CN115261147A - A kind of method that utilizes carbon-based solid acid to catalyze synthesis of biodiesel - Google Patents
A kind of method that utilizes carbon-based solid acid to catalyze synthesis of biodiesel Download PDFInfo
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- 239000011973 solid acid Substances 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 239000003225 biodiesel Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 49
- 230000015572 biosynthetic process Effects 0.000 title description 11
- 238000003786 synthesis reaction Methods 0.000 title description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 55
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- 239000002699 waste material Substances 0.000 claims abstract description 37
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
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- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 3
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 3
- 229940073769 methyl oleate Drugs 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 3
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- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical group 0.000 description 1
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- 239000002283 diesel fuel Substances 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
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Abstract
Description
技术领域technical field
本发明属于废物资源化技术领域,具体涉及一种利用炭基固体酸催化合成生物柴油的方法。The invention belongs to the technical field of waste recycling, and in particular relates to a method for catalytically synthesizing biodiesel with carbon-based solid acid.
背景技术Background technique
为了应对化石燃料的大量消耗以及日益增长的环境问题,开发更多的绿色和可再生能源已成为发展的新需求。其中,生物柴油具有闪点高、含硫量低、十六烷值高和运输安全性好等诸多优点,还可以与柴油混合使用,因此被视为化石燃料的优秀替代品。生物柴油一般由动植物油脂在酸性或碱性条件下,通过酯化反应或酯交换反应制得。但为了降低生产成本,经常选择游离脂肪酸含量较高的废弃油脂作为原料。其直接与碱性催化剂反应时会产生皂化,因此需要先通过酸性催化下的预酯化将游离脂肪酸转化为甲酯。In response to the massive consumption of fossil fuels and growing environmental concerns, developing more green and renewable energy has become a new demand for development. Among them, biodiesel has many advantages such as high flash point, low sulfur content, high cetane number and good transportation safety, and can also be mixed with diesel oil, so it is regarded as an excellent substitute for fossil fuels. Biodiesel is generally produced from animal and vegetable oils through esterification or transesterification under acidic or alkaline conditions. However, in order to reduce production costs, waste oils with higher free fatty acid content are often selected as raw materials. When it directly reacts with a basic catalyst, it will produce saponification, so the free fatty acid needs to be converted into methyl ester by pre-esterification under acid catalysis.
在实际生产中往往采用廉价易得且催化效果好的均相酸催化剂(如浓硫酸、盐酸等)催化酯化反应。然而,它们会残留在甲醇中,带来催化剂分离回收困难、设备腐蚀严重及大量废液环境污染等问题。相比之下,多相催化剂能有效解决上述问题,降低整体的生产成本。其中,炭基固体酸催化剂具有成本较低、比表面积大、表面官能团丰富、可再生等特点,引发了诸多学者的深入研究。为了充分利用生物质能源和降低催化剂的制备成本,考虑首先将废弃生物质热解后的生物炭作为前驱体,再经浓硫酸磺化制得酸催化剂。In actual production, a homogeneous acid catalyst (such as concentrated sulfuric acid, hydrochloric acid, etc.) is often used to catalyze the esterification reaction. However, they will remain in methanol, causing problems such as difficulty in catalyst separation and recovery, serious equipment corrosion, and environmental pollution of a large amount of waste liquid. In contrast, heterogeneous catalysts can effectively solve the above problems and reduce the overall production cost. Among them, carbon-based solid acid catalysts have the characteristics of low cost, large specific surface area, rich surface functional groups, and reproducibility, which have triggered in-depth research by many scholars. In order to make full use of biomass energy and reduce the cost of catalyst preparation, it is considered to first use biochar after pyrolysis of waste biomass as a precursor, and then sulfonate it with concentrated sulfuric acid to prepare an acid catalyst.
