CS232648B1 - A method for producing liquid molybdenum concentrate - Google Patents

Abstract

The invention relates to a method of producing liquid molybdenum concentrate from deactivated molybdenum or molybdenum and cobalt or molybdenum and other metal containing catalysts or adsorbents or other substances. In one to ten cycles, preferably in two to four cycles, each part by mass of molybdenum contained in the deactivated catalyst or adsorbent or other molybdenum-containing substance is allowed to react with 1.25 to 12.9 parts by mass of ammonia or potassium hydroxide or sodium hydroxide in the form of their aqueous solutions at a temperature of 20 to 80 °C in a batch or countercurrent continuous method

Description

232648

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for the production of molybdenum molybdenum concentrate from deactivated molybdenum containing catalysts or other molybdenum containing an aqueous solution of ammonia and / or alkali hydroxide.

Molybdenum is one of the basic micro elements necessary for the harmonious development of certain types of cultures. Research has shown that molybdenum is a key component of the nitrogenase and nitrate reductase enzymes. The increased demand for molybdenum in most cultures growing on podes with higher nitrate content is explained by the presence of this. micronutrients in nitrated reductase, which controls the nitrate assimilation. In the function of stimulator and catalyst, molybdenum participates in protein formation, supports nitrogenase activity, and processes the nitrogen nitrogen transformation and its transformation to NH 3. Molybdenum is not only involved in the process of fixation of atmospheric nitrogen, but directly affects the physical chemical composition and activity of the cells of the bacteria Azobac ter Chlorococcum a. Clostritium butyricum. In the presence of molybdenum, the fastness of the N-fixing process is increased by 6 - 7 times, which is particularly important in the cultivation of bovine plants. In the case of leguminous materials, molybdenum is concentrated in the roots of the roots in which the azobacterial bacteria symbiotic live annually 40-50 kg N from the air. In the process of nitrogen fixation, molybdenum may be partially substituted by vanadium.

The sensitivity of the cultures to molybdenum is different. Among the molybdenum-sensitive cultures, peas, bean beans, clover, safflower, cauliflower, hops, vines, sugar beet and the like can be included.

Typical visual symptoms of molybdenum deficiency are necrotic spots of the nail that indicate reduced nitrogen assimilation. The symptoms of Mo deficiency may sometimes be the result of an unbalanced ratio between nitrogen and molybdenum, for example, at high nitrogen doses. The deficiencies in plant nutrition caused by the lack of molybdenum are most often corrected by curing interventions, by application of aqueous molybdenum solutions or by ammonium or on the leaf.

Uncommonly is the application of water-soluble molybdenum compounds, molybdenum oxide, molybdenum sulphide, optionally mineral or inactivated catalysts containing these compounds.

The preparation of molybdenum concentrates and preparations is the subject of MS. AO No. 213 814, AO 213 813, AO 199 324, AO 210 821, AO 210 820, AO 213 066 and AO 214 215. The use of ammonium molybdenum is limited due to its high cost and import character in agricultural practice.

It has now been found that liquid molybdenum concentrate equivalent to the solutions used can be made from deactivating polybdenum or molybdenum and cobalt or polybdenum and other metal-containing catalysts or adsorbents or other substances by the process of the invention.

In one to ten cycles, preferably two to four cycles, of batch or countercurrent continuous processes, each part by weight of molybdenum contained in a deactivated catalyst or adsorbent or other polybenzene-containing compound of 1.25 is reacted. and 12.9 parts by weight, preferably 2.5 to 10.65 parts by weight of ammonia or potassium hydroxide or sodium hydroxide at 20 to 80 ° C, preferably 20 to 50 ° C, and a clear product after separation isolated by sedimentation, filtration or centrifugation.

It has also been found that aqueous ammonia solution having a concentration of 2.5 to 20% by weight of NI-I3 or potassium hydroxide having a concentration of 2.5 to 50% by weight of KOH or sodium hydroxide by concentration of 2.5 to 40 may also be used for the reaction. % by weight of NaOH.

By leaching molybdenum-containing dis-activated catalysts or adsorbents, optionally other molybdenum-containing ammonia or sodium hydroxide or potassium hydroxide, molybdenum, generally present as MoO, is isolated in the corresponding water-soluble molybdenum, ammonium, potassium, and the like. sodium.

It has also been found that while in monocyclic extraction, the maximum yield of molybdenum in solution, at the choice of optimal reaction conditions, is in the range of 40-71 ° C, for multi-cycle extraction! yields of up to 98% - depending on the number of cycles, temperature and concentration of the base reactant. Furthermore, it was found that the yield is inversely proportional to the base concentration and directly proportional to the reaction temperature, which appears to be related to the solubility of the molybdenum compounds. The advantage of the process according to the invention is, in particular, that it makes it possible to obtain a molybdenum liquid concentrate, which is an equivalent substitute for the ammonium and sodium molybdate solutions used, using less valuable further unusable waste (petrochemical, nitrogenous, etc.). . A further advantage is that in the case of the treatment of molybdenum catalysts also containing cobalt ammonia, the concentrate enriched in another 100-element element is extracted from the system in the form of a water-soluble amocomplex.

