MXPA01004178A

MXPA01004178A - Catalyst and process for preparing 1,3-propanediol

Info

Publication number: MXPA01004178A
Application number: MXPA/A/2001/004178A
Authority: MX
Inventors: Juan Pedro Arhancet; William Joseph Carrick; Paul Himelfarb; Mohammad Shahjahan Kazi; Robert Alfred Plundo; Joseph Broun Powell
Original assignee: Juan Pedro Arhancet; William Joseph Carrick; Paul Himelfarb; Kazi Mohammed Shahjahan; Robert Alfred Plundo; Joseph Broun Powell
Priority date: 1998-10-29
Filing date: 2001-04-26
Publication date: 2002-03-05

Abstract

A solid, particulate catalyst composition comprising an active nickel component in which the nickel constitutes from 25 to 60 wt%of the catalyst composition;a molybdenum component in which the molybdenum constitutes from 5 to 20 wt%of the catalyst composition;and from 10 to 50 wt%of a binder material comprising at least one of oxides of silicon, and silicates and oxides of zinc, aluminium, zirconium, magnesium and calcium, each of the aluminium, calcium and zinc present in an amount no greater than 2 wt%;and a process for the selective hydrogenation of 3-hydroxypropanal to 1,3-propanediol in aqueous solution, using said catalyst composition.

Description

CATALYST AND PROCESS FOR PREPARING 1,3-PROPANODIOL Background of the Invention. The present invention relates to the manufacture of 1,3-propanediol. In one aspect, the present invention relates to an improved catalyst for hydrogenating 3-hydroxypropanal for 1,3-propanediol which exhibits a prolonged catalyst life in the hydrogenation reaction environment. In a further aspect, the present invention relates to an improved process for preparing 1,3-propanediol from 3-hydroxypropanal. 1,3-propanediol, a chemical intermediate in the preparation of polyesters, can be prepared by the hydrogenation of 3-hydroxypropanal in an aqueous solution. The selective hydrogenation of 3-hydroxypropanal 'to 1,3-propanediol is complicated by the high reactivity of 3-hydroxypropanal and the relatively low solubility of hydrogen in an aqueous solution. Hydrogenation in a percolator bed configuration is favored by a small catalyst particle size. However, the catalyst breaking force is decreased REF: 129147 significantly with a reduced catalyst particle size. A common approach to increase the breaking strength of nickel-based volume catalysts is to increase the amount of calcium in the binder. However, in the aqueous hydrogenation environment, calcium and other soluble binder components are rapidly leached from the catalyst. This has two negative effects on the synthesis of the process. First, as the water is evaporated off of 1,3-propanediol, the leached binder material is deposited in the evaporation column, resulting in a waste of time and equipment cleaning costs. Second, the removal of these soluble components from the particular catalyst reduces the breaking strength of the catalyst, resulting in less effective flow in the catalyst bed as the catalyst areas collapse and eventually clog the bed. GB-A-1085171 relates to a process for the production of molybdenum-containing nickel silicate catalysts which are particularly suitable for the hydrogenation of mixtures of sulfur-containing aldehydes, ketones and esters which are obtained from olefins by the reaction with carbon monoxide and hydrogen in an oxo synthesis. GB-A-1085171 seeks to overcome the problems exhibited by the prior art of hydrogenation catalysts in which the ketones which are obtained in the oxo synthesis at the same time are not appreciably hydrogenated and are problematic in the next distillation of the reaction mixture. of hydrogenation because these form mixtures with the azeotropic alcohols and consequently can only be separated with difficulty from the desired alcohols. GB-A-1085171 provides a catalyst that has been prepared by adding an aqueous solution prepared from liquid sodium silicate and sodium molybdate and which is 0.5 to 3 moles with respect to silicon and has a sodium: silicon ratio of 0.7. 1 to 7: 1 and a molybdenum: silicon ratio of 0.004: 1 to 0.2: 1, at a temperature from 0 to 100 ° C while stirring, such amount of 1 to 3 moles of nickel salt solution that the amount of nickel added is from 10% by weight less to 10% by weight more than the amount equivalent to the sodium content of the solution, separating the precipitate obtained from the solution, washing with water, molding it, optionally calcining it at a temperature of 250 ° to 400 ° C and then reducing it with hydrogen at a temperature of 300 ° to 500 ° C, preferably 350 ° to 400 ° C. The problem of the leaching of calcium and other soluble binder components and their subsequent effects on the strength of catalyst breakage are neither identified nor addressed in GB-A-1085171. Description of the invention. It is therefore an object of the present invention to provide a catalyst and a process designed particularly for the hydrogenation of 3-hydroxypropanal for 1,3-propanediol in an aqueous solution. Particularly, it is an object of the present invention to provide a catalyst for the hydrogenation of 3-hydroxypropanal having a reduced leachable content without a significant reduction of the breaking strength in the reaction environment.

