CN101768077B - Method for preparing high-purity adipic acid dimethyl ester by catalytic gas stripping coupling technology - Google Patents
Method for preparing high-purity adipic acid dimethyl ester by catalytic gas stripping coupling technology Download PDFInfo
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Abstract
The invention discloses a method for preparing high-purity adipic acid dimethyl ester by catalytic gas stripping coupling technology. The method comprises the following steps: carrying out countercurrent contact on adipic-acid-containing liquid phase, methanol gas and inert gas in a gas stripping tower and carrying out reaction to generate water which is gas-stripped to the gas phase and recovered from the top of the gas stripping tower; obtaining high-purity adipic acid dimethyl ester from the tower bottom. The method of the invention features simple process, high purity of produced adipic acid dimethyl ester, no need of further refining and direct application as raw material for preparing 1,6-hexanediol.
Description
Technical field
The present invention relates to a kind of preparation method of dimethyl adipate, be specifically related to a kind of method for preparing high-purity adipic acid dimethyl ester in a reactor by reaction-gas stripping coupling technology.
Background technology
Esterification is a kind of typical reversible reaction, generally need to be at an acidic catalyst, under the katalysis as sulfuric acid etc., by corresponding acid or acid anhydrides and pure esterification.Due to the restriction that is subject to chemical equilibrium, generally can not disposablely obtain very high once through yield, need follow-uply refiningly just to meet the requirements of purity, unreacted raw material need to recycle.Esterifier generally adopts tank reactor or tubular reactor, intermittence or operate continuously.
CN200410020789.3 discloses a kind of method for preparing dimethyl adipate, described method adopts the esterifying catalyst that loads on activated carbon, reaction pressure is at 0.2-5MPa, dimethyl adipate in product, hexanodioic acid, water and methyl alcohol etc., then the process rectifying separation obtains the dimethyl adipate of purity 99.5%; Unreacted hexanodioic acid recycles after separating with methyl alcohol; The shortcoming of above technique is to adopt more complicated catalyzer, and it is high that catalyzer prepares cost, and in order to guarantee liquid phase reaction, reaction needed is carried out under condition of high voltage, and technical process is complicated, needs making with extra care through multistep.
In addition, be used for the dimethyl adipate of standby 1, the 6-hexylene glycol purposes of Hydrogenation, the unreacted acid of trace and the water of generation all will be avoided as far as possible, because they can cause undesirable infringement to the catalyzer that adopts in follow-up hydrogenation technique; In order to satisfy the needs of hydrogenation technique, must acid and water be dropped to a very low level through follow-up making with extra care, and follow-up sepn process, the process of particularly dimethyl adipate being separated with hexanodioic acid, energy consumption is higher.
Disclose a kind of continuous esterification device in CN200620122552.0, its described reactor is a kind of fixed-bed tube reactor.Although device structure is simple, but the pressure drop of column of fixed-bed process is large, gas-to-liquid contact is insufficient, and the chemical equilibrium that is limited by esterification is controlled, and is difficult to obtain purity very high, acid and the very little esters product of water-content, the transformation efficiency of acid is 99% left and right, can not be directly used in equally standby 1, the 6-hexylene glycol of Hydrogenation, also need further purify through the refining means such as rectifying, thereby increase the investment of production cost and separation circuit.
WO9008127 discloses a kind of technology and equipment of esterification, the method adopts a kind of tubular reactor, and inside is divided into a plurality of beds, and solid catalyst is loose to be piled up in bed, alcohol steam reaches with acid, solid catalyst in the mode of bubbling in acid solution and contacts, and reacts under certain pressure.Still contain a certain amount of unreacted acid in tower bottoms, need again with excessive alcohol together by the fixed-bed reactor that esterifying catalyst is housed, remove not reacted acid thereby further react, finally obtain in fact not containing the esters product of acid, in the method, the transformation efficiency of acid is still limited, and in order to solve unreacted acid and alcohol excess, also needs to increase new equipment, make technique more complicated, increased production cost.
In general, adopt autoclave or fixed bed esterification technique to be difficult to directly obtain the sufficiently high ester of purity, it is feasible making with extra care by the follow-up operations such as rectifying, but cost is very high.
