CN109851483A - A kind of extraction catalytic rectification method preparing dimethoxym ethane - Google Patents
A kind of extraction catalytic rectification method preparing dimethoxym ethane Download PDFInfo
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Abstract
A kind of extraction catalytic rectification method preparing dimethoxym ethane by methanol and formalin, it include: that dimethoxym ethane is prepared by methanol and formalin in catalyst rectifying column, the catalytic rectifying tower includes conversion zone and rectifying section, filling solid catalyst A in the conversion zone；Methanol and formalin are introduced into catalytic rectifying tower, is contacted with solid catalyst A in the conversion zone, obtains dimethoxym ethane；The solid catalyst A is solid acid catalyst；Contain extractant in the conversion zone.Compared with traditional catalytic rectification process, have the advantages that the methanol and content of formaldehyde in dimethoxym ethane product are low, dimethoxym ethane product purity is high, low energy consumption.
Description
Technical field
The present invention relates to a kind of extraction catalytic rectification methods that dimethoxym ethane is prepared by methanol and formalin.
Background technique
Dimethoxym ethane is also known as dimethoxymethane, molecular formula CH3OCH2OCH3, it is a kind of colourless, nontoxic environment amenable
Industrial chemicals.Methanol and formalin are generallyd use through aldol reaction to prepare, reaction equation is as follows,
Japanese Asahi Kasei Corporation discloses a kind of raw by formalin and methanol in 1020450 C of Chinese patent CN
The catalytic rectification method for producing dimethoxym ethane, using the auxiliary reactor form being arranged in outside catalytic rectifying tower, with macropore or gel-type
Cation exchange resin is catalyst.
102351666 A of Chinese patent CN discloses one kind by formalin and methanol continuous production of high-concentration methylal
Catalytic rectification method, also use auxiliary reactor form.
100344596 C of Chinese patent Authorization Notice No. CN discloses a kind of continuous reaction rectification and liquid-liquid extraction combines
The method for preparing dimethoxym ethane, the dimethoxym ethane obtained after reactive distillation, methanol, water mixture be obtained by extraction in liquid-liquid extraction tower
Dimethoxym ethane, extractant are glycerine or dimethanolamine.
102070417 A of Chinese patent CN discloses a kind of catalytic distillation by formalin and methanol production dimethoxym ethane
Technique and its production equipment, using cation exchange resin as catalyst, using the catalytic rectifying tower for being filled with Catalyst capsule.
Due to, there are a large amount of water (water that the water and reaction brought into including formalin generate), making this in reaction process
Reaction is limited by chemical balance.The general limitation for breaking chemical balance using catalytic rectification process at present, but need larger
Reflux ratio, energy consumption it is higher.
Summary of the invention
According to the one aspect of the application, provide a kind of extraction catalytic rectification method for preparing dimethoxym ethane, this method by
Methanol and formalin prepare dimethoxym ethane, using extraction catalytic rectification method, have compared with traditional catalytic rectification method
The advantages of low energy consumption.
The extraction catalytic rectification method for preparing dimethoxym ethane, comprising: by methanol and formalin in catalyst rectifying column
Solution prepares dimethoxym ethane, and the catalytic rectifying tower includes conversion zone and rectifying section, filling solid catalyst A in the conversion zone；
Methanol and formalin are introduced into catalytic rectifying tower, contacts, obtains with solid catalyst A in the conversion zone
To dimethoxym ethane；
The solid catalyst A is solid acid catalyst；
Contain extractant in the conversion zone.
Optionally, the rectifying section is located at the conversion zone top；
Some or all of described rectifying section filling solid catalyst B.
Optionally, the extractant is added in the methanol and/or formalin.
Optionally, in the liquid phase material in the conversion zone extractant account for gross mass percentage be 20wt%~
80wt%.
Optionally, the extractant is selected from least one of halogenated hydrocarbons, aromatic hydrocarbons, alkane, cycloalkane.
Preferably, the halogenated hydrocarbons is selected from least one of dichloroethanes, dichloropropane, chlorobenzene, bromobenzene.
Preferably, the aromatic hydrocarbons is in benzene, toluene, ethylbenzene, dimethylbenzene, n-proplbenzene, isopropylbenzene, the first and second benzene, butylbenzene
At least one.
Preferably, the alkane selected from n-hexane, normal heptane, normal octane, carbon number be 6-10 isoparaffin in extremely
Few one kind.
Preferably, the cycloalkane in hexamethylene, methyl cyclopentane, hexahydrotoluene, ethyl cyclohexane extremely
Few one kind.
Optionally, the solid catalyst A is selected from storng-acid cation exchange resin, molecular sieve, metal oxide, bears
At least one of supported type metal oxide.
Further, the acid molecular sieve catalyst is selected from HZSM-5 molecular sieve, HBeta zeolite molecular sieve, HMCM-22
At least one of zeolite molecular sieve.
Still further, the solid catalyst A is selected from sulphonated stryrene divinyl benzene copolymer resin, perfluorinated sulfonic acid
At least one of resin, HZSM-5 molecular sieve, HBeta zeolite molecular sieve, HMCM-22 zeolite molecular sieve.
