CN106946666A - The synthesis technique of trimethyl orthoformate - Google Patents
The synthesis technique of trimethyl orthoformate Download PDFInfo
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- CN106946666A CN106946666A CN201710169033.2A CN201710169033A CN106946666A CN 106946666 A CN106946666 A CN 106946666A CN 201710169033 A CN201710169033 A CN 201710169033A CN 106946666 A CN106946666 A CN 106946666A
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- C07C41/60—Preparation of compounds having groups or groups
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Abstract
The invention belongs to trimethyl orthoformate technical field, the synthesis technique of trimethyl orthoformate is disclosed, it comprises the following steps：Step 1）Dispensing, step 2）Crystallize into salt, alcoholysis, step 3）Distillation.Synthesis technique environment friendly of the present invention is strong, energy-saving and emission-reduction, can the production of technical scale metaplasia, the product purity height of synthesis.
Description
Technical field
The invention belongs to trimethyl orthoformate technical field, and in particular to the synthesis technique of trimethyl orthoformate.
Background technology
Trimethyl orthoformate also known as trimethoxy-methane（Trimethyloxymethane）, abbreviation original acid A ester
（Methyl orthoformate）, be a kind of colourless liquid for having a penetrating odor, it is inflammable, meet water and decompose, can be dissolved in ethanol,
Ether etc..It is a kind of important organic synthesis intermediate, the synthesis for a variety of medicine, dyestuff and spices etc..
The synthesis of current trimethyl orthoformate mainly includes following method：（1）Two-step mode technique：With chloroform and methanol
Sodium is two synthesis trimethyl orthoformates of raw material；（2）One step technique：One-step method uses chloroform, methanol, NaOH for original
Material, with tributyl benzyl ammonium chloride（PTC）For phase transfer catalyst, that is, realize the alternate transfer of solid-liquid, step generation orthoformic acid
Trimethyl, some commercial plants are produced using this technology.（3）Hydrogen cyanide method：The method is with absolute methanol, hydrogen cyanide
And hydrochloric acid reaction, be further continued for being made trimethyl orthoformate with methanol reaction, this Guttae Phacosylini with the hydrogen cyanide of other product by-products most
To be favourable, feature is obtained with reduced investment.But process uses the hydrogen cyanide of severe toxicity for raw material, it is necessary to which refrigerating plant, is sealed to equipment
' production process security requirement is higher for property.
The content of the invention
In order to overcome the defect of prior art, the invention provides the synthesis technique of trimethyl orthoformate.
The present invention is achieved by the following technical solution：
The synthesis technique of trimethyl orthoformate, it comprises the following steps：Step 1）Dispensing, step 2）Crystallize into salt, alcoholysis, step
3）Distillation.
Specifically, the synthesis technique comprises the following steps：
Step 1）Dispensing：1800kg solvent and 286kg methanol are added into neutralization reaction kettle, treats that temperature in the kettle is down to -7 DEG C
When, with 100~150m3/ h speed starts to lead to hydrogen chloride into kettle, and whole venting process is 60~80min, stops logical hydrogen chloride
Before, add 200kg methylene amine；Strict temperature control -13~-11 DEG C at the end of ventilation；
Step 2）Crystallize into salt, alcoholysis：Control neutralization reaction kettle temperature slowly rises, and control kettle temperature is controlled 0 in -4 DEG C of 15min
DEG C 5~10min；With 0 DEG C of beginning, salt time 30min is controlled, salt is crystallized into 25~45 DEG C, salt-forming reaction is finished；Into salt
After end, 503 kilograms of methanol are added into neutralization reaction kettle, are put again into alcoholysis kettle after being stirred 1 hour in neutralization reaction kettle；
Control alcoholysis reaction temperature at 50~80 DEG C, the time is 3.5h；Ammonium chloride and liquid is collected by centrifugation；
Step 3）Distillation：Liquid is carried out in low boiling tower, and methanol and methyl formate enter low-boiling-point substance surge tank from overhead extraction；Low boiling
Tower reactor solvent and trimethyl orthoformate enter topping still, and trimethyl orthoformate is produced from the top of tower, solvent get to solvent column after
Continuous purification, is re-used after purification；Material in low-boiling-point substance surge tank squeezes into methanol distillation column with pump, and methyl formate is adopted from tower top
Go out, tower reactor Methanol Recovery is re-used.
Preferably, the synthesis technique also comprises the following steps：Step 4）Thick ester purification step.
Preferably, the step 4）Thick ester purification step, comprises the following steps：
The thick ester of the impurity of class containing piperazine 0.005%~0.01% is directly distilled；Or,
Thick ester of the impurity of class containing piperazine higher than 0.01% is squeezed into thick ester processing kettle, is led to HCl processing, is made s-triazine content≤0.03%,
After being handled again through resin tower s-triazine content below 0.07% when squeeze into finished product rectifying column, trimethyl orthoformate from overhead extraction,
Enter tank field after qualified, tower bottoms is reclaimed.
