CN1434015A - Process for preparing propionaldehyde from ethylene - Google Patents
Process for preparing propionaldehyde from ethylene Download PDFInfo
- Publication number
- CN1434015A CN1434015A CN 02113273 CN02113273A CN1434015A CN 1434015 A CN1434015 A CN 1434015A CN 02113273 CN02113273 CN 02113273 CN 02113273 A CN02113273 A CN 02113273A CN 1434015 A CN1434015 A CN 1434015A
- Authority
- CN
- China
- Prior art keywords
- rhodium
- water
- phosphine
- soluble
- concentration
- 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.)
- Granted
Links
Abstract
The present invention relates to a method for preparing propaldehyde by making dilute ethylene (containing other gas olefine and gas paraffin and inert gas) and carbon oxide and hydrogen gas produce reaction in the water phase containing water-soluble rhodium complex composite catalyst to prepare propaldehyde. It its reaction system the externally-added water-soluble phosphine ligand and sodium trisulfonate triphenyl phosphine oxide and one kind of water soluble phosphate and/or phosphorite whose concentration is 1X10 to the minus sixth-1X10 to the minus third mole/1 are contained. Said invention can make the selectivity for producing propaldehyde by using ethylene with low concentration be above 98%, and its process for separating and collecting propadehyde is simple, and the loss of rhodium catalyst is low.
Description
The invention relates to the rare ethene of a kind of usefulness is that raw material carries out the method that hydroformylation reaction prepares propionic aldehyde.
In the industrial production, existing a large amount of rudimentary unsaturated hydrocarbons components, fail to be made full use of, in the tail gas as refinery catalytic cracking generation, contain 10～22% ethene, is the senior organic important source material of preparation source.As, by adopting the method for hydroformylation reaction, can will be converted into propionic aldehyde.In this method, be catalyzer usually with the rhodium compound, rhodium catalyst uses with the form of phosphine composition, is dissolved in the organic solvent, and catalyzed reaction is a homogeneous reaction.
Relating to aspect the rare ethene hydroformylation system propionic aldehyde of homogeneous catalysis, U.S. Pat 5,675,041 adopts the oil soluble rhodium catalyst, by the C that contains alkynes
2～C
5Mixed olefins is feedstock production C
3～C
6Aldehyde.Owing to be to be raw material with the Sweet natural gas; make earlier contain ethene, synthetic gas (being carbon monoxide and hydrogen), and the mixed gas of other various ingredients after; prepare propionic aldehyde through hydroformylation reaction again; need in the reaction to add large amount of organic as solvent; the transformation efficiency of ethene is lower; and the product more complicated that reaction generates has all brought difficulty for the utilization of separation, purifying and the unreacting gas of propionic aldehyde.
In Chinese patent CN 1125712, the method for the low-concentration olefinic preparing aldehyde by hydro formylating that contains 5～40% 2～6 carbon atoms that is obtained by fluid catalytic cracking with load liquid phase rhodium phosphine complex catalyst has been described.Catalytic active component in the used load liquid-phase catalyst of this method still is oil-soluble rhodium phosphine complex catalyzer, and in use, the product aldehyde that can be generated dissolves lentamente and runs off.
(US 6 at Chinese patent CN 1168129A; 049,011) in, adopts the rare ethene hydroformylation prepared in reaction of oil soluble rhodium phosphine complex catalyst propionic aldehyde; the content of ethene is 30～75wt% in used rare ethene, and other component is rudimentary gaseous olefin, gaseous alkanes and hydrogen, nitrogen etc.In embodiment, only use methane as the component beyond the ethene.Be reflected at four polyoxyethylene glycol as carrying out in the homogeneous system of solvent, the transformation efficiency of ethene is not high.
When the oil soluble homogeneous catalyst was used for the rare ethene hydroformylation of catalysis, the factors such as accumulative total of contained trace impurity in system can cause disadvantageous effect to catalyzed reaction in the dissolving of other hydro carbons in organic solvent, the rare ethene, can cause the poisoning and deactivation of catalyzer.Simultaneously, because rhodium catalyst is dissolved in the organic solvent, after reaction was finished, catalyzer and reaction product all were dissolved in the organic solvent, thereby product was finished by the distillatory method with separating generally of catalyzer.With this understanding, high boiling point by-products produced in reaction system, the accumulation easily of propionic aldehyde condensation reaction generation, high boiling point by-products produced removing needs carry out under higher temperature, makes a large amount of catalyzer need heating at high temperature, also easily cause the decomposition and the inactivation of catalyzer, cause the loss of catalyzer.
Above-mentioned shortcoming can be avoided by using the water-soluble rhodium catalyst system; as U.S. Pat 4; 248,802 and US 4,808; described in 758; the solvability of rhodium complex in water can realize by using the sulfonation triaryl phosphine, in this system, during the water-soluble rhodium catalyzer is soluble in the aqueous phase; the hydroformylation product is dissolved in the organic phase, therefore is called the biphasic catalysis system.Use the method for biphasic catalysis system; after hydroformylation reaction is finished, be separated by simple two, the catalyzer that can will be dissolved in the water separates with organic phase; thereby avoided employed distillating method in the homogeneous catalysis, promptly in the separating of catalyzer and organic phase, avoided heat-processed.The hydroformylation reaction that has proved light alkenes such as ethene, propylene has good reactive behavior in the two-phase system that the water-soluble rhodium catalyzer exists.But do not see that water-soluble rhodium catalyzer biphasic catalysis system is used for the rare ethene hydroformylation of catalysis prepares propionic aldehyde.
