WO2011000233A1

WO2011000233A1 - Comprehensive utilization method of rice hull for producing active carbon, rice hull tar and water glass or silicon phosphate

Info

Publication number: WO2011000233A1
Application number: PCT/CN2010/071457
Authority: WO
Inventors: 成如山; 成果
Original assignee: 湖南益阳粒粒晶粮食购销有限公司
Priority date: 2009-06-29
Filing date: 2010-03-31
Publication date: 2011-01-06
Also published as: CN101700883A; CN101700883B

Abstract

A comprehensive utilization method of rice hull for producing active carbon with strong absorbency, rice hull tar, and water glass or silicon phosphate, comprises the following steps: slowly feeding rice hull to carbonization furnace by a sieve, carbonizing it and depositing in the furnace to form carbonized rice hull and produce gas, condensing the gas to obtain rice hull tar, treating carbonized rice hull with sodium hydroxide or phosphoric acid to obtain active carbon and water glass or silicon phosphate. The method is simple, cost-efficient and environmentally friendly, and therefore it is suitable for large-scale industrial production. The obtained rice hull active carbon does not contain heavy metal ions toxic to human body, such as Pb, Ge, Cd and As, and other hazardous substance, and can be used as purificant, decolorizing agent and catalyst, which are required in the food, environmental protection and medicine sectors. The obtained water glass is a harmless or nontoxic water-soluble inorganic binder. The rice hull tar is regenerative biomass energy.

Description

稻壳综合利用制取活性炭和稻壳焦油并联产水玻璃或磷酸硅的方法技术领域 Method for preparing activated carbon and rice husk tar to produce water glass or silicon phosphate by comprehensive utilization of rice husk

本发明涉及稻壳综合开发利用的方法，具体涉及由稻壳制取活性炭（包括粉末状和颗粒状）和稻壳焦油，并联产得到水玻璃、磷酸硅的方法。 The invention relates to a method for comprehensive development and utilization of rice husk, in particular to a method for preparing activated carbon (including powder and granules) and rice hull tar from rice husk, and producing water glass and silicon phosphate in parallel.

背景技术 Background technique

稻壳中富含有碳、 Si0₂及碳氢氧有机物，另外还含有多种微量元素（见表 1 )，其中，钙 0.03-0.22%，铁 0.005-0.08 %，钾 0.06-0.4% ,钠 0.015-0.24% ,镁 0.015-0.03 % , 磷 0.015-0.2%，钼 0.03 %，铝 0.003 %，几乎不含任何有害于人类身心健康的物质。 The rice husk is rich in carbon, SiO ₂ and hydrocarbon-hydrogen organic compounds, and also contains various trace elements (see Table 1), of which calcium 0.03-0.22%, iron 0.005-0.08%, potassium 0.06-0.4%, sodium 0.015-0.24%, magnesium 0.015-0.03%, phosphorus 0.015-0.2%, molybdenum 0.03 %, aluminum 0.003%, almost no substances harmful to human health.

表 1.稻壳的组成成分

稻壳的利用虽自古有之，如当燃料取热、制刷牙粉、化妆面白粉、保温灰等，但基本上都是一烧了之，利用率极低。近 30年来由于科技的发展和资源的越来越贫瘠，从而促使人们对稻壳利用进行研究，近 10年来确有很大的进展。如用稻壳单纯制成活性炭或白炭黑（SiO₂)的报道有之，有的还申请了国家发明专利，但终因技术不成熟，使得产品质量低、收率低、成本高而未正式工业化生产，所以至今国内外市场上尚无稻壳活性炭和稻壳白炭黑及稻壳水玻璃销售。 Table 1. Composition of rice husk

Although the use of rice husks has existed since ancient times, such as when fuel is used for heat, brushing powder, make-up white powder, and heat-insulating ash, it is basically burnt and the utilization rate is extremely low. In the past 30 years, due to the development of science and technology and the increasing poverty of resources, people have been making research on the utilization of rice husks. In the past 10 years, great progress has been made. For example, the use of rice husks for purely activated carbon or white carbon black (SiO ₂ ) has been reported, and some have applied for national invention patents. However, due to the immature technology, the products are of low quality, low yield and high cost. Formally industrialized production, so there is no sales of rice husk activated carbon and rice husk white carbon and rice husk water glass in the domestic and foreign markets.

如专利号 93103043.9 《制取无定型白炭黑和活性炭新工艺》中，是将稻壳在 600-650°C条件下活化，再经碳酸钠（Na₂C0₃)浸洗和水洗，先后制成活性炭和白炭黑。因温度范围很窄、温度又低，能与 Na₂CO₃反应的 SiO₂不多，这就使得活性炭中存有的大量 Si0₂占领着炭粒上的孔隙（特别是微孔），因而使得活性炭的吸附性很低；与此同时，游离出来的 SiO₂很少，使得白炭黑的产量也很低，使得成本过高而无法工业化生产。又如专利号 ZL99811256.9 《苛化煮解稻壳灰制备的高活性炭及其制备方法》中，也只在 426-76CTC范围内进行炭化和活化，其产品质量、产率也低，成本亦高，以致无法投产。再如，专利号 ZL200610081581.1 《利用稻壳和竹木废料制备的活性炭板料》中，制出的不是活性炭而是农村冬天的烤火竹炭、木炭、稻壳炭，这是因为既没有达到活化所要求的高温，又没有经过酸（或碱）洗和水洗的活化关键工艺。 For example, in Patent No. 93103043.9, “New Process for Preparation of Amorphous Silica and Activated Carbon”, the rice husk is activated at 600-650 ° C, and then washed with sodium carbonate (Na ₂ C0 ₃ ) and washed with water. Activated carbon and white carbon black. Due to the narrow temperature range and low temperature, there is not much SiO ₂ which can react with Na ₂ CO ₃ , which makes a large amount of SiO ₂ present in the activated carbon occupy pores (especially micropores) on the carbon particles, thus Active The adsorption of carbon is very low; at the same time, the amount of free SiO _{2 is} small, so that the production of white carbon black is also low, making the cost too high to be industrially produced. Another example is the patent No. ZL99811256.9 "Highly activated carbon prepared by caustic soda ash ash and its preparation method", which is also carbonized and activated only in the range of 426-76 CTC, and its product quality and productivity are also low, and the cost is also low. High enough to be put into production. For example, Patent No. ZL200610081581.1 "Activated Activated Carbon Sheet Prepared from Rice Husk and Bamboo Waste" produces not the activated carbon but the rural winter charcoal, charcoal, and rice husk charcoal, because neither activation is achieved. The required high temperature, without the key process of activation by acid (or alkali) washing and water washing.

