CN103974927A - Method for producing formic acid by reacting carbon dioxide with hydrogen - Google Patents

Method for producing formic acid by reacting carbon dioxide with hydrogen Download PDF

Info

Publication number
CN103974927A
CN103974927A CN201280059095.3A CN201280059095A CN103974927A CN 103974927 A CN103974927 A CN 103974927A CN 201280059095 A CN201280059095 A CN 201280059095A CN 103974927 A CN103974927 A CN 103974927A
Authority
CN
China
Prior art keywords
phase
formic acid
mixture
lower floor
tertiary amine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201280059095.3A
Other languages
Chinese (zh)
Inventor
T·绍布
O·贝
A·迈尔
D·M·弗莱斯
R·胡戈
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of CN103974927A publication Critical patent/CN103974927A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0202—Alcohols or phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
    • B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • B01J2531/98—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases

Abstract

The invention relates to a method for producing formic acid, comprising the following steps: (a) reacting, in a homogeneously catalyzed manner, a reaction mixture (Rg) containing carbon dioxide, hydrogen, at least one polar solvent selected from the group comprising methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and water, and at least one tertiary amine of general formula (A1) NR1R2R3, in which R1, R2, and R3 represent independently of one another an unbranched or branched, acyclic or cyclic, aliphatic, araliphatic, or aromatic group having 1 to 16 carbon atoms, wherein individual carbon atoms can also be substituted independently of one another with a hetero group selected from the groups -O- and >N- and two or all three residues can also be bonded to one another to from a chain comprising at least four atoms, in the presence of at least one coordination catalyst, which contains at least one element selected from groups 8, 9, and 10 of the periodic system, in a hydrogenation reactor in order to obtain, optionally after adding water, a two-phase hydrogenation mixture (H) containing an upper phase (O1), which contains the at least one coordination catalyst and the at least one tertiary amine (A1), and a lower phase (U1), which contains the at least one polar solvent, residues of the at least one coordination catalyst, and at least one formic acid/amine adduct of general formula (A2), NR1R2R3 * xi HCOOH, in which xi is in the range of 0.4 to 5 and R1, R2, R3 have the meanings stated above; (b) processing the hydrogenation mixture (H) obtained in step (a) according to one of the following steps:; (b1) phase-separating the hydrogenation mixture (H) obtained in step (a) in a first phase-separating device into the upper phase (O1) and the lower phase (U1), or (b2) extracting the at least one coordination catalyst from the hydrogenation mixture (H) obtained in step (a) in an extraction unit with an extracting agent containing the at least one tertiary amine (A1) in order to obtain a raffinate (R1) containing the at least one formic acid/amine adduct (A2) and the at least one polar solvent and an extract (E1) containing the at least one tertiary amine (A1) and the at least one coordination catalyst, or (b3) phase-separating the hydrogenation mixture (H) obtained in step (a) in a first phase-separating device into the upper phase (O1) and the lower phase (U1) and extracting the residues of the at least one coordination catalyst from the lower phase (U1) in an extraction unit by means of an extracting agent containing the at least one tertiary amine (A1) in order to obtain a raffinate (R2) containing the at least one formic acid/amine adduct (A2) and the at least one polar solvent and an extract (E2) containing the at least one tertiary amine (A1) and the residues of the at least one coordination catalyst; (c) separating the at least one polar solvent from the lower phase (U1), from the raffinate (R1), or from the raffinate (R2) in a first distillation device in order to obtain a distillate (D1) containing the at least one polar solvent, which is fed back into the hydrogenation reactor in step (a), and a two-phase bottom mixture (S1) containing an upper phase (O2), which contains the at least one tertiary amine (A1), and a lower phase (U2), which contains the at least one formic acid/amine adduct (A2); (d) optionally processing the bottom mixture (S1) obtained in step (c) by phase separation in a second phase-separating device into the upper phase (O2) and the lower phase (U2); (e) cleaving the at least one formic acid/amine adduct (A2) contained in the bottom mixture (S1) or optionally in the lower phase (U2) in a thermal cleaving unit in order to obtain the at least one tertiary amine (A1), which is fed back to the hydrogenation reactor in step (a), and formic acid, which is discharged from the thermal cleaving unit, wherein carbon monoxide is added to the lower phase (U1), the raffinate (R1), or the raffinate (R2) directly before and/or during step (c) and/or carbon monoxide is added to the bottom mixture (S1) or optionally the bottom phase (U2) directly before and/or during step (e).

