Catalyst and method for producing 1,3-propane diol

 

Solid granular catalyst composition to obtain 1,3-propane diol containing Nickel component is active, in which Nickel is from 25 to 60 wt.% from the composition of the catalyst; molybdenum component, in which the molybdenum content is from 5 to 20 wt.% from the composition of the catalyst; and from 10 to 50 wt.% the binder material containing at least one of silicon oxides and silicates and oxides of zinc, aluminum, zirconium, magnesium and calcium, each of these aluminium, calcium and zinc is present in an amount of not more than 2 wt.%; and method for selective hydrogenation of 3-hydroxypropyl 1,3-propandiol in aqueous solution using a given catalytic composition. The catalytic composition has a low content of leachable components, and a crushing strength in the reaction medium decreases slightly, provides the 1,3-propane diol with high output with less downtime due to the use of soluble materials binder. 3 N. and 7 C.p. f-crystals, 1 tab., 4 Il.

The present invention relates to the production of 1,3-propane diol. One aspect of the present invention relates a long service life under the conditions of the hydrogenation process. Another aspect of the present invention relates to an improved process for the preparation of 1,3-propane diol 3-hydroxypropane.

1,3-Propandiol, intermediate product upon receipt polyesters may be obtained by hydrogenation of 3-hydroxypropane in aqueous solution. However, selective hydrogenation of 3-hydroxypropyl 1,3-propandiol is complicated by the high reactivity of 3-hydroxypropane and relatively low solubility of hydrogen in aqueous solution.

Hydrogenation in the configuration filtrating layer contributes to the small particle size catalyst. However, when reducing the particle size of the catalyst is greatly reduced strength of the catalyst crush strength. The traditional approach to increasing the strength of the massive crush strength of catalysts based on Nickel is to increase the calcium content in the binder. However, in the conditions of hydrogenation in water calcium and other soluble components of the binder quickly leach from the catalyst. This leads to two negative consequences for the process of synthesis. First, when the water is separated from 1,3-propane diol evaporation, leached material binder is deposited in the evaporator column that is of onenew of granulated catalyst reduces the strength of the catalyst crush strength, which reduces the efficiency of the flow in the catalyst bed, because there is less surface of the catalyst and finally blocked the catalyst bed.

The UK patent GB-A-1085171 relates to a method for containing molybdenum dikelilingi of a catalyst which is particularly suitable for the hydrogenation of sulfur-containing mixtures of aldehydes, ketones and esters, obtained by the interaction of olefins with carbon monoxide and hydrogen in the oxo-synthesis.

In the patent GB-A-1085171 tried to overcome the problems inherent in the hydrogenation catalysts of the prior art, in which ketones, simultaneously resulting in the oxo-synthesis, not fully hydronauts, and followed by distillation gidrirovannoe reaction mixture complications arise because ketones form azeotropic mixtures with alcohols and, therefore, can be separated from the desired alcohols with great difficulty.

In the patent GB-A-1085171 developed a catalyst that is obtained by adding to the aqueous solution prepared from water glass and sodium molybdate, the molar ratio of the silicon is from 0.5 to 3 and in which the ratio of sodium:silica varies from 0.7:1 to 7:1, and the ratio of molybdenum:Creator Nickel salts, to the number of added Nickel was from 10 wt.% less than 10 wt.% more quantity, equivalent to the sodium content in the solution, separating the precipitate obtained from the solution, washed with water, molded, optionally calcined at a temperature of from 250 to 400C and then restore the catalyst with hydrogen at a temperature of from 300 to 500C., preferably from 350 to 400C.

The problem of leaching of calcium and other soluble binder components and their subsequent effect on the strength of the catalyst crush strength was not defined and was not discussed in the patent GB-A-1085171.

Therefore, the present invention is the provision of catalyst and method specifically developed for the hydrogenation of 3-hydroxypropyl 1,3-propandiol in aqueous solution. A specific object of the present invention is the development of a catalyst for hydrogenation of 3-hydroxypropane, which has a low content of leachable components, and the strength of the catalyst crush strength in the reaction medium decreases slightly.

