CN102442894B - Method for preparing propionic aldehyde from ethylene in refinery dry gas - Google Patents
Method for preparing propionic aldehyde from ethylene in refinery dry gas Download PDFInfo
- Publication number
- CN102442894B CN102442894B CN201010297500.8A CN201010297500A CN102442894B CN 102442894 B CN102442894 B CN 102442894B CN 201010297500 A CN201010297500 A CN 201010297500A CN 102442894 B CN102442894 B CN 102442894B
- Authority
- CN
- China
- Prior art keywords
- dry gas
- propionic aldehyde
- ethene
- gas
- oil refinery
- 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.)
- Active
Links
Abstract
The invention discloses a method for preparing propionic aldehyde from ethylene in refinery dry gas so as to provide a technology for directly preparing propionic aldehyde from low-concentration ethylene in refinery dry gas. The method comprises the following steps: pressurizing raw dry gas in a pressurization system; feeding the obtained high-pressure dry gas into a purification system, and removing impurities; mixing the purified refinery dry gas and carbon monoxide containing no catalyst poison to form raw gas for hydroformylation reaction; carrying out hydroformylation reaction together with additional carbon monoxide under the action of a catalyst and a catalyst ligand; and discharging in a gas phase manner, and passing through a separation system, thus obtaining the propionic aldehyde product.
Description
Technical field
The present invention relates to the method for utilizing of ethene in a kind of oil refinery dry gas, specifically a kind ofly directly utilize ethene and hydrogen in oil refinery dry gas, prepare the method for propionic aldehyde with reaction of carbon monoxide.
Background technology
Oil refinery dry gas mainly comes from the secondary processing of crude oil, and as catalytic cracking, thermally splitting, delayed coking etc., wherein the dry gas amount of catalytic cracking is maximum, and productive rate is the highest.In oil refinery dry gas, contain 10～20% ethene, 20～40% hydrogen, and nitrogen, methane, ethane and a small amount of carbon monoxide, carbonic acid gas, propane, propylene etc.
External refinery utilizes oil refinery dry gas to be used as Ethylene Unit Feedstocks as far back as the just industrialization eighties in 20th century.Domestic oil refining and chemical enterprise make a big difference in structure and layout Yu abroad.First domestic oil refining enterprises scale is generally less than normal, scattered distribution, and dry-gas recovery is difficult to occur scale device.Secondly, most oil refining enterprise do not have ethene process matched therewith, even some oiling mating type, but the geographical position of its ethene and oil refining is at a distance of also far away, brings difficulty to the further refining of ethene with utilization.Domestic plant catalytic cracking dry gas is used as industrial fuel gas, domestic fuel gas substantially, and remaining torch of setting fire is burnt, and causes the serious wasting of resources.Along with developing rapidly of China petroleum refining industry crude oil depth processing, the catalytic cracked dry gas of by-product is also rolling up, and how to make full use of this part valuable industrial chemicals, develops new comprehensive utilization process, the comprehensive benefit that improves refinery, has caused people's common concern.
At present, the utilization for ethene in oil refinery dry gas mainly adopts separation and recovery technology and the large class of chemical utilization technology two.The technique for dry gas Separation and Recovery that success has been developed at present has the process integration of low temperature separation process, Separation by Complexation, solvent extraction, cold oil absorption, membrane sepn, pressure-variable adsorption and these technology.At present, the technology of the direct processing and utilization technique comparative maturity of ethene in oil refinery dry gas is had to preparing ethylbenzene from dry gas, dry gas system is to methyl-ethyl benzene, dry gas epoxy ethane, dry gas ethylene dichloride processed etc.
In catalytic cracked dry gas, ethylene concentration is generally lower, and it is carried out to Separation and Recovery utilization, has the shortcoming that facility investment and processing charges are higher.Therefore, develop it and directly utilize technology to there is good economy, because directly processing and utilization investment and process cost are low, be particularly useful for the limited medium-sized and small enterprises of tolerance.
