CN1056300A - The preparation method of carboxylic acid - Google Patents
The preparation method of carboxylic acid Download PDFInfo
- Publication number
- CN1056300A CN1056300A CN90102635.2A CN90102635A CN1056300A CN 1056300 A CN1056300 A CN 1056300A CN 90102635 A CN90102635 A CN 90102635A CN 1056300 A CN1056300 A CN 1056300A
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- China
- Prior art keywords
- catalyst
- iodide
- carboxylic acid
- hydrogen
- alcohol
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims description 26
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 239000010948 rhodium Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 39
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 36
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 31
- 239000003381 stabilizer Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 230000006315 carbonylation Effects 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 13
- 229940107816 ammonium iodide Drugs 0.000 claims description 11
- 150000004694 iodide salts Chemical class 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000012429 reaction media Substances 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000005956 quaternization reaction Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 10
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract description 10
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 abstract description 5
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002460 imidazoles Chemical class 0.000 abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 abstract description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- VJXRKZJMGVSXPX-UHFFFAOYSA-N 4-ethylpyridine Chemical compound CCC1=CC=NC=C1 VJXRKZJMGVSXPX-UHFFFAOYSA-N 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- -1 rhodium (III) compound Chemical class 0.000 description 9
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- NURQLCJSMXZBPC-UHFFFAOYSA-N 3,4-dimethylpyridine Chemical class CC1=CC=NC=C1C NURQLCJSMXZBPC-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001511 metal iodide Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 2
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- MDICIVRGHCTEQJ-UHFFFAOYSA-N 1-methyl-1,2-dihydropyridin-1-ium iodide Chemical compound [I-].C[NH+]1CC=CC=C1 MDICIVRGHCTEQJ-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- VFLYBWGSQGMWHP-UHFFFAOYSA-N 3-methyl-1h-imidazol-3-ium;iodide Chemical compound [I-].C[N+]=1C=CNC=1 VFLYBWGSQGMWHP-UHFFFAOYSA-N 0.000 description 1
- GCNTZFIIOFTKIY-UHFFFAOYSA-N 4-hydroxypyridine Chemical compound OC1=CC=NC=C1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method that contains the acid (as acetate) of (n+1) individual carbon atom by liquid phase, the catalytic carbonylation reaction of rhodium from alcohol (as the methyl alcohol) preparation that contains n carbon atom is provided.The method is characterized in that and use a kind of catalyst stabilizer that it is selected from the imidazoles iodide of some kind, pyridine iodide and the pyridone iodide that alkyl replaces.Most preferably use methyl quaternized and, those compounds that the 4-lutidine is derived and from amine 2-ethyl-4-methylimidazole, 4-methylimidazole, 4-ethylpyridine, 4-tert .-butylpyridine and 3.
Description
The present invention relates to the method that a kind of improved preparation contains the carboxylic acid of n+1 carbon atom, this method is to make the pure carbonylation that contains n carbon atom in the presence of rhodium catalyst.Especially, the present invention relates to use rhodium catalyst, the carbonylation reaction by methyl alcohol prepares acetate.
Producing acetate by the catalytic methanol carbonylation of rhodium is known method of carrying out industrial-scale production.This method is the example in the class similarity method, and the alcohol that wherein contains n carbon atom changes into the carboxylic acid that contains n+1 carbon atom by carbonylation (promptly and reaction of carbon monoxide).Alcohol normally carries out in liquid phase in the presence of the promotor of rhodium catalyst and the iodide derivative that contains alcohol with the reaction of carbon monoxide.In English Patent 1233121 this method having been carried out further general the description, is acetate and describe methanol conversion in detail at applicable industry catalysis (Applied Industrial Catalysis) the 1st volume 275-296 page or leaf (1983).
