CN102911053B - Method for synthesizing dialkyl maleate via catalyst split-packed mode - Google Patents
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Abstract
The invention discloses a method for synthesizing dialkyl maleate via a catalyst split-packed mode. The method comprises the steps of synthesizing the dialkyl maleate on a catalytic distillation reaction device; passing in liquid phase raw materials containing monoalkyl nakeate from the upper portion of the catalytic distillation reaction device; passing in gas phase raw materials of alkyl alcohols from the lower portion of the catalytic distillation reaction device; reacting in the presence of a resin catalyst and under the condition of catalytic distillation to form the dialkyl maleate. The method is characterized in that at least 12 pieces of tower plates are arranged in the catalytic distillation reaction device; at least 10 pieces of the tower plates are loaded with the resin catalyst; the 1-8 pieces of the tower plates downward from the position of the liquid phase raw materials at the upper portion of the catalytic distillation reaction device are loaded with the resin catalyst A; and the other pieces of the tower plates loaded with the resin catalyst are loaded with the resin catalyst B. The method allows the conversion rate of the monoalkyl nakeate at the bottom of the tower to be higher than or equal to 99.5%, and can prolong the service life of the catalyst to longer than 500 hours.
Description
Technical field
The present invention relates to a kind of chemical catalysis process, be specifically related to a kind of filling method synthesizing the catalyzer of dialkyl maleate, this filling method is particularly useful for catalytic distillation reaction process.
Background technology
Dimethyl maleate (Dimethyl Maleate) is being commonly called as of dimethyl maleate (DMM), colourless viscous liquid, boiling point (101.3KPa) 200.4 DEG C, fusing point :-19.0 DEG C, relative density (25 DEG C/4 DEG C) 1.1462g/cm
3.
The multipolymer of dimethyl maleate and other material can be made into the multiple coating, binding agent, optical material, shrink-resistant agent etc. with property and purposes.Therefore, both at home and abroad the demand of dimethyl maleate is also increased increasingly.
One of derived product that dimethyl maleate is important is BDO (BDO), tetrahydrofuran (THF) (THF) and the gamma-butyrolactone (GBL) that Hydrogenation obtains.BDO is a kind of important basic organic chemical industry raw material, mainly for the production of tetrahydrofuran (THF), and polybutyl terapthalate (PBT), gamma-butyrolactone and urethane (PU) etc.In recent years, due to increasing rapidly of thermoplastic elastic fiber and elastomerics demand, as the PTMEG (polytetramethylene ether diol) of monomer, the in great demand of PTMG (PTMG), make upstream raw material 1,4-butyleneglycol demand also increases fast, each large BDO manufacturer such as BASF, SISAS etc. expand energy one after another in the world.At present, world's yearly capacity has broken through 1,000,000 tons, but China's still a large amount of dependence on import.
Tetrahydrofuran (THF) is a kind of excellent solvent and important Organic Chemicals, and its maximum purposes generates PTMG with BDO polycondensation, and self polycondensation generates PTMEG.In addition, tetrahydrofuran (THF) also has very important application in medicine is produced.It is predicted, the domestic demand to tetrahydrofuran (THF) of China is by with the speed increment in year 30%.
Gamma-butyrolactone is a kind of important Organic Chemicals and fine-chemical intermediate, also be that a kind of functional, solvability is strong, good electrical property, stability are high, nontoxic, the high boiling solvent of use safety, have a wide range of applications in fields such as petrochemical complex, medicine, agricultural chemicals, its maximum purposes produces N-Methyl pyrrolidone.N-Methyl pyrrolidone has extensive use in pharmacy, makeup, weaving, food, paint and electronic industry.It is a kind of excellent solvent and extraction agent, and acetonitrile can be replaced from C
4extracting divinyl (being called NMP method) in cut, it is little that this method has toxicity, corrosion-free, efficiency is high, can save energy the advantage such as 50%, and also can be used for the aspect such as lube oil finishing, acetylene concentration, have good result, Petrochemical Enterprises is larger to its demand.
