus C and the D region that is separated.Herein, each letter has following implication:
C1=has the tower body of internals
Vaporizer at the bottom of C2=tower
D=phase separation container
H=interchanger
The stream (4) that will comprise formic acid and tertiary amine (I) feeds in tower body C1.Depend on the composition comprising the charging of formic acid and tertiary amine (I) in infeed water distilling apparatus C and source, formic acid by distillation as overhead product via stream (5), remove via stream (5b) via stream (5a) and/or as side product as side product, wherein follow following three schemes especially.
When still there is the secondary component of boiling point lower than formic acid in the charging feeding water distilling apparatus C, first scheme plays a role usually.Now described secondary component is separated removing as stream (5).Then formic acid (such as having the formic acid content of at the most 100 % by weight) is separated via stream (5a).Then usual water-containing formic acid (such as having the formic acid content of 75-95 % by weight) to be removed via stream (5b).Water-containing formic acid in stream (5b) can optionally be back in step (b) with except anhydrating.
When feed in water distilling apparatus C there is not secondary component or disadvantageous effect is not caused to required formic acid quality and the secondary component of boiling point lower than formic acid time, alternative plan plays a role usually.In this case, now formic acid (such as having the formic acid content of at the most 100 % by weight) is separated via stream (5).Then usual water-containing formic acid (such as having the formic acid content of 75-95 % by weight) to be removed via stream (5a).Water-containing formic acid in stream (5a) can optionally be back in step (b) with except anhydrating.In this case, stream (5b) can usually be saved.
When required formic acid quality obtains by stream (5), third program plays a role usually.Such as when the water in the charging feeding water distilling apparatus C and boiling point lower than the secondary component content of formic acid so low to such an extent as to its content meets the specification of quality needed for formic acid time, the way it goes.Therefore, the program may be particularly important for obtaining the formic acid with 75-95 % by weight content.
In tower body C1, the side that the feed points of stream (4) is usually located at stream (5a)/(5b) is got between the bottom of tower body C1, or in a more preferred embodiment, be arranged in the region, the 4th, bottom of available separation level.The bottom product of tower body C1 takes out as stream (6).Stream (6a) is fed in vaporizer C2 at the bottom of tower to heat.The steam and the optional liquid stream comprising tertiary amine (I) and/or formic acid that contain formic acid are recycled in tower body C1 via stream (6x).The shunting (6b) of discharging at the bottom of tower is fed in phase separation container D via optional interchanger H (described stream cools wherein).Upper phase is recycled in device A as stream (8).Lower floor's liquid phase is recycled in water distilling apparatus C as stream (7).
Replace stream (7) to be recycled in vaporizer C2 at the bottom of tower, also stream (7) can be recycled in the bottom of tower body C1 wholly or in part.
Fig. 3 shows the inventive method at the simplified block diagram of water distilling apparatus C with another preferable configuration in D region that is separated.Herein, each letter has following implication:
C1=has the tower body of internals
Vaporizer at the bottom of C2=tower
Phase separation container in D1=circulating evaporator
D2=phase separation container
H=interchanger
The stream (4) that will comprise formic acid and tertiary amine (I) feeds in tower body C1.Depend on the composition comprising the charging of formic acid and tertiary amine (I) in the described water distilling apparatus C of infeed and source, formic acid by distillation as overhead product via stream (5), remove via stream (5b) via stream (5a) and/or as side product as side product, wherein follow two schemes mentioned in the description relevant with Fig. 2 especially.The side that the feed points feeding the stream (4) in tower body C1 is usually located at stream (5a) is got between the bottom of tower body C1, or in a more preferred embodiment, is arranged in the region of bottom the 4th available separation level.The bottom product of tower body C1 takes out as stream (6) and feeds in the phase separation container D1 of steamer circulation.Lower floor's liquid phase feeds vaporizer C2 at the bottom of tower as stream (6a) and hankers to carry out adding.The steam and the optional liquid stream comprising tertiary amine (I) and/or formic acid that contain formic acid are fed in tower body C1 via stream (6x).In circulating evaporator D1, the upper phase of phase separation container feeds in phase separation container D2 via optional interchanger H (described stream cools wherein) as stream (6b).Upper phase is recycled in device A as stream (8).Lower floor's liquid phase is recycled in water distilling apparatus C as stream (7).
In simplifying procedures, in the scheme of Fig. 3, also can save phase separation container D2 and optional interchanger H and upper phase can be used as stream (6b) removes from the phase separation container of circulating evaporator D1 and be recycled in device A as stream (8).
Replace stream (7) and/or stream (6a) to be recycled in vaporizer C2 at the bottom of tower, also stream (7) and/or stream (6a) can be recycled in the bottom of tower body C1 wholly or in part.
Fig. 4 shows the simplified block diagram of the inventive method another preferable configuration in water distilling apparatus C and the D region that is separated.Herein, each letter has the implication identical with Fig. 2.The difference of Fig. 4 scheme and Fig. 2 scheme is that the charging (it optionally carries out via interchanger H) of phase separation container D is not the bottom deriving from tower body C1, but derives from the bottom of vaporizer C2 at the bottom of tower.In this scenario, replace stream (7) to be recycled in vaporizer C2 at the bottom of tower, also stream (7) can be recycled to wholly or in part the bottom of tower body C1.
Fig. 5 shows the simplified block diagram of the inventive method another preferable configuration in water distilling apparatus C and the D region that is separated.Herein, each letter has the implication identical with Fig. 2.The difference of Fig. 5 scheme and Fig. 2 scheme is that the stream (4) that will not comprise formic acid and tertiary amine (I) feeds in tower body C1, but feeds in vaporizer C2 at the bottom of tower.In this scenario, replace stream (7) to be recycled in vaporizer C2 at the bottom of tower, also stream (7) can be recycled to wholly or in part the bottom of tower body C1.