Beneficial effect of the present invention mainly includes：After above-mentioned operation is handled, the present invention is without residue generation, processing reaction
Mild condition, with low cost, suitable for industrialization large-scale production, product purity reaches more than 99.8%..
Brief description of the drawings
The process route chart of Fig. 1 distilation steps of the present invention
The refined process route chart of the thick ester of Fig. 2 present invention.
Embodiment
In order that those skilled in the art more fully understand the technical scheme in the application, have below in conjunction with the application
Body embodiment, is more clearly and completely described, it is clear that described embodiment is only the application one to the present invention
Divide embodiment, rather than whole embodiments.Based on the embodiment in the application, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, should all belong to the scope of protection of the invention.
Embodiment 1
The synthesis technique of trimethyl orthoformate, it includes following process：
React post：
(1) preparation
1st, check whether motor is in normal condition, crawl stirring checks steering, speed of agitator is adjusted using frequency converter, and inspection is regarded
Whether mirror lamp is powered.
2nd, check that reactor bottom valve, charging valve see whether be closed, and some other valve on off state
It is whether correct.
3rd, 3. check that whether sensitive each regulating valve, electronic scale and instrument be handy, field data show with Central Control Room whether one
Cause, accurately.
4th, check in reactor whether totally dry, whether salt solution is supplied normally, and whether device for absorbing tail gas can normally make
With.
5th, check whether each raw material measuring tank gets the raw materials ready, get the raw materials ready and whether meet production needs（Indices including raw material）.
6th, had friendly relations with ice maker room personnel's ditch, it is ensured that brine ice can be used normally during driving, main behaviour contacts with hydrolysis post,
Ensure chlorination Hydrogen Energy regular supply.
(2) get the raw materials ready work
When confirming that the yield of imidization post methylene amine is a collection of enough, get the raw materials ready in time.
1st, feed personnel inspection related valve pipeline, records the quantity of solvent in now solvent measuring tank and valved tube chanting of folk tales to the accompaniment of simple percussion instruments
Condition, is then checked one time by main behaviour, is confirmed errorless and is recorded, and notifies charging personnel charging, A, fixing pipe charging process：Open anti-
Kettle inlet valve is answered, the backward solvent for neutralizing addition 1800kg in crystallization kettle is confirmed through main behaviour, when charging is soon finished, main behaviour notifies
Charging personnel close solvent tank outlet valve and kettle inlet valve, and record now solvent tank internal solvent amount and charging beginning and ending time, main
Behaviour opens stirring, notifies that Central Control Room will neutralize the control of kettle rotating speed at 70% (about 110 turns）, it is main behaviour check kettle in add feed liquid position be
It is no normal, main behaviour notify alcoholysis personnel inspection baiting valve whether material leakage.B, flexible pipe charging process：During solubilizer, main behaviour is by solvent
The joint of charge pipe, which is connected to, to be washed on kettle mouthful, and feed people's manual labour solvent charging valve, confirms that backward neutralize in crystallization kettle adds through main behaviour
1800kg（1750kg）Solvent, charging is when soon finishing, and main behaviour notifies that charging personnel close solvent tank outlet valve and kettle washes kettle
Valve, and now solvent tank internal solvent amount and charging beginning and ending time are recorded, main behaviour opens stirring, notifies that Central Control Room will neutralize kettle rotating speed
Control is at 70% (about 110 turns）, whether normally main grasp check feed liquid position is added in kettle, main to grasp notice alcoholysis personnel inspection baiting valve
Whether material leakage.
2nd, the cooling of cryosel penstock is opened, when temperature drops to -5~-2 DEG C, the methanol in the charging good methanol tank of personnel record
Amount, opens cooling kettle inlet valve, after confirming through main behaviour, opens the methanol that methanol measuring tank outlet valve adds 286kg into kettle, plus
Material is when soon finishing, and main behaviour notifies that charging personnel close methanol outlet valve and reactor inlet valve, charging personnel record it is good this
When quantity of methyl alcohol and charging initial time, continue cool simultaneously notifies hydrogen chloride post prepare supply hydrogen chloride.