In 1989, develop MALEIC ANHYDRIDE esterification produce ethyl maleate technique by Davy Mckee company of Britain, object is that hydrogenation produces BDO.This technique carries out esterification by MALEIC ANHYDRIDE and excess ethyl alcohol mixing first to generate ethyl maleate.Single-esterification carries out under 0.1MPa, 50 ~ 80 DEG C of conditions, does not need catalyzer, and yield is 99%.Mono ethyl ester carries out double esterification reaction more further and generates ethyl maleate with ethanol.This step adopts catalyzer rectification process, and solid acidic ion exchange resin is catalyzer, and temperature of reaction 100 ~ 130 DEG C, pressure are 0.1MPa, dibasic acid esters yield can 98%.By rectifying, excess ethyl alcohol and water are removed from reactor, the further distilation of ethyl maleate gas of generation, removes unreacted mono ethyl ester and makes it to loop back in reactor.The by product burning accounting for resultant total amount 1% is removed.Mix with the ethanol looped back from product rectification again after rectifying dewaters from the excess ethyl alcohol of reactive moieties recovery and return esterifier.
On this basis, Davy Mckee company have developed again with methyl alcohol is the MALEIC ANHYDRIDE esterification technique of esterifying agent.The advantage of this technique is: adopt catalyzer rectification process, after esterification, the separation of first alcohol and water becomes easy; Add the volatility of dimethyl maleate, the operating restraint making it gas phase hydrogenation broadens; Up to 99.5%, therefore there is not the purification of dimethyl maleate in the conversion rate of esterification of MALEIC ANHYDRIDE, does not need unreacted MALEIC ANHYDRIDE and mono-methyl circulation, only have pure methanol loop; Enormously simplify flow process, total investment of engineering reduces 15% than the former.
MALEIC ANHYDRIDE esterification generates dimethyl maleate (DMM) technique and realizes in two steps.First react after cis-butenedioic anhydride and methanol mixed and generate monomethyl maleate (MMM), have a small amount of monomethyl maleate (MMM) to react with methyl alcohol further simultaneously and generate dimethyl maleate (DMM).Then, monomethyl maleate (MMM), under the effect of acid resin catalyst, carries out esterification further with methyl alcohol and generates dimethyl maleate (DMM).
The single-esterification of MALEIC ANHYDRIDE and methyl alcohol is strong exothermal reaction, the transformation efficiency that MALEIC ANHYDRIDE is converted into monomethyl maleate (MMM) is approximately 85%, the monomethyl maleate (MMM) of about 12% reacts with methyl alcohol further and generates the two methyl esters (DMM) of toxilic acid simultaneously, sees formula (1).
(1)
Monomethyl maleate (MMM), under resin catalyst exists, carries out esterification further with methyl alcohol and generates the two methyl esters (DMM) of toxilic acid, generate water simultaneously, see formula (2).
(2)
Double esterification reaction device is equipped with strong-acid cation-exchange resin and column plate forms by a series of.Liquid flows through each block of column plate from top to bottom, is reacted to dibasic acid esters gradually by monoesters.Methyl alcohol enters from double esterification reaction device bottom, is then vaporized by reaction tower reboiler.The methanol steam generated from reboiler and methyl ester liquid counter current contact is backward passes through reaction tower.The transformation efficiency generating dimethyl maleate in tower can reach 99.5%.The a small amount of methyl alcohol entering double esterification reaction device generates dme, discharges from the logistics of double esterification reaction device top gas phase.
Because single-esterification is a first order reaction, when not needing catalyzer, just can react, a large amount of heats is released in reaction process, but single-esterification can not complete reaction, and the conversion rate of maleic anhydride of general single-esterification can reach 97% ~ 98%, the cis-butenedioic anhydride of residue 2% ~ 3% needs to react in double esterification catalytic rectifying tower, make double esterification tower charging several pieces of plate temperature of reaction superelevation, have a strong impact on the work-ing life of catalyzer.
Double esterification reaction in double esterification catalytic rectifying tower needs catalyzer to be in boiling state, therefore, require catalyzer not only to have certain activity but also require that catalyzer has certain size-grade distribution, wet true density, wet volume density and certain physical strength, the requirement of double esterification reaction can be met like this.Use the resin catalyst of single kind in existing double esterification catalytic rectifying tower, monolith is shorter for work-ing life.
Summary of the invention
For the deficiencies in the prior art, the invention provides the method for a kind of catalyst segments filling synthesis dialkyl maleate.This filling method is particularly useful for double esterification catalytic distillation reaction process, can work-ing life of effective extending catalyst.
