KR101896799B1

KR101896799B1 - Method of recovering and converting rhenium oxide in dibutyl muconate manufacturing process

Info

Publication number: KR101896799B1
Application number: KR1020160161890A
Authority: KR
Inventors: 정하은; 윤나경; 홍채환; 전성완
Original assignee: 현대자동차주식회사
Priority date: 2016-11-30
Filing date: 2016-11-30
Publication date: 2018-09-07
Also published as: KR20180062042A

Abstract

The present invention relates to a method for recovering and converting rhenium oxide used in a process for producing dibutyl muconate, which is an intermediate for the production of adipic acid, and more particularly, to a process for recovering and converting rhenium oxide using mucic acid dibutyl ester (DODH) reaction by refluxing the reaction solution containing dibutyl ester, a rhenium oxide catalyst and an acid catalyst at a predetermined temperature for a predetermined period of time to perform a deoxydehydration (DODH) reaction, Collecting rhenium oxide as a precipitate precipitated by agitation force or centrifugal force by mixing a non-polar hydrocarbon solvent in a reaction solvent, drying the recovered rhenium oxide in the form of particles, adding hydrogen peroxide water thereto, And rhenic acid, followed by evaporation of the aqueous hydrogen peroxide to obtain perrhenic acid It said, provides a possible effectively to recover the rhenium oxide catalyst used, by using the hydrogen peroxide solution to the recovered rhenium oxide converted to the rhenium acid method.

Description

[0001] METHOD OF RECOVERING AND CONVERTING RHENIUM OXIDE IN DIBUTYL MUCONATE MANUFACTURING PROCESS [0002]

The present invention relates to a method for recovering rhenium oxide used in a process for producing dibutyl muconate, which is an intermediate for the production of adipic acid, and more particularly, to a method for recovering rhenium oxide as a catalyst in a process for producing dibutyl muconate To a process for recovering and converting rhenium oxide in a dibutyl muconate production process for selectively recovering rhenium oxide from a reaction solution containing it and converting it into perrhenic acid (HReO ₄ ) form.

In the automotive parts and materials industry, which is closely related to petroleum resources, the environmental issues and consumer consciousness have been improved. As a result, interest in using alternative raw materials in response to depletion of petroleum resources and application of biomaterials Is increasing. Recent reports from the European Institute of Biotechnology and the European Polysaccharide Network of Excellence (EPNOE) at the Utrecht University in the Netherlands predict that the use of biomaterials will surge in the next decade, Is expected to be marketable enough to replace up to 90% of petroleum extraction materials.

Nylon 66, which is a typical nylon material among various nylon materials, is one of the parts that require high temperature characteristics among automobile parts due to heat resistance, abrasion resistance, and chemical resistance. .

This nylon 66 is produced by dehydration polymerization of hexamethylenediamine and adipic acid. The adipic acid used as a monomer is generally derived from crude oil and is obtained from benzene obtained from the crude oil refining process by using cyclohexanone It is produced through a chemical synthesis process using an intermediate. However, this manufacturing process poses problems such as unstable oil prices, the use of benzene as a toxic substance, and the production of environmental pollution byproducts including nitrogen oxides (NOx), and thus it is necessary to replace with environmentally friendly bioprocessing technology. 66, it is important to synthesize adipic acid, which is a monomer of nylon 66, from biomass.

Accordingly, the inventors of the present invention have developed a method for producing dibutyl muconate as an intermediate for the production of adipic acid from biomass such as marine resources, which is an eco-friendly material, by using galactose derived from marine resources The mucic acid was prepared by the reaction of the prepared mucic acid with an ester and then the mucic acid dibutylester was prepared by the esterification reaction. Then, deoxydihydration (deoxydehydration) DODH) reaction to produce diabutyl muconate.

However, in the production process of dibutyl muconate as described above, rhenium oxide is used as one of the catalysts that is put in order to perform the dioxydihydration (DODH) reaction efficiently. This rhenium (Re) Or recovered as a by-product in the molybdenum smelting process. Since it is not present as a sole mineral resource, it is very important to secure expensive rhenium resources, and thus it is necessary to recover the used rhenium oxide catalyst.

