CN109180636A - It is a kind of to extract the device and method that synthesizing triformol is coupled with catalysis technique - Google Patents
It is a kind of to extract the device and method that synthesizing triformol is coupled with catalysis technique Download PDFInfo
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- CN109180636A CN109180636A CN201811323284.2A CN201811323284A CN109180636A CN 109180636 A CN109180636 A CN 109180636A CN 201811323284 A CN201811323284 A CN 201811323284A CN 109180636 A CN109180636 A CN 109180636A
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Abstract
The invention discloses the device and method that a kind of extraction couples with catalysis technique synthesizing triformol, including be sequentially connected heat exchanger, methylal oxidation reactor, extract catalytic tower, separator, fractionating column；Air and oxidic raw materials, which are introduced into heat exchanger shell pass, to be heated, then into carrying out oxidation reaction in methylal oxidation reactor, oxidation reaction obtain the high oxidation product of temperature enter in heat exchanger tube pass exchange heat after obtain temperature reduction oxidation product, the oxidation product that temperature reduces enters back into extraction catalytic tower and carries out polymerization reaction, and polymerizate successively obtains product metaformaldehyde after extraction, separation, fractionation.The present invention is using extraction catalytic distillation coupling technique, produce high-purity metaformaldehyde product, defect and drawback existing for the technologies such as existing water absorption, concentration, sulfuric acid catalysis, extraction drying are overcome, having started one, process conditions are mild, process flow is short, investment is small, the new technology of quick, efficient low-consume, clean and environmental protection.
Description
Technical field
This technology is related to methylal oxidation, and then the method and apparatus of synthesizing triformol, belong to fine chemical technology
Field.
Background technique
Metaformaldehyde is important industrial chemicals, very widely used.The synthetic technology route of comparative maturity is at present: with
Sulfuric acid is catalyst synthesizing triformol, and is thus to give synthesis trimerization first using the formalin of 35-55% as raw material
The process bands of aldehyde carry out inadequate natural endowment: three waste discharge is more, production environment is poor, long flow path, invests the problems such as big, production equipment is corroded,
Therefore it is imperative to develop a kind of energy-efficient, clean and environmental protection new technology.
Existing synthetic method are as follows: the formaldehyde for generating 35-55% content is water-soluble for methanol oxidation → oxidation product water absorbs →
Liquid → 100 DEG C of reduced pressure → heating → entering enamel reaction still → uses 2-10% sulfuric acid catalysis → evaporation and concentration metaformaldehyde water
Extracting and refining → the drying of solution → again (or freezing) obtains final finished.And this technology be with methylal oxidation product, directly into
Enter in a multi-stage fixed-bed catalytic tower, a kind of new technology of synthesizing triformol product under the action of module catalyst.
Summary of the invention
This technology problem to be solved be for existing for sulfuric acid catalysis synthesizing triformol in the prior art it is congenital not
Foot, and a kind of extract is provided and couples the device and method of synthesizing triformol with catalysis technique, overcome existing water absorption techniques,
Concentration technique, sulfuric acid catalysis technology, defect and drawback existing for extraction drying technology etc., started a process conditions it is mild,
Process flow is short, investment is small, the method and device of quick, efficient low-consume, clean and environmental protection.
To achieve the goals above, this technology uses following scheme:
It is a kind of to extract the device that synthesizing triformol is coupled with catalysis technique, including heat exchanger, the dimethoxym ethane being sequentially connected
Oxidation reactor, extraction catalytic tower, separator, fractionating column；Air and oxidic raw materials are introduced into quilt in heat exchanger shell pass
Heating, then into carrying out oxidation reaction in methylal oxidation reactor, oxidation reaction obtain the high oxidation product of temperature into
The oxidation product of temperature reduction is obtained after entering into heat exchanger tube pass heat exchange, the oxidation product that temperature reduces enters back into extraction catalysis
Polymerization reaction is carried out in reaction tower, polymerizate successively obtains product metaformaldehyde after extraction, separation, fractionation, and feature exists
In:
The heat exchanger is tubular heat exchanger, solidifiable substance import 6B is equipped with above the side wall of shell side, lower section is equipped with heat
Material outlet 6A, the bottom of tube side are equipped with feed inlet 6D, and top is equipped with discharge port 6C,；Wherein: solidifiable substance import 6B with can mention
It is connected heat for the device of air and/or dimethoxym ethane；
The methylal oxidation reactor, top is equipped with feed inlet 1A, bottom is equipped with discharge port 1B, sets above side wall
There are import 1D, lower section to be equipped with outlet 1C, in which: feed inlet 1A is connected with the hot material outlet 6A of heat exchanger；Discharge port 1B with
The feed inlet 6D of heat exchanger is connected；It is equipped with waste heat boiler between import 1D, outlet 1C, exports the import phase of 1C and waste heat boiler
Connection, import 1D are connected with the outlet of waste heat boiler, and waste heat boiler provides heat for oxidation reaction；
The extraction catalytic tower, top is equipped with exhaust outlet 2C, bottom is equipped with discharge port 2B, be equipped with below side wall into
Material mouth 2A, top are equipped with extractant feed opening 2D；Wherein: feed inlet 2A is connected with the discharge port 6C of heat exchanger；Extractant adds
Material mouth 2D is connected with the device for being capable of providing extractant；Exhaust outlet 2C point is two-way, all the way with the solidifiable substance import of heat exchanger
6B is connected, to return to and recycle air, another way is directly connected with exhaust treatment system, and after processing will
Gas emptying；
The separator, one end is equipped with feed inlet 3A, the other end is equipped with discharge port 3C, bottom is equipped with dilute formalin
Export 3B；Wherein: feed inlet 3A is connected with the discharge port 2B of extraction catalytic tower；Dilute formalin outlet 3B and storage
The device of dilute formalin is connected；
The fractionating column, top is equipped with gaseous phase outlet 4B, bottom is equipped with discharge port 4D, is equipped with feed inlet above side wall
Refluxing opening 4C is equipped with above 4A, another side wall；Wherein: feed inlet 4A is connected with the discharge port 3C of separator；Gaseous phase outlet 4B
It is connected with condenser, drainer, reflux pump in turn；The outlet of reflux pump is divided into two-way, is connected all the way with refluxing opening 4C, another
Road is connected to recycle extractant with the extractant feed opening 2D of extraction catalytic tower；Discharge port 4D and stored product three
The device of polyformaldehyde is connected.
