CN104072367B - A kind of continuous production method of 2,2,4-trimethyl-1,3-pentanediol mono isobutyrate - Google Patents
A kind of continuous production method of 2,2,4-trimethyl-1,3-pentanediol mono isobutyrate Download PDFInfo
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Abstract
The invention discloses a kind of 2,2,4-trimethyl-1, the continuous production method of 3-pentanediol mono isobutyrate, adopting the fixing bed continuous reaction technique of two-step method and solid base catalyst, described catalyst is the solid base catalyst Cs-K/SiO being prepared from for the double; two alkali metal active component of carrier loaded caesium and potassium with ball-type silicon oxide2；Described method adopts two series connection calandria type fixed bed reactors, wherein preheated isobutylaldehyde raw material initially enters First calandria type fixed bed reactor, there is aldol reaction, then the aldol condensate obtained enters second calandria type fixed bed reactor, Cannizzaro reaction in molecule occurs, and successive reaction obtains purpose product.The present invention adopts two-step method to fix bed continuous reaction technique, and not only isobutylaldehyde conversion rate and product selectivity are high, and production efficiency is high, and operation is simple, is conducive to energy-saving and emission-reduction, has large-scale continuous IP prospecting.
Description
Technical field
The invention belongs to field of fine chemical, relate to a kind of 2,2,4-trimethyl-1, the continuous preparation method of 3-pentanediol mono isobutyrate.
Background technology
2,2,4-trimethyl-1,3-pentanediol mono isobutyrate (abbreviation alcohol ester-12) is a kind of high boiling point, containing multi-functional binary alcohol esters, being colourless transparent liquid at normal temperatures, boiling point is 255 DEG C, water insoluble, can being directly or indirectly used as coating additive, lubricant, solvent, plastic additive etc., purposes is widely.Along with the increasingly stringent of legislations of environmental protection and improving constantly of aqueous architectural coating Industry code requirements, alcohol ester-12 is because having the filming function of excellence, the advantage such as nontoxic, become the coalescents of the famous aqueous architectural coating (being generally emulsion paint) in the whole world, it is widely used in vinylacetate homopolymerization and copolymer emulsion, acrylate homopolymerization and copolymer emulsion, vinyl acetate/acrylate copolymer emulsion, styrene/methacrylic acid ester copolymer emulsion, vinyl acetate/tertiary ethylene carbonate copolymer emulsion, the multiple coating systems such as phenylethylene ethylene/propenoic acid ester/methyl methacrylate/glycidyl methacrylate multi-copolymerization emulsion.
It is known that the synthetic route of alcohol ester-12 mainly has following two: (1) isopropylformic acid. and 2,2,4-trimethyl-1,3-pentanediol direct esterification prepares；(2) isobutylaldehyde Cannizzaro reaction in aldol reaction and molecule prepares.Compared with the former, adopting isobutylaldehyde Cannizzaro in aldol reaction and molecule that alcohol ester-12 is synthesized, because cost of material is low and product selectivity is high, have more economy, the synthetic method about alcohol ester-12 has following patent disclosure.
Chinese patent CN1098712A discloses with the synthetic method of the NaOH two-step method batch tank technique being catalyst, so-called two-step method and first step operation are under sig water effect, isobutylaldehyde carries out low temperature aldol reaction, second step operation is under high alkali liquid effect, carry out Cannizzaro reaction in molecule, isobutylaldehyde conversion rate is up to 69%, product selectivity is up to 89%, but there is many shortcomings in the method: low conversion rate, course of reaction are formed a large amount of by-product, product difficulty separates, and complex technical process, it is necessary to washing step, discharge of wastewater is big.
Chinese patent CN1429809A discloses the synthetic method of the two sections of pipe reaction techniques being catalyst with concentrated NaOH solution, and first paragraph pipe reaction temperature is low, is 30～40 DEG C；Second segment pipe reaction temperature is higher, is about 90 DEG C, and the method can realize the heterogeneous successive reaction of liquid liquid, but conversion per pass is very low, and only 60%, selectivity is not high yet, and about 88%, and last handling process is complicated, it is necessary to point mutually and washing step, discharge of wastewater is big.
