TW383240B - Method for re-manufacturing a cobalt/manganese/bromine catalyst from residue containing used catalyst - Google Patents

Abstract

A process for recovering a solution of Co and Mn acetates and other valuable components of a waste residue of used catalyst discharged from a plant for the liquid-phase, homogeneously catalyzed oxidation of alkylaromatic compounds, to produce polycarboxylic aromatic acids. The residue is pyrolized in a reaction zone provided forming molten metal in an electric arc or molten metal furnace under conditions which convert essentially all carbon in the residue mainly to CO, hydrogen and compounds vaporized in an effluent from the reaction zone. The effluent is passed through a liquid-gas-contacting means to yield a quench or scrubber stream. The residue may also be sludge from a pond in which the residue is stored. The alloy recovered is atomized to form a powder metal which is then digested in acetic acid, and/or aqueous hydrogen bromide, and/or mixtures thereof with the quench or scrubber stream, to form the corresponding salts. In addition to Mn and bromine (Br) values from the effluent, these values may also be recovered from the slag, if desired. Substantially pure Co may be recovered and exported, particularly if earthy residue from a sludge pond is processed to benefit the environment.

Description

Printed A7 JB7_ by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (Reference to related applications: This application is an application serial number 08 / 68δ, 194 on July 29, 1996, and was issued on June 2, 1998 Extension of US Patent No. 5,759,229 to be issued. Field of the Invention: The present invention relates to a method for producing a cobalt / manganese catalyst for the oxidation of alkyl aromatic compounds. It is needless to say that it is used in a catalytic process. In the catalyst residue, cobalt (Co), manganese (Mn) and bromine (Br) are recovered, and the recovered material is reorganized into a catalyst. Explanation of the internal problem: It is known that in the used catalyst, Co , Mn, and Br are valuable and recyclable. How can the recovered catalyst be reused in the process from the recovered residue? The purpose of the present invention is to recover the gold tincture component and the value of bromine from the residue (defined below), and then BACKGROUND OF THE INVENTION Monoalkylaromatic polycarboxylic acids, such as isophthalic acid (IPA), terephthalic acid (butan), trimellitic acid (L ^ 1), 2,6- # dicarboxylic acid Acids (2,6-〇RAN), etc., are obtained from the appropriate pre-alkyl aromatic compounds under the pressure of the liquid phase , Are all catalytic oxidation, produced by large-scale equipment, and recovered from the generated logistics (refer to the "Arooco ^ Mid-Century® method," or "Mid-Century" method for short). Catalytic reaction and air in It is carried out in the presence of a solvent of the acetic acid / water mixture as a solvent of the reactant. The residue generated in the process is an undesired stream containing a catalyst component. The residue contains an oxygen-containing mixture derived from the reaction product of the reactant, Including local oxidation and dealkylation of aromatic compounds, tars, and cyclic brominated aromatic compounds-3-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --------- ----- ^ -------- Order --------- line (please read the precautions on the back before filling this page) Printed by A7 B7_ V. Description of the invention (2) Mixtures such as basic oxidation, most of which are used with catalysts such as Co-Mn-Br or Co-Mn-Br-Ce (钸) or Co_Mn-Br-Zr (l§) And other components are mismatched. Each compound includes acetate, bromide, and bromoacetate of Co and Mn; many aromatic and polycyclic carboxylic acids, aromatic Polycyclic anhydrides; mixed aromatic and polycyclic carboxylic anhydrides, including cyclic-brominated aromatic compounds; and acetic acid, hydrobromic acid, and any of the foregoing aromatic carboxylic acids of unknown composition of Co and / or Mη complexes and anions Although the residue is the smallest, it is usually 0.1 to 25% by weight of the polycarboxylic acid produced, even if it is often less than about 10¾. The net amount of these residues produced in industrial factories in the next year is very large, so it is expected Recover gold tincture components, especially Co and Mn, and bromine components, namely Br and Br compounds. In the following, for brevity, use "B" value to refer to molecular Br, or bromides such as HBr and Mn Br2, or Value of bromine content or stream. At present, the residue has been treated by the following main methods: (i) incineration M provides fly ash for further processing, that is, recovers the contained gold dust; or (i 〖) discharges into the residue pool regardless of the contained Co, Mη and The value of Br is lost in the loach-like residue, or its impact on the environment; or (Π) Precipitation of valuable gold tincture into carbonates, dilution of the remaining organic components and halides, followed by anaerobic digestion and Dissolve gold tincture carbonate in acetic acid to reconstitute the catalyst; or, Uv) burn the radon residue to form oxides and M oxides for other uses. "The term" residue J "refers to both the factory residue M and the soil-like residue. If they are not included, they are specifically referred to as one or the other. Refer to Figure 1 to illustrate the current industrial use of residues. Recycling-4- This paper size is applicable to Chinese National Standard (CNS) A4 (210x 297 mm) (Please read the precautions on the back before filling this page) Order --------- Line 丨 Ministry of Economy Wisdom Printing of clothing A7 B7_ by the Consumer Cooperative of the Property Bureau V. Invention description (3) The main steps in the catalyst method are granted to Holzhauer et al., US Pat. Nos. 4, 876, 386 and 4,786, 621. It is destroyed by incineration and the catalyst component is converted into ash. This ash is difficult and / or expensive to convert into the shape of the catalyst that can be used in the oxidation of methyl substitution. More specifically, the residual stream is in step 2 It is incinerated to produce mixed gold oxide oxide fly ash, which is collected in step 3. Because not all Co and Mn are converted from the residue to fly ash and collected, the rest is lost to the incinerator residue and discharged. Go to step 6. Collected The ash (from the incinerator in step 2) was washed with water to remove soluble salts and sodium bromide in step 4 and discarded (step 5). In the next kneading step 7, the washed ash contains the major weight and the largest proportion (> 50 %) Of Co and Mn, which are digested and converted to the acetate and bromide of Co and Mn, and are extracted by M before returning to the catalyst storage (step 9). The material not extracted from the washed ash is discarded ( Step 6). The catalyst is fed into the reservoir (9) for processing (step 10). From step 10, a portion of the media M is internally recycled to step 11, and in step 9 the catalyst is returned to the reservoir. It is reused in the liquid-phase oxidation reactor in step 10, or it is directly returned to the process, and the product expected from the reaction is separated and sent elsewhere for further processing. The residue 潦 1 is generated from the flushing stream in step 11. This residue is then incinerated to start another new recovery and reuse. As proved, some parts of the catalyst contained in the catalyst are usually from 30¾ to 40¾, depending on the fly ash quality and operating conditions, and even The residual content of 90¾ is lost from the system, and all of them are inevitable. In the procedure just explained, the Co and Mn not lost in step 3 -5- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------- --II ------ 11 ^ -.-------- ^ (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ V. Invention Explanation (4), it is extracted from fly ash with aqueous acetic acid solution and reduced with hydrazine. This is caused by the M10% hydrazine solution flowing in acetic acid aqueous solution. This recovery procedure causes a large part of the loss of Co and Mn .Although there are economic incentives (a) to recover substantially both K and bromine of the main gold pupa (Co and Mη) from the residue, and (b) to break the main organics contained in the pupa residue, it has not been seen in previous techniques What is suggested is far less than what is done today. Changed from incineration to other methods to treat fly ash, that is, discharged to a sludge pond, and after a period of time, a residue such as soil is obtained, which represents a large amount of recyclables mainly called Co and Mη and from bromine to bromide Accumulation of things. This kind of accumulation, although controversial and considered as harmless waste, also represents a valuable resource. If it can be recycled, it will be conducive to the reconstruction of environmental safety. Discharging such waste into the pond often causes contamination such as mud, such as silica, alumina, clay, etc. I know that the prior art did not deal with these two organic residues, that is, residues such as soil and organic residues that are the source of soil residues. The residue was treated with sodium carbonate to become carbonate, followed by dilution and anaerobic digestion to recover Jin Jiao, which was allegedly inefficient (experimental metal recovery was approximately 50¾) and expensive, costing approximately as incineration. In addition, bromide was not recovered in this process. The anaerobic digestion of organic compounds is also inefficient. Care must be taken to control the condition M to maintain active biological colonization, and in the end, sludge to be treated is still produced. Μ Calcination of the residue, and the use of oxides produced by sintering for other purposes, requires a large central cell to enable efficient operation and cannot recover halides; moreover, the catalyst cannot be fed back to the manufacturing plant, forcing the manufacturing plant to respond to Co And the major fluctuations in the supply market -6 — This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) < Please read the precautions on the back before filling this page)-^ ----- --- Order --------- Line—Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_V. Invention Description (5), which in turn caused high price instability. The method of the present invention accomplishes recovery of two residues. Destroy the organic residue, separate its components, add this stream to the appropriate high temperature metallurgical processing system, and combine it with the most oxygen-containing gas needed to work. For "high temperature metallurgical processing system", it means that the metal components are brought into a reduced molten state in a high temperature metallurgical system. Such systems include: u) direct introduction of organic residues into the molten gold bath as detailed in the mother case; or (Π) the use of electricity or the strength of a plasma or torch to directly or indirectly heat the organic residues To the molten metal; or (iii) MH heating to the organic residue to enter the molten metal pool; or (ίν) to add the organic residue to the molten salt or In the molten glass pool, and the molten gold tincture is separated and collected from the bottom of the system. The related high-temperature metallurgical processing system taught by the related prior art can be used to destroy hazardous waste, which is summarized as follows: The method of destroying organic waste in an aerobic molten metal bath must maintain a high temperature to a sufficient level. The residue is converted into an oxide of carbon, and the gold tincture is converted into a form that is soluble in the melt. Those melts with a viscosity of more than 10 centipoise have been used to destroy toxic chemicals and inject more than stoichiometric oxygen into organic waste added to the bath, as disclosed in U.S. Patent No. 4,474,714. Other references that teach melting baths that destroy toxic chemicals have been discussed in the '194 application, the indications of which are included as references and fully explained. The '194 application mother's case specifically teaches how M — molten gold bath, can be used to treat residues from the Mid-Century factory and capture Co and -7- (Please read the notes on the back before filling this page ) i -------- line—

