CN104694014A - Method and device for preparing rosin ester by coupling catalytic esterification and separation - Google Patents
Method and device for preparing rosin ester by coupling catalytic esterification and separation Download PDFInfo
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- CN104694014A CN104694014A CN201510082024.0A CN201510082024A CN104694014A CN 104694014 A CN104694014 A CN 104694014A CN 201510082024 A CN201510082024 A CN 201510082024A CN 104694014 A CN104694014 A CN 104694014A
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Abstract
The invention relates to a method for preparing rosin ester by coupling catalytic esterification and separation, which comprises the following operation steps: (1) mixing an alcohol compound, a rosin and a solvent, and dissolving; (2) putting the dissolved substance in the step (1) into an esterification reactor, and introducing 0.01-10.0-MPa CO2 to perform esterification reaction at 150-300 DEG C; (3) recovering the gas phase in the esterification reaction process, sending the gas phase into a gas-liquid separator through an expander, and returning the separated CO2 and newly supplemented CO2 into the esterification reactor through a turbine compressor; and (4) after reacting in the esterification reactor for 1.0-8.0 hours, relieving the pressure, and taking the obtained product out of the esterification reactor. The invention aims to provide a preparation method which has the advantages of lower cost and high rosin ester quality.
Description
Technical field
The invention belongs to rosin deep process technology field, relate to method and equipment thereof that a kind of catalytic esterification-separation coupling prepares rosin ester.
Background technology
Rosin ester is most important kind in rosin deep processing, accounts for more than 60% of rosin deep processed product.Because rosin acid has the luxuriant and rich with fragrance skeleton structure of three rings, make carboxyl greatly sterically hindered, cause esterification activation energy high, and the viscosity of rosin reaction system is large again, cause the interphase transfer difficulty between reactant, therefore need under the acidic metal oxide catalyzer such as ZnO and hot conditions, rosin acid just can carry out esterification.But under the high temperature conditions, decarboxylation side reaction easily occurs rosin acid, the esterification yield of rosin ester product and quality product is caused to reduce.In order to improve speed of response and the quality product of rosin ester, in the light and odorlessness of rosin ester, many R&D works are done.
In technology today, catalyzer is adopted to be prepared in the technology of rosin ester to after rosin deep processing, catalyzer uses metal catalyst to carry out esterification to rosin mostly, thus obtain rosin ester, but using metal catalyst to carry out catalysis can make metal ion pollute rosin ester, if use the rosin ester after being contaminated by the metal ions to be used as making food, human body has bad impact after using.And, in technology today to the preparation of rosin ester because employ metal catalyst, sometimes even use noble metal catalyst to carry out catalyzed reaction production, cause the problems such as production cost is higher, make profit in the process of producing rosin ester not high.
Summary of the invention
The present invention, for solving the problems of the technologies described above, invents method and equipment thereof that a kind of catalytic esterification-separation coupling prepares rosin ester, aims to provide a kind of cost lower, the preparation method that rosin ester quality is good.
For realizing the object of the invention, technical solution of the present invention is as follows:
Catalytic esterification-separation coupling prepares the method for rosin ester, comprises following operation steps:
(1) by alcohol compound, rosin and solvent, dissolve;
(2) material after dissolving in step (1) is put into esterifier, pass into the CO of 0.01 ~ 10.0MPa
2carry out esterification, esterification reaction temperature is 150 ~ 300 DEG C;
(3) carry out extraction to the gas phase in esterification reaction process, gas phase enters gas-liquid separator by decompressor, CO after being separated
2and the new CO supplemented
2get back in esterifier by turbocompressor;
(4), after in esterifier, reaction 1.0 ~ 8.0h reduces pressure, products obtained therefrom takes out in esterifier.
Preferably, according to mol ratio alcohol compound in step (1): rosin=1:1 ~ 10:1 mixing, adds the solvent that raw materials quality mark is 0 ~ 50%.
Preferably, the gas phase flow rate flowed out from esterifier in step (2) ~ (3) is 0 ~ 12000m
3/ h, pressure are 0 ~ 10.0MPa, temperature is 150 ~ 300 DEG C; Be 0 ~ 0.5MPa through expander step-down or throttling expansion step-down, cooling is 0 DEG C ~ 50 DEG C, then flows back to esterifier through turbocompressor pressurization, and gas flow is 0 ~ 10000m
3/ h, pressure is 0 ~ 10.0MPa, and temperature is 150 DEG C ~ 300 DEG C.
Preferably, in step (3), the temperature of gas-liquid separator is 0 ~ 50 DEG C, and pressure is 0.0 ~ 0.5MPa, and liquid flow rate is 0 ~ 100m
3/ h, gas flow is 0 ~ 10000m
3/ h.Preferably, described solvent is the one in turps, methylcarbonate, mineral essential oil, 200# solvent oil.
Preferably, the one in described alcohol compound glycerol, methyl alcohol, ethanol.
Wherein, the gas phase in esterification reaction process described in step (2) contains alcohol compound steam, water vapour, CO
2.
Catalytic esterification-separation coupling prepares an equipment for rosin ester method, comprising: esterifier, and it comprises: multiple heating tube, is located at esterifier inside; And gas distributor, it comprises inlet mouth and multiple shower nozzle for being vented;
Decompressor, it is connected with described esterifier; And turbocompressor, it is connected with described decompressor, and drives described turbocompressor work by described decompressor, and the air outlet of described turbocompressor is connected with described esterifier.
Preferably, in technique scheme, described gas distributor is in " L " type, and its bottom is annulus tubulose, and this ring tube is evenly provided with multiple shower nozzle for being vented, and described shower nozzle is obliquely installed.