Summary of the invention
For above technological deficiency, the invention provides a kind of method for preparing highly purified dimethyl adipate, the dimethyl adipate of the method preparation can be directly used in the raw material of standby 1, the 6-hexylene glycol of Hydrogenation.
The method of the invention comprises: in gas stripping column, the liquid phase that contains hexanodioic acid from the top of tower internal reaction section from top to bottom, the methanol gas that adds with bottom from gas stripping column internal reaction section and the rare gas element that added by the gas stripping column tower reactor are in the conversion zone counter current contact, under solid esterification catalyst action in conversion zone, hexanodioic acid and methyl alcohol carry out esterification, generate highly purified dimethyl adipate.
In the method for the invention, in gas stripping column, the liquid phase that contains hexanodioic acid from the top of tower internal reaction section from top to bottom, with the methanol gas that adds from the methanol feeding pipe in the bottom of gas stripping column internal reaction section and rare gas element counter current contact conversion zone of adding in the tower reactor of gas stripping column, hexanodioic acid and methyl alcohol generation esterification under the esterifying catalyst effect, the water of methyl alcohol, rare gas element and generation by the gas stripping column overhead extraction, obtains dimethyl adipate with gas form in the tower reactor of gas stripping column; The total content of the hexanodioic acid in above-mentioned dimethyl adipate, first alcohol and water is less than 0.01wt%.
In the inventive method, the reaction pressure of esterification is normal pressure or a little higher than normal pressure, and the present invention is preferably the 1-1.5 normal atmosphere.
In the inventive method, described esterification is preferably reacted between 110 ℃-180 ℃ between 100 ℃-180 ℃.
In the inventive method, described rare gas element is the rare gas element of high temperature, preferably 120-300 ℃, and the more preferably rare gas element of 170-250 ℃; And preferably introduce rare gas element in the bottom of the tower reactor of gas stripping column, described rare gas element is nitrogen preferably.
In the method for the invention, described methyl alcohol can liquid state or the form of gaseous state add; Preferably enter with the lower position of gas form by gas stripping column.The feeding temperature of methyl alcohol should be not less than 65 ℃, preferably 65-180 ℃; The top hole pressure of methanol feeding pipe is the 1-3 normal atmosphere, preferably 1-1.5 normal atmosphere.
Esterifying catalyst of the present invention includes but not limited to as molecular sieve, solid super-strong acid, heteropolyacid and ion exchange resin etc.; Described esterifying catalyst is preferably solid acid catalyst, further sulfonic acid type strong-acid ion exchange resin preferably, and it can be any commercial sulfonic acid type strong-acid ion exchange resin.As one of preferred embodiment of the invention, the specific surface area 20-50m of described sulfonic acid type strong-acid ion exchange resin
2/ g, preferred 30-40m
2/ g; Mean pore size 15-30nm, preferred 20-25nm; Pore volume is preferably greater than 0.2ml/g greater than 0.1ml/g; Particle diameter 0.4-1.2mm, exchange capacity is more than or equal to 3.0mmol/g; The further preferred D008 resin of described resin, Amb-16 or Amb-36 resin, the best is the D008 resin.
Solid acid catalyst has the advantages that cost is low, application is ripe, easy to use; The present invention adopts solid acid catalyst, can avoid the problems such as corrosion that liquid acid catalyst brings and aftertreatment be loaded down with trivial details.
In the method for the invention, the described liquid phase that contains hexanodioic acid is comprised of hexanodioic acid and liquid diluent, described liquid diluent is preferably the mixture of methyl alcohol or methyl alcohol and dimethyl adipate, and the molar content of hexanodioic acid is 5%-30% in containing the liquid phase of hexanodioic acid, and preferred 10% to 20%.
The liquid phase stream that contains hexanodioic acid of the present invention is entered by the stripping tower upper position; The described liquid phase stream that contains hexanodioic acid is the liquid phase stream that contains hexanodioic acid of high temperature, preferably 90-200 ℃, and the more preferably liquid phase stream that contains hexanodioic acid of 110-180 ℃.