II nnnn II This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by A7 B7_ of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs; 5. Description of the invention (6) Valuable gold of η is mainly used for In the same golden tin melt bath. Similar results can be achieved with electric or plasma arc systems, many examples of which are known. U.S. Patent No. 4,431,612 to Be 丨 丨 et al. Describes the use of a high-current DC arc containing a liquid pit including a molten bath, where M is a molten gold tincture from a mixture of chlorinated waste (PCB, etc. and PCB contaminated materials) The accumulated gold element is added to the system of molten metal bath. U.S. Patent No. 5,534,659 to Springer et al. Describes the use of a plasma arc to treat organic and inorganic waste, isolates molten gold tincture and its slag, and adds water vapor to the system to ensure that all carbon-containing components are converted to carbon monoxide and carbon dioxide. In Prrceedings of the Internationa 1 Syaiposiun on Enviromental Technologies: "Plasma Systems and Applications", October 8-11, 1995, Allanta, Georg 丨 a, p. 251, Reteeh Corporation Published, which describes a device that uses a plasma torch to treat waste in a centrifugal chamber, which discharges molten gold tincture through a central hole, and then uses spraying to make the metal powdery. U.S. Patent No. 3,744,779 to Perry records the use of sufficient heat to recover valuable metals in waste materials, and to destroy organic compounds by distillation, and to recover molten gold osmium in the absence of oxygen. U.S. Patent 3,770,419 to Brown describes a pyrolysis system that produces molten gold drawers from metal-containing waste. U.S. Patent No. 4,230,043 issued to 0 ^^ 〇41 'describes a system of polybrominated polybrominated biphenyls exposed at 3,000 T to the by-products and ore of steel making ~ ~ (Please read the notes on the back before filling this page) -I 乂-------- Order --------- line 丨 II nn This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Employees' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Preparing A7 B7__ 5. Description of the invention (7) Acid and powdered reducing metal. U.S. Patent No. 5,085,738 to Harr is described in the absence of oxygen for thermal conversion of molten waste in molten lead pools to destroy organic waste. U.S. Patent No. 3,890,908 to Klenck et al. Describes pyrolysis and destruction of waste in molten gold tincture or glass baths. U.S. Patent No. 4,2,46,255 to Grantham et al. Describes the addition of a PCB and an oxygen source to a molten salt bath to treat the PCB. The pyrolysis and destruction of wastes is an active research, and it is mentioned here only the important variables that can be applied to the technology represented by the high temperature metallurgy step. The above-mentioned various teachings or suggestions: There is no reason why or how to provide alloys of Co, Mn and C alloy powders with effective media to reconstitute catalysts containing Co and Mn acetate mixtures. Under appropriate process conditions, the erosion inflow of organic residues is provided to a so-called high temperature metallurgical method, which will result in two generated streams and a slag: U) one containing carbon monoxide, hydrogen and valuable bromine Gas phase; (ί) molten metal containing cobalt, manganese, carbon, etc .; and K depends on the composition of the feed, so that the composition of the slag mainly contains gold oxides other than Co and Mn, regardless of the application for the mother case '194 specifically stated that a considerable amount of Mη can be directed to the slag. Of course, the molten gold produced is of the shape of a Co / Mn or Co / Mn / C alloy, without the motive to produce a powder, and then in acetic acid Continue to digest the powder, or absorb the generated gas in an acetic acid aqueous solution to obtain a stream of a quenching tower or a scrubbing tower (hereinafter referred to as "quenching stream J"), or in a mixture of acetic acid and quenching stream Unless the purpose is to remake the Mid-Century catalyst. Even so, the previous technology has not taught -9-This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) (Please read the back Please fill in this page again for attention) nn I ^ nnn f— n. ^ 1 nn Printed by A7 B7_ of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs; 5. Description of the invention (8) How to make this digestion satisfactory and complete. Catalyst etch for Mid-Century method For the preparation of human solutions, any of several methods can be used at present. Co and Mη gold tincture are respectively digested in glacial acetic acid or concentrated acetic acid aqueous solution and added to the reactor respectively, so that the precise control of the two acetates of Co and Mη Alternatively, cobalt acetate or manganese acetate can be prepared by digestion with their respective gold hydroxides. These hydroxides are usually digested with a strong acid such as nitric acid, precipitated by treatment with alkali, washed with water, and collected insoluble Hydroxide (see U.S. Patent 1,637,281 to S chat ζ) 〇 The direct preparation of cobalt acetate from gold tincture has problems and requires a large excess of metal. Prior art techniques used bromide salts compatible with gold tincture as accelerators Or increase the pressure and use oxygen to obtain effective digestion. If Co is powdered, it can be taken into the container, and the digestibility of 50¾ can be obtained in 50¾acetic acid. After 2 hours, it is still only 86¾ Cobalt is digested. For substantial complete conversion, an activator must be added (see U.S. Patent 3,133,942, Example 4, etc. issued to Hahi). It is therefore not necessary to expect that cobalt can be substantially completely digested without oxygen. The shape of an electrolyte tablet made of cobalt (a tablet of 1/8 "by 1 1/4 ") is sought, and U.S. Patent 4,921,986 issued to Po X indicates that increasing the pressure will increase the oxygen concentration in the solution. In the present invention The alloy obtained in the Gaoli metallurgy system has its main components: cobalt, manganese and carbon, and the amount of carbon is determined by the treatment of the molten alloy. In the effective process of reorganizing a Co / Mn / c catalyst, within a reasonable time In less than 24 hours, for the obtained alloy, each metal is substantially complete. The paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page. ) iy ------- Order --------- line — _ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_25. Description of the invention (9) The critical point of total digestion. For the term "substantially completely digesting j", I mean that C ο / Μ η 蹰 has at least 90 S: digested. Local digestion, unless proportional, is due to changes in the Co / Μη ratio received from the waste. It is not suitable for channeling, and the ratio needs to be readjusted. The problem of discarding undigested materials, or treating or reprocessing still exists. The prior art did not teach the digestion of Co / Mn / C alloys in acetic acid. Alloy C is successfully transformed into powder M for non-alcoholic glacial acetic acid, a non-alcoholic solution of acetic acid, or a mixture of non-alcoholic acetic acid and a quenched stream. There is no suggestion; and, it is not recommended that the degree of powder be less than 5000 Micron, preferably from about 5 micrometers to 1000 micrometers, and most preferably from 45 micrometers to 500 micrometers, so that it itself is in the aforementioned digestive juice, and even the gold tincture is substantially completely digested by atmospheric pressure, and it is not necessary in the aforementioned solution Digestion using super-atmospheric pressure. It has been well known that Mη powder is easily digested in hot acetic acid; while cobalt is locally digested in 80¾: acetic acid (20¾ water), and even residuals remain under the influence of atmospheric pressure. Generally, the amount of carbon present in the alloy is less than Co or M but greater than 0.5¾. The carbon held in the alloy is most limited by the saturation limit. This limit can be as high as 7¾ based on the total weight of the alloy, and varies with the alloy It depends on the composition (see CR Acad. Sc. Paris, Vol. 264, p. 28, p. 284, January 16, 1967). It is well known that as little as 0.03¾ carbon in stainless steel has ribs to resist grains Corrosion can be expected to increase the difficulty of digesting carbon-containing alloys (see Corweion Resistance Tab les by Schweitzer, Philip, p. Vii, published by Marcel Dekker). Corrosion is a rate Slow-1 1-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------------- 4 ^ ------- Order --- ------ (Please read the precautions on the back before filling this page) A7 B7__ printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs; _5. Description of the invention (1G) Accepted. In addition, it is known that it is not possible to predict the corrosion rate of an alloy from data on the individual composition and corrosion rate of the alloy, Even if the alloy is completely digested, it is impossible to predict how easily the alloys of Co and Mη can be substantially and completely digested in the above digestion solution. Regardless of the corrosion rate of the Co / Mη alloy, if carbon is present in the alloy, the predicted rate will be reduced. The work is complicated. G. Arrivaut (Process-Verbaux, 195, pp. 107-114) describes the preparation and digestion of a dry Co / Mn alloy. Contains Mn60-85S! The combination is fully digested with ammonium chloride, hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid. In an acetic alcohol solution, only local digestion occurs, and most of the unreacted metal is rich in cobalt. Arrivaut is not taught to digest Co / Mn in acetic acid solutions, not in dilute alcohol systems. Arrivaut also noticed that the remaining substance was a water-conducting powder. (See Melor, JW's Comprehensive Treatise on Inorganic & Theoretical Cheaistry (Complete Collection of Inorganic and Theoretical Chemistry), Book XIV, p. 544, published by Longmans, Green & Co, Hew York >. Especially for the use of catalysts In the Mid-Century method, the gas generated in the reaction zone is absorbed to obtain a quenched stream. The absorbent stream used may be an aqueous solution of acetic acid, or a mixture of acetic acid and HBr, and / or MnBr 2, and other absorptions in the stream. The reaction product absorbed by the circulation is circulated in the zone. Because of the changes in the components of the logistics, both acetic acid and HBr, and the changes in M and other components, the effect on the powder alloy cannot be predicted. The method of the present invention is particularly suitable for these two residues. Logistically recover all Co, Mπ, and Br that are substantially valuable. The meaning of "all substance" is more than (please read the notes on the back before filling out this page) 1 n ί order · n I nnnn II »< nn ϋ nn ϋ I n ϋ II nn I) nn ϋ _ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B 7_ V. Description of the invention (11) 90S: Generally more than 95¾, preferably more than 99¾ can be recovered. The reproduction catalyst operated by this method has the same ratio as the input residue. "Input residue" means a separate stream, a collection of multiple streams from an existing Mid-Century plant, or various plants that produce the same or different products, or individual streams of earthy residues, or earthy residue liquids And factory residue logistics. Another advantage of the present invention is that the existing devices used for the equipment from fly ash Co and Mη valuables can be used to recover Co / Mn / C alloy from the catalyst, thereby reducing costs. Summary of the invention It has been discovered that the Co and Mn components in the catalytic organic waste residue used in the oxidation of alkyl aromatic compounds can be used to etch the waste into the high temperature metallurgical reaction zone to produce Mn / Co / C alloys. Recovered, the ratio of Mn / Co is in the range of from about 5; 1 to 1: 5, and the amount of carbon presented is in the range of 0 to 7% of the alloy's weight; at the same time, the bromine-containing valuables are released. Gas; forming alloy gold tincture powder with a basic particle size of less than 5000 microns; and substantially completely digesting the powder with a non-alcoholic digestion solution to form a solution of Co and Mn acetate. The digestion liquid is glacial acetic acid, or an aqueous acetic acid solution, or a mixture of acetic acid and a quenched stream obtained by absorbing the generated gas from the reaction zone. It has also been found that the combination of the above gas phase and molten gold tincture obtained from high temperature metallurgical processes provides an etch-in stream from which gold tincture acetate solutions can be recovered and reused in the Mid-Century process. An overarching objective of the present invention is to provide a method for converting waste residues into powdered Co / Mn / C alloys by applying Chinese National Standard (CNS) A4 specification (210 X 297) at Mid-Century paper size. Mm) I--I i III 1 IIII '— — — — — I — ^ * III 111 —-(Please read the notes on the back before filling out this page) Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ V. Description of the invention (12) The catalyst residue used in the method, the alloy produced by M pyrometallurgy, is obtained by spraying without leaving a residue containing a large amount of gold tincture, and it is not necessary to use a solvent such as oxygen, Relocation agent, activator, accelerator or accelerator. A special object is to provide a method for substantially equal collection of valuable B r in the residue. Another special purpose is to make the molten alloy ultra-cooled in the flow stream under sufficient pressure and speed to make Co / Mn / C powder, so that the molten alloy becomes particles smaller than 5000 microns, and then substantially completely digested in acetic acid. The powdered Co and Mn are formed in the acetate solution of cobalt and manganese in acetic acid; or in the quenched stream, or a mixture of acetic acid, water, and quenched stream, etc., to substantially completely digest the powder; if there is Carbon in the alloy gives a finely divided carbon residue. Yet another special purpose is to provide a method that is particularly beneficial to the economical recovery of valuable gold dust from the sludge ponds, such as soil residues, and the abandonment of the environment; bromine is also removed from the soil-like residues (if present). Recycling, which can be processed at the same time as plant residues are being processed. Because the Co, Mη and Br compounds recovered from the added earth-like residue will exceed the need to supplement the poor catalysts from the plant residues generated from the process, the excess Co, Mη and Br compounds can be used for Other purposes. Another particular object is to provide a method for digesting powders of Co / Mn / C compounds in acetic acid or quenched streams, or mixtures thereof, substantially in a single step. Another special purpose is to provide a method for recovering from the exhaust gas containing -14- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