According to the invention, there is provided a catalyst composition comprising, in solid particle form, (a) an active nickel component in which the nickel constitutes from 25 to 60% by weight of the catalyst composition; (b) a molybdenum component in which the molybdenum constitutes from 5 to 20% by weight of the catalyst composition, and (c) from 10 to 50% by weight, based on the weight of the catalyst composition, of a binder material comprising at least one of the oxides of silicon and silicates and oxides of zinc, aluminum, zirconium, magnesium and calcium, each of said aluminum, calcium, and zinc present in an amount not greater than 2% by weight, based on weight of the catalyst composition. In addition, according to the invention, there is provided a process for preparing 1/3-propanediol, comprising (a) contacting, in an aqueous reaction mixture at a temperature of at least 30 ° C, 3-hydroxypropanal and hydrogen in the presence of a solid particulate catalyst composition comprising (i) an active nickel component in which the nickel constitutes from 25 to 60% by weight of the catalyst composition; (ii) a molybdenum component in which the molybdenum constitutes from 5 to 20% by weight of the catalyst composition; Y (iii) from 10 to 50% by weight of a binder material selected from at least one of the silicon oxides and silicates and oxides of zinc, aluminum, zirconium, magnesium and calcium, each of said aluminum, calcium and zinc present in an amount not greater than 2% by weight, based on the weight of the catalyst composition, to produce a mixture of aqueous product comprising 1/3-propanediol; and (b) recovering the 1,3-propanediol from the aqueous product mixture. The use of the catalyst described in the hydrogenation of aqueous 3-hydroxypropanal allows the production of 1,3-propanediol in high yields with a reduced loss of time from the effects of the use of soluble binder materials. Brief description of the Figures. The present invention is now described with reference to the accompanying drawings in which: Figure 1 is a trace of the catalyst activity over time for a hydrogenation catalyst of 3-hydroxypropanal according to the invention. Figure 2 is a trace of the catalyst activity over time for a hydrogenation catalyst of 3-hydroxypropanal according to the invention. Figure 3 is a trace of a catalyst activity over time for a conventional nickel hydrogen catalyst. Figure 4 is a trace of a catalytic activity over time for a 3-hydroxypropanal hydrogen catalyst according to the invention. The hydrogenation catalyst contains, as the largest active component, from 25 to 60% by weight of nickel (as Ni0), preferably from to 45% by weight. The nickel in the active catalyst is predominantly in reduced form. The catalyst contains from 5 to 20% by weight of molybdenum (as Mo °), preferably from 6 to 16% by weight. Molybdenum is present in the catalyst in both metal and oxide form. Molybdenum has a binding function and is also a promoter of activity.

The binder portion of the catalyst acts as a "glue" to hold the separated components together and to provide a resistance to the breakdown of the pressure flow through the catalyst bed.The binder constitutes from 10 to 50% by weight of the catalyst and it makes silicon oxides, and silicates and zinc oxide, zirconium, calcium, magnesium and / or aluminum Typically, the catalyst contains from 30 to 70, preferably from 35 to 55% by weight of silicon, from 0 to 2, preferably from 0 to 1% by weight of zinc, and from 0 to 2% by weight of aluminum The binder contains no more than 2% by weight of calcium, and preferably contains 0-1% by weight of calcium. The preferred catalyst composition does not contain zinc or calcium The preferred catalyst composition for the hydrogenation of 3-hydroxypropanal for 1,3-propanediol in an aqueous solution contains about 35% by weight of nickel and about 8-12% by weight of molybdenum, with the binder material balanced as described above.

