TW536532B - Process for the production of 1,3-propanediol by hydrogenating 3-hydroxypropionaldehyde - Google Patents

Abstract

A process for the production of 1,3-propanediol by heterogeneously catalyzed hydrogenation of 3-hydroxypropionaldehyde in an aqueous solution at 30 DEG to 180 DEG C, a hydrogen pressure of 5 to 300 bar and a pH value of 2.5 to 7.0, wherein ruthenium on an oxide support is used as the catalyst.

Description

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S V. Description of the invention (1) January field (please read the notes on the back before filling out this page). This post is about a method for preparing propylene glycol by hydrogenating 3-hydroxypropanal. As a background, 1,3-propanediol is used as a monomer unit of polyesters and polyurethanes and is used as a starting material to polymerize cyclic compounds. A number of different methods are known to prepare 1,3-propanediol, starting from a structural unit or from any of the Cs structural units, e.g., propionaldehyde. When using propionaldehyde, this compound is first hydrated in the presence of an acid catalyst, where 3-hydroxypropionaldehyde (3-hydroxypropionaldehyde) is formed. When unreacted acrolein is separated, the water-containing reaction mixture formed during hydration still contains, in addition to 85% of 3-hydroxypropanal, about 80%. Zinheptanediol and other organic ingredients in a smaller proportion by weight. This reaction mixture is hydrogenated in the presence of a hydrogenation catalyst to prepare 1,3-propanediol. According to Hatch et al. US Pat. No. 2,434,110, catalysts suitable for hydrogenating 3-hydroxypropanal are those containing one or more metals having hydrogenation, such as Fe, Co, Cu, Ag, Mo, V, Zr, Ti, Th, and Ta. Copper / chrome oxides of Raney nickel and Adkins can also be used as catalysts. According to the intermediate standards of the Ministry of Consumer Affairs and printed by UJT-Consumer Cooperatives, according to Arntz et al. DE-PS 39 26 136, this catalyst can be in the form of a suspension or a support or a fixed bed catalyst; a homogeneous catalyst can also be used catalyst. The suspended catalysts mentioned are Raney nickel (which can be doped with other different catalytically active metals) and starting activated carbon. Catalytic hydrogenation in the prior art is accompanied by a small amount of catalytically active elements. This paper size is applicable to Chinese national standard ((, NS) Λ4 specifications (210X29 * 7 Gongchu) 536532 A7 B7. V. Description of the invention (2 The risk that the element will be discharged into the product stream as a collapsible compound makes it necessary to use further steps to separate the pollutants it generates. This is especially observed when using suspended catalysts such as Raney nickel. Hydrogenation The method of action may be characterized by transformation, selectivity, and reachable space-time production of I. Transformation means that the π precipitate (in this case, hydroxypropionaldehyde) is hydrogenated to convert it to Έ: the mole number of the substance. Conversion is usually stated as introduction Percentage of moles of the precipitates: ΗΑΡΑι conversion (% ΗΡΑ was converted erbium χ 100 ΑΡΑ supply relative mol number, the selectivity of the hydrogenation method is to measure its conversion into the desired product conversion Molar number of the precipitate: Molar number of the selective alcohol X 100 Molar number and hourly yield of HPA Another important characteristic of the continuous hydrogenation method, state its per unit time and The amount of product can be obtained by volume. It is important when hydrogenating 3-¾-propionaldehyde into propylene glycol on a large industrial scale. Consider the economic viability of its hydrogenation method and its product's shellfish, conversion and selectivity. It should be as close as possible. Its hydrogenation and rosalization allow propylene glycol to be separated from the water, as are the remaining 3-monopropionaldehyde and the second product contained in the product stream. However, the knife for this distillation Ionization is very difficult to separate the remaining 3-hydroxypropionaldehyde from the second product 'and the stagnation point of acetic acid and propylene glycol due to the reaction between the remaining 3-hydroxypropanal and 1,3-propanediol The points are very close and even impossible. Therefore, the lower the conversion and the selectivity, the worse the quality of the product can be obtained. -5 Please 'first. Clothes page