Korean Registered Patent No. 10-1600334 (Feb.

In view of the above, the present invention resides in a method for recovering rhenium oxide used as a catalyst in a process for producing dibutyl muconate, which is an intermediate for the production of adipic acid, by a precipitation method using a hydrocarbon solvent, It is an object of the present invention to provide a method for recovering and converting rhenium oxide, which converts a material into perrhenic acid (HReO ₄ ), which is industrially useful by applying hydrogen peroxide (H ₂ O ₂ ) to the recovered rhenium oxide particles .

In one aspect, the present invention relates to a process for recovering and converting rhenium oxide in a process for producing dibutyl muconate comprising the steps of:

Specifically, a reaction solution in which mucic acid dibutyl ester, a rhenium oxide catalyst and an acid catalyst are added to a reaction solvent is refluxed and stirred at a constant temperature for a certain period of time to perform deoxydehydration (DODH) reaction After completion of the deoxydehydration (DODH) reaction, only the precipitate separated by agitation or centrifugal force and precipitated in the lower part is mixed with a non-polar hydrocarbon solvent, thereby obtaining a granular rhenium oxide (S120), and recovering the recovered granular rhenium oxide. The recovered granular rhenium oxide is converted into perrhenic acid by adding hydrogen peroxide solution (H ₂ O ₂ ) for a predetermined period of time, To obtain perrhenic acid (S130).

The step of recovering the rhenium oxide (S120) may include the nonpolar hydrocarbon solvent at a ratio of 15 to 60 mL with respect to the entire sediment, and preferably about 30 mL of the nonpolar hydrocarbon solvent may be added. The amount of the non-polar hydrocarbon solvent can be changed within a range in which the rhenium oxide can be recovered.

The step (S130) of obtaining the perrhenic acid may include drying the non-polar hydrocarbon solvent by evaporating the non-polar hydrocarbon solvent from the recovered granular rhenium oxide, adding 2 to 7 times the aqueous hydrogen peroxide to the dried rhenium oxide volume ratio, Can be converted to perrhenic acid.

In addition, since the recovered rhenium oxide in the form of particles is dispersed in a nonpolar hydrocarbon solvent, the nonpolar hydrocarbon solvent is evaporated from the recovered rhenium oxide, dried, and then the hydrogen peroxide solution 2 to 7 times the volume of the dried rhenium oxide The rhenium oxide can be converted into perrhenic acid by mixing and mixing.

The concentration of hydrogen peroxide used herein may be 30 to 40% (v / v), and it is preferable to use 35% (v / v) aqueous hydrogen peroxide. This is the hydrogen peroxide water mixed with water and hydrogen peroxide in the ratio of 70 ~ 60: 30 ~ 40 volume.

If the concentration of hydrogen peroxide is out of the above range, the reaction between the recovered rhenium oxide and hydrogen peroxide (H ₂ O ₂ ) does not occur uniformly, so that the transition from the rhenium oxide to the perrhenic acid is not properly performed, The production rate of perrhenic acid is low.

Then, hydrogen peroxide solution is added to the recovered and dried rhenium oxide, and the air in the solution is subjected to a gas bubbling treatment for about 5 to 10 days to convert the rhenium oxide into perrhenic acid, The resulting liquid material is concentrated to obtain a final product, perrhenic acid.

The non-polar hydrocarbon solvent may be any one selected from the group consisting of aromatic hydrocarbons and aliphatic hydrocarbons, but is not limited thereto. Any non-polar hydrocarbon solvent may be used as the non-polar hydrocarbon solvent in the related art.

For example, the non-polar hydrocarbon solvent may be at least one selected from the group consisting of hexane, heptane, octane, benzene, toluene and xylene.

