Method of fabricating diol containing bis-cycloaliphate

Abstract

A method is provided for fabricating a diol containing a bis-cycloaliphate. The diol is hydrogenated with hydrogen and a catalyst. Therein, the diol has a bis-aromatic. The catalyst comprises an active metal and a catalyst carrier. The active metal is a VIII-B-group transition element. The catalyst carrier is an oxide of IV-B-group element. Thus, the diol containing the bis-cycloaliphate is generated.

Claims

1. A method of fabricating a diol containing a bis-cycloaliphate, the method comprising: placing a catalyst comprising one or more active metal selected from a group consisting of nickel, platinum, palladium, ruthenium (Ru), and rhodium (Rh) and a catalyst carrier of an oxide of one or more of titanium, zirconium, or hafnium in a reactor; placing a diol solution comprising a diol selected from a group consisting of bisphenol A (BPA) and ethoxylated bisphenol A (BPAEO) where the BPAEO has a structure as follows: ##STR00006## and m+n=24 and a solvent with hydrogen in the reactor; and processing a reaction at 60 bar or less and at 40120 C. to obtain a product having a structure of ##STR00007## where m+n=2 to 4.

2. The method according to claim 1, wherein said solvent is selected from a group consisting of a monohydric alcohol and a combination of monohydric alcohols, said monohydric alcohol being selected from a group consisting of methanol, ethanol, propanol, isopropanol, isobutanol, cyclohexanol, and nonanol.

3. The method according to claim 1, wherein said active metal occupies 0.58 weight percent of said catalyst.

4. The method according to claim 1, wherein said reactor has a pressure of 150 bar.

5. The method according to claim 1, wherein said reaction has a temperature of 50100 degrees Celsius.

6. The method according to claim 1, wherein said reactor is selected from a group consisting of a batchwise reactor, a stir-tank reactor, a trickle-bed reactor, a bubble-column reactor, and a multi-tube reactor.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The present invention will be better understood from the following detailed description of the preferred embodiment according to the present invention, taken in conjunction with the accompanying drawings, in which

(2) FIG. 1 to FIG. 6 are the views showing results and conditions of hydrogenation with the diol containing the bis-aromatic.

DESCRIPTION OF THE PREFERRED EMBODIMENT

(3) The following description of the preferred embodiment is provided to understand the features and the structures of the present invention.

(4) Please refer to FIG. 1 to FIG. 6, which are views showing results and conditions of hydrogenation with the diol containing the bis-aromatic. As shown in the figures, the present invention is a method of fabricating a diol containing a bis-cycloaliphate, where the method processes hydrogenation with a diol containing a bis-aromatic in the presence of hydrogen and a catalyst. The diol is a bisphenol A (BPA) or an ethoxylated bisphenol A (BPAEO), where the BPAEO has a structure as follows:

(5) ##STR00002##
and m+n=24. Basically, the BPAEO uses the catalyst to obtain a product of a diol containing a bis-cycloaliphate through hydrogenation in the presence of hydrogen, where the product has a structure as follows:

(6) ##STR00003##
and m+n=24.

(7) At first, a catalyst is placed in a reactor. Then, a diol solution containing a bis-aromatic is pumped into the reactor accompanying with hydrogen fed in for hydrogenation. The reactor is a continuous reactor like a trickle-bed reactor, a stir-tank reactor, a bubble-column reactor, or a multi-tube reactor; or a non-continuous reactor like a batchwise reactor. The reactor has a reaction pressure of 160 bar while a preferred reaction pressure is 140 bar and a best reaction pressure is 120 bar, and a reaction temperature of 40120 degrees Celsius ( C.) while a preferred reaction temperature is 40100 C. and a best reaction temperature is 4080 C.

(8) The present invention processes the reaction under the condition of the existence of the catalyst. The catalyst is contained in the reactor. The catalyst comprises a catalyst carrier and an active metal. Therein, the catalyst carrier is an oxide of an element of IV-B group in the periodic table; the oxide of the element of IV-B group is an oxide of a metal or a combination of metals and the metal is titanium (Ti), zirconium (Zr), or hafnium (Ha); the active metal is a transition metal of VIII-B-group element in the periodic table, which is nickel (Ni), platinum (Pt), palladium (Pd), ruthenium (Ru), or rhodium (Rh); or is a combination of some of the above elements; and the active metal occupies 0.512 weight percent (wt %) of said catalyst while 0.510 wt % is preferred and 0.58 wt % is the best.

