CN102649714B - Aldehyde production method - Google Patents
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- CN102649714B CN102649714B CN201110046399.3A CN201110046399A CN102649714B CN 102649714 B CN102649714 B CN 102649714B CN 201110046399 A CN201110046399 A CN 201110046399A CN 102649714 B CN102649714 B CN 102649714B
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Abstract
The invention relates to an aldehyde production method, and mainly solves the technical problems in the prior art that the target product is high in energy consumption and low in yield. The method adopts methanol, dimethyl ether or a mixture of the two as a raw material I and a synthesis gas as a raw material II and comprises the following steps: (a) the raw material I enters a first reactor at first to be in contact with an SAPO-34 molecular sieve based catalyst I to produce a first stream reaction effluent containing C2-C4 olefin; and (b) the first stream reaction effluent and the raw material II enter a second reactor to be in contact with a rhodium-containing liquid catalyst II, so as to produce a second stream reaction effluent containing aldehyde. By adopting the technical scheme, the problems are better solved, and the method provided by the invention can be used for industrial increase production of aldehyde.
Description
Technical field
The present invention relates to a kind of method of producing aldehyde, particularly about taking methyl alcohol or dme and synthetic gas as raw material, the method for producing aldehyde by methanol-to-olefins and olefin hydroformylation coupling.
Background technology
Under catalyst action, there is hydroformylation reaction in alkene and carbon monoxide and hydrogen
The aldehyde generating can be made into corresponding alcohol through hydrogenation.Millions of ton of meter/year of throughput of synthol in this way in the world.There is hydroformylation reaction and generate propionic aldehyde, butyraldehyde or valeral in ethene, propylene or butylene and carbon monoxide and hydrogen, and further hydrogenation generation butanols, amylalcohol or hexanol are exactly one of them important chemical process under the effect of rhodium carbonyl catalyst.And with regard at present traditional method, the alkene of the raw material of olefin hydroformylation is mainly from traditional petroleum refining industry, especially all monomer products after separating of system.
On the one hand, in the last few years, along with the fast development of China's coal chemical technology, especially methanol-to-olefins technology developed gradually, and started to move towards the industrialization, and it is predicted that the olefin hydrocarbon making by coal technology of China will reach more than 1,000 ten thousand tons in planning in addition.And the maximum feature of methanol-to-olefins is; in its reaction product, the alpha-olefin of C2～C5 accounts for the more than 90% of total olefin; this part alkene is the optimum feed stock of olefin hydroformylation exactly; can be not directly do not enter hydroformylation reaction device and react with synthetic gas the mixture that generates corresponding aldehyde by separating; this is energy efficient not only, and the selectivity of object product is also high simultaneously.Therefore, the coupling technique of development methanol-to-olefins and hydroformylation of olefin unit, and then it is significant to realize the scale operation of alcohol by new raw material route.And the report of the rarely seen this respect of prior art.
In addition; for hydroformylation of olefin, be mass transfer limited speech process, in prior art, the main path of reactor reinforcing mass transfer is to increase mass transfer interface; for not adding the bubbling style of stirring and answering device, only have by suitable gas distributor and tighten and improve mass transfer.In this bubbling style back-mixing equipment (as tower kind equipment), owing to there is no the input of mixing energy, it is enough thin that bubble can not reach, in order there to be enough mass transfer areas, just must there is enough large space, this just makes comparison in equipment huge, and the utilising efficiency of equipment is just lower, and investment is also large.To there being the tank reactor of stirring, although the input of mixing energy can make bubble attenuate, thereby increase mass transfer interface, the efficiency of its increase is very limited.