但在固体酸催化实际催化生产生物柴油的过程中,催化剂较失效现象成为需要解决的难题。这是因为酯化反应中一般需要一次性加入过量的甲醇以加快反应的进行。但是一方面,甲醇容易与同样是极性的磺酸基团结合,造成负载不牢固的活性基团大量浸出;另一方面,过量的甲醇与磺酸基团在高温下同样会发生酯化反应,在催化剂表面形成磺酸酯,造成催化剂的失活。为了提高催化剂的重复利用性能,有研究者通过对催化剂进一步改性来提升其催化活性。但若要从根本上解决这一问题,需要开发一种减少甲醇与催化剂接触时间的方法。However, in the process of solid acid catalysis to catalyze the actual production of biodiesel, the phenomenon of catalyst failure has become a problem that needs to be solved. This is because it is generally necessary to add excess methanol at one time in the esterification reaction to speed up the reaction. But on the one hand, methanol is easy to combine with the same polar sulfonic acid groups, resulting in a large amount of leaching of active groups that are not firmly loaded; on the other hand, excess methanol and sulfonic acid groups will also undergo esterification reaction at high temperature , forming sulfonate on the surface of the catalyst, resulting in deactivation of the catalyst. In order to improve the reusability of catalysts, some researchers have further modified the catalysts to enhance their catalytic activity. But to fundamentally solve this problem, it is necessary to develop a method to reduce the contact time of methanol with the catalyst.
发明内容Contents of the invention
本申请的主要目的在于提供一种使用甲醇蒸汽和/或乙醇蒸汽替代传统的液体甲醇或乙醇,提升催化剂的催化效率,延长催化剂的使用寿命的利用炭基固体酸催化合成生物柴油的方法。The main purpose of this application is to provide a method of using methanol vapor and/or ethanol vapor to replace traditional liquid methanol or ethanol, improve the catalytic efficiency of the catalyst, and prolong the service life of the catalyst. The method of using carbon-based solid acid to catalyze the synthesis of biodiesel.
为了实现上述目的,本发明提供如下技术方案:In order to achieve the above object, the present invention provides the following technical solutions:
一种利用炭基固体酸催化合成生物柴油的方法,包括以下步骤:A method utilizing carbon-based solid acid to catalyze biodiesel synthesis, comprising the following steps:
向废弃油脂中加入炭基固体酸催化剂,同时向废弃油脂中通入甲醇蒸汽和/或乙醇蒸汽,冷凝回流进行酯化反应,待反应结束、分离得所述生物柴油。Adding a carbon-based solid acid catalyst to the waste oil, while passing methanol vapor and/or ethanol vapor into the waste oil, condensing and refluxing for esterification, and separating the biodiesel after the reaction is completed.
采用醇蒸汽可以使油脂与催化剂在短时间内和更多的醇类接触,提高活性;同时该方法减缓了催化剂表面酸性基团的损失速率,延长了催化剂寿命。The use of alcohol vapor can make the grease and the catalyst contact with more alcohols in a short time to improve the activity; at the same time, this method slows down the loss rate of the acidic groups on the surface of the catalyst and prolongs the life of the catalyst.
上述一种利用炭基固体酸催化合成生物柴油的方法,作为一种优选的实施方案,所述废弃油脂为餐饮废油、废弃动物脂肪、工业废弃酸化油。As a preferred embodiment of the above-mentioned method for synthesizing biodiesel with carbon-based solid acid catalysis, the waste oil is catering waste oil, waste animal fat, and industrial waste acidified oil.
上述一种利用炭基固体酸催化合成生物柴油的方法,作为一种优选的实施方案,所述废弃油脂与所述炭基固体酸催化剂的重量比为100:6-12。In the method for synthesizing biodiesel with carbon-based solid acid catalyst, as a preferred embodiment, the weight ratio of the waste oil to the carbon-based solid acid catalyst is 100:6-12.
上述一种利用炭基固体酸催化合成生物柴油的方法,作为一种优选的实施方案,所述甲醇蒸汽和/或乙醇蒸汽与废弃油脂的摩尔比为5:1-15:1;The method for synthesizing biodiesel using carbon-based solid acid catalysis, as a preferred embodiment, the molar ratio of methanol vapor and/or ethanol vapor to waste oil is 5:1-15:1;
当为甲醇蒸汽和乙醇蒸汽的混合醇蒸汽时,甲醇蒸汽和乙醇蒸汽的质量比为99:1-9:1。When it is the mixed alcohol vapor of methanol vapor and ethanol vapor, the mass ratio of methanol vapor and ethanol vapor is 99:1-9:1.