Description

By making carbonic acid gas and hydrogen reaction, prepare the method for formic acid
Invention is described
The present invention relates to a kind of method of preparing formic acid, comprise carbonic acid gas is reacted to form formic acid-amine adduct, subsequently by described formic acid-amine adduct thermolysis formic acid and tertiary amine in hydrogenation reactor with hydrogen under the catalyzer that comprises periodictable the 8th, 9 Huo10 family elements, tertiary amine and polar solvent exist.
Formic acid becomes free formic acid and tertiary amine with the adducts thermal decomposition of tertiary amine, the intermediate of therefore preparing as formic acid.
Formic acid is a kind of product of important and widespread use.Its acidifying of for example producing for animal-feed, as sanitas, as sterilizing agent, as the auxiliary agent in weaving and leather industry, as the mixture with its salt for the deicing of aircraft and runway and as the composite structure unit of chemical industry.
The above-mentioned adducts of formic acid and tertiary amine can be prepared with the whole bag of tricks, for example (i) is by tertiary amine and formic acid direct reaction, (ii) pass through under tertiary amine exists by methyl formate hydrolysis formic acid, (iii) by the catalytic hydration of carbon monoxide under existing at tertiary amine or (iv) by carbonic acid gas being hydrogenated to formic acid under tertiary amine existence.The concrete advantage of a rear method of catalytic hydrogenation carbonic acid gas is that carbonic acid gas can obtain in a large number with regard to its source and is flexibly.
EP0181078 has described a kind of method that adducts by thermolysis formic acid and tertiary amine is prepared formic acid.According to EP0181078, the method for preparing formic acid comprises the steps:
I) make carbonic acid gas and hydrogen react to obtain the adducts of formic acid and volatility tertiary amine under volatility tertiary amine and catalyzer existence,
It is ii) in vaporizer, the adducts of formic acid and volatility tertiary amine is separated with gaseous component with catalyzer,
It is iii) in distillation tower or phase-separating device, unreacted volatility tertiary amine is separated with the adducts of volatility tertiary amine with formic acid,
Iv) with the lower and more weak nitrogen base of volatility, as the volatility tertiary amine in the adducts of 1-normal-butyl imidazoles alkali displacement formic acid and volatility tertiary amine,
V) adducts of the lower and more weak nitrogen base of thermolysis formic acid and described volatility is to obtain formic acid and the lower and more weak nitrogen base of described volatility.
In EP0181078, must be with the lower and more weak nitrogen base of volatility, as the volatility tertiary amine in 1-normal-butyl imidazoles displacement formic acid adducts before thermolysis.Therefore, the method for EP0181078 is very complicated, especially with regard to definitely essential alkali displacement.
Another remarkable shortcoming of the method for EP0181078 is being separated in vaporizer under catalyzer exists according to the above-mentioned steps ii of EP0181078 of adducts of formic acid and volatility tertiary amine) carry out.
This catalysis the adducts of formic acid and volatility tertiary amine according to following reaction equation, resolve into again carbonic acid gas, hydrogen and volatility tertiary amine:
This productive rate that decomposes again the adducts that causes formic acid and volatility tertiary amine significantly reduces, and therefore causes the productive rate of target product formic acid to reduce.
In EP0329337, propose to add and suppress the inhibitor of catalyzer as the solution of this problem.As preferred inhibitor, mention carboxylic acid, carbon monoxide and oxygenant.Therefore, the preparation of formic acid comprises above in the step I described in EP0181078)-v), wherein in step I) afterwards and at step I i) before or during add inhibitor.
The shortcoming of EP0329337 method is not only complicated alkali displacement (step I v)), and be the following fact: if use carboxylic acid as inhibitor, hydrogenation (step (i)) together with the tertiary amine of described inhibitor and recirculation, this has disturbed the building-up reactions that forms the adducts of formic acid and volatility tertiary amine.When using carbon monoxide and oxygenant, according to the method for EP0329337, possibility reversible inhibition catalyzer also can be by described catalyst recycle to this reaction really.Yet a basic shortcoming of EP0329337 is that the most of catalyzer existing in described method is suppressed.Therefore, most repressed catalyzer is being reused for hydrogenation (step I)) before must the method at EP0329337 in reactivate in step externally.This needs a large amount of reagent and high-energy input and time consumption of suppressing with the repressed catalyzer of reactivate.
In addition, according to the whole bottoms from low-boiling-point substance separation being recycled to hydrogenation to avoid the loss of catalyzer in the method for EP0329337.In order to prevent that hydrogenation space-time yield from reducing, and must evaporate the formic acid from bottoms in addition completely.
WO2010/149507 described a kind of by tertiary amine, transition-metal catalyst with have>=200 * 10 -30there is lower hydrogenation carbonic acid gas and prepare the method for formic acid in the high bp polar solvent of the Cm static factor, described polar solvent is for example ethylene glycol, glycol ether, triglycol, polyoxyethylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 1,4-butyleneglycol, dipropylene glycol, 1,5-pentanediol, 1,6-hexylene glycol and glycerine.The reaction mixture that acquisition comprises formic acid-amine adduct, tertiary amine, high bp polar solvent and catalyzer.According to WO2010/149507, according to following steps, this reaction mixture is carried out to aftertreatment:
1) be separated this reaction mixture to obtain the upper strata phase that comprises tertiary amine and catalyzer and the lower floor's phase that comprises formic acid-amine adduct, high bp polar solvent and catalyst residue; Described upper strata is recycled in hydrogenation mutually,
2) with tertiary amine, extract described lower floor to obtain the extraction liquid that comprises tertiary amine and catalyst residue and the raffinate that comprises high bp polar solvent and formic acid-amine adduct; Described extraction liquid is recycled in described hydrogenation,
3) in distillation tower by described raffinate thermolysis with obtain the distillate comprise formic acid and comprise free uncle amine and the tower of high bp polar solvent at the bottom of mixture; Described high bp polar solvent is recycled in hydrogenation.
With respect to EP0181078 and EP0329337, the advantage of WO2010/149507 method is that it does not carry out complicated alkali displacement step (step (iv)) and allows with its activity form separation and catalyst recycle.
Yet, although the shortcoming of WO2010/149507 method is to use and is separated (step 1)) and extraction (step 2)), the separation of catalyzer not completely always, make in step 3 thus) in the thermolysis carried out in distillation tower, trace catalyzer contained in raffinate can resolve into carbonic acid gas and hydrogen and tertiary amine by catalysis formic acid-amine adduct again.Another shortcoming is to be that, in the thermolysis of formic acid-amine adduct of carrying out in distillation tower, esterification occurs for formed formic acid and high bp polar solvent (glycol and polyvalent alcohol).This causes the productive rate of target product formic acid to reduce.
The object of this invention is to provide a kind of method of preparing formic acid by hydrogenation carbonic acid gas, described method does not have the shortcoming of above-mentioned prior art or only with significantly reduction degree, has these shortcomings, and obtains dense formic acid with high yield and high purity.In addition, described method should be carried out more simply than method described in prior art, particularly should allow simpler hydrogenation reactor discharging aftertreatment technology design, simpler processing step, number of process steps still less or more simply install.In addition, described method also should be able to and be used additive to carry out as inhibitor with low-down energy expenditure.Because the even a small amount of catalyzer that only can realize with very high expense in the active catalyst of uniform dissolution and the complete separated and thermolysis of product stream will cause formic acid significantly loss due to high temperature, therefore also should guarantee before distillation, trace catalyzer to be converted into inactive substance and hydrogenation not to be caused to disadvantageous effect.
This object can realize by a kind of method of preparing formic acid, and it comprises the steps:
(a) make to comprise carbonic acid gas, hydrogen, at least one is selected from the reaction mixture (Rg) of 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 the tertiary amine of at least one general formula (A1)
NR 1R 2R 3(A1)
Wherein:
R 1, R 2, R 3in the every kind of situation of respectively doing for oneself independently of one another, there is the not branching of 1-16 carbon atom or branching, acyclic or cyclic aliphatic, araliphatic or aromatic group, 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 to form the chain that comprises at least four atoms
Under existing, in hydrogenation reactor, there is homogeneous catalytic reaction to obtain the two-phase hydrogenated mixture (H) that comprises following component after optional interpolation water in the coordination catalyst that comprises at least one element that is selected from periodictable the 8th, 9 He10 families at least one:
Upper strata phase (U1), it comprises described at least one coordination catalyst and described at least one tertiary amine (A1), and
Lower floor's phase (L1), it comprises described at least one polar solvent, the residue of described at least one coordination catalyst and the formic acid-amine adduct of at least one general formula (A2),
NR 1R 2R 3*x iHCOOH (A2)
Wherein:
X ifor 0.4-5, and
R 1, R 2, R 3as defined above,
(b) according to one of following steps, the hydrogenated mixture (H) of gained in step (a) is carried out to aftertreatment:
(b1) in first-phase tripping device, the hydrogenated mixture (H) of gained in step (a) is separated into upper strata phase (U1) and lower floor's phase (L1), or
(b2) in extraction cells by least one coordination catalyst of extraction in the hydrogenated mixture (H) of the extraction agent that comprises at least one tertiary amine (A1) gained from step (a) to obtain:
Raffinate (R1), it comprises described at least one formic acid-amine adduct (A2) and described at least one polar solvent, and
Extraction liquid (E1), it comprises described at least one tertiary amine (A1) and described at least one coordination catalyst,
Or
(b3) in first-phase tripping device, the hydrogenated mixture (H) of step (a) gained is separated into upper strata phase (U1) and lower floor's phase (L1), and the residue that extracts described at least one coordination catalyst by the extraction agent that comprises described at least one tertiary amine (A1) from lower floor's phase (L1) in extraction cells is to obtain:
Raffinate (R2), it comprises described at least one formic acid-amine adduct (A2) and described at least one polar solvent, and
Extraction liquid (E2), the residue that it comprises described at least one tertiary amine (A1) and described at least one coordination catalyst,
(c) in the first distillation unit Zhong Cong lower floor phase (L1), raffinate (R1) or raffinate (R2) separated described at least one polar solvent to obtain:
Distillate (D1), it comprises described at least one polar solvent and is recirculated in the hydrogenation reactor of step (a), and
Mixture at the bottom of two-phase tower (S1), it comprises:
Upper strata phase (U2), it comprises described at least one tertiary amine (A1), and
Lower floor's phase (L2), it comprises described at least one formic acid-amine adduct (A2),
(d) optionally in second-phase tripping device, by being separated, mixture (S1) at the bottom of the tower of gained in step (c) is carried out to aftertreatment to obtain upper strata phase (U2) and lower floor's phase (L2),
(e) in thermal decomposition unit, make at the bottom of tower contained described at least one formic acid-amine adduct (A2) in mixture (S1) or optional lower floor's phase (L2) decompose to obtain described at least one tertiary amine (A1) in the hydrogenation reactor that is recycled to step (a) and the formic acid of discharging from thermal decomposition unit
Wherein be close to step (c) before and/or during step (c), carbon monoxide be added in lower floor's phase (L1), raffinate (R1) or raffinate (R2), and/or
Mixture (S1) or optional lower floor's phase (L2) at the bottom of being close to step (e) before and/or during step (e), carbon monoxide being added into tower.
Found by the inventive method, can obtain formic acid with high yield.Particularly advantageously the inventive method can be saved the alkali displacement (step (iv)) itself of EP0329337 and EP0181078 method.The inventive method allows effective separation to be the coordination catalyst of its activity form, and also separated coordination catalyst is recycled in the hydrogenation reactor of step (a).In addition, the use of inhibitor has prevented that formic acid-amine adduct (A2) from decomposing again, and this causes formic acid productive rate to improve.In addition, the inventive method can be recycled to hydrogenation with its activity form by most coordination catalyst, makes only must add a small amount of inhibitor and only sub-fraction coordination catalyst must suppressed to reactivate afterwards thus.In addition, can by the coordination catalyst suppressing by carbon monoxide in thermolysis, via amine, the thermal decomposition unit in step (e) be recycled in the hydrogenation of step (a), and reactivate again under reaction conditions therein.In addition, the whole bottom products from thermolysis must be recycled to step (a), thereby avoid catalyst loss in the methods of the invention.This tool has the following advantages: formic acid must completely always not evaporate to prevent the reduction of space-time yield in hydrogenation in the bottom product of thermolysis, and this is to be biphase mixture because of the bottom product from thermolysis.Be separated and separablely go out to comprise the amine phase of repressed coordination catalyst and can be recirculated to hydrogenation.Can be back to mutually thermolysis by what comprise formic acid.
Can also be by the repressed coordination catalyst of formerly thermal treatment reactivate of amine phase.In addition, the present invention's polar solvent used remove the esterification that has prevented the formic acid of gained in the thermal decomposition unit of step (e), this causes formic acid productive rate to improve equally.In addition, find that surprisingly polar solvent used according to the invention causes formic acid-amine adduct (A2) concentration in gained hydrogenated mixture (H) in step (a) to compare increase with high bp polar solvent used in WO2010/149507.This makes to use less reactor, and this has saved again cost.
Hereinafter, term " step " and " processing step " synonym are used.
the preparation of formic acid-amine adduct (A2); Processing step (a)
In the processing step (a) of the inventive method, make to comprise carbonic acid gas, hydrogen, at least one comprises at least one coordination catalyst that is selected from the element of periodictable the 8th, 9 He10 families, reaction mixture (Rg) that 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 the tertiary amine of at least one general formula (A1) reacts in hydrogenation reactor.
In processing step (a), carbonic acid gas used can be solid-state, liquid state or gaseous state.Also can use the carbonated industry of bag can obtain gaseous mixture, as long as these mixtures are gone up substantially not containing carbon monoxide (the volume ratio <1% of CO).In the carbonic acid gas hydrogenation of processing step (a), hydrogen used is generally gaseous state.Carbonic acid gas and hydrogen also can comprise rare gas element, as nitrogen or rare gas.Yet the content of these gases is advantageously lower than 10mol%, the carbonic acid gas based in hydrogenation reactor and hydrogen total amount.Although can tolerate equally in a large number, yet they cause the higher pressure of use in reactor conventionally, and this is compression energy further.
Carbonic acid gas and hydrogen can be used as independent material stream and introduce in processing step (a).In processing step (a), also can use the mixture that comprises carbonic acid gas and hydrogen.
In the method for the invention, the carbonic acid gas hydrogenation for processing step (a) by least one tertiary amine (A1).For the present invention, term " tertiary amine (A1) " refer to a kind of tertiary amine (A1) and two or more tertiary amines (A1) mixture the two.
Preferably to tertiary amine used in the inventive method (A1), selected or made it to mate with polar solvent, thereby make in processing step (a) hydrogenated mixture (H) that (optionally after adding water) obtain for two-phase mixture at least.Hydrogenated mixture (H) comprises upper strata phase (U1) and lower floor's phase (L1), its at the middle and upper levels phase (U1) comprise described at least one coordination catalyst and described at least one tertiary amine (A1), residue and at least one formic acid-amine adduct (A2) that lower floor's phase (L1) comprises described at least one polar solvent, described coordination catalyst.
Tertiary amine (A1) should be rich in upper strata phase (U1), and upper strata phase (U1) should comprise the major portion of tertiary amine (A1).For the present invention, " be rich in " relevant with tertiary amine (A1) or " major portion " mean the part by weight >50% of free uncle amine (A1) in upper strata phase (U1), free uncle amine (A1) gross weight based in liquid phase (being upper strata phase (U1) and the lower floor's phase (L1) in hydrogenated mixture (H)).
For the present invention, free uncle amine (A1) is not with the tertiary amine (A1) of formic acid-amine adduct (A2) form bonding.
The part by weight of the free uncle amine (A1) in upper strata phase (U1) is preferably >70%, >90% particularly, in each case based on hydrogenated mixture (H) gross weight of the free uncle amine (A1) of phase (U1) and lower floor's phase (L1) at the middle and upper levels.
Tertiary amine (A1) is selected by simple experiment conventionally, wherein under the processing condition of processing step (a), by test, determines phase behavior and the solvability of tertiary amine (A1) in liquid phase (upper strata phase (U1) and lower floor's phase (L1)).In addition, can in tertiary amine (A1), add non-polar solvent as aliphatic series, aromatics or araliphatic solvent.Preferred non-polar solvent is for example octane, toluene and/or dimethylbenzene (o-Xylol, m-xylene, p-Xylol).
Be preferred for the amine that the tertiary amine in the inventive method is following general formula:
NR 1R 2R 3(A1)
Radicals R wherein 1, R 2, R 3identical or different, and respectively do for oneself independently of one another and there is in each case 1-16 carbon atom, the not branching of preferred 1-12 carbon atom or branching, acyclic or ring-type, aliphatic series, araliphatic or aromatic group, wherein each carbon atom also can be selected from independently of one another-O-and the assorted group of >N-replace, and two or three groups also can be connected to each other to form the chain that comprises at least four atoms.In particularly preferred embodiments, use the tertiary amine of general formula (A1), condition is add up at least 9 of carbon atom.
As suitable tertiary amine (A1), for example can mention:
● Tri-n-Propylamine, tri-n-butylamine, tri-n-amyl amine, three normal hexyl Amines, three positive heptyl amices, tri-n-octyl amine, tri-n-nonylamine, three n-Decylamines, three n-undecane base amine, three dodecyl amine, three n-tridecane base amine, three n-tetradecane base amine, three Pentadecane base amine, three n-hexadecyl amine, tris-(2-ethylhexyl)amine.
● dimethyl decyl amine, dimethyl lauryl amine, dimethyl tetradecylamine, ethyl two (2-propyl group) amine, dioctyl methylamine, dihexyl methylamine.
● three cyclopentamine, tricyclohexyltin amine, three cycloheptylamines, three cyclooctylamines and the derivative being replaced by one or more methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl or 2-methyl-2-propyl thereof.
● dimethylcyclohexylamine, methyl bicyclic hexylamine, diethyl cyclohexylamine, ethyl dicyclohexyl amine, dimethyl cyclopentamine, methyl bicyclic amylamine.
● triphenylamine, methyldiphenylamine, ethyl pentanoic, propyl group pentanoic, butyl pentanoic, 2-ethylhexyl pentanoic, xylidine, Diethyl Aniline, dipropyl aniline, dibutyl aniline, two (2-ethylhexyl) aniline, tribenzylamine, methyl dibenzylamine, ethyl dibenzylamine and the derivative being replaced by one or more methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl or 2-methyl-2-propyl thereof.
● N-C 1-C 12alkylpiperidine, N, N-bis--C 1-C 12alkylpiperazine, N-C 1-C 12alkyl pyrrolidone, N-C 1-C 12alkyl imidazole and the derivative being replaced by one or more methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl or 2-methyl-2-propyl thereof.
● 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (" DBU "), Isosorbide-5-Nitrae-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 ").In the method for the invention, also can use the mixture of two or more different tertiary amines (A1).Particularly preferably use wherein radicals R 1, R 2, R 3independently selected from C 1-C 12alkyl, C 5-C 8the amine of cycloalkyl, benzyl and phenyl is as the tertiary amine in the inventive method (A1).
Particularly preferably use saturated amine, only comprise the amine of singly-bound as the tertiary amine in the inventive method (A1).
Very particularly preferably use wherein radicals R 1, R 2, R 3independently selected from C 5-C 8the amine, particularly tri-n-amyl amine of the general formula of alkyl (A1), three normal hexyl Amines, three positive heptyl amices, tri-n-octyl amine, dimethylcyclohexylamine, methyl bicyclic hexylamine, dioctyl methylamine and dimethyl decyl amine are as the tertiary amine in the inventive method.
In embodiments of the present invention, use the tertiary amine of a kind of general formula (A1).
Especially, use wherein radicals R 1, R 2, R 3independently selected from C 5alkyl and C 6the amine of the general formula of alkyl (A1) is as tertiary amine.In the methods of the invention, most preferably use three normal hexyl Amines as the tertiary amine of general formula (A1).
In the method for the invention, tertiary amine (A1) preferably exists with liquid form in all processing steps.Yet this is not absolute requirement.Also enough is that tertiary amine (A1) is at least dissolved in suitable solvent.Suitable solvent in principle for to carbonic acid gas hydrogenation be chemically inert those, wherein said tertiary amine (A1) and catalyzer are easy to be dissolved in wherein and wherein on the contrary, described polar solvent and formic acid-amine adduct (A2) are slightly soluble in wherein.Therefore, can be in principle chemically inert non-polar solvent, for example, as aliphatic hydrocrbon, aromatic hydrocarbon or araliphatic hydrocarbon, octane and higher alkane, toluene, dimethylbenzene.
In the method for the invention, at least one is selected to 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 for the carbonic acid gas hydrogenation of processing step (a).
For the present invention, term " polar solvent " refer to a kind of polar solvent and two or more polar solvents mixture the two.
Preferably so that the mode that the phase behavior in the hydrogenation reactor of processing step (a) preferably meets following standard to the inventive method in polar solvent used selected or made it mate with tertiary amine (A1): should be preferably so that in processing step (a), optionally after interpolation water, the hydrogenated mixture (H) of acquisition is that at least the mode of two-phase mixture is selected polar solvent.Described polar solvent should be rich in lower floor's phase (L1), and lower floor's phase (L1) should comprise the major portion of described polar solvent.For the present invention, the in the situation that of described polar solvent, " be rich in " or " major portion " means the polar solvent part by weight >50% in lower floor's phase (L1), the polar solvent gross weight in the liquid phase based on hydrogenation reactor (upper strata phase (U1) and lower floor's phase (L1)).
Polar solvent part by weight preferred >70%, particularly >90% in lower floor's phase (L1), in each case the polar solvent gross weight based in upper strata phase (U1) and lower floor's phase (L1).
The selection that meets the polar solvent of above-mentioned standard is undertaken by simple experiment conventionally, wherein under the processing condition of processing step (a), by test, determines phase behavior and the solvability of polar solvent in liquid phase (upper strata phase (U1) and lower floor's phase (L1)).
Described polar solvent can be the mixture of pure polar solvent or two or more polar solvents, as long as the mixture of described polar solvent or polar solvent meets with regard to the hydrogenation reactor of processing step (a) phase (U1) and lower floor's phase (L1) at the middle and upper levels) phase behavior and the above-mentioned standard with regard to solvability.
In embodiments of the present invention, first in step (a), obtain single-phase hydrogenated mixture, and transferred into two-phase hydrogenated mixture (H) by adding water.
In another embodiment of the inventive method, in step (a), directly obtain two-phase hydrogenated mixture (H).The two-phase hydrogenated mixture (H) obtaining according to this embodiment directly can be delivered to the aftertreatment of step (b).Also can before the further aftertreatment of step (b), in two-phase hydrogenated mixture (H), additionally add water.This can improve partition ratio P k.
When the mixture of alcohol (being selected from methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols and 2-methyl isophthalic acid-propyl alcohol) and water is used as to polar solvent, ratio to alcohol and water is selected, thereby makes to form together with formic acid-amine adduct (A2) and tertiary amine (A1) at least two-phase hydrogenated mixture (H) that comprises upper strata phase (U1) and lower floor's phase (L1).
For wherein the mixture of alcohol (being selected from methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols and 2-methyl isophthalic acid-propyl alcohol) and water being used as to the situation of polar solvent, also can be selected the ratio of alcohol and water, thereby make first to form single-phase hydrogenated mixture (H) together with formic acid-amine adduct (A2) and tertiary amine (A1), by adding water, change into two-phase hydrogenated mixture (H) subsequently.
In another particularly preferred embodiment, the mixture of water, methyl alcohol or water and methyl alcohol is used as to polar solvent.
Preferably do not use glycol and manthanoate thereof, polyvalent alcohol and manthanoate thereof, sulfone, sulfoxide and open chain or cyclic amide as polar solvent.In preferred embodiments, in reaction mixture (Rg), there are not these polar solvents.
In the processing step of the inventive method (a), polar solvent used or the mol ratio of solvent mixture and tertiary amine used (A1) are generally 0.5-30, are preferably 1-20.
Coordination catalyst for carbonic acid gas hydrogenation in the inventive method processing step (a) comprises at least one element that is selected from periodictable the 8th, 9 Huo10 families (according to IUPAC nomenclature).Periodictable the 8th, 9 Huo10 families comprise Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt.In processing step (a), can use the mixture of a kind of coordination catalyst or two or more coordination catalysts.Preferably use a kind of coordination catalyst.For the present invention, term " coordination catalyst " refer to a kind of coordination catalyst and two or more coordination catalysts mixture the two.