Propionic aldehyde is realized suitability for industrialized production from the 1950's, industrial process mainly contains ethene oxo synthesis, propyl alcohol oxidation style, propylene oxide isomerization method, the third rare aldehyde hydrogenation method and by-product method at present.Therein ethylene oxo synthesis is the main method of current industrial production propionic aldehyde.Ethene oxo synthesis is divided into again high pressure cobalt method and low pressure rhodium method, and reaction process is ethene and carbon monoxide and hydrogen reaction generation propionic aldehyde.U.S. combinating carbide company in 1975 builds up first set ethene low pressure oxo synthesis in the world and produces propionic aldehyde full scale plant.Low pressure oxo synthesis has that catalyst activity is high, selectivity good, reaction conditions is gentle, in production process, do not produce corrosive medium, the advantages such as raw material and general facilities consume low, and facility investment is few are main production method and the developing direction of external production propionic aldehyde at present.Low pressure oxo synthesis is divided into again oil soluble rhodium phosphine complex catalyst system and water-soluble rhodium phosphine complex compound catalyst system.
Relating to rare ethene hydroformylation propionic aldehyde reverse side processed; in Chinese patent CN1125712; described with liquid phase rhodium phosphine complex catalyst cupport on porous support, 2～6 carbon atom low-concentration olefinics containing 5～40% that catalysis is obtained by fluid catalytic cracking are the method for raw material preparing aldehyde by hydro formylating.Catalytic active component in the method load liquid-phase catalyst used is oil soluble rhodium phosphine complex catalyzer, and in use, the product aldehyde that can be generated dissolves lentamente and runs off, and technology is immature.
Chinese patent CN1594256 is that to take oil refinery dry gas and synthetic gas be raw material production propionic aldehyde; its process is through pressure-changed adsorption concentrating ethene by refinery gas; after purification, together with synthetic gas, under the effect of water-soluble rhodium phosphine complex compound catalyst system, through hydroformylation reaction, prepare propionic aldehyde.Complex technical process, facility investment is high.
Chinese patent CN1434015 uses the rare ethene that contains 40～95% ethene and other hydro carbons and rare gas element together with synthetic gas, and under the effect of water-soluble rhodium complex compound composite catalyst, hydroformylation reaction is prepared propionic aldehyde.This method is had relatively high expectations to material concentration.
US Patent No. 5675041 adopts oil soluble rhodium catalyst, by the C2～C5 hydrocarbon mixture containing alkene and alkynes, is that raw material is prepared C3～C6 aldehyde.It is to take Sweet natural gas as raw material, and first making containing hydrocarbon mixtures such as ethene, acetylene is raw material and synthetic gas (carbon monoxide and hydrogen), through hydroformylation reaction, prepares mixed aldehyde.
In US Patent No. 6049011, adopt the rare ethene hydroformylation reaction of oil soluble rhodium phosphine complex catalyst to prepare propionic aldehyde, in rare ethene used, the content of ethene is 30～75%, other component is rudimentary gaseous olefin, gaseous alkanes and hydrogen nitrogen etc.
Above-mentioned homogeneous reaction patent all fails to provide a kind of ethene and hydrogen that simultaneously utilizes oil refinery dry gas the inside to contain, and in the situation that not changing gas raw material concentration, directly carries out the method that hydroformylation reaction is prepared propionic aldehyde.
Summary of the invention
The technical problem to be solved in the present invention:
In view of not providing at present oil refinery dry gas low-concentration ethane directly to utilize the technology of preparing propionic aldehyde; the invention is intended to provide a kind of oil refinery dry gas without concentrate; only need to purify the catalyzer poison that the inside is contained; before dry gas carries out hydroformylation, the poisonous substance of catalyzer requires to be purified to a suitable concentration.Then directly utilize ethene and hydrogen in oil refinery dry gas, carry out low pressure homogeneous phase hydroformylation reaction with together with additional carbon monoxide, with the method for gas phase discharging, prepare propionic aldehyde.
Technical scheme of the present invention comprises following steps:
In the preferred oil refinery dry gas of the present invention, the molar content of ethene is 10～15%, and the molar content of hydrogen is 20～35%, and the mol ratio of ethene and hydrogen is the oil refinery dry gas of 1: 1.5～1: 2.5.
The first step, raw material dry gas 1 enters compression system A pressurization, and pressure adds to 1.5～2.5Mpa, discharges the dry gas 2 that forms high pressure after a small amount of lime set.
