TW415965B - A process for the recovery of cobalt and/or manganese from ash containing cobalt and/or manganese as oxides thereof - Google Patents

Abstract

Cobalt and/or manganese is recovered from the ash obtained following incineration of the catalyst containing residue arising from the liquid phase oxidation of an aromatic carboxylic acid such as terephthalic acid. Recovery is effected by contacting the ash with an organic acid or an organic acid anhydride such as acetic anhydride, optionally in the presence of bromide ions (e.g. HBr). So that the cobalt and/or manganese metals are recovered as monocarboxylic acid soluble salts thereof thus permitting recycle thereof to liquid phase oxidation process.

Description

415965 iL C7 V. Creation Instructions (3): The acetic acid is used to solidly collect these gold tinctures. U.S. Patent No. 4, 5 4 fi, 202 describes the method of adding glacial acetic acid, or a mixture of glacial acetic acid and water, and heating the mixture in a S reactor with a history and mixing device. A method for solidly collecting cobalt and manganese from solid ash of an aromatic carboxylic acid incinerator. Although I understand that the hydrobromide will react with the gaseous phase of cobalt and manganese, the reaction described in this case does not include bromine when it participates in the policy of the Central Bureau of Standards of the Ministry of Economic Affairs, the Shellfish Consumer Cooperative, and the manganese gas of the invention The ash of the compound is in the form of contact with or without the use of bromoanhydride and preferably recovers the acetate salt. 1 The phase oxidation treatment step of the present invention, especially of aromatic carboxylic acids such as bromine, contains catalyzed gold. Circumstances in the collection method In the method, there is an attractive bromine that can greatly improve the gas obtained after the invention is based on the hydrazone. However, the use of cobalt and / or steps involves: the provider is also a In the method of recovering cobalt or manganese, in the case of ions, it promotes the recovery of ash and an organic acid or cobalt or manganese. The resulting cobalt or manganese is their respective water-soluble appearance. It is suitable for the production of aromatic carboxylic acid. A carboxylic acid composed of a catalytic system obtained by applying a solution of cobalt or manganese or a promoter in a solvent via a hydrocarbon precursor is used in渉 and the treatment of residual materials due to the mother liquor net flow. The painting of cobalt and manganese can use acetic acid or acetic anhydride to evolve the ion ions without introducing bromine. F, no need to rely on the effect of grazing. In the theoretical understanding, the following Pyrolysis (exemplified by cobalt or gasified manganese, although its dissolution is a fatty acid or fatty acid anhydride, the ions of the compounds return to the line, but the reaction depends on high temperature and pressure, such as incineration). It was originally very difficult, such as, using- ------- ly ------- Order ----------- Φ (t read the precautions on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 Specifications (210X297 mm)

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 415965 A7 __B7 V. Description of the invention (/) The present invention is an aromatic aromatic carboxylic acid. For example, the production method of p-phthalic acid and isobismuth acid β For commercial manufacturing, the method is nothing more than hiding para-xylene from the same air and placing it in a lower-order aliphatic carboxylic acid solvent (such as acetic acid), and a dissolved heavy metal catalytic system (usually It is a promoter of cobalt, manganese and monobromide) to carry out gasification reaction in the liquid phase. Β Extracts an acetic acid slurry that exists in the solution from the retort, and applies a solid-liquid phase separation method to generate Crude grade acid crystal rhenium (the crystal can be further processed), and at the same time, a mother liquor filtrate is generated. In addition to the catalyst and promotion for the gasification reaction, the components in the mother liquor also include Dissolved para-acids and many different by-products and impurities. There are more than one source of concomitant products and impurities. For example, a few impurities in the para-xylene feed for reaction treatment may also be local gas caused by the endless gold oxidation of para-xylene. A chemical product or a concomitant product produced in the reaction of p-xylene gasification to a pivalic acid. A large part of the recovered mother liquor is extracted and recycled to the gasification reaction method, so that the catalyst and the accelerator are recycled to the oxidation reaction method, and at the same time, a small part of the oil is taken As a net flow, the solvent is collected in a solvent system to control the amplitude of impurities and accompanying products in the reaction process to a tolerable range. As far as the solvent recovery system is concerned, the net stream of the mother liquor must be subjected to an evaporation process in order to return a considerable amount of the fatty acid solvent and water (which can be returned to the gasification reaction method) existing in the net stream of the mother liquor. Exclude it, leaving one that contains acid, impurities, and accompanying products (please read the note on the back before filling this page)

* 1T-This paper size applies to China National Standard (CNS) A4 specification (2 丨 0X297 mm)