Described coordination catalyst preferably comprises at least one element that is selected from Ru, Rh, Pd, Os, Ir and Pt, and particularly preferably at least one is selected from the element of Ru, Rh and Pd.Described coordination catalyst very particularly preferably comprises Ru.
Preferably use the corrdination type compound of above-mentioned element as coordination catalyst.The preferred homogeneous catalysis of reaction in processing step (a) is carried out.
For the present invention, the catalytic activity part that " homogeneous catalysis " means coordination catalyst is present in liquid reaction medium with solution form at least partly.In preferred embodiments, in processing step (a) used at least 90%, more preferably at least 95%, particularly preferably surpassing 99% coordination catalyst is present in liquid reaction medium with solution form, most preferably described coordination catalyst whole (100%) is present in liquid reaction medium with solution form, in each case based on existing coordination catalyst total amount in liquid reaction medium.
The amount of the metal component of the coordination catalyst in processing step (a) is generally 0.1-5000 ppm by weight, be preferably 1-800 ppm by weight, be particularly preferably 5-800 ppm by weight, in each case the total liquid reaction mixture (Rg) based in described hydrogenation reactor.Described coordination catalyst is selected so that it is rich in upper strata phase (U1) to the major portion that upper strata phase (U1) comprises described coordination catalyst.For the present invention, the in the situation that of coordination catalyst, " being rich in " or " major portion " means the partition ratio P of described coordination catalyst k=[the coordination catalysis agent concentration in upper strata phase (U1)]/[the coordination catalysis agent concentration in lower floor's phase (L1)] >1.Preferred allocation FACTOR P k>1.5, particularly preferably partition ratio P k>4.The selection of described coordination catalyst is undertaken by simple experiment conventionally, wherein under the processing condition of processing step (a), by test, determines phase behavior and the solvability of coordination catalyst in liquid phase (upper strata phase (U1) and lower floor's phase (L1)).
Due to its good solubility in tertiary amine, preferably by the homogeneous phase coordination catalyst of the element that comprises periodictable the 8th, 9 Huo10 families and at least one phosphino-, especially a metal-organic complex is as the coordination catalyst in the inventive method, described phosphino-has at least one not branching with 1-12 carbon atom or branching, acyclic or cyclic aliphatic group, and wherein each carbon atom also can be replaced by >P-.Term " branching cyclic aliphatic group " also comprises such as-CH 2-C 6h 11group.Suitable group is for example 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, 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.Described not branching or branching, acyclic or cyclic aliphatic group preferably comprise at least 1 carbon atom and are preferably no more than 10 carbon atoms.In the situation that the only cyclic group in above-mentioned intended scope, the quantity of carbon atom is 3-12, is preferably at least 4, is preferably no more than 8.Preferred group is ethyl, 1-butyl, sec-butyl, 1-octyl group and cyclohexyl.
Described phosphino-can comprise 1,2 or 3 above-mentioned not branching or branching, acyclic or cyclic aliphatic group.These groups can be identical or different.Described phosphino-preferably comprises 3 above-mentioned not branching or branching, acyclic or cyclic aliphatic group, and wherein particularly preferably whole three groups are all identical.Preferred phosphine is P (positive C nh 2n+1) 3, wherein n is 1-10, particularly preferably two (dicyclohexyl phosphino-) ethane of tri-n-butyl phosphine, tri-n-octyl phosphine and 1,2-.
As mentioned above, each carbon atom in above-mentioned not branching or branching, acyclic or cyclic aliphatic group also can be replaced by >P-.Therefore, also comprise multiple tooth as bidentate or three tooth phosphine parts.These preferably include following group:
If described phosphino-comprises the group that is different from above-mentioned not branching or branching, acyclic or cyclic aliphatic group, these groups are generally used for those in the phosphine part of metal-organic coordination catalyzer corresponding to other conventionally.The example that can mention is phenyl, tolyl and xylyl.
Described Metal-organic complex can comprise one or more, and for example 2,3 or 4 above-mentionedly have at least one not phosphino-of branching or branching, acyclic or cyclic aliphatic group.All the other parts of described Metal-organic complex can have different character.The illustrative example that can mention is hydride, fluorochemical, muriate, bromide, iodide, manthanoate, acetic ester, propionic ester, carboxylicesters, acetylacetonate, carbonyl, DMSO, oxyhydroxide, trialkylamine, alkoxide.
Described homogeneous catalyst can be with the directly preparation or only under reaction conditions and add under suitable phosphine part by conventional criteria title complex as [M (p-Cymene) Cl of its activity form 2] 2, [M (benzene) Cl 2] n, [M (COD) (allyl group)], [MCl 3xH 2o], [M (acetylacetonate) 3], [M (COD) Cl 2] 2, [M (DMSO) 4cl 2] preparation, wherein M is the element of periodictable the 8th, 9 Huo10 families.
The preferred homogeneous phase coordination catalyst of the inventive method institute is selected from [Ru (P nbu 3) 4(H) 2], [Ru (P n-octyl 3) 4(H) 2], [Ru (P nbu 3) 2(1,2-two (dicyclohexyl phosphino-) ethane) (H) 2], [Ru (P n-octyl 3) 2(1,2-two (dicyclohexyl phosphino-) ethane) (H) 2], [Ru (PEt 3) 4(H) 2], [Ru (P n-octyl 3) (two (dicyclohexyl phosphino-) ethane of 1,2-) (CO) (H) 2], [Ru (P n-octyl 3) (1,2-two (dicyclohexyl phosphino-) ethane) (CO) (H) (HCOO)], [Ru (P normal-butyl 3) (two (dicyclohexyl phosphino-) ethane of 1,2-) (CO) (H) 2], [Ru (P normal-butyl 3) (1,2-two (dicyclohexyl phosphino-) ethane) (CO) (H) (HCOO)], [Ru (the positive ethyl of P 3) (two (dicyclohexyl phosphino-) ethane of 1,2-) (CO) (H) 2], [Ru (the positive ethyl of P 3) (1,2-two (dicyclohexyl phosphino-) ethane) (CO) (H) (HCOO)], [Ru (P n-octyl 3) (two (dicyclohexyl phosphino-) methane of 1,1-) (CO) (H) 2], [Ru (P n-octyl 3) (1,1-two (dicyclohexyl phosphino-) methane) (CO) (H) (HCOO)], [Ru (P normal-butyl 3) (two (dicyclohexyl phosphino-) methane of 1,1-) (CO) (H) 2], [Ru (P normal-butyl 3) (1,1-two (dicyclohexyl phosphino-) methane) (CO) (H) (HCOO)], [Ru (the positive ethyl of P 3) (two (dicyclohexyl phosphino-) methane of 1,1-) (CO) (H) 2], [Ru (the positive ethyl of P 3) (1,1-two (dicyclohexyl phosphino-) methane) (CO) (H) (HCOO)], [Ru (P n-octyl 3) (two (diphenylphosphino) ethane of 1,2-) (CO) (H) 2], [Ru (P n-octyl 3) (1,2-two (diphenylphosphino) ethane) (CO) (H) (HCOO)], [Ru (P normal-butyl 3) (two (diphenylphosphino) ethane of 1,2-) (CO) (H) 2], [Ru (P normal-butyl 3) (1,2-two (diphenylphosphino) ethane) (CO) (H) (HCOO)], [Ru (the positive ethyl of P 3) (two (diphenylphosphino) ethane of 1,2-) (CO) (H) 2], [Ru (the positive ethyl of P 3) (1,2-two (diphenylphosphino) ethane) (CO) (H) (HCOO)], [Ru (P n-octyl 3) (two (diphenylphosphino) methane of 1,1-) (CO) (H) 2], [Ru (P n-octyl 3) (1,1-two (diphenylphosphino) methane) (CO) (H) (HCOO)], [Ru (P normal-butyl 3) (two (diphenylphosphino) methane of 1,1-) (CO) (H) 2], [Ru (P normal-butyl 3) (1,1-two (diphenylphosphino) methane) (CO) (H) (HCOO)], [Ru (the positive ethyl of P 3) (two (diphenylphosphino) methane of 1,1-) (CO) (H) 2], [Ru (the positive ethyl of P 3) (1,1-two (diphenylphosphino) methane) (CO) (H) (HCOO)].
By these catalyzer, can in carbonic acid gas hydrogenation, obtain and be greater than 1000h -1tOF (inversion frequency) value.
The hydrogenation of the carbonic acid gas in processing step (a), in liquid phase, is preferably carried out under the total pressure of the temperature of 20-200 ℃ and 0.2-30MPa (definitely).Described temperature is preferably at least 30 ℃, and particularly preferably at least 40 ℃, and be preferably no more than 150 ℃, and be particularly preferably no more than 120 ℃, be very particularly preferably no more than 80 ℃.Total pressure is preferably at least 1MPa (definitely), is particularly preferably at least 5MPa (definitely), and preferably not higher than 20MPa (definitely).
In preferred embodiments, the hydrogenation in processing step (a) is carried out under the pressure of the temperature of 40-80 ℃ and 5-20MPa (definitely).
In processing step (a), the dividing potential drop of carbonic acid gas is generally at least 0.5MPa, is preferably at least 2MPa, is conventionally no more than 8MPa.In preferred embodiments, the hydrogenation in processing step (a) is carried out under the partial pressure of carbon dioxide of 2-7.3MPa.
In processing step (a), the dividing potential drop of hydrogen is generally at least 0.5MPa, is preferably at least 1MPa, and is conventionally no more than 25MPa, is preferably no more than 15MPa.In preferred embodiments, in processing step (a), hydrogenation is carried out under 1-15MPa hydrogen partial pressure.
Hydrogen in reaction mixture in described hydrogenation reactor (Rg) and the mol ratio of carbonic acid gas are preferably 0.1-10, are particularly preferably 1-3.
The mol ratio of the carbonic acid gas in the reaction mixture in described hydrogenation reactor (Rg) and tertiary amine (A1) is preferably 0.1-10, is particularly preferably 0.5-3.
As hydrogenation reactor, can use in principle and be suitable for all reactors of carrying out gas/liquid reactions under fixed temperature and setting pressure giving.Appropriate criteria reactor for gas-liquid reaction system is for example described in K.D.Henkel, " Reactor Types and Their Industrial Applications ", Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCHVerlaggmbH & Co.KGaA, DOI:10.1002/14356007.b04_087, in the 3.3rd chapter " Reactors forgas-liquid reactions ".The example that can mention is stirred-tank reactor, tubular reactor and bubbling column reactor.
In the method for the invention, the hydrogenation of carbonic acid gas can intermittently or be carried out continuously.In discontinuous method, in reactor, pack required liquid and optional solid feed and auxiliary agent into, subsequently at required temperature injecting carbon dioxide and polar solvent to required pressure.After reaction finishes, conventionally described reactor is reduced pressure and formed two liquid phases are separated from one another.In continuation method, introduce continuously raw material and auxiliary agent (comprising carbonic acid gas and hydrogen).Therefore, from reactor, discharge continuously liquid phase so that the liquid level in described reactor on average keeps constant.Preferred continuous hydrogenation carbonic acid gas.
In reaction mixture (Rg), the mean residence time of contained component in hydrogenation reactor is generally 5 minutes to 5 hours.
Homogeneous catalytic hydrogenation in processing step (a) has obtained the hydrogenated mixture (H) that comprises described coordination catalyst, polar solvent, tertiary amine (A1) and described at least one formic acid-amine adduct (A2).
For the present invention, term " formic acid-amine adduct (A2) " refers to the mixture of a kind of formic acid-amine adduct (A2) and two or more formic acid-amine adducts (A2).When two or more tertiary amines (A1) during for reaction mixture (Rg), are obtained to the mixture of two or more formic acid-amine adducts (A2) in processing step (a).
In the preferred embodiment of the inventive method, the hydrogenated mixture (H) that the reaction mixture that comprises a kind of tertiary amine (A1) (Rg) is comprised to a kind of formic acid-amine adduct (A2) for processing step (a) with acquisition.
In the particularly preferred embodiment of the inventive method, by comprising the reaction mixture (Rg) of three normal hexyl Amines as tertiary amine (A1), for processing step (a), to obtain, comprise the hydrogenated mixture (H) corresponding to three normal hexyl Amines of following formula (A3) and the formic acid-amine adduct of formic acid:
N (n-hexyl) 3* x ihCOOH (A3)
In general formula (A2) or formic acid-amine adduct (A3), radicals R 1, R 2, R 3have above to the tertiary amine of formula (A1) to implication, the preferred version that wherein this place is stated is applicable similarly.
At general formula (A2) with (A3), x ifor 0.4-5.Coefficient x irepresent formic acid-amine adduct (A2) or average composition (A3), formic acid-amine adduct (A2) or (A3) in the ratio of bonding tertiary amine (A1) and bonding formic acid.
Coefficient x ican for example by the alcoholic solution with KOH, to phenolphthalein acid-base titration, measure formic acid content determines.Coefficient x ialso can determine by gas chromatography determination amine content.Formic acid-amine adduct (A2) or accurate composition (A3) depend on many parameters, as existence and the character of the concentration of formic acid and tertiary amine (A1), pressure, temperature, other components, particularly polar solvent.
Therefore, formic acid/amine adduct (A2) or composition (A3), i.e. coefficient x ican change with each processing step.Therefore, for example, there is the formic acid-amine adduct (A2) of higher formic acid content or (A3) conventionally after removing polar solvent, form, wherein from formic acid-amine adduct (A2), remove excessive bonding tertiary amine (A1) and form second-phase.
Processing step (a) obtains formic acid-amine adduct (A2) or (A3), wherein x conventionally ifor 0.4-5, be preferably 0.7-1.6.
Formic acid-amine adduct (A2) is rich in lower floor's phase (L1), the major portion that lower floor's phase (L1) comprises described formic acid-amine adduct.For the present invention, " be rich in " or " major portion " means formic acid-amine adduct (A2) part by weight >50% in lower floor's phase (L1) with regard to formic acid-amine adduct (A2), formic acid-amine adduct (A2) gross weight based in liquid phase in hydrogenation reactor (upper strata phase (U1) and lower floor's phase (L1)).
Formic acid-amine adduct (A2) part by weight in lower floor's phase (L1) is preferably >70%, be in particular >90%, in each case formic acid-amine adduct (A2) gross weight based in upper strata phase (U1) and lower floor's phase (L1).
the aftertreatment of hydrogenated mixture (H); Processing step (b)
In the carbonic acid gas hydrogenation of processing step (a) hydrogenated mixture (H) of gained preferably there are two liquid phases and in processing step (b) according to step (b1), (b2) or one of (b3) to its further aftertreatment.
According to the aftertreatment of processing step (b1)
In preferred embodiments, according to step (b1) to further aftertreatment of hydrogenated mixture (H).Therefore, the present invention also provides a kind of method of preparing formic acid, and it comprises the steps:
(a) make to comprise carbonic acid gas, hydrogen, at least one is selected from the reaction mixture (Rg) of 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 the tertiary amine of at least one general formula (A1)
NR 1R 2R 3(A1)
Wherein:
R 1, R 2, R 3in the every kind of situation of respectively doing for oneself independently of one another, there is the not branching of 1-16 carbon atom or branching, acyclic or cyclic aliphatic, araliphatic or aromatic group, 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 to form the chain that comprises at least four atoms
Under existing, in hydrogenation reactor, there is homogeneous catalytic reaction to obtain the two-phase hydrogenated mixture (H) that comprises following component after optional interpolation water in the coordination catalyst that comprises at least one element that is selected from periodictable the 8th, 9 He10 families at least one:
Upper strata phase (U1), it comprises described at least one coordination catalyst and described at least one tertiary amine (A1), and
Lower floor's phase (L1), it comprises described at least one polar solvent, the residue of described at least one coordination catalyst and the formic acid-amine adduct of at least one general formula (A2),
NR 1R 2R 3*x iHCOOH (A2)
Wherein:
X ifor 0.4-5, and
R 1, R 2, R 3as defined above,
(b1) in first-phase tripping device, the hydrogenated mixture (H) of gained in step (a) is separated into upper strata phase (U1) and lower floor's phase (L1),
(c) in the first distillation unit Zhong Cong lower floor phase (L1) separated described at least one polar solvent to obtain: distillate (D1), it comprises described at least one polar solvent and is recirculated in the hydrogenation reactor of step (a), and
Mixture at the bottom of two-phase tower (S1), it comprises:
Upper strata phase (U2), it comprises described at least one tertiary amine (A1), and
Lower floor's phase (L2), it comprises described at least one formic acid-amine adduct (A2),
(d) optionally in second-phase tripping device, by being separated, mixture (S1) at the bottom of the first tower of gained in step (c) is carried out to aftertreatment to obtain upper strata phase (U2) and lower floor's phase (L2),
(e) in thermal decomposition unit, make at the bottom of tower contained described at least one formic acid-amine adduct (A2) in mixture (S1) or optional lower floor's phase (L2) decompose to obtain described at least one tertiary amine (A1) in the hydrogenation reactor that is recycled to step (a) and the formic acid of discharging from thermal decomposition unit
Wherein in being close to step (c) before and/or carbon monoxide being added into lower floor's phase (L1) during step (c) and/or
At the bottom of being close to step (e) before and/or during step (e), carbon monoxide being added into tower in mixture (S1) or optional lower floor's phase (L2).
Lower floor's phase (L1) of the residue that herein, further aftertreatment comprises described at least one formic acid-amine adduct (A2), described at least one polar solvent and described at least one coordination catalyst with acquisition to the hydrogenated mixture (H) of gained in processing step (a) by being separated in first-phase tripping device and the upper strata phase (U1) that comprises described at least one coordination catalyst and described at least one tertiary amine (A1).
In preferred embodiments, upper strata phase (U1) is recycled in hydrogenation reactor.In preferred embodiments, lower floor's phase (L1) is fed in the first water distilling apparatus of processing step (c).Also can be advantageously will comprise unreacted carbonic acid gas and be present in another liquid phase on described two liquid phases and the gas phase that comprises unreacted carbonic acid gas and/or unreacted hydrogen is recycled in hydrogenation reactor.What may wish is for example from described method, to discharge liquid phase or the gas phase that undesirable by product or impurity, discharge part upper strata phase (U1) and/or a part comprise carbonic acid gas or carbonic acid gas and hydrogen.
In processing step (a), the separation of the hydrogenated mixture (H) of gained is conventionally separated and is carried out by gravity.Suitable phase-separating device is such as for being found in such as E.M ü ller etc., " Liquid-liquidExtraction ", in Ullman ' s Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH VerlaggmbH & Co.KGaA, DOI:10.1002/14356007.b93_06, standard set-up and standard method in the 3rd chapter " Apparatus ".Generally speaking, be rich in the liquid phase of formic acid-amine adduct (A2) and polar solvent heavier and form lower floor's phase (L1).
Described being separated can be for example undertaken by being decompressed to approximately or approaching normal atmosphere and described liquid hydrogenated mixture being for example cooled to approximately or approaching envrionment temperature.
For the present invention, found when selecting the appropriate combination of polar solvent and tertiary amine (A1), in system of the present invention, be rich in lower floor's phase (L1) of formic acid-amine adduct (A2) and polar solvent and be rich in the upper strata phase (U1) of tertiary amine (A1) and coordination catalyst, even if described two liquid phases are also very well separated under the pressure significantly raising.Therefore, polar solvent in the inventive method and tertiary amine (A1) are selected, so that be rich in lower floor's phase (L1) of formic acid-amine adduct (A2) and polar solvent, be recycled to hydrogenation reactor with the separated and upper strata phase (U1) that is rich in the upper strata phase (U1) of tertiary amine (A1) and coordination catalyst and can under the pressure of 1-30Mpa (definitely), carry out.Corresponding to the total pressure in hydrogenation reactor, described pressure is preferably no more than 15Mpa (definitely).Therefore, can be in first-phase tripping device, described two liquid phases (upper strata phase (U1) and lower floor's phase (L1)) are separated from one another and under not significantly improving pressure, upper strata phase (U1) is recycled in hydrogenation reactor under decompression in advance not.
Also can directly in hydrogenation reactor, be separated.In this embodiment, hydrogenation reactor plays first-phase tripping device simultaneously, and processing step (a) and (b1) all carry out in hydrogenation reactor.Now, upper strata phase (U1) is retained in the first water distilling apparatus of hydrogenation reactor Zhong Bingjiang lower floor phase (L1) infeed processing step (c).
In one embodiment, method of the present invention can be in hydrogenation reactor pressure and temperature identical with first-phase tripping device or roughly the same under carry out, wherein for the present invention, roughly the same mean pressure reduction for +/-0.5 bar or the temperature difference be at the most 10 ℃ of +/-at the most.
Also find surprisingly in this system situation, even at the temperature of the rising of the temperature of reaction corresponding in hydrogenation reactor, described two liquid phases (upper strata phase (U1) and lower floor's phase (L1)) are also separated from one another easily.In this case, cooling with being separated and treating the upper strata phase (U1) of recirculation with post-heating of implementing process step (b1) without carrying out, this has saved energy equally.
According to the aftertreatment of processing step (b3)
In another preferred embodiment, according to step (b3) to further aftertreatment of hydrogenated mixture (H).Therefore, the present invention also provides a kind of method of preparing formic acid, and it comprises the steps:
(a) make to comprise carbonic acid gas, hydrogen, at least one is selected from the reaction mixture (Rg) of 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 the tertiary amine of at least one general formula (A1)
NR 1R 2R 3(A1)
Wherein:
R 1, R 2, R 3in the every kind of situation of respectively doing for oneself independently of one another, there is the not branching of 1-16 carbon atom or branching, acyclic or cyclic aliphatic, araliphatic or aromatic group, 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 to form the chain that comprises at least four atoms
Under existing, in hydrogenation reactor, there is homogeneous catalytic reaction to obtain the two-phase hydrogenated mixture (H) that comprises following component after optional interpolation water in the coordination catalyst that comprises at least one element that is selected from periodictable the 8th, 9 He10 families at least one:
Upper strata phase (U1), it comprises described at least one coordination catalyst and described at least one tertiary amine (A1), and
Lower floor's phase (L1), it comprises described at least one polar solvent, the residue of described at least one coordination catalyst and the formic acid-amine adduct of at least one general formula (A2),
NR 1R 2R 3*x iHCOOH (A2)
Wherein:
X ifor 0.4-5, and
R 1, R 2, R 3as defined above,
(b3) in first-phase tripping device, the hydrogenated mixture (H) of step (a) gained is separated into upper strata phase (U1) and lower floor's phase (L1), and the residue that extracts described at least one coordination catalyst by the extraction agent that comprises described at least one tertiary amine (A1) from lower floor's phase (L1) in extraction cells is to obtain:
Raffinate (R2), it comprises described at least one formic acid-amine adduct (A2) and described at least one polar solvent, and
Extraction liquid (E2), the residue that it comprises described at least one tertiary amine (A1) and described at least one coordination catalyst,
(c) in the first distillation unit from raffinate (R2) separated described at least one polar solvent to obtain: distillate (D1), it comprises described at least one polar solvent and is recirculated in the hydrogenation reactor of step (a), and
Mixture at the bottom of two-phase tower (S1), it comprises:
Upper strata phase (U2), it comprises described at least one tertiary amine (A1), and
Lower floor's phase (L2), it comprises described at least one formic acid-amine adduct (A2),
(d) optionally in second-phase tripping device, by being separated, mixture (S1) at the bottom of the first tower of gained in step (c) is carried out to aftertreatment to obtain upper strata phase (U2) and lower floor's phase (L2),
(e) in thermal decomposition unit, make at the bottom of tower contained described at least one formic acid-amine adduct (A2) in mixture (S1) or optional lower floor's phase (L2) decompose to obtain described at least one tertiary amine (A1) in the hydrogenation reactor that is recycled to step (a) and the formic acid of discharging from thermal decomposition unit
Wherein in being close to step (c) before and/or carbon monoxide being added into raffinate (R2) during step (c) and/or
Mixture (S1) or optional lower floor's phase (L2) at the bottom of being close to step (e) before and/or during step (e), carbon monoxide being added into tower.
As above, to as described in processing step (b1), make the hydrogenated mixture (H) of gained in processing step (a) in first-phase tripping device, be separated into lower floor's phase (L1) and be recycled to the upper strata phase (U1) in hydrogenation reactor herein.With regard to being separated in processing step (b3), applicable similarly with regard to the content (comprising its preferred version) processing step (b1) Suo Shu.According in the aftertreatment of step (b3), be separated and also can directly in hydrogenation reactor, carry out.In this embodiment, hydrogenation reactor plays first-phase tripping device simultaneously.Then, upper strata phase (U1) is retained in hydrogenation reactor Zhong Bingjiang lower floor phase (L1) infeed extraction cells.
In extraction cells, use subsequently at least one tertiary amine (A1) as extraction agent, the lower floor's phase (L1) obtaining after being separated to be extracted with separation and removes coordination catalyst residue, thus the extraction liquid (E2) that obtains the raffinate (R2) that comprises described at least one formic acid-amine adduct (A2) and described at least one polar solvent and comprise described at least one tertiary amine (A1) and coordination catalyst residue.
In preferred embodiments, identical tertiary amine (A1) contained in the reaction mixture of processing step (a) (Rg) is used as to extraction agent, thereby makes to be applicable to similarly processing step (b3) with regard to the content (comprising preferred version) processing step (a) Suo Shu.
In preferred embodiments, the extraction liquid (E2) of gained in processing step (b3) is recycled in the hydrogenation reactor of processing step (a).This makes coordination catalyst that can efficient recovery costliness.In preferred embodiments, raffinate (R2) is fed in the first water distilling apparatus of processing step (c).
Preferably the tertiary amine obtaining in the thermal decomposition unit at processing step (e) (A1) is used as to the extraction agent in processing step (b3).In preferred embodiments, the tertiary amine obtaining in the thermal decomposition unit at processing step (e) (A1) is recycled in the extraction cells of processing step (b3).