Fig. 6 shows the simplified block diagram of the inventive method another preferable configuration in water distilling apparatus C and the D region that is separated.Herein, each letter has the implication identical with Fig. 3.The difference of Fig. 6 scheme and Fig. 3 scheme is that the stream (4) that will not comprise formic acid and tertiary amine (I) feeds in tower body C1, but feeds in vaporizer C2 at the bottom of tower.In this scenario, replace stream (7) and/or stream (6a) to be recycled in vaporizer C2 at the bottom of tower, also stream (7) and/or stream (6a) can be recycled to wholly or in part the bottom of tower body C1.
Fig. 7 shows the simplified block diagram of the inventive method another preferable configuration in water distilling apparatus C and the D region that is separated.Herein, each letter has the implication identical with Fig. 2.The difference of Fig. 7 scheme and Fig. 5 scheme is that the charging (it optionally carries out via interchanger H) of phase separation container D is not the bottom deriving from tower body C1, but derives from the bottom of vaporizer C2 at the bottom of tower.In this scenario, replace stream (7) to be recycled in vaporizer C2 at the bottom of tower, also stream (7) can be recycled to wholly or in part the bottom of tower body C1.
Described below is some specific embodiments of the inventive method specific application area.
Concentrated formic acid
Dilute and/or pollute the general embodiment of formic acid based on method described under Fig. 1 a and 1b for concentrated or purification.The formic acid that formic acid source via stream (1) is dilution and/or pollutes.In the device A that such as can be static mixer, mixing nozzle, stirred vessel, reaction tower (such as at lower-boiling impurity) or extraction tower (as when water-containing formic acid), mix the stream (2) to form the secondary component (impurity) comprising formic acid, tertiary amine (I) and diluting solvent (as water) and/or pollution by stream (1) with available from the tertiary amine (I) of stream (8).Then make described stream via in stream (2) access to plant B, secondary component is partially or completely separated removing wherein.
When lower boiling secondary component, these also can such as remove by using so-called reaction tower to be separated in device A itself.In this case, the mixing of formic acid source and tertiary amine (I) is such as carried out in reaction tower or the reactor that is connected with distillation tower, and wherein lower boiling secondary component removes by distillation simultaneously.
If will concentrate through water-reducible formic acid, then most of water can be separated removing in device B.If used is diluted to through water-reducible formic acid the degree making stream (2) be separable into two-phase, then preferred by phase separation container be used as device B.Aqueous phase deposits mutually as lower floor and can be removed.Upper strata comprises formic acid and tertiary amine (I) mutually and feeds in water distilling apparatus C via stream (4).In this case, device A with B may be combined with into a device (such as extraction tower), wherein water-containing formic acid is fed the top of described tower and amine (I) is fed the bottom of described tower.Then the water of poor formic acid is taken out at the bottom of tower, then will comprise formic acid and amine (I) and still can optionally comprise taking out at tower top of a small amount of water.In order to improve the water content being separated or reducing the phase comprising amine (I) and formic acid, auxiliary agent can be added as non-polar hydrocarbon, as octane or decane.Depend on the required formic acid concn of product, the stream (4) comprising formic acid and tertiary amine (I) advantageously can be made further to dewater in middle distillation tower, only fed in water distilling apparatus C after this.
Water distilling apparatus C and the structure be separated in D region such as can carry out according to Fig. 2-7.By the secondary component of boiling point between formic acid and tertiary amine (I) in water distilling apparatus C, such as, also can remove as side stream.The boiling point of tertiary amine (I) can be selected suitably, become possibility to make the side of secondary component get.Depend on that it is measured, any secondary component residued in bottom can such as be removed from lower floor or upper phase by suitable method (as evaporation, distillation or absorption on the activated carbon) in tributary.
By described concentrated, such as water-containing formic acid can be concentrated into 100 % by weight.
Formic acid is obtained by methyl formate hydrolysis
The preferred embodiment being obtained formic acid by methyl formate hydrolysis is reproduced in Fig. 8 by simplified block diagram.Herein, each letter has following implication:
A=is for being hydrolyzed methyl-formiate and producing the device comprising the stream of formic acid and tertiary amine (I)
B=is for separating of the water distilling apparatus of removing secondary component
C=is for obtaining the water distilling apparatus of formic acid
D=phase separation container
Methyl-formiate (stream (1a) and (3b)), water (stream (1b) and (3c)) and tertiary amine (I) (stream (8)) are fed in device A.In principle, all devices that fluid streams can be made to carry out weak thermopositive reaction wherein all can be used as device A.Stirring tank, tubular reactor or tube bundle reactor can be mentioned as an example, not there are internals in each case or there are internals (such as bed, random packing, metal perforated plate etc.).Device A preferably adiabatically runs or runs by cooling.Therefore, the hydrolysis of methyl-formiate forms the stream comprising formic acid, tertiary amine (I), methyl alcohol, water and methyl-formiate, to remove and feed device B as stream (2) from device A.The composition of the conversion of methyl-formiate and stream (2) therefore depend primarily on feed device A described three kinds of incoming flow methyl-formiates, the type of water and the relative feed rate of tertiary amine (I), tertiary amine used (I), the residence time and temperature of reaction.The condition favourable to each reaction system can easily be determined by those skilled in the art, such as, determined by tentative experiment.Reaction is carried out usually at the temperature of 80-150C and the absolute pressure of 0.4-25MPa.In stream (2), the mol ratio of formic acid and tertiary amine (I) is generally 0.5-3, and this scope also can exist deviation certainly.
Now, in water distilling apparatus B, so-called secondary component is separated removing from stream (2).These secondary components are mainly: (i) unconverted methyl-formiate, it can be used as low-boiler and is separated removing via stream (3b), (ii) methyl alcohol, it is formed in hydrolytic process and the compound that boils in can be used as equally is separated removing from stream (3a), (iii) unconverted water, it is separated removing as the compound that boils in other via stream (3c).The unconverted raw material methyl-formiate and water that are separated removing are recycled in device A via stream (3b) and (3c) respectively.The methyl alcohol separated via stream (3a) can again for such as preparing methyl-formiate.Formic acid and tertiary amine (I) remove via stream (4).This also comprises the water of residual volume.Depend on the embodiment of the method, these can account for some % by weight or even tens of % by weight of stream (4).Water content in stream (4) preferably≤20 % by weight, particularly preferably≤10 % by weight, very particularly preferably≤5 % by weight.Water distilling apparatus B does not change or only changes the mol ratio of formic acid and tertiary amine (I) indistinctively, thus makes this mol ratio be also 0.5-3 usually in stream (4), certainly also can there is deviation within the scope of this.