Second step, high pressure dry gas 2 enters purification system B, in oil refinery dry gas, containing following impurity need to remove, iron carbonyl (5～50ppm) hydrogen sulfide (20～200ppm) oxygen (10～100ppm) acetylene (300～3000ppm) water (500～5000ppm), purification system is the fixed bed scavenging tower that a set of series winding shown in Fig. 2 connects, and is respectively iron carbonyl scavenging tower, hydrogen sulfide scavenging tower, oxygen scavenging tower, acetylene purification tower, water scavenging tower.Gac is housed respectively, makes iron carbonyl content be less than 1ppm, be preferably less than 0.1ppm; Zinc oxide desulfurization catalyzer, makes hydrogen sulfide content be less than 1ppm, is preferably less than 0.1ppm; Platinum sulfide catalyzer, makes oxygen level be less than 1ppm; Selective hydrogenation catalyst, makes acetylene content be less than 50ppm, is preferably less than 10ppm.Molecular sieve, makes water-content be less than 100ppm, is preferably less than 10ppm.
The 3rd step, the oil refinery dry gas after purification with containing not forming hydroformylation reaction unstripped gas 3 together with the carbon monoxide of catalyzer poison.Unstripped gas 3 is passed into hydroformylation reaction device C, and reactor C is that stainless steel stirs autoclave, and reactor is with gas distributor.Unstripped gas passes at the bottom of reactor still, the ethene containing in oil refinery dry gas under the effect of oil soluble rhodium catalyst and catalyst ligand and hydrogen with together with additional carbon monoxide, carry out hydroformylation reaction and generate propionic aldehyde.
Hydroformylation reaction catalyzer used is oil soluble using rhodium complex catalysts, i.e. three (triphenyl phosphorus) carbonyl hydrogen rhodium, and the add-on of catalyzer is counted 200～500ppm with metal rhodium.
In catalyst ligand triphenylphosphine used and rhodium catalyst, the mol ratio of metal rhodium is 50～100: 1.
The solvent that hydroformylation reaction is used can adopt any can be mutually miscible with propionic aldehyde product, and can dissolve the organic solvent of aforementioned rhodium catalyst and catalyst ligand.Comprise aliphatic series and aromatic hydrocarbon (as heptane, hexanaphthene, benzene, toluene etc.), ether and polyether (as tetrahydrofuran (THF) and tetraethylene glycol dimethyl ether), aldehyde (as propionic aldehyde, butyraldehyde etc.), the polycondensation product of products of oxo synthesis aldehyde (as trimerization propionic aldehyde, trimerization butyraldehyde), etc.
The carbon monoxide of allocating into and the ratio of ethene are 1～1.2: 1
90 ℃～110 ℃ of hydroformylation reaction temperature, hydroformylation reaction pressure 1.0～2.0Mpa, in unstripped gas, the transformation efficiency of ethene is greater than 75%, and the transformation efficiency of optimal ethylene is greater than 80%, and the conversion rate of ethene is greater than 2.0mol/l.hr.
The 4th step, unstripped gas 3 passes into continuously, utilizing the reaction end gas contain in a large number nonreactive alkane and permanent gases to carry product propionic aldehyde secretly discharges from reactor gaseous phase outlet, form gaseous stream 4, gaseous stream 4 enters condenser system D, through condenser, this part material is divided into non-condensable gas phase and organic phase.Non-condensable gas phase 5 contains a large amount of hydro carbons inflammable gass, can be used as fuel and enters exhaust gas recovery system.Organic phase is thick propionic aldehyde streams, and wherein a part is as refluxing 6, and to control reactor liquid level, most of thick propionic aldehyde streams 7 enters separation system E.
Thick propionic aldehyde streams 7, after separation system E separation, forms byproduct stream 9, and product stream 8, is propionic aldehyde product.
The invention has the beneficial effects as follows:
In view of the worsening shortages of petroleum resources, ethene and hydrogen are all important industrial chemicals, and as fuel, burning even is in vain all the significant wastage to resource.The inventive method provides one directly to utilize ethene in oil refinery dry gas and the new operational path of hydrogen; oil refinery dry gas only need to purify the hydroformylation reaction catalyzer poison of the inside; without its component being carried out to separation, the means such as concentrated, can carry out hydroformylation reaction together with carbon monoxide and prepare propionic aldehyde.