In above-mentioned technical proposal, catalyst A is filled in the methylal oxidation reactor, catalyst A is that iron molybdenum is urged
Agent, iron-molybdic catalyst preferably with patent of invention CN201710307041.9 or utility model patent CN201720485329.0 or
Type, the proportion phase of the catalyst active component used or active catalyst in utility model patent CN201720483709.0
Together.
In above-mentioned technical proposal, the methylal oxidation reactor, structure and utility model patent
The structure of the equipment of methanol oxidation in CN201720483709.0 is identical, feed inlet 1A, discharge port 1B be equal to it is described
Methanol oxidation equipment inlet port and outlet port, the side wall of outer shell of the equipment of the methanol oxidation top,
Lower section opens up the import 1D, outlet 1C.
In above-mentioned technical proposal, the extraction catalytic tower, internal top be equipped with demister, internal top and
Lower section is equipped with distributor, and the distributor of lower section is connected with feed inlet 2A, distributor and the extractant feed opening 2D phase of top
Connection.
In above-mentioned technical proposal, the extraction catalytic tower, inside is filled with catalyst B, and catalyst B is located above
Distributor, lower section distributor between；Catalyst B is macropore cation resin, any one in superpower acid resin, preferably
D006 type acid resin catalyst, D008 type high temperature resistant acidic resin catalysis for the production of Kai Rui environmental protective chemical industry limited liability company
Agent.
In above-mentioned technical proposal, the filling form of the extraction catalytic tower internal accelerator B is preferably modular,
Loadings are N sections, 1≤N≤100, every section of height 1-3m；Modular is preferably according to patent of invention CN204685110U
(2015202973481) the novel plug filler of the loading catalyst disclosed in is configured.
In above-mentioned technical proposal, the extraction catalytic tower is added to the extraction in it from extractant feed opening 2D
Agent be the alkane of purified petroleum benzin, aromatic hydrocarbons, carbon number greater than 4, any one or two kinds or more in cycloalkane with arbitrary proportion mixing and
At mixture.
In above-mentioned technical proposal, the separator, the interior coalescer for being equipped with extractant, and be located at close to feed inlet 3A
One end.
In above-mentioned technical proposal, the fractionating column, tower is interior to be filled with tower internals, and tower internals is structured packing, in column plate
Any one；If structured packing, filling number of segment is N, and 1≤N≤100, every section of height is 1-3 meters；If column plate, then manage
It is M, 1≤M≤100 by plate number.
In above-mentioned technical proposal, the fractionating column, side wall lower section is equipped with reboiler.
In above-mentioned technical proposal, the waste heat boiler, heat exchanger (shell and tube), condenser, drainer, reflux pump reboiling
Device, coalescer, distributor, demister are common commercial equipment.
A kind of method that the present invention also provides extractions to couple synthesizing triformol with catalysis technique, comprising the following steps:
(1) oxidation reaction: oxidic raw materials and air, after being preheated to 100-200 DEG C, under the catalytic action of catalyst A into
Row oxidation reaction obtains the higher oxidation product of temperature after oxidation reaction, and the oxidation product of temperature reduction is obtained after exchanging heat；
(2) polymerization reaction: the oxidation product that temperature reduces carries out polymerization reaction under the catalytic action of catalyst B, generates
Metaformaldehyde aqueous solution；Metaformaldehyde aqueous solution forms the extractant containing metaformaldehyde after being extracted agent extraction, and reacts surplus
The emptying of residual air body a part, another part are back in step (1) and are recycled；
(3) separate: the extractant dehydration containing metaformaldehyde obtains dilute formalin and the extraction containing metaformaldehyde
Phase；Dilute formalin is otherwise utilized after collecting；And the extraction phase containing metaformaldehyde is fractionated；
(4) be fractionated: the extraction phase containing metaformaldehyde obtained in step (3) is fractionated in a heated state, is obtained
Gas phase and liquid phase；Gas phase is extractant, and liquid-phase extraction agent, a part reflux are obtained after condensing, and a part is back to step (2)
In recycle；Liquid phase is product metaformaldehyde finished product, is collected or harvests.
In above-mentioned technical proposal, flow chart as shown in Figure 1, method specifically includes the following steps:
(1) oxidation reaction: oxidic raw materials and air are entered in the shell side of heat exchanger by solidifiable substance import 6B and are preheated,
It is exported after being preheated to 100-200 DEG C by hot material outlet 6A and is imported into methylal oxidation reactor by feed inlet 1A, at it
Oxidation reaction is carried out under the catalytic action of interior catalyst A；Oxidation product at the discharge port 1B of methylal oxidation reactor
Temperature is 200-450 DEG C；200-450 DEG C of oxidation product is exported by discharge port 1B and imported into heat exchanger by feed inlet 6D
It exchanges heat in tube side, temperature is exported by discharge port 6C after being reduced to 95-105 DEG C and imported into extraction catalysis by feed inlet 2A
In reaction tower；
(2) polymerization reaction: the oxidation product in step (1) enters in extraction catalytic tower, catalyst B in it
Under catalytic action, gas and liquid two phases countercurrent reaction occurs and generates metaformaldehyde aqueous solution；On reaction residual gas continues in tower
Row, and metaformaldehyde with reaction residual gas air-flow continue uplink and be extracted agent feed opening 2D addition, adverse current and under
Extractant extract and be absorbed, extractant absorbs after metaformaldehyde that density is bigger can come downwards to tower bottom, from the discharging of tower bottom
Mouth 2B is exported and is imported into separator by feed inlet 3A；And react residual gas and will continue to go upward at demister in tower,
Demister thoroughly retains the extractant wherein carried secretly, residual gas to exhaust outlet 2C, and a part is emptied through processing, another part
It is imported into heat exchanger together with oxidic raw materials as solidifiable substance import 6B according to the heated rear return oxygen of operation described in step (1)
Change and is recycled in reactor；
(3) separate: the extractant in step (2) is entered in separator after absorbing metaformaldehyde by feed inlet 3A, is being divided
From being further dehydrated under the action of the coalescer inside device, dilute formalin and the extraction phase containing metaformaldehyde are obtained；It is dilute
Formalin is discharged by dilute formalin outlet 3B of separator bottom, and otherwise utilized after collection；And contain trimerization first
The extraction phase of aldehyde is exported by discharge port 3C and is imported into fractionating column by feed inlet 4A；
(4) it is fractionated: after the extraction phase containing metaformaldehyde obtained in step (3) enters fractionating column, in fractionating column
It is fractionated under the heated condition of reboiler (10), obtains gas phase and liquid phase；Gas phase is extractant, and gas phase is arranged through gaseous phase outlet 4B
Out, it followed by two-way is divided into after condenser, return tank, reflux pump, is back in fractionating column from refluxing opening 4C all the way, another way
It is back in extraction catalytic tower and is recycled by extractant feed opening 2D；Liquid phase is product metaformaldehyde finished product, by tower bottom
Discharge port 4D discharge and be collected or harvest.