Optionally, the acid molecular sieve catalyst is made of at least one of described acidic molecular sieve with binder.
Further, the binder is aluminium oxide.
Optionally, the solid catalyst B is in silica, aluminium oxide, active carbon, magnesium silicate, potassium aluminosilicate
At least one.
Optionally, the operating pressure of the catalytic rectifying tower is 0~1MPa of gauge pressure.In the application, pressure is gauge pressure.
Optionally, the temperature of the catalytic rectifying tower conversion zone is 45~180 DEG C.
Optionally, the reflux ratio of the catalytic rectifying tower is 0.3~3.
Preferably, the reflux ratio of the catalytic rectifying tower is 0.5~1.5.
Optionally, the methanol is fed from the lower part of the conversion zone.
Optionally, the formalin is from the top of the conversion zone, the middle part of the rectifying section and/or the rectifying
The lower part charging of section.
The molar ratio of methanol and formaldehyde is 2~2.2 in all materials being introduced into catalytic rectifying tower.
In catalytic rectifying tower conversion zone, methanol and formalin are raw through aldol reaction under the action of catalyst A
At dimethoxym ethane, overall reaction formula is shown in front reaction equation (1).And in fact, only having few part formaldehyde with first in formalin
The form of aldehyde monomer molecule exists, and most formaldehyde are with methylene glycol (HOCH2OH is abbreviated as MG, be hydrated by monomer formaldehyde and
Come) and different polymerization degree polyoxymethylene glycol (HO (CH2O)nH is abbreviated as MGn, n > 1) form exist.MG,MGnAnd
Catalyst is not required between water, monomer formaldehyde to be mutually converted.
The methanol of addition is reacted with methylene glycol first generates hemiacetal (HOCH2OCH3, it is abbreviated as HF), which is not required to urge
Agent can carry out, and reaction equation is as follows:
The hemiacetal of generation can continue to react with methanol under the action of catalyst A, generate dimethoxym ethane (CH3OCH2OCH3,
It is abbreviated as DMM), reaction equation is as follows:
The dimethoxym ethane of generation leaves conversion zone under rectifying action and is enriched with and produces to tower top, and reacts the Shui Hejia generated
The water that aldehyde aqueous solution is brought into is produced from catalytic rectifying tower tower reactor, to break the chemical balance of above-mentioned reaction, promote the above reaction
Forward direction carries out, and reaches the complete conversion of formaldehyde.
And in every level-one of conversion zone, which nevertheless suffers from the limitation of chemical balance, and formaldehyde conversion does not surpass generally
50% is crossed, thus needs biggish reflux ratio, energy consumption higher.
The present invention proposes, certain density extractant is kept in catalytic rectifying tower conversion zone, makes the liquid phase in conversion zone
Material is divided into immiscible two-phase (water phase and extraction phase), can further break the limitation of chemical balance, keep conversion zone each
Formaldehyde conversion in grade substantially exceeds equilibrium conversion, so as to reduce reflux ratio, reduce energy consumption.
In the presence of suitable extractant, methanol and formaldehyde are primarily present in water phase, can be contacted, be expanded with catalyst A
It dissipates to enter inside its particle and carries out reaction and generate dimethoxym ethane, the dimethoxym ethane of generation enters extraction phase due to extraction.It is extracting
In the case where catalyst A mutually cannot be infiltrated, extraction phase will not enter inside its particle to be contacted with the activated centre on its surface, that is, is extracted
The dimethoxym ethane in phase is taken not decompose under the action of catalyst A；It, can be in the case where extraction phase can infiltrate catalyst A
Catalyst A is only placed in the water phase channel in catalytic rectifying tower conversion zone, contacts water phase material successively with catalyst A, is anti-
Ying Hou, then be in contact with extraction, extract, and such reaction, extraction process are repeated several times in conversion zone, avoiding problems extractions
Phase and the contact of catalyst A are taken, i.e. dimethoxym ethane in extraction phase will not decompose under the action of catalyst A.Although in this way, water phase
In condensation reaction still limited by chemical balance, but a large amount of dimethoxym ethane is enriched in extraction phase, thus in conversion zone
In every level-one, formaldehyde conversion can substantially exceed equilibrium conversion.
The distribution ratio (the ratio between dimethoxym ethane concentration and dimethoxym ethane concentration in water phase in extraction phase) of dimethoxym ethane is greater than methanol, formaldehyde
Distribution ratio (the ratio between methanol, concentration of formaldehyde in the concentration and water phase of methanol, formaldehyde in extraction phase), that is, can reach and break chemistry
Balance the effect of limitation.
