CN101618304B - Esterification reactor - Google Patents
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- CN101618304B CN101618304B CN2008100122018A CN200810012201A CN101618304B CN 101618304 B CN101618304 B CN 101618304B CN 2008100122018 A CN2008100122018 A CN 2008100122018A CN 200810012201 A CN200810012201 A CN 200810012201A CN 101618304 B CN101618304 B CN 101618304B
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Abstract
The invention provides an esterification reactor, which is suitably used for the esterification reaction of carboxylic acid and alcohols. The reactor consists of a plurality of tower plates; each tower plate is provided with a liquid dropping pipe and an air raising pipe; the air raising pipes are connected with a rotary air distributor consisting of an air guiding pipe, fan blades and nozzles; each tower plate remains liquid at a certain liquid level, and a solid catalyst is remained in the liquid; and the liquid phase is a carboxylic acid containing components, and flows downward from one esterification tower plate to the other esterification tower plate in the reactor and makes the counter-current reaction with the raised alcohol vapor. The esterification reactor has the advantages of complete contact of gas, liquid and solid phases, high reaction efficiency, high utilization rate of reactor volume and the like, and is suitably used for various esterification reaction processes.
Description
Technical field
The present invention relates to a kind of reactor, be applicable to that particularly carboxylic acids and alcohols material carry out the reactor of esterification.
Background technology
Esterification is the process that is generated ester by monoacid, binary acid or polyacid (also can be acid anhydrides under the specified conditions) and alcohol or aldehydes matter reaction, and esterification is generally reversible balanced reaction.These alcohol, aldehydes matter can be monohydric alcohol, dihydroxylic alcohols or polyalcohol.With the monoesters is that the example course of reaction is as follows:
R
1Can be the organic group of a hydrogen atom or unit price, R
2It is the organic group of unit price.When reactant was acid anhydrides, reaction was divided into for two steps:
R
3Be divalent organic group, R
4It is the unit price organic group.
The most frequently used catalyst is a sulfuric acid and as the sulfur-bearing organic acid of benzene sulfonic acid etc.But these catalyst are homogeneous catalyst, though catalytic effect is very good, must just can obtain ester phase product through after the neutralization reaction, and neutralization procedure is used highly basic reagent (as sodium hydroxide solution) always, and this process has following shortcoming:
1, esterification is the reaction that balances each other, and unreacted carboxylic acid can be participated in neutralization reaction, and separates very difficulty of unreacted carboxylic acid from the carboxylic acid salt solution, so neutralization procedure can cause tangible significant loss in this technology;
2, have the ester of part to be dissolved in the alkali lye in the neutralization reaction process, have the part ester to be dissolved in the alkali lye with sodium-salt form, the loss amount of ester depends on the solubility of ester in alkali lye;
3, the organic carboxylate that produces in the water-washing process can aggravate problem of environmental pollution;
4, when containing LCFA in the product, can form highly basic soap with the strong base solution reaction, hard soap is a surfactant, meets water and forms stable emulsion, is difficult to carry out water-oil separating.Adopting homogeneous catalyst to carry out continuous esterification has a lot of shortcomings, adopts intermittent reaction usually, and product quality is not high.
5, adopting another shortcoming of homogeneous catalyst is that ester is mixed with sulfur component in mutually, and sulfur component will have a strong impact on the subsequent process operation.
For addressing this problem, development in laboratory is a kind of to be the technology of Catalyst Production dimethyl maleate with the acid-exchange resin.At patent EP-A-0255399 this technology is set forth.Describe according to patent, liquid phase is a monomethyl maleate, with pure steam continuous flow upstream prepared in reaction dimethyl maleate in the zone of esterification catalyst is housed, solid catalyst is deposited in the guard on the column plate in the trickle bed mode in the tower, and liquid phase flows downward and the more and more higher pure steam of concentration is being equipped with the esterification zone counter current contacting reaction of catalyst.Another kind of reactor types is one group of continuous stirred tank that links to each other.Liquid phase flows to next reactor by a reactor, and pure steam flows to previous reactor by next reactor simultaneously.This mode of operation complicated operation, and reaction efficiency is lower.
