CN107074711A - Improved formaldehyde recovery method - Google Patents
Improved formaldehyde recovery method Download PDFInfo
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- CN107074711A CN107074711A CN201580047127.1A CN201580047127A CN107074711A CN 107074711 A CN107074711 A CN 107074711A CN 201580047127 A CN201580047127 A CN 201580047127A CN 107074711 A CN107074711 A CN 107074711A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Abstract
The invention provides the improved method that unreacting acetal is reclaimed in a kind of butynediols synthetic reaction product from butynediols synthesis reactor downstream.
Description
Technical field
During butanediol is manufactured by the raw material comprising acetylene, formaldehyde and hydrogen, for commercial petroleum chemical plant
For operation, the cost associated with the recycling of unreacting acetal is critical.The present invention relates to a kind of improved method, institute
State method be used for optimize the unreacting acetal from butynediols reactor product recycling in energy use.More specifically
Ground, methods described includes：The stream comprising unreacting acetal is fed in butynediols synthesis reactor downstream and is maintained at special
Tower under fixed condition；Removed from tower and include the top stream of formaldehyde, water and methanol, for recycling and handling to remove
Methanol；And removing includes the bottom steam of butynediols, water, methanol and the formaldehyde less than 1wt% (by weight) from tower,
For further handling with the butanediol of quality needed for producing.It is accomplished by the following way energy-optimised：In overhead product condensation
Rise steam (has been produced) in tower reboiler by steam condensate in device/steam lift unit, and has passed through tower reboiler
The middle compressor transmission used carrys out the steam of condenser/steam lift unit；Or carried in overhead condenser/steam
The steam condensate rise steam simply produced in device unit in tower reboiler is risen, and transmits condenser/steam lifting
The steam produced in device unit is with as needed for other techniques.
Background technology
In the current method of manufacture butanediol, acetylene and formaldehyde are converted to butynediols, and butynediols is hydrogenated again
And form butanediol.By acetylene and formaldehyde synthesizing butynediol for example in K.Weissermel, H.-J.Arpe,《Industry is organic
Chemical (Industrielle Organische Chemie) [Industrial Organic Chemistry]》, the 5th edition,
It is described in page 1998, Wiley-VCH, 110 and 111.In addition to copper, in appropriate circumstances, in this synthesis
In usually used catalyst can include bismuth and silica (SiO2) or aluminum oxide (Al2O3).Butynediols is hydrogenated to
Butanediol has been described many times.For example, U.S. Patent No. 5,068,468 is disclosed and urged by the nickel-copper of solid supported
Hydrogenation of the agent to butynediols, and U.S. Patent No. 4,153, No. 578 thunder Buddhist nuns for describing at a particular pressure by suspension
Nickel-molybdenum (Raney nickel-molybdenum) catalyst hydrogenates the two-phase method of butynediols.Patent publication DD-A 272
644 disclose by nickel-SiO2Catalyst is to the hydride suspension of aqueous butynediols, EP-B 0 319 208, DE-A 19 41
633 and DE-A 20 40 501 discloses the general method for hydrogenation for being applicable to butynediols.
Butynediols can be by preparing comprising following reactant mixture in reaction vessel：The aqueous solution containing formaldehyde,
Acetylene and suspended catalyst.For example, U.S. Patent No. 4,584, No. 418A describes a kind of prepared in single container for closing
Into the method for the cupfic acetylide catalyst of butynediols, wherein making acetylene bubbling by reactor under 90 DEG C and atmospheric pressure.
In another example, U.S. Patent No. 5,444, No. 169A disclose it is a kind of in the presence of suspended catalyst by containing formaldehyde
The aqueous solution by the method with acetylene reaction and synthesizing butynediol, wherein the solution by several reactors in cascaded fashion
Conveying, the solution discharged from first reactor of cascade to penultimate reactor is supplied to next reaction in cascade
Device, acetylene is introduced in each reactor, and is only rich in butynediols from last reactor discharge in cascade
Solution.Catalyst is separated with solution in each independent reactor of cascade above last reactor, to prevent from urging
Agent escapes reactor.