According to the invention is designed catalytic composition in the form of solid granules containing: (a) Nickel component is active, in which the Nickel is 5 to 20 wt.% from the composition of the catalyst; and (C) from 10 to 50 wt.%, based on the weight of the composition of the catalyst, the binder material containing at least one of silicon oxides and silicates and oxides of zinc, aluminum, zirconium, magnesium and calcium, each of these aluminium, calcium and zinc is present in an amount of not more than 2 wt.%, based on the weight of the catalytic composition.

In addition, according to the invention, a method of obtaining 1,3-propane diol, comprising: a) contacting 3-hydroxypropane and hydrogen in the aqueous reaction mixture at a temperature at least 30C in the presence of a solid granular catalyst composition comprising (i) Nickel component is active, in which Nickel is from 25 to 60 wt.% from the composition of the catalyst; (ii) a molybdenum component, in which the molybdenum content is from 5 to 20 wt.% from the catalytic composition; and iii) 10 to 50 wt.% the binder material selected from at least one of silicon oxides and silicates, and oxides of zinc, aluminum, zirconium, magnesium and calcium, each of these aluminium, calcium and zinc is present in an amount of not more than 2 wt.%, based on the weight of the catalytic composition, with the formation of water of the mixture of products containing 1,when the hydrogenation of aqueous 3-hydroxypropyl provides obtaining 1,3-propane diol with high output with less downtime due to the use of soluble materials binder.

Now the present invention will be described with reference to the accompanying drawings, in which:

Fig.1 is a graph showing the dependence of catalyst activity from the time when the hydrogenation of 3-hydroxypropane on the catalyst according to the invention; and

Fig.2 is a graph showing the dependence of catalyst activity from the time when the hydrogenation of 3-hydroxypropane on the catalyst according to the invention; and

Fig.3 is a graph showing the dependence of activity over time for a conventional catalytic hydrogenation.

Fig.4 is a graph showing the dependence of catalyst activity from the time when the hydrogenation of 3-hydroxypropane on the catalyst according to the invention.

As the main active component of the hydrogenation catalyst contains from 25 to 60 wt.% Nickel (in the form of nonvalence Ni0), preferably from 25 to 45 wt.%. In the active Nickel catalyst is mostly restored.

The catalyst contains from 5 to 20 wt.% molybdenum (as Mo0), preferably from 6 to 16 wt.%. The molybdenum catalyst is both metal and oxide. Molybdenum plays the role of a binder, and an active promoter.

The connecting part of the ka is sdavlivaya under the action of differential pressure on the layer of catalyst. Binder is from 10 to 50 wt.% from catalyst and consists of silicon oxides and silicates and oxides of zinc, zirconium, calcium, magnesium and/or aluminum. Typically, the catalyst may contain from 30 to 70 wt.%, preferably from 35 to 55 wt.%, silicon; from 0 to 2 wt.%, preferably from 0 to 1 wt.%, zinc; and from 0 to 2 wt.% aluminum. The binding agent may contain not more than 2 wt.% calcium and preferably will contain 0-1 wt.% of calcium. In a preferred variant embodiment, the catalyst contains almost no zinc or calcium. The preferred catalyst composition for the hydrogenation of 3-hydroxypropyl 1,3-propandiol in the aqueous solution contains about 35 wt.% Nickel and about 8-12 wt.% molybdenum, and the rest is a binder material, which is described above.

