技术领域technical field
本发明属于羟基金属氧化物制备技术领域，具体涉及一种羟基氧化铁的制备方法及其应用。The invention belongs to the technical field of preparation of metal oxyhydroxide, and in particular relates to a preparation method and application of iron oxyhydroxide.
背景技术Background technique
作为一种重要的工业材料，羟基氧化铁具有广泛的应用价值，在重金属粒子吸附、有机物降解、固相/液相脱硫、煤液化等领域展示了非常优越的应用前景。As an important industrial material, ferric oxyhydroxide has a wide range of application values, and has shown excellent application prospects in the fields of heavy metal particle adsorption, organic matter degradation, solid-phase/liquid-phase desulfurization, and coal liquefaction.
制备羟基氧化铁粉体常采用化学溶液(湿法)制备，通过控制一定的反应条件，如反应物浓度、pH值、搅拌速度、或氧化速度等制得。诸如，中国专利CN101070491A公开了一种羟基氧化铁的制备方法，其特征是采用含Cl-离子亚铁盐与碱性沉淀剂反应生成中间相，后经氧化剂氧化而成羟基氧化铁，或在含SO42-亚铁盐与碱性沉淀剂反应体系中添加含Cl-、含HPO42-等离子导晶剂制备羟基氧化铁。但是，上述方法制备得到的羟基氧化铁比表面积较低，不能满足实际应用要求。为此，中国专利文献CN106185988A，公开了一种制备高比表面羟基氧化铁并联产硫酸铵的工艺，包括以下步骤：(1)将固体硫酸亚铁与固体碳酸铵和/或固体碳酸氢铵混捏，并在混捏过程中添加水以形成浆料，控制混捏过程中所述浆料的pH值为6.5～7，且混捏结束时所述浆料的pH值为7～8；(2)对步骤(1)得到的所述浆料进行固液分离，分别收集固相和液相，将所述液相蒸干即得硫酸铵；(3)采用水将所述固相配成浆液，向所述浆液中加入双氧水以发生氧化反应，待反应结束后过滤，滤饼即为羟基氧化铁。该方案通过选用双氧水作为氧化剂，而获得比表面积大及氧化能力强的无定形羟基氧化铁。但是上述文献中，化学反应沉淀加工过程常常在搅拌罐或混捏机中采用间歇方式进行，不能连续化大规模生产，同时存在微观混合差、难以控制产品质量、不同加工批次的产品颗粒的粒径分布存在很大差异，颗粒粒径大、形状难以控制等缺点，此外，比表面积也有待于进一步提高。The preparation of iron oxyhydroxide powder is usually prepared by chemical solution (wet method), which is obtained by controlling certain reaction conditions, such as reactant concentration, pH value, stirring speed, or oxidation speed. For example, Chinese patent CN101070491A discloses a kind of preparation method of ferric oxyhydroxide, it is characterized in that adopting the reaction ofCl- ion ferrous salt and alkaline precipitant to generate intermediate phase, and then oxidized by oxidant to form ferric oxyhydroxide, or in containing ferrous oxyhydroxide. Ferric oxyhydroxide was prepared by adding Cl- and HPO42- plasma crystal guiding agents to the reaction system of SO42- ferrous salt and alkaline precipitant. However, the iron oxyhydroxide prepared by the above method has a low specific surface area, which cannot meet the requirements of practical application. For this reason, Chinese patent document CN106185988A discloses a process for preparing high specific surface iron oxyhydroxide and co-producing ammonium sulfate, comprising the following steps: (1) combining solid ferrous sulfate with solid ammonium carbonate and/or solid ammonium bicarbonate Kneading, and adding water during the kneading process to form a slurry, the pH value of the slurry during the kneading process is controlled to be 6.5-7, and the pH value of the slurry at the end of the kneading is 7-8; (2) to The slurry obtained in the step (1) is subjected to solid-liquid separation, the solid phase and the liquid phase are collected respectively, and the liquid phase is evaporated to dryness to obtain ammonium sulfate; (3) the solid phase is prepared into a slurry by using water, and the solution is added to the slurry. Hydrogen peroxide is added to the slurry to generate an oxidation reaction, and after the reaction is completed, it is filtered, and the filter cake is ferric oxyhydroxide. In this scheme, amorphous iron oxyhydroxide with large specific surface area and strong oxidizing ability is obtained by selecting hydrogen peroxide as the oxidant. However, in the above-mentioned documents, the chemical reaction precipitation process is often carried out in a batch mode in a stirring tank or a kneader, which cannot be continuously produced on a large scale. At the same time, there are poor micro-mixing, difficulty in controlling product quality, and particle size of product particles in different processing batches. There is a big difference in the diameter distribution, and the particle size is large and the shape is difficult to control. In addition, the specific surface area needs to be further improved.