The rhenium oxide catalyst used in the step of performing the deoxydehydration (DODH) reaction (S110) may be selected from the group consisting of rhenium (VII) (Re ₂ O ₇ ) and L _x ReO _y Amine, halogen, phenylsilyl, phosphine, alkoxy having 1 to 10 carbon atoms, alkyl having 1 to 10 carbon atoms or COOR wherein R is a carbon number of 1 And x and y are each independently an integer of 0 to 7 and x + y = 7), and preferably at least one selected from the group consisting of rhenium (VII) ( Re ₂ O ₇ ) can be used.

The acid catalyst may be selected from the group consisting of para-toluene sulfonic acid, methyl sulfonic acid, boron trifluoride, aluminum chloride, and sulfuric acid. And para-toluene sulfonic acid can be preferably used. Of these, para-toluene sulfonic acid may be used.

The reaction solvent may be any one selected from the group consisting of heptanol and butanol, and preferably butanol may be used.

Meanwhile, in the step of performing the deoxydehydration (DODH) reaction, the reaction solution is subjected to a deoxydehydration (DODH) reaction by reflux stirring at 100 to 200 ° C for 12 to 72 hours .

Various types of catalysts containing metal oxides are widely used as core materials in all fields such as the automobile industry. Especially, as the rapid growth of the automobile industry and the enforcement of environmental regulations are strengthened, there is a need for a technology for the recycling and the recycling of spent catalysts in which the functions thereof are discarded. These waste catalysts contain various metals as precious metals and thus have a very high recycling value.

Accordingly, the present invention relates to a technology for recycling a noble metal catalyst. According to the method for recovering and converting rhenium oxide in the process for producing dibutyl muconate according to the present invention as described above, deoxidation (deoxydehydration) In the process for producing dibutyl muconate in the dibutyl ester, the rhenium oxide introduced into the noble metal catalyst is recovered again by the precipitation method and converted into perrhenic acid (HReO ₄ ) form using hydrogen peroxide, And rhenic acid can be obtained.

Since ammonium perrhenate can be produced from the finally obtained perrhenic acid, and ammonium perrhenate is a valuable product having a high added-value that can be traded as a valuable product, it is possible to produce perrhenic acid Which has a large industrial ripple effect.

1 is a flowchart schematically showing a method for recovering and converting rhenium oxide in a process for producing dibutyl muconate according to an embodiment of the present invention.
Figure 2 shows a sequence of reaction formulas for preparing dibutyl muconate according to one embodiment of the present invention.
Figure 3 is a photograph of the finally obtained perrhenic acid material according to one embodiment of the present invention.

Hereinafter, the method for recovering and converting rhenium oxide in the process for producing dibutyl muconate according to the present invention will be described in detail with reference to the accompanying drawings. As an example, And may be implemented in different forms, and thus are not limited to those described herein.

It is to be understood that the terms such as " comprises " or " adding ", as used herein, are not necessarily to be construed as necessarily including the various elements or steps described in the specification, Some steps may not be included and should be construed as further including additional components or steps.

In addition, the process conditions such as the number of repetitions, the temperature and the time of each step to be described are not particularly limited as long as they do not deviate from the object of the present invention.

FIG. 1 shows a process for recovering and converting rhenium oxide in a process for producing dibutyl muconate according to the present invention. As shown in FIG. 1, a step (S110) of performing a deoxydehydration (DODH) A step S120 of collecting rhenium oxide in the form of particles by mixing a nonpolar hydrocarbon solvent in the reaction solution, and a step S130 of converting the rhenium oxide into perrhenic acid by adding hydrogen peroxide to the recovered rhenium oxide, .

The step of performing the dioxidization reaction (S110) comprises the steps of preparing the dibutyl muconate of the present invention by adding mucic acid dibutylester, rhenium oxide catalyst and acid catalyst to the reaction solvent, Followed by hydration reaction to produce dibutyl muconate.

