CN110078600A - A kind of reactive distillation process device and method for polymethoxy dimethyl ether synthesis - Google Patents

A kind of reactive distillation process device and method for polymethoxy dimethyl ether synthesis Download PDF

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Publication number
CN110078600A
CN110078600A CN201910307875.9A CN201910307875A CN110078600A CN 110078600 A CN110078600 A CN 110078600A CN 201910307875 A CN201910307875 A CN 201910307875A CN 110078600 A CN110078600 A CN 110078600A
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reactive distillation
tower
dimethyl ether
distillation column
formaldehyde
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CN110078600B (en
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高鑫
孟莹
李洪
李鑫钢
从海峰
韩振为
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Tianjin University
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/58—Separation; Purification; Stabilisation; Use of additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention provides a kind of reactive distillation process device and method for polymethoxy dimethyl ether synthesis, the process is to provide the technical grade dimethoxym ethane of product chain sealing end and provide the metaformaldehyde of product chain growth, paraformaldehyde, one or more kinds of mixtures of gaseous formaldehyde are raw material, anhydrous presence in reaction system, reaction obtains the right polymethoxy dimethyl ether mix products of poly under acidic catalyst effect, through polymethoxy dimethyl ether reactive distillation column centrifugation, tower reactor produces the reaction product that the degree of polymerization is greater than 2, the DMM2 of overhead extraction low polymerization degree, the complete dimethoxym ethane of unreacted；It is separated after tower reactor production through product purification tower, obtains target product DMM3~5, the DMM2 of low polymerization degree and the DMM6-10 for crossing high polymerization degree are back to polymethoxy dimethyl ether reactive distillation column；The complete dimethoxym ethane of unreacted is utilized as feedstock circulation.The present invention utilizes reactive distillation feature, and reaction process is greatly improved the conversion ratio of formaldehyde substance, improved the selectivity and yield of DMM3-5 with dimethoxym ethane excess.

Description

A kind of reactive distillation process device and method for polymethoxy dimethyl ether synthesis
Technical field
The invention belongs to chemical production technology and equipment technical fields, are related to polymethoxy dimethyl ether, are a kind of use by it In the reactive distillation process device and method of polymethoxy dimethyl ether synthesis.
Background technique
Polymethoxy dimethyl ether is the low molecular weight acetal polymer using methoxyl group as main chain, structural formula are as follows: CH3O (CH2O) nCH3, abbreviation DMMn (or PODEn).When n=3~8 (especially 3~5), substance Cetane number with higher And oxygen content, and element sulphur is not present in substance, it is a kind of diesel oil oxygenation agent of function admirable, exhaust gas from diesel vehicle can be greatly reduced The discharge amount of middle carbon monoxide and oxynitrides, does not generate sulfide.The addition of the substance is not necessarily to vehicle motor simultaneously It is transformed the combustibility that diesel oil just can be improved, is had great popularization value.
The synthesis material of DMMn mainly has dimethoxym ethane, methanol and dimethyl ether and formalin, metaformaldehyde, paraformaldehyde. Wherein dimethoxym ethane and metaformaldehyde, paraformaldehyde or gaseous formaldehyde are reacted due to that will not introduce water in its system, can reduce water Bring separating difficulty improves product quality, has greater advantage in operating cost.Such as: patent CN104355973B is proposed A kind of fixed bed reaction rectifying to prepare the method for polymethoxy dimethyl ether using dimethoxym ethane and metaformaldehyde be reactant in fixation It is separated after carrying out secondary tandem reaction in bed reactor and reactive distillation column through multistep, one kind that patent CN104974025A is proposed The method for producing polymethoxy dimethyl ether, this method are reactant with dimethoxym ethane and paraformaldehyde, through fluidized-bed reactor into Row reaction carries out the separation of reactant and reaction product by three rectifying, extracting rectifying and rectification under vacuum series units, such Process selection dimethoxym ethane is reactant, and in polymer reactor, reactant is unable to reach higher conversion by Equilibrium limit Rate is largely DMM2 in reaction product, and the selectivity and yield of target product DMM3~5 are lower, the recycle stock in process Amount is big, brings that energy consumption is high, the low defect of process economy；And patent CN104722249A proposes a kind of dimethoxym ethane and gaseous formaldehyde The method for obtaining polymethoxy dimethyl ether is reacted by two formulas of filler reaction tower and multistage reaction tower, though this method is using instead Rectifying column is answered to carry out second step reaction, but the introducing of methanol can reduce the conversion ratio of reaction in reactive distillation column and target product is received Rate, and stream stock internal circulating load between three towers is larger causes process energy consumption larger.Patent CN108484371A proposes a kind of tubulation Formula floating bed reactor prepares the process of polymethoxy dimethyl ether；It is anti-that German Jakob Burgera etc. proposes a kind of elder generation The technology that should be separated afterwards, the group of DMM3~5 becomes 33.43% after the method reactor reaction.But existing anhydrous trimerization first Aldehyde preparation need to be by technical process such as extraction and multistep rectifying, and manufacturing cost is higher, and the anhydrous metaformaldehyde market price is higher, gather Methoxyl group dimethyl ether is limited for process economy, and the reaction in reactor is still by reaction balance limitation, reaction conversion Rate and target product be not selectively still high, and recycle stream plume amount is larger, and process economy needs to be further improved.
Summary of the invention
In view of the above problems and defect, the object of the present invention is to provide one kind synthesizes for polymethoxy dimethyl ether Reactive distillation process device and method, using it is provided by the invention using reactive distillation as core process prepare high-purity DMM3~5 have very high reaction conversion ratio, can be effectively controlled reaction temperature, shorten reaction time, reduce recycle stream stock Amount improves the yield and selectivity of target product DMM3~5, and for simultaneous reactions process with dimethoxym ethane excess, chain propagation reaction object is anti- High conversion rate is answered, is reduced in subsequent separation process because formaldehyde is existing to separate complexity, the simple, equipment with process flow The advantages that investing lower, easy to operate, stable product quality, lower energy consumption.
The first technical solution of the invention is as follows:
A kind of reactive distillation process device for polymethoxy dimethyl ether synthesis of the invention, including polymethoxy diformazan Ether reactive distillation column, first class product treating column, secondary product treating column, light component knockout tower, dimethoxym ethane mixer, DMM2 mixing Device, it is characterised in that:
The polymethoxy dimethyl ether reactive distillation column overhead is furnished with complete condenser, and tower reactor is furnished with reboiler, polymethoxy Material inlet is set on dimethyl ether reactive distillation column tower, DMM6~10 recycles feed inlet, DMM2 recycles feed inlet, tower reactor setting Liquid phase produce mouth, tower top or for infinite reflux or setting liquid phase produce mouth, wherein material inlet be two, respectively with chain growth original Expect that feeding line and dimethoxym ethane mixer outlet pipeline are connected.
The first class product treating column and secondary product treating column is furnished in tower top equipped with complete condenser, tower reactor to boil again Liquid phase feeding mouth is arranged in device, tower body, and tower top, tower reactor are equipped with liquid phase extraction mouth, wherein first class product treating column material inlet It produces mouth with polymethoxy dimethyl ether reactive distillation column tower bottom liquid phase to connect by pipeline, overhead extraction mouth and DMM2 mixer are fed Pipeline is connected；Secondary product treating column material inlet and first class product treating column tower bottom liquid phase extraction mouth are connected by pipeline, and two Grade product purification tower tower reactor liquid phase extraction mouth recycles feed inlet with DMM6~10 and is connected by pipeline, secondary product refined tower top Liquid phase produces mouth and is connected with target product extraction pipeline.
The light component knockout tower, tower top are furnished with reboiler equipped with complete condenser, tower reactor, and tower top, tower reactor are equipped with liquid phase Mouth is produced, light component knockout tower setting feed inlet is connected with polymethoxy dimethyl ether reactive distillation column overhead extraction mouth, and tower reactor is adopted Outlet is connected with DMM2 mixer feeding line, and overhead extraction mouth is connected with dimethoxym ethane mixer feed inlet, and the equipment is according to anti- It answers system and catalyst characteristics and chooses whether to exist, then polymethoxy dimethyl ether reactive distillation column is infinite reflux behaviour if it does not exist Make.
Polymethoxy dimethyl ether reactive distillation column is made of rectifying section, conversion zone and stripping section or conversion zone and stripping section Composition or conversion zone and rectifying section composition；Rectifying section and stripping section tower internals are filler or tower tray；Conversion zone loads acid solid Catalyst, tower internals are catalytic filler type or catalysis tower plate type tower internals.
Two liquid phase reactor object feed inlets and two circulations are set on the conversion zone of polymethoxy dimethyl ether reactive distillation column Material feed inlet；Or a liquid phase reactor object feed inlet and two are set on the conversion zone of polymethoxy dimethyl ether reactive distillation column A vapor-phase reactant feed inlet is arranged in recycle stock feed inlet, conversion zone or stripping section.