发明内容 Summary of the invention

为克服现有技术中稻壳制取活性炭和白炭黑方法中产量低、产品质量不高及生产成本昂贵的缺陷，提出一种可工业化的综合利用稻壳生产活性炭及其它产品的方法，填补目前工业化生产的空白。本发明提供的技术方案为：一种稻壳综合利用制取活性炭和稻壳焦油并联产水玻璃或磷酸硅的方法，包括如下歩骤： In order to overcome the defects of low yield, low product quality and high production cost in the preparation of activated carbon and white carbon black in rice husk in the prior art, an industrialized comprehensive method for producing activated carbon and other products using rice husk is proposed, which fills the current A gap in industrial production. The technical solution provided by the invention is as follows: A method for comprehensively utilizing rice husk to prepare activated carbon and rice hull tar to produce water glass or silicon phosphate in parallel, comprising the following steps:

( 1 ) 底部具有加热装置的炭化活化炉设置温度为 700-900°C，将稻壳通过振动筛以 1000-2000kg/小时的速度从加热炉顶部筛入炉内，筛下的稻壳在炉内炭化活化形成炭壳沉积，同时释放出气体； (1) The carbonization activation furnace with heating device at the bottom is set at a temperature of 700-900 ° C, and the rice husk is sieved into the furnace from the top of the furnace through a vibrating screen at a speed of 1000-2000 kg / hour. The rice husk under the sieve is in the furnace. Internal carbonization activates to form carbon shell deposits while releasing gas;

(2) 将上述所得的气体从加热炉顶部抽出，经过冷凝得到液态稻壳焦油；将上述炭壳加入到为其重量 2-3倍的氢氧化钠溶液或磷酸溶液中，加热至 100-150°C，搅拌并保温 2-5小时，过滤得到滤液和炭渣，所述氢氧化钠质量浓度为 5-10% , 磷酸溶液质量浓度为 30-50%; (2) The gas obtained above is taken out from the top of the heating furnace and condensed to obtain liquid rice husk tar; the carbon shell is added to a sodium hydroxide solution or a phosphoric acid solution which is 2-3 times its weight, and heated to 100-150 °C, stirring and holding for 2-5 hours, filtering to obtain filtrate and carbon residue, the sodium hydroxide mass concentration is 5-10%, the phosphoric acid solution mass concentration is 30-50%;

(3) 加入氢氧化钠溶液时得到的滤液浓缩至密度为 l-1.5g/cm³，得水玻璃；炭渣水洗， 400-500°C保温干燥 3-5小时，再加入 2-3倍重量的质量浓度为 1-5%的稀磷酸溶液， 100-150°C保温 2-3小时，过滤并以水洗除去磷酸， 400-500°C保温干燥 3-5小时，取出后得稻壳活性炭；加入磷酸溶液时得到的滤液浓缩至密度为 1.2-1.5g/cm³, 得糊状物，将糊状物在 700-800°C保温 1-3小时，得磷酸硅粉末；炭渣水洗除去磷酸， 400-50CTC保温干燥 3-5小时，取出后得稻壳活性炭。 (3) The filtrate obtained by adding sodium hydroxide solution is concentrated to a density of l-1.5g/cm ³ to obtain water glass; the carbon residue is washed with water, dried at 400-500 ° C for 3-5 hours, and then added 2-3 times. Weight concentration of 1-5% dilute phosphoric acid solution, 100-150 ° C for 2-3 hours, filtered and washed with water to remove phosphoric acid, 400-500 ° C insulation After drying for 3-5 hours, the rice husk activated carbon is obtained after taking out; the filtrate obtained when the phosphoric acid solution is added is concentrated to a density of 1.2-1.5 g/cm ³ to obtain a paste, and the paste is kept at 700-800 ° C for 1 - After 3 hours, the silicon phosphate powder was obtained; the carbon residue was washed with water to remove the phosphoric acid, and the mixture was dried at 400-50 CTC for 3-5 hours, and the rice hull activated carbon was obtained after taking out.

歩骤（1 ) 所述稻壳为普通稻壳或稻壳粒；所述稻壳粒的制备方法为：稻壳按常规方法除尘，然后粉碎至直径 0.2毫米以下，得到稻壳粉；将所述稻壳粉与步骤（2) 所述稻壳焦油按 1 : 0.5-0.7的重量比混合，并搅拌均勾，通过制粒机制成稻壳粒。 The rice husk of the step (1) is an ordinary rice husk or rice husk; the preparation method of the rice husk is as follows: the rice husk is dusted according to a conventional method, and then pulverized to a diameter of 0.2 mm or less to obtain rice hull powder; The rice hull powder is mixed with the rice husk tar according to the step (2) in a weight ratio of 1:0.5-0.7, and stirred and hooked, and the rice husk is prepared by a granulator.

歩骤（1 )原料稻壳为普通稻壳时，将所述稻壳活性炭粉碎成粉末与歩骤（2) 所得稻壳焦油按照 1 : 1-1.2的重量比混合，通过制粒机制成炭粒；在 500-60CTC 烘烤 0.5-1小时除去上述焦油；然后加入 1-2倍重量的磷酸溶液， 100-150°C保温浸泡 2-3小时，所述磷酸体积浓度为 1-5«¾；浸泡后的炭粒过滤并以水洗除去磷酸， 400-50CTC保温干燥 3-5小时，得到颗粒状稻壳活性炭。所述颗粒状包括如球粒、橄球粒、柱粒针、片状等。 Step (1) When the raw rice husk is an ordinary rice husk, the rice husk activated carbon is pulverized into a powder and the rice hull tar obtained by the step (2) is mixed according to a weight ratio of 1: 1-1.2, and the carbon is produced by a granulator. Granule; Baking at 500-60 CTC for 0.5-1 hour to remove the above tar; then adding 1-2 times weight of phosphoric acid solution, soaking at 100-150 ° C for 2-3 hours, the phosphoric acid concentration is 1-5 «3⁄4 The soaked carbon particles are filtered and washed with water to remove phosphoric acid, and dried at 400-50 CTC for 3-5 hours to obtain granulated rice hull activated carbon. The granules include, for example, spherulites, spherulites, spheroidal needles, flakes and the like.

歩骤（2) 所述冷凝介质为水或液氨冷凝。 Step (2) The condensing medium is water or liquid ammonia condensing.

在本发明的技术方案中，加热炉内温度达到约 800°C，由于加热炉内温度越往下越高，致使被筛下的稻壳迅速炭化（在筛底时已使稻壳中水分基本挥发完），当落到炉底时，因炭化放出气体中的含有的部分可燃性气体便着火燃烧，可使底部升温至约 900-1000°C，由于稻壳不断在炉内下落，也不断有气体在燃烧，致使炉内温度基本保持原态分布。但先落到炉底部且已炭化的稻壳其本身还来不及着火燃烧，便被后落下的炭化稻壳覆盖，下层炭化稻壳虽处于高温，但因得不到空气（氧气）而不会燃烧，只会在高温下继续炭化与活化。 In the technical solution of the present invention, the temperature in the heating furnace reaches about 800 ° C, and the temperature in the heating furnace is higher, so that the rice husk under the sieve is rapidly carbonized (the moisture in the rice husk is basically volatilized at the bottom of the sieve). Finish), when it falls to the bottom of the furnace, part of the flammable gas contained in the gas released by the carbonization will be burned by fire, and the bottom temperature can be raised to about 900-1000 ° C. Since the rice husk continuously falls in the furnace, gas is continuously present. During combustion, the temperature inside the furnace remains substantially the same. However, the rice husk that first fell to the bottom of the furnace and has been charred is too late to be burned, and it is covered by the carbonized rice husk that falls behind. The lower carbonized rice husk is at a high temperature, but it does not burn because it does not get air (oxygen). , will continue to carbonization and activation only at high temperatures.