'〆ί --- III Order · — 111111 * 1 ^ II n .1 nnn ϋ I n II ϋ nn ϋ nnnnn _ _ Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7__ 5. Description of the invention (13) Yes Μγ The quenched streams of solutions such as Bγ · 2 and HBr, and the Co and Mn salt solutions obtained from powder digestion, produce a Co and Mn salt solution used as a catalyst in the Mid-Century process. It is also a general purpose of the present invention to provide a system for preparing a Co / Mn catalyst solution from an alloy of Co and Mn gold, usually having a carbon weight of 0.2¾ to 5¾, derived from the aforementioned organic residue, Including: high temperature metallurgical equipment with a thermochemical reaction zone, receiving the residue therein; etching the residue into the feeding equipment of the high temperature metallurgical equipment; controlling operating factors, including the pressure in the thermochemical reaction zone and The temperature enables the equipment in the range from about 1100 ° F to about 2500 P to effectively convert all carbon-containing substances into carbon monoxide and carbon dioxide, and the remainder of the residue becomes a Co / Mn / C alloy, in which the Co presents The amount is the most per 100 parts of alloy weight, from about 10 parts to about 80 parts, and the carbon is less than 7 parts; for equipment for excluding gas emissions from the reaction zone and a part of the alloy; for Equipment for pulverizing the alloy into powders having a particle size range of less than 5000 microns; and, equipment for substantially completely digesting Co and Mn derived from the powder in acetic acid, hydrobromic acid, or a mixture thereof. The drawings briefly explain the foregoing and other objects and advantages of the present invention. It is best to refer to the following detailed description, and the schematic diagram of the preferred embodiment of the present invention. The same codes shown in the drawings represent the same elements, and among them: 1 阃 is a schematic flow chart illustrating the steps used in today's industrial methods to recover the valuable substances of Co and Mη from fly ash collected from the Mid-Centu'y method incineration residue. -15- This paper standard applies to China National Standard (CNS) A4 Specification (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) Order --------- Online! Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation A7 B7_ V. Description of the invention (14) Figure 2 is a schematic flow chart illustrating that in this patent application method, from the residue collected from the same Mid-Century method, Co, Mη and Br are substantially collected according to the most. Re-deployment, re-consolidate the discharge liquid, and reconstitute each step to produce Co / Mn / B "catalyst. The same process also explains that in this patent-pending method, the Duru factory is operated Waste stream to produce Co / Mn ratio is the desired melt, or even each step of pure cobalt, etc. Fig. 3 is a schematic flow chart illustrating the steps in the method shown in Fig. 2. Among the described methods, the conversion soil The residues are combined. The Co, Mn, and Br produced are partially exported beyond the need to regenerate the exhausted catalyst. Figure 4 illustrates the known design and construction of the reactor, providing substantial It is a pure molten cobalt solution. The fifth step is a schematic process that explains the steps in the method shown in FIG. 2 and details the unit operation for the reuse of the required catalyst. The FIG. 6 is similar to the figure 5. Process, but the condition is that the gold tincture is digested in a proportional form for the treatment of the residue. The ratio of Co to Mn in the solution is the same as that found in the alloy, so that the excess gold tin can be removed. Keep it and reuse it. For a more detailed explanation than the accompanying detailed example, Figure 2 illustrates the main steps of the preferred specific example of the novel method. In step 1, the residue is collected and dewatered. Then, A molecular oxygen-containing gas, preferably oxygen, is etched into the heat from the oxygen source 2 Chemical reaction zone, or water erosion by water vapor. One of the reaction zones is based on the Chinese paper standard (CNS) A4 (210 X 297 mm). (Please read the precautions on the back before filling This page) Order --------- line 丨 'Printed by A7 B7_, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (15) Reactor, containing molten Co / Mn alloy (step 3). Residue The material is added to the melt, and is converted into a molten alloy and a slag layer floating on the surface of the slag in the presence of oxygen (step 8). The steam leaving the reactor becomes an exhaust gas hip containing CO and H2, K And bromine-containing substances, mainly HBr and MnBr2. The bromine-containing component is collected in step 4 in an aerator or other liquid-gas-contact device. The smoke from the scrubber mainly contains C0 and H2, which are diverted to step 5 to use its fuel value or for some other economic purpose. The molten alloy is sprinkled from the bath 3 and sprayed to form alloy powder, which is collected as the fine alloy powder in step 6. The alloy powder is then reacted with an aqueous acetic acid solution or hydrobromic acid, separately or compounded, or selected for reaction with the recovered valuable bromine-containing product (step 4). For the desired composition of the Co / Mn catalyst prepared in step 8, it is also possible to add MnO from the slag, or Co (0Ac) 2 or a MnBr2 solution made from the MnO slag. The reconstituted catalyst is stored in step 9, preferably, the particles including unreacted alloys or carbon are removed by 滹 K, and the conventional uranium metal is removed by conventional treatment. The stored catalyst is fed to the reactor in the OMid-Century method as required to synthesize the required reaction product. Then, the M conventional equipment obtains this product, and uses the internal circulation of step 11 to return a part of the catalyst to the process and a part to the residual stream. Part of the internal circulation catalyst can be returned to the storage place in step 9 while the residue is discharged to step 1, where the process is re-started. The circuit formed by each of steps 9, 10, and 11 results in the discharge of the steps and the desired carboxylic acid distillation. The details of the procedures and the equipment used are known and have been used in China with Mid-Century paper standards. National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) -n OJ · nn 1_1 n I n I line! Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ V. Description of Invention (16) One or more patents related to the methods are described. References to certain U.S. patents are 4,162,991; 4,266,084; 4,311,521; 4,794, 195; 4,876,385; 4,876,386; 5,081,290; and 5,181,290; MS, of which special disclosures related to the operating conditions of the procedures that produce recyclable residues are listed as references As explained here. Details of the method and equipment used to remove the corroded metal are also well known and are described in one or more patents related to the Mid-Century method. Reference is made to Figure 3, which illustrates the treatment of soil-like residues in combination with plant residues. Outside the extent of steps 1 to 8 in the second figure above, the residues such as soil and plant residues are treated together as follows: The residues such as soil are removed from the sludge pond, dried in a dryer 12, and dried The soil residue and oxygen from 2 were eroded into the reactor of 3. Optionally, soil residues can be combined with plant residues when both are dried in step 1. Therefore, the soil residue that has been dried from step 12 is fed to the reaction zone in step 3, and the Br compound is recovered in step 4 by any of the absorbent agents M used in the scrubbing method. As before, C0 and Η2 can be recovered and used in step 5. Blocking of the alloy can be prevented by removing the melt from the bath in step 13. As before, if substantially pure cobalt is used in the reactor and the oxygen of the scene is added to K to convert all Ηη in the residue, then substantially pure Co can be oiled out at 14, and its removal is not like MnBr2 steam For M η 0, it is M slag exclusion. Components such as silica, clay and magnesia are also discharged. As before, Br is recovered in step 4 and excess Br valuables are removed. 1 8-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before reading) Fill out this page) — III — — — — II —II n — — — — — — — — — — — — — — — — I. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ V. Description of the invention ( 17) For other purposes. The catalyst is stored if it is no longer needed, and excess Co / Mn alloy is extracted and output in step 13, or an excess of oxygen is formed in the alloy ingot or a powdered alloy is formed. If substantially pure Co is recovered in step 14, then the most stoichiometric oxygen is fed into the reactor, the substantially pure C0 melt, and then Mn is removed from the melt MnO. MnO was removed to the slag and removed at 15. After the reaction product is distilled from step 10, the residue is also obtained conventionally in step 1. This residue, together with the residue taken from the catalyst cycle in step 11, is fed into step 3, and enters the molten alloy bath in the reactor indicated in Figure 4. . The reactor 20 is a cylindrical induction furnace with a net-shaped furnace body 23, and the induction coil 2 is embedded in a refractory lining 22 of a reactor having 75¾ alumina, and a slag discharge port 33 with a water-cooled shadow gate is installed. There is a tight-closing gate 38, which periodically opens and discharges slag 40. Preferably, a rutile fiber insulation layer is filled between the outer surface of the reactor-attached fire wall 22 and the inner surface of the mesh 23. The molten alloy 30 is held in the lower part of the reactor; the level of the melt is preferably maintained below the slag discharge port 33. The lower part of the reactor is preferably provided with a 95¾ magnesite solid mixture 27, which is filled between the lower steel outer surface of the reactor and an ultra-strong refractory brick support structure 28 in which alumina-alumina is combined with 90¾. The hot gas is directed from the reactor through an exhaust nozzle 24, through a pressure plug, and to a water scrubber (not shown). To feed the reactor 20, the residue is introduced thereinto through a nozzle 25, and is introduced into the melt 30 by mixing the residue with oxygen. If necessary, oxygen can also be injected into the molten alloy bath through a separation tube. Excessive accumulation of molten alloys can be achieved through the discharge of molten alloys. -19- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