V. Creative Instructions (ίΗ) Acetic anhydride can be easily dissolved in the case of using monobromide. Bromide can be introduced at the beginning stage, so that the reaction between the anhydride and ash can be used. The case of bromide ions intervened smoothly. However, the opposite is also possible, after the acid or anhydride has reacted with the ash before the bromide ion is introduced. The amount of Australian plum used '--------- / ------:-Order --------- Jing (_Please read the precautions on the back before filling in this Page) The printed standard of the printed papers of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) ί ~~~

415965 A7 B7 printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China (5) Invention description (2) Several concentrates such as heavy metal catalysts present in the filtrate of the original mother liquor, such as condensate β, are residues. It can be regarded as waste disposal, but if there is still economic value at all, it can be further used for treatment, in order to recover valuable components, such as gold catalyst, for recycling. The typical downstream processing mode for this residue includes: catalytic recovery, thermal decomposition, to remove all the radon components in the residue (for example, an incineration treatment in a high temperature furnace), or An aerobic or aerobic biological treatment to reduce the need for chemical oxygen (COD). Therefore, the gist of the present invention is to exist in the third stage or the fourth stage, and the catalyst metal has reached a certain level of intervention, through the pyrolysis method of the above-mentioned residues, so that these exist in The prototype state in the residue is the method of degassing the components of the catalytic gold hurricane and recovering them. Therefore, the catalytic gold tincture is insoluble in water and can only be slightly soluble in acid. 6 US Patent No. 3341470 What is shown in the case is a method of incineration of the residue into an ash gaseous substance, and then dissolving the ash thus obtained in sulfuric acid containing chloride therein. The components of manganese and cobalt are treated with sodium osmium acid solution, so that the drill and manganese can be recovered in the form of precipitation of sulfonic acid. The phosphonium salt thus recovered is then treated with acetic acid to obtain The acetate is operated back to the gasification reaction method. In the case of U.S. Patent No. 4,786,661, the cobalt, which is present in the form of its acetate, is recovered from the mixed gold osmium oxide composed of fly ash and slag in the ash content of incinerated ash. Manganese and other metals, this method is based on cobalt metal or hydrazine (hydrazine > combined with rhenium agent, under the conditions of near boiling point or reflux temperature and atmospheric pressure (please read the precautions on the back before (Fill in this page) The size of the paper used for this edition is in accordance with the Chinese national standard (CNS > A4 size (210X297 mm) 415965 iL C7. V. Creation Instructions (3)) The acetic acid is used to collect these gold tinctures. US Patent No. 4 No. 5 4 fi, No. 202 shows the method of adding glacial acetic acid, or a mixture of glacial acetic acid and water, and heating the mixture in a S reactor with a calendar and mixing device. A method for the solid recovery of cobalt and manganese in the ash of an aromatic carboxylic acid incinerator. Although I understand that hydrobromic acid reacts with the gaseous phase of cobalt and manganese, the reaction described in this case does not participate in the economy without bromine Central Bureau of Standardization The ash of the manganese gaseous substance produced by the present invention is in the form of contact with or without the use of bromoanhydride and preferably recovers the acetate form. 1 The present invention is particularly composed of aromatic carboxylic acids such as bromine). The oxidation treatment step contains my hair catalyzed by gold, and the method in the collection method has an attractive bromine that can greatly improve the gas obtained after the hydrazone of the present invention is used. However, the use of cobalt and / or steps involves: In the case where the provider is also a method for recovering cobalt or manganese from its contents, in the case of ions, it promotes the recovery of ash and an organic acid or the recovery of cobalt or manganese. The resulting cobalt or manganese is Each of them is soluble in water. It is applicable to the catalysis obtained by the application of a hydrocarbon precursor in the production of aromatic carboxylic acids via a cobalt or manganese or a promoter The monocarboxylic acid composed of the system is treated with radon and the residual material due to the net flow of the mother liquor. The painting of cobalt and manganese can be evolved using acetic acid or acetic anhydride without introducing bromine. The effect of animal husbandry. Understand that after pyrolysis (instantiated cobalt or gasified manganese, its dissolution although a fatty acid or fatty acid anhydride, the ions of the compounds return to the line, but the reaction depends on high temperature and pressure, such as incineration treatment) was originally very difficult, such as, Used --------- ly ------- Order ----------- Φ (t read the precautions on the back before filling this page) This paper size is applicable to Chinese countries 橾 隼(CNS) A4 specification (210X297 mm)

V. Creative Instructions (ίΗ) Acetic anhydride can be easily dissolved in the case of using monobromide. Bromide can be introduced at the beginning stage, so that the reaction between the anhydride and ash can be used. The case of bromide ions intervened smoothly. However, the opposite is also possible, after the acid or anhydride has reacted with the ash before the bromide ion is introduced. The amount of Australian plum used '--------- / ------:-Order --------- Jing (_Please read the precautions on the back before filling in this Page) The printed standard of the printed papers of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) ί ~~~