The method of catalyst segments type of feed synthesis dialkyl maleate of the present invention comprises following content: the synthesis carrying out dialkyl maleate on catalytic distillation reaction unit, liquid phase feed containing maleic acid mono alkyl ester enters from catalytic distillation reaction unit top, alkyl alcohol phase feed enters from catalytic distillation reaction unit bottom, exist at resin catalyst and under catalytic distillation condition, carry out reaction and generate dialkyl maleate, in catalytic distillation reaction unit, at least 12 blocks of column plates are set, loaded resin catalyzer at least 10 blocks of column plates, loaded resin catalyst A on 1 ~ 8 block of column plate that wherein catalytic distillation device upper aqueous phase feedstock place is downward, loaded resin catalyst B on the column plate of other loaded resin catalyzer, the character of resin catalyst A is as follows: volume-exchange capacity is 0.85mol/L ~ 1.0 mol/L, halogen mass content is 24% ~ 28%, the character of resin catalyst B is as follows: volume-exchange capacity is 0.5mol/L ~ 0.65 mol/L, halogen mass content 8% ~ 10%.
In the inventive method, 15 ~ 45 blocks of column plates are preferably set in catalytic distillation reaction unit, wherein more than at least 10 pieces column plates, preferably loaded resin catalyzer on more than 15 pieces column plates.
In the inventive method, the operational condition of catalytic distillation reaction is generally: the mol ratio 1:1.5 ~ 1:5 of maleic acid mono alkyl ester/alkyl alcohol, be preferably 1:2.5 ~ 1:3.5, the cumulative volume air speed of the liquid phase feeding containing maleic acid mono alkyl ester to resin catalyst is 0.2h
-1~ 2.0h
-1, be preferably 0.6 h
-1~ 1.0h
-1, temperature of reaction is 90 DEG C ~ 160 DEG C, is preferably 110 DEG C ~ 135 DEG C, obtains dialkyl maleate product after catalytic distillation reaction at the bottom of tower.The transformation efficiency etc. that the selection of concrete technology condition and catalytic distillation device stage number can reach according to the character of reaction raw materials and requirement is specifically determined by those skilled in the art.
In the inventive method, resin catalyst is the further character of A, volume-exchange capacity is 0.85mol/L ~ 1.0 mol/L, be preferably 0.85mol/L ~ 0.90mol/L, wet volume density 0.8g/ml ~ 0.9 g/ml, is preferably 0.8g/ml ~ 0.85 g/ml, wet true density 1.15g/ml ~ 1.25 g/ml, be preferably 1.15g/ml ~ 1.20 g/ml, halogen mass content 24% ~ 28%, be preferably 24% ~ 26%(with butt quality for benchmark).
In the inventive method, resin catalyst is the further character of B, volume-exchange capacity is 0.5mol/L ~ 0.65 mol/L, wet volume density 0.75g/ml ~ 0.85 g/ml, be preferably 0.75g/ml ~ 0.80 g/ml, wet true density 1.1g/ml ~ 1.25 g/ml, be preferably 1.1g/ml ~ 1.15 g/ml, content of halogen 8% ~ 10%, is preferably 8.5% ~ 9.5%(with butt quality for benchmark).
In the inventive method, resin catalyst A and resin catalyst B is preferably vinylbenzene and divinylbenzene polymer resin, and halogen is wherein preferably chlorine or bromine.Resin catalyst can select the commercially available commodity meeting Property requirements, also can synthesize by this area ordinary method.
In the inventive method, the alkyl that dialkyl maleate, maleic acid mono alkyl ester and alkyl alcohol are corresponding is the alkyl of C1 ~ C4, be preferably methyl or ethyl, most preferably be methyl, corresponding for dialkyl maleate be dimethyl maleate, ethyl maleate etc., maleic acid mono alkyl ester and alkyl alcohol etc. all have identical alkyl.
In the inventive method, the liquid phase feeding containing maleic acid mono alkyl ester is the material containing maleic acid mono alkyl ester that maleic anhydride and alkyl alcohol are not having to be obtained by reacting under catalyzer.
The present invention produces the production process of dialkyl maleate by optimizing catalytic rectification process, at guarantee raw material maleic acid mono alkyl ester transformation efficiency and object product dialkyl maleate optionally under prerequisite, substantially increase the activity stability of integer catalyzer, extend the running period of device, reduce catalyzer cost, improve the economy of production equipment.