(9) The catalyst carrier is obtained by dissolving a IV-B-group metal salt into a solvent, and, then, an alkaline solution is gradually added in to adjust the pH value of the mixed solution to 812. The IV-B-group metal salt is zirconium oxychloride (ZrOCl.sub.2), zirconium oxynitrate (ZrO(NO.sub.3).sub.2), zirconyl hydroxynitrate (ZrO(OH)NO.sub.3), zirconium oxysulfate (ZrOSO.sub.4), titanium oxychloride (TiOCl.sub.2), or titanium oxynitrate (TiO(NO.sub.3).sub.2), or is a mixture of some of the above compounds. The alkaline solution is a solution of sodium hydroxide, potassium hydroxide, sodium carbonate, or ammonia solution; or a mixed solution of some of the above compounds.

(10) Then, the above solution is stayed still for 124 hours (hrs) under a room temperature of 25110 C. Then, the above solution is processed through filtration, water washing, and drying to form the catalyst carrier. In a state-of-use, a drying temperature is 100150 C., and a drying time is 1224 hrs.

(11) Then, a metal of Ruthenium is processed to be loaded on the catalyst carrier by using a precursor containing the metal of Ru like ruthenium chloride hydrate (RuCl.sub.3.nH.sub.2O), ruthenium trinitro-nitrite (Ru(NO.sub.3).sub.3.NO), or ruthenium oxide (RuO.sub.2). In a state-of-use, The precursor containing the metal of Ru is impregnated into the catalytic carrier through deposition precipitation or incipient wetness impregnation, where the impregnation is processed at a room temperature of 2560 C. for a time of 15 hrs, and the concentration range of Ru is 15 wt %.

(12) Then, drying and calcination are processed. In a state-of-use, a drying temperature is 100150 C., a drying time is 1224 hrs; a calcination temperature is 300550 C., and a calcination time is 418 hrs.

(13) Then, a hydrogenation reaction is followed as described below.

(14) The prepared catalyst is put into the reactor. The catalyst comprises the catalyst carrier of the oxide of the element of IV-B group and the active metal of the VIII-B group transition element contenting 15 wt %. The reactor is a continuous reactor like a trickle-bed reactor, a stir-tank reactor, a bubble-column reactor, or a multi-tube reactor; or a non-continuous reactor like a batchwise reactor.

(15) Then, a diol solution containing a bis-aromatic is put in the reactor and hydrogen is simultaneously fed into the reactor. The diol solution containing the bis-aromatic comprises a reactant (a diol containing the bis-aromatic) and a solvent. The reaction is processed in the presence of the solvent or a diluent, The choice of solvent or diluent needs to consider compatibility with the principal reactant to avoid phase separation or immiscibility, and not to involve in the reaction during hydrogenation; and, furthermore, the product itself obtained after the hydrogenation can also be used as the solvent or diluent. In a state-of-use, the solvent is a monohydric alcohol or a combination of monohydric alcohols, and the monohydric alcohol is methanol, ethanol, propanol, isopropanol, isobutanol, cyclohexanol, or nonanol. In a state-of-use, the diol solution containing the bis-aromatic has a concentration of 530 wt %.

(16) In a state-of-use, the reactor containing the catalyst, hydrogen, and the diol solution containing the bis-aromatic is heated up for hydrogenation to form a corresponding diol containing a bis-cycloaliphate. In a state-of-use, the temperature of the reaction is 50100 C. In another state-of-use, the temperature of the reaction is 5070 C. and the pressure of the reaction is 550 bar. In another state-of-use, the pressure of the reaction is 520 bar. The time of the reaction is appropriately adjusted according to the type of the reactor and the quality of the product. For a continuous reactor like a trickle-bed reactor or a multi-tube reactor, a space velocity must be set; and, for a stirred-tank reactor or a non-continuous batchwise reactor, the time of the reaction must be appropriately adjusted according to the quality of the product. After removing the solvent of the product obtained after hydrogenation, a desired hydrogenated product is obtained and the solvent is recycled.

(17) [Fabrication] Catalyst A

(18) 24.6 grams (g) of nitrate of zirconium oxide is dissolved in 200 milli-liters (mL) of deionized water; and, then, sodium carbonate or ammonia (or a mixture of both) is added for coprecipitation to be followed with a stay of 424 hrs. Then, the solution obtained after being stayed is filtered, washed, and dried. Then, after a process of high-temperature calcination at 600800 C., a catalyst carrier is obtained.

(19) 10 g of 2030-meshed particles of the catalyst carrier is obtained after crushing and sieving. Through incipent wetness impregnation, an appropriate amount of a solution of ruthenium chloride or ruthenium(III) nitrosyl nitrate is impregnated onto the catalyst carrier. Then, after a process of high-temperature calcination at 400 C., a catalyst (Catalyst A) containing 3 wt % of ruthenium is obtained.