Extraction in processing step (b3) is carried out conventionally under the pressure of the temperature of 30-100 ℃ and 0.1-8MPa.Described extraction also can be carried out under hydrogen pressure.
The extraction of coordination catalyst can, at any suitable device known to the person skilled in the art, preferably be carried out in the combination of counter-current extraction tower, mixer-settler cascade or mixer-settler cascade and counter-current extraction tower.
Optionally, not only by described coordination catalyst but also each component of a certain proportion of polar solvent available from lower floor's phase (L1) to be extracted is dissolved in to extraction agent is in tertiary amine (A1).This is not shortcoming for described method, because a certain amount of polar solvent that will not extract feeds in solvent removal, and therefore can save vaporization energy in some cases.
According to the aftertreatment of processing step (b2)
In another preferred embodiment, according to step (b2) to further aftertreatment of hydrogenated mixture (H).Therefore, the present invention also provides a kind of method of preparing formic acid, and it comprises the steps:
(a) make to comprise carbonic acid gas, hydrogen, at least one is selected from the reaction mixture (Rg) of 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 the tertiary amine of at least one general formula (A1)
NR 1R 2R 3(A1)
Wherein:
R 1, R 2, R 3in the every kind of situation of respectively doing for oneself independently of one another, there is the not branching of 1-16 carbon atom or branching, acyclic or cyclic aliphatic, araliphatic or aromatic group, 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 to form the chain that comprises at least four atoms
Under existing, in hydrogenation reactor, there is homogeneous catalytic reaction to obtain the two-phase hydrogenated mixture (H) that comprises following component after optional interpolation water in the coordination catalyst that comprises at least one element that is selected from periodictable the 8th, 9 He10 families at least one:
Upper strata phase (U1), it comprises described at least one coordination catalyst and described at least one tertiary amine (A1), and
Lower floor's phase (L1), it comprises described at least one polar solvent, the residue of described at least one catalyzer and the formic acid-amine adduct of at least one general formula (A2),
NR 1R 2R 3*x iHCOOH (A2)
Wherein:
X ifor 0.4-5, and
R 1, R 2, R 3as defined above,
(b2) in extraction cells by least one coordination catalyst of extraction in the hydrogenated mixture (H) of the extraction agent that comprises at least one tertiary amine (A1) gained from step (a) to obtain:
Raffinate (R1), it comprises described at least one formic acid-amine adduct (A2) and described at least one polar solvent, and
Extraction liquid (E1), it comprises described at least one tertiary amine (A1) and described at least one coordination catalyst,
(c) in the first distillation unit from raffinate (R1) separated described at least one polar solvent to obtain: distillate (D1), it comprises described at least one polar solvent and is recirculated in the hydrogenation reactor of step (a), and
Mixture at the bottom of two-phase tower (S1), it comprises:
Upper strata phase (U2), it comprises described at least one tertiary amine (A1), and
Lower floor's phase (L2), it comprises described at least one formic acid-amine adduct (A2),
(d) optionally in second-phase tripping device, by being separated, mixture (S1) at the bottom of the tower of gained in step (c) is carried out to aftertreatment to obtain upper strata phase (U2) and lower floor's phase (L2),
(e) in thermal decomposition unit, make at the bottom of tower contained described at least one formic acid-amine adduct (A2) in mixture (S1) or optional lower floor's phase (L2) decompose to obtain at least one tertiary amine (A1) in the hydrogenation reactor that is recycled to step (a) and the formic acid of discharging from thermal decomposition unit
Wherein in being close to step (c) before and/or carbon monoxide being added into raffinate (R1) during step (c) and/or
At the bottom of being close to step (e) before and/or during step (e), carbon monoxide being added into tower in mixture (S1) or optional lower floor's phase (L2).
Herein, at the lower hydrogenated mixture (H) by gained in processing step (a) that is not separated in advance, directly feed in extraction cells.The described content (comprising preferred version) of processing step (b3) extraction is applicable to processing step (b2) similarly above.
Use subsequently at least one tertiary amine (A1) hydrogenated mixture (H) to be extracted with separating catalyst in extraction cells as extraction agent, thus the extraction liquid (E1) that obtains the raffinate (R1) that comprises described at least one formic acid-amine adduct (A2) and described at least one polar solvent and comprise described at least one tertiary amine (A1) and described at least one coordination catalyst.
In preferred embodiments, identical tertiary amine (A1) contained in the reaction mixture of processing step (a) (Rg) is used as to extraction agent, thereby makes the content (comprising preferred version) processing step (a) Suo Shu to be applicable to processing step (b2) similarly above.
In preferred embodiments, the extraction liquid (E1) of gained in processing step (b2) is recycled in the hydrogenation reactor of processing step (a).This makes coordination catalyst that can efficient recovery costliness.In preferred embodiments, raffinate (R1) is fed in the first water distilling apparatus of processing step (c).
Preferably the tertiary amine obtaining in the thermal decomposition unit at processing step (e) (A1) is used as to the extraction agent in processing step (b2).In preferred embodiments, the tertiary amine obtaining in the thermal decomposition unit at processing step (e) (A1) is recycled in the extraction cells of processing step (b2).
Extraction in processing step (b2) is carried out conventionally under the pressure of the temperature of 30-100 ℃ and 0.1-8MPa.Described extraction also can be carried out under hydrogen pressure.
The extraction of coordination catalyst can, at any suitable device known to the person skilled in the art, preferably be carried out in the combination of counter-current extraction tower, mixer-settler cascade or mixer-settler cascade and counter-current extraction tower.
Optionally, not only by described coordination catalyst but also by each component of a certain proportion of polar solvent available from hydrogenated mixture to be extracted (H), be dissolved in extraction agent, in tertiary amine (A1).This is not shortcoming for described method, because a certain amount of polar solvent that will not extract feeds in solvent removal, and therefore can save vaporization energy in some cases.
the inhibition of trace catalyzer
By the inhibition of the coordination catalyst of carbon monoxide, can be close to step (c) before and/or during step (c) and/or be close to step (e) and carry out before and/or during step (e).
In one embodiment, only suppress to carry out before and/or during step (c) being close to step (c).
In one embodiment, only suppress to carry out before and/or during step (e) being close to step (e).
In another embodiment, feeding in raw material of carbon monoxide is being close to step (c) before and/or during step (c) and be close to step (e) and carry out before and/or during step (e).
suppress step (c)
Be close to step (c) before and/or during step (c) using carbon monoxide as inhibitor (decomposing inhibitor) add the lower floor's phase (L1) obtaining according to processing step (b1), the raffinate (R1) obtaining according to processing step (b2) or the raffinate (R2) that obtains according to processing step (b3) in.
Although the aftertreatment of the present invention of hydrogenated mixture (H) makes effectively separated described coordination catalyst and is recirculated in the hydrogenation reactor of step (a), yet in the aftertreatment of processing step (b1), lower floor's phase (L1) still comprises the residue of described coordination catalyst.According in the aftertreatment of processing step (b2), raffinate (R1) still comprises the coordination catalyst of trace.In the situation that according to the aftertreatment of processing step (b3), raffinate (R2) also still comprises the coordination catalyst of trace.
The lower floor's phase (L1) obtaining according to processing step (b1) comprises <100ppm, preferred <80ppm, the coordination catalyst residue that particularly <60ppm measures, the in each case gross weight based on lower floor's phase (L1).
The raffinate (R1) obtaining according to processing step (b2) comprises <30ppm, preferred <20ppm, the trace coordination catalyst that particularly <10ppm measures, the in each case gross weight based on raffinate (R1).
The raffinate (R2) obtaining according to processing step (b3) comprises <30ppm, preferred <20ppm, the trace coordination catalyst that particularly <10ppm measures, the in each case gross weight based on raffinate (R2).
Coordination catalyst residue in lower floor's phase (L1), raffinate (R1) or raffinate (R2) or trace coordination catalyst cause formic acid-amine adduct (A2) in further aftertreatment to resolve into tertiary amine (A1), carbonic acid gas and hydrogen again.The decomposition again of the free formic acid that can be contained in lower floor's phase (L1), raffinate (R1) or raffinate (R2) or be formed by formic acid-amine adduct (A2) in further aftertreatment also can be by described coordination catalyst residue or the catalysis of trace coordination catalyst.Now, formic acid resolves into carbonic acid gas and hydrogen.
In order to prevent that this from decomposing or minimizing it, be close to step (c) before and/or during add carbon monoxide as inhibitor.
In embodiments of the invention, add described inhibitor before or during step (c) being close to step (c).In another embodiment of the present invention, be close to step (c) before and during add described at least one inhibitor.In another embodiment, add before described at least one inhibitor being close to step (c).In another embodiment, only during step (c), add described inhibitor.
For the present invention, " being close to step (c) before " refers to and carbon monoxide is being added into the charging of the first water distilling apparatus or directly introducing in the first water distilling apparatus.The interpolation of inhibitor can be carried out continuously or intermittently.
Described inhibitor changes into inactive form (repressed coordination catalyst) by coordination catalyst.In inhibition, at least one part of coordination catalyst is replaced by carbon monoxide.Now, eliminate and be originally included in a part in active coordination catalyst.After suppressing, the part of elimination is free with it, and the metal component form (free ligand) that is not bonded to coordination catalyst exists.This has prevented the decomposition of formic acid-amine adduct (A2) or free formic acid, and this is because there is carbon monoxide, and coordination catalyst (being its suppressed form) no longer can catalysis formic acid-amine adduct (A2) or the decomposing again of free formic acid.
Under existing without carbon monoxide, this reaction can again be reversed under free ligand exists, and carries out thus the regeneration of repressed coordination catalyst.Now, carbon monoxide is eliminated and is replaced by free ligand by repressed coordination catalyst, forms active coordination catalyst.If repressed catalyzer is recycled to hydrogenation via unhindered amina (upper strata phase (U3)) again, regeneration can directly be carried out in the hydrogenation in step (a).Can also in step formerly, the thermal treatment by repressed catalyzer add rapid regeneration.
Can use the gas that comprises carbon monoxide as inhibitor.In a preferred embodiment, using content is 99 % by weight, preferably 99.5 % by weight, the especially pure carbon monoxide of 99.9 % by weight, the in each case gross weight of the gas streams based on as inhibitor.Can also use the mixture (being called synthetic gas or oxygen-containing gas (oxo gas)) of carbon monoxide and hydrogen, this is because it more easily obtains than pure carbon monoxide conventionally.Its carbon monoxide content is preferably 10-90 % by weight.In another embodiment, carbon monoxide can also circulate as recycle stream by the waste gas that comprises carbon monoxide of the distillation unit available from thermal decomposition unit being reused for to inhibition.Gas streams as inhibitor preferably consists of carbon monoxide.
The catalytically-active metals component of the coordination catalyst that described inhibitor be take based on the first water distilling apparatus and/or thermal decomposition unit is 0.5-1000, and the mol ratio that is preferably 1-30 is used.
In step (c), repressed coordination catalyst and free ligand are preferably present in upper strata phase (U2) with the form of enrichment.Now upper strata comprises tertiary amine (A1) and repressed coordination catalyst and free ligand mutually.The carbon monoxide (free carbon monoxide) that is not bonded to the metal component of repressed coordination catalyst is discharged and can be reused for the inhibition of catalyzer by the first water distilling apparatus.The embodiment of the step with regard to repressed coordination catalyst (e) and preferred situation are applicable to step (c) similarly.
inhibition in step (e)
In another embodiment of the present invention, add described inhibitor before or during step (e) being close to step (e).In another embodiment of the present invention, be close to step (e) before and during step (e), adding described at least one inhibitor.In another embodiment, only add before described at least one inhibitor being close to step (e).In another embodiment, only during step (e), add described inhibitor.
For the present invention, " being close to step (e) before " refers to and inhibitor is being added into the charging of thermal decomposition unit or directly adding in thermal decomposition unit.The interpolation of inhibitor can be carried out continuously or intermittently.
In preferred embodiments, in step (e), repressed coordination catalyst is rich at upper strata phase (U3).The free ligand that now upper strata phase (U3) comprises tertiary amine (A1) and repressed coordination catalyst and coordination catalyst.The coordination catalyst being suppressed by carbon monoxide can be recycled to the hydrogenation in step (a) by thermolysis via upper strata phase (U3).Now, the free ligand of the coordination catalyst that selective basis the present invention uses, makes it preferably with enriched form, be present in upper strata phase (U3) together with repressed coordination catalyst.
With regard to repressed catalyzer, " being rich in " means with regard to processing step (e), partition ratio P iCC (e)=[the repressed catalyst concn in upper strata phase (L3)]/[the repressed catalyst concn in lower floor's phase (U3)] >1.Partition ratio P iCC (e)preferably>=2, particularly preferably>=5.
With regard to free ligand, " being rich in " means with regard to processing step (e), partition ratio P fL (e)=[the free ligand concentration in upper strata phase (L3)]/[the free ligand concentration in lower floor's phase (U3)] >1.Partition ratio P fL (e)preferably>=2, particularly preferably>=5.
This makes upper strata phase (U3) to be recycled in hydrogenation reactor and does not lose significant quantity coordination catalyst.
The carbon monoxide (free carbon monoxide) that is not bonded to the metal component of repressed coordination catalyst is discharged and can be reused for the inhibition of catalyzer by thermal decomposition unit.
Under existing without carbon monoxide, repressed coordination catalyst can be converted into its activity form (reactivate) again.Supposing to be now bonded to the carbon monoxide of the metal component of repressed coordination catalyst eliminates and is replaced by free ligand.In one embodiment, the reactivate of repressed coordination catalyst can carry out in processing step (a).Now, upper strata phase (U3) is circulated in processing step (a) by thermal decomposition unit.
In a preferred embodiment, the repressed coordination catalyst that is included in upper strata phase (U3) is being recycled to step (a) reactivate before., under existing without carbon monoxide, repressed coordination catalyst is heat-treated for this reason, thereby repressed coordination catalyst is converted into activity form before being recycled to step (a), and improve thus the space-time yield in hydrogenation.In thermal treatment, upper strata phase (U3) is heated to 100-200 ℃ at 10 millibars to the pressure of 10 bar.
removing of polar solvent; Processing step (c)
In processing step (c), in the first water distilling apparatus, described polar solvent is separated with lower floor's phase (L1), raffinate (R1) or raffinate (R2).By mixture (S1) at the bottom of the first water distilling apparatus acquisition distillate (D1) and two-phase tower.Distillate (D1) comprises separated and is recycled to the polar solvent in the hydrogenation reactor of step (a).Mixture at the bottom of tower (S1) comprises upper strata phase (U2) and lower floor's phase (L2), and it comprises tertiary amine (A1) at the middle and upper levels mutually, and lower floor comprises formic acid-amine adduct (A2) mutually.In embodiments of the present invention, the separated described polar solvent of part in the first water distilling apparatus of processing step (c), thus at the bottom of making tower, mixture (S1) still comprises still unsegregated polar solvent.In processing step (c), contained for example 5-98 % by weight polar solvent in separable lower floor phase (L1), raffinate (R1) or raffinate (R2), preferable separation 50-98 % by weight, more preferably 80-98 % by weight, the polar solvent of 80-90 % by weight particularly preferably, in each case based on contained polar solvent gross weight in lower floor's phase (L1), raffinate (R1) or raffinate (R2).Now the carbon monoxide as decomposing inhibitor can be added into charging or directly with gaseous form, introduce the first water distilling apparatus.
In another embodiment of the inventive method, in the first water distilling apparatus of processing step (c), described polar solvent is removed in separation completely.For the present invention, " completely separation remove " means to remove contained 98 % by weight that surpass in lower floor's phase (L1), raffinate (R1) or raffinate (R2), preferably surpass 98.5 % by weight, particularly preferably surpass 99 % by weight, particularly surpass the polar solvent of 99.5 % by weight, in each case based on contained polar solvent gross weight in lower floor's phase (L1), raffinate (R1) or raffinate (R2).
In preferred embodiments, distillate (D1) separated in the first water distilling apparatus is recycled in the hydrogenation reactor of step (a).When the mixture of one or more alcohol and water is used as to polar solvent, also can from the first water distilling apparatus, take out low water distillate (D1 wa) and rich water distillate (D1 wr).Described rich water distillate (D1 wr) comprise over 50 % by weight, preferably surpass 70 % by weight, particularly preferably surpass 80 % by weight, particularly surpass contained water in the distillate (D1) of 90 % by weight.Described low water distillate (D1 wa) comprise and be less than 50 % by weight, be preferably less than 30 % by weight, be particularly preferably less than 20 % by weight, be particularly less than contained water in the distillate D1 of 10 % by weight.
In particularly preferred embodiments, by low water distillate (D1 wa) be recycled in the hydrogenation reactor of step (a).By rich water distillate (D1 wr) be added in upper strata phase (U1).
Described polar solvent and lower floor's phase (L1), raffinate (R1) or raffinate (R2) separated can be for example carries out at vaporizer or in comprising the distillation unit of vaporizer and tower, and wherein said tower provides orderly packing elements, loose heap packing elements and/or column plate.
Removing at least partly preferably of described polar solvent forms under the column bottom temperature of free formic acid and carries out under setting pressure can't help formic acid-amine adduct (A2).In the first water distilling apparatus, the coefficient x of formic acid-amine adduct (A2) ibe generally 0.4-3, be preferably 0.6-1.8, be particularly preferably 0.7-1.7.
The column bottom temperature of the first water distilling apparatus is generally at least 20 ℃, is preferably at least 50 ℃, is particularly preferably at least 70 ℃, and is conventionally no more than 210 ℃, is preferably no more than 190 ℃.Temperature in the first water distilling apparatus is generally 20-210 ℃, is preferably 50-190 ℃.Pressure in the first water distilling apparatus is generally at least 0.001MPa (definitely), be preferably at least 0.005MPa (definitely), be particularly preferably at least 0.01MPa (definitely), and conventionally not higher than 1MPa (definitely), preferably not higher than 0.1MPa (definitely).Pressure in the first water distilling apparatus is generally 0.0001-1MPa (definitely), is preferably 0.005-0.1MPa (definitely), is particularly preferably 0.01-0.1MPa (definitely).
During being to remove polar solvent in the first water distilling apparatus, can at the bottom of the tower of the first water distilling apparatus, obtain formic acid-amine adduct (A2) and free uncle amine (A1), this be because polar solvent remove process in form the formic acid-amine adduct with low amine content.Therefore mixture (S1) at the bottom of the tower that formation comprises formic acid-amine adduct (A2) and free uncle amine (A1).Depend on isolated polar solvent amount, mixture at the bottom of tower (S1) is included in formic acid-amine adduct (A2) of forming in the liquid phase of the first water distilling apparatus and possible free uncle amine (A1).For further aftertreatment, optionally in processing step (d) to tower at the bottom of further aftertreatment of mixture (S1), feed subsequently in processing step (e).Also mixture (S1) at the bottom of the tower available from processing step (c) directly can be fed in processing step (e).
In processing step (d), can in second-phase tripping device, mixture (S1) at the bottom of the tower of gained in step (c) be separated into upper strata phase (U2) and lower floor's phase (L2).According to processing step (e), lower floor's phase (L2) is further carried out to aftertreatment subsequently.In preferred embodiments, the upper strata phase (U2) available from second-phase tripping device is recycled in the hydrogenation reactor of step (a).In another preferred embodiment, the upper strata phase (U2) available from second-phase tripping device is recycled in extraction cells.With regard to the content (comprising preferred version) described in first-phase tripping device, be applicable to similarly processing step (d) and second-phase tripping device.
Therefore, in one embodiment, method of the present invention comprises step (a), (b1), (c), (d) and (e).In another embodiment, method of the present invention comprises step (a), (b2), (c), (d) and (e).In another embodiment, method of the present invention comprises step (a), (b3), (c), (d) and (e).In another embodiment, method of the present invention comprises step (a), (b1), (c) and (e).In another embodiment, method of the present invention comprises step (a), (b2), (c) and (e).In another embodiment, method of the present invention comprises step (a), (b3), (c) and (e).
Therefore, in one embodiment, method of the present invention forms by step (a), (b1), (c), (d) with (e).In another embodiment, method of the present invention forms by step (a), (b2), (c), (d) with (e).In another embodiment, method of the present invention forms by step (a), (b3), (c), (d) with (e).In another embodiment, method of the present invention forms by step (a), (b1), (c) with (e).In another embodiment, method of the present invention forms by step (a), (b2), (c) with (e).In another embodiment, method of the present invention forms by step (a), (b3), (c) with (e).
the decomposition of formic acid-amine adduct (A2); Processing step (e)
By in mixture (S1) at the bottom of the tower obtaining according to step (c) or lower floor's phase (L2) infeed thermal decomposition unit of optionally obtaining according to step (d) aftertreatment after further to react.
In described thermal decomposition unit, be contained at the bottom of tower in mixture (S1) or the formic acid-amine adduct (A2) being optionally contained in lower floor's phase (L2) resolves into formic acid and tertiary amine (A1).Now the carbon monoxide as decomposing inhibitor can be added into charging or directly with gaseous form, introduce thermal decomposition unit.
Formic acid is discharged from described thermal decomposition unit.Tertiary amine (A1) is recycled in the hydrogenation reactor of step (a).Tertiary amine available from thermal decomposition unit (A1) can be directly recycled in hydrogenation reactor.Also can first the tertiary amine available from thermal decomposition unit (A1) be recycled in the extraction cells of processing step (b2) or processing step (b3), make subsequently in its hydrogenation reactor that passes into step (a) by extraction cells; This embodiment is preferred.
In preferred embodiments, thermal decomposition unit comprises after-fractionating device and third phase tripping device, there is to decompose the distillate (D2) of discharging (taking-up) to obtain from after-fractionating device in formic acid-amine adduct (A2) wherein in after-fractionating device, with mixture (S2) at the bottom of the two-phase tower that comprises upper strata phase (U3) and lower floor's phase (L3), its at the middle and upper levels phase (U3) comprise described at least one tertiary amine (A1), lower floor's phase (L3) comprises described at least one formic acid-amine adduct (A2) and described at least one inhibitor.
In preferred embodiments, except tertiary amine (A1), upper strata phase (U3) comprises repressed coordination catalyst and free ligand.
The formic acid obtaining in after-fractionating device for example (i), via tower top, (ii) only takes out from after-fractionating device via side-draw via tower top with via side-draw or (iii).If formic acid takes out via tower top, obtain purity up to the formic acid of 99.99 % by weight.When taking out via side-draw, obtain water-containing formic acid, now particularly preferably comprise the mixture of approximately 85 % by weight formic acid.The water content that depends on mixture (S1) at the bottom of the tower feeding in thermal decomposition unit or optional lower floor's phase (L2), formic acid can be most of as overhead product or most ofly take out via side-draw.Necessary, also can only via side-draw, take out formic acid, preferably there is the formic acid content of approximately 85 % by weight, now the required water yield also can provide by add extra water in after-fractionating device.The thermolysis of formic acid/amine adduct (A2) is carried out conventionally under the processing parameter of the known pressure of prior art, temperature and device structure.These are for example described in EP0181078 or WO2006/021411.Suitable after-fractionating device is the distillation tower for conventionally containing random packing elements, structured packing and/or column plate for example.
The column bottom temperature of after-fractionating device is generally at least 130 ℃, is preferably at least 140 ℃, is particularly preferably at least 150 ℃, and is conventionally no more than 210 ℃, is preferably no more than 190 ℃, is particularly preferably no more than 185 ℃.Pressure in after-fractionating device is generally at least 1hPa (definitely), be preferably at least 50hPa (definitely), be particularly preferably at least 100hPa (definitely), and conventionally not higher than 500hPa (definitely), particularly preferably not higher than 300hPa (definitely), particularly preferably not higher than 200hPa (definitely).