Embodiment
Production process below by way of dimethyl maleate illustrates the solution of the present invention and effect.Dimethyl maleate production process requires that monomethyl maleate transformation efficiency is more than 99.5%, and reaction tower bottom product does not need fractionation more directly can produce the feed needs of BDO device as hydrogenation method.The liquid phase feeding of catalytic rectifying tower is the charging containing monomethyl maleate that maleic anhydride and methyl alcohol obtain under on-catalytic condition.
According to above requirement, catalytic rectifying tower is bottom-up adds up to 30 blocks of column plates (numbering from bottom to top 1 ~ 30), monomethyl maleate charging is on the 30th block of plate of top, and resin catalyst A is seated at least one piece that is numbered 30 ~ 20 blocks of column plates from top to bottom.Foot 1 ~ 8 block of column plate can not loaded resin catalyzer, only plays refinery distillation.Other needs the column plate loaded resin catalyst B of loading catalyst.Reaction conditions controls: the mol ratio 1:2.5 ~ 1:3.5 of monomethyl maleate/methyl alcohol, the volume space velocity to all catalyzer of liquid phase feeding is 0.7 h
-1~ 0.9h
-1, temperature of reaction is 110 DEG C ~ 135 DEG C and carries out building-up reactions, obtains dimethyl maleate at the bottom of tower.
In the specific embodiment of the invention, resin catalyst A and resin catalyst B is prepared as follows:
(1) after being mixed completely by Ben Yi Xi ﹑ divinylbenzene, add pore-creating agent, add in aqueous phase by suitable feed rate, regulate mixing speed, control the degree of uniformity of oil droplet.Intensification makes oil droplet solidify, then reaction mass Guo Lv ﹑ Xi Di ﹑ is dry, collect qualified polymkeric substance Archon and carry out physical structure stabilization treatment, add Cuiization Ji ﹑ halogen after physical structure stabilization terminates and carry out halogenating reaction, halogen add-on adjusts according to index request.Add sulphonating agent after reaction terminates and carry out sulfonation reaction.After reaction mass is washed, carry out active group stabilization treatment, after active group stabilization terminates, be resin catalyst finished product.
(2) after being mixed completely by Ben Yi Xi ﹑ divinylbenzene, add pore-creating agent, add in aqueous phase by suitable feed rate, regulate mixing speed, control the degree of uniformity of oil droplet.Intensification makes oil droplet solidify, then reaction mass Guo Lv ﹑ Xi Di ﹑ is dry, collect qualified polymkeric substance Archon and carry out physical structure stabilization treatment, add Cuiization Ji ﹑ halogen after physical structure stabilization terminates and carry out halogenating reaction, halogen add-on adjusts according to index request.Add sulphonating agent after reaction terminates and carry out sulfonation reaction.After reaction mass is washed, carry out active group stabilization treatment, after active group stabilization terminates, be resin catalyst finished product.The physico-chemical property of the resin catalyst B prepared by aforesaid method is in table 2.
Embodiment 1
Synthetic resins catalyzer according to a conventional method:
1) first will account for after oil phase quality 64% vinylbenzene, 7.5% divinylbenzene, 27.5% pore-creating agent and 1% initiator fully mix, stand-by.
2) then will account for after aqueous phase quality 99.84% deionized water, 0.15% polyvinyl alcohol and 0.01% methylene blue fully mix, and heat up, when temperature rises to 60 DEG C, according to suitable feed rate, oil phase is added in aqueous phase, regulate mixing speed; Control the degree of uniformity of oil droplet, after having fed in raw material, be warming up to 80 DEG C and maintain 1 ~ 2 hour.Then be warming up to 95 DEG C ~ 100 DEG C, oil droplet is solidified.Solidify after 10 hours, stop stirring, lower the temperature simultaneously.Question response temperature is down to about 75 DEG C, reaction mass is put into filtration washing still and filters, filtrate discharge, and in upper strata pearl body use, 80 DEG C of hot washes for several times, then dry, collects 20 ~ 50 purpose polymers pearl bodies.Water oil phase ratio is 4.5:1.