, ^ -------- Order --------- I tn ϋ nin I nnnnnd I-Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_V. Description of Invention (18) Release 2 8 Withdraw a part and take precautions i :. Characteristics of factories and earthy residues, and their pretreatment: The residues may contain from about 〇1S: to about 4 5 ί: the weight (wt) of the total of C 0 and M η, based on K anhydrous, Usually from about 2¾ to 10¾ weight, and contains the least amount of other gold tinctures, especially Ce and Zr, usually each dry residue is less than 1S: the most weight appears most, and other gold tinctures are carefully added or used as a catalyst. Media accelerator, or inevitably, M corrosion products are normal. By "dry residue" is meant a wet content of less than 100 Γ by weight. Usually in the residue, it is mainly Μηη, and the weight ratio of Mn / Co is as high as 5: 1. Although there are several examples of M Co, the Co / Mn ratio is in the range from 1: 1 to about 5: 1; Usually the Mη / Co ratio is from 1: 2 to 5: 1. Factory residues usually contain a mixture of ingredients. For illustration, the composition of a residue extracted from the patent literature is shown in Table 1. It can be understood that a specific residue will change depending on the feed and processing conditions, and the method of the present invention is not limited by the special case of the composition of the residue. (Please read the notes on the back before filling out this page) -20- — — — —— — — ^ --------- I,. ----— I II ----- --- -------- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. A7 B7. 5. Description of the invention (19) Table 1: Residues of phthalic acid made from acetic acid and anhydrous basis: Ingredients% by weight Phthalic acid 19.7 Benzo_ 14.8 Toluic acid 26 .8 Methyl life acid 2.6 Trimellitic acid and stearic acid 4.3 4-Postyl benzyl m 9 .1 toluene m 0 .4 benzaldehyde 0 .004 terephthalic acid 0.2 m acid methyl benzoic acid 0 • 02 formamyl acetate 0. 1 benzyl benzate 0. 07 benzene m 2 Co product 4. 2 Cobalt acetate 4. 5 Acetic acid 1 Mg 8 Bromide 2. 2 Iron 0. 09 Na 0. 3 Toxijin 鼷 0 .02 -21-(Please read the precautions on the back before filling in this Page) This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm). Property Office employee printed A7 _B7_ five consumer cooperative described invention (2G) the residue of the melt before being injected Co / Mn or Co bath, Feng preferably be thoroughly dried to remove water. The advantage for dry feed is complete economics, where the increase in cost is due to heating the water. Significant changes in sludge composition are the age of the plant, the time it stays in the pond, K and any additions to the pond water or process emissions. Sludge will also contain living organisms with varying composition, usually less than the organic ingredients listed in Table 1. Furthermore, clay, colloid, flocculant, and sedimentation agent, etc. can also be present, depending on the field conditions. Unlike several methods, the recovery of Co and Mn in the present invention is very insensitive to the additional pollution caused by clay, colloids, and flocculants. Generally the impurities introduced are in the form of Si02, Al2O3, MgO, and FeM clays, colloids and flocculants. All S2O2, A2O3 and MgO will all be distributed to the slag phase under this reaction condition. Although there is no strict requirement for the present invention, it is preferable that the sludge is dried before being added to the molten bath. Drying can be performed separately in the factory residual stream, or the stream can be solidified or dried. The nature and operating conditions of the melt is to operate this procedure. The reactor is charged with Co and Mn gold in any convenient form. The ratio of the Co / Mn alloy produced is about the same as that of the residue fed in the Mid-Century method. The Co: Mn ratio formed during volume equilibrium is the same. The initial heating of the feed is produced by the induction coil. Or, instead, any other suitable method of generating hot feed, such as transferring molten alloy from the electric arc furnace to the reactor. Once the material is melted and reaches the melting paper size of the Co / Mn alloy to be formed, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applicable (please read the precautions on the back before filling this page) — — — — — — II — — — — — — — — — I 1 — — — — — — — — — — — I — I [II--II-Intellectual Property Office, Ministry of Economic Affairs, Consumer Cooperative Printing

At _B7_ 5. Description of the invention (21) For the degree of 上 on point κ, inject the oxygen-containing residue into the melt. The temperature of the melt can be increased to its required value, reaching an operating range threshold of from about 1 5 5 υ to about 2 5 Ο Ο υ. It is not necessary to add additional carbonaceous substances to the residue to meet the chemical needs of the thermochemical reaction. The thermal energy of the molten alloy stimulates the disproportionation of organics in the residue, which converts it into CO, Η2, and Br, mainly MHBr and MnBr2, are released. The thermochemical reaction can be exothermic, endothermic, or neutral. It depends on the amount and composition of carbonaceous matter in the residue when the general anhydrous residue is fed into the reactor, and M and oxygen are the most important. If it is endothermic, it must be heated to maintain the temperature in the bath, which can be supplied by the electric power in the induction coil, or directly added to the bath for the purpose of maintaining the temperature. These fuels can be provided from natural gas, propane, or any other source of thermal energy from the exhaust or waste streams of other plants (such as brominated organic compounds derived from exhaust streams), are cheaper than electricity, and are independent of the residues becoming Co, Chemical conversion of Mn and Br. Once the reactor enters the lotus car, the Mn / Co ratio can be fed to the residue in a wide range without sacrificing the function of adjusting Mn / Co in the molten bath. If the Mη content is found to be higher than expected in the bath, the excess Mη can be removed with excess oxygen if necessary. On the other hand, plutonium has no reason to increase the Mn content in the bath relative to the present cobalt in normal circumstances, but M can be added to Mn 0 or Mn residues. Those that must be strictly defined are the residues in the melt to be converted into Co or Co / Hn alloys, especially the alloys to be recovered. The ratio of Co: Mn in the melt need not be strictly limited. In general, both Co and Mη are donated aerobic to the paper. The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)-V " · — IIIIII ^ I I--IIIII. ./ ϋ ϋ nn ϋ ϋ ϋ I nn I ϋ nnn ϋ _ V. Description of the invention (22 A7 B7, bromine reduction rate, oxygen purity, and carbon content under non-layers. The fcfc is carbon and slag residue, and the amount of calculation is not quantified. The melt residual force is set in the upper oxygen rate to measure the actual oxygen into the earth pressure surrounding parts. Fanjiesheng often chooses the production of Mη gas for CO surplus. It needs to be more than the amount of residual gas. The actual excess of Mη is based on multiple uses and internal use such as Turning the U part tired or qi is phasor to benefit its bath beard. After being used or looking at qi, it should only be less than two. It should be small and it should be steamed and other supplies should not be melted. BΓ contains all the slags. Surplus in, Μη. The amount is still in the melt, Pakistan, on the return of the residual Mn to receive carbon foreign objects. No bromine in the gas is self-reported. The surrounding R belongs to the inherent C0 qiming and the slackness is beyond the limit. Jinjin is the strength of the surrounding and recyclables C0 in the accumulation and conversion of M and the alloy standard. In the ratio, the remaining residues must be collected in the hydrogen. ^: 1 ^ Gold is also returned to the factory. ^ The slag can be larger than 10 hours. 0 \. ^ 3 \ Heju's industrial residual fuses are in the middle of the bromine. CO4CO can be ruled. It should always be 1 liquid-carrying liquid, material 1 is the same, cobalt is, if you choose whether to reverse the hydrogenation in the bath to 1: 1: phase though, the hydrogen is careful, the best, please read the back first Please note this page before filling in this page) The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs prints and constructs M for operation. The reaction is carried out by exposing each reactant to procedural conditions for a sufficient period of time to ensure its full effect. I define this The numerical value of the time is the rate of adding cobalt divided by the total mass of the melted metal phase. This method is related to "Weight Hourly Space Velocity" (KWHSV). The appropriate range of operating conditions is 0. . Between 1 hour and 1 X 105 hours -1, preferably between 102 hours and 24 hours