Chinese patent CN1325841A discloses the synthetic method of the two-step method batch tank technique of a kind of improvement, and namely first step aldol condensation operation adopts dilute NaOH solution to make catalyst, and in second step molecule, Cannizzaro reaction process adopts with Ba (OH)2·8H2O makes catalyst.This synthetic method is substantially better than above-mentioned Chinese patent CN1098712A, and when conversion per pass quite (58～64%), product selectivity brings up to 96% from 89%, and product color number (platinum cobalt colorimetric) is reduced to No. 20 from No. 50, and color and luster is more shallow.But the method there is also many shortcomings: adopt dilute NaOH solution to make the catalyst of first step reaction process, a large amount of waste water, contaminated environment can be produced；Adopt Ba (OH)2·8H2O makes the catalyst of second step reaction process, due to Ba (OH)2·8H2O belongs to highly toxic material, and reacting middle catalyst consumption is more again, a large amount of poisonous waste residue that can produce, and does not meet environmental protection theory.
Chinese patent CN1417195A discloses with powder Ba (OH)2·H2O is the synthetic method of the one-step method batch tank technique of catalyst, and namely so-called one-step method carries out Cannizzaro reaction in aldol condensation and molecule in same reactor simultaneously.The conversion per pass of the method reaches 86.9%, and selectivity is up to more than 98%, but catalyst Ba (OH)2·H2O, falls within highly toxic material, and this technique is high to the prescription of raw material, isobutylaldehyde is moisture, isopropylformic acid. time, then isobutylaldehyde conversion rate, purpose product selectivity is on the low side, does not have industrial prospect.Reacting middle catalyst large usage quantity, the poisonous waste residue of generation is more, does not also meet environmental protection theory.
Chinese patent CN101948386A discloses the synthetic method of the one-step method batch tank technique being catalyst with sodium alkoxide.Compared with Chinese patent CN1098712A, conversion per pass and selectivity are all significantly improved, but post-reaction treatment needs washing, has a large amount of discharge of wastewater, and equipment corrosion is serious.
US Patent No. 6794325B discloses the synthetic method of the one-step method batch technology being pulverulent solids base catalyst with sodium hydroxide Modified K 10 montmorillonite.The conversion per pass of the method reaches 94.5%, and selectivity is up to more than 95.3%, but the response time that this technique needs is long, reaches 200 hours.
In recent years, solid base application in catalyst preparation increasingly causes the concern of people, its advantage be easy to operate, post processing is simple, energy-conservation, three waste discharge is few, therefore in the today advocating environmental friendliness and energy-saving and emission-reduction, solid base is expected to become eco-friendly catalysis material of new generation.
Chinese patent CN1817850A discloses the use of houghite as the solid base catalyst of Cannizzaro reaction in molecule, adopt two-step method batch tank technique synthesis alcohol ester-12, obtain better effects: once through yield is up to 87%, and reaction condition is gentle, and catalyst can be recycled.Chinese patent CN101838197A discloses the use of the metal-oxide of alkali modification as the solid base catalyst of Cannizzaro reaction in molecule, adopt two-step method batch tank technique synthesis alcohol ester-12, also better effects is obtained: once through yield is up to 80%, reaction condition is gentle, the recyclable recycling of catalyst.
In sum, no matter prior art is one-step method batch tank technique, or two step method batch tank technique, the different aspect problem such as all have that production efficiency is low, production cost is high, energy consumption is big or three waste discharge is many, be difficulty with large-scale continuous cleaning commercial production.Above-mentioned be catalyst with NaOH solution two sections of pipe reaction techniques there is also aftertreatment technology complexity, it is necessary to point operation such as phase, washing, not there is industrial prospect.
Summary of the invention
For the deficiency that above-mentioned prior art exists, it is an object of the present invention to provide a kind of 2,2,4-trimethyl-1, the continuous production method of 3-pentanediol mono isobutyrate, with a kind of novel high-activity solid base for catalyst, adopts the fixing bed continuous reaction technique of two-step method to prepare goal object.