In each example of the butynediols manufacturing step of butanediol manufacture method, unreacting acetal is useful group
Point, it should be recovered and recycle, so that whole process is commercially more favourable.This is generally by finally by butine
Glycol synthesis reactor effluent is fed in destilling tower to complete, wherein remove methanol, formaldehyde and water from tower top, and from bottom of towe
Remove butynediols, water and methanol and a small amount of formaldehyde.This can be the operation of energy-intensive；If butynediols reacts
Device is operated under relatively low formaldehyde conversion, then especially so.In order to obtain the formaldehyde of low concentration, it is necessary to longer stop
Time, and large-scale butynediols reactor is needed to use, or even with a series of this kind of reactors, this causes very
High capital cost.In order that with the formaldehyde of higher concentration, it is necessary to which the reactor residence time of much shorter, this causes to reclaim formaldehyde
High-energy cost.Therefore need a kind of for this recovery and the method for the simple economy of recycling.
The content of the invention
The invention provides unreacting acetal, warp are reclaimed and recycled in a kind of synthetic reaction product stream from butynediols
The improved method of Ji.The embodiment of the inventive method comprises the following steps：A) reaction product comprising unreacting acetal is fed
To tower under given conditions is kept, the tower is associated with reboiler；B) from step a) tower remove comprising formaldehyde, water and
The vapour phase top stream of methanol, and its at least a portion is delivered to the condenser/steam lifting kept under given conditions
In device, wherein raise steam by steam condensate or boiler feedwater by the heat exchange with vapour phase top stream, and from vapour phase
Top stream produces process condensate stream；C) liquid phase for including butynediols, water, formaldehyde and methanol is removed from step a) tower
Bottom steam；D) removing step b) process condensate stream, and its at least a portion is sent back to step a) tower as returning
Stream；E) devaporation is removed from step b) condenser/steam lift, and steam is delivered to step a's) by compressor
The reboiler of tower；And the part of steam condensate for coming from the reboiler of tower in step a) f) is delivered to the cold of step c)
Condenser/steam lift.
Another embodiment of the inventive method comprises the following steps：A) reaction product comprising unreacting acetal is combined
Thing is fed to the tower kept under given conditions, and specified conditions include：Tower top temperature is 115 to 150 DEG C, and column bottom temperature is
130 to 170 DEG C, the tower is associated with reboiler；B) removed from step a) tower comprising water, methanol and at least 25wt%
The vapour phase top stream of formaldehyde, and by its 80 to 100wt% be partially transferred to keep condenser/steaming under given conditions
In vapour lifter, wherein steam is raised by steam condensate or boiler feedwater by the heat exchange with vapour phase top stream, and
Process condensate stream is produced from the vapour phase top stream；C) from step a) tower remove comprising butynediols, water, methanol and
The at most liquid phase bottom steam of 1wt% formaldehyde；D) removing step b) process condensate stream, and by its 50 to 70wt% portion
Dispensing returns in step a) tower and is used as backflow；E) devaporation is removed from step b) condenser/steam lift, and is passed through
Steam is delivered to the reboiler of step a) tower by compressor；And will f) come from the steam condensation of the reboiler of tower in step a)
A part for thing is delivered to step c) condenser/steam lift.
An alternative embodiment of the invention includes above-mentioned steps, and wherein step e) compressor lifts condenser/steam
The pressure of device product increases by 2 to 10 times.