I The size of the paper is similar, Guanjia County r ^ y ^ i: (210X 297 mm) A7 B7 · W6532 V. Description of the invention (3) In order to produce 13-propanediol economically, It is also important that hydrogenation exhibits high activity. For the production of propylene glycol, the goal should therefore be to find a method that must use the least possible amount of catalyst; for example, it should be possible to achieve the maximum possible conversion of 3-hydroxypropanal to 1,3-propanediol with a small volume of catalyst. The conversion, selectivity, and space-time yield are affected by the characteristics of the catalyst and the conditions of hydrogenation, such as the reaction temperature, hydrogen pressure, and duration of the hydrogenation or the liquid hourly space velocity in the case of continuous hydrogenation (liquid hourly space velocity) (LHSV) 〇 When hydrogenated 3-hydroxypropanal becomes 丨, propylene glycol, it should be noted that its main reaction is linearly dependent on hydrogen pressure and time (space rate in continuous processes), and its reaction temperature is almost no influences. In contrast, the formation temperature of the second product is exponentially dependent. Under the same other conditions, it was observed that the formation of the second product was doubled every 0 ° C, which correspondingly reduced the selectivity. Increasing hydrogen pressure has a relatively positive effect on selectivity, although the positive effect of pressure on selectivity is less significant than the negative effect of increasing temperature, because hydrogen pressure only linearly increases its main reaction rate, and An increase in temperature exponentially increases the speed of the second-stage reaction. An important quality specification for catalysts used in hydrogenation processes is their operating life. A good catalyst should have a fixed conversion and selectivity when weathered 3-¾-propane becomes ι, 3-propanediol during its life span. Known prior hydrogenation techniques, especially those based on nickel catalysts, have shown inappropriate long-term stability in this regard. It is accompanied by the frequent replacement of the entire catalyst package, which is also known to be disposed of. This paper size is applicable to the Chinese national standard Hua ((He 184 specifications (210X 297))--(Please read first Please note on the back of this page and fill in this page again.) The standard of the Ministry of Economic Affairs and the U <Printed by the Ministry of Economic Affairs and Cooperatives t The central standard of the Ministry of Economic Affairs ^ mT printed by Hezhu Co., Ltd. 536532 A7 _____ B7— __ 5. Description of the invention ( 4) and deal with the problem of nickel-containing compounds. From 1991 Engelhard brochure Exceptional Technologies, it was learned that in the presence of ruthenium / Escalit, hydrogenated aliphatic carbonyl compounds were converted into corresponding alcohols. . From Degussa's authoritative precious metal catalyst brochure (Degussa brochure

