KR102283565B1 - Multi-compartment continuous stirring hydration reactor and method for preparating 2-Butyl alchol using the same - Google Patents

Abstract

The present invention relates to a reaction mechanism used for preparing secondary butyl alcohol by hydrating normal butene using an aqueous heteropoly acid solution as a catalyst. More specifically, it relates to a method of improving the conversion rate by dividing zones inside the reactor and maximizing the stirring and residence times in each zone as in a batch reactor.

Description

Multi-compartment continuous stirring hydration reactor and method for preparating 2-Butyl alcohol using the same

The present invention prepares secondary butyl alcohol by hydrating normal butene using an aqueous heteropoly acid solution as a catalyst, and more specifically, by reacting in a continuously stirred hydration reactor having multiple zones, secondary butyl alcohol with improved conversion rate It relates to an obtainable apparatus and a method for producing secondary butyl alcohol.

The normal butene hydration reaction is a single normal butene or a mixture of normal butenes, which is 1-butene, cis-2-butene, or trans-2-butene as butene. As a reaction for producing secondary butyl alcohol using the secondary butyl alcohol, the secondary butyl alcohol is again subjected to dehydrogenation and is used to produce methyl-ethyl-ketone (MEK).

Sulfuric acid is traditionally used for hydration of normal butene, but the reaction temperature and pressure are not high, but there are disadvantages in that there are environmental problems caused by the use of sulfuric acid, corrosion problems of equipment, and processing cost problems. In order to solve these shortcomings, a process using an acid catalyst that replaces sulfuric acid such as ion exchange resin and heteropoly acid has been developed.

Among them, a process using a heteropolyacid catalyst applies a method in which an aqueous solution of heteropolyacid and normal butene react and hydrate directly. The reaction conditions use conditions that make normal butene supercritical, and the solubility of normal butene in water increases in the supercritical region, which is known to be advantageous for normal butene hydration. In addition, unlike a process using sulfuric acid or a process using an ion exchange resin as a catalyst, since water does not exit the reactor with the product and does not form an azeotrope, it is more advantageous in separation.

The present inventors have also invented a reaction mechanism that can further improve the conversion rate of normal butene hydration by securing a longer time for normal butene to pass through the aqueous layer in the reactor and maximizing mass transfer by stirring.

Republic of Korea Patent Publication No. 10-1341814 (2013.12.10.) Republic of Korea Patent Publication No. 10-1828123 (2018.02.05.)

An object of the present invention is to provide an apparatus for producing secondary butyl alcohol by hydrating normal butene in a continuous stirred reactor in the form of connecting several batch reactors using an aqueous heteropolyacid solution as a catalyst, and more improved conversion and efficiency The aim is to provide a method for preparing secondary butyl alcohol through the above apparatus.

The present invention provides 1-butene as butene in a continuous stirred hydration reactor having multiple zones in which the raw materials in each zone are stirred and hydrated by separating zones inside the continuous reactor like a batch reactor in order to solve the above technical problem , cis-2-butene or trans-2-butene, characterized in that for preparing secondary butyl alcohol by hydration reaction of a single normal butene or a mixture thereof with an aqueous solution of heteropolyacid as a catalyst filled in the reactor A stirred hydration reactor and a method for producing secondary butyl alcohol using the continuously stirred hydration reactor are provided.

The present invention is a continuously stirred hydration reactor (100) having multiple batch reaction zones connected in series for the production of secondary butyl alcohol from normal butene, and a fluid passageway in a partition plate (150) dividing the batch reaction zones. Raw material flow comprising a gap between the shaft 130 and the partition plate 150 passing through 151 and the agitator shaft hole 152, and containing no solid material in the continuously stirred hydration reactor 100 The butene used may include any one or more selected from 1-butene, cis-2-butene, and trans-2-butene. There is, the butene is converted to secondary butyl alcohol using the heteropolyacid aqueous solution 103 as a catalyst, in which case the content of iso-butene is preferably minimized.

The hydration reaction that takes place in the continuously stirred hydration reactor 100 is possible in both a batch type or a continuous type reactor, but generally the reaction is performed using a continuous type reactor, and more preferably, there are 5 or more batch reactor zones inside the reactor. In the batch reactor zone, each agitator 140 and a plate for compartment dividing the reaction zone 150 are installed between the stirrer and adjacent stirrers to divide the zones by dividing the continuous stirring type with multiple zones. react in a hydration reactor.

The batch reaction zone moves the butenes and products of the zone through a fluid passageway 151 in a partition plate 150 located between each reaction zone, and passes through the stirrer shaft hole 152 of the reactor 100. Through the clearance between the shaft 130 and the partition plate 150 including the agitator shaft hole, a small amount of fluid in the reaction zone is moved to the adjacent reaction zone to ensure sufficient reaction time and the secondary Allow products containing butyl alcohol to pass to the next adjacent reaction zone.