According to the result of a large amount of fundamental researchs, can be sure of that rhodium compound relevant with catalysis in these methods is the negatively charged ion (Rh(CO) of rhodium (I)
2I
2)
-The result of Mechanism Study shows, plays katalysis by the circulating reaction step, and it mainly comprises iodide derivative by alcohol to (Rh(CO)
2I
2)
-The oxidation addition generate rhodium (III), make (Rh(CO) by reduction elimination acid iodide from rhodium (III) compound subsequently
2I
2)
-Regeneration.This oxidation reduction cycle between rhodium (I) and rhodium (III) oxidation state has produced problem, because produced slightly soluble under certain conditions or be insoluble to rhodium (III) compound in this method reaction medium, and RhI for example
3Or Rh(CO) I
2-
5Salt.Therefore the trend that catalyst precipitation occurred, and irreversibly removed the rhodium in the catalyst recirculation for all actual purpose.This from reaction medium and catalyst recirculation the loss catalyzer be unacceptable because at first it will cause that the productive rate of this method reduces, secondly be because extremely valuable rhodium is difficult to reclaim.
Found very low and/or be less than 14-15%(weight when carbon monoxide concentration) when carrying out this reaction in the presence of the water, sedimentary trend maximum takes place in insoluble rhodium (III) compound.For technical scale, before a kind of trend can cross that part of carbonylation of methanol device that forces down to carbon monoxide and bring some problems, and the latter means that most of carbonylation of methanol devices are about 14-15%(weight normally in carbonylation reactor, in normal concentration) water in the presence of operate.
The method of a kind of solution rhodium (III) compound precipitation problem has been described in EP55618 and EP161874.EP55618 discloses for the insufficient pure carbonylation apparatus of those carbon monoxide (for example flash tank, transfer lime, circular route), can stop the sedimentary trend of rhodium catalyst by add catalyst stabilizer in device.Preferred stablizer is (a) N, N, N
1, N
1-tetramethyl-O-Phenylene Diamine and 2,3 ' two pyridines, (b) molecular formula is (R
1) (R
2) P-R
3-P(R
4) (R
5) the replacement diphosphine, (c) molecular formula is HOOC-Y-COOH and (HOOC-Y
2) (HOOC-Y
3) NY
1N(Y
4COOH) (Y
5COOH) binary or polycarboxylic acid, and (d) germanium, antimony, tin or alkali-metal compound.
Relevant european patent application 1538341 is pointed out to use imidazoles or thiol stabilizer.This application has been enumerated use N-Methylimidazole.
EP161874 points out, if use the catalyst stabilizer that is selected from metal iodide and quaternary ammonium iodide, can reduce the trend of catalyst precipitation under the low water condition.Preferred stablizer is basic metal and alkaline earth metal iodide, for example lithium iodide.Quaternary ammonium iodide-N-methyl pyridine iodide are also disclosed especially.
The prior art of above-mentioned discussion shows by using a kind of catalyst stabilizer, can reduce the trend of rhodium catalyst with insoluble rhodium (III) compound precipitation.But recent findings when using quaternary ammonium iodide, for example problem occurred when N-Methylimidazole iodide and N-methyl pyridine iodide, and promptly iodide itself cause generating the sl. sol. rhodium complex that contains, thereby have caused the rhodium loss.
According to the present invention, it provides a kind of in the presence of rhodium catalyst, by carbon monoxide and the alcohol reaction that contains n carbon atom, preparation contains the method for the carboxylic acid of n+1 carbon atom, this method comprises to be sent into alcohol and/or described alcohol in the carbonylation reactor with carbon monoxide with the ester of carboxylic acid, and to discharge carboxylic acid in the carbonylation reactor.This method is characterised in that: keep the reaction medium in the carbonylation reactor to contain in reaction process: (a) at least one quantitative water, and (b) a kind of catalyst stabilizer, it is selected from the quaternary ammonium iodide with following general formula:
Wherein R and R
1Independently be selected from hydrogen or C respectively
1-C
20Alkyl, condition are at least one R
1Not hydrogen, (d) with pure corresponding iodide derivative, (e) ester of carboxylic acid and described alcohol, (f) rhodium catalyst and (g) described carboxylic acid.