Preferably, in technique scheme, described heating tube is multiple, is distributed on described esterifier inside in parallel; Described gas distributor has multiple, and described multiple gas distributor is interconnected, and described each gas distributor is located between described heating tube.
Preferably, in technique scheme, described for, also comprise: dissolution kettle, the anti-esterifier of itself and described hydrogenation is inner; Described gas distributor has multiple, and described multiple gas distributor is interconnected, and described each gas distributor is located between described heating tube.
Preferably, in technique scheme, the described equipment preparing rosin ester method for catalytic esterification-separation coupling, also comprises: dissolution kettle, and it is connected with described esterifier, for dissolving the raw material needed for production; Gas-liquid separator, its inlet mouth is connected with described decompressor, and air outlet is connected with turbocompressor; Knockout tower, its discharge port is connected with described turbocompressor; And reflux pump, it is connected with described knockout tower, for being delivered in described esterifier by isolated liquid solvent.
The inventive method alcohol compound and rosin is added to melt after still melts be pressed into esterifier, passes into CO
2, make temperature and pressure arrive CO
2super/subcritical state, utilizes super/subcritical CO
2be dissolved in the water of alcohol compound, rosin and esterification generation, form protonic acid, then using formed protonic acid as catalyzer, rosin ester and water are generated to alcohol compound and rosin catalytic esterification.Under the hot conditions of esterification, alcohol compound water vapour is recycled CO together with the water vapor mixture phase materials of generation
2carry secretly and constantly flow out in esterifier, enter in decompressor, and make expander acting drive turbocompressor, to reach expansion-compression self-circulation.Mixing gaseous substance, mainly CO is flowed out by esterifier
2, from super/subcritical state transition is that namely low-temp low-pressure normality is called Trans-critical cycle state, form pressure drop from super/subcritical state to the transition of low-temp low-pressure normality, thus expander done work.The gas mixture phase materials flowed out in esterifier flows through gas-liquid separator from decompressor to carry out condensation and is separated with gas, liquid, and gained liquid is alcohols and the aqueous solution; CO
2gas is as circulation and the new CO supplemented
2esterifier is flowed back to after turbocompressor pressurization.Gained alcohol compound, water mixed liquid body after being separated from gas-liquid separator, enter knockout tower and be separated, the water obtained flows out from knockout tower, and alcohol compound then enters in reflux pump, and circulation enters in esterifier and participates in reaction.Because the mixing gaseous substance flowed out from esterifier contains alcohol compound, CO
2with the steam of water and solvent, and the gas of pressurized circulation is only noncondensable gas CO
2, this is because after expander step-down cooling, the vapor condensation of alcohol compound, water and solvent is that liquid is separated from gas-liquid separator, and the gas only remaining noncondensable gas CO for circulating
2the gas flow of visible driving decompressor is greater than the flow of turbocompressor pressurized recirculating gas, also that is to say that work of expansion that decompressor is made is greater than the compression work needed for turbocompressor, the required energy increased of system lactonizes the reaction heat and heating coil heat supply of releasing to improve solvent vapo(u)r flow by esterifier.The new CO supplemented is passed in turbocompressor
2gas, decompressor directly promotes turbocompressor pressurization CO
2circulating involuting system, and then pass in esterifier.
Because the esterification of alcohol compound and rosin is with CO
2for catalyst precursor, both saved catalyzer cost and turn avoid the pollution to product such as the metal catalyst that adds ZnO, and the water that acid and alcohol generate through esterification is again by CO
2carry secretly and constantly flow out esterifier, thus the feedback inhibition eliminating water byproduct accumulation and cause, break the chemical equilibrium of the esterification of carboxylic acid and alcohol, improve esterification speed and equilibrium conversion, realize the object of esterification-separation coupling; Again due to CO
2the bubbling that constantly circulates in esterifier flows, and enhances the stirring to rosin high viscosity thing and Mass and heat transfer, and CO
2also produce " supercavitation " effect, both the agitator in economization esterifier is installed, decrease again the sterically hindered of carboxyl on the transmission resistance of rosin high viscosity storeroom and the luxuriant and rich with fragrance skeleton of three rings to greatest extent, greatly increase heat and mass transfer speed and the reaction efficiency of esterifier (2).Moreover, CO
2" same to molecule " effect can also be produced, Gum Rosin acid decarboxylation can be suppressed to generate CO
2side reaction, thus improve the reaction preference of rosin ester and yield and quality product.
Compared with prior art, beneficial effect of the present invention:
1, with super/subcritical CO
2be dissolved in the water of alcohol compound, rosin and esterification generation, the protonic acid formed substitutes the metal catalysts such as ZnO and prepares rosin ester, avoid metal ion to the pollution of rosin ester, particularly prepare food grade rosin ester product, the product safety and reliability that the inventive method is produced is a kind of green catalysis esterification process and cleaner production process.
2, the water that generates of alcohol compound and esterification of rosin esterification is by CO
2constantly be entrained with esterifier, thus the feedback inhibition eliminating product accumulation and cause, break alcohol and Esterification reactive chemistry balances, reaction is constantly carried out towards the direction generating rosin ester, thus improve esterification speed and equilibrium conversion, realize the coupling of the esterification of rosin acid and alcohol-be separated.
3, Trans-critical cycle CO is adopted
2expand-compression self-circulation technology, makes the high pressure CO flowed out from Trans-critical cycle reactor
2turbocompressor pressurization noncondensable gas CO is directly promoted through expander with the steam of water, alcohol compound and solvent
2circulating involuting system, decreases heat to power output process: the exergy loss of heat energy → mechanical energy → electric energy → mechanical energy, improves the heat power efficiency of thermal power transfer.
