技术领域technical field
本发明涉及一种用于煤直接液化的催化剂，特别涉及一种含有两种主活性组分铁和碱复配的煤直接液化催化剂。属于煤炭资源化转化领域。The invention relates to a catalyst for direct coal liquefaction, in particular to a catalyst for direct coal liquefaction containing two main active components, iron and alkali. It belongs to the field of coal resource conversion.
技术背景technical background
我国能源结构为富煤贫油少气，能源结构不合理，一定程度上影响了我国国民经济的发展。目前石油消费量的日益增加进一步加剧了国内石油供需的矛盾。我国煤炭资源丰富，但优质煤炭资源依旧短缺，大量低阶煤无法得到有效利用从而造成资源浪费，如何将这部分低阶煤加以资源化转化利用成为目前煤炭高效清洁利用的研究热点。my country's energy structure is rich in coal, poor in oil and little in gas, and the energy structure is unreasonable, which affects the development of my country's national economy to a certain extent. The current increase in oil consumption has further exacerbated the contradiction between domestic oil supply and demand. my country is rich in coal resources, but there is still a shortage of high-quality coal resources. A large amount of low-rank coal cannot be effectively utilized, resulting in waste of resources. How to transform and utilize this part of low-rank coal has become a research hotspot in the efficient and clean utilization of coal.
煤炭直接液化技术是煤炭资源化转化的重要手段之一，其原理是在高温高压条件下，煤、溶剂、催化剂和气相氢气混合相互反应，使煤的大分子结构发生断裂并转化为液体燃料。由于煤中含有较多的芳香结构，故煤液化粗油含有较多的芳香化合物，这也为煤炭直接液化制化工原料提供了可行路径。煤直接液化过程的核心技术之一为催化剂，由于煤直接液化工艺的特殊性，使用后的催化剂回收成本高，通常煤直接液化催化剂为一次性可弃型催化剂，故要求其具有价格低廉、较高的活性以及较高的油产率等特点。铁基催化剂由于具有价格低廉的特点一直是煤液化领域的研究热点，也形成了一些煤直接液化的铁基催化剂专利：CN104923231、CN103706381A、CN103706380B、CN1853776A、CN100457261C、CN1231326A、CN1109734C、CN1226466A、CN1117632C等，这些专利报道的催化剂都是单一的铁活性组分。本课题组对煤直接液化铁基催化剂也进行了大量研究，发现：在复配少量碱金属的条件下，煤直接液化的转化率和油收率明显增加，沥青质明显减少，特别适合于含水系统下煤的直接液化。目前，尚未查到涉及铁与碱金属复合催化剂的文献报道。Coal direct liquefaction technology is one of the important means of coal resource conversion. Its principle is that under high temperature and high pressure conditions, coal, solvent, catalyst and gas phase hydrogen mix and react with each other, so that the macromolecular structure of coal is broken and converted into liquid fuel. Because coal contains more aromatic structures, crude oil from coal liquefaction contains more aromatic compounds, which also provides a feasible path for direct coal liquefaction to chemical raw materials. One of the core technologies of the direct coal liquefaction process is the catalyst. Due to the particularity of the direct coal liquefaction process, the cost of catalyst recovery after use is high. Usually, the direct coal liquefaction catalyst is a disposable catalyst, so it is required to be cheap, relatively High activity and high oil yield and so on. Iron-based catalysts have always been a research hotspot in the field of coal liquefaction due to their low price, and some iron-based catalyst patents for direct coal liquefaction have also been formed: CN104923231, CN103706381A, CN103706380B, CN1853776A, CN100457261C, CN1231326A, CN1109734C, CN1226466A, CN2C111, etc. The catalysts reported in these patents all have a single iron active component. The research group has also conducted a lot of research on iron-based catalysts for direct coal liquefaction, and found that: under the condition of compounding a small amount of alkali metal, the conversion rate and oil yield of direct coal liquefaction are significantly increased, and asphaltenes are significantly reduced, especially suitable for water-containing catalysts. Direct liquefaction of coal under the system. At present, there is no literature report related to the composite catalyst of iron and alkali metal.