415965 A? ___ B7 V. Description of the invention (y) For each cobalt or manganese, use 0.5 ~ 1.5 or 1.8 moles, as long as it does not exceed 2. Q moles, which is acceptable. For the practical operation of the method of the present invention, the amount of bromide to be used may be approximately equivalent to the equivalent of the cobalt or manganese component in the ash. If the amount of bromide used is less than the molar equivalent of the cobalt or manganese component in the ash, the metal recovery efficiency will be relatively reduced. However, radon may not be a disadvantage, because operating under a relatively bromine-deficient body can actually promote the elastic adjustment of the final bromide to metal ratio, and can reduce or even eliminate it. The demand for offgas processing containing ingredients is β. In this case, the residual material containing the cobalt / manganese content remaining after the method treatment can be recycled for further processing by the method of the present invention. & Preferably, the bromide used is hydrogen bromide, but other bromides such as ethyl bromide are also possible. Therefore, in accordance with one preferred embodiment of the present invention, about one mole of hydrogen bromide is preferably used for each ear of gold tincture present in the ash. For example, in the case where the ash also contains a manganese-containing gas, the proportion of hydrogen bromide used is one mole to one mole for the two types of Jinyang. »However, a larger amount of bromide can also be used. However, in this case, the bromine generated in the reaction method may cause problems in the treatment and disposal of the bromine-containing gas. However, this may not be entirely disadvantageous. Of course, the amount of bromide is large, but it is conducive to the control of the ratio of bromide to golden hurricane in the catalyst / promoter system in the Han to Yi gasification reaction method for producing aromatic carboxylic acids. In the case where bromide ions are used, the bromide is preferably introduced into a liquid medium, for example, it can be placed in a fatty acid (for example, the vinegar paper size applies the Chinese National Standard (CNS) Λ4 Specifications (210X297 mm) 4 (Please read the precautions on the back before filling this page) Order printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 415965 Α7 Β7 V. Description of the invention (r) Acid) or dissolve in water β The organic acid anhydride used can be acetic anhydride, the eucalyptic acid used is Acetic Acid, and a mixture of an organic acid and an organic acid is proven to be extremely effective. It is best that this mixture contains an acid And an acid anhydride of a relative plaque, for example, a mixture of acetic acid and acid anhydride can be used for the reaction method. If water is present in the reaction mixture containing an organic anhydride, the anhydride can be completely or partially hydrolyzed to the corresponding acid, and the resulting acid anhydride mixture is used in the reaction method. The ash containing metal vapors may be wet. Ash and slag can be recovered from a single-state gasification method, or it can be produced after being dried in a dry state, and then processed after being washed. "I found that in the reaction method, the water that appears, if Exceeding a certain amount may adversely affect the recovery of metal. The reaction method is preferably carried out under dry conditions, but if some water is retained, it will not cause a significant adverse effect on the recovery of cobalt or manganese. The weight percentage of the water component in the mixture in the reaction is preferably controlled to 30% or less, and it is better to maintain it to 20 × or less, and it is more desirable to suppress it to 15 × or less. The mixture of water involved in the reaction can be made by using Shanghai ash or, for example, putting thallium bromide in water to form an aqueous solution. In the case of the intervention of an organic anhydride, the wet ash is introduced into the reaction method, and it can be reacted with the anhydride to form a corresponding acid, and a part of the water is excluded. Therefore, If you use Mae ash, and you want to carry out the reaction operation under relatively dry conditions, you can add wet ash in an organic anhydride, so that water can react with it to generate an organic acid. This paper size applies to China National Standards (CNS) Α4 specifications (210 × 297 mm) (Please read the precautions on the back before filling this page)