炭化后的稻壳加入氢氧化钠溶液，其中的二氧化硅与 NaOH反应生成水玻璃即硅酸钠溶液： Na₂O.XSi0₂ ，水玻璃的生成反应 2NaOH+X SiO2→Na₂O X SiO₂+H₂O , 式中 X为水玻璃模数。 The carbonized rice husk is added with a sodium hydroxide solution, wherein the silica reacts with NaOH to form a water glass, ie, a sodium silicate solution: Na ₂ O.XSi0 ₂ , the formation reaction of water glass 2 NaOH + X SiO2 → Na ₂ OX SiO ₂ + H ₂ O , where X is the water glass modulus.

炭化的稻壳经碱煮后再加入稀磷酸浸泡，用磷酸（H₃P0₄) 浸泡的原理为：第一、 H₃P0₄是非氧化酸，在长时间浸煮搅拌过程中不会对产品与设备造成损失，磷酸挥发损失也少；第二、 H₃P0₄是小分子酸，能进入炭粉内的超微孔（φ ^ ΐηη ) 内与其中烧蚀物起反应并将溶入酸液中,使微孔容积增大,从而提高活性炭的吸附功能；第三、在碱煮与水洗过程中，可能炭中还残留了 Si0₂,在 400°C干燥中又可能产生 Si0₂，用 H₃P0₄煮洗时，这些 Si0₂将于 H₃PO₄发生下列反应而生成可溶于水的磷酸硅，被水带出碳粒（或孔），从而在活性炭中提高炭的比例，以提高其碘吸附性。反应式为 The carbonized rice husk is soaked in alkali and then added with dilute phosphoric acid. The principle of immersion with phosphoric acid (H ₃ P0 ₄ ) is as follows: First, H ₃ P0 ₄ is a non-oxidizing acid, which will not be used in the process of prolonged digestion and stirring. Loss of phosphoric acid loss with equipment; second, H ₃ P0 ₄ is a small molecular acid that can enter the ultramicropores (φ ^ ΐηη ) in the carbon powder and react with the ablated material and dissolve the acid liquid, so that the pore volume is increased, thereby improving the adsorption function of activated carbon; third, alkali cooking and the washing process, the possibility still remained carbon Si0 _2, and Si0 ₂ may be generated at 400 ° C was dried, treated with When H ₃ P0 _{4 is} boiled, these SiO ₂ will react with H ₃ PO ₄ to form water-soluble silicon phosphate, which is taken out of the carbon particles (or pores), thereby increasing the proportion of carbon in the activated carbon. To improve its iodine adsorption. The reaction formula is

4H₃PO₄+3SiO₂→Si₃(PO₄)₄+6H₂O 炭化的稻壳还可直接加入磷酸浸泡，使其中大量 SiO₂与磷酸反应生成磷酸硅，同时剩余炭渣直接采用清水洗涤即可得到活性炭。利用稻壳生产活性炭并联产得到的磷酸硅是水玻璃的最佳固化剂：按高模数水玻璃重量的约 1/70加入此固化剂，搅拌均勾后约半个小时，将其按一定比例与固态粉末（如活性炭）混合搅拌均匀，并压制成型，经高温固化并冷却后，将其浸泡在水中，则永不松散损坏。磷酸硅的两种形态 Si₃(P0₄)₄和 SiP₂0₇的固化效果是一样的，但从成本而言，前者要低些，故多用此种固化剂。 4H ₃ PO ₄ +3SiO ₂ →Si ₃ (PO ₄ ) ₄ +6H ₂ O The carbonized rice husk can also be directly immersed in phosphoric acid so that a large amount of SiO ₂ reacts with phosphoric acid to form silicon phosphate, and the remaining carbon residue is directly washed with water. Activated carbon is obtained. Silicon phosphate produced by parallel production of activated carbon from rice husk is the best curing agent for water glass: Add this curing agent to about 1/70 of the weight of high modulus water glass, stir it for about half an hour, press it Mix and mix with a solid powder (such as activated carbon) in a certain proportion, and press-form. After solidification and cooling at high temperature, soak it in water, it will never loosely damage. The curing effect of the two forms of silicon phosphate, Si ₃ (P0 ₄ ) ₄ and SiP ₂ 0 ₇ , is the same, but the former is lower in terms of cost, so the curing agent is often used.

本发明技术方案得到的活性炭为不规则形状，可以是粉末状的，也可以是颗粒状。普通稻壳炭化后通常在干燥后粉碎成粉末，或干燥前磨成粉浆再进行干燥。颗粒状的活性炭也具有重要的市场应用价值，在自来水、饮用水的处理、化工催化及食品、药品脱色等领域中，颗粒状活性炭使流体的通过率高，并且易于分离彻底，因此应用更为广泛。本发明还提供了一种技术方案为将粉末状活性炭与稻壳焦油混合，通过制粒机制成颗粒状活性炭，或者将稻壳按照同样方法先制成颗粒，再炭化活化得到。 The activated carbon obtained by the technical solution of the present invention has an irregular shape and may be in the form of a powder or a pellet. Ordinary rice hulls are usually pulverized into powder after drying, or ground into a slurry before drying and then dried. Granular activated carbon also has important market application value. In the fields of tap water, drinking water treatment, chemical catalysis, food and drug decolorization, granular activated carbon has high fluid passing rate and is easy to separate thoroughly, so the application is more widely. The invention also provides a technical solution for powdery The activated carbon is mixed with the rice hull tar, and the granulated activated carbon is formed by a granulator, or the rice husk is first granulated according to the same method, and then activated by carbonization.

本发明所得活性炭及其颗粒主要以碘值来衡量其吸附能力。若某活性炭的碘值越高，则表示该活性炭吸附小分子物质的能力强，因为小分子通常认定其直径≤1.2纳米（nm)，而吸附这些小分子的活性炭粒上的孔直径纳米的微孔。所以，若某活性炭的碘值高，则表明其微孔发达。反之，若微孔发达，则吸附碘这类小分子物质的能力就强。由表 2可知：表 2.炭化与活化技术参数 The activated carbon and its particles obtained by the present invention mainly measure the adsorption capacity by the iodine value. If the iodine value of an activated carbon is higher, it means that the activated carbon has a strong ability to adsorb small molecular substances, because small molecules generally have a diameter of ≤1.2 nm (nm), and the pore diameter of the activated carbon particles adsorbing these small molecules is nanometer-sized. hole. Therefore, if the iodine value of a certain activated carbon is high, it indicates that the micropores are developed. Conversely, if the micropores are developed, the ability to adsorb small molecules such as iodine is strong. It can be seen from Table 2: Table 2. Carbonization and activation technical parameters

*碘值是衡量活性炭吸附诸如碘分子大小的物质分子的能力。因碘分子属于小分子范畴，故国内外都用碘值来衡量活性炭吸附小分子物质的能力。如碘值为 110 (实际为 110mg/g)，就是 lg活性炭吸附碘分子达到饱和时，可吸附 llOmg碘。 *Iodine value is a measure of the ability of activated carbon to adsorb a substance molecule such as the size of an iodine molecule. Since iodine molecules belong to the category of small molecules, iodine values are used both domestically and internationally to measure the ability of activated carbon to adsorb small molecules. For example, when the iodine value is 110 (actually 110 mg/g), lgOg can absorb llOmg of iodine when the iodine molecule is saturated with iodine.