3) catalyzer of 380 Kg20 order ~ 50 purpose polymers pearl bodies and 2 Kg is added 1300 Kg 1,2-ethylene dichloride fully swelling after, add the halogen of 160 Kg, react 12 hours under 0 DEG C ~ 10 DEG C conditions, after reaction terminates, carry out sulfonation reaction.
4) by 3420 Kg 20% oleums (sulphur trioxide mass concentration), slowly add in reactor, controlling temperature of reaction is 35 DEG C.React 12 hours, after reaction terminates, it is neutral for being washed till washing water with deionized water.Resin catalyst A can be obtained.
The physico-chemical property of table 1 resin catalyst A.
| Sequence number | Physico-chemical property | Technical indicator |
| 1 | Rate of small round spheres after mill, % (1h) | ≥95.00 |
| 2 | Exchange capacity, molL -1 | 0.85～1.0 |
| 3 | Water content, % by weight | 56～59 |
| 4 | Wet volume density, gml -1 | 0.8～0.9 |
| 5 | Wet true density, gml -1 | 1.15～1.25 |
| 6 | Granularity, %(0.5 ~ 0.9mm) | ≥95.00 |
| 7 | Content of halogen, % by weight | 24～28 |
Loaded resin catalyst A on all column plates of catalytic distillation conversion unit, the mol ratio 1:3 of charging monomethyl maleate/methyl alcohol, volume space velocity 0.74 h to catalyzer of liquid phase feeding
-1, temperature of reaction 110 DEG C ~ 135 DEG C, initial reaction temperature 110 DEG C, when transformation efficiency is undesirable, improves transformation efficiency, until lift temperature to 135 DEG C by improving temperature of reaction.Test-results is in table 3.
Embodiment 2
The present embodiment basic step is with embodiment 1, and difference is the halogen adding 80 Kg, 3420 Kg 98% sulfuric acid, the resin catalyst B of system.
Table 2 resin catalyst B physico-chemical property.
| Sequence number | Physico-chemical property | Technical indicator |
| 1 | Rate of small round spheres after mill, % | ≥96.00 |
| 2 | Exchange capacity, molL -1 | 0.5～0.65 |
| 3 | Water content, % by weight | 48～50 |
| 4 | Wet volume density, gml -1 | 0.75～0.85 |
| 5 | Wet true density, gml -1 | 1.1～1.25 |
| 6 | Granularity, %(0.5 ~ 0.9mm) | ≥96.00 |
| 7 | Content of halogen, % by weight | 8～10 |
All column plates of catalytic distillation conversion unit all load B kind resin catalyst, and reaction conditions is with embodiment 1, and test-results is in table 3.
Embodiment 3
The present embodiment basic step is with embodiment 1 and embodiment 2, difference is two kinds of catalyzer segmentation from top to bottom fillings, resin catalyst is seated on No. 30 column plates, resin catalyst B is seated on 6 ~ No. 29 column plates, 1 ~ No. 5 column plate not loading catalyst, reaction conditions is with embodiment 1, and test-results is in table 3.
Embodiment 4
The present embodiment basic step is with embodiment 1 and embodiment 2, and difference is that resin catalyst A is seated on 25 ~ No. 30 column plates, and resin catalyst B is seated on 3 ~ No. 24 column plates, 1 ~ No. 2 column plate not loading catalyst by two kinds of catalyzer segmentation from top to bottom fillings.Reaction conditions is with embodiment 1, and test-results is in table 3.
Embodiment 5
The present embodiment basic step is with embodiment 1 and embodiment 2, and difference is that resin catalyst A is seated on 19 ~ No. 30 column plates, and resin catalyst B is seated on 1 ~ No. 18 column plate by two kinds of catalyzer segmentation from top to bottom fillings.Reaction conditions is with embodiment 1, and test-results is in table 3.
Table 3 test-results (monomethyl maleate transformation efficiency, quality %).
