CN102442894A - Method for preparing propionic aldehyde from ethylene in refinery dry gas - Google Patents
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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 is a kind of directly utilize ethene and hydrogen in the oil refinery dry gas, prepares 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 like catalytic cracking, thermally splitting, delayed coking etc., wherein the dry gas amount of catalytic cracking is maximum, and productive rate is the highest.Contain 10～20% ethene in the oil refinery dry gas, 20～40% hydrogen, and nitrogen, methane, ethane and a spot of carbon monoxide, carbonic acid gas, propane, propylene etc.
External refinery utilizes oil refinery dry gas to be used as the ethylene unit raw material as far back as the just industriallization eighties in 20th century.Domestic oil refining and chemical enterprise on structure and layout with very big difference is abroad arranged.At first the domestic oil refining enterprises scale is generally less than normal, and layout is disperseed, and dry gas reclaims and is difficult to occur the scale device.Secondly, most oil refining enterprises do not have the ethene process matched therewith, even some oiling mating type, but the geographical position of its ethene and oil refining brings difficulty with utilization for the further refining of ethene at a distance of also far away.Domestic plant catalytic cracking dry gas is used as industrial fuel gas, domestic fuel gas basically, and remaining torch of then setting fire is burnt, and causes the serious wasting of resources.Along with developing rapidly of China petroleum refining industry crude oil deep 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; Improve the comprehensive benefit of refinery, caused people's common concern.
At present, mainly adopt separation and recovery technology and chemical utilization technology two big classes to the utilization of ethene in the oil refinery dry gas.The technology that is used for the dry gas Separation and Recovery of success exploitation has low temperature separation process, Separation by Complexation, solvent extraction, cold oil absorption, membrane sepn, transformation absorption and these technological process integrations at present.At present, the technology of the direct processing and utilization technology comparative maturity of ethene in the oil refinery dry gas is had preparing ethylbenzene from dry gas, dry gas system is to methyl-ethyl benzene, dry gas epoxy ethane, dry gas system ethylene dichloride etc.
Ethylene concentration is generally lower in the catalytic cracked dry gas, and it is carried out the Separation and Recovery utilization, has the higher shortcoming of facility investment and processing charges.Therefore, develop its direct utilization technology and have excellent economy,, be particularly useful for the limited medium-sized and small enterprises of tolerance because direct processing and utilization investment and process cost are low.
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, third rare aldehyde hydrogenation method and the by-product method at present.The therein ethylene oxo synthesis is that the main method of producing propionic aldehyde is gone up in industry at present.The ethene oxo synthesis is divided into high pressure cobalt method and low pressure rhodium method again, and reaction process is ethene and carbon monoxide and hydrogen reaction generation propionic aldehyde.U.S. combinating carbide company built up the first cover ethene low pressure oxo synthesis production propionic aldehyde full scale plant in the world in 1975.The low pressure oxo synthesis has the catalyst activity height, selectivity is good, reaction conditions is gentle; Do not produce corrosive medium in the production process; Advantages such as raw material and general facilities consume low, and facility investment is few are external at present main working method and developing direction of producing propionic aldehyde.The low pressure oxo synthesis is divided into oil soluble rhodium phosphine complex catalyst system and water-soluble rhodium phosphine complex compound catalyst system again.
Relating to rare ethene hydroformylation system propionic aldehyde reverse side; In Chinese patent CN1125712; Described with liquid phase rhodium phosphine complex catalyst cupport on porous support, catalysis is the method for raw material preparing aldehyde by hydro formylating by 5～40% 2～6 carbon atom low-concentration olefinics of containing that fluid catalytic cracking obtains.Catalytic active component in the used load liquid-phase catalyst of this method is an 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 to be the raw material production propionic aldehyde with oil refinery dry gas and synthetic gas; Its process is through pressure-changed adsorption concentrating ethene with refinery gas; Purify the back with synthetic gas, under the effect of water-soluble rhodium phosphine complex compound catalyst system, prepare propionic aldehyde through hydroformylation reaction.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 with synthetic gas, and under the effect of water-soluble rhodium complex compound composite catalyst, hydroformylation reaction prepares propionic aldehyde.This method is had relatively high expectations to material concentration.