Stream (4) is fed in water distilling apparatus C.Herein, formic acid by distillation as overhead product via stream (5), remove via stream (5b) via stream (5a) and/or as side product as side product.Fig. 2 is also applicable to this embodiment with the explanation be separated via stream (5), (5a) and/or (5b) except formic acid removal is relevant.Depend on underlying condition, namely, especially feed the composition of the incoming flow (4) in water distilling apparatus C and required formic acid purity, in this embodiment, formic acid can obtain with stream (5a) using stream (5) or as side product via tower top.Then water-containing formic acid is taken out as side product via stream (5a) or (5b).In every case, formic acid or water-containing formic acid even may be enough to only to remove via stream (5) as overhead product.Therefore, depend on specific embodiments, can save side stream (5b) or even side stream (5a) and (5b) the two.With regard to the possible embodiment of water distilling apparatus C, the form that also can be designed to be integrated with phase separator may be it should be noted that, as shown in Figure 1 b.In addition, may it should be noted that the structure of Fig. 2-7 is also that water distilling apparatus C institute is preferred certainly.
The bottom product of water distilling apparatus C is fed in phase separation container D as stream (6).As described above, this also can be integrated in water distilling apparatus C according to Fig. 1 b certainly.In phase separation container D, bottom product is separated into two liquid phases.As described in when the embodiment of Fig. 2-7, optionally can be connected with interchanger between water distilling apparatus C and phase-separating device D to cool the tower bottoms stream removed.Although with regard to formic acid content, lower floor's phase separation temperature causes slightly good separation usually, but owing to using interchanger, this causes extra cost and energy expenditure.Therefore, in each case, merits and demerits should be considered.Upper phase available from phase separation container D is recycled in device A via stream (8).Lower floor's liquid phase is recycled in water distilling apparatus C via stream (7).Depend on the amount of secondary component, residuing in any secondary component in two recycle streams can such as be removed with point streamed by suitable method (as evaporation, distillation or adsorb on the activated carbon) from lower floor or upper phase.
Being obtained in another preferred embodiment of formic acid by methyl formate hydrolysis, according to Fig. 9, methyl-formiate stream (1a) is introduced in water distilling apparatus B.If can be used as methyl-formiate that stream (1a) obtains still pollute by the methyl alcohol of residual volume (such as by the previous methyl-formiate synthesis phase under methanol fractions transforms and insufficient methyl-formiate aftertreatment cause), then this embodiment is normally favourable.Therefore, by directly being fed in water distilling apparatus B by stream (1a), existing methyl alcohol can be used as stream (3a) and separates, and is such as recycled in methyl-formiate synthesis phase.By the program, even can save the methyl-formiate/separating methanol in methyl-formiate synthesis phase completely, therefore can save whole distillation tower, and therefore also can save the energy of run duration.
Obtained in another preferred embodiment of formic acid by methyl formate hydrolysis, according to Figure 10 by methyl-formiate stream (1a) and the two introducing water distilling apparatus of current (1b) B.With regard to current (1b), provide if the condensation product of heat or steam can be used as water source, then owing to being used in water distilling apparatus B thus by wherein stored heat energy, this embodiment is normally favourable.
In order to abundant reaction, should further be mentioned that in another embodiment, certainly also by methyl-formiate stream (1a) introducing device A, and current (1b) can be introduced in water distilling apparatus B.If such as can provide low pressure excess steam, then this is favourable.
In the scheme of Fig. 8-10, with regard to the structure of water distilling apparatus B, the concrete scheme with, two or even three distillation towers is possible.Figure 11 a shows the structure with a distillation tower.Figure 11 b-11e shows the difference structure with two distillation towers.Figure 12 a-12c shows the difference structure with three distillation towers.For the structure of water distilling apparatus B, preferably there is the scheme of one or two distillation tower.For the reason of complete reaction, should it is mentioned that these also can be set to the form of thermocouple tower or next door tower, particularly when having the embodiment of one or two distillation tower.
The inventive method comprises formic acid and tertiary amine stream by thermal separation obtains formic acid with high yield and high purity.Described method can be carried out simply and reliably.The formic acid obtained has low colour and high color value stability.
The inventive method also ensure only by the formic acid of minute quantity or even substantially not by formic acid from the processing step that formic acid distillation is separated in containing returning in formic acid source in amine recycle stream.In recycle stream, the formic acid of higher amount can cause process flow to increase, and therefore can cause higher fund cost and the energy waste of Geng Gao.Particularly recirculation wherein formic acid by cause methyl-formiate transformation efficiency to reduce methyl formate hydrolysis situation under, this is useful especially.Therefore, in the method for not carrying out being separated, when by fractionation by distillation formic acid, must carry out obtaining low formic acid concn for a long time in the amine stream of recirculation with high separation rate.Therefore, any fault of lower separation rate that causes occurred at water distilling apparatus run duration directly will involve steps downstream.In the worst case, device may be made stably to run again, and device must run under the ability reduced, or necessity, even stop.This means part or even full scale production rate loss.On the contrary, in the methods of the invention, being separated and the upper phase be separated being recycled in step (a) the high mutability obtaining separation rate by the downstream of the fractionation by distillation of formic acid in the processing step (c).In step (c), the formic acid not being separated removing is present in the lower floor's liquid phase be separated.Therefore, the operation of the processing step that can easily regulate formic acid distillation to be separated is to be suitable for the requirement of the whole technique optimized and to be changed.Therefore, the inventive method also comparatively operation troubles is less likely to occur.