Power Precious Metal Catalysts (published 6/95) is known to hydrogenate aliphatic aldehydes to alcohols when a ruthenium catalyst on a support is stored. In this case, alumina is used as its support. Yaz (August 1: 1 ^ 2) et al. European Patent No. £?-; 8 535 565 discloses a kind of i,% propanediol produced by heterogeneously catalyzed hydrogenation of 3-hydroxypropanal in an aqueous solution. The production method, wherein the catalyst on the carrier comprises dioxin, wherein the finely divided platinum is present in an amount of from 0.5 to 5% by weight relative to the carrier. This method is disadvantageous in that rather high hydrogenation pressures are necessary 'to provide a substantially constant and high degree of conversion over the life of the catalyst. In addition, due to its low activity, a considerable amount of platinum catalyst is needed to achieve a sufficiently high amount of conversion. Due to the high price of platinum, it correspondingly increases the cost of the hydrogenation method. Inventing Fej Water The object of the present invention is to provide a method of hydrogenation without the disadvantages described in the prior art methods. The present invention provides a method for preparing 'propanediol' from 3-hydroxypropionic acid by hydrogenation of heterogeneous catalysis, which is in a water / hydration solution at a temperature of 30 ° C to 180 ° C. The hydrogen pressure is 5 It is carried out at a temperature of 300 bar and a pH of 2.5 to 7.0. The characteristic is that the catalyst used is a carrier composed of an oxide phase. The standard lambda scale and the national standard of Sichuan (210 × 297 mm) ( Read the precautions on the back before filling this page)-Binding-Book 536532 A7 B7, V. Description of the invention (catalysts on 5 'better oxides. Phases can resist acid media, (please read first, read the back Note: Please fill in this page again): Where, the preferred amount is relative to the oxidized phase (M to 2. wt%. Suitable: The preferred oxidized phase as a carrier material includes and _ .; The method of the present invention is The catalyst enables the conversion of 2- to 4-by-door, 3-to-propyl-propene, and 2-to-y-butanyl. It can maintain this highly fixed transformation even at low hydrogen pressure, such as below 90 bar. The catalyst on the other side, such as 〇2, is unsatisfactory under low hydrogen pressure. DETAILED DESCRIPTION OF THE INVENTION The method of the present invention includes the presence of a ruthenium catalyst on a support, which is subjected to hydrogenation to form ^, wind, and 3-propene, wherein the support includes an oxidized phase. Preferably, _ is It is present in the carrier in a finely dispersed state in an amount of 0.1 to 20% by weight relative to the oxidized phase. Examples of oxide materials suitable for use as the oxidized phase include dioxide &amp;, Si〇2, Al203 and / Or the mixed oxides, such as aluminum silicate. Other suitable oxidizing phases include MgO, pyrolites, and / or cones of cones. These materials are described, for example, in CaWyM Supports and Supported Catalysts ) 'Author M — ，% Printed by the Ministry of Consumer Affairs and printed by the UT Consumer Cooperative

Verlag, BUUenvorthS 1987, Chapters 2 and 3. It is also possible to use a mixture of oxidized phases as the carrier material. It can resist the oxidizing phase of the acidic medium and is preferred. These oxidized phases include substances selected from the group consisting of titanium dioxide, SiO2, and / or mixed oxides thereof, such as aluminum silicate. Zeolites and / or zirconia can also resist acidic media. Alumina and magnesia have lower acid resistance. -8- This paper size applies Chinese National Standard (rNS) Λ4 specification (210X 297 Gongchu) 536532 A7 V. Description of the invention (6)-In the preferred embodiment of the present invention, titanium and / or silicon oxide and Qin Mixed oxides of silicon, silicon and aluminum are used as the oxidation phase. (Please read and read the notes on the reverse side before filling out this page) The titanium dioxide used can be pyrolyzed titanium dioxide, especially obtained by hydrolysis with a fire drum. The pyrolyzed titanium dioxide used here can, for example, be obtained by flame hydrolysis of tetra-titanium oxide and has a high BET surface area of 40 to 60 m2 / g and a total pore volume of 0.25 to 0.75 ml / g, with an average major particle size 20 nm, density is 3.7 g / cm3, χ-light structure is 20 to 40% rutile and 80 to 60% anatase, and it is crushed by less than 0.5% by weight of dioxide and oxide And iron oxide pollution. Pyrolytic titanium dioxide, such as the substance P25 mentioned by Degussa, is particularly suitable as a carrier for catalytically active ingredients and has an average bet specific surface area (measured according to DIN 6613 1) of an average of 50 m2 / g. The oxide can be modeled, for example, in the form of small spheres, granules, or extruded using methods known in the art, such as those described in U.S. Patent No. 5,364,984 to Arntz et al. The coating of the oxidized phase can be based on the initial wet method (InCipient Wetness Method), which is published in the preparation of the catalyst (preparati〇I1 〇f