发明内容SUMMARY OF THE INVENTION
因此，本发明要解决的技术问题在于克服现有技术中羟基氢氧化铁的制备工艺不能连续生产，产品粒度分布不均匀、颗粒粒径大，比表面积低等缺陷，从而提供一种连续化生产高比表面积羟基氢氧化铁的制备方法及其应用。Therefore, the technical problem to be solved by the present invention is to overcome the defects in the prior art that the preparation process of ferric hydroxide cannot be continuously produced, the product particle size distribution is uneven, the particle size is large, and the specific surface area is low, thereby providing a continuous production The preparation method of high specific surface area ferric hydroxide and its application.
为解决上述技术问题，本发明采用如下技术方案：In order to solve the above-mentioned technical problems, the present invention adopts the following technical solutions:
一种羟基氧化铁的制备方法，包括以下步骤：A preparation method of iron oxyhydroxide, comprising the following steps:
(1)在超重力条件下，将Fe2+金属盐溶液和碱溶液混合，同时，使含氧气体与反应液进行逆向接触，得反应混合浆液；(1) under the condition of supergravity, Fe2+ metal salt solution and alkali solution are mixed, meanwhile, make oxygen-containing gas and reaction liquid carry out reverse contact, obtain reaction mixed slurry;
(2)将所述反应混合浆液进行气液分离，所得液体在搅拌和鼓泡氧化的条件下陈化，制得含有羟基氧化铁的悬浊液；(2) gas-liquid separation is carried out with the reaction mixture slurry, and the obtained liquid is aged under the conditions of stirring and bubbling oxidation to obtain a suspension containing ferric oxyhydroxide;
(3)将所述悬浊液进行液固分离，固相经洗涤、烘干，得到羟基氢氧化铁。(3) liquid-solid separation is carried out on the suspension, and the solid phase is washed and dried to obtain ferric hydroxide.
进一步地，控制步骤(1)所述反应混合浆液的pH为6.0-14.0，优选为7.0-12.0。pH通过酸度计测定。Further, the pH of the reaction mixture slurry in step (1) is controlled to be 6.0-14.0, preferably 7.0-12.0. pH is determined by pH meter.
进一步地，所述含Fe2+金属盐溶液为氯化亚铁、硫酸亚铁、硝酸亚铁及乙酸亚铁中的一种或几种。Further, the Fe2+ -containing metal salt solution is one or more of ferrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate.
进一步地，其中含Fe2+溶液的浓度为0.1-3mol/L，优选为0.2-2mol/L。Further, the concentration of the Fe2+ -containing solution is 0.1-3 mol/L, preferably 0.2-2 mol/L.
进一步地，所述碱溶液为碳酸钠、碳酸氢钠、碳酸氢铵、氨水、氢氧化钠、氢氧化钾中的一种或几种，当选用多种碱的时候，其配比没有特别要求。Further, described alkali solution is one or more in sodium carbonate, sodium bicarbonate, ammonium bicarbonate, ammoniacal liquor, sodium hydroxide, potassium hydroxide, when selecting multiple alkalis, its proportioning does not have special requirements .
进一步地，所述碱溶液的浓度为0.5-15mol/L，优选为1-10mol/L。Further, the concentration of the alkaline solution is 0.5-15 mol/L, preferably 1-10 mol/L.
进一步地，所述步骤(1)选用旋转填充床超重力反应器，可以使用的填料包括，但不限于金属材料和非金属材料，如丝网、多孔板等。所述旋转填充床超重力反应器的转速为100-10000rpm，优选为300-5000rpm。Further, in the step (1), a rotating packed bed supergravity reactor is selected, and the fillers that can be used include, but are not limited to, metal materials and non-metal materials, such as wire mesh, perforated plates, and the like. The rotating speed of the rotating packed bed supergravity reactor is 100-10000rpm, preferably 300-5000rpm.