In above-mentioned technical proposal, in step (1), the oxidic raw materials are dimethoxym ethane, methanol, any one in dimethyl ether
Kind, two or more mixture mixed with arbitrary proportion.
In above-mentioned technical proposal, in step (1), after the oxidic raw materials mix with air, wherein the quality of oxygen contains
Amount are as follows: 5-20%, feedstock quality air speed are 0.1-10.0h-1。
In above-mentioned technical proposal, in step (1), catalyst A be iron-molybdic catalyst, iron-molybdic catalyst preferably with patent of invention
CN201710307041.9 or utility model patent CN201720485329.0 or utility model patent CN201720483709.0
In the catalyst active component used or active catalyst type, proportion it is identical.
Reaction condition in above-mentioned technical proposal, in step (1), in methylal oxidation reactor are as follows: temperature 200-450
DEG C, pressure 0-1.0MPa.
In above-mentioned technical proposal, in step (2), gas and liquid two phases countercurrent reaction is referred to: oxidation product is gas phase, oxidation
Formaldehyde in product is also gas phase, and formaldehyde carries out polymerization reaction under the catalytic action of the catalyst B in extraction catalytic tower
(autohemagglutination) generates metaformaldehyde aqueous solution；And react residual gas and continue uplink in tower, the metaformaldehyde of generation is also with anti-
The air-flow of residual gas is answered to continue uplink, extractant that metaformaldehyde is added from extractant feed opening 2D, top-down is inhaled
It receives, density is bigger after extractant absorption metaformaldehyde can come downwards to tower bottom；And react the formaldehyde in residual gas also can be by from upper
Extractant under and absorbs, and the extractant for absorbing formaldehyde is liquid phase, absorb formaldehyde extractant density it is larger also can downlink and
And it flows from above to below always；Reaction residual gas is uplink always, reacts the formaldehyde in residual gas and absorbs formaldehyde
Extractant in formaldehyde also carry out polymerization reaction, be macroscopically gas-liquid counter current reaction.
In above-mentioned technical proposal, in step (2), the catalyst B is macropore cation resin, in superpower acid resin
Any one, preferably Kai Rui environmental protective chemical industry limited liability company production D006 type acid resin catalyst, the resistance to height of D008 type
Warm acid resin catalyst.
In above-mentioned technical proposal, in step (2), the oxidation product in extraction catalytic tower is entered, feedstock quality is empty
Speed is 0.1-5.0h-1。
In above-mentioned technical proposal, in step (2), the extractant is the alkane of purified petroleum benzin, aromatic hydrocarbons, carbon number greater than 4, cycloalkanes
Any one in hydrocarbon or two kinds or more the mixtures being mixed in any proportion.
In above-mentioned technical proposal, in step (2), the extractant, dosage is the quality of metaformaldehyde aqueous solution
0.1-10.0 times, feedstock quality air speed: 0.1-10.0h-1。
In above-mentioned technical proposal, in step (2), the extraction catalytic tower, reaction condition are as follows: tower top temperature 60-
90 DEG C, pressure 0.1-0.5MPa, 60-120 DEG C of bottom temperature, pressure 0.1-0.6MPa.
In above-mentioned technical proposal, in step (2), catalyst B, the number of segment of filling is N, and 1≤N≤100, every section of height is 1-
3m；Loading pattern is preferably modular, and filling of the form as disclosed in patent CN204685110U (2015202973481) is urged
The novel plug filler of agent.
In above-mentioned technical proposal, in step (3), the separator, operating condition are as follows: inlet temperature: 30-120 DEG C, behaviour
Make pressure: 0.1-1.0MPa.
In above-mentioned technical proposal, in step (4), the fractionating column, operating condition are as follows: tower top temperature: 70-100 DEG C；Tower
Bottom temperature: 100-150 DEG C；Operating pressure: 0.1-1.0Mpa.
In above-mentioned technical proposal, in step (4), the reflux ratio is 0.1-3.0.
The advantages of the technical program is: dimethoxym ethane mixes with air the product after oxidation, in the effect of module catalyst
Under, catalytic distillation coupling technique is extracted with this technology-use, produces high-purity metaformaldehyde product, existing water is overcome and absorbs skill
Defect and drawback existing for art, concentration technique, sulfuric acid catalysis technology, extraction drying technology etc., have started a process conditions temperature
With, process flow is short, invest it is small, it is quick；Efficient low-consume, new technology both with many advantages of clean and environmental protection.
Detailed description of the invention
Fig. 1 is the flow chart for the method that present invention extraction couples synthesizing triformol with catalysis technique；
Fig. 2 is the structural schematic diagram for the device that present invention extraction couples synthesizing triformol with catalysis technique；
Fig. 3 is the schematic diagram of internal structure of extraction catalytic tower of the invention；
Wherein: 1, methylal oxidation reactor, 2, extraction catalytic tower, 3, separator, 4, fractionating column, 5, waste heat boiler
Furnace, 6, heat exchanger, 7, condenser, 8, return tank, 9, reflux pump, 10, reboiler, 11, coalescer, 12, distributor, 13, foam removal
Device, 14, catalyst B.
