CN103917551A - Process for the preparation of formic acid by reaction of carbon dioxide with hydrogen - Google Patents

Process for the preparation of formic acid by reaction of carbon dioxide with hydrogen Download PDF

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Publication number
CN103917551A
CN103917551A CN201280054841.XA CN201280054841A CN103917551A CN 103917551 A CN103917551 A CN 103917551A CN 201280054841 A CN201280054841 A CN 201280054841A CN 103917551 A CN103917551 A CN 103917551A
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phase
alkyl
formic acid
amine
tertiary amine
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T·绍布
M·帕齐基
D·M·弗莱斯
R·帕切洛
A·迈尔
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis

Abstract

The invention relates to a process for the preparation of formic acid by reaction of carbon dioxide with hydrogen.

Description

Prepare the method for formic acid by carbonic acid gas and hydrogen reaction
Describe
The present invention relates to a kind of method of preparing formic acid, wherein carbonic acid gas and hydrogen react and form formic acid-amine adduct in hydrogenation reactor under the existence of catalyzer, tertiary amine and polar solvent that contains at least one element that is selected from the periodic table of elements 8,9 or 10 families and at least one and have with at least one the phosphine part of the organic group of at least 13 carbon atoms, and described formic acid-amine adduct is thermal dissociation formic acid and corresponding tertiary amine subsequently.
The adducts of formic acid and tertiary amine can thermal dissociation become free formic acid and tertiary amine, so as the intermediate of preparing in formic acid.
Formic acid is important multipurpose product.Formic acid for example in the production of animal-feed for acidifying, as sanitas, as sterilizing agent, as the auxiliary agent in fabric and leather industry, with the deicing for aircraft and railway of the mixture of its salt, and in chemical industry, be used as synthesis unit.
The adducts of described formic acid and tertiary amine can be prepared by variety of way, for example (i) is by the direct reaction of tertiary amine and formic acid, (ii) under the existence of tertiary amine, be hydrolyzed into formic acid by methyl-formiate, (iii) under the existence of tertiary amine by the catalytic hydration of carbon monoxide, or (iv) carbonic acid gas tertiary amine exist under be hydrogenated to formic acid.It is that carbonic acid gas can obtain in a large number and is being flexibly aspect its source that the catalytic hydrogenation of rear a kind of carbonic acid gas has special advantage.
WO2010/149507 has described a kind of method of preparing formic acid, wherein carbonic acid gas hydrogenation under the existence of tertiary amine, transition-metal catalyst and high bp polar solvent, and described high bp polar solvent has the static factor and is>=200*10 -30cm, for example, be ethylene glycol, glycol ether, triglycol, polyoxyethylene glycol, 1,3-PD, 2-methyl isophthalic acid, ammediol, BDO, dipropylene glycol, 1,5-PD, 1,6-hexylene glycol and glycerine.The reaction mixture obtaining contains formic acid-amine adduct, tertiary amine, high bp polar solvent and catalyzer.Reaction mixture is processed according to following steps according to WO2010/149507:
1) reaction mixture is separated, and obtains the upper strata phase that contains tertiary amine and catalyzer and the lower floor's phase that contains formic acid-amine adduct, high bp polar solvent and relict catalyst; Upper strata is recycled in hydrogenation mutually,
2), by tertiary amine extraction lower floor phase, obtain the extract that contains tertiary amine and relict catalyst and the raffinate that contains high boiling point polarity and formic acid-amine adduct; Extract is recycled in hydrogenation,
3) by raffinate thermal dissociation in distillation tower, obtain the overhead product that contains formic acid, and mixture at the bottom of the tower that contains free uncle amine and high bp polar solvent, and high bp polar solvent is recycled in hydrogenation.
Although the shortcoming of method is through being separated (step 1) described in WO2010/149507) and extraction (step 2)), but removing of catalyzer is incomplete, and the catalyzer trace substance existing in raffinate in distillation tower in step 3) in thermal dissociation process in can be according to the following formula catalysis formic acid-amine adduct be dissociated into again carbonic acid gas and hydrogen and tertiary amine:
Dissociation causes the productive rate of the adducts of formic acid and tertiary amine significantly to reduce again, and then the productive rate of formic acid target product reduces.
Another shortcoming is that, in the thermal dissociation process at formic acid-amine adduct in distillation tower, esterification can occur for the formic acid forming and high bp polar solvent (glycol and polyvalent alcohol).This causes the productive rate of formic acid target product further to reduce.
The object of this invention is to provide a kind of hydrogenation by carbonic acid gas and prepare the method for formic acid, and can substantially fully remove catalyzer.Novel method should have the shortcoming (if any) of prior art in the degree obviously reducing, and can obtain concentrated formic acid with high yield and high purity.In addition, this method should be to carry out than the simpler mode of method described in prior art, more specifically carries out the more simple process design of aftertreatment, simpler operation stage in the discharging to from hydrogenation reactor, reduces aspect the operation stage or simpler equipment of number.In addition, this method also should be carried out with low-down energy consumption.
This object realizes by a kind of method of preparing formic acid, comprises the following steps:
(a) make reaction mixture (Rg) in hydrogenation reactor, under the existence of at least one transition metal complex as catalyzer, carry out homogeneous catalytic reaction, wherein reaction mixture (Rg) contains carbonic acid gas, hydrogen, tertiary amine that at least one is selected from the polar solvent of methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 2-methyl isophthalic acid-the third alcohol and water and has general formula (A1):
NR 1R 2R 3 (A1),
Wherein
Radicals R 1, R 2, R 3branching or branching, acyclic or ring-type, aliphatic, araliphatic or aromatics group independently of one another, it has 1-16 carbon atom in each case, wherein each carbon atom also can be selected from independently of one another-O-and the assorted group of >N-replace, and two or all three groups also can be connected to each other and form the chain that contains in each case at least four atoms
Described transition metal complex contains at least one element that is selected from the periodic table of elements 8,9 and 10 families and at least one and has the phosphine part of the organic group of at least 13 carbon atoms with at least one,
Optionally, after adding water, obtain the two-phase hydrogenated mixture (H) that contains following component:
Upper strata phase (U1), it contains catalyzer and tertiary amine (A1), and
Lower floor's phase (L1), formic acid-amine adduct that it contains at least one polar solvent, relict catalyst and has general formula (A2):
NR 1R 2R 3*x i HCOOH (A2)
Wherein
X i0.4-5, and
R 1, R 2, R 3separately as defined above,
(b) hydrogenated mixture (H) obtaining in step (a) is processed according to one of following steps:
(b1) hydrogenated mixture (H) obtaining is separated into upper strata phase (U1) and lower floor's phase (L1) in first-phase tripping device in step (a),
Or
(b2) in extraction cells, extract from hydrogenated mixture (H) extraction agent that contains tertiary amine (A1) obtaining step (a), obtain:
Raffinate (R1), it contains formic acid-amine adduct (A2) and at least one polar solvent, and
Extract (E1), it contains tertiary amine (A1) and catalyzer,
Or
(b3) hydrogenated mixture (H) obtaining is separated into upper strata phase (U1) and lower floor's phase (L1) in first-phase tripping device in step (a), and in extraction cells, use the extraction agent that contains tertiary amine (A1) from lower floor's phase (L1) extracting catalyst resistates, obtain:
Raffinate (R2), it contains formic acid-amine adduct (A2) and at least one polar solvent, and
Extract (E2), it contains tertiary amine (A1) and relict catalyst,
(c) in the first water distilling apparatus from lower floor's phase (L1), from raffinate (R1) or from raffinate (R2) separating at least one polar solvent, obtain:
Overhead product (D1), it contains at least one polar solvent, and by this solvent cycle in the hydrogenation reactor in step (a), and
Two-phase bottom mixture (B1), it contains:
Upper strata phase (U2), it contains tertiary amine (A1), and
Lower floor's phase (L2), it contains formic acid-amine adduct (A2),
(d) optionally by the bottom mixture (B1) obtaining in step (c) in second-phase tripping device by the processing that is separated, obtain upper strata phase (U2) and lower floor's phase (L2),
(e) formic acid-amine adduct (A2) existing and/or formic acid-amine adduct (A2) dissociation in thermal dissociation unit that may exist are obtained to corresponding tertiary amine (A1) and formic acid in lower floor's phase (L2) in bottom mixture (B1), described tertiary amine (A1) is recycled in the hydrogenation reactor in step (a), formic acid is discharged from thermal dissociation unit.
Discovery now can obtain formic acid with high yield by the inventive method.Compared with prior art, the inventive method can more effectively be removed the transition metal complex as catalyzer, and is recycled in the hydrogenation reactor in step (a).This has prevented the dissociation again of formic acid-amine adduct (A2) very significantly, and this makes the gain in yield of formic acid.Remove polar solvent used according to the present invention, prevented in addition the formic acid generation esterification that obtains in step (e) in thermal dissociation unit, this has also improved formic acid productive rate.In addition, be surprised to find now, compared with the high bp polar solvent using in WO2010/149507, use polar solvent of the present invention can be increased in formic acid-amine adduct (A2) concentration in the hydrogenated mixture (H) obtaining in step (a).This makes to use less reactor, and then saves cost.
Term " step " and " operation stage " use as synonym in this article.
prepare formic acid-amine adduct (A2); Operation stage (a)
In the methods of the invention, in operation stage (a), in hydrogenation reactor, make reaction mixture (Rg) transform, reaction mixture (Rg) contains carbonic acid gas, hydrogen, at least one is selected from the polar solvent of methyl alcohol, ethanol, 1-propyl alcohol, n-butyl alcohol, 2-butanols, 2-methyl isophthalic acid-the third alcohol and water, and has the tertiary amine of general formula (A1).This reaction is to carry out under the existence of catalyzer.Catalyzer used is at least one transition metal complex, and it contains at least one element that is selected from the periodic table of elements 8,9 or 10 families and at least one and have the phosphine part of at least 13 carbon atoms.
The carbonic acid gas using in operation stage (a) can be solid, liquid or gaseous state.Also can use the available gaseous mixture that contains carbonic acid gas in technical scale, as long as they do not basically contain carbon monoxide (the volume ratio <1% of CO).The hydrogen using in will the carbonic acid gas hydrogenation in operation stage (a) is generally gaseous state.Carbonic acid gas and hydrogen also can contain rare gas element, for example nitrogen or rare gas.But, their content advantageously below 10 % by mole, the total amount meter of the carbonic acid gas based in hydrogenation reactor and hydrogen.Although also can tolerate in some cases larger consumption, so general more high pressure in reactor of needing to use, this so need further compression energy.
Carbonic acid gas and hydrogen can be used as independent material stream and add operation stage (a).Also can in operation stage (a), use the mixture that contains carbonic acid gas and hydrogen.
In the methods of the invention, in operation stage (a), in the hydrogenation of carbonic acid gas, use at least one tertiary amine (A1).In the present invention, " tertiary amine (A1) " is interpreted as and represents a kind of (a kind) tertiary amine (A1), or the mixture of two or more tertiary amines (A1).
The tertiary amine (A1) using in the methods of the invention is preferably selected to make or it selects to make the hydrogenated mixture (H) of acquisition in operation stage (a) together with polar solvent coupling, optionally adding after water, it is two-phase at least.Hydrogenated mixture (H) contains: upper strata phase (U1), and it contains catalyzer and tertiary amine (A1); With lower floor's phase (L1), it contains at least one polar solvent, relict catalyst and formic acid-amine adduct (A2).
Tertiary amine (A1) is that enrichment is present in upper strata phase (U1), this means that upper strata phase (U1) contains most tertiary amine (A1)." enrichment " mentioned about tertiary amine (A1) or " major part " should be interpreted as in the present invention and represent that based at liquid phase, i.e. the gross weight meter of the free uncle amine (A1) in upper strata phase (U1) and the lower floor's phase (L1) in hydrogenated mixture (H), the part by weight of the free uncle amine (A1) in upper strata phase (U1) is greater than 50%.
Free uncle amine (A1) is interpreted as that expression is not with the tertiary amine (A1) of formic acid-amine adduct (A2) form bonding.