进一步地，步骤(2)选用带有搅拌器的陈化罐，陈化时间为10-300min，优选为30-180min。浆液经由进样泵泵入带有搅拌器的陈化罐，陈化罐底部及侧面排布加热管、鼓泡管，浆液在保温、含氧气体鼓泡氧化的情况下陈化。Further, step (2) selects an aging tank with a stirrer, and the aging time is 10-300min, preferably 30-180min. The slurry is pumped into the aging tank with a stirrer through the injection pump. The bottom and side of the aging tank are arranged with heating pipes and bubbling pipes. The slurry is aged under the condition of thermal insulation and bubbling and oxidation of oxygen-containing gas.
进一步地，所述陈化的温度为20-90℃，优选为30-80℃。Further, the aging temperature is 20-90°C, preferably 30-80°C.
进一步地，所述羟基氧化铁为α-羟基氧化铁、β-羟基氧化铁、γ-羟基氧化铁、δ-羟基氧化铁和无定形羟基氧化铁中的一种。Further, the iron oxyhydroxide is one of alpha-iron oxyhydroxide, beta-iron oxyhydroxide, gamma-iron oxyhydroxide, delta-iron oxyhydroxide and amorphous iron oxyhydroxide.
一种上述制备方法制备得到的羟基氧化铁在加氢裂化反应中的应用。An application of the ferric oxyhydroxide prepared by the above preparation method in hydrocracking reaction.
进一步地，所述羟基氧化铁直接用作催化剂，或者与成型助剂混捏成型后使用。如与粘结剂、助溶剂、成型剂等一起混捏成型，制得不同形状，如球形、圆柱形、三叶草形等，作为固定床催化剂，也可以以粉体直接使用，作为浆液床、沸腾床、悬浮床催化剂。Further, the iron oxyhydroxide is directly used as a catalyst, or is used after kneading and forming with a forming aid. For example, it can be kneaded together with binder, co-solvent, forming agent, etc. to obtain different shapes, such as spherical, cylindrical, clover-shaped, etc. As a fixed bed catalyst, it can also be used directly as powder, as slurry bed, ebullated bed, etc. , suspended bed catalyst.
本发明技术方案，具有如下优点：The technical scheme of the present invention has the following advantages:
1.本发明提供的羟基氢氧化铁的制备方法，首次将超重力技术应用在制备羟基氧化铁工艺中。超重力反应器是一种使微观混合和传质得到极大强化的反应器。与含氧气体逆向接触，体系中Fe(OH)2中的部分Fe(Ⅱ)与含氧气体中的氧气反应，氧化为Fe(Ⅲ)，形成“绿锈”(green rusts)，绿锈是一类含Fe(Ⅱ)和Fe(Ⅲ)的过渡态化合物，超重力反应条件加速了氧气与Fe2+的反应速率，可以瞬间生成大量绿锈晶核。与常规制备方法相比，超重力反应器微观混合均匀化用时较短，这样就缩短了金属盐和沉淀剂的接触时间，使成核过程在微观、均匀的环境中快速进行，并且可以在形成高浓度晶核的同时，抑制晶核的生长，制备出较小的晶粒。1. The preparation method of ferric oxyhydroxide provided by the present invention applies the hypergravity technology in the process of preparing ferric oxyhydroxide for the first time. A hypergravity reactor is a reactor that greatly enhances micro-mixing and mass transfer. In reverse contact with oxygen-containing gas, part of Fe(II) in Fe(OH)2 in the system reacts with oxygen in oxygen-containing gas to oxidize to Fe(III), forming "green rusts". Green rust is A class of transition-state compounds containing Fe(II) and Fe(III), the hypergravity reaction conditions accelerate the reaction rate of oxygen and Fe2+ , which can instantly generate a large number of green rust nuclei. Compared with the conventional preparation method, the micro-mixing and homogenization time of the hypergravity reactor is shorter, which shortens the contact time between the metal salt and the precipitant, and enables the nucleation process to proceed rapidly in a microscopic and homogeneous environment, and can be formed during the formation process. At the same time of high concentration of crystal nucleus, the growth of crystal nucleus is inhibited, and smaller crystal grains are prepared.