Specific embodiment
The specific embodiment of technical solution of the present invention is described in detail below, but the present invention is not limited in being described below
Hold:
Present invention firstly provides the devices that a kind of extraction couples with catalysis technique synthesizing triformol: including what is be sequentially connected
Heat exchanger 6, methylal oxidation reactor 1, extraction catalytic tower 2, separator 3, fractionating column 4；Air and oxidic raw materials are advanced
Enter and be heated into heat exchanger shell pass, then into oxidation reaction is carried out in methylal oxidation reactor, oxidation reaction is obtained
The high oxidation product of temperature enters and obtains the oxidation product of temperature reduction in heat exchanger tube pass after heat exchange, the oxidation that temperature reduces
Product enters back into extraction catalytic tower and carries out polymerization reaction, and polymerizate successively obtains product after extraction, separation, fractionation
Metaformaldehyde, as shown in Figures 2 and 3:
The heat exchanger 6 is tubular heat exchanger, is equipped with solidifiable substance import 6B above the side wall of shell side, lower section is equipped with
Hot material outlet 6A, the bottom of tube side are equipped with feed inlet 6D, and top is equipped with discharge port 6C,；Wherein: solidifiable substance import 6B with can
The device for providing air and/or dimethoxym ethane is connected heat；
The methylal oxidation reactor 1, top is equipped with feed inlet 1A, bottom is equipped with discharge port 1B, the top of side wall
Outlet 1C is equipped with equipped with import 1D, lower section, in which: feed inlet 1A is connected with the hot material outlet 6A of heat exchanger 6；Discharge port 1B
It is connected with the feed inlet 6D of heat exchanger；Be equipped with waste heat boiler 5 between import 1D, outlet 1C, export 1C and waste heat boiler into
Mouth is connected, and import 1D is connected with the outlet of waste heat boiler, and waste heat boiler provides heat for oxidation reaction；Methylal oxidation is anti-
It answers and is filled with catalyst A in device；
The extraction catalytic tower 2, top is equipped with exhaust outlet 2C, bottom is equipped with discharge port 2B, is equipped with below side wall
Feed inlet 2A, top are equipped with extractant feed opening 2D；Wherein: feed inlet 2A is connected with the discharge port 6C of heat exchanger 6；Extractant
Feed opening 2D is connected with the device for being capable of providing extractant；Exhaust outlet 2C point is two-way, all the way with the solidifiable substance of heat exchanger into
Mouth 6B is connected, to return to and recycle air, another way is directly connected with exhaust treatment system, and after processing
Gas is emptied；Extract catalytic tower inside top be equipped with demister 13, it is internal above and below be equipped with distributor
12, the distributor of lower section is connected with feed inlet 2A, and the distributor of top is connected with extractant feed opening 2D；Upper and lower distribution
Catalyst B is equipped between device；
The separator 3, it is water-soluble that one end is equipped with feed inlet 3A, the other end is equipped with discharge port 3C, bottom is equipped with dilute formaldehyde
Liquid exports 3B；Wherein: feed inlet 3A is connected with the discharge port 2B of extraction catalytic tower；Dilute formalin outlet 3B and storage
The device for depositing dilute formalin is connected；It is equipped with the coalescer 11 of extractant in separator, and is located at close to feed inlet 3A's
One end；
The fractionation 4, top is equipped with gaseous phase outlet 4B, bottom is equipped with discharge port 4D, be equipped with above side wall feed inlet 4A,
Refluxing opening 4C is equipped with above another side wall；Wherein: feed inlet 4A is connected with the discharge port 3C of separator；Gaseous phase outlet 4B is successively
It is connected with condenser 7, drainer 8, reflux pump 9；The outlet of reflux pump is divided into two-way, is connected all the way with refluxing opening 4C, another
Road is connected to recycle extractant with the extractant feed opening 2D of extraction catalytic tower；Discharge port 4D and stored product three
The device of polyformaldehyde is connected；
The fractionating column 4, is filled with tower internals in tower, and tower internals is structured packing, any one in column plate；If
Structured packing, filling number of segment are N, and 1≤N≤100, every section of height is 1-3 meters；If column plate, then number of theoretical plate is M, 1≤M
≦100；Reboiler 10 is installed below fractionation tower side wall.
In the present invention, catalyst A in methylal oxidation reactor 1 is iron-molybdic catalyst, iron-molybdic catalyst preferably with hair
Bright patent CN201710307041.9 or utility model patent CN201720485329.0 or utility model patent
The type and proportion of the catalyst active component used or active catalyst in CN201720483709.0 are identical: MOO360-
78%, Fe2O320-39%, other elements oxide 0.1-2.0%；The other elements oxide be IIIA, IV A or
The oxide of any one or two kinds of elements in VIII group in the oxide of element is formed with the mass ratio mixture of 0.1-1:1
Mixture；The other elements oxide is preferably Al2O3。
In the present invention, the methylal oxidation reactor (1), structure preferably with utility model patent
The structure of the equipment of methanol oxidation in CN201720483709.0 is identical: its main body is oxidation reactor, oxidation reactor
Be made of shell and internal component, the internal component be from top to bottom followed successively by stainless steel cloth, upper spacer, tubulation, under every
Plate, the top of the shell is equipped with feed inlet, bottom is equipped with discharge port；Feed inlet 1A, discharge port 1B be equal to it is described
The inlet port and outlet port of the equipment of methanol oxidation, the side wall of outer shell of the equipment of the methanol oxidation top, under
Import 1D described in Fang Kaishe, outlet 1C:
In the oxidation reactor, the stainless steel cloth of peptizaiton, the lower part peace of stainless steel cloth have been installed in top
The dress upper spacer, weld more below upper spacer described in tubulation, the end welding of the tubulation lower clapboard；
The tubulation, it is arranged evenly in equilateral triangle each other；(when oxidation reactor is commercial plant, tubulation
It is for more and arranged evenly in equilateral triangle each other；But when carrying out small-scale test, for save the cost, oxidation is anti-