S1T printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs' A7 B7 V. Description of the Invention (L) The hydrolysis of the anti-plaque will generate heat, so when the heat has ceased and no longer occurs, it means that the hydrolysis has been completed, Thereafter, an anhydride or a dry acid may be added to terminate the trimming reaction method. However, if there is too much water in the ash, it can not be eliminated by the hydrolysis of the anhydride, or the user is an acid rather than an anhydride, so that the water present therein is sufficient to adversely affect the whole filling reaction. It can be dried before the ash content is introduced into the reaction tank. The organic acid generated by the hydrolysis of the anhydride by the water contained in the reaction method is preferably used in the s-position of the reaction method. For example, it can be returned to an aromatic acid precursor gasification reaction method. The ash content is generated from this reaction method. The amount of acid agent generated is directly proportional to the amount of water in the catalytic-recovery reaction mixture. Therefore, the amount of water allowed in the reaction mixture should be added. Control so that the ratio of the recovered catalyst to the acid acid produced is just suitable for direct input back to the initial oxidation reaction method. "In the Ministry of Economic Affairs. Central Standards Bureau employee consumption cooperation Read the notes on the back and fill in this page) US Patent No. 44 91) No. 297 shows that the cobalt and manganese in the state of their respective oxalate dihydrate salts are directly from the gasified mother liquor Sink out and recover, and then place the oxalate dihydrate in acetic acid or acetic anhydride and interact with ethynyl bromide, hydrogen bromide, or a mixture of both to convert it into a soluble in acetic acid. Within the form. However, the US Patent No. 4490297 did not deal with the incineration of the residue, nor did it discuss how to recover the cobalt or manganese in the third or fourth phase with their respective gaseous forms. problem. In this same U.S. Patent No. 44 90 2 9 7 it is mentioned that for each mole of cobalt or manganese oxalate dihydrate, 2 to 4, preferably 2 to 2 or 2 Hydrogen bromide and 3 ~ 4, especially preferably 3 · 1 ~ 3_5 mole of acetic anhydride. This paper size applies Chinese National Standard (CNS) Α4 specification {21〇X 297 mm)

—V 1: Produce '415965 A? B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (' Ϊ) 1 But what I found quite a surprise is that * I bromine is used In the case of compounds, especially in the case of thallium bromide, even if the dosage of 1 1 I used is lower than the standard stoichiometric standard «recovery rate of gold tincture can be larger 1 I please increase 1 I! And if Bromide can be added to the ash. For every mole of metal, see Read II 1 I. For a mole of bromide, the recovery efficiency is close to 100%. Since the number of bromide used on the back 1 I 1 is limited to each mole of cobalt or bolus injection 1 1 to match the degree of the bromide of moore, the bromine recovered from the metal The chemical term and the ratio of I to catalyzed gold tincture are suitable for direct return to the gasification of aromatic acids. Fill in 0 pages of this I reaction method, J 1 1 Incineration can be rubbed with any appropriate technology.% Via High-temperature ballasting is used in a way that the plant can generate J-liquid or solid based on ash for treatment. 1 Order I In terms of a more precise view of the invention »it is provided by the use of 1 to produce an aromatic carboxylic acid, such as 9-the 1 1 method of producing p-ortho- or isobismuth acid * where 1 I The aromatic precursor is placed in the catalytic system containing the plant cobalt or manganese compound 1 1 A "C" ~ Cb in a carboxylic acid solvent »for a gasification treatment β 1 [the oil produced in the reaction plaque contains a presence A slurry of aromatic 1 1 aromatic acid crystals in the mother liquor of the dissolving matrix, and then use this slurry as a solid-liquid phase separation 1 | process, and extract at least a part of the mother liquor for processing * to produce 1 I or Manganese residue 〇1 This residue is subjected to a pyrolysis treatment J to produce a gaseous product containing cobalt or a shovel 1 1 ash residue 1 I It is best to use __. Organic with the intervention of bromide ions Acid or 1 1 1 This paper size applies to Chinese national standards (CNS> 厶 4 specifications (210X297 PCT)

v / 415965 A7 B7 V. Description of the Invention (S) Organic acid anhydride is treated as a process to recover the cobalt or manganese present in salt-formed amidines and soluble in the former ammonium carboxylic acid. When bromide ions are present, bromide ions can be present from the beginning, or bromine ions can be introduced after the organic acid (or anhydride) begins to react. The recovered plutonium and / or manganese are preferably recycled into the area of the gasification plaque. In the case of using bromide ions, a clear and advantageous factor of the method of the present invention is that among the recovered components, the final bromide-to-metal ratio can be achieved without the help of a patent such as the US patent. In the case where the bromide concentration in the solution is trimmed or disposed of as described in Case 44 90297, it is smoothly returned to the gasification area, because the bromide ion treatment in the recovery method of the present invention In general, it can maintain a standard stoichiometric principle, and for every bromide, it can extract exactly one mole of the cobalt or manganese component β, although as in US Patent No. 4,786,621 It is pointed out that hydrobromic acid can be used as a reducing agent when recovering cobalt and manganese from the residue obtained from the production method of benzene (1,2,4) tricarboxylic acid. However, in this case, the bromide The ratio of gold tincture is not ideal. The same is true for the case of U.S. Patent No. 4298580, which advocates the use of hydrobromic acid to precipitate out the cobalt and shovel components presented in the form of its bromide ( A mole of gold Must be equipped with at least two molar hydrobromic acid). Due to its high ratio of brominated metal component, is not ideal. As far as the ideal implementation method of the present invention is concerned, the reason why it can be carried out without using a small amount of bromide is mainly due to the intervention of anhydrides. This paper size is applicable to the Chinese National Standard {CNS) A4 specification (210X297 (Mm) (Please read the notes on the back before filling out this page) — Ding ♦ -6 Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs / N. ·-. ---: .. Λάά ^: β /