In the method for the invention, as preferred embodiment, the molar flow of rare gas element is 3-30kmol/hm
2, preferred 12-24kmol/h, further preferred 15-21mol/h, further preferred 18-19kmol/hm
2
The molar flow that contains the liquid phase stream of hexanodioic acid is 3-30kmol/hm
2, preferred 9-24kmol/hm
2, further preferred 12-18kmol/hm
2, preferred 15-16kmol/hm further
2(pressing hexanodioic acid calculates).
The feeding rate of methyl alcohol be make methyl alcohol to mole multiple of hexanodioic acid be 3-30 doubly, preferred 6-25 doubly, further preferred 10-20 doubly, most preferably 14-16 is doubly.
In the method for the invention, described gas stripping column can be selected this area commonly used tray column or packing tower, and catalyzer is with pack into packing tower or be loaded on the column plate of tray column of form of bio-carrier; The preferred tray column of gas stripping column of the present invention, thus make solid acid catalyst easily load and unload.The preferred column plate form of described tray column can form as disclosed in WO9008127 (the particularly tray column of embodiment 1), adopts the column plate with flow deflector, perhaps disclosed combined trapezoid spray tray form in CN200610013530.5.Preferred column plate can effectively increase the turbulence of catalyzer and liquid on column plate, strengthens the contact between gas-liquid, liquid-solid phase, thereby improves mass-transfer efficiency, increases the utilization ratio of catalyzer.
As one of preferred embodiment, board-like gas stripping column of the present invention has height and the 10-30 level column plate of 5-24m, preferred 12-20 level column plate; Tray spacing is preferably 50-80cm.Wherein, condenser and tower reactor are looked and are respectively the first step and last step column plate.When column plate when numbering and condenser and tower reactor are considered as respectively the first step and last step column plate from top to bottom, the feed entrance point (namely adding the implantation site) that contains the liquid phase stream of hexanodioic acid is generally between 3rd level column plate and the 5th grade of column plate, and the feed entrance point of methyl alcohol is between level column plate third from the bottom and level V column plate reciprocal.
Conversion zone of the present invention refers to the conversion zone that is made of the column plate that catalyzer is housed in gas stripping column, i.e. conversion zone between the introducing position of the introducing position of the liquid phase stream that contains hexanodioic acid and methyl alcohol." at the rare gas element that tower reactor adds " refer on the liquid level of tower reactor, or the position between the bottom of the liquid level of tower reactor and tower reactor, or in the bottom of tower reactor.
In the method for the invention, the liquid phase stream that contains hexanodioic acid adds with the upper position of liquid form by gas stripping column; Methyl alcohol can add with the form of liquid or gas, preferably adds with the lower position of gas form by gas stripping column; Hexanodioic acid contacts with the adverse current form on column plate with methyl alcohol, reacts under the effect of solid acid catalyst; The water that generates is taken reaction system out of by the gas stripping of air lift gas, promotes whole reaction process and carries out to the direction that generates the purpose product.Water content in gas phase reduces by column plate from top to bottom, deepens gradually thereby promote the esterification degree, makes hexanodioic acid at the final dimethyl adipate that transforms fully of tower reactor; The water that the reaction of methyl alcohol and hexanodioic acid generates with gas form by the gas stripping column overhead extraction.
In the inventive method, the heavy constituents such as the acid in the cold recovery gas phase is introduced at the top of gas stripping column and ester.The cold of gas stripping column tower top is provided by gas stripping column overhead condenser or cold water-free methyl alcohol.The reflux ratio that gas stripping column uses is between 0.1-1, and preferred reflux ratio is at 0.1-0.5, described reflux ratio=trim the top of column flow/overhead extraction flow.
In the method for the invention, preferably described " liquid phase stream that contains hexanodioic acid " is to react by hexanodioic acid and methyl alcohol the product that obtains in a pre-reactor; Further preferably described " liquid phase material that contains hexanodioic acid " is to be reacted in a pre-reactor by hexanodioic acid and methyl alcohol, then through flash distillation remove portion light constituent, for example, removes resulting logistics after the water of unreacted methyl alcohol and generation; The molar content of preferred hexanodioic acid is 5%-30%, preferred 10% to 20%.
In the method for the invention, improve the feeding temperature that contains the hexanodioic acid liquid phase stream and be conducive to improve speed of response, and increase the ability that steaming dewaters, but too high temperature can reduce the life-span of catalyzer.The temperature that the present invention preferably contains the liquid phase stream of hexanodioic acid is 90-200 ℃, preferred 110-180 ℃.
