TW200825186A - Recycling method of zinc oxide - Google Patents

Abstract

A recycling method of zinc oxide is disclosed and includes the steps of alkaline treatment and chemical precipitation. The granular composite mainly containing zinc oxide is obtained from the materials comprising zinc oxide, iron oxide, zinc iron oxide, and lead oxide. In addition, the present invention can optionally go further to mix this composite with a mineralizer with pH value between 8 and 13 to form a mixture. Finally, this mixture is proceeded by a hydrothermal reaction in the hermetical environment with the temperature of 100 DEG C to 250 DEG C to produce a rod composite mainly containing zinc oxide.

Description

200825186 IX. INSTRUCTIONS: [Technical field to which the invention pertains] The present invention relates to a method for recycling 4 rituals, in particular to a use of the > valley method to be recycled by the ancestor< After the word is dissolved to obtain a first extract having a higher content, a method of precipitating a composition mainly composed of granular oxidation is carried out by chemical precipitation, and selectively further The composition mainly composed of rice oxidized and hydrothermally reacted with the _ mineralizer, thereby obtaining a method of a composition mainly composed of a rod-shaped oxidized word. [Prior Art] Zinc oxide (Zn〇) can be applied to various industries such as plastics industry, electronic parts, coatings, pharmaceuticals and cosmetics. For example, adding oxidation words to paints is very helpful for the mixing of paints, and By controlling the consistency, the penetration degree and the sealing property, α., thereby improving the drying property and chalkiness of the film formed by the paint, reducing the degree of color and yellowing thereof, and enhancing the UV and mildew resistant properties. This is an important additive in paints such as zinc oxide, outdoor paint and white lacquer. ΒΘ L is a rod-shaped zinc oxide, generally known as one-dimensional zinc oxide, which has a more economical value. Considered as a new type of semiconductor material with excellent optical and electrical properties. At present, there are zinc oxide semiconductor optoelectronic devices such as ultraviolet light-emitting diodes, light-emitting diodes (LEDs) and semiconductor lasers (LDs), which can be widely used in optical communication networks, photoelectric displays, photoelectric storage, and photovoltaics. In areas such as conversion and photodetection. Taking the field of optoelectronic display as an example, flat panel display technology is the basic requirement of terminal display 5 200825186 in the information age. At present, the main flat panel display technologies are liquid crystal (LCD), cathode ray tube (CRT), plasma (PDP), and fluorescent tube. (VFD) and light-emitting diode (LED), wherein the light-emitting diode has a lower driving voltage when applied to a flat panel display screen, and can be matched with an integrated circuit, and has both multi-color display and long life. The advantage of quick response is an ideal flat panel display device. At present, there are products of monochrome displays, such as red and green LEDs, but color displays have not yet been commercialized. The main reason is that the brightness or color purity of indigo electroluminescence is not practical. Color display can not be realized by using three primary colors, and white electroluminescent materials are mostly broadband radiation. The effective brightness of the three primary colors filtered by the filter is reduced, and the practical requirements are not met. The development of zinc oxide-based light-emitting diodes will be Promote LED products to full color display. However, the one-dimensional oxidation of high economic value is mostly made directly from the costly raw materials. In recent years, environmental awareness has increased, and waste recycling has been emphasized. The waste ash (electric arc ratio (7) (10) 2, referred to as EAF dust) produced by steel mills has become a source of refined iron and iron because of the large amount of iron and zinc compounds. One of the important sources of zinc. Typical dust collection ash includes dozens of compounds such as iron oxide, zinc oxide, lead oxide, tin oxide, cadmium oxide, magnesium oxide, emulsified nickel, copper oxide, etc., wherein the zinc content percentage can reach 30wt/〇 to 4〇wt°/ . 'Thus' is based on the search for zinc from dust collection ash in a variety of ways based on the search for lower cost zinc and the better recyclability of steel mill waste. The method for recovering zinc from dust collecting ash can be roughly classified into a dry type and a wet type return method. For example, Taiwan's special wealth application number 931 () 5475 is revealed - a dry type back to the method of 200825186 f words 'the case is to first collect dust ash, and remove impurities such as chlorine and impurities at 945~955 °c, , 隹 π 、, β _ / , and then to zinc oxide and zinc iron spinel (ZnFe2〇4: sintered particles of the 'reuse carbon monoxide as a reducing agent to make zinc and t original metal n, and finally, (4) The zinc in the point will be collected by vapor in the form of vapor and will be collected into the condensing equipment to be condensed into metal zinc powder. The purity is higher than 99.5%' and is recovered in the form of sponge iron. Dry recovery method: Although the production efficiency is higher, the equipment cost of the investment required is large, and the energy consumption to the temperature is much higher.