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 415965 V. Invention Description (1) and the formation of bromoacetate with cobalt or manganese. In short, the method of the present invention can be represented by the following chemical formula: M2 0¾ + 2A〇i 0 + 2HBp-2M (Ac) i Br + Ha 0 wherein the letter M may represent cobalt and or thallium simultaneously. But of course, the actual reaction involved is more complicated than that represented by the above formula, because fly ash is a complex mixture of oxides in a highly oxidized state. A small amount of hydrobromic acid can be gasified to bromine gas, which is highly corrosive and sufficient to cause environmental pollution. I have found that after adding Shao Li's hydrocarbon post compound to the reaction method, this mono bromine gas post compound can be annihilated in a large amount. The hydrocarbon house can be used as a precursor for a gasification process in operation; for example, "for the production of osmic acid, it is dimethylbenzyl; for the production of isoxalic acid, it is meta-xylene". However, because the amount of hydrocarbons boxed for this purpose is small, only a sticky hydrocarbon is sufficient. Other compounds can be added to inhibit the gasification of bromide to bromine, including some reducing compounds such as formic acid, formaldehyde and acetaldehyde. As mentioned earlier, the resulting solution containing cobalt or manganese salts is particularly suitable for direct return to the gasification plaque domain. In the case where the oxidation method involves a partial recycling process of the mother liquor containing the catalytic component therein, it is highly likely that the loss of the bromide ion promoter (mainly in the form of a volatile organic bromide) will occur. In this case, it is necessary to supplement the catalyst to increase the feed of bromide ions to ensure that the ratio of bromide to the total catalytic metal in the gasification reaction method can be maintained at the necessary level. The increased supply of bromide The amount depends on the amount of mother liquor recycled. The ratio of the bromide to the gold hurricane component of the finally recovered solution can be easily adjusted, and the Chinese National Standard (CNS) A4 specification {210 × 297 mm) is applied to this paper scale (please read the precautions on the back before filling this page) ) '1, π 415965 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs' invention description (β) promotes the ratio to be achieved. Therefore, in the case of using the bromide ion in the catalytic thin recovery method of the present invention, Before recovering the amount of bromide used in the process, the amount of bromide required for the bromide component in the mother liquor recycled from the gasification reaction method should be considered. In addition, the residue to be treated is in the residue. The amount of cobalt / manganese is also taken into account. In this way, the amount of bromide to be reduced in the circulation of the mother liquor, i.e., by making an appropriate decision on the amount of bromide used in the catalyst recovery method, is obtained. The organic acid or acid anhydride used in the catalyst recovery method is preferably the same, or the #anhydride derived from the same acid as the acid used as a solvent for the aromatic acid in the oxidation reaction plate. In this way, the recovered tritiated solution can be directly returned to the gasification anti-eyelash method. The oxidation of aromatic acids is generally carried out in a solution of acetic acid. Therefore, in terms of catalytic recovery, whether acetic acid or acetic anhydride is used, it is extremely convenient. As for the removal of the contaminating gold rhenium components present in the residue, including iron, copper, and chromium, after the anhydride / bromide treatment of the present invention is completed, such as according to British Patent No. 1413488 and The known technology shown in case No. 1319172 can be processed and removed. Alternatively, for example, ion-exchange treatment to remove iron. HS The following examples of tilting will be used to further illustrate the present invention for better understanding. . Example 1 In a reflux state, a fly ash weighing 0.9985 g and containing approximately 333 wt% of cobalt; ~ 36 × of cobalt and manganese, together with 25 al of acetic anhydride and 33¾ of hydrogen bromide, were placed in The paper size of HBr, which weighs 1.5 grams and 0_0061 mol, is applicable to the Chinese National Standard (CNS) A4 specification (210X29? Mm) ~~ 1 (Please read the precautions on the back before filling this page) Order in the Ministry of Economic Affairs The quasi-stationary consumer work cooperative print κ 415965 Α7 _ Β7 V. Description of the invention (I 丨) The glacial acetic acid was stirred and heated for two hours. After the mixture was cooled, the mixture was cooled with 5G ml of distilled water. Dilute in order to decompose the excess anhydride. The solution so produced is filtered once, and distilled water is added to U to make it a pink solution. This solution was analyzed by an atomic emission photometer, and it was found that the solution contained 0.23X manganese and 0.236% cobalt, and the total amount of gold was O.C08 Mor !! 1.2 Moore's Gold ", plus the addition of 1 mole of bromide ion» elemental bromine added previously, the result of X-ray fluorescence analysis is 0.384X, so the bromide in this solution is The ratio of the components is β.82. This result shows that the amount of bromide produced was lost by 0.10 4 g & the residue weight was 0.291 7 g. Example 2 In a flowing state, put 1.002 grams in weight and contained about 333 to 363 weight percents; fly ash of cobalt and manganese, together with 25 Bl of acetic anhydride and 33¾ of hydrogen bromide, It was stirred and heated in glacial acetic acid consisting of 2.5 g, 0.0102 M ear of HBr for two hours. This mixture was cooled and then diluted with 50 Bl of distilled water to decompose the excess anhydride. The solution thus obtained was subjected to a filtration treatment, and distilled water was added to 100 Bi to make it a pink solution. Β This solution was analyzed by atomic emission, and it was found to contain 0.283 ϋ manganese and Q. The total mole value of the 2983! Cobalt and gold tincture components is 0.0102, which is shown as the extraction of 1 mole of gold tincture plus the 1 bromine element bromine element added previously. The total bromine is X The result of light fluorescence analysis was 0.597%, so the ratio of bromide to gold tincture in the solution was 1.03. The amount of bromide formed was 0,219 grams. The residue weighed 0.1113 grams. This paper size is applicable to S countries naked (CNS) A4 specification (210X297 mm) Ί7 (Please read the precautions on the back before filling this page) Order 415965 A7 B7 V. Description of the invention (丨 >) Example 3 Under reflux, the brominated gas weighing 25 grams and containing the fly ash of cobalt and shovel with a weight ratio of about 33X ~ 36X, respectively, and the equivalent of 2 50 b1 of acetic anhydride and 33¾ are placed in a weight of 75 G, 0.3056 moles of HBr in glacial acetic acid, mix and heat for two hours. At the beginning of heating, bromine gas was released at the same time. This mixture is cooled and then diluted with 100 »1 of distilled gland water to decompose the excess anhydride. The resulting solution was filtered, and distilled water was added to 5QQ ml to make it a pink solution. Analysis by atomic emission shows that the solution contains 1.49¾ of manganese and 1.53X of cobalt. The total amount of gold is 0.26 5 deciles. It also includes 0.87 moles of metal and 1 mole of the original addition. Bromine ions were extracted together. The X-ray fluorescence analysis result of the bromine binding amount was 4.6% (total 0.288 moles), so the final bromide-to-metal component ratio was 1.52β. The analysis showed a loss of 796. The weight of the residual material is 1.1 grams, 16.56% of which is cobalt and 16.33% of which is shovel β. Therefore, the recovery rate of palladium manganese recovered in the solution is more than 97.5%. Implementation 钶 4 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling this page) It will weigh 10 grams and contain fly ash of cobalt and manganese with a weight percentage of approximately 3355 ~ 36 ×, which is better than 90 acetic anhydride and 33 × bromide. Thorium, stir in glacial acetic acid consisting of 30 g, 0.122 moles of HBr and 10 _1 para-xylene to inhibit the formation of bromine, and then heat in a flowing state for 2 hours. Nothing was seen Bromine gas is released. This mixture is cooled and then steamed with 70 Dilute it to filter the remaining anhydride solution β, so the resulting solution is filtered, and the organic layer is separated. The water layer is added to the paper according to the Chinese National Standard (CNS) A4 specification (210X297 mm) 4〆415965 Duo printed A7 B7 produced by the Central Bureau of Standards, Ministry of Economic Affairs and Consumer Cooperation _V. Description of the invention (〇) Steamed water to 500 Bl to make it a pink solution. The organic layer was analyzed by gas-colored method. And mass spectrometry were analyzed simultaneously, and the results showed that the structure was roughly a mixture of p-xylene, p-xylyl bromide, methyl aminate, and 4'4-dimethyl bi benzyl, and these components were all It is the precursor of spider acid. After the pink aqueous solution is analyzed by atomic emission method, it shows that it contains 0.604 $ of shovel and 0.618X of cobalt. The total amount of gold plaque is 0.1 0 7 deciles, showing the total amount is Extraction of 0.88 gold ears together with the bromide ions originally added 1 ear ^ Fen Example 5 will weigh 5 grams and each of them will contain about 33 IΪ ~ 363: weight fly ash Serving at 20G ° C and It was mixed with 40 ml of acetic anhydride under the pressure of thoron in the green state and heated for 2 hours. Then the pressure rose to 75 Psie. After the mixture was cooled to the ambient temperature, it was diluted with 50 b1 of distilled water to dilute it. The excess anhydride is decomposed. The resulting solution is treated with a filtration treatment and added with steamed water to 200 nl to make it a brown solution. Analysis by atomic radiation shows that the solution contains 0.46X The manganese and cobalt of 0.4 5 3 !, the reversion rate of the gold tincture component in the original material is 50Ϊ. Residue weighs 2.4 grams. Example 6 A fly ash consisting of 39.3 × of manganese and 38.U of cobalt was weighed to about 1 gram, as determined by ICP / AES. Contrast with the proper amount of acetic acid, water and HBr to achieve the percentage values of various waters as shown in Table 1, and the ratio of gold tincture component to bromide. This paper size applies to China National Standards (CNS) Λ4 Regulation (210 × 297 mm) (Please read the note on the back before filling this page)