U.S. Pat 5675041 adopts the oil soluble rhodium catalyst, is feedstock production C3～C6 aldehyde by the C2 that contains alkene and alkynes～C5 hydrocarbon mixture.It is to be raw material with the Sweet natural gas, and processing hydrocarbon mixtures such as containing ethene, acetylene earlier is raw material and synthetic gas (carbon monoxide and hydrogen), prepares mixed aldehyde through hydroformylation reaction.
In U.S. Pat 6049011, adopt the rare ethene hydroformylation prepared in reaction of oil soluble rhodium phosphine complex catalyst propionic aldehyde, the content of ethene is 30～75% in used rare ethene, 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 utilizes the oil refinery dry gas the inside to contain simultaneously, and under the situation that does not change gas raw material concentration, directly carries out the method that hydroformylation reaction prepares propionic aldehyde.
Summary of the invention
The technical problem that the present invention will solve:
In view of not providing at present the oil refinery dry gas low-concentration ethane directly to utilize the technology of preparation propionic aldehyde; The invention is intended to provide a kind of oil refinery dry gas to need not to carry dense; Only need to purify the catalyzer poison that the inside is contained; Before dry gas carried out hydroformylation, the poisonous substance of catalyzer required to be purified to a suitable concentration.Directly utilize ethene and hydrogen in the oil refinery dry gas then, carry out low pressure homogeneous phase hydroformylation reaction, prepare propionic aldehyde with the method for gas phase discharging with the carbon monoxide that adds.
Technical scheme of the present invention comprises following steps:
The molar content of ethene is 10～15% in the preferred oil refinery dry gas of the present invention, and the molar content of hydrogen is 20～35%, and the mol ratio of ethene and hydrogen is 1: 1.5～1: 2.5 a oil refinery dry gas.
The first step, raw material dry gas 1 get into compression system A pressurization, and pressure adds to 1.5～2.5Mpa, form highly compressed dry gas 2 after discharging a small amount of lime set.
Second step; High pressure dry gas 2 gets into purification system B; Containing following impurity in the oil refinery dry gas need remove; (((((500～5000ppm), purification system is the fixed bed scavenging tower that a cover polyphone shown in Figure 2 connects to 300～3000ppm) water to 10～100ppm) acetylene to 20～200ppm) oxygen to 5～50ppm) hydrogen sulfide to iron carbonyl, 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 less than 1ppm, preferably less than 0.1ppm; The zinc oxide desulfurization catalyzer makes hydrogen sulfide content less than 1ppm, preferably less than 0.1ppm; The platinum sulfide catalyzer makes oxygen level less than 1ppm; Select hydrogenation catalyst, make acetylene content less than 50ppm, preferably less than 10ppm.Molecular sieve makes water-content less than 100ppm, preferably less than 10ppm.
In the 3rd step, the oil refinery dry gas after the purification forms hydroformylation reaction virgin gas 3 with the carbon monoxide that does not contain catalyzer poison.Virgin gas 3 is fed hydroformylation reaction device C, and reactor drum C is that stainless steel stirs autoclave, and reaction kettle has gas distributor.Virgin gas feeds at the bottom of the reaction kettle still, and the ethene and the hydrogen that under the effect of catalyst ligand, contain in the oil refinery dry gas at the oil soluble rhodium catalyst carry out hydroformylation reaction generation propionic aldehyde with the carbon monoxide that adds.
The used catalyzer of hydroformylation reaction is the 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.
The mol ratio of metal rhodium is 50～100: 1 in used catalyst ligand triphenylphosphine and the rhodium catalyst.