Referring to FIG. 2, the step of performing the dioxydihydration reaction of the present invention (S110) comprises reacting a micic acid of formula (1) derived from galactose derived from marine resources with butanol To prepare mucic acid dibutyl ester of formula (2). Then, deoxydehydration (DODH) reaction is carried out by adding mucic acid dibutylester, a rhenium oxide catalyst and an acid catalyst prepared in a reaction solvent and refluxing the mixture at a constant temperature for a certain period of time, Butyl muconate. &Lt; / RTI >

At this time, the reaction solvent may be any one selected from the group consisting of heptanol and butanol. The rhenium oxide catalyst may be selected from the group consisting of rhenium (VII) (Re ₂ O ₇ ) as shown in Formula 4 below and para-toluene sulfonic acid (p-TsOH) Can be used.

In the dioxidation (DODH) reaction step (S110), reflux stirring may be performed at a reaction temperature of 100 to 200 ° C for 12 to 72 hours, preferably at 116 ° C for 24 hours.

Here, if the reaction temperature is lower than 100 ° C or higher than 200 ° C, the reaction yield is decreased due to an increase in by-products, and the energy consumption is too high at a high reaction temperature.

If the reaction time is less than 12 hours, the production yield of dibutyl muconate decreases because the deoxydehydration (DODH) reaction is not performed properly. If the reaction time exceeds 72 hours, the yield of dibutyl muconate is lowered And only the whole process time is increased, so it is preferable to perform the process within the range of the temperature and the process time.

The step of recovering the rhenium oxide (S120) is a step of recovering the rhenium oxide, which is the catalyst used in the reaction solution in which the dioxidation (DODH) reaction has been carried out, by the solvent extraction method. Specifically, the rhenium (VII) (Re ₂ O ₇ ) added as a catalyst in the dioxydihydration (DODH) reaction step (S110) is reacted with the rhenium oxide (ReOx) in the oxidized state after participating in the dioxydihydration (DODH) ) Is mixed with a non-polar hydrocarbon solvent to reduce the overall polarity of the reaction solution and recover the solid state rhenium oxide (ReOx) by precipitation using centrifugal force or centrifugal force.

Here, rhenium oxide (ReOx) is either of the group consisting of nitric rhenium (ReO), rhenium dioxide (ReO _2), rhenium trioxide (ReO _3), and rhenium peroxide (Perrhenate, ReO _4).

In the step of recovering the rhenium oxide (S120), when the dioxidation (DODH) reaction is terminated, the reaction solution is separated by a precipitation method such as centrifugation and a substance having a relatively large specific gravity. Hexane or heptane as a nonpolar hydrocarbon solvent is added to the separated bottom precipitate, the nonpolar hydrocarbon solvent is completely evaporated by using a rotary evaporator, and then the rhenium oxide (ReOx) in the form of particles is recovered.

Then, the step of converting to perrhenic acid (S130) is performed by adding the recovered rhenium oxide (ReOx) in the step of recovering the rhenium oxide (S120) into hydrogen peroxide (H ₂ O ₂ ) The air in the solution is converted into perrhenic acid by rubbing bubbling with rhenium oxide, and the obtained liquid material is then concentrated using a rotary evaporator to obtain O ₃ Re Is a step of obtaining perrhenic acid having a morphology structure of -O-ReO ₃ (H ₂ O) ₂ .

[Chemical Formula 5]

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are for illustrating the present invention, and the present invention is not limited by the following examples, comparative examples and experimental examples, and can be variously modified and changed.

In Example 1, 0.5 mmol (162 mg) of mucic acid dibutyl ester, 5 mol% (14 mg) of rhenium (VII) (Re ₂ O ₇ ), para-toluenesulfonic acid (5 mg) (6 mg) was added to a 30 mL butanol solution, and the mixture was refluxed and stirred at 116 ° C for 24 hours in a dean-stark method to conduct deoxydehydration (DODH) do.

After the completion of the reaction, the reaction solution is centrifuged to separate the precipitate having a relatively large specific gravity into a solution layer having a relatively large specific gravity, and 30 mL of hexane as a nonpolar hydrocarbon solvent is added to the separated precipitate. Thereafter, hexane is completely evaporated using a rotary evaporator, and then rhenium oxide (ReOx) in the form of particles is recovered.