The m P wet recovery rule is to use an acidic solution, a salt solution or an alkaline solution to dissolve the zinc, and then send the solution to a refining process, so that the refinement is carried out by the cathode, but refining will be required It consumes a lot of energy. Among them, the acid-dissolving method with more mature technology is the most commonly used material, but the dissolution rate of strong acid for zinc and lead must reach 95% or more under temperature and pressure, and the dissolution rate of iron is also over 60%. Subsequent iron removal burden is aggravated. If the compound in the dust collection ash is dissolved by the solution method, the dissolution rate of the word is lower than that of the acid solution method because the alkali solution method cannot dissolve the ZnFhh phase. Therefore, US Patent No. 5,667,553 f discloses a combination fire. Method and method for recovering zinc oxide by separating and recovering zinc oxide from a raw material containing iron, zinc 'cadmium and lead, which is firstly purified by pyrometallurgical means. a dust-collecting ash containing lead oxide, oxidized cadmium and cadmium oxide, and then impregnated with a weakly alkaline ammonia-ammonium carbonate solution, "the claws also produce a lead-containing sediment and the lead-containing ammonium carbonate solution" , a deposit and a leach liquor containing cadmium and cadmium, 7 200825186 The precipitate is separated from the extract, and the cadmium precipitate is separated by adding the metal to the extract. And removing the ammonia water from the leach solution, thereby obtaining - carbonated (ZnC〇3) sinking matter, and then using a rotating kiln or a fluidized bed to repel the heat Water and carbon dioxide, To a higher economic value of oxidation, but the operation of the method is cumbersome and requires the use of fire method, the cost is not low, and because the ammonia-ammonium carbonate solution is a weak alkaline solution, the effect of dissolution is limited. In addition, although rotating parties or fluidized beds can handle dust ash in large quantities and quickly to produce zinc oxide, rotary kiln or fluidized bed needs to rely on large, complex and costly equipment, and this The equipment can not produce the same quality products. The main method of recovering zinc from the dust collection ash in the country is to refine the electroplating factory after passing through the dip shell and electrolyze the zinc from the cathode. Precipitation. In Taiwan, most of the steel-making Wei first uses the Waelz Process technique (the treatment of dust collection ash, so that the dust collection ash becomes a higher zinc content of crude emulsified zinc (CrUde Zn〇), and then large Part of the crude zinc oxide is sent to 曰本* for refining treatment. The cost of zinc oxide produced in this way is high. Therefore, for the industry, there is still a need to develop an oxidation which is inexpensive and practical. The method, if it is from an environmental point of view, there is still a need to provide a treatment method that can make the dust collection ash a better resource. [Summary of the invention] Since it is obtained from the raw material of dust collecting ash or crude zinc oxide The wet recycling method of oxidized words is mostly treated with acid solution or solution treatment, and then subjected to an electrolysis step that requires a large amount of energy. After refining to obtain pure zinc, it is converted into an oxidation word. The cost is high. Therefore, the method of recovering zinc oxide from dust ash is mostly dry fire treatment, and the cost of the equipment in the fire method is not low and is suitable for processing large-scale and quantity dust collection. Ash, so each steel mill must transport (4) ash to the treatment plant for treatment 'can not be directly processed in the steelmaking waste, increasing the chance of collecting dust and ash air. ’,

The chemical precipitation of the precipitant increases the zinc oxide content. Therefore, the applicant of this case thought about the method of collecting zinc oxide. This method does not cooperate with the chemical precipitation method. From the dust collection, the added value of dust ash pollution ash reuse can be reduced. In addition to this simple step and low cost, it is necessary to use the fire method, but to separate and recover the oxygen air by alkali ash or coarse oxidation, and at the same time improve the dust collection, only by selecting appropriate An object of the present invention is to provide a method for recovering zinc oxide comprising the following steps: (4) - mixing a raw material containing zinc oxide, iron oxide, zinc iron oxide, and lead oxide with a lye liquid In order to obtain a first leaching solution containing iron sink; exhibiting and 3 words and lead, wherein the lye is selected from sodium hydroxide solution, potassium hydroxide solution, ammonia water or a combination thereof; 13) separating the first extract from the iron-containing precipitate; (hooking in the first extract / λ!, and the force of zinc bismuth to know a wrong precipitate and a second containing zinc a leach solution; (d) separating the second leach solution from the lead-containing precipitate; (e) adjusting the pH of the second leachate to less than 13 by using an acid to cause chemistry Precipitating the reaction, and thereby obtaining a composition mainly composed of granular zinc oxide. Optionally, the present invention The step further comprises a step 9 200825186 (f) after the step (e), the step (f) is such that the composition mainly composed of granular zinc oxide and the pH value is between 8 and 13. The mineralizer is mixed to form a mixture, and the mixture is subjected to a hydrothermal reaction in a closed environment having a temperature of from 100 t to 250 ° to obtain a composition mainly composed of rod-shaped zinc oxide. Embodiments of the present invention for recovering zinc oxide by recovering and purifying zinc oxide from a recovered raw material comprising zinc oxide, iron oxide, zinc iron oxide, and lead oxide, the method comprising The following steps: (mixing the raw material with a lye to obtain an iron-containing precipitate and a first-lead extract containing the same, wherein the test solution is selected from the group consisting of sodium oxynitride and potassium oxychloride a solution, ammonia or a combination thereof; (b) separating the first extract from the iron-containing precipitate; (4) adding zinc powder to the first extract to obtain - containing the faulty temple and - a second extract containing zinc; (4) the second enthalpy, liquid and The substance is separated; (4) the pH of the first extract is adjusted to less than 13, by using an acid, and the granule is oxidized by the granules. The composition is mainly composed. Preferably, the raw material is dust ash or crude oxidation, and the method is also suitable for recovering oxidation/ground from dust ash or crude zinc oxide raw material. It is obtained from the soil of the main raw materials. The electric arc furnace steelmaking plant is better, and it is suitable for the liquid test in the step (4) of the present invention. The alkali hearing of the specific money used in the invention is as follows: liquid. Sodium solution 10 200825186 杈佳地'This step (a) is carried out at a temperature not higher than 100 ° C, and more preferably the 'far step (a) is carried out at a temperature between 70 ° C and 80 ° C . Preferably, the acid used in the step (e) is hydrochloric acid, nitric acid, sulfuric acid, vinegar I or a combination thereof, and more preferably, the acid used in the step (ii) is a salt oxime. In the specific example of the present invention, chemical precipitation is carried out by adding hydrochloric acid having a concentration of 2 M to obtain a zinc-containing precipitate. Before the hydrochloric acid is added, the pH of the second extract of the specific example of the present invention is greater than 14. When the pH of the first extract of the child is adjusted to 13 by hydrochloric acid, a precipitate is produced, and the fragrance is produced. The lower the pH, the greater the amount of the precipitate. Preferably, the pH of the second extract is adjusted to be between 10 and 125. Preferably, the method for recovering zinc oxide of the present invention further comprises a step (e,) after the step (0), wherein the composition is washed with water and dried to obtain a powdery shape. The composition of the granular zinc oxide is mainly composed. The reaction mechanism of each step in the method is presumed as follows: when the raw material of the step (a) is mixed with the alkali liquid, the zinc oxide and the lead oxide in the raw material are mainly The reaction of sodium hydroxide is carried out, and the reaction formula is as shown in the following formulas (I) and (II), and the iron-containing oxide and other impurities form an iron-containing precipitate.