Answering device is Pilot Unit, and tubulation is single)；
The bale packing catalyst of multiple cylinders is filled with inside the tubulation；
The outer diameter of the bale packing catalyst is equal to the internal diameter of the tubulation of methanol oxidation device；
Internal diameter >=25mm, preferably >=60mm, the further preferably >=80mm of the tubulation, every tubulation length >=1500mm,
It is preferred that >=2000mm, further preferably >=3000mm；
Number N >=5 of filling bale packing catalyst in tubulation described in every, preferably >=10；
The height of the bale packing catalyst is >=100mm, preferably >=200mm, further preferably >=300mm；
The bale packing catalyst include stainless steel flat screen, stainless steel ripple silk net and catalyst active component (
Exactly catalyst A of the invention): the catalyst active component is evenly distributed on the stainless steel flat screen, institute
The stainless steel ripple silk net stated tiles with it be superimposed the catalyst active component that backpack cover residence is stated after, by border seal, with one end
The bale packing catalyst of solid cylindrical shape is rolled into for axle center；
The catalyst active component is spherical shape, bar shaped, cylinder or cube shaped；Spherical diameter, bar shaped
Length, width and height, cylindrical diameter and height, cube shaped side length are both needed to the net greater than stainless steel flat screen
The mesh side length of hole side length and stainless steel ripple silk net；The mesh side length and stainless steel corrugation of the stainless steel flat screen
The equal < 2mm of the mesh side length of net；
The catalyst active component is compounded by the component of following mass percent: MOO360-78%,
Fe2O320-39%, other elements oxide 0.1-2.0%；The other elements oxide is in IIIA, IV A or VIII group
Mixture made of mass ratio mixture of the oxide of any one or two kinds of elements in the oxide of element with 0.1-1:1；
The other elements oxide is preferably Al2O3；
The bale packing Catalyst packing is placed from top to bottom in tubulation, the alternate angle of two adjacent bale packing catalyst
≥10o；Alternate angle is the angle of the horizontal center of circle line of edge line when adjacent bale packing catalyst rolls；
The bale packing catalyst, each distribution for packing the catalyst active component on catalyst are uniformly that is, one
The sendout of active catalyst on each section of a bale packing catalyst is uniformity；Multiple bale packing Catalyst packings are arranging
Guan Shi, axially, from top to bottom, the catalyst active component packed in catalyst uniformly increase, the bale packing catalyst at top
In catalyst active component is minimum, the catalyst active component in bale packing catalyst of bottom is most；
Axially, from top to bottom, pack catalyst in catalyst active component uniformly increase, increased amplitude according to
Following formula calculate:
K=(an+1-an)/an, K are constant and 0 < k < 1；
An is the quality of the active catalyst of n-th layer；
An+1 is the quality of (n+1)th layer of active catalyst, i.e., the quality of one layer of active catalyst below n-th layer；
N=1,2,3,4,5,6......n natural positive integer；
As k=1, active catalyst is to be uniformly distributed in as entire tubulation；As 0 < k < 1 then along under tubulation axial direction
It being gradually increased on each section, i.e., more arrives the lower part of reactor tubulation, amount contained by active catalyst is more on each section, and
It and is uniformly increased.
In the present invention, point of distributor, lower section that the catalyst B 14 in the extraction catalytic tower 2 is located above
Between cloth device (as shown in Figure 3)；Catalyst B is macropore cation resin, any one in superpower acid resin, preferably triumphant auspicious
D006 type acid resin catalyst, the D008 type high temperature resistant acidic resin catalyst of environmental protective chemical industry limited liability company production.
In the present invention, the filling form of the 2 internal accelerator B of extraction catalytic tower is preferably modular, filling
Amount is N sections, 1≤N≤100, every section of height 1-3m；Modular can be according to patent of invention CN204685110U
(2015202973481) the novel plug filler of the loading catalyst disclosed in is configured: the New-type mould of loading catalyst
Block filler includes catalyst elements and supporting adn fixing device；It is metal lath inner layer metal that the catalyst elements, which are by outer layer,
Being filled with catalyst in closing basket made of after silk screen is compound, (catalyst is catalyst B of the invention, that is, replaces with this hair
Any one in the macropore cation resin of bright needs, superpower acid resin) the long column shape structure that constitutes afterwards；The branch
Supportting fixed device includes support frame and fixing belt；The support frame is the plate structure for being evenly equipped with several through-holes；Described is more
A catalyst elements pass through the through-hole support of support frame one by one, are fixed with anchor band around the support frame；In use, will urge
Agent unit is inserted into support frame, is fixed with fixing belt and constitutes one group of module filler, multiple groups module filler is layered spelling in tower
After dress, installation anti-wall flow circle in periphery is further ensured that the firm and catalytic distillation effect of catalytic distillation structure, while pacifying into tower
It is more convenient when dress；The catalyst elements cross section is round or polygon (being circle in embodiment)；The support
Frame at least two (being 4 in embodiment)；The support frame is that round or polygon plate structure (is in embodiment
It is round)；The fixing belt, support frame are sheet metal；The fixing belt is strip, be transversely with longitudinal direction (embodiment
In be transverse direction) be packaged the support frame.
In the present invention, the extractant being added in extraction catalytic tower from extractant feed opening 2D is preferably purified petroleum benzin, virtue
The alkane of hydrocarbon, carbon number greater than 4, any one or two kinds or more the mixtures being mixed in any proportion in cycloalkane.
In the present invention, the waste heat boiler 5, heat exchanger (shell and tube) 6, condenser 7, drainer 8,9 reboiling of reflux pump
Device 10, coalescer 11, distributor 12, demister 13 are common commercial equipment.