The catalyst can be prepared by any process that incorporates the active nickel component, the molybdenum component and the binder material in a solid volume form. In general, the catalyst preparation involves mixing nickel oxide, the binder material such as attapulgite clay, and molybdenum trioxide powder in a homogeneous powder. Next, a solution of colloidal silica in sufficient water to form a mixture that can be extruded is stirred into the solid mixture. The wet mix is then extruded through a beading punch with 0.10-0.18 cm (0.040-0.070 inches) in diameter in the pits. The extrudates are dried at 100-125 ° C for a sufficient time to reduce the moisture content to less than about 5% by weight. The dried extrudates are then calcined in air at 450-550 ° C for at least about 3 hours until the desired strength develops. Before use, the catalyst is reduced under hydrogen gas to a temperature within the range of 350 to 450 ° C for a sufficient time for the reduction of at least 60% of the nickel. If the reduced catalyst is not used immediately, it is cooled to room and stored under a protective medium such as 1,3-propanediol until used. Exemplary illustrative catalyst preparations are provided in Examples 2 and 3. The catalyst is in particulate form, with particle size and shape such as to provide sufficient catalyst activity dependent on another process variable such as the flow ratio and Pressure. Preferred catalyst particles are less than 0.32 cm (1/8 inch) in diameter (across the width of the cross section of the particle), preferably 0.08-0.16 cm (1 / 16-1 / 32 inch), to provide an optimal balance of the geometric surface area and the resistance to breakage. The preferred catalyst forms to make the catalyst bed longer are trilobal and cylindrical. The catalyst will preferably exhibit an activity of at least 10 h.Vircular volume fractionation, preferably at least 20, in the selective hydrogenation of 3-hydroxypropanal for 1,3-propanediol. The catalyst has an improved stability in the reaction environment and a good physical integrity during the active life of the catalyst. The hydrogenation of 3-hydroxypropanal for 1,3-propanediol can be carried out in an aqueous solution at a temperature of at least 30 ° C, generally within the range of 50 to 175 ° C, under a positive hydrogen pressure of at least 689 kPa (100 psig), generally within the range of 1379-13790 kPa (200 to 2000 psig). Hydrogenation of HPA for PDO is described in US-5786524. The hydrogenation process of the invention is particularly designed to be used in a process for preparing 1,3-propanediol by the hydroformylation of ethylene oxide, as described for example in US-A-5463145 and US-A-3687981, or from acrolein, as described in US-A-5093537. In such processes, 3-hydroxypropanal is an intermediate product that is hydrogenated in an aqueous solution for 1,3-propanediol. In one such process, ethylene oxide (reacted with carbon monoxide and hydrogen) is hydroformylated at a temperature within the range of 50 to 140 ° C and a CO / H2 pressure within the range of 3447-34474 kPa (500 to 5000) psig), preferably 60 to 90 ° C and 6895-24132 kPa (1000 to 3500 psig), in the presence of an appropriate hydroformylation catalyst such as cobalt or rhodium carbonyl to produce a hydroformylation product mixture containing 3-hydroxypropanal / 1 , 3-propanediol and hydroformylation reaction sub-products. The 3-hydroxypropanal component is removed by extraction in water and passed through a hydrogenation reaction vessel in the form of an aqueous solution having a concentration of 3-hydroxypropanal of less than 15% by weight, preferably less than 10% by weight, based on the weight of the aqueous solution. The hydrogenation of 3-hydroxypropanal for 1,3-propanediol is carried out as described above to form a hydrogenation product mixture containing 1,3-propanediol as the major product, which is recovered by appropriate means such as from lation Example 1 Conventional Preparation of the 1,3-propanediol Catalyst.