Two product purification towers and a light component knockout tower tower internals are filler, tower tray.
A kind of reactive distillation process method for polymethoxy dimethyl ether synthesis of the invention includes the following steps:
Step 1, it will thus provide the dimethoxym ethane of product chain sealing end and metaformaldehyde, paraformaldehyde or the object of offer product chain growth The mixing of matter passes through polymethoxy dimethyl ether reactive distillation column from dimethoxym ethane mixer and chain propagation reaction object feeding line respectively Two liquid phase feeding mouths on conversion zone are fed respectively or dimethoxym ethane and gaseous formaldehyde react essence from polymethoxy dimethyl ether respectively It evaporates on tower raw material liquid phase feed inlet and a gas-phase feed mouth is fed respectively, reacted；
Step 2, high boiling point product DMM3~10 (containing micro DMM2) for reacting generation are reacted by polymethoxy dimethyl ether Rectifying column stripping section isolates reaction zone, produces from polymethoxy dimethyl ether reactive distillation column tower reactor liquid phase, reacts the low of generation Degree of polymerization product DMM2 and the complete dimethoxym ethane of unreacted are isolated instead by polymethoxy dimethyl ether reactive distillation column rectifying section Area is answered, is produced from polymethoxy dimethyl ether reactive distillation column tower top liquid phase pipeline；
Step 3, polymethoxy dimethyl ether reactive distillation column tower reactor extraction liquid phase are delivered to first class product treating column and second level Product purification tower carries out product purification, and first class product refined tower top isolates DMM2 and is delivered to DMM2 mixer, secondary product Refined tower top isolates high-purity target product DMM3~5 from the extraction pipeline extraction of tower top liquid phase；Tower reactor is isolated excessively high poly- Right product DMM6~10 produce from tower reactor liquid phase output pipeline and are delivered to polymethoxy dimethyl ether reactive distillation column circulation Material feed inlet；
Step 4, polymethoxy dimethyl ether reactive distillation column overhead or total reflux operation, are all back to polymethoxy diformazan Ether reactive distillation column overhead, or light component separation is carried out to be delivered to light component knockout tower after the extraction of certain reflux ratio liquid phase, gently Component knockout tower tower reactor isolates low polymerization degree product DMM2, and it is mixed through mixer to isolate DMM2 with first class product refined tower top It is back to polymethoxy dimethyl ether reactive distillation column reaction zone after conjunction and carries out secondary response, overhead extraction dimethoxym ethane enters first contracting It is reacted with after the mixing of dimethoxym ethane raw material into polymethoxy dimethyl ether reactive distillation column in aldehyde and mixer.
In the step 1, polymethoxy dimethyl ether reactive distillation column raw material metaformaldehyde or paraformaldehyde or gas phase first The quality of aldehyde and dimethoxym ethane is 0.6-4.5 than preferred scope.
In the step 2, the operating pressure preferred scope of polymethoxy dimethyl ether reactive distillation column is absolute pressure 2-7atm, The preferred scope of overhead reflux ratio is 0.1-5 or infinite reflux, and catalyst uses acidic solid catalyst, preferred acidic resin catalysis Agent or acid molecular sieve catalyst, usage amount preferred scope are 20-300kg/m3, the reaction of polymethoxy dimethyl ether reactive distillation column Section tower internals is catalytic filler or catalysis tower tray, and catalytic filler height is 2-5 meters, and catalysis tower tray is 8-35 block；It rectifying section and mentions Evaporating section tower internals is filler or tower tray, and rectifying section packed height is 1-5 meters, and tower tray is 5-30 block, and profit reduction and reserving section packed height is 0.5-4 meters, tower tray is 3-25 block.
In the step 3, first class product refined tower top operating pressure preferred scope is absolute pressure 0.5-1.5atm, tower top Reflux ratio preferred scope is 0.1-5, and tower internals is filler or tower tray, and packed height is 1-5 meters, and tower tray is 10-45 block；Second level produces Product refined tower top operating pressure preferred scope is absolute pressure 0.5-1.5atm, and overhead reflux is 0.2-3, tower internals than preferred scope For filler or tower tray, packed height is 1-5 meters, and tower tray is 10-45 block.
In the step 4, it is absolute pressure 0.5-1.8atm that light component, which separates column overhead operating pressure preferred scope, and tower top returns Stream is 0.1-3 than preferred scope, and tower internals is filler or tower tray, and packed height is 1-5 meters, and tower tray is 8-45 block.
Second of technical solution of the invention:
The raw material into the reactive distillation column of polymethoxy dimethyl ether is limited as anhydrous dimethoxym ethane and anhydrous metaformaldehyde.
The process includes formaldehyde preparation workshop section, oxymethylene polymerization workshop section, dimethoxym ethane preparation workshop section, polymethoxy dimethyl ether Reactive distillation prepares workshop section.Material benzenemethanol obtains formalin through processes such as oxidation reaction, absorptions in formaldehyde preparation workshop section, The product section obtains anhydrous metaformaldehyde through the Reaction Separation in oxymethylene polymerization workshop section-separation process, and another part contracts through first Aldehyde prepares workshop section and carries out reacting the anhydrous dimethoxym ethane of acquisition with methanol, and dimethoxym ethane enters polymethoxy dimethyl ether with metaformaldehyde and reacts Rectifying prepares the reacted separation of workshop section-separation process and obtains high-purity target product DMM3-5.
It includes methanol evaporator, gas mixer, preheater, oxidation reactor, water absorption tower that formaldehyde, which prepares workshop section,.Raw material Industrial methanol is gasificated into methanol gas through methanol evaporator, after enter in gas mixer with oxygen mix；Gaseous mixture is through pre- Hot device enters oxidation reactor progress methanol oxidation after being preheated to reaction temperature, obtains formaldehyde gas；Formaldehyde gas and Other gaseous impurities are then gone through in water absorption tower, are absorbed formaldehyde gas using water, are obtained formalin, foreign gas is then Go out from absorbing tower top row.
Oxymethylene polymerization workshop section includes oxymethylene polymerization reactive distillation column, Steam soak equipment, metaformaldehyde treating column.Formaldehyde system The formalin of standby workshop section's extraction enters in oxymethylene polymerization reactive distillation column, carries out polymerization reaction and generates metaformaldehyde, trimerization The mixture of formaldehyde and formaldehyde, water is produced by reactive distillation column separate rear part point from tower top with gas phase, and Partial Liquid Phase is returned Stream, and the water for being not involved in reaction produces after reactive distillation column separates from tower reactor.Overhead extraction metaformaldehyde and formaldehyde, water Gas phase mixture enters Steam soak equipment and carries out UF membrane, and water phase enters the per-meate side of Steam soak equipment and adopt through film Out, the mixed phase of metaformaldehyde, formaldehyde and minor amount of water enters metaformaldehyde afterwards and refines through Steam soak equipment retention side extraction Tower produces anhydrous metaformaldehyde through the rectifying column centrifugation tower reactor, and overhead extraction metaformaldehyde, formaldehyde are mixed with the liquid phase of water Object, which, which subsequently enters, carries out secondary separation in Steam soak equipment.
It includes dimethoxym ethane reactive distillation column that dimethoxym ethane, which prepares workshop section,.Formaldehyde prepare workshop section in formalin and methanol with The micro- excessive form of formaldehyde, which is added, is reacted and is separated into dimethoxym ethane reactive distillation column, and dimethoxym ethane reactive distillation column overhead is adopted Anhydrous dimethoxym ethane out, tower reactor produce the water containing trace formaldehyde.
It is identical as the first technical solution that polymethoxy dimethyl ether reactive distillation prepares workshop section.
Formaldehyde is prepared in workshop section, and the gas phase extraction temperature of methanol evaporator is higher than the methanol boiling temperature 0 under environmental pressure ~5 DEG C；The mass ratio of methanol steam and oxygen is the preferred mass of the oxygen in reactant methanol and air in gas mixer Than being 0.7~1.5；Mixture preheating temperature and reaction temperature difference are preferably -20 DEG C~20 DEG C by preheater before reacting；Oxidation is anti- Answering catalysts in device is metal or metal oxide catalyst, preferably iron-molybdic catalyst, and catalyst usage amount is 50- 280kg/m3, reaction preferable temperature is 200~800 DEG C；In water absorption tower formaldehyde and the quality of water charging preferably than for 0.4~ 2.3, tower internals is filler, and packed height is 1-8 meters；Content of formaldehyde is preferably 30-70% in this workshop section's product formalin.