ZnO+2NaOH-> Na2Zn02+H20 (1)

Pb〇+2NaOH-> Na2Pb02+H20 (π) In addition, in order to increase the percentage of the oxidized content in the composition containing zinc oxide, the applicant of the present application further proceeds to the step ((in the case of the first extract) Zinc powder is added to thereby reduce and precipitate metal lead, and the ruthenium type can be expressed by the following formula (III).

Zn + Na2Pb02 - > Na2Zn02 + Pb 200825186 And the chemical precipitation reaction of the step (e), if hydrochloric acid is taken as an example, the reaction formula is the following formula (IV). (IV)

Na2Zn02 + 2HCl-> Zn0 + 2NaCl + H20 Alternatively, the composition of the present invention which is mainly composed of granular zinc oxide can be further 700. (3 simmering to increase the crystallinity of the zinc oxide 〇

Alternatively, the above alkali-soluble reaction is repeated to obtain a composition having a more granular oxidized content. The zinc oxide content can be increased by subjecting the composition to another liquid test or salt dissolution treatment, but a composition having a high zinc oxide content can be obtained by the method of the present invention alone. In view of the high added value of the rod-shaped oxidized word, the present invention further comprises a step (f) after the step (4), in which the crystalline form of the zinc oxide in the composition is changed into a rod shape. The oxidation term, the step (1) is such that the composition mainly composed of granular oxidized words is mixed with a mineralizer having a pH between 8 and 13 to form a mixture, and the mixture is allowed to be - There is a hydrothermal reaction in a closed environment at a temperature of 1 GGC to 25 G ° C to obtain a composition mainly composed of rod-shaped zinc oxide. Preferably, the method for recovering the oxidation word of the present invention further comprises a step of the step (7), wherein the (four) (f,) is used to clean the composition of the zinc oxide-based composition, and dried, and further dried. It is obtained as a composition mainly composed of zinc unzinc.知虱虱车父"ί地' the pain in the step (f) deionized water, or the like: 乳化 emulsified nano solution, ammonia and 兮 also into a dish, and σ 'better, the mine The agent is a solid-liquid ratio of ammonia water to cyanide water of between 0.0015 g/mL or so. · 0125 12 200825186 between g/mL. Optionally, the mixture in the step (f) further comprises cetyltrimethyammoniun bromide (CTAB), polyethylene glycol (Polyoxyethylene Glycol; PEG), ethylenediamine (ethylenediamine; EDA). ), trisodium citrate, sodium sulphate sulphate (SDS) 〇, more preferably, the amount of hexamethylene sulphate ammonium in the step (f) is the volume of the mineralizer 1 vol% to 3 vol%. When the raw material to be treated further includes an oxide of cerium, for example, dust collecting ash, the method for recovering zinc oxide of the present invention may further comprise a step (b') after the step (b), the step (b') Causing a calcium-containing compound to be mixed with the first leaching to form a calcium citrate precipitate, and by separating the formed calcium citrate precipitate to obtain a sputum-removing first extract, the calcium-containing The compound is calcium hydroxide (Ca(OH)2), calcium carbonate (CaC03), or a combination of ones. Preferably, the compound containing #5 is a hydroxide mother. Preferably, the calcium-containing compound is used in an amount of from 3 to 4 times the amount of cerium in the raw material. The amount of antimony in the raw material can be estimated by taking a small amount of raw material samples by X-ray fluorescence diffraction analyzer (XRF) and ultraviolet light analyzer (UV) analysis method. The reaction mechanism of ruthenium is exemplified by calcium hydroxide. The reaction formula is the following formulas (IV) and (V). Most of the ruthenium in the raw material is in the form of ruthenium dioxide, which will be treated first after alkali treatment. Sodium citrate (Na2Si〇3) is formed, and sodium citrate is further reacted with the calcium hydroxide to form a calcium citrate 13 200825186 (CaSi〇3) precipitate, which is further removed from the raw material.

Si02+2Na0H-.Na2Si03+H20 (Iy)

Na2Si〇3+^£^^2Na〇H+^^ j In addition, 'this step (b,) may also be such that the activated carbon is mixed with the first :) extract for the adsorption of the compound containing the stone, and borrowed The activated carbon containing the compound containing Shishi is adsorbed from the separation surface to obtain a first leach solution, and the potted compound contains a compound or a dioxane. Preferably, the amount of the active carbon is from 3 to $ _ of the cerium content of the raw material. When the raw material to be treated further includes an oxide of steel, the first extract in the step (4) further contains copper, and the precipitate obtained in the step (4) further contains copper. The reaction mechanism for the reduction and precipitation of the copper-containing oxide is copper and m) and (VII). The reaction formula is as follows

CuO+2NaOH~> Na2Cu02+H2〇 (VI)