The technical scheme is that and be achieved in that:
A kind of 2,2,4-trimethyl-1, the continuous production method of 3-pentanediol mono isobutyrate, react including Cannizzaro in isobutylaldehyde aldol reaction and molecule, it is characterized in that, adopt the fixing bed continuous reaction technique of two-step method with solid base for catalyst, described solid base catalyst is the solid base catalyst Cs-K/SiO being prepared from for the double; two alkali metal active component of carrier loaded caesium and potassium with ball-type silicon oxide2；The fixing bed continuous reaction technique of described two-step method adopts two series connection calandria type fixed bed reactors loading described solid base catalyst, wherein preheated isobutylaldehyde raw material initially enters First calandria type fixed bed reactor, there is aldol reaction, then the aldol condensate obtained enters second calandria type fixed bed reactor, Cannizzaro reaction in molecule occurs, and successive reaction obtains goal object 2,2,4-trimethyl-1,3-pentanediol mono isobutyrate.
Preferably, in described method, First calandria type fixed bed reactor inlet temperature controls within 35～50 DEG C, and outlet temperature is within the scope of 50～65 DEG C；Second calandria type fixed bed reactor inlet temperature controls within 110～150 DEG C, and outlet temperature is within the scope of 120～160 DEG C.
Preferably, in described method, the air speed of two calandria type fixed bed reactors is 0.3～1h-1, the reaction pressure of two reactors is 0.3～1MPa.
Because this reaction is relatively strong exothermal reaction, the fixed bed reactors selected by continuous reaction technique of the present invention are the calandria type fixed bed reactors of two series connection, to solve the heat-obtaining problem in course of reaction.The solid base catalyst of the novel high-activity that the present invention adopts, is the solid base catalyst Cs-K/SiO being prepared from for the double; two alkali metal active component of carrier loaded caesium and potassium with ball-type silicon oxide2。
Specifically, the technological process of the fixing bed continuous reaction technique of two-step method of the present invention is as shown in Figure 1.Highly active solid base catalyst Cs-K/SiO is all loaded in two series connection calandria type fixed bed reactors2, the shell side at reactor passes into cooling medium.
First step reaction process is: isobutylaldehyde raw material is through delivery pump1Deliver to heat exchanger2Preheating, then with air speed 0.3～0.5h-1From First calandria type fixed bed reactor3Top enters beds, carries out aldol reaction.Reactor inlet temperature controls within 35～50 DEG C.Because exothermic heat of reaction is relatively big, adopt shell side to pass into cooling water, control reactor outlet temperature within the scope of 50～65 DEG C.
Second step reaction process is: from First calandria type fixed bed reactor3The aldol condensate that bottom is discharged enters heat exchanger4Heat up, with identical air speed from second calandria type fixed bed reactor5Top enters beds, carries out Cannizzaro reaction in molecule.Reactor inlet temperature controls within 110～150 DEG C.Pressure is 0.3～1MPa.Adopt reactor shell side to pass into conduction oil, control reactor outlet temperature within the scope of 120～160 DEG C.
3rd step full gear operation is: from second calandria type fixed bed reactor5The reaction product that bottom is discharged delivers to dealdehyder tower8Carry out flash distillation, the condensed device of overhead gas9The unreacted isobutylaldehyde of extraction after condensation.Unreacted isobutylaldehyde can recycle.
Thick product after full gear is from dealdehyder tower8Tower reactor is discharged, and through rectification under vacuum, can obtain highly purified 2,2,4-trimethyl-1,3-pentanediol mono isobutyrate, purity more than 99.5%, and product appearance is colourless, and color number (platinum cobalt colorimetric) is lower than No. 10, and steady quality.
Novel high-activity solid base catalyst of the present invention is the solid base catalyst Cs-K/SiO being prepared from for the double; two alkali metal active component of carrier loaded caesium and potassium with ball-type silicon oxide2.Its preparation method is as follows: first prepare ball-type silica support with roller forming method, particle diameter is preferably 2～4mm, then adopting equi-volume impregnating supported catalyst active component presoma cesium salt and potassium salt, wherein cesium salt is selected from cesium carbonate, cesium nitrate, cesium acetate etc., it is preferable that cesium carbonate；Potassium salt is selected from potassium acetate, potassium carbonate, potassium nitrate etc., it is preferable that potassium acetate.Last drying and roasting obtain finished catalyst Cs-K/SiO2, it is preferable that wherein the load capacity of caesium is (with Cs2O counts) it is 10～15wt%, the load capacity of potassium is (with K2O counts) it is 2～5wt%.