Hydroformylation reaction workshop section adopts be product with gas phase discharging, the technique that gas phase tail gas does not circulate, and traditional hydroformylation reaction workshop section gas phase discharging is to adopt tail gas to loop back in a large number reactor, utilizes the circulation of tail gas that product propionic aldehyde is taken out of from reactor.Therefore this technology is simpler than the method technique of traditional hydroformylation reaction workshop section gas phase discharging circulation of tail gas.Utilize technology to compare with other oil refinery dry gas, present method technique is simple, plant investment is little, energy consumption is low, has significant social benefit and economic benefit.
Accompanying drawing explanation
Fig. 1 is that oil refinery dry gas and carbon monoxide homogeneous phase hydroformylation reaction are prepared propionic aldehyde process flow diagram;
Fig. 2 is oil refinery dry gas refining plant schematic flow sheet.
Embodiment
Embodiment 1
The first step, the compressed system of oil refinery dry gas of pressure 0.7Mpa adds to 2.3Mpa by pressure and forms high pressure oil refinery dry gas.
Second step, the flow velocity that the oil refinery dry gas that contains ethene 12.5% (molar content), hydrogen 26% (molar content) and methane, ethane, nitrogen, a small amount of propane, propylene, carbonic acid gas etc. is controlled with 5000ml/min by under meter passes through refining plant, contains iron carbonyl 10ppm, hydrogen sulfide 150ppm, oxygen 70ppm, acetylene 3000ppm, water 3000ppm in oil refinery dry gas.Refining plant is comprised of the fixed-bed reactor of five series windings, and each fixed-bed reactor can be controlled separately temperature.Respectively iron carbonyl scavenging tower, hydrogen sulfide scavenging tower, oxygen scavenging tower, acetylene purification tower, water scavenging tower.Iron carbonyl scavenging tower is equipped with 200ml gac, control 180 ℃ of temperature, hydrogen sulfide scavenging tower is equipped with 200ml zinc oxide desulfurization catalyzer, control 80 ℃ of temperature, oxygen scavenging tower is equipped with the deoxidation of 200ml platinum sulfide catalyzer, controls 180 ℃ of temperature, and acetylene purification tower is equipped with 100ml selective hydrogenation catalyst for removing acetylene, control temperature 50 C, water scavenging tower is equipped with 500ml molecular sieve dehydration.Oil refinery dry gas contains iron carbonyl 0.1ppm, hydrogen sulfide 0.1ppm, oxygen 1ppm, acetylene 5ppm, water 10ppm after refining plant.
The 3rd step, the oil refinery dry gas after purification passes into hydroformylation reaction device together with the carbon monoxide of 630ml/min, and reactor is that stainless steel stirs autoclave, and reactor is with gas distributor.Unstripped gas passes at the bottom of reactor still, catalyzer three (triphenyl phosphorus) the carbonyl hydrogen rhodium that hydroformylation reaction is used, and the add-on of catalyzer is counted 200ppm with metal rhodium.In catalyst ligand triphenylphosphine used and rhodium catalyst, the mol ratio of metal rhodium is 50: 1.The solvent that hydroformylation reaction is used is propionic aldehyde.Reaction solution volume 500ml.90 ℃ of hydroformylation reaction temperature, hydroformylation reaction pressure 2.0Mpa, the ethene containing in oil refinery dry gas and hydrogen with together with additional carbon monoxide, carry out hydroformylation reaction and generate propionic aldehyde.Conversion of ethylene 83.5%, the ethene of conversion generates the selectivity 97.5% of propionic aldehyde, the conversion rate 2.79mol/l.hr of ethene.
The 4th step, unstripped gas passes into continuously, utilizes the reaction end gas that contains in a large number nonreactive alkane and permanent gases to carry product propionic aldehyde secretly from the discharge of reactor gaseous phase outlet, forms gaseous stream, gaseous stream enters condenser system, through condenser, this part material is divided into non-condensable gas phase and organic phase.Organic phase is thick propionic aldehyde streams, and wherein a part is as backflow, and to control reactor liquid level, most of streams enters separation system.Thick propionic aldehyde, after separation system separation, forms byproduct stream, and product stream, is propionic aldehyde product.