2.本发明提供的羟基氧化铁的制备方法，将超重力反应沉淀过程与鼓泡陈化过程在不同的反应器中进行，把晶核生成和晶核生长的过程分开。通过调节鼓泡陈化的温度、时间、搅拌程度等参数来控制晶核生长的环境。优选能够制备得到纳米级或亚微米级的羟基氧化铁，具有平均粒径小、比表面积大、粒径分布均匀的特点。2. In the preparation method of ferric oxyhydroxide provided by the present invention, the supergravity reaction precipitation process and the bubbling aging process are carried out in different reactors, and the processes of crystal nucleus generation and crystal nucleus growth are separated. The growth environment of crystal nucleus can be controlled by adjusting parameters such as temperature, time and stirring degree of bubbling and aging. Preferably, nano-scale or sub-micron-scale iron oxyhydroxide can be prepared, which has the characteristics of small average particle size, large specific surface area and uniform particle size distribution.
3.本发明提供的羟基氢氧化铁的制备方法，可以实现连续工业化生产。超重力反应器出口浆液直接泵入鼓泡塔陈化，陈化后的浆液直接进入分离、洗涤、干燥等装置单元制得羟基氧化铁。克服了常规制备方法采用搅拌釜或鼓泡塔间歇操作而带来的传质速率慢、生产效率低、批次间重复性差、质量不稳定以及不能连续化生产的问题。3. The preparation method of ferric hydroxide provided by the present invention can realize continuous industrial production. The slurry at the outlet of the hypergravity reactor is directly pumped into the bubbling tower for aging, and the aged slurry directly enters the separation, washing, drying and other equipment units to obtain iron oxyhydroxide. It overcomes the problems of slow mass transfer rate, low production efficiency, poor repeatability between batches, unstable quality and incapability of continuous production caused by the conventional preparation method using a stirred tank or a bubbling tower for intermittent operation.
4.本发明制备得到的羟基氧化铁用作重质油加氢裂化催化剂，具有优异的加氢活性，气体收率降低，馏分油收率提高，转化率均在92％以上。4. The ferric oxyhydroxide prepared by the present invention is used as a heavy oil hydrocracking catalyst, and has excellent hydrogenation activity, the gas yield is reduced, the distillate yield is increased, and the conversion rate is all above 92%.
具体实施方式Detailed ways
本发明提供的羟基氧化铁制备方法的具体详细的操作步骤为：在两个储罐中分别配置含有Fe2+金属盐溶液、碱溶液；两种溶液经由计量泵泵入超重力旋转床反应器中，通过液体分布器喷入旋转床，两种溶液在超重力反应器中接触，进行液-液反应；含氧气体从反应器底部通过气体分布器喷入旋转床，与反应液逆向接触，进行气-液反应；经旋转床甩出的浆液经液体出口离开超重力反应器，气体经气液分离后从气体出口逸出；浆液经由进样泵泵入串联的陈化罐经鼓泡氧化、搅拌、加热等操作，制得含有羟基氧化铁的悬浊液；悬浊液经液固分离、洗涤、烘干等常规操作即制得羟基氧化铁粉体。下面通过具体的实施例进行说明。The specific and detailed operation steps of the method for preparing iron oxyhydroxide provided by the present invention are as follows: two storage tanks are respectively equipped with Fe2+ metal salt solution and alkaline solution; the two solutions are pumped into the supergravity rotating bed reactor via a metering pump In the process, the liquid distributor is sprayed into the rotating bed, and the two solutions are contacted in the hypergravity reactor to carry out liquid-liquid reaction; the oxygen-containing gas is sprayed into the rotating bed from the bottom of the reactor through the gas distributor, and is in reverse contact with the reaction liquid, Carry out gas-liquid reaction; the slurry thrown out by the rotating bed leaves the hypergravity reactor through the liquid outlet, and the gas escapes from the gas outlet after gas-liquid separation; the slurry is pumped into the series-connected aging tank through the sampling pump and oxidized by bubbling , stirring, heating and other operations to obtain a suspension containing iron oxyhydroxide; the suspension liquid is subjected to conventional operations such as liquid-solid separation, washing and drying to obtain iron oxyhydroxide powder. The following description will be given through specific embodiments.
