JPH0436741B2 - - Google Patents

Description

[Detailed description of the invention]

In the present invention, the nickel catalyst used in the hydrogenation process of oils and fats is made into a nickel sulfate solution, treated with a chelate resin or a combination of a chelate resin and an adsorbent, and impurities contained in the nickel catalyst solution are removed. This invention relates to a method for regenerating a nickel catalyst. Nickel catalysts are currently one of the most common catalysts used in hydrogenation processes, and are used in many industries including the oil and fat industry. However, used nickel catalysts are contaminated with metals such as iron, zinc, and copper, as well as impurities such as phosphorus compounds and sulfur compounds, making it impossible to reuse them as they are. . Therefore, the used nickel catalyst is either sold or disposed of at a low price, or the used nickel catalyst is heated with sulfuric acid to make a nickel sulfate solution, and then mixed with sulfuric acid powder, sodium hypochlorite, hydrogen peroxide, etc. A disposal method has been adopted in which impurity metals are removed as metal hydroxides by oxidizing with an oxidizing agent and then adding an alkali. However, the treatment method that removes metal hydroxides cannot remove impurities such as iron, zinc, and copper to low concentrations, and even if the treated nickel sulfate solution is post-treated as a nickel catalyst, its catalytic ability is still insufficient. Because it is inferior to the nickel catalyst used,
There are disadvantages such as increased usage. Therefore, the present inventors conducted intensive research to solve these drawbacks, and found that by adding sulfuric acid to the nickel catalyst used and heating it, the resulting nickel sulfate solution was treated with a chelate resin to produce iron, zinc, and copper. It was discovered that impurities such as can be almost completely adsorbed and removed. In addition, if the nickel sulfate solution contains a large amount of sulfur compounds or phosphorus compounds as impurities, either before or after treatment with the chelate resin,
Activated clay, activated alumina, activated carbon, as adsorbents
It has been found that impurities can be almost completely adsorbed and removed by treatment using an inorganic adsorbent such as bone char or a porous polymer adsorbent. Furthermore, the regenerated nickel catalyst obtained by post-treating the nickel sulfate solution obtained by treating a chelate resin or a combination of a chelate resin and an adsorbent using a conventional method has a catalytic performance almost equivalent to that of a commercially available nickel catalyst. It was confirmed that the catalyst could be used satisfactorily as a catalyst in the hydrogenation process. The performance test as a catalyst was conducted by determining activity and selectivity. Furthermore, examples of conventional post-treatment methods include wet methods. The method is to add a carrier such as diatomaceous earth or alumina and sodium carbonate to a nickel sulfate solution, separate the resulting precipitate into solid and liquid, wash it with water, and then undergo a drying and reduction process to obtain a nickel catalyst. The chelate resin that has adsorbed impurities such as iron, zinc, and copper according to the present invention can be easily regenerated with acid or alkali and used again to treat nickel sulfate solution. The chelate resin in the present invention has at least one of iminodiacetic acid group, iminopropionic acid group, iminodipropionic acid group, aminoalkylene phosphate group, dithiocarbamate group, etc. as a functional group, and has styrene- It is a chelate resin made from any one of the group consisting of divinylbenzene copolymer resin, phenolic resin, epoxy resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, and urea resin. These chelate resins can be those produced according to conventional methods. For example, as a chelate resin using styrene-divinylbenzene as a resin base, after chloromethylating its aromatic nucleus, a chelate resin is produced by reacting with iminodiacetic acid, iminopropionic acid, or iminodipyropionic acid to introduce the corresponding functional group. Resin, chloromethylated resin is reacted with polyalkylene polyamine, then formaldehyde,
Chelate resins that introduce aminoalkylenephosphonic acid groups by reacting alkylating agents such as paraformaldehyde and trioxane with phosphorylating agents such as phosphorous acid and phosphorus trihalide, and reacting polyalkylene polyamines with chloromethylated resins. Examples include chelate resins in which dithiocarbamic acid groups are introduced by reacting carbon disulfide in the presence of an alkali metal hydroxide. Chelate resins using phenolic resins and urea resins as resin bases include aminoalkylene phosphonic acid groups obtained by reacting iminodiacetic acid, iminopropionic acid, iminodipropionic acid, and polyalkylene polyamines with alkylating agents and phosphorylating agents. A compound obtained by condensing a compound having a dithiocarbamic acid group by reacting a polyalkylene polyamine with carbon disulfide in the presence of sodium hydroxide, and aldehydes and phenols or aldehydes, phenols and urea. Examples include chelate resins having corresponding functional groups and resin matrix. As a chelate resin that uses epoxy resin as a resin base,