In a typical group catalyst preparation, a precipitation tank was filled with 2200 parts of nickel chloride solution (97-98% NiCl2), 70 parts of Microcel E (0.8 solids), and 130 parts of aluminum from a solution of sodium aluminate. After the precipitation is complete, the liquid is completely emptied and the solids are washed with deionized water several times. The solid mass (calcium silicate nickel) is dried and calcined in the air at 390-410 ° C. A 3.79 liter (one gallon) plow type mixer was loaded with 730 parts of technical grade nickel silicate silicate (93-97% NiCaSiA10x), 125 parts of Microcel E (0.8 solids) and 125 parts of bentonite clay. (0.8 solids) and mixed for 2 minutes. Next, a solution containing 600 'parts of deionized water and 16-20 parts of molybdenum of an ammonium molybdate solution was stirred in the mixture, and mixing continued for 5-10 minutes. The wet mix was then extruded through a beading punch with 0.15-0.18 cm (0.06 in. To 0.07 in.) Diameter trilobular shape. The extrusions were dried overnight at 100-125 ° C. The dry intermediate was then reduced with hydrogen at 445-455 ° C to reduce the nickel content of about 90%, based on the total nickel. Example 2 Preparation of the Catalyst of the Invention. A plow-type mixer of 3.79 liters (one gallon) was loaded with 750 parts of a technical grade nickel oxide (93-97% NiO), 498 parts Attagel-30 attapulgite clay (0.8 solids), and 185 powder parts of molybdenum trioxide (Mo03) and mixed for 2-3 minutes. A solution of 796 parts of Nalco 2327, a colloidal silica colloid (available from Nalco Chemical Company), in 200 parts of deionized water, was added to the dry mixture with stirring. Agitation continued for 5 minutes. About 60 parts of additional deionized water was added to the mixture and stirring continued for another 5 minutes. The wet mix was then extruded through a single three-insert celcon containing 0.10 cm (0.040 in.) Diameter pits. The extrudates were dried at 110 ° C, and then measured / sieved and calcined in air at 500 ° C for about 3 hours in a stationary ceramic cementation box. The extrudates were then reduced with hydrogen at 420-430 ° C to a reduced nickel content of 90%, based on the total nickel. Example 3 Preparation of the Catalyst of the Invention. A one-gallon paddle mixer (3.79 liters) was charged with 735 parts of technical-grade nickel oxide (93-97% NiO), 355 parts of Attagelg Attapulgite 30 clay (0.8 solids) and 286 parts of molybdenum trioxide powder (Mo03) and mixed for 2 minutes. A solution of 795 parts of colloidal silica Nalco 2327 in 225 parts of deionized water was added to the solid mixture with stirring, and stirring continued for 10 minutes. The wet mix was then extruded through a beading punch with holes of 0.10-0.18 cm (0.040-0.070 in.) In diameter. The extrudates were dried overnight at 100-125 ° C. The dry intermediate was then calcined in air at 500 ° C for about 3 hours and subsequently reduced with hydrogen at 420-430 ° C to a reduced nickel content of 90%, based on the total nickel.

Example 4 Hydrogenation of 3-hydroxypropanal. Four runs of hydrogenation catalyst (catalysts A, B, C, D of Table 1) were run in a percolating bed reactor of 3.05 cm (1.2 in.) In diameter. The reactor was charged with 400 L of the selected hydrogenation catalyst. The reactor was pressurized to 10342 kPa (1500 psig) with hydrogen, and a stream of deionized, degassed water was fed into the reactor. Part of the current leaving the reactor was continuously returned to the interior and mixed with the input feed so that the superficial liquid velocity (mL / s of liquid entering the reactor divided by cm2 of the cross-sectional area of the reactor) in the reactor outside of the reactor. between 0.3 and 0.8 cm / s. When the desired temperature of 60 ° C was reached in the reactor, the fed water was discontinued and an aqueous stream containing about 30% 3-hydroxypropanal was fed. The heat of the reaction was removed by heat exchange in the re-circulation loop. The pressure was maintained by the continuous addition of hydrogen to replace the gas consumed. Food and product samples were taken periodically and the concentration of 3-hydroxypropanal was determined. Assuming a first-order reaction ratio with respect to the concentration of 3-hydroxypropanal, a constant of the apparent reaction ratio was calculated for each of the feed / product pairs of the 3-hydroxypropanal concentrations. The activity of the catalyst for hydrogenating the 3-hydroxypropanal was calculated as the constant reaction ratio, expressed in units of liquid volume / volume of catalyst particles / time. The reaction ratios of the catalysts. A to D were measured over a period of about 30 days. Catalyst C is a nickel, standard hydrogenation catalyst immediately, which contains a relatively low content of molybdenum (1.8% by weight). The catalysts A, B and D are catalysts of the invention designed for a more stable hydrogenation of 3-hydroxypropanal in an aqueous solution. The results are shown in Figures 1 to 4 and Table 1. Since the reaction ratio is primarily limited by the diffusion ratio of the reagents within the catalyst particles, the small transverse extrudates give constants of reaction ratio more favorable. The breaking force of the catalyst particles is reduced with the transverse dimension of the reduced extrudate. Catalyst C was too weak to be extruded using 1/32 in. Holes and therefore extruded using 0.16 cm (1/16 inch) holes. Calcium, when present in the catalyst, is almost completely leached within a short period of time, causing an embedding of the heat exchanger used for the evaporation of the water in a subsequent 1,3-propanediol concentration step. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

YOU See Figure 1. "See Figure 3 See Figure 'See Figure 50.08 cm (1. / 32 in.)