Zn+Na2Cu〇2—Na2Zn〇2+Cu f A small amount of oxides containing (=) metals are usually present in the raw materials of this treatment, and the reaction mechanism is also related to: 3 nickel. The following is a further description of the present invention by way of example only, and is not intended to limit the scope of the present invention. » f ear% can be.糸 不 不 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作 操作The average value of the zinc oxide weight percentage is 50% by weight based on the total weight of the crude zinc oxide. 3. Cetyltrimethylammonium bromide: purchased from Jingming Chemical. Microstructure of Composition The following examples were carried out by scanning electron microscopy (SEM, available from Hitachi) to observe the microstructure of each composition. First, each sample was uniformly dispersed in an alcohol solution, and a few drops of the solution were dropped on a carbon paste, and dried, and finally, after vapor deposition on the surface, SEM observation was carried out. Component Analysis The following examples were performed by X-ray diffraction (XRD) using X-ray diffraction (XRD) to determine the crystal phase of the composition. The operating conditions were: Cu target (Κα1 = 1.54 persons), graphite two-pole single light. Graphite back Monochromator, Step scanning analysis, 20=2〇-70. (step 0.01o, step time 2.), voltage 401 <:\^, current 3〇111 eight. Metal Element Analysis The following example is performed by repeating the sample to be sent to a Canadian ACME professional laboratory to obtain the metal element content ratio of the sample. The laboratory is certified by the international IS09002, and the applicant is requested to use the analysis method of Group 7AR (full suit). In this method, 1 gram of sample was separately weighed and dissolved in a total volume of 100 ml with an aqueous solution of Wang (HC1-HN03_H20), and then analyzed by an inductively coupled plasma spectrometer (ICP/ES). Separation and recovery of zinc oxide from dust collection ash 15 200825186 <Example 1 > The procedure of this example is as follows: (1) In this example, 1 gram of dust collection ash is firstly immersed in 10 ml of 5 M NaOH. 'And placed in a Teflon beaker, heated by a water bath and stirred for 2 hours for alkali treatment, thereby obtaining an iron-containing precipitate and a first extract containing zinc and wrong, wherein the temperature control of the water Between 70 ° C and 80 ° C; (2) separating the iron-containing precipitate and the first extract containing zinc and lead (3) adding the powder to the first extract Reducing elements such as lead and copper to obtain a precipitate and a second extract; (4) separating the precipitate and the second extract; (5) adding the second extract 2M HC1 adjusts the pH to 12.5 to carry out a precipitation reaction to obtain a zinc-containing precipitate; (6) washing the zinc-containing precipitate with 50 C of water to remove sodium chloride, and drying it to obtain a powder and A composition mainly composed of granular zinc oxide. <Example 2> Example 2 was obtained in the same manner as in Example 1 to obtain the composition mainly composed of granular zinc oxide, except that the present examples were in the steps (2) and (3). ) also includes a step (2,), which adds 〇·2g

Ca(OH)2 was added to the first leach solution and the precipitate CaSi03 produced by centrifugation was removed <Example 3> Example 3 was obtained in the same manner as in Example 1 to obtain the pellet. Oxygen 16 200825186 A zinc-based composition, the only point of which is that the present embodiment further comprises a step (2) and a step (2,) between steps (2) and (3). The step (2') is carried out by adding 2 Μ HC1 to the first extract to adjust the pH to 4, and the step (2,,) is adding 〇·5 gram of activated carbon to the first extract for supplying The ruthenium is adsorbed, and the activated carbon adsorbed on the ruthenium is removed by centrifugation. The applicant of this case is to further understand the content change of each element in the dust ash after the empirical solution treatment, and invites the ACME special # laboratory to analyze the dust collection ash by the method of up 7ar( ), and the step 1 of the embodiment 1 ) 3 iron / children after treatment; temples, and examples! Samples such as the composition of the granular zinc oxide obtained in the same manner as in 2, and the main elemental components and their contents of the samples were obtained as shown in Table 1. Among them, it should be specially stated that the dust ash of the general steelmaking plant will contain 1.8~4.8wt% of cerium oxide (〇2), but the Gr〇up 7AR analysis method cannot measure the strontium element itself. Table 1 Element Pb Cu Zn (ZnO) A g Ni Co Mn Fe Cd Ca P Cr Mg A1 Na Unit wt % wt% wt% gm/ mt wt% wt% wt % wt % wt% wt % wt % wt% wt % Wt % wt % Dust ash 3.78 0.288 33.48 (23.43) 89 0.034 0.002 1.33 18.6 0.071 3.71 0.0 8 3 0.212 1.11 0.41 1.79 Iron-containing sediment 0.41 0.178 8.59 (10.69) 77 0.02 0.002 1.97 26.0 0.035 4.09 0.09 0.235 1.26 0.72 4.92 Implementation Example 1 0.98 0.038 66.8 (83.15) <2 < • 001 < .001 0.01 < .01 0.005 0.01 0.03 0.001 < .01 < .01 0.99 Example 2 2.83 0.031 66.97 (83.36) 11 0.002 < .001 0.03 0.01 ..004 0.17 0.07 < .001 < .01 < .01 0.35 17 200825186 (two hundred data can be seen, the composition obtained in examples 1 and 2, zinc two; broad ratio from the original The amount of 3:1 in the untreated raw material becomes 66.8 wt% or more, and the L*^ is less, and the percentage of the soil content is significantly reduced: the method has increased the percentage of the content of the word by two sets of dust ash. Most of the words (> 70wt%) are, only about 3〇wt% are in the presence of the iron tipping phase, the H line exists in the large meteorite phase. Zinc ferrite phase due to the composition / II: Γ was dissolved in the post-processing by step ⑴ will be present in the iron-containing precipitate, therefore shellfish January Example

The weight percentage of the weight of the oxygen atoms in the analysis of the components 1 and 2, plus the weight of the oxygen atom, can be inferred by the ratio conversion, the composition of the granular zinc oxide obtained by the method of the second zinc oxide obtained by the present invention. 2 has an oxidation number of 8 〇 wt% or more, wherein the composition obtained in Example 1 contains 83.15 wt% of oxidized words, and the composition obtained in Example 2 contains 83% by weight of zinc oxide. Further, most of the zinc oxide contained in the iron-containing precipitate in the table should be zinc iron spinel because the zinc oxide in this structure is not easily decomposed and dissolved. If the user wants a higher content of zinc oxide strontium to repeat the above-mentioned test dissolution reaction, a composition having a granular zinc oxide content of more than 80% by weight or more is obtained. Further hydrothermal treatment Table 2