An alternative embodiment of the invention includes above-mentioned steps, but also includes before above-mentioned steps：At reaction conditions
The mixture comprising the aqueous solution containing formaldehyde, acetylene and suspended catalyst is set to be reacted in reaction vessel, to produce comprising not
The reaction product composition of reaction formaldehyde.Therefore, an alternative embodiment of the invention comprises the following steps：1) at reaction conditions
The mixture comprising the aqueous solution containing formaldehyde, acetylene and suspended catalyst is reacted in reaction vessel, fourth is included to produce
Acetylenic glycols, water, the reaction product of unreacting acetal and methanol；2) by it is comprising butynediols, water, unreacting acetal and methanol,
Step 1) reaction product be fed to and keep tower under given conditions, the tower is associated with reboiler；3) from step 2)
Removed in tower and include the vapour phase top stream of formaldehyde, water and methanol, and by its 80 to 100wt% be partially transferred to be maintained at
Condenser/steam lift under the conditions of multiple, wherein by the heat exchange with vapour phase top stream by steam condensate or pot
Stove feedwater rise steam, and produce process condensate stream from the vapour phase top stream；4) from step 2) tower in remove bag
Liquid phase bottom steam containing butynediols, water, formaldehyde and methanol；5) removing step 3) process condensate stream, and by its 50
Send back to step 2 to 70wt% part) tower in as backflow, and the remainder of the process condensate stream is sent back to
Step 1) reaction vessel be used as recycling；6) from step 3) condenser/steam lift in remove devaporation, and pass through pressure
Steam is delivered to step 2 by contracting machine) tower reboiler；And step 2 7) will be come from) in tower reboiler condensate one
Be partially transferred to step 3) condenser/steam lift.
Brief description of the drawings
Fig. 1 shows the schematic flow diagram of the embodiment of the inventive method.
Embodiment
The result of further investigation in view of the foregoing, we have found that, we can be economical and effectively from butine
Unreacting acetal is reclaimed in the butynediols synthetic reaction product compositions in glycol synthesis reactor downstream.Methods described includes：
Reaction product comprising unreacting acetal is fed to the tower kept under given conditions, the tower is associated with reboiler；From
The vapour phase top stream for including formaldehyde, water and methanol is removed in tower, and at least a portion of the top stream of recovery is transmitted
Into the condenser/steam lift kept under given conditions；Removed from tower condenser/steam lift and include butine two
The liquid phase stream of alcohol, water, methanol and unreacting acetal, for being recycled to butynediols reactor and providing tower backflow；Pass through
Heat exchange with tower vapour phase top stream raises steam in condenser/steam lift；Removed from condenser/steam lift
Devaporation, and transmit steam to increase steam pressure by compressor before steam is delivered into tower reboiler；Then will more
The steam condensate of high pressure is passed back to condenser/steam lift from reboiler, for the rise of further steam.
One embodiment of methods described includes：Reaction product composition comprising unreacting acetal is fed to and is maintained at
Tower under specified conditions；The vapour phase top stream for including formaldehyde, water and methanol is removed, and by the top stream of recovery at least
A part is delivered to the condenser/steam lift kept under given conditions；From including butynediols, water, methanol and not anti-
Removing liquid phase bottom steam in the tower of formaldehyde is answered, and its at least a portion is delivered to the reboiler kept under given conditions；
Steam product and condensate are removed from condenser/steam lift, and is lifted by compressor condenser in future/steam
The steam product of device is delivered to reboiler；Remove top stream from condenser/steam lift, and by its at least a portion
Tower top is delivered to as backflow；Condensate is delivered to the top of condenser/steam lift from reboiler, and by tower top material
Stream is delivered to tower from reboiler.
Term butynediols (" BYD ") represents compound structure HOCH2C ≡ CCH2OH.Term butanediol (" BDO ") is represented
Compound structure HOCH2CH2CH2CH2OH.Pressure represents with kPa.A, wherein 98.7kPa=1bar=0.987 atmospheric pressure,
" A " represents absolute pressure, unless otherwise indicated.