-— — — — — — — — — — — — — — — — — — — — II--II--— II-III _ I This paper size is applicable to China National Standard (CNS) A4 (210 X 297 male) (%) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, A7 B7_ V. Invention Description (23) and 104 hours. The upper limit of the residence time will be required to recover the lowest degree of C0 in the residue, and the residue has the highest concentration of carbonaceous matter to be destroyed. The chemometer temperature and oxygenation rate can be used to control the chemical composition in the system. If, as generally expected, a low-carbon melt should be obtained, higher temperatures are obviously better, if there is a higher oxygenation rate. If all the added manganese is kept in the melt or in the gas-phase MnBr2, some carbon must be accumulated in the metal alloy phase. If all manganese is removed from the molten phase, the reaction must be driven to sufficient oxygen to achieve a purity of 95 + ¾. Because all the desired substances can be solidly collected regardless of the distribution of the three-phase combination, the choice of operating conditions, and the distribution of subsequent products become related to the local economic characteristics and convenience. The stoichiometry of oxygenation must take into account the above considerations and balance the other needs appropriately. The highest level of oxygen stoichiometry is the amount of oxygen required to convert all existing carbon into carbon monoxide without converting to carbon dioxide, or to convert gold tin oxide to gold tin oxide, or to make hydrogen into water. The maximum amount of oxygen added to comply with this chemistry must take into account the oxygen or oxygen input to the feed. The amount of divalent gold sulfide entering the system is calculated by dividing the oxygen equivalent by the amount of oxygen, except that it becomes a bromide compound and the vapor phase leaves the system. The organic residues of the Mid-Century process usually contain large amounts of oxygen, with a carbon to oxygen ratio of 7/2 or higher. Residues such as soil also have the most carbon and oxygen content. If you want to change the Co / Mn ratio K in the feed, remove one or all of the paper sizes. The Chinese National Standard (CNS) A4 specification (210 X 297 mm) applies (please read the precautions on the back before filling this page). 6J · -------- Line! Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Inventive Note (24) The manganese and oxygen must be fully increased to make the response reach the desired M η 0 amount. Finally, if the fuel added to the exothermic system is used to maintain temperature, its carbon and oxygen content will also be calculated on a stoichiometric basis. This can be expressed as follows: To be added 〇2 gas mole number = Κΐ〇ΐ-0 t〇t + Mn〇x -Co + 2-Mn + 2} / 2 where C tQt is the total mole of carbon fed The number, including any carbon in the fuel added, is the total atomic equivalent of oxygen in the feed, and Mn% is the Mmol number of M oxides to be removed,

Co + 2 is the divalent cobalt in the feed, and Mη + 2 is the divalent manganese in the feed, which will be maintained in the bath and will not be removed as MηO or Mr »Br2 in the vapor phase. . Reactor Design and Construction A suitable reactor for performing this reaction is disclosed in U.S. Patents 5,191,154; 5,301,620; 5,358,697; 5,396,850; 5,43 3,572; 5,435,982; 5,436,210 and 5,491,279, K, and references cited therein, together Included as a reference. However, the invention is not limited by the teachings of these specific designs. The design of a reactor suitable for this invention is not part of the subject matter of the present invention. Refer to Section 5 (a), which shows a flow diagram that schematically illustrates the steps and processing units for digesting powdered alloys. M and the released gas after the valuable objects are absorbed in the quenching liquid or scrubbing gas stream. Recover valuable things. The molten Co / Mn alloy from the container 3 of the furnace, such as a fused paper, applies the Chinese National Standard (CNS) A4 specification (210x297 mm) (Please read the precautions on the back before filling this page)- ----- Order * ------ III · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ ^ V. Description of the Invention (25) Melt metal or electric arc is periodically discharged and causes a sprayer 6, where the melt is quenched with a high-speed fluid flow, usually with room temperature water, with a scraping force in the range from 6 to about 20 bar, to produce a powder. Niu Xiao-gas from the furnace is led to a liquid quenching tower or scrubber 4 in which an acetic acid aqueous solution, HB "acid aqueous solution, and a circulating scrub gas stream preferably from a scrubber storage tank 4a are introduced. Scrubber The stream is usually an aqueous solution of acetic acid, Hf? R acid, MnBr2, NaBr and other reaction products, such as those absorbed in the recycling of the stream passing through the reaction zone. The cleaned gas can be defogged and refined according to conventional knowledge. The heat was previously removed in 5 to remove traces of acidic substances. The scrubber liquid was discharged from the scrubber storage tank 4a in a continuous cycle, and supplementary liquid was added continuously or periodically when needed. Derived from the content of 4a Bromine valuables can be recovered and returned to the Mid-Century method by the conventional method, or mixed in the metal acetate stream before or after the digestion of each gold tint. The gas discharged from the scrubber 4, It mainly includes (: 0 and Η 2, according to conventional methods, it can be dehazed and chain lifted before being stored in 5M to recover its calorific value or used as synthetic oxygen, and K is used to remove trace acid substances. Purified gas from 4a Vessel flow is introduced into a digester 7 with corrosion, Powder metal has been fed in from the sprayer 6. The digester 7 is usually a glass fiber reinforced resin with a glass lining or a stainless steel tank tower, with vent holes for the safe release of radon gas, and is equipped with, for example, steam Coil heating device. Gold tincture is digested in a mixture of acetic acid and water, selected to meet the needs for further processing and utilization of the catalyst. From 4a recirculated scrubber liquid, one or all of K can be used as digestive juice, -27- According to the composition of the desired media related to the bromine content, -27- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------------- ---- Order --------- line (please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7_ V. Description of Invention (26) The digestive effect is carried out at about atmospheric pressure and within a temperature range from about 120 ° C to 1401C, either Lianyungang or batch type, until all Co and Mn have essentially become salts in the solution. If used Batch, usually digestion is completed in less than 72 hours, if M η will be Mn oxygen from slag If the same materials are collected, the molten zhang is also digested in the digestive juice. The solution stream is sprinkled from the digester 7, and the suspended carbon particles are usually removed through 漶 M, and then processed in a container] 6 using conventional steps. In order to remove the unnecessary gold dust caused by equipment corrosion, it is usually iron, chromium and nickel, but others may also appear. Generally, the treatment to remove these precipitated corrosion metals from the solution is to remove by K filtration. The resulting Co / Mn salt solution can be evaporated to adjust the degree of K, or add 2 amounts of conventionally prepared cobalt acetate and / or manganese, mixed with the solution from the scrubbing liquid tank 4a, or stored in 9 M for M id-Century method Make any combination before use. Referring to FIG. 6, there is shown a specific example similar to that shown in FIG. 5 above, but the digestion rate of the C0 and Mn components is controlled so that various salts are provided in the salt solution removed from the digester 7. Ratio between. Under this circumstance, the gold maggots that come into play can be left in the reactor or can be removed from the reactor and stored in the storage tank 7a for the next batch of digestion. Digestion This method provides many opportunities for K to be integrated into plant operations, both waste heat supply and consumption, through a heat exchanger, to provide CO / Η2, or to recover heat as fuel K, or as a feed for chemical reactions. The present invention can also be integrated in a conventional manner into a conventional operation for the oxidation of alkyl aromatics, and the means of integration do not form part of the present invention. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) IIII ^ IIIII — — — — — — — — — — — — — — — 1 — — —. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ V. Description of the invention (27) Recycling and recycling of material catalysts from molten baths, first disperse the molten metal to produce powder metal, Then, the metal powder is mixed with an aqueous acetic acid solution, or an acetic acid / hydrobromic acid mixed aqueous solution, or an acidic stream containing manganese bromide, or any combination thereof, and the temperature thereof ranges from 80 ° to 100 scoops to generate a metal acetate salt. HBr can be added as needed. Many methods of producing metal powder are from Andrew J. Yale and John J. Dunkley, edited and taught by "Atomization of Melts" (Oxidation of Melts), Oxford Science Publications, Oxford. Metal powder is preferred A metal powder manufacturing system produced and sold by Atomising Sy stems Limited, Sheffiold, England. Another method is to recover alloy or pure cobalt from MCo / Mn alloy ingots, especially K clay-like residues for exporters, or from Gold solids without solid particles obtained directly from the melt. Recycling substances from the slag phase and any method of periodic or continuous removal of slag can be used, depending on the slag produced. Slag can be Μ pulverization, inlaying, or another K reduction treatment to produce a solid shape M for chemical use or disposal. If the slag contains a large proportion of M η 0 with a large proportion, it can be economically recovered from the melt Valuables. This can be accomplished by any conventional acidic or alkaline method. In these cases, the value of Mn is returned to the catalytic sequence. Aqueous acetic acid and / or hydrobromic acid are more suitable. Jiazhi Liquor. Collection of valuable materials of Mη and Br from steam phase. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) ------------------- ---- Order ------- I-line (please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7_ V. Description of the invention (28) In the steam phase The value of Mn and Br transferred in the medium is preferably recovered by any conventional unit operation that removes material from the vapor phase. These unit operations include condensation, sublimation (condensation), quenching and water, or Concentrated or diluted acetic acid, or hydrobromic acid aqueous solution for scrubbing exhaust gas. The scrubber is usually operated in a recirculation mode to achieve an equilibrium concentration of MηΒ 2 and HBr in the scrubbing solution. These operations can be performed at Atmospheric pressure or super-atmospheric pressure up to 20 bar and raised to 2501C, this is the appropriate condition for these procedures. After the bromine content is most removed, the heat energy (BTU content) of the exhaust gas can be used in the feed boiler This energy can also be directly converted into electricity by a device such as a fuel cell.基本 The basic source of the material for the recombination catalyst is the molten gold extracted from the bath. Compared with the use of atomization to reduce the particle size reduction technology, the particle size of the solid metal particles is reduced to enable lower temperature and pressure. Digestion of metal salts with large surface area, washing solution of slag and vapor phase, these two other materials are less of one kind of collected material, and their recombination is usually required for recombination catalyst. Although active catalyst is generally considered It is a complex of Co / Mn and ΗΒ ″ or a bromide salt. In some cases, the bromine content of the aromatic oxidation reaction is treated separately. In these cases, the scrubbing stream of the bromine-containing compound can be recycled separately from the recombination of the Co and Mη acetate catalysts. However, because the valuables such as Co, Mη, and Br from the soil-like residue may exceed the need of the catalyst, they must be reused immediately. Such excess can be used. This paper is applicable to Chinese National Standard (CNS) A4. Specifications (210 x 297 mm) ^ ------- Order --------- (Please read the notes on the back before filling out this page) Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs B7_ V. Description of the invention (29) The catalyst M is reproduced for storage. Therefore, it is clear that the treatment of the factory residues can be carried out as usual, and the soil-like residues can be processed into the products exported from the factory as needed, and try to dispose of the place where the sludge pond is frozen as much as possible. The soil-like residue is to be treated, and the catalyst is not reprocessed for use by the factory. In fact, only the substantial steps of recovering the economically valuable components of the soil residue are required. Illustrative example For each residue treated in the following examples, the average molecular composition is approximately equivalent to benzoic acid (C7 Η 6 〇 2). The residue here essentially contains Co and M η 锞 acetate, and Η B r, and the remaining organics are represented by K benzoic acid. "Mor" stands for kilogram-mor. The weight percentages of Br and Co in the residue fed to the reactor are kept the same in the following examples, when the reactor pressure is 10 atm (atmospheric pressure). In each case, the recovered gold tin melt was sprayed and transformed into a catalyst for reproduction. Example 1 In the residue feed, the Co / Mn ratio = 1/1; in the reprocessed catalyst, the Co / Mn ratio = 1/1; in the reformed catalyst, Mn was recovered from the alloy melt, and MnBr2 was recovered from The scrubber is recovered and MπO is recovered from the slag.