实施例1Example 1
配置0.5mol/L的FeCl2溶液和2.0mol/L的NaOH溶液。采用丝网为填料的旋转填充床超重力反应器，转速为1000转每分钟。含氧气体从反应器底部通过气体分布器喷入旋转床。调节含Fe2+溶液和碱液相对流量，使反应器出口浆液pH为9.0。出口浆液经由进样泵泵入陈化罐。陈化罐加热温度为20℃，搅拌、含氧气体鼓泡氧化，陈化时间为30分钟。陈化后浆液经分离、洗涤、烘干等常规操作制得样品A。Prepare 0.5mol/L FeCl2 solution and 2.0mol/LNaOH solution. A rotating packed bed hypergravity reactor with wire mesh as filler was used, and the rotation speed was 1000 rpm. Oxygen-containing gas is injected into the rotating bed from the bottom of the reactor through a gas distributor. The relative flow rate of Fe2+ -containing solution and alkali solution was adjusted so that the pH of the slurry at the outlet of the reactor was 9.0. The outlet slurry is pumped into the aging tank via the injection pump. The heating temperature of the aging tank is 20° C., stirring and oxygen-containing gas bubbling and oxidation, and the aging time is 30 minutes. After aging, the slurry was separated, washed, and dried to obtain sample A.
实施例2Example 2
配置1.0mol/L的FeSO4溶液和2.8mol/L的NaCO3和NaHCO3混合碱溶液，其中NaCO3和NaHCO3的摩尔比为1:1。采用丝网为填料的旋转填充床超重力反应器，转速为1500转每分钟。含氧气体从反应器底部通过气体分布器喷入旋转床。调节含Fe2+溶液和碱液相对流量，使反应器出口浆液pH为8.0。出口浆液经由进样泵泵入陈化罐。陈化罐加热温度为40℃，搅拌、含氧气体鼓泡氧化，陈化时间为10分钟。陈化后浆液经分离、洗涤、烘干等常规操作制得样品B。Prepare 1.0mol/LFeSO4 solution and 2.8mol/LNaCO3 andNaHCO3 mixed alkali solution, wherein the molar ratio ofNaCO3 andNaHCO3 is 1:1. A rotating packed bed hypergravity reactor with wire mesh as filler was used, and the rotating speed was 1500 rpm. Oxygen-containing gas is injected into the rotating bed from the bottom of the reactor through a gas distributor. Adjust the relative flow rate of Fe2+ -containing solution and alkali solution, so that the pH of the reactor outlet slurry is 8.0. The outlet slurry is pumped into the aging tank via the injection pump. The heating temperature of the aging tank is 40° C., stirring and oxygen-containing gas bubbling and oxidation, and the aging time is 10 minutes. After aging, the slurry was separated, washed, and dried to obtain sample B.
实施例3Example 3
配置1.5mol/L的Fe(NO3)2溶液和3.4mol/L的NH4OH和NH4HCO3混合碱溶液。采用丝网为填料的旋转填充床超重力反应器，转速为2000转每分钟。含氧气体从反应器底部通过气体分布器喷入旋转床。调节含Fe2+溶液和碱液相对流量，使反应器出口浆液pH为7。出口浆液经由进样泵泵入陈化罐。陈化罐加热温度为45℃，搅拌、含氧气体鼓泡氧化，陈化时间为90分钟。陈化后浆液经分离、洗涤、烘干等常规操作制得样品C。Prepare 1.5mol/L Fe(NO3 )2 solution and 3.4mol/L NH4 OH and NH4 HCO3 mixed alkali solution. A rotating packed bed hypergravity reactor with wire mesh as filler was used, and the rotating speed was 2000 rpm. Oxygen-containing gas is injected into the rotating bed from the bottom of the reactor through a gas distributor. The relative flow of Fe2+ -containing solution and alkali solution was adjusted so that the pH of the slurry at the outlet of the reactor was 7. The outlet slurry is pumped into the aging tank via the injection pump. The heating temperature of the aging tank is 45° C., stirring and oxygen-containing gas bubbling and oxidation, and the aging time is 90 minutes. After aging, the slurry was separated, washed, and dried to obtain sample C.