In oxymethylene polymerization workshop section, a liquid phase reactor object feed inlet, conversion zone is arranged in oxymethylene polymerization reactive distillation column conversion zone Using Reaction Separation tower internals, tower internals is catalytic filler or catalysis tower tray, and catalytic filler height is 2-6 meters, and catalysis tower tray is 8-30 block, rectifying section and stripping section use filler or tower tray, and rectifying section filler is 1-5 meters, and tower tray is 4-25 block, stripping section filler It is 0.5-3 meters, tower tray is 2-15 block；The operating pressure of oxymethylene polymerization reactive distillation column is preferably 0.1~2atm of absolute pressure, and tower top returns Stream than preferably 0.5~5, catalyst use acidic resins or acid molecular sieve catalyst, catalyst usage amount be 20~ 300kg/m3；In Steam soak equipment the per-meate side of infiltrating and vaporizing membrane be negative-pressure operation, preferred pressure range 100-600kPa, Infiltrating and vaporizing membrane is permeable molecular screen membrane, preferably NaA film；Metaformaldehyde treating column tower internals uses filler or tower tray, filler Height is 2-6 meters, and tower tray is 8-40 block, and tower top operating pressure preferred scope is absolute pressure 0.5-2atm, and overhead reflux is than preferred model It encloses for 0.5-5.
Dimethoxym ethane is prepared in workshop section, and two liquid phase reactor object feed inlets are arranged on the conversion zone of dimethoxym ethane reactive distillation column, Conversion zone uses Reaction Separation tower internals, and tower internals is catalytic filler or catalysis tower tray, and catalytic filler height is 1.5-5 meters, urges Change tower tray is 6-25 block, and rectifying section and stripping section use filler or tower tray, and rectifying section filler is 1-5 meters, and tower tray is 4-25 block, is mentioned Evaporating section filler is 1-5 meters, and tower tray is 4-25 block；Operating pressure preferred scope is absolute pressure 0.3-1.5atm, reaction raw materials formalin The quality of formaldehyde and methanol is 0.46-0.5 than preferred scope in solution, and catalyst uses acidic solid catalyst (preferred acidic Molecular sieve catalyst), catalyst usage amount preferred scope is 20-300kg/m3, and overhead reflux is 0.5-10 than preferred scope.
The process unit for realizing second of technical solution includes formaldehyde preparation device；Oxymethylene polymerization device；Dimethoxym ethane preparation Device；Polymethoxy dimethyl ether reactive distillation preparation facilities, the formaldehyde preparation device include sequentially connected methanol evaporation Device, gas mixer, preheater, oxidation reactor, water absorption tower；The oxymethylene polymerization device includes oxymethylene polymerization reaction essence Evaporate tower, Steam soak equipment, metaformaldehyde treating column；The dimethoxym ethane preparation facilities includes dimethoxym ethane reactive distillation column；Water The tower reactor extraction mouth on absorption tower connects the feed inlet and dimethoxym ethane reactive distillation of oxymethylene polymerization reactive distillation column by pipeline respectively The reaction-ure feeding mouth of tower；Reaction-ure feeding mouth is arranged in oxymethylene polymerization reactive distillation column；Oxymethylene polymerization reactive distillation column overhead is adopted Outlet connection Steam soak equipment, Steam soak equipment retain the feed inlet of side extraction mouth connection metaformaldehyde treating column, trimerization The tower reactor extraction mouth of formaldehyde treating column connects polymethoxy dimethyl ether reactive distillation column material inlet；Dimethoxym ethane reactive distillation column Conversion zone on two reaction-ure feeding mouths are set, the overhead extraction mouth of dimethoxym ethane reactive distillation column connects poly- methoxy by pipeline Base dimethyl ether reactive distillation column material inlet.Polymethoxy dimethyl ether reactive distillation preparation facilities and the first technical solution Device is identical.
The third technical solution of the invention:
The raw material into the reactive distillation column of polymethoxy dimethyl ether is limited as anhydrous dimethoxym ethane and anhydrous gaseous formaldehyde.
The process includes formaldehyde preparation workshop section；Gaseous formaldehyde prepares workshop section；Dimethoxym ethane prepares workshop section；Polymethoxy two Methyl ether reactive distillation prepares workshop section.Material benzenemethanol generates formaldehyde through oxidation reaction in formaldehyde preparation workshop section, and reactor extraction contains The gaseous mixture of formaldehyde obtains formalin through absorption process after the mixing gas phase, through dimethoxym ethane system after the formalin of part Standby workshop section, which react with methanol, obtains anhydrous dimethoxym ethane；Part formalin is by the evaporation in gaseous formaldehyde preparation workshop section Device, Steam soak equipment, adsorbent equipment, obtain anhydrous gaseous formaldehyde；Dimethoxym ethane and gaseous formaldehyde enter polymethoxy dimethyl ether Reactive distillation prepares the reacted separation of workshop section-separation process and obtains high-purity target product DMM3-5.
Wherein formaldehyde preparation workshop section, dimethoxym ethane preparation workshop section are identical as second of technical solution.Polymethoxy dimethyl ether is anti- Answer rectifying preparation workshop section identical as the first technical solution.
It includes sequentially connected formalin evaporator, Steam soak equipment, adsorbent equipment that gaseous formaldehyde, which prepares workshop section,. The part formalin that absorption tower generates in formaldehyde preparation workshop section enters gaseous formaldehyde preparation workshop section, becomes gas by evaporator The water vapour in Steam soak equipment removal mixing gas phase is entered after phase, mixes gas phase after entering suctions water removal afterwards In residual water vapor, obtain anhydrous gaseous formaldehyde.
Gaseous formaldehyde is prepared in workshop section, and the gas phase extraction temperature of formalin evaporator is higher than the mixing under environmental pressure 10~60 DEG C of object boiling temperature；The per-meate side of infiltrating and vaporizing membrane is negative-pressure operation in Steam soak equipment, and preferred pressure range is 100-600kPa, infiltrating and vaporizing membrane are permeable molecular screen membrane, preferably NaA film；Adsorbent equipment takes capillary pressure device, inhales Attached gas phase water content is not more than 0.01%.
The device for realizing the technical program includes formaldehyde preparation device；Gaseous formaldehyde preparation facilities；Dimethoxym ethane preparation facilities； Polymethoxy dimethyl ether reactive distillation preparation facilities, the formaldehyde preparation device include sequentially connected methanol evaporator, gas Body mixer, preheater, oxidation reactor, water absorption tower；The gaseous formaldehyde preparation facilities includes sequentially connected formaldehyde Aqueous solution evaporator, Steam soak equipment, adsorbent equipment；The dimethoxym ethane preparation facilities includes dimethoxym ethane reactive distillation column； The tower reactor extraction mouth on water absorption tower connects the feed inlet and dimethoxym ethane reactive distillation of formalin evaporator by pipeline respectively The reaction-ure feeding mouth of tower；The outlet of formalin evaporator connects Steam soak equipment, and the outlet of Steam soak equipment connects Adsorbent equipment is connect, the outlet of adsorbent equipment connects polymethoxy dimethyl ether reactive distillation column material inlet；Dimethoxym ethane reaction essence Two reaction-ure feeding mouths of setting on the conversion zone of tower are evaporated, the overhead extraction mouth of dimethoxym ethane reactive distillation column connects poly- by pipeline Methoxyl group dimethyl ether reactive distillation column material inlet；Polymethoxy dimethyl ether reactive distillation preparation facilities and the first technical side The device of case is identical.
The advantages of the present invention:
1, the reactive distillation process method of the used polymethoxy dimethyl ether of the present invention uses dimethoxym ethane and anhydrous chain growth Reactant is raw material, eliminates the defects of water reacts system and separate the presence of bring back reaction and high separation complexity.
2, the present invention uses the advantage of reactive distillation processes, excessive using dimethoxym ethane reactant, and it is anti-to greatly improve chain growth Object conversion ratio is answered, later separation difficulty caused by existing because of formaldehyde is reduced, simultaneous reactions rectifying can in time take away reaction product Reaction zone prevents the excessively high polymerization of polymethoxy dimethyl ether, while breaking reaction balance limitation, promotes DMM2 to continue polymerization and generates Target product DMM3~5 reduce DMM2 production quantity, reduce the recycle stream stock amount of DMM2 and DMM6~10, effectively improve DMM3~5 Yield and selectivity.
3, process of the invention is with cheap industrial methanol for single raw material.Technique gives full play to reactive distillation The advantages of tower, effectively control reaction time, break reaction balance limitation, improve the reaction conversion ratio respectively reacted in process, Reaction Xiang Geng great degree of polymerization direction can be also prevented to carry out in polymethoxy dimethyl ether polymerization process simultaneously, to improve mesh Mark the yield of product DMM3~5 and selectivity.
4, the present invention is with the water in Steam soak equipment removal reactant, eliminate in the process system each substance and water it Between azeotropic situation, and make to bring about the desired sensation by excessive be added of dimethoxym ethane in reactive distillation in polymethoxy dimethyl ether preparation process Phase formaldehyde or paraformaldehyde fully reacting are reduced because formaldehyde and water have the complexity for leading to product purification process.