At the bottom of the tower obtaining at the bottom of the tower of after-fractionating device, mixture (S2) is two-phase mixture.In preferred embodiments, the upper strata phase (U3) that comprises tertiary amine (A1), repressed coordination catalyst and free ligand and the lower floor's phase (L3) that comprises formic acid-amine adduct (A2) and inhibitor will be also separated into therein in the third phase tripping device of mixture at the bottom of tower (S2) infeed thermal decomposition unit.Upper strata phase (U3) is discharged and is recycled in the hydrogenation reactor of step (a) from the third phase tripping device of thermal decomposition unit.This recirculation can be directly recycled in the hydrogenation reactor of step (a) or first will upper strata phase (U3) feeds in the extraction cells of step (b2) or step (b3) and pass into thus in the hydrogenation reactor of step (a).Then, the lower floor's phase (L3) obtaining in third phase tripping device is supplied to be back in the after-fractionating device of thermal decomposition unit.Formic acid-amine adduct (A2) contained in lower floor's phase (L3) is decomposed again in after-fractionating device, again obtain formic acid and free uncle amine (A1) mixture (S2) at the bottom of forming two-phase tower at the bottom of the tower of the after-fractionating device of thermal decomposition unit again, then it is fed again in the third phase tripping device of thermal decomposition unit with further aftertreatment.
The catalyzer being suppressed by carbon monoxide is present in upper strata phase (U3) with the form of enrichment.In one embodiment, after being recycled to hydrogenation reactor, make the repressed catalyzer comprising in upper strata phase (U3) in step (a), be converted into again activity form under hydrogenation conditions.
In another embodiment, under existing without carbon monoxide, at the temperature of 100-200 ℃, repressed catalyzer is heat-treated before being recycled to step (a).For the purpose of the present invention, " not having carbon monoxide pressure of tension " means in repressed reactivation of catalyst, only exists key in the carbon monoxide of repressed coordination catalyst or the displacement of the free ligand in repressed coordination catalyst is eliminated and is re-activated.
To in the thermal decomposition unit of mixture at the bottom of tower (S1) or optional lower floor's phase (L2) introducing processing step (e), can be undertaken by introducing in after-fractionating device and/or third phase tripping device.In preferred embodiments, mixture at the bottom of tower (S1) or optional lower floor's phase (L2) are introduced in the after-fractionating device of thermal decomposition unit.In another embodiment, mixture at the bottom of tower (S1) or optional lower floor's phase (L2) are introduced in the third phase separation vessel of thermal decomposition unit.
In another embodiment, mixture at the bottom of tower (S1) or optional lower floor's phase (L2) are introduced to the after-fractionating device of thermal decomposition unit and the third phase tripping device of thermal decomposition unit in the two.For this reason, mixture at the bottom of tower (S1) or optional lower floor's phase (L2) are divided into two share streams, a whiff of material stream is introduced in after-fractionating device and one subflow introduced in the 3rd tripping device of thermal decomposition unit.
The present invention illustrates by following drawings and Examples, and the present invention is not limited to this.
Accompanying drawing has at length shown:
Fig. 1 is the skeleton diagram of the preferred embodiment of the inventive method,
Fig. 2 is the skeleton diagram of another preferred embodiment of the inventive method,
Fig. 3 is the skeleton diagram of another preferred embodiment of the inventive method,
Fig. 4 is the skeleton diagram of another preferred embodiment of the inventive method,
Fig. 5 is the skeleton diagram of another preferred embodiment of the inventive method,
Fig. 6 is the skeleton diagram of another preferred embodiment of the inventive method.
Fig. 7,8,9 and 10 is the diagram of inhibition test H1, H2, H3 and H4.
In Fig. 1-6, Reference numeral has following implication:
fig. 1
I-1 hydrogenation reactor
II-1 the first water distilling apparatus
III-1 (thermal decomposition unit) third phase tripping device
IV-1 (thermal decomposition unit) after-fractionating device
The carbonated material stream of 1 bag
The 2 material streams that comprise hydrogen
3 comprise formic acid-amine adduct (material stream of (A2), catalyst residue, polar solvent; (lower floor's phase (L1))
4 carbon monoxide material streams
The 5 material streams that comprise polar solvent; (distillate (D1))
The 6 material streams that comprise tertiary amine (A1) (upper strata phase (U2)) and formic acid-amine adduct (A2) (lower floor's phase (L2)); Mixture at the bottom of tower (S1)
The 7 material streams that comprise formic acid-amine adduct (A2) and inhibitor; Lower floor's phase (L3)
The 8 material streams that comprise tertiary amine (A1) (upper strata phase (U3)) and formic acid-amine adduct (A2) and inhibitor (lower floor's phase (L3)); Mixture at the bottom of tower (S2)
The 9 material streams that comprise formic acid; (distillate (D2))
The 10 material streams that comprise tertiary amine (A1); Upper strata phase (U3)
fig. 2
I-2 hydrogenation reactor
II-2 the first water distilling apparatus
III-2 (thermal decomposition unit) third phase tripping device
IV-2 (thermal decomposition unit) after-fractionating device
V-2 first-phase tripping device
VI-2 extraction cells
The carbonated material stream of 11 bag
The 12 material streams that comprise hydrogen
The material stream that 13a comprises hydrogenated mixture (H)
The material stream that 13b comprises lower floor's phase (L1)
The material stream that 13c comprises raffinate (R2)
The 14 material streams that comprise carbon monoxide
The 15 material streams that comprise distillate (D1)
The 16 material streams that comprise mixture (S1) at the bottom of tower
The 17 material streams that comprise lower floor's phase (L3)
The 18 material streams that comprise mixture (S2) at the bottom of tower
The 19 material streams that comprise formic acid; (distillate (D2))
The 20 material streams that comprise upper strata phase (U3)
The 21 material streams that comprise extraction liquid (E2)
The 22 material streams that comprise upper strata phase (U1)
fig. 3
I-3 hydrogenation reactor
II-3 the first water distilling apparatus
III-3 (thermal decomposition unit) third phase tripping device
IV-3 (thermal decomposition unit) after-fractionating device
V-3 first-phase tripping device
VI-3 extraction cells
The carbonated material stream of 31 bag
The 32 material streams that comprise hydrogen
The material stream that 33a comprises hydrogenated mixture (H)
The material stream that 33b comprises lower floor's phase (L1)
The material stream that 33c comprises raffinate (R2)
The 34 material streams that comprise carbon monoxide
The 35 material streams that comprise distillate (D1)
The 36 material streams that comprise mixture (S1) at the bottom of tower
The 37 material streams that comprise lower floor's phase (L3)
The 38 material streams that comprise mixture (S2) at the bottom of tower
The 39 material streams that comprise formic acid; (distillate (D2))
The 40 material streams that comprise upper strata phase (U3)
The 41 material streams that comprise extraction liquid (E2)
The 42 material streams that comprise upper strata phase (U1)
fig. 4
I-4 hydrogenation reactor
II-4 the first water distilling apparatus
III-4 (thermal decomposition unit) third phase tripping device
IV-4 (thermal decomposition unit) after-fractionating device
V-4 first-phase tripping device
VI-4 extraction cells
VII-4 second-phase tripping device
The carbonated material stream of 51 bag
The 52 material streams that comprise hydrogen
The material stream that 53a comprises hydrogenated mixture (H)
The material stream that 53b comprises lower floor's phase (L1)
The material stream that 53c comprises raffinate (R2)
The 54 material streams that comprise carbon monoxide
The 55 material streams that comprise distillate (D1)
The material stream that 56a comprises mixture (S1) at the bottom of tower
The material stream that 56b comprises lower floor's phase (L2)
The material stream that 56c comprises upper strata phase (U2)
The 57 material streams that comprise lower floor's phase (L3)
The 58 material streams that comprise mixture (S2) at the bottom of tower
The 59 material streams that comprise formic acid; (distillate (D2))
The 60 material streams that comprise upper strata phase (U3)
The 61 material streams that comprise extraction liquid (E2)
The 62 material streams that comprise upper strata phase (U1)
fig. 5
I-5 hydrogenation reactor
II-5 the first water distilling apparatus
III-5 (thermal decomposition unit) third phase tripping device
IV-5 (thermal decomposition unit) after-fractionating device
V-5 first-phase tripping device
VI-5 extraction cells
The carbonated material stream of 71 bag
The 72 material streams that comprise hydrogen
The material stream that 73a comprises hydrogenated mixture (H)
The material stream that 73b comprises lower floor's phase (L1)
The material stream that 73c comprises raffinate (R2)
The 74 material streams that comprise carbon monoxide
75 comprise low water distillate (D1 wa) material stream
The 76 material streams that comprise mixture (S1) at the bottom of tower
The 77 material streams that comprise lower floor's phase (L3)
The 78 material streams that comprise mixture (S2) at the bottom of tower
The 79 material streams that comprise formic acid; (distillate (D2))
The 80 material streams that comprise upper strata phase (U3)
The 81 material streams that comprise extraction liquid (E2)
The 82 material streams that comprise upper strata phase (U1)
83 comprise rich water distillate (D1 wr) material stream
fig. 6
I-6 hydrogenation reactor
II-6 the first water distilling apparatus
III-6 (thermal decomposition unit) third phase tripping device
IV-6 (thermal decomposition unit) after-fractionating device
VI-6 extraction cells
The carbonated material stream of 91 bag
The 92 material streams that comprise hydrogen
The material stream that 93a comprises hydrogenated mixture (H)
The material stream that 93c comprises raffinate (R1)
The 94 material streams that comprise carbon monoxide
The 95 material streams that comprise distillate (D1)
The 96 material streams that comprise mixture (S1) at the bottom of tower
The 97 material streams that comprise lower floor's phase (L3)
The 98 material streams that comprise mixture (S2) at the bottom of tower
The 99 material streams that comprise formic acid; (distillate (D2))
The 100 material streams that comprise upper strata phase (U3)
The 101 material streams that comprise extraction liquid (E1)
fig. 7,8,9 and 10
T[min] test period, in minute
FA[%] be the % by weight of the formic acid of formic acid-amine adduct (A3) form, the gross weight based on formic acid used in formic acid-amine adduct (A3) form
FA-D[%] % by weight of the formic acid that decomposes, the gross weight of the formic acid based on using with formic acid-amine adduct (A3) form
use the FA[% of inhibitor (passing into carbon monoxide)] value
use the FA-D[% of inhibitor (passing into carbon monoxide)] value
do not use the FA[% of inhibitor] value
do not use the FA-D[% of inhibitor] value
In the embodiment of Fig. 1, the carbonated material stream 1 of bag and the material stream 2 that comprises hydrogen are fed in hydrogenation reactor I-1.Other material stream (not shown) can be fed in hydrogenation reactor I-1 to compensate any loss of tertiary amine (A1) or coordination catalyst.
In hydrogenation reactor I-1, make carbonic acid gas and hydrogen have lower reaction at the coordination catalyst of tertiary amine (A1), polar solvent and the element that comprises at least one periodictable the 8th, 9 He10 families.This has obtained the two-phase hydrogenated mixture (H) that comprises upper strata phase (U1) and lower floor's phase (L1), its at the middle and upper levels phase (U1) comprise coordination catalyst and tertiary amine (A1), and lower floor's phase (L1) comprises polar solvent, coordination catalyst residue and formic acid-amine adduct (A2).
Lower floor's phase (L1) is fed in water distilling apparatus II-1 as material stream 3.Upper strata phase (U1) is retained in hydrogenation reactor I-1.In the embodiment of Fig. 1, hydrogenation reactor I-1 plays first-phase tripping device simultaneously.
Inhibitor is added in material stream 3 continuously or intermittently as material stream 4.In the first water distilling apparatus II-1, using lower floor's phase (L1) be separated into comprise polar solvent and as material stream 5 be recycled to the distillate (D1) in hydrogenation reactor I-1 and comprise upper strata phase (U2) and the two-phase tower of lower floor's phase (L2) at the bottom of mixture (S1), its at the middle and upper levels phase (U2) comprise tertiary amine (A1) and repressed coordination catalyst, lower floor's phase (L2) comprises formic acid-amine adduct (A2).
Mixture (S1) at the bottom of tower is fed in the third phase tripping device III-1 of thermal decomposition unit as material stream 6.
In the third phase tripping device III-1 of thermal decomposition unit, mixture at the bottom of tower (S1) is separated to obtain the upper strata phase (U3) that comprises tertiary amine (A1) and repressed coordination catalyst and the lower floor's phase (L3) that comprises formic acid-amine adduct (A2).
Upper strata phase (U3) is recycled in hydrogenation reactor I-1 as material stream 10.Lower floor's phase (L3) is fed in the after-fractionating device IV-1 of thermal decomposition unit as material stream 7.In after-fractionating device IV-1, formic acid-amine adduct (A2) contained in lower floor's phase (L3) is resolved into formic acid and free uncle amine (A1).In after-fractionating device IV-1, obtain mixture (S2) at the bottom of distillate (D2) and two-phase tower.
The distillate that comprises formic acid (D2) is discharged from water distilling apparatus IV-1 as material stream 9.Using comprising containing the upper strata phase (U3) of tertiary amine (A1) with containing mixture (S2) at the bottom of the two-phase tower of lower floor's phase (L3) of formic acid-amine adduct (A2), as material stream 8, be recycled in the third phase tripping device III-1 of thermal decomposition unit.In third phase tripping device III-1, mixture at the bottom of tower (S2) is separated into upper strata phase (U3) and lower floor's phase (L3).Upper strata phase (U3) is recycled in hydrogenation reactor I-1 as material stream 10.Lower floor's phase (L3) is recycled in after-fractionating device IV-1 as material stream 7.
In the embodiment of Fig. 2, the carbonated material stream 11 of bag and the material stream 12 that comprises hydrogen are fed in hydrogenation reactor I-2.Other material stream (not shown) can be fed in hydrogenation reactor I-2 to compensate any loss of tertiary amine (A1) or coordination catalyst.
In hydrogenation reactor I-2, make carbonic acid gas and hydrogen have lower reaction at the coordination catalyst of tertiary amine (A1), polar solvent and the element that comprises at least one periodictable the 8th, 9 He10 families.This has obtained the two-phase hydrogenated mixture (H) that comprises upper strata phase (U1) and lower floor's phase (L1), its at the middle and upper levels phase (U1) comprise coordination catalyst and tertiary amine (A1), lower floor's phase (L1) comprises polar solvent, coordination catalyst residue and formic acid-amine adduct (A2).
Hydrogenated mixture (H) is fed in first-phase tripping device V-2 as material stream 13a.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 in hydrogenation reactor I-2 as material stream 22.Lower floor's phase (L1) is fed in extraction cells VI-2 as material stream 13b.In this extraction cells VI-2, be used as material stream 20 (upper strata phase (U3)) and be recycled to tertiary amine (A1) the extraction lower floor's phase (L1) in extraction cells VI-2 by third phase tripping device III-2.
Raffinate (R2) and extraction liquid (E2) in extraction cells VI-2, have been obtained.Raffinate (R2) comprises formic acid-amine adduct (A2) and polar solvent and it is fed in the first water distilling apparatus II-2 as material stream 13c.Extraction liquid (E2) comprises tertiary amine (A1) and coordination catalyst residue its and is recycled in hydrogenation reactor I-2 as material stream 21.
Inhibitor is added in material stream 13c continuously or intermittently as material stream 14.In the first water distilling apparatus II-2, raffinate (R2) is separated into and comprises polar solvent and as mixture (S1) at the bottom of material stream 15 is recycled to distillate (D1) in hydrogenation reactor I-2 and two-phase tower.
Mixture at the bottom of tower (S1) comprises upper strata phase (U2) and lower floor's phase (L2), its at the middle and upper levels phase (U2) comprise tertiary amine (A1) and repressed coordination catalyst, lower floor's phase (L2) comprises formic acid-amine adduct (A2).Mixture (S1) at the bottom of tower is fed in after-fractionating device IV-2 as material stream 16.
In after-fractionating device IV-2, make at the bottom of tower contained formic acid-amine adduct in mixture (S1) resolve into formic acid and free uncle amine (A1).In after-fractionating device IV-2, obtained mixture (S2) at the bottom of distillate (D2) and tower.
The distillate that comprises formic acid (D2) is discharged from after-fractionating device IV-2 as material stream 19.Using comprising containing the upper strata phase (U3) of the coordination catalyst of tertiary amine (A1) and suppressed dose and containing mixture (S2) at the bottom of the two-phase tower of lower floor's phase (L3) of formic acid-amine adduct (A2), as material stream 18, be recycled in the third phase tripping device III-2 of thermal decomposition unit.
In the third phase tripping device III-2 of thermal decomposition unit, mixture at the bottom of tower (S2) is separated to obtain the upper strata phase (U3) that comprises tertiary amine (A1) and repressed coordination catalyst and the lower floor's phase (L3) that comprises formic acid-amine adduct (A2).
Upper strata phase (U3) available from third phase tripping device III-2 is recycled in extraction cells VI-2 as material stream 20.Lower floor's phase (L3) is fed in the after-fractionating device IV-2 of thermal decomposition unit as material stream 17.In after-fractionating device IV-2, make formic acid-amine adduct (A2) contained in lower floor's phase (L3) resolve into formic acid and free uncle amine (A1).As mentioned above, then in after-fractionating device IV-2, again obtain mixture (S2) at the bottom of distillate (D2) and tower.
In the embodiment of Fig. 3, the carbonated material stream 31 of bag and the material stream 32 that comprises hydrogen are fed in hydrogenation reactor I-3.Other material stream (not shown) can be fed in hydrogenation reactor I-3 to compensate any loss of tertiary amine (A1) or coordination catalyst.
In hydrogenation reactor I-3, make carbonic acid gas and hydrogen have lower reaction at tertiary amine (A1), polar solvent and the coordination catalyst that comprises at least one periodictable the 8th, 9 He10 family elements.This has obtained the two-phase hydrogenated mixture (H) that comprises upper strata phase (U1) and lower floor's phase (L1), its at the middle and upper levels phase (U1) comprise coordination catalyst and tertiary amine (A1), lower floor's phase (L1) comprises polar solvent, coordination catalyst residue and formic acid-amine adduct (A2).
Hydrogenated mixture (H) is fed in first-phase tripping device V-3 as material stream 33a.In first-phase tripping device V-3, hydrogenated mixture (H) is separated into upper strata phase (U1) and lower floor's phase (L1).
Upper strata phase (U1) is recycled in hydrogenation reactor I-3 as material stream 42.Lower floor's phase (L1) is fed in extraction cells VI-3 as material stream 33b.In this extraction cells VI-3, be used as and expect that stream 40 (upper strata phase (U3)) extract lower floor's phase (L1) by the tertiary amine (A1) being recycled in extraction cells VI-3 of the third phase tripping device III-3 of thermal decomposition unit.
Raffinate (R2) and extraction liquid (E2) in extraction cells VI-3, have been obtained.Raffinate (R2) comprises formic acid-amine adduct (A2) and polar solvent and it is fed in the first water distilling apparatus II-3 as material stream 33c.Extraction liquid (E2) comprises tertiary amine (A1) and coordination catalyst residue and it is recycled in hydrogenation reactor I-2 as material stream 41.
Inhibitor is added in material stream 33c continuously or intermittently as material stream 34.In the first water distilling apparatus II-3, raffinate (R2) is separated into and comprises described polar solvent and as mixture (S1) at the bottom of material stream 35 is recycled to distillate (D1) in hydrogenation reactor I-3 and two-phase tower.
Mixture at the bottom of tower (S1) comprises upper strata phase (U2) and lower floor's phase (L2), its at the middle and upper levels phase (U2) comprise tertiary amine (A1) and repressed coordination catalyst, lower floor's phase (L2) comprises formic acid-amine adduct (A2).
Mixture (S1) at the bottom of tower is fed in the third phase tripping device III-3 of thermal decomposition unit as material stream 36.
In the third phase tripping device III-3 of thermal decomposition unit, mixture at the bottom of tower (S1) is separated to obtain the upper strata phase (U3) of the catalyzer that comprises tertiary amine (A1) and suppressed dose and the lower floor's phase (L3) that comprises formic acid-amine adduct (A2).
Upper strata phase (U3) is recycled in extraction cells VI-3 as material stream 40.Lower floor's phase (L3) is fed in the after-fractionating device IV-3 of thermal decomposition unit as material stream 37.In after-fractionating device IV-3, formic acid-amine adduct (A2) contained in lower floor's phase (L3) is resolved into formic acid and free uncle amine (A1).In after-fractionating device IV-3, obtained mixture (S2) at the bottom of distillate (D2) and tower.
The distillate that comprises formic acid (D2) is discharged from water distilling apparatus IV-3 as material stream 39.Mixture (S2) at the bottom of the two-phase tower that comprises upper strata phase (U3) and lower floor's phase (L3) is recycled in the third phase tripping device III-3 of thermal decomposition unit as material stream 38, its at the middle and upper levels phase (U3) comprise tertiary amine (A1), lower floor's phase (L3) comprises formic acid-amine adduct (A2).Mixture (S2) at the bottom of knockout tower in third phase tripping device III-3.Upper strata phase (U3) is recycled in extraction cells VI-3.Lower floor's phase (L3) is recycled in after-fractionating device IV-3.
In the embodiment of Fig. 4, the carbonated material stream 51 of bag and the material stream 52 that comprises hydrogen are fed in hydrogenation reactor I-4.Other material stream (not shown) can be fed in hydrogenation reactor I-4 to compensate any loss of tertiary amine (A1) or coordination catalyst.
In hydrogenation reactor I-4, make carbonic acid gas and hydrogen have lower reaction at tertiary amine (A1), polar solvent and the coordination catalyst that comprises at least one periodictable the 8th, 9 He10 family elements.This has obtained the two-phase hydrogenated mixture (H) that comprises upper strata phase (U1) and lower floor's phase (L1), its at the middle and upper levels phase (U1) comprise coordination catalyst and tertiary amine (A1), lower floor's phase (L1) comprises polar solvent, coordination catalyst residue and formic acid-amine adduct (A2).
Hydrogenated mixture (H) is fed in first-phase tripping device V-4 as material stream 53a.In first-phase tripping device V-4, hydrogenated mixture (H) is separated into upper strata phase (U1) and lower floor's phase (L1).
Upper strata phase (U1) is recycled in hydrogenation reactor I-4 as material stream 62.Lower floor's phase (L1) is fed in extraction cells VI-4 as material stream 53b.In this extraction cells VI-4, be used as material stream 60 (upper strata phase (U3)) and by second-phase tripping device VII-4, be recycled to tertiary amine (A1) the extraction lower floor's phase (L1) in extraction cells VI-4 by the third phase tripping device III-4 of thermal decomposition unit with as material stream 56c.
Raffinate (R2) and extraction liquid (E2) in extraction cells VI-4, have been obtained.Raffinate (R2) comprises formic acid-amine adduct (A2) and polar solvent and it is fed in the first water distilling apparatus II-4 as material stream 53c.Extraction liquid (E2) comprises tertiary amine (A1) and coordination catalyst residue its and is recycled in hydrogenation reactor I-4 as material stream 61.
Inhibitor is added in material stream 53c continuously or intermittently as material stream 54.In the first water distilling apparatus II-4, raffinate (R2) is separated into and comprises polar solvent and as mixture (S1) at the bottom of material stream 55 is recycled to distillate (D1) in hydrogenation reactor I-4 and two-phase tower.
Mixture at the bottom of tower (S1) comprises upper strata phase (U2) and lower floor's phase (L2), its coordination catalyst that phase (U2) comprises tertiary amine (A1) and suppressed dose at the middle and upper levels, and lower floor's phase (L2) comprises formic acid-amine adduct (A2).Mixture (S1) at the bottom of tower is fed in after-fractionating device VII-4 as material stream 56a.
In after-fractionating device VII-4, mixture at the bottom of tower (S1) is separated into upper strata phase (U2) and lower floor's phase (L2).Upper strata phase (U2) is recycled in extraction cells VI-4 by after-fractionating device VII-4 as material stream 56c.
Lower floor's phase (L2) is fed in after-fractionating device IV-4 as material stream 56b.
In after-fractionating device IV-4 Zhong Jiang lower floor's phase (L2), contained formic acid-amine adduct (A2) resolves into formic acid and free uncle amine (A1).In after-fractionating device IV-4, obtained mixture (S2) at the bottom of distillate (D2) and tower.
The distillate that comprises formic acid (D2) is discharged from after-fractionating device IV-4 as material stream 59.Mixture (S2) at the bottom of the two-phase tower that comprises upper strata phase (U3) and lower floor's phase (L3) is recycled in the third phase tripping device III-4 of thermal decomposition unit as material stream 58, its coordination catalyst that phase (U3) comprises tertiary amine (A1) and suppressed dose at the middle and upper levels, lower floor's phase (L3) comprises formic acid-amine adduct (A2).
In the third phase tripping device III-4 of thermal decomposition unit, mixture at the bottom of tower (S2) is separated to obtain the upper strata phase (U3) that comprises tertiary amine (A1) and repressed coordination catalyst and the lower floor's phase (L3) that comprises formic acid-amine adduct (A2).
Upper strata phase (U3) is recycled in extraction cells VI-4 by third phase tripping device III-4 as material stream 60.Lower floor's phase (L3) is fed in the after-fractionating device IV-4 of thermal decomposition unit as material stream 57.In after-fractionating device IV-4 Zhong Jiang lower floor's phase (L3), contained formic acid-amine adduct (A2) resolves into formic acid and free uncle amine (A1).Then as mentioned above, in after-fractionating device IV-4, again obtain mixture (S2) at the bottom of distillate (D2) and tower.
In the embodiment of Fig. 5, the carbonated material stream 71 of bag and the material stream 72 that comprises hydrogen are fed in hydrogenation reactor I-5.Other material stream (not shown) can be fed in hydrogenation reactor I-5 to compensate any loss of tertiary amine (A1) or coordination catalyst.
In hydrogenation reactor I-5, make carbonic acid gas and hydrogen have lower reaction at tertiary amine (A1), polar solvent and the coordination catalyst that comprises at least one periodictable the 8th, 9 He10 family elements.This has obtained the two-phase hydrogenated mixture (H) that comprises upper strata phase (U1) and lower floor's phase (L1), its at the middle and upper levels phase (U1) comprise coordination catalyst and tertiary amine (A1), lower floor's phase (L1) comprises polar solvent, coordination catalyst residue and formic acid-amine adduct (A2).