发明内容Contents of the invention
本发明了一种煤直接液化铁碱复合催化剂。该铁碱复合催化剂适合于不同气氛和不同溶剂系统下煤的直接液化，对煤的转化率和油收率的提高具有明显的促进作用，不仅原料廉价易得，而且制备过程简单，具有极好的应用前景。本发明提供了煤直接液化铁碱复合催化剂，采用如下技术方案：The invention discloses an iron-alkali composite catalyst for coal direct liquefaction. The iron-alkali composite catalyst is suitable for the direct liquefaction of coal under different atmospheres and different solvent systems, and can significantly promote the improvement of coal conversion and oil yield. Not only is the raw material cheap and easy to obtain, but also the preparation process is simple and has excellent application prospects. The invention provides an iron-alkali composite catalyst for direct coal liquefaction, which adopts the following technical scheme:
一种用于煤直接液化的铁碱复合催化剂，其特征在于，所述的复合催化剂主要含有铁活性组分和碱活性组分，包括负载型复合催化剂和混配型复合催化剂，An iron-alkali composite catalyst for direct coal liquefaction, characterized in that the composite catalyst mainly contains iron active components and alkali active components, including supported composite catalysts and mixed composite catalysts,
所述负载型催化剂是通过如下方法制备的：将铁活性组分和碱活性组分通过化学反应负载在煤的表面结构上，即：将煤粉、铁盐溶液、碱溶液及添加剂混合搅拌反应后进行干燥处理，得到负载型铁碱复合催化剂；其中，水与干燥煤粉的质量比为(0.5～5):1，铁盐溶液中Fe原子质量与干燥煤粉质量之比为(0.1～0.5):1，添加剂与铁盐溶液中Fe原子摩尔比为(0～0.1):1，碱溶液中碱性金属原子与铁盐溶液中Fe原子的摩尔比为(0.001～5):1。The supported catalyst is prepared by the following method: the iron active component and the alkali active component are supported on the surface structure of the coal through a chemical reaction, that is, the coal powder, the iron salt solution, the alkali solution and the additive are mixed and stirred to react Carry out drying treatment afterward, obtain loaded iron-alkali composite catalyst; Wherein, the mass ratio of water and dry coal powder is (0.5～5):1, and the ratio of Fe atomic mass and dry coal powder mass in iron salt solution is (0.1～ 0.5):1, the molar ratio of Fe atoms in the additive to the iron salt solution is (0-0.1):1, and the molar ratio of the alkaline metal atoms in the alkaline solution to the Fe atoms in the iron salt solution is (0.001-5):1.
所述负载型催化剂制备中的添加剂包括碱金属的磷酸盐、磷酸氢盐、磷酸二氢盐、乙二胺四乙酸盐、丙二胺四乙酸盐、丁二胺四乙酸盐中的一种或几种的混合物，优选乙二胺四乙酸盐、丙二胺四乙酸盐或丁二胺四乙酸盐中的一种或几种；主要是控制活性相的分散度和铁活性组分的晶体大小，或者提供复合催化剂的碱性组分，可以添加也可以不添加，优选添加。Additives in the preparation of the supported catalyst include alkali metal phosphate, hydrogen phosphate, dihydrogen phosphate, ethylenediaminetetraacetate, propylenediaminetetraacetate, butylenediaminetetraacetate A mixture of one or more, preferably one or more of ethylenediaminetetraacetate, propylenediaminetetraacetate or butyldiaminetetraacetate; mainly to control the dispersion of the active phase and iron The crystal size of the active component, or the basic component providing the composite catalyst, may or may not be added, preferably added.
所述负载型催化剂制备中的铁盐溶液中的铁盐包括含亚铁离子和铁离子的硫酸盐、氯化物、硝酸盐、草酸盐、甲酸盐等中的一种或几种的混合物，优选含亚铁离子的硫酸盐和/或氯化物。The iron salt in the iron salt solution in the preparation of the supported catalyst includes one or more mixtures of sulfate, chloride, nitrate, oxalate, formate, etc. containing ferrous ions and iron ions , preferably sulfate and/or chloride containing ferrous ions.
所述负载型催化剂制备中的碱溶液中碱包括碱金属或碱土金属的氢氧化物、碳酸盐、碳酸氢盐、偏铝酸盐、硅酸盐、硫酸盐、氯化物、硝酸盐、草酸盐、甲酸盐等中的一种或几种混合物，优选碱金属Na或K的氢氧化物、碳酸盐、偏铝酸盐或硅酸盐中的一种或几种。The alkali in the alkaline solution in the preparation of the supported catalyst includes hydroxides, carbonates, bicarbonates, metaaluminates, silicates, sulfates, chlorides, nitrates, oxalates of alkali metals or alkaline earth metals. One or more mixtures of salts, formates, etc., preferably one or more of alkali metal Na or K hydroxides, carbonates, metaaluminates or silicates.
所述的反应时间优选10分钟以上，反应温度优选25～80℃。The reaction time is preferably more than 10 minutes, and the reaction temperature is preferably 25-80°C.