The concentration of extractant should be maintained at 20-80wt% in catalytic rectifying tower conversion zone.In the case where having, extractant is with tower
Kettle moisture produces together, can be by the extraction of appropriate flow to stablize the concentration of extractant in conversion zone in required range
Agent is introduced into catalytic rectifying tower, to supplement the extractant of extraction.It is desired that the boiling point or extractant and water of extractant
For the boiling point of the azeotropic mixture of formation between dimethoxym ethane and the boiling point of water, such extractant can be dense needed for conversion zone holding
Degree without being not required to supplement, while also saving the expense of recycling extractant with tower top, the extraction of tower reactor fraction substantially.When a small amount of
When extractant produces together with tower reactor moisture, the extractant after split-phase mutually can directly be returned to catalytic rectifying tower.
The effect of catalytic rectifying tower rectifying section first is that make the formaldehyde in upflowing vapor enter liquid phase material return conversion zone
The reaction was continued.This process can regard a kind of reactive absorption process as, i.e. formaldehyde in steam dissolves first in the form of monomer molecule
Into liquid phase, the formaldehyde dissolved in liquid phase again in liquid phase water or methanol react and generate methylene glycol or hemiacetal；This reaction
Process, which is not required to catalyst, to be carried out, but reaction speed is slower.In catalytic rectifying tower rectifying section loading catalyst B, can promote
The free formaldehyde dissolved in liquid phase is reacted to generate methylene glycol and polyoxymethylene glycol or react generation half with methanol with water and be contracted
Aldehyde, while dimethoxym ethane will not be made to decompose；It is greatly improved the reaction speed that formaldehyde generates methylene glycol or hemiacetal in this way, thus fast
Speed reduces the concentration of formaldehyde monomers molecule in liquid phase material, improves the motive force of formaldehyde absorption process, is conducive in upflowing vapor
Formaldehyde return conversion zone the reaction was continued, reduce dimethoxym ethane product in concentration of formaldehyde.
Reaction raw materials methanol is generally introduced from the lower part of catalytic rectifying tower conversion zone.Reaction raw materials formalin can be from urging
The upper end for changing distillation column reactor section introduces or introduces from the middle part of catalytic rectifying tower rectifying section.Since dimethoxym ethane and methanol can be formed
Low-boiling azeotrope (azeotropic group becomes dimethoxym ethane 93wt%, methanol 7wt%), thus the dimethoxym ethane product of overhead extraction usually contains
There is a certain amount of methanol；The benefit that reaction raw materials formalin is introduced from the middle part of catalytic rectifying tower rectifying section is can to make
It is reacted with the methanol of dimethoxym ethane azeotropic with the methylene glycol in formalin, generates (104 DEG C) of the higher hemiacetal of boiling point returns
Conversion zone, so that the purity of overhead extraction dimethoxym ethane can be improved.Loading catalyst B can promote the progress of the reaction in rectifying section,
Reach better effect.
Reaction raw materials formalin can use concentration of formaldehyde for the aqueous solution of 10-55wt%, can contain a small amount of first
Alcohol.
The beneficial effect that the present invention can generate include: reduce dimethoxym ethane production process energy consumption, improve dimethoxym ethane product it is pure
Degree.
Detailed description of the invention
Fig. 1 is the extraction catalytic distillation schematic device of methanol and formaldehyde dimethoxym ethane in a kind of embodiment of the application.
Fig. 2 is the extraction catalytic distillation schematic device of methanol and formaldehyde dimethoxym ethane in a kind of embodiment of the application.
Fig. 3 is the extraction catalytic distillation schematic device of methanol and formaldehyde dimethoxym ethane in a kind of embodiment of the application.
Fig. 4 is the extraction catalytic distillation schematic device of methanol and formaldehyde dimethoxym ethane in a kind of embodiment of the application.
Specific embodiment
The present invention is described in detail below by embodiment, but the invention is not limited to these embodiments.
Unless otherwise instructed, the reaction raw materials in embodiments herein, catalyst, catalytic distillation equipment filler (Φ 3
5 × 5 millimeters of × 3 millimeters of stainless steel Dixon rings, Φ stainless steel Dixon rings) and stainless steel cloth Bao Jun pass through commercial sources buy, institute
It is analytical reagents with raw material, wherein the content of formaldehyde of formalin is 38wt%, and 3wt% containing methanol
Wherein, perfluorinated sulfonic resin (abbreviation Nafion-H resin) is bought from DuPont Corporation.Sulfonated phenylethylene-diethyl
Alkene benzene copolymer storng-acid cation exchange resin is bought from Dandong Mingzhu Special Type Resin Co., Ltd. (goods number D005).
Analysis method is as follows in embodiments herein:
The constituent analysis of material, the i.e. content of dimethoxym ethane, methanol, water, formaldehyde and other ingredients are carried out using gas-chromatography
Analysis.
Tower top and the load of tower reactor are measured using electronic balance and stopwatch.
Embodiment 1
As shown in Fig. 2, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter, load 3 × 3 millimeters of stainless steel Dixon rings of Φ.Reaction
0.97 meter of effective height of section, loads uniformly mixed 5 × 5 millimeters of stainless steel θ nets of 15 stainless steel cloth packets and 1300 milliliters of Φ
Ring, altogether equipped with 500 milliliters of Nafion-H resins as catalyst in stainless steel cloth packet.