Document CN 97195745.2 discloses a kind of production method of alcohol aldehyde; this invention part relates to for the production of one or more replacements or unsubstituted alcohol aldehyde as the method for 6-hydroxyl hexanal; it comprises makes one or more replacements or unsubstituted alkadiene carry out hydroformylation reaction at hydroformylation reaction catalyzer under as the existence of metal-organophosphorus ligand coordination catalyst as divinyl, and carries out hydroformylation reaction to produce one or more replacements or unsubstituted alcohol aldehyde at hydroformylation reaction catalyzer under as the existence of metal-organophosphorus ligand coordination catalyst.Part of the present invention also relates to and contains one or more replacements or the unsubstituted alcohol aldehyde reaction mixture as principal reaction product.But the selectivity of the alcohol aldehyde of this invention is lower than 90%.
Document CN92115053.9 discloses a kind of method of synthesis of aldehyde by hydroformylation of olefins, this disclosure of the invention a kind of method of synthesis of aldehyde by hydroformylation of olefins.The above alkene of C3 or C3, carbon monoxide and hydrogen, make catalyzer with cobalt octacarbonyl, and the stablizer that quaternary ammonium salt is catalyzer generates aldehyde under 100～130 DEG C, 5.5～8.5MPa reaction conditions.But the selectivity of aldehyde is lower than 90%.
The EP0023745A3 patent that Imperial Chemical Industries of Britain (ICI) propose, mentions rotating bed and can be used for the processes such as absorption, parsing, distillation, but does not disclose the utilisation technology of industrially scalable.CN1064338A discloses the method for utilizing rotating bed to carry out oil-field flooding deoxidation; CN1116146A discloses a kind of method of preparing ultrafine particle under super gravity field.
Super gravity field technology is the new technology that early eighties just occurs; its internal mechanism is also continuing exploration; research for application and development is still constantly being carried out; new Application Areas is also in continuous developing; it is not also applied to the production report of hydroformylation of olefin for now as efficient mass transfer and conversion unit about high-efficiency rotating packed-bed reactor.
Summary of the invention
Technical problem to be solved by this invention is to overcome in previous literature technology to exist object product energy consumption high, the technical problem that selectivity is low.A kind of method of new production aldehyde is provided.It is low that the method has energy consumption, the advantage that selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing aldehyde, and taking methyl alcohol, dme or its mixture as raw material I, synthetic gas is raw material II, comprises the following steps:
A) first raw material I enters in the first reactor and contacts with SAPO-34 molecular sieve catalyst I, generates the first strand of reaction effluent that contains C2～C4 alkene;
B) first strand of reaction effluent, enters in the second reactor and contacts with the liquid catalyst II of rhodium-containing with raw material II, generates the second segment reaction effluent that contains aldehyde;
Wherein, in first strand of reaction effluent, the gas mole ratio of C2～C4 alkene and raw material II is 0.1～2: 1, and in raw material II synthetic gas, the mol ratio of CO and hydrogen is 0.3～3: 1.
Catalyst I I in technique scheme, in total catalyst weight umber, preferably includes 1～50 part of rhodium complex, 10～1000 parts of phosphine parts and 200～6000 parts of solvents; Solvent is preferably selected from the aromatic solvent of water, alcohol or C6～C9.Catalyst I I, in total catalyst weight umber, more preferably comprises 1～40 part of rhodium complex, 10～800 parts of phosphine parts and 200～4000 parts of solvents; Solvent is more preferably selected from the aromatic solvent of water or C6～C9.
The first reactor preferred operations condition in technique scheme: temperature of reaction is 200～530 DEG C, reaction weight space velocity is 0.1～100 hour
-1, reaction pressure is-0.1～1MPa; More preferably operational condition of the first reactor: temperature of reaction is 350～500 DEG C, reaction weight space velocity is 2～50 hours
-1, reaction pressure is-0.07～0.5MPa; The second reactor preferred operations condition: temperature of reaction is 40～160 DEG C, reaction pressure is 0.5～10MPa.More preferably operational condition of the second reactor: temperature of reaction is 60～150 DEG C, reaction pressure is 1.0～5.0MPa.The mol ratio of C2～C4 alkene and rhodium is preferably 0.5～60: 1.The second reactor preferably adopts rotary packed bed reactor, and its rotating speed is preferably 200～5000rpm, and rotating speed is 300～3000rpm more preferably.