甲醇蒸汽和/或乙醇蒸汽的加入方法为:将甲醇和/或乙醇装入单口烧瓶中,并使用带有不锈钢管的塞子堵住瓶口;加热单口烧瓶,控制产生的甲醇蒸汽和/或乙醇蒸汽以0.5~1mL/min速率通入废弃油脂中,不锈钢管的出口需延伸至废弃油脂的液面下,可对溢出的甲醇蒸汽和/或乙醇蒸汽进行回收,重复利用。The method of adding methanol vapor and/or ethanol vapor is as follows: put methanol and/or ethanol into a single-necked flask, and use a stopper with a stainless steel tube to block the bottle mouth; heat the single-necked flask to control the generated methanol vapor and/or ethanol The steam is passed into the waste oil at a rate of 0.5-1mL/min, and the outlet of the stainless steel tube needs to extend below the liquid level of the waste oil, so that the overflowed methanol vapor and/or ethanol vapor can be recovered and reused.
上述一种利用炭基固体酸催化合成生物柴油的方法,作为一种优选的实施方案,酯化反应的温度为70-100℃,酯化反应的时间为2-15h。As a preferred embodiment of the above-mentioned method for synthesizing biodiesel with carbon-based solid acid catalysis, the temperature of the esterification reaction is 70-100° C., and the time of the esterification reaction is 2-15 hours.
上述一种利用炭基固体酸催化合成生物柴油的方法,作为一种优选的实施方案,待反应液中的酸值≤2mg·KOH/g时酯化反应完成。As a preferred embodiment of the above-mentioned method for synthesizing biodiesel with carbon-based solid acid catalysis, the esterification reaction is completed when the acid value in the reaction solution is ≤ 2 mg·KOH/g.
上述一种利用炭基固体酸催化合成生物柴油的方法,作为一种优选的实施方案,所述炭基固体酸催化剂的制备方法为:Above-mentioned a kind of method that utilizes carbon-based solid acid to catalyze the synthesis of biodiesel, as a kind of preferred embodiment, the preparation method of described carbon-based solid acid catalyst is:
(1)粉碎农作物秸秆、干燥,将干燥的农作物秸秆粉在惰性氛围下进行热解,待热解完毕,采用去离子水洗涤去除灰分,过滤,干燥滤饼;(1) Crushing and drying the crop straw, pyrolyzing the dried crop straw powder in an inert atmosphere, after the pyrolysis is completed, washing with deionized water to remove ash, filtering, and drying the filter cake;
(2)将滤饼与浓硫酸混合进行磺化处理,待磺化结束,采用去离子水洗涤、过滤至滤液呈中性,干燥滤饼得炭基固体酸催化剂。(2) Mix the filter cake with concentrated sulfuric acid for sulfonation treatment. After the sulfonation is completed, wash with deionized water, filter until the filtrate is neutral, and dry the filter cake to obtain a carbon-based solid acid catalyst.
农作物秸秆可为小麦秸秆、玉米秸秆、大豆秸秆等,也可采用花生壳、木屑、竹子或香蕉秸秆代替。The crop stalks can be wheat stalks, corn stalks, soybean stalks, etc., and can also be replaced by peanut shells, sawdust, bamboo or banana stalks.
本发明所述炭基固体酸催化剂可重复使用,若所述的催化剂失效可重新进行磺化,磺化方法与上述相同。The carbon-based solid acid catalyst of the present invention can be used repeatedly, and if the catalyst fails, sulfonation can be carried out again, and the sulfonation method is the same as above.
