Granular hydrogenation catalyst nickel/transition alumina (options), the catalyst precursor concentrate and method for producing the catalyst

 

Usage: petrochemistry. The granular catalyst for the hydrogenation of fats or oils, containing from 5 to 75 wt.% Nickel is produced by suspendirovanie powder of the transition alumina having the average surface diameter D[3,2] in the range from 1 μm to 20 μm in aqueous solution emeakaroha complex of Nickel followed by heating to precipitate insoluble compounds Nickel and then restoring the last. Catalysts containing up to 55 wt.% Nickel, have a surface area of Nickel of more than 130 m2/g of Nickel. Catalysts having a higher content of Nickel, obtained using alumina having an average pore diameter of more than 12 μm, can have a smaller surface area of the Nickel. The technical result is an increase in the activity and selectivity of the catalyst. 4 N. and 11 C.p. f-crystals, 8 PL.

The present invention relates to catalysts and, in particular, the catalysts suitable for use in the hydrogenation, in particular the hydrogenation of oils and fats.

Oils and fats are often partially or completely hydronaut periodic suspension process by suspension of powdered Nickel catalyst in oil or LM>/img>With, perhaps under pressure, for example, at an absolute pressure up to 30 bar (3 MPa). For the partial hydrogenation pressure is usually below 10 bar (1 MPa abs., for example, from 2 to 4 bar (0.2 to 0.4 MPa) abs. For hydrogenation of oils or grease the catalyst should have high activity, so that a given degree of hydrogenation can be achieved in a short period of time and/or that could be used a small amount of Nickel. In the case of partial hydrogenation, the catalyst should also have good selectivity, so as to minimize excessive hydrogenation of oils and fats. In addition, it is desirable that the residual catalyst was easy to filter out from providerone oil or fat, and that the catalyst had good properties from the point of view of reuse.

Frequently used for this type catalysts are Nickel on a substrate, such as aluminum oxide, and is characterized by, among other things, high surface area Nickel per gram of Nickel. Typical catalysts having a high Nickel content, is described in EP 0168091, where the catalyst is prepared by precipitation of the Nickel compound and then adding a soluble compound of aluminum in the received catalyst precursor recovered catalyst typically has a surface area of the Nickel of the order of from 90 to 150 m2on 1 g of the total Nickel. The catalysts have an atomic ratio of Nickel/aluminum in the range from 2 to 10. The recovered catalysts have an atomic ratio of Nickel/aluminum > 2, where at least 70 wt.% all of the Nickel is reduced to atomic Nickel, and have a total Nickel content of more than about 66 wt.% .

In US-A-4191664 and US-A-4064152 describe thermally stable catalysts type Nickel/alumina obtained by the precipitation of Nickel hydroxide powder carrier hydrated oxide of aluminum.

The hydrogenation catalysts of the type Nickel/alumina, having a total Nickel content of from 5 to 40 wt. % as well as having a large surface area of Nickel, obtained by various methods described in US 4490480. In the method according to the last link, Nickel-amically complex, in particular ammicht Nickel carbonate, is heated in the presence of transitional forms of alumina. This leads to the precipitation of Nickel compounds such as Nickel hydroxide or basic Nickel carbonate, forming a homogeneous mixture of aluminum oxide.

In this latter method, the alumina powder may be suspended in a solution of a complex of Nickel, or molded particles, such as spheres is as aluminum, impregnated with a solution of a complex of Nickel. Although the described catalysts having a surface area of Nickel of more than 130 m21 g total Nickel, and even in some cases more than 20021 g total Nickel, all such products with highly developed surface produced by the method described above impregnation using molded particles of aluminum oxide; the catalysts obtained by suspendirovanie oxide powder of aluminum, Nickel complex, have a surface area of Nickel significantly less than 130 m21 g of total Nickel. Although the catalysts obtained using pre-formed particles of aluminum oxide of a certain shape, suitable methods of hydrogenation with a fixed layer, they are not suitable for the above-mentioned periodic suspension hydrogenation process, because of the size, they tend to fall out of suspension, and, in case of partial hydrogenation, they tend to lead to excessive hydrogenation of fats and oils. In the above patent US 4490480 noted that the catalysts suitable for periodic suspension hydrogenation, can be obtained by grinding the catalyst with a large surface of Nickel, obtained is the development of such catalysts according to this technique includes additional technological operations of forming the aluminum oxide in the formed particles and the subsequent stage of crushing.