所述负载型催化剂制备中的煤为低阶煤或中低阶煤，优选低阶煤，煤粉粒度小于100μm。The coal used in the preparation of the supported catalyst is low-rank coal or medium-low rank coal, preferably low-rank coal, and the coal powder particle size is less than 100 μm.
所述负载型催化剂制备过程中发生的化学反应主要是水合铁化合物的生成反应及氧化反应，以控制铁活性组分的物相型式及晶体结构，这两类反应可以发生，也可以不发生；优选水合铁化合物的生成反应和氧化反应都发生。The chemical reactions that occur during the preparation of the supported catalyst are mainly the generation reaction and oxidation reaction of the hydrated iron compound to control the phase type and crystal structure of the iron active component. These two types of reactions may or may not occur; Preferably, both the formation reaction and the oxidation reaction of the hydrated iron compound take place.
所述混配型催化剂是将含铁的物质与含碱的物质直接混合而制得，碱性金属原子与Fe原子的摩尔比为(0.001～5):1。The mixed type catalyst is prepared by directly mixing iron-containing substances with alkali-containing substances, and the molar ratio of basic metal atoms to Fe atoms is (0.001-5):1.
所述混配型催化剂中含铁的物质包括含铁的矿物、亚铁离子或铁离子的氧化物、硫化物、氢氧化物、硫酸盐、氯化盐、硝酸盐、碳酸盐、草酸盐、甲酸盐等中的一种或几种混合物，优选含铁的矿物、铁的氢氧化物和/或硫化物中的一种或几种。Iron-containing substances in the mixed catalyst include iron-containing minerals, ferrous ions or oxides, sulfides, hydroxides, sulfates, chlorides, nitrates, carbonates, oxalic acid One or more mixtures of salt, formate, etc., preferably one or more of iron-containing minerals, iron hydroxides and/or sulfides.
所述混配型催化剂中含碱的物质主要是含碱的矿物、碱金属或碱土金属的氢氧化物、碳酸盐、偏铝酸盐、硅酸盐、碳酸氢盐、硫酸盐、氯化盐、草酸盐、甲酸盐等中的一种或几种的混合物，优选含碱的矿物、碱金属Na或K的氢氧化物、碳酸盐、偏铝酸盐或硅酸盐中的一种或几种。The alkali-containing substances in the mixed catalyst are mainly alkali-containing minerals, hydroxides, carbonates, metaaluminates, silicates, bicarbonates, sulfates, chlorinated One or more mixtures of salt, oxalate, formate, etc., preferably alkali-containing minerals, alkali metal Na or K hydroxide, carbonate, metaaluminate or silicate one or several.
本发明的铁碱复合催化剂用于各种煤直接液化，主要包括：不同煤种的直接液化(低阶至中等偏高阶煤)、不同苛刻条件的液化(温和液化和苛刻条件液化)、不同气氛下的直接液化(纯H2气氛、富氢气氛或合成气气氛)、不同溶剂系统下的直接液化(有机溶剂系统、含水的有机溶剂系统或水溶剂系统)，优选温和液化、合成气气氛、含水的有机溶剂系统条件下的直接液化。The iron-alkali composite catalyst of the present invention is used for direct liquefaction of various coals, mainly including: direct liquefaction of different coal types (low-rank to medium to high-rank coal), liquefaction of different severe conditions (mild liquefaction and harsh condition liquefaction), different Direct liquefaction under atmosphere (pureH2 atmosphere, hydrogen-rich atmosphere or syngas atmosphere), direct liquefaction under different solvent systems (organic solvent system, aqueous organic solvent system or water solvent system), preferably mild liquefaction, syngas atmosphere , Direct liquefaction under the condition of aqueous organic solvent system.