Claims

Claims Having described the invention as above, the content of the following claims is claimed as property: 1. A catalyst composition, characterized in that it comprises, in a solid particulate form, (a) an active nickel component in which the nickel constitutes from 25 up to 60% by weight of the catalyst composition; (b) a molybdenum component in which the molybdenum constitutes from 5 to 20% by weight of the catalyst composition; and (c) from 10 to 50% by weight, based on the weight of the catalyst composition, of a binder material comprising at least one of the silicon oxides and silicates and oxides of zinc, aluminum, zirconium, magnesium and calcium, each of the aluminum, calcium and zinc present in an amount not greater than 2% by weight, based on the weight of the catalyst composition.
2. The catalyst composition according to claim 1, characterized in that the molybdenum constitutes from 6 to 16% by weight of the catalyst composition.
3. The catalyst composition according to claim 1 or 2, characterized in that the particles are at least 0.32 cm (1/8 in.) In diameter.
4. The catalyst composition according to claims 1, 2 or 3, characterized in that the nickel constitutes from 25 to 45% by weight of the catalyst composition.
5. The catalyst composition according to any of the preceding claims, characterized in that each of the aluminum, calcium and zinc present in an amount not greater than 1% by weight, based on the weight of the catalyst composition.
6. A process for preparing 1,3-propanedio 1, characterized in that it comprises: (a) contacting, in an aqueous reaction mixture at a temperature of at least 30 ° C, 3-hydroxypropanal and hydrogen in the presence of a composition solid particulate catalyst comprising: (i) an active nickel component in which the nickel constitutes from 25 to 60% by weight of the catcher composition; (ii) a molybdenum component in which the molybdenum constitutes from 5 to 20% by weight of the catalyst composition; and (iii) from 10 to 50% by weight, based on the weight of the catalyst composition, of a binder material comprising at least one of the oxides of silicon and silicates and oxides of zinc, aluminum, zirconium, magnesium and calcium, each of the aluminum, calcium and zinc present in an amount not greater than 2% by weight, based on the weight of the catalyst composition, to produce a mixture of aqueous product comprising 1,3-propanediol; and (b) recovering the 1,3-propanediol from the aqueous product mixture.
7. The process according to claim 6, characterized in that the molybdenum constitutes from 6 to 16% by weight of the catalyst composition.
8. The process according to claim 6 or 7, characterized in that the solid particles are less than 0.32 cm (1/8 in.) In diameter. The process according to claims 6, 7 or 8, characterized in that, in the catalyst composition, each of zinc and calcium is present in an amount not greater than 1% by weight, based on the weight of the catalyst composition . 10. A process for preparing 1,3-propanediol, characterized in that it comprises: (a) contacting ethylene oxide with carbon monoxide and hydrogen under hydro formation conditions and in the presence of an effective amount of a hydroformylation catalyst, to form a reaction product mixture comprising 3-hydroxypropanal; (b) removing the 3-hydroxypropanal from the reaction product mixture and forming an aqueous solution thereof; (c) adding to the aqueous solution of 3-hydroxypropanal a solid particle hydrogenation catalyst composition comprising (i) an active nickel component in which the nickel constitutes from 25 to 60% by weight of the catalyst composition; (ii) a molybdenum component in which the molybdenum constitutes from 5 to 20% by weight of the catalyst composition; and (iii) from 10 to 50% by weight, based on the weight of the catalyst composition, of a binder material comprising at least one of the oxides of silicon and silicates and oxides of zinc, aluminum, zirconium, magnesium and calcium, each of the aluminum, calcium and zinc present in an amount not greater than 2% by weight, based on the weight of the catalyst composition; (d) heating the aqueous solution of 3-hydroxypropanal to a temperature of at least 30 ° C under a positive hydrogen pressure of at least 68948 kPa (100 psig), to produce a mixture of hydrogenation product comprising 1, 3- propanediol; and (e) recovering 1,3-propanediol from the hydrogenation product mixture. CATALYST AND PROCESS FOR PREPARING 1,3- PROPANODIOL Summary of the Invention Disclosed is a solid particulate catalyst composition comprising an active nickel component in which nickel constitutes from 25 to 60% by weight of the catalyst composition; a molybdenum component in which the molybdenum constitutes from 5 to 20% by weight of the catalyst composition; and from 10 to 50% by weight of a binder material comprising at least one of the silicon oxides, and silicates and oxides of zinc, aluminum, zirconium, magnesium and calcium, each of the aluminum, calcium and zinc present in an amount not greater than 2% by weight; and a process for the selective hydrogenation of 3-hydroxypropanal for 1,3-propanediol in an aqueous solution using said catalyst composition.