Preferably, the part by weight of the free uncle amine (A1) in upper strata phase (U1) is to be greater than 70%, especially be greater than 90%, in each case the gross weight meter of the free uncle amine (A1) in upper strata phase (U1) and the lower floor's phase (L1) based in hydrogenated mixture (H).
Conventionally by simple experimental selection tertiary amine (A1), wherein under the processing condition of operation stage (a), detect by experiment phase behavior and the solubleness of tertiary amine (A1) in liquid phase (upper strata phase (U1) and lower floor's phase (L1)).Non-polar solvent can be added in addition to tertiary amine (A1), for example aliphatic series, aromatics or araliphatic solvent.Preferred non-polar solvent is for example octane, toluene and/or dimethylbenzene (o-Xylol, m-xylene, p-Xylol).
Preferably there is the tertiary amine of general formula (A1), wherein radicals R 1, R 2, R 3identical or different, and be branching or branching, acyclic or ring-type, aliphatic, araliphatic or aromatics group independently of one another, it has 1-16 carbon atom in each case, preferably 1-12 carbon atom, wherein each carbon atom also can be selected from independently of one another-O-and the assorted group of >N-replace, and two or all three groups also can be connected to each other and form the chain that contains in each case at least four atoms.In an especially preferred embodiment, use the tertiary amine with general formula (A1), prerequisite is that the sum of carbon atom is at least 9.
The example of suitable tertiary amine (A1) is:
Three n-propyl amine, three-n-butylamine, three-n-pentyl amine, three-n-hexyl amine, three-n-heptyl amine, three-n-octylamine, three-n-nonyl amine, three-positive decyl amine, 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.
Dimethyl decyl amine, dimethyl lauryl amine, dimethyl tetradecylamine, ethyl two (2-propyl group) amine, dioctyl methylamine, dihexyl methylamine.
Three cyclopentyl amine, thricyclohexyl amine, three cycloheptylaminos, three ring octyl amines, and their derivative being replaced by one or more methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl or 2-methyl-2-propyl.
Dimethylcyclohexylam,ne, methyl bicyclic hexyl amine, diethyl cyclo-hexylamine, ethyl dicyclohexylamine, dimethylcyclopentyl amine, methyl bicyclic amylamine.
Triphenylamine, methyldiphenyl base amine, ethyl diphenylamine, propyl group diphenylamine, butyl diphenyl amine, 2-ethylhexyl diphenylamine, 3,5-dimethylphenyl amine, diethyl phenyl amine, dipropyl phenyl amine, dibutyl phenyl amine, two (2-ethylhexyl) phenyl amine, tribenzyl amine, methyl dibenzyl amine, ethyl dibenzyl amine, and their derivative being replaced by one or more methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl or 2-methyl-2-propyl.
N-C 1-C 12-Alkylpiperidine, N, N-bis--C 1-C 12-alkylpiperazine, N-C 1-C 12-alkyl pyrrolidone, N-C 1-C 12-alkyl imidazole, and their derivative being replaced by one or more methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl or 2-methyl-2-propyl.
1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (" DBU "), 1,4-diazabicyclo [2.2.2] octane (" DABCO "), N-methyl-8-azabicyclo [3.2.1] octane (" tropane "), N-methyl-9-azabicyclo [3.3.1] nonane (" granatane "), 1-azabicyclo [2.2.2] octane (" rubane ").
Also can use in the methods of the invention the mixture of the different tertiary amines (A1) of two or more.
Particularly preferably, the tertiary amine (A1) using is in the methods of the invention such amine, wherein radicals R 1, R 2, R 3be selected from independently of one another C 1-C 12alkyl, C 5-C 8cycloalkyl, benzyl and phenyl.
Particularly preferably, the tertiary amine (A1) using is in the methods of the invention saturated amine, only contains the amine of singly-bound.
Very particularly preferably, the tertiary amine using is in the methods of the invention the amine of general formula (A1), wherein radicals R 1, R 2, R 3be selected from independently of one another C 5-C 8alkyl, especially three n-pentyl amine, three n-hexyl amine, three n-heptyl amine, three n-octylamine, dimethylcyclohexylam,ne, methyl bicyclic hexyl amine, dioctyl methylamine and dimethyl decyl amine.
In one embodiment of the invention, use the tertiary amine of a kind of (a kind) general formula (A1).
More particularly, tertiary amine used is the amine of general formula (A1), wherein radicals R 1, R 2, R 3be selected from independently of one another C 5alkyl and C 6alkyl.The tertiary amine of the general formula (A1) most preferably, using is in the methods of the invention three n-hexyl amine.
Preferably, tertiary amine (A1) is to exist with liquid form in all operation stages of the inventive method.But this is not indispensable.If tertiary amine is at least dissolved in suitable solvent, this is also enough.Suitable solvent is to be chemically inert those solvents for the thermal dissociation of the hydrogenation of carbonic acid gas in principle, and these solvents also can dissolve tertiary amine (A1) and catalyzer well, but be difficult to dissolve polar solvent and formic acid-amine adduct (A2).So operable solvent comprises chemically inert non-polar solvent in principle, for example aliphatic series, aromatics or araliphatic hydrocarbon, for example octane and higher alkane, toluene and dimethylbenzene.
In the methods of the invention, in operation stage (a), use at least one polar solvent in the hydrogenation of carbonic acid gas, it is selected from methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 2-methyl isophthalic acid-the third alcohol and water.
In the present invention, " polar solvent " is interpreted as the mixture that represents a kind of (1) polar solvent or two or more polar solvents.
Polar solvent preferably selects to make the hydrogenated mixture (H) obtaining in operation stage (a), optionally after adding water, is two-phase at least.Polar solvent should be present in lower floor's phase (L1) in enrichment, that is, lower floor's phase (L1) should contain most polar solvent." enrichment " mentioned about polar solvent or " major part " should be interpreted as the gross weight meter that represents the polar solvent based in liquid phase (upper strata phase (U1) and lower floor's phase (L1)) in the present invention, and the part by weight of the polar solvent in lower floor's phase (L1) is greater than 50%.
Preferably, the part by weight of the polar solvent in lower floor's phase (L1) is to be greater than 70%, is especially greater than 90%, in each case the gross weight meter of the polar solvent based in upper strata phase (U1) and lower floor's phase (L1).
Meet the polar solvent of above-mentioned standard conventionally by simple experimental selection, wherein under the processing condition of operation stage (a), detect by experiment phase behavior and the solubleness of polar solvent in liquid phase (upper strata phase (U1) and lower floor's phase (L1)).
Polar solvent can be a kind of pure polar solvent, or the mixture of two or more polar solvents.
In an embodiment of the inventive method, in step (a), first obtain single-phase hydrogenated mixture, convert it into the hydrogenated mixture (H) of two-phase by adding water.
In another embodiment of the inventive method, in step (a), directly obtain the hydrogenated mixture (H) of two-phase.The two-phase hydrogenated mixture (H) obtaining by this embodiment can directly add according in the processing of step (b).Also can before the further processing of step (b), add in addition water to two-phase hydrogenated mixture (H).This can cause partition ratio P kincrease.
In a further preferred embodiment, polar solvent used is water, methyl alcohol, or the mixture of water and methyl alcohol.
The acid amides of glycol and manthanoate thereof, polyvalent alcohol and manthanoate thereof, sulfone, sulfoxide and open chain or ring-type is not preferably used as polar solvent.In a preferred embodiment, in reaction mixture (Rg), there are not these polar solvents.
Generally 0.5-30 for the mol ratio between polar solvent or solvent mixture and the tertiary amine used (A1) of the operation stage (a) of the inventive method, preferred 1-20.
In the operation stage (a) of the inventive method, for the hydrogenation of carbonic acid gas, contain at least one element that is selected from the periodic table of elements 8,9 and 10 families (IUPAC name) and at least one as the transition metal complex of catalyzer and there is the phosphine part of the organic group of at least 13 carbon atoms with at least one.The element of the periodic table of elements 8,9 and 10 families contains Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt.In operation stage (a), catalyzer used can be a kind of (1) transition metal complex, or the mixture of two or more transition metal complexes.In the present invention, " transition metal complex " represents a kind of (1) transition metal complex, or the mixture of two or more transition metal complexes.
Preferably, contain at least one and be selected from the element of Ru, Rh, Pd, Os, Ir and Pt as the transition metal complex of catalyzer, particularly preferably at least one is selected from the element of Ru, Rh and Pd.Very particularly preferably, transition metal complex contains Ru.
The transition metal complex that is preferably used as catalyzer contains at least one phosphine part, described phosphine part has the organic group of 13-30 carbon atom with at least one, preferably there is 14-26 carbon atom, more preferably there is 14-22 carbon atom, especially preferably there is 15-22 carbon atom, especially have 16-20 carbon atom, wherein said organic group is connected with the phosphorus atom of phosphine part.
In a further preferred embodiment, contain at least one and have the bidentate phosphine ligands of general formula (I) as the transition metal complex of catalyzer:
Wherein
R 11, R 12, R 13, R 14unsubstituted independently of one another or at least mono-substituted-C 13-C 30alkyl ,-(phenyl)-(C 7-C 24alkyl) ,-(phenyl)-(C 4-C 24alkyl) 2,-(phenyl)-(C 3-C 24alkyl) 3,-(phenyl)-(O-C 7-C 24alkyl) ,-(phenyl)-(O-C 4-C 24alkyl) 2,-(phenyl)-(O-C 3-C 24alkyl) 3,-(cyclohexyl)-(C 7-C 24alkyl) ,-(cyclohexyl)-(C 4-C 24alkyl) 2,-(cyclohexyl)-(C 3-C 24alkyl) 3,-(cyclohexyl)-(O-C 7-C 24alkyl) ,-(cyclohexyl)-(O-C 4-C 24alkyl) 2or-(cyclohexyl)-(O-C 3-C 24alkyl) 3, wherein substituting group is Xuan Zi – F ,-Cl ,-Br ,-OH, – OR a,-COOH ,-COOR a,-OCOR a,-CN ,-NH 2,-N (R a) 2with-NHR a;
R 15, R 16be independently of one another hydrogen or-C 1-C 4alkyl, or form unsubstituted or at least mono-substituted phenyl or cyclohexyl ring together with the carbon atom connecting with them, wherein substituting group is Xuan Zi – OCOR a,-OCOCF 3,-OSO 2r a,-OSO 2cF 3,-CN ,-OH ,-OR a,-N (R a) 2,-NHR awith-C 1-C 4alkyl;
R abe-C 1-C 4alkyl, and
N, m are 0,1 or 2 independently of one another.
About R 11, R 12, R 13and R 14group Ti is Dao – C 13-C 30alkyl represents the alkyl with 13-30 carbon atom of straight chain or branching in the present invention.These groups comprise and are selected from following straight chain or the alkyl of branching: tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl and triacontyl.-C 13-C 30alkyl is preferably nonbranched, is straight chain.
Preferred alkyl (C 13-C 30alkyl) be the alkyl (– C with 14-26 carbon atom of straight chain or branching 14-C 26alkyl), more preferably there is 14-22 carbon atom (– C 14-C 22alkyl), especially preferably there is 15-22 carbon atom (– C 15-C 22alkyl) and especially there is 16-20 carbon atom (– C 16-C 20alkyl), preferably straight chained alkyl.
About R 11, R 12, R 13and R 14group Ti is Dao – (phenyl)-(C 7-C 24alkyl) represent to have in the present invention the group of general formula (II), they are connected with the phosphorus atom of phosphine part (I) via phenyl ring.-C 7-C 24alkyl can be connected with phenyl ring on 2,3 or 4, and can be straight chain or branching.Phenyl ring is preferably without except-C 7-C 24any other substituting group outside alkyl.-C 7-C 24alkyl can be unsubstituted or at least mono-substituted.-C 7-C 24alkyl is straight chain and unsubstituted preferably.
Preferred – (phenyl)-(C 7-C 24alkyl) alkyl in group is alkyl (Ji ， – (phenyl)-(C with 7-18 carbon atom of straight chain or branching 7-C 18alkyl)).Particularly preferably be alkyl (Ji ， – (phenyl)-(C with 7-12 carbon atom 7-C 12alkyl)).