Hydrogenated mixture (H) is fed in first-phase tripping device V-5 as material stream 73a.In first-phase tripping device V-5, hydrogenated mixture (H) is separated into upper strata phase (U1) and lower floor's phase (L1).
Upper strata phase (U1) is recycled in hydrogenation reactor I-5 as material stream 82.Lower floor's phase (L1) is fed in extraction cells VI-5 as material stream 73b.Now, be used as and expect that stream 80 (upper strata phase (U3)) extract lower floor's phase (L1) by the tertiary amine (A1) being recycled in extraction cells VI-5 of the third phase tripping device of thermal decomposition unit.
Raffinate (R2) and extraction liquid (E2) in extraction cells VI-5, have been obtained.Raffinate (R2) comprises formic acid-amine adduct (A2) and polar solvent and it is fed in the first water distilling apparatus II-5 as material stream 73c.Extraction liquid (E2) comprises tertiary amine (A1) and coordination catalyst residue its and is recycled in hydrogenation reactor I-5 as material stream 81.
Inhibitor is added in material stream 73c continuously or intermittently as material stream 74.In the first water distilling apparatus II-5, raffinate (R2) is separated into rich water distillate (D1 wr), low water distillate (D1 wa) and two-phase tower at the bottom of mixture (S1).By rich water distillate (D1 wr) as material stream 83, be added in material stream 73a.By low water distillate (D1 wa) as material stream 75, be recycled in hydrogenation reactor I-5.The prerequisite of Fig. 5 embodiment is as polar solvent by the mixture of one or more alcohol and waters.
Mixture at the bottom of tower (S1) comprises upper strata phase (U2) and lower floor's phase (L2), its at the middle and upper levels phase (U2) comprise tertiary amine (A1) and repressed coordination catalyst, lower floor's phase (L2) comprises formic acid-amine adduct (A2).
Mixture (S1) at the bottom of tower is fed in the third phase tripping device III-5 of thermal decomposition unit as material stream 76.
In the third phase tripping device III-5 of thermal decomposition unit, mixture at the bottom of tower (S1) is separated to obtain upper strata phase (U3) and lower floor's phase (L3), its at the middle and upper levels phase (U3) comprise tertiary amine (A1) and repressed coordination catalyst, lower floor's phase (L3) comprises by formic acid-amine adduct (A2).
Upper strata phase (U3) is recycled in extraction cells IV-5 as material stream 80.Lower floor's phase (L3) is fed in the after-fractionating device IV-5 of thermal decomposition unit as material stream 77.In after-fractionating device IV-5 Zhong Jiang lower floor's phase (L3), contained formic acid-amine adduct (A2) resolves into formic acid and free uncle amine (A1).In after-fractionating device IV-5, obtained mixture (S2) at the bottom of distillate (D2) and tower.
The distillate that comprises formic acid (D2) is discharged from water distilling apparatus IV-5 as material stream 79.Mixture (S2) at the bottom of the two-phase tower that comprises upper strata phase (U3) and lower floor's phase (L3) is recycled in the third phase tripping device III-5 of thermal decomposition unit as material stream 78, its at the middle and upper levels phase (U3) comprise tertiary amine (A1) and repressed coordination catalyst, lower floor's phase (L3) comprises formic acid-amine adduct (A2).Mixture (S2) at the bottom of knockout tower in third phase tripping device III-5.Upper strata phase (U3) is recycled in extraction cells VI-5 as material stream 80.Lower floor's phase (L3) is recycled in after-fractionating device IV-5 as material stream 77.
In the embodiment of Fig. 6, the carbonated material stream 91 of bag and the material stream 92 that comprises hydrogen are fed in hydrogenation reactor I-6.Other material stream (not shown) can be fed in hydrogenation reactor I-6 to compensate any loss of tertiary amine (A1) or coordination catalyst.
In hydrogenation reactor I-6, make carbonic acid gas and hydrogen have lower reaction at tertiary amine (A1), polar solvent and the coordination catalyst that comprises at least one periodictable the 8th, 9 He10 family elements.This has obtained the two-phase hydrogenated mixture (H) that comprises upper strata phase (U1) and lower floor's phase (L1), its at the middle and upper levels phase (U1) comprise coordination catalyst and tertiary amine (A1), lower floor's phase (L1) comprises polar solvent, coordination catalyst residue and formic acid-amine adduct (A2).
Hydrogenated mixture (H) is fed in extraction cells VI-6 as material stream 93a.
In this extraction cells VI-6, be used as and expect that stream 100 (upper strata phase (U3)) are recycled to tertiary amine (A1) the extraction hydrogenated mixture (H) in extraction cells VI-6 by the third phase tripping device III-6 of thermal decomposition unit.
Raffinate (R1) and extraction liquid (E1) in extraction cells VI-6, have been obtained.Raffinate (R1) comprises formic acid-amine adduct (A2) and polar solvent and it is fed in the first water distilling apparatus II-6 as material stream 93c.Extraction liquid (E1) comprises tertiary amine (A1) and coordination catalyst and it is recycled in hydrogenation reactor I-6 as material stream 101.
Inhibitor is added in material stream 93c continuously or intermittently as material stream 94.In the first water distilling apparatus II-6, by raffinate (R1) be separated into comprise polar solvent and using it as material stream 95, be recycled to distillate (D1) in hydrogenation reactor I-6 and two-phase tower at the bottom of mixture (S1).
Mixture at the bottom of tower (S1) comprises upper strata phase (U2) and lower floor's phase (L2), its at the middle and upper levels phase (U2) comprise tertiary amine (A1) and repressed coordination catalyst, lower floor's phase (L2) comprises formic acid-amine adduct (A2).
Mixture (S1) at the bottom of tower is fed in the third phase tripping device III-6 of thermal decomposition unit as material stream 96.
In the third phase tripping device III-6 of thermal decomposition unit, mixture at the bottom of tower (S1) is separated to obtain upper strata phase (U3) and lower floor's phase (L3), its at the middle and upper levels phase (U3) comprise tertiary amine (A1) and repressed coordination catalyst, lower floor's phase (L3) comprises formic acid-amine adduct (A2).
Upper strata phase (U3) is recycled in extraction cells IV-6 as material stream 100.Lower floor's phase (L3) is fed in the after-fractionating device IV-6 of thermal decomposition unit as material stream 97.In after-fractionating device IV-6, formic acid-amine adduct (A2) contained in lower floor's phase (L3) is resolved into formic acid and free uncle amine (A1).In after-fractionating device IV-6, obtained mixture (S2) at the bottom of distillate (D2) and tower.
The distillate that comprises formic acid (D2) is discharged from water distilling apparatus IV-6 as material stream 99.Mixture (S2) at the bottom of the two-phase tower that comprises upper strata phase (U3) and lower floor's phase (L3) is recycled in the third phase tripping device III-6 of thermal decomposition unit as material stream 98, its coordination catalyst that phase (U3) comprises tertiary amine (A1) and suppressed dose at the middle and upper levels, lower floor's phase (L3) comprises formic acid-amine adduct (A2).Mixture (S2) at the bottom of knockout tower in third phase tripping device III-6.Upper strata phase (U3) is recycled in extraction cells VI-6 as material stream 100.Lower floor's phase (L3) is recycled in after-fractionating device IV-6 as material stream 97.
Below by embodiment and accompanying drawing, set forth the present invention.
Embodiment
Embodiments of the invention A-1 to A-6 (hydrogenation and be separated, the aftertreatment of hydrogenation reactor discharging)
Under inert conditions, in being equipped with the 250ml Hastelloy C autoclave of magnetic stirring bar, pack tertiary amine (A1), polar solvent and coordination catalyst into.Described autoclave is airtight and at room temperature inject CO subsequently 2.Then inject H 2and stirring the described reactor of (700rpm) lower heating.After the required reaction times, described autoclave is cooling and described hydrogenated mixture (H) is reduced pressure.Obtain two-phase hydrogenated mixture (H), its at the middle and upper levels phase (U1) be rich in still free tertiary amine (A1) and coordination catalyst, lower floor's phase (L1) is rich in polar solvent and formed formic acid-amine adduct (A2).Formic acid total content in formic acid-amine adduct (A2) is by using the 0.1N KOH in MeOH and using " Mettler ToledoDL50 " titration apparatus potentiometric titration to measure.By it, calculate inversion frequency (=TOF; The definition of TOF is referring to J.F.Hartwig, Organotransition Metal Chemistry, the 1st edition, 2010, University Science Books, Sausalito/California, the 545th page) and speed of reaction.The composition of described two-phase passes through gas chromatography determination.Ruthenium content is measured by atomic absorption spectrometry (=AAS).Each test parameter and the results are shown in table 1.1.
Embodiment A-1 shows in the methods of the invention to A-6, even if in the situation that the water yield that changes tertiary amine (A1), polar solvent, coordination catalyst (with regard to part and metal component), catalytic amount and add also obtains 0.98mol kg at the most -1h -1height to very high speed of reaction.All systems of studying have all formed two-phase, its at the middle and upper levels phase (U1) be rich in each case still free tertiary amine (A1) and coordination catalyst, lower floor's phase (L1) is rich in polar solvent and formed formic acid-amine adduct (A2) in each case.
K ru(the c in upper strata phase (U1) ruc in/lower floor phase (L1) ru) be the partition ratio of the metal component of the coordination catalyst between upper strata phase (U1) and lower floor's phase (L1).C in upper strata phase (U1) rufor the concentration of the metal component of the coordination catalyst in upper strata phase (U1), and c in lower floor's phase (L1) ruconcentration for the metal component of the coordination catalyst in lower floor's phase (L1).
Embodiment A-7 are to A-12 (being used glycol and methyl alcohol to carry out hydrogenation as solvent)
Under inert conditions, at the 100ml or the 250ml HastelloyC autoclave that are equipped with oar formula or magnetic stirring apparatus, pack tertiary amine (A1), polar solvent and coordination catalyst into.Described autoclave is airtight and at room temperature inject CO subsequently 2.Then inject H 2and stirring the described reactor of (700-1000rpm) lower heating.After the given reaction times, described autoclave is cooling and described hydrogenated mixture (H) is reduced pressure.After reaction, talk about suitably in reaction discharging and add water, and described 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 tertiary amine (A1) and coordination catalyst, polar solvent and formed formic acid-amine adduct (A2) are rich in mutually in lower floor.Separated described phase subsequently, and measure the formic acid content of lower floor's phase (L1).Formic acid total content in formic acid-amine adduct (A2) is by using the 0.1N KOH in MeOH and using " Mettler Toledo DL50 " titration apparatus potentiometric titration to measure.Parameter and the result of each test provide in table 1.2 and 1.3.
Embodiment A-7 are presented under comparable conditions to A-12, when using methanol/water mixture as polar solvent, compare as polar solvent with using glycol, obtain the formic acid of greater concn in Ke lower floor phase (L1).
Table 1.2
Table 1.3
Embodiments of the invention C-1 to C-11 (water is added in hydrogenation and being separated after reaction)
Under inert conditions, in being equipped with the 250ml Hastelloy C autoclave of magnetic stirring bar, pack tertiary amine (A1), polar solvent and coordination catalyst into.Described autoclave is airtight and at room temperature inject CO subsequently 2.Inject subsequently H 2and stirring the described reactor of (700rpm) lower heating.After the required reaction times, described autoclave is cooling and described hydrogenated mixture (H) is reduced pressure.Except as otherwise noted, otherwise this obtains two-phase hydrogenated mixture (H) after adding water, its at the middle and upper levels phase (U1) be rich in still free tertiary amine (A1) and coordination catalyst, lower floor's phase (L1) is rich in polar solvent, water and formed formic acid-amine adduct (A2).Formic acid total content in formic acid-amine adduct (A2) is by using the 0.1N KOH in MeOH and using " Mettler Toledo DL50 " titration apparatus potentiometric titration to measure.By it, calculate inversion frequency (=TOF; The definition of TOF is referring to J.F.Hartwig, Organotransition Metal Chemistry, the 1st edition, 2010, University Science Books, Sausalito/California, the 545th page) and speed of reaction.Ruthenium content passes through aas determination.The composition of described two-phase is by vapor-phase chromatography and proton N MR spectrographic determination.The parameter of each test is shown in 1.4-1.7 with the results are shown in.
In the embodiment of test C-1 to C-9, after reaction, there is disadvantageous Ru partition ratio k ru.Therefore, make subsequently product phase, material stream (3,13a), 33a), 53a), 73a), 93a)) mix to form two-phase mixture with water, its at the middle and upper levels phase (U1) mainly comprise tertiary amine (A1) and alcohol, lower floor's phase (L1) comprises formic acid-amine adduct (A2), alcohol and water, owing to adding water, has obtained the Ru partition ratio improving between these two phases.In addition, can realize the very high speed of reaction up to 1.64mol/kg/ hour.In the embodiment of the controlled trial with C3 and C8 (test C-10 and C-11 in table 1.7) contrast, in described reaction, add the water of total amount.Can be clear that, in the situation of solvent used and catalyzer, the water that adds this amount in hydrogenation causes the rear worse ruthenium partition ratio of reaction and/or lower speed of reaction herein herein.
Table 1.4
Table 1.5
Table 1.6
Table 1.7: add water in reaction
Embodiment D1-D4 (extraction of coordination catalyst)
Under inert conditions, in being equipped with the 100ml Hastelloy C autoclave of paddle stirrer, pack tertiary amine (A1), polar solvent and coordination catalyst into.Described autoclave is airtight and at room temperature inject CO subsequently 2.Inject subsequently H 2and stirring the described reactor of (1000rpm) lower heating.After the given reaction times, described autoclave is cooling and described hydrogenated mixture (H) is reduced pressure.After reaction, in hydrogenated mixture, add water, and described mixture is at room temperature stirred 10 minutes.This obtains two-phase hydrogenated mixture (H), its at the middle and upper levels phase (U1) be rich in still free tertiary amine (A1) and homogeneous catalyst, lower floor's phase (L1) is rich in polar solvent and formed formic acid-amine adduct (A2).By lower floor's phase (L1) separated and under inert conditions with fresh tertiary amine (at room temperature stirring 10 minutes, the subsequently separated described phase) processing of same amount (tertiary amine quality is corresponding to the quality of lower floor's phase) three times.Formic acid total content in formic acid-amine adduct is by using the 0.1N KOH in MeOH and using " Mettler Toledo DL50 " titration apparatus potentiometric titration to measure.Ruthenium content is measured by AAS.Each test parameter and the results are shown in table 1.8.
Embodiment D-1 to D-4 shows by the water yield that changes described catalyzer and add during formation formic acid and the ruthenium content of product phase (raffinate R2) can be down to and be less than 1ppm ruthenium.
Table 1.8
Embodiment E 1-E5 (recycling of catalyzer and the extraction of catalyzer)
Under inert conditions, in being equipped with the 100ml Hastelloy C autoclave of paddle stirrer, pack tertiary amine (A1), polar solvent and coordination catalyst into.Described autoclave is airtight and at room temperature inject CO subsequently 2.Inject subsequently H 2and stirring the described reactor of (1000rpm) lower heating.After the reaction times, described autoclave is cooling and described hydrogenated mixture (H) is reduced pressure.After reaction, in reaction discharging, add water, and described mixture is at room temperature stirred 10 minutes.This obtains two-phase hydrogenated mixture (H), its at the middle and upper levels phase (U1) be rich in still free tertiary amine (A1) and coordination catalyst, lower floor's phase (L1) is rich in polar solvent and formed formic acid-amine adduct (A2).Subsequently the described method that is separated and passes through is hereinafter described measured to the formic acid content of lower floor's phase (L1) and the ruthenium content of two phases.Then, with fresh tertiary amine (A1), the upper strata phase (U1) that comprises ruthenium catalyst is complemented to 37.5g, and under the reaction conditions with identical above with identical solvent by it again for hydrogenation CO 2.After reaction finishes and adds water, separated lower floor's phase (L1) is also mixed it three times (at room temperature stirring 10 minutes, subsequently separated described phase) to extract described catalyzer under inert conditions with the fresh tertiary amine (A1) of same amount (amine quality is corresponding to the quality of lower floor's phase).Formic acid total content in formic acid-amine adduct (A2) is by using the 0.1N KOH in MeOH and using " Mettler Toledo DL50 " titration apparatus potentiometric titration to measure.Ruthenium content is measured by AAS.The parameter of each test is shown in 1.9-1.10 with the results are shown in.
Embodiment E-1 shows that to E-5 the water yield (before and after reaction) and the reaction conditions that change catalyzer, add allow active catalyst again for hydrogenation CO 2and allow only by single extraction, just the ruthenium content of product phase to be down to the low 2ppm of reaching.
Table 1.9
Table 1.10
Embodiment F 1-F4 (the thermal separation of polar solvent; Step (c))
Under reduced pressure by rotatory evaporator, alcohol and water (is comprised to formic acid-amine adduct from product phase; Corresponding to lower floor's phase (L1), raffinate (R1) or raffinate (R2)) in distillation remove.At the bottom of tower, form two-phase mixture (trialkylamine and formic acid-amine adduct phase; Corresponding to mixture at the bottom of tower (S1)), and separated described two phases, by using the 0.1N KOH in MeOH and using " Mettler Toledo DL50 " titration apparatus potentiometric titration to measure the formic acid content of lower floor's phase (L2).Amine and alcohol content pass through gas chromatography determination.Each test parameter and the results are shown in table 1.1.
Embodiment F-1 shows in the methods of the invention to F-4, can be from product phase (lower floor's phase (L1) under mild conditions; Raffinate (R1) or raffinate (R2)) in separated opposed polarity solvent, thereby obtain relative rich containing lower floor's phase (L2) of formic acid and mainly comprise the upper strata phase (U2) of tertiary amine.
Table 1.22
Embodiment G1 and G2 (thermal separation of polar solvent and trialkylamine/solvent/formic acid mixtures and the decomposition of formic acid-amine adduct)
Under reduced pressure by rotatory evaporator, from product phase, (comprise formic acid-amine adduct; Corresponding to lower floor's phase (L1), raffinate (R1) or raffinate (R2)) in distillation remove alcohol and water.At the bottom of tower, form two-phase mixture (trialkylamine and formic acid-amine adduct phase; And separated described two-phase mixture at the bottom of tower (S1)).By vapor-phase chromatography with by using the 0.1N KOH in MeOH and using " MettlerToledo DL50 " titration apparatus potentiometric titration to measure the distillate (major portion that comprises first alcohol and water; Distillate (D1)), upper strata phase (comprises free trialkylamine; Upper strata phase (U2)) and lower floor's phase (comprise formic acid-amine adduct; Lower floor's phase (L2)) composition.Then, by the 10cm Vigreux post in vacuum distillation plant by tertiary amine (A2) thermolysis in lower floor's phase (L2) of formic acid and first step.After all formic acid decomposes, obtain the single-phase tower bottom distillate (S2) that comprises pure tertiary amine (A2) and can use it for the described catalyzer of extraction and be recycled in hydrogenation.Formic acid and residuary water are present in distillate (D2).The composition of tower bottom distillate (S2) and distillate is by vapor-phase chromatography with by using " Mettler Toledo DL50 " titration apparatus to measure the 0.1N KOH potentiometric titration formic acid in MeOH.Each test parameter and the results are shown in table 1.12.
Embodiment G1-G2 shows in the methods of the invention, can be under mild conditions from product mutually separated opposed polarity solvent, thereby obtain relative rich containing lower floor's phase (L3) of formic acid and mainly comprise the upper strata phase (U3) of tertiary amine.Then can at higher temperature, make formic acid separated containing the tertiary amine (A1) of this lower floor's phase (L3) of formic acid with relative rich, and retain free uncle amine (A1).The formic acid obtaining in this way still comprises some water, and it can be separated with formic acid by the tower with higher separating power.Can be by the tertiary amine obtaining in solvent removal and thermolysis (A1) for extracting described catalyzer.
Table 1.12
Embodiment H1-H4 (the inhibition of the coordination catalyst in solvent removal and thermal decomposition process; Step (c) and (e))
The decomposition run of the decomposition of solvent removal and formic acid-amine adduct (A2) is carried out in the three neck glass flask of 250mL that provide reflux exchanger and argon shield.Being suppressed in process of the test of coordination catalyst by CO undertaken by the metal melt (metal frit) that CO bubbling is passed into solution (5-6L CO/h) by it.Reaction mixture is boiled under refluxing.In reaction process, by partition, by syringe, take out sample and be used for measuring phase ratio and formic acid concn.Formic acid concn is by being used " Mettler Toledo DL50 " titration apparatus to measure the 0.1N KOH potentiometric titration in MeOH.
Synthesizing of the catalyzer stock solution (CS1) of inhibition test: in air, by 3.15g[Ru (COD) Cl 2] be placed in 1.2L Hastelloy autoclave and add 150g trihexylamine (THA).Enclosed high pressure still, uses N subsequently 2test has or not leaks and uses N 2rinse.By 4.66g1, the mixture of 2-dicyclohexyl phosphino-ethane, 8.19g tri octyl phosphine, 567g THA, 57.25g MeOH and 6.3g water sucks in autoclave by applying vacuum under argon gas subsequently.Then autoclave is under agitation heated to 70 ℃ and inject 160g CO 2.Inject H 2to 120 bar and by pressure, in reaction process, pass through to inject other H 2and remain under 120 bar.After 4 hours, make autoclave be cooled to RT and be decompressed to barometric point.Under agitation 20g water is added in reaction discharging and obtain two-phase mixture.Separation of phases.This obtains the upper strata phase that 501g comprises trihexylamine and active catalyst (1900ppm Ru), and 156g lower floor phase (680ppm Ru), and lower floor is abandoned mutually.Upper strata comprises mutually 83.5% ruthenium used and is used as subsequently the catalyzer stock solution (CS1) of inhibition test.
Inhibition in the thermolysis of formic acid-amine adduct (A2); Step (e): test H-1
200ppm is [Ru (P n-octyl 3) 4(H) 2] Ru, 20mg dcpe (1,2-dicyclohexyl phosphino-ethane) and 80g formic acid-trihexylamine adducts (A3) (N (Hex) of form 3: FA=1:1.5; 20.4 % by weight formic acid (FA)) be placed in each case 250ml glass beaker and be heated to 130 ℃.Carry out wherein CO being passed into first test of (" passing into CO ").Carry out wherein will not adding the second test of CO (" not using inhibitor ").Formic acid decomposition (FA-D[%]) and formic acid concn (FA[%]) by sampling and titration determination.The result of the first and second experiments is presented in Fig. 7 with the form of scheming.
Embodiment H-1 demonstrates in the methods of the invention, because the decomposition of the formic acid of coordination catalyst residue under the thermolysis condition at formic acid-amine adduct may be to a great extent suppressed by the interpolation of CO.Inhibition in solvent removal (step (c)): test H-2
11.1g catalyzer stock solution CS1,53.9g trihexylamine, 25g methyl alcohol, 2g water and 7.8g formic acid are placed in to 250ml glass beaker and heating under refluxing.Carry out wherein CO being passed into first test of (" passing into CO ").Carry out wherein will not adding the second test of CO (" not using inhibitor ").Formic acid decomposition and formic acid concn (FA[%]) by sampling and titration determination.The result of the first and second experiments is presented in Fig. 8 with the form of scheming.
Embodiment H-2 demonstrates in the methods of the invention, because the decomposition of the formic acid of catalyst residue under solvent removal (step (c)) condition may be to a great extent suppressed by the interpolation of CO.
Inhibition and catalyst recycle in solvent removal (step (c)): test H-3
11.1g catalyzer stock solution CS1,53.9g trihexylamine, 25g methyl alcohol, 2g water and 7.8g formic acid are placed in to 250ml glass beaker and heating under refluxing.Carry out wherein CO being passed into first test of (" passing into CO ").Carry out wherein will not adding the second test of CO (" not using inhibitor ").Formic acid decomposition and formic acid concn (FA[%]) by sampling and titration determination.The result of the first and second experiments is presented in Fig. 9 with the form of scheming.
Then, the amine of the repressed coordination catalyst that comprises major portion is separated out and for CO 2hydrogenation.For this reason, 37.5g is placed in to 100mlHC autoclave available from amine phase, 12.5g methyl alcohol and the 1g water of inhibition test.This autoclave is by N 2inerting is also injected 10g CO 2(22 bar).At 70 ℃, inject H subsequently 2to 80 bar and by pressure, within the reaction times, pass through to inject other H 2and remain under 80 bar.The formic acid concn of product in was mutually 1.6% and after 16 hours, is 4.3% after 2 hours.
Embodiment H-3 demonstrates in the methods of the invention, and repressed coordination catalyst can be converted into activity form under hydrogenation conditions again.
Inhibition in solvent removal (step (c)) and the hot reactivate of catalyzer: test H-4
11.1g catalyzer stock solution CS1,53.9g trihexylamine, 25g methyl alcohol, 2g water and 7.8g formic acid are placed in to 250ml glass beaker, under refluxing, heat and CO is passed into reaction mixture (" passing into CO ").Formic acid decomposition and formic acid concn (FA[%]) by sampling and titration determination.The result of the first and second experiments is presented in Figure 10 with the form of scheming.
Subsequently this reaction mixture boiled other 10 hours under refluxing and do not add CO with the repressed coordination catalyst of reactivate.After this, formic acid decomposes completely.Then, the amine of the coordination catalyst that comprises major portion is separated out and is used further to CO 2hydrogenation.For this reason, 37.5g is placed in to 100ml HC autoclave available from amine phase, 12.5g methyl alcohol and the 1g water of inhibition test.This autoclave is by N 2inerting is also injected 10gCO 2(21 bar).At 70 ℃, inject H subsequently 2to 80 bar and by pressure, within the reaction times, pass through to inject other H 2and remain under 80 bar.After 1 hour, the formic acid concn of product in is mutually 5.5%.Ruthenium partition ratio between amine phase and product phase is 18.8.
Embodiment H-4 demonstrates in the methods of the invention, repressed coordination catalyst can be by without thermal treatment and be converted into again activity form and then significantly faster in hydrogenation under hydrogenation conditions under CO, also demonstrate coordination catalyst be preferentially present in amine mutually in, even suppress and reactivate after.