上述一种利用炭基固体酸催化合成生物柴油的方法,作为一种优选的实施方案,步骤(1)中,所述农作物秸秆干燥的温度为80℃-180℃,干燥的时间为6-36h;所述惰性氛围为氮气氛围;热解的温度为200-600℃,热解的时间为1-5h。The above-mentioned method for synthesizing biodiesel using carbon-based solid acid catalysis, as a preferred embodiment, in step (1), the drying temperature of the crop stalks is 80°C-180°C, and the drying time is 6-36h ; The inert atmosphere is a nitrogen atmosphere; the pyrolysis temperature is 200-600°C, and the pyrolysis time is 1-5h.
上述一种利用炭基固体酸催化合成生物柴油的方法,作为一种优选的实施方案,步骤(2)中,滤饼与浓硫酸的重量比为1:20-1:150;The above-mentioned method for utilizing carbon-based solid acid to catalyze biodiesel synthesis, as a preferred embodiment, in step (2), the weight ratio of filter cake to concentrated sulfuric acid is 1:20-1:150;
所述磺化处理为:在60-200℃的温度下加热0.5-10h。The sulfonation treatment is: heating at a temperature of 60-200° C. for 0.5-10 hours.
上述一种利用炭基固体酸催化合成生物柴油的方法,作为一种优选的实施方案,步骤(2)中,所述干燥的温度为80℃-180℃,所述干燥的时间为10-36h。The method for synthesizing biodiesel by using carbon-based solid acid catalysis as a preferred embodiment, in step (2), the drying temperature is 80°C-180°C, and the drying time is 10-36h .
本发明的有益效果为:本发明所述利用炭基固体酸催化合成生物柴油的方法使用甲醇蒸汽和/或乙醇蒸汽代替传统的液体甲醇参与酯化反应,降低了甲醇的消耗量,有效提高了催化剂的催化性能及废弃油脂的转化率,从整体上降低了生物柴油的生产成本。The beneficial effects of the present invention are: the method of utilizing carbon-based solid acid to catalyze biodiesel synthesis in the present invention uses methanol vapor and/or ethanol vapor instead of traditional liquid methanol to participate in the esterification reaction, which reduces the consumption of methanol and effectively improves the The catalytic performance of the catalyst and the conversion rate of waste oil reduce the production cost of biodiesel as a whole.
本发明所述利用炭基固体酸催化合成生物柴油的方法以废弃生物质为原料合成了炭基固体酸催化剂,在降低催化剂成本的同时,增强了催化剂的可回收性能与重复利用性。The method for synthesizing biodiesel with carbon-based solid acid catalysis in the present invention uses waste biomass as a raw material to synthesize a carbon-based solid acid catalyst, while reducing the cost of the catalyst and enhancing the recyclability and reusability of the catalyst.
具体实施方式Detailed ways
为了使本技术领域的人员更好地理解本申请方案,下面将结合案例对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请一部分的实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都应当属于本申请保护的范围。In order to enable those skilled in the art to better understand the solution of the present application, the technical solution in the embodiment of the application will be clearly and completely described below in conjunction with a case. Obviously, the described embodiment is only a part of the embodiment of the application. rather than all examples. Based on the embodiments in this application, all other embodiments obtained by persons of ordinary skill in the art without creative efforts shall fall within the scope of protection of this application.
实施例1Example 1
实施例1所述利用炭基固体酸催化合成生物柴油的方法,包括以下步骤:The method for utilizing carbon-based solid acid catalysis to synthesize biodiesel described in embodiment 1 may further comprise the steps:
取一定量的小麦秸秆破碎通过40目的筛网,于105℃下干燥12h;将干燥后的粉末转移至坩埚中,并放入热解马弗炉中,设置氮气流速为80ml/min,在350℃下热解1.5h。将产物与一定量的去离子水混合后洗涤、过滤,以去除灰分。收集过滤后的生物炭于105℃下干燥12h。A certain amount of wheat straw was crushed and passed through a 40-mesh sieve, and dried at 105°C for 12 hours; the dried powder was transferred to a crucible, and placed in a pyrolysis muffle furnace with a nitrogen flow rate of 80ml/min. Pyrolysis at ℃ for 1.5h. The product is mixed with a certain amount of deionized water, washed and filtered to remove ash. The filtered biochar was collected and dried at 105 °C for 12 h.