Formalin inlet amount 14ml/min, 40 DEG C of feeding temperature, from rectifying section upper end, 40 centimeters are fed down；First
Alcohol inlet amount 15.2ml/min, 60 DEG C of feeding temperature, the endfeed under conversion zone；Extractant uses ethylbenzene, first with larger flow
A certain amount of ethylbenzene is added into tower, inlet amount is changed to 0.4ml/min later.Catalytic rectifying tower operating pressure is normal pressure, tower top
Reflux ratio is 1；After stable operation, 50-72 DEG C of conversion zone temperature, ethyl-benzene level is 30-35wt% in conversion zone gaseous phase materials；Tower
Ejection doses be 14.8g/min, material group become dimethoxym ethane 98.8wt%, methanol 1.0wt%, water 0.2wt%, formaldehyde~
0.04wt%；Tower reactor load be 12.7g/min, material group become water 97wt%, ethylbenzene 2.8wt%, methanol and formaldehyde <
0.02wt%.
Embodiment 2
As shown in Fig. 2, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter, load 3 × 3 millimeters of stainless steel Dixon rings of Φ.Reaction
0.97 meter of effective height of section, loads uniformly mixed 5 × 5 millimeters of stainless steel θ nets of 15 stainless steel cloth packets and 1300 milliliters of Φ
Ring, altogether equipped with 500 milliliters of D005 storng-acid cation exchange resins as catalyst in stainless steel cloth packet.
Formalin inlet amount 14ml/min, 40 DEG C of feeding temperature, from rectifying section upper end, 40 centimeters are fed down；First
Alcohol inlet amount 15.4ml/min, 60 DEG C of feeding temperature, the endfeed under conversion zone；Extractant use mixed xylenes, first with compared with
A certain amount of mixed xylenes is added into tower for big flow, and inlet amount is changed to 0.5ml/min later.Catalytic rectifying tower operating pressure
For normal pressure, overhead reflux ratio is 1；After stable operation, 50-72 DEG C of conversion zone temperature, mixed xylenes in conversion zone gaseous phase materials
Content is 40-45wt%；Tower top load is 14.9g/min, and material group becomes dimethoxym ethane 97.8wt%, methanol 2.0wt%, water
0.2wt%, formaldehyde~0.03wt%；Tower reactor load is 12.8g/min, and material group becomes water 97wt%, mixed xylenes
2.9wt%, methanol and formaldehyde < 0.02wt%.
Embodiment 3
As shown in Fig. 2, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter, load 3 × 3 millimeters of stainless steel Dixon rings of Φ.Reaction
0.97 meter of effective height of section, loads uniformly mixed 5 × 5 millimeters of stainless steel θ nets of 15 stainless steel cloth packets and 1300 milliliters of Φ
Ring, altogether equipped with 500 milliliters of D005 storng-acid cation exchange resins as catalyst in stainless steel cloth packet.
It is 10wt% as reaction raw materials that pure formalin reagent, which will be analyzed, and be diluted with water to content of formaldehyde, wherein methanol
Content is diluted to 0.78wt%.The inlet amount 46.5ml/min of 10wt% formalin, 50 DEG C of feeding temperature, from rectifying section
40 centimeters are fed down at end；Methanol inlet amount 13.2ml/min, 60 DEG C of feeding temperature, the endfeed under conversion zone；Extractant
Using isopropylbenzene and dichloroethanes (weight ratio 1:5) mixture, a certain amount of extractant is first added into tower with larger flow, it
Laggard doses is changed to 0.6ml/min.Catalytic rectifying tower operating pressure is 0.1MPa (gauge pressure), and overhead reflux ratio is 0.7；Operation is steady
After fixed, 55-78 DEG C of conversion zone temperature, isopropylbenzene and dichloroethane content are 28-36wt% in conversion zone gaseous phase materials；Tower top goes out
Doses is 12.8g/min, material group become dimethoxym ethane 97.8wt%, methanol 2.0wt%, water 0.2wt%, formaldehyde~
0.03wt%；Tower reactor load be 47g/min, material group become water 99.9wt%, other < 0.1wt%.
Embodiment 4
As shown in Fig. 2, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter, load 3 × 3 millimeters of stainless steel Dixon rings of Φ.Reaction
0.97 meter of effective height of section, loads uniformly mixed 5 × 5 millimeters of stainless steel θ nets of 15 stainless steel cloth packets and 1300 milliliters of Φ
Ring, altogether equipped with 500 milliliters of D005 storng-acid cation exchange resins as catalyst in stainless steel cloth packet.