Description complexity among patent EP-A-0255399 and the patent WO-A-88/00937.The column plate of a plurality of band guards is arranged in the reaction tower, and ion-exchange resin catalyst is contained in the guard.This compound reactor system need carry out continued operation to mixer, is difficult to implement.WO-A-90/08127 discloses a kind of esterifier and technology, uses the plate column plate-type reactor, but need in every layer of column plate reaction compartment of reactor vertical plate washer be set, to increase the contact effect of reaction mass.This mode effect is limited, can not make bed temperature and hydrodynamics even, is difficult to effectively improve the service efficiency of reactor.
Summary of the invention
The present invention is the acidic catalyst with solid particle, and the consersion unit of prepared in reaction ester, the acidic catalyst of solid particle load easily and are easy to and suspend, and are suitable for carrying out continuous stirring.The esterification reaction process that it is catalyst that the present invention is applicable to various microgranular ion exchange resin.
The multilayer column plate is installed in the esterifier of the present invention, solid esterification catalyst bulk storage is on column plate, connect downspout and riser on the column plate, liquid level on downspout upper opening and the column plate is suitable, the downspout lower openings stretches into below the adjacent lower floor column plate liquid level, riser is provided with gas distributor at the opening on column plate top, gas distributor is rotary gas distributor, gas distributor is by air entraining pipe, fan sheet and nozzle constitute, air entraining pipe is "T"-shaped structure, the air entraining pipe top manifold can be two or many, the top manifold end is provided with nozzle, top manifold fixed fan sheet, air entraining pipe bottom tube connector is connected with the sleeve movable connection structure with riser, and gas distributor can horizontally rotate around riser.
When esterifier of the present invention used, column plate quantity can require specifically to determine according to the character and the reaction back product quality of reaction mass, is generally 3～50.All keep certain liquid and certain solid esterification catalyst on each column plate.Raw material is acid constituents such as monoacid, binary acid, polyacid, acid anhydrides and composition thereof and alkoxide component such as monohydric alcohol, dihydroxylic alcohols, polyalcohol, phenol and composition thereof.Reactor is made up of many esterification column plates of installing up and down, keeps certain amount of fluid and solid catalyst on each column plate, and downspout is connected with the esterification column plate, and the liquid phase of requirement in reactor keeps the solid catalyst on the column plate when flowing through the esterification column plate downwards; Riser is connected with the esterification column plate, and steam is by the reaction zone that enters under the column plate on the column plate, and stirs liquid phase and solid catalyst wherein on the column plate.Heavy ends such as carboxyl acid component or alkoxide component are from the column plate charging of top, and light component such as carboxylic acid or alkoxide component are by the bottom feed of the column plate of lowermost end simultaneously.The water that light component entrainment with steam esterification generates is gone out by reactor top, and obtains heavy ends such as carboxylate by the reactor bottom.
The present invention is a steam with the light component in the reactant, and light component can be carboxylic acid or alcohol.By steam the water that esterification generates is taken out of, do not influenced the quality of its heavy ends such as carboxylate simultaneously.Therefore require in essence to locate under the pressure at first block of column plate (top tray), the boiling point of esterifier outlet mixed vapour, the boiling point that perhaps exports in the mixed vapour light component will be starkly lower than the boiling point of any one component under this condition in heavy ends such as carboxylic acid, alcohol or the carboxylate product.In general, boiling point differs at least 15 ℃ under same pressure, is preferably more than 25 ℃.
Single-esterification refers to that the unary fatty acid here refers to comprise the aliphatic acid of 6～26 carbon, or two or more mixture wherein with unary fatty acid and alkanol or acid anhydrides and reaction of alkanol generation unary fatty acid ester among the present invention.Particularly the alkanol of 1～10 carbon number makes Arrcostab.