4, super/subcritical CO
2the bubbling that constantly circulates in esterifier flowing is stirred and is produced " supercavitation " effect, enhance the heat and mass transfer of high viscosity material in reactor, not only the sterically hindered of carboxyl on the transmission resistance of high viscosity rosin storeroom and three rings luxuriant and rich with fragrance skeletons was installed but also decreased to greatest extent to the agitator of economization esterifier, substantially increases heat and mass transfer and the esterification effect of esterifier.
5, super/subcritical CO
2produce " same to molecule " effect at esterifier, suppress Gum Rosin acid decarboxylation to generate CO
2side reaction, thus improve reaction preference and the quality product of rosin ester, reduce production cost and loss.
6, esterifier adopts super/subcritical CO
2carry out bubbling stirring, do not need mechanical stirring device is installed, be more conducive to the manufacture of high-tension apparatus, operation, maintenance and leakproof.
Accompanying drawing explanation
Fig. 1 is that catalytic esterification-separation coupling prepares rosin ester method flow diagram, and wherein 1 is dissolution kettle, and 2 is esterifiers, and 3 is decompressors, and 4 is gas-liquid separators, and 5 is turbocompressors, and 6 is knockout towers, and 7 is reflux pumps.
Fig. 2 is the structural representation according to esterifier of the present invention, and wherein 21 is opening for feeds, and 22 is air outlets, and 23 is discharge ports, and 24 is heating coils, and 25 is gas distributor, and 251 is inlet mouths, and 252 is shower nozzles.
Fig. 3 is the structural representation according to gas distributor single in esterifier of the present invention.
Fig. 4 is the vertical view according to gas distributor single in esterifier of the present invention.
Embodiment
Further describe the present invention referring to embodiment, to make those skilled in the art can implement according to this with reference to specification sheets word, scope is not limited by embodiments of the present invention.
Embodiment 1
As shown in accompanying drawing 1-4, prepare the device of rosin ester method for catalytic esterification-separation coupling, comprising: dissolution kettle 1, esterifier 2, decompressor 3, gas-liquid separator 4, turbocompressor 5, knockout tower 6, reflux pump 7.
The discharge port of dissolution kettle 1 is connected with the opening for feed of described esterifier 2, and dissolution kettle 1 is for dissolving the raw material needed for production.Esterifier 2, cylindrical, the top of esterifier is provided with opening for feed 21, air outlet 22, and bottom is provided with discharge port 23, and esterifier 2 comprises heating tube 24, and be heating coil, it is located at esterifier inside; Gas distributor 25, it comprises inlet mouth 251 and multiple shower nozzle 252 for being vented; Decompressor 3 is connected with the air outlet of described esterifier 2.Turbocompressor 5 is connected with described decompressor 3, and drives described turbocompressor 5 to work by described decompressor 3, and the air outlet of described turbocompressor 5 is connected with described esterifier 2.Gas-liquid separator 4 is connected with described decompressor 3, for separating of the mixing gas phase produced after reaction, isolates gas and liquid.The inlet mouth of knockout tower 6 is connected with described gas-liquid separator 4, for removing the gas needing to remove; Reflux pump 7 is connected with knockout tower 4, for being delivered in described esterifier 2 by isolated liquid solvent.
Preferably, described gas distributor 25 is in " L " type, and its bottom is annulus tubulose, and this ring tube is evenly provided with multiple shower nozzle 252 for being vented, and described shower nozzle is " L " type, becomes same direction to be obliquely installed.Pipe is in the form of a ring evenly equipped with multiple exhaust shower nozzle, makes gaseous emission more even, make fully to contact with gas as the material in esterifier, accelerate speed of reaction.The gas of the shower nozzle ejection be inclined to set tilts to spray gas toward same direction, makes bubble be contorted motion in esterifier 2, the material reacted fully is contacted with gas, fast reaction speed.
Preferably, described heating tube 24 is multiple, is distributed on described esterifier 2 inside in parallel; Described gas distributor 25 has multiple, and described multiple gas distributor 25 is interconnected, and the ring tube of described each gas distributor 25 is located between described heating tube 24.
Utilize above-mentioned device as reaction unit, a kind of catalytic esterification-separation coupling prepares rosin ester method:
By glycerine (glycerol) and rosin in molar ratio 1:1 add and melt still 1, the glycerine added again and rosin weight 50% turps, heating, melt, form mixture, pass into CO2 and material is compressed into esterifier 2, be warming up to 150 DEG C subsequently, the not open close CO2 of entering is 7.2Mpa to esterifier 2 internal pressure, then esterifier 2 air outlet valve is opened, make the water vapor produced in esterification reaction process, glycerin vapor, turps steam, CO2 mixing gaseous substance constantly flows out, discharge≤12000m3/h, pressure≤10.0MPa, gas-liquid separator 4 is entered after decompressor 3 throttling expansion, to expand step-down or throttling expansion step-down≤0.5MPa through decompressor 3, lower the temperature≤50 DEG C, the gas phase flowed out from esterifier 2 contains water vapor, glycerin vapor, turps steam, CO2 mixing gaseous substance, but water vapor, glycerin vapor, these materials flowed out of turps steam expand after step-down enters gas-liquid separator 4 through decompressor 3, water vapor, glycerin vapor, turps vapor condensation is separated from gas-liquid separator 4 for liquid, enter in knockout tower 6, the water of gained goes out from tower bottom flow by knockout tower 6, remaining glycerine, turps is returned systemic circulation and is used.And the CO2 separated from gas-liquid separator 4 enters pressurized circulation in turbocompressor 5 and returns esterifier 2 and carry out esterification, flow back to esterifier 2, gas flow≤10000m3/h, pressure≤10.0MPa through turbocompressor 5 pressurization.It is that above-mentioned decompressor 3 expansion work promotion turbocompressor 6 pressurizes that turbine compressor 5 carries out acting.And the pressure maintaining esterifier is 7.2MPa, after reaction 0.5h, esterifier 2 is heated to 275 DEG C, controlling temperature of reaction remains within the scope of 270 DEG C ~ 275 DEG C, reaction pressure is 7.2MPa, react 5.0h at this point in the reaction, obtain product, gained rosin ester flows out from the discharge port of esterifier 2.After testing, gained rosin ester acid number is 4.9mgKOH/g.