The objective of the invention is to overcome the shortcoming that the rare ethene hydroformylation of homogeneous catalysis prepares the propionic aldehyde technology, providing a kind of is under the condition of solvent at water by water-soluble rhodium phosphine complex catalyst, the method for the rare ethene hydroformylation system propionic aldehyde of catalysis.
The method for preparing propionic aldehyde provided by the invention comprises, in the liquid phase that the complex catalyst system that water and water-soluble rhodium phosphine complex are formed exists, rare ethene and carbon monoxide and hydrogen reacted in autoclave.Wherein, described complex catalyst system is except that containing rhodium complex, also comprise the water-soluble phosphine ligand that (1) adds, total phosphine part (total here phosphine part comprises contained phosphine part in the phosphine part that adds and the catalyzer) is 2～200 with the mol ratio of rhodium, and the phosphine part has following general formula:
In the formula, Ar
1, Ar
2, Ar
3Represent aryl or pyridyl, x
1, x
2, x
3Can be the same or different, each represents carboxylate group or sulfonate group, y
1, y
2, y
3Can be the same or different, each representative contains straight or branched alkyl, the alkoxyl group of 1～20 carbon atom, and M is basic metal or alkaline-earth metal ions; n
1, n
2, n
3Can be the same or different, represent 0～4 integer; M1, m2, m3 are 0 or 1, but m=(m1+m2+m3) is not less than 1; (2) one or more water-soluble phosphates and/or phosphite, phosphoric acid salt is M
2HPO
4And/or MH
2PO
4, phosphite is M
2HPO
3And/or MH
2PO
3(M is lithium, sodium, potassium or ammonium ion), described water-soluble phosphate and/or the phosphite concentration in the aqueous solution is 1 * 10
-6～6 * 10
-3Mol; (3) oxide compound of outer adding water soluble aryl or pyridyl phosphine, its concentration is 1 * 10
-6～5 * 10
-3Mol.
Using rhodium complex catalysts of the present invention can be conventional rhodium complex, as, rhodium dicarbonyl acetylacetonate Rh (CO)
2(acac), many rhodium carbonyls Rh
4(CO)
12, Rh
6(CO)
16Deng, also can be as ZL 96 120056.1, the ZL96 120649.7 water-soluble rhodium phosphine complex of describing.
Described rhodium complex preferred formula is RhX (CO) L
1 uL
2 vAnd/or HRh (CO) L
1 iL
2 jRhodium complex.
Wherein, L
1Represent three (a sulfonate phenyl) phosphine, its general formula is P (m-C
6H
4SO
3M)
3Described three-(a sulfonate phenyl) phosphines refer to that (its chemical formula is P (m-C to three-(a sodium sulfonate phenyl) phosphines
6H
4SO
3Na)
3, be called for short TPPTS), three-(a sulfonic acid lithium phenyl) (its chemical formula is P (m-C to phosphine
6H
4SO
3Li)
3), (its chemical formula is P (m-C to three-(a potassium sulfonate phenyl) phosphines
6H
4SO
3K)
3), three-(a sulfonic acid rubidium phenyl) (its chemical formula is P (m-C to phosphine
6H
4SO
3Rb)
3), three-(a sulfonic acid caesium phenyl) (its chemical formula is P (m-C to phosphine
6H
4SO
3Cs)
3) in one or more, be preferably three-(a sodium sulfonate phenyl) phosphines, three-(a sulfonic acid lithium phenyl) phosphine, three-(a potassium sulfonate phenyl) phosphine, three-(a sulfonic acid rubidium phenyl) phosphine or three-(a sulfonic acid caesium phenyl) phosphine, three-(a sodium sulfonate phenyl) phosphines more preferably, be preferably TPPTS.
Wherein, L2 represents two-(a sulfonate phenyl) Phenylphosphines, and its general formula is PhP (m-C
6H
4SO
3M)
2), wherein, Ph refers to phenyl, P refers to phosphorus atom, m-C
6H
4SO
3M refers to a sulfonate phenyl, and M refers to alkalimetal ion.Described two-(a sulfonate phenyl) Phenylphosphines refer to that (its chemical formula is PhP (m-C to two-(a sodium sulfonate phenyl) Phenylphosphines
6H
4SO
3Na)
2, be called for short TPPDS), two-(a sulfonic acid lithium phenyl) (its chemical formula is PhP (m-C to Phenylphosphine
6H
4SO
3Li)
2), (its chemical formula is PhP (m-C to two-(a potassium sulfonate phenyl) Phenylphosphines
6H
4SO
3K)
2), two-(a sulfonic acid rubidium phenyl) (its chemical formula is PhP (m-C to Phenylphosphine
6H
4SO
3Rb)
2) and two-(a sulfonic acid caesium phenyl) (its chemical formula is PhP (m-C to Phenylphosphine
6H
4SO
3Cs)
2) in one or more, be preferably two-(a sodium sulfonate phenyl) Phenylphosphines, two-(a sulfonic acid lithium phenyl) Phenylphosphine, two-(a potassium sulfonate phenyl) Phenylphosphine, two-(a sulfonic acid rubidium phenyl) Phenylphosphine or two-(a sulfonic acid caesium phenyl) Phenylphosphine, be preferably TPPDS.
