CN103084187B - Carbon-based solid acid and preparation method thereof - Google Patents

Carbon-based solid acid and preparation method thereof Download PDF

Info

Publication number
CN103084187B
CN103084187B CN201210547711.1A CN201210547711A CN103084187B CN 103084187 B CN103084187 B CN 103084187B CN 201210547711 A CN201210547711 A CN 201210547711A CN 103084187 B CN103084187 B CN 103084187B
Authority
CN
China
Prior art keywords
carbon
acid
based solid
shell
solid acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201210547711.1A
Other languages
Chinese (zh)
Other versions
CN103084187A (en
Inventor
任庆功
陈诚
李为民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Medical Device Industry Development Co ltd
Suzhou Medical Device Industry Development Group Co ltd
Original Assignee
Changzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changzhou University filed Critical Changzhou University
Priority to CN201210547711.1A priority Critical patent/CN103084187B/en
Publication of CN103084187A publication Critical patent/CN103084187A/en
Application granted granted Critical
Publication of CN103084187B publication Critical patent/CN103084187B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

本发明提供了一种碳基固体酸及其制备方法,本发明利用新鲜果壳为原料,将新鲜果壳水洗、烘干并粉碎至需要的粒度后,加入到活化剂溶液中浸泡活化,将活化好的果壳烘干后,在加热条件下碳化,制备成活性炭,将制成的活性炭材料研磨成粉末后,在酸溶液中煮沸,然后抽滤,用蒸馏水漂洗并干燥,将干燥后的活性炭材料加热,经磺化剂磺化,将磺化后的混合液缓缓地倒入冷水中并不断搅拌,抽滤、烘干所得黑色固体粉末即为碳基固体酸。本发明制备的碳基固体酸具有比表面积大,催化性较高的优点。

The invention provides a carbon-based solid acid and a preparation method thereof. The invention uses fresh fruit shells as raw materials. After the fresh fruit shells are washed with water, dried and crushed to a required particle size, they are added to an activator solution for soaking and activation. After the activated fruit shell is dried, it is carbonized under heating conditions to prepare activated carbon. After the activated carbon material is ground into powder, it is boiled in an acid solution, then suction filtered, rinsed with distilled water and dried. The dried The activated carbon material is heated and sulfonated by a sulfonating agent. The sulfonated mixture is slowly poured into cold water and stirred continuously. The black solid powder obtained by suction filtration and drying is carbon-based solid acid. The carbon-based solid acid prepared by the invention has the advantages of large specific surface area and high catalytic performance.

Description

一种碳基固体酸及其制备方法A kind of carbon-based solid acid and preparation method thereof

技术领域technical field

本发明涉及一种固体酸及其制备方法,特别涉及一种碳基固体酸及其制备方法。The invention relates to a solid acid and a preparation method thereof, in particular to a carbon-based solid acid and a preparation method thereof.

背景技术Background technique

由于酸催化剂的广泛应用以及绿色化工的要求,近年来以低碳生产为目标的绿色催化工艺和催化剂的开发,已成为催化研究的热点。只有采取工艺及催化剂的改进才能实现科技创新与绿色环保相结合,才能带来企业的高效益和社会高效益的同步增长。为克服液体酸催化剂对生产设备的腐蚀性;常与原料和产物形成均相体,造成反应后处理的繁杂;工艺上不利于实现连续化生产要求等缺点,固体酸逐步取代传统的液体酸催化剂,使之广泛应用于化工生产的各个领域是必然的发展方向。通过人们对固体酸近半个世纪的开发,到目前为止,已有大量以前由液体酸参与的化学工艺过程被固体酸所代替。Due to the wide application of acid catalysts and the requirements of green chemical industry, the development of green catalytic processes and catalysts targeting low-carbon production has become a hotspot in catalytic research in recent years. Only by improving the process and catalyst can the combination of scientific and technological innovation and green environmental protection be realized, and the simultaneous growth of high corporate and social benefits can be brought about. In order to overcome the corrosiveness of liquid acid catalysts to production equipment; often form a homogeneous body with raw materials and products, resulting in complicated post-reaction treatment; the process is not conducive to the realization of continuous production requirements and other shortcomings, solid acid gradually replaces traditional liquid acid catalysts It is an inevitable development direction to make it widely used in various fields of chemical production. Through the development of solid acid for nearly half a century, so far, a large number of chemical processes previously involved in liquid acid have been replaced by solid acid.