As everyone knows, on the earth, all substances are all because gravity is by earth attraction, super gravity field is the environment more much bigger than earth gravity intensity of field, and material suffered power under super gravity field is called hypergravity, utilizes hypergravity the principles of science and the practical technique that produces is called high-gravity technology.
High-gravity technology is the new technology of strengthening polyphasic flow transmission and reaction process, since eighties of last century is come out, at home and abroad paid attention to widely, due to it broad applicability and have that the volume that legacy equipment do not have is little, lightweight, energy consumption is low, easy running, easy-maintaining, safety, the advantage such as can conform reliably, flexibly and more, make high-gravity technology have wide commercial applications prospect in the industrial circles such as environmental protection and material biochemical industry.But high-gravity technology, also mainly in the application and development stage, embodies a concentrated reflection of the gas-solid fluidization technology of hypergravity and two aspects of hypergravity gas-liquid mass transferring technology at present.
Under the Elevated Gravity of large hundreds of times to thousand times than earth gravity field, huge shearing force is torn into liquid liquid film, brin, the drop of micron to nano grade, produce huge, the quick phase interface upgrading, greatly increase gas-to-liquid contact specific surface area, make 1～3 order of magnitude of raising in interphase mass transfer speed ratio tradition tower, microcosmic mixes and mass transfer process is greatly strengthened.Make the production efficiency of unit equipment volume obtain the raising of 1～2 order of magnitude.
Rotating bed super gravity field device, as the equipment that produces super gravity field, it is made up of gas and liquid inlet tube, rotor, gas and liquid exit conventionally.Its principle of work be gas phase through gas inlet tube by tangentially introducing rotor exocoel, under the effect of gaseous tension, enter filler by rotor outer rim place.Liquid is introduced rotor internal cavity by liquid inlet tube, through shower nozzle sprinkle on rotor inner edge.The liquid that enters rotor is subject to the effect of filler (catalyzer) in rotor, and circumferential speed increases, and the centrifugal force producing pushes it against rotor outer rim.In this process, liquid is by the surface-area that filler (catalyzer) disperses, crushing-type becomes greatly, constantly updates, and tortuous runner has aggravated the renewal of fluid surface.Like this, fabulous mass transfer and reaction conditions have been formed at internal rotor.Liquid leaves overweight machine through liquid outlet tube after being thrown shell and collect by rotor.Gas leaves rotor from rotor center, is drawn by gas outlet tube, completes mass transfer and reaction process.
Research shows; methyl alcohol by SAPO-34 olefins reaction process processed in; in reaction product, the alpha-olefin of C2～C5 accounts for the more than 90% of total olefin; this part alkene is the optimum feed stock of olefin hydroformylation exactly; can be not directly do not enter hydroformylation reaction device and react with synthetic gas the mixture that generates corresponding aldehyde by separating; this is energy efficient not only, and the selectivity of object product is also high simultaneously.In addition, the present invention, in hydroformylation reaction process, has also adopted rotary packed bed reactor, utilizes the very big mass-transfer efficiency of this reactor, further improves reaction efficiency, reduces energy consumption, improves the selectivity of object product.