18 200825186 Example 7 150 12 Figure 3 (b) Rod-shaped dispersion 300 nm /5 0 nm Example 8 200 12 Figure 3 (c) Rod-shaped dispersion 700 nm / 40 nm Example 9 0.1: 30 10 200 12 Figure 4 (a) Rod-shaped 〇 radiative flower shape 10 μ m /2 β m Example 10 12 200 12 Figure 4 (b) Rod-shaped 〇-radiated flower shape 800 nm / 400 nm Example 11 0.2:30 0.6 10 200 6 Figure 5 Rod-shaped dispersion 600 nm / lOOnrn Example 12 12 200 6 Figure 6 Rod-shaped 〇 Radiation flower shape 2.5 β m / 250 nm Example 13 0.2: 30 10 200 6 Figure does not show rod-like 〇 radiation flower shape 600 nm / OOnm Example 14 13 200 6 The figure shows that the rod-shaped 〇-radiated flower shape 2.5 μ m /250 nm [Note 1] The solid-liquid ratio refers to the mixing ratio of the composition mainly composed of granular zinc oxide and the mineralizer NH4OH. [Note 2] The granulated oxidized sources of all the examples in Table 1 were the compositions obtained in Example 2. [Note 3] The symbol 0 in the table indicates that the single crystal cross section is hexagonal. <Examples 4, 5 > Example 4 is obtained by dissolving 0.2 g of a composition mainly composed of granular zinc oxide prepared in Example 2 in 30 ml of a mineralizer NH4OH having a pH of 10, and together It was placed in a stainless steel pressure tank and placed in an oven at 150 ° C for 12 hours of hydrothermal reaction. The powder obtained by the hydrothermal reaction is washed with water three times and then dried to obtain a powdery composition containing rod-shaped zinc oxide. In Example 5, the rod-like zinc oxide-based composition was obtained in the same manner as in Example 4 except that the temperature in the oven was 200 〇C 〇 <Comparative Examples 1, 2 > In Comparative Example 1, the composition mainly composed of the rod-shaped oxygen 19 200825186 was obtained in the same manner as in Example 4, except that the ratio (10)H was not the composition obtained in Example 2'. Granular zinc oxide was prepared according to the procedure of Example 但是, but steps (3) and (4) were not carried out, i.e., no zinc powder was added. On the other hand, in Comparative Example 2, the composition which is mainly composed of the oxidized oxidized word was produced in the same manner as in the case of (4) 1, except that the pH of the mineralizer used in Comparative Example 2 was 12.

The Applicant has further confirmed that the compositions obtained by the method of the present invention are mainly oxidized, so that the compositions obtained in Examples 2, * and 5 and Comparative Examples 1 and 2 were respectively ground. The powder was further analyzed by XRD analysis of Example 2, Example 4, Comparative Example 实施, Example 5 and Comparative Example 2 in the order of (4) to (e) in Fig. 1, which can be seen from the figure. In addition to the formation of zinc oxide, there are also the formation of heterogeneous phases such as zinc citrate (ZnjiO4) and zinc sulphate (PbZnSi〇4), which should be dissolved in the alkaline solution. The resulting heterophase. After the addition of zinc powder, the main phase is oxidation, and a small amount of zinc citrate, the lead sulfate phase has disappeared, indicating that zinc powder can effectively remove lead. See Table 2 and Figures 2(a) and (b). Figure 2 is a scanning electron microscope (SEM) to observe the crystal morphology of the composition of the child. It can be found that there is indeed complete rod oxidation after hydrothermal reaction. Zinc crystal formation. <Examples 6 to 8> Examples 6 to 8 were obtained in the same manner as in Example 4, and the rod-shaped zinc oxide-based composition was obtained, except that the examples 6 to 8 were used. The mineralizer NH40H has a pH of 12 and the temperatures in the oven are 10 ° C, 150 ° C and 200 ° C, respectively. 20 200825186 / See Table 2 and Figures 3 (a), (b) and (c), Figure 3 is an SEM image of the compositions obtained in Examples 6 to 8, which can be found in comparison with Examples 4 and 5. When the pH value is 12, the formation of U-zinc oxide in the form of rod-like crystals can be clearly seen in the SEM image obtained by the hydrothermal reaction under a lower reaction temperature, that is, under 1 Torr. In addition, as the temperature increases, the length/diameter ratio (L/D) of a single rod-shaped zinc oxide tends to increase. <Examples 9 and 1> Example 9 was obtained in the same manner as in Example 5, and the composition was mainly composed of rod oxygen (4), and the difference was only in the case of hydrothermal reaction. The amount of the composition mainly composed of granular zinc oxide is 〇·1 g. In the case of Example 10, the rod-like zinc oxide-based composition was obtained in the same manner as in Example 9, except that the mineralizer NH4〇H had a pH of 12. See Table 2 and Figures 4(4) and (b) for the SEMW of the composition obtained in Example 9 and ι, wherein the hydrothermal reaction of Figure 4 (4) is carried out in an environment of 10, 8 (8) The shell is carried out in a pH (four) u environment, regardless of the pH value of 10 or 12, the overall crystal form of the rod-like zinc oxide-based composition under SEM is a flower flower (flowerhke) and each The cross-face of a single crystal is hexagonal, because the single crystals grow in the 3D direction from the core, which is greatly different from the random dispersion shown in (4) to (4) of Fig. 3. It can be inferred that the percentage of the initial granular oxidized word will result in a different overall crystal form of the oxidized word.

Addition of CTAB 21 200825186 <Examples 11 and 12 &gt; Reference Table 2, Fig. 5 and Fig. 6' Example u is the composition of the granular zinc oxide mainly obtained by the example 2, G & 2 g Soluble in % mL: mineralizer NH4〇H with a pH of 10, and Wo Shi A, _ ,

Wei added 0.6 liters of CTAB together into an iron can cage, and then placed in a stainless steel autoclave for 6 hours of hydrothermal reaction, the temperature inside the oven is a fan. c. The powder obtained after the hydrothermal reaction is washed with water to obtain a powdery composition mainly composed of rod-shaped zinc oxide.