More specifically, the diameter of the fluid passage 151 of the partition plate 150 is preferably 1 to 5 mm, and the gap between the shaft 130 and the partition plate 150 is 3 mm or less. Preferably, the back mixing and loss of reaction pressure can be suppressed through the very small diameter of the fluid passage and the gap between the shaft 130 and the partition plate 150. If the diameter of the fluid passage is less than 1 mm, the fluid It is not easy to move

In the secondary butyl alcohol manufacturing method of the present invention, a heteropolyacid aqueous solution 103 is filled in the reactor 100, a raw material 101 containing normal butene is supplied into the reactor 100, and the heteropolyacid aqueous solution (103) is used as a catalyst to convert the raw material 101 containing normal butene into secondary butyl alcohol, and normal butene, which forms a supercritical gas phase in the reactor 100, is included in the liquid phase The obtained product is extracted into the gas phase to exit the reactor, and thereafter, normal butene in the supercritical state and the secondary butyl alcohol are separated.

At this time, it is preferable that the reaction temperature of the hydration reaction is 150 ~ 250 ℃, the reaction pressure is 60 ~ 300 bar, more preferably 100 ~ 200 bar.

In addition, the raw material 101 containing normal butene supplied to the n-butene supply port 110 at the lower portion of the reactor 100 preferably has a content in the flow of at least 50 wt%, more preferably 70 wt% or more, The flow rate of butene to be used ^{is preferably LHSV 0.2 to 5 hr -1} , more preferably LHSV 1 to 2 ^{hr -1.}

In the step of separating the butene and the generated secondary butyl alcohol, the raw material 101 containing normal butene is injected into the lower part of the reactor 100, and the injected butene passes through the dispersion plate 120 located at the lower part of the reactor. It forms microbubbles and is injected into the reactor. The butene injected through the dispersion plate forms microbubbles, and has the effect of efficiently dispersing in the heteropolyacid aqueous solution. The dispersion plate is in the form of a perforated disk, and the diameter of the hole drilled in the dispersion plate is preferably 1 to 5 mm.

Secondary butyl alcohol was extracted from the liquid reaction product prepared from the reactor using normal butene in a supercritical state (140° C., 40 bar or more) from the reactor 100, and exited from the reactor in a gas phase together with the normal butene. Then, the secondary butyl alcohol is purified, separated and recovered by separating the reaction product 105 including the secondary butyl alcohol from the normal butene in a separation column.

The continuously stirred hydration reactor of the present invention is a reactor for producing secondary butyl alcohol that directly hydrates normal butene using an aqueous heteropoly acid solution as a catalyst. The conversion rate when used can be greatly improved. At the same time, since the simplicity of the separation process, which is an advantage of the supercritical butene hydration reaction, is not lost, it is possible to efficiently prepare secondary butyl alcohol.

In particular, by minimizing the mass transfer resistance between butene and the aqueous catalyst solution through the stirrer, the catalyst hydration reaction activity of the present invention is enhanced, and by dividing the zones in the reactor of the present invention, the residence time of butene in the reactor is increased, so that butene is converted to secondary butyl The efficiency of conversion to alcohol is maximized.

1 is a schematic diagram of a preferred embodiment of a reactor 100 of the present invention.
2 is a schematic diagram of a partition plate 150 .
3 is a schematic diagram of the dispersion plate 120 .

Hereinafter, preferred embodiments of the present invention will be described in detail, but the scope of the present invention is not limited to the following examples.

According to the present invention, the continuously stirred hydration reactor 100 having multiple zones for hydration reaction by stirring the raw materials in each zone by separating zones like a batch reactor inside the continuously stirred hydration reactor 100 and using this reactor 1 -Butene, cis-2-butene, or trans-2-butene, the raw material 101 comprising any one selected from the group consisting of normal butene or a mixture thereof is hydrated with an aqueous solution of heteropolyacid 103 as a catalyst stored in the reactor. to provide a method for preparing secondary butyl alcohol for producing secondary butyl alcohol at a higher conversion rate.

The interior of the reactor 100 is filled with an aqueous solution of heteropolyacid 103 to cover the uppermost batch reaction zone. The raw material 101 containing normal butene is injected through the n-butene supply port 110 at the bottom, and the normal butene passing through the dispersion plate 120 located at the bottom of the reactor 100 forms microbubbles in the reactor. injected inside. The injected normal butene causes a hydration reaction with an aqueous heteropoly acid solution 103 as a catalyst stored in each reactor inner zone, and the produced materials pass through the heteropoly acid aqueous solution 103 layer to divide each reaction zone partition plate 150 It moves to the adjacent reaction zone through a gap between the fluid passage 151 and the shaft 130 and the agitator shaft hole 152, which is a movement passage located in the . At this time, mass transfer is maximized by agitating the reactants by the stirrer 140 in each reaction zone in the shaft 130 of the reactor, and the fluid passage 151 and the shaft 130 and the partition plate 150 are partitioned. A small amount of fluid including butene and product moves through the gap between the plates 150 . In the case of the fluid passage 151, the pore size is small so that the reaction mixture in each zone maximizes the residence time in the zone so that the reaction time can be sufficiently secured, and at the same time, the product containing secondary butyl alcohol is adjacent to the next Allow it to pass through the area. Through this, the conversion rate of normal butene to secondary butyl alcohol may be improved.