Catalyst) 'Delmon, B., Jacobs, P.A., Poncald, G. (eds.), Amsterdam Elsevier, 1976, p. 13. In the end, the water absorption capacity of the carrier is determined. An aqueous ruthenium chloride solution was prepared at a concentration corresponding to the subsequent magic coating. The carrier is supported with an aqueous solution of ruthenium chloride which is consistent with its water absorption capacity so that the entire total capacity of the solution is absorbed. The filled carrier is then dried, preferably in an inert gas at 20 to 100 degrees Celsius under atmospheric pressure, such as neon, helium, argon, nitrogen or air. This drying step can also be performed under pressure or the paper size] China S Winter Standard Winter (CNS) Λ4 Specification (21〇χ 297 公 楚) 5 ___ The standard of the Ministry of Economics and η-τ disappears in cooperation Du printed by A7 B7 —— Description of Invention (7) Xing Erzhong made progress. This dried saturated carrier is then reduced to metal with hydrogen, preferably at a temperature of 100 ° C to 500 ° C for a period of 20 minutes to an hour '. Generally at atmospheric pressure and the hydrogen concentration is mixed with nitrogen. ^ To 100%. This reduced catalyst is then optionally cleaned to be free of chlorine, preferably &lt; 100 ppm C1. This preparation provides finely dispersed ruthenium in a catalyst carrier. The size of silica is measured by electron microscope, which is usually between i and 5 nm. The total amount of ruthenium placed on the support relative to the weight of the oxidized phase is from 0 "to 20% by weight, preferably from about 01 to 10% by weight, and most preferably from 0.5 to 5% by weight. 3-Hydroxypropanal is reacted with hydrogen in the presence of a ruthenium catalyst on a carrier using known techniques. For example, agitated reactors or flow reactors can be used to fixate bed bug reactions which are particularly suitable for industrial scale hydrogenation. In such a reactor, the liquid reaction mixture is passed or dropped over the fixed-bed catalyst with the introduced hydrogen. In order to determine the good distribution of hydrogen in the reaction mixture and the uniform distribution of the gas / liquid mixture across the entire fixed bed, the liquid reaction mixture and hydrogen can be passed through a stationary mixer before the fixed bed. Cork_Kirk-〇thmer