The monoacid here comprises similar aliphatic acid and two kinds or two or more mixtures such as aliphatic acid such as capric acid, dodecylic acid, tetradecanoic acid, linoleic acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachic acid, isostearic acid.Aliphatic acid can be made by natural triglyceride hydrolysis, as cottonseed oil, rapeseed oil, palm oil and animal oil such as lard, butter, fish oil etc.Can select Components of Mixed Acid in the mode of rectifying if necessary, as obtain the acid of boiling point that boiling point is not less than the acid of C8～C10 by separation; Perhaps separate and obtain the acid that boiling point is not higher than C22 acid boiling point; Or isolate the higher acid of boiling point and the lower acid of boiling point obtains mixed acid such as the acid of boiling point between the boiling point of the acid of C8～C22.Fatty acid mixt also can contain unsaturated olefin(e) acid such as oleic acid.These fatty acid mixts can be made fatty acid methyl ester admixture with the methyl alcohol reaction, and fatty acid methyl ester repeated hydrogenation system alkanol is as C
8To C
20Alkanol (also being the washing agent alcohols usually), can separate the preparing washing agent to alkanol.
The present invention also is applicable to another kind of method of producing the carboxyl acid esters, both production binary fatty acid ester, the ester (C of binary cycloaliphatic ring family
4To C
8) and saturated or unsaturated dicarboxylic acid ester.Product is made by alkanol and dicarboxylic acids or its acid anhydrides or dicarboxylic acids and acid anhydride mixture reaction thereof.Dicarboxylic esters of producing such as oxalate diester, maleic acid diester, succinic diester, fumaric acid diester, penta diester, heptan, diester, azelaoyl also comprised oxolane, comprised that all are from C
1To C
10The alkyl acid ester.Any contain dicarboxylic acids or its acid anhydrides (if existence) or dicarboxylic acids and composition thereof can be as the raw material of producing this dicarboxylic esters.C
7To C
20The preparation of monobasic alkyl aromatic ester and composition thereof also be applicable to the present invention, as benzoic acid and the acid of 1-naphthols etc.The present invention is equally applicable to C
8To C
20The aromatic carboxylic acid esters of aromatic acid, acid anhydride and composition thereof preparation binary.The present invention is equally applicable to polyacid and prepares polynary ester.Polyacid has: citric acid, pyromellitic acid dianhydride etc.The present invention is equally applicable to prepare binary alcohol esters and polyol ester, dihydroxylic alcohols such as ethylene glycol, propane diols etc., polyalcohol such as glycerine, sorbierite, sweet mellow wine, xylitol etc.
In the two kinds of light component carboxylic acids of mentioning among the present invention and alcohol, light component is an alcohols usually.For example methyl alcohol is light component when the fatty acid mixt reaction system fatty acid methyl ester that methyl alcohol and triglyceride hydrolysis make.But then, prepare dibutyl ester by butyric acid and glycol reaction, then butyric acid is a light component.Same is light component with the acetate in acetate and propane diols prepared in reaction third diethylester.
Esterification condition temperature in the reactor is a normal temperature to 200 ℃, as temperature range at 80 ℃ to 180 ℃, preferred 100 ℃ to 135 ℃.Requiring the Thermodynamically stable of esterification catalyst, dividing the relevant temperature and the kinetics of pressure, selecting this operating temperature under the condition with the steam group of esterifier bottom steam inlet.Reactor bottom inlet steam pressure limit be 0.1MPa to 3MPa, be preferably 0.2MPa between the 2.5MPar.Reactor air speed scope is 0.1h
-1To 10h
-1, 0.2h especially
-1To 5h
-1
The liquid phase that alcohol, acid or its mixture are formed and the ester product of circulation and solvent or diluent are by the top charging of reactor.Can also not having pre-esterification reactor under the catalytic condition earlier to entering pure and mild acid before the reactor under given conditions, also can be the pre-esterification reactor that has under the catalytic condition.For example acid anhydrides such as maleic anhydride and phthalic anhydride and fatty alcohol such as methyl alcohol, ethanol, tert-butyl alcohol reaction, obtain under the condition that relaxes relatively monoesters as: do not have under the condition of catalysis reaction equation at 60 ℃, 0.5MPa as follows:
Be alkyl such as methyl, ethyl, butyl.This monoesters also is a monoacid.Further reaction is as follows:
The result is that product is the mixture that contains monoesters, dibasic acid esters, water and alkanol.Add excessive alkanol if desired again, make monoesters in reactor, further react the generating portion diester.