About R 11, R 12, R 13and R 14group Ti is Dao – (phenyl)-(O-C 6-C 24alkyl) represent to have in the present invention the group of general formula (II), they are connected with the phosphorus atom of phosphine part (I) via phenyl ring.-O-C 7-C 24alkyl can be connected with phenyl ring via oxygen on 2,3 or 4, and can be straight chain or branching.Phenyl ring is preferably without except-C 7-C 24any other substituting group outside alkyl.-C 7-C 24alkyl can be unsubstituted or at least mono-substituted.-C 7-C 24alkyl is straight chain and unsubstituted preferably.Preferred – (phenyl)-(C 7-C 24alkyl) alkyl in group is alkyl (Ji ， – (phenyl)-(C with 7-18 carbon atom of straight chain or branching 7-C 18alkyl)).Particularly preferably be alkyl (Ji ， – (phenyl)-(C with 7-12 carbon atom 7-C 12alkyl)).
About R 11, R 12, R 13and R 14group Ti is Dao – (cyclohexyl)-(C 7-C 24alkyl) represent to have in the present invention the group of general formula (IV), they are connected with the phosphorus atom of phosphine part (I) via cyclohexyl ring.-C 7-C 24alkyl can be connected with cyclohexyl ring on 2,3 or 4, and can be straight chain or branching.Cyclohexyl ring is preferably without except-C 7-C 24any other substituting group outside alkyl.-C 7-C 24alkyl can be unsubstituted or at least mono-substituted.-C 7-C 24alkyl is straight chain and unsubstituted preferably.Preferred – (cyclohexyl)-(C 7-C 24alkyl) alkyl in group is alkyl (Ji ， – (cyclohexyl)-(C with 7-18 carbon atom of straight chain or branching 7-C 18alkyl)).Particularly preferably be alkyl (Ji ， – (cyclohexyl)-(C with 7-12 carbon atom 7-C 12alkyl)).
About R 11, R 12, R 13and R 14group Ti is Dao – (cyclohexyl)-(O-C 7-C 24alkyl) represent to have in the present invention the group of logical formula V, they are via cyclohexyl ring (wave key; 1) be connected with the phosphorus atom of phosphine part (I).-O-C 7-C 24alkyl is connected with cyclohexyl ring on 2,3 or 4 via Sauerstoffatom, and can be straight chain or branching.Cyclohexyl ring is preferably without except-C 7-C 24any other substituting group outside alkyl.-O-C 7-C 24alkyl can be unsubstituted or at least mono-substituted.-C 7-C 24alkyl is straight chain and unsubstituted preferably.Preferred – (cyclohexyl)-(O-C 7-C 24alkyl) alkyl in group is alkyl (Ji ， – (cyclohexyl)-(O-C with 7-18 carbon atom of straight chain or branching 7-C 18alkyl)).Particularly preferably be alkyl (Ji ， – (cyclohexyl)-(O-C with 7-12 carbon atom 7-C 12alkyl)).
Wave key table in formula II, III, IV and V shows with phosphine part (I) phosphorus atom and is connected the phenyl ring of (1) or the key of cyclohexyl ring.
In formula II, III, IV and V ,-C 7-C 24alkyl or-O-C 7-C 24alkyl is preferably connected with phenyl ring or cyclohexyl ring in 4-position.Phenyl ring or cyclohexyl ring be Dai You – C on 4-position preferably 7-C 18alkyl or-O-C 7-C 18alkyl.Phenyl ring or cyclohexyl ring be Dai You – C on 4-position especially preferably 7-C 12alkyl or-O-C 7-C 12alkyl.
About R 11, R 12, R 13and R 14group Ti is Dao – (phenyl)-(C 4-C 24alkyl) 2represent in the present invention the group being connected with the phosphorus atom of phosphine part (I) via phenyl ring, and phenyl ring is with Liang – C 4-C 24alkyl.– C 4-C 24alkyl can be in (2,3), and (2,4), (2,5), (2,6), (3,4) or (3,5) position is connected with phenyl ring, preferably (3,5) position.– C 4-C 24alkyl can be straight chain or branching.Phenyl ring is preferably without except two-C 4-C 24any other substituting group outside alkyl.-C 4-C 24alkyl can be unsubstituted or at least mono-substituted.-C 4-C 24alkyl is preferably unsubstituted.
Preferred – (phenyl)-(C 4-C 24alkyl) 2in alkyl be alkyl (Ji ， – (phenyl)-(C with 4-18 carbon atom of straight chain or branching 4-C 18alkyl) 2).Particularly preferably be alkyl (Ji ， – (phenyl)-(C with 4-12 carbon atom 4-C 12alkyl) 2), especially there is alkyl (Ji ， – (phenyl)-(C of 4-6 carbon atom 4-C 6alkyl) 2).The example of suitable alkyl is the tertiary butyl.
About R 11, R 12, R 13and R 14group Ti is Dao – (phenyl)-(– O-C 4-C 24alkyl) 2represent in the present invention the group being connected with the phosphorus atom of phosphine part (I) via phenyl ring, and phenyl ring is with Liang – O-C 4-C 24alkyl.– O – C 4-C 24alkyl can be in (2,3), (2,4), (2,5), (2,6), (3,4) or (3,5) position are connected with phenyl ring, preferred (3,5).– O-C 4-C 24alkyl can be straight chain or branching.Phenyl ring is preferably without except two-O-C 4-C 24any other substituting group outside alkyl.-O-C 4-C 24alkyl can be unsubstituted or at least mono-substituted.-O-C 4-C 24alkyl is preferably unsubstituted.
Preferred – (phenyl)-(O-C 4-C 24alkyl) 2in alkyl be alkyl (Ji ， – (phenyl)-(O-C with 4-18 carbon atom of straight chain or branching 4-C 18alkyl) 2).Particularly preferably be alkyl (Ji ， – (phenyl)-(O-C with 4-12 carbon atom 4-C 12alkyl) 2), especially there is alkyl (Ji ， – (phenyl)-(O-C of 4-6 carbon atom 4-C 6alkyl) 2).The example of suitable-O-alkyl is tert.-butoxy.
Dui Yu – (cyclohexyl)-(C 4-C 24alkyl) 2he – (cyclohexyl)-(O-C 4-C 24alkyl) 2, be correspondingly suitable for Guan Yu – (phenyl)-(C above 4-C 24alkyl) 2with-(phenyl)-(O-C 4-C 24alkyl) 2described details and preferable range.
-(phenyl)-(C 3-C 24alkyl) 3,-(phenyl)-(O-C 3-C 24alkyl) 3,-(cyclohexyl)-(C 3-C 24alkyl) 3,-(cyclohexyl)-(O-C 3-C 24alkyl) and-(cyclohexyl)-(O-C 3-C 24alkyl) 3be interpreted as and be illustrated in 1 phenyl ring and cyclohexyl ring being connected with the phosphorus atom of phosphine part (I), described phenyl ring or cyclohexyl ring are with San – C 3-C 24alkyl or San – O-C 3-C 24alkyl.-C 3-C 24alkyl or-O-C 3-C 24alkyl can be in (2,3,4), (2,3,5), (2,4,6), (3,4,5) or (2,3,6) position are connected with phenyl ring or cyclohexyl ring.
Particularly preferably be phosphine part (I), wherein R 11, R 12, R 13and R 14group is identical.
Particularly preferably be in addition the phosphine part of general formula (I), wherein
R 11, R 12, R 13, R 14unsubstituted independently of one another or at least mono-substituted-C 13-C 30alkyl ,-(phenyl)-(C 7-C 24alkyl) ,-(phenyl)-(C 4-C 24alkyl) 2,-(phenyl)-(O-C 7-C 24alkyl) ,-(phenyl)-(O-C 4-C 24alkyl) 2,-(cyclohexyl)-(C 7-C 24alkyl) ,-(cyclohexyl)-(C 4-C 24alkyl) 2,-(cyclohexyl)-(O-C 7-C 24alkyl) or-(cyclohexyl)-(O-C 4-C 24alkyl) 2, wherein substituting group is Xuan Zi – F ,-Cl ,-Br ,-OH, – OR a,-COOH ,-COOR a,-OCOR a,-CN ,-NH 2,-N (R a) 2with-NHR a;
R 15, R 16be independently of one another hydrogen or-C 1-C 4alkyl, or form unsubstituted or at least mono-substituted phenyl ring or cyclohexyl ring together with the carbon atom connecting with them, wherein substituting group is Xuan Zi – OCOR a,-OCOCF 3,-OSO 2r a,-OSO 2cF 3,-CN ,-OH ,-OR a,-N (R a) 2,-NHR awith-C 1-C 4alkyl;
R abe-C 1-C 4alkyl, and
N, m are 0,1 or 2, are all preferably 0 or 1, are especially all 0.
Particularly preferably be in addition the phosphine part of general formula (I), wherein
R 11, R 12, R 13, R 14unsubstituted independently of one another or at least mono-substituted-C 13-C 30alkyl ,-(phenyl)-(C 7-C 24alkyl) ,-(phenyl)-(O-C 7-C 24alkyl) ,-(cyclohexyl)-(C 7-C 24alkyl) or-(cyclohexyl)-(O-C 7-C 24alkyl), wherein substituting group is Xuan Zi – F ,-Cl ,-Br ,-OH, – OR a,-COOH ,-COOR a,-OCOR a,-CN ,-NH 2,-N (R a) 2with-NHR a;
R 15, R 16be independently of one another hydrogen or-C 1-C 4alkyl, or form unsubstituted or at least mono-substituted phenyl ring or cyclohexyl ring together with the carbon atom connecting with them, wherein substituting group is be selected from-OCOR a,-OCOCF 3,-OSO 2r a,-OSO 2cF 3,-CN ,-OH ,-OR a,-N (R a) 2,-NHR awith-C 1-C 4alkyl;
R abe-C 1-C 4alkyl, and
N, m are 0,1 or 2, are all preferably 0 or 1, are especially all 0.
Particularly preferably be in addition the phosphine part of general formula (I), wherein
R 11, R 12, R 13, R 14unsubstituted independently of one another or at least mono-substituted-C 13-C 30alkyl, wherein substituting group is Xuan Zi – F ,-Cl ,-Br ,-OH, – OR a,-COOH ,-COOR a,-OCOR a,-CN ,-NH 2,-N (R a) 2with-NHR a;
R 15, R 16be independently of one another hydrogen or-C 1-C 4alkyl,
R abe-C 1-C 4alkyl, and
N, m are 0.
The more preferably phosphine part of general formula (I), wherein
R 11, R 12, R 13, R 14unsubstituted-C independently of one another 13-C 30alkyl;
R 15, R 16all hydrogen, and
N, m are 0.
The most preferably phosphine part of general formula (I), wherein
R 11, R 12, R 13, R 14all unsubstituted-C 12-C 20alkyl, preferred unsubstituted C 12-C 18alkyl and more preferably C 13-C 18alkyl;
R 15, R 16all hydrogen, and
N, m are 0.
Particularly preferred bidentate phosphine ligands (I) is selected from 1,2-bis-(two tetradecyl phosphino-) ethane, 1,2-bis-(two pentadecyl phosphino-) ethane, 1,2-bis-(double hexadecyl phosphino-) ethane and 1,2-bis-(two octadecyl phosphino-) ethane.
Wherein n and m are that 0 general formula (I) phosphine part can for example pass through 1 of general formula (VIII), 2-bis-(dichlorophosphinyl) ethane compounds reacts to obtain according to following reaction formula 1 (RE1) with the grignard compound of general formula (IX), wherein the R in formula (IX) and (I) 17as above for R 11, R 12, R 13, R 14institute defines, and preferable range is also correspondingly suitable for.For the R in formula (VIII) 15and R 16, be correspondingly suitable for definition and preferable range for phosphine part (I).
1,2-bis-(dichlorophosphinyl) ethane and butyl grignard compound general reacts can be referring to Jack Lewis, etc., Journal of Organometallic Chemistry, 433 (1992), 135 – 139.