In the present invention, the temperature that improves charging methyl alcohol is conducive to improve speed of reaction, and in the present invention, the temperature of described methyl alcohol is 65-180 ℃; Pressure is the 1-3 normal atmosphere, preferred 1-1.5 normal atmosphere.
Methyl alcohol can effectively be taken the moisture in reaction solution out of with the gas stripping of gas form to reaction system, and driving a reaction carries out to the direction that is conducive to generate the purpose product.But because the restriction of thermodynamic(al)equilibrium, when water-content was low, the in the end steaming water effect on a few deblocking reaction plates was extremely slow, has limited the further intensification of level of response.Simultaneously, be subjected to the restriction of thermodynamic(al)equilibrium, the light constituent in tower bottoms particularly methanol content is still very high.
Find by research, by introduce the way of high temperature inert gas air lift in tower reactor, can solve the above-mentioned problem easily, realize the highly purified dimethyl adipate of preparation in a gas stripping column, and can significantly not increase the difficulty of subsequent disposal.
The temperature of rare gas element of the present invention is 120-300 ℃, more preferably 170-250 ℃.Rare gas element can be at the overhead condenser of catalysis gas stripping column, perhaps easily realizes separating and recycling at the overhead condenser place of methanol distillation column; And more than increasing stripping section length, improve the economy that tower reactor reboiler thermal load is come with intensification rare gas element air lift on facility investment and energy consumption.
Introduce rare gas element at the bottom of gas stripping column, can increase significantly stripping section and steam the ability of removing light constituent, and can strengthen the esterification column plate, especially last several esterification column plates except outlet capacity, simultaneously, can also improve the turbulence of liquid and catalyzer on column plate, strengthen the effect of gas-to-liquid contact, further improve the mass transfer ability, further improve the level of response of esterification, make hexanodioic acid trend towards 100% and be converted into dimethyl adipate.Thereby need not increase equipment investment, need not just can obtain containing hardly the dimethyl adipate product of methyl alcohol, acid and moisture under the condition of the very high thermal load of tower bottom reboiler maintenance.
The typical temperature and pressure that reaction conditions in the catalysis gas stripping column uses when comprising the methyl alcohol distillation, the general temperature of using is at 65-180 ℃, and pressure is about 1-3atm.Temperature of reaction raises and is conducive to improve speed of response, the present invention preferably adopts resistant to elevated temperatures strongly acidic ion-exchange resin catalyst, concrete temperature of reaction those skilled in the art can select the 110-180 ℃ of actual temp in temperature range according to different resins, the ion exchange resin of for example selecting Rohm and Haas company to sell with trade mark Amberlyst-16wet, the suitable temperature of conversion zone is generally 110 ℃; Selection Rohm and Haas company is with the resin of trade mark Amberlyst-Amb-36, and the suitable temperature of reaction of conversion zone is generally 180.Because ion exchange resin is cheap than other solid acid catalyst, preparation and industrial application are ripe, and be easy to use, and therefore, in the present invention, preferred strong-acid ion exchange resin is catalyzer.
Contain methanol vapor and water vapour from the gaseous stream of gas stripping column top discharge, also may contain the seldom dimethyl adipate of amount.In order to reach the purpose that reclaims the dimethyl adipate of trace in gas phase, can install one or more additional column plate additional on the esterification column plate of the superiors, make the dimethyl adipate in gas phase turn back to again the esterification column plate.Substantially the gaseous stream that does not contain dimethyl adipate is discharged from tower top.Can use overhead condenser that the trim the top of column cold is provided, perhaps replace overhead condenser to reflux with water-free low-temp methanol.Increase quantity of reflux and can improve the ability that reclaims the dimethyl adipate in gas phase, but quantity of reflux crosses conference and significantly reduce temperature of reaction on the esterification column plate, reduce speed of reaction, increase reboiler, so preferred less reflux ratio, the preferred 0.1-1 of reflux ratio, more preferably 0.1-0.5 in reality.