Embodiment 2
The first step, the compressed system of oil refinery dry gas of pressure 0.7Mpa adds to 1.5Mpa by pressure and forms high pressure oil refinery dry gas.
Second step, the flow velocity that the oil refinery dry gas that contains ethene 12.5% (molar content), hydrogen 26% (molar content) and methane, ethane, nitrogen, a small amount of propane, propylene, carbonic acid gas etc. is controlled with 4000ml/min by under meter passes through refining plant, contains iron carbonyl 10ppm, hydrogen sulfide 150ppm, oxygen 70ppm, acetylene 3000ppm, water 3000ppm in oil refinery dry gas.Refining plant is comprised of the fixed-bed reactor of five series windings, and each fixed-bed reactor can be controlled separately temperature.Respectively iron carbonyl scavenging tower, hydrogen sulfide scavenging tower, oxygen scavenging tower, acetylene purification tower, water scavenging tower.Iron carbonyl scavenging tower is equipped with 200ml gac, control 180 ℃ of temperature, hydrogen sulfide scavenging tower is equipped with 200ml zinc oxide desulfurization catalyzer, control 80 ℃ of temperature, oxygen scavenging tower is equipped with the deoxidation of 200ml platinum sulfide catalyzer, controls 180 ℃ of temperature, and acetylene purification tower is equipped with 100ml selective hydrogenation catalyst for removing acetylene, control temperature 50 C, water scavenging tower is equipped with 500ml molecular sieve dehydration.Oil refinery dry gas contains iron carbonyl 0.1ppm, hydrogen sulfide 0.1ppm, oxygen 1ppm, acetylene 5ppm, water 10ppm after refining plant.
The 3rd step, the oil refinery dry gas after purification passes into hydroformylation reaction device together with the carbon monoxide of 630ml/min, and reactor is that stainless steel stirs autoclave, and reactor is with gas distributor.Unstripped gas passes at the bottom of reactor still, catalyzer three (triphenyl phosphorus) the carbonyl hydrogen rhodium that hydroformylation reaction is used, and the add-on of catalyzer is counted 300ppm with metal rhodium.In catalyst ligand triphenylphosphine used and rhodium catalyst, the mol ratio of metal rhodium is 50: 1.The solvent that hydroformylation reaction is used is propionic aldehyde.Reaction solution volume 500ml.100 ℃ of hydroformylation reaction temperature, hydroformylation reaction pressure 1.0Mpa, the ethene containing in oil refinery dry gas and hydrogen with together with additional carbon monoxide, carry out hydroformylation reaction and generate propionic aldehyde.Conversion of ethylene 80.5%, the ethene of conversion generates the selectivity 97.8% of propionic aldehyde.The conversion rate 2.14mol/l.hr of ethene.
The 4th step, unstripped gas passes into continuously, utilizes the reaction end gas that contains in a large number nonreactive alkane and permanent gases to carry product propionic aldehyde secretly from the discharge of reactor gaseous phase outlet, forms gaseous stream, gaseous stream enters condenser system, through condenser, this part material is divided into non-condensable gas phase and organic phase.Non-condensable gas contains a large amount of hydro carbons inflammable gass mutually, can be used as fuel.Organic phase is thick propionic aldehyde streams, and wherein a part is as backflow, and to control reactor liquid level, most of streams enters separation system.Thick propionic aldehyde, after separation system separation, forms byproduct stream, and product stream, is propionic aldehyde product.
Embodiment 3
The first step, the compressed system of oil refinery dry gas of pressure 0.7Mpa adds to 1.8Mpa by pressure and forms high pressure oil refinery dry gas.