p Example 12 is obtained by the steps of Example 1丨} π ^ , and Shell Example 11 to obtain the rod-shaped zinc oxide-based composition, and the difference is that the u is only The pH value of the mineralizer NH4OH is 12 〇. The crystal form of the composition mainly composed of rod-shaped oxidized words obtained by adding CTAB by sEM observation. When the mineralizer PH value is 1G, the cross section of the single crystal is It is round and the whole shape is dispersed as shown in Figure 5. When the pH of the mineralizer is 12, the cross section of the single crystal is hexagonal, and the overall shape is radial, as shown in ® 6. In addition, from the length and diameter of the rod-shaped zinc oxide, it can be seen that the addition of CTAB can promote one-dimensional growth of the oxidation word. &lt;Examples 13 and 14&gt; Referring to Table 2, Example 13 obtained the same composition as the rod-shaped zinc oxide in the same manner as in Example u, except that the reactant was taken The composition mainly composed of granular zinc oxide obtained in Example 3. In the same manner as in Example 13, the same procedure as in Example 13 was carried out to prepare the composition mainly composed of a rod-shaped oxidized word, except that the mineralizer 22 200825186 nh4〇h〇h value was 13. The crystal morphology diagrams of the compositions of the examples 13 and 14 which are mainly composed of rod-shaped oxidized words are similar to those of the implementation of the life &quot;2, and are in the form of radiation. The above-mentioned synthesis, the oxidation word after hydrothermal treatment can be known. It will change from granular zinc oxide to a rod-shaped oxidation word with high economic value. Separation and chemical vaporization of zinc in straight AAik zinc &lt;Example 15&gt;

f Example 15 was obtained in the same manner as in Example 1 to obtain a composition mainly composed of granular oxidized words, which differed only in that the raw material in the step (1) was! The crude oxidation of the grams. The present invention (IV) icp/es composition analysis The results are shown in Table 3. The composition obtained in the present example contained 91.9 wt% of granular zinc oxide. Further hydrothermal treatment &lt;Example 16&gt; The procedure of this example was as follows: (1) The composition of the granular oxidized word obtained by G.2 g of Example 15 was dissolved in 30 ml. A mineralizer NH4OH towel with a pH of 1 , was placed in a non-recorded steel pressure tank, and then placed in an oven at a temperature of 20 (TC) for 6 hours to obtain a product; (2) After the product was washed with water three times and dried, a powder-like composition mainly composed of a rod-shaped zinc oxide was obtained. <Example 17> Referring to Table 4, this example was the same as Example 16. The procedure of 23 200825186 to the rod-shaped zinc oxide-based composition differs only in that the pH of the mineralizer ΝΗ40Η in the step (1) is 12. <Example 15~ (Comparative description of 17) (a) to (c) in Fig. 7 are compositional analysis charts obtained by analyzing the compositions of the rod-shaped zinc oxides of Examples 15, 16 and 17 by XRD, respectively. It can be seen that the heterophase can indeed be removed after treatment by the recycling method of the present invention. Further, as can be seen from the data of Table 3, Examples 15 to 17 The percentage of zinc oxide in the composition is changed from only about 5 〇 plus % to about 90% by weight in the original crude zinc oxide, and the composition obtained in Example 16 contains 97.65 wt% of rod-shaped zinc oxide. The composition obtained in 17 contained 98.47 wt% of a rod-shaped oxidation word.

Pb wt %

Cu wt%

Zn (ZnO)

Ag

Ni

Co

Mn

Fe

Cd

Ca

Cr wt% gm / mt wt% wt% wt % f Example 15 Example 16 Example! Wt % wt% wt %'

Wt % wt%

Mg Wt % A1 wt %

Na wt % 0.24 0.001 78.05 (91.90)

I 1 &lt; • 001 :.001 ..01 :.01 .001 :.01 0.01 &lt;.001 :.01 0.1 :.01 0.02 ..001 :.00! :.01 0.01 • 01 :.001 : .001 &lt;2 &lt;2 &lt; .001 0.001 78.45 (97.65) 0.003 0.002 0.19 0.33 0.01 &lt;.001 :.01 0.01 0.01

&lt;Example 18&gt; Referring to Table 4, this example obtained the composition mainly composed of rod-shaped zinc oxide in the same manner as in Example 16, except that the pellet (1) was granulated. The composition of the zinc oxide-based composition is 〇·1 g, and the hydrothermal reaction time of 24 200825186 is 3 hours. <Example 19> Referring to Table 4, in the present embodiment, the composition mainly composed of noon-like zinc hydride was prepared in the same manner as in Example 18, except that the step (1) was used. The mineralizer has a pH of 12. &lt;Example 20&gt; Referring to Table 4, this example was carried out in the same manner as in Example 18 to clarify the composition mainly composed of rod-shaped zinc oxide, which is different in this step.

The amount of the composition mainly composed of granular zinc oxide in the step (1) was 公 5 g. <Example 21> Referring to Table 4, in the present example, the composition mainly composed of rod-shaped zinc oxide was produced in the same manner as in Example 2, except that the ore in the step (1) was obtained. The pH of the agent NH4〇H is 12. &lt;Example 22&gt; Referring to Table 4, in the same manner as in Example 18, the rod-shaped zinc oxide-based composition was obtained, except that the step (1) was a pellet. The amount of the zinc oxide-based composition is 〇·2 g, and the step (1) further adds CTAB. <Example 23> Referring to Table 4, in the same manner as in Example 22, the composition mainly composed of a rod-shaped oxidized word was obtained, and the difference was that the ore in the step (1) The pH of the ΝΗ4ΟΗ is 12. <Example 24> Referring to Table 4' This example was carried out in the same manner as in Example 18, and the difference was that the composition was mainly composed of a rod-shaped oxidized word (1). Add CTAB. &lt;Example 25&gt; Referring to Table 4, in the same manner as in Example 24, the rod-shaped zinc oxide-based composition was obtained, except that the ore in the step (1) was obtained. The pH of the agent NH4〇H is 12.