近年来,碳基磺酸化的固体酸作为一种新的,在水中能保持强的质子酸性和稳定性的固体酸而倍受关注。根据对文献的总结,对于碳基磺酸化的固体酸的合成大致有两种思路:第一种是对磺酸化的多环芳香化合物进行不完全碳化。在这种合成方法中,对芳香化合物的磺酸化是反应的第一个阶段,而后得到的磺酸化的芳香化合物在浓硫酸的作用下加热进行不完全碳化。但是,这种方法制备的固体酸在温度超过100℃的液相反应中,易发生芳香化台物的溶脱或者导致严重的失活。另外,在高温浓硫酸的条件下进行碳化的实验操作是十分危险的,因此也限制这种试验方法的推广;第二种的合成方法是对有机化合物先进行不完全碳化后再磺酸化。这种合成方法的提出是在基于安全合成的基础上,以低毒或无毒的物质为原料来制备目标材料。日常生活中常见的蔗糖、葡萄糖、淀粉、纤维素等都被用作碳源在高温下隔绝空气焙烧,使之分解成含有许多小的碳片的无定形碳。再通过磺酸化的方法在无定形碳上引入磺酸基团。相对第一种台成方法,该方法不仅简单而且安全性好。此外,能从自然界中大量存在的资源中合成具有实用价值的高活性的固体酸也是这一合成方法的优势所在。In recent years, carbon-based sulfonated solid acids have attracted much attention as a new solid acid that can maintain strong protic acidity and stability in water. According to the summary of the literature, there are roughly two ideas for the synthesis of carbon-based sulfonated solid acids: the first is the incomplete carbonization of sulfonated polycyclic aromatic compounds. In this synthesis method, the sulfonation of aromatic compounds is the first stage of the reaction, and then the obtained sulfonated aromatic compounds are heated under the action of concentrated sulfuric acid for incomplete carbonization. However, the solid acid prepared by this method is prone to elution or severe deactivation of the aromatized compound in the liquid phase reaction at a temperature exceeding 100 °C. In addition, the experimental operation of carbonization under the condition of high-temperature concentrated sulfuric acid is very dangerous, so it also limits the promotion of this test method; the second synthesis method is to carry out incomplete carbonization and then sulfonation of organic compounds. This synthesis method is proposed on the basis of safe synthesis, and the target material is prepared from low-toxic or non-toxic substances as raw materials. Sucrose, glucose, starch, and cellulose, which are common in daily life, are used as carbon sources and roasted at high temperatures in isolation from the air to decompose them into amorphous carbon containing many small carbon sheets. Then introduce sulfonic acid groups on the amorphous carbon by sulfonation. Compared with the first method, this method is not only simple but also safe. In addition, the ability to synthesize highly active solid acids with practical value from abundant resources in nature is also the advantage of this synthesis method.

Takagaki等以葡萄糖为原料制备了碳基固体酸(Acid-catalyzed reactions on flexiblepolycyclic aromatic carbon in amorphous carbon,Takagaki et al,Catal Today,2006);王督等以淀粉为原料制备了新型的碳基固体酸催化剂(碳基固体酸催化高酸值生物柴油原料降酸效果,王督等,农业工程学报,2009,25);马芳等人以玉米秸秆为原料制备了碳基固体酸催化剂(玉米秸秆固体酸催化剂及催化合成生物柴油的工艺研究,马芳等,西北农林科技大学学报,2010,38);李立强以煤基活性炭为载体,腐殖酸钠为碳源制备了复合碳基固体酸(复合碳基固体酸催化剂的制备和应用,李立强,宁夏大学硕士学位论文,2010)。Takagaki et al prepared carbon-based solid acid with glucose as raw material (Acid-catalyzed reactions on flexible polycyclic aromatic carbon in amorphous carbon, Takagaki et al, Catal Today, 2006); Wang Du et al prepared a new type of carbon-based solid acid with starch as raw material Catalyst (carbon-based solid acid catalyzed acid reduction effect of high acid value biodiesel feedstock, Wang Du et al., Journal of Agricultural Engineering, 2009, 25); Ma Fang et al. prepared carbon-based solid acid catalyst (corn stalk solid Acid catalyst and catalytic synthesis of biodiesel, Ma Fang et al., Journal of Northwest A&F University, 2010, 38); Li Liqiang prepared composite carbon-based solid acid (composite carbon-based solid acid (composite Preparation and Application of Carbon-Based Solid Acid Catalyst, Li Liqiang, Master Thesis of Ningxia University, 2010).