The employed solvent of hydroformylation reaction can adopt any can be miscible each other with the propionic aldehyde product, and can dissolve the organic solvent of aforementioned rhodium catalyst and catalyst ligand.Comprise aliphatic series and aromatic hydrocarbon (like heptane, hexanaphthene, benzene, toluene etc.), ether and polyether (like THF and tetraethylene glycol dimethyl ether), aldehyde (like propionic aldehyde, butyraldehyde etc.), the polycondensation product of products of oxo synthesis aldehyde (like the trimerization propionic aldehyde, the trimerization butyraldehyde), or the like.
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, the transformation efficiency of ethene is greater than 75% in the virgin gas, 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; Virgin gas 3 feeds continuously; Utilizing the reaction end gas that contains nonreactive alkane and permanent gases in a large number to carry the product propionic aldehyde secretly discharges from the reaction kettle gaseous phase outlet; Form gaseous stream 4, gaseous stream 4 gets into condenser system D, through condensing surface 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 gets into exhaust gas recovery system.Organic phase is thick propionic aldehyde streams, and wherein a part is as refluxing 6, and with control reaction kettle liquid level, most of thick propionic aldehyde streams 7 gets into separation system E.
Thick propionic aldehyde streams 7 forms byproduct stream 9 and product stream 8 after separating through separation system E, is the propionic aldehyde product.
The invention has the beneficial effects as follows:
In view of the worsening shortages of petroleum resources, ethene and hydrogen all are important chemical material, as fuel even to burn in vain all be the significant wastage to resource.The inventive method provides the ethene and the new operational path of hydrogen that directly utilize in the oil refinery dry gas; Oil refinery dry gas only need purify the hydroformylation reaction catalyzer poison of the inside; Need not its component such as is separated, concentrates at means, can carry out hydroformylation reaction with carbon monoxide and prepare propionic aldehyde.
Hydroformylation reaction workshop section adopts be product with the gas phase discharging, gas phase tail gas is round-robin technology not, and traditional hydroformylation reaction workshop section gas phase discharging is to adopt tail gas to loop back reaction kettle in a large number, utilizes the circulation of tail gas that the product propionic aldehyde is taken out of from reaction kettle.Therefore present technique is simpler than traditional hydroformylation reaction workshop section gas phase discharging tail gas round-robin method technology.Utilize compared with techniques with other oil refinery dry gas, present method technology is simple, plant investment is little, energy consumption is low, has remarkable social benefit and economic benefit.
Description of drawings
Fig. 1 is that oil refinery dry gas and carbon monoxide homogeneous phase hydroformylation reaction prepare the propionic aldehyde process flow diagram;
Fig. 2 is an oil refinery dry gas refining plant schematic flow sheet.
Embodiment
Embodiment 1
The first step, the oil refinery dry gas of pressure 0.7Mpa adds to 2.3Mpa through compression system with pressure and forms the high pressure oil refinery dry gas.
Second step; The oil refinery dry gas that contains ethene 12.5% (molar content), hydrogen 26% (molar content) and methane, ethane, nitrogen, small amounts of propane, propylene, carbonic acid gas etc. by under meter control with the flow velocity of 5000ml/min through refining plant, contain iron carbonyl 10ppm, hydrogen sulfide 150ppm, oxygen 70ppm, acetylene 3000ppm, water 3000ppm in the oil refinery dry gas.Refining plant is made up of the fixed-bed reactor of five polyphones, but each fixed-bed reactor independent control temperature.Be respectively iron carbonyl scavenging tower, hydrogen sulfide scavenging tower, oxygen scavenging tower, acetylene purification tower, water scavenging tower.The iron carbonyl scavenging tower is equipped with the 200ml gac, and 180 ℃ of controlled temperature, hydrogen sulfide scavenging tower are equipped with 200ml zinc oxide desulfurization catalyzer; 80 ℃ of controlled temperature; The oxygen scavenging tower is equipped with the deoxidation of 200ml platinum sulfide catalyzer, and 180 ℃ of controlled temperature, acetylene purification tower are equipped with 100ml selects hydrogenation catalyst to be used to remove acetylene; 50 ℃ of controlled temperature, the water scavenging tower is equipped with the 500ml molecular sieve dehydration.Oil refinery dry gas contains iron carbonyl 0.1ppm, hydrogen sulfide 0.1ppm, oxygen 1ppm, acetylene 5ppm, water 10ppm through behind the refining plant.