Embodiment 2
The reaction unit used is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
By ethanol and rosin in molar ratio 3:1 add and melt still 1, the glycerine added again and rosin weight 25% methylcarbonate, heating, melt, form mixture, pass into CO2 and material is compressed into esterifier 2, be warming up to 150 DEG C subsequently, the not open close CO2 of entering is 0.01Mpa to esterifier 2 internal pressure, then esterifier 2 air outlet valve is opened, make the water vapor produced in esterification reaction process, glycerin vapor, methylcarbonate steam, CO2 mixing gaseous substance constantly flows out, discharge is≤12000m3/h, pressure is≤10.0MPa, gas-liquid separator 4 is entered after decompressor 3 throttling expansion, expand step-down or throttling expansion step-down for≤0.5MPa through decompressor 3, cooling≤~ 50 DEG C, the gas phase flowed out from esterifier 2 contains water vapor, glycerin vapor, methylcarbonate steam, CO2 mixing gaseous substance, but water vapor, glycerin vapor, these materials flowed out of methylcarbonate steam expand after step-down enters gas-liquid separator 4 through decompressor 3, water vapor, glycerin vapor, methylcarbonate vapor condensation is separated from gas-liquid separator 4 for liquid, enter in knockout tower 6, the water of gained goes out from tower bottom flow by knockout tower 6, remaining glycerine, methylcarbonate is returned systemic circulation and is used.And the CO2 separated from gas-liquid separator 4 enters pressurized circulation in turbocompressor 5 and returns esterifier 2 and carry out esterification, flow back to esterifier 2 through turbocompressor 5 pressurization, gas flow is≤10000m3/h, and pressure is≤10.0MPa.It is that above-mentioned decompressor 3 expansion work promotion turbocompressor 6 pressurizes that turbine compressor 5 carries out acting.And the pressure maintaining esterifier is 7.2MPa, after reaction 0.5h, esterifier 2 is heated to 290 DEG C, controlling temperature of reaction remains within the scope of 280 DEG C ~ 300 DEG C, reaction pressure is 0.01MPa, react 7.5h at this point in the reaction, obtain product, gained rosin ester flows out from the discharge port of esterifier 2.After testing, gained rosin ester acid number is 3.9mgKOH/g.
Embodiment 3
The reaction unit used is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
By glycerine (glycerol) and rosin in molar ratio 5:1 add and melt still 1, the glycerine added again and rosin weight 10% 200# solvent oil, heating, melt, form mixture, pass into CO2 and material is compressed into esterifier 2, be warming up to 100 DEG C subsequently, the not open close CO2 of entering is 3.0Mpa to esterifier 2 internal pressure, then esterifier 2 air outlet valve is opened, make the water vapor produced in esterification reaction process, glycerin vapor, 200# solvent oil steam, CO2 mixing gaseous substance constantly flows out, discharge is≤12000m3/h, pressure is≤10.0MPa, gas-liquid separator 4 is entered after decompressor 3 throttling expansion, expand step-down or throttling expansion step-down for≤0.5MPa through decompressor 3, lower the temperature≤50 DEG C, the gas phase flowed out from esterifier 2 contains water vapor, glycerin vapor, 200# solvent oil steam, CO2 mixing gaseous substance, but water vapor, glycerin vapor, these materials flowed out of 200# solvent oil steam expand after step-down enters gas-liquid separator 4 through decompressor 3, water vapor, glycerin vapor, 200# solvent oil vapor condensation is separated from gas-liquid separator 4 for liquid, enter in knockout tower 6, the water of gained goes out from tower bottom flow by knockout tower 6, remaining glycerine, 200# solvent oil is returned systemic circulation and is used.And the CO2 separated from gas-liquid separator 4 enters pressurized circulation in turbocompressor 5 and returns esterifier 2 and carry out esterification, flow back to esterifier 2 through turbocompressor 5 pressurization, gas flow is≤10000m3/h, and pressure is≤10.0MPa.It is that above-mentioned decompressor 3 expansion work promotion turbocompressor 6 pressurizes that turbine compressor 5 carries out acting.And the pressure maintaining esterifier is 3.0MPa, after reaction 1.0h, esterifier 2 is heated to 280 DEG C, controlling temperature of reaction remains within the scope of 270 DEG C ~ 290 DEG C, reaction pressure is 3.0MPa, react 3.5h at this point in the reaction, obtain product, gained rosin ester flows out from the discharge port of esterifier 2.After testing, gained rosin ester acid number is 2.4mgKOH/g.