(3) hydrogen chloride is led to
When temperature in the kettle is down to -7~-12 DEG C, main behaviour has recorded kettle temperature and time, opens hydrogen chloride intake valve, with 100~
150m3/ h speed starts to lead to hydrogen chloride into kettle, and now, main behaviour will confirm that the hydrogen chloride bottom insert canal of next kettle is unimpeded, ventilation
During, keep slowly heating up in kettle（Or do not heat up）, note whether there is smog in many observation kettles in venting process, ensure as far as possible
Completely, main behaviour notes reacting phenomenon in observation kettle to hydrogen chloride absorption, calculates the intake of hydrogen chloride, hydrogen intake to be chlorinated is fast
When reaching requirement, notify that phosphorus trichloride is stopped in hydrolysis post, when reaching requirement, notify that chlorine press is stopped in hydrolysis post, stop logical
Hydrogen chloride, record stops logical time and now kettle temperature, and strict temperature control is no more than -7 DEG C at the end of ventilation, and whole venting process is about
60~80min is needed, is stopped before logical hydrogen chloride, main behaviour and charging personnel methylene amine from the standby 200kg to methylene amine measuring tank, and carry out
Record.
(4) salt is crystallized into
After 1. ventilation terminates, control temperature notifies that Central Control Room heightens speed of agitator to 80% at -13~-11 DEG C（About 120 turns）, beat
Reactor inlet valve is driven, imines metering tank valve is opened after confirming through main behaviour and adds methylene amine, plus methylamine time control to exist into kettle
15 minutes or so, add after methylene amine with 80 kilograms of solvent washing pipelines, now crystallize kettle temperature when personnel record feeds well, when
Between and phenomenon.
2. adding after methylene amine, charging personnel close charging valve and kettle inlet valve, perform and record and carry out the standby of next kettle
Material, crystallization personnel record's good time and temperature, note observing temperature in the kettle situation of change, reacting phenomenon and time temperature are recorded at any time
Degree, beforehand control kettle temperature slowly rises, when kettle temperature rises to -8 DEG C or so, and control kettle temperature is treated in kettle in -4~-1 DEG C of about 15min
When temperature rises obvious（When dividing oil reservoir）, big chilled brine valve is opened, is controlled in 0 DEG C or so about 5~10min.With 0 DEG C of beginning,
Salt time 30min or so is controlled, during into salt to maximum temperature, reaction is finished, and has recorded time and temperature, controls into salt highest
25~45 DEG C of temperature, from whole crystallization salification process used time about 120min or so after methylene amine is added, crystallization is finished in notice and controlled
Stirring is down to low speed by room.Adding temperature after methylene amine has after small size decline, is transferred to temperature-rise period, forbids in temperature-rise period
Temperature in the kettle declines again, it is ensured that kettle temperature is the process risen all the time, and crystallization will close brine ice in advance before completing, prevent from having crystallized
Into rear sharp temperature drop.
(5) alcoholysis reaction
1st, after terminating into salt, crystallization personnel notify that alcoholysis post personnel carry out first time blowing, and crystallization personnel see liquid level in kettle, alcohol
The main behaviour of solution opens alcoholysis kettle inlet valve and stirring, opens neutralization kettle baiting valve and is discharged to alcoholysis kettle, during one and half coil pipe to be put down,
Crystallization personnel notify closing baiting valve, have recorded blowing initial time.
When the 2nd, neutralizing temperature in the kettle≤38 DEG C, notify that charging personnel are added in 503 kilograms of alcoholysis methanol, kettle into neutralization kettle
Material slowly rises, and the desalinization of soil by flooding or leaching time, no longer heating was defined to add after alcoholysis methanol, and such as temperature is higher than 35 DEG C, and temperature has decline to become
It can be directly discharged in alcoholysis kettle during gesture, such as be less than 35 DEG C, put again into alcoholysis kettle after 1 hour neutralizing stirring in kettle.
3rd, splicing is finished, and alcoholysis pair behaviour closes kettle stirring, opens sample tap, and measurement reaction liquid air chi is simultaneously sampled, sampled
Sample tap is closed after finishing, stirring is opened, sample is delivered to laboratory detection C-And pH value（3~5）, main manipulation alcoholysis reaction processed
Temperature starts alcoholysis pair behaviour's sampling after alcoholysis timing, alcoholysis 3.5h when temperature reaches 55 DEG C and starts rise at 50~80 DEG C,
The content of the components such as laboratory detection trimethyl, methyl formate, methanol is delivered to, main behaviour notifies the main behaviour's splicing of centrifugation.
(6) neutralization crystallization kettle is washed
1st, crystallization personnel are obtained after the notice that blowing is finished, and the snap joint of kettle pump discharge and are just bled off in alcoholysis methanol with washing
Connected with kettle, and open the valve on fast interface, notify that the main behaviour of alcoholysis washes kettle, now, the main behaviour of alcoholysis, which uses, washes the fast of kettle liquid kettle
Quick coupling is connected with the rapid pipe connecting on vomit pipe, opens the valve on rapid pipe connecting, notifies that neutralization personnel prepare to wash kettle, together
When open wash kettle liquid pump start to neutralize kettle charging, and carry out the time record, all covered to liquid coil pipe charging finish, crystallize
Personnel notify that alcoholysis personnel close feed pump, and make a record, and wash after 10~15min of kettle, neutralize crystallization personnel closing and quickly connect
Valve on pipe, snap joint of dismantling notifies that the main behaviour of alcoholysis washes kettle and finished, the main behaviour of alcoholysis, neutralization crystallization personnel, which carry out, washes kettle note
Record, the main behaviour of alcoholysis, which opens, neutralizes kettle baiting valve blowing, treats that blowing finishes the valve closed on rapid pipe connecting, removes snap joint,
Wash kettle end of operation.