The present invention has solved the problem that proposes above by using some selected quaternary ammonium iodide.Having shown that described quaternary ammonium iodide had both made what set is used for impelling under the sedimentary very serious condition of rhodium and does not also produce the sl. sol. rhodium complex that contains.Selected quaternary ammonium iodide also has other advantage, promptly with respect to ordinary method when water-content in the carbonylation reactor is low, they can prevent precipitation especially effectively.Really, they are more superior than disclosed stablizer among the EP161874.
Above the preferred specific embodiments of described method be that carboxylic acid and rhodium catalyst and catalyst stabilizer are discharged from carbonylation reactor.Then with carboxylic acid, rhodium catalyst and catalyst stabilizer by a zone that with respect to carbonylation reactor, lacks carbon monoxide, and in this zone with carboxylic acid and other component separating.Rhodium catalyst and catalyst stabilizer be recycled in carbonylation reactor thereafter.In preferred concrete enforcement, this separation and circulation means be characterised in that, when carbon monoxide lacked, rhodium catalyst and catalyst stabilizer were always together.
When a certain amount of water in the carbonylation reactor is the common consumption (14-15% weight) of conventional carbonylation of methanol device, can use the present invention and described specific embodiments.When the content of water is lower than conventional amount used (for example in 0.1-12% weight, preferred 0.5-8% weight) in carbonylation reactor, this technology particularly suitable.
The alcohol that contains n carbon atom says it can is any alcohol that contains 1-20 carbon atom and have a hydroxyl at least in principle, preferably contains the simple function Fatty Alcohol(C12-C14 and C12-C18) of 1-8 carbon atom.More preferably methyl alcohol, ethanol and propyl alcohol, and methyl alcohol is most important.Because the method for acetic acid from methanol is industrial confirmed technology.
The synthetic chemistry metering of this method can be represented with following equation:
R
2OH+CO→R
2COOH
R wherein
2It is the organic moiety that satisfies the defined standard of leading portion.Equation can easily be determined the carboxylic acid that given alcohol is produced thus.At methyl alcohol (R
2=CH
3) and ethanol (R
2=C
2H
5) situation under, the carboxylic acid of production is respectively acetate and propionic acid.
Though method of the present invention can discontinuously be carried out, and in most of the cases preferably carries out continuously.In the operate continuously process, alcohol and/or described alcohol are sent in the carbonylation reactor with water (in the maintenance reactor certain density rhodium catalyst to be arranged), iodide derivative and the catalyst stabilizer of the ester of product carboxylic acid and carbon monoxide, capacity.Be appreciated that back four kinds of compositions do not consume in this process, they are recycled to the reactor continuously from product stream, just add essential raw material once in a while.Each composition is corresponding with sending into continuously in carbonylation reactor, discharges the product stream that contains product carboxylic acid, water, rhodium catalyst, iodide derivative and catalyst stabilizer continuously.Net result is that carbonylation reactor reaches stable state, and keeps liquid reaction medium to contain the composition of stable state, wherein contains ester, rhodium catalyst and the carboxylic acid of water, catalyst stabilizer, iodide derivative, carboxylic acid and the alcohol of constant.In fact contain free alcohol seldom in the carbonylation reactor, because between carboxylic acid and the alcohol esterification can take place rapidly.
For method of the present invention, preferably when stable state in the composition of liquid reaction medium the content range of each composition as follows:
The general range preferable range
wt% wt%
Water 0.1-12 0.5-8
Carboxylic acid and pure ester 0.1-10 2-8
Iodide derivative 5-20 10-16
Catalyst stabilizer 2-20 10-20
Rhodium catalyst (ppm) 100-1800 300-1200
For concrete methanol carbonylation to synthesize acetic acid, preferred compositing range is water (0.5%-8%), methyl acetate (2-8%), methyl iodide (10-16%), catalyst stabilizer (10-20%) and rhodium catalyst (300-1200ppm), and all the other are acetate and trace impurity.