In addition to above-mentioned manufacture BYD method, one embodiment of this method also includes：Single or a series of contain
In the reaction vessel for having internal ramp (such as candle filter, the catalyst for separating suspension from reaction product), by
Reactant mixture manufacture BYD comprising the aqueous solution containing formaldehyde, acetylene and suspended catalyst.In this kind of reaction vessel, urge
Agent solid is gathered as pie on the filter, and this can be removed by backwashing each filter, anti-to avoid blocking
Answer device container.The product for including BYD, water, unreacting acetal and methanol is reclaimed from reaction vessel.Another reality of this method
Applying example includes：In reaction vessel, manufactured by the reactant mixture comprising the aqueous solution containing formaldehyde, acetylene and suspended catalyst
Product slurry stream comprising BYD, water, unreacting acetal, methanol and suspended catalyst, is thus delivered to by BYD from reaction vessel
Filter outside reaction vessel, removes the catalyst of suspension in the filter, and BYD, water, unreacted are included so as to allow to reclaim
The product of formaldehyde and methanol.
Generally comprised for the BYD synthetic reaction product compositions in BYD synthesis reactor downstream used herein (in Solid Free
On the basis of)：30 to 50wt% BYD, 40 to 60wt% water, 1 to 15wt% unreacting acetal and 2 are to 7wt%'s
Methanol.
Reaction vessel used in manufacturing BYD method can include the presently used one kind of this method.It is such
Reaction vessel can be bubble column, wherein acetylene and other gases are injected in the bottom of reactor, to be reacted and will urged
Agent solid is maintained at suspended state；Or can be stirred tank reactor, catalyst solid is maintained at outstanding by it using agitator
Floating state simultaneously aids in gas to disperse；Or some combinations thereofs.Reaction condition in such reaction vessel includes：Temperature is
40 to 110 DEG C, such as 60 to 110 DEG C, pressure is 0 to 200kPa.A, such as 9 to 110kPa.A, and pH is 3 to 9.Reaction is held
The content of device is stirred by one or both of mechanical means (such as agitator) and gas injection.
The catalyst used in the reaction vessel for manufacturing BYD is suspended in product slurry stream as solid, the product slurry
Stream includes BYD, water, unreacting acetal and methanol, and the catalyst can be added to reaction zone or produce in the reaction region.Institute
Copper can be included by stating catalyst, and catalyst precarsor can include the compound of copper, such as, such as copper carbonate.
The new improved method of the present invention includes：Designed for reducing the side of the variable cost associated with this method
In method, recycle tower (" tower ") using formaldehyde and reclaimed not from the BYD synthetic reaction product compositions in BYD synthesis reactor downstream
Reaction formaldehyde.Tower used is conventional distil-lation tower, wherein steam heating is implemented in the bottom of tower by reboiler, and by cold
Condenser/steam lift implements water cooling at the top of tower.Methods described utilizes tower top using water as external workflow body
Available heat in distillate.Working fluid is evaporated by being exchanged heat in condenser/steam lift with overhead.
Then the low-pressure steam is compressed within the compressor, is subsequently used as the heating medium of tower reboiler.Then, will again it be boiled from tower
The high pressure condensate of device sends back to condenser/steam lift, makes the condensate evaporative and recompresses.This steam is pressed again
Contracting scheme (loop) significantly reduces the consumption of high steam and the consumption of cooling water.
Tower used herein may include presently used one kind in this unit operation, such as, such as one paving disc type
Tower or packed column.The holding condition of tower includes：Head temperature is 115 to 150 DEG C, and bottom temp is 130 to 170 DEG C.Tower top pressure
Power is 100 to 600kPa.A.
In the new method, most tower energy requirement is provided by above-mentioned loop；However, when condenser/steam is carried
Rise device in available heat be less than reboiler needed for heat when, if for example, reduce tower in steam blowing, directly supply
General steam to reboiler causes the difference between two kinds of energy rates.Allowed using water as working fluid in identical heat exchange
General steam is directly injected into device.This not only no longer to need have individually auxiliary reboiler, and also add heat pump
The control in loop and the free degree of operation.