2nd, every batch of blowing is finished, and is washed neutralization crystallization kettle once with kettle liquid is washed, is put into after 10~15min of the desalinization of soil by flooding or leaching and washes kettle liquid kettle,
Wash that ammonium chloride in kettle liquid is more, finished product content（≥23%）When higher, notify that centrifugation personnel are centrifuged, alcoholysis post is in principle
Often wash 8 batches and put and once wash kettle liquid, first get to supernatant in neutralization kettle, then ammonium chloride in kettle centrifuge, centrifugation three to four times
When, disposably change entirely once, the additional amount for washing kettle liquid is reduced as far as possible.
Post is distilled, flow chart is shown in accompanying drawing 1：
One）Preparation
1. checking public work, electrically whether normal, can steam, brine ice, recirculated water regular supply.
2. check whether tower reactor pump, feed pump, dnockout pumps etc. work well.
3. check whether reaction flow container, continuous tower, batch column and pans, surge tank liquid level gauge are intact.
4. whether check tower and pans has a vacuum leak, and whether instrument is sensitive handy.
5. whether the open and-shut mode of check valve is correct.
Two）Operating procedure
1. continuous tower is driven
A. continuous tower plays circulation
The reaction solution liquid level of tank field reaction flow container is met after circulation liquid level, is started charging and is played circulation, reaction flow container enters with low boiling tower
Expect the pipeline valve of pump connection, valve, low boiling tower inlet valve are opened before and after pump, drive low boiling tower feed pump, adjust spinner flowmeter, adjust
Amount of restriction size, after reaction solution is filtered, enters low boiling tower feed preheater and preheats laggard low boiling tower, low boiling tower liquid level shows
Show in 100 ~ 110cm（Highest 120cm）When, the valves such as related backflow, recirculated water, salt solution are opened, low tower reactor pump is driven, pump is adjusted
Rotating speed fed to topping still, when topping still surge tank liquid level is shown in 70 ~ 80cm, open related backflow, recirculated water, salt
The valves such as water, drive crude distillation column liquid pump, regulation rotating speed is fed to solvent column, when liquid level is shown in 20~30cm, open related
The valve such as backflow, recirculated water, salt solution, open solvent tower bottoms pump, regulation rotating speed is to reaction flow container charging（Remember：Shut
To the valve of solvent tank）, continuous tower, which starts to beat, to be circulated, and after low boiling tower, topping still, the tower liquid level of solvent column three are steady, continuous tower is opened
Beginning vacuumizes.
B. continuous tower is vacuumized
The exhaust-valve of topping still pans is closed, the inlet valve of pans is driven, vacuum valve on pans is driven, starts slowly to vacuumize,
When vacuum is about -0.07~-0.075MPa, solvent column pans exhaust-valve is closed, pans inlet valve, vacuum valve is opened and opens
Beginning is vacuumized, during about -0.090~-0.096MPa of vacuum, and continuous tower, which is vacuumized, to be finished.
C. continuous tower temperature tower
When topping still is vacuumized, low boiling tower starts to warm up warm tower, opens low boiling tower reboiler drain valve and steam inlet valve, passes through
Pneumatic control valve adjusts admission pressure, and admission pressure control is in 0.4~0.6MPa, and kettle temperature is raised to 105~115 DEG C, open condenser,
Cooler inlet/outlet valve, reflux ratio is adjusted after infinite reflux to tower top stabilization, begins with extraction, material is through overhead condenser, distribution
Device a, part is back to low boiling tower, and a part enters three buildings low-boiling-point substance pans after cooler again, when solvent column is vacuumized,
Topping still starts warm tower, opens topping still reboiler drain valve and steam inlet valve, is adjusted by adjusting pneumatic diaphragm control valve
Admission pressure, when kettle temperature is raised to 120~130 DEG C, opens condenser, cooler inlet/outlet valve, infinite reflux is stable to tower top temperature
Regulation reflux ratio starts discharging afterwards, and material is through topping still top condenser, and a part is back to topping still, and a part is again through topping still
Enter thick tower pans after cooler cooling, solvent column, which is exhausted, starts warm tower after vacuum, open solvent column reboiler draining valve and
Steam inlet valve, adjusts admission pressure, initial steam pressure control is in 0.9~0.95MPa, kettle temperature liter by adjusting pneumatic diaphragm control valve
During to 130~140 DEG C, overhead condenser, cooler inlet/outlet valve are opened.Fed into return tank, treat that return tank liquid level reaches
During 30~40cm, solvent column forced refluence pump is opened, backflow spinner flowmeter is adjusted to 80-200L/h, infinite reflux to tower top temperature
After stable, regulation extraction spinner flowmeter starts extraction with backflow spinner flowmeter flow, and extraction is put down with maintaining the reflux for tank liquid level
Based on weighing apparatus, or it is adjusted in combination with result of laboratory test, Produced Liquid is beaten to tank field reaction flow container, phegma through second floor reaction liquid pipe
Overhead reflux is used as into solvent column.