Wherein, u and v are 0～2 integer, and u+v=2.I and j are 0～3 integer, and i+j=3.X represents chlorine, bromine or iodine ion.Be preferably complex compound RhCl (CO) (TPPTS)
2And/or HRh (CO) (TPPTS)
3
In rhodium, the concentration of described catalyzer in the aqueous solution is 1 * 10
-4～1 * 10
-2Mol is preferably 2 * 10
-4～4 * 10
-3Mol.Described catalyzer can solid form adds, and form that also can the aqueous solution adds, and with RhCl
33H
2O, Rh (CO)
2(acac) (acac is acetylacetone based), Rh (OAc)
3Above-mentioned rhodium complex etc. form adding and TPPTS and the generation of TPPDS reaction in.
Described general formula is RhX (CO) L
1 uL
2 vRhodium complex, can adopt following method preparation: with the halogenide of rhodium or the halid hydrate, three of rhodium-(a sulfonate phenyl) phosphine, two-(a sulfonate phenyl) Phenylphosphine or three-(a sulfonate phenyl) phosphine and two-(a sulfonate phenyl) Phenylphosphine is raw material, halogenide with rhodium is dissolved in the ethanol earlier, the halid alcoholic solution of rhodium is added in the reactor, with the air in the inert gas replacement reactor, then, charge into carbon monoxide atmosphere.Three-(a sulfonate phenyl) phosphines, two-(a sulfonate phenyl) Phenylphosphine or three-(a sulfonate phenyl) phosphine and two-(a sulfonate phenyl) Phenylphosphine is dissolved in the deoxidation distilled water, this drips of solution is added in the reactor, at 60～90 ℃, stirring reaction 1～3 hour, be cooled to room temperature, add dehydrated alcohol and promptly generate throw out.The throw out that generates with alcohol washing is to pH=5～7, at 60～90 ℃, and 10
3～10
4The pressure of handkerchief is dry down, and getting general formula is RhX (CO) L
1 uL
2 vUsing rhodium complex catalysts.Wherein, three-(a sulfonate phenyl) phosphines, two-(a sulfonate phenyl) Phenylphosphine or three-(a sulfonate phenyl) phosphine and two-(a sulfonate phenyl) Phenylphosphine that adds and the mol ratio of rhodium are 1～5, be preferably 1～3, the pressure of carbon monoxide is normal pressure～0.2 MPa, is preferably normal pressure～0.1 MPa.Wherein, the halogenide of rhodium can be rhodium chloride, bromination rhodium or iodate rhodium or their hydrate, preferred rhodium chloride or its hydrate.Described three (a sulfonate phenyl) preferred TPPTS of phosphine.Described two (a sulfonate phenyl) preferred TPPDS of Phenylphosphine.Described alcohol can be one or more in the various liquid alcohols, preferred alcohol.Described rare gas element can be one or more in nitrogen, helium, neon, the argon gas, is preferably nitrogen.
Described general formula is HRh (CO) L
1 iL
2 jUsing rhodium complex catalysts can adopt the preparation of following method: with the halogenide of rhodium or the halid hydrate of rhodium, three-(a sulfonate phenyl) phosphines, two-(a sulfonate phenyl) Phenylphosphines or three-(a sulfonate phenyl) phosphine and two-(a sulfonate phenyl) Phenylphosphine is a raw material, halogenide with rhodium is dissolved in the ethanol earlier, the halid alcoholic solution of rhodium is added in the reactor, with the air in the inert gas replacement reactor, then, be heated to 60～100 ℃, preferred 70～80 ℃, charge into carbon monoxide atmosphere, stirring reaction 10～60 minutes, preferred 30～50 minutes.Three-(a sulfonate phenyl) phosphines, two-(a sulfonate phenyl) Phenylphosphine or three-(a sulfonate phenyl) phosphine and two-(a sulfonate phenyl) Phenylphosphine is dissolved in the deoxidation distilled water, this drips of solution is added in the reactor, the pH of regulator solution is 8～14, the mol ratio that feeds hydrogen and carbon monoxide is 0.1～5 the hydrogen and the gas mixture of carbon monoxide, under said temperature, continue reaction 2～6 hours, preferred 3～4 hours, getting general formula was HRh (CO) L
1 iL
2 jUsing rhodium complex catalysts.Wherein, the mol ratio of three of adding-(a sulfonate phenyl) phosphine, two-(a sulfonate phenyl) Phenylphosphine or three-(a sulfonate phenyl) phosphine and two-(a sulfonate phenyl) Phenylphosphine and rhodium is 1～5, is preferably 1～3.Wherein, the compound of rhodium refers to dissolve in one or more in the rhodium compound in the alcohol, the halogenide of preferred rhodium, and as rhodium chloride, bromination rhodium or iodate rhodium or their hydrate, more preferred rhodium chloride or its hydrate.Described three (a sulfonate phenyl) preferred TPPTS of phosphine.Described two (a sulfonate phenyl) preferred TPPDS of Phenylphosphine.Described alcohol can be one or more in the various liquid alcohols, preferred alcohol.