Claims (14)

1. a method of preparing formic acid, it comprises the steps:
(a) make to comprise carbonic acid gas, hydrogen, at least one is selected from the reaction mixture (Rg) of 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 the tertiary amine of at least one general formula (A1)
NR 1R 2R 3(A1)
Wherein:
R 1, R 2, R 3in the every kind of situation of respectively doing for oneself independently of one another, there is the not branching of 1-16 carbon atom or branching, acyclic or cyclic aliphatic, araliphatic or aromatic group, 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 to form the chain that comprises at least four atoms
Under existing, in hydrogenation reactor, there is homogeneous catalytic reaction to obtain the two-phase hydrogenated mixture (H) that comprises following component after optional interpolation water in the coordination catalyst that comprises at least one element that is selected from periodictable the 8th, 9 He10 families at least one:
Upper strata phase (U1), it comprises at least one coordination catalyst and at least one tertiary amine (A1), and
Lower floor's phase (L1), formic acid-amine adduct that it comprises at least one polar solvent, at least one coordination catalyst residue and at least one general formula (A2),
NR 1R 2R 3*x iHCOOH (A2)
Wherein:
X ifor 0.4-5, and
R 1, R 2, R 3as defined above,
(b) according to one of following steps, the hydrogenated mixture (H) of gained in step (a) is carried out to aftertreatment:
(b1) in first-phase tripping device, the hydrogenated mixture (H) of gained in step (a) is separated into upper strata phase (U1) and lower floor's phase (L1), or
(b2) in extraction cells by least one coordination catalyst of extraction in the hydrogenated mixture (H) of the extraction agent gained from step (a) that comprises described at least one tertiary amine (A1) with acquisition:
Raffinate (R1), it comprises at least one formic acid-amine adduct (A2) and at least one polar solvent, and
Extraction liquid (E1), it comprises at least one tertiary amine (A1) and at least one coordination catalyst, or
(b3) in first-phase tripping device, the hydrogenated mixture (H) of step (a) gained is separated into upper strata phase (U1) and lower floor's phase (L1), and the residue that extracts at least one coordination catalyst in extraction cells by the extraction agent that comprises at least one tertiary amine (A1) from lower floor's phase (L1) is to obtain:
Raffinate (R2), it comprises at least one formic acid-amine adduct (A2) and at least one polar solvent, and
Extraction liquid (E2), it comprises at least one tertiary amine (A1) and at least one coordination catalyst residue,
(c) in the first water distilling apparatus Zhong Cong lower floor phase (L1), raffinate (R1) or raffinate (R2) separated described at least one polar solvent to obtain:
Distillate (D1), it comprises at least one polar solvent and is recirculated in the hydrogenation reactor of step (a), and
Mixture at the bottom of two-phase tower (S1), it comprises:
Upper strata phase (U2), it comprises at least one tertiary amine (A1), and
Lower floor's phase (L2), it comprises at least one formic acid-amine adduct (A2),
(d) optionally in second-phase tripping device, by being separated, mixture (S1) at the bottom of the tower of gained in step (c) is carried out to aftertreatment to obtain upper strata phase (U2) and lower floor's phase (L2),
(e) in thermal decomposition unit, make contained at least one formic acid-amine adduct (A2) in mixture (S1) at the bottom of tower or optional lower floor's phase (L2) decompose to obtain at least one tertiary amine (A1) in the hydrogenation reactor that is recycled to step (a) and the formic acid of discharging from thermal decomposition unit
Wherein be close to step (c) before and/or during step (c), carbon monoxide be added in lower floor's phase (L1), raffinate (R1) or raffinate (R2), and/or
Mixture (S1) or optional lower floor's phase (L2) at the bottom of being close to step (e) before and/or during step (e), carbon monoxide being added into tower.
2. according to the method for claim 1, wherein according to step (b1), the hydrogenated mixture (H) of gained in step (a) is further carried out to aftertreatment, and upper strata phase (U1) is recycled in the hydrogenation reactor of step (a), and Bing Jiang lower floor phase (L1) feeds in the first water distilling apparatus of step (c).
3. according to the method for claim 1, wherein according to step (b2), the hydrogenated mixture (H) of gained in step (a) is further carried out to aftertreatment, wherein described at least one tertiary amine (A1) obtaining in the thermal decomposition unit at step (e) is used as to extraction agent, extraction liquid (E1) is recycled in the hydrogenation reactor of step (a), and raffinate (R1) is fed in the first water distilling apparatus of step (c).
4. according to the method for claim 1, wherein according to step (b3), the hydrogenated mixture (H) of gained in step (a) is further carried out to aftertreatment, wherein described at least one tertiary amine (A1) obtaining in the thermal decomposition unit at step (e) is used as to extraction agent, extraction liquid (E2) is recycled in the hydrogenation reactor of step (a), and raffinate (R2) is fed in the first water distilling apparatus of step (c).
5. according to the method for any one in claim 1-4, wherein thermal decomposition unit comprises after-fractionating device and third phase tripping device, and the decomposition of formic acid-amine adduct (A2) is carried out obtaining in after-fractionating device: the distillate that comprises formic acid and discharge from after-fractionating device (D2) and comprise upper strata phase (U3) and the two-phase tower of lower floor's phase (L3) at the bottom of mixture (S2), its at the middle and upper levels phase (U3) comprise described at least one tertiary amine (A1) and repressed coordination catalyst and free ligand, lower floor's phase (L3) comprises described at least one formic acid-amine adduct (A2).
6. according to the method for claim 5, wherein mixture (S2) at the bottom of the tower obtaining is separated into upper strata phase (U3) and lower floor's phase (L3) in the third phase tripping device of thermal decomposition unit in after-fractionating device, and upper strata phase (U3) is recycled in the hydrogenation reactor of step (a), lower floor's phase (L3) is recycled in the after-fractionating device of thermal decomposition unit.
7. according to the method for claim 6, wherein upper strata phase (U3) is recycled in step (b2) or extraction cells (b3).
8. according to the method for any one in claim 1-7, wherein mixture (S1) or optional lower floor's phase (L2) at the bottom of the first tower obtaining in step (c) are recycled in the after-fractionating device of thermal decomposition unit.
9. according to the method for any one in claim 1-8, wherein mixture (S1) or optional lower floor's phase (L2) at the bottom of the first tower obtaining in step (c) are recycled in the third phase tripping device of thermal decomposition unit.
10. according to the method for any one in claim 1-9, wherein according to step (d) to the tower of step (c) gained at the bottom of mixture (S1) further carry out aftertreatment, upper strata phase (U2) is recycled in the extraction cells of step (b2), and Bing Jiang lower floor phase (L2) feeds in the thermal decomposition unit of step (e).
11. according to the method for any one in claim 1-10, wherein incites somebody to action wherein radicals R 1, R 2, R 3independently selected from C 5-C 6alkyl, C 5-C 8the tertiary amine of the general formula of cycloalkyl, benzyl and phenyl (A1) is as tertiary amine.
12. according to the method for any one in claim 1-11, wherein three normal hexyl Amines is used as to tertiary amine (A1).
13. according to the method for any one in claim 1-12, wherein the mixture of water, methyl alcohol or water and methyl alcohol is used as to polar solvent.
14. according to the method for any one in claim 5-13, wherein by upper strata phase (U3) thermal treatment at 100-200 ℃, is then recirculated in hydrogenation reactor with the repressed coordination catalyst of reactivate.
CN201280059095.3A 2011-10-07 2012-10-02 Method for producing formic acid by reacting carbon dioxide with hydrogen Pending CN103974927A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11184297.7 2011-10-07
EP11184297 2011-10-07
PCT/EP2012/069458 WO2013050367A2 (en) 2011-10-07 2012-10-02 Method for producing formic acid by reacting carbon dioxide with hydrogen