实施例4Example 4
配置1.8mol/L的FeSO4溶液和4.0mol/L的KOH碱溶液。采用孔板为填料的旋转填充床超重力反应器，转速为2500转每分钟。含氧气体从反应器底部通过气体分布器喷入旋转床。调节含Fe2+溶液和碱液相对流量，使反应器出口浆液pH为7.5。出口浆液经由进样泵泵入陈化罐。陈化罐加热温度为90℃，搅拌、含氧气体鼓泡氧化，陈化时间为120分钟。陈化后浆液经分离、洗涤、烘干等常规操作制得样品D。Prepare 1.8mol/LFeSO4 solution and 4.0mol/L KOH alkali solution. A rotating packed bed hypergravity reactor with orifice plate as filler was used, and the rotating speed was 2500 rpm. Oxygen-containing gas is injected into the rotating bed from the bottom of the reactor through a gas distributor. The relative flow of Fe2+ -containing solution and alkali solution was adjusted so that the pH of the slurry at the outlet of the reactor was 7.5. The outlet slurry is pumped into the aging tank via the injection pump. The heating temperature of the aging tank is 90° C., stirring and oxygen-containing gas bubbling and oxidation, and the aging time is 120 minutes. After aging, the slurry was separated, washed, and dried to obtain sample D.
实施例5Example 5
配置2.0mol/L的FeCl2溶液和4.6mol/L的NaCO3和NaHCO3混合碱溶液。采用孔板为填料的旋转填充床超重力反应器，转速为3000转每分钟。含氧气体从反应器底部通过气体分布器喷入旋转床。调节含Fe2+溶液和碱液相对流量，使反应器出口浆液pH为6。出口浆液经由进样泵泵入陈化罐。陈化罐加热温度为40℃，搅拌、含氧气体鼓泡氧化，陈化时间为300分钟。陈化后浆液经分离、洗涤、烘干等常规操作制得样品E。Prepare 2.0mol/L FeCl2 solution and4.6mol /LNaCO3 andNaHCO3 mixed alkali solution. A rotating packed bed hypergravity reactor with orifice plate as filler was used, and the rotating speed was 3000 rpm. Oxygen-containing gas is injected into the rotating bed from the bottom of the reactor through a gas distributor. Adjust the relative flow rate of Fe2+ -containing solution and alkali solution, so that the pH of the reactor outlet slurry is 6. The outlet slurry is pumped into the aging tank via the injection pump. The heating temperature of the aging tank is 40° C., stirring and oxygen-containing gas bubbling and oxidation, and the aging time is 300 minutes. After aging, the slurry was separated, washed, and dried to obtain sample E.
对比例1Comparative Example 1
配置1.2mol/L的FeCl2溶液和3.0mol/L的NH4OH和NH4HCO3混合碱溶液，采用并流沉淀方法，搅拌、加热保温40℃。调节两种溶液的相对流量，使混合后溶液pH为8.0。沉淀结束后陈化120分钟。陈化后浆液经分离、洗涤、烘干等常规操作制得样品F。Prepare 1.2mol/L FeCl2 solution and 3.0mol/L NH4 OH and NH4 HCO3 mixed alkaline solution, adopt co-current precipitation method, stir, heat and keep at 40°C. The relative flow rates of the two solutions were adjusted so that the pH of the solution after mixing was 8.0. Aged for 120 minutes after precipitation. After aging, the slurry was separated, washed, and dried to obtain sample F.
对比例2Comparative Example 2
配置1.2mol/L的FeCl2溶液和3.0mol/L的NH4OH和NH4HCO3混合碱溶液，采用将含Fe2+溶液滴加到碱液中的方法，搅拌、加热保温40℃。调节混合后溶液pH为8.0。沉淀结束后陈化120分钟。陈化后浆液经分离、洗涤、烘干等常规操作制得样品G。Prepare 1.2mol/L FeCl2 solution and 3.0mol/L NH4 OH and NH4 HCO3 mixed alkaline solution, adopt the method of dropping Fe2+ solution into the alkaline solution, stir, heat and keep at 40°C. The pH of the mixed solution was adjusted to 8.0. Aged for 120 minutes after precipitation. After aging, the slurry was separated, washed, and dried to obtain sample G.