The catalysts obtained directly from a powder of aluminum oxide size of 60-70 microns, containing 18-28 wt.% Nickel and having a surface area of Nickel up to 123 m21 g of Nickel, also described in the aforementioned patent US 4490480. However, applicants have found that such materials have a relatively low activity in the hydrogenation of oils.

Currently, applicants have found that catalysts of the type Nickel/aluminum oxide having a high activity and/or good selectivity, can be manufactured by the method described above, which uses a suspension of alumina powder, if you use an alumina powder having particles of small size. Despite the use of particles of aluminum oxide is small in size, catalysts unexpectedly easily filtered out from providerone fat or oil.

In GB 926235 were offered hydrogenation catalysts in this way when using diatomaceous earth as a carrier. However, applicants have found that catalysts made using diatomaceous earth particles of small size, in contrast to the transitional forms of alumina, does not have large areas of the surface of Nickel.

That is the future from 5 to 75 wt.% total Nickel, including the suspension of the powder transient polymorphic forms of aluminum oxide, hereinafter in this description referred to as “transition alumina”, having an average surface diameter D[3,2] in the range from 1 μm to 20 μm with an aqueous solution emeakaroha complex of Nickel, heating the suspension to cause decomposition emeakaroha complex of Nickel with deposition of insoluble Nickel compounds, filtering off the solid precipitate from the aqueous medium, drying and, if desired, after calcination of the solid residue, and recovering the solid residue.

The term “total Nickel” applicants mean the amount of Nickel in elemental or combined form. Usually, however, at least 70 wt.% total Nickel in the recovered catalyst is in the elemental state.

The term “average surface diameter D[3,2]”, otherwise known average diameter Sauter (Sauter), defined M. Alderliesten in the article “A Nomenclature for Mean Particle Diameters”; Anal. Proc., vol. 21, May 1984, pages 167-172, and is calculated on the basis of the analysis of particle size, which is convenient to carry out laser diffraction, for example, when using the device Malvern Mastersizer.

The transition alumina can be from -aluminum oxide. These materials can be obtained by calcining the hydroxides of aluminum at 400-750With and generally have a surface area according to BET in the range of 150-400 m2/, alternatively, the transition alumina can be from the group-oxides of aluminum, which includes high-temperature form, such asand-oxides of aluminum, which can be obtained by heating the oxides of aluminumgroup to temperatures above approximately 800C.-aluminium oxides typically have a surface area according to BET in the range from 50 to 150 m2/year Transitional alumina containing less than 0.5 mol of water per mol of Al2O3and the actual content of water depends on the temperature to which they were heated. The aluminum oxide must be porous, preferably having a pore volume of at least 0.2 ml/g, in particular in the range from 0.3 to 1 ml/,

Preferably, a small aluminium oxide particles had a relatively large average pore diameter of, because, as it turns out, the use of such oxides of aluminum gives the catalysts especially XB particular in the range from 15 to 30 nm. (The term “average pore size” applicants understand quadruple pore volume, measured by desorption branch of the isotherm physisorption nitrogen at a relative pressure of 0.98, divided by the surface area according to BET). During the preparation of the catalyst of the Nickel compounds are precipitated in the pores of the aluminum oxide, and, thus, the average pore diameter of the catalyst will be less than the applied aluminum oxide, and decreases in proportion to the increase of Nickel. Preferably, the recovered catalyst had an average pore diameter of at least 10 nm, more preferably 15 nm and in particular in the range from 15 to 25 nm.