①随着温度的升高，稻壳炭化与活化后的微孔，中孔（2nm< <50nm)、大孔 ( >50nm) 均会增多，故碘值随温度升高而增加；但升到约 1100°C后，微孔的一部分将变成中孔，当变成中孔的微孔量超过微孔增加量时，碘值减少。 1 With the increase of temperature, the micropores, mesopores (2nm<<50nm) and macropores (>50nm) of carbonized and activated rice husks will increase, so the iodine value increases with temperature; After about 1100 ° C, a part of the micropores will become a mesopores, and when the amount of micropores which become a mesopores exceeds the increase of the micropores, the iodine value decreases.

②经碱煮干燥后，一方面因微孔增加，另一方面因包裹 Si0₂的细胞膜被烧蚀的多，裸露的 SiO₂多，碱煮后脱离炭粒者也多，使炭粒上的微孔也增加，故碘值增加。但当升到 1100°C后，原有微孔中的一部分变成中孔，另一方面裸露的 Si0₂ 分子团增加，碱煮后脱离炭粒的 810₂团也多，这主要是增加了炭粒的中孔，微孔增的量没有微孔变成中孔的那么多，故碘值会减少。 ② After drying by alkaline cooking, on the one hand due to micropores increases, on the other hand because the membrane is wrapped Si0 ₂ ablated multiple, multi bare SiO _2, from a base boiled carbon particles are also many, the upper carbon particles The micropores also increase, so the iodine value increases. However, when it rises to 1100 ° C, a part of the original micropores becomes a mesopores, and on the other hand, the exposed Si0 ₂ The molecular group increases, and there are many 810 ₂ groups that are separated from the carbon particles after alkali boiling. This mainly increases the mesopores of the carbon particles. The amount of micropores increases without the micropores becoming as many as the mesopores, so the iodine value is reduced.

③碱煮与稀磷酸处理后水洗并固液分离干燥，炭粒上既无 Si0₂又无水玻璃（依生成水玻璃的反应式与稻壳的成分，可算出未水洗前的干燥炭加水玻璃，若重 552kg, 则滤去水玻璃 272kg后，只剩炭 280kg，而所吸的碘量相等，故相等重量的炭应是相等重量的炭加干燥水玻璃所吸碘量的 552/272 2倍），则其碘值应增加近 1倍。但当升到 1100°C后，一是因微孔减少，二是因 SiO₂定晶化（即 SiO₂ 近于晶态，不能与碱反应生成可溶于水的水玻璃，因而在水洗后仍以 Si02留在炭粒内），这就使得 1kg 这样的炭与 SiO₂混合干燥物中，炭重只占总重的 280/552=51 %，故其中微孔也只能占同等重量纯活性炭的 51%。综合这两点，所以使 liocrc以后的活性炭碘值只有< 1100°0下炭化与活化所得活性炭碘值的一半左右。 3 Alkali cooking and dilute phosphoric acid treatment, water washing and solid-liquid separation and drying, there is no Si0 ₂ and no water glass on the carbon particles (according to the reaction formula of the water glass and the composition of the rice husk, the dry carbon water glass before the water washing can be calculated If weigh 552kg, after filtering 272kg of water glass, only 280kg of carbon will be left, and the amount of iodine absorbed will be equal. Therefore, the equivalent weight of carbon should be 552/272 2 of the equivalent weight of carbon plus dry water glass. Double), then its iodine value should be increased by nearly 1 time. But when raised to 1100 ° C, one is due to reduced micropores, the second is that after a given crystallization SiO ₂ (i.e. SiO ₂ close to the crystalline state, can not generate water-soluble sodium silicate is reacted with a base, thus washing Still leaving Si02 in the carbon particles), which makes 1kg of such carbon and SiO ₂ mixed dry matter, the carbon weight only accounts for 280/552=51% of the total weight, so the micropores can only account for the same weight. 51% of activated carbon. Combining these two points, so the iodine value of activated carbon after liocrc is only about half of the activated carbon iodine value obtained by carbonization and activation at <1100°0.

④酸煮和水洗后，微、中、大孔的烧蚀物被清除，从而使微孔容积增加，使碘值亦增加，但升到 1100°C后，因①与②及③的原因，使微孔减少和炭的重量比减少，从而使碘值亦减少。 4 After the acid is boiled and washed, the ablated substances in the micro, medium and large pores are removed, so that the volume of the micropore is increased and the iodine value is also increased, but after rising to 1100 ° C, due to the reasons of 1 and 2 and 3, The micropores are reduced and the weight ratio of char is reduced, so that the iodine value is also reduced.

由上述实验数据与分析可知，稻壳中 Si0₂由活性非定晶型变成非活性定晶型的最高温度约为 liocrc (即约 iioo°c以下为活性非定晶型，约 iioo°c以上为非活性定晶型）而不是其他温度。 It can be seen from the above experimental data and analysis that the maximum temperature of SiO ₂ from the active uncrystallized form to the inactive crystallization type in rice husk is about liocrc (ie, about iioo °c or less is active non-crystallized, about iioo °c The above is inactive stereotypes) and not other temperatures.

⑤稻壳活性炭孔隙结构的分析。若稻壳炭化后，壳内 SiO₂全都是活性非晶型的，且 Si0₂经碱煮和水洗后全都生成了水玻璃而被滤除，又经酸煮和水洗后孔中的残留物也被清除掉了，而且若 SiO₂让出的全都是能吸附碘分子的那些微孔，即使在炭化与活化过程中不产生另外吸附碘分子的微孔，活性炭的碘值也可达到 1587mg/g.计算如下；稻壳炭中 SiO₂ (重量） /C (重量）=3/4,其摩尔比为 SiO₂ ( mol ) /C(mol)=(3/60)/(4/12)=3/20,其分子数之比亦为 3/20; Analysis of the pore structure of 5 rice husk activated carbon. If the rice husk is carbonized, the SiO _{2 in the} shell is all active amorphous, and the SiO ₂ is formed by the water glass after alkali boiling and washing, and the residue in the pore after the acid boiling and washing is also It is removed, and if SiO ₂ is all the micropores that can adsorb iodine molecules, the iodine value of activated carbon can reach 1587mg/g even if no micropores for adsorbing iodine molecules are generated during carbonization and activation. Calculated as follows; SiO ₂ (weight) / C (weight) = 3 / 4 in rice husk charcoal, the molar ratio of which is SiO ₂ ( mol ) / C (mol) = (3 / 60) / (4 / 12) = 3 / 20, The ratio of the number of molecules is also 3/20;

若 SiO₂让出的空全被碘分子进驻，则炭中碘分子数 /C分子数 =3/20，两者重量比 = (3*127) /(20*12)=1.5875.即 lg稻壳活性炭最多可吸附碘 1587毫克。但实侧值最大约为 1000mg/g。 If the SiO ₂ gives up all the iodine molecules, the number of iodine molecules in the carbon / C molecules = 3 / 20, the weight ratio of the two = (3 * 127) / (20 * 12) = 1.5875. Shell activated carbon can adsorb up to 1587 mg of iodine. However, the real side value is at most about 1000 mg/g.