: vy V 415965 A7 B7 V. Description of the invention () V /) This mixture was searched and mixed and treated as a stream for 2 hours. As a result, the entire plaque was dark green and bromine gas was generated. This mixture was left to cool overnight, and 5Q stl of distilled water was added separately. After the filtration process, the obtained filtrate was added with distilled water to 然后, and then followed by ICP / AES analysis and processing. The results are not as good as Table 1. The results show that the presence of water in the mixture produced by the reaction can reduce the recovery of cobalt and shovel. Table 1 (Please read the notes on the back before filling out this page) Moisture printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economy X Manganese recovery% Cobalt recovery χ 0 81.6 82. 3 4,4 80 73.6 14.4 71.3 70 19.4 59 57.2 23.4 57. 9 56.4 28.1 56.9 5 5.6 51.3 41.8 43 This paper size is applicable to China National Standard (CNS) M specification (210X297 mm) A7 B7 Tibet 415965 i. Description of the invention (^ r) Example 7 will be repeated 25 grams of fly ash containing 39.3X of manganese and 38.35¾ of cobalt are stirred with 250 ml of glacial acetic acid and 60.5 ml — 8Br of 33% acetic acid to achieve a total ratio of 1: 1. Bromide ratio. The formation of a small amount of bromine gas can be observed. The mixture was then heated under a simmer for 2 hours to generate more bromine gas. Then, the radon mixture was cooled, left to stand, and then distilled water was added to 500 Bl, and filtered. Residues were dried under room overflow and _ its net weight (1.9 g) β. This filtrate was added with distilled water to 100 ml and analyzed by ICP / AES. The recovery rate of metal components in the solution was calculated. As a result, it was found that the manganese was 78¾ and the cobalt was 76JK. This solution was also analyzed by X-ray fluorescence, and it was found that it contained bromide in an amount of 2.03¾ by weight. Example 8 Extract 1.37 97 g from the dry residue obtained in Example 7 and use 25 Bl of glacial acetic acid and 3.34 al of 33X HBr stored in acetic acid for further extraction treatment. The estimation of the metal content in the residue is based on the ratio of the total amount of bromide to bromide. This mixture was subjected to reflux treatment for 2 hours, then cooled and left overnight, and then distilled water was added to 50 al ^ After the filtration treatment, the filtrate was added with distilled water to 100 BU and analyzed by ICP / AES. It can be achieved that the manganese is calculated as 23S based on the estimation of the composition of gold in the residue, and the recovery of cobalt is 86X. The amount of bromide in the solution is determined by X-ray fluorescence. Its weight percentage value is 1.23%. This result shows that the residual material extracted from a first gold tincture ingredient is enough to be recycled to a second extraction paper ruler and read with the Chinese National Standard (CNS) Λ4 specification f 210; < .29_7 public牦) 1 1 (please read the notes on the back before filling this page)