Encyclopedia of Chemical Technology), 3rd edition, Vol. 19, pages 880-914 (especially pages 884) and particularly preferred drip bed reactors. The Wuhuan drop-bed reactor is designed to provide a low liquid retention time, thereby reducing the degree of acrolein side reactions such as 3-hydroxypropionaldehyde due to higher selectivity. An aqueous solution having a ¾propionic acid concentration of 2 to 20% by weight and a pH of 2.5 to 7.0 is fed into the reactor. In the continuous process, the paper scale is applicable to the Chinese National Standard (rNS) Λ4 specification (210x297 mm) (# -Read first, read the precautions on the back, and then fill out this page) One pack, 1T 536532 ^ -Λβ, τ. Digestive seal ^: A7 B7 Ⅴ. Description of the invention (8) It is better that the liquid rate is 2 between 0.1 and 10 h · 1. The hydrogenation reaction is carried out at a temperature of 30 ° C to 180 ° C and a hydrogen pressure of 5 to 300 bar, preferably a hydrogen pressure of less than 90 bar, and most preferably from 60 to 60 bar. An advantage of the present invention is that high fixed conversions can be obtained at lower hydrogen pressures when compared to other catalysts. For example, Arntz et al., U.S. Patent No. 5,364,984, of a platinum catalyst on a carrier is generally required to use a hydrogen gas pressure higher than about 90 bar for its analogue agent to obtain high pressure. And fixed conversions. Example The catalyst was tested under steady state conditions to determine its long-term performance. Hydrogenation in a Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, Vol. 19, 880-914 (especially page 884) drip bed with a reactor volume of 14 ml Continuously under the device. The device consists of a liquid container, a fixed bed reactor and a liquid separator. Its reaction temperature is adjusted by a heat transfer medium / oil circuit. Its pressure and hydrogen flow are electronically controlled. 3-Borylpropene is successively added from the pump to the hydrogen stream while the aqueous solution is introduced into the top of the reactor (dripping bed device). As the mixture flows through the reactor, its products are removed from the separator at regular intervals. In each example, 50 ml of catalyst was used, and the concentration of 3-hydroxypropionaldehyde in the precipitate solution was 10% by weight, and the p 之 値 of the precipitate was approximately 4.0. Its hydrogenation temperature is 40 degrees Celsius, the hydrogenation pressure is 40 bar, and its liquid loading, LHSV, is 1 ·, 0 h · 1. Table 1 summarizes the test results based on different examples. The residual 3-hydroxypropanal concentration in the reaction product was measured by GC and used to calculate its conversion result. In all cases-11-This paper size applies to China's S standard (C'NS) Λ4 specification (210X 297 mm) -------- install-t-(please read _ read the first ^ * Please fill in this page for the items of interest) Order 536532 A7 B7 — V. In the description of the invention (9), the 'selectivity is greater than 98% (measured by gas chromatograph with its 3-propanediol concentration). i (read first, read the notes on the back, and then fill out this page) The catalyst is prepared according to the following: 1. The water absorption of the carrier is determined by the grams of water per 100 grams of the carrier. 2. RuCl3 was dissolved in distilled water and charged with 25 ml of the carrier (see Table 丨). 3. Introduce 250 ml of the carrier into a coated pan and pour the RuC "solution over the carrier while the pan is rotating. 4. Dry the coated carrier in air and room temperature for 16 hours, and then The air was heated in a tubular furnace to 200 degrees Celsius. 5. Then the catalyst was reduced with hydrogen at 200 degrees Celsius for 8 hours, and then cooled to room temperature with hydrogen. 6. Washed with three 40 ml portions of distilled water The reduced catalyst is gas-free. The carrier used has the following characteristics: Carrier 1: Silicone from Grace (0.8-1.2 mm) Name: V432 Carrier 2: Activated carbon from Norit (2.3 mm diameter) Name ·· Norit CNR 11 5 (olivine) Carrier 3: Activated carbon from Norit (0.8 mm in diameter) Name: Norit R0X (peat) Carrier 4: It is obtained by flame hydrolysis from Degussa AG Pyrene oxide P2 is formed by pyrolysis. The carrier is tempered (at 950 ° C-12 °). This paper size applies Chinese standard ((, NS) Λ4 specification (210X 297mm) 536532 A7 B7 — 5 , Description of the invention (10) 12 hours) and as in EP 535 565 Carrier 5: A1203 from Rhone-Poulence (1.1-1.3 mm in diameter) Name: Spheralite 521 When coating the carrier, keep the following conditions: Table 1 Carrier water absorption (g / 100g carrier) Carrier ( (G) RuC13 (g) Water (g) Carrier 1 Si09 V432 126 115 11.8 145 Carrier 2 Norit 1 Extra 67 105 10.8 56 Carrier 3 Norit Rox 0.8 80 107 11.1 68 Carrier 4 Ti02 EP 0 535 565 25 100 10.2 14 Carrier 5 A190 , 74 100 22.8 52 ---------- (Please read the precautions on the back before filling in this page.) -This paper size applies to China National Standards (CNS) Λ4 specification (210X297 mm) 536532-, A7 B7 ^ V. Description of the invention (11) Table 2 Numbered catalyst carrier operating time (h) Conversion (%) VB 1 2 % Pt / Ti02 according to EP 0 535 565 * 20 60 VB 2 2% Pt / Ti02 according to EP 0 535 565 * 300 45 VB 3 5% Ru / activated carbon support 2 26 71 VB 4 5% Ru / activated carbon support 2 216 47 VB 5 5% Ru / activated carbon support 3 24 99.7 VB 6 5% Ru / activated carbon support 3 96 60 Β1 5% Ru / Ti02 support 4 19 84 Β2 5% Ru / Ti09 support 4 233.5 84 Β3 5% Ru / Si02 support 1 48 90 Β4 5% Ru / SiO? Support 1 434 89 Β5 10% Ru / A1203 support 5 72 79 Β6 10% Ru / A190, support 5 240 77 * P25 Ti02 is tempered (950 ° C for 12 hours) and is extruded (please read &gt; the precautions on the back before filling out this page) U_T-Consumer Price印 ^-A comparison between the results of comparative examples VB 1 and VB2 and the results according to the examples (B 1 to B6) of the present invention shows that the ruthenium catalyst according to the present invention is the most excellent because of its higher activity, That is, it has higher conversion than the Pt / Ti02 catalyst of the prior art. Comparative examples VB1 to VB6 show that platinum is in dioxide-14- This paper size applies Chinese National Standard ("NS" Λ4 specification (210x297 mm)) Exhaust &gt; 32 V. Description of the invention (12) A7 B7 Ruthenium catalysts exhibit poor long-term performance on activated carbon supports. Both (the catalyst is deactivated after only a few hundred hours. Although the RU / activated carbon supports used in Comparative Examples VB5 and VB6 have high initial activity (in After 24 hours of operation, the conversion is 99.7%), and the conversion is almost reduced at 72 J hours when the additional time is exceeded. When using the training 2 catalyst, the conversion phase after 300 hours of operation and 20 hours of operation = Its conversion is reduced by about 25%. In contrast, according to the present invention, the oxide support (ruthenium catalyst is surprisingly showing no tendency to deactivate. The present example uses the catalyst on the oxide support to exceed 4: At the time of running, its conversion remains substantially constant. In this case, the maximum conversion reduction can be observed with an example of Ru / A12〇3 catalyst ^ is the time between the 24 hours of operation and the 72 hours between the material turn =, The conversion of the surname is only reduced by about 2.5%. The sentence Yu Si 2 and Ti 0 2 (Example B1) Fortune spine ^ exhibits high activity, and its activity is substantially maintained when the operation time exceeds 200 hours. Fixed. May be described in the above specific embodiments, so it can be changed and modified without departing from the spirit and scope of the present invention (please read the precautions on the back before filling this page). -15- 4 paper standards, _: County (―C, NS) Λ4 size (2K) xi97 male f)