It is that 100-200 ℃, carbon monoxide pressure are in 10-200 normal atmosphere that carbonylation reactor should keep temperature.Preferably temperature is that 140-200 ℃, pressure are 10-100 normal atmosphere.Carbonylation reaction takes place rapidly with this understanding.
Preferably at least one R group and R in the three class catalyst stabilizers as defined above
2Group is identical, and it comprises the organic moiety of alcohol, iodide derivative and carboxylic acid.And each R
1Under the defined in front condition of group can be hydrogen or C
1-C
8Alkyl, preferably hydrogen or C
1-C
6Alkyl.Preferred examples is those R separately in (1) class and (2) class catalyst stabilizer
1Group is selected from the catalyst stabilizer of hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl and the tertiary butyl.
A particularly preferred class catalyst stabilizer is following cationic iodide salt:
(ⅰ) R wherein
1And R
2It is methyl
(ⅱ) R
5Be hydrogen
(ⅲ) R
3Be C
1-C
20Alkyl or hydrogen
And (ⅳ) R
4Be C
1-C
20Alkyl
Most preferred example is (1) R in this type of
3=C
2H
5, R
1, R
2And R
4=CH
3And R
5=H or (2) R
3And R
5=H and R
1, R
2And R
4=CH
3Catalyst stabilizer.
The catalyst stabilizer of another kind of particularly important is following cationic iodide salt
R wherein
6Be hydrogen or methyl, R
7Be C
1-C
4Alkyl, R
1It is methyl.Preferred examples is (1) R
6=H and R
7=C
2H
5, (2) R
6=H and R
7=t-C
4H
9And (3) R
6And R
7=CH
3
The quaterisation of the organic iodide by corresponding amine and general formula R I can prepare catalyst stabilizer, and the general formula of these amine is as follows:
R group in the organic iodide can be identical or different with any R group in the corresponding amine.Certainly preferably to carrying out quaternized with the corresponding amine of preferred catalyst stablizer as defined above.The R group is exactly R in the case
2Therefore begin or when charging or interpolation recycle stream, may generate catalyst stabilizer on the spot when this method by sending into corresponding amine.Experience shows that under this method operational condition the quaternization of these amine can take place rapidly.In case the generation quaternization just can make this catalyst stabilizer circulation according to ordinary method.
Specify the present invention by the following examples:
Experimental technique
A. the preparation of catalyst stabilizer
The associated amines of 25mmol is dissolved in the acetate with the 25mmol methyl iodide, with this mixture in pressurized vessel, under nitrogen atmosphere, be heated to 180 ℃ 12 hours.