In addition, due to condition comparatively gentle in the thermal separation with regard to temperature program(me), the erosion rate therefore in water distilling apparatus, lower than the method for prior art, wherein strives that the formic acid content at the bottom of tower is significantly lower.Therefore, expect that the erosion rate at the temperature of low 10C reduces 2-3 doubly usually.Secondly first this have active effect to the stability of tower material, also has active effect to the content (in the inventive method, it is lower than the correlation method of prior art) of the undesirable trace extraneous metal at the bottom of tower.With regard to trace extraneous metal, except lower concentration, even also there is another advantage.This is based on the following fact: corroding metal exists only in lower floor's liquid phase of polarity substantially, therefore mainly comprises the upper phase of tertiary amine (I) in principle not containing extraneous metal.The extraneous metal dissolved can with oriented approach via lower floor's liquid phase, optionally discharges via purge stream or at least localization via the recycle stream in step (f).Therefore, extraneous metal yet not recirculation or be only recycled in formic acid source (established technology step (a)) with minimum degree, therefore it does not have any detrimental action herein and in processing step subsequently.In contrast, in prior art approaches, extraneous metal is recycled in processing step (a) together with comprising the single-phase bottom product of tertiary amine (I), and it deposits in a device herein with in downstream unit part as time goes by.As time goes by, these will have a negative impact to operability.
In addition, due to condition comparatively gentle in thermal separation, the advantage of the inventive method is that water distilling apparatus can run at a lower temperature.Therefore, such as low energy steam also can be used to run described water distilling apparatus.
In addition, more gentle condition makes the formic acid that loses due to thermolysis less.
Especially, also the inventive method and methyl formate hydrolysis (as formic acid source) can be combinationally used, and press the preparation method of the methyl formate hydrolysis of distillation downstream dehydration to compare relative to applicable industry being implemented and comprising having by extraction auxiliary agent or two, there are industry and economic advantages.
Embodiment
Embodiment 1-10
First tertiary amine needed for 1 mole is placed in the glass flask by magnetic stirrer, and drips 1 mole of formic acid (98-100 % by weight) based on every mole of amine nitrogen under ice cooling, 4.Add after terminating, described solution be warmed to room temperature (about 20C) and stir 30 minutes to guarantee that biphase equilibrium exists.After this, to be separated described by separating funnel and to weigh.Each mutually in, formic acid content is by for being the NaOH titration determination (terminal is determined: electromotive force) of 0.1N in Virahol.Amine content is assumed to the residual volume to 100%.Then by forming the mol ratio calculating formic acid and amine.Each testing data is shown in Table 1.The tertiary amine that embodiment 1-10 display wide region is selected and formic acid define two-phase mixture.
Comparative examples 11-14 and embodiment 12 and 13
Embodiment 11-14 is similar to embodiment 3 to carry out, and difference is the addition (being expressed as the total mol ratio of formic acid/amine) changing formic acid.Result is shown in Table 2.
Two phase behaviours of these indication examples as system also can be depending on formic acid/amine mol ratio.
Comparative examples 15 and embodiment 16-17
In comparative examples 15, first 1 moles dicyclohexyl amine is placed in the glass flask by magnetic stirrer, and at room temperature drips 0.21 mole of formic acid (98-100 % by weight).Add after terminating, by described solution stirring 30 minutes.Products therefrom is solid (see table 3).
In embodiment 16-17, equally first 1 moles dicyclohexyl amine is placed in the glass flask by magnetic stirrer, and at room temperature adds 0.21 mole of formic acid (98-100 % by weight).But, after this at room temperature stir 10 minutes, then drip 0.5g solvent based on every gram of amine used.Add after terminating, stir 30 minutes.After this, to be separated described by separating funnel and to weigh.Each mutually in, formic acid content by methyl alcohol be the NaOH of 0.1N relative to dibromothymolsulfonphthalein titration determination, and in two-phase, pass through the content of gas chromatography determination tertiary amine and glycol in each case.Result is shown in Table 3.
Described embodiment demonstrates such as when not being separated (such as in comparative examples 15), by adding suitable polar solvent, can cause and be separated into two liquid phases, wherein formic acid with higher concentration be present in together with polar solvent lower floor mutually in.
Comparative examples 18 and embodiment 19-21
These embodiments are carried out as described in embodiment 15-17, but use 1 mole of dimethyl n lauryl amine and 0.23 mole of formic acid.Result is shown in Table 4.Now also find to be separated into two liquid phases by adding suitable polar solvent initiation.
Comparative examples 22 and embodiment 23-24
These embodiments are carried out as described in embodiment 15-17, but use 1 mole of dimethyl n tetradecylamine and 0.26 mole of formic acid.Result is shown in Table 5.In formic acid/dimethyl n tetradecyl amine system, add suitable polar solvent and also cause and be separated into two liquid phases.
Laboratory equipment 1
Laboratory equipment 1 is for studying step (c) and (d) of the inventive method.The simplified block diagram of laboratory equipment 1 is shown in Figure 13.Wherein each letter has following implication:
C1=has the tower body (internal diameter 32mm) of 18 bubble decies and condenser and is positioned at the controlled still head of tower top
(surface-area is 0.046m to vaporizer at the bottom of C2=tower
2and wiper blade speed is 500min
-1oil heating type thin-film evaporator
D=is phase separation container (oil heating type, cumulative volume is 0.3L) independently
Each device of laboratory equipment 1 is made up of glass, and pipe connecting is made up of Teflon.Laboratory equipment 1 under reduced pressure runs continuously.
In all experiments in laboratory equipment 1, in each case, formic acid content is measured by the NaOH potentiometric titration in water being 0.5N, and water content measures according to Karl Fischer.In each case, every other organic constituent passes through gas chromatography determination.
Laboratory equipment 1 relates to and to be separated for formic acid distillation and can the necessary process components be separated of recirculation upper phase independently and lower floor's liquid phase, its model of formic acid especially also for being obtained by methyl formate hydrolysis in advance for concentrated and purification (such as).