这个结果表明，还有与碘值 587mg/g相当的微孔容积之中孔、大孔被 Si0₂ 分子团占据；再加上在炭化与活化过程中产生（不是 SiO₂让出）的微孔、中孔、大孔，就使得稻壳活性炭的微、中、大孔也很发达。这就预示着稻壳活性炭可广泛用于食品、医药、脱色、水净化等领域。 This result indicates that the pores and macropores of the micropore volume corresponding to the iodine value of 587 mg/g are occupied by the Si0 ₂ molecular group; plus the micropores generated during carbonization and activation (not by SiO ₂ ) The medium, large and large holes make the micro, medium and large pores of rice husk activated carbon very developed. This indicates that rice hull activated carbon can be widely used in food, medicine, decolorization, water purification and other fields.

此外，本发明所得稻壳焦油中含低沸点（ 250°C ) 油约 15 %，中沸点 (≤300°C ) 油 20 % , 高沸点（ 400°C ) 油 30%，超高沸点（≤600°C ) 油 10 % , 余者为固态油渣（类似于沥青）。因此，可用于燃料油的生产。 In addition, the rice husk tar obtained by the invention contains about 15% of low boiling point (250 ° C) oil, 20% of medium boiling point (≤300 ° C) oil, 30% of high boiling point (400 ° C) oil, and ultra high boiling point (≤ 600 ° C) 10% oil, the remainder is solid oil residue (similar to asphalt). Therefore, it can be used for the production of fuel oil.

综上所述，本发明以常见稻壳为原料，制取活性炭，工艺简单，产率高；还有成本低、污染小的特点，适合大规模工业化生产；所得稻壳活性炭不含对人体有毒的铅、镉、砷、汞等重金属离子及其他有毒有害物质，是食品、医药、环保领域急需的净化剂、脱色剂、催化剂。本发明的方法联产能得到水玻璃或磷酸硅固化剂，是无毒无害的水性无机胶粘剂，应用范围广。另外，还能得到具有制备燃料油价值的稻壳焦油。本发明技术方案能使稻壳综合利用率大大提高（几乎能达到 100%)，具有广阔的市场前景以及良好的社会效益和经济价值。附图说明 In summary, the invention adopts common rice husk as raw material to prepare activated carbon, has simple process and high yield; and has the characteristics of low cost and small pollution, and is suitable for large-scale industrial production; the obtained rice husk activated carbon is not toxic to human body. Heavy metal ions such as lead, cadmium, arsenic and mercury, and other toxic and harmful substances, are urgently needed purification agents, decolorizing agents and catalysts in the fields of food, medicine and environmental protection. The method of the invention combines the production capacity to obtain a water glass or a silicon phosphate curing agent, and is a non-toxic and harmless water-based inorganic adhesive, and has a wide application range. In addition, rice husk tar having a value for preparing fuel oil can be obtained. The technical scheme of the invention can greatly improve the comprehensive utilization rate of rice husk (almost 100%), and has broad market prospects as well as good social and economic value. DRAWINGS

图 1是本发明的稻壳综合利用图。 Fig. 1 is a view showing the comprehensive utilization of rice husks of the present invention.

具体实施方式 detailed description

实施例 1 将稻壳制成高吸附值的活性炭与高模数水玻璃，其歩骤为： Example 1 The rice husk is made into a high adsorption value activated carbon and a high modulus water glass, and the steps are as follows:

将纯净稻壳运送到的加热炭化活化炉顶的不锈钢筛内，向炉内通电加热，调节电压，使炉底温度达到约 80CTC，炉顶达到约 400°C，并保持稳定，开动电机使钢筛作水平振动，以便将筛上的稻壳不断筛入炉内并炭化成为炭壳，与此同时开动抽风机，将炉内气体（含有可燃气体）抽出，经炉顶筛内的稻壳而流向冷凝器。不锈钢筛开始振动约 20分钟后，炉内堆聚了约 180kg炭壳（已筛下约 500kg稻壳），此时将炭化稻壳，转入盛有氢氧化钠碱溶液的池内。 The pure rice husk is transported to the stainless steel screen of the heated carbonization activated furnace top, and the furnace is energized and heated to adjust the voltage so that the furnace bottom temperature reaches about 80 CTC, the furnace top reaches about 400 ° C, and remains stable, and the motor is driven to make the steel The sieve is horizontally vibrated, so that the rice husk on the sieve is continuously sieved into the furnace and charred to become a carbon shell, and at the same time, the exhaust fan is started to extract the gas (containing combustible gas) in the furnace, and the rice husk in the top of the furnace is passed through the sieve. Flow to the condenser. After the stainless steel screen began to vibrate for about 20 minutes, about 180 kg of carbon shell (about 500 kg of rice husk had been sieved) was piled up in the furnace. At this time, the carbonized rice husk was transferred into a tank containing sodium hydroxide alkali solution.

按以上歩骤不断进行每炉每天（8小时）可炭化与活化稻壳约 12吨，可得已炭化与活化稻壳约 4.2吨。经检测，此炭化的碘值约为 300mg/_g。 According to the above steps, about 12 tons of carbonized and activated rice husks per day (8 hours) per furnace can be continuously obtained, and about 4.2 tons of carbonized and activated rice husks can be obtained. The carbonized iodine value was determined to be about 300 mg/ _g .

碱池中 NaOH溶液浓度为，％，重量为已炭化与活化稻壳重量的 2.3倍，即若每 20分钟浸一池，则池内应有这种溶液 400kg，其中浸稻壳炭约 180kg。趁热将池内溶液与炭渣搅拌均匀，并立即用真空机将其抽于反应釜内，边搅拌边给反应釜加热，当升到约 130°C，边搅拌边保温 3小时。保温后趁热将釜内料流放至真空过滤机内，使其液固分离。得液体约 350kg (密度约为 1.2g/cm ³)。将分离后的液体（即水玻璃）浓缩，以达到 1.4g/cm³的密度或 42波美浓度。 The concentration of the NaOH solution in the alkali pool is, %, and the weight is 2.3 times the weight of the carbonized and activated rice hulls. That is, if the pool is immersed every 20 minutes, the solution should have 400 kg of the solution, and the immersed rice shell charcoal is about 180 kg. The solution in the pool was uniformly stirred with the carbon residue, and immediately pumped into the reaction vessel by a vacuum machine, and the reactor was heated while stirring. When it was raised to about 130 ° C, it was kept warm for 3 hours while stirring. After the heat preservation, the liquid in the kettle is placed in a vacuum filter to separate the liquid and solid. A liquid of about 350 kg (density of about 1.2 g/cm ³ ) was obtained. The separated liquid (i.e., water glass) was concentrated to achieve a density of 1.4 g/cm ³ or a concentration of 42 Baume.