The catalyst may be obtained by any method, which introduces a component of active Nickel, molybdenum component and a binder material in the form of a solid mass. Typically, the preparation of the catalyst involves mixing Nickel oxide, binder material, such as attapulgite clay, and powder of molybdenum trioxide in a homogeneous powder. Then in a mixture of solids mixed with the colloid solution is that the crude mixture is extruded through a matrix disc with holes with a diameter of 0.10 to 0.18 cm (0,040-0,070 inch). Product extrusion dried at 100-125C for a time sufficient to reduce the moisture content to less than about 5 wt.%. Then the dried extrudate calcined in air at 450-550C for approximately 3 h to achieve the desired strength. Before use the catalyst restore gaseous hydrogen at a temperature in the range of 350-450C for a time sufficient to recover at least 60% Nickel. If the recovered catalyst is not used immediately, then it is cooled to ambient temperature and stored until use in a protective environment, such as 1,3-propandiol. Illustration of the preparation of the catalyst described in examples 2 and 3.

The catalyst is in granular form, and the size and shape of the particles is such as to provide sufficient catalyst activity, which depends on other process variables such as flow rate and pressure. Preferably the catalyst particles have a diameter less than that of 0.32 cm (1/8 inch, width of the cross section of the particles), preferably of 0.08 to 0.16 cm (1/16-1/32 inch) to provide the optimum ratio of geometric surface area and strength to crushing. Preferred fo is respectfully during selective hydrogenation of 3-hydroxypropyl 1,3-propandiol the catalyst has an activity of at least 10 h-1on the volume fraction of the catalyst, preferably at least 20 h-1. The catalyst has improved stability in the reaction medium and good physical integrity during the active life of the catalyst.

Hydrogenation of 3-hydroxypropyl 1,3-propandiol can be carried out in aqueous solution at a temperature at least 30C, usually in the range from 50 to 175C., at a pressure of hydrogen of at least 689 kPa (100 psi), usually in the range 1379-13790 kPa (200-2000 pounds/square inch). Hydrogenation of 3-hydroxypropyl 1,3-propandiol described in U.S. patent No. 5786524.

The method of hydrogenation according to the invention is designed specifically for use in a method of producing 1,3-propane diol by hydroformylation of ethylene oxide, as described, for example, in U.S. patent No. 5463145 and 3687981, or from acrolein, as described in U.S. patent No. 5093537.

In these methods, the 3-hydroxypropyl is an intermediate compound, which is subjected to hydrogenation to 1,3-propane diol in aqueous solution. In one such method, the ethylene oxide is subjected to hydroformylation (interaction with carbon monoxide and hydrogen) at a temperature in the range from 50 to 140C. and the pressure/H2in the interval outstay a suitable catalyst hydroformylation, such as a cobalt carbonyl or rhodium, in order to obtain a mixture of products of hydroformylation containing 3-hydroxypropane, 1,3-propandiol and the reaction by-products of hydroformylation. Component 3-hydroxypropyl is removed by extraction with water and fed into the hydrogenation reactor in the form of an aqueous solution having a concentration of 3-hydroxypropane less than 15 wt.%, preferably less than 10 wt.%, based on the weight of aqueous solution. Hydrogenation of 3-hydroxypropyl 1,3-propandiol is carried out, as described above, to obtain a mixture of products of hydrogenation, containing as the main product of 1,3-propandiol, which is marked with suitable means, such as distillation.

Example 1

Obtaining traditional catalyst for 1,3-propane diol

In a typical periodic method of producing catalyst in the tank for the deposition load of 2200 parts of a solution of Nickel chloride (97-98% NiCl2), 70 parts of reagent Microcel E (0,8 solids) and 130 parts of alumina from the sodium aluminate solution. After deposition, the liquid decanted, and the solid is washed several times with deionized water. Solid mass (silicate of Nickel-calcium), dried and calcined at walikota Nickel-calcium technical grade (93-97% NiCaSiAlOx), 125 parts of reagent Microcel E (0,8 solids) and 125 parts of bentonite clay (0,8 solids) and stirred for 2 minutes Then the mixture is mixed with a solution containing 600 parts of deionized water and 16 to 20 parts of molybdenum from the solution of ammonium molybdate, and stirring is continued for 5-10 minutes Then wet blend is extruded through a matrix disc with three holes with a diameter of 0.15 to 0.18 cm (0.06 to 0.07 inch). Product extrusion dried at 100-125C during the night. Then the dried intermediate product is reactivated by hydrogen at a temperature of 445-455C until the content of the recovered Nickel approximately 90%, based on the whole Nickel.