On the other hand, regardless of the content of Nickel in the catalyst, the particle size of the catalyst is substantially the same as the particle size of the transition alumina, and thus the catalysts usually have an average surface diameter D[3,2] in the range from 1 to 20 microns and preferably less than 10 μm, in particular less than 8 microns.

The catalysts according to the invention contain from 5 to 75 wt.% total Nickel, preferably less than 70 wt.% total Nickel. Catalysts containing up to about 55%, preferably from 5 to 45 wt.% total Nickel, usually have an area of the surface is 2 1 g total Nickel.

Thus, the present invention also features a powder catalyst hydrogenation type Nickel/transition alumina containing from 5 to 55 wt.% total Nickel having a surface area of Nickel, at least 130 m2per gram of total Nickel and weighted mean surface diameter D[3,2] in the range from 1 μm to 20 μm.

The surface area of the Nickel can be determined as described in “Physical and Chemical Aspects of Adsorbents and Catalysts”, edited by B. G. Linsen, Academic Press, 1970 (London and New York, pages 494 and 495, and is the surface area restored, i.e., elemental Nickel in the catalyst.

Applicants have found that in General the surface area of the Nickel catalysts obtained in the method according to the invention, has a tendency to decrease with increasing Nickel content. However, applicants have also discovered that catalysts made using alumina with large pores and containing relatively large amounts of Nickel are unexpectedly active and selective, even if they do not have such a large surface area of the Nickel. Thus, suitable catalysts containing at least 20 wt.% total Nickel having an average pore diameter of more than 10 xadow aluminum with large pores.

Accordingly, the present invention also features grainy or granular (i.e., in the form of particulate - grains or granules), the hydrogenation catalyst type Nickel/transition alumina containing from 20 to 75 wt.% total Nickel having a surface area of Nickel, at least 110 m2per gram of total Nickel-weighted average surface diameter D[3,2] in the range from 1 μm to 20 μm and an average pore diameter of at least 10 nm, more preferably 12 nm and in particular in the range from 15 to 25 nm.

Catalysts containing at least 20 wt.% total Nickel having a surface area of Nickel up to 80 m2/g total Nickel, exhibit good activity and selectivity, provided that the average pore diameter of greater than 15 nm.

Accordingly, the present invention also offers granular hydrogenation catalyst Nickel/transition alumina containing from 20 to 75 wt.% total Nickel having a surface area of Nickel, at least 80 m2per gram of total Nickel-weighted average surface diameter D[3,2] in the range from 1 μm to 20 μm, and an average pore diameter of at least 15 nm.

The catalysts can be obtained by suspendirovanie powder EP product of the dissolution of the basic Nickel carbonate in a solution of ammonium carbonate in aqueous ammonium hydroxide, with obtaining a product with the desired Nickel content. The solution emeakaroha complex of Nickel preferably has a pH in the range of 9 to 10.5. Then the suspension is heated, for example, to a temperature in the range from 60 to 100With to induce the decomposition emeakaroha complex of Nickel with the release of ammonia and carbon dioxide and the precipitation of insoluble compounds Nickel, for example, basic Nickel carbonate on the surface and in the pores of the transition alumina. Then the alumina bearing besieged compound of Nickel is filtered off from the aqueous medium and dried. It can be calcined in air, for example, at a temperature in the range from 250 to 450°C for the decomposition of precipitated Nickel compound to Nickel oxide. When the recovery of Nickel oxide is generated large surface area of the Nickel. Alternatively, the precipitated Nickel compound can be restored directly, i.e. without having the stage of calcination. This recovery with or without the use of the previous stage of the calcination can be carried out by heating to a temperature in the range from 250 to 450In the presence of hydrogen.

As noted above, these catalysis sunflower oil. Alternatively, the catalysts may be used in other hydrogenation reactions, such as hydrogenation of olefinic compounds, such as waxes, nitro or nitrile compounds, for example, by conversion of nitrobenzene to aniline or conversion of NITRILES to amines. They can also be used for the hydrogenation of paraffin wax to remove them traces of unsaturation.