The present invention provides a kind of method for extracting and coupling synthesizing triformol with catalysis technique, comprising the following steps:
(1) oxidation reaction: after oxidic raw materials and air be preheated in heat exchanger 6 or heating mixes, by 1A mouthfuls of feed inlet
It enters in methylal oxidation reactor 1, in it under catalyst A effect, oxidation reaction occurs, generate oxidation product by discharging
1B mouthfuls of discharges of mouth, exchange heat through heat exchanger, are imported in the extraction catalytic tower 2 equipped with module catalyst by 2A mouthfuls of feed inlet；
(2) built-in distributor is equipped at feed inlet 2A, oxidation product enters in extraction catalytic tower through distributor,
Under the catalytic action of module catalyst, gas and liquid two phases countercurrent reaction occurs, generates metaformaldehyde aqueous solution, and added by extractant
The extractant of 2D mouthfuls of material mouth entrance is absorbed, and the extract liquor for absorbing metaformaldehyde aqueous solution is discharged by 2B mouthfuls of discharge port, remaining
Gas continues to go upward to reaction tower exhaust outlet 2C in tower, and residual gas a part is emptied through processing, and another part returns to first contracting
Oxidation of aldehydes reactor cycles utilize；
(3) being generated by extraction catalytic tower, by 2B mouthfuls of discharge port be discharged absorb the extraction of metaformaldehyde aqueous solution
Take liquid to import the feed inlet 3A of separator, and by built-in coalescer 11 further separation after, extraction phase is imported point by discharge port 3C
The feed inlet 4A of tower is evaporated, the dilute formalin of raffinate phase-exports 3B mouthfuls of discharges by dilute formalin, imports holding vessel and collects separately
Use it for anything else
(4) under the heat effect of 4 reboiler of fractionating column, gas phase (extractant) exports extraction phase through gaseous phase outlet 4B,
Import condenser, drainer, reflux pump and divide two-way: refluxing opening 4C mouthfuls of a routing flows back into fractionating column, and another way is by extractant
Feed opening 2D is back to extraction catalytic tower and recycles, and discharge port 4D mouthfuls of fractionation column bottom is discharged being refined, high-purity
Metaformaldehyde finished product.
The method of the present invention and device are illustrated below with reference to specific embodiment.
Embodiment 1:
A kind of method of methylal oxidation and synthesizing triformol, comprising the following steps:
(1) methylal oxidation reacts: after 7.6g dimethoxym ethane is preheated to 100-150 DEG C with the preheated device 6 of 7.28L air, by
Feed inlet 1A is entered in methylal oxidation reactor, and feedstock quality air speed is 0.15h-1, the iron-molybdic catalyst in it is (the same as specially
The embodiment 1:M of sharp CN201720483709.0OO374%, Fe2O325%, Al2O3It is 1.0%；) catalytic action under carry out
Oxidation reaction, the reaction condition in methylal oxidation reactor are as follows: temperature: 300 DEG C, under normal pressure state；14L oxidation has been obtained to produce
Object；The temperature of oxidation product at methanol oxidation device discharge port 1B is 260-350 DEG C, and oxidation product is changed through heat exchanger (6)
Heat, temperature are entered in extraction catalytic tower (2) after being reduced to 95-105 DEG C by feed inlet 2A；
Methylal oxidation reactor used in the present embodiment, single tubulation internal diameter are 25mm, and the length of every tubulation is
1500mm, every tubulation are provided with 10 bale packing catalyst, and the alternate angle of two adjacent bale packing catalyst is 15 degree；1st layer
The quality that (i.e. top layer) packs active constituent in catalyst is 5g, and the quality of active constituent is 6g in the 2nd layer of bale packing catalyst,
That is K=0.2.
(2) polymerization reaction: the 14L oxidation product that step (1) obtains, Feed space velocities 0.2h-1, in extraction catalytic tower
(2) under the catalytic action of D006 catalyst, liquid phase countercurrent reaction occurs and generates 10.8g metaformaldehyde aqueous solution, reacts item
Part are as follows: 75 DEG C of tower top temperature, 0.15MPa, 100 DEG C of bottom temperature, 0.20MPa；Reaction residual gas continues to go upward in tower
Exhaust outlet 2C, a part are emptied through processing, and another part in feed inlet 1A Returning oxidation reactor by recycling；And trimerization first
Aldehyde aqueous solution after discharge port 2B, feed inlet 3A followed by entering in separator (3)；
D006 catalyst in the extraction catalytic distillation tower, loadings are 5 sections, and every section of height is 2m；According to invention
The novel plug filler of loading catalyst disclosed in patent CN204685110U (2015202973481) is arranged to module
Formula；
The extractant is purified petroleum benzin, and additional amount is twice of 15.2g, that is, metaformaldehyde of amount, feedstock quality air speed:
0.64h-1。
(3) separate: the metaformaldehyde aqueous solution as obtained in step (2) enters separator by separator feed inlet 3A
Afterwards, raffinate phase and the further Relatively centralized of extraction phase under the action of coalescer；And the dilute formalin of raffinate phase-is by separator
Outlet at bottom 3C discharge, and it is otherwise utilized after collecting, and extraction phase is followed by entering fractionation after discharge port 3B, feed inlet 4A
In tower (4)；Inlet temperature: 90-100 DEG C, pressure: 0.20MPa.
(4) it is fractionated: after the obtained extraction phase in step (2) enters fractionating column, in the reboiler (10) of fractionating column
It is fractionated under heat effect, reaction condition are as follows: tower top temperature: 70-90 DEG C；Column bottom temperature: 100-150 DEG C；Operating pressure:
0.1-0.50Mpa obtains gas phase and liquid phase；Gas phase is extractant, and gas phase is discharged through exhaust outlet II (4B) and enters condenser
(7) it is condensed in, the extract liquor of 15.2g liquid is obtained after condensation followed by drainer (8), reflux pump and is divided into two after (9)
Road is back in fractionating column from refluxing opening (4C) all the way, and control reflux ratio is 0.2, and another way is returned from extract liquor import (3B)
It is recycled into extraction tower；Liquid phase is product metaformaldehyde finished product, and 8.8g purification, high-purity metaformaldehyde finished product is by tower bottom
Discharge port 4D discharge and be collected or harvest；
The fractionating column (4), the interior filling internals of tower are stainless steel corrugated plate packing, and filling number of segment is 3 sections, every section of height
For 2m.
In the present embodiment, the yield of metaformaldehyde is 95% or more, purity is nearly 100%.
Embodiment 2:
A kind of method of methanol oxidation and synthesizing triformol, method and step is same as Example 1, except that handle
The inlet amount of dimethoxym ethane increases 1 times, and it is nearly 100% for 95% or more, purity that the yield of metaformaldehyde, which increases still,.