Example 2

Obtaining a catalyst according to the invention

In the mixer scraper type capacity with 3.79 l (1 Gal) load 750 technical parts of Nickel oxide technical grade (93-97% NiO), 498 parts attapulgite clay Attagel-30 (0,8 solids) and 185 parts of a powder of molybdenum trioxide (Moo3) and stirred for 2-3 minutes In the dry mixture with stirring solution 796 parts of reagent Nalco 2327 - colloidal silicates (supplied by the company Nalco Chemical Co.) 200 parts of deionized water. Stirring is continued in accordance with the continue for another 5 minutes Then the wet blend is extruded through a separate silikonovye triple box that has holes with a diameter of 0.10 cm (0.040 inch). Product extrusion dried at 110C, then calibrate/sieved and calcined in air at 500C for approximately about 3 h in a stationary ceramic crucible. Then the extrudate is reactivated by hydrogen at 420-430C until the content of the recovered Nickel approximately 90%, based on the whole Nickel.

Example 3

Obtaining a catalyst according to the invention

In the mixer scraper type capacity with 3.79 l (1 Gal) load 735 technical parts of Nickel oxide technical grade (93-97% NiO), 355 parts attapulgite clay Attagel-30 (0,8 solids) and 286 parts of a powder of molybdenum trioxide (Moo3) and stirred for 2 minutes In a mixture of solids was added with stirring a solution 795 parts of colloidal silicates Nalco 2327 in 225 parts of deionized water and stirring is continued for 10 minutes Then wet blend is extruded through a matrix disc with holes with a diameter of 0.10 to 0.18 cm (0,040-0,070 inch). Product extrusion dried at 100-125C during the night. Then the dried intermediate product is calcined in air at 500C approx the military of Nickel approximately 90%, in the calculation for the whole Nickel.

Example 4

Hydrogenation of 3-hydroxypropane

In the reactor with a filtering layer with a diameter of 3.05 cm was carried out mileage four hydrogenation catalysts (catalysts a, b, C, D in the table). Charged to the reactor 400 ml of the selected catalytic hydrogenation. In the reactor, introducing hydrogen to a pressure 10342 kPa (1500 f/inch2and then into the reactor continuously served the flow of deionized, degassed water. The portion of the stream exiting the reactor, continuously return to the entrance to the reactor and mixed with the incoming raw material so that the flow velocity of the liquid in the reactor (the amount of fluid (ml/s) entering the reactor, referred to the cross-sectional area of the reactor in cm2) accounted for between 0.3 and 0.8 cm/s When the desired temperature 60C in the reactor feed water stop and start feeding an aqueous stream containing about 30% 3-hydroxypropane. The heat of reaction is given by heat exchange in the recirculation circuit. Pressure support due to the continuous addition of hydrogen to replace the reacted gas. Periodically take samples of the raw product and determine the concentration of 3-hydroxypropane. Assuming that the reaction is first monstanto reaction rate for each pair of concentrations of 3-hydroxypropane in raw materials and product. The activity of the catalyst in relation to the hydrogenation of 3-hydroxypropane calculated as the reaction rate constant expressed in units: volume of liquid/volume of catalyst particles per unit time.

For catalysts A-D reaction rate is measured over a period of about 30 days. The catalyst is a standard bulk Nickel hydrogenation catalyst having a relatively small content of molybdenum (1.8 wt.%). Catalysts a, b and D are the catalysts according to the invention, designed to improve the stability of the hydrogenation of 3-hydroxypropane in aqueous solution. The results are presented in Fig.1-4 and in table (all these quantities have dimensions wt.%).