As noted above, in this method of hydrogenation required amount of catalyst suspended in loading oil or fat and the mixture is heated, possibly under pressure, with the introduction of hydrogen, for example, by bubbling through the mixture. It is convenient to load the catalyst in the vessel for hydrogenation in concentrate catalyst particles dispersed in a suitable medium carrier, for example, the cured soy oil. The preferred amount of catalyst in the specified concentrate is such that the concentrate has a total Nickel content of from 5 to 30%, preferably from 10 to 25 wt.%.

Alternatively, in some cases, recovery may be performed in situ. Thus, the precursor comprising a transition alumina and unrestored connection of Nickel, for example, the oxide may be in the form of a concentrate, i.e. dispersive, and the mixture is heated under bubbling hydrogen through the mixture.

Accordingly, the applicants also propose that the predecessor of the hydrogenation catalyst containing a transition alumina and reducible compound of Nickel, which when recovering hydrogen at a temperature in the range from 250 to 450With gives granular hydrogenation catalyst containing from 5 to 55 wt.% total Nickel having a surface area of Nickel, at least 130 m2per gram of total Nickel and weighted mean surface diameter D[3,2] from 1 μm to 20 μm, preferably less than 10 microns.

Applicants also propose that the predecessor of the hydrogenation catalyst containing a transition alumina and reducible compound of Nickel, which when recovering hydrogen at a temperature in the range from 250 to 450With gives granular hydrogenation catalyst containing from 20 to 75 wt.% total Nickel having a surface area of Nickel, at least 80 m2per gram of total Nickel and weighted mean surface diameter D[3,2] from 1 μm to 20 μm, preferably less than 10 microns and an average pore diameter of more than 10 nm.

The invention is illustrated by the following examples, VDI Nickel surface are determined, as described in “Physical and Chemical Aspects of Adsorbents and Catalysts”, edited by B. G. Linsen, Academic Press, 1970 (London and New York, pages 494 and 495, when using a recovery time of 1 hour.

Example 1

Used aluminum oxide is a transition alumina typewith a surface area of about 108 m2/g and a pore volume of about of 0.42 ml/g and having an average surface diameter D[3,2] a 3.87 μm. The average diameter of the pores, thus, is about 16 nm.

The original solution containing amically Nickel complex was obtained by dissolving per liter of starting solution of 52.1 g of basic Nickel carbonate (48% Ni, 20% CO3), with 37.4 g of ammonium carbonate (32,5% NH3, 55% CO3) and 133 g of 30% NH3water.

Particles of aluminum oxide and sufficient to obtain approximately 33 grams of Nickel per 100 g of aluminum oxide, the amount of the original solution was loaded into a mixing vessel equipped with a fridge. pH of aqueous solution was 10.2. The mixture was heated to boiling and maintained under stirring and careful boiling at about 96With up until the solution became transparent after about 90 minutes and Then the solid precipitate was filtered, washed and then dried during the night is icela 19,6 %, then restored by passing hydrogen through a bed of the catalyst when heated to 430C.

The recovered catalyst (referred to as catalyst A) had a total Nickel content of 24.7% and a surface area of Nickel of about 187 m21 g total Nickel (about 46 m21 g of catalyst). The average diameter of pores of the catalyst was approximately 9,5 nm, and the surface area BET was $ 135 m2/,

Weighted average on the surface of the particle diameter of the recovered catalyst was similar to that applied by the transitional alumina.

Example 2 (comparative)

The catalyst, designated as catalyst B, was obtained in accordance with the methods of EP 0168091, using as alkaline precipitant solution containing 66.6 g of sodium carbonate and 25.4 g of sodium hydroxide per liter, and the solution containing 35 grams of Nickel per liter. These two solutions are continuously fed into the vessel for deposition. This deposition was used at room temperature (22C) the average processing time (delay time) 30 s and the energy of mixing 25 kW/m3. The solution emerging from this vessel for deposition was continuously applied to the stabilization reactor, liter, also continuously applied to the stabilization reactor under moderate stirring at energy consumption 2 kW/m3. The slurry leaving the second reactor was collected in a third vessel and maintained at 60With over five hours. The suspension is then filtered and washed with water at 70C. the Washed precipitate resuspendable in water at 70C and then subjected to spray drying. Elemental analysis of the dried spray drying of the product gave the following composition: 45,6% Nickel, 4.0% aluminum, 0.02% sodium. Dried spray dried product was recovered at 430With in a stream of hydrogen for 30 minutes and then was used as catalyst C. the surface area of the Nickel was 115 m21 g total Nickel.