(20) The present invention discloses a hydrogenation reaction with a catalyst comprising a catalyst carrier and an active metal along with a diol containing a bis-aromatic to be processed by using the diol containing the bis-aromatic as a reactant to obtain the following results under the following conditions:

(21) [State-of-Use 1]

(22) 2 mL of 2030-meshed Catalyst A is filled in the reactor for reduction at 250 C. in a hydrogen atmosphere, where, after cooling, isopropanol is used as a solvent to obtain a solution containing 10 wt % of BPA fed into the reactor by a feeding pump for hydrogenation. After the reaction, the products are collected for quantitative measurement. The conversion and selectivity are analyzed by gas chromatograph (GC), respectively. The operating conditions and the corresponding results are shown in FIG. 1

(23) [State-of-Use 2]

(24) 2 mL of 2030-meshed Catalyst A is filled in the reactor for reduction at 250 C. in a hydrogen atmosphere, where, after cooling, isopropanol is used as a solvent to obtain a solution containing 10 wt % of BPA fed into the reactor by a feeding pump for hydrogenation. After the reaction, the products are collected for quantitative measurement. The conversion and selectivity are analyzed by gas chromatograph (GC), respectively. The operating conditions and the corresponding results are shown in FIG. 2

(25) [State-of-Use 3]

(26) 2 mL of 2030-meshed Catalyst A is filled in the reactor for reduction at 250 C. in a hydrogen atmosphere, where, after cooling, isopropanol is used as a solvent to obtain a solution containing 15 wt % of BPA fed into the reactor by a feeding pump for hydrogenation. After the reaction, the products are collected for quantitative measurement. The conversion and selectivity are analyzed by gas chromatograph (GC), respectively. The operating conditions and the corresponding results are shown in FIG. 3.

(27) [State-of-Use 4]

(28) 2 mL of 2030-meshed Catalyst A is filled in the reactor for reduction at 250 C. in a hydrogen atmosphere, where, after cooling, isopropanol is used as a solvent to obtain a solution containing 15 wt % of BPA fed into the reactor by a feeding pump for hydrogenation. After the reaction, the products are collected for quantitative measurement. The conversion and selectivity are analyzed by gas chromatograph (GC), respectively. The operating conditions and the corresponding results are shown in FIG. 4

(29) [State-of-Use 5]

(30) 7 mL of 2030-meshed Catalyst A is filled in the reactor for reduction at 250 C. in a hydrogen atmosphere, After cooling, isopropanol is obtained as a solvent to obtain a BPAEO, which has a structure as follows (where m+n=2 has a portion of 85%; m+n=3, 12%; and m+n=4, 3%):

(31) ##STR00004##
A solution containing 10 wt % of the BPAEO is fed into the reactor by a feeding pump for hydrogenation. After the reaction, the products are collected for quantitative measurement. The conversion and selectivity are analyzed by liquid chromatography-UV (LC-UV) while product selectivity is calculated with OH value. The operating conditions and the corresponding results are shown in FIG. 5:
[State-of-Use 6]

(32) 7 mL of 2030-meshed Catalyst A is filled in the reactor for reduction at 250 C. in a hydrogen atmosphere, After cooling, isopropanol is obtained as a solvent to obtain a BPAEO4, whose structure is shown as follows (where m+n=4):

(33) ##STR00005##
A solution containing 10 wt % of the BPAEO4 is fed into the reactor by a feeding pump for hydrogenation. After the reaction, the products are collected for quantitative measurement. The conversion and selectivity are analyzed by liquid chromatography-UV (LC-UV) while product selectivity is calculated with OH value. The operating conditions and the corresponding results are shown in FIG. 6:

(34) Thus, the present invention provides a method hydrogenating a diol containing a bis-aromatic, where a corresponding diol containing a bis-cycloaliphate is fabricated at a low temperatures under a low pressure. In the mean time, the present invention has the following advantages: the temperature for reaction is only 50100 C.; the pressure is 150 bar, the conversion reaches more than 99.8%; and, at the same time, the product selectivity reaches more than 98%, while by-product formation is limited and the cost of separation and purification that follows is reduced to further improve overall economic efficiency.

(35) To sum up, the present invention is a method of fabricating a diol containing a bis-cycloaliphate, where a method is provided to generate a corresponding diol containing a bis-cycloaliphate through hydrogenation with a diol solution containing a bis-aromatic; the hydrogenation is processed in an environment of a low pressure (<50 bar) and a low temperature (<100 C.), the conversion reaches more than 99.8% and the product selectivity reaches more than 98%; and, thus, by-product formation is limited and the cost of separation and purification that follows is reduced to improve overall economic efficiency.

(36) The preferred embodiment herein disclosed is not intended to unnecessarily limit the scope of the invention. Therefore, simple modifications or variations belonging to the equivalent of the scope of the claims and the instructions disclosed herein for a patent are all within the scope of the present invention.