Embodiment 4
The reaction unit used is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
By glycerine (glycerol) and rosin in molar ratio 10:1 add and melt still 1, the glycerine added again and rosin weight 20% mineral essential oil, heating, melt, form mixture, pass into CO2 and material is compressed into esterifier 2, be warming up to 200 DEG C subsequently, the not open close CO2 of entering is 10.0Mpa to esterifier 2 internal pressure, then esterifier 2 air outlet valve is opened, make the water vapor produced in esterification reaction process, glycerin vapor, white spirits oil vapour, CO2 mixing gaseous substance constantly flows out, discharge is≤12000m3/h, pressure is≤10.0MPa, gas-liquid separator 4 is entered after decompressor 3 throttling expansion, expand step-down or throttling expansion step-down for≤0.5MPa through decompressor 3, lower the temperature≤50 DEG C, the gas phase flowed out from esterifier 2 contains water vapor, glycerin vapor, white spirits oil vapour, CO2 mixing gaseous substance, but water vapor, glycerin vapor, these materials flowed out of white spirits oil vapour expand after step-down enters gas-liquid separator 4 through decompressor 3, water vapor, glycerin vapor, white spirits oil vapour is condensed into liquid state and separates from gas-liquid separator 4, enter in knockout tower 6, the water of gained goes out from tower bottom flow by knockout tower 6, remaining glycerine, mineral essential oil is returned systemic circulation and is used.And the CO2 separated from gas-liquid separator 4 enters pressurized circulation in turbocompressor 5 and returns esterifier 2 and carry out esterification, flow back to esterifier 2 through turbocompressor 5 pressurization, gas flow is≤10000m3/h, and pressure is≤10.0MPa.It is that above-mentioned decompressor 3 expansion work promotion turbocompressor 6 pressurizes that turbine compressor 5 carries out acting.And the pressure maintaining esterifier is 10.0MPa, after reaction 0.5h, esterifier 2 is heated to 200 DEG C, controlling temperature of reaction remains within the scope of 190 DEG C ~ 210 DEG C, reaction pressure is 10.0MPa, react 7.5h at this point in the reaction, obtain product, gained rosin ester flows out from the discharge port of esterifier 2.After testing, gained rosin ester acid number is 2.4mgKOH/g.
Embodiment 5
The reaction unit used is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
By glycerine (glycerol) and rosin in molar ratio 6:1 add and melt still 1, the glycerine added again and rosin weight 15% turps, heating, melt, form mixture, pass into CO2 and material is compressed into esterifier 2, be warming up to 150 DEG C subsequently, the not open close CO2 of entering is 6.0Mpa to esterifier 2 internal pressure, then esterifier 2 air outlet valve is opened, make the water vapor produced in esterification reaction process, glycerin vapor, turps steam, CO2 mixing gaseous substance constantly flows out, discharge is≤12000m3/h, pressure is≤10.0MPa, gas-liquid separator 4 is entered after decompressor 3 throttling expansion, expand step-down or throttling expansion step-down for≤0.5MPa through decompressor 3, lower the temperature≤50 DEG C, the gas phase flowed out from esterifier 2 contains water vapor, glycerin vapor, turps steam, CO2 mixing gaseous substance, but water vapor, glycerin vapor, these materials flowed out of turps steam expand after step-down enters gas-liquid separator 4 through decompressor 3, water vapor, glycerin vapor, turps vapor condensation is separated from gas-liquid separator 4 for liquid, enter in knockout tower 6, the water of gained goes out from tower bottom flow by knockout tower 6, remaining glycerine, turps is returned systemic circulation and is used.And the CO2 separated from gas-liquid separator 4 enters pressurized circulation in turbocompressor 5 and returns esterifier 2 and carry out esterification, flow back to esterifier 2 through turbocompressor 5 pressurization, gas flow is≤10000m3/h, and pressure is≤10.0MPa.It is that above-mentioned decompressor 3 expansion work promotion turbocompressor 6 pressurizes that turbine compressor 5 carries out acting.And the pressure maintaining esterifier is 6.0MPa, after reaction 0.5h, esterifier 2 is heated to 180 DEG C, controlling temperature of reaction remains within the scope of 170 DEG C ~ 190 DEG C, reaction pressure is 6.0MPa, react 0.5h at this point in the reaction, obtain product, gained rosin ester flows out from the discharge port of esterifier 2.After testing, gained rosin ester acid number is 9.1mgKOH/g.
Embodiment 6
The reaction unit used is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
By glycerine (glycerol) and rosin in molar ratio 4:1 add and melt still 1, heating, melt, form mixture, pass into CO2 and material is compressed into esterifier 2, be warming up to 150 DEG C subsequently, the not open close CO2 of entering is 5.0Mpa to esterifier 2 internal pressure, then esterifier 2 air outlet valve is opened, make the water vapor produced in esterification reaction process, glycerin vapor, CO2 mixing gaseous substance constantly flows out, discharge is≤12000m3/h, pressure is≤10.0MPa, gas-liquid separator 4 is entered after decompressor 3 throttling expansion, expand step-down or throttling expansion step-down for≤0.5MPa through decompressor 3, lower the temperature≤50 DEG C, the gas phase flowed out from esterifier 2 contains water vapor, glycerin vapor, CO2 mixing gaseous substance, but water vapor, these materials flowed out of glycerin vapor expand after step-down enters gas-liquid separator 4 through decompressor 3, water vapor, glycerin vapor is condensed into liquid state and separates from gas-liquid separator 4, enter in knockout tower 6, the water of gained goes out from tower bottom flow by knockout tower 6, remaining glycerine is returned systemic circulation and is used.And the CO2 separated from gas-liquid separator 4 enters pressurized circulation in turbocompressor 5 and returns esterifier 2 and carry out esterification, flow back to esterifier 2 through turbocompressor 5 pressurization, gas flow is≤10000m3/h, and pressure is≤10.0MPa.It is that above-mentioned decompressor 3 expansion work promotion turbocompressor 6 pressurizes that turbine compressor 5 carries out acting.And the pressure maintaining esterifier is 5.0MPa, after reaction 0.5h, esterifier 2 is heated to 160 DEG C, controlling temperature of reaction remains within the scope of 150 DEG C ~ 170 DEG C, reaction pressure is 5.0.0MPa, react 2.5h at this point in the reaction, obtain product, gained rosin ester flows out from the discharge port of esterifier 2.After testing, gained rosin ester acid number is 3.2mgKOH/g.