D. sample, detect
When the extraction of tower tends to be steady, from tower top, tower reactor, pans sampling detection, according to testing result and to main in material
The requirement of constituent content is wanted, appropriate regulation reflux ratio or bottom temperature make extraction material reach requirement standard, when solvent tower reactor is molten
During agent content ＞ 99.9%, tower reactor changes back tank field solvent tank, and notifies that distillation personnel are controlled in workshop has changed related valve.
2.1#, 2# Ta Kaita
A. when the material of low-boiling-point substance surge tank is met into tower liquid level, 1# is opened（2#）The air bleeding valve of tower, inlet valve, drive surge tank pump
Front and rear valve, opens dnockout pumps to 1#（2#）Tower is fed, and when tower reactor liquid level reaches 180cm, termination of pumping shuts pump valve, 1#（2#）Tower enters
Expect valve, air bleeding valve, the emptying valve on tail gas condenser is opened.1# tower pans exhaust-valve, baiting valve are opened, vacuum valve is closed,
Begin to rehearse water valve, opens steam valve normal pressure temperature tower, adjusts steam pressure, opens overhead condenser, cooler inlet/outlet valve, infinite reflux to tower
Push up after temperature stabilization, regulation reflux ratio starts discharging, and material is back to 1# through overhead condenser, distributor, a part（2#）Tower,
A part enters 1# after being cooled down through cooler（2#）Tower pans.When tower top temperature reaches 35 DEG C, tower top material is taken to detect, first
Switch pans during sour methyl ester content ＞ 90% and adopt methyl formate, the methyl formate content of extraction it is low get to low-boiling-point substance surge tank,
When tower top temperature reaches 45~60 DEG C and during steep temperature rise, switching pans, which change, adopts thick methyl esters, as 66 DEG C of bottom temperature ＞, tower top
During temperature >=58~60 DEG C, when taking tower bottoms detection methanol content ＞ 92%, steam off stops extraction, and infinite reflux to temperature is dropped
Stop tower after lower, close condenser, cooler inlet/outlet valve, tower reactor methanol squeezes into recovery methanol tank and is used as alcoholysis methanol, and tower top is thick
Methyl formate is put into thick methyl formate surge tank.
B. when the full laggard 1# towers of tails tank, 1# towers air bleeding valve, inlet valve are driven, feed pump is driven and starts charging, when liquid level is aobvious
Show that charging terminates in 180cm, pump valve, inlet valve, air bleeding valve are closed in termination of pumping, the exhaust-valve closed on tail gas condenser, pass connects
By the exhaust-valve on tank, baiting valve, vacuum valve are driven, starts to vacuumize, vacuum is opened and steamed in -0.055~-0.065MPa
Steam valve, adjusts admission pressure by pneumatic diaphragm control valve and starts warm tower, open overhead condenser, cooler inlet/outlet valve, entirely
It is back to regulation reflux ratio after tower top temperature stabilization and starts discharging, material is back to tower through overhead condenser, distributor, a part
Kettle a, part enters 1# pans after being cooled down through cooler.Pans material switches pans in 1000L or so, and samples inspection
Material content is surveyed, thick ester surge tank, reaction flow container or tails tank are put into according to front three ester content different choice, process is produced
In, take tower top sample to detect each component content in Produced Liquid at any time, when tower top temperature steeply rises, trimethyl in sampling detection tower reactor
Content, as front three ester content ＜ 10%, steam off valve stops extraction, after infinite reflux is fallen to temperature, closes condenser, cold
But device inlet/outlet valve, stops tower, it is for sale that tower reactor squeezes into discarded tails tank.