_ 26 200825186 Table 4 Example solid-liquid ratio (g/mL) CTAB amount (mL) pH reaction time corresponding XRD pattern Example 16 0.2:30 0 10 6 Figure 7(b) Example 17 12 6 Figure 7 ( c) Example solid-liquid ratio (g/mL) CTAB amount (mL) pH reaction time corresponding to SEM single crystal morphology overall morphology L/D Example 18 0.1:30 10 3 Solid not showing flaky petal shape 500nm / 20nm Example 19 0 12 3 Figure 5 shows no rod-shaped radiation pattern 1 β m /1 50 nm Example 20 0.05: 30 10 3 Figure 8 Sheet-like petal shape 500 nm / 20 nm Example 21 12 3 Figure 9 Rod-shaped radial flower shape &gt 2 U m /250nm Example 22 0.2:30 10 3 Figure is not shown in the form of sheet-like petal 600m / 20nm Example 23 0.6 12 3 Figure does not show rod-like 〇 radiative flower shape 400nm / OOnm Example 24 0.1:30 10 3 Fig. 3 shows no sheet-like petal shape 500 nm / 20 nm. Example 25 12 3 Fig. 2 shows no rod-shaped radial flower shape &gt; 2 /zm /100 nm φ [In 丨] Table 4 shows the sources of granular oxidized words in all the examples. The i composition prepared in Example 15. [Note 2] The hydrothermal reaction temperatures of all the examples in Table 4 were 2 〇〇〇c. It can be seen from Examples 16 to 25 that the crude zinc oxide raw material can be recovered by the alkali solution, the chemical precipitation and the hydrothermal method in sequence, and the zinc oxide having a high purity can be recovered. As in Example 17, the analysis contains up to 99% by weight of oxidation. The zinc composition was observed from the SEM image, and its crystal morphology was roughly divided into a sheet shape and a rod shape. When the pH of the mineralizer was 1 ( (Example 2, the single crystal form was a sheet, and the overall morphology was Petal-like, as shown in Figure 8; when the mineralizer pH 27 200825186 is 12 a (Example 21) 'single crystal shape is rod-shaped, whole-flowered, as shown in the figure. No matter flaky oxidation Words or rod-shaped oxygen = are of considerable economic value, and the flaky zinc oxide is often used as an additive in white pigments or as a flux in glazes, which is excellent in optics and electricity. (4) It is regarded as a potential infinite conductor material and can be used as an electrode. t In summary, the applicant of the present application by means of dust collecting ash or impregnation in the pre-treatment step of the test solution Dissolution rate of zinc

f, other metals are different, get - the zinc content percentage is higher than the dust collection of the dust-collecting ash, and restore the metal such as the wrong and copper, and then obtain the content percentage of the first extract higher The second extract extracts and precipitates the composition of the granular oxidized content up to 8Qwt% _92wt% by the chemical (four) method, and the conventional technique needs to be refined into metal #, and then the part which is prepared into the oxidized word is greatly reduced. The cost of recycling. In addition, the present invention pushes the cow-inspection #, and progresses in the hydrothermal reaction of the composition mainly composed of granular zinc oxide, which not only dissolves the impurities, but also increases the percentage of the oxidized content in the composition, and makes The crystal form of the zinc oxide is changed from a granular shape to a rod-like oxidation word having a higher practical value. For example, the composition P 3 obtained in Example 17 has a rod-shaped oxidation word of approximately 99% by weight, which means that the present invention is confirmed by dissolution. The chemical precipitation method can obtain a composition of a rod-like oxidized content of a series of _ _ , , 'V. Although some of the overall crystalline forms of the rod-shaped oxidized words are scattered and entangled, they are all concentrated in the industry (4), so the present invention can achieve high economic value at low cost. Oxidation remarks, money #purpose of waste making. 28 200825186 The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, that is, the simple equivalent change of the scope of the invention and the description of the invention. And modifications are still within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an X-ray diffraction apparatus (XRD) analysis diagram, and FIGS. 1(a) to (e) respectively show the granular zinc oxide of Example 2, and Example 4, Comparative Example i The main components of the composition of the rod-shaped zinc oxide based on the examples 5 and 2; FIG. 2 is a scanning electron microscope (SEM) diagram illustrating a composition mainly composed of rod-shaped zinc oxide. Crystal form, which is a composition of a granular zinc oxide obtained by alkali-dissolving dust ash and a mixture ratio of g.2g/30mL, and hydrothermal treatment under an environment of ρΗ value of 1〇 The reaction was carried out for 12 hours, wherein the reaction temperature of the graph (a) was 15 〇〇c, and the reaction temperature of the graph (1) was 200 ° C; FIG. 3 is an SEM image showing a composition mainly composed of a rod-shaped oxidized word. The crystal form is a mixture of particulate zinc oxide-based composition obtained by alkali-dissolving dust ash and NH40H at a mixing ratio of g.2g/30mL, and water is carried out at a pH of 12. The thermal reaction was carried out for 12 hours, wherein the reaction temperature of the diagram (a) was loot, the reaction temperature of the diagram (b) was 15 〇t, and the reaction temperature of the diagram (4) was 200 ° C; Figure M shows the crystal form of a composition mainly composed of rod-shaped zinc oxide, which is a composition mainly composed of granular oxidized words obtained by alkali-dissolving dust ash and NH4〇H as o. The mixing ratio of lg/30 mL was hydrothermally reacted at a reaction temperature of 29 200825186 200 ° C for 12 hours, wherein the pH of the figure (10 was 10, and the pH of the figure (b) was 12; FIG. 5 is an SEM image A crystal form of a composition mainly composed of rod-shaped zinc oxide, which is a composition of granular zinc oxide obtained by dissolving dust ash with NH4OH and CTAB at 0.2 g/30 mL/0.6. The mixing ratio of mL is hydrothermally reacted for 6 hours at a pH of 1 Torr and a reaction temperature of 2 Torr. Figure 6 is an SEM image showing a composition mainly composed of rod-shaped zinc oxide. The crystalline form is a composition of granular zinc oxide obtained by dissolving dust ash with NH4OH and CTAB at 0.2 g/30 mL/0.6 mL, at a pH of 12 and a reaction temperature of 200°. The hydrothermal reaction was carried out for 6 hours in the environment of C; FIG. 7 is an XRD analysis diagram, and FIGS. 7(a) to (c) respectively show the composition of the granular zinc oxide based on Example 15, And the main components of the composition mainly composed of the rod-shaped oxidized words in Examples 16 and 7; FIG. 8 is an SEM image showing the crystal form of a composition mainly composed of a rod-shaped zinc oxide, which is mainly oxidized. a composition obtained by dissolving zinc with alkali is hydrothermally reacted with NaOH at a mixing ratio of g. 5 g / 30 mL for 3 hours at a pH of 10 and a reaction temperature of 200 ° C; and FIG. 9 is An SEM image illustrates the crystal form of a composition mainly composed of rod-shaped zinc oxide, which is obtained by mixing a composition of crude zinc oxide with alkali and NaOH at a mixing ratio of 5 g/30 mL. The hydrothermal reaction was carried out for 3 hours in an environment having a pH of 12 and a reaction temperature of 200 °C. [Main component symbol description] 30 200825186