Publications (1)

Publication Number Publication Date
CN103974927A true CN103974927A (en) 2014-08-06

Family

ID=46963751

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201280059095.3A Pending CN103974927A (en) 2011-10-07 2012-10-02 Method for producing formic acid by reacting carbon dioxide with hydrogen

Country Status (10)

Country Link
EP (1) EP2763950A2 (en)
JP (1) JP2014530216A (en)
KR (1) KR20140074373A (en)
CN (1) CN103974927A (en)
BR (1) BR112014008338A2 (en)
CA (1) CA2851175A1 (en)
IN (1) IN2014DN03122A (en)
RU (1) RU2014118032A (en)
SG (1) SG11201400997TA (en)
WO (1) WO2013050367A2 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201112231D0 (en) 2011-07-15 2011-08-31 Verdant Bioproducts Ltd Micro-organism
US8596013B2 (en) 2012-04-04 2013-12-03 Valinge Innovation Ab Building panel with a mechanical locking system
US9428438B2 (en) 2012-11-27 2016-08-30 Basf Se Process for preparing formic acid
WO2016024293A1 (en) 2014-08-12 2016-02-18 Council Of Scientific & Industrial Research Metal catalyzed process for reduction of co2 to sodium formate and formic acid

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0095321A2 (en) * 1982-05-22 1983-11-30 BP Chemicals Limited Production of formate salts
EP0329337A2 (en) * 1988-02-17 1989-08-23 BP Chemicals Limited The production of formic acid from a nitrogenous base, carbon dioxide and hydrogen
WO2010149507A2 (en) * 2009-06-26 2010-12-29 Basf Se Method for producing formic acid

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8424672D0 (en) 1984-09-29 1984-11-07 Bp Chem Int Ltd Production of formic acid
DE102004040789A1 (en) 2004-08-23 2006-03-02 Basf Ag Process for the preparation of formic acid
KR20090123972A (en) * 2007-03-23 2009-12-02 바스프 에스이 Method for producing formic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0095321A2 (en) * 1982-05-22 1983-11-30 BP Chemicals Limited Production of formate salts
EP0329337A2 (en) * 1988-02-17 1989-08-23 BP Chemicals Limited The production of formic acid from a nitrogenous base, carbon dioxide and hydrogen
WO2010149507A2 (en) * 2009-06-26 2010-12-29 Basf Se Method for producing formic acid

Also Published As

Publication number Publication date
SG11201400997TA (en) 2014-09-26
BR112014008338A2 (en) 2017-04-18
JP2014530216A (en) 2014-11-17
CA2851175A1 (en) 2013-04-11
WO2013050367A3 (en) 2013-10-03
EP2763950A2 (en) 2014-08-13
KR20140074373A (en) 2014-06-17
IN2014DN03122A (en) 2015-05-22
WO2013050367A2 (en) 2013-04-11
RU2014118032A (en) 2015-11-20

Similar Documents

Publication Publication Date Title
CN103282338A (en) Method for producing formic acid by reacting carbon dioxide with hydrogen
CN102574762B (en) Method for producing formic acid
CN102596878B (en) Process for preparing formic acid by reaction of carbon dioxide with hydrogen
FI86842B (en) Integrated method for production of formic acid
CN101808972B (en) Carbonylation process for the production of acetic acid using metal-pincer ligand catalysts
EP2910540B1 (en) Novel ruthenium complex and method for preparing methanol and diol
CA2681508A1 (en) Process for preparing formic acid
UA88901C2 (en) Process for preparing carboxylic acids and derivatives thereof
CN103974927A (en) Method for producing formic acid by reacting carbon dioxide with hydrogen
CN101830806B (en) Method and device for co-producing dimethyl carbonate and dimethyl oxalate
CN103080061A (en) Process for preparing formic acid by reaction of carbon dioxide with hydrogen
US20130123526A1 (en) Process for preparing formic acid by reaction of carbon dioxide with hydrogen
CN103649036A (en) Process for the preparation of formic acid by reacting carbon dioxide with hydrogen
US20130090496A1 (en) Process for preparing formic acid by reacting carbon dioxide with hydrogen
US8877965B2 (en) Process for preparing formic acid by reaction of carbon dioxide with hydrogen
US20130012739A1 (en) Process for preparing formic acid by reacting carbon dioxide with hydrogen
CN103917551A (en) Process for the preparation of formic acid by reaction of carbon dioxide with hydrogen
US20120071690A1 (en) Production of formamides
CN103998409B (en) Prepare the method for formic acid
EP2858970A1 (en) Process for preparing formic acid
CN104024203A (en) Method For Producing Formic Acid

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140806