将5g干燥后的生物炭与100g浓硫酸混合,在150℃下加热4h.冷却至室温后多次加入去离子洗涤、过滤直至滤液呈中性。所得过滤固体在105℃下烘干10h制得炭基固体酸催化剂成品。使用滴定法测定该催化剂的磺酸密度为1.51mmol/g。Mix 5g of dried biochar with 100g of concentrated sulfuric acid and heat at 150°C for 4h. After cooling to room temperature, add deionized washing and filter until the filtrate is neutral. The obtained filtered solid was dried at 105° C. for 10 h to obtain a finished carbon-based solid acid catalyst. The sulfonic acid density of the catalyst was determined by titration to be 1.51 mmol/g.
称取30g废弃油脂(餐饮废油)置于连接冷凝装置的三口烧瓶中,加入3g炭基固体酸催化剂。称取160g甲醇和乙醇的混合醇(甲醇与乙醇的质量比为9:1)置于单口烧瓶中,并将其与三口烧瓶连接。将单口烧瓶于85℃下水浴加热,将产生的甲醇蒸汽和乙醇蒸汽的混合醇蒸汽通过不锈钢管通入废弃油脂液面下,并将三口烧瓶在76℃下加热4h进行酯化反应,待反应结束(待反应液中的酸值≤2mg·KOH/g时酯化反应完成),将酯化产物经过离心将剩余甲醇、油酸甲酯(生物柴油)、水和催化剂分离。通过计算得出脂肪酸的转换率为99.32%。Weigh 30g of waste oil (restaurant waste oil) into a three-necked flask connected to a condensing device, and add 3g of carbon-based solid acid catalyst. Weigh 160 g of mixed alcohol of methanol and ethanol (the mass ratio of methanol to ethanol is 9:1) and place it in a single-necked flask, and connect it to the three-necked flask. Heat the one-necked flask in a water bath at 85°C, pass the generated mixed alcohol vapor of methanol vapor and ethanol vapor through a stainless steel tube under the liquid surface of the waste oil, and heat the three-necked flask at 76°C for 4 hours to carry out esterification reaction. After the end (the esterification reaction is completed when the acid value in the reaction solution is ≤ 2mg·KOH/g), the esterification product is centrifuged to separate the remaining methanol, methyl oleate (biodiesel), water and catalyst. The conversion rate of fatty acid was calculated to be 99.32%.
脂肪酸转化率=(废弃油脂酸值-生物柴油酸值)/废弃油脂酸值×100%Fatty acid conversion rate = (acid value of waste oil - biodiesel acid value) / acid value of waste oil × 100%
酸值的测试方法为:称取1g左右的油脂样品料置于锥形瓶中;将50mL乙醇转移至装有待测油脂样品的锥形瓶中,充分混合;加入0.5mL酚酞指示剂,用KOH-乙醇标准溶液滴定,滴定过程中充分摇动,至颜色发生变化,并且保持15s不褪色,即为滴定终点。The test method of the acid value is: weigh about 1g of the oil sample material and place it in the conical flask; transfer 50mL of ethanol to the conical flask containing the oil sample to be tested, and mix thoroughly; add 0.5mL of phenolphthalein indicator, and use KOH-ethanol standard solution was titrated, and the titration process was shaken sufficiently until the color changed and remained unchanged for 15 seconds, which was the end point of the titration.
酸值=(V×c×56.1)/mAcid value=(V×c×56.1)/m
式中:V——滴定消耗的KOH-乙醇标准溶液的体积,mL;In the formula: V—the volume of KOH-ethanol standard solution consumed by titration, mL;
c——KOH-乙醇标准溶液的浓度,mol/L;c—concentration of KOH-ethanol standard solution, mol/L;
56.1——KOH的摩尔质量,g/mol;56.1——Molar mass of KOH, g/mol;
m——试样的质量,g。m - the mass of the sample, g.