Iminodiacetic acid, iminopropionic acid, iminodipropionic acid, a polyalkylene polyamine compound having an aminoalkylene phosphonic acid group, a polyalkylene polyamine compound having a dithiocarbamate group, etc. are reacted with a crosslinking agent such as ethylenediamine, diethylenetriamine, etc., and a bisepoxide compound. Examples include chelate resins obtained by As a chelate resin using acrylic resin, vinyl chloride resin, or vinylidene chloride resin as a resin base, acrylic resin, vinyl chloride resin, or vinylidene chloride resin is reacted with a polyalkylene polyamine, and then monochloroacetic acid, monochloropropionic acid, and an alkylating agent are used. Examples include chelate resins made by reacting a phosphorylating agent, sodium hydroxide, carbon disulfide, etc., and having corresponding resin bases and functional groups. Moreover, among the adsorbents in the present invention, the porous polymer adsorbents have −CO ₂ −, − as active groups.
_NO2 , -OH, _-NH2 , -COOH, -SH, _-SO3H ,
or not have any of the above active groups, and the resin base includes styrene-divinylbenzene copolymer resin, phenol resin, epoxy resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin. , a porous polymeric adsorbent made of any one of the group of urea resins. In the present invention, the nickel sulfate solution can be treated using a chelate resin or a combination of a chelate resin and an adsorbent, such as a batch method in a container, an upward flow or a downward flow after filling a resin column with the chelate resin or adsorbent. Examples include, but are not limited to, a column method using a one-time method or a circulation method in which a nickel sulfate solution is passed through in a countercurrent flow. When treating the nickel sulfate solution in the present invention, a conventional method for removing metals as impurities is used as a pretreatment, and the treated solution is treated with the chelate resin of the present invention or a combination of the chelate resin and an adsorbent. It is also possible. If the conventional method and the present invention are used together in this way, the content of metal as an impurity can be reduced in advance, so the load on the chelate resin can be reduced, compared to the case of the present invention alone. More economical. Hereinafter, the present invention will be explained in detail with reference to Examples. Example 1 A nickel catalyst used in the soybean oil hydrogenation step was heated with sulfuric acid to obtain a nickel sulfate solution. Next, it has an iminodiacetic acid group as a functional group,
After separately filling two columns (inner diameter 80 mmφ) with chelate resin 1 having a phenol-formalin resin as a matrix and activated carbon 1, a nickel sulfate solution containing the above impurities (containing 4.5% Ni) was added. , chelate resin, and activated carbon were passed in this order at a flow rate of SV3 (per tower) in a downward flow. Table 1 shows the water quality of the impurity-containing nickel sulfate solution, Table 2 shows the water quality of the chelate resin treatment solution, and Table 3 shows the water quality of the activated carbon treatment solution. The activated carbon treatment solution with a liquid flow rate of up to 60/-R is collected, diatomaceous earth and sodium carbonate are added to this solution as post-treatment, the resulting precipitate is separated into solid and liquid, and the resulting solid content is washed with water and dried. , Regenerated nickel was obtained through a reduction process. Table 4 shows the composition of the precipitate obtained by adding sodium carbonate. Performance tests were conducted on the regenerated nickel catalyst and the new nickel catalyst to determine their activity and selectivity. The results are shown in Table-5. From Table 5, the regenerated nickel catalyst (Example 1) has almost the same performance as the new nickel catalyst. The activity of the nickel catalyst is determined using the AOCS test method.
In accordance with TZ-1a-78, conditions were determined to hydrogenate IV135 soybean oil to IV80 in 60 minutes using a standard nickel catalyst, and hydrogenation was performed using a regenerated nickel catalyst under the same conditions. The degree of decrease in IV (ΔIV) was measured, and the ratio of both degrees of decrease in IV was determined, which was determined as the activity of the regenerated nickel catalyst. Activity of regenerated nickel catalyst = ΔIV/(135−
80). Selectivity of nickel catalyst is determined by AOCS test method TZ 1a
-79, the hydrogenation reaction of soybean oil was carried out, and the ratio (SR) of the hydrogenation rate to linoleic acid groups and the hydrogenation rate to oleic acid groups was determined.
The larger the value, the faster the hydrogenation rate for linoleic acid groups than for oleic acid groups, indicating that an oil or fat containing highly purified oleic acid as a constituent fatty acid can be obtained.