Embodiment 25
Embodiment 25 is implemented in laboratory equipment 1.Water distilling apparatus is under the tower top pressure of the tower body C1 of 0.01MPa (definitely) and the reflux ratio of reflux and overhead product is run for 4 times.The mixture (formic acid: amine mol ratio=1.3) of the tri-n-octyl amine of 585g/h and formic acid is fed the top of thin-film evaporator C2 via stream (4).The lower part outlet temperature of described thin-film evaporator is 143 DEG C.The gaseous state discharging of described vaporizer is fed in tower body C1 as stream (6x).The liquid discharging of tower body is fed the top of thin-film evaporator C2 as stream (6a).The overhead product obtained by tower body C1 as stream (5) is 99 % by weight formic acid of 45.5g/h.This formic acid only comprises the organic impurity of 13 weight ppm and APHA colour is 1, and it also remains unchanged after even at room temperature storing 9 days.
The liquid discharging of described thin-film evaporator is passed in phase separation container D as stream (6b).This container D runs at the temperature of 30 DEG C.Upper phase is taken out as stream (8) continuously with 367g/h.Stream (8) comprise 98.5 % by weight tri-n-octyl amine and only 1.4 % by weight formic acid, this correspond to 0.1 formic acid: amine mol ratio.Lower floor's liquid phase is taken out as stream (7) continuously with 164g/h.Stream (7) comprises the tri-n-octyl amine of 86 % by weight and the formic acid of 14 % by weight, and this corresponds to the formic acid of 1.25: amine mol ratio.In a word, the formic acid in stream (6b): ratio=0.43 of amine.
Lose by measuring by hydrogen ratio mensuration Exhaust Gas speed and Exhaust Gas composition owing to decomposing the formic acid caused, carbonic acid gas and carbon monoxide decomposition product pass through gas chromatography determination.Only the formic acid of 0.3% decomposes, based on the formic acid obtained with overhead product form.
Embodiment 25 demonstrates and present invention obtains very pure and that colour is stable formic acid, obtain two liquid phases by the bottom discharge of described water distilling apparatus simultaneously, wherein upper phase is almost all made up of tri-n-octyl amine, therefore be very suitable for being recycled in step (a), lower floor's liquid phase comprises the formic acid of 14 % by weight and the tri-n-octyl amine of 86 % by weight, and it is very suitable for being recycled in step (b) and/or (c).
Embodiment 26
Embodiment 26 is similar to embodiment 25 and implements, and except collecting from the stream (7) of embodiment 25 as stream (4), but uses the synthetic mixture of tri-n-octyl amine and formic acid.As tower body C2 overhead product and comprise the organic by-products of 22 weight ppm with the product that stream (5) obtains and APHA colour for 2.Owing to decomposing the pole low value of the formic acid loss maintenance 0.3% caused, based on the formic acid obtained as overhead product.
Embodiment 26 confirms that the lower floor's liquid phase available from step (d) can be recycled in step (c) via stream (7) by the formic acid quality that can result through distillation acquisition without a doubt and not with obviously declining.
Embodiment 27
Embodiment 27 is same to be implemented in laboratory equipment 1.Described water distilling apparatus is under the tower top pressure of the tower body C1 of 0.015MPa (definitely) and the reflux ratio of reflux and overhead product is run for 4 times.The mixture (formic acid: amine mol ratio=1.5) of three normal hexyl Amines of 533g/h and formic acid is fed the top of thin-film evaporator C2 via stream (4).The temperature at described thin-film evaporator lower part outlet place is 158 DEG C.The gaseous state discharging of described vaporizer is fed in tower body C1 as stream (6x).The liquid discharging of described tower body is fed the top of thin-film evaporator C2 as stream (6a).Be 99 % by weight formic acid of 78g/h available from the overhead product of tower body C1 as stream (5).This formic acid only comprises the organic impurity of 25 weight ppm and APHA colour is 5, and it also remains unchanged after even at room temperature storing 49 days.
The liquid discharging of described thin-film evaporator is passed in phase separation container D as stream (6b).This container D runs at the temperature of 80 DEG C.Upper phase is taken out as stream (8) continuously with 364g/h.Stream (8) comprise 99.0 % by weight three normal hexyl Amines and only 1.0 % by weight formic acid, this correspond to 0.06 formic acid: amine mole.Lower floor's liquid phase is taken out as stream (7) continuously with 73g/h.Stream (7) comprises three normal hexyl Amines of 78 % by weight and the formic acid of 20 % by weight, and this corresponds to the formic acid of 1.5: amine mol ratio.In a word, the formic acid in stream (6b): ratio=0.26 of amine.
Lose by measuring by hydrogen ratio mensuration Exhaust Gas speed and Exhaust Gas composition owing to decomposing the formic acid caused, carbonic acid gas and carbon monoxide decomposition product pass through gas chromatography determination.Only the formic acid of 0.2% decomposes, based on the formic acid obtained as overhead product.
Even if embodiment 27 demonstrates when processing condition change, especially also when using different from embodiment 25 tertiary amine, the very pure and formic acid of colour stable can be obtained by the inventive method.In this case, also two liquid phases are obtained by the bottom discharge of described water distilling apparatus, and upper phase is almost complete is made up of three normal hexyl Amines, therefore be very suitable for being recycled in step (a), lower floor's liquid phase comprises the formic acid of 20 % by weight and three normal hexyl Amines of 78 % by weight, and it is very suitable for being recycled in step (b) and/or (c).
Embodiment 28
Embodiment 28 is substantially similar to embodiment 27 and implements, and except collecting from the stream (7) of embodiment 27 as stream (4), but uses the synthetic mixture of three normal hexyl Amines and formic acid.This mixture of 518g/h is fed the top of thin-film evaporator C2 via stream (4).The temperature at described thin-film evaporator lower part outlet place is 160 DEG C.Be 99 % by weight formic acid of 76g/h available from the overhead product of tower body C1 as stream (5).This formic acid only comprises the organic impurity of 31 weight ppm and APHA colour is 3.
The liquid discharging of described thin-film evaporator is passed in phase separation container D as stream (6b).This container D runs at the temperature of 80 DEG C.Upper phase is taken out as stream (8) continuously with 407g/h.Stream (8) comprise 98.0 % by weight three normal hexyl Amines and only 1.4 % by weight formic acid, this correspond to 0.08 formic acid: amine mol ratio.Lower floor's liquid phase is taken out as stream (7) continuously with 7g/h.Stream (7) comprises three normal hexyl Amines of 79 % by weight and the formic acid of 19 % by weight, and this corresponds to the formic acid of 1.4: amine mol ratio.In a word, existing in stream (6b) formic acid: ratio=0.1 of amine.Formic acid loss is caused to be 0.7% owing to decomposing, based on the formic acid obtained with overhead product form.