In the 3rd step, the oil refinery dry gas after the purification feeds the hydroformylation reaction device with the carbon monoxide of 630ml/min, and reactor drum is that stainless steel stirs autoclave, and reaction kettle has gas distributor.Virgin gas feeds at the bottom of the reaction kettle 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.The mol ratio of metal rhodium is 50: 1 in used catalyst ligand triphenylphosphine and the rhodium catalyst.The employed solvent of hydroformylation reaction is a propionic aldehyde.Reaction solution volume 500ml.90 ℃ of hydroformylation reaction temperature, hydroformylation reaction pressure 2.0Mpa, ethene that contains in the oil refinery dry gas and hydrogen carry out hydroformylation reaction with the carbon monoxide that adds 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; Virgin gas feeds continuously, utilizes the reaction end gas that contains nonreactive alkane and permanent gases in a large number to carry the product propionic aldehyde secretly and discharges from the reaction kettle gaseous phase outlet, forms gaseous stream; Gaseous stream gets into condenser system, through condensing surface 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 with control reaction kettle liquid level, most of streams gets into separation system.Thick propionic aldehyde forms byproduct stream after separating through separation system, and product stream, is the propionic aldehyde product.
The first step, the oil refinery dry gas of pressure 0.7Mpa adds to 1.5Mpa through compression system with pressure and forms the high pressure oil refinery dry gas.
Second step; The oil refinery dry gas that contains ethene 12.5% (molar content), hydrogen 26% (molar content) and methane, ethane, nitrogen, small amounts of propane, propylene, carbonic acid gas etc. by under meter control with the flow velocity of 4000ml/min through refining plant, contain iron carbonyl 10ppm, hydrogen sulfide 150ppm, oxygen 70ppm, acetylene 3000ppm, water 3000ppm in the oil refinery dry gas.Refining plant is made up of the fixed-bed reactor of five polyphones, but each fixed-bed reactor independent control temperature.Be respectively iron carbonyl scavenging tower, hydrogen sulfide scavenging tower, oxygen scavenging tower, acetylene purification tower, water scavenging tower.The iron carbonyl scavenging tower is equipped with the 200ml gac, and 180 ℃ of controlled temperature, hydrogen sulfide scavenging tower are equipped with 200ml zinc oxide desulfurization catalyzer; 80 ℃ of controlled temperature; The oxygen scavenging tower is equipped with the deoxidation of 200ml platinum sulfide catalyzer, and 180 ℃ of controlled temperature, acetylene purification tower are equipped with 100ml selects hydrogenation catalyst to be used to remove acetylene; 50 ℃ of controlled temperature, the water scavenging tower is equipped with the 500ml molecular sieve dehydration.Oil refinery dry gas contains iron carbonyl 0.1ppm, hydrogen sulfide 0.1ppm, oxygen 1ppm, acetylene 5ppm, water 10ppm through behind the refining plant.
In the 3rd step, the oil refinery dry gas after the purification feeds the hydroformylation reaction device with the carbon monoxide of 630ml/min, and reactor drum is that stainless steel stirs autoclave, and reaction kettle has gas distributor.Virgin gas feeds at the bottom of the reaction kettle 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.The mol ratio of metal rhodium is 50: 1 in used catalyst ligand triphenylphosphine and the rhodium catalyst.The employed solvent of hydroformylation reaction is a propionic aldehyde.Reaction solution volume 500ml.100 ℃ of hydroformylation reaction temperature, hydroformylation reaction pressure 1.0Mpa, ethene that contains in the oil refinery dry gas and hydrogen carry out hydroformylation reaction with the carbon monoxide that adds 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; Virgin gas feeds continuously, utilizes the reaction end gas that contains nonreactive alkane and permanent gases in a large number to carry the product propionic aldehyde secretly and discharges from the reaction kettle gaseous phase outlet, forms gaseous stream; Gaseous stream gets into condenser system, through condensing surface 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 with control reaction kettle liquid level, most of streams gets into separation system.Thick propionic aldehyde forms byproduct stream after separating through separation system, and product stream, is the propionic aldehyde product.