Wherein n and m are 0 and R wherein 11, R 12, R 13, R 14not replace or at least mono-substituted-C independently of one another 12-C 30those general formulas (I) phosphine part of alkyl for example can pass through 1 of general formula (X) in addition, 2-bis-(dihydro phosphino-) ethane compounds reacts to obtain according to following reaction formula 2 (RE2) with the terminal olefine of general formula (XI), wherein for the R in formula (XI) and (I) 18, be correspondingly suitable for above-mentioned for R 11, R 12, R 13, R 14definition and preferable range.For the R in formula (X) 15and R 16, be correspondingly suitable for definition and preferable range for phosphine part (I).
1,2-bis-(dihydro phosphino-) ethane and terminal olefine (CH 2=CHCH 2-OCH 3) general reaction can be referring to Warren K.Miller etc., Inorganic Chemistry2002,41,5453 – 5465.
Wherein n and m are that those general formulas (I) phosphine part of 0 for example can react to obtain according to following reaction formula 3 (RE3) with the alkine compounds of general formula (XIII) by single phosphine compound of general formula (XII) in addition, the wherein R in formula (XII) and (I) 17as above for R 11, R 12, R 13, R 14institute defines, and is also correspondingly suitable for preferable range.For the R in formula (XIII) 15and R 16, be correspondingly suitable for definition and preferable range for phosphine part (I).
Single phosphine compound and alkine compounds general reacts can be referring to US3, and 681,481.
In an especially preferred embodiment, the bidentate phosphine ligands that contains one (a kind) general formula (I) as the transition metal complex of catalyzer and and at least one there is the monodentate monophosphorus ligand of the organic group of 1-20 carbon atom with at least one.
" number of teeth " represents that phosphine part can form the number from one or more phosphorus atom of phosphine part to the key of central transition metal atom in the present invention.In other words, monodentate phosphine ligand can form a key from phosphorus atom to central transition metal atom; Bidentate phosphine ligands can form two keys from phosphorus atom to central transition metal atom.
Preferred monodentate monophosphorus ligand is the monophosphorus ligand of general formula (Ia):
PR 19R 20R 21 (Ia)
Wherein
R 19, R 20, R 21be independently of one another unsubstituted or at least Dan replace – C 1-C 20alkyl ,-phenyl ,-benzyl, – cyclohexyl Huo – (CH 2)-cyclohexyl,
Wherein substituting group is Xuan Zi – C 1-C 20alkyl ,-F ,-Cl ,-Br ,-OH, – OR a,-COOH ,-COOR a,-OCOR a,-CN ,-NH 2,-N (R a) 2with-NHR a;
R abe-C 1-C 4alkyl.
– C 1-C 20alkyl can be straight chain or branching.For R 19, R 20, R 21suitable group for example comprises: methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 1-(2-methyl) propyl group, 2-(2-methyl) propyl group, 1-amyl group, 1-hexyl, 1-heptyl, 1-octyl group, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl, 1-octadecyl, 1-nonadecyl, 1-eicosyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group, methylcyclopentyl, methylcyclohexyl, 1-(2-methyl) amyl group, 1-(2-ethyl) hexyl, 1-(2-propyl group) heptyl and norcamphyl.
Preferably monodentate monophosphorus ligand (Ia), wherein three R 19, R 20, R 21group is identical.Particularly preferably be and there is formula P (n-C qh 2q+1) 3monodentate monophosphorus ligand (Ia), wherein q is 1-20, especially wherein q is 1-12.Most preferably, monodentate monophosphorus ligand (Ia) is to be selected from three-normal-butyl phosphine, three-n-hexyl phosphine, and three-n-octyl phosphine, three-positive decyl phosphine and three-dodecyl phosphine.
Transition metal complex as catalyzer preferably contains a kind of bidentate phosphine ligands (I) and two kinds of monodentate monophosphorus ligands (Ia), is wherein correspondingly suitable for definition and preferable range for bidentate phosphine ligands (I) and monodentate monophosphorus ligand (Ia).
Transition metal complex can contain other part in addition, for example, comprise hydride, fluorochemical, muriate, bromide, iodide, formate, acetate, propionic salt, carboxylate salt, acetyl pyruvate, carbonyl, DMSO, oxyhydroxide, trialkylamine, alkoxide.
Transition metal complex as catalyzer can directly be prepared with its activity form, or from conventional standard complex preparation, for example [M (p-cumene) Cl 2] 2, [M (benzene) Cl 2] n, [M (COD) (allyl group)], [MCl 3x H 2o], [M (acetylacetonate) 3], [M (COD) Cl 2] 2, [M (DMSO) 4cl 2], wherein M is the element of the periodic table of elements 8,9 or 10 families, wherein only under the reaction conditions of operation stage (a), adds corresponding phosphine part (scene).
In the methods of the invention, preferably at least one is selected from following transition metal complex to catalyzer used:
[Ru (P nbu 3) 2(1,2-bis-(two tetradecyl phosphino-) ethane) (H) 2],
[Ru (P nhexyl 3) 2(1,2-bis-(two tetradecyl phosphino-) ethane) (H) 2],
[Ru (P noctyl group 3) 2(1,2-bis-(two tetradecyl phosphino-) ethane) (H) 2],
[Ru (P ndecyl 3) 2(1,2-bis-(two tetradecyl phosphino-) ethane) (H) 2],
[Ru (P nbu 3) 2(1,2-bis-(two pentadecyl phosphino-) ethane) (H) 2],
[Ru (P nhexyl 3) 2(1,2-bis-(two pentadecyl phosphino-) ethane) (H) 2],
[Ru (P noctyl group 3) 2(1,2-bis-(two pentadecyl phosphino-) ethane) (H) 2],
[Ru (P ndecyl 3) 2(1,2-bis-(two pentadecyl phosphino-) ethane) (H) 2],
[Ru (P nbu 3) 2(1,2-bis-(double hexadecyl phosphino-) ethane) (H) 2],
[Ru (P nhexyl 3) 2(1,2-bis-(double hexadecyl phosphino-) ethane) (H) 2],
[Ru (P noctyl group 3) 2(1,2-bis-(double hexadecyl phosphino-) ethane) (H) 2],
[Ru (P ndecyl 3) 2(1,2-bis-(double hexadecyl phosphino-) ethane) (H) 2],
[Ru (P nbu 3) 2(1,2-bis-(two octadecyl phosphino-) ethane)) (H) 2],
[Ru (P nhexyl 3) 2(1,2-bis-(two octadecyl phosphino-) ethane) (H) 2],
[Ru (P noctyl group 3) 2(1,2-bis-(two octadecyl phosphino-) ethane) (H) 2],
[Ru (P ndecyl 3) 2(1,2-bis-(two octadecyl phosphino-) ethane) (H) 2],
[Ru (P nbu 3) (1,2-bis-(two tetradecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P nhexyl 3) (1,2-bis-(two tetradecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P noctyl group 3) (1,2-bis-(two tetradecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P ndecyl 3) (1,2-bis-(two tetradecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P nbu 3) (1,2-bis-(two pentadecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P nhexyl 3) (1,2-bis-(two pentadecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P noctyl group 3) (1,2-bis-(two pentadecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P ndecyl 3) (1,2-bis-(two pentadecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P nbu 3) (1,2-bis-(double hexadecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P nhexyl 3) (1,2-bis-(double hexadecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P noctyl group 3) (1,2-bis-(double hexadecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P ndecyl 3) (1,2-bis-(double hexadecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P nbu 3) (1,2-bis-(two octadecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P nhexyl 3) (1,2-bis-(two octadecyl phosphino-) ethane)) (CO) (H) 2],
[Ru (P noctyl group 3) (1,2-bis-(two octadecyl phosphino-) ethane) (CO (H) 2],
[Ru (P ndecyl 3) (1,2-bis-(two octadecyl phosphino-) ethane) (CO) (H) 2],
[Ru (P nbu 3) (1,2-bis-(two tetradecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P nhexyl 3) (1,2-bis-(two tetradecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P noctyl group 3) (1,2-bis-(two tetradecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P ndecyl 3) (1,2-bis-(two tetradecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P nbu 3) (1,2-bis-(two pentadecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P nhexyl 3) (1,2-bis-(two pentadecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P noctyl group 3) (1,2-bis-(two pentadecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P ndecyl 3) (1,2-bis-(two pentadecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P nbu 3) (1,2-bis-(double hexadecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P nhexyl 3) (1,2-bis-(double hexadecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P noctyl group 3) (1,2-bis-(double hexadecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P ndecyl 3) (1,2-bis-(double hexadecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P nbu 3) (1,2-bis-(two octadecyl phosphino-) ethane) (CO) (H) (HCOO)],
[Ru (P nhexyl 3) (1,2-bis-(two octadecyl phosphino-) ethane)) (CO) (H) (HCOO)],
[Ru (P noctyl group 3) (1,2-bis-(two octadecyl phosphino-) ethane) (CO (H) is (HCOO)] and
[Ru (P ndecyl 3) (1,2-bis-(two octadecyl phosphino-) ethane) (CO) (H) (HCOO)].
Thus, in the hydrogenation of carbonic acid gas, can reach and be greater than 1000h -1tOF value (turnover frequency) and be greater than 100 partition ratio P k.
" homogeneous catalysis " represents that catalyzer exists with the form being dissolved at least in part in liquid reaction medium in the present invention.In a preferred embodiment, at least 90% catalyzer used in operation stage (a) is to be dissolved in liquid reaction medium, more preferably at least 95%, especially be preferably greater than 99%, catalyzer is to be most preferably dissolved in (100%) in liquid reaction medium, in each case the catalyzer total amount meter based on existing in liquid reaction medium (liquid phase of reaction mixture (Rg)) completely.
In operation stage (a), be used as in the transition metal complex of catalyzer, the amount of metal component is generally 0.1-5000ppm by weight, preferred 1-800ppm by weight, particularly preferably 5-800ppm by weight, the liquid reaction mixture based in hydrogenation reactor (Rg) total amount meter in each case.Catalyzer preferably selects to make its enrichment to be present in upper strata phase (U1), this means that upper strata phase (U1) contains most catalyzer.Represent in the present invention the partition ratio P of catalyzer about " enrichment " described in catalyzer and " major part " k=[concentration of catalyzer in upper strata phase (U1)]/[concentration of catalyzer in lower floor's phase (L1)] is>=10.Preferred allocation FACTOR P kbe>=50, particularly preferably partition ratio P kbe>=100.
Be used as the transition metal complex of catalyzer, can in the hydrogenation of carbonic acid gas, reach and be greater than 1000h -1tOF value (turnover frequency).(the metal component mole number of the mole number of TON=formic acid-amine adduct (A2)/in catalyzer was counted based on the reaction times; The metal component mole number of the mole number of TOF=formic acid-amine adduct (A2)/in catalyzer was counted according to the reaction times hourly).Turnover frequency (TOF) and turnover number (TON); Can be referring to about the definition of TOF and TON: J.F.Hartwig, organotransition metal chemistry (Organotransition Metal Chemistry), the 1st edition, 2010, University Science Books, the 545th page of Sausalito/California).
So the present invention also provides transition metal complex and the purposes as catalyzer thereof, especially in the method for preparing formic acid, be used as the purposes of catalyzer.
Therefore, the present invention also provides a kind of transition metal complex, and it contains at least one element that is selected from the periodic table of elements 8,9 and 10 families and at least one and have the phosphine part of general formula (I).
Therefore the present invention also provides a kind of transition metal complex, and it contains at least one phosphine part with general formula (I) and at least one and have the monodentate phosphine ligand of general formula (Ia).
Therefore, the present invention also provides transition metal complex in the method for preparing formic acid, to be used as the purposes of catalyzer.
In operation stage (a), the hydrogenation of carbonic acid gas is to carry out in liquid phase, preferably under total absolute pressure of the temperature of 20-200 DEG C and 0.2-30MPa, carries out.Described temperature is preferably at least 30 DEG C, and particularly preferably at least 40 DEG C, and preferably at the most 150 DEG C, particularly preferably at the most 120 DEG C, very particularly preferably at the most 80 DEG C.Total pressure is preferably at least 1MPa absolute pressure, particularly preferably 5MPa absolute pressure at least, preferably 20MPa absolute pressure at the most.
In a preferred embodiment, the hydrogenation in operation stage (a) is to carry out under total absolute pressure of the temperature of 40-80 DEG C and 5-20MPa.