In order that the efficiency of this method is maximized, we can use the shell and tube heat exchanger of standard as condenser/
Steam lift.When formaldehyde vapor is contacted with cold surface (for example, when water condensation to the cold when), it is contemplated that paraformaldehyde can be promoted
Formed, so as to promote the fouling of exchanger.This method condenses overhead in the case of being included in no cold surface, therefore subtracts
Few exchanger fouling.
Condenser/steam lift used herein can include presently used one kind in the operation of this unit, all
Such as, for example there is the shell and tube heat exchanger of steam formation in shell-side.The maintaining item of condenser/steam lift used herein
Part includes 0 to 400kPa.A pressure, to raise saturated vapor.
Tower reboiler used herein can include presently used one kind in the operation of this unit, such as, for example, stand
Formula thermosyphon or forced circulation heater.The holding condition of reboiler used herein includes 400 to 1400kPa.A pressure
Power.
Step e) used herein compressor can include presently used one kind in the operation of this unit, such as,
Such as reciprocating or axial compressor, or steam jet ejector or hot press.Compressor will be risen in condenser/steam lift
The pressure of high steam increases by 2 to 10 times, such as, such as 3 to 5 times.
In the method, the top stream reclaimed from tower includes at least 25wt% formaldehyde, and the tower reclaimed from tower
Bed material stream includes at most 1wt% formaldehyde.More specifically, the top stream reclaimed from tower comprising 25 to 35wt% formaldehyde,
50 to 60wt% water and 5 to 15wt% methanol；And the bottom steam reclaimed from tower comprising 50 to 60wt% BYD,
40 to 50wt% water, 0 to ＜ 0.1wt% methanol and 0.2 to 1wt% formaldehyde.
In the step b) of this improved method, by the 80 of the top stream removed from step a) tower to 100wt%'s
Partly (such as 93 to 100wt% parts) are delivered to condenser/steam lift, and wherein steam is handed over by the heat with condensate flow
Change and raise.This can be by, for example, being realized using the flow-dividing control of simple control loop.In condenser/steam lifting
Steam is raised in device can be by, for example, raising steam to realize using shell and tube heat exchanger on shell-side.Further,
In the step e) of this improved method, in condenser/steam lift the 0 of elevated steam to 100wt% part (for example
80 to 100wt% part) compressed so that the reboiler of step a) tower is used.This can be by, for example, reciprocating compression
Machine or turbo-compressor and thermosiphon reboiler or forced circulating reboiler are realized.
Referring in particular to accompanying drawing, as the example of this method, Fig. 1 shows one embodiment of the present of invention, wherein BYD manufactures
Liquid phase effluent (on the basis of Solid Free) in the BYD manufacturing steps of method is included：37wt% BYD, 10wt% is not
The methanol of reaction formaldehyde, 49wt% water and 4wt%, formaldehyde recycling is delivered to via pipeline 1 by the liquid phase effluent
Tower 100, makes head temperature and 160 DEG C of bottom temp that recycling tower 100 remains 148 DEG C.Via pipeline 2 from tower 100
Top removes the vapor phase product of the formaldehyde comprising 30wt%, 58wt% water and 12wt% methanol, from there through using simple
The flow-dividing control of control loop (not shown) its 7wt% part is removed via pipeline 4, remainder is passed via pipeline 5
It is delivered to and raises condenser/steam lift 110 that side remains 250kPa.A in steam.Via pipeline 6 from tower 100 recovered liquid
Phase bottom steam, the liquid phase bottom steam include be similar to 54wt% BYD, 45wt% water, ＜ 0.1wt% methanol with
And ＜ 1wt% formaldehyde.Make ＜ 1wt% a small amount of outflow in the flow-dividing control by using simple control loop (not shown)
In the case that thing reaches reboiler 130, the remainder of liquid phase bottom steam, i.e., 95 to 100wt%, such as 98 to 100wt%,
Refined butynediols is recovered as, to be further processed into butanediol.In view of the reboiler 130 integral with tower 100
Tower side (process side), as generally acknowledged engineering practice, reboiler 130 is there is provided enough steam by the bottom temp of tower 100
Maintain 160 DEG C.