Used three-(a sulfonate phenyl) phosphines and two-(a sulfonate phenyl) Phenylphosphine can adopt ZL 96 120055.3 described method preparations.Wherein, the preparation of two-(a sulfonate phenyl) Phenylphosphines, different just with SO
3Be reduced to 4～7 with the mol ratio of triphenylphosphine.
In the described water-soluble phosphine ligand general formula, Ar
1, Ar
2, Ar
3Represent aryl or pyridyl, preferred phenyl, naphthyl or pyridyl, more preferred phenyl.x
1, x
2, x
3Represent carboxylate group or sulfonate group, preferred sulfonate group.y
1, y
2, y
3Can be the same or different, each representative contains straight or branched alkyl, the alkoxyl group of 1～20 carbon atom.M is basic metal or alkaline-earth metal ions, is preferably alkalimetal ion, more preferred sodium ion.n
1, n
2, n
3Can be the same or different, represent 0～4 integer, be preferably 0.The described total phosphine part and the mol ratio of rhodium are 2～200, are preferably 5～100.
Under the preferable case, contain m=(m1+m2+m3)=1 in the described water-soluble phosphine ligand general formula, 2 or 3 water-soluble phosphine ligand in the described reaction system simultaneously, the mol ratio of the water-soluble phosphine ligand of m=1 and m=2 is 0.02～0.5, preferred 0.04～0.1, the mol ratio of the water-soluble phosphine ligand of m=2 and m=3 is 0.1～10, is preferably 0.2～5.
The concentration of phosphoric acid salt and/or phosphite is 0～6 * 10 described in the water-soluble rhodium phosphine complex catalyst system of the present invention
-3Mol is preferably 5 * 10
-5～8 * 10
-4Mol.
Water-soluble aryl of the present invention or pyridyl phosphine oxide have following general formula:
In the formula, Ar
1, Ar
2, Ar
3Represent aryl or pyridyl, x
1, x
2, x
3Can be the same or different, each represents carboxylate group or sulfonate group, y
1, y
2, y
3Can be the same or different, each representative contains straight or branched alkyl, the alkoxyl group of 1～20 carbon atom, and M is basic metal or alkaline-earth metal ions; n
1, n
2, n
3Can be the same or different, represent 0～4 integer; M1, m2, m3 are 0 or 1, but m=(m1+m2+m3) is not less than 1.
Water-soluble aryl of the present invention and/or pyridyl phosphine oxide are three (-sodium sulfonate phenyl) phosphine oxide (being abbreviated as OTPPTS) and/or two (-the sodium sulfonate phenyl) phenylphosphine oxide (being abbreviated as OTPPDS), its concentration is 0～5 * 10
-3Mol is preferably 5 * 10
-5～6 * 10
-4Mol.
The present invention, described pH value of aqueous solution is for being 2～11, preferred 4～8.The pH value of solution can be regulated with various buffered soln.Also can regulate by any buffered soln.
The temperature of reaction of ethene hydroformylation system propionic aldehyde of the present invention is 20～150 ℃, preferred 50～130 ℃, and more preferred 60～110 ℃.Reaction pressure 0.1～6.0 MPa, preferred 1.0～5.0 MPas.
The volume ratio of water of the present invention and oil phase is 1～30, is preferably 2～10.
The source of ethylene raw of the present invention can be the ethene that produces from petroleum cracking, or from the ethene that Sweet natural gas prepares, also can be the ethene from synthesis gas preparation.The ethylene raw in above-mentioned source; through carrying the dense rare ethene that the back forms of handling; be used as the olefin feedstock of hydroformylation reaction of the present invention; the content of ethene is 40～95% (volumes) in described rare ethene, and other composition is gaseous hydrocarbons (comprising alkane, alkene and alkynes) and/or rare gas element (comprising nitrogen, argon gas, helium) and hydrogen, carbon monoxide and carbonic acid gas etc.In described rare ethene, the content of propylene is no more than 15% (volume) at most, and butene content is no more than 3% (volume) at most, and acetylene content is no more than 1% (volume) at most, and carbon dioxide content is no more than 2% (volume) at most.
Can contain organic solvent in the reaction system of the present invention.These solvents can be the condensation products of propionic aldehyde or propionic aldehyde, as 2-methyl-2-pentenals, also can be in liquid alkane, naphthenic hydrocarbon or the aralkyl hydrocarbon one or more.As, heptane, octane, nonane, decane, undecane, dodecane, hexanaphthene, methylcyclohexane, benzene, toluene etc.Preferred propionic aldehyde, naphthenic hydrocarbon and/or aromatic hydrocarbons, particularly propionic aldehyde, benzene, toluene and hexanaphthene.