本发明主要优势是：铁碱复合催化剂中的铁活性组分和碱活性组分具有很好的协同作用，能明显提高煤的转化率和油收率，减少了沥青质及残渣的生成，减轻了残渣的处理负荷；适合于温和条件下的直接液化，降低了液化过程的苛刻程度；适于合成气气氛下煤的直接液化，不需采用纯氢气氛或富氢气氛，减少了制氢成本；适于含水系统下煤的直接液化，不需要对原料进行干燥，减少了干燥成本；负载型催化剂采用煤作为载体，不采用其它惰性材料作为载体，减少了残渣量。因此，本发明的复合催化剂不仅原料廉价易得、制备过程简单，而且催化活性高，具有极好的应用前景。The main advantages of the present invention are: the iron active component and the alkali active component in the iron-alkali composite catalyst have a good synergistic effect, which can significantly improve the conversion rate of coal and oil yield, reduce the generation of asphaltenes and residues, reduce the It reduces the processing load of residue; it is suitable for direct liquefaction under mild conditions, which reduces the harshness of the liquefaction process; it is suitable for direct liquefaction of coal under syngas atmosphere, without using pure hydrogen atmosphere or hydrogen-rich atmosphere, which reduces the cost of hydrogen production ; Suitable for direct liquefaction of coal in water-containing system, without drying raw materials, reducing drying costs; supported catalyst uses coal as a carrier instead of other inert materials as a carrier, reducing the amount of residue. Therefore, the composite catalyst of the invention not only has cheap and easy-to-obtain raw materials and a simple preparation process, but also has high catalytic activity and has excellent application prospects.
附图说明Description of drawings
图1是实施例中FC6铁碱复合催化剂的XRD图谱。图1说明了FC6催化剂中铁活性组分主要以γ-FeOOH形式存在，少量以α-FeOOH形式存在；钠活性组分以Na2CO3形式存在。Fig. 1 is the XRD spectrum of FC6 iron-base composite catalyst in the embodiment. Figure 1 shows that the iron active component in the FC6 catalyst mainly exists in the form of γ-FeOOH, and a small amount exists in the form of α-FeOOH; the sodium active component exists in the form of Na2 CO3 .
具体实施方式detailed description
实施例Example
以下通过举实例来进一步详细说明本发明，但本发明并不限于这些实施例。The present invention is further described in detail by giving examples below, but the present invention is not limited to these embodiments.
实施例1-5Example 1-5
实施例1-5制备的催化剂为负载型复合催化剂FC1-5，其制备过程为：将煤粉、铁盐溶液、碱溶液及添加剂混合搅拌反应后进行干燥处理，其制备原料和条件如下表：The catalyst prepared in Examples 1-5 is a supported composite catalyst FC1-5, and its preparation process is as follows: coal powder, iron salt solution, alkali solution and additives are mixed and stirred for reaction and then dried. The raw materials and conditions for its preparation are as follows:
实施例6-7Example 6-7
实施例6-7所制备的催化剂为混合型复合催化剂FC6-7。其中，FC6是由铁的氢氧化物与碳酸钠直接混配而成，钠原子与铁原子的摩尔比为0.1:1；FC7是由硫酸铁与硅酸钾直接婚配而成，钾原子与铁原子的摩尔比为0.2:1。The catalyst prepared in Example 6-7 is a mixed composite catalyst FC6-7. Among them, FC6 is made by directly mixing iron hydroxide and sodium carbonate, and the molar ratio of sodium atom to iron atom is 0.1:1; FC7 is made by directly matching iron sulfate and potassium silicate, and potassium atom and iron atom The molar ratio of atoms is 0.2:1.
以实施例1-7所制备的铁碱复合催化剂FC1-7为煤直接液化的催化剂，在500mL的高温高压反应釜上进行了煤的直接液化实验，其实验条件及结果如下表：With the iron-alkali composite catalyst FC1-7 prepared in Examples 1-7 as the catalyst for direct liquefaction of coal, the direct liquefaction experiment of coal was carried out on a 500mL high-temperature and high-pressure reactor, and its experimental conditions and results are as follows:
说明：合成气指CO和H2的混合气(CO:H2＝1.5:3.5)；油指正己烷可溶物；沥青质指正己烷不溶-四氢呋喃可溶物；转化率等于沥青质、油、气和水的产率之和。Explanation: Syngas refers to the mixed gas of CO and H2 (CO:H2 =1.5:3.5); oil refers to n-hexane soluble matter; asphaltene refers to n-hexane-insoluble-tetrahydrofuran soluble matter; the conversion rate is equal to asphaltene, oil , the sum of the production rates of gas and water.
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| CN201710453268.4ACN107349948A (en) | 2017-06-15 | 2017-06-15 | A kind of iron alkali composite catalyst for DCL/Direct coal liquefaction |
| Application Number | Priority Date | Filing Date | Title |
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| CN201710453268.4ACN107349948A (en) | 2017-06-15 | 2017-06-15 | A kind of iron alkali composite catalyst for DCL/Direct coal liquefaction |
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| CN107349948Atrue CN107349948A (en) | 2017-11-17 |
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| CN201710453268.4APendingCN107349948A (en) | 2017-06-15 | 2017-06-15 | A kind of iron alkali composite catalyst for DCL/Direct coal liquefaction |
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