Formalin inlet amount 12ml/min, 50 DEG C of feeding temperature, from rectifying section upper end, 40 centimeters are fed down；First
Alcohol inlet amount 13.2ml/min, 60 DEG C of feeding temperature, the endfeed under conversion zone；Extractant uses chlorobenzene and bromobenzene (weight ratio
A certain amount of extractant is first added with larger flow into tower for 9:1) mixture, and inlet amount is changed to 1ml/min later.Catalysis essence
Evaporating tower operating pressure is 0.1MPa (gauge pressure), and overhead reflux ratio is 0.7；After stable operation, 55-78 DEG C of conversion zone temperature, reaction
Chlorobenzene and bromobenzene content are 20-26wt% in section gaseous phase materials；Tower top load is 12.8g/min, and material group becomes dimethoxym ethane
97.6wt%, methanol 2.2wt%, water 0.2wt%, formaldehyde~0.04wt%；Tower reactor load is 11.7g/min, material composition
For water 91wt%, chlorobenzene and bromobenzene 9wt%, methanol and formaldehyde < 0.02wt%.
Embodiment 5
As shown in figure 4, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter, load 3 × 3 millimeters of stainless steel Dixon rings of Φ.Reaction
0.97 meter of effective height of section, 2 × 5-7 millimeters of mixed packing Φ 5 × 5 millimeters of stainless steel θ nets of bar shaped molecular sieve catalyst and Φ
Ring, volume ratio 1:2, molecular sieve catalyst group become 70wt%HBeta zeolite and 30wt% alumina binder.
Paraformaldehyde reagent and suitable quantity of water are mixed and heated to the formalin that content of formaldehyde 55wt% is made after dissolution
As reaction raw materials, wherein being free of methanol.55wt% formalin inlet amount 10.8ml/min, 100 DEG C of feeding temperature, from essence
Evaporating section upper end, 40 centimeters are fed down；Methanol inlet amount 18ml/min, 100 DEG C of feeding temperature, the endfeed under conversion zone；Extraction
It takes agent using the first and second benzene and n-proplbenzene (weight ratio 1:1) mixture, a certain amount of extractant is first added into tower with larger flow,
Inlet amount is changed to 0.6ml/min later.Catalytic rectifying tower operating pressure is 0.5MPa (gauge pressure), and overhead reflux ratio is 1；Operation is steady
After fixed, 110-136 DEG C of conversion zone temperature, the first and second benzene and n-proplbenzene content are 30-35wt% in conversion zone gaseous phase materials；Tower top goes out
Doses is 16.9g/min, and material group becomes dimethoxym ethane 97.9wt%, methanol 2wt%, water 0.1wt%, formaldehyde~0.03wt%；
Tower reactor load is 9.3g/min, material group become water 96.5wt%, the first and second benzene and n-proplbenzene 3.5wt%, methanol and formaldehyde <
0.02wt%.
Embodiment 6
As shown in Fig. 2, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter, load 3 × 3 millimeters of stainless steel Dixon rings of Φ.Reaction
0.97 meter of effective height of section, 2 × 5-7 millimeters of mixed packing Φ 5 × 5 millimeters of stainless steel θ nets of bar shaped molecular sieve catalyst and Φ
Ring, volume ratio 1:2, molecular sieve catalyst group become 70wt%HMCM-22 zeolite and 30wt% alumina binder.
Formalin inlet amount 15.9ml/min, 100 DEG C of feeding temperature, from rectifying section upper end down 40 centimeters into
Material；Methanol inlet amount 17.4ml/min, 110 DEG C of feeding temperature, the endfeed under conversion zone；Extractant use butylbenzene, first with compared with
A certain amount of butylbenzene is added into tower for big flow, and inlet amount is changed to 0.8ml/min later.Catalytic rectifying tower operating pressure is
0.6MPa (gauge pressure), overhead reflux ratio are 1；After stable operation, 120-142 DEG C of conversion zone temperature, fourth in conversion zone gaseous phase materials
Benzene content is 50-56wt%；Tower top load is 16.9g/min, and material group becomes dimethoxym ethane 97.9wt%, methanol 2wt%, water
0.1wt%, formaldehyde~0.03wt%；Tower reactor load is 14.8g/min, and material group becomes water 95wt%, butylbenzene 5wt%, first
Pure and mild formaldehyde < 0.02wt%.
Embodiment 7
As shown in Fig. 2, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter, load 3 × 3 millimeters of stainless steel Dixon rings of Φ.Reaction
0.97 meter of effective height of section, loads uniformly mixed 5 × 5 millimeters of stainless steel θ nets of 15 stainless steel cloth packets and 1300 milliliters of Φ
Ring, altogether equipped with 500 milliliters of D005 storng-acid cation exchange resins as catalyst in stainless steel cloth packet.
Formalin inlet amount 15.9ml/min, 50 DEG C of feeding temperature, from rectifying section upper end, 40 centimeters are fed down；
Methanol inlet amount 17.4ml/min, 60 DEG C of feeding temperature, the endfeed under conversion zone；Extractant is using n-hexane, normal heptane, different
A certain amount of extractant is first added with larger flow into tower for heptane, normal octane and isooctane (respectively accounting for 20wt%) mixture, it
Laggard doses is changed to 0.6ml/min.Catalytic rectifying tower operating pressure is normal pressure, and overhead reflux ratio is 1.5；After stable operation, instead
50-70 DEG C of section temperature is answered, extraction agent content is 20-26wt% in conversion zone gaseous phase materials；Tower top load is 16.9g/min,
Material group becomes dimethoxym ethane 97.9wt%, methanol 2wt%, water 0.1wt%, formaldehyde~0.03wt%；Tower reactor load is
14.6g/min, material group become water 96.5wt%, extractant 3.5wt%, methanol and formaldehyde < 0.02wt%.