Reaction system of the present invention also can not contain the organic solvent that adds.
Compare with prior art, the present invention has following advantage:
(1) the anti-poisoning capability of water-soluble rhodium phosphine complex complex catalyst system is strong, except that not water funk and, can tolerate sulfide, nitride, the CO of high level
2Deng, iron carbonyl, nickle carbonoxide etc. there is stronger anti-poisoning capability.For example in ethene hydroformylation system propionic aldehyde, the iron level of accumulative total reaches 20 mg/litre in the aqueous catalyst solution, and when nickel content reached 0.7 mg/litre, water-soluble rhodium phosphine complex compound catalyst still had good catalytic activity and selectivity.
(2) water-soluble rhodium phosphine complex composite catalyst catalyzed ethylene hydroformylation reaction system propionic aldehyde, speed of response is fast.
(3) adopt in the two-phase system of water-soluble rhodium phosphine complex composite catalyst, the selectivity that ethene hydroformylation generates propionic aldehyde is not less than 98%.
When (4) water-soluble rhodium phosphine complex composite catalyst is made raw material with rare ethene, contained C in described rare ethene
1～C
4Alkane is difficult to dissolving, C in water
3～C
4Alkene solubleness in water is very low, therefore can not produce detrimentally affect to water-soluble rhodium phosphine complex complex catalyst system catalyzed ethylene hydroformylation reaction.And the C in rare ethene
1～C
4Alkane and C
3～C
4Alkene dissolves in the organic solvent, influences the catalytic ethene hydroformylation reaction of oil soluble rhodium phosphine complex, causes the complicated of product, increases the separation purification difficulty of product propionic aldehyde.
(5) with the used amount of ligand of the two-phase system of water-soluble rhodium phosphine complex composite catalyst far below being the homogeneous catalysis system of catalyzer with the oil soluble rhodium phosphine complex.
(6) water-soluble rhodium phosphine complex composite catalyst easily with product propionic aldehyde Separation and Recovery with recycle, and with water as the solvent environmentally safe.Because the selectivity of water-soluble rhodium phosphine complex composite catalyst is good, the by product growing amount is few, the Separation and Recovery and the discharging of by product have therefore been reduced.
Embodiment 1
With 40 milliliters of distilled water, 10 milliliters of propionic aldehyde, RhCl (CO) (TPPTS)
2(pressing the method preparation described in the ZL 96 120056.1), TPPTS (pressing the preparation of method described in the ZL 96 120055.3), SODIUM PHOSPHATE, MONOBASIC (chemical pure, Chengdu chemical reagent factory produces) add 250 milliliters and be with in the churned mechanically stainless steel autoclave, the add-on of each material makes that rhodium concentration is 9.2 * 10 in the aqueous solution
-4Mol, the mol ratio of TPPTS and rhodium are 30: 1, and the concentration of Sodium phosphate dibasic is 4 * 10
-4The concentration of mol, pH value of aqueous solution are 6.4, three (-sodium sulfonate phenyl) phosphine oxide (OTPPTS) is 8 * 10
-5Mol.Behind the reactor decompression vacuum pumping, be 1: 1 synthetic gas displacement 3 times with the mol ratio of hydrogen and carbon monoxide, feed rare ethene and synthetic gas and make and react stagnation pressure and reach 3.0 MPas, contain the methane of 5% (volume) in the used ethene.In temperature is 80 ℃, keep reaction stagnation pressure 3.0 MPas, ethene, hydrogen and carbon monoxide pressure of tension are 1.0 MPas, stirring velocity is continuously feeding under 400 rev/mins the condition, the input speed of rare ethene (ethene and methane blended gas) is 17.1 liters/hour, and synthetic gas (mol ratio of carbon monoxide and hydrogen is 1: 1) input speed is 36.0 liters/hour.Conversion of ethylene is 93.3%, and propionic aldehyde content is 98.4% (weight) in the product liquid.
Embodiment 2
Prepare propionic aldehyde by the method described in the example 1, different is to add 7 milliliters of propionic aldehyde in the system, and the concentration of Sodium phosphate dibasic is 6 * 10
-4The concentration of mol, pH value of aqueous solution are 7.6, three (-sodium sulfonate phenyl) phosphine oxide (OTPPTS) is 2 * 10
-4Mol, ethylene content is 91.3% (volume) in used rare ethene, methane content is 5.5% (volume), propylene content is 2.2% (volume), nitrogen 1% (volume), 90 ℃ of temperature of reaction, the flow of rare ethene is 22.5 liters/hour, and the flow velocity of synthetic gas is 49.3 liters/hour.Conversion of ethylene is 91.0%, does not detect hydroformylation of propene product-butyraldehyde in the product, and rhodium content is 0.026ppm in the thick propionic aldehyde.