B. the solubleness of the quaternary ammonium iodide salt of test method-rhodium catalyst
Cold mixture and other methyl iodide and the rhodium storing solution that is dissolved in aqueous acetic acid are mixed, obtain having the testing liquid of following composition:
Rhodium 550ppm
Water 2%(weight)
Methyl iodide 2%(weight)
The acetate surplus
Above-mentioned testing liquid was stirred 1 hour at 25 ℃, analyze water, iodide ion and soluble rhodium in the gained solution.Gained the results are shown in the following table:
| Additive | Water (% w/w) | Iodine (% w/w) | Final Rh (ppm) | The %Rh precipitation |
| N-methylimidazole 3-picoline imidazoles 2-ethyl imidazol(e) 2-ethyl-4-methylimidazole benzimidazole 1; 2-methylimidazole 4-methylimidazole pyridine 2; 6-lutidines 3; 5-lutidines 3,4-lutidines 4-tert .-butylpyridine 2 hydroxy pyrimidine 3-pyridone 4-pyridone | 2.19 2.06 2.36 2.49 2.19 2.81 2.44 2.07 1.98 2.19 2.23 2.27 1.96 1.92 2.00 2.49 | 13.93 12.47 18.92 19.39 13.37 13.57 11.13 12.84 13.23 14.14 10.39 11.98 10.56 7.87 13.05 10.50 | 190.6 18.5 149.4 79.1 515.4 59.8 79.0 519.8 38.4 41.8 260.7 569.8 527.4 494.9 395.7 500.3 | 57.3 96.4 66.5 82.3 5.0 89.7 85.6 5.1 92.9 92.3 52.1 〈0.1 〈0.1 9.4 27.3 8.1 |
The result shows with respect to foregoing material (for example N-Methylimidazole, 3-picoline or imidazoles), uses quaternized (R=CH
3) 4-methylimidazole, 2-ethyl-4-methylimidazole (type (1) R of form
1=CH
3And C
2H
5), 3,4-lutidine (type (2) R
1=CH
3), rhodium (III) precipitation can take place in 4-tert .-butylpyridine, 2 hydroxy pyrimidine and 4-pyridone hardly.
C. the comparison of quaternary ammonium iodide stablizer and lithium iodide
Below experiment confirm quaternary ammonium iodide stablizer of the present invention not only than the easier dissolving of the disclosed stablizer in front (for example imidazoles), and they prevent that the sedimentary ability of rhodium is better than alkaline metal iodide under the temperature that improves.
(ⅰ) preparation of catalyzer storing solution
Rhodium triiodid (1.57g), water (7.4g), hydroiodic acid HI (0.92g) and acetate (34.0g) are placed Fischer Porter pipe.Seal with its purification and after charging into the 8barg carbon monoxide, be heated to then 130 ℃ 4 hours.RhI during this period
3Dissolving obtains clarifying orange solution.
(ⅱ) test method-iodide are to the stabilization of rhodium catalyst
In embodiment 1, catalyzer storing solution (2.0g) and methyl iodide (0.50g) are added to LiI(25mmol) acetate (19.15g) solution in and stirred 5 minutes.After the sampling, with this mixture at 1 crust nitrogen lower seal in Fischer Porter pipe, and be heated to 180 ℃ 22 hours, the sampling of cooling back is with the centrifugal post analysis of two duplicate samples (Rh), (H
2O) and (I
-).For embodiment 2 to 4, according to the described method of solubility experiment with amine quaternized after, use catalyzer storing solution and methyl iodide to handle according to the method for embodiment 1.
The results are shown in the following table:
Embodiment additive water
1Iodide
2The final Rh %Rh of Initial R h
(%w/w) (%w/w) (ppm) (ppm) precipitation
1 LiI 2.20 10.25 517.2 183.8 64.5
23,4-lutidine 2.09 11.92 500.6 281.3 43.8
3 4-tert .-butylpyridine 1.96 10.08 521.3 243.9 53.2
4 4-methylimidazoles 1.76 11.43 522.3 243.5 53.4
1The mean value of initial and final water concentration
2Final iodide concentration
Use the catalyst precipitation of the minimizing of selected quaternary ammonium iodide record to show that these quaternary ammonium iodides are more effective stablizers for rhodium catalyst under test conditions.
Claims (10)
1, a kind of method that in the presence of rhodium catalyst, contains the carboxylic acid of (n+1) individual carbon atom by carbon monoxide and the pure prepared in reaction that contains n carbon atom, this method comprises to be sent into alcohol and/or alcohol in the carbonylation reactor with carbon monoxide with the ester of carboxylic acid, and from carbonylation reactor, discharge carboxylic acid, it is characterized in that in reaction process, keeping the liquid reaction medium in the carbonylation reactor to contain: (a) at least one quantitative water; (b) a kind of catalyst stabilizer, it is selected from the quaternary ammonium iodide with following general formula:
Wherein R and R
1Independently be selected from hydrogen or C respectively
1-C
20Alkyl, condition are at least one R
1Not hydrogen, (d) with pure corresponding iodide derivative, (e) ester of carboxylic acid and alcohol, (f) rhodium catalyst and (g) carboxylic acid.