Adopting technical scheme of the present invention, adopt successively SAPO-34 and rhodium-containing liquid catalyst, taking methyl alcohol or dme and synthetic gas as raw material, is 200～530 DEG C in the first reactor reaction temperature, and reaction weight space velocity is 1～100 hour
-1, reaction pressure is-0.1～1MPa; The second reactor: temperature of reaction is 40～160 DEG C, reaction pressure is 0.5～10MPa, and under the condition that rotating speed is 200～5000rpm, raw material availability is high, and the overall selectivity of aldehyde can be greater than 98%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Taking methyl alcohol as raw material I, synthetic gas is raw material II, comprises the following steps: a) first raw material I enters in the first reactor and contact with SAPO-34 molecular sieve catalyst I, generates the first strand of reaction effluent that contains C2～C4 alkene; B) the first strand of reaction effluent that contains C2～C4 alkene, enters in the second reactor and contacts with the liquid catalyst II of rhodium-containing with raw material II, generates the second segment reaction effluent that contains aldehyde; Wherein, in first strand of reaction effluent, the gas mole ratio of C2～C4 alkene and raw material II is 0.5: 1, and in raw material II synthetic gas, the mol ratio of CO and hydrogen is 1: 1.The liquid catalyst II of rhodium-containing adopts document CNCN200910058201.6[embodiment 1] in rhodium catalyst be catalyzer.Be 450 DEG C in the first reactor reaction temperature, reaction weight space velocity is 3 hours
-1, reaction pressure is 0.2MPa; The second reactor (this reactor adopts with rotating bed super gravity field device reaction device in embodiment 1 in patent CN1895766A identical (following identical)): temperature of reaction is 80 DEG C, reaction pressure is 1.0MPa, rotating speed is under the condition of 500rpm, its reaction result is, the transformation efficiency of methyl alcohol is that the selectivity of the aldehyde of 100%, C3～C5 is 98.2%.
[embodiment 2]
Taking methyl alcohol as raw material I, synthetic gas is raw material II, comprises the following steps: a) first raw material I enters in the first reactor and contact with SAPO-34 molecular sieve catalyst I, generates the first strand of reaction effluent that contains C2～C4 alkene; B) the first strand of reaction effluent that contains C2～C4 alkene, enters in the second reactor and contacts with the liquid catalyst II of rhodium-containing with raw material II, generates the second segment reaction effluent that contains aldehyde; Wherein, in first strand of reaction effluent, the gas mole ratio of C2～C4 alkene and raw material II is 0.8: 1, and in raw material II synthetic gas, the mol ratio of CO and hydrogen is 1.5: 1.The liquid catalyst II of rhodium-containing adopts document CN CN200910058201.6[embodiment 1] in rhodium catalyst be catalyzer.Be 530 DEG C in the first reactor reaction temperature, reaction weight space velocity is 6 hours
-1, reaction pressure is 0.5MPa; The second reactor: temperature of reaction is 140 DEG C, reaction pressure is 5.0MPa, under the condition that rotating speed is 1000rpm, its reaction result is that the selectivity of the aldehyde that the transformation efficiency of methyl alcohol is 100%, C3～C5 is 98.2%.
[embodiment 3]
Taking dme as raw material I, synthetic gas is raw material II, comprises the following steps: a) first raw material I enters in the first reactor and contact with SAPO-34 molecular sieve catalyst I, generates the first strand of reaction effluent that contains C2～C4 alkene; B) the first strand of reaction effluent that contains C2～C4 alkene, enters in the second reactor and contacts with the liquid catalyst II of rhodium-containing with raw material II, generates the second segment reaction effluent that contains aldehyde; Wherein, in first strand of reaction effluent, the gas mole ratio of C2～C4 alkene and raw material II is 0.3: 1, and in raw material II synthetic gas, the mol ratio of CO and hydrogen is 3: 1.The liquid catalyst II of rhodium-containing adopts document CN CN200910058201.6[embodiment 2] in rhodium catalyst be catalyzer.Be 500 DEG C in the first reactor reaction temperature, reaction weight space velocity is 3 hours
-1, reaction pressure is-0.01MPa; The second reactor: temperature of reaction is 120 DEG C, reaction pressure is 2.0MPa, under the condition that rotating speed is 3000rpm, its reaction result is that the selectivity of the aldehyde that the transformation efficiency of dme is 100%, C3～C5 is 99.1%.