The water consumed during the hydration reaction may be replenished through a make-up water line 160 located in each zone.

After passing through the various reaction zones inside the hydration reactor of the present invention in the same manner as described above, unreacted normal butene and the extracted product materials come out of the reactor 100 through the product outlet 170, which is a line at the top of the reactor. The temperature of the reaction is 150 ~ 250 ℃, the pressure is 60 bar or more and 300 bar or less, more preferably 100 ~ 200 bar. Make-up water (102) consumed during the reaction can be replenished using make-up water lines in each zone.

The present invention can use either a continuous or batch reactor, but generally a continuous reactor is used.

[Example]

Normal butene hydration reaction using a continuously stirred hydration reactor having multiple zones as shown in FIG. 1

Heteropolyacid aqueous solution was injected into a continuously stirred hydration reactor, butene was continuously injected using a pump, and a continuous reaction was carried out at a reaction temperature of 200 °C and a reaction pressure of 200 bar. The conversion of butene was confirmed by GC analysis of the product exiting the reactor. As a result, the conversion of butene was 15% and the selectivity of secondary butyl alcohol was 99.5%.

[Comparative example]

Normal butene hydration reaction using continuous bubble column reactor without stirring device

In a conventional continuous bubble column reactor without a divided reaction zone and no stirring device, an aqueous solution of heteropolyacid was used as a catalyst to hydrate butene at a temperature of 200° C. and a pressure of 200 bar. The conversion of butene was confirmed by GC analysis of the reaction product. As a result, the conversion of butene was 5.7%, and the selectivity of secondary butyl alcohol was 96.8%.

[Examples and Comparative Examples]

When the hydration reaction was carried out in the continuously stirred hydration reactor having multiple zones of Example, the conversion rate to produce secondary butyl alcohol was greatly improved to 15% due to the improvement of mass transfer power by stirring inside the reactor.

100: continuously stirred hydration reactor
101: raw material
102: Make-up water
103: Heteropolyacid aqueous solution
104: heteropolyacid aqueous solution-butene interface
105: product
110: n-butene supply port
120: dispersion plate
130: shaft (Shaft)
140: agitator
150: partition plate
151: fluid passage
152: agitator shaft hole
160: make-up water line (Make-up water line)
170: product outlet

Claims (7)

A continuous stirred reactor having multiple batch reaction zones for the production of secondary butyl alcohol from normal butene, one fluid passageway 151 on a partition plate 150 dividing the batch reaction zone and a stirrer shaft hole ( and a gap between the shaft 130 passing through 152 and the partition plate 150,
The fluid passage 151 on each partition plate 150 is located on the opposite side with respect to the fluid passage 151 and the shaft 130 on the other adjacent partition plate 150,
Through the gap between the partition plate 150 and the shaft 130 passing through the fluid passage 151 and the agitator shaft hole 152, the fluid in the batch reaction zone containing secondary butyl alcohol as a product is adjacent to each other. A continuously stirred hydration reactor, characterized in that it can be moved to a batch reaction zone. The method according to claim 1, wherein the normal butene includes at least one selected from 1-butene, cis-2-butene, and trans-2-butene, and is converted to secondary butyl alcohol using an aqueous heteropoly acid solution 103 as a catalyst. A continuously stirred hydration reactor, characterized in that The continuously stirred hydration reactor according to claim 1, wherein five or more batch reaction zones are provided. 4. A continuously stirred hydration reactor according to claim 3, wherein said batch reaction zone comprises a stirrer (140) coupled to a shaft (130) of said continuously stirred hydration reactor (100). delete Using the continuously stirred hydration reactor according to any one of claims 1 to 4, the heteropoly acid aqueous solution 103 is filled in the reactor 100, and then the raw material 101 containing the normal butene is supplied. , using the heteropolyacid aqueous solution 103 as a catalyst, converting normal butene contained in the raw material 101 into secondary butyl alcohol as a product, and supercritical state in the continuously stirred hydration reactor 100 Secondary characterized in that the normal butene forming the gas phase of the liquid phase extracts the product contained in the liquid phase into the gas phase, exits the reactor, and then separates the normal butene in the supercritical state and the secondary butyl alcohol as a product A method for producing butyl alcohol. The method of claim 6, wherein the raw material 101 is supplied to the normal butene supply port 110 at the bottom of the continuously stirred hydration reactor 100, and the supplied raw material 101 has a content of normal butene in the flow. 50wt% or more, the flow rate of the raw material 101 is LHSV 0.20 ~ 5.00 hr^-One A method for producing secondary butyl alcohol, characterized in that

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