The bath of Co / Mn / Mn0 / C (609/325/37/29) contains 1000 kg of molten gold tincture and slag, and maintains a predetermined equilibrium composition in a reactor with a pressure of 22001 ^ and 10atm. Virtually all MnO exists in the melt, forming an insoluble layer on the Co / Mn slag. Dry factory residues, including 2S! Co, 2% Mn and 4% Br, all by weight, M292 This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) (Please read the back Please fill in this page before ordering) Order --------- Online! Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7_ 'V. Description of the invention (3G) kg / h and oxygen injected into the molten alloy. W H S V based on C 0 is 0.0 6 15 8 hours 4. The equivalent feed rate (Mole / hour) of the feed is as follows: C = 14.83; 0 = 4.82 (contained in the residue); Co = 0.099; and Mn = 0.0 54 (the rest of the Mn that is attracted by the residue is in the slag Zhongcheng Mη0, or left in the reactor exhaust gas is ^ 8 feet 2). The amount of oxygen injected was about 159.7 kg / hour (4.93 kg moles), and the exhaust gas generated by the reactor was caused to a water scrubber. During the balancing operation, about 70.4 kg of molten gold tincture was oiled out every 8 hours, and the powder was sprayed with high-pressure water to produce a powder with an average particle size of 100 microns. The composition of each particle is essentially the same as the melt under the slag. In the same 8-hour period, the collected 1,040 liters (L) of scrubber water contained 76.2 kg of ^ 8, "2 and 36.6 kg by". "0 in the slag, about 0.35 kg / The rate of hours accumulates. The level of the slag Μ was extracted regularly to the 詷 section, and the extracted slag was sprayed with water mash under high pressure to draw 100 micrometers. 70.4 kg of sprayed gold tincture, 1,040 liters of polyester water and 1,19 kg of glacial acetic acid (HOAc.) Were combined in a heated container with an air outlet, and the temperature was raised to 90¾, so that U 和 3.8¾ 重量。 Solution of mixed acetate and bromide of Co and Mn, Co and Mn in the solution were 4. U and 3.8¾ weight. There is virtually no free acid during this time. In a similar situation, the sprayed slag was digested at 90T with HOAc to produce a solution of Mn (0Ac) 2. The desired level of Mn in the reconstituted media, the required amount of K is adjusted to this mixture Mn (0Ac) 2 and adjusted to the mixture / Mn = 1/1. The reproduced catalyst is filtered to remove carbon suspended in the alloy. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) II n I ϋ ϋ I One-port, n I n II nn III -n ϋ n ϋ I u I nnn ϋ nnn .1 ϋ I nn I · Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ V. Description of the invention (31) Example 2 Co / Mn ratio in the residue feed = 1 / 2; Co / Mn ratio in the remanufactured catalyst = 1/1; Mn that is not needed in the melt is made into MπO with a sufficient amount of oxygen, and KMη0 will be eliminated in the melt. In the bath of Co / Mn / MnO / C (341/194/463 / 1.4), containing 000 kg of molten metal and slag, in the reactor at a pressure of 10atm and 2200T) to maintain a predetermined equilibrium composition. Virtually all MnO is present in the melt, forming an insoluble layer on the Co / Mn alloy. 292 kg / h of dry plant residues containing 2iUC0, 8! KMn and 4! UBr, > 乂 weight were injected into the molten alloy with oxygen. Co-based WHSV is 0.01075 hours 4. The equivalent feed rate (mol / h) of the feed is as follows: C = 14.2; 0 = 4.95; C0 = 0.099; and Mn = 0.06 (the remaining Mη is in the slag or leaves the reactor in the exhaust gas) . The amount of oxygen injected was about 150.5 kg / hr (4.7 kg mol), and the exhaust gas from the reactor was directed to the water scrubber. During the balance operation, about 73.1 kg of molten fusion gold is withdrawn every 8 hours and sprayed out to form a powdered gold tincture, as in Example 1 above. The composition of each particle is substantially the same as the melt under the slag. In an 8-hour cycle, 1,040 liters of scrubber water was collected to contain 69.3 kg of M η B r 2 and 4 1.2 kg of Η B r. The rate of M η 0 κ was about 7.9 kg / hour accumulated in the slag, and the slag was drawn out and sprayed with water under high pressure. 7 3.1 kilograms of sprayed gold tincture, 1040 liters of polyester water and 122 kilograms of glacial acetic acid are combined in a heated container with an air outlet, and the temperature rises to 90 ° C, becoming the acetate of Co and Mη Mixed solution with bromide, in which the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order --------- line 丨 · -II nnnnnn II nn · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7_ V. Description of the Invention (32)

Co and Μη were 4. U and 3.9%, Μ by weight. There was virtually no free acid during this time. As shown in Example 1 of K, if necessary, the slag is digested with Η0 A c in a solution of bovine Mn (0Ac) 2, and this solution is added as required. M / Co // Mn ratio. As described above, the regenerated catalyst was passed through; 滹 K removed the suspended carbon in the alloy. Cell Example 3 is substantially the recovery of Co; the Co / Mn ratio in the residue feed == 1/2. Virtually all Mη was removed into the slag with sufficient oxygen.

The bath of Co / Mn / MnO / C (548/11/424/17) contains 1000 kg of molten metal and slag in the reactor at 1500t: while maintaining a predetermined equilibrium under a pressure of 10atn. Virtually all MnO is removed to the melt, and the slag forms an insoluble layer on the molten metal. 292 kg / hour of dry factory residue containing 2U0, 2; KMη and 4S! Br, was injected into the molten alloy with oxygen by weight. WHSV based on Co is 0.010 28 hours -1. The maximum feed rate (mol / h) is as follows: C = 14.8.3; 0 = 4.82; C0 = 0.099; and Mη = 0.002 (the remaining Mη is in the melt or left in the exhaust gas in). The amount of oxygen injected was about 163.8 kg / hour (5.12 kg mole), and the radon from the reactor was directed to the water scrubber. In the balanced operation, about 47.6 kg of Co (95 + r), which is substantially about every 8 hours, is oiled out. Molten metal can be exported from the factory, or molten gold can be sprayed as in Example 1 above to produce powder. The composition of the gold particles is essentially the same as the melt under the slag. In an 8-hour cycle, 1040 liters of scrubber water were collected, containing 66.4 kg of 1 ^ 2 and 41.5 kg of 1 ^ ". 1 < 11 10 and about 4.5 kg of this paper size are applicable to China National Standard (CNS) A4 specifications (210 x 297 mm) ^ ----------------- line (Please read the precautions on the back before filling out this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ V. Invention description The rate of (33) / hour accumulates in the slag. The slag level M is regularly removed and adjusted, and the slag drawn out as shown in Example 1 is dispersed to 100 microns (average) Granules) Μη content is recovered when not needed. Cell Example 4 Co / Mn ratio in the residue feed = 1/1, Co / Mn ratio in the reprocessed catalyst = 1/1; Mn is the recovery of alloy-containing melts, and ΜμΒγ2 is recovered from the scrubber (no Mn0 is converted from the slag. The effect of changing the temperature and pushing oxygen is also explained. C〇 / Mn / Mn0 / C (662/325 / 8.9 / 2.8) bath, containing 1,000 kg of molten gold tincture and slag, in a reactor at 2000t: while maintaining a predetermined equilibrium composition under a pressure of 10atm. All ΜηΟ is removed to the melt, An insoluble layer was formed on the molten gold tincture. A dry plant residue of 292 kg / hr containing 2! KCO, 2% Mη and UBr was injected into the molten alloy with oxygen by weight. Based on Co The WHSV is 5.δ86 × 10 for 3 hours. The equivalent rate of feed (mol / h) is as follows. C = 14.83; G = 4.82; C0 = 0,099; and Mη = 0.554 (the remaining Mη is in the melt Or left in the exhaust gas). The amount of injected oxygen is about 160.8 kg / hour (5.0 3 kg moles), and the exhaust gas from the reactor is led to the water scrubber. In the balanced operation, about 8 hours 69.6 kg of molten alloy was drawn out and sprayed to form metal powder as in Example 1. The composition of the metal particles was essentially the same as the melt under the slag. During an 8-hour period, 1,040 litres were collected. Water containing 90.3 kg of M η B r 2 and 2 4.2 kg of Η B r. M η 0 κ accumulates in the slag at a rate of about 0.8 kg / hour. Slag level M timing extraction -35- This paper size applies _ National Standard (CNS) A4 specification (210x 297 mm) I ---------- — — — — — 1111111 ^ — — —— — — — — (Please read the notes on the back before filling out this page) Duty printing of employee cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7_ V. Description of the invention (34) For adjustment, the extracted economic benefits are as follows: Example 1 was scattered. 69.6 kg of gold tincture powder, scrubber water and 127 kg of glacial acetic acid were combined as in Example 1 to produce a mixed solution of acetate and bromide of Co and Mη, where Co and Mη in this solution were 4.1% and 4.0¾. Μ weight meter. There is essentially no free acid in between. As in Example 1 on M, if necessary, digest the slag with acetic acid to produce a Mn (OAc) 2 solution, and add as much of this solution as necessary to provide M the desired 1/1 Co in the reforming catalyst. / M η ratio. As before, the regenerated catalyst is filtered to remove carbon suspended in the alloy. Example 5 The Co / Mn ratio in the feed of the residue is = 1/1, and K is substantially removed from the molten gold tincture, which is a condition for substantially producing pure cobalt (99 + ¾).