| Working time/h | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| 100 | 98.6 | 99.5 | 99.5 | 99.6 | 99.7 | 99.5 |
| 200 | 97.5 | 99.6 | 99.7 | 99.5 | 99.7 | 99.6 |
| 300 | 96.8 | 99.7 | 99.5 | 99.6 | 99.7 | 99.5 |
| 400 | 97.8 | 99.8 | 99.6 | 99.7 | 99.6 | 99.6 |
| 500 | 98.6 | 99.6 | 99.6 | 99.8 | 99.8 | 99.7 |
| 600 | 99.2 | 99.5 | 99.8 | 99.5 | 99.8 | 99.7 |
| 700 | 97.3 | 99.7 | 99.6 | 99.6 | 99.7 | 99.6 |
| 800 | 96.9 | 99.6 | 99.7 | 99.5 | 99.7 | 99.5 |
| 900 | 95.9 | 99.5 | 99.6 | 99.7 | 99.6 | 99.6 |
| 1000 | 98.9 | 99.7 | 99.7 | 99.7 | 99.7 | 99.5 |
| 1100 | 99.5 | 99.5 | 99.6 | 99.6 | 99.5 | 99.6 |
| 1200 | 98.7 | 99.6 | 99.6 | 99.5 | 99.6 | 99.7 |
| 1300 | 97.6 | 99.6 | 99.8 | 99.8 | 99.7 | 99.8 |
| 1400 | 98.4 | 99.7 | 99.7 | 99.6 | 99.7 | 99.6 |
| 1500 | 97.6 | 99.5 | 99.7 | 99.5 | 99.5 | 99.7 |
| 1600 | 94.6 | 99.8 | 99.8 | 99.8 | 99.8 | 99.5 |
| 1700 | 98.6 | 99.8 | 99.6 | 99.7 | 99.7 | 99.6 |
| 1800 | 97.9 | 99.7 | 99.7 | 99.7 | 99.7 | 99.6 |
| 1900 | 98.7 | 99.6 | 99.5 | 99.6 | 99.7 | 99.5 |
| 2000 | 97.9 | 99.6 | 99.6 | 99.8 | 99.6 | 99.8 |
| 2100 | 96.7 | 99.5 | 99.7 | 99.5 | 99.5 | 99.7 |
| 2200 | 95.9 | 99.8 | 99.8 | 99.6 | 99.6 | 99.5 |
| 2300 | 97.8 | 99.7 | 99.8 | 99.7 | 99.8 | 99.8 |
| 2400 | 94.9 | 99.6 | 99.7 | 99.7 | 99.5 | 99.6 |
| 2500 | 96.7 | 99.8 | 99.8 | 99.5 | 99.8 | 99.7 |
| 2600 | 98.6 | 99.5 | 99.6 | 99.6 | 99.7 | 99.6 |
| 2700 | 97.8 | 99.5 | 99.6 | 99.7 | 99.6 | 99.7 |
| 2800 | 95.6 | 99.7 | 99.7 | 99.7 | 99.5 | 99.7 |
| 2900 | 97.9 | The 99.8(cycle is 2900h) | 99.8 | 99.5 | 99.8 | 99.8 |
| 3000 | 94.6 | 98.7 | 99.8 | 99.8 | 99.7 | 99.7 |
| 3100 | 96.7 | 98.6 | 99.7 | 99.6 | 99.6 | 99.6 |
| 3200 | 98.6 | 98.8 | 99.5 | 99.7 | 99.5 | 99.5 |
| 3300 | 97.6 | 98.5 | The 99.6(cycle is 3300h) | 99.5 | 99.6 | 99.7 |
| 3400 | 95.8 | 97.7 | 98.7 | 99.7 | 99.7 | 99.6 |
| 3500 | 96.9 | 96.4 | 97.5 | The 99.5(cycle is 3500h) | 99.5 | The 99.5(cycle is 3500h) |
| 3600 | 96.8 | 95.3 | 97.6 | 98.6 | 99.6 | 98.6 |
| 3700 | 96.8 | 94.5 | 96.5 | 97.5 | 99.5 | 97.5 |
| 3800 | 95.9 | 96.9 | 96.9 | The 99.5(cycle is 3800h) | 97.4 | |
| 3900 | 94.9 | 95.8 | 95.8 | 97.8 | 96.8 |
Embodiment 6
The present embodiment basic step is with embodiment 1 and embodiment 2, and difference is that resin catalyst A is seated on 17 ~ No. 30 column plates, and resin catalyst B is seated on 4 ~ No. 16 column plates, and 1 ~ No. 3 column plate does not fill catalyzer by two kinds of catalyzer segmentation from top to bottom fillings.Reaction conditions is with embodiment 1, and test-results is in table 3.