The first step, the oil refinery dry gas of pressure 0.7Mpa adds to 1.8Mpa through compression system with pressure and forms the high pressure oil refinery dry gas.
Second step; The oil refinery dry gas that contains ethene 10.5% (molar content), hydrogen 23% (molar content) and methane, ethane, nitrogen, small amounts of propane, propylene, carbonic acid gas etc. by under meter control with the flow velocity of 5000ml/min through refining plant, contain iron carbonyl 20ppm, hydrogen sulfide 120ppm, oxygen 50ppm, acetylene 3100ppm, water 3500ppm in the oil refinery dry gas.Refining plant is made up of the fixed-bed reactor of five polyphones, but each fixed-bed reactor independent control temperature.Be respectively iron carbonyl scavenging tower, hydrogen sulfide scavenging tower, oxygen scavenging tower, acetylene purification tower, water scavenging tower.The iron carbonyl scavenging tower is equipped with the 200ml gac, and 180 ℃ of controlled temperature, hydrogen sulfide scavenging tower are equipped with 200ml zinc oxide desulfurization catalyzer; 80 ℃ of controlled temperature; The oxygen scavenging tower is equipped with the deoxidation of 200ml platinum sulfide catalyzer, and 180 ℃ of controlled temperature, acetylene purification tower are equipped with 100ml selects hydrogenation catalyst to be used to remove acetylene; 50 ℃ of controlled temperature, the water scavenging tower is equipped with the 500ml molecular sieve dehydration.Oil refinery dry gas contains iron carbonyl 0.1ppm, hydrogen sulfide 0.1ppm, oxygen 1ppm, acetylene 5ppm, water 10ppm through behind the refining plant.
In the 3rd step, the oil refinery dry gas after the purification feeds the hydroformylation reaction device with the carbon monoxide of 580ml/min, and reactor drum is that stainless steel stirs autoclave, and reaction kettle has gas distributor.Virgin gas feeds at the bottom of the reaction kettle 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.The mol ratio of metal rhodium is 50: 1 in used catalyst ligand triphenylphosphine and the rhodium catalyst.The employed solvent of hydroformylation reaction is a toluene.Reaction solution volume 500ml.110 ℃ of hydroformylation reaction temperature, hydroformylation reaction pressure 1.5Mpa, ethene that contains in the oil refinery dry gas and hydrogen carry out hydroformylation reaction with the carbon monoxide that adds 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; Virgin gas feeds continuously, utilizes the reaction end gas that contains nonreactive alkane and permanent gases in a large number to carry the product propionic aldehyde secretly and discharges from the reaction kettle gaseous phase outlet, forms gaseous stream; Gaseous stream gets into condenser system, through condensing surface 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 with control reaction kettle liquid level, most of streams gets into separation system.Thick propionic aldehyde forms byproduct stream after separating through separation system, and product stream, is the propionic aldehyde product.