5, the present invention merely with two Steam soak equipment and an air separation column with regard to the subtractive process of achievable gaseous formaldehyde, Merely with a Steam soak equipment and a rectifying column with regard to the subtractive process of achievable metaformaldehyde reactant, work is effectively shortened Skill process and process unit number reduce energy consumption.
6, reaction temperature, reaction time and reaction process can in polymethoxy dimethyl ether reactive distillation column of the present invention Control, can make full use of reactive distillation advantage that the above substance of reaction product DMM3 is isolated reaction zone in time, reduce excessively high polymerization The trend that substance generates is spent, the conversion ratio of reactant and the reaction yield of target product DMM3~5 are improved, reduces recycle stream stock object Doses.
Detailed description of the invention
Fig. 1 is the first technical solution process flow diagram of the invention；
Fig. 2 is second of technical solution process flow diagram of the invention；
Fig. 3 is the third technical solution process flow diagram of the invention.
Specific embodiment
The invention will be further described with reference to the accompanying drawing and by specific embodiment, and following embodiment is descriptive , it is not restrictive, this does not limit the scope of protection of the present invention.
The first technical solution, as shown in Figure 1.
A kind of reactive distillation process method for polymethoxy dimethyl ether synthesis, includes the following steps:
Step 1, it will thus provide the dimethoxym ethane of product chain sealing end and metaformaldehyde, paraformaldehyde or the object of offer product chain growth The mixing of matter passes through polymethoxy dimethyl ether reactive distillation column 1 from dimethoxym ethane mixer and chain propagation reaction object feeding line respectively Two liquid phase feeding mouths on conversion zone are fed respectively or dimethoxym ethane and gaseous formaldehyde react essence from polymethoxy dimethyl ether respectively It evaporates on tower raw material liquid phase feed inlet and a gas-phase feed mouth is fed respectively, reacted；
Step 2, high boiling point product DMM3~10 (containing micro DMM2) for reacting generation are reacted by polymethoxy dimethyl ether Rectifying column stripping section isolates reaction zone, produces from polymethoxy dimethyl ether reactive distillation column tower reactor liquid phase, reacts the low of generation Degree of polymerization product DMM2 and the complete dimethoxym ethane of unreacted are isolated instead by polymethoxy dimethyl ether reactive distillation column rectifying section Area is answered, is produced from polymethoxy dimethyl ether reactive distillation column tower top liquid phase pipeline；Polymethoxy dimethyl ether reactive distillation column overhead Equipped with complete condenser 7, tower reactor is furnished with reboiler 8.
Step 3, polymethoxy dimethyl ether reactive distillation column tower reactor extraction liquid phase are delivered to first class product treating column 4 and second level Product purification tower 5 carries out product purification, and first class product refined tower top isolates DMM2 and is delivered to DMM2 mixer 3, and second level produces Product refined tower top isolates high-purity target product DMM3~5 from the extraction pipeline extraction of tower top liquid phase；Tower reactor is isolated excessively high Product DMM6~10 of the degree of polymerization produce from tower reactor liquid phase output pipeline and are delivered to polymethoxy dimethyl ether reactive distillation column and follow Ring material feed inlet；
Step 4, polymethoxy dimethyl ether reactive distillation column overhead or total reflux operation, are all back to polymethoxy diformazan Ether reactive distillation column overhead, or light component separation is carried out to be delivered to light component knockout tower 2 after the extraction of certain reflux ratio liquid phase, gently Component knockout tower tower reactor isolates low polymerization degree product DMM2, isolates DMM2 with first class product refined tower top and mixes through DMM2 Polymethoxy dimethyl ether reactive distillation column reaction zone is back to after device mixing and carries out secondary response, and overhead extraction dimethoxym ethane enters It is reacted with after the mixing of dimethoxym ethane raw material into polymethoxy dimethyl ether reactive distillation column in dimethoxym ethane mixer 6.
Technology and equipment of the invention is widely used in by dimethoxym ethane and anhydrous chain propagation reaction object (metaformaldehyde, poly Formaldehyde, gaseous formaldehyde) reaction prepares polymethoxy dimethyl ether, and it is pure in reaction conversion ratio, product in order to better illustrate the present invention The advantage of degree, product yield is chosen wherein three application examples and is illustrated, but and is not so limited the suitable of this technology and equipment Use range.
Embodiment 1:
The method of the present invention is used for dimethoxym ethane and metaformaldehyde and reacts polymethoxy dimethyl ether process processed in acid condition, It is identical as process of the present invention, including the purification of polymethoxy dimethyl ether reactive distillation column, first class product treating column, secondary product Tower, light component knockout tower, dimethoxym ethane mixer, DMM2 mixer.Dimethoxym ethane and metaformaldehyde are respectively from two on conversion zone Liquid phase feeding mouth enters in polymethoxy dimethyl ether reactive distillation column, and dimethoxym ethane feed inlet is under metaformaldehyde feed inlet Side.The mass ratio of polymethoxy dimethyl ether reactive distillation column raw material metaformaldehyde and dimethoxym ethane is 4.5, and polymethoxy dimethyl ether is anti- Answering rectifying column operating pressure is absolute pressure 4atm, and overhead reflux ratio is 0.5, and catalyst uses acid resin catalyst, and catalyst makes Dosage preferred scope is 200kg/m3, polymethoxy dimethyl ether reactive distillation column conversion zone tower internals is catalytic filler, and catalysis is filled out Material height is 4 meters；Rectifying section and stripping section tower internals are filler, and rectifying section packed height is that 3 meters of profit reduction and reserving section packed heights are 3 Rice.First class product refined tower top operating pressure is absolute pressure 1atm, and for overhead reflux than 0.1, tower internals is filler, and packed height is 3 meters；Secondary product refined tower top operating pressure is absolute pressure 1atm, and overhead reflux is 0.2 than preferred scope, and tower internals is to fill out Material, packed height are 4 meters.It is absolute pressure 0.5atm that light component, which separates column overhead operating pressure, and overhead reflux is than preferred scope 0.1, tower internals is filler, and packed height is 4 meters.
After the above process, up to 99.5%, the purity of target product DMM3~5 can reach reactant metaformaldehyde conversion ratio Total recovery to 99.6%, DMM3~5 can achieve 98.5% or more.
Embodiment 2:
The method of the present invention is used for dimethoxym ethane and paraformaldehyde and reacts polymethoxy dimethyl ether process processed in acid condition, It is identical as process of the present invention, including the purification of polymethoxy dimethyl ether reactive distillation column, first class product treating column, secondary product Tower, light component knockout tower, dimethoxym ethane mixer, DMM2 mixer.Dimethoxym ethane and paraformaldehyde are respectively from two on conversion zone Liquid phase feeding mouth enters in polymethoxy dimethyl ether reactive distillation column, and dimethoxym ethane feed inlet is under paraformaldehyde feed inlet Side.The mass ratio of polymethoxy dimethyl ether reactive distillation column raw material paraformaldehyde and dimethoxym ethane is 2, polymethoxy dimethyl ether reaction Rectifying column operating pressure is absolute pressure 2atm, and overhead reflux ratio is infinite reflux, and catalyst uses acid molecular sieve catalyst, catalyst Usage amount is 100kg/m3, polymethoxy dimethyl ether reactive distillation column conversion zone tower internals is catalysis tower tray, and catalysis tower tray is 25 Block；Rectifying section and stripping section tower internals are tower tray, and tower tray is 20 pieces, and tower tray is 15 pieces.First class product refined tower top operation pressure Power is absolute pressure 0.5atm, and overhead reflux ratio is 2, and tower internals is tower tray, and tower tray is 30 pieces；Secondary product refined tower top operation pressure Power is absolute pressure 0.5atm, and overhead reflux ratio is 1.5, and tower internals is tower tray, and tower tray is 30 pieces.
After the above process, up to 99.3%, the purity of target product DMM3~5 can reach reactant paraformaldehyde conversion ratio Total recovery to 99.5%, DMM3~5 can achieve 98% or more.
Embodiment 3:
The method of the present invention is used for dimethoxym ethane and gaseous formaldehyde and reacts polymethoxy dimethyl ether process processed in acid condition, It is identical as process of the present invention, including the purification of polymethoxy dimethyl ether reactive distillation column, first class product treating column, secondary product Tower, light component knockout tower, dimethoxym ethane mixer, DMM2 mixer.Dimethoxym ethane and gaseous formaldehyde are respectively from the liquid phase on conversion zone The gas-phase feed mouth of feed inlet and stripping section has respectively entered in polymethoxy dimethyl ether reactive distillation column, and dimethoxym ethane feed inlet Above gaseous formaldehyde feed inlet.The mass ratio of polymethoxy dimethyl ether reactive distillation column raw material gaseous formaldehyde and dimethoxym ethane is 0.6, polymethoxy dimethyl ether reactive distillation column operating pressure is absolute pressure 7atm, and overhead reflux ratio is 5, and catalyst is using acid tree Rouge catalyst, catalyst usage amount are 300kg/m3, polymethoxy dimethyl ether reactive distillation column conversion zone tower internals is that catalysis is filled out Material, catalytic filler height are 3.5 meters；Rectifying section and stripping section tower internals are filler, and rectifying section packed height is 2.5 meters, profit reduction and reserving Section packed height is 2 meters.First class product refined tower top operating pressure is absolute pressure 1.5atm, and overhead reflux ratio is 5, and tower internals is Filler, packed height are 3.5 meters；Secondary product refined tower top operating pressure is absolute pressure 1.5atm, and overhead reflux ratio is 3, tower Internals are filler, and packed height is 3.5 meters.It is absolute pressure 1.8atm that light component, which separates column overhead operating pressure, and overhead reflux ratio is 3, tower internals is filler, and packed height is 2 meters.