In catalysis gas stripping process of the present invention, esterification and air lift act in gas stripping column carries out simultaneously, when methanol steam flows to next higher column plate from a lower column plate, the water that the methanol steam that upwards flows generates with esterification, therefore the liquid that contains hexanodioic acid flows downward from a column plate to the lower column plate of the next one, along with it flows to tower lower floor, it runs into more and more dried condition.This mode causes enzymatic synthesis condition more and more to trend towards 100% changing into dimethyl adipate.
The excessive methanol that contains in the gas phase of gas stripping column overhead extraction is removed wherein water and other impurity through a methanol distillation column separation and purification, and the methyl alcohol after making with extra care is sent into the catalysis gas stripping column and recycled.
Water content in the methyl alcohol of circulation is larger on the transformation efficiency impact of acid in the catalysis gas stripping column, and the acidity of methanol distillation column tower bottoms is also closely related with the water content of methanol steam, too high water content can make methanol column tower bottoms acidity too high, causes serious corrosion.Water content in the methyl alcohol of preferred cycle utilization is controlled at below 0.01%.
The purity of the inventive method products therefrom is high, need not further to make with extra care, and can directly use as the raw material for preparing 1,6-hexylene glycol by shortening.Simultaneously, the method in the present invention, flow process is simple, and required equipment is few, invests low; Take full advantage of reaction heat, energy consumption is low; Catalyst performance is good, and cost is low, easily change, after namely process conveniently, have excellent device economy.In addition, the technique that proposes in the present invention, pollution-free, without corrosion, without sewage discharge is the technique of environmental protection.
Embodiment
Have now and further illustrate the present invention by following examples, but the present invention is not limited to this.
Embodiment 1
Tower diameter is the gas stripping column of 100mm, adopts the tray column with flow deflector, atmospheric operation, 15 grades of column plates (condenser and tower reactor are considered as respectively the 1st and the 15th grade of column plate), distance between plates is 60mm, liquid layer thickness 50mm on plate, and the liquid holdup of every grade of column plate is about 200-245ml.On 3-13 level column plate, loose heap has strongly acidic ion-exchange resin catalyst, adopts D008 type dimethyl adipate special-purpose catalyst, and the catalyzer dry weight on every grade of column plate is about 15% of liquid mass on every grade of column plate.The feeding rate of the hexanodioic acid liquid phase that is comprised of hexanodioic acid and dimethyl adipate is 500mol/h, and the molar content of hexanodioic acid is 20%, and feeding temperature is 110 ℃, is added by the 3rd level column plate.Methyl alcohol is 15 times to mole multiple of hexanodioic acid, is added 120 ℃ of the feeding temperatures of methyl alcohol by 12 grades of column plates belows.N
2Gas is added by tower reactor (or bottom of tower reactor), and 170 ℃ of temperature, molar flow are 600mol/h.There is no catalyzer on the 2nd grade of column plate, be used for reclaiming the heavy component in gas phase, total reflux ratio 0.106.Tower reactor reboiler 4kw.Every grade of column plate is provided with the thermometric galvanic couple, and is provided with thief hole, can supply sampling analysis tower top and tower reactor extraction, and the liquid phase on column plate at different levels forms.
Result is as shown in table 1.
The result of table 1 example 1
Annotate: CH
4O, HA, H
2O and DMH be nail alcohol, hexanodioic acid, water and dimethyl adipate respectively, same meaning in the example of back.
Under the condition of this example, the product purity that tower reactor obtains can reach 99.99%, and the hexanodioic acid transformation efficiency can reach 99.99%, and the content of methyl alcohol, acid and water can be directly used in standby 1, the 6-ethylene glycol of Hydrogenation less than 0.01%.
Embodiment 2
Be the N of 500mol/h with flow
2Carry out air lift, the trim the top of column ratio is that 0.11,4 plate advances hexanodioic acid, and 12 plates advance methyl alcohol, on 4-13 level column plate, catalyzer are housed.Other experiment condition is identical with example 1.Result is as shown in table 2.
The result of table 2 example 2
Conversion zone reduces, air lift N
2Flow reduces, and the transformation efficiency of hexanodioic acid still can reach 99.99%, and the dimethyl adipate purity that obtains in tower reactor still can reach 99.98%.
Embodiment 3
Tower top is with 20 ℃ of pure methanol eddies, 220mol/h.Other experiment condition is identical with example 2.Result is as shown in table 3.