现有技术中,碳基固体酸的合成起始原料大多以蔗糖、葡萄糖、淀粉、纤维素,成本较高且造成资源浪费。在制备碳基固体酸的现有技术中,最终得到的产品大多为无孔的,比表面积低,机械性能差,这就限制了很多的反应物分子特别是那些大分子反应物接近催化剂表面的活性位。In the prior art, the starting materials for the synthesis of carbon-based solid acids are mostly sucrose, glucose, starch, and cellulose, which are costly and cause waste of resources. In the prior art of preparing carbon-based solid acids, the final products are mostly non-porous, with low specific surface area and poor mechanical properties, which limits many reactant molecules, especially those macromolecular reactants close to the surface of the catalyst. Active site.

发明内容Contents of the invention

本发明所要解决的技术问题是:现有技术中,碳基固体酸的制备所采用的原料成本较高且造成资源浪费;制备出的产品比表面积较低。The technical problem to be solved by the present invention is: in the prior art, the cost of raw materials used in the preparation of carbon-based solid acid is relatively high and causes waste of resources; the specific surface area of the prepared product is relatively low.

为了解决这一技术问题,本发明采用的技术方案是:本发明提供了一种碳基固体酸,该碳基固体酸是利用新鲜果壳为原料,制备而成的,所制得的碳基固体酸比表面积在1000m2/g以上,酸值在2.5mmol/L以上。In order to solve this technical problem, the technical solution adopted by the present invention is: the present invention provides a carbon-based solid acid, which is prepared by using fresh fruit shells as raw materials, and the prepared carbon-based solid acid The specific surface area of solid acid is above 1000m 2 /g, and the acid value is above 2.5mmol/L.

本发明还提供了一种制备上述碳基固体酸的方法,具体步骤为:The present invention also provides a method for preparing the above-mentioned carbon-based solid acid, the specific steps are:

(1)新鲜果壳的预处理:将风干的新鲜果壳用水反复洗至没有杂质存在,然后将洗干净的果壳放入烘箱中干燥,去除水分,筛选出品相较好的果壳,在破碎机中破碎至10~50目备用,作为优选:新鲜果壳为坚果的果壳,选自板栗壳、松子壳、核桃壳、椰子壳、菱角壳或花生壳中的1种或几种的组合物,(1) Pretreatment of fresh husks: Wash the air-dried fresh husks repeatedly with water until no impurities exist, then put the washed husks in an oven to dry, remove water, and screen out better-looking husks. Crushing in a crusher to 10-50 meshes for later use, preferably: fresh shells are nut shells, selected from one or more of chestnut shells, pine nut shells, walnut shells, coconut shells, water chestnut shells or peanut shells combination,

作为优选:破碎后的粒度为10~30目,进一步地:粒度为20目;Preferably: the particle size after crushing is 10-30 mesh, further: the particle size is 20 mesh;

(2)果壳的活化:按料液比1:2~20g/mL,将预处理后的果壳加入到活化剂浓度为20~50wt%的溶液中浸泡2~12h,然后将浸泡好的果壳在烘箱中烘干,以除去多余的水分,(2) Activation of fruit shells: According to the ratio of material to liquid 1:2 ~ 20g/mL, add the pretreated fruit shells into a solution with an activator concentration of 20 ~ 50wt% and soak for 2 ~ 12 hours, and then soak the soaked The husks are oven dried to remove excess moisture,

作为优选:料液比为1:2~10g/mL,进一步地:料液比为1:5g/mL,As preferred: the ratio of solid to liquid is 1:2~10g/mL, further: the ratio of solid to liquid is 1:5g/mL,