将分离后的炭渣倒入清水池内搅拌，以洗去其中残存的水玻璃与灰份及悬浮杂质。将清净后的纯炭渣放入炉中干燥，在炉温 400Ό时保温 4小时，然后停电降温，当降到 200°C以下时，出炉。经检测，此活性炭的碘值约为 580mg/g。 The separated carbon residue is poured into a clean water tank and stirred to wash away the remaining water glass and ash and suspended impurities. The cleaned pure carbon residue is placed in a furnace for drying, and is kept at a furnace temperature of 400 Torr for 4 hours, then is powered off and cooled, and when it is lowered to 200 ° C or lower, it is discharged. The activated carbon has an iodine value of about 580 mg/g.

将干燥出炉后的炭粉浸入装有磷酸（H₃P0₄) 溶液中的反应釜内，并边升温边搅拌，当升到约 130°C时，保持 2小时。釜内磷酸溶液的浓度约为 2%，重量约为干燥炭粉重量的 2.5倍（约 250kg)。保温搅拌后，趁热放入真空过滤机内进行液固分离。将其中液体储存、沉淀，除去悬浮物和沉淀物，所得液体再补加适量的磷酸，下次还可以做同样的用途。将得到的炭渣倒入清水池内搅拌清洗， 1小时后再入离心机内进行液固分离。分离后将炭渣送入炉内加热干燥，当炉温达到The dried carbon powder was immersed in a reaction vessel containing a phosphoric acid (H ₃ P0 ₄ ) solution, stirred while raising the temperature, and maintained at about 130 ° C for 2 hours. The concentration of the phosphoric acid solution in the kettle was about 2% and the weight was about 2.5 times the weight of the dried carbon powder (about 250 kg). After the heat is stirred, the mixture is placed in a vacuum filter to perform liquid-solid separation. The liquid is stored, precipitated, and the suspended matter and the precipitate are removed, and the obtained liquid is further supplemented with an appropriate amount of phosphoric acid, and the same use can be performed next time. Pour the obtained carbon residue into the clear water tank and stir it for cleaning. 1 small Then, re-enter the centrifuge to perform liquid-solid separation. After separation, the carbon residue is sent to the furnace for heating and drying, when the furnace temperature reaches

400°C时保温 3小时，关电冷却，当冷到低于 200°C时，取出。取出后送入雷蒙磨粉碎机内粉碎并分级过筛（或气流筛），则得到所需粒度（目数）的稻壳粉末活性炭。对该产品进行碘值、灰份、含水量等诸项检测；碘值约为 950m_g/g，合格者密封包装入库。 Keep at 400 ° C for 3 hours, turn off the electricity, and when it is cold to below 200 ° C, take it out. After being taken out, it is sent to a Raymond mill and pulverized and classified into a sieve (or an air flow sieve) to obtain a rice husk powder activated carbon having a desired particle size (mesh number). The product is tested for iodine value, ash content, water content, etc.; the iodine value is about 950 m _g / g, and the qualified person is sealed and put into storage.

数据的理论依据：水玻璃的生成反应 2NaOH+X.SiO₂→Na₂O.X.SiO₂+H₂O... 式中 X为水玻璃模数，即 Si0₂/Na₂0=X，若取 X = 3.5则上式为 Theoretical basis of the data: Formation reaction of water glass 2NaOH+X.SiO ₂ →Na ₂ OXSiO ₂ +H ₂ O... where X is the water glass modulus, ie Si0 ₂ /Na ₂ 0=X, if X = 3.5, the above formula is

2NaOH+3.5SiO₂→Na₂O+3.5SiO₂+H₂O 2NaOH+3.5SiO ₂ →Na ₂ O+3.5SiO ₂ +H ₂ O

重量比： 80 210 272 18 Weight ratio: 80 210 272 18

因 500kg 稻壳中有 SiO₂75kg，故让其全部生成水玻璃，则需Since there are 75kg of SiO _{2 in the} 500kg rice husk, it is necessary to produce all the water glass.

NaOH80x75/210=28kg_; 若其含量为 96%，则需此 NaOH28/0.96=29.2kg。 NaOH 80x75/210 = 28kg _; if its content is 96%, this NaOH28/0.96=29.2kg is required.

为了在反应釜内能搅拌，需加水 370kg，故 NaOH溶液总量为 490kg，浓度为 28.6/490 = 7%。 In order to stir in the reactor, 370 kg of water is required, so the total amount of NaOH solution is 490 kg, and the concentration is 28.6/490 = 7%.

实施例 2 Example 2

在生产活性炭与水玻璃的同时，生产出稻壳焦油的方法，其歩骤为：实施例 1 中炉内热气流经冷凝器时，气体便冷凝成液态储存，生产 1 吨活性炭可得焦油约 1吨。 In the production of activated carbon and water glass, the method for producing rice hull tar is as follows: In the first embodiment, when the hot gas in the furnace passes through the condenser, the gas is condensed into a liquid storage, and the production of 1 ton of activated carbon can obtain tar about 1 Ton.

经初步检测，焦油中含低沸点（ 250°C ) 油约 15 %，中沸点（ 300°C ) 油 20%，高沸点（ 400°C ) 油 30%，超高沸点（ 600°C ) 油 10%，余者为固态油渣（类似于沥青）。 After preliminary testing, the tar contains about 15% low boiling point (250 ° C) oil, 20% medium boiling point (300 ° C) oil, high boiling point (400 ° C) oil 30%, ultra high boiling point (600 ° C) oil 10%, the remainder is solid oil residue (similar to asphalt).