, 1T-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 Prepared is A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention Description (丨 u) method to achieve further metal component recovery. Examples 9 to 1 4 A series of synthetic 〃 fly ash 备 compounds were prepared to provide samples with a weight percentage of cobalt of 2: 1, 1: 1, and 1: 2. These counterfeit products are obtained from ash residues from a plant where a pair of known metal raw materials are subjected to p-xylene gasification treatment, and are left to stand overnight at a high temperature of 550 ° C. Before subjecting it to a second degree of ashing treatment, a quantitative amount of cobalt acetate solution was added thereto to generate a desired ratio of cobalt to manganese, and the weights of manganese and cobalt were measured by ICP / AES, respectively. Take each sample of synthetic fly ash residue and rinse it with distilled water to remove the sodium content and dry it. Both the rinsed and unrinsed samples were subjected to an extraction process as described below. Accurately _ Measure about 1 gram of fly ash and mix it with 25 ail of acid insertion and HBr containing about 33% of the content of acetic acid. In order to achieve a total of 1: 1 metal, The ratio of the amount to the Australian compound. This mixture was subjected to a stream of 2 畤 迺, and then the bromine gas was generated. Β This mixture was cooled overnight, and distilled water was added to 50 · 1 β. Then, the filtrate was added with distilled water 100 * 1, and the residue was dried at room temperature to analyze its metal components by ICP / AES, and its bromide was analyzed by X-ray fluorescence. The results are shown in Table 2 ^ Table 2 (Please read the notes on the back before filling this page)