Even if embodiment 28 confirms when using the tertiary amine different from embodiment 26, the lower floor's liquid phase available from step (d) can be recycled in step (c) via stream (7) by the formic acid quality that also can result through distillation acquisition without a doubt and not with obviously declining.
Comparative examples 29
Comparative examples 29 is same to be implemented in laboratory equipment 1.Described water distilling apparatus is under the tower top pressure of the tower body C1 of 0.015MPa (definitely) and the reflux ratio of reflux and overhead product is run for 4 times.The mixture (formic acid: amine mol ratio=1.5) of three normal hexyl Amines of 492g/h and formic acid is fed the top of thin-film evaporator C2 via stream (4).The temperature at described thin-film evaporator lower part outlet place is 171C.The gaseous state discharging of described vaporizer is fed in tower body C1 as stream (6x).The liquid discharging of tower body is fed the top of thin-film evaporator C2 as stream (6a).As the overhead product of tower body C1, obtain 99 % by weight formic acid of 72g/h with stream (5).The APHA colour of this formic acid is 10, however its at room temperature only store within 7 days, just rise to 20 afterwards.
Pass in phase separation container D using the liquid discharging of described thin-film evaporator as stream (6b), described container D runs at the temperature of 80 DEG C.But, only obtain single-phase liquid discharging.This discharging comprises three normal hexyl Amines of 99.2 % by weight and the formic acid of 0.7 % by weight.Again pass through to form by hydrogen ratio mensuration Exhaust Gas speed and Exhaust Gas and measure owing to decomposing the formic acid loss caused, carbonic acid gas and carbon monoxide decomposition product pass through gas chromatography determination.Now be measured as the high formic acid decomposition value of 1.9%, based on the formic acid obtained with overhead product form.
Comparative examples 29 shows when obtaining single-phase liquid by water distilling apparatus, and the decomposition of formic acid increases.Embodiment 30
In embodiment 30, laboratory equipment 1 runs as described in embodiment 27, and difference is that the stainless steel plate (20mm × 50mm × 3mm) made by the material by material number being 1.4406,1.4462 and 1.4439 to be in each case arranged on bottom tower body C1 and bottom thin-film evaporator C2.Make described device run 15 days continuously subsequently, be two bursts of liquid streams (7) and (8) again merge and mix to set up the formic acid of 1.5 with fresh anhydrous formic acid with another difference of embodiment 27: the constant ratio of three normal hexyl Amines.This mixture is used as feed steam (4).After 15 days, the content of stream (7) and (8) middle corroding metal Cr, Fe, Mo and Ni is by ICP-MS (inductively coupled plasma mass spectrometry) quantitative assay.In upper phase (stream (8)), the content of all corroding metals is all lower than the detection limit of 1 weight ppm.Lower floor's liquid phase (stream (7)) comprises Cr, the Fe of 42 weight ppm of 32 weight ppm, the Ni of the Mo of 7 weight ppm and 2 weight ppm.
Embodiment 30 demonstrates described corroding metal and is especially present in lower floor's liquid phase, therefore can be discharged by suitable measure even in a controlled manner thus.The upper phase be recycled in step (a) does not in fact contain corroding metal.
Laboratory equipment 2
Laboratory equipment 2 is for studying the step (b) of the inventive method or being particularly useful for the dehydration that research comprises the mixture of formic acid, tertiary amine (I) and water.Laboratory equipment 2 comprises to be made up of glass and to have the continuous operation distillation tower (internal diameter=32mm) of 20 bubble decies.Heat is introduced via (chuck) bottom oil heating type.Tower top place is condenser and still head, can set up reflux ratio whereby.Tower charging is fed in tower at the 9th bubble deck (from bottom number).Described tower is at environmental stress and be run under the reflux ratio of 0.5 in each case.
Embodiment 31
Embodiment 31 is implemented in laboratory equipment 2.Mixture 230g/h being comprised 8.0 % by weight water, 30.5 % by weight formic acid and 61.5 % by weight three normal hexyl Amines feeds in tower, and this corresponds to the formic acid of 2.9: the formic acid of amine mol ratio and 79:21: quality ratio.In the steady state, the column bottom temperature of 155 DEG C is set up.Overhead product comprises the water only with 0.16 % by weight formic acid substantially.Bottom product comprise 32.7 % by weight formic acid, 65.8 % by weight three normal hexyl Amines and only 1.5 % by weight water, this corresponds to the formic acid of 2.9: the formic acid of amine mol ratio and 96:4: quality ratio.Therefore, the secondary component water of removing 81% is separated.
Embodiment 32
Embodiment 32 is similar to embodiment 31 and implements, the mixture that difference is 262g/h to comprise 8.2 % by weight water, 40.6 % by weight formic acid and 51.3 % by weight three normal hexyl Amines feeds in tower, and this corresponds to the formic acid of 4.6: the formic acid of amine mol ratio and 83:17: quality ratio.In the steady state, the column bottom temperature of 137 DEG C is set up.Overhead product comprises the water only with 0.05 % by weight formic acid substantially.Bottom product comprise 43.4 % by weight formic acid, 54.7 % by weight three normal hexyl Amines and only 1.9 % by weight water, this corresponds to the formic acid of 4.6: the formic acid of amine mol ratio and 96:4: quality ratio.Therefore, the secondary component water of removing 77% is separated.
Even if embodiment 31 and 32 demonstrates better simply distillation, the water of about 80% also can be separated without doubt from formic acid and the aqueous mixture of three normal hexyl Amines.