The dividing potential drop of carbonic acid gas in operation stage (a) is generally at least 0.5MPa, preferably 2MPa at least, and be generally 8MPa at the most.In a preferred embodiment, the hydrogenation in operation stage (a) is to carry out under the partial pressure of carbon dioxide at 2-7.3MPa.
The dividing potential drop of hydrogen in operation stage (a) is generally at least 0.5MPa, preferably 1MPa at least, and be generally 25MPa at the most, preferably 15MPa at the most.In a preferred embodiment, the hydrogenation in operation stage (a) is to carry out under the hydrogen partial pressure at 1-15MPa.
In reaction mixture (Rg) in hydrogenation reactor, preferably 0.1-10 of the mol ratio between hydrogen and carbonic acid gas, particularly preferably 1-3.
In reaction mixture (Rg) in hydrogenation reactor, the mol ratio between carbonic acid gas and tertiary amine (A1) is generally 0.1-10, preferably 0.5-3.
Hydrogenation reactor used can use any reactor being applicable in the gas/liquid reaction under fixed temperature and setting pressure in principle.The suitable standard reaction device for gas-liquid reaction system is for example referring to K.D.Henkel, " type of reactor and their industrial application (Reactor Types and Their Industrial Applications) ", Ullmann's industrial chemistry encyclopaedia (Ullmann's Encyclopedia of Industrial Chemistry), 2005, Wiley-VCH Verlag GmbH & Co.KGaA, DOI:10.1002/14356007.b04_087, the 3.3rd chapter " for the reactor (Reactors for gas-liquid reactions) of gas-liquid reaction ".Example comprises stirred-tank reactor, tubular reactor or bubble-column reactor.
In the methods of the invention, the hydrogenation of carbonic acid gas can intermittently or carry out continuously.The in the situation that of periodical operation, in reactor, pack required liquid and any feeding-in solid body and auxiliary agent into, and subsequently carbonic acid gas and polar solvent are injected to the required pressure reaching under temperature required.After reaction completes, reactor generally carries out decompress(ion), and two liquid phases that form are separated from one another.In continuous operation mode, add continuously the charging and the auxiliary agent that comprise carbonic acid gas and hydrogen.According to corresponding mode, liquid phase is taken out from reactor continuously, thereby make the liquid level in reactor keep on average constant.The continuous hydrogenation reaction of preferably carbon dioxide.
The mean residence time of the component existing in reaction mixture (Rg) in hydrogenation reactor is generally 10 minutes to 5 hours.
In the hydrogenation of homogeneous catalysis, in operation stage (a), the hydrogenated mixture (H) obtaining contains catalyzer, polar solvent, tertiary amine (A1) and at least one formic acid-amine adduct (A2).
" formic acid-amine adduct (A2) " represents a kind of (1) formic acid-amine adduct (A2) in the present invention, or the mixture of two or more formic acid-amine adducts (A2).When use two or more tertiary amines (A1) in reaction mixture used (Rg) time, in operation stage (a), obtain the mixture of two or more formic acid-amine adducts (A2).
In a preferred embodiment of the inventive method, the reaction mixture (Rg) using in operation stage (a) contains the hydrogenated mixture (H) of one (a kind) tertiary amine (A1) to obtain containing one (a kind) formic acid-amine adduct (A2).
In a particularly preferred embodiment of the inventive method, the reaction mixture (Rg) using in operation stage (a) contains three n-hexyl amine as tertiary amine (A1), obtain the hydrogenated mixture (H) of the formic acid-amine adduct (A2) that contains three n-hexyl amine and formic acid, it is corresponding to following formula (A3):
N (n-hexyl) 3* x ihCOOH (A3)
In formic acid-amine adduct of general formula (A2), R 1, R 2, R 3corresponding to the definition to tertiary amine (A1) Suo Shu, be wherein correspondingly suitable for preferable range separately.
At general formula (A2) with (A3), x iin the scope of 0.4-5.Coefficient x iformic acid-amine adduct (A2) or average composition (A3) are provided, i.e. ratio at formic acid-amine adduct (A2) or between the tertiary amine (A1) that (A3), key connects and key formic acid even.
Coefficient x ican for example measure by measuring formic acid content, wherein formic acid content is by carrying out acid base titration mensuration with alcohol-KOH solution phenolphthalein.In addition, coefficient x ialso can for example detect amine content by vapor-phase chromatography measures.Formic acid-amine adduct (A2) or actual composition (A3) depend on many parameters, existence and character thereof, the especially polar solvent of concentration, pressure, temperature and other component of for example formic acid and tertiary amine (A1).
So, formic acid-amine adduct (A2) or composition (A3), i.e. coefficient x i, also can in each operation stage, change.For example, after removing polar solvent, general formation has the formic acid-amine adduct (A2) of higher formic acid content or (A3), the tertiary amine (A1) that excessive key connects discharges from formic acid-amine adduct (A2), and forms second-phase.
In operation stage (a), generally obtain such formic acid-amine adduct (A2) or (A3), wherein x iin the scope of 0.4-5, preferably 0.7-1.6.
Formic acid-amine adduct (A2) is that enrichment is present in lower floor's phase (L1), and lower floor's phase (L1) contains most formic acid-amine adduct (A2).The part by weight that it should be understood that in the present invention the formic acid-amine adduct (A2) in lower floor's phase (L1) about " enrichment " or " major part " formic acid-amine adduct (A2) Suo Shu is to be greater than 50%, based on the gross weight meter of the formic acid-amine adduct (A2) in liquid phase (upper strata phase (U1) and lower floor's phase (L1)) in hydrogenation reactor.
Preferably, the part by weight of the formic acid-amine adduct (A2) in lower floor's phase (L1) is to be greater than 70%, especially be greater than 90%, in each case the gross weight meter of the formic acid-amine adduct (A2) based in upper strata phase (U1) and lower floor's phase (L1).
the processing of hydrogenated mixture (H); Operation stage (b)
The hydrogenated mixture (H) obtaining in hydrogenation at carbonic acid gas in operation stage (a) preferably has two liquid phases, optionally adding after water, and be further processed according to step (b1), (b2) or (b3) in operation stage (b).
Process according to operation stage (b1)
In a preferred embodiment, hydrogenated mixture (H) is further processed according to step (b1).
In this case, hydrogenated mixture (H) processing that is separated in first-phase tripping device obtaining in operation stage (a), obtain the lower floor's phase (L1) that contains formic acid-amine adduct (A2), at least one polar solvent and relict catalyst, and the upper strata phase (U1) that contains catalyzer and tertiary amine (A1).
Because the partition ratio (Pk) of the transition metal complex as catalyzer is compared with prior art significantly improved, so can substantially fully remove catalyzer by being separated.The amount of the metal component in the catalyzer existing in lower floor's phase (L1) is generally less than 4ppm by weight, preferably be less than by weight 3ppm, more preferably be less than by weight 2ppm, especially be preferably less than or equal to by weight 1ppm, count based on lower floor's phase (L1) in each case.
Relict catalyst can be optionally extraction by subsequently from further dilution of lower floor's phase (L1) (processing according to operation stage b3).Due to the partition ratio (P of the transition metal complex as catalyzer k) be significantly improved, so can substantially fully remove the operation as the transistion metal compound of catalyzer by being separated, so can save follow-up extraction.
In a preferred embodiment, upper strata phase (U1) is recycled to hydrogenation reactor.In a preferred embodiment, lower floor's phase (L1) is supplied to the water distilling apparatus in operation stage (c).Also can be advantageously by any other liquid phase that contains unconverted carbonic acid gas existing on described two liquid phases, and any gas phase that contains unconverted carbonic acid gas and/or unconverted hydrogen, hydrogenation reactor be supplied to.For example, can it is desirable for by discharge from technique a part of upper strata phase (U1) and/or a part the liquid phase that contains carbonic acid gas or carbonic acid gas and hydrogen or gas phase discharge unwanted by product or impurity.
The hydrogenated mixture (H) obtaining in operation stage (a) is generally separated to operate by weight and separates.Suitable phase separation container is for example standard set-up and standard method, referring to such as E.M ü ller etc., " liquid-liquid extraction (Liquid-Liquid Extraction) ", Ullmann's industrial chemistry encyclopaedia (Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co.KGaA, DOI:10.1002/14356007.b03_06, the 3rd chapter " device (Apparatus) ".
Be separated and can be for example for example approximately or after approaching envrionment temperature carry out unziping to approximately or approach normal atmosphere and liquid reaction mixture is cooled to.
In the present invention, find the in the situation that of system of the present invention, be that lower floor's phase (L1) is rich in formic acid-amine adduct (A2) and polar solvent and upper strata phase (U1) and is rich in tertiary amine (A1) and catalyzer, two liquid phases also can even also can be very effectively separated from one another under the pressure significantly improving.Therefore, in the methods of the invention, select polar solvent and tertiary amine (A1) can under 1-30MPa absolute pressure, carry out to the cyclical operation of hydrogenation reactor with lower floor's phase (L1) of making to be rich in formic acid-amine adduct (A2) and polar solvent and the lock out operation and the upper strata phase (U1) that are rich between the upper strata phase (U1) of tertiary amine (A1) and catalyzer.According to the total pressure in hydrogenation reactor, this pressure is preferably at most 20MPa absolute pressure.Therefore, even can not in advance decompress(ion) in the situation that by separated from one another in first-phase tripping device two liquid phases (upper strata phase (U1) and lower floor's phase (L1)), and in the situation that not having remarkable pressure to increase, upper strata phase (U1) is recycled to hydrogenation reactor.
Also can in hydrogenation reactor, directly be separated.In this embodiment, hydrogenation reactor plays the effect of first-phase tripping device simultaneously, and operation stage (a) and (b1) all carry out in hydrogenation reactor.In this case, upper strata phase (U1) is retained in hydrogenation reactor, and lower floor's phase (L1) is fed in the first water distilling apparatus in operation stage (c).
In one embodiment, the inventive method is preferably carried out by this way: the pressure and temperature in hydrogenation reactor and in first-phase tripping device is identical or approximately identical; In the present invention, " approximately identical " represents that pressure gap is at most +/-0.5MPa, or temperature contrast is at most 10 DEG C of +/-.
Also shockingly find, in system of the present invention, very effectively separated from one another at the temperature that two liquid phases (upper strata phase (U1) and lower floor's phase (L1)) also can raise at the temperature of reaction meter with respect in hydrogenation reactor.In this case, for being separated in operation stage (b1), do not need to carry out yet cooling, and the upper strata phase (U1) that need to will not circulate with post-heating, this has also saved the energy.
Process according to operation stage (b3)
In a further preferred embodiment, hydrogenated mixture (H) is further processed according to step (b3).
In this case, as above for described in operation stage (b1), the hydrogenated mixture (H) obtaining in operation stage (a) separates in first-phase tripping device, obtain lower floor's phase (L1) and upper strata phase (U1), and be recycled in hydrogenation reactor.About being separated, be also correspondingly applicable to operation stage (b3) for details operation stage (b1) Suo Shu and preferable range.In the situation that operating according to operation stage (b3), also can directly in hydrogenation reactor, be separated.In this embodiment, hydrogenation reactor plays the effect of first-phase tripping device simultaneously.In this case, upper strata phase (U1) is retained in hydrogenation reactor, and lower floor's phase (L1) is fed in extraction cells.
The tertiary amine (A1) that the lower floor's phase (L1) obtaining after being separated is used as extraction agent subsequently in extraction cells extracts, thereby remove relict catalyst, obtain the raffinate (R2) that contains formic acid-amine adduct (A2) and at least one polar solvent, and the extract (E2) that contains tertiary amine (A1) and relict catalyst.
In a preferred embodiment, extraction agent used is and identical tertiary amine used (A1) in reaction mixture (Rg) in operation stage (a), therefore for being also correspondingly applicable to operation stage (b3) about details tertiary amine (A1) Suo Shu and preferable range in operation stage (a).
In a preferred embodiment, the extract (E2) obtaining in operation stage (b3) is recycled to the hydrogenation reactor in operation stage (a).This makes effectively to reclaim catalyzer.In a preferred embodiment, raffinate (R2) is fed in the first water distilling apparatus in operation stage (c).