This paper scale applies Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) -iV. Rickets 415 ^ 65 A7 B7 V. Description of the invention (β) mm Serial number mm mam mm Moving back booth 0® 0® * Percent mmmm ΙΜΜ 100 volumes 1 2.2: 1 no 65 75 0.29 2 1.1: 1 no 63 71 0.43 3 1: 2.2 no 73 55 0.37 4 2.2: 1 yes 68 79 0.29 5 1.1: 1 yes 58 67 0.31 6 1: 2.2 Yes 72 54 0.34 (Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 1 5 ~ 1 9 Take a weight of about 1g and the manganese contains Cobalt content has been determined by ICP / AES. Its fly ash content is 39, 3X and 38.4X, and 25 al of glacial acetic acid, as well as HBr reaction in osmic acid with a measured amount of 33X to achieve various Ratio of gold tincture to bromide. In each case with different ratios, the reactants were simply mixed and allowed to stand for about 18 hours before adding distilled water to 50 Bl. The resulting mixture was subjected to a filtration treatment, and the filtrate was added with distilled water to 10 fl ml, and then analyzed by ICP / AES. The ratio of the golden hurricane component to the bromide and the maximum value of the recovered gold contact component are shown in Table 3 β1. The paper size is in accordance with Chinese National Standard (CNS) 8 and 4 (2ί〇 × 297 mm)

415965 A7 s__ll V. Description of the invention (e) Table 3 Example No. of the ratio of gold tincture components to bromide weight percentage of manganese recovery weight percentage value of cobalt recovery ft percentage value 15 1: 1 41.7 44.1 16 2: 1 28 28.7 17 4: 1 16.5 18.2 18 8: 1 11.4 11.7 19 1: 2 53.4 54.7 (Please read the notes on the back before filling this page)

Printed by the 1T Shellfish Consumer Cooperative of the Ministry of Economic Affairs of the Ministry of Economic Affairs, the above results show that a relatively high percentage of gold tincture can be recovered using a room temperature method, but if the reactant is heated to the flow temperature, it will be collected. The amount can further increase β. After increasing the ratio of bromide to metal, the recovery rate of gold tincture can be increased, but within the range of the ratio of gold tincture to bromide with a large value difference. Recycling operation. This paper size applies to China National Standard (CNS) Α4 specification (210 × 297 mm)

Claims (1)

No. ’’ 7 3 3 I ’m making * reading the old application for patent Fan Xin Λ8 (: 18 '% 08. Bu 1) 8 patent application scope 2 A method for recovering palladium and / or manganese from ash containing cobalt oxide and / or oxygen content, the steps include: using an organic acid, or an organic anhydride, or a mixture of the foregoing, in In the presence of bromide (the amount of bromide is: between 0.5 and 2 moles per mole of cobalt or manganese), contact with ash, in the reaction mixture It contains water below 30% by weight, and its temperature is between the ambient temperature and the countercurrent temperature, so that the components of rhenium and manganese can be recovered in the form of soluble salts. According to the method in the first patent application, the organic anhydride is acetic acid, the organic acid is acetic acid, and the bromide is involved in the reaction in the form of hydrogen bromide or acetamidine bromide. 111--I I-- 彳 — I-(Please read the notes on the back before filling in this page) Γ The Ministry of Economic Affairs Central # Associate BureauBei Gong Consumer Cooperative Co., Ltd. Printing policy This paper standard applies to Chinese Coder Slope (CNS) A4 specifications (210X297 public thin) No. '7 3 3 I made * read the old application patent Fan Xin Λ8 (: 18'% 08. Bu 1) 8 patent application scope 2 A method for recovering palladium and / or manganese from ash containing cobalt oxide and / or oxygen content, the steps include: using an organic acid, or an organic anhydride, or a mixture of the foregoing, in In the presence of bromide (the amount of bromide is: between 0.5 and 2 moles per mole of cobalt or manganese), contact with ash, in the reaction mixture It contains water below 30% by weight, and its temperature is between the ambient temperature and the countercurrent temperature, so that the components of rhenium and manganese can be recovered in the form of soluble salts. According to the method in the first patent application, the organic anhydride is acetic acid, the organic acid is acetic acid, and the bromide is involved in the reaction in the form of hydrogen bromide or acetamidine bromide. 111--I I-- 彳 — I-(Please read the notes on the back before filling in this page) Γ The Ministry of Economic Affairs Central # Associate BureauBei Gong Consumer Cooperative Co., Ltd. Printing policy This paper standard applies to Chinese Coder Slope (CNS) A4 specifications (210X297 male thin)