Laboratory equipment 3
Laboratory equipment 3 for studying the step (a) of the inventive method and (b), more specifically for studying methyl formate hydrolysis and distillation subsequently removes the first alcohol and water of unconverted methyl-formiate, formation.The simple block diagram of laboratory equipment 3 is shown in Figure 14.Wherein each letter has following implication:
A1=stirring tank (volume 3.5L, electric heating type)
A2=tubular reactor (internal diameter is 80mm, and long is 1200mm, is filled with 2mm granulated glass sphere, electric heating type)
B1=has tower body, and (internal diameter is 55mm, and (packing height of each filler is 1.3m, and specific surface area is 750m to be equipped with fabric filler
2/ m
3), wherein feed points is between two bed of packings) and oil heating type falling-film evaporator (surface-area 0.45m
2) water distilling apparatus
B2=has tower body, and (internal diameter is 55mm, and (packing height of each filler is 1.3m, and specific surface area is 750m to be equipped with fabric filler
2/ m
3), wherein feed points is between two bed of packings) and oil heating type falling-film evaporator (surface-area 0.15m
2) water distilling apparatus
The nickel-base alloy that the device of laboratory equipment 3 and pipeline are 2.4610 by material number is formed.In order to measurement quality flow, use coriolis flowmeter.Laboratory equipment 3 runs continuously.
Embodiment 33
Embodiment 33 is implemented in laboratory equipment 3.Via volume pump, 853g/h methyl-formiate is metered in reactor A 1 via stream (8) via stream (1b) and 1535g/h tri-normal hexyl Amine via stream (1a), 256g/h water.Reactor A 1 is run under 130 DEG C and 1.2MPa gauge pressure.The discharging of reactor A 1 is passed in the post-reactor A2 run under 130 DEG C and 1.2MPa gauge pressure equally.Gained stream (2) is for comprising the product mixtures of 58.1 % by weight three normal hexyl Amine, 15.0 % by weight formic acid, 10.4 % by weight methyl alcohol, 3.8 % by weight water and 12.7 % by weight methyl-formiates, and this corresponds to the formic acid of 1.51: amine mol ratio.Stream (2) is reduced pressure and passes in the tower body of water distilling apparatus B1.0.18MPa (definitely) tower top pressure and 1.7 reflux ratio under, the overhead product taken out as stream (3b) is for substantially comprising the mixture of formed methyl alcohol and unconverted methyl-formiate.The bottom product obtained as stream (3d) is the mixture of 74.9 % by weight three normal hexyl Amine, 5.3 % by weight water, 19.8 % by weight formic acid and 0.1 % by weight methyl alcohol of 1990g/h.Bottom temp in tower body is 133 DEG C.Stream (3d) is reduced pressure and passes in the tower body of water distilling apparatus B2.Acquisition is got and the recirculation being recycled to the water-containing formic acid in step (b) according to the description of Fig. 2 by 69g/h water-containing formic acid (formic acid content is 82.5 % by weight) additionally infeed tower body to simulate the side that can be used as distillation tower in step (c) via stream (5a).As the overhead product of water distilling apparatus B2,0.11MPa (definitely) tower top pressure and 1.7 reflux ratio under take out 92g/h, it comprises water and 0.1% formic acid substantially.The bottom product obtained via stream (4) under the tower body bottom temp of 160 DEG C is the mixture of 76.9 % by weight three normal hexyl Amine, 21.2 % by weight formic acid and 1.9 % by weight water of 1949g/h.Formic acid in stream (4): the mol ratio of amine is 1.61.
Embodiment 33 demonstrates the inventive method, and when being hydrolyzed methyl-formiate and carry out aftertreatment by removing secondary component (especially residual methyl-formiate, the first alcohol and water formed) to it subsequently, the stream being rich in formic acid and three normal hexyl Amines in a large number can be obtained.Shown in as indirect in embodiment 27 and 28, then this stream can be used for the very pure formic acid of fractionation by distillation.
Table 1
Table 2
Table 3
Table 4
Table 5
Claims (12)
1. comprise the stream material of formic acid and tertiary amine (I) by thermal separation and obtain the method for formic acid, wherein:
A () generation comprises the liquid stream of formic acid that mol ratio is 0.5-5 and tertiary amine (I) by tertiary amine (I) and formic acid source being merged;
B () is from the secondary component being present in the 10-100 % by weight in described stream available from separation the liquid stream of step (a); With
C () takes out formic acid by distilling under the absolute pressure of the column bottom temperature of 100-300 DEG C and 30-3000hPa in water distilling apparatus from available from the liquid stream of step (b);
Wherein:
Tertiary amine (I) used is the amine of the boiling point had under 1013hPa absolute pressure than high at least 5 DEG C of formic acid;
In addition, select for the separation rate in water distilling apparatus described in the tertiary amine (I) in step (a) and step (c), to make to form two liquid phases in discharging at the bottom of the tower of water distilling apparatus described in step (c) under the prevailing conditions in step (d), wherein said separation rate is 10-99.9%;
D () is separated into two liquid phases by step (c) available from discharging at the bottom of the tower in described water distilling apparatus, wherein upper phase has formic acid and tertiary amine (I) mol ratio of 0-0.5, and lower floor's liquid phase has formic acid and tertiary amine (I) mol ratio of 0.5-5;
E the upper phase be separated is recycled in step (a) by step (d) by (); With
F the lower floor's liquid phase be separated is recycled in step (b) and/or (c) by step (d) by ().
2. method according to claim 1, wherein in step (a), the stream comprising formic acid and tertiary amine (I) is produced by hydrolysis methyl-formiate under the existence of water and tertiary amine (I).
3. method according to claim 1, wherein in step (a), the stream comprising formic acid and tertiary amine (I) is prepared by dilute formic acid under the existence of tertiary amine (I).
4. method as claimed in one of claims 1-3, the formic acid that the liquid stream wherein produced in step (a) has 1-99 % by weight adds tertiary amine (I) concentration, based on the total amount of this stream.
5. method as claimed in one of claims 1-3, wherein in step (c), feeds the stream comprising formic acid and tertiary amine (I) that bottom the 4th is available to be separated in the region of level.
6. method as claimed in one of claims 1-3, wherein in step (c), feeds the stream comprising formic acid and tertiary amine (I) in vaporizer at the bottom of the tower of described water distilling apparatus.
7. method as claimed in one of claims 1-3, wherein selects the separation rate in water distilling apparatus described in step (c) to make formic acid in discharging at the bottom of tower and tertiary amine (I) mol ratio for 0.1-2.0.