实施例2Example 2
实施例2所述利用炭基固体酸催化合成生物柴油的方法,包括以下步骤:The method for utilizing charcoal-based solid acid catalysis to synthesize biodiesel described in embodiment 2 may further comprise the steps:
取一定量的竹子破碎通过40目的筛网,于105℃下干燥12h;将干燥后的粉末转移至坩埚中,并放入热解马弗炉中,设置氮气流速为100ml/min,在250℃下热解1.5h。将产物与一定量的去离子水混合后洗涤、过滤,以去除灰分。收集过滤后的生物炭于105℃下干燥12h。Take a certain amount of bamboo and crush it through a 40-mesh sieve, and dry it at 105°C for 12 hours; transfer the dried powder to a crucible, and put it into a pyrolysis muffle furnace, set the nitrogen flow rate to 100ml/min, and dry it at 250°C Under pyrolysis for 1.5h. The product is mixed with a certain amount of deionized water, washed and filtered to remove ash. The filtered biochar was collected and dried at 105 °C for 12 h.
将5g干燥后的生物炭与100g浓硫酸混合,在150℃下加热4h,冷却至室温后多次加入去离子洗涤、过滤直至滤液呈中性。所得过滤固体在105℃下烘干10h制得炭基固体酸催化剂成品。使用滴定法测定该催化剂的磺酸密度为1.25mmol/g。Mix 5g of dried biochar with 100g of concentrated sulfuric acid, heat at 150°C for 4h, cool to room temperature, add deionized washes several times, and filter until the filtrate is neutral. The obtained filtered solid was dried at 105° C. for 10 h to obtain a finished carbon-based solid acid catalyst. The sulfonic acid density of the catalyst was determined by titration to be 1.25 mmol/g.
称取30g废弃油脂(废弃动物脂肪)置于连接冷凝装置的三口烧瓶中,加入3g炭基固体酸催化剂。称取160g甲醇置于单口烧瓶中,并将其与三口烧瓶连接。将单口烧瓶于74℃下水浴加热,将产生的甲醇蒸汽通过不锈钢管通入废弃油脂液面下,并将三口烧瓶在76℃下加热4h进行酯化反应,待反应结束(待反应液中的酸值≤2mg·KOH/g时酯化反应完成),将酯化产物经过离心将剩余甲醇、油酸甲酯(生物柴油)、水和催化剂分离。通过计算得出脂肪酸的转换率为97.54%。Weigh 30 g of waste oil (waste animal fat) and place it in a three-neck flask connected to a condensing device, and add 3 g of a carbon-based solid acid catalyst. Weigh 160g of methanol and place it in a one-necked flask, and connect it with a three-necked flask. The one-necked flask was heated in a water bath at 74°C, the generated methanol vapor was passed through a stainless steel tube under the liquid surface of the waste oil, and the three-necked flask was heated at 76°C for 4h to carry out the esterification reaction. The esterification reaction is completed when the acid value is less than or equal to 2mg·KOH/g), and the esterification product is centrifuged to separate the remaining methanol, methyl oleate (biodiesel), water and catalyst. The conversion rate of fatty acid was calculated to be 97.54%.
实施例3Example 3
实施例3所述利用炭基固体酸催化合成生物柴油的方法,包括以下步骤:The method for utilizing carbon-based solid acid catalysis to synthesize biodiesel described in embodiment 3 may further comprise the steps:
取一定量的花生壳破碎通过40目的筛网,于105℃下干燥12h;将干燥后的粉末转移至坩埚中,并放入热解马弗炉中,设置氮气流速为80ml/min,在350℃下热解1.5h。将产物与一定量的去离子水混合后洗涤、过滤,以去除灰分。收集过滤后的生物炭于105℃下干燥12h。Take a certain amount of peanut shells and crush them through a 40-mesh sieve, and dry them at 105°C for 12 hours; transfer the dried powder to a crucible, and put it into a pyrolysis muffle furnace, set the nitrogen flow rate to 80ml/min, Pyrolysis at ℃ for 1.5h. The product is mixed with a certain amount of deionized water, washed and filtered to remove ash. The filtered biochar was collected and dried at 105 °C for 12 h.