Since the reaction rate is limited mainly by the rate of diffusion of the reactants within the catalyst particles, to die with a smaller cross-section obtained higher values of the reaction rate constants. The strength of the catalyst particles in the crushing decreases with decreasing value of the cross section of the extrudate. The catalyst is too fragile for the extrusion with the use of holes of 0.08 cm (1/32 inch), and therefore it is subjected to extrusion using holes a period of time, which leads to contamination of the heat exchanger used for evaporation of the water at the subsequent stage of concentration of 1,3-propane diol.

Claims

1. Catalytic composition for obtaining 1,3-propane diol in the form of solid granules containing (a) component is active Nickel where Nickel is from 25 to 60 wt.% from the composition of the catalyst; (b) a molybdenum component, in which the molybdenum content is from 5 to 20 wt.% from the composition of the catalyst; and (c) from 10 to 50 wt.%, based on the weight of the composition of the catalyst, a binder containing at least one of silicon oxides and silicates and oxides of zinc, aluminum, zirconium, magnesium and calcium, each of these aluminium, calcium and zinc is present in an amount of not more than 2 wt.%, based on the weight of the catalytic composition.

2. The catalytic composition under item 1, in which the molybdenum is from 6 to 16 wt.% from the composition of the catalyst.

3. The catalytic composition under item 1 or 2, in which the particle diameter is less than 0,32 see

4. The catalytic composition according to any one of paragraphs.1, 2 or 3, in which the Nickel is from 25 to 45 wt.% from the composition of the catalyst.

5. To the et in the amount of not more than 1 wt.%, based on the weight of the catalytic composition.

6. The method of obtaining 1,3-propane diol, comprising (a) contacting 3-hydroxypropane and hydrogen in the aqueous reaction mixture at a temperature at least 30C in the presence of a solid granular catalyst composition comprising (i) Nickel component is active, in which Nickel is from 25 to 60 wt.% from the composition of the catalyst; (ii) a molybdenum component, in which the molybdenum content is from 5 to 20 wt.% from the catalytic composition; and iii) 10 to 50 wt.%, based on the weight of the catalytic composition, the binder material containing at least one of silicon oxides and silicates and oxides of zinc, aluminum, zirconium, magnesium and calcium, each of these aluminium, calcium and zinc is present in an amount of not more than 2 wt.%, based on the weight of the catalytic composition, with the formation of water of the mixture of products containing 1,3-propandiol; and (b) the allocation of 1,3-propane diol from an aqueous mixture of products.

7. The method according to p. 6, in which the molybdenum is from 6 to 16 wt.% from the composition of the catalyst.

8. The method according to p. 6 or 7, in which the diameter of the solid particles is less than 0,32 see

9. The method according to any of paragraphs.6, 7, or 8, in which the catalytic Kumkoy composition.

10. The method of obtaining 1,3-propane diol, comprising a) contacting of ethylene oxide with carbon monoxide and hydrogen under conditions of hydroformylation and in the presence of an effective amount of catalyst hydroformylation, with formation of a mixture of reaction products containing 3-hydroxypropyl, b) removing the 3-hydroxypropane from a mixture of reaction products with the formation of aqueous 3-hydroxypropyl; (c) adding to an aqueous solution of 3-hydroxypropane solid granular composition of the hydrogenation catalyst containing (i) a component of active Nickel where Nickel is from 25 to 60 wt.% from the composition of the catalyst; (ii) a molybdenum component, in which the molybdenum content is from 5 to 20 wt.% from the catalytic composition; and iii) 10 to 50 wt.%, based on the weight of the catalytic composition, the binder material containing at least one of silicon oxides and silicates and oxides of zinc, aluminum, zirconium, magnesium and calcium, each of these aluminium, calcium and zinc is present in an amount of not more than 2 wt.%, based on the weight of the catalytic composition; (d) heating the aqueous solution of 3-hydroxypropane to a temperature at least 30C, with excess ol; and (e) the allocation of 1,3-propane diol from a mixture of the products of hydrogenation.

 

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