[embodiment 4]
Taking dme as raw material I, synthetic gas is raw material II, comprises the following steps: a) first raw material I enters in the first reactor and contact with SAPO-34 molecular sieve catalyst I, generates the first strand of reaction effluent that contains C2～C4 alkene; B) the first strand of reaction effluent that contains C2～C4 alkene, enters in the second reactor and contacts with the liquid catalyst II of rhodium-containing with raw material II, generates the second segment reaction effluent that contains aldehyde; Wherein, in first strand of reaction effluent, the gas mole ratio of C2～C4 alkene and raw material II is 0.9: 1, and in raw material II synthetic gas, the mol ratio of CO and hydrogen is 1.2: 1.The liquid catalyst II of rhodium-containing adopts document CN200510085899.2[embodiment 9] in rhodium catalyst be catalyzer.Be 480 DEG C in the first reactor reaction temperature, reaction weight space velocity is 2 hours
-1, reaction pressure is 0.2MPa; The second reactor: temperature of reaction is 100 DEG C, reaction pressure is 2.5MPa, under the condition that rotating speed is 800rpm, its reaction result is that the selectivity of the aldehyde that the transformation efficiency of dme is 100%, C3～C5 is 98.3%.
[comparative example 1]
Adopt catalyzer and reaction conditions and the raw material of [embodiment 1], just the second reactor adopts conventional tank reactor, and its reaction result is that the selectivity of the aldehyde that the transformation efficiency of methyl alcohol is 95%, C3～C5 is 91.8%.
Claims (1)
1. produce the method for the aldehyde of C3～C5 for one kind, taking dme as raw material I, synthetic gas is raw material II, comprises the following steps: a) first raw material I enters in the first reactor and contact with SAPO mono-34 molecular sieve catalyst I, generates the first strand of reaction effluent that contains C2～C4 alkene; B) the first strand of reaction effluent that contains C2～C4 alkene, enters in the second reactor and contacts with the liquid catalyst II of rhodium-containing with raw material II, generates the second segment reaction effluent that contains aldehyde; Wherein, in first strand of reaction effluent, the gas mole ratio of C2～C4 alkene and raw material II is 0.3: 1, and in raw material II synthetic gas, the mol ratio of CO and hydrogen is 3: 1; Be 500 DEG C in the first reactor reaction temperature, reaction weight space velocity is 3 hours
-1, reaction pressure is-0.01MPa; The second reactor: temperature of reaction is 120 DEG C, reaction pressure is 2.0MPa, under the condition that rotating speed is 3000rpm, its reaction result is that the selectivity of the aldehyde that the transformation efficiency of dme is 100%, C3～C5 is 99.1%; Catalyst I I represents to consist of with weight part: 200 parts, water, 0.1 part of Trimethyllaurylammonium bromide, rhodium catalyst presoma Rh (acac)
20.2 part, 0.8 part of o-two-(diphenylphosphine ylmethyl) the benzene sodium salt of sulfonation biphosphine ligand; The second reactor is rotary packed bed reactor.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422837A (en) * | 2001-12-06 | 2003-06-11 | 中国科学院大连化学物理研究所 | Method for producing organoaldehyde prepared by hydroformylating of olefin |
| CN1743064A (en) * | 2004-09-02 | 2006-03-08 | 中国石油化工股份有限公司 | Method for conducting catalytic reaction in ultragravity field |
| CN101402538A (en) * | 2008-11-21 | 2009-04-08 | 中国石油化工股份有限公司 | Method for improving yield of light olefins |
| CN101462932A (en) * | 2009-01-21 | 2009-06-24 | 成都欣华源科技有限责任公司 | Method for preparing aldehyde by hydroformylation of light olefins |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422837A (en) * | 2001-12-06 | 2003-06-11 | 中国科学院大连化学物理研究所 | Method for producing organoaldehyde prepared by hydroformylating of olefin |
| CN1743064A (en) * | 2004-09-02 | 2006-03-08 | 中国石油化工股份有限公司 | Method for conducting catalytic reaction in ultragravity field |
| CN101402538A (en) * | 2008-11-21 | 2009-04-08 | 中国石油化工股份有限公司 | Method for improving yield of light olefins |
| CN101462932A (en) * | 2009-01-21 | 2009-06-24 | 成都欣华源科技有限责任公司 | Method for preparing aldehyde by hydroformylation of light olefins |
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