Embodiment 8
As shown in Fig. 2, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter, load 3 × 3 millimeters of stainless steel Dixon rings of Φ.Reaction
0.97 meter of effective height of section, loads uniformly mixed 5 × 5 millimeters of stainless steel θ nets of 15 stainless steel cloth packets and 1300 milliliters of Φ
Ring, altogether equipped with 500 milliliters of D005 storng-acid cation exchange resins as catalyst in stainless steel cloth packet.
Formalin inlet amount 15.9ml/min, 50 DEG C of feeding temperature, from rectifying section upper end, 40 centimeters are fed down；
Methanol inlet amount 17.4ml/min, 60 DEG C of feeding temperature, the endfeed under conversion zone；Extractant uses hexamethylene, methyl ring penta
A certain amount of extraction is first added in alkane, hexahydrotoluene, ethyl cyclohexane (respectively accounting for 25wt%) mixture with larger flow into tower
Agent, inlet amount is changed to 0.6ml/min later.Catalytic rectifying tower operating pressure is normal pressure, and overhead reflux ratio is 1.5；Stable operation
Afterwards, 50-70 DEG C of conversion zone temperature, extraction agent content is 35-42wt% in conversion zone gaseous phase materials；Tower top load is 16.9g/
Min, material group become dimethoxym ethane 97.9wt%, methanol 2wt%, water 0.1wt%, formaldehyde~0.04wt%；Tower reactor load is
14.6g/min, material group become water 96.4wt%, extractant 3.6wt%, methanol and formaldehyde < 0.02wt%.
Embodiment 9
As shown in Fig. 2, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter, load 3 × 3 millimeters of stainless steel Dixon rings of Φ.Reaction
0.97 meter of effective height of section, loads uniformly mixed 5 × 5 millimeters of stainless steel θ nets of 15 stainless steel cloth packets and 1300 milliliters of Φ
Ring, altogether equipped with 500 milliliters of D005 storng-acid cation exchange resins as catalyst in stainless steel cloth packet.
Formalin inlet amount 12.1ml/min, 40 DEG C of feeding temperature, from rectifying section upper end, 40 centimeters are fed down；
Methanol inlet amount 14.5ml/min, 60 DEG C of feeding temperature, the endfeed under conversion zone；Extractant uses isopropylbenzene, first with larger
A certain amount of isopropylbenzene is added into tower for flow, and inlet amount is changed to 0.6ml/min later.Catalytic rectifying tower operating pressure is normal
Pressure, overhead reflux ratio are 0.3；After stable operation, 45-75 DEG C of conversion zone temperature, isopropyl benzene content is in conversion zone gaseous phase materials
20-28wt%；Tower top load is 13.8g/min, and material group becomes dimethoxym ethane 91wt%, methanol 8wt%, water 0.8wt%, first
Aldehyde~0.03wt%；Tower reactor load be 11.2g/min, material group become water 95wt%, isopropylbenzene 5wt%, methanol and formaldehyde <
0.02wt%.
Embodiment 10
As shown in Fig. 2, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter；3-5 millimeters of mixed packing Φ of silica gel in rectifying section
3 × 3 millimeters of stainless steel Dixon rings of ball and Φ, volume ratio 1:3；Stripping section loads 3 × 3 millimeters of stainless steel Dixon rings of Φ.Reaction
0.97 meter of effective height of section, loads uniformly mixed 5 × 5 millimeters of stainless steel θ nets of 15 stainless steel cloth packets and 1300 milliliters of Φ
Ring, altogether equipped with 500 milliliters of D005 storng-acid cation exchange resins as catalyst in stainless steel cloth packet.
Formalin inlet amount 20.2ml/min, 60 DEG C of feeding temperature, from rectifying section upper end, 40 centimeters are fed down；
Methanol inlet amount 22ml/min, 60 DEG C of feeding temperature, the endfeed under conversion zone；Extractant use 1,2- dichloropropane, first with
A certain amount of 1,2- dichloropropane is added into tower for larger flow, stops charging later.Catalytic rectifying tower operating pressure is
0.2MPa (gauge pressure), overhead reflux ratio are 3；After stable operation, 70-80 DEG C of conversion zone temperature, 1,2- in conversion zone gaseous phase materials
Dichloropropane content is 60-80wt%；Tower top load is 21.3g/min, and material group becomes dimethoxym ethane 98wt%, methanol
1.8wt%, water 0.1wt%, formaldehyde~0.01wt%；Tower reactor load is 17.8g/min, and material group becomes water 99.9wt%,
Other < 0.1wt%.