8. method as claimed in one of claims 1-3, wherein removes the metal be present in lower floor's liquid phase of being formed according to step (d) and metallic compound from described lower floor liquid phase.
9. method as claimed in one of claims 1-3, the amine that tertiary amine (I) wherein used is general formula (Ia):
NR
1R
2R
3(Ia)，
Wherein radicals R
1-R
3identical or different and independently of one another in each case there is the straight or branched of 1-16 carbon atom, acyclic or cyclic aliphatic, araliphatic or aromatic group, wherein each carbon atom also can be selected from the assorted group replacement of-O-and >N-independently of one another, and two or all three groups can link each other, thus form the chain comprising at least four atoms in each case.
10. method according to claim 9, tertiary amine (I) wherein used is wherein radicals R
1-R
3be independently from each other C
1-C
12alkyl, C
5-C
8the amine of the general formula (Ia) of cycloalkyl, benzyl and phenyl.
11. methods according to claim 10, tertiary amine (I) wherein used is wherein radicals R
1-R
3be independently from each other C
5-C
8the amine of the general formula (Ia) of alkyl.
12. methods as claimed in one of claims 1-3, wherein said separation rate is 25-99.5%.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10167679 | 2010-06-29 | ||
| EP10167679.9 | 2010-06-29 | ||
| EP10187280 | 2010-10-12 | ||
| EP10187280.2 | 2010-10-12 | ||
| PCT/EP2011/060770 WO2012000964A1 (en) | 2010-06-29 | 2011-06-28 | Method for producing formic acid |
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| CN102958894A CN102958894A (en) | 2013-03-06 |
| CN102958894B true CN102958894B (en) | 2015-04-15 |
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|---|---|
| EP (1) | EP2588440A1 (en) |
| JP (1) | JP2013533869A (en) |
| KR (1) | KR20130088838A (en) |
| CN (1) | CN102958894B (en) |
| BR (1) | BR112012032211A2 (en) |
| CA (1) | CA2801580A1 (en) |
| RU (1) | RU2013103601A (en) |
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| WO (1) | WO2012000964A1 (en) |
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| US8877965B2 (en) | 2010-06-29 | 2014-11-04 | Basf Se | Process for preparing formic acid by reaction of carbon dioxide with hydrogen |
| RU2013133653A (en) * | 2010-12-21 | 2015-01-27 | Басф Се | METHOD FOR PRODUCING FORMIC ACID AS A RESULT OF INTERACTION OF CARBON DIOXIDE WITH HYDROGEN |
| US8742171B2 (en) | 2011-06-09 | 2014-06-03 | Basf Se | Process for preparing formic acid |
| US8993819B2 (en) | 2011-07-12 | 2015-03-31 | Basf Se | Process for preparing cycloheptene |
| US8703994B2 (en) | 2011-07-27 | 2014-04-22 | Basf Se | Process for preparing formamides and formic esters |
| US8946462B2 (en) | 2011-11-10 | 2015-02-03 | Basf Se | Process for preparing formic acid by reaction of carbon dioxide with hydrogen |
| US8889905B2 (en) | 2011-12-20 | 2014-11-18 | Basf Se | Process for preparing formic acid |
| WO2013092403A1 (en) * | 2011-12-20 | 2013-06-27 | Basf Se | Method for producing formic acid |
| US8835683B2 (en) | 2011-12-20 | 2014-09-16 | Basf Se | Process for preparing formic acid |
| US9428438B2 (en) | 2012-11-27 | 2016-08-30 | Basf Se | Process for preparing formic acid |
| CN104812731A (en) * | 2012-11-27 | 2015-07-29 | 巴斯夫欧洲公司 | Method for producing formic acid |
| CN110980763B (en) * | 2019-12-24 | 2022-10-18 | 福州大学 | Modification method and application of molecular sieve |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101006038A (en) * | 2004-08-23 | 2007-07-25 | 巴斯福股份公司 | Method for the production of formic acid |
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| DE2545658C2 (en) | 1975-10-11 | 1985-12-19 | Basf Ag, 6700 Ludwigshafen | Process for the production of carboxylic acids from their aqueous solutions |
| DE2744313A1 (en) | 1977-10-01 | 1979-04-12 | Basf Ag | PROCESS FOR THE PRODUCTION OF FORM ACID |
| GB8307611D0 (en) | 1983-03-18 | 1983-04-27 | Bp Chem Int Ltd | Formic acid |
| DE3428319A1 (en) | 1984-08-01 | 1986-02-13 | Hüls AG, 4370 Marl | Process for the production of anhydrous or largely anhydrous formic acid |
| GB8424672D0 (en) | 1984-09-29 | 1984-11-07 | Bp Chem Int Ltd | Production of formic acid |
| DE4211141A1 (en) | 1992-04-03 | 1993-10-07 | Basf Ag | Process for the preparation of formic acid by thermal cleavage of quaternary ammonium formates |
| BRPI0809156A2 (en) | 2007-03-23 | 2014-09-16 | Basf Se | PROCESS FOR PREPARING FORMIC ACID. |
| DE102009046310B4 (en) | 2008-11-24 | 2018-10-25 | Basf Se | Process for the distillative recovery of pure 1,3-butadiene from crude 1,3-butadiene |
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- 2011-06-28 BR BR112012032211A patent/BR112012032211A2/en not_active IP Right Cessation
- 2011-06-28 WO PCT/EP2011/060770 patent/WO2012000964A1/en active Application Filing
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- 2011-06-28 KR KR1020137002200A patent/KR20130088838A/en not_active Application Discontinuation
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| SG186264A1 (en) | 2013-01-30 |
| JP2013533869A (en) | 2013-08-29 |
| CN102958894A (en) | 2013-03-06 |
| KR20130088838A (en) | 2013-08-08 |
| RU2013103601A (en) | 2014-08-10 |
| BR112012032211A2 (en) | 2016-11-29 |
| WO2012000964A1 (en) | 2012-01-05 |
| CA2801580A1 (en) | 2012-01-05 |
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