The present invention adopts the fixing bed continuous reaction technique of two-step method to prepare 2,2,4-trimethyls-1 first, 3-pentanediol mono isobutyrate, compared with prior art, not only isobutylaldehyde conversion rate and product selectivity are high, and production efficiency is high, operation is simple, pilot process is made without being separated and washing, and product purity is high, steady quality, be conducive to energy-saving and emission-reduction, there is large-scale continuous industrial prospect.
The present invention will be further described by the examples below, but the present invention is not limited only to these embodiments.Essence and the invention scope of the present invention can be fully understood by these embodiments, further appreciate that feature and the advantage of two-step method continuous fixed bed reaction or continuous technique of the present invention and novel high-activity solid base catalyst used.
Accompanying drawing explanation
Fig. 1 fixes bed continuous reaction synthesis technique schematic flow sheet；
In figure, 1, feedstock transportation pump, 2, First heat exchanger, 3, First calandria type fixed bed reactor, 4, second heat exchanger, 5, second calandria type fixed bed reactor, 6, pans, 7, second delivery pump, 8, dealdehyder tower, 9, condenser, 10, reboiler.
Detailed description of the invention
Embodiment 1 solid base catalyst Cs-K/SiO2Preparation
1, prepared by catalyzed by solid base agent carrier
Step (1) molding bonded: not baked commercially available gross porosity II type porous silica gel (Qingdao product) is ground screening, obtains the silica white of 200～300 orders, as spin raw material.Being placed on the rustless steel rotating disk of tumbling disk granulator by above-mentioned silica white, rotating disk rotates with the speed of 36 revs/min.Concentration 25%(is counted with SiO2) JA-25 Ludox (micelle mean diameter is 10～20nm) be sprayed onto on powder body by spray gun and make spin seed.Per kilogram silica white uses 0.5～0.7 liter of Ludox.Being then slowly added into raw material powder and JA-25 Ludox, when the mean diameter of a ball (taking the meansigma methods of 20) of rolling is to 2～3mm, stops adding Ludox, but continue to keep rotating disk to rotate 30 minutes, period prevents adhesion between spheroid from adding raw material powder.Then being transferred in sugar coating machine by the ball rolled, rotating disk rotates with the speed of 36 revs/min and carries out spherome surface polishing in 20 minutes, to remove the floating powder of spherome surface and to make spheroid have more smooth outer surface.
Step (2) gelling: spheroid step (1) obtained moves in hermetic container and stands, and carries out gelling aging, and gelling aging temperature 10 DEG C, gelling ageing time is 240 hours.
Step (3) airing: step (2) is obtained spheroid be moved in dish airing.
Airing temperature is 20 DEG C, and airing relative humidity is 60%, and the airing time is 2 days.
Step (4) dries: by step (3) spheroid move in baking oven, 110 DEG C dry 6 hours.
Step (5) roasting: by step (4) spheroid move in Muffle furnace, at 600 DEG C of roastings 6 hours, then natural cooling, prepare White-opalescent balling-up silica gel.
After measured, ball-type silica support particle diameter 2～3.5mm, compressive resistance is more than 6kg/ granule, and bulk density is 0.45g/cm3, specific surface area is 175m2/ g, through wet dry-cure fragmentation rate less than 1%, wear rate less than 3%, average pore size 12nm.
2, solid base catalyst Cs-K/SiO2Preparation
The preparation of step (1) co-impregnation liquid
In preparation still, it is initially charged 20 liters of deionized waters, starts stirring, be subsequently adding 1.50 kilograms of cesium carbonates and 0.81 kilogram of potassium acetate, be dissolved to clear solution.
Step (2) sprays method load cesium carbonate and potassium nitrate
Take the White-opalescent balling-up silica-gel carrier 25 liters that step 1 obtains, put in coating pan, open sugar coating machine, rotating speed is 12 revs/min, by spray gun, measure 15 liters of co-impregnation liquid are slowly sprayed on carrier, sprays about 1.5 hours, then sugar coating machine is kept to be rotated further again 2 hours, until wet bulb surface is adhered to without obvious liquid.