3.3#, 4# Ta Kaita
When thick trimethyl after piperazine is removed in smart ester surge tank meets a collection of consumption, before and after the inlet valve, air bleeding valve, pump of opening 3# towers
Valve, starts charging, and 3# tower reactor liquid levels stop smart ester feed pump when being shown in 180cm, charging terminates, and closes pump terminal valve, tower row
Air valve, inlet valve.Finishing column exhaust-valve is opened, steam inlet valve, drain valve is opened and starts warm tower, is adjusted by adjusting air bladder
Valve regulation initial steam pressure is saved, condenser, cooler inlet/outlet valve is opened, infinite reflux is stable to tower top temperature, and regulation reflux ratio starts
Extraction, material is through overhead condenser, distributor, and a part is back to finished product 3# towers, and a part enters into after being cooled down through cooler
Product pans, early stage collection front-end volatiles, produced quantity unsuitable excessive, about 200L/h, the first tank about 500~600L switching pans,
Second tank about 1000L takes liquid of top of the tower detection chemical examination, can change during front three ester content ＞ 99% and adopts finished product, while adjusting tower enters vapour
Pressure and reflux ratio control are surely produced.When bottom temperature rises comparatively fast, steam pressure, which rises very fast and extraction, to be reduced, tower reactor liquid level ＜
During 10cm, steam control valve valve position zero, steam off valve stops extraction, and infinite reflux to temperature is fallen, and closes condenser, cold
But device inlet/outlet valve, tower bottoms squeezes into tails tank or set steams.
The operation of 4.4# tower continuous stills
A. feed.When smart ester surge tank meets a collection of consumption, open 4# towers air bleeding valves, smart ester inlet valve, smart ester tank outlet valve,
Smart ester delivery pump outlet valve, opens smart ester delivery pump and pump inlet valve starts charging, when tower reactor liquid level reaches 100cm, closes
Pump discharge valve and smart ester delivery pump, stop charging.
B. Wen Ta and front-end volatiles are adopted.Close tower air bleeding valve, smart ester inlet valve, open 4# towers condenser, cooler and under, by force
The exhaust-valve of return tank processed, then open drain valve and steam inlet valve starts warm tower, adjusted by adjusting pneumatic diaphragm control valve
Tower reactor temperature, opens overhead condenser, cooler inlet/outlet valve, when tower top has extraction, opens tower top outlet valve, discharge pipe to pressure
Valve on return tank, closes forced refluence tank exhaust-valve when front-end volatiles in forced refluence tank reach 1/2 liquid level, opens strong
Return tank baiting valve processed, makes liquid be full of reflux pump and its pipeline, first drives by-passing valve and be then turned on forced refluence pump, start into tower
Backflow, reflux ratio is controlled by the spinner flowmeter of forced refluence pump, and first infinite reflux is stable to tower top temperature, opens front-end volatiles
The exhaust-valve and forced refluence tank of pans adjust capacity of returns to the valve of front-end volatiles pans, start to produce front-end volatiles.
C. feed.Open 4# tower continuous feed valves and smart ester delivery pump outlet valve starts to 4# tower continuous feeds, pass through stream
Gauge adjusts inlet amount, ensures that bottom temperature is stable during charging, after charging is stable, and 4# is opened after tower reactor, tower top temperature are stable
Cooler salt solution inlet/outlet valve is adopted in tower side, and the valve that the exhaust-valve and side for opening finished product pans are adopted on pipeline starts to produce into
Product.And front three ester content in detection Produced Liquid is sampled, sampling detection at any time, treats that front three ester content is qualified and cuts at once during extraction
Pans are changed, underproof feed liquid gets to front-end volatiles tank together with front-end volatiles, and canful rear enclosure is steamed.Qualified finished product is put to finished product meter
Beaten after measuring tank metering through finished product transfering material pump to tank field finished product basin.
Thick ester refines post, and flow chart is shown in accompanying drawing 2：
(1) preparation
1. getting the raw materials ready before resin treatment
1. soft water：Thick ester refines post personnel and opens underground heat water pot water intaking valve（Exhaust-valve is generally normally opened）, to hot water
Enter hot water in tank, after hot-water cylinder close to after full water, hot water in hot-water cylinder is beaten to hot-water cylinder top with heat-exchanger pump and cools down water softening tank
（Exhaust-valve is generally normally opened）Cooling, hot-water cylinder continues into hot water, and heat-exchanger pump outlet valve is closed after making, and closes heat-exchanger pump
And pump inlet valve, hot-water cylinder, which is filled, closed after hot water water intaking valve stopping water inlet, for washing resin.Winter soft water is existing to use existing standby,
Carry out relative recording.With cooling water control water softening tank temperature, softened water pump inlet valve is first opened, turn on pump opens water softening tank before pump
Valve, plays self-loopa, opens cooling water outlet valve, then opens cooling water water intaking valve, stops during 60 DEG C of control water temperature, closes entering for cooling water
Go out valve, the water intaking valve of pump is closed in pump discharge valve, termination of pumping.
2. methanol：Using methanol in methanol pans, the consumption record of methanol is carried out.
2. the processing before resin use
3. check whether interlock circuit is normal, and whether flowmeter, instrument are sensitive and accurate.
4. ensure brine ice, cooling soft water energy regular supply, it is ensured that low ester methanol kettle is dried, and methanol bottom valve is closed.