The above-described receiving repeated with the receipt of the same catalyst, designated as catalyst C. Hydrogenating characteristics of the catalysts were determined by using two different oils as follows.

In the first experiment used soybean oil with IV 133,5 and containing 1.8 million-1R, 1600 million-1free fatty acids, 100 million-1water, and 0 million-1soap and S.

200 g butter Denmark. The mixture was heated to 160With hydrogen was barbotirovany through the suspension at a pressure of 2 bar (0.2 MPa) abs. The hydrogenation was performed isothermal. The amount of absorbed oil hydrogen controlled, and the experiment was stopped as soon as the used amount of hydrogen required to reduce IV to 70. The reaction time to achieve IV 70 used as a measure of catalyst activity.

In the second experiment used sunflower oil with IV 132 and containing 0.4 m-1R, 800 million-1free fatty acids, 600 million-1water, 4 million-1soap and 0.5 million-1S. Hydrogenation was performed as described above, but at 120C and at a pressure of 4 bar (0.4 MPa) abs. and determined the time needed to reach the IV 80.

The results are shown in table. 1.

It is seen that the catalyst in accordance with the invention was significantly more active than the catalysts of comparison, and because the time of hydrogenation decreased and/or could be used a smaller amount of Nickel.

The selectivity of the catalysts was evaluated on the basis of offsetting the melting point, solid fat content at 10With 20C, 30To and maintained at a pressure of 3 bar (0.3 MPa) abs. in a vessel having in its bottom an outlet opening area of 0.5 cm2. This hole contains a base of steel wire, which was attached pre-coated with 0.02 g of accelerator filter fabric in such a way that all the oil was filtered through filter cloth. The time taken to filter 120 g butter, used as a measure of filterability. Selectivity and filterability are presented in table. 2.

Example 3

The method of example 1 was repeated, but using such quantities emeakaroha complex of Nickel, to get approximately 50 g of Nickel per 100 g of alumina. The recovered catalyst had a total Nickel content of 33.7% and a surface area of Nickel 161 m21 g total Nickel.

Example 4

The method of example 1 was repeated, but using different amounts of solution emmakate Nickel carbonate in relation to the amount of aluminum oxide for some predshestvennikom Nickel.

Example 5

The method of example 4 was repeated using aluminum oxide with a large diameter pores. Used aluminum oxide represented a transitional alumina type- Al2O3with a surface area of approximately 145 m2/g and a pore volume of about of 0.85 ml/g and having an average surface diameter D[3,2] of 2.08 μm. The average diameter of pores was approximately 23 nm. As in example 4, was obtained a number of catalysts (catalysts G, H, I, J and K) with different Nickel content.

The physical properties of the catalysts of examples 4 and 5 are presented in table. 3.

Comparison of catalysts F and shows that while a smaller pore size of the substrate of aluminum oxide, the introduction of a large number of Nickel leads to a small surface area of the Nickel, the use of aluminum oxide with a large pore size allows to obtain catalysts having a relatively large surface area of the Nickel. Catalysts (except for catalysts F and K) were tested as in examples 1-2, and the results are shown in table. 4-5.

Example 6

Samples predecessors used to obtain Katyusha examples obtaining catalysts L and M, respectively, and then tested as described above. The surface area of the Nickel was determined for catalyst L, and it was 114 m2/g total Nickel, i.e., close to square (115 m2/g total Nickel) of the respective catalyst - catalyst J, restored at 430C. the Results are shown in table. 6, 7.