Examples detailed above is technical conception and technical characteristics to illustrate the invention, can not be limited with this of the invention
Protection scope.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (10)
1. a kind of extract the method for coupling synthesizing triformol with catalysis technique, which comprises the following steps:
(1) oxidation reaction: oxidic raw materials and air after being preheated to 100-200 DEG C, carry out oxygen under the catalytic action of catalyst A
Change reaction, obtain the higher oxidation product of temperature after oxidation reaction, the oxidation product of temperature reduction is obtained after exchanging heat；
(2) polymerization reaction: the oxidation product that temperature reduces carries out polymerization reaction under the catalytic action of catalyst B, generates trimerization
Formalin；Metaformaldehyde aqueous solution forms the extractant containing metaformaldehyde after being extracted agent extraction, and reacts remaining gas
The emptying of body a part, another part are back in step (1) and are recycled；
(3) separate: the extractant dehydration containing metaformaldehyde obtains dilute formalin and the extraction phase containing metaformaldehyde；
Dilute formalin is otherwise utilized after collecting；And the extraction phase containing metaformaldehyde is fractionated；
(4) be fractionated: the extraction phase containing metaformaldehyde obtained in step (3) is fractionated in a heated state, obtains gas phase
And liquid phase；Gas phase is extractant, and liquid-phase extraction agent, a part reflux are obtained after condensing, and a part is back in step (2) and follows
Ring utilizes；Liquid phase is product metaformaldehyde finished product, is collected or harvests.
2. the method according to claim 1, wherein specifically includes the following steps:
(1) oxidation reaction: oxidic raw materials and air are entered in the shell sides of heat exchanger (6) by solidifiable substance import 6B and are preheated,
It is exported after being preheated to 100-200 DEG C by hot material outlet 6A and is imported into methylal oxidation reactor (1) by feed inlet 1A,
Oxidation reaction is carried out under the catalytic action of catalyst A in it；Oxidation at the discharge port 1B of methylal oxidation reactor produces
The temperature of object is 200-450 DEG C；200-450 DEG C of oxidation product is exported by discharge port 1B and imported into heat exchange by feed inlet 6D
It exchanges heat in the tube side of device (6), temperature is exported by discharge port 6C after being reduced to 95-105 DEG C and imported into extraction by feed inlet 2A
It takes in catalytic tower (2)；
(2) polymerization reaction: the oxidation product in step (1) enters in extraction catalytic tower (2), catalyst B in it
Under catalytic action, gas and liquid two phases countercurrent reaction occurs and generates metaformaldehyde aqueous solution；On reaction residual gas continues in tower
Row, and metaformaldehyde with reaction residual gas air-flow continue uplink and be extracted agent feed opening 2D addition, adverse current and under
Extractant extract and be absorbed, extractant absorbs after metaformaldehyde that density is bigger can come downwards to tower bottom, from the discharging of tower bottom
Mouth 2B is exported and is imported into separator (3) by feed inlet 3A；And it reacts residual gas and will continue to go upward to demister in tower
(13) at, demister thoroughly retains the extractant wherein carried secretly, residual gas to exhaust outlet 2C, and a part is emptied through processing,
Another part is imported into heat exchanger together with oxidic raw materials heated according to operation described in step (1) as solidifiable substance import 6B
It is recycled in Returning oxidation reactor afterwards；
(3) separate: the extractant in step (2) is entered in separator after absorbing metaformaldehyde by feed inlet 3A, in separator
It is further dehydrated under the action of internal coalescer (11), obtains dilute formalin and the extraction phase containing metaformaldehyde；It is dilute
Formalin is discharged by dilute formalin outlet 3B of separator bottom, and otherwise utilized after collection；And contain trimerization first
The extraction phase of aldehyde is exported by discharge port 3C and is imported into fractionating column (4) by feed inlet 4A；
(4) it is fractionated: after the extraction phase containing metaformaldehyde obtained in step (3) enters fractionating column, in boiling again for fractionating column
It is fractionated under the heated condition of device (10), obtains gas phase and liquid phase；Gas phase is extractant, and gas phase is discharged through gaseous phase outlet 4B,
It is divided into two-way after (9) followed by condenser (7), return tank (8), reflux pump, is back in fractionating column from refluxing opening 4C all the way,
Another way is back in extraction catalytic tower by extractant feed opening 2D and is recycled；Liquid phase is product metaformaldehyde finished product,
It is discharged by the discharge port 4D of tower bottom and is collected or harvests.
3. according to the method described in claim 2, it is characterized by: the oxidic raw materials are dimethoxym ethane, first in step (1)
Any one in alcohol, dimethyl ether, two or more mixture mixed with arbitrary proportion；
After the oxidic raw materials mix with air, the wherein mass content of oxygen are as follows: 5-20%, feedstock quality air speed are 0.1-
10.0h-1；
The catalyst A is iron-molybdic catalyst；
Reaction condition in the methylal oxidation reactor (1) are as follows: 200-450 DEG C of temperature, pressure 0-1.0MPa.
4. according to the method described in claim 2, it is characterized by: the catalyst B is macroporous cation in step (2)
Any one in resin, superpower acid resin；
The extractant be the alkane of purified petroleum benzin, aromatic hydrocarbons, carbon number greater than 4, any one or two kinds or more in cycloalkane with
The mixture that arbitrary proportion mixes；
The oxidation product in extraction catalytic tower (2) is entered, feedstock quality air speed is 0.1-5.0h-1；
The extractant, dosage are 0.1-10.0 times of the quality of metaformaldehyde aqueous solution, feedstock quality air speed: 0.1-
10.0h-1；
The extraction catalytic tower (2), reaction condition are as follows: 60-90 DEG C of tower top temperature, pressure 0.1-0.5MPa, tower reactor temperature
Spend 60-120 DEG C, pressure 0.1-0.6MPa.
5. according to the method described in claim 2, it is characterized by: in step (3), the separator (3), operating condition
Are as follows: inlet temperature: 30-120 DEG C, operating pressure: 0.1-1.0MPa；
The fractionating column (4), operating condition are as follows: tower top temperature: 70-100 DEG C；Column bottom temperature: 100-150 DEG C；Operating pressure:
0.1-1.0Mpa；In step (4), the reflux ratio is 0.1-3.0.