Second step, the flow velocity that the oil refinery dry gas that contains ethene 10.5% (molar content), hydrogen 23% (molar content) and methane, ethane, nitrogen, a small amount of propane, propylene, carbonic acid gas etc. is controlled with 5000ml/min by under meter passes through refining plant, contains iron carbonyl 20ppm, hydrogen sulfide 120ppm, oxygen 50ppm, acetylene 3100ppm, water 3500ppm in oil refinery dry gas.Refining plant is comprised of the fixed-bed reactor of five series windings, and each fixed-bed reactor can be controlled separately temperature.Respectively iron carbonyl scavenging tower, hydrogen sulfide scavenging tower, oxygen scavenging tower, acetylene purification tower, water scavenging tower.Iron carbonyl scavenging tower is equipped with 200ml gac, control 180 ℃ of temperature, hydrogen sulfide scavenging tower is equipped with 200ml zinc oxide desulfurization catalyzer, control 80 ℃ of temperature, oxygen scavenging tower is equipped with the deoxidation of 200ml platinum sulfide catalyzer, controls 180 ℃ of temperature, and acetylene purification tower is equipped with 100ml selective hydrogenation catalyst for removing acetylene, control temperature 50 C, water scavenging tower is equipped with 500ml molecular sieve dehydration.Oil refinery dry gas contains iron carbonyl 0.1ppm, hydrogen sulfide 0.1ppm, oxygen 1ppm, acetylene 5ppm, water 10ppm after refining plant.
The 3rd step, the oil refinery dry gas after purification passes into hydroformylation reaction device together with the carbon monoxide of 580ml/min, and reactor is that stainless steel stirs autoclave, and reactor is with gas distributor.Unstripped gas passes at the bottom of reactor still, catalyzer three (triphenyl phosphorus) the carbonyl hydrogen rhodium that hydroformylation reaction is used, and the add-on of catalyzer is counted 250ppm with metal rhodium.In catalyst ligand triphenylphosphine used and rhodium catalyst, the mol ratio of metal rhodium is 50: 1.The solvent that hydroformylation reaction is used is toluene.Reaction solution volume 500ml.110 ℃ of hydroformylation reaction temperature, hydroformylation reaction pressure 1.5Mpa, the ethene containing in oil refinery dry gas and hydrogen with together with additional carbon monoxide, carry out hydroformylation reaction and generate propionic aldehyde.Conversion of ethylene 76.5%, the ethene of conversion generates the selectivity 97.7% of propionic aldehyde.The conversion rate 2.15mol/l.hr of ethene.
The 4th step, unstripped gas passes into continuously, utilizes the reaction end gas that contains in a large number nonreactive alkane and permanent gases to carry product propionic aldehyde secretly from the discharge of reactor gaseous phase outlet, forms gaseous stream, gaseous stream enters condenser system, through condenser, this part material is divided into non-condensable gas phase and organic phase.Non-condensable gas contains a large amount of hydro carbons inflammable gass mutually, can be used as fuel.Organic phase is thick propionic aldehyde streams, and wherein a part is as backflow, and to control reactor liquid level, most of streams enters separation system.Thick propionic aldehyde, after separation system separation, forms byproduct stream, and product stream, is propionic aldehyde product.
Claims (10)
1. a method of utilizing ethene in oil refinery dry gas to prepare propionic aldehyde, the molar content of selecting ethene in oil refinery dry gas is 10～15%, the molar content of hydrogen is 20～35%, and the mol ratio of ethene and hydrogen is that the oil refinery dry gas of 1: 1.5～1: 2.5 is raw material, carries out successively in accordance with the following steps:
The first step, raw material dry gas enters compression system pressurization, and pressure adds to 1.5～2.5Mpa, discharges the dry gas that forms high pressure after a small amount of lime set;
Second step, high pressure dry gas enters purification system, by the impurity removal containing in oil refinery dry gas;
The 3rd step, oil refinery dry gas after purification with containing not forming hydroformylation reaction unstripped gas together with the carbon monoxide of catalyzer poison, unstripped gas is passed into hydroformylation reaction device, reactor is that stainless steel stirs autoclave, and reactor is with gas distributor, unstripped gas passes at the bottom of reactor still, the ethene containing in oil refinery dry gas under the effect of oil soluble rhodium catalyst and catalyst ligand and hydrogen with together with additional carbon monoxide, carry out hydroformylation reaction and generate propionic aldehyde;
The 4th step, unstripped gas passes into continuously, utilizing the reaction end gas contain in a large number nonreactive alkane and permanent gases to carry product propionic aldehyde secretly discharges from reactor gaseous phase outlet, form gaseous stream, gaseous stream enters condenser system, through condenser, this part material is divided into non-condensable gas phase and organic phase, non-condensable gas contains a large amount of hydro carbons inflammable gass mutually, can be used as fuel and enter exhaust gas recovery system, organic phase is thick propionic aldehyde streams, wherein a part is as backflow, to control reactor liquid level, most of thick propionic aldehyde streams enters separation system, form byproduct stream and product stream, be propionic aldehyde product.