On the other hand, when final products are monobasic acid ester, contain in sulfonic group and/or carboxylic acid group's the reactor of ion exchange resin the preferential monobasic acid ester that generates of carboxylic acid and alcohol reaction in adding.
Cat head discharging in the present invention is a mixed vapour.The mixed vapour that light component in reactor (normally alkoxide component) is formed carries out stripping so that it gets back to reactor to carboxylate product and other composition (normally carboxylic acid composition).Overhead vapours separates its component with condensing mode, and water that esterification generates and light component (normally alcohol) recycle after the light component drying.Water vapour on the esterification column plate of the bottom is few more, and the esterification conversion ratio is more near 100%, and the carboxylic acid content at the bottom of the tower in the product of reactor bottom is low more.Yet the influence of the pure steam that the esterification balance is often supplied (being light component steam), as the alkylol steam of sufficient drying will be provided in reactor, when the pure steam of drying reduces, just need to change the operation of liquid phase feeding, make it reach product requirement with the quality that improves the ester product.This will cause the reaction between the alcohol, the reaction depend between the alcohol and water influence each other and pure moisture from effect.The water in the pure steam will be less than 5mol% in the reactor when using methanol steam, most preferably less than 1mol%.
Contain many column plates in the reactor.Although have only the reaction of two or three block of column plate sometimes, have 5 to 20 or more esterification column plate usually in the reactor.The time of staying of designing on every block of esterification column plate is 1 minute to 120 minutes, particularly 5 to 60 minutes.Can design according to the control index.
Solid catalyst is for containing-SO
3The granular ion exchange resin of H/-COOH.Proper resin has " DZH large porous strong acid resin ", " NKC-9 ", " D001 ", " ZG C 132 ", " CT450 " etc., can specifically select according to the type of esterification, specifically can select various suitable commercial products.
On the different column plate different catalyst is housed in the reactor, even the filling concentration on Tong the column plate is also different.The particulate on every block of column plate or the loadings corresponding requirements catalyst weight of beaded catalyst: the liquid weight ratio is at least 0.2%; for example the resin concentration scope is calculated as 2% to 20% with dried resin; preferred 5% to 10%, the catalyst that filling is enough under the selected time of staying and relevant operating condition is to reach molecular balance or near molecular balance.To such an extent as to catalyst that on the other hand can not sc makes the ascending air of column plate bottom and gas distributor be difficult to it is stirred into suspension.
The catalyst granules diameter should be enough big so that its easily retained by cover on the column plate or similar devices.Yet the particle of catalyst is big more just be hard to keep more suspension state and catalyst surface area is reduced, so catalyst granules again can not be too big, proper catalyst granules diameter range is 0.1mm to 5mm, is preferably 0.4mm to 0.8mm.
On the esterification column plate, provide one or more washing column plate to hold back product and solvent and/or the reagent in the reactor.
A distributor is installed at the bottom of the liquid of esterification column plate and the solid catalyst blending surface in reactor, and ascending air here blows out, and forms bubble and promotes the distributor agitated liquid and solid catalyst suspension.Distributor is rotatable gas distributor.The nozzle location of rotary gas distributor preferably is lower than fan sheet position, makes air-flow upwards drive the fan sheet and rotates, and has mixing effect, and then improved the stirring intensity of gas, liquid, solid three-phases, improve the uniformity of reaction system, improve reaction efficiency, improve the reactor volume utilization rate.
Note avoiding the part to have solid esterification catalyst precipitation to get off, because may cause side reaction to take place like this, perhaps focus appears in the part as far as possible.Can guarantee by ascending air and gas distributor can to make catalyst granules remain on suspended state by the distributor of column plate reasonable in design to the stirring action of liquid.In order to reach this purpose, partial esterification column plate or more (preferably whole column plates) will be set as the inclined-plane to the turbulent region by the distributor manufacturing at least.The inclination angle is preferentially selected more than or equal to the dwell angle in the liquid phase of solid catalyst on column plate.The purpose that adopts this angle is that catalyst all when operating and liquid all move and do not have the blind area, because the blind area can cause some side reactions.