实验例Experimental example
1.样品的比表面和孔结构测试1. Specific surface and pore structure testing of samples
本实施例和对比例中制备的羟基氧化铁样品的比表面积和孔结构的测定在美国Micrometric公司ASAP 2020M型全自动比表面及微孔孔径分布仪上进行。测试前，先将样品在100℃下抽真空(小于10-5Torr)2小时预处理，再在液氮条件下进行氮气吸脱附测定。表面积按照Berrett-Emmett-Teller(BET)方法计算，孔体积和孔径分布依据脱附支按照Berret-Joyner-Halenda(BJH)模型计算。样品的晶粒大小采用Debye-Scherrer方程计算：D＝kλ/βcosθ，其中D为晶粒大小(nm)；K为Scherrer常数，取K＝0.9；λ为X射线波长；β为衍射峰半高宽度(FWHM)；θ为Bragg衍射角度。The determination of the specific surface area and pore structure of the iron oxyhydroxide samples prepared in this example and the comparative example was carried out on the ASAP 2020M automatic specific surface area and micropore pore size distribution analyzer of Micrometric Company in the United States. Before the test, the samples were pretreated by vacuuming (less than 10-5 Torr) at 100°C for 2 hours, and then nitrogen adsorption and desorption measurements were carried out under the condition of liquid nitrogen. The surface area was calculated according to the Berrett-Emmett-Teller (BET) method, and the pore volume and pore size distribution were calculated according to the Berret-Joyner-Halenda (BJH) model according to the desorption branch. The grain size of the sample is calculated by the Debye-Scherrer equation: D=kλ/βcosθ, where D is the grain size (nm); K is the Scherrer constant, taking K=0.9; λ is the X-ray wavelength; β is the half height of the diffraction peak Width (FWHM); θ is the Bragg diffraction angle.
对实施例1-5和对比例中的羟基氧化铁样品进行测试，实验结果见下表:The ferric oxyhydroxide samples in Examples 1-5 and Comparative Examples are tested, and the experimental results are shown in the following table:
表1样品的比表面和孔结构测试结果Table 1 Test results of specific surface and pore structure of samples
2.样品加氢裂化反应性能测试2. Sample hydrocracking reaction performance test
本发明采用超重力反应器连续化制备的羟基氧化铁样品在重质油悬浮床加氢裂化反应中的应用：The present invention adopts the application of the ferric oxyhydroxide sample prepared continuously by the hypergravity reactor in the heavy oil suspension bed hydrocracking reaction:
评价条件：在高压釜反应体系中，以克拉玛依高钙超稠油为原料油、超重力反应器制备的羟基氧化铁和硫化剂一起加入高压釜中。先用氮气置换，再通入氢气，在一定温度和压力下进行硫化和反应，最后收集气体产物和液体产物。具体反应条件为：在300ml反应釜中，初始压力为12.0MPa，硫化过程分两段，分别为温度为250℃、30分钟和350℃、30分钟；反应温度为440℃。反应压力在初始压力一定的情况下，会在小范围内波动。所以保持初始压力相同，即可。根据以下公式计算原料油转化率和馏分油收率，作为反应效果的评价指标：Evaluation conditions: In the autoclave reaction system, using Karamay high calcium super heavy oil as the raw material oil, iron oxyhydroxide prepared in the supergravity reactor and vulcanizing agent are added into the autoclave together. It is first replaced with nitrogen, and then hydrogen is introduced to conduct sulfidation and reaction at a certain temperature and pressure, and finally collect gaseous products and liquid products. The specific reaction conditions are as follows: in a 300ml reaction kettle, the initial pressure is 12.0MPa, the vulcanization process is divided into two sections, and the temperature is respectively 250°C for 30 minutes and 350°C for 30 minutes; the reaction temperature is 440°C. The reaction pressure will fluctuate within a small range when the initial pressure is constant. So keep the initial pressure the same. Calculate the conversion rate of feedstock oil and the yield of distillate oil according to the following formula, as the evaluation index of the reaction effect:
转化率＝520℃以下组分质量(含气体)/原料油质量×100％Conversion rate = mass of components below 520°C (including gas) / mass of raw oil × 100%
气体收率＝(原料油-液体产物质量)/原料油质量×100％Gas yield=(feedstock oil-liquid product mass)/feedstock oil mass×100%
馏分油收率＝520℃以下液体组分质量/原料油质量×100％Distillate oil yield=mass of liquid components below 520℃/mass of feedstock oil×100%
表2样品加氢裂化反应性能测试结果Table 2 Sample hydrocracking reaction performance test results
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Obviously, the above-mentioned embodiments are only examples for clear description, and are not intended to limit the implementation manner. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. There is no need and cannot be exhaustive of all implementations here. And the obvious changes or changes derived from this are still within the protection scope of the present invention.
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| CN201711194462.1ACN108101116B (en) | 2017-11-24 | 2017-11-24 | A kind of preparation method and application of iron oxyhydroxide |
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