Preferably, the extraction agent using in operation stage (b3) is the tertiary amine (A1) obtaining in the thermal dissociation unit in operation stage (e).In a preferred embodiment, the tertiary amine (A1) obtaining in the thermal dissociation unit in operation stage (e) is recycled in the extraction cells in operation stage (b3).
Extraction in operation stage (b3) generally 0-150 DEG C, preferably under the pressure of the temperature of 30-100 DEG C and 0.1-8MPa, carry out.Extraction also can be carried out under hydrogen pressure.
The extraction of catalyzer can be carried out well known to a person skilled in the art in any appropriate device, preferably counter-current extraction tower, the cascade of mixing tank-settling vessel, or the combination of mixing tank-settling vessel and counter-current extraction tower.
Also passable, together with catalyzer, a certain proportion of will being also dissolved in extraction agent tertiary amine (A1) from each component of the polar solvent of lower floor's phase (L1) extraction.This is not disadvantageous for the present invention, and this is because the amount of the polar solvent being extracted does not need to be fed to removal of solvents operation, and then has saved in some cases evaporation energy.
Process according to operation stage (b2)
In a further preferred embodiment, hydrogenated mixture (H) is further processed according to step (b2).
In this case, the hydrogenated mixture (H) obtaining in operation stage (a) is all directly fed to extraction cells in the situation that not being separated in advance.About extraction, be also correspondingly applicable to operation stage (b2) for details operation stage (b3) Suo Shu and preferable range.
In this case, the tertiary amine that hydrogenated mixture (H) is used as extraction agent in extraction cells extracts, thereby remove catalyzer, obtain the raffinate (R1) that contains formic acid-amine adduct (A2) and at least one polar solvent, and the extract (E2) that contains tertiary amine (A1) and catalyzer.
In a preferred embodiment, extraction agent used is and identical tertiary amine used (A1) in reaction mixture (Rg) in operation stage (a), therefore for being also correspondingly applicable to operation stage (b2) about details tertiary amine (A1) Suo Shu and preferable range in operation stage (a).
In a preferred embodiment, the extract (E2) obtaining in operation stage (b2) is recycled in the hydrogenation reactor in operation stage (a).This makes effectively to reclaim catalyzer.In a preferred embodiment, raffinate (E1) is fed in the first water distilling apparatus in operation stage (c).
Preferably, the extraction agent using in operation stage (b2) is the tertiary amine (A1) obtaining in the thermal dissociation unit in operation stage (e).In a preferred embodiment, the tertiary amine (A1) obtaining in the thermal dissociation unit in operation stage (e) is recycled in the extraction cells in operation stage (b2).
Extraction in operation stage (b2) generally 0-150 DEG C, preferably under the pressure of the temperature of 30-100 DEG C and 0.1-8MPa, carry out.Extraction also can be carried out under hydrogen pressure.
The extraction of catalyzer can be carried out well known to a person skilled in the art in any appropriate device, preferably counter-current extraction tower, the cascade of mixing tank-settling vessel, or the combination of mixing tank-settling vessel and counter-current extraction tower.
Also passable, together with catalyzer, a certain proportion of will being also dissolved in extraction agent tertiary amine (A1) from each component of the polar solvent of hydrogenated mixture (H) extraction.This is not disadvantageous for the present invention, and this is because the amount of the polar solvent being extracted does not need to be fed to removal of solvents operation, and then has saved in some cases evaporation energy.
remove polar solvent; Operation stage (c)
In operation stage (c), by polar solvent in the first water distilling apparatus from lower floor's phase (L1), remove from raffinate (R1) or from raffinate (R2).In the first water distilling apparatus, obtain the bottom mixture (B1) of overhead product (D1) and two-phase.Overhead product (D1) comprises the polar solvent being removed, and is recycled in a preferred embodiment in the hydrogenation reactor in step (a).Bottom mixture (B1) comprises the upper strata phase (U2) that contains tertiary amine (A1), and the lower floor's phase (L2) that contains formic acid-amine adduct (A2).In an embodiment of the inventive method, in the first water distilling apparatus, in operation stage (c), polar solvent is partly removed, so bottom mixture (B1) comprises the polar solvent being not yet removed.In operation stage (c), can remove the polar solvent existing of for example 5-98 % by weight in lower floor's phase (L1), in raffinate (R1) or in raffinate (R2), preferably 50-98 % by weight, more preferably 80-98 % by weight, especially preferably 80-90 % by weight, in each case the gross weight meter of the polar solvent based on existing in lower floor's phase (L1), in raffinate (R1) or in raffinate (R2).
In another embodiment of the inventive method, in the first water distilling apparatus, in operation stage (c), polar solvent is completely removed, " remove completely " in the present invention represent to remove be greater than 98 % by weight in lower floor's phase (L1), the polar solvent existing in raffinate (R1) or in raffinate (R2), be preferably greater than 98.5 % by weight, especially be preferably greater than 99 % by weight, especially be greater than 99.5 % by weight, in each case based in lower floor's phase (L1), the gross weight meter of the polar solvent existing in raffinate (R1) or in raffinate (R2).
In a preferred embodiment, the overhead product (D1) of removing in the first water distilling apparatus is recycled to the hydrogenation reactor in step (a).
Polar solvent can for example be removed from lower floor's phase (L1), raffinate (R1) or raffinate (R2) vaporizer or in the distillation unit being made up of vaporizer and tower, and described structured packing for tower, random packing and/or column plate are filled.
The operation of removing at least partly of polar solvent is preferably under setting pressure, can not form bottom temp when free formic acid and carry out from formic acid-amine adduct (A2).The coefficient x of the formic acid-amine adduct (A2) in the first water distilling apparatus inormally 0.4-3, preferably 0.6-1.8, especially preferably 0.7-1.7.
Generally speaking, the bottom temp in the first water distilling apparatus is at least 20 DEG C, preferably at least 50 DEG C, and especially preferably at least 70 DEG C, and be conventionally at most 210 DEG C, be preferably at most 190 DEG C.Normally 20 DEG C-210 DEG C of temperature in the first water distilling apparatus, preferably 50 DEG C-190 DEG C.Normally 0.001MPa absolute pressure at least of pressure in the first water distilling apparatus, preferably 0.005MPa absolute pressure at least, especially preferably 0.01MPa absolute pressure at least, and be normally at most 1MPa absolute pressure, be preferably at most 0.1MPa absolute pressure.Pressure in the first water distilling apparatus normally in 0.0001MPa absolute pressure to 1MPa absolute pressure, preferably 0.005MPa absolute pressure to 0.1MPa absolute pressure and, especially preferably 0.01MPa absolute pressure is to 0.1MPa absolute pressure.
In the first water distilling apparatus, remove in the operation of polar solvent, formic acid-amine adduct (A2) and free uncle amine (A1) can appear at the bottom of the first water distilling apparatus, and this is to have obtained having the formic acid-amine adduct (A2) compared with low amine content because remove polar solvent.The bottom mixture (B1) that this formation contains formic acid-amine adduct (A2) and free uncle amine (A1).According to the amount of the polar solvent being removed, bottom mixture (B1) comprises formic acid-amine adduct (A2) and the possible free uncle amine (A1) forming in the first water distilling apparatus bottom.Bottom mixture (B1) is optionally further processed in operation stage (d), is then fed to operation stage (e).Also bottom mixture (B1) directly can be fed to operation stage (e) from operation stage (c).
In operation stage (d), the bottom mixture (B1) obtaining in step (c) can be separated into upper strata phase (U2) and lower floor's phase (L2) in second-phase tripping device.Lower floor's phase (L2) is further processed according to operation stage (e) subsequently.In a preferred embodiment, be recycled to the hydrogenation reactor in step (a) from the upper strata phase (U2) of second-phase tripping device.In a further preferred embodiment, be recycled to extraction cells from the upper strata phase (U2) of second-phase tripping device.For operation stage (d) and second-phase tripping device, be correspondingly suitable for about details and preferable range described in first-phase tripping device.
In one embodiment, therefore the inventive method comprises step (a), (b1), (c), (d) and (e).In another embodiment, the inventive method comprises step (a), (b2), (c), (d) and (e).In another embodiment, the inventive method comprises step (a), (b3), (c), (d) and (e).In another embodiment, the inventive method comprises step (a), (b1), (c) and (e).In another embodiment, the inventive method comprises step (a), (b2), (c) and (e).In another embodiment, the inventive method comprises step (a), (b3), (c) and (e).
In one embodiment, the inventive method forms by step (a), (b1), (c), (d) with (e).In another embodiment, the inventive method forms by step (a), (b2), (c), (d) with (e).In another embodiment, the inventive method forms by step (a), (b3), (c), (d) with (e).In another embodiment, the inventive method forms by step (a), (b1), (c) with (e).In another embodiment, the inventive method forms by step (a), (b2), (c) with (e).In another embodiment, the inventive method forms by step (a), (b3), (c) with (e).
the dissociation of formic acid-amine adduct (A2); Operation stage (e)
The bottom mixture (B1) obtaining according to step (c) or the lower floor's phase (L2) obtaining, optionally, after processing according to step (d), be supplied to thermal dissociation unit further to transform.
In bottom mixture (B1) and/or the formic acid-amine adduct (A2) that may exist in lower floor's phase (L2) be in thermal dissociation unit, to be dissociated into formic acid and corresponding tertiary amine (A1).
Formic acid is discharged from thermal dissociation unit.Tertiary amine (A1) is recycled to the hydrogenation reactor in step (a).Tertiary amine (A1) from thermal dissociation reactor can be recycled directly to hydrogenation reactor.Also tertiary amine (A1) first can be recycled to the extraction cells operation stage (b2) or operation stage (b3) from thermal dissociation unit, then be recycled to the hydrogenation reactor in step (a) via extraction cells; This embodiment is preferred.
In a preferred embodiment, thermal dissociation unit comprises after-fractionating device and third phase tripping device, formic acid-amine adduct (A2) is the overhead product (D2) of dissociation to obtain containing formic acid and to discharge (taking-up) from after-fractionating device in after-fractionating device, and the two-phase that contains upper strata phase (U3) and lower floor's phase (L3) bottom mixture (B2), wherein said upper strata phase (U3) comprises tertiary amine (A1), and lower floor's phase (L3) comprises formic acid-amine adduct (A2).
The formic acid obtaining in after-fractionating device can for example take out with upper/lower positions from after-fractionating device: (i) top, and (ii) top and via side-draw material, or (iii) only via side-draw material.In the time taking out formic acid from top, the formic acid obtaining has the purity of 99.99 % by weight at the most.In the situation that taking out via side-draw material, obtain moisture formic acid, particularly preferably contain in this case the mixture of the 85 % by weight formic acid of having an appointment.According to being fed to thermal dissociation unit or being optionally fed to the water-content that the bottom mixture (B1) of lower floor's phase (L2) has, formic acid can take out as top product using improved degree, or takes out via side-draw material with improved degree.If necessary, also can only take out formic acid via side-draw material, preferable formic acid content is approximately 85 % by weight, and the required water yield also can be optionally by adding extra water to realize to after-fractionating device in this case.The thermal dissociation of formic acid-amine adduct (A2) is carried out according to the known processing parameter about pressure, temperature and apparatus structure of prior art conventionally.These are for example referring to EP0181078 or WO2006/021411.Suitable after-fractionating device is for example distillation tower, and it comprises random packing, structured packing and/or column plate conventionally.
Generally speaking, the bottom temp in after-fractionating device is at least 130 DEG C, preferably at least 140 DEG C and especially preferably at least 150 DEG C, and be conventionally at most 210 DEG C, and be preferably at most 190 DEG C, be especially preferably at most 185 DEG C.Normally 1hPa absolute pressure at least of pressure in after-fractionating device, preferably 50hPa absolute pressure at least, especially preferably 100hPa absolute pressure at least, and be conventionally at most 500hPa, especially be preferably at most 300hPa absolute pressure, be especially preferably at most 200hPa absolute pressure.