Embodiment 7
The reaction unit used is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
By glycerine (glycerol) and rosin in molar ratio 1:1 add and melt still 1, the glycerine added again and rosin weight 45% turps, heating, melt, form mixture, pass into CO2 and material is compressed into esterifier 2, be warming up to 150 DEG C subsequently, the not open close CO2 of entering is 7.2Mpa to esterifier 2 internal pressure, then esterifier 2 air outlet valve is opened, make the water vapor produced in esterification reaction process, glycerin vapor, turps steam, CO2 mixing gaseous substance constantly flows out, discharge is≤12000m3/h, pressure is≤10.0MPa, gas-liquid separator 4 is entered after decompressor 3 throttling expansion, expand step-down or throttling expansion step-down for≤0.5MPa through decompressor 3, lower the temperature≤50 DEG C, the gas phase flowed out from esterifier 2 contains water vapor, glycerin vapor, turps steam, CO2 mixing gaseous substance, but water vapor, glycerin vapor, these materials flowed out of turps steam expand after step-down enters gas-liquid separator 4 through decompressor 3, water vapor, glycerin vapor, turps vapor condensation is separated from gas-liquid separator 4 for liquid, enter in knockout tower 6, the water of gained goes out from tower bottom flow by knockout tower 6, remaining glycerine, turps is returned systemic circulation and is used.And the CO2 separated from gas-liquid separator 4 enters pressurized circulation in turbocompressor 5 and returns esterifier 2 and carry out esterification, flow back to esterifier 2 through turbocompressor 5 pressurization, gas flow is≤10000m3/h, and pressure is≤10.0MPa.It is that above-mentioned decompressor 3 expansion work promotion turbocompressor 6 pressurizes that turbine compressor 5 carries out acting.And the pressure maintaining esterifier is 7.2MPa, after reaction 0.5h, esterifier 2 is heated to 275 DEG C, controlling temperature of reaction remains within the scope of 270 DEG C ~ 280 DEG C, reaction pressure is 7.2MPa, react 2.0h at this point in the reaction, obtain product, gained rosin ester flows out from the discharge port of esterifier 2.After testing, gained rosin ester acid number is 8.4mgKOH/g.
Embodiment 8
The reaction unit used is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
By glycerine (glycerol) and rosin in molar ratio 1:1 add and melt still 1, the glycerine added again and rosin weight 3% methylcarbonate, heating, melt, form mixture, pass into CO2 and material is compressed into esterifier 2, be warming up to 150 DEG C subsequently, the not open close CO2 of entering is 8.0Mpa to esterifier 2 internal pressure, then esterifier 2 air outlet valve is opened, make the water vapor produced in esterification reaction process, glycerin vapor, methylcarbonate steam, CO2 mixing gaseous substance constantly flows out, discharge is≤12000m3/h, pressure is≤10.0MPa, gas-liquid separator 4 is entered after decompressor 3 throttling expansion, expand step-down or throttling expansion step-down for≤0.5MPa through decompressor 3, lower the temperature≤50 DEG C, the gas phase flowed out from esterifier 2 contains water vapor, glycerin vapor, methylcarbonate steam, CO2 mixing gaseous substance, but water vapor, glycerin vapor, these materials flowed out of methylcarbonate steam expand after step-down enters gas-liquid separator 4 through decompressor 3, water vapor, glycerin vapor, methylcarbonate vapor condensation is separated from gas-liquid separator 4 for liquid, enter in knockout tower 6, the water of gained goes out from tower bottom flow by knockout tower 6, remaining glycerine, methylcarbonate is returned systemic circulation and is used.And the CO2 separated from gas-liquid separator 4 enters pressurized circulation in turbocompressor 5 and returns esterifier 2 and carry out esterification, flow back to esterifier 2 through turbocompressor 5 pressurization, gas flow is≤10000m3/h, and pressure is≤10.0MPa.It is that above-mentioned decompressor 3 expansion work promotion turbocompressor 6 pressurizes that turbine compressor 5 carries out acting.And the pressure maintaining esterifier is 8.0MPa, after reaction 0.5h, esterifier 2 is heated to 200 DEG C, controlling temperature of reaction remains within the scope of 190 DEG C ~ 210 DEG C, reaction pressure is 8.0MPa, react 1.5h at this point in the reaction, obtain product, gained rosin ester flows out from the discharge port of esterifier 2.After testing, gained rosin ester acid number is 11.2mgKOH/g.
Embodiment 9
The reaction unit used is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
By methyl alcohol and rosin in molar ratio 2:1 add and melt still 1, the glycerine added again and rosin weight 35% turps, heating, melt, form mixture, pass into CO2 and material is compressed into esterifier 2, be warming up to 200 DEG C subsequently, the not open close CO2 of entering is 1.0Mpa to esterifier 2 internal pressure, then esterifier 2 air outlet valve is opened, make the water vapor produced in esterification reaction process, glycerin vapor, turps steam, CO2 mixing gaseous substance constantly flows out, discharge is≤12000m3/h, pressure is≤10.0MPa, gas-liquid separator 4 is entered after decompressor 3 throttling expansion, expand step-down or throttling expansion step-down for≤0.5MPa through decompressor 3, lower the temperature≤50 DEG C, the gas phase flowed out from esterifier 2 contains water vapor, glycerin vapor, turps steam, CO2 mixing gaseous substance, but water vapor, glycerin vapor, these materials flowed out of turps steam expand after step-down enters gas-liquid separator 4 through decompressor 3, water vapor, glycerin vapor, turps vapor condensation is separated from gas-liquid separator 4 for liquid, enter in knockout tower 6, the water of gained goes out from tower bottom flow by knockout tower 6, remaining glycerine, turps is returned systemic circulation and is used.And the CO2 separated from gas-liquid separator 4 enters pressurized circulation in turbocompressor 5 and returns esterifier 2 and carry out esterification, flow back to esterifier 2 through turbocompressor 5 pressurization, gas flow is≤10000m3/h, and pressure is≤10.0MPa.It is that above-mentioned decompressor 3 expansion work promotion turbocompressor 6 pressurizes that turbine compressor 5 carries out acting.And the pressure maintaining esterifier is 1.0MPa, after reaction 0.5h, esterifier 2 is heated to 250 DEG C, controlling temperature of reaction remains within the scope of 245 DEG C ~ 255 DEG C, reaction pressure is 1.0MPa, react 4.5h at this point in the reaction, obtain product, gained rosin ester flows out from the discharge port of esterifier 2.After testing, gained rosin ester acid number is 3.1mgKOH/g.