Embodiment 3
Prepare propionic aldehyde by method described in the example 2, different is with HRh (CO) (TPPTS)
3Be catalyzer, add 20 milliliters of propionic aldehyde in the system, the concentration of SODIUM PHOSPHATE, MONOBASIC is 6 * 10
-4Mol, pH value of aqueous solution are 4.5, and the mol ratio of TPPTS and rhodium is 50: 1, and the mol ratio of TPPDS and rhodium is 30: 1, and the concentration of two (-sodium sulfonate phenyl) phenylphosphine oxide (OTPPDS) is 1 * 10
-4Mol, the content of ethene is 67.3% (volume) in rare ethene, and the content of methane is 22.1% (volume), and the content of propylene is 8.6% (volume), a nitrogen content 2% (volume).Rare ethylene feed speed is 19.9 liters/hour, and the synthetic gas input speed is 29.5 liters/hour.Conversion of ethylene is 66.5%, and thick propionic aldehyde is through gc analysis, and wherein propionic aldehyde content is 98.5% (weight), butyraldehyde 0.88% (weight), and other is 0.62% (weight).
Embodiment 4～11
Prepare propionic aldehyde by the method described in the example 2, the composition of catalyzer, rare ethene composition, reaction conditions and conversion of ethylene are listed in the table one.Table 1 embodiment 4～11
A.TPPTS/TPPDS (mol ratio): 5: 1; B.TPPTS/TPPDS (mol ratio): 3: 1; C.TPPTS/TPPDS (mol ratio): 1: 1
| Embodiment | Temperature ℃ | Pressure MPa | Rare ethene is formed % (volume) | Input speed L/h | ??????[Rh] ?×10 -4Mol | ????OTPPTS ??×10 -4Mol | The P/Rh mol ratio | Phosphoric acid salt * 10 -4Mol | ????pH | The Water/Org volume ratio | Transformation efficiency % | ||
| Ethene | Methane | Ethylene raw | ????CO+H 2 | ||||||||||
| ??4 | ????90 | ????3.0 | ????73.3 | ????24.7 | ????18.32 | ????30.9 | ?????9.2 | ????40 | ????50 a | ??NaH 2PO 4，4 | ????5.5 | ????4 | ????76.9 |
| ??5 | ????90 | ????4.0 | ????45.0 | ????45.0 | ????20.5 | ????15.0 | ?????9.2 | ????5 | ????50 | ??KH 2PO 4，4 | ????5.5 | ????4 | ????43.5 |
| ??6 | ????80 | ????4.5 | ????95 | ????5 | ????14.0 | ????28.9 | ?????5 | ????10 | ????10 | ??NaH 2PO 3，2 | ????6.5 | ????4 | ????80 |
| ??7 | ????90 | ????2.0 | ????91 | ????9 | ????12.3 | ????25.0 | ?????9.2 | ????7 | ????30 | ??Na 2HPO 3，7 | ????7.2 | ????4 | ????89.2 |
| ??8 | ????70 | ????3.0 | ????86.7 | ????13.3 | ????11.7 | ????23.3 | ?????9.2 | ????15 | ????60 b | ??NaH 2PO 4，4 | ????6.5 | ????6 | ????72.5 |
| ??9 | ????100 | ????3.0 | ????86.7 | ????13.3 | ????17.6 | ????33.6 | ?????9.2 | ????8 | ????30 a | ??NaH 2PO 4，4 | ????6.5 | ????4 | ????89.3 |
| ??10 | ????65 | ????4.8 | ????70 | ????30 | ????11.3 | ????9.8 | ?????9.2 | ????8 | ????90 c | ??NH 4H 2PO 4，4 | ????6.5 | ????3 | ????68.4 |
| ??11 | ????90 | ????1.0 | ????95 | ????5 | ????6.5 | ????13.5 | ?????9.2 | ????8 | ????30 | ??LiH 2PO 4，4 | ????6.5 | ????3 | ????56.1 |
Claims (9)
1. one kind prepares the method for propionic aldehyde by ethene, is included in the liquid phase of the complex catalyst system that water and water-soluble rhodium phosphine complex form, will ethene with carbon monoxide and hydrogen feeding autoclave in react, it is characterized in that:
(1) used rhodium phosphine complex complex catalyst system is by RhCl (CO) (TPPTS)
2And/or
HRh (CO) (TPPTS)
3And add phosphine part three (-sodium sulfonate phenyl) phosphine (TPPTS) and/or two (
-sodium sulfonate phenyl) Phenylphosphine (TPPDS) is formed, and the mol ratio of phosphine part and rhodium is 2～200;
(2) concentration of composite catalyst counts 1 * 10 with rhodium
-4～1 * 10
-2Mol;
(3) contain one or more water-soluble phosphates M in the reaction system
2HPO
4And/or MH
2PO
4, one or more
Water-soluble phosphite is M
2HPO
3And/or MH
2PO
3, M is lithium, sodium, potassium or ammonium ion, its concentration
Be 0～1 * 10
-3Mol;
(4) contain the oxide compound three that adds water-soluble phosphine ligand (-sodium sulfonate phenyl) phosphine oxide in the reaction system
(OTPPTS) and/or two (-sodium sulfonate phenyl) phenylphosphine oxide (OTPPDS), its concentration be 0～
1 * 10
-3Mol;
(5) temperature of reaction is at 20～150 ℃;
(6) Fan Ying pH is 2～11;
(7) Fan Ying pressure is at 0.1～6.0MPa;
(8) concentration of used ethene is 40%～94% (volume);
2. method according to claim 1, the mol ratio that it is characterized in that phosphine part and rhodium is 2～100.