Claims (7)
1. method of utilizing ethene in the oil refinery dry gas to prepare propionic aldehyde; The molar content of selecting ethene in the 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 1: 1.5～1: 2.5 oil refinery dry gas is a raw material, carries out successively according to following steps:
The first step, raw material dry gas get into the compression system pressurization, and pressure adds to 1.5～2.5Mpa, form the highly compressed dry gas after discharging a small amount of lime set;
In second step, the high pressure dry gas gets into purification system, with the impurity removal that contains in the oil refinery dry gas;
The 3rd step; Oil refinery dry gas after the purification forms the hydroformylation reaction virgin gas with the carbon monoxide that does not contain catalyzer poison; Virgin gas is fed the hydroformylation reaction device, and reactor drum is that stainless steel stirs autoclave, and reaction kettle has gas distributor; Virgin gas feeds at the bottom of the reaction kettle still, and the ethene and the hydrogen that under the effect of catalyst ligand, contain in the oil refinery dry gas at the oil soluble rhodium catalyst carry out hydroformylation reaction generation propionic aldehyde with the carbon monoxide that adds;
In the 4th step, virgin gas feeds continuously, utilizes the reaction end gas that contains nonreactive alkane and permanent gases in a large number to carry the product propionic aldehyde secretly and discharges from the reaction kettle gaseous phase outlet; Form gaseous stream, gaseous stream gets into condenser system, through condensing surface 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 gets into exhaust gas recovery system, and organic phase is thick propionic aldehyde streams; Wherein a part is as backflow, and with control reaction kettle liquid level, most of thick propionic aldehyde streams gets into separation system; Form byproduct stream and product stream, be the propionic aldehyde product.
2. a kind of method of utilizing ethene in the oil refinery dry gas to prepare propionic aldehyde according to claim 1, the impurity that removes comprises 5～50ppm iron carbonyl, 20～200ppm hydrogen sulfide, 10～100ppm oxygen, 300～3000ppm acetylene, 500～5000ppm water.
3. a kind of method of utilizing ethene in the oil refinery dry gas to prepare propionic aldehyde according to claim 1; Purification system is the fixed bed scavenging tower that a cover polyphone connects; Be 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 less than 1ppm, preferably less than 0.1ppm; The zinc oxide desulfurization catalyzer makes hydrogen sulfide content less than 1ppm, preferably less than 0.1ppm; The platinum sulfide catalyzer makes oxygen level less than 1ppm; Select hydrogenation catalyst, make acetylene content less than 50ppm, preferably less than 10ppm; Molecular sieve makes water-content less than 100ppm, preferably less than 10ppm.
4. a kind of method of utilizing ethene in the oil refinery dry gas to prepare propionic aldehyde according to claim 1; The used catalyzer of hydroformylation reaction is the 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 the mol ratio of metal rhodium is 50～100: 1 in used catalyst ligand triphenylphosphine and the rhodium catalyst.
5. a kind of method of utilizing ethene in the oil refinery dry gas to prepare propionic aldehyde according to claim 1, the employed solvent of hydroformylation reaction can adopt any can be miscible each other with the propionic aldehyde product, and can dissolve the organic solvent of aforementioned rhodium catalyst and catalyst ligand; Comprise aliphatic series and aromatic hydrocarbon (like heptane, hexanaphthene, benzene; Toluene etc.); Ether and polyether (like THF and tetraethylene glycol dimethyl ether), aldehyde (like propionic aldehyde, butyraldehyde etc.); The polycondensation product of products of oxo synthesis aldehyde (like the trimerization propionic aldehyde, the trimerization butyraldehyde).
6. a kind of method of utilizing ethene in the oil refinery dry gas to prepare propionic aldehyde according to claim 1, the ratio of carbon monoxide and ethene is 1～1.2: 1
7. a kind of method of utilizing ethene in the 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; The transformation efficiency of ethene is greater than 75% in the virgin gas, and the transformation efficiency of optimal ethylene is greater than 80%, and the conversion rate of ethene is greater than 2.0mol/l.hr.
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Cited By (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 |
| CN109311666A (en) * | 2016-06-30 | 2019-02-05 | 陶氏环球技术有限责任公司 | The technique for converting propionic aldehyde for methane |
-
2010
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Non-Patent Citations (2)
| Title |
|---|
| 杨富等: "干气氢甲酰化合成丙醛研究进展", 《化学工程师》 * |
| 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》 * |
Cited By (3)
| 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 |
| CN109311666A (en) * | 2016-06-30 | 2019-02-05 | 陶氏环球技术有限责任公司 | The technique for converting propionic aldehyde for methane |
| CN109311666B (en) * | 2016-06-30 | 2022-07-19 | 陶氏环球技术有限责任公司 | Process for converting methane to propanal |
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