实施例 3 Example 3

将稻壳制成水玻璃的固化剂一磷酸硅 [Si₃(PO₄)₄或 SiP₂O₇]的方法，其步骤为：按实施例 1 歩骤所生产的已炭化稻壳，趁热落入盛有磷酸溶液的池内，并迅速搅拌均匀，池内磷酸溶液的浓度约为 40%，溶液重量为落入池内壳炭重量的 2.5倍（约 430kg)。加热至 100-150°C，搅拌并保温 2-5小时，过滤得到滤液和炭渣，固液分离后得磷酸硅水溶液约 300kg，浓度约为 38波美度，密度约为 1. 43g/_Cm ³。将上述磷酸硅水溶液进行干燥到糊状物，再将糊状物装入到高温的瓷桶里（或坩埚）内，加盖，入炉。以 60°C/小时的速度升温到约 720°C，保温 1〜3 小时。保温后，停电降温让其自然冷却到 10CTC以下，取出炉内物品。坩埚内的白色粉末即为磷酸硅约 190kg。 The rice husk is made into a curing agent for water glass, silicon silicate [Si ₃ (PO ₄ ) ₄ or SiP ₂ O ₇ ], and the steps are as follows: The carbonized rice husk produced according to the first embodiment is heated. Drop into the pool containing phosphoric acid solution, and stir quickly, the concentration of phosphoric acid solution in the pool is about 40%, and the weight of the solution is the weight of the shell carbon falling into the tank. 2.5 times (about 430kg). And the density is about 1. 43g / _Cm , the concentration is about 38, and the density is about 1. 43g / _Cm. ³ . The above aqueous solution of silicon phosphate is dried to a paste, and the paste is placed in a high-temperature ceramic drum (or crucible), capped, and placed in a furnace. The temperature was raised to about 720 ° C at a rate of 60 ° C / hour, and kept for 1 to 3 hours. After the heat preservation, the power is cooled down and allowed to cool naturally below 10 CTC, and the contents of the furnace are taken out. The white powder in the crucible is about 190 kg of silicon phosphate.

使已炭化与活化稻壳中的 SiO₂全部都生成 Si₃(PO₄)₄，则需要 H₃P0₄164k_g (即需要浓度 85 %的磷酸 193kg); 为使酸溶液中的炭渣能被搅拌，则应向溶液内加水 190kg (反应后可产水 46kg)，故酸溶液（不包括炭渣）总重为 193+190+46 = 430kg, 其中纯磷酸为 164kg，故溶液内酸的浓度约为 164/430=38%，密度约为 1.36g/cm³。 To make Si ₃ (PO ₄ ) ₄ all of the SiO ₂ in the carbonized and activated rice husks, H ₃ P0 ₄ 164k _g (that is, 193 _kg of phosphoric acid with a concentration of 85%) is required; in order to enable the carbon residue in the acid solution When it is stirred, 190kg of water should be added to the solution (46kg of water can be produced after the reaction), so the total weight of the acid solution (excluding carbon residue) is 193+190+46 = 430kg, of which 164kg is pure phosphoric acid. The concentration is about 164/430 = 38% and the density is about 1.36 g/cm ³ .

若要制作不怕水解的稻壳活性炭型材产品（如饮水机内的活性炭滤筒，则磷酸溶液重量应减为约 400kg，其浓度降为约 31 % (只加磷酸 124kg)。这是为了使炭中有约 20kg的 SiO₂因缺乏磷酸而无法反应成磷酸硅，而只能以 Si0₂存于炭中；酸煮后不再水洗而直接入炉在 400 °C高温下干燥与活化，使其中的磷酸硅变成固态粉末；再用碱煮时，炭中的 Si0₂将变成水玻璃，再与其中的磷酸硅反应，便能生成固化水玻璃；将炭渣压成产品时，干燥后即可成为不怕水解的活性炭型材产品。 To make a rice straw activated carbon profile product that is not afraid of hydrolysis (such as the activated carbon filter cartridge in the water dispenser, the weight of the phosphoric acid solution should be reduced to about 400kg, and its concentration is reduced to about 31% (only 124kg of phosphoric acid is added). This is to make charcoal in about 20kg of SiO ₂ due to lack of phosphoric acid can not be reacted to silicon, and can only be stored in the char Si0 _2; acid no longer boiled water directly into the furnace at a drying temperature of 400 ° C activation, wherein The silicon phosphate becomes a solid powder; when it is boiled with alkali, the SiO ₂ in the carbon will become water glass, and then reacted with the silicon phosphate to form a solidified water glass; when the carbon residue is pressed into a product, after drying It can be an activated carbon profile product that is not afraid of hydrolysis.

实施例 4 Example 4

将稻壳制成颗粒状（如球粒、橄球粒、柱粒针、片状）活性炭的方法，其歩骤为： A method of making rice hulls into granules (such as spherulites, spherulites, columnar needles, and flakes) of activated carbon, the steps of which are:

按实施例 1制得的稻壳活性炭与稻壳焦油，按 1 : 1的重量比混合并搅拌均勾，再进行以下歩骤：将上述混合物送入制粒机内，经挤压或滚轮制成所需要的炭粒（如球粒）；将炭粒入炉烤干，再入活性炉内缓慢升温到 500〜600°C保持约 30分钟，使炭粒内外的焦油烧蚀；将已烧除焦油的炭粒放到炉外自冷，当降到约 150°C时，将其倒入浓度约 2 %，重约为炭粒重的 1.3倍的稀磷酸液内，保温静泡约 4小时；倒入真空过滤机内进行液固分离；将分离后得到湿炭粒，倒入清水池内，用清水不断冲洗约 2 小时，直至无酸性为止；将冲洗后的湿炭粒摊开自干或直接入炉干燥，再缓慢升温到 400°C后保温 4小时；当冷却到约 80°C后出炉自冷。 The rice hull activated carbon prepared in accordance with Example 1 and the rice husk tar were mixed and stirred in a weight ratio of 1:1, and the following steps were carried out: The above mixture is sent to a granulator, and the desired carbon particles (such as pellets) are formed by extrusion or rolling; the carbon particles are baked in a furnace, and then slowly heated to 500~600 ° C in the active furnace. After about 30 minutes, the tar inside and outside the carbon particles is ablated; the tar-burned carbon particles are placed outside the furnace to be self-cooling, and when it is lowered to about 150 ° C, it is poured into a concentration of about 2%, and the weight is about carbon. In a dilute phosphoric acid solution with a weight of 1.3 times, the foam is kept for about 4 hours; poured into a vacuum filter to perform liquid-solid separation; after separation, wet carbon particles are obtained, poured into a clear water tank, and continuously rinsed with water for about 2 hours. Until no acidity; the washed wet carbon particles are spread out from the dry or directly into the oven to dry, and then slowly heated to 400 ° C and then kept for 4 hours; when cooled to about 80 ° C, the furnace is self-cooling.

冷却到接近室温时，进行碘值检测碘值达 950mg/g。 When cooled to near room temperature, the iodine value was measured to an iodine value of 950 mg/g.

实施例 5 Example 5

将稻壳直接制成颗粒状（如球、椭球、柱、针、片状）活性炭的方法，其歩骤为： A method of directly forming rice husks into granular form (such as spheres, ellipsoids, columns, needles, and flakes) of activated carbon, the steps of which are:

将稻壳用风车吹抛，除去其中的沙、石、硬物和灰尘，以得到纯净稻壳；用粉碎机将稻壳粉碎到约 80目（粉粒直径约 0.1毫米）的稻壳粉粒；将稻壳与实施例 1所得到的稻壳焦油，按 1 : 0.5〜0.7的重量比混合并搅拌均匀；将上述混合壳粉送入制粒机，将其制成所需要的稻壳粉粒（如直径为 5毫米，长 6毫米的圆柱颗粒），并让其自干、吹干或晒干。 The rice husk is blown with a windmill to remove sand, stone, hard matter and dust to obtain a pure rice husk; the rice husk is pulverized by a pulverizer to a rice husk powder of about 80 mesh (the diameter of the powder is about 0.1 mm). The rice hull obtained from the rice hull obtained in Example 1 is mixed in a weight ratio of 1:0.5 to 0.7 and stirred uniformly; the mixed shell powder is fed into a granulator to prepare the desired rice husk powder. Granules (eg 5 mm diameter, 6 mm long cylindrical particles) and allowed to dry, dry or dry.