The bottom mixture (B2) obtaining in the bottom of after-fractionating device is two-phase.In a preferred embodiment, bottom mixture (B2) is fed to the third phase tripping device of thermal dissociation unit, and is separated into the upper strata phase (U3) that comprises tertiary amine (A1) and the lower floor's phase (L3) that comprises formic acid-amine adduct (A2) here.Upper strata phase (U3) is discharged from the third phase tripping device of thermal dissociation unit, and be recycled to the hydrogenation reactor in step (a).Described circulation can directly arrive the hydrogenation reactor in step (a); Or upper strata phase (U3) is first fed to the extraction cells in step (b2) or step (b3), then and then is fed to the hydrogenation reactor in step (a).The lower floor's phase (L3) obtaining in third phase tripping device is supplied to the after-fractionating device of thermal dissociation unit again.Formic acid-the amine adduct (A2) existing in lower floor's phase (L3) then carries out other dissociation in after-fractionating device, again obtain formic acid and free uncle amine (A1), and in the bottom of the after-fractionating device of thermal dissociation unit, again form other two-phase bottom mixture (B2), then it is fed to again to the third phase tripping device of thermal dissociation unit to be further processed.
Bottom mixture (B1) and/or optionally lower floor's phase (L2) can be supplied to the after-fractionating device of thermal dissociation unit and/or in third phase tripping device in operation stage (e).In a preferred embodiment, by bottom mixture (B1) and/or optionally lower floor's phase (L2) add the after-fractionating device of thermal separation unit.In another embodiment, by bottom mixture (B1) and/or optionally lower floor's phase (L2) add the third phase separation vessel of thermal dissociation unit.
In another embodiment, by bottom mixture (B1) and/or optionally lower floor's phase (L2) all add the after-fractionating device of thermal dissociation unit, and add the third phase tripping device of thermal dissociation unit.For this purpose, by bottom mixture (B1) and/or optionally lower floor's phase (L2) be divided into two son material streams, in this case a son material stream is fed to after-fractionating device, and a son material stream is fed to the third phase tripping device of thermal dissociation unit.
Below by drawings and Examples explanation the present invention, but do not limit the scope of the invention.
Each accompanying drawing shows:
Fig. 1 is the schema of a preferred embodiment of the inventive method,
Fig. 2 is the schema of another preferred embodiment of the inventive method.
In Fig. 1 and 2, each symbol is as given a definition:
fig. 1
I-1 hydrogenation reactor
II-1 the first water distilling apparatus
III-1 third phase tripping device (in thermal dissociation unit)
IV-1 after-fractionating device (in thermal dissociation unit)
The 1 material stream that contains carbonic acid gas
The 2 material streams that contain hydrogen
3 contain formic acid-amine adduct (material stream of (A2), relict catalyst, polar solvent; (lower floor's phase (L1))
The 5 material streams that contain polar solvent; (overhead product (D1))
The 6 material streams that contain tertiary amine (A1) (upper strata phase (U2)) and formic acid-amine adduct (A2) (lower floor's phase (L2)); Bottom mixture (B1)
The 7 material streams that contain formic acid-amine adduct (A2); Lower floor's phase (L3)
The 8 material streams that contain tertiary amine (A1) (upper strata phase (U3)) and formic acid-amine adduct (A2) (lower floor's phase (L3)); Bottom mixture (B2)
The 9 material streams that contain formic acid; (overhead product (D2))
The 10 material streams that contain tertiary amine (A1); Upper strata phase (U3)
fig. 2
I-2 hydrogenation reactor
II-2 the first water distilling apparatus
III-2 third phase tripping device (in thermal dissociation unit)
IV-2 after-fractionating device (in thermal dissociation unit)
V-2 first-phase tripping device
VI-2 extraction cells
The 11 material streams that contain carbonic acid gas
The 12 material streams that contain hydrogen
The material stream that 13a contains hydrogenated mixture (H)
The material stream that 13b contains lower floor's phase (L1)
The material stream that 13c contains raffinate (R2)
The 15 material streams that contain overhead product (D1)
The 16 material streams that contain bottom mixture (B1)
The 17 material streams that contain lower floor's phase (L3)
The 18 material streams that contain bottom mixture (B2)
The 19 material streams that contain formic acid; (overhead product (D2))
The 20 material streams that contain upper strata phase (U3)
The 21 material streams that contain extract (E2)
The 22 material streams that contain upper strata phase (U1)
According in the embodiment of Fig. 1, the material stream 1 that contains carbonic acid gas and the material stream 2 that contains hydrogen are fed to hydrogenation reactor I-1.Can supply other material stream (not shown) to hydrogenation reactor I-1, thus the tertiary amine (A1) that compensation occurs or any loss of catalyzer.
In hydrogenation reactor I-1, carbonic acid gas and hydrogen transform under tertiary amine (A1), polar solvent and the existence as the transition metal complex of catalyzer.This has obtained the hydrogenated mixture (H) of two-phase, it comprises the upper strata phase (U1) that contains catalyzer and tertiary amine (A1), and the lower floor's phase (L1) that contains polar solvent, relict catalyst and formic acid-amine adduct (A2).
Lower floor's phase (L1) is fed to water distilling apparatus II-1 as material stream 3.Upper strata phase (U1) is retained in hydrogenation reactor I-1.According in the embodiment of Fig. 1, hydrogenation reactor I-1 plays the effect of first-phase tripping device simultaneously.
In the first water distilling apparatus II-1, lower floor's phase (L1) is separated into the overhead product (D1) that contains polar solvent, and it is recycled to hydrogenation reactor I-1 as material stream 5; And be separated into the bottom mixture (B1) of two-phase, it comprises the upper strata phase (U2) that contains tertiary amine (A1) and the lower floor's phase (L2) that contains formic acid-amine adduct (A2).
Be fed to the third phase tripping device III-1 of thermal dissociation unit using bottom mixture (B1) as material stream 6.
In the third phase tripping device III-1 of thermal dissociation unit, bottom mixture (B1) separates, obtain the upper strata phase (U3) that contains tertiary amine (A1), and the lower floor's phase (L3) that contains formic acid-amine adduct (A2).
Upper strata phase (U3) is recycled to hydrogenation reactor I-1 as material stream 10.Be fed to the after-fractionating device IV-1 of thermal dissociation unit using lower floor's phase (L3) as material stream 7.Formic acid-the amine adduct (A2) existing in lower floor's phase (L3) is separated into formic acid and free uncle amine (A1) in after-fractionating device IV-1.In after-fractionating device IV-1, obtain overhead product (D2) and two-phase bottom mixture (B2).
The overhead product that contains formic acid (D2) is discharged from water distilling apparatus IV-1 as material stream 9.To comprise the upper strata phase (U3) that contains tertiary amine (A1) and the two-phase of the lower floor's phase (L3) that contains formic acid-amine adduct (A2) bottom mixture (B2) as the material stream 8 third phase tripping device III-1 that are recycled in thermal dissociation unit.In third phase tripping device III-1, bottom mixture (B2) is separated into upper strata phase (U3) and lower floor's phase (L3).Upper strata phase (U3) is recycled to hydrogenation reactor I-1 as material stream 10.Lower floor's phase (L3) is recycled to after-fractionating device IV-1 as material stream 7.
According in the embodiment of Fig. 2, the material stream 11 that contains carbonic acid gas and the material stream 12 that contains hydrogen are fed to hydrogenation reactor I-2.Can supply other material stream (not shown) to hydrogenation reactor I-2, thus the tertiary amine (A1) that compensation occurs or any loss of catalyzer.
In hydrogenation reactor I-2, carbonic acid gas and hydrogen transform under tertiary amine (A1), polar solvent and the existence as the iron complex of catalyzer.This has obtained the hydrogenated mixture (H) of two-phase, it comprises the upper strata phase (U1) that contains catalyzer and tertiary amine (A1), and the lower floor's phase (L1) that contains polar solvent, relict catalyst and formic acid-amine adduct (A2).
Hydrogenated mixture (H) is fed to first-phase tripping device V-2 as material stream 3a.In first-phase tripping device V-2, hydrogenated mixture (H) is separated into upper strata phase (U1) and lower floor's phase (L1).
Upper strata phase (U1) is recycled to hydrogenation reactor I-2 as material stream 22.Lower floor's phase (L1) is recycled to extraction cells VI-2 as material stream 13b.Lower floor's phase (L1) is used tertiary amine (A1) extraction here, and it is recycled to extraction cells VI-2 as material stream 20 (upper strata phase (U3)) from third phase tripping device III-2.
In extraction cells VI-2, obtain raffinate (R2) and extract (E2).Raffinate (R2) comprises formic acid-amine adduct (A2) and polar solvent, and is fed to the first water distilling apparatus II-2 as material stream 13c.The resistates that extract (E2) comprises tertiary amine (A1) and composition catalyst, and be recycled to hydrogenation reactor I-2 as material stream 21.
In the first water distilling apparatus II-2, raffinate (R2) is separated into the overhead product (D1) that contains polar solvent, set it as material stream 15 and be recycled to hydrogenation reactor I-2, and be separated into the bottom mixture (B1) of two-phase.
Bottom mixture (B1) comprises the upper strata phase (U2) that contains tertiary amine (A1) and the lower floor's phase (L2) that contains formic acid-amine adduct (A2).Bottom mixture (B1) is fed to after-fractionating device IV-2 as material stream 16.
Formic acid-the amine adduct existing in bottom mixture (B1) is separated into formic acid and free uncle amine (A1) in after-fractionating device IV-2.In after-fractionating device IV-2, obtain overhead product (D2) and bottom mixture (B2).
The overhead product that contains formic acid (D2) is discharged from after-fractionating device IV-2 as material stream 19.To comprise the upper strata phase (U3) that contains tertiary amine (A1) and the two-phase of the lower floor's phase (L3) that contains formic acid-amine adduct (A2) bottom mixture (B2) as the material stream 18 third phase tripping device III-2 that are recycled in thermal dissociation unit.
In third phase tripping device III-2 in thermal dissociation unit, bottom mixture (B2) separates, obtain the upper strata phase (U3) that contains tertiary amine (A1), and the lower floor's phase (L3) that contains formic acid-amine adduct (A2).
Be recycled to extraction cells VI-2 using upper strata phase (U3) from third phase tripping device III-2 as material stream 20.Using lower floor's phase (L3) as the material stream 17 after-fractionating device IV-2 that are fed in thermal dissociation unit.Formic acid-the amine adduct (A2) existing in lower floor's phase (L3) is separated into formic acid and free uncle amine (A1) in after-fractionating device IV-2.In after-fractionating device IV-2, as mentioned above.Obtain other overhead product (D2) and other bottom mixture (B2).
Embodiment
Synthetic inner complex phosphine part:
Two (two pentadecyl phosphino-) ethane: (15% in tetrahydrofuran (THF) (THF) by the pentadecyl bromination magnesium of 250ml; 119mmol) first add in the four neck flasks with internal thermometer, nitrogen protection, metal/water condenser and agitator of 1L, and be cooled to-30 DEG C.Subsequently, drip 1 of 5.5g (23.8mmol) in 30 minutes, the solution of 2-bis-(dichlorophosphinyl) ethane in the THF of 100ml is settled out a large amount of solids in this process.Then this mixture was heated to room temperature in 1 hour, and under the internal temperature of 50 DEG C, stirs 2 hours subsequently again, this obtains linen suspension.It is progressively mixed, and with in ice-cooled, add the saturated and degassed NH of 95ml 4cl solution is to obtain white suspension.Add wherein the degassed water of other 65ml, and go out throw out via G2 frit suction filtration under argon gas.Product washes with water once, and by the THF washed twice of 20ml, and drying under reduced pressure.The product that this obtains 22.2g (93.5%) is the form of white powder.
31p NMR (CDCl 3) :-26.8ppm (s); Ultimate analysis: calculated value: C79.6%, H13.8%, P6.6%; Detected value: C79.5%, H14.0%, P6.3%, Br0.04%, Cl0.06%, O<0.5%.