Embodiment 11
As shown in figure 3, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter；2 × 4-6 millimeters of mixed packing Φ in rectifying section
3 × 3 millimeters of stainless steel Dixon rings of aluminium oxide bar shaped particle and Φ, volume ratio 1:3；3 × 3 millimeters of Φ of stripping section filling is stainless
Steel Dixon ring.0.97 meter of conversion zone effective height, 2 × 5-7 millimeters of mixed packing Φ of 5 × 5 milli of bar shaped molecular sieve catalyst and Φ
Rice stainless steel Dixon ring, volume ratio 1:2, molecular sieve catalyst group become 80wt%HZSM-5 and 20wt% alumina bound
Agent.
Formalin inlet amount 13.8ml/min, 100 DEG C of feeding temperature, the endfeed from conversion zone；Methanol inlet amount
16.8ml/min, 80 DEG C of feeding temperature, the endfeed under conversion zone；Extractant uses benzene, is first added with larger flow into tower
A certain amount of benzene, inlet amount is changed to 0.5ml/min later.Catalytic rectifying tower operating pressure is 0.5MPa (gauge pressure), overhead reflux
Than being 0.5；After stable operation, 110-140 DEG C of conversion zone temperature, benzene content is 32-50wt% in conversion zone gaseous phase materials；Tower top
Load is 16g/min, and material group becomes dimethoxym ethane 90wt%, methanol 9wt%, water 0.8wt%, formaldehyde~0.02wt%；Tower
Kettle load is 12.6g/min, and material group becomes water 96.5wt%, benzene 3.5wt%, methanol and formaldehyde < 0.02wt%.
Embodiment 12
As shown in figure 4, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter；3 × 4-6 millimeters of mixed packing Φ in rectifying section
3 × 3 millimeters of stainless steel Dixon rings of active carbon particle and Φ, volume ratio 1:3；Stripping section loads 3 × 3 millimeters of stainless steel θ nets of Φ
Ring.0.97 meter of conversion zone effective height, 2 × 5-7 millimeters of mixed packing Φ of 5 × 5 milli of bullion oxide catalyst and Φ
The group of rice stainless steel Dixon ring, volume ratio 1:2, metal oxide catalyst becomes 30wt%Fe2O3, 70wt%TiO2。
Formalin inlet amount 27.5ml/min, 150 DEG C of feeding temperature, the endfeed from conversion zone；Methanol inlet amount
32.5ml/min, 120 DEG C of feeding temperature, the endfeed under conversion zone；Extractant uses toluene, first with larger flow to Ta Neijia
Enter a certain amount of toluene, stops charging later.Catalytic rectifying tower operating pressure is 1MPa (gauge pressure), and overhead reflux ratio is 1；Operation
After stabilization, 160-175 DEG C of conversion zone temperature, toluene level is 50-60wt% in conversion zone gaseous phase materials；Tower top load is
31.1g/min, material group become dimethoxym ethane 92wt%, methanol 7.5wt%, water 0.5wt%, formaldehyde~0.02wt%；Tower reactor goes out
Doses is 24.3g/min, material group become water 99.9wt%, other < 0.1wt%.
Embodiment 13
As shown in Fig. 2, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter；2 × 4-6 millimeters of mixed packing Φ in rectifying section
3 × 3 millimeters of stainless steel Dixon rings of mixture and Φ of magnesium silicate and each 50wt% of potassium aluminosilicate particle, volume ratio 1:3；It mentions
Evaporate section filling 3 × 3 millimeters of stainless steel Dixon rings of Φ.0.97 meter of conversion zone effective height, the bar shaped that 2 × 5-7 millimeters of mixed packing Φ
5 × 5 millimeters of stainless steel Dixon rings of metal oxide supporting catalyst and Φ, volume ratio 1:2, metal oxide-loaded catalysis
The group of agent becomes 12wt%MoO3/Al2O3。
Formalin inlet amount 9.7ml/min, 120 DEG C of feeding temperature, from rectifying section upper end, 40 centimeters are fed down；
Methanol inlet amount 10.8ml/min, 90 DEG C of feeding temperature, the endfeed under conversion zone；Extractant uses hexamethylene, first with larger
A certain amount of hexamethylene is added into tower for flow, stops charging later.Catalytic rectifying tower operating pressure is 0.6MPa (gauge pressure), tower
Pushing up reflux ratio is 1.5；After stable operation, 120-135 DEG C of conversion zone temperature, conversion zone gaseous phase materials cyclohexane content is 60-
70wt%；Tower top load is 10.4g/min, and material group becomes dimethoxym ethane 96wt%, methanol 3.5wt%, water 0.4wt%, first
Aldehyde~0.01wt%；Tower reactor load be 8.5g/min, material group become water 99.9wt%, other < 0.1wt%.