After the above process, up to 99.2%, the purity of target product DMM3~5 can achieve reactant formaldehyde conversion The total recovery of 99.1%, DMM3~5 can achieve 97.8% or more.
Second of technical solution, as shown in Figure 2.
A kind of process of dimethoxym ethane and metaformaldehyde route methanol DMMn, including formaldehyde prepare workshop section；Formaldehyde is poly- Close workshop section；Dimethoxym ethane prepares workshop section；Polymethoxy dimethyl ether reactive distillation prepares workshop section.Material benzenemethanol is in formaldehyde preparation workshop section Formalin is obtained through processes such as oxidation reaction, absorptions, the product section is through Reaction Separation-separation in oxymethylene polymerization workshop section Process obtains anhydrous metaformaldehyde, and another part react with methanol through dimethoxym ethane preparation workshop section obtains anhydrous dimethoxym ethane, first Acetal and metaformaldehyde enter polymethoxy dimethyl ether reactive distillation preparation workshop section it is reacted separate-separation process obtains high-purity Target product DMM3-5.
It includes sequentially connected methanol evaporator 9, gas mixer 10, preheater 11, oxidation reaction that formaldehyde, which prepares workshop section, Device 12, water absorption tower 13.Primary industry methanol is gasificated into methanol gas through methanol evaporator, after enter in gas mixer with Oxygen mix；The preheated device of gaseous mixture enters oxidation reactor progress methanol oxidation after being preheated to reaction temperature, obtains Formaldehyde gas；Formaldehyde gas and other gaseous impurities are then gone through in water absorption tower, are absorbed formaldehyde gas using water, are obtained first Aldehyde aqueous solution, foreign gas then go out from absorbing tower top row.
Oxymethylene polymerization workshop section includes oxymethylene polymerization reactive distillation column 14, Steam soak equipment 15, metaformaldehyde treating column 16. The formalin of formaldehyde preparation workshop section extraction enters in oxymethylene polymerization reactive distillation column, carries out polymerization reaction and generates trimerization first The mixture of aldehyde, metaformaldehyde and formaldehyde, water divides from tower top by oxymethylene polymerization reactive distillation column separate rear part with gas phase Extraction, Partial Liquid Phase reflux, and the water for being not involved in reaction produces after the separation of oxymethylene polymerization reactive distillation column from tower reactor.Tower top The gas phase mixture of extraction metaformaldehyde and formaldehyde, water enters Steam soak equipment and carries out UF membrane, and water phase enters steaming through film The per-meate side and extraction, the mixed phase of metaformaldehyde, formaldehyde and minor amount of water of vapour penetration equipment are adopted through Steam soak equipment retention side Out, enter metaformaldehyde treating column afterwards, produce anhydrous metaformaldehyde through the metaformaldehyde rectifying column centrifugation tower reactor, tower top is adopted The liquid phase mixture of metaformaldehyde, formaldehyde and water out, the mixture subsequently enter Steam soak equipment in middle carry out secondary separation.
It includes dimethoxym ethane reactive distillation column 17 that dimethoxym ethane, which prepares workshop section,.Formaldehyde prepares the formalin and methanol in workshop section By formaldehyde it is micro- it is excessive in the form of be added and reacted and separated into dimethoxym ethane reactive distillation column, dimethoxym ethane reactive distillation column overhead Anhydrous dimethoxym ethane is produced, tower reactor produces the water containing trace formaldehyde.
It is identical as the first technical solution that polymethoxy dimethyl ether reactive distillation prepares workshop section.
In order to better illustrate the present invention in the advantage of reaction conversion ratio, product purity, product yield and energy consumption, it is chosen In 3 application examples be illustrated, but and be not so limited the scope of application of this technology and equipment.
Embodiment 4
Formaldehyde is prepared in workshop section, and the gas phase extraction temperature of methanol evaporator is higher than the methanol boiling temperature 0 under environmental pressure ℃；The mass ratio of methanol steam and oxygen is 1.5 in gas mixer；React before preheater by mixture preheating temperature with react Temperature difference is 20 DEG C；Catalysts are iron-molybdic catalyst in oxidation reactor, and the dosage of catalyst is 280kg/m3, oxidation is instead Answering device reaction temperature is 200 DEG C；Formaldehyde and the mass ratio of water charging are 0.4 in water absorption tower, and packed height is 6 meters；This workshop section Content of formaldehyde is 30% in product formalin.
In oxymethylene polymerization workshop section, the operating pressure of oxymethylene polymerization reactive distillation column is absolute pressure 0.1atm, and overhead reflux ratio is 5, catalyst is acid resin catalyst, and catalyst usage amount is 300kg/m3, the catalysis of oxymethylene polymerization reactive distillation column conversion zone Packed height is 4 meters, and rectifying section filler is 2 meters, and stripping section filler is 1 meter；Steam soak equipment pressure is 600kPa；Trimerization first Aldehyde refined tower top operating pressure is absolute pressure 2atm, and overhead reflux ratio is 5, and packed height is 5 meters.
Dimethoxym ethane is prepared in workshop section, and dimethoxym ethane reactive distillation column operating pressure is absolute pressure 0.3atm, reaction raw materials formalin The mass ratio of formaldehyde and methanol is 0.5 in solution, and catalyst uses acid molecular sieve catalyst, and catalyst usage amount is 300kg/ m3, overhead reflux ratio is 0.5, and conversion zone catalytic filler height is 3 meters, and rectifying section filler is 3 meters, and stripping section filler is 3 meters.
Polymethoxy dimethyl ether reactive distillation is prepared in workshop section, and the operating pressure of polymethoxy dimethyl ether reactive distillation column is The mass ratio of absolute pressure 6atm, reaction raw materials metaformaldehyde and dimethoxym ethane is 0.6, and catalyst is acid resin catalyst, catalyst Usage amount is 200kg/m3, overhead reflux ratio is 5, and conversion zone catalytic filler height is 4 meters, and rectifying section packed height is 3 meters, is mentioned Evaporating section packed height is 3 meters；First class product refined tower top operating pressure is absolute pressure 0.5atm, and overhead reflux ratio is 0.1, filler Height is 3 meters；Secondary product treating column tower internals tower top operating pressure is absolute pressure 0.5atm, and overhead reflux ratio is 0.2, and filler is high Degree is 4 meters；It is absolute pressure 0.5atm that light component, which separates column overhead operating pressure, and overhead reflux ratio is 0.1, and packed height is 4 meters.
After the above process, up to 99.3%, the purity of target product DMM3~5 can achieve reactant methanol total conversion The total recovery of 99.4%, DMM3~5 can achieve 98.2% or more.
Embodiment 5
Formaldehyde is prepared in workshop section, and the gas phase extraction temperature of methanol evaporator is higher than the methanol boiling temperature 5 under environmental pressure ℃；The mass ratio of methanol steam and oxygen is 1.5 in gas mixer；React before preheater by mixture preheating temperature with react Temperature difference is -20 DEG C；Catalysts iron-molybdic catalyst in oxidation reactor, catalyst amount 80kg/m3, reaction temperature is 800℃；Formaldehyde and the mass ratio of water charging are 2.3 in water absorption tower, and packed height is 5 meters；This workshop section's product formalin Middle content of formaldehyde is 70%.
In oxymethylene polymerization workshop section, the operating pressure of oxymethylene polymerization reactive distillation column is absolute pressure 2atm, and overhead reflux ratio is 0.5, catalyst is acid molecular sieve catalyst, and catalyst usage amount is 50kg/m3, it is 20 pieces that conversion zone, which is catalyzed tower tray, rectifying Duan Tapan is 15 pieces, and stripping section tower tray is 10 pieces；Steam soak equipment pressure is 100kPa；The operation of metaformaldehyde refined tower top Pressure is absolute pressure 0.5atm, and overhead reflux ratio is 0.5, and tower tray is 35 pieces.
Dimethoxym ethane is prepared in workshop section, and dimethoxym ethane reactive distillation column operating pressure is absolute pressure 1.5atm, reaction raw materials formalin The mass ratio of formaldehyde and methanol is 0.46 in solution, and catalyst is acid molecular sieve catalyst, and catalyst usage amount is 20kg/ M3, overhead reflux ratio are 10, and it is 15 pieces that conversion zone, which is catalyzed tower tray, and rectifying section tower tray is 15 pieces, and stripping section tower tray is 15 pieces.