Thereafter, 35% (v / v) hydrogen peroxide solution (water and hydrogen peroxide volume ratio 65:35) was mixed with the rhenium oxide (ReOx) in an amount twice the amount of the recovered rhenium oxide (ReOx) The liquid material obtained after bubbling for about 5 days to 10 days while air is introduced is evaporated by using a rotary evaporator to recover the final object.

Example 2 was carried out in the same manner as in Example 1 except that the amount of 35% (v / v) hydrogen peroxide (water and hydrogen peroxide volume ratio 65:35) was 7 times the amount of rhenium oxide (ReOx) .

Example 3 was carried out in the same manner as in Example 1, except that 30 mL of heptane was added as the non-polar hydrocarbon solvent.

Example 4 was prepared by adding 30 mL of heptane as a nonpolar hydrocarbon solvent and adding 7 times the amount of 35% (v / v) hydrogen peroxide (water and hydrogen peroxide volume ratio 65:35) to rhenium oxide (ReOx) The same procedure as in Example 1 was carried out.

Comparative Example 1 and Comparative Example 2 were the same as Example 1, except that in Comparative Example 1, 35% (v / v) aqueous hydrogen peroxide solution was added to the precipitate in the absence of a non-polar hydrocarbon input to the precipitate separated by centrifugation (Water and hydrogen peroxide volume ratio of 65:35) was added in an amount of twice the volume of the precipitate. In Comparative Example 2, the amount of hydrogen peroxide solution (water and hydrogen peroxide volume ratio 65:35) of 35% (v / v) Was added in an amount of 7 times the volume of the precipitate, and the conversion of the rhenium oxide was carried out in the same manner as in Example 1.

Comparative Example 3 and Comparative Example 4 were carried out in the same manner as in Example 1 except that 30 mL of hexane was added to the separated precipitate as a nonpolar hydrocarbon solvent to recover rhenium oxide (ReOx), followed by the addition of water instead of hydrogen peroxide In Comparative Example 3, twice as much water as rhenium oxide (ReOx) was added, and in Comparative Example 4, 7 times as much water as rhenium oxide (ReOx) was added.

Table 1 below shows the results of confirming whether or not a perrhenic acid in a solid state is obtained in a reaction solution in which a dioxydihydration (DODH) reaction has been performed through Examples 1 to 4 and Comparative Examples 1 to 4 .

Here, "and whether the rhenium acid production" is in the solid state, as shown in that after the completion of the reaction means obtained if the solid form of the acid and the rhenium, and the rhenium acid 3 _{O 3 ReO-ReO 3 (H} 2 O) ₂ , and has a characteristic of yellowing at room temperature. Therefore, when the material obtained at room temperature is recovered in the form of perrhenic acid in the form of solid, it is indicated by "O", and when it is not recovered because of the production of rhenic acid, it is indicated by "X".

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) 162 mg 162 mg 162 mg 162 mg 162 mg 162 mg 162 mg 162 mg (B) 14 mg 14 mg 14 mg 14 mg 14 mg 14 mg 14 mg 14 mg (C) 6 mg 6 mg 6 mg 6 mg 6 mg 6 mg 6 mg 6 mg (D) Hexane
process Hexane
process Heptane
process Heptane
process process
none process
none Hexane
process Hexane
process (E) Volume ratio
Twice Volume ratio
7 times Volume ratio
Twice Volume ratio
7 times Volume ratio
Twice Volume ratio
7 times - - (F) - - - - - - Volume ratio
Twice Volume ratio
7 times Reaction temperature 116 ° C 117 ℃ 116 ° C 116 ° C 116 ° C 117 ℃ 116 ° C 116 ° C (G) ○ ○ ○ ○ X X X X (A): [Mucic acid dibutyl ester (manufactured by Hyundai Motor Company)] Amount
(B): [Re ₂ O ₇ catalyst (Alfa Aesar, UK)]
(C): [para-toluenesulfonic acid (Sigma Aldrich, USA)] Amount
(D): Treatment of the precipitate with hydrocarbons
(E): hydrogen peroxide dosage for rhenium oxide in recovered particle form
(F): Water input to rhenium oxide in the recovered particle form
(G): presence or absence of rhenium acid

As shown in Table 1, when the non-polar hydrocarbon solvent was not used as in Comparative Examples 1 and 2, the rhenium oxide (ReOx) used as the catalyst could not be recovered. If the hydrogen peroxide solution was not treated as in Comparative Examples 3 and 4, , It was confirmed that rhenium oxide can not be called as perrhenic acid and rhenium acid can not be produced.