At the preferred device that prevents the liquid suck-back of installing of the esterification column plate that has ascending air to pass through (one or more are preferably whole), prevent that the device of liquid suck-back generally is installed in the riser, generally adopt the backward stop valve arrangement.Protective cover is installed on the dependency structure, and protective cover generally is installed in the upper opening of downspout, and the mesh diameter of protective cover is generally less than the particle diameter that uses catalyst, effectively to prevent esterification catalyst spilling to lower channel from the esterification column plate.Prevented fully that by such method solid catalyst runs off to next piece column plate from a column plate.
Esterifier of the present invention uses solia particle or beaded catalyst, has avoided the great number of issues that uses homogeneous catalyst to bring.Reactor of the present invention uses rotary gas distributor simultaneously, has improved reaction efficiency, has improved reactor and has held the title utilization rate, has improved the disposal ability of entire reaction system.
Description of drawings
Fig. 1 is a kind of tower plate structure schematic diagram that comprises downspout and riser of esterifier of the present invention.
Fig. 2 is the tower plate structure schematic diagram that esterifier another kind of the present invention comprises downspout and riser.
Fig. 3 be esterifier of the present invention the third comprise the tower plate structure schematic diagram of downspout and riser.
Fig. 4 is the rotary gas distributor concrete structure of an esterifier of the present invention schematic diagram.
The specific embodiment
The invention provides and a kind ofly be applicable to that with carboxylic acid and alcohol be the reactor of the technology of feedstock production carboxylate, wherein carboxylic acid can be monoacid, binary acid, polyacid, acid anhydrides and composition thereof; Alcohol can be monohydric alcohol, dihydroxylic alcohols, polyalcohol, phenol and composition thereof.Under enzymatic synthesis condition, carboxylic acid reacts with pure counter current contacting in reactor.Reactor is made up of polylith esterification column plate, and a downspout and a riser all are installed on every block of column plate, and riser connects rotatable gas distributor, and gas distributor is made of air entraining pipe, fan sheet and nozzle.The rotation of rising by bubble and fan sheet improves the mixed effect of suspension.Have certain amount of fluid on the column plate and solid catalyst is housed, the ion exchange resin that particularly has a kind of among sulfonic group and the carboxylic acid group or all have.Downspout and riser are installed on column plate, and downspout can make liquid flow to next fast column plate, keeps the solid acid catalyst on the column plate simultaneously ' riser makes steam enter column plate by under the column plate, and the suspension of while agitated liquid and solid acid catalyst.Heavy ends can be acid or pure, enter reactor with liquid form from uppermost column plate; Light component can be an alcohol or sour, enters reactor from the bottom of nethermost column plate.Contain the water that light component and esterification generate in the steam.
As shown in Figure 1, in the middle of reactor wall 2, be provided with a level every or baffle plate 4, form reactor trays, a downward downspout 5 and a riser that makes progress 6 are arranged on the column plate, form first stage reactor 3.
An axial conical section 7 is arranged on the column plate 4, the riser 6 that rises for gas in the middle of the cone, what ring section 8 tilted is connected on the contiguous reactor wall 2.Can stop liquid on the column plate, liquid level 9 depends on the height of downspout 5 on column plate 4.All be equipped with on every block of column plate and contain sulfonic ion exchange resin such as DZH large porous strong acid resin particle 10.Ion-exchange particulate on the column plate is stirred into suspension in liquid.In order to prevent that the logical liquid of ion-exchange particulate from letting out together, installed guard 11 in the downspout upper end from downspout 5.The angle of cone 7 and ring section 8 requires more than or equal to DZH large porous strong acid resin or other solid esterification catalyst granules the dwell angle in the liquid on esterification column plate 4.