Comparative example 1
Catalytic distillation synthesizing dimethoxym ethane
As shown in Figure 1, catalytic rectifying tower includes overhead condensate reflux device, rectifying section, conversion zone, stripping section and tower reactor.Tower
50 millimeters of body internal diameter, rectifying section and stripping section effective height are 0.57 meter, load 3 × 3 millimeters of stainless steel Dixon rings of Φ.Reaction
0.97 meter of effective height of section, loads uniformly mixed 5 × 5 millimeters of stainless steel θ nets of 15 stainless steel cloth packets and 1300 milliliters of Φ
Ring, altogether equipped with 500 milliliters of D005 storng-acid cation exchange resins as catalyst in stainless steel cloth packet.
Formalin inlet amount 12.1ml/min, 40 DEG C of feeding temperature, from rectifying section upper end, 40 centimeters are fed down；
Methanol inlet amount 14.5ml/min, 60 DEG C of feeding temperature, the endfeed under conversion zone.Catalytic rectifying tower operating pressure is normal pressure,
Overhead reflux ratio is 0.3；After stable operation, 45-72 DEG C of conversion zone temperature；Tower top load is 13.8g/min, and material group becomes
Dimethoxym ethane 85wt%, methanol 9.6wt%, water 1.2wt%, formaldehyde 4.2wt%；Tower reactor load is 10.7g/min, material composition
For water 97wt%, methanol 1.4wt%, formaldehyde 1.6wt%.
The comparative example illustrates to keep certain density extractant in conversion zone compared with embodiment 9, can be identical
Higher formaldehyde conversion is assigned compared with low reflux ratio, obtains the dimethoxym ethane product of higher purity.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of extraction catalytic rectification method for preparing dimethoxym ethane, which is characterized in that by methanol and first in catalyst rectifying column
Aldehyde aqueous solution prepares dimethoxym ethane, and the catalytic rectifying tower includes conversion zone and rectifying section, and filling solid is catalyzed in the conversion zone
Agent A；
Methanol and formalin are introduced into catalytic rectifying tower, is contacted with solid catalyst A in the conversion zone, obtains first
Acetal；
The solid catalyst A is solid acid catalyst；
Contain extractant in the conversion zone.
2. the method according to claim 1, wherein the rectifying section is located at the conversion zone top；
Some or all of described rectifying section filling solid catalyst B.
3. the method according to claim 1, wherein adding the extraction in the methanol and/or formalin
Take agent.
4. the method according to claim 1, wherein in the conversion zone, the total matter of extractant Zhan in liquid phase material
The percentage of amount is 20wt%~80wt%.
5. the method according to claim 1, wherein the extractant is selected from halogenated hydrocarbons, aromatic hydrocarbons, alkane, ring
At least one of alkane；
Preferably, the halogenated hydrocarbons is selected from least one of dichloroethanes, dichloropropane, chlorobenzene, bromobenzene；
Preferably, the aromatic hydrocarbons in benzene, toluene, ethylbenzene, dimethylbenzene, n-proplbenzene, isopropylbenzene, the first and second benzene, butylbenzene extremely
Few one kind；
Preferably, the alkane is at least one in the isoparaffin of 6-10 selected from n-hexane, normal heptane, normal octane, carbon number
Kind；
Preferably, the cycloalkane in hexamethylene, methyl cyclopentane, hexahydrotoluene, ethyl cyclohexane at least one
Kind.
6. the method according to claim 1, wherein the solid catalyst A is handed over selected from highly acidic cation
Change at least one of resin, molecular sieve, metal oxide, load metal oxide.
7. according to the method described in claim 2, it is characterized in that, the solid catalyst B is selected from silica, oxidation
At least one of aluminium, active carbon, magnesium silicate, potassium aluminosilicate.
8. method according to claim 1 or 2, which is characterized in that the operating pressure of the catalytic rectifying tower is gauge pressure 0
~1MPa.
9. method according to claim 1 or 2, which is characterized in that the reflux ratio of the catalytic rectifying tower is 0.3~3；
Preferably, the reflux ratio of the catalytic rectifying tower is 0.5~1.5.
10. method according to claim 1 or 2, which is characterized in that the methanol is fed from the lower part of the conversion zone；
The formalin from the lower part on the top of the conversion zone, the middle part of the rectifying section and/or the rectifying section into
Material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110559678A (en) * | 2019-10-21 | 2019-12-13 | 无锡赫利邦化工科技有限公司 | rectifying tower for synthesizing and separating polymethoxy dimethyl ether and use method thereof |
| CN112225650A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Refining method for obtaining high-purity methylal by purifying industrial-grade methylal |
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| CN101092337A (en) * | 2007-07-03 | 2007-12-26 | 南京师范大学 | Method for preparing methylal by combining reaction rectification and extraction |
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| CN112225650A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Refining method for obtaining high-purity methylal by purifying industrial-grade methylal |
| CN112225650B (en) * | 2019-07-15 | 2023-06-06 | 中国石油化工股份有限公司 | Refining method for obtaining high-purity methylal by purifying industrial-grade methylal |
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| CN110559678B (en) * | 2019-10-21 | 2024-02-27 | 无锡赫利邦化工科技有限公司 | Rectifying tower for synthesizing and separating polymethoxy dimethyl ether and application method thereof |
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