Co / Mn / Mn0 / C (48 5 / 4.5 / 509.3 / 7) bath contains 1000 kg of molten metal and slag. In the reactor at 1700 it maintains a predetermined equilibrium composition under a scraping force of 10atm. All MnO is removed to the slag, forming an insoluble calendar on top of the molten gold. 292 kg / h of dry T. plant residue, containing 2! KC0, 2S! Mn and 4U ", by weight, injected into molten gold painting with oxygen. The WHSV based on Co is 0.0119 hours ^. The maximum feed rate (mol / h) is as follows: C = 14.83; 0 = 4.82; C0 = 0.099; and Mn = 0.0001 (the remaining Hn is in the slag or left in the exhaust gas). Inject it The amount of oxygen is about 190.4 kg / hour (5,95 kg moles), and the exhaust gas from the reactor is led to the water scrubber. In the equilibrium operation, about 47.1 kg per 8 hours The pure cobalt (99 + ¾) is extracted. The molten gold tin can also be exported from the factory by being sickled into ingots. ~ 3 6-This paper size applies to China National Standard (CNS) A4 (210x297 mm) (please first Read the notes on the back and fill out this page) -I --- II ----- II IIII —II--II --- II ---- II --- I. Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative Print A7 B7_ V. Description of the invention (35) Or spray the molten gold tincture to produce powder as described in the above Example. The composition of the gold tincture particles is substantially the same as the melt under the slag. During the 8-hour period, The collection of 1,040 liters of scrubber water, containing 65.9 kg of M η B r 2 and 66 kg of Η B r. These collections can be stored for future reprocessing catalysts, or exported for other purposes Use. The rate of accumulation of Mn0 in the slag is about fi kg / hour. The level of the slag can be periodically removed and adjusted, and the extracted molten metal is sprayed to 100 microns (average particle size), as in the above-mentioned case example 1 As required, the content of Mn is recovered. Example 6 In the residue feed, the Co / Mn ratio = 1/3, and the recovered melt is remanufactured by KCo / Mn = 3/1.

Co / Mn / MnO / C (285/694/0/21) bath, containing 1000 kg of molten gold tincture and slag, was maintained at a predetermined equilibrium composition at 20001C under a force of 10atmM in the reactor. The 292 kg / h dry plant residue, containing 2! KCo, 6% Mn and UBr, M weight, was injected into the molten gold tincture with oxygen. The Co-based WHSV is 5.83 × 103 hours. The maximum feed rate (mol / h) is as follows: C = 13.6; 0 = 5.07; C0 = 0.099; and Mn = 0,26 (the remaining Mη is in the slag or left in the exhaust gas). The maximum injected oxygen is about 1.3 1 kg / hour (4.1 10 kg mol), and the exhaust gas from the reactor is swept to the water scrubber. During the balancing operation, about 60 kg of molten alloy is withdrawn every 8 hours and sprayed to form metal powder. Example 1 as described above. The composition of gold tincture powder is the same as the melt under melting. In the 8-hour cycle, collect 1,040 liters of scrubber water, containing 98.3 paper sizes applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) I -------- IIII ^-I I- -1 — — Order · --I --- (Please read the notes on the back before filling out this page) Printed clothing A7 B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (36) Kilogram Heart (^ 「 2 and 8.6 kg 丨 彳 1 ^. No ^ 0 accumulates in the slag. The melt level is adjusted periodically. 1 β 0 kg of spray metal, 1 0 40 litres of polyester water and 3 2 9 kg of The combination of glacial acetic acid as in Example 1 produces a mixed acetate and bromide solution of Co and Mn, where Co and Mn are 3.6¾ and 10.62, respectively, based on retake. There is essentially no free acid in the meantime. Also the same as above The remanufactured catalyst absolutely removed the suspended carbon in the alloy. Example 7 Co / Mn ratio in the residue feed = 1/3; the gaseous oxygen push in Example 6 increased the effect by 1¾; the result one increased Mπ0 formed in the slag reduces the carbon in the alloy; the catalyst MCo / Mn = l / 3 is reprocessed. The bath liquid maintains the same balance as the cell example 6 Chenghe was fed with the same amount of dry plant residues (292 kg / hour) under the same temperature and pressure conditions, and the Co-based WHSV was 5.96X 103 hours-1. The rate (mol / hour) is as follows: · C = 1 3 · 6; 0 = 5 · 0 7;

Co = 0.099; and Mn = 0.25 (the remaining Mη is in the slag or left in the exhaust gas). The maximum injected oxygen is about 132.8 kg / hour (4.15 kg moles), and the exhaust gas from the reactor is directed to the water scrubber. In the operation of equilibrium, the composition of the bath agent is Co./Mn/Mn0/C (288/683/22/6 MW). Approximately 157 kg of molten alloy is withdrawn every 8 hours and dispersed to form metal powder, as in Example 1. The composition of the metal powder is essentially the same as the melt under the slag. In an 8-hour cycle, 1,040 liters of scrubber water were collected, containing 99 kg of M η B r 2 and 18 · 1 kg of Η B r. Μ η 0 Μ 0. 4 5 kg / This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) — · ί ----— ί— order * ----- I--line (Please read the notes on the back before filling out this page) A7 _B7_ printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs; 5. The invention description (37) hours accumulated in Rongji. The slag level is regularly withdrawn and adjusted. 157 kg of sprayed gold tincture, 1,040 liters of scrubber water, and 3,23 kg of glacial acetic acid were used to marinate Example 1 to produce a mixed solution of acetate and bromide of Co and Mη, where Co and Mη 3.6¾ and 10.5¾, respectively, by weight. There is essentially no free acid in between. Same as in Example 1 above, if necessary, digest the slag in HOAc to produce a solution of Mn (0Ac) 2, and add this solution as needed in the reforming catalyst, K provides the Co / Mn ratio as desired 1/3. As described above, the remanufactured catalyst is passed through the MM to remove suspended carbon from the alloy. Cell Example 8 The residue feed is a mixture of plant residues and earthy residues from a special sludge tank. There is no liner at the bottom of the tank. A bath of Co / Mn / Mn0 / C (409/244/337 / δ.8), containing 1,000 kg of molten gold tincture and slag, maintained in the reactor at 1900¾ and 10 at in Zhaoli Of the composition. All M η 0 exists substantially in the melt, forming an insoluble layer on the Co / Mn alloy. 292 kg / hr of dry plant residue, containing 2! I! Co, 2% Mn and 4SiBr, Μ by weight, and 3 8.9 kg / hr of dry earthy residue, containing 15 U ο, 3 0 X Μ η, 2 6. 2 5K 0, 8. 3 S; A 1, 8. 7 S: S i, and 10. 3 S; C, by weight, into a mixture, which is injected into the molten alloy with oxygen. in. Co-based WHSV is 0.017 hours -1. The equivalent rate of feed (mol / h) is as follows: C = 15.16; 0 = 5.46; Co = 0.2; and Mn = 0,13 (the remaining Mη is in the melt, or left the reactor in the exhaust gas ). The amount of injected oxygen is about 154.7 kg / hour (4.83 kg moles), and the exhaust gas emitted from the reactor is subject to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) for this paper size ------ ------- it — — — — — — — — Order------- II (Please read the notes on the back before filling out this page) Printed by A7 _B7_ V. Description of the invention (38) Guided water scrubber. During the balancing operation, about 149 kg of molten alloy is withdrawn every 8 hours and sprayed out to form metal powder, as in Example 1 on K. The composition of the particles is essentially the same as the melt under the slag. During the 8-hour period, 1,040 liters of scrubbing water was collected, containing 95 kg of M η B r 2 and 2 1.3 kg of Η B r. No M η Ο K accumulated at a rate of about 9.3 kg / hour. The slag level is regularly extracted and adjusted at 8-hour intervals. The extracted slag is sprayed down to 100 meters (average particle size) with water under high pressure. Combining 149 kg of sprayed metal, 1 040 liters of scrubber water and 323 kg of glacial acetic acid in a heated container with a vent, the temperature rose to 90t :, resulting in a mixture of acetate and bromide of C0 and Mη, where C0 and Mη are 7.3¾ and 6.3¾, respectively, by K weight. There is essentially no free acid in between. As in Example 1 on K, if necessary, the slag is digested with Η 0 A c to produce