Polymethoxy dimethyl ether reactive distillation is prepared in workshop section, and the operating pressure of polymethoxy dimethyl ether reactive distillation column is The mass ratio of absolute pressure 2atm, reaction raw materials metaformaldehyde and dimethoxym ethane is 4.5, and catalyst is acid molecular sieve catalyst, catalysis Agent usage amount is 300kg/m3, and overhead reflux ratio is infinite reflux, and it is 25 pieces that conversion zone, which is catalyzed tower tray, and rectifying section tower tray is 20 pieces, Stripping section tower tray is 15 pieces；First class product refined tower top operating pressure is absolute pressure 1.5atm, and overhead reflux ratio is 5, and tower tray is 30 pieces；Secondary product treating column tower internals tower top operating pressure is absolute pressure 1.5atm, and overhead reflux ratio is 3, and tower tray is 30 pieces；It is poly- Methoxyl group dimethyl ether reactive distillation column is that then overhead extraction object needs not move through light component knockout tower for total reflux operation.
After the above process, up to 99.5%, the purity of target product DMM3~5 can achieve reactant methanol total conversion The total recovery of 99.5%, DMM3~5 can achieve 98.1% or more.
Embodiment 6
Formaldehyde is prepared in workshop section, and the gas phase extraction temperature of methanol evaporator is higher than the methanol boiling temperature 3 under environmental pressure ℃；It is 1.2 that the mass ratio of methanol steam and oxygen, which is the mass ratio of the oxygen in reactant methanol and air, in gas mixer； Mixture preheating temperature and reaction temperature difference are 10 DEG C by preheater before reacting；Catalysts are that iron molybdenum is urged in oxidation reactor Agent, the dosage of catalyst are 150kg/m3, reaction temperature is 600 DEG C in oxidation reactor；In water absorption tower formaldehyde and water into The mass ratio of material is 2, and filler is 6 meters；Content of formaldehyde is 67% in this workshop section's product formalin.
In oxymethylene polymerization workshop section, the operating pressure of oxymethylene polymerization reactive distillation column is absolute pressure 1atm, and overhead reflux ratio is 1, Catalyst is acid resin catalyst, and catalyst usage amount is 200kg/m3, conversion zone catalytic filler height is 4.5 meters, rectifying Section filler is 2.5 meters, and stripping section filler is 0.5 meter；Steam soak equipment pressure is 400kPa；Metaformaldehyde refined tower top behaviour Making pressure is absolute pressure 0.8atm, and overhead reflux ratio is 1.5, and packed height is 4 meters.
Dimethoxym ethane is prepared in workshop section, and dimethoxym ethane reactive distillation column operating pressure is absolute pressure 1atm, and reaction raw materials formaldehyde is water-soluble The mass ratio of formaldehyde and methanol is 0.5 in liquid, and catalyst is acid molecular sieve catalyst, and catalyst usage amount is 150kg/m3, Overhead reflux ratio is 2, and conversion zone catalytic filler height is 4 meters, and rectifying section filler is 2 meters, and stripping section filler is 2 meters.
Polymethoxy dimethyl ether reactive distillation is prepared in workshop section, and the operating pressure of polymethoxy dimethyl ether reactive distillation column is The mass ratio of absolute pressure 5atm, reaction raw materials metaformaldehyde and dimethoxym ethane is 4, and catalyst uses acid resin catalyst, catalyst Usage amount is 220kg/m3, and overhead reflux ratio is 1, and conversion zone catalytic filler height is 3.5 meters, and rectifying section packed height is 2.5 Rice, stripping section packed height are 2 meters；First class product refined tower top operating pressure is absolute pressure 1atm, and overhead reflux ratio is 0.8, Packed height is 3.5 meters；Secondary product treating column tower internals tower top operating pressure is absolute pressure 1atm, and overhead reflux ratio is 2, filler Height is 3.5 meters；It is absolute pressure 1atm that light component, which separates column overhead operating pressure, and overhead reflux ratio is 2, and packed height is 2 meters.
After the above process, up to 99.6%, the purity of target product DMM3~5 can achieve reactant methanol total conversion The total recovery of 99.5%, DMM3~5 can achieve 98.8% or more.
The third technical solution, as shown in Figure 3.
A kind of methanol prepares the process of polymethoxy dimethyl ether, including formaldehyde prepares workshop section；Gaseous formaldehyde prepares work Section；Dimethoxym ethane prepares workshop section；Polymethoxy dimethyl ether reactive distillation prepares workshop section.Material benzenemethanol is in formaldehyde preparation workshop section through oxygen Change, which is reacted, generates formaldehyde, gaseous mixture of the reactor extraction containing formaldehyde, obtains formalin through absorption process after the mixing gas phase, React with methanol through dimethoxym ethane preparation workshop section after the formalin of part and obtains anhydrous dimethoxym ethane；Part formalin warp Cross gaseous formaldehyde preparation workshop section in evaporator, Steam soak equipment, adsorbent equipment, obtain anhydrous gaseous formaldehyde；Dimethoxym ethane with Gaseous formaldehyde enters the polymethoxy dimethyl ether reactive distillation preparation reacted separation of workshop section-separation process and obtains high-purity target and produce Object DMM3-5.
Formaldehyde prepares workshop section, dimethoxym ethane preparation workshop section with the second technical solution.The preparation of polymethoxy dimethyl ether reactive distillation Workshop section is the same as the first technical solution.
Gaseous formaldehyde preparation workshop section includes sequentially connected formalin evaporator 18, Steam soak equipment 19, absorption Device 20.The part formalin that absorption tower generates in formaldehyde preparation workshop section enters gaseous formaldehyde preparation workshop section, through pervaporation Device enters the water vapour in Steam soak equipment removal mixing gas phase after becoming gas phase, after entering suctions water removal afterwards The residual water vapor in gas phase is mixed, anhydrous gaseous formaldehyde is obtained.
In order to better illustrate the present invention in the advantage of reaction conversion ratio, product purity, product yield and energy consumption, it is chosen In 3 application examples be illustrated, but and be not so limited the scope of application of this technology and equipment.
Embodiment 7
Formaldehyde is prepared in workshop section, and the gas phase extraction temperature of methanol evaporator is higher than the methanol boiling temperature 0 under environmental pressure ℃；The mass ratio of methanol steam and oxygen is 0.7 in gas mixer；React before preheater mixture preheating temperature with react Temperature difference is -20 DEG C；Oxidation reactor reaction temperature is 800 DEG C, and catalysts are iron-molybdic catalyst in oxidation reactor, is urged The dosage of agent is 80kg/m3；Formaldehyde and the mass ratio of water charging are 0.4 in water absorption tower, and packed height is 6 meters；This workshop section Content of formaldehyde is 30% in product formalin.
Gaseous formaldehyde is prepared in workshop section, and the gas phase extraction temperature of formalin evaporator is higher than the mixing under environmental pressure 10 DEG C of object boiling temperature；The per-meate side of infiltrating and vaporizing membrane is negative-pressure operation, pressure 100kPa, absorption dress in Steam soak equipment It sets and takes capillary pressure device, gas phase water content is 0.009% after absorption.
Dimethoxym ethane is prepared in workshop section, and dimethoxym ethane reactive distillation column operating pressure is absolute pressure 0.3atm, reaction raw materials formalin The mass ratio of formaldehyde and methanol is 0.5 in solution, and catalyst uses acid molecular sieve catalyst, and catalyst usage amount is 50kg/ m3, overhead reflux ratio is 0.5, and conversion zone catalytic filler height is 3 meters, and rectifying section filler is 3 meters, and stripping section filler is 3 meters.
Polymethoxy dimethyl ether reactive distillation is prepared in workshop section, and polymethoxy dimethyl ether reactive distillation column operating pressure is exhausted The mass ratio of pressure 2atm, reaction raw materials gas phase formaldehyde and dimethoxym ethane is 4.5, and catalyst is acid resin catalyst, and catalyst makes Dosage is 300kg/m3, overhead reflux ratio is infinite reflux, and it is 25 pieces that conversion zone, which is catalyzed tower tray, and rectifying section tower tray is 20 pieces, stripping Duan Tapan is 15 pieces；First class product refined tower top operating pressure is absolute pressure 0.5atm, and overhead reflux ratio is 0.1, packed height It is 3 meters；Secondary product treating column column overhead operating pressure is absolute pressure 0.5atm, and overhead reflux ratio is 0.2, and packed height is 4 meters.
After the above process, up to 98.8%, the purity of target product DMM3~5 can achieve reactant methanol total conversion The total recovery of 99.2%, DMM3~5 can achieve 98.0% or more.