Claims (1)
1. the method for a catalyst segments type of feed synthesis dialkyl maleate, catalytic distillation reaction unit carries out the synthesis of dialkyl maleate, liquid phase feed containing maleic acid mono alkyl ester enters from catalytic distillation reaction unit top, alkyl alcohol phase feed enters from catalytic distillation reaction unit bottom, exist at resin catalyst and under catalytic distillation condition, carry out reaction and generate dialkyl maleate, it is characterized in that: in catalytic distillation reaction unit, at least 12 blocks of column plates are set, loaded resin catalyzer at least 10 blocks of column plates, loaded resin catalyst A on 1 ~ 8 block of column plate that catalytic distillation device upper aqueous phase feedstock place is downward, loaded resin catalyst B on the column plate of other loaded resin catalyzer, resin catalyst A and resin catalyst B is vinylbenzene and divinylbenzene polymer resin, the character of resin catalyst A is as follows: volume-exchange capacity is 0.85mol/L ~ 1.0 mol/L, halogen mass content is 24% ~ 28%, the character of resin catalyst B is as follows: volume-exchange capacity is 0.5mol/L ~ 0.65 mol/L, halogen mass content 8% ~ 10%.
2. in accordance with the method for claim 1, it is characterized in that: 15 ~ 45 blocks of column plates are set in catalytic distillation reaction unit, wherein loaded resin catalyzer on more than at least 10 pieces column plates.
3. in accordance with the method for claim 1, it is characterized in that: the operational condition of catalytic distillation reaction is: the mol ratio 1:1.5 ~ 1:5 of maleic acid mono alkyl ester/alkyl alcohol, the cumulative volume air speed of the liquid phase feeding containing maleic acid mono alkyl ester to resin catalyst is 0.2h
-1~ 2.0h
-1, temperature of reaction is 90 DEG C ~ 160 DEG C, obtains dialkyl maleate product after catalytic distillation reaction at the bottom of tower.
4. in accordance with the method for claim 1, it is characterized in that: the operational condition of catalytic distillation reaction is: the mol ratio of maleic acid mono alkyl ester/alkyl alcohol is 1:2.5 ~ 1:3.5, and the cumulative volume air speed of the liquid phase feeding containing maleic acid mono alkyl ester to resin catalyst is 0.6 h
-1~ 1.0h
-1, temperature of reaction is 110 DEG C ~ 135 DEG C, obtains dialkyl maleate product after catalytic distillation reaction at the bottom of tower.
5. in accordance with the method for claim 1, it is characterized in that: resin catalyst is wet volume density 0.8g/ml ~ 0.9 g/ml of A, and wet true density is 1.15g/ml ~ 1.25 g/ml, and halogen mass content is 24% ~ 26%.
6. in accordance with the method for claim 1, it is characterized in that: resin catalyst is the wet volume density of B is 0.75g/ml ~ 0.85 g/ml, and wet true density is 1.1g/ml ~ 1.25 g/ml, and halogen mass content is 8.5% ~ 9.5%.
7. according to the method described in claim 1,4 or 5, it is characterized in that: halogen is chlorine or bromine.
8. in accordance with the method for claim 1, it is characterized in that: the alkyl that dialkyl maleate, maleic acid mono alkyl ester and alkyl alcohol are corresponding is the alkyl of C1 ~ C4.
9. according to the method described in claim 1 or 4, it is characterized in that: the alkyl that dialkyl maleate, maleic acid mono alkyl ester and alkyl alcohol are corresponding is methyl.
10. according to the method described in claim 1 or 8, it is characterized in that: the liquid phase feeding containing maleic acid mono alkyl ester is the material containing maleic acid mono alkyl ester that maleic anhydride and alkyl alcohol are not having to be obtained by reacting under catalyzer.
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| CN115745772A (en) * | 2022-09-30 | 2023-03-07 | 云南大为恒远化工有限公司 | Method for producing succinic acid by esterification and hydrogenation of maleic anhydride |
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| CN101314564A (en) * | 2007-06-01 | 2008-12-03 | 上海焦化有限公司 | Preparation of maleic acid di-methyl ester |
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| CN101314564A (en) * | 2007-06-01 | 2008-12-03 | 上海焦化有限公司 | Preparation of maleic acid di-methyl ester |
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| Title |
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| DZH型顺丁烯二酸酐酯化树脂催化剂的开发;霍稳周等;《工业催化》;20050831;第13卷(第8期);40-44 * |
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