For a solution of Mn (0Ac) 2, add this solution to M as needed to provide the desired Co / Mn ratio in the catalyst. As before, the reprocessed catalyst is purged to remove suspended carbon from the alloy. Example 9 Digestion of a mixture of C 0 and M η metal powders which is substantially about, as a control example: Co and Mr »powders, finely divided, with particle sizes ranging from +325 mesh (45 microns) to -100 mesh (150 microns) ), American Standard Test Queue, obtained from Alfa-Aesar. Co powder is black and Mn powder is silver. 1.57 g of Co and 3.13 g of Mn were placed in a 250-ml round-bottomed flask together, and an organic heat pack and a water-cooled reflux condenser were mixed and mixed. Add glacial acetic acid (133.3 g) to the flask. Before the water was added, violent gas was observed. Plus -40- This paper size applies Chinese National Standard (CNS) A4 (210 x 297 mm) — — — — — — — — — — — I · IIIIIIJ · 1111! 111 II-(Please read the note on the back first Please fill in this page for further information.) Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed 5 A7 B7_ V. Description of the invention (39) When water (27.7 g), the rate of gas formation increases. The remaining solution was irritated and light brown during this period. At the beginning of heating, the occurrence of gas increases and then decreases. No silver powder was observed in the flask, indicating that all of the manganese had been substantially digested. When the system reaches reflux, the gas begins to occur again, and the formation of an isochromatic color indicates that C0 begins to react. After 2 2.5 hours, the heating was stopped, and the sample was washed and washed. Unreacted cobalt (magnetic, black powder, 0.27 g) was recovered. The solution was analyzed as before, containing 0.71% CO and 1.67! KMn. After a reasonable period of time, the Co powder cannot be substantially completely digested in acetic acid, and even under reflux conditions, it is proved that such incomplete digestion may also occur in Co in Co / Mn alloys. Example 10 A Co / Mn / C alloy, which is made from molten Co metal and Mn metal together with carbon dust in a graphite-lined induction furnace, is masked with an inert (hydrogen) atmosphere. The melt was allowed to equilibrate and then dispersed by contact with aerobic high-pressure water spray. The obtained powder size was sieved into two parts with a US standard No. 80 test sieve, one larger than 180 microns and the other smaller (i.e. an 80 mesh). This powder represents a product obtained from a thermochemical reaction zone, whether it is a molten gold bath, an electric arc furnace, or other high-temperature metallurgical equipment. It has a thermochemical reaction zone in which used catalyst is dewatered. Remnants. Material analysis indicated 47.5S! Co, 51.3S! Mn, and 0.9¾ carbon. One 4.95 g of 80 mesh alloy powder was placed in a 250 ml round bottom flask, equipped with a heating bag and a water-cooled reflux condenser. Add glacial acetic acid (129.6 g) and water (22.2 g) to the flask and start heating in the flask but not -41-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)-* '* --------- Order -------- (Please read the notes on the back before filling out this page) Printed clothing A7 _B7_ by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ) Scratch. The liquid quickly developed a reddish color, and the solution turned purple when it reached a flow. A diluted sample of the purple liquid taken after one-hour digestion indicated 0.04 5¾ cobalt and 0.0 5 4¾ manganese. After 75 hours and heating stops, the sample is filtered and washed with water and isopropanol. Smallest (0.25 g) of non-magnetic, non-flaming tincture toner was recovered as a solid residue. After the digestion was stopped, the liquid in the flask was analyzed to determine the concentration of tritium in each metal. Analysis indicated 0.853: Co, and 0.93! KMr). The solid residue at the bottom of the flask contains 57.7% Co, 37.4: SMn, and carbon. The weight of oxygen in metal oxides is determined by equilibrium. Example 1 1 M 5.2 g of an 80-mesh alloy powder was placed in a 250-ml round-bottomed flask, equipped with a heating bag and a water-cooled reflux condenser. Add glacial acetic acid (133.3 g) and water (27.2 g) to the flask and begin heating. As in Example 10, the liquid quickly developed a reddish color, and the solution was purple at the beginning of reflux. Heat for 19 hours to stop fh, rinse the sample and wash with water and isopropanol. Recovered non-magnetic, non-flammable black powder is used as solid residue. In a case similar to Cellulite Example 9, after the digestion was stopped, the liquid M in the flask was analyzed to determine the concentration of each metal salt. Analysis indicated 0.84% Co, and 0.92 iKMri. The solid residue at the bottom of the flask was found to contain 54.4 iSC0, 41.0% Mn, and carbon. The weight of oxygen in the gold oxide was determined by equilibrium. This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) i ------- Order --------- line (Please read the precautions on the back before filling this page )

Claims (1)

A8 B8 C8 D8 6. Scope of patent application 1. A method for manufacturing manganese / cobalt catalyst from organic residues of catalyst used in alkyl aromatic compound oxidation equipment. This method includes, (Please read the precautions on the back first) Fill in this page again) ia) Send the spent catalyst residues to the high temperature metallurgical reaction zone. K produces bovine manganese, cobalt, and carbon alloys with a Mn / Co ratio ranging from about 5; 1 to 1: 5 , And the early amount of carbon is in the range of 0 to 7¾ weight of the alloy; (b) released gas, which contains valuables of C0, H2 and bromine; (c) the alloy is formed into a basic particle size of less than 5000 Micron metal powder; and (d) contacting the metal powder with a non-alcoholic digestive fluid, the digestive fluid is selected from the group consisting of glacial acetic acid, an aqueous acetic acid solution, and a mixture of acetic acid and a quenching or scrubbing stream, a scrubbing stream Obtained from absorbing the gas generated in the reaction zone, the degree of occurrence is from about 80 ° to 150 ° and under atmospheric pressure; therefore, the powder is substantially i: completely converted into the acetate solution of Co and Mη. 2. If the method of applying for the first item of the patent scope, The residue is selected from the group consisting of T. plant residues and soil-like residues. 3. If the method of the scope of patent application is No. 1, where the alloy contains carbon, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs There is at least less than Co or Mη in the system, and it is within the range of 0.2¾ to 5¾ of the weight of the alloy. 4. For the method of applying for the first item of the patent park, the powder has a range of from 5 microns to about Basic particle size in the range of 1000 microns. 5. For the method in the first item of the patent application scope, in which the Co and Mn in the solution are in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Printed by the Consumers' Cooperative of the Ministry of Intellectual Property Bureau A8 B8 C8 D8 6. The concentration of acetate in the scope of patent application is adjusted to the ratio required for use as a catalyst. 6. The method of item 1 of the patent application chart It includes absorbing the exhaust gas in an absorbent zone in an absorbent. The absorbent is selected from the group consisting of water, aqueous acetic acid solution, and a recycle stream mixture from the absorbent zone. The recycle stream is essentially composed of acetic acid and bromine 7. The method according to item 1 of the scope of patent application, wherein Mη and Co in the acetate solution are in a ratio substantially equal to Mη in the catalyst from which the residue is derived. The ratio is the same as Co. 8. As in the method of claim 3, the Mn / Co ratio is in the range from about 4: 1 to 1: 2, and the carbon content of rhenium is within the weight of the alloy. The range is from 0.5¾ to 7¾. 9. A Co and Mn gold alloy derived from the organic residue of the catalyst used in the oxidation process of the alkyl aromatic compound to prepare the Co / Mn catalyst solution. System, including Π) high temperature metallurgical equipment with thermochemical reaction zone, receiving the residue in the reaction zone; Π i) feed device for uranium to enter the residue into the high temperature metallurgical equipment; Uv) for Various equipment control operating factors include pressure and temperature in the thermochemical reaction zone. In the range from about 1150C to about 250 °, it effectively converts all carbon-containing substances into carbon monoxide and carbon dioxide, and makes the residue into cobalt, Manganese molten alloy, where the COK per 100 The most alloys are in the range of about 10 to 80 parts; -44- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) f -------- order --- ------ line (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 VI. Patent application scope (V) is used to remove exhaust gas from the reaction zone And the alloy; a piece of equipment; (ί 丨) for pulverizing the alloy to a size range less than 500 microns; (vi) for the exposure of the exhaust gas to a liquid Equipment for dissolving CO and Η2 with the dissolved part, the liquid is composed of water, acetic acid and the soluble, and is used to produce bovine quenching or scrubbing gas stream; U i Π) is used to pour out quenching or scrubbing gas from step U ν) Equipment for logistics; and (ίχ.) Equipment for substantially completely digesting Co and Mn in the powder in acetic acid, hydrobromic acid μ and a mixture with the quenched substance 潦. 10. The system as claimed in claim 9 wherein the high temperature metallurgical equipment is a furnace containing a Co./Mn alloy melting bath. 11. The system of claim 9 wherein the high temperature metallurgical equipment is an electric arc furnace. 12. The system according to item 9 of the scope of patent application, wherein the high-temperature metallurgical equipment is a plasma arc grate. 13. The system according to item 9 of the patent application park includes a liquid-gas contact device for absorbing exhaust gas containing bromine compounds. 14. The system of item 9 of the scope of patent application, wherein the equipment for pulverizing the powder includes equipment for contacting the molten alloy stream with a high-speed flowing liquid under high pressure. 15. —A manganese / cobalt catalyst recovered from the organic residues of the catalyst used in the oxidation of alkyl aromatic compounds. The catalyst is prepared by: (a) feeding the spent catalyst residues Entered into the high temperature metallurgical reaction zone, K produces bovine manganese, cobalt and carbon alloys. It has a range from about 5; 1 to 1: 5-4 5 ~ This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) n II · n I If nnn nI (Please read the notes on the back before filling out this page) Printed by A8 B8 g_ of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs; 6. Mn / Co ratio for patent application scope, The amount of carbon present is within the range of 0 to 7% of the weight of the alloy; (b) the released exhaust gas contains C 0, Η 2 and bromine valuables; (c) the metal powder forming the alloy has Basic particle size of less than 5000 microns; (d) contacting the powder alloy with a non-alcoholic digestive fluid selected from the group consisting of glacial acetic acid, an aqueous acetic acid solution, and a mixture of acetic acid and a quenched or scrubbed gas stream Groups, scrubbers are obtained from the radon generated at the reaction zone of the equipment, the temperature at which it occurs At about 80 ° to 150 ° C and about atmospheric pressure; during this time the powder is substantially completely converted into a solution of the acetates of Co and Mη. 16. In the case of the application of the remanufactured catalyst in item 15 of the patent scope, the residue ✓ is selected from the group consisting of factory residues and soil-like residues. 17. The remanufactured catalyst of item 5 of the patent application, which contains at least the carbon present in Co or Mn, and is within the range of 0.25% to 5% based on the total weight of the alloy. 18. In the case of the application of the reproduction catalyst of item 15 of the patent scope, wherein the powder has a basic particle size ranging from 5 microns to about 1,000 microns. 19. For example, the reproduction catalyst of item 15 of the patent application, wherein the acetate concentration of Co and Mη in the solution is adjusted to meet the ratio required for use as a catalyst. 20. The remanufactured catalyst according to item 15 of the patent application range, wherein the Mn / Cct t [: ratio is in a range from about 2: 1 to 1: 2, and the carbon is 0.5 for the alloy-channeling 0.5. It is present in an amount ranging from% to 7¾. -46- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) --- II--III----^ -------- ^ · 11111111 (Please read the (Please fill in this page again)