Be connected to cross pipe 13 around the cone riser, the air-flow that rises in the riser 6 enters cross pipe 13, and cross folds into the reaction mass bottom downwards, and rotary gas distributor 12 is installed in the end.Riser 6 is equipped with check valve 14 to prevent the liquid suck-back.Rising steam is separated into bubble 17 after entering reaction mass.
15 is the downspout that last block column plate comes among Fig. 1.The liquid level 16 of downspout 15.Height H adds what fricative pressure determined by the liquid level of lastblock column plate and the pressure of distributor generation thereof on the column plate liquid level.
Monobasic, binary or polybasic carboxylic acid or its mixture contact with the pure steam counter-flow of rising with liquid form when reactor operation.Every block of column plate all is the esterification district that esterification catalyst is housed separately, all carries out esterification and remove the water that esterification generates simultaneously under the effect of catalyst.Pure steam vaporization that the water that esterification generates in reactor is risen and the top that is entrained to reactor.In liquid phase stream during through reactor, when liquid phase is fallen next piece column plate from a column plate the liquid phase concentration liquid of acid more and more lower, on column plate, contact again with the pure steam of drying more and more.Molecular balance is moved to the direction of producing ester, and moisture reduction gradually in the process that descends on column plate along with liquid phase has simultaneously effectively suppressed the back reaction of ester phase hydrolysis.
By design, require to make carboxylic acid content in the bottom product less than 1mol% to the liquid residence time of the number of plates in the reactor and every fast column plate.By enough pure steam is provided, promote gas distributor 12 and produce laterally stirring, 17 pairs of suspension of the bubble of Shang Shenging radially stir simultaneously, have guaranteed the suspended state of acid-exchange resin particulate in suspension in the liquid phase circulation effectively.The inclination angle of inclined plane of cone 7 and ring section 8 tilts to the below of distributor, so that the suspension below does not have tangible resin to stagnate.If desired, can add inert gas in ascending air, what add usually is byproduct of reaction ether.For example acidic catalyst can promote the alcohol reaction to generate ether.Can generate when using methyl alcohol when dimethyl ether uses ethanol as raw material and can generate diethyl ether as raw material.These two kinds may be used to guarantee the liquid suspension on the column plate or are used to take away the water that esterification generates.
What Fig. 2 illustrated is a kind of every section DESIGN OF REACTOR scheme that is applicable to the less reactor of ratio 1.In this programme, in reactor wall 2, will there be a conical dividing plate that reactor is separated fully, leave a downspout and a riser at dividing plate.Cone or be greater than every 20 inclination angle and equal solid catalyst particle static tilt angles in the liquid on column plate.Install one on the riser and axially divide gas cloth device 27 and a backward stop valve 24.A cover is installed to hold back solid catalyst such as the DZH large porous strong acid resin on the column plate on the downspout.Use the same method among Fig. 2 and express the bubble 29 that stirs suspension on the column plate and the catalyst granules 28 in the suspension.The pure steam that rises is via the nozzle ejection of gas distributor 27, and the body distributor of taking offence of trying hard to recommend of generation rotates, and the radial load that makes progress that bubble produces suspends to guarantee solid particle, and distributor stirs the horizontal motive force of generation to add strong mixing.Guarantee that in this way the resin in the suspension all remains on suspended state.
What Fig. 3 described is a kind of reactor design that is applicable to laboratory or commercial use.Connect a conical baffle plate 50 in the reactor wall 2.The inclination angle of baffle plate 50 is more than or equal to the static stocking angle of this solid catalyst.Rotary gas distributor 55 is installed on the riser 51.Downspout 52 is equipped with screen cloth cap 53 and fluid-tight bucket 54.The upper end of downspout 52 is installed like this so that on column plate, keep the liquid of proper height.Methanol steam is being carried secretly by the steam process of the esterification generation of beneath column plate and passing through riser 51 shown in 60, the nozzle ejection from gas distributor 55 as shown in arrow 61 again.The bubble that the pure steam of ejection produces radially stirs suspension particle, and produced simultaneously horizontal motive force promotes the distributor rotation, and the fan sheet on the distributor makes suspension horizontal stirring as shown in arrow 62, has effectively strengthened the back-mixing effect of suspension.