Two (two octadecyl phosphino-) ethane: (0.5M is in THF by the octadecyl bromination magnesium of 100ml; 50mmol) first add in the four neck flasks with internal thermometer, nitrogen protection, metal/water condenser and agitator of 1L, and be cooled to-30 DEG C.Subsequently, drip 1 of 2.3g (10mmol) in 40 minutes, the solution of 2-bis-(dichlorophosphinyl) ethane in the THF of 100ml is settled out a large amount of solids in this process.Then this mixture was heated to room temperature in 1 hour, and under the internal temperature of 50 DEG C, stirs 2 hours subsequently again, this obtains linen suspension.It is progressively mixed, and with in ice-cooled, add the saturated and degassed NH of 50ml 4cl solution is to obtain white suspension.Add wherein the degassed water of other 50ml, and go out throw out via G2 frit suction filtration under argon gas.Product washes with water once, and by the THF washed twice of 10ml, and drying under reduced pressure.The product that this obtains 11.0g (88.0%) is the form of white powder.
31P NMR(CDCl 3):-26.1ppm(s)。
Comparative example (A1-a and A1-b) and the embodiment of the present invention (A2-a, A2-b, A3-a and A3-b)) prove carbonic acid gas (CO 2) hydrogenation and as the recycling of the transition metal complex of catalyzer.
In being made by hastelloy C and thering is the 100ml of paddle stirrer or 250ml autoclave (hydrogenation reactor), under inert conditions, add tertiary amine (A1), polar solvent and catalyzer.Close subsequently autoclave, and injecting carbon dioxide at room temperature.Then inject hydrogen (H 2), and stirring reactor heating in (1000ppm).After the reaction times, cooling autoclave, and by hydrogenated mixture (H) decompress(ion), add water, and this mixture is at room temperature stirred 10 minutes.
Obtain two-phase hydrogenated mixture (H), its at the middle and upper levels phase (U1) be rich in free tertiary amine (A1) and catalyzer, lower floor's phase (L1) is rich in polar solvent and formic acid-amine adduct (A2) of forming.
These separate mutually subsequently, and detect the formic acid content (being the form of formic acid-amine adduct (A2)) of lower floor's phase (L1) and the ruthenium content (C of this two-phase by following method ru).Then use fresh tertiary amine (A1) that the upper strata phase (U1) that contains ruthenium catalyst is supplied to 85g, and under reaction conditions same as described above by same solvent again for the hydrogenation (referring to A1-b and A2-b) of carbonic acid gas.After reaction completes and adds water, except sub-cloud phase (L1), and mix three times (at room temperature stirring 10 minutes and separate subsequently described phase) with extracting catalyst with the fresh tertiary amine (A1) of same amount (quality of amine is corresponding to the quality of lower floor's phase) under inert conditions.
Formic acid total content in formic acid-amine adduct (A2) detects by potentiometric titration, wherein uses 0.1N KOH and use " Mettler Toledo DL50 " titrator in MeOH to carry out.Ruthenium content detects by AAS.The parameter of each experiment and the results are shown in table 1.
Comparative example (A1-a and A1-b) and the embodiment of the present invention (A2-a, A2-b, A3-a and A3-b) show that described catalyzer can be recycled to CO 2hydrogenation in and reuse there.According to the present invention as the transition metal complex of catalyzer can be only by being just separated by dilution to the 1ppm being less than or equal to by weight.

Claims (15)

1. a method of preparing formic acid, comprises the following steps:
(a) make reaction mixture (Rg) in hydrogenation reactor, under the existence of at least one transition metal complex as catalyzer, carry out homogeneous catalytic reaction, wherein reaction mixture (Rg) contains carbonic acid gas, hydrogen, tertiary amine that at least one is selected from the polar solvent of methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 2-methyl isophthalic acid-the third alcohol and water and has general formula (A1):
NR 1R 2R 3 (A1),
Wherein
Radicals R 1, R 2, R 3branching or branching, acyclic or ring-type, aliphatic, araliphatic or aromatics group independently of one another, it has 1-16 carbon atom in each case, wherein each carbon atom also can be selected from independently of one another-O-and the assorted group of >N-replace, and two or all three groups also can be connected to each other and form the chain that contains in each case at least four atoms
Described transition metal complex contains at least one element that is selected from the periodic table of elements 8,9 and 10 families and at least one and has the phosphine part of the organic group of at least 13 carbon atoms with at least one,
Optionally, after adding water, obtain the two-phase hydrogenated mixture (H) that contains following component:
Upper strata phase (U1), it contains catalyzer and tertiary amine (A1), and
Lower floor's phase (L1), formic acid-amine adduct that it contains at least one polar solvent, relict catalyst and has general formula (A2):
NR 1R 2R 3*x i HCOOH (A2)
Wherein
X i0.4-5, and
R 1, R 2, R 3separately as defined above,
(b) hydrogenated mixture (H) obtaining in step (a) is processed according to following steps:
(b1) hydrogenated mixture (H) obtaining is separated into upper strata phase (U1) and lower floor's phase (L1) in first-phase tripping device in step (a),
Or
(b2) in extraction cells, extract from hydrogenated mixture (H) extraction agent that contains tertiary amine (A1) obtaining step (a), obtain:
Raffinate (R1), it contains formic acid-amine adduct (A2) and at least one polar solvent, and
Extract (E1), it contains tertiary amine (A1) and catalyzer,
Or
(b3) hydrogenated mixture (H) obtaining is separated into upper strata phase (U1) and lower floor's phase (L1) in first-phase tripping device in step (a), and in extraction cells, use the extraction agent that contains tertiary amine (A1) from lower floor's phase (L1) extracting catalyst resistates, obtain:
Raffinate (R2), it contains formic acid-amine adduct (A2) and at least one polar solvent, and
Extract (E2), it contains tertiary amine (A1) and relict catalyst,
(c) in the first water distilling apparatus from lower floor's phase (L1), from raffinate (R1) or from raffinate (R2) separating at least one polar solvent, obtain:
Overhead product (D1), it contains at least one polar solvent, and by this solvent cycle in the hydrogenation reactor in step (a), and
Two-phase bottom mixture (B1), it contains:
Upper strata phase (U2), it contains tertiary amine (A1), and
Lower floor's phase (L2), it contains formic acid-amine adduct (A2),
(d) optionally by the bottom mixture (B1) obtaining in step (c) in second-phase tripping device by the processing that is separated, obtain upper strata phase (U2) and lower floor's phase (L2),
(e) formic acid-amine adduct (A2) existing and/or formic acid-amine adduct (A2) dissociation in thermal dissociation unit that may exist are obtained to corresponding tertiary amine (A1) and formic acid in lower floor's phase (L2) in bottom mixture (B1), described tertiary amine (A1) is recycled in the hydrogenation reactor in step (a), formic acid is discharged from thermal dissociation unit.
2. according to the method for claim 1, wherein contain at least one element that is selected from Ru, Rh and Pd and at least one phosphine part as the transition metal complex of catalyzer, described phosphine part has the organic group of 13-30 carbon atom with at least one, preferably there is 14-26 carbon atom, more preferably there is 14-22 carbon atom, especially preferably there is 15-22 carbon atom, especially there is 16-20 carbon atom.
3. according to the method for claim 1 or 2, wherein contain at least one and have the bidentate phosphine ligands of general formula (I) as the transition metal complex of catalyzer:
Wherein
R 11, R 12, R 13, R 14unsubstituted independently of one another or at least mono-substituted-C 13-C 30alkyl ,-(phenyl)-(C 7-C 24alkyl) ,-(phenyl)-(C 4-C 24alkyl) 2,-(phenyl)-(C 3-C 24alkyl) 3,-(phenyl)-(O-C 7-C 24alkyl) ,-(phenyl)-(O-C 4-C 24alkyl) 2,-(phenyl)-(O-C 3-C 24alkyl) 3,-(cyclohexyl)-(C 7-C 24alkyl) ,-(cyclohexyl)-(C 4-C 24alkyl) 2,-(cyclohexyl)-(C 3-C 24alkyl) 3,-(cyclohexyl)-(O-C 7-C 24alkyl) ,-(cyclohexyl)-(O-C 4-C 24alkyl) 2or-(cyclohexyl)-(O-C 3-C 24alkyl) 3, wherein substituting group is Xuan Zi – F ,-Cl ,-Br ,-OH, – OR a,-COOH ,-COOR a,-OCOR a,-CN ,-NH 2,-N (R a) 2with-NHR a;
R 15, R 16be independently of one another hydrogen or-C 1-C 4alkyl, or form unsubstituted or at least mono-substituted phenyl or cyclohexyl ring together with the carbon atom connecting with them, wherein substituting group is Xuan Zi – OCOR a,-OCOCF 3,-OSO 2r a,-OSO 2cF 3,-CN ,-OH ,-OR a,-N (R a) 2,-NHR awith-C 1-C 4alkyl;
R abe-C 1-C 4alkyl, and
N, m are 0,1 or 2 independently of one another.
4. according to the method for any one in claim 1-3, wherein contain one and have bidentate phosphine ligands and at least one monodentate monophosphorus ligand of general formula (I) as the transition metal complex of catalyzer, described monodentate monophosphorus ligand has the organic group of 1-20 carbon atom with at least one.
5. according to the method for any one in claim 1-4, wherein monodentate monophosphorus ligand has general formula (Ia):
PR 19R 20R 21 (Ia)
Wherein
R 19, R 20, R 21be independently of one another unsubstituted or at least Dan replace – C 1-C 20alkyl ,-phenyl ,-benzyl, – cyclohexyl Huo – (CH 2)-cyclohexyl,
Wherein substituting group is Xuan Zi – C 1-C 20alkyl ,-F ,-Cl ,-Br ,-OH, – OR a,-COOH ,-COOR a,-OCOR a,-CN ,-NH 2,-N (R a) 2with-NHR a;
R abe-C 1-C 4alkyl.
6. according to the method for any one in claim 3-5, wherein bidentate phosphine ligands (I) is selected from 1,2-bis-(two tetradecyl phosphino-) ethane, 1,2-bis-(two pentadecyl phosphino-) ethane, 1,2-bis-(double hexadecyl phosphino-) ethane and 1,2-bis-(two octadecyl phosphino-) ethane.
7. according to the method for any one in claim 4-6, wherein monodentate phosphine ligand (Ia) is to be selected from three-normal-butyl phosphine, three-n-hexyl phosphine, and three-n-octyl phosphine, three-positive decyl phosphine and three-dodecyl phosphine.
8. according to the method for any one in claim 1-7, wherein tertiary amine used is the tertiary amine with general formula (A1), wherein radicals R 1, R 2, R 3be selected from independently of one another C 5-C 6alkyl, C 5-C 8cycloalkyl, benzyl and phenyl.
9. according to the method for any one in claim 1-8, wherein tertiary amine used (A1) is three n-hexyl amine.
10. according to the method for any one in claim 1-9, wherein polar solvent used is the mixture of water, methyl alcohol or water and methyl alcohol.
11. according to the method for any one in claim 1-10, wherein thermal dissociation unit comprises after-fractionating device and the 3rd water distilling apparatus, and formic acid-amine adduct (A2) is that dissociation obtains the overhead product (D2) that contains formic acid in after-fractionating device, its after-fractionating device is discharged; And obtaining two-phase bottom mixture (B2), it comprises the upper strata phase (U3) that contains corresponding tertiary amine (A1) and the lower floor's phase (L3) that contains formic acid-amine adduct (A2).
12. according to the method for claim 11, the bottom mixture (B2) wherein obtaining in after-fractionating device is separated into upper strata phase (U3) and lower floor's phase (L3) in the 3rd water distilling apparatus of thermal dissociation unit, and upper strata phase (U3) is recycled to the hydrogenation reactor in step (a), lower floor's phase (L3) is recycled in the after-fractionating device of thermal dissociation unit.
13. 1 kinds of transition metal complexes, it contains at least one element that is selected from the periodic table of elements 8,9 and 10 families and at least one phosphine part with general formula (I) according to claim 3.
14. according to the transition metal complex of claim 13, and it contains phosphine part and at least one monodentate phosphine ligand with general formula (Ia) according to claim 5 with general formula (I) according to claim 3.
15. according to the transition metal complex of claim 13 or 14 purposes as catalyzer in the method for preparing formic acid.
CN201280054841.XA 2011-11-10 2012-11-07 Process for the preparation of formic acid by reaction of carbon dioxide with hydrogen Pending CN103917551A (en)

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