2,, it is characterized in that at least one R group is identical with the organic moiety of the alcohol with n carbon atom according to the method for claim 1.
3,, it is characterized in that each R according to the method for claim 1 or 2
1Group independently is selected from hydrogen or C
1-C
8Alkyl.
4,, it is characterized in that each R according to the method for claim 3
1Group independently is selected from hydrogen or C
1-C
6Alkyl.
5,, it is characterized in that catalyst stabilizer is a kind of following cationic iodide salt according to the method for claim 1
R wherein
1And R
2Be methyl, R
5Be hydrogen, R
3Be C
1-C
20Alkyl or hydrogen, R
4Be C
1-C
20Alkyl.
6,, it is characterized in that the selecting catalyst stablizer makes R according to the method for claim 5
3=C
2H
5, R
4=CH
3, or R
3=H, R
4=CH
3
7,, it is characterized in that catalyst stabilizer is a kind of following cationic iodide salt according to the method for claim 1
R wherein
6Be hydrogen or methyl, R
7Be C
1-C
4Alkyl, R
1It is methyl.
8,, it is characterized in that the selecting catalyst stablizer makes (1) R according to the method for claim 7
6=H, R
7=C
2H
5, or (2) R
6=H, R
7=t-C
4H
9, or (3) R
6And R
7=CH
3
9,, it is characterized in that in carbonylation reactor, keeping the water of 0.5-8% weight according to the method for claim 1.
10, according to the method for claim 1, it is characterized in that in carbonylation reactor, using and pure corresponding iodide derivative, corresponding amine is carried out quaternization, thereby produce described catalyst stabilizer on the spot.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90102635.2A CN1031260C (en) | 1990-05-07 | 1990-05-07 | Process for preparing carboxylic acids |
| DD90341824A DD295336A5 (en) | 1990-05-07 | 1990-06-19 | PROCESS FOR THE PREPARATION OF CARBON ACIDS |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90102635.2A CN1031260C (en) | 1990-05-07 | 1990-05-07 | Process for preparing carboxylic acids |
| DD90341824A DD295336A5 (en) | 1990-05-07 | 1990-06-19 | PROCESS FOR THE PREPARATION OF CARBON ACIDS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1056300A true CN1056300A (en) | 1991-11-20 |
| CN1031260C CN1031260C (en) | 1996-03-13 |
Family
ID=36763176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90102635.2A Expired - Fee Related CN1031260C (en) | 1990-05-07 | 1990-05-07 | Process for preparing carboxylic acids |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1031260C (en) |
| DD (1) | DD295336A5 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393689C (en) * | 2005-09-06 | 2008-06-11 | 西南化工研究设计院 | Low pressure methanol carboxylating process to synthesize acetic acid |
| CN101781247B (en) * | 2009-06-26 | 2013-01-02 | 上海海事大学 | New method for synthesizing substituted 3-quinoline carboxylic acid and analogue |
-
1990
- 1990-05-07 CN CN90102635.2A patent/CN1031260C/en not_active Expired - Fee Related
- 1990-06-19 DD DD90341824A patent/DD295336A5/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393689C (en) * | 2005-09-06 | 2008-06-11 | 西南化工研究设计院 | Low pressure methanol carboxylating process to synthesize acetic acid |
| CN101781247B (en) * | 2009-06-26 | 2013-01-02 | 上海海事大学 | New method for synthesizing substituted 3-quinoline carboxylic acid and analogue |
Also Published As
| Publication number | Publication date |
|---|---|
| DD295336A5 (en) | 1991-10-31 |
| CN1031260C (en) | 1996-03-13 |
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