What Fig. 4 described is the design of optional commentaries on classics gas distributor, and gas distributor 73 is made of air entraining pipe bottom tube connector 77, air entraining pipe top manifold 74, nozzle 75 and fan sheet 78, is socketed in the riser 70.Tube connector 77 bottoms, air entraining pipe bottom are ring baffle 79, and envelope has bead 80 on the baffle plate 79.The top of bead is to be connected annular on the riser 70 every 81.Such design guarantees that steam is fixed on rotation smoothly on the riser 70 by gas distributor.Tube connector top, air entraining pipe bottom is equipped with check (non-return) valve 82.Fan sheet 78 is connected on the air entraining pipe top manifold 74, and air entraining pipe top manifold 74 can be arc pipe, and air entraining pipe top manifold end connects nozzle 76.Nozzle 76 has check (non-return) valve 75 upwards and enters gas distributor 73 to prevent liquid phase and catalyst granules.Nozzle 76 tiltedly tilts the below to reactor center, and angle of inclination (and vertical line angle) is between 27 ° to 53 °.Gas phase enters air entraining pipe bottom tube connector 77 shown in arrow 85, promote gas distributor 73 and suspend, and and for example sprays as arrow 87 from nozzle 76 shown in the arrow 86.Promote the gas distributor rotation simultaneously, fan sheet 78 stirs liquid phase and moves shown in arrow 88.Gas distributor can be provided with one or more according to the scale of reactor among Fig. 4 on each column plate, by the direction of simple change air entraining pipe tube connector 77 and associated one-way valve, can be used for the structure that as shown in Figure 1 steam flows through gas distributor from the top down.
Theoretical cam curve in the reactor is not must be consistent with number of actual plates, and the theoretical cam curve of reactor may change along with the variation of acid in the charging, if the acid in the charging changes, the acid content at the bottom of the tower in the methyl esters product also may change.
Mentioned the common ether of esterification byproduct above like binary.The yield of accessory substance ether depends on the operating temperature of reactor.Therefore the operating temperature that reduces reactor can reduce any production of by-products.Yet the conversion ratio of the low more acid generation of temperature ester is low more in theory.Under this condition, need the method that the excessive alcohol of ester phase product adding reacts is again improved the conversion ratio of ester phase.Usually contain the ester and the number acid raw material of 97mol% to 99mol% in the ester phase product, the mixing mol ratio that adds the excessive pure and mild ester of alcohol (as methyl alcohol) is between 2: 1 to 4: 1 as 3: 1.
Acid is the downward vapor stream of liquid phase stream alcohol for rising in the column plate explanation of Fig. 1, Fig. 2.Boiling point as tartaric acid is lower than alcohol, and so pure and mild acid constituents can be exchanged, and is that alcohol is liquid phase, then makes progress and pure counter current contacting to dirty acid vapor from the column plate of reactor.
Further specify method of the present invention and effect below by embodiment.The percentage composition that relates to is a molar content.
Embodiment:
Laboratory reactor, internal diameter are 60mm, and material is a glass, and 10 blocks of column plates are installed up and down in the reactor.Reactor is incubated and is heated by the external electric torrid zone.Every block of column plate all has independently temperature-controlling system.First block of column plate is as washing not loaded resin of column plate.Second block of column plate is as the charging aperture of acid starting material.All the other 8 blocks of column plates all are equipped with a certain amount of strong acid ion exchange resin.Setting rotary gas distributor as shown in Figure 4 is 1 on the column plate of loaded resin catalyst.Methyl alcohol is heated to 150 ℃, and methanol steam enters reactor by the column plate of reactor lowermost end.On every fast column plate 200ml liquid is arranged.The resin loadings is calculated as 18% of liquid weight on the column plate with dried resin on the column plate.Water and a spot of accessory substance dimethyl ether that the reaction overhead gas contains unreacted methanol, esterification generation are cooled.Usually tower head is installed the liquid flooding device with the ester product loss rate in the control reactor.