2. a kind of method of utilizing ethene in oil refinery dry gas to prepare propionic aldehyde according to claim 1, the impurity removing comprises 5～50ppm iron carbonyl, 20～200ppm hydrogen sulfide, 10～100ppm oxygen, 300～3000ppm acetylene and 500～5000ppm water.
3. a kind of method of utilizing ethene in oil refinery dry gas to prepare propionic aldehyde according to claim 1, purification system is the fixed bed scavenging tower that a set of series winding connects, respectively iron carbonyl scavenging tower, hydrogen sulfide scavenging tower, oxygen scavenging tower, acetylene purification tower, water scavenging tower, gac is housed respectively, makes iron carbonyl content be less than 1ppm; Zinc oxide desulfurization catalyzer, makes hydrogen sulfide content be less than 1ppm; Platinum sulfide catalyzer, makes oxygen level be less than 1ppm; Selective hydrogenation catalyst, makes acetylene content be less than 50ppm; Molecular sieve, makes water-content be less than 100ppm.
4. a kind of method of utilizing ethene in oil refinery dry gas to prepare propionic aldehyde according to claim 3, makes iron carbonyl content be less than 0.1ppm; Make hydrogen sulfide content be less than 0.1ppm; Make acetylene content be less than 10ppm; Make water-content be less than 10ppm.
5. a kind of method of utilizing ethene in oil refinery dry gas to prepare propionic aldehyde according to claim 1; hydroformylation reaction catalyzer used is oil soluble using rhodium complex catalysts; i.e. three (triphenyl phosphorus) carbonyl hydrogen rhodium; the add-on of catalyzer is counted 200～500ppm with metal rhodium, and in catalyst ligand triphenylphosphine used and rhodium catalyst, the mol ratio of metal rhodium is 50～100: 1.
6. a kind of method of utilizing ethene in oil refinery dry gas to prepare propionic aldehyde according to claim 1; the solvent that hydroformylation reaction is used adopts can be mutually miscible with propionic aldehyde product; and can dissolve the organic solvent of aforementioned rhodium catalyst and catalyst ligand; comprise aliphatic series and aromatic hydrocarbon; ether, the polycondensation product of aldehyde or products of oxo synthesis aldehyde.
7. a kind of method of utilizing ethene in oil refinery dry gas to prepare propionic aldehyde according to claim 6, described aliphatic series and aromatic hydrocarbon are heptane, hexanaphthene, benzene or toluene, described ether is tetrahydrofuran (THF) or tetraethylene glycol dimethyl ether, described aldehyde is propionic aldehyde or butyraldehyde, and the polycondensation product of described products of oxo synthesis aldehyde is trimerization propionic aldehyde or trimerization butyraldehyde.
8. a kind of method of utilizing ethene in oil refinery dry gas to prepare propionic aldehyde according to claim 1, the ratio of carbon monoxide and ethene is 1～1.2: 1.
9. a kind of method of utilizing ethene in oil refinery dry gas to prepare propionic aldehyde according to claim 1; 90 ℃～110 ℃ of hydroformylation reaction temperature; hydroformylation reaction pressure 1.0～2.0Mpa, in unstripped gas, the transformation efficiency of ethene is greater than 75%, and the conversion rate of ethene is greater than 2.0mol/l.hr.