5. check thick ester processing kettle, it is ensured that dried in kettle, totally, it is ensured that valve open-close state is correct, it is ensured that emptying is unobstructed
（Tail gas absorption can be used normally）.
(2) operating procedure
1. hydrochlorination s-triazine
1. thick ester meets a collection of consumption and front three ester content is in 94~96%, methanol content 3~4%, and rectifying post personnel notify
Refined post personnel can provide thick ester, thick ester refine the good refining kettle of post personnel inspection it is eligible after open kettle exhaust-valve and
Inlet valve, notifies that rectifying post personnel enter thick ester, when thick ester is fed close to reach refining kettle volume 90%, notifies rectifying hilllock
Position personnel stop, into thick ester, closing inlet valve, and charging is finished, and open kettle stirring, open -5 DEG C of brine ice outlet valves and water intaking valve
Give the cooling of thick ester, close brine ice water intaking valve, open valve before and after refining kettle hydrogen chloride intake valve, flowmeter, hydrogen chloride supervisor with
Valve between branch pipe（Valve opening amplitude is small）, adjust flowmeter early gate, start logical hydrogen chloride, hci flow 15 ~
25kg/h（Ensure the absorption of hydrogen chloride）, adjust -5 DEG C of cryosel water valves.
2. remove the methanol in resin
While thick ester refining kettle enters thick ester, before the refined post personnel of thick ester open dirt discharging valve successively from resin tower bottom valve
Valve, then open moisture in aqueous methanol bottom of the tube dirt discharging valve, sampling detection methanol（Take several times is needed during sampling more）, now
Resin can be used, and carry out relative recording.
3. the use of resin
Opening has the thick ester distillation still after logical complete HCI and arranged to the valve between resin tower bottom valve on thick ester conveyance conduit and resin tower
Empty valve, then the thick ester outlet valve in resin tower top is opened successively to interval tower reactor（Or smart ester surge tank）Valve and essence between feed pipe
Ester inlet valve, batch column exhaust-valve, open thick ester delivery pump and pump inlet valve, by adjust flowmeter early gate control thick ester with
1500 ~ 2000L/h flow velocity is flowed into by resin tower bottom, and top flows out to interval tower reactor, makes a record, and thick ester flow velocity is steady
It is fixed, resin tower exhaust-valve is closed when thick ester covers upper plastic end enclosure in resin tower, thick ester flows out at the top of resin tower, 10min
The content of laboratory personnel's s-triazine from the thick ester of resin tower top discharge pipe sample tap sampling analysis afterwards, after testing result comes out,
Laboratory personnel should notify that thick ester refines the content of s-triazine in the thick ester of post personnel immediately, and thick ester refines post personnel and does easy to remember
Record, when s-triazine content is higher than 0.007% in thick ester, turns down thick ester flow velocity, from the thick ester of sample tap sampling detection after 30min
The content of middle s-triazine, repeats this operation until s-triazine content is less than 0.007% in thick ester, when s-triazine content is low in thick ester
When 0.007%, thick ester starts to flow into resin tower from resin tower bottom, and smart ester surge tank is flowed out to from resin tower top, continues to adjust
After high thick ester flow velocity, 10min from sample tap sample the thick ester of detection in s-triazine content, until s-triazine content is close to 0.007%
When stop speed-raising, the closing pump discharge valve and thick ester delivery pump when thick ester is put down completely in distillation still（Then pump inlet is turned off
Valve, opens pump discharge valve.）, close the thick ester outlet valve of resin tower top, the valve on discharge pipe and thick ester inlet valve, distillation still
Bottom valve, terminates the operation of this kettle, turns off resin tower bottom valve, thick ester outflow valve and thick ester effuser to smart ester surge tank
Thick ester after valve, pending lower batch of logical hydrogen chloride.Resin can lose the ability of processing s-triazine after continuously using repeatedly, when thick
Ester when s-triazine content almost no longer declines after resin tower resin inactivate, use another resin tower instead again after resin inactivation and continue
Thick ester is handled, this resin tower can be continuing with after needing scrubbed regeneration.
(3) washing of resin
1. a large amount of thick esters can be adsorbed during the thick ester of resin treatment, it is necessary to first cemented out with methanol, to reduce loss.
2. or do not soak by several times, directly backwashed with soft water.Intake by resin tower bottom, by top with per hour not
Less than 10m3/ h traffic flow backwash 2 hours（Mainly wash away some in resin dirtier impurity and methanol）.
(4) recycling of resin
1. the regeneration of resin
Resin repeatedly adsorbed and inactivated after s-triazine, now needs the hydrochloric acid with about 5% to reactivate resin, is set after activation
Fat can be recycled.
2. cool down soft water washing resin（The watery hydrochloric acid adsorbed during displacement resin regeneration）：Press《Processing before resin use》
Soft water washing operation is carried out in step.