The result of table 3 example 3
Embodiment 4
Methyl alcohol and hexanodioic acid added the 500ml four-hole bottle in 6: 1 in molar ratio, and anhydrous catalyzer add-on is 15% of hexanodioic acid, reacted under the atmospheric boiling condition, and the mensuration system is in the same time acid number not, relatively the performance of catalyzer.
With reference to GB1668-81, the acid number X (mgKOH/g) of system calculates by formula (1):
X＝c*V*56.11/m (1)
The concentration of c-potassium hydroxide (or sodium hydroxide) standardized solution in formula, mol/L;
V-consumes the volume of potassium hydroxide (or sodium hydroxide) standardized solution, ml;
The quality of m-sample, g;
56.11-potassium hydroxide molar mass.
The Performance Ratio of table 4D008 and Amb-16, Amb-36
By table 4 result as seen, the D008 catalyzer is compared Amb-16, Amb-36 catalyzer, and the reaction of hexanodioic acid and methyl alcohol is had more excellent catalytic performance.
Comparative Examples 1
On the 4-14 plate, catalyzer is housed, hexanodioic acid adds at the 4th grade of column plate, and methanol gas adds in tower reactor, without N
2Air lift, without reboiler, tower top is established condenser, reflux ratio 0.16, other condition is identical with embodiment 1.Result is as shown in table 5.
The result of table 5 Comparative Examples 1
Increase the length of conversion zone, the content of unreacted hexanodioic acid can continue to reduce, but the content of first alcohol and water, especially methyl alcohol is high.
Comparative Examples 2
Increase tower bottom reboiler, reboiler 1.8kw, reflux ratio 0.15.Other experiment condition is identical with Comparative Examples 1.Result is as shown in table 6.
The result of table 6 Comparative Examples 2
Comparative Examples 3
Reboiler is 5kw, and tower reactor does not have N
2Air lift is equipped with catalyzer on 4-12 level column plate, and hexanodioic acid adds at the 4th plate, methyl alcohol charging below 12 plates.Other experiment condition is identical with embodiment 2.Result is as shown in table 7.
The result of table 7 Comparative Examples 3
Keep still being difficult to directly obtain the very high dimethyl adipate of purity under the condition of the very high thermal load of tower bottom reboiler in tower reactor.Due to the impact of catalyzer heat resistance, the load of tower bottom reboiler is restricted.
The advantage that embodiment compares with Comparative Examples is, keeps very high thermal load in the situation that need not tower bottom reboiler, and the purity of the dimethyl adipate product that obtains in tower reactor is greatly improved, and can reach more than 99.99%.
Amb-16 in above-described embodiment and Comparative Examples, Amb-36 are respectively the commodity ion-exchange resin catalysts that Rohm and Haas company sells with trade mark Amberlyst-16wet and Amberlyst-36wet, and D008 is the commodity ion exchange resin that Hebei triumphant auspicious chemical industry company limited sells with trade mark D008.
Claims (20)
1. a method that is prepared dimethyl adipate by hexanodioic acid and methyl alcohol reaction, is characterized in that, described method comprises:
In the conversion zone of gas stripping column, the liquid phase that contains hexanodioic acid from the top of tower internal reaction section from top to bottom, the methanol gas from bottom to top that adds with bottom from tower internal reaction section and the rare gas element counter current contact conversion zone that is added by tower reactor, under solid esterification catalyst action in conversion zone, hexanodioic acid and methyl alcohol carry out esterification, namely obtain highly purified dimethyl adipate in the gas stripping column tower reactor; Wherein the temperature of conversion zone is 110 ℃-180 ℃, and the pressure of conversion zone is 1-1.5 normal atmosphere;
Wherein, described rare gas element is the nitrogen of 120～300 ℃; The liquid phase that contains hexanodioic acid is 90-200 ℃;
The structure of described gas stripping column is: have height and 10-30 stage number of 5-24m, distance between plates is 50-80cm; Wherein overhead condenser and tower reactor are respectively the first step and last step column plate.
2. method according to claim 1, is characterized in that, described rare gas element is the nitrogen of 170～250 ℃; The liquid phase that contains hexanodioic acid is 110-180 ℃.
3. method according to claim 1, is characterized in that, described stage number is 12-20.