Claims (1)

536532 Patent Application No. 87109562 Amendment to Patent Application Scope (June 90) Scope of patent application Printed by the Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 1. A method for preparing 1,3-propanediol, comprising: hydrogenation in the presence of heterogeneous catalysts 3. hydrogenation in aqueous solution, the hydrogenation progresses / m The temperature is from 30C to 180 ° C, the hydrogen pressure is 5 to 300 bar and the pH is 2.5 to 7.0. The catalyst is a supported catalyst containing an oxide phase, and the ruthenium above the oxide machine is relative to the total of the oxide phase. The amount is from 0.1 to 20% by weight. 〇2. The method according to the scope of application of the patent, wherein the oxidized phase contains at least one member selected from the group consisting of Ti〇2, Si〇2, A1Λ, Mg〇, The retarded stone oxidizes t and w complex oxides, and the mixed oxide includes at least two members selected from the group consisting of Ti02, SiO2 * a1203. 3. The method as claimed in item 2 of the patent scope, wherein the oxidized phase contains at least one member selected from the group consisting of Ti02, Si02, Shi Ximing Ming, beach stones and dioxide junctions. 4. The method of claim 2 or claim 3, wherein the amount of the finely divided ruthenium placed in the oxidizing phase is from 0.1 to 100% by weight. 5. The method of claim 2 or claim 3, wherein the amount of the finely dispersed ruthenium in the oxidation phase is from 0.5 to 5% by weight. 6. The method of claim 5 in which the oxidized phase is impregnated with ruthenium (using an aqueous solution of a ruthenium compound), and then reduced in a hydrogen stream for 20 minutes to 24 hours at a temperature of 100t: to 500eC. 7. The method according to item 1 of the scope of patent application, wherein the hydrogenation step is performed at a hydrogen pressure of less than 90 bar. 8. The method according to item 7 in the scope of patent application, in which the hydrogenation step is carried out by pressing the paper with hydrogen gas from the applicable country (CNS) of Japan (210X297). (Please read the precautions on the back before filling this page ) Order 536532 The patent application scope is from 10 bar to 60 bar. 9. The method according to item 7 or 8 of the scope of patent application, a choice of which is free of Si02 and Ti (V rounds). The chemical phase contains at least 10. The method according to item 9 of the patent scope, wherein hydrogen The steps are performed in the drip bed counter (please read the precautions on the back before filling this page)-IΦ Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -2- This paper applies Chinese National Standard (CNS) A4 Specifications (2 丨 〇 &gt; &lt; 297 mm)