Embodiment 10
The reaction unit used is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
By glycerine (glycerol) and rosin in molar ratio 9:1 add and melt still 1, the glycerine added again and rosin weight 24% methylcarbonate, heating, melt, form mixture, pass into CO2 and material is compressed into esterifier 2, be warming up to 150 DEG C subsequently, the not open close CO2 of entering is 4.0Mpa to esterifier 2 internal pressure, then esterifier 2 air outlet valve is opened, make the water vapor produced in esterification reaction process, glycerin vapor, methylcarbonate steam, CO2 mixing gaseous substance constantly flows out, discharge is≤12000m3/h, pressure is≤10.0MPa, gas-liquid separator 4 is entered after decompressor 3 throttling expansion, expand step-down or throttling expansion step-down for≤0.5MPa through decompressor 3, lower the temperature≤50 DEG C, the gas phase flowed out from esterifier 2 contains water vapor, glycerin vapor, methylcarbonate steam, CO2 mixing gaseous substance, but water vapor, glycerin vapor, these materials flowed out of methylcarbonate steam expand after step-down enters gas-liquid separator 4 through decompressor 3, water vapor, glycerin vapor, methylcarbonate vapor condensation is separated from gas-liquid separator 4 for liquid, enter in knockout tower 6, the water of gained goes out from tower bottom flow by knockout tower 6, remaining glycerine, methylcarbonate is returned systemic circulation and is used.And the CO2 separated from gas-liquid separator 4 enters pressurized circulation in turbocompressor 5 and returns esterifier 2 and carry out esterification, flow back to esterifier 2 through turbocompressor 5 pressurization, gas flow is≤10000m3/h, and pressure is≤10.0MPa.It is that above-mentioned decompressor 3 expansion work promotion turbocompressor 6 pressurizes that turbine compressor 5 carries out acting.And the pressure maintaining esterifier is 4.0MPa, after reaction 1.5h, esterifier 2 is heated to 270 DEG C, controlling temperature of reaction remains within the scope of 265 DEG C ~ 275 DEG C, reaction pressure is 4.0MPa, react 2.5h at this point in the reaction, obtain product, gained rosin ester flows out from the discharge port of esterifier 2.After testing, gained rosin ester acid number is 1.7mgKOH/g.
Embodiment 11
The reaction unit used is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
By glycerine (glycerol) and rosin in molar ratio 1:1 add and melt still 1, the glycerine added again and rosin weight 5% turps, heating, melt, form mixture, pass into CO2 and material is compressed into esterifier 2, be warming up to 160 DEG C subsequently, the not open close CO2 of entering is 8.0Mpa to esterifier 2 internal pressure, then esterifier 2 air outlet valve is opened, make the water vapor produced in esterification reaction process, glycerin vapor, turps steam, CO2 mixing gaseous substance constantly flows out, discharge is≤12000m3/h, pressure is≤10.0MPa, gas-liquid separator 4 is entered after decompressor 3 throttling expansion, expand step-down or throttling expansion step-down for≤0.5MPa through decompressor 3, lower the temperature≤50 DEG C, the gas phase flowed out from esterifier 2 contains water vapor, glycerin vapor, turps steam, CO2 mixing gaseous substance, but water vapor, glycerin vapor, these materials flowed out of turps steam expand after step-down enters gas-liquid separator 4 through decompressor 3, water vapor, glycerin vapor, turps vapor condensation is separated from gas-liquid separator 4 for liquid, enter in knockout tower 6, the water of gained goes out from tower bottom flow by knockout tower 6, remaining glycerine, turps is returned systemic circulation and is used.And the CO2 separated from gas-liquid separator 4 enters pressurized circulation in turbocompressor 5 and returns esterifier 2 and carry out esterification, flow back to esterifier 2 through turbocompressor 5 pressurization, gas flow is≤10000m3/h, and pressure is≤10.0MPa.It is that above-mentioned decompressor 3 expansion work promotion turbocompressor 6 pressurizes that turbine compressor 5 carries out acting.And the pressure maintaining esterifier is 8.0MPa, after reaction 0.5h, esterifier 2 is heated to 200 DEG C, controlling temperature of reaction remains within the scope of 190 DEG C ~ 210 DEG C, reaction pressure is 8.0MPa, react 5.5h at this point in the reaction, obtain product, gained rosin ester flows out from the discharge port of esterifier 2.After testing, gained rosin ester acid number is 4.4mgKOH/g.