Embodiment 8
Formaldehyde is prepared in workshop section, and the gas phase extraction temperature of methanol evaporator is higher than the methanol boiling temperature 5 under environmental pressure ℃；The mass ratio of methanol steam and oxygen is 1.5 in gas mixer；React before preheater mixture preheating temperature with react Temperature difference is 20 DEG C；Oxidation reactor reaction temperature is 200 DEG C, and catalyst is iron-molybdic catalyst, catalyst amount 280kg/ m3；Formaldehyde and the mass ratio of water charging are 2.3 in water absorption tower, and packed height is 5 meters；First in this workshop section's product formalin Aldehyde is 70%.
Gaseous formaldehyde is prepared in workshop section, and the gas phase extraction temperature of formalin evaporator is higher than the mixing under environmental pressure 60 DEG C of object boiling temperature；The per-meate side of infiltrating and vaporizing membrane is negative-pressure operation, pressure 600kPa, absorption dress in Steam soak equipment It sets and takes capillary pressure device, gas phase water content is 0.009% after absorption.
Dimethoxym ethane is prepared in workshop section, and dimethoxym ethane reactive distillation column operating pressure is absolute pressure 1.5atm, reaction raw materials formalin The mass ratio of formaldehyde and methanol is 0.46 in solution, and catalyst is acid molecular sieve catalyst, and catalyst usage amount is 300kg/ m3, overhead reflux ratio is 10, and it is 15 pieces that conversion zone, which is catalyzed tower tray, and rectifying section tower tray is 15 pieces, and stripping section tower tray is 15 pieces.
Polymethoxy dimethyl ether reactive distillation is prepared in workshop section, and polymethoxy dimethyl ether reactive distillation column operating pressure is exhausted The mass ratio of pressure 7atm, reaction raw materials gas phase formaldehyde and dimethoxym ethane is 0.6, and catalyst is acid resin catalyst, and catalyst makes Dosage is 50kg/m3, overhead reflux ratio is 0.1, and conversion zone catalytic filler height is 4 meters, and rectifying section packed height is 3 meters, Stripping section packed height is 3 meters；First class product refined tower top operating pressure is absolute pressure 1.5atm, and overhead reflux ratio is 5, tower tray It is 30 pieces；Secondary product treating column column overhead operating pressure is absolute pressure 1.5atm, and overhead reflux ratio is 3, and tower tray is 30 pieces；Light group Dividing knockout tower column overhead operating pressure is absolute pressure 1.8atm, and overhead reflux ratio is 3, and tower tray is 35 pieces.
After the above process, up to 99.1%, the purity of target product DMM3~5 can achieve reactant methanol total conversion The total recovery of 99.1%, DMM3~5 can achieve 97.9% or more.
Embodiment 9
Formaldehyde is prepared in workshop section, and the gas phase extraction temperature of methanol evaporator is higher than the methanol boiling temperature 3 under environmental pressure ℃；The mass ratio of methanol steam and oxygen is 0.9 in gas mixer；React before preheater mixture preheating temperature with react Temperature difference is -5 DEG C；Oxidation reactor reaction temperature is that catalysts are iron-molybdic catalyst in 600 DEG C of oxidation reactors, catalysis The dosage of agent is 150kg/m3；Formaldehyde and the mass ratio of water charging are 2 in water absorption tower, and filler is 6 meters；This workshop section's product formaldehyde Formaldehyde in aqueous solution content is 67%.
Gaseous formaldehyde is prepared in workshop section, and the gas phase extraction temperature of formalin evaporator is higher than the mixing under environmental pressure 50 DEG C of object boiling temperature；The per-meate side of infiltrating and vaporizing membrane is negative-pressure operation, pressure 400kPa, absorption dress in Steam soak equipment It sets and takes capillary pressure device, gas phase water content is 0.007% after absorption.
Dimethoxym ethane is prepared in workshop section, and dimethoxym ethane reactive distillation column operating pressure is absolute pressure 1atm, and reaction raw materials formaldehyde is water-soluble The mass ratio of formaldehyde and methanol is 0.5 in liquid, and catalyst is acid molecular sieve catalyst, and catalyst usage amount is 300kg/m3, Overhead reflux ratio is 3, and conversion zone catalytic filler height is 4 meters, and rectifying section filler is 2 meters, and stripping section filler is 2 meters.
Polymethoxy dimethyl ether reactive distillation is prepared in workshop section, and polymethoxy dimethyl ether reactive distillation column operating pressure is exhausted The mass ratio of pressure 6atm, reaction raw materials gas phase formaldehyde and dimethoxym ethane is 3, and catalyst uses acid resin catalyst, and catalyst makes Dosage is 200kg/m3, and overhead reflux ratio is 2, and conversion zone catalytic filler height is 3.5 meters, and rectifying section packed height is 2.5 Rice, stripping section packed height are 2 meters；First class product refined tower top operating pressure is absolute pressure 1atm, and overhead reflux ratio is 0.5, Packed height is 3.5 meters；Secondary product treating column column overhead operating pressure is absolute pressure 1atm, and overhead reflux ratio is 2, packed height It is 3.5 meters；Light component knockout tower column overhead operating pressure is absolute pressure 1atm, and overhead reflux ratio is 2, and packed height is 2 meters.
After the above process, up to 99.1%, the purity of target product DMM3~5 can achieve reactant methanol total conversion The total recovery of 99.3%, DMM3~5 can achieve 98.2% or more.
A kind of reactive distillation process device and method for polymethoxy dimethyl ether synthesis proposed by the present invention, has passed through Preferred embodiment is described, related technical personnel obviously can not depart from the content of present invention, in spirit and scope to herein The equipment and process flow is modified or suitably changes and forms, Lai Shixian the technology of the present invention.In particular It is that all similar replacements and change are apparent to those skilled in the art, they are considered as being included in In spirit of that invention, range and content.

Claims (10)

1. a kind of reactive distillation process method for polymethoxy dimethyl ether synthesis, it is characterised in that:
The dimethoxym ethane for providing product chain sealing end and the raw material for providing product chain growth are reacted by polymethoxy dimethyl ether respectively Two throat-feds in distillation column reactor section；In conversion zone filling solid acid catalyst, the high boiling point product of generation is reacted DMM3~10, part low polymerization degree product DMM2 isolate reaction zone by polymethoxy dimethyl ether reactive distillation column stripping section, It is produced from polymethoxy dimethyl ether reactive distillation column tower reactor liquid phase, reacts the part DMM2 and the complete dimethoxym ethane of unreacted of generation Reaction zone is isolated by polymethoxy dimethyl ether reactive distillation column rectifying section, from polymethoxy dimethyl ether reactive distillation column overhead The extraction of liquid phase pipeline；
Polymethoxy dimethyl ether reactive distillation column tower reactor Produced Liquid is mutually successively delivered to first class product treating column and secondary product essence Tower processed carries out product purification, and first class product refined tower top isolates DMM2 and is delivered to DMM2 mixer, secondary product treating column Tower top isolates high-purity target product DMM3~5 from the extraction pipeline extraction of tower top liquid phase；Tower reactor isolated high polymerization degree Product DMM6~10 produced from tower reactor liquid phase output pipeline and be delivered to polymethoxy dimethyl ether reactive distillation column recycle stock into Material mouth；
Polymethoxy dimethyl ether reactive distillation column overhead or total reflux operation are all back to polymethoxy dimethyl ether reactive distillation Column overhead, or light component separation, light component knockout tower are carried out to be delivered to light component knockout tower after the extraction of certain reflux ratio liquid phase Tower reactor isolates low polymerization degree product DMM2, isolates after DMM2 is mixed through mixer and is back to first class product refined tower top Polymethoxy dimethyl ether reactive distillation column reaction zone carries out secondary response, and overhead extraction dimethoxym ethane enters dimethoxym ethane and mixer In with dimethoxym ethane raw material mixing after enter polymethoxy dimethyl ether reactive distillation column reacted.
2. the reactive distillation process method according to claim 1 for polymethoxy dimethyl ether synthesis, it is characterised in that: The process further includes providing the dimethoxym ethane of product chain sealing end and providing the preparation process of the raw material of product chain growth, described The raw material for providing product chain growth is metaformaldehyde, which prepares workshop section, first by starting material including formaldehyde of methanol Aldehyde polymerization workshop section, dimethoxym ethane prepare workshop section, and material benzenemethanol obtains first through oxidation reaction, water absorption process in formaldehyde preparation workshop section Aldehyde aqueous solution, formalin respectively enters oxymethylene polymerization workshop section and dimethoxym ethane preparation workshop section, in oxymethylene polymerization workshop section by anti- - anhydrous the metaformaldehyde of separation process acquisition should be separated, react with methanol obtaining anhydrous dimethoxym ethane in dimethoxym ethane preparation workshop section, Anhydrous dimethoxym ethane and anhydrous metaformaldehyde enter polymethoxy dimethyl ether reactive distillation column and obtain by Reaction Separation-separation process High-purity target product DMM3-5.