Under about 800kPa.A, any desired fresh boiler feedwater is supplied under its bubble point temperature via pipeline 14
It is given to condenser/steam lift 110.Under about 250kPaa.A pressure, via pipeline 8 from condenser/steam lift
110 remove steam product, and remove steam condensate purging from condenser/steam lift 110 via pipeline 13.Via pipe
Line 10 is released the process condensate stream of condenser/steam lift 110, and the process condensate stream includes 30wt% first
The methanol of aldehyde, 58wt% water and 12wt%, wherein by using the flow-dividing control of simple control loop (not shown), warp
The 35wt% of process condensate stream part is removed by pipeline 11 to be used to recycle, and passes its 65wt% part via pipeline 12
The top of tower 100 is delivered to as backflow.
The steam product of pipeline 8 is delivered to compressor 120 under about 250kPa.A pressure, and about
Drawn it out under 1000kPa.A pressure via pipeline 9 from compressor 120.The product of pipeline 9 is delivered to reboiler 130, passed through
The high steam of fresh supplemented is delivered to reboiler 130 by pipeline 15.Via pipeline 17 by the condensate from reboiler 130
It is delivered to condenser/steam lift 110.
The disclosures of all patents, patent application, test procedure, priority document, article, publication, handbook and
Other documents are entirely incorporated into herein by quoting, and the degree of reference makes this disclosure and the present invention and non-contravention, and
It is for this all permissions being incorporated to are allowed.
When listing numerical lower limits and numerical upper limits herein, cover the scope from any lower limit to any upper limit.
Although the illustrative embodiment of the present invention has had been described in detail, it is to be understood that, do not departing from the essence of the present invention
In the case of refreshing and scope, to those skilled in the art, various other modifications will be apparent, and this area
Technical staff can easily make these modifications.Therefore, this is not meant to that the scope of claims of the present invention is limited to
Embodiments described herein and description, on the contrary, claims, which should be interpreted to include, is present in obtaining in the present invention
All features of novelty of patent, including all spies that its equivalent will be considered as by those skilled in the art in the invention
Levy.
Claims (13)
1. changing for unreacting acetal is reclaimed in a kind of butynediols synthetic reaction product from butynediols synthesis reactor downstream
Enter method, it comprises the following steps：
A) reaction product comprising unreacting acetal is fed to the tower kept under given conditions, the tower is related to reboiler
Connection；
B) removed from the step a) tower and include the vapour phase top stream of formaldehyde, water and methanol, and by the vapour phase tower
At least a portion of liftout stream, which is delivered to, to be kept in condenser/steam generator under given conditions, wherein by with it is described
The heat exchange of vapour phase top stream produces steam by steam condensate or boiler feedwater, and is produced from the vapour phase top stream
Process condensate stream；
C) the liquid phase bottom steam for including butynediols, water, formaldehyde and methanol is removed from the step a) tower；
D) removing step b) the process condensate stream, and at least a portion of the process condensate stream is sent back into step
Suddenly tower a) is used as backflow；
E) devaporation is removed from the step b) condenser/steam generator, and is transmitted the steam by compressor
To the reboiler of the step a) tower；And
F) part for the steam condensate of reboiler from tower described in step a) is delivered to the step c) condensation
Device/steam generator.
2. according to the method described in claim 1, wherein the vapour phase top stream of the tower from step a) is comprising extremely
Few 25 weight % formaldehyde, and the liquid phase bottom steam of the tower from step a) includes at most 1 weight % first
Aldehyde.
3. according to the method described in claim 1, the condition of the wherein step a) tower includes：Tower top temperature is 115 to 150
DEG C, column bottom temperature is 130 to 170 DEG C.