6. a kind of extract the device for coupling synthesizing triformol with catalysis technique, including heat exchanger (6), the dimethoxym ethane being sequentially connected
Oxidation reactor (1), extraction catalytic tower (2), separator (3), fractionating column (4)；Air and oxidic raw materials, which are introduced into, to be changed
It is heated in hot device shell side, then into oxidation reaction is carried out in methylal oxidation reactor, oxidation reaction obtains temperature height
Oxidation product enter in heat exchanger tube pass exchange heat after obtain temperature reduction oxidation product, temperature reduce oxidation product again
Polymerization reaction is carried out in into extraction catalytic tower, polymerizate successively obtains product trimerization first after extraction, separation, fractionation
Aldehyde, it is characterised in that:
The heat exchanger (6) is tubular heat exchanger, solidifiable substance import 6B is equipped with above the side wall of shell side, lower section is equipped with heat
Material outlet 6A, the bottom of tube side are equipped with feed inlet 6D, and top is equipped with discharge port 6C,；Wherein: solidifiable substance import 6B with can mention
It is connected heat for the device of air and/or dimethoxym ethane；
The methylal oxidation reactor (1), top is equipped with feed inlet 1A, bottom is equipped with discharge port 1B, sets above side wall
There are import 1D, lower section to be equipped with outlet 1C, in which: feed inlet 1A is connected with the hot material outlet 6A of heat exchanger (6)；Discharge port 1B
It is connected with the feed inlet 6D of heat exchanger；Waste heat boiler (5) are equipped between import 1D, outlet 1C, export 1C and waste heat boiler
Import is connected, and import 1D is connected with the outlet of waste heat boiler, and waste heat boiler provides heat for oxidation reaction；
The extraction catalytic tower (2), top is equipped with exhaust outlet 2C, bottom is equipped with discharge port 2B, be equipped with below side wall into
Material mouth 2A, top are equipped with extractant feed opening 2D；Wherein: feed inlet 2A is connected with the discharge port 6C of heat exchanger (6)；Extractant
Feed opening 2D is connected with the device for being capable of providing extractant；Exhaust outlet 2C point is two-way, all the way with the solidifiable substance of heat exchanger into
Mouth 6B is connected, to return to and recycle air, another way is directly connected with exhaust treatment system, and after processing
Gas is emptied；
The separator (3), one end is equipped with feed inlet 3A, the other end is equipped with discharge port 3C, bottom is equipped with dilute formalin
Export 3B；Wherein: feed inlet 3A is connected with the discharge port 2B of extraction catalytic tower；Dilute formalin outlet 3B and storage
The device of dilute formalin is connected；It is equipped with the coalescer (11) of extractant in separator (3), and is located at close to feed inlet 3A
One end；
The fractionating column (4), top is equipped with gaseous phase outlet 4B, bottom is equipped with discharge port 4D, be equipped with above side wall feed inlet 4A,
Refluxing opening 4C is equipped with above another side wall；Wherein: feed inlet 4A is connected with the discharge port 3C of separator；Gaseous phase outlet 4B is successively
It is connected with condenser (7), drainer (8), reflux pump (9)；The outlet of reflux pump is divided into two-way, is connected all the way with refluxing opening 4C
It connects, another way is connected to recycle extractant with the extractant feed opening 2D of extraction catalytic tower；Discharge port 4D and storage
The device for depositing product metaformaldehyde is connected.
7. device according to claim 6, it is characterised in that: the methylal oxidation reactor (1), structure with it is practical
The structure of the equipment of methanol oxidation in new patent CN201720483709.0 is identical, feed inlet 1A, discharge port 1B etc.
The inlet port and outlet port of the equipment of the methanol oxidation are same as, in the side wall of outer shell of the equipment of the methanol oxidation
Top, lower section open up the import 1D, outlet 1C；Catalyst A is filled in the methylal oxidation reactor (1).
8. device according to claim 6, it is characterised in that: the extraction catalytic tower (2), internal top is set
Have demister (13), it is internal above and below be equipped with distributor (12), the distributor of lower section is connected with feed inlet 2A, on
The distributor of side is connected with extractant feed opening 2D；Catalyst B (14), catalyst B are filled with inside extraction catalytic tower
Between the distributor of the distributor, lower section that are located above；Being added to the extractant in it from extractant feed opening 2D is purified petroleum benzin, virtue
The alkane of hydrocarbon, carbon number greater than 4, any one or two kinds or more the mixtures being mixed in any proportion in cycloalkane.
9. device according to claim 8, it is characterised in that: described extraction catalytic tower (2) the internal accelerator B's
Filling form is modular, and loadings are N sections, 1≤N≤100, every section of height 1-3m；Modular is according to patent of invention
The novel plug filler of loading catalyst disclosed in CN204685110U (2015202973481) is configured.
10. device according to claim 6, it is characterised in that: the fractionating column (4), tower is interior to be filled with tower internals, tower
Internals are structured packing, any one in column plate；If structured packing, filling number of segment is N, 1≤N≤100, every section of height
It is 1-3 meters；If column plate, then number of theoretical plate is M, 1≤M≤100；The fractionating column (4), side wall lower section are equipped with reboiler
(10)。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256399A (en) * | 2019-07-29 | 2019-09-20 | 凯瑞环保科技股份有限公司 | A kind of device and method that methylal oxidation produces metaformaldehyde |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106957221A (en) * | 2017-05-05 | 2017-07-18 | 凯瑞环保科技股份有限公司 | The device and method of polymethoxy dimethyl ether is produced in a kind of methanol oxidation |
| CN108395422A (en) * | 2018-05-16 | 2018-08-14 | 凯瑞环保科技股份有限公司 | A kind of the synthesis extracting process and device of metaformaldehyde |
| CN108409707A (en) * | 2018-05-16 | 2018-08-17 | 凯瑞环保科技股份有限公司 | A kind of the catalytic distillation synthetic method and device of metaformaldehyde |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106957221A (en) * | 2017-05-05 | 2017-07-18 | 凯瑞环保科技股份有限公司 | The device and method of polymethoxy dimethyl ether is produced in a kind of methanol oxidation |
| CN108395422A (en) * | 2018-05-16 | 2018-08-14 | 凯瑞环保科技股份有限公司 | A kind of the synthesis extracting process and device of metaformaldehyde |
| CN108409707A (en) * | 2018-05-16 | 2018-08-17 | 凯瑞环保科技股份有限公司 | A kind of the catalytic distillation synthetic method and device of metaformaldehyde |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110256399A (en) * | 2019-07-29 | 2019-09-20 | 凯瑞环保科技股份有限公司 | A kind of device and method that methylal oxidation produces metaformaldehyde |
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