Therefore, the precipitate recovered in the reaction solution in which the dioxydihydration (DODH) reaction was carried out as in Examples 1 to 4 was treated with a non-polar hydrocarbon solvent and then treated with 35% aqueous hydrogen peroxide to remove the rhenium oxide ReOx) into an industrially useful and rhenium acid.

As described above, the rhenium oxide recovery and conversion method in the dibutyl muconate production process according to the present embodiment is a process for producing dibutyl muconate (intermediate product of adipic acid) from biomass through deoxydehydration (DODH) Method, the rhenium oxide is recovered as a nonpolar hydrocarbon solvent, and hydrogen peroxide is recovered from the recovered rhenium oxide, thereby obtaining a highly pure perrhenic acid easily and efficiently.

Claims

Performing a deoxydehydration (DODH) reaction by stirring a reaction solution containing mucic acid dibutyl ester, a rhenium oxide catalyst, and an acid catalyst in a reaction solvent at a constant temperature for a certain period of time under reflux;
Recovering the particles of rhenium oxide by adding a non-polar hydrocarbon solvent to the precipitate which is separated from the reaction solvent by centrifugal force or centrifugal force after the deoxydehydration (DODH) reaction is completed; And
The non-polar hydrocarbon solvent is evaporated from the recovered granular rhenium oxide, and then hydrogen peroxide solution (H ₂ O ₂ ) 2 to 7 times the volume of the dried rhenium oxide is added, and air in the solution is subjected to gas bubbling treatment And converting the rhenium oxide to perrhenic acid and then evaporating the hydrogen peroxide water to obtain perrhenic acid. The process for producing dibutyl muconate according to claim 1, Oxide recovery and conversion method.

delete

The method according to claim 1,
Wherein said gas bubbling treatment is performed for 5 to 10 days. &Lt; Desc / Clms Page number 20 >

The method according to claim 1,
Wherein the hydrogen peroxide solution has a concentration of 30-40% (v / v). &Lt; RTI ID = 0.0 > 11. < / RTI >

The method according to claim 1,
Wherein the non-polar hydrocarbon solvent is at least one selected from the group consisting of hexane, heptane, octane, benzene, toluene and xylene.

The method according to claim 1,
Wherein the rhenium oxide catalyst is selected from the group consisting of rhenium (VII) (Re ₂ O ₇ ) and L _x ReO _{y wherein} L = amine, halogen, phenylsilyl, phosphine, alkoxy of 1 to 10 carbons, COOR (wherein R is alkyl having 1 to 10 carbon atoms), x and y are each independently an integer of 0 to 7, and x + y = 7), characterized in that dibutyl Method for recovery and conversion of rhenium oxide in a muconate manufacturing process.

The method according to claim 1,
The acid catalyst may be selected from the group consisting of para-toluene sulfonic acid, methyl sulfonic acid, boron trifluoride, aluminum chloride, and sulfuric acid. Lt; RTI ID = 0.0 > (II) < / RTI > in the process for preparing dibutyl muconate.

The method according to claim 1,
Wherein the reaction solvent is at least one selected from the group consisting of heptanol and butanol, and the method for recovering and converting rhenium oxide in the process for producing dibutyl muconate.

The method according to claim 1,
Wherein the step of performing the deoxydehydration (DODH) reaction is performed at a temperature of 100-200 < 0 > C.

The method according to claim 1,
Wherein the step of performing the deoxydehydration (DODH) reaction is performed for 12 to 72 hours. &Lt; RTI ID = 0.0 > 11. < / RTI >