This shows that these catalysts having a relatively high Nickel content, can be obtained satisfactory catalysts using low temperature recovery. In particular, it is noted that while the catalyst To high Nickel content (67,3% ) during recovery at 430With had a relatively low surface area of Nickel (88 m2/g total Nickel), characteristics of the corresponding catalyst, i.e. the catalyst M, recovered at a lower temperature 360With, were similar to or better than catalyst H, which was significantly lower Nickel content (35.5 per cent ), but significantly more surface area Nickel (117 m2/g total Nickel).

Example 7

the and aluminum: ALCOA HiQ7412F, brand Q1037 and Q1058 respectively. Brand Q1037 had an average surface diameter D[3,2] of 4.4 μm, a pore volume of 0.44 ml/g and surface area BET 137 m2/g, which gave an average pore diameter of about 13 nm. Brand Q1058 had a particle size (d 3,2) of 1.5 μm, a pore volume of 0.34 ml/g and surface area BET 117 m2/g, which gave an average pore diameter of about 12 nm. The catalysts were obtained using relations aluminum oxide:Nickel 2,25 mass.

Characteristics of hydrogenation catalysts tested using soybean oil as described in example 2, and the results are shown in table. 8.

Claims

1. Granular hydrogenation catalyst Nickel/transition alumina containing from 5 to 75 wt.% total Nickel having a surface area of Nickel, at least 80 m2per gram of total Nickel and weighted mean surface diameter D[3,2] in the range from 1 to 20 microns.

2. The granular catalyst under item 1, having a surface area of Nickel, at least 110 m2per gram of total Nickel.

3. The granular catalyst under item 1 or 2, containing from 5 to 55 wt.% total Nickel having a surface area of Nickel, at least 130 m2per gram of total Nickel is having a total Nickel content in the range from 20 to 35 wt.%.

5. The granular catalyst under item 3 or 4, having an average pore diameter of more than 10 nm.

6. The granular catalyst under item 1, containing from 20 to 75 wt.% total Nickel having a surface area of Nickel, at least 80 m2per gram of total Nickel-weighted average surface diameter D[3,2] in the range of 1 to 20 μm and an average pore diameter of more than 15 nm.

7. The granular catalyst under item 6, which has a surface area of Nickel of more than 110 m2per gram of total Nickel.

8. The granular catalyst under item 1, containing from 20 to 75 wt.% total Nickel having a surface area of Nickel, at least 110 m2per gram of total Nickel, and particles having average surface diameter D[3,2] in the range of 1 to 20 μm and an average pore diameter of more than 10 nm.

9. The granular catalyst according to any one of paragraphs.1-8 having a total Nickel content of less than 70 wt.%.

10. The granular catalyst according to any one of paragraphs.1-9, having an average surface diameter D[3,2] of less than 10 microns.

11. The catalyst precursor comprising a transition alumina and reducible compound of Nickel, which when recovering hydrogen at a temperature in the range from 250 to 450With network granulated cacao from 5 to 75 wt.% total Nickel, including the suspension of the powder of the transition alumina, having an average surface diameter D[3,2] in the range from 1 to 20 microns, in an aqueous solution emeakaroha complex of Nickel, heating the slurry to decompose emeakaroha complex of Nickel with deposition of insoluble Nickel compounds, filtering off the solid precipitate from the aqueous medium, drying and, optionally, after calcination of the solid residue, and recovering the solid residue.

13. The method according to p. 12, in which the alumina powder has an average pore diameter of at least 12 nm.

14. The method according to p. 12 or 13, in which the transition aluminium oxide is a-aluminum oxide.

15. The concentrate containing from 10 to 25 wt.% Nickel, including granular catalyst according to any one of paragraphs.1-10, or the catalyst precursor under item 11, or granular catalyst obtained by the method according to any of paragraphs.12-14, dispersed in the carrier.

Priority items:

27.07.1999 on PP.1-3, 5-9, 11-13;

02.02.1999 on PP.4, 10, 14-15.

 

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EFFECT: enhanced sorption and photo-catalytic parameters; reproducibility of catalyst properties.

7 cl, 68 ex

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