Step (3) dries
The wet bulb sample that step (2) obtains after dry 12 hours, is cooled to room temperature, namely obtains dry bulb in the baking oven of 120 DEG C.
Step (4) roasting
The dry bulb obtained in step (3) is placed in Muffle furnace, in air atmosphere, calcines 5 hours under 500 DEG C of conditions, be cooled to room temperature and take out, namely obtain silica-gel sphere supported catalyst Cs-K/SiO2.Its metal forms: Cs load capacity is (with Cs2O) being calculated as 11%, K load capacity is (with K2O) 3% it is calculated as.
Change the load capacity of active component Cs and K, prepare the load capacity of caesium (with Cs2O counts) it is 10～15%, the load capacity of potassium is (with K2O count) be 2～5% other Cs-K/SiO2Solid base catalyst.
Embodiment 2
Adopt the fixing bed continuous reaction technique of described two-step method to prepare 2,2,4-trimethyl-1,3-pentanediol mono isobutyrate, technological process as it is shown in figure 1, but the unreacted isobutylaldehyde of elimination do not recycle.Adopt two series connection calandria type fixed bed reactors, the solid base catalyst Cs-K/SiO in every reactor2Total filling amount is 20 liters.
First step reaction process is: isobutylaldehyde raw material is through delivery pump1Deliver to heat exchanger2Preheating, then with air speed 0.3h-1From First calandria type fixed bed reactor3Top enters beds, carries out aldol reaction.Reactor inlet temperature is 35 DEG C.Because exothermic heat of reaction is relatively big, shell side is adopted to pass into cooling water heat-obtaining, reactor outlet temperature 50 C.
Second step reaction process is: from First calandria type fixed bed reactor3The aldol condensate that bottom is discharged enters heat exchanger4Heat up, with first step reacting phase with air speed from second calandria type fixed bed reactor5Top enters beds, carries out Cannizzaro reaction in molecule.Reactor inlet temperature is 130 DEG C.Reactor shell side passes into conduction oil, and reactor outlet temperature is 140 DEG C, and pressure is 0.4MPa.
3rd step full gear operation: from second calandria type fixed bed reactor5The reaction product that bottom is discharged enters pans6, then through delivery pump7Deliver to dealdehyder tower8Carry out flash distillation, from the tower top condensed device of isolated gas phase fraction9Condensation, and separate and the unreacted isobutylaldehyde of extraction under certain reflux ratio.
The thick product of full gear is from dealdehyder tower8Tower reactor is discharged, and delivers to rectifying and purifying system (not illustrating in Fig. 1), carries out rectification under vacuum, can obtain highly purified alcohol ester-12 product.
During device even running 15 days, GC analytical data shows, isobutylaldehyde conversion per pass 92%, removes the thick product after unreacted isobutylaldehyde and consists of 2,2,4-trimethyl-1,3-pentanediol mono isobutyrate 96%, 2,2,4-trimethyl-1,3-pentanediol 2%, other component 2%.Thick product, through rectification and purification, can obtain purity more than 99.5% alcohol ester-12 product and steady quality.
Embodiment 3
Except unreacted isobutylaldehyde recycling use, other condition is identical with embodiment 2, and the technological process of the present embodiment is as shown in Figure 1.
First step reaction process: dealdehyder tower8The unreacted isobutylaldehyde of elimination is returned to heat exchanger2Before, and with through delivery pump1The fresh isobutylaldehyde raw material mixing of conveying, enters heat exchanger2Preheating.Material after preheating is with air speed 0.3h-1From First calandria type fixed bed reactor3Top enters beds, carries out aldol reaction.Reactor inlet temperature is 35 DEG C.Because exothermic heat of reaction is relatively violent, adopting reactor shell side to pass into cooling water, controlling reactor outlet temperature is 50 DEG C.
Second step reaction process: from First calandria type fixed bed reactor3The aldol condensate that bottom is discharged enters heat exchanger4Heating, the material after heating with first step reacting phase with air speed from second calandria type fixed bed reactor5Top enters beds, carries out Cannizzaro reaction in molecule.Reactor inlet temperature is 130 DEG C.Adopting reactor shell side to pass into conduction oil, controlling reactor outlet temperature is 140 DEG C, and pressure is 0.4MPa.