3. method according to claim 1 is characterized in that described rhodium concentration is 2 * 10
-4～4 * 10
-3Mol.
4. method according to claim 1 is characterized in that one or more water-soluble phosphates are Na
2HPO
4And/or NaH
2PO
4, one or more water-soluble phosphites are Na
2HPO
3And/or NaH
2PO
3, its concentration is 2 * 10
-4～7 * 10
-4Mol.
5. method according to claim 1, the concentration that it is characterized in that the water-soluble phosphine ligand oxide compound is 5 * 10
-5～6 * 10
-4Mol.
6. method according to claim 1 is characterized in that the temperature of reacting is 60～110 ℃.
7. method according to claim 1 is characterized in that the pH that reacts is 4～8.
8. method according to claim 1 is characterized in that the pressure that reacts is 1.0～5.0MPa.
9. method according to claim 1, the concentration that it is characterized in that ethene are 60～95% (volumes).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02113273 CN1202064C (en) | 2002-01-25 | 2002-01-25 | Process for preparing propionaldehyde from ethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02113273 CN1202064C (en) | 2002-01-25 | 2002-01-25 | Process for preparing propionaldehyde from ethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1434015A true CN1434015A (en) | 2003-08-06 |
| CN1202064C CN1202064C (en) | 2005-05-18 |
Family
ID=27628381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02113273 Expired - Lifetime CN1202064C (en) | 2002-01-25 | 2002-01-25 | Process for preparing propionaldehyde from ethylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1202064C (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115433A (en) * | 2010-12-06 | 2011-07-06 | 淄博诺奥化工有限公司 | Synthesis method of propionaldehyde by low-pressure carbonyl of ethylene |
| CN104936940A (en) * | 2013-01-22 | 2015-09-23 | 沙特基础工业公司 | Method for making methyl methacrylate from propionaldehyde and formaldehyde via oxidative esterification |
| CN106278786A (en) * | 2015-05-21 | 2017-01-04 | 中国科学院大连化学物理研究所 | A kind of alkane and CO2the method producing hydroformylation raw material |
| CN109364997A (en) * | 2012-12-04 | 2019-02-22 | 陶氏技术投资有限责任公司 | Bidentate ligands for hydroformylation ethylene |
| CN109456154A (en) * | 2018-11-14 | 2019-03-12 | 成都欣华源科技有限责任公司 | A method of fatty aldehyde is prepared by hydroformylation reaction |
| CN111039765A (en) * | 2019-12-19 | 2020-04-21 | 四川大学 | Method for preparing 3-alkoxy propionaldehyde |
| WO2020242924A1 (en) * | 2019-05-24 | 2020-12-03 | Eastman Chemical Company | Recycle content propionaldehyde |
| CN112844488A (en) * | 2021-01-13 | 2021-05-28 | 成都欣华源科技有限责任公司 | Catalyst composition and application thereof in styrene hydroformylation reaction |
| CN113351249A (en) * | 2021-04-29 | 2021-09-07 | 四川大学 | Catalytic system for preparing aldehyde by catalyzing hydroformylation of internal olefin |
| US11319262B2 (en) | 2019-10-31 | 2022-05-03 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
| US11939534B2 (en) | 2019-11-07 | 2024-03-26 | Eastman Chemical Company | Recycle content alpha olefins and fatty alcohols |
| US11945998B2 (en) | 2019-10-31 | 2024-04-02 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
| US11946000B2 (en) | 2019-05-24 | 2024-04-02 | Eastman Chemical Company | Blend small amounts of pyoil into a liquid stream processed into a gas cracker |
-
2002
- 2002-01-25 CN CN 02113273 patent/CN1202064C/en not_active Expired - Lifetime
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115433B (en) * | 2010-12-06 | 2013-09-11 | 淄博诺奥化工有限公司 | Synthesis method of propionaldehyde by low-pressure carbonyl of ethylene |
| CN102115433A (en) * | 2010-12-06 | 2011-07-06 | 淄博诺奥化工有限公司 | Synthesis method of propionaldehyde by low-pressure carbonyl of ethylene |
| CN109364997A (en) * | 2012-12-04 | 2019-02-22 | 陶氏技术投资有限责任公司 | Bidentate ligands for hydroformylation ethylene |
| CN104936940A (en) * | 2013-01-22 | 2015-09-23 | 沙特基础工业公司 | Method for making methyl methacrylate from propionaldehyde and formaldehyde via oxidative esterification |
| CN104936940B (en) * | 2013-01-22 | 2018-12-21 | 沙特基础工业公司 | The method that methyl methacrylate is prepared by oxidative esterification by propionic aldehyde and formaldehyde |
| CN106278786B (en) * | 2015-05-21 | 2019-08-06 | 中国科学院大连化学物理研究所 | A kind of alkane and CO2The method for producing hydroformylation raw material |
| CN106278786A (en) * | 2015-05-21 | 2017-01-04 | 中国科学院大连化学物理研究所 | A kind of alkane and CO2the method producing hydroformylation raw material |