4. method according to claim 1, is characterized in that, the reflux ratio that in described method, gas stripping column uses is between 0.1-1.
5. method according to claim 4, is characterized in that, the reflux ratio that in described method, gas stripping column uses is between 0.1-0.5.
6. method according to claim 4, is characterized in that, the solid esterifying catalyst is solid acid.
7. method according to claim 6, is characterized in that, described solid acid is the sulfonic acid type strong-acid ion exchange resin.
8. method according to claim 7, is characterized in that, the specific surface area of described sulfonic acid type strong-acid ion exchange resin is 20-50m
2/ g; Mean pore size is 15-30nm; Pore volume is greater than 0.1ml/g; Particle diameter 0.4-1.2mm; Exchange capacity is greater than 3.0mmol/g.
9. method according to claim 8, is characterized in that, the specific surface area of described sulfonic acid type strong-acid ion exchange resin is 30-40m
2/ g; Mean pore size is 20-25nm; Pore volume is greater than 0.2ml/g.
10. method according to claim 7, is characterized in that, described sulfonic acid type strong-acid ion exchange resin is D008 resin, Amb-16 or Amb-36 resin.
11. method according to claim 6 is characterized in that, the described liquid phase that contains hexanodioic acid is comprised of hexanodioic acid and liquid diluent, and the molar content that contains hexanodioic acid in the liquid phase of hexanodioic acid is 5%-30%.
12. method according to claim 11 is characterized in that, the molar content that contains hexanodioic acid in the liquid phase of hexanodioic acid is 10% to 20%.
13. according to claim 11 or 12 described methods is characterized in that described liquid diluent is comprised of methyl alcohol and dimethyl adipate.
14. method according to claim 13 is characterized in that, the feeding temperature of described methyl alcohol is 65-180 ℃, and pressure is 1-3atm.
15. method according to claim 14 is characterized in that, the feed pressure of described methyl alcohol is 1-1.5atm.
16. method according to claim 14 is characterized in that, the molar flow of described rare gas element is 3-30kmol/hm
2The feeding rate that contains the liquid phase of hexanodioic acid is 3-30kmol/hm
2
The feeding rate of methyl alcohol be make methyl alcohol to mole multiple of hexanodioic acid be 3-30 doubly.
17. method according to claim 16 is characterized in that, the molar flow of described rare gas element is 12-24kmol/h; The feeding rate that contains the liquid phase of hexanodioic acid is 9-24kmol/hm
2
The feeding rate of methyl alcohol be make methyl alcohol to mole multiple of hexanodioic acid be 6-25 doubly.
18. method according to claim 17 is characterized in that, the molar flow of described rare gas element is 15-21mol/h; The feeding rate that contains the liquid phase of hexanodioic acid is 12-18kmol/hm
2
The feeding rate of methyl alcohol be make methyl alcohol to mole multiple of hexanodioic acid be 10-20 doubly.
19. method according to claim 18 is characterized in that, the molar flow of described rare gas element is 18-19kmol/hm
2The feeding rate that contains the liquid phase of hexanodioic acid is 15-16kmol/hm
2
The feeding rate of methyl alcohol be make methyl alcohol to mole multiple of hexanodioic acid be 14-16 doubly.
20. method according to claim 1 is characterized in that, the described feed entrance point that contains the liquid phase of hexanodioic acid is between the 3rd column plate and the 5th column plate; The feed entrance point of methyl alcohol is between the 3rd column plate reciprocal and the 5th column plate reciprocal.
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| DD125970A1 (en) * | 1976-09-10 | 1977-06-08 | ||
| CN101134725A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method and equipment for continuous esterification production of adipic acid dimethyl ester |
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2010
- 2010-01-15 CN CN 201010000495 patent/CN101768077B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD125970A1 (en) * | 1976-09-10 | 1977-06-08 | ||
| CN101134725A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method and equipment for continuous esterification production of adipic acid dimethyl ester |
Non-Patent Citations (2)
| Title |
|---|
| "酯化法制备1,6-己二酸二甲酯";石鸣彦等;《石化技术与应用》;200805;第26卷(第3期);257-259 * |
| 石鸣彦等."酯化法制备1 6-己二酸二甲酯".《石化技术与应用》.2008 |
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