将5g干燥后的生物炭与100g浓硫酸混合,在150℃下加热4h。冷却至室温后多次加入去离子洗涤、过滤直至滤液呈中性。所得过滤固体在105℃下烘干10h制得炭基固体酸催化剂成品。使用滴定法测定该催化剂的磺酸密度为1.32mmol/g。Mix 5 g of dried biochar with 100 g of concentrated sulfuric acid and heat at 150 °C for 4 h. After cooling to room temperature, add deionized washing several times, and filter until the filtrate is neutral. The obtained filtered solid was dried at 105° C. for 10 h to obtain a finished carbon-based solid acid catalyst. The sulfonic acid density of the catalyst was determined by titration to be 1.32 mmol/g.
称取30g废弃油脂(餐饮废油)置于连接冷凝装置的三口烧瓶中,加入3g炭基固体酸催化剂。称取160g甲醇和乙醇的混合醇(甲醇与乙醇的质量比为9:1)置于单口烧瓶中,并将其与三口烧瓶连接。将单口烧瓶于85℃下水浴加热,将产生的甲醇蒸汽和乙醇蒸汽的混合醇蒸汽通过不锈钢管通入废弃油脂液面下,并将三口烧瓶在76℃下加热4h进行酯化反应,待反应结束(待反应液中的酸值≤2mg·KOH/g时酯化反应完成),将酯化产物经过离心将剩余甲醇、油酸甲酯(生物柴油)、水和催化剂分离。通过计算得出脂肪酸的转换率为97.14%。Weigh 30g of waste oil (restaurant waste oil) into a three-necked flask connected to a condensing device, and add 3g of carbon-based solid acid catalyst. Weigh 160 g of mixed alcohol of methanol and ethanol (the mass ratio of methanol to ethanol is 9:1) and place it in a single-necked flask, and connect it to the three-necked flask. Heat the one-necked flask in a water bath at 85°C, pass the generated mixed alcohol vapor of methanol vapor and ethanol vapor through a stainless steel tube under the liquid surface of the waste oil, and heat the three-necked flask at 76°C for 4 hours to carry out esterification reaction. After the end (the esterification reaction is completed when the acid value in the reaction solution is ≤ 2mg·KOH/g), the esterification product is centrifuged to separate the remaining methanol, methyl oleate (biodiesel), water and catalyst. The conversion rate of fatty acid was calculated to be 97.14%.
实施例4Example 4
实施例4与实施例2的不同之处在于:采用的醇为乙醇,即采用乙醇蒸汽进行酯化反应,其余操作与实施例2相同。通过测定反应前后酸值的变化计算脂肪酸的转换率为98.76%。The difference between Example 4 and Example 2 is that the alcohol used is ethanol, that is, the esterification reaction is carried out with ethanol vapor, and the rest of the operations are the same as in Example 2. The conversion rate of fatty acid was calculated as 98.76% by measuring the change of acid value before and after the reaction.
对比例1Comparative example 1
对比例1所述利用炭基固体酸催化合成生物柴油的方法与实施例1所述的方法不同之处在于:对比例1所述利用炭基固体酸催化合成生物柴油采用的醇为液体甲醇和液体乙醇的混合醇进行酯化反应,其余操作与实施例1相同。The difference between the method of utilizing carbon-based solid acid to catalyze the synthesis of biodiesel described in Comparative Example 1 and the method described in Example 1 is that the alcohols used in the synthesis of biodiesel by utilizing carbon-based solid acid to catalyze the synthesis of biodiesel described in Comparative Example 1 are liquid methanol and The mixed alcohol of liquid ethanol carries out esterification reaction, all the other operations are identical with embodiment 1.
对比例2Comparative example 2
对比例2所述利用炭基固体酸催化合成生物柴油的方法与实施例4所述的方法不同之处在于:The difference between the method described in Comparative Example 2 and the method described in Example 4 utilizing carbon-based solid acid to catalyze the synthesis of biodiesel is:
对比例2所述利用炭基固体酸催化合成生物柴油采用的醇为液体乙醇进行酯化反应,其余操作与实施例4相同。The alcohol used in the synthesis of biodiesel by carbon-based solid acid as described in Comparative Example 2 is liquid ethanol for esterification, and the rest of the operations are the same as in Example 4.