Embodiment 12
The reaction unit used is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
By glycerine (glycerol) and rosin in molar ratio 3:1 add and melt still 1, the glycerine added again and rosin weight 20% methylcarbonate, heating, melt, form mixture, pass into CO2 and material is compressed into esterifier 2, be warming up to 200 DEG C subsequently, the not open close CO2 of entering is 5.6Mpa to esterifier 2 internal pressure, then esterifier 2 air outlet valve is opened, make the water vapor produced in esterification reaction process, glycerin vapor, methylcarbonate steam, CO2 mixing gaseous substance constantly flows out, discharge is≤12000m3/h, pressure is≤10.0MPa, gas-liquid separator 4 is entered after decompressor 3 throttling expansion, expand step-down or throttling expansion step-down for≤0.5MPa through decompressor 3, lower the temperature≤50 DEG C, the gas phase flowed out from esterifier 2 contains water vapor, glycerin vapor, methylcarbonate steam, CO2 mixing gaseous substance, but water vapor, glycerin vapor, these materials flowed out of methylcarbonate steam expand after step-down enters gas-liquid separator 4 through decompressor 3, water vapor, glycerin vapor, methylcarbonate vapor condensation is separated from gas-liquid separator 4 for liquid, enter in knockout tower 6, the water of gained goes out from tower bottom flow by knockout tower 6, remaining glycerine, methylcarbonate is returned systemic circulation and is used.And the CO2 separated from gas-liquid separator 4 enters pressurized circulation in turbocompressor 5 and returns esterifier 2 and carry out esterification, flow back to esterifier 2 through turbocompressor 5 pressurization, gas flow is≤10000m3/h, and pressure is≤10.0MPa.It is that above-mentioned decompressor 3 expansion work promotion turbocompressor 6 pressurizes that turbine compressor 5 carries out acting.And the pressure maintaining esterifier is 5.6MPa, after reaction 0.5h, esterifier 2 is heated to 295 DEG C, controlling temperature of reaction remains within the scope of 290 DEG C ~ 300 DEG C, reaction pressure is 5.6MPa, react 1.5h at this point in the reaction, obtain product, gained rosin ester flows out from the discharge port of esterifier 2.After testing, gained rosin ester acid number is 4.1mgKOH/g.
In the specific embodiment of the invention, if equipment is in not response behaviour, when neither adding reaction gas, in reactive system, flow is all 0, and extraction gas phase temperature etc. is also.
Claims (10)
1. catalytic esterification-separation coupling prepares a method for rosin ester, it is characterized in that, comprises following operation steps:
(1) by alcohol compound, rosin and solvent, dissolve;
(2) material after dissolving in step (1) is put into esterifier, pass into the CO of 0.01 ~ 10.0MPa
2carry out esterification, esterification reaction temperature is 150 ~ 300 DEG C;
(3) carry out extraction to the gas phase in esterification reaction process, gas phase enters gas-liquid separator by decompressor, CO after being separated
2and the new CO supplemented
2get back in esterifier by turbocompressor;
(4), after in esterifier, reaction 1.0 ~ 8.0h reduces pressure, products obtained therefrom takes out in esterifier.
2. catalytic esterification-separation coupling prepares the method for rosin ester according to claim 1, it is characterized in that: according to mol ratio alcohol compound in step (1): rosin=1:1 ~ 10:1 mixing, adds the solvent that raw materials quality mark is 0 ~ 50%.
3. catalytic esterification-separation coupling prepares the method for rosin ester according to claim 1, it is characterized in that: the gas phase flow rate flowed out from esterifier in step (2) ~ (3) is 0 ~ 12000m
3/ h, pressure are 0 ~ 10.0MPa, temperature is 150 ~ 300 DEG C; Be 0 ~ 0.5MPa through expander step-down or throttling expansion step-down, cooling is 0 DEG C ~ 50 DEG C, then flows back to esterifier through turbocompressor pressurization, and gas flow is 0 ~ 10000m
3/ h, pressure is 0 ~ 10.0MPa, and temperature is 150 DEG C ~ 300 DEG C.
4. catalytic esterification-separation coupling prepares the method for rosin ester according to claim 1, it is characterized in that: in step (3), the temperature of gas-liquid separator is 0 ~ 50 DEG C, and pressure is 0.0 ~ 0.5MPa, and liquid flow rate is 0 ~ 100m
3/ h, gas flow is 0 ~ 10000m
3/ h.
5. catalytic esterification-separation coupling prepares the method for rosin ester according to claim 1, it is characterized in that: described solvent is the one in turps, methylcarbonate, mineral essential oil, 200# solvent oil; One in described alcohols chemical combination glycerol, methyl alcohol, ethanol.
6. catalytic esterification-separation coupling prepares an equipment for rosin ester method as claimed in claim 1, it is characterized in that, this equipment comprises:
Esterifier, it comprises: multiple heating tube, is located at esterifier inside; And gas distributor, it comprises inlet mouth and multiple shower nozzle for being vented;
Decompressor, it is connected with described esterifier; And turbocompressor, it is connected with described decompressor, and drives described turbocompressor work by described decompressor, and the air outlet of described turbocompressor is connected with described esterifier.
7. equipment according to claim 6, is characterized in that: preferably, and in technique scheme, described gas distributor is in " L " type, and its bottom is annulus tubulose, and this ring tube is evenly provided with multiple shower nozzle for being vented, and described shower nozzle is obliquely installed.
8. equipment according to claim 6, it is characterized in that: in technique scheme, described heating tube is multiple, and to be distributed on described esterifier inner in parallel; Described gas distributor has multiple, and described multiple gas distributor is interconnected, and described each gas distributor is located between described heating tube.
9. equipment according to claim 6, is characterized in that: in technique scheme, described for, also comprise: dissolution kettle, itself and the anti-esterifier of described hydrogenation are inner; Described gas distributor has multiple, and described multiple gas distributor is interconnected, and described each gas distributor is located between described heating tube.
10. equipment according to claim 6, it is characterized in that: in technique scheme, the described equipment preparing rosin ester method for catalytic esterification-separation coupling, also comprises: dissolution kettle, it is connected with described esterifier, for dissolving the raw material needed for production; Gas-liquid separator, its inlet mouth is connected with described decompressor, and air outlet is connected with turbocompressor; Knockout tower, its discharge port is connected with described turbocompressor; And reflux pump, it is connected with described knockout tower, for being delivered in described esterifier by isolated liquid solvent.
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