Reactor is opened and is used the dodecanoate loaded resin when making.After the methanol steam on every block of column plate and temperature are all stablized, begin the phase reactor charging, contain the myristic acid of 50mol% laurate, 40mol% laurate and 10mol% in the material.Product ester to reactor bottom is monitored, until reaching molecular balance.Liquid phase analysis on the different column plates the results are shown in following table 1; Column plate is numbered 1 to 10 from top to bottom, and the column plate of cat head is No. 1, and the column plate at the bottom of the tower is No. 10.
Table 1 embodiment reaction effect
Comparative example
With equipment identical and process conditions with embodiment, just rotary gas distributor is fixed, do not produce turning effort, reaction effect sees Table 2.
Table 2 comparative example reaction effect
Claims (7)
1. esterifier, the multilayer column plate is installed in the reactor, solid esterification catalyst bulk storage is on column plate, connect downspout and riser on the column plate, liquid level on downspout upper opening and the column plate is suitable, the downspout lower openings stretches into below the adjacent lower floor column plate liquid level, riser is provided with gas distributor at the opening on column plate top, it is characterized in that: gas distributor is rotary gas distributor, gas distributor is by air entraining pipe, fan sheet and nozzle constitute, air entraining pipe is "T"-shaped structure, the air entraining pipe top manifold is two or many, and the top manifold end is provided with nozzle, top manifold fixed fan sheet, air entraining pipe bottom tube connector is connected with the sleeve movable connection structure with riser, and gas distributor can horizontally rotate around riser;
Wherein: the partial esterification column plate will be set as the inclined-plane to the turbulent region by the distributor manufacturing at least;
Wherein: the backward stop valve arrangement that prevents the liquid suck-back is installed in riser;
Wherein: the nozzle tape of gas distributor has check (non-return) valve upwards, enters gas distributor to prevent liquid phase and catalyst granules.
2. according to the described reactor of claim 1, it is characterized in that: esterifier column plate quantity is 3～50.
3. according to the described reactor of claim 1, it is characterized in that: solid esterification catalyst granules diameter range is 0.1mm to 5mm.
4. according to the described reactor of claim 1, it is characterized in that: the nozzle location of rotary gas distributor is lower than fan sheet position, makes air-flow upwards drive the fan sheet and rotates.
5. according to the described reactor of claim 1, it is characterized in that: the inclination angle of esterification column plate that is set as the inclined-plane to the turbulent region by the distributor manufacturing is more than or equal to the dwell angle in the liquid phase of solid catalyst on column plate.
6. according to the described reactor of claim 1, it is characterized in that: the upper opening at downspout is installed protective cover.
7. according to the described reactor of claim 1, it is characterized in that: the nozzle of gas distributor tiltedly tilts the below to reactor center, and the angle of inclination is between 27 ° to 53 °.
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| CN102671573A (en) * | 2011-03-13 | 2012-09-19 | 江苏新宏大集团有限公司 | Gas distributor |
| CN102908956B (en) * | 2011-08-01 | 2015-06-17 | 中国石油化工股份有限公司 | Esterification reactor and production method of dimethyl maleate |
| CN102908955B (en) * | 2011-08-01 | 2015-11-18 | 中国石油化工股份有限公司 | The preparation method of macroporous plate esterifier and dimethyl maleate |
| CN105817185B (en) * | 2016-03-29 | 2018-07-03 | 北京石油化工学院 | A kind of rotary gas feed distributor suitable for heterophase reactor |
| CN109678657A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The method that high carbon dicarboxylic acid continuously hydrogen adding prepares high-carbon dihydric alcohol |
| CN108283820B (en) * | 2018-01-04 | 2020-10-16 | 中石化上海工程有限公司 | Reactive distillation column plate with claw type gas distributor |
| CN112844249B (en) * | 2020-12-24 | 2022-10-25 | 河南金丹乳酸科技股份有限公司 | Process for preparing ethyl lactate by catalytic esterification |
| CN116251540A (en) * | 2023-02-15 | 2023-06-13 | 常州瑞华化工工程技术股份有限公司 | Bubbling bed reactor and method for continuous dehydration and esterification |
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