3. moisture in air purging resin：Press《Processing before resin use》The hollow gas purge operations of step are carried out.
4. moisture in methanol replacement resin：Purged with air after resin, thick ester refines post personnel and closes related valve,
Resin tower bottom valve is opened to the valve between low water methanol kettle D kettles on aqueous methanol pipeline, resin tower top row water valve to aqueous methanol
Valve and D bottoms valve between pump on aqueous methanol pipeline, open aqueous methanol pump and pump inlet valve starts to play circulation, wash resin
Pump discharge valve, aqueous methanol pump and pump inlet valve are closed after 1 ~ 2 hour, pump discharge valve is opened, resin tower exhaust-valve is opened, waits to set
Aqueous methanol is put into after D kettles in fat, closes resin tower bottom valve, exhaust-valve, D kettles inlet valve, resin tower top row water valve to containing water beetle
Aqueous methanol in D kettles, is squeezed into useless methanol tank, dnockout terminates by the valve between alcohol pump discharge valve on pipeline using aqueous methanol pump,
Pump discharge valve and aqueous methanol pump are closed, pump inlet valve and D bottoms valve, resin tower bottom valve is turned off, resin tower exhaust-valve is opened
And methanol inlet valve, press《Processing before resin use》The operation of methanol replacement moisture is carried out in step.
5. the use of resin：Carried out by normal operating.
By above-mentioned operation, the present invention can obtain the trimethyl orthoformate that purity is more than 99.8%.
Above in association with specific embodiment, invention has been described, it will be appreciated by those skilled in the art that these are retouched
It is all exemplary to state, and is not limiting the scope of the invention.Those skilled in the art can be according to essence of the invention
God and principle make various variants and modifications to the present invention, and these variants and modifications are also within the scope of the invention.
Claims (4)
1. the synthesis technique of trimethyl orthoformate, it comprises the following steps：Step 1）Dispensing, step 2）Salt, alcoholysis are crystallized into, is walked
Rapid 3）Distillation.
2. synthesis technique according to claim 1, it is characterised in that the synthesis technique comprises the following steps：
Step 1）Dispensing：1800kg solvent and 286kg methanol are added into neutralization reaction kettle, treats that temperature in the kettle is down to -7 DEG C
When, with 100~150m3/ h speed starts to lead to hydrogen chloride into kettle, and whole venting process is 60~80min, stops logical hydrogen chloride
Before, add 200kg methylene amine；Strict temperature control -13~-11 DEG C at the end of ventilation；
Step 2）Crystallize into salt, alcoholysis：Control neutralization reaction kettle temperature slowly rises, and control kettle temperature is controlled 0 in -4 DEG C of 15min
DEG C 5~10min；With 0 DEG C of beginning, salt time 30min is controlled, salt is crystallized into 25~45 DEG C, salt-forming reaction is finished；Into salt
After end, 503 kilograms of methanol are added into neutralization reaction kettle, are put again into alcoholysis kettle after being stirred 1 hour in neutralization reaction kettle；
Control alcoholysis reaction temperature at 50~80 DEG C, the time is 3.5h；Ammonium chloride and liquid is collected by centrifugation；
Step 3）Distillation：Liquid is carried out in low boiling tower, and methanol and methyl formate enter low-boiling-point substance surge tank from overhead extraction；Low boiling
Tower reactor solvent and trimethyl orthoformate enter topping still, and trimethyl orthoformate is produced from the top of tower, solvent get to solvent column after
Continuous purification, is re-used after purification；Material in low-boiling-point substance surge tank squeezes into methanol distillation column with pump, and methyl formate is adopted from tower top
Go out, tower reactor Methanol Recovery is re-used.
3. synthesis technique according to claim 1 or 2, it is characterised in that further, the synthesis technique is also included such as
Lower step：Step 4）Thick ester purification step.
4. synthesis technique according to claim 3, it is characterised in that the step 4）Thick ester purification step, including it is as follows
Step：
The thick ester of the impurity of class containing piperazine 0.005%~0.01% is directly distilled；Or,
Thick ester of the impurity of class containing piperazine higher than 0.01% is squeezed into thick ester processing kettle, is led to HCl processing, is made s-triazine content≤0.03%,
After being handled again through resin tower s-triazine content below 0.07% when squeeze into finished product rectifying column, trimethyl orthoformate from overhead extraction,
Enter tank field after qualified, tower bottoms is reclaimed.
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| CN109180441A (en) * | 2018-07-24 | 2019-01-11 | 江苏远大仙乐药业有限公司 | A kind of synthetic method of triethyl orthoformate |
| CN110272394A (en) * | 2019-07-12 | 2019-09-24 | 抚顺顺特化工有限公司 | A kind of preparation method of s-triazine |
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