Claims (1)

200825186 X. Patent application scope: The method of seeding (4) zinc oxide comprises the following steps: (4) ordering - mixing the raw materials containing oxidation, iron oxide, iron oxide, and oxidation, with the test liquid to obtain an iron-containing sediment a temple and a first extract of the sputum containing sputum and sputum, wherein the lye is selected from the group consisting of sodium hydroxide solution, potassium hydroxide solution, ammonia water or a combination thereof; (9) the first extract and the first extract The iron-containing sulphate is divided into: (C) adding a pulverized powder to the 8 haidi extract to obtain a lead-containing precipitate and a zinc-containing second extract; (d) the second The extract is separated from the lead-containing precipitate; (4) the pH of the second extract is adjusted to be less than: 3' by using -acid to cause a chemical sinking reaction, thereby obtaining a granular shape A composition mainly composed of zinc oxide. 2. The method for recovering zinc oxide according to item 1 of the patent scope, wherein the raw material of the 5 HM is dust collecting ash. 3. According to the method of item 2 of the patent application scope for the recovery of emulsified words, the "black dust collection ash is obtained from the main collection of scrap steel. 'Steel is the main original electric arc furnace The steelmaking plant in the method of claim 1 of the patent scope for the recovery of zinc oxide in the method 'the raw material is crude oxidation. 1 according to the scope of the patent application of the first method for the recovery of zinc oxide' side steps The alkali solution of (a) is a sodium hydroxide solution. It is a method for recovering zinc oxide according to the first claim of the patent application. The side step (4) is carried out at a temperature not exceeding - 32 200825186 7. Patent application The method of claim 6 for recovering oxidized words, wherein the step (a) is carried out at a temperature ranging from Chuanqi to ribs." 8. According to the scope of claim 1 for recovering zinc oxide The method, wherein the acid used in the step (e) is hydrochloric acid, nitric acid, sulfuric acid or acetic acid. 9. The method for recovering zinc oxide according to item 8 of the patent application, wherein the acid used in the step (e) is hydrochloric acid. 10. The method for recovering zinc oxide according to the scope of the patent application, wherein the acid of the step (e) adjusts the pH of the second extract to a medium of 10 to 12. 5 between. U. The method for recovering oxidized words according to claim 1 of the patent application, further comprising a step (e,) after the step (e), the composition is washed with water and dried. . 12. The method for recovering oxidation terminology according to item i of the patent application scope, further comprising a step (1) after the step (e), wherein the step (f) is the composition of the granular zinc oxide-based composition A mineralizer having a pH between 8 and 13 is mixed to form a mixture, and the mixture is hydrothermally reacted in a closed environment having a temperature between 100 C and 250 ° C. A composition mainly composed of rod-shaped zinc oxide was prepared. 13. The method for recovering zinc oxide according to claim 12, wherein the mineralizer used in the step (f) is sodium hydroxide solution, ammonia water, deionized water, or a combination thereof. . 14. The method for recovering oxidation word according to claim 13 of the patent application, wherein 'the ammonia water, and the solid-liquid ratio when the composition mainly composed of granular zinc oxide is mixed with ammonia water is 〇〇〇 Between 125g/mL and 〇〇125 g/mL 33 200825186 15· According to the method of claim 2, the method for recovering zinc oxide, wherein the temperature in the step (f) is between 150 ° C and Between 200 ° C. 16. The method for recovering zinc oxide according to item 12 of the scope of the patent application, wherein, in addition, the step (f,) after the step (f), the step (Γ) is: 7jc cleaning A composition mainly composed of rod-shaped zinc oxide is dried. • 17. The method for recovering zinc oxide according to the scope of patent application ,12, wherein the mixture in νν (f) further contains cetyltrimethylammonium chloride. 1 8 · According to the method of applying for patents, Weng J is used to recover the oxidation word, the volume of the 亥°hai mineralizer, the amount of cetyltrimethyl lanthanum in this step (f) It is between 1ν〇1%υν〇1%^. A soil 19. According to the method of claim 1, the method for recovering zinc oxide, the raw material further comprises (4) an oxide, and the wire method further comprises a step after the step (b), ^) (b) ordering a compound containing a mother and the ab to form a sulphate, and by separating and generating the &quot; 鷇 鷇 鷇 ' 儿 儿 儿 儿 儿 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得In the leach solution, the antimony-containing compound is a combination of hydrogen peroxide, carbon, or the like. 2 〇 ·Based on the patent application||The method of 19th, which is used to recover zinc oxide, the compound containing calcium is calcium hydroxide. 21. According to the method of oxidizing words in the poem of the 19th paragraph of the patent, in the middle, the amount of the compound containing the compound is 3 / 4 of the content of the stone in the raw material. The method for recovering the oxidation word, the 34 200825186 ι the raw material further includes the oxide of the stone, and the step (b') after the method (8) 'the step (b,) is to make the activated carbon and the: The mixture is mixed for adsorption, and the first leach solution for removing the cockroach is obtained by adsorbing 矽66 and car 妷 from the surface. / / 23 · According to the scope of the patent application No. 22 Ji Xitian =, Gu Di 22 of the method for recovering zinc oxide, the amount of the activated carbon is 3 to 4 times the amount of antimony in the raw material. 4. The method for recovering zinc oxide according to Item 1 of the scope of the patent application, wherein the β-ray raw material further comprises an oxide of copper, and the first extract in the step (a) further comprises a female steel. The lead-containing precipitate obtained in the step (c) further contains steel. 35