3. the reactive distillation process method according to claim 1 for polymethoxy dimethyl ether synthesis, it is characterised in that: The process further includes providing the dimethoxym ethane of product chain sealing end and providing the preparation process of the raw material of product chain growth, described The raw material for providing product chain growth is anhydrous gaseous formaldehyde, which prepares work by starting material including formaldehyde of methanol Section, gaseous formaldehyde preparation workshop section, dimethoxym ethane prepare workshop section, and material benzenemethanol generates first through oxidation reaction in formaldehyde preparation workshop section Aldehyde obtains formalin through water absorption process, and part formalin react obtaining through dimethoxym ethane preparation workshop section with methanol Obtain anhydrous dimethoxym ethane；Part formalin obtains anhydrous gaseous formaldehyde by gaseous formaldehyde preparation workshop section；Anhydrous dimethoxym ethane with Anhydrous gaseous formaldehyde enters the reacted separation of polymethoxy dimethyl ether reactive distillation column-separation process and obtains high-purity target product DMM3-5。
4. the reactive distillation process method according to claim 2 or 3 for polymethoxy dimethyl ether synthesis, feature exist In: the formaldehyde preparation workshop section includes sequentially connected methanol evaporator, gas mixer, preheater, oxidation reactor, water Absorption tower, primary industry methanol are gasificated into formaldehyde gas through methanol evaporator, after enter in gas mixer with oxygen mix； The preheated device of gaseous mixture enters oxidation reactor progress methanol oxidation after being preheated to reaction temperature, obtains formaldehyde gas； Formaldehyde gas and other gaseous impurities are then gone through in water absorption tower, are absorbed formaldehyde gas using water, are obtained high-concentration formaldehyde Aqueous solution, foreign gas then go out from absorbing tower top row.
5. the reactive distillation process method according to claim 2 or 3 for polymethoxy dimethyl ether synthesis, feature exist In: described dimethoxym ethane preparation workshop section include dimethoxym ethane reactive distillation column, formaldehyde prepare part formalin in workshop section with Methanol by formaldehyde it is micro- it is excessive in the form of be added separately to be reacted and separated in dimethoxym ethane reactive distillation column, dimethoxym ethane reaction essence It evaporates column overhead and produces anhydrous dimethoxym ethane, tower reactor produces the water containing trace formaldehyde.
6. the reactive distillation process method according to claim 2 for polymethoxy dimethyl ether synthesis, it is characterised in that: The oxymethylene polymerization workshop section includes oxymethylene polymerization reactive distillation column, Steam soak equipment, metaformaldehyde treating column, formaldehyde preparation The formalin of workshop section's extraction enters in oxymethylene polymerization reactive distillation column, carries out polymerization reaction and generates metaformaldehyde, trimerization first The mixture of aldehyde and formaldehyde, water is produced by oxymethylene polymerization reactive distillation column separate rear part point from tower top with gas phase, part Liquid-phase reflux, and the water for being not involved in reaction produces after the separation of oxymethylene polymerization reactive distillation column from tower reactor, overhead extraction trimerization The gas phase mixture of formaldehyde and formaldehyde, water enters Steam soak equipment and carries out UF membrane, and water phase enters Steam soak through film and sets Standby per-meate side and extraction, the mixed phase of metaformaldehyde, formaldehyde and minor amount of water is rear to enter through Steam soak equipment retention side extraction Metaformaldehyde treating column produces anhydrous metaformaldehyde, overhead extraction trimerization first through the metaformaldehyde rectifying column centrifugation tower reactor The liquid phase mixture of aldehyde, formaldehyde and water, which, which subsequently enters, carries out secondary separation in Steam soak equipment.
7. the reactive distillation process method according to claim 3 for polymethoxy dimethyl ether synthesis, it is characterised in that: The gaseous formaldehyde preparation workshop section includes sequentially connected formalin evaporator, Steam soak equipment, adsorbent equipment, first The part formalin that absorption tower generates in aldehyde preparation workshop section enters gaseous formaldehyde preparation workshop section, evaporates by formalin Device enters the water vapour in Steam soak equipment removal mixing gas phase after becoming gas phase, and it is mixed to enter suctions removing afterwards The residual water vapor in gas phase is closed, anhydrous gaseous formaldehyde is obtained.
8. a kind of technique dress of the reactive distillation process method according to claim 1 for polymethoxy dimethyl ether synthesis It sets, it is characterised in that: described including polymethoxy dimethyl ether reactive distillation column, first class product treating column, secondary product treating column Polymethoxy dimethyl ether reactive distillation column overhead be furnished with complete condenser, tower reactor be furnished with reboiler, polymethoxy dimethyl ether reaction essence It evaporates and two material inlets, the recycling of DMM6~10 feed inlet, DMM2 recycling feed inlet is set on tower tower, tower reactor is arranged liquid phase and produces Mouthful, tower top or for infinite reflux or setting liquid phase produce mouth, two of them material inlet respectively with chain growth feedstock pipeline And dimethoxym ethane mixer outlet pipeline is connected；Polymethoxy dimethyl ether reactive distillation column tower top liquid phase produces mouth connection light component point From tower, the light component separation column overhead is furnished with reboiler equipped with complete condenser, tower reactor, and tower top, tower reactor are equipped with liquid phase extraction Mouthful, light component knockout tower setting feed inlet is connected with polymethoxy dimethyl ether reactive distillation column overhead extraction mouth, light component separation Tower tower reactor extraction mouth is connected with DMM2 mixer feeding line, and light component knockout tower overhead extraction mouth and dimethoxym ethane mixer are fed Mouth is connected；The first class product treating column and secondary product treating column is furnished with reboiler equipped with complete condenser, tower reactor in tower top, Liquid phase feeding mouth is arranged in tower body, and tower top, tower reactor are equipped with liquid phase extraction mouth, wherein first class product treating column material inlet and poly- Methoxyl group dimethyl ether reactive distillation column tower bottom liquid phase produces mouth and passes through pipeline company, overhead extraction mouth and DMM2 mixer feeding line It is connected；Secondary product treating column material inlet and first class product treating column liquid phase extraction mouth are connected by pipeline, secondary product essence Tower tower reactor liquid phase extraction mouth processed recycles feed inlet with DMM6~10 and is connected by pipeline, the extraction of secondary product refined tower top liquid phase Mouth is connected with target product extraction pipeline.
9. process unit according to claim 8, it is characterised in that: further include formaldehyde preparation device, oxymethylene polymerization device, Dimethoxym ethane preparation facilities, the formaldehyde preparation device include sequentially connected methanol evaporator, gas mixer, preheater, Oxidation reactor, water absorption tower；The oxymethylene polymerization device includes oxymethylene polymerization reactive distillation column, Steam soak equipment, three Polyformaldehyde treating column；The dimethoxym ethane preparation facilities includes dimethoxym ethane reactive distillation column；The tower reactor extraction mouth point on water absorption tower The feed inlet of oxymethylene polymerization reactive distillation column and the reaction-ure feeding mouth of dimethoxym ethane reactive distillation column are not connected by pipeline；Formaldehyde Reaction-ure feeding mouth is arranged in polymerization reaction rectifying column；Oxymethylene polymerization reactive distillation column overhead extraction mouth connects Steam soak equipment, The feed inlet of extraction mouth connection metaformaldehyde treating column is surveyed in the retention of Steam soak equipment, and the tower reactor of metaformaldehyde treating column produces mouth Connect polymethoxy dimethyl ether reactive distillation column material inlet；Two reactions are set on the conversion zone of dimethoxym ethane reactive distillation column The overhead extraction mouth of object feed inlet, dimethoxym ethane reactive distillation column connects polymethoxy dimethyl ether reactive distillation column raw material by pipeline Feed inlet.
10. process unit according to claim 8, it is characterised in that: further include formaldehyde preparation device, gaseous formaldehyde preparation Device, dimethoxym ethane preparation facilities, the formaldehyde preparation device includes sequentially connected methanol evaporator, gas mixer, pre- Hot device, oxidation reactor, water absorption tower；The gaseous formaldehyde preparation facilities includes sequentially connected formalin evaporation Device, Steam soak equipment, adsorbent equipment；The dimethoxym ethane preparation facilities includes dimethoxym ethane reactive distillation column；Water absorption tower Tower reactor produces mouth and connects the feed inlet of formalin evaporator and the reactant of dimethoxym ethane reactive distillation column by pipeline respectively Feed inlet；The outlet of formalin evaporator connects Steam soak equipment, and the outlet of Steam soak equipment connects adsorbent equipment, The outlet of adsorbent equipment connects polymethoxy dimethyl ether reactive distillation column material inlet；The conversion zone of dimethoxym ethane reactive distillation column Two reaction-ure feeding mouths of upper setting, the overhead extraction mouth of dimethoxym ethane reactive distillation column connect polymethoxy dimethyl ether by pipeline Reactive distillation column material inlet.
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