The following examples illustrate the invention. Example 1 «. ί X '

207.77 wt% was charged to a reaction vessel equipped with a back-cooler and stirrer. 100 parts by weight of dilute ammonia water of 232848 5 concentration of 10% NH3 and with constant agitation were added. parts of a granulated molybdenum-containing cobalt-containing deactivated catalyst comprising 8.47% Mo and 2.96% Co. The reaction mixture was stirred at 28 ° C for 1 hour. After separation, a solid fraction of 198.8 wt. in the filtrate of composition: 2.1 wt. Moa 0,142 parts, co. which corresponds to a yield of 49.3% Mo and 9.5% Co. Example 2

As in Example 1, 207.77 wt.% Of the Mo and Co-deactivated catalyst of the same composition of Example 1 were added to 50 wt. dilute ammonia water at 5% NH 3. The reaction mixture was stirred for 1 h at 25 ° C. Upon separation of the solid, 200.0 wt. parts of filtrate of composition: 1.43% by weight of Mo and 0.033% by weight of Co, corresponding to a yield of 67.5% by weight of Mo and 4.5% by weight of Co Example 3

As in Example 1, a quantity of 207.77 wt.% Of a 50 wt.% Deactivated catalyst containing 8.47 wt.% Mo and 2.96 wt. ammonia water of 5% NH3. The resulting reaction mixture was stirred at 80 ° C for 1 hour. After the reaction time and filtration of the solid residue, 198 wt. parts of the filtrate of composition: 1.5% Mo and 0.03% Co, corresponding to 70.1% Mo and 4.0% Co. Example 4

By the procedure of Example 1, to a 50 part by weight granulated deactivated Mo-Co catalyst having a composition of 8.47% by weight Mo and 2.96% by weight Co was added 247.56% by weight of a 10% aqueous solution of COH. The reaction mixture was stirred at 25 ° C for 1 h. After the reaction time, the extracted solid residue was filtered off and 240.32 wt. % of the filtrate of composition: 1.26 wt%, Mo, represents a yield of 71.5 wt% Mo. * Example 5

207.77 wt.% Was introduced into the apparatus as in Example 1 in the first cycle. 5 parts by weight of aqueous ammonia and 50 parts by weight of inactivated Mo-Co catalyst having a composition of 8.47 percent by weight of Mo and 2.96 percent by weight of Co. The reaction mixture was stirred at 23 ° C for 1 hour. After the reaction time had elapsed, the liquid phase separated and the same amount of aqueous ammonia solution was added to the solid residue in the second cycle, the reaction mixture was stirred at 24 ° C and the liquid phase was separated from the solid residue. This procedure was repeated twice more, thus the extraction was performed in 4 cycles, the total reaction time was 4 hours at an average temperature of 24 ° C. A total of 827.66 wt. parts of a clear liquid phase with an average composition of 0.41% by weight of Moa 0.015% by weight Co.

The mass composition of the clear liquid phase of the individual cycles was as follows: I cycle 0.91% Mo; 0.02% Co II. cycle 0.45% Mo; 0.025% Co III. cycle 0.16% Mo; 0.01% Co IV. cycle 0.12% Mo; 0.006% Co.

The total yield was 80.13% Mo and 8.4% Co. Example 6

The procedure, the reactants and the cycles used were the same as in Example 5, except that the extraction was carried out at 80 ° C. A total of 839.33 parts by weight of a clear liquid phase having an average composition of 0.495% by weight of Mo and 0.0022% by weight of Co were obtained.

The mass composition of the clear liquid phase of the individual cycles was as follows: I. cycle 1.65% Mo; 0.0085% Co II. cycle 0.28% Mo; 0.0007% Co III. cycle 0.072% Mo; IV. cycle 0.060% Mo;

The total yield was 98.1% Mo and 1.25% Co. Example 7

Procedure and number of cycles as in Example 5. Up to the first cycle, 103.88 parts by weight of an aqueous ammonia solution having a concentration of 10% NH 3 were introduced and 50 parts by weight of the granulated deactivated Mo-Co catalyst having a composition of 8.47% were dispensed. Mo and 2.96% Co. The reaction mixture was stirred for 1 hour at 23 C’C for the first cycle, after which the clear liquid phase separated. An equal amount of ammonia water of the same concentration was fed to the solid residue in each cycle. The total net extraction time was 4 hours and a total of 424.56 parts by weight of the clear liquid phase with an average weight composition of 0.82% Mo 'and 0.041% Co was obtained.

The mass composition of the clear liquid phase of the individual cycles was as follows: I. cycle 1.89% Mo; 0.085% Co II. cycle 0.92% Mo; 0.046% Co

Claims (4)

SUBJECT Process for the production of liquid molybdenum concentrate from inactivated molybdenum or molybdenum and cobalt or molybdenum and other metal-containing catalysts or adsorbents or other substances, characterized in that in one to ten cycles, preferably two to four cycles, batch or countercurrent continuous each part by weight of molybdenum contained in the deactivated catalyst or absorbent or other molybdenum-containing substance is reacted in the same manner with from 1.25 to 1.25 moles. 12.9 parts by weight, preferably 2.5 to 10.05 parts by weight, of ammonia or potassium hydroxide or hydroxide It claims sodného- at 20 to 80 C, preferably at 20 to 50 ^Q C and the pure product was isolated after separation. 2. A process as claimed in claim 1, wherein an aqueous ammonia solution having a concentration of 2.5 to 20% by weight, preferably 5 to 10% by weight, of NH3 is used. 3. The method of claim 1, wherein an aqueous solution of potassium hydroxide at a concentration of 2.5 to 50% by weight, preferably 5 to 20% by weight, of KOH is used. 4. The method according to claim 1, wherein an aqueous solution of sodium hydroxide at a concentration of 2.5 to 40% by weight, preferably 5 to 20% by weight, of NaOH is used. Severography, n, p ,, plant 7, Most Price 2,40 Kčs