3rd step full gear operation: from second calandria type fixed bed reactor5The reaction product that bottom is discharged enters pans6, then through delivery pump7Deliver to dealdehyder tower8Carry out flash distillation, from the tower top condensed device of isolated gas phase fraction9Condensation, and under certain reflux ratio the unreacted isobutylaldehyde of extraction.Unreacted isobutylaldehyde recycles.
The thick product of full gear is from dealdehyder tower8Tower reactor is discharged, and delivers to rectifying and purifying system (not illustrating in Fig. 1), carries out rectification under vacuum, can obtain highly purified 2,2,4-trimethyl-1,3-pentanediol mono isobutyrate product.
During device even running 15 days, GC analytical data shows, isobutylaldehyde total conversion reaches 96%, and product selectivity reaches 97%.Thick product, through rectification and purification, can obtain purity more than 99.5% alcohol ester-12 product and steady quality.
Embodiment 4～8
Prepare 2,2,4-trimethyl-1 according to method substantially the same manner as Example 3,3-pentanediol mono isobutyrate, except second calandria type fixed bed reactor inlet temperature and outlet temperature different from embodiment 3 except, other condition is identical.Experimental result is in Table 1.
Table 1
Claims (6)
1. one kind 2,2,4-trimethyl-1, the continuous production method of 3-pentanediol mono isobutyrate, react including Cannizzaro in isobutylaldehyde aldol reaction and molecule, it is characterized in that, adopt the fixing bed continuous reaction technique of two-step method with solid base for catalyst, described catalyst is the solid base catalyst Cs-K/SiO being prepared from for the double; two alkali metal active component of carrier loaded caesium and potassium with ball-type silicon oxide2, wherein the load capacity of caesium is with Cs2O is calculated as 10～15wt%, and the load capacity of potassium is with K2O is calculated as 2～5wt%, and described carrier ball-type silicon oxide particle diameter is 2～4mm；The fixing bed continuous reaction technique of described two-step method adopts two series connection calandria type fixed bed reactors loading described solid base catalyst, preheated isobutylaldehyde raw material initially enters First calandria type fixed bed reactor, there is aldol reaction, then the aldol condensate obtained enters second calandria type fixed bed reactor, Cannizzaro reaction in molecule occurs, and successive reaction obtains purpose product 2,2,4-trimethyl-1,3-pentanediol mono isobutyrate.
2. continuous production method according to claim 1, it is characterised in that: First calandria type fixed bed reactor inlet temperature controls within 35～50 DEG C, and outlet temperature is within the scope of 50～65 DEG C；Second calandria type fixed bed reactor inlet temperature controls within 110～150 DEG C, and outlet temperature is within the scope of 120～160 DEG C.
3. continuous production method according to claim 1, it is characterised in that: the air speed of two calandria type fixed bed reactors is 0.3～1h-1。
4. continuous production method according to claim 1, it is characterised in that: the reaction pressure of two calandria type fixed bed reactors is 0.3～1MPa.
5. continuous production method according to claim 1, it is characterised in that: described solid base catalyst Cs-K/SiO2Its preparation method is as follows: first prepare ball-type silica support with roller forming method, then adopts equi-volume impregnating supported catalyst active component presoma cesium salt and potassium salt, and last drying and roasting obtain described solid base catalyst Cs-K/SiO2。
6. continuous production method according to claim 5, it is characterised in that: described cesium salt is cesium carbonate, cesium nitrate or cesium acetate；Described potassium salt is potassium acetate, potassium carbonate or potassium nitrate.
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| CN107698446A (en) * | 2017-09-15 | 2018-02-16 | 润泰化学股份有限公司 | A kind of automatic production method of the pentanediol mono isobutyrate of 2,2,4 trimethyl 1,3 |
| CN109535121A (en) * | 2019-01-17 | 2019-03-29 | 江苏天音化工有限公司 | A method of preparing 2- methyl -2- isobutyl group -4- methylol -1,3-dioxolane |
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