将稻壳粉粒按实施例 1 歩骤送入炭化炉顶的不锈钢筛内，筛孔直径应选取既可使壳粉粒顺利筛下，又不致使壳粉粒倾泻而下的合适直径。 The rice hull powder is fed into the stainless steel sieve at the top of the carbonization furnace according to the first embodiment. The diameter of the sieve hole should be selected to allow the shell powder to be smoothly sieved without causing the shell powder to pour down and the appropriate diameter.

最终得到活性炭颗粒的碘值约为 900mg/g。 The iodine value of the activated carbon particles was finally obtained to be about 900 mg/g.

Claims

权利要求、一种稻壳综合利用制取活性炭和稻壳焦油并联产水玻璃或磷酸硅的方法，其特征在于，包括如下歩骤： The invention provides a method for comprehensively utilizing rice husk to produce activated carbon and rice hull tar in parallel with water-producing glass or silicon phosphate, which comprises the following steps:

( 1 ) 底部具有加热装置的炭化活化炉设置温度为 700-90(TC，将稻壳通过振动筛以 1000-2000kg/小时的速度从加热炉顶部筛入炉内，筛下的稻壳在炉内炭化活化形成炭壳沉积，同时释放出气体； (1) The carbonization activation furnace with heating device at the bottom is set at a temperature of 700-90 (TC, the rice husk is sieved into the furnace from the top of the furnace through a vibrating screen at a speed of 1000-2000 kg/hour, and the rice husk under the sieve is in the furnace. Internal carbonization activates to form carbon shell deposits while releasing gas;

(2) 将上述所得的气体从加热炉顶部抽出，经过冷凝得到液态稻壳焦油；将上述炭壳加入到为其重量 2-3 倍的氢氧化钠溶液或磷酸溶液中，加热至 100-150°C，搅拌并保温 2-5小时，过滤得到滤液和炭渣，所述氢氧化钠质量浓度为 5-10%，磷酸溶液质量浓度为 30-50%; (2) The gas obtained above is taken out from the top of the heating furnace and condensed to obtain liquid rice husk tar; the carbon shell is added to a sodium hydroxide solution or a phosphoric acid solution 2-3 times its weight, and heated to 100-150 °C, stirring and holding for 2-5 hours, filtering to obtain filtrate and carbon residue, the sodium hydroxide mass concentration is 5-10%, the phosphoric acid solution mass concentration is 30-50%;

(3) 加入氢氧化钠溶液时得到的滤液浓缩至密度为 l-1.5_g/cm³，得水玻璃；炭渣水洗，400-500°C保温干燥 3-5小时，再加入 2-3倍重量的质量浓度为 1-5% 的稀磷酸溶液，100-150°C保温 2-3小时，过滤并以水洗除去磷酸， 400-500°C 保温干燥 3-5小时，取出后得稻壳活性炭；加入磷酸溶液时得到的滤液浓缩至密度为 1.2-1.5g/cm³，得糊状物，将糊状物在 700-80(TC保温 1-3小时，得磷酸硅粉末；炭渣水洗除去磷酸， 400-500°C保温干燥 3-5小时，取出后得稻壳活性炭。 (3) The filtrate obtained by adding sodium hydroxide solution is concentrated to a density of l-1.5 _g / cm ³ to obtain water glass; the carbon residue is washed with water, dried at 400-500 ° C for 3-5 hours, and then added 2-3 times. The weight concentration is 1-5% of dilute phosphoric acid solution, 100-150 ° C for 2-3 hours, filtered and washed with water to remove phosphoric acid, 400-500 ° C heat preservation and drying for 3-5 hours, after removal, get rice husk activated carbon The filtrate obtained by adding the phosphoric acid solution is concentrated to a density of 1.2-1.5 g/cm ³ to obtain a paste, and the paste is heated at 700-80 (TC for 1-3 hours to obtain a silicon phosphate powder; the carbon residue is washed with water) Phosphoric acid, dried at 400-500 ° C for 3-5 hours, and taken out to obtain rice husk activated carbon.

、根据权利要求 1 所述的方法，其特征在于，歩骤（1 ) 所述稻壳为普通稻壳或稻壳粒；所述稻壳粒的制备方法为：稻壳按常规方法除尘，然后粉碎至直径 0.2毫米以下，得到稻壳粉；将所述稻壳粉与步骤（2)所述稻壳焦油按 1 : 0.5-0.7的重量比混合，并搅拌均勾，通过制粒机制成稻壳粒。、根据权利要求 1 所述的方法，其特征在于，歩骤（1 ) 所述稻壳为普通稻壳时，将所述稻壳活性炭粉碎成粉末，并与歩骤（2)所得稻壳焦油按照 1 : 1-1.2的重量比混合，通过制粒机制成炭粒；在 500-60CTC烘烤 0.5-1小时除去上述焦油；然后加入 1-2倍重量的磷酸溶液， 100-150°C保温浸泡 2-3 小时，所述磷酸体积浓度为 1-5%; 浸泡后的炭粒过滤并以水洗除去磷酸， 400-500°C保温干燥 3-5小时，得到颗粒状稻壳活性炭。 The method according to claim 1, wherein the rice husk of the step (1) is an ordinary rice husk or rice husk; the preparation method of the rice husk is: the rice husk is dusted according to a conventional method, and then Crushing to a diameter of 0.2 mm or less to obtain rice hull powder; mixing the rice husk powder with the rice hull tar according to the step (2) in a weight ratio of 1:0.5-0.7, stirring and hooking, and preparing rice by a granulator Shell particles. The method according to claim 1, wherein when the rice husk is a common rice husk, the rice husk activated carbon is pulverized into a powder, and the rice hull tar obtained by the mashing (2) is obtained. Follow 1 : Mixing the weight ratio of 1-1.2, making carbon particles by granulator; baking the tar at 500-60 CTC for 0.5-1 hour; then adding 1-2 times weight of phosphoric acid solution, soaking at 100-150 ° C 2- After 3 hours, the volume concentration of the phosphoric acid is 1-5%; the carbon particles after soaking are filtered and washed with water to remove the phosphoric acid, and dried at 400-500 ° C for 3-5 hours to obtain granulated rice hull activated carbon.

4、根据权利要求 1 所述的方法，其特征在于，歩骤（2) 所述冷凝介质为水或液氨。 4. The method according to claim 1, wherein the condensing medium is water or liquid ammonia.