本发明所述利用炭基固体酸催化合成生物柴油催化剂可重复性的研究,研究结果如表1所示:The present invention utilizes the research on the reproducibility of carbon-based solid acid catalysis to synthesize biodiesel catalyst, and the research results are as shown in table 1:
表1Table 1
备注:Remark:
表格中蒸汽酯化首次为实施例1所述炭基固体酸催化剂的磺酸密度,酯化率。In the table, steam esterification is the sulfonic acid density and esterification rate of the carbon-based solid acid catalyst described in Example 1 for the first time.
表格中蒸汽酯化重复4次为:按照实施例1所述的方法,重复催化合成生物柴油4次,即炭基固体酸催化剂重复使用4次。In the table, steam esterification was repeated 4 times: according to the method described in Example 1, biodiesel was catalyzed and synthesized 4 times, that is, the carbon-based solid acid catalyst was reused 4 times.
表格中蒸汽酯化重复8次为:按照实施例1所述的方法,重复催化合成生物柴油8次,即炭基固体酸催化剂重复使用8次。In the table, steam esterification was repeated 8 times: according to the method described in Example 1, biodiesel was catalyzed and synthesized 8 times, that is, the carbon-based solid acid catalyst was reused 8 times.
表格中对比例1液体酯化重复4次为:按照对比例1所述的方法,重复催化合成生物柴油4次,即催化剂重复使用4次。In the table, the liquid esterification of Comparative Example 1 was repeated 4 times: according to the method described in Comparative Example 1, the catalytic biodiesel was synthesized 4 times, that is, the catalyst was reused 4 times.
表格中对比例2液体酯化重复4次为:按照对比例2所述的方法,重复催化合成生物柴油4次,即催化剂重复使用4次。In the table, the liquid esterification of Comparative Example 2 was repeated 4 times: according to the method described in Comparative Example 2, the catalytic biodiesel was synthesized 4 times, that is, the catalyst was reused 4 times.
从表1可以看出:虽然在首次酯化时两者的催化活性接近,但在液体酯化中重复使用4次后的催化剂失活明显,脂肪酸转化率不足80%。相比之下,使用甲醇蒸汽和乙醇蒸汽的混合醇蒸汽酯化重复利用8次,脂肪酸转化率仍高于80%。It can be seen from Table 1 that although the catalytic activities of the two catalysts were close to each other during the first esterification, the catalyst was obviously deactivated after repeated use for 4 times in liquid esterification, and the conversion rate of fatty acid was less than 80%. In contrast, the mixed alcohol vapor esterification using methanol vapor and ethanol vapor was reused 8 times, and the fatty acid conversion was still higher than 80%.
表1显示了两种酯化重复利用催化剂过程中催化剂磺酸密度的变化。液体酯化重复利用4次后,磺酸密度就降至0.32mmol g-1;而蒸汽酯化重复4次后磺酸密度为0.92mmolg-1,表现出良好的催化性能。Table 1 shows the change of catalyst sulfonic acid density during the process of two esterification recycling catalysts. The density of sulfonic acid decreased to 0.32mmol g -1 after the liquid esterification was repeated 4 times; while the density of sulfonic acid was 0.92mmolg -1 after the vapor esterification was repeated 4 times, showing good catalytic performance.
炭基固体酸催化剂能起到催化作用主要是因为表面负载了磺酸基团以及羧酸等弱酸基团,而磺酸起主要作用。磺酸密度可以视为衡量其催化活性的指标之一。The carbon-based solid acid catalyst can play a catalytic role mainly because the surface supports weak acid groups such as sulfonic acid groups and carboxylic acids, and sulfonic acid plays the main role. The density of sulfonic acid can be regarded as one of the indicators to measure its catalytic activity.
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员,在不脱离本发明方法的前提下,还可以做出若干改进和补充,这些改进和补充也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the method of the present invention, some improvements and supplements can also be made, and these improvements and supplements should also be considered Be the protection scope of the present invention.
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