10. according to a kind of method of utilizing ethene in oil refinery dry gas to prepare propionic aldehyde claimed in claim 9, in unstripped gas, the transformation efficiency of ethene is greater than 80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010297500.8A CN102442894B (en) | 2010-09-30 | 2010-09-30 | Method for preparing propionic aldehyde from ethylene in refinery dry gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010297500.8A CN102442894B (en) | 2010-09-30 | 2010-09-30 | Method for preparing propionic aldehyde from ethylene in refinery dry gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102442894A CN102442894A (en) | 2012-05-09 |
| CN102442894B true CN102442894B (en) | 2014-08-06 |
Family
ID=46005880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010297500.8A Active CN102442894B (en) | 2010-09-30 | 2010-09-30 | Method for preparing propionic aldehyde from ethylene in refinery dry gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102442894B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103499670A (en) * | 2013-10-15 | 2014-01-08 | 天津渤海化工有限责任公司天津碱厂 | Method for evaluating precious metal homogeneous catalyst |
| KR102379397B1 (en) * | 2016-06-30 | 2022-03-28 | 다우 글로벌 테크놀로지스 엘엘씨 | Method for converting methane to propanal |
-
2010
- 2010-09-30 CN CN201010297500.8A patent/CN102442894B/en active Active
Non-Patent Citations (4)
| Title |
|---|
| 利用天然气和轻油制丙醛新工艺开发;王彦宾等;《天然气化工》;20031231;第28卷(第1期);第8-9、14页 * |
| 干气氢甲酰化合成丙醛研究进展;杨富等;《化学工程师》;20050228(第2期);第42-43页 * |
| 杨富等.干气氢甲酰化合成丙醛研究进展.《化学工程师》.2005,(第2期),第42-43页. |
| 王彦宾等.利用天然气和轻油制丙醛新工艺开发.《天然气化工》.2003,第28卷(第1期),第8-9、14页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102442894A (en) | 2012-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Van Santen | Modern heterogeneous catalysis: an introduction | |
| CN100595180C (en) | Improvements in or relating to hydroformylation | |
| CN103373910B (en) | Method for preparing propanal by refinery dry gas | |
| CN111646885B (en) | Method for preparing aldehyde based on Fischer-Tropsch low-carbon hydrocarbon hydroformylation | |
| CN103772125B (en) | Take oil refinery dry gas as the method for waste ethylbenzene | |
| CN101565353B (en) | Preparation method for 2-propyl enanthol | |
| CN101279872B (en) | Method for preparing low-carbon olefin hydrocarbon with oxocompound | |
| CN103772126B (en) | Take oil refinery dry gas as the combined method of waste ethylbenzene | |
| CN104262152A (en) | Production method of methyl glycolate | |
| JP2009179591A (en) | Method for producing methanol | |
| CN103459565B (en) | The manufacture method of hydrocarbon feed | |
| CN107021453A (en) | The production technology of hydrogen and carbon monoxide in a kind of hydroformylation of olefin | |
| CN102442894B (en) | Method for preparing propionic aldehyde from ethylene in refinery dry gas | |
| CN107973677B (en) | Device and method for preparing mixed aromatic hydrocarbon with low content of oxygen-containing compound through methanol aromatization | |
| CN101671571B (en) | Method for preparing biofuels with lignocellulose biomass by hydrolyzation and reformation | |
| CN103193581A (en) | Device and method for coproduction of 1,3-butadiene and ethyl tert butyl ether from methanol to olefin (DMTO) byproduct coal-based mixing C4 | |
| CN113045391B (en) | Gas-liquid dual-cycle hydroformylation continuous reaction device and process | |
| CN101077465A (en) | Carbonyl synthesis gallop gas-releasing recovery method | |
| CN101768062B (en) | Industrial method for simultaneously preparing propaldehyde and butyraldehyde by catalytic dry gas concentrating gas | |
| CN102137834B (en) | Offgas cleanup in olefin hydroformylation | |
| WO1989006642A2 (en) | Impurity removal from carbon monoxide and/or hydrogen-containing streams | |
| CN103130623A (en) | Reaction system and reaction method of gas-liquid double-circulation hydroformylation of preparing butyraldehyde with propylene | |
| CN104447195B (en) | Method for producing chemical product methanol, natural gas or synthetic oil by using calcium carbide furnace tail gas | |
| CN101668869A (en) | Cobalt recovery from cobalt catalysed hydroformylation reactions | |
| EA001723B1 (en) | Process for producing of motor fuels from hydrocarbons |
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 |