| CN109456154A (en) * | 2018-11-14 | 2019-03-12 | 成都欣华源科技有限责任公司 | A method of fatty aldehyde is prepared by hydroformylation reaction |
| US11946000B2 (en) | 2019-05-24 | 2024-04-02 | Eastman Chemical Company | Blend small amounts of pyoil into a liquid stream processed into a gas cracker |
| WO2020242924A1 (en) * | 2019-05-24 | 2020-12-03 | Eastman Chemical Company | Recycle content propionaldehyde |
| US11787754B2 (en) | 2019-10-31 | 2023-10-17 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
| US11945998B2 (en) | 2019-10-31 | 2024-04-02 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
| US11319262B2 (en) | 2019-10-31 | 2022-05-03 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
| US11939534B2 (en) | 2019-11-07 | 2024-03-26 | Eastman Chemical Company | Recycle content alpha olefins and fatty alcohols |
| CN111039765B (en) * | 2019-12-19 | 2021-05-14 | 四川大学 | Method for preparing 3-alkoxy propionaldehyde |
| CN111039765A (en) * | 2019-12-19 | 2020-04-21 | 四川大学 | Method for preparing 3-alkoxy propionaldehyde |
| CN112844488B (en) * | 2021-01-13 | 2023-03-10 | 成都欣华源科技有限责任公司 | Catalyst composition and application thereof in styrene hydroformylation reaction |
| CN112844488A (en) * | 2021-01-13 | 2021-05-28 | 成都欣华源科技有限责任公司 | Catalyst composition and application thereof in styrene hydroformylation reaction |
| CN113351249B (en) * | 2021-04-29 | 2023-02-03 | 四川大学 | Catalytic system for preparing aldehyde by catalyzing hydroformylation of internal olefin |
| CN113351249A (en) * | 2021-04-29 | 2021-09-07 | 四川大学 | Catalytic system for preparing aldehyde by catalyzing hydroformylation of internal olefin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1202064C (en) | 2005-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1202064C (en) | Process for preparing propionaldehyde from ethylene | |
| CN1032538C (en) | Sulfonated 2,2'-bis (diphenxlphosphinomethyl)-1,1'-binaphthaline and preparation of same | |
| CN1210513A (en) | Method of preparing aldehydes by hydroformylation with rhodium catalyst and recovery of the rhodium catalyst by extraction | |
| CN101160272A (en) | Hydroformylation process with improved iso-selectivity | |
| CN1293941C (en) | Hydroformylation process using novel phosphite-metal catalyst system | |
| JPS5833209B2 (en) | Improved hydroformation method | |
| CN101462932A (en) | Method for preparing aldehyde by hydroformylation of light olefins | |
| CN109456154A (en) | A method of fatty aldehyde is prepared by hydroformylation reaction | |
| JPH0549344B2 (en) | ||
| CN100391912C (en) | Epoxide stabilization of fluorophosphite-metal catalyst system in hydroformylation process | |
| EP0195656B1 (en) | Improved rhodium catalyzed hydroformylation of internal olefins | |
| CN1095821C (en) | Method for hydro-formylation of olefinic unsaturated compound | |
| JPH0140019B2 (en) | ||
| EP2342210B1 (en) | Acetylene tolerant hydroformylation catalysts | |
| CN1547506A (en) | Stabilization of fluorophosphite-containing catalysts | |
| CN101054342A (en) | Process of continuously preparing n-pentanal | |
| CN1227835A (en) | Process for preparing aldehydes | |
| US4273936A (en) | Rhodium-catalyzed oxidation process for producing carboxylic acids | |
| CN109896939B (en) | Composition and method for preparing aldehyde by two-phase catalytic hydroformylation | |
| CN1134392C (en) | Hydroformylation process | |
| CN1096286A (en) | The method for preparing the alkadiene alcohol compound | |
| CN101053843A (en) | Water soluble ligand rhodium complex catalyst used for preparing aldehyde with dicyclopentadiene hydroformylation | |
| CN111470957B (en) | Composition and method for preparing aldehyde by two-phase catalytic hydroformylation | |
| US20040024247A1 (en) | Process for the carbonylation of ethylenically unsaturated compounds and bidentate diphosphine composition used in this process | |
| Herwig et al. | Aqueous biphasic hydroformylation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Nanjing Rongxin Chemical Co., Ltd. Assignor: Sichuan University Contract record no.: 2010320001220 Denomination of invention: Process for preparing propionaldehyde from ethylene Granted publication date: 20050518 License type: Exclusive License Open date: 20030806 Record date: 20101217 |
|
| CX01 | Expiry of patent term |
Granted publication date: 20050518 |
|
| CX01 | Expiry of patent term |