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[Table] Comparative Example 1 Added 0.7% Sarashi powder to a nickel sulfate solution obtained by heating with sulfuric acid in the same manner as in Example 1, and heated at 50°C.
The mixture was stirred under heating for 2 hours. Next, a caustic soda aqueous solution was added to adjust the pH to 5, and after stirring for 2 hours, the resulting precipitate was separated into solid and liquid. The obtained nickel sulfate solution was post-treated in the same manner as in Example 1 to obtain a regenerated nickel catalyst. Table 4 shows the composition of the precipitate produced by adding diatomaceous earth and sodium carbonate to the alkali-treated nickel sulfate solution, and Table 5 shows the performance test results of the purified nickel catalyst. Example 2 The nickel catalyst used in the fish oil hydrogenation process was heated with sulfuric acid to obtain an aqueous nickel sulfate solution. Next, a column (inner diameter 120 mmφ) was filled with a chelate resin 3 having an aminomethyl phosphate group as a functional group and having a styrene-divinylbenzene copolymer resin as its base material, and then a nickel sulfate solution containing the above impurities ( (containing 4.1% Ni) was circulated at a flow rate of SV2 upward flow. Next, 1% activated alumina was added to the nickel sulfate obtained by the chelate resin treatment, and the mixture was stirred for 1 hour, followed by solid-liquid separation. Table 6 shows the water quality of the nickel sulfate solution before the chelate resin treatment and the nickel sulfate solution after the same treatment. Next, the treated nickel sulfate solution was post-treated in the same manner as described in Example 1 to obtain a regenerated nickel catalyst.

[Table] Example 3 Sulfuric acid was added to the nickel catalyst used in the palm oil hydrogenation process and heated to obtain a nickel sulfate solution (containing 4.7% Ni). Next, 5% of a chelate resin having an iminopropionic acid group and using an epoxy resin as a matrix was added to the nickel sulfate solution, and the mixture was stirred in the reaction vessel for 2 hours. The resulting nickel sulfate solution was post-treated in the same manner as described in Example 1 to obtain a regenerated nickel catalyst. Example 4 The nickel catalyst used in the rapeseed oil hydrogenation step was heated with sulfuric acid to obtain a nickel sulfate solution (containing 4.6% Ni). Next, a chelate resin 3 having a dithiocarbamic acid group and having a resorcinol-formalin resin as a matrix and an internal surface area of 560
After filling two columns (inner diameter 120 mmφ) with the polymer adsorbent 3 based on a styrene-divinylbenzene copolymer resin with m ² /g,
The nickel sulfate solution containing the above impurities was passed through the polymer adsorbent and the chelate resin in this order at a flow rate of SV5 in a downward flow. The nickel sulfate solution that flowed out to a liquid flow rate of 80/-R was post-treated in the same manner as in Example 1 to obtain a regenerated nickel catalyst. Example 5 Using the regenerated nickel catalysts obtained in Examples 2, 3, and 4, a soybean oil hydrogenation reaction test was conducted to determine the activity and selectivity of each catalyst. The results are shown in Table-7.

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Claims (1)

[Claims] 1. Sulfuric acid is added to the nickel catalyst used in the hydrogenation process of fats and oils to make a nickel sulfate solution, and the functional groups are iminodiacetic acid group, iminopropionic acid group, iminodipropionic acid group, aminoalkylene phosphate group, and dithiocarbamate group. A chelate resin comprising at least one of the following, and whose resin base is any one of the group consisting of styrene-divinylbenzene copolymer resin, phenol resin, epoxy resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, and urea resin. Alternatively, impurities in the nickel sulfate solution can be removed by treatment with a combination of the chelating resin and adsorbent, and then diatomaceous earth or alumina and sodium carbonate are added to the treated nickel sulfate solution to solidify the resulting precipitate. A method for regenerating a nickel catalyst, which is characterized by liquid separation, washing with water, drying, and reduction to obtain a nickel catalyst.