4. according to the method described in claim 1, wherein the steam produced in the step b) condenser/steam generator
Pressure be 0 to 400kPa.A, and the step a) reboiler steam pressure be 400 to 1400kPa.A.
5. according to the method described in claim 1, wherein the step e) compressor makes the pressure of the steam increase by 2 to 10
Times.
6. according to the method described in claim 1, wherein being delivered to the step b) condenser/steaming from the step a) tower
The part of the top stream of vapour generator is 80 to 100 weight %.
7. a kind of method for manufacturing butanediol, it comprises the following steps：
1) mixture comprising the aqueous solution containing formaldehyde, acetylene and suspended catalyst is made at reaction conditions in reaction vessel
Reaction, to produce the reaction product for including butynediols, water, unreacting acetal and methanol；
2) step 1 that butynediols, water, unreacting acetal and methanol will be included) the reaction product be fed to and be maintained at special
Tower under fixed condition, the tower is associated with reboiler；
3) from step 2) the tower in remove and include the vapour phase top stream of formaldehyde, water and methanol, and by the vapour phase tower
Being partially transferred to of 80 to 100 weight % of liftout stream keeps condenser/steam generator under multiple conditions, wherein passing through
Heat exchange with the vapour phase top stream produces steam by steam condensate or boiler feedwater, and from the vapour phase tower top material
The raw process condensate logistics of miscarriage；
4) from step 2) the tower in remove comprising butynediols, water, formaldehyde and methanol liquid phase bottom steam；
5) removing step 3) the process condensate stream, and by 50 to 70 weight % of process condensate stream part
Send back to step 2) the tower in as backflow, and the remainder of the process condensate stream is sent back into step 1) institute
Reaction vessel is stated as recycling；
6) from step 3) the condenser/steam generator in remove devaporation, and the steam is passed through compressor and biography
Be delivered to step 2) the tower the reboiler；And
7) step 2 will be come from) described in the part of condensate of the reboiler of tower be delivered to step 3) the condensation
Device/steam generator.
8. method according to claim 7, wherein from step 2) the tower the vapour phase top stream comprising extremely
Few 25 weight % formaldehyde, and from step 2) the liquid phase bottom steam of the tower include at most 1 weight % first
Aldehyde.
9. method according to claim 7, wherein step 1) the suspended catalyst include the compound of copper.
10. method according to claim 7, wherein step 1) reaction condition include：Temperature is 40 to 110 DEG C, pressure
It is 3 to 9 for 0 to 200kPa.A, and pH value.
11. method according to claim 7, wherein step 2) described in the specified conditions of tower include：Tower top temperature is 115
To 150 DEG C, column bottom temperature is 130 to 170 DEG C.
12. method according to claim 7, wherein in step 3) the condenser/steam generator in the steaming that produces
The pressure of vapour be 0 to 400kPa.A, and step 2) the reboiler steam pressure be 400 to 1400kPa.A.
13. method according to claim 7, wherein step 6) the compressor by the pressure increase by 2 of the steam to
10 times.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201462046079P | 2014-09-04 | 2014-09-04 | |
| US62/046,079 | 2014-09-04 | ||
| PCT/US2015/047711 WO2016036655A1 (en) | 2014-09-04 | 2015-08-31 | Improved formaldehyde recovery method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107074711A true CN107074711A (en) | 2017-08-18 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580047127.1A Pending CN107074711A (en) | 2014-09-04 | 2015-08-31 | Improved formaldehyde recovery method |
Country Status (2)
| Country | Link |
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| CN (1) | CN107074711A (en) |
| WO (1) | WO2016036655A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107089901A (en) * | 2017-06-27 | 2017-08-25 | 查都（上海）科技有限公司 | A kind of 1,4 butynediols purification systems |
| CN110092711A (en) * | 2019-05-20 | 2019-08-06 | 中国石化长城能源化工（宁夏）有限公司 | A kind of formaldehyde separation method of butanol purifying technique |
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