作为优选:活化剂为金属盐或无机酸,选自氯化锌、氯化铝、氯化铵、氯化钙、氯化氢、磷酸、硫酸、硝酸、硫化钾或铁盐中的1种或几种的组合物,进一步地:活化剂溶液为30wt%的氯化锌;Preferably: the activator is a metal salt or an inorganic acid, selected from one or more of zinc chloride, aluminum chloride, ammonium chloride, calcium chloride, hydrogen chloride, phosphoric acid, sulfuric acid, nitric acid, potassium sulfide or iron salt The composition, further: activator solution is the zinc chloride of 30wt%;

(3)果壳的碳化:将步骤(2)中活化得到的果壳,在保护气氛下加热至400~600℃,碳化2~15h,制备活性炭,将活性炭研磨成粉末,在酸溶液中煮沸,然后抽滤,用蒸馏水漂洗、干燥后得到活性炭材料,(3) Carbonization of fruit shells: heat the shells obtained in step (2) to 400-600°C under a protective atmosphere, carbonize them for 2-15 hours to prepare activated carbon, grind the activated carbon into powder, and boil in acid solution , then suction filtered, rinsed with distilled water, and dried to obtain an activated carbon material,

作为优选:保护气氛选自氮气、二氧化碳、氩气、氦气或氖气中的1种或几种组合气氛,进一步地:保护气氛为氮气和/或二氧化碳,Preferably: the protective atmosphere is selected from one or more combination atmospheres of nitrogen, carbon dioxide, argon, helium or neon, further: the protective atmosphere is nitrogen and/or carbon dioxide,

作为优选:加热温度为400~500℃,进一步地:温度为450℃,As preferably: heating temperature is 400~500 ℃, further: temperature is 450 ℃,

作为优选:碳化时间为2~10h,进一步地:碳化时间为2~6h,Preferably: the carbonization time is 2 to 10 hours, further: the carbonization time is 2 to 6 hours,

作为优选:酸溶液选自盐酸、磷酸、柠檬酸、硫酸或草酸中的1种或几种,其浓度为0.5~1.5mol/L,进一步地:酸溶液为1mol/L的盐酸;Preferably: the acid solution is selected from one or more of hydrochloric acid, phosphoric acid, citric acid, sulfuric acid or oxalic acid, and its concentration is 0.5-1.5 mol/L, further: the acid solution is 1 mol/L hydrochloric acid;

(4)活性炭材料的磺化:将步骤(3)中得到的活性炭材料,在80~200℃条件下,经磺化剂磺化6~15h,磺化后的混合液缓缓地倒入冷水中并不断搅拌,抽滤、烘干所得黑色固体粉末即为碳基固体酸,(4) Sulfonation of activated carbon material: The activated carbon material obtained in step (3) is sulfonated with a sulfonating agent for 6-15 hours at 80-200°C, and the sulfonated mixture is slowly poured into cold water and stirring continuously, the black solid powder obtained by suction filtration and drying is the carbon-based solid acid.

作为优选:磺化温度为120~200℃,进一步地:磺化温度为150℃,Preferably: the sulfonation temperature is 120-200°C, further: the sulfonation temperature is 150°C,

作为优选:磺化时间为6~10h,进一步地:磺化时间为8~10h,Preferably: the sulfonation time is 6-10h, further: the sulfonation time is 8-10h,

作为优选:磺化剂选自浓硫酸、发烟硫酸、氯磺酸或氨基磺酸中的1种或几种的组合,进一步地:磺化剂选自浓硫酸、发烟硫酸和氯磺酸1种或几种的组合,再进一步:磺化剂为浓硫酸。Preferably: the sulfonating agent is selected from one or more combinations of concentrated sulfuric acid, oleum, chlorosulfonic acid or sulfamic acid, further: the sulfonating agent is selected from concentrated sulfuric acid, oleum and chlorosulfonic acid A combination of one or more, and further: the sulfonating agent is concentrated sulfuric acid.

本发明具有如下有益效果:The present invention has following beneficial effect:

选用新鲜果壳作为原料,制备碳基固体酸,降低了固体酸的制备成本,开辟了果壳高质化的新途径,有效地提高了对果壳的利用率,符合了国家目前可持续发展方针。相比较现有技术中,以稠环化合物为原料制备碳基固体酸的反应条件安全,产品色泽好,制得的碳基固体酸具有较大的比表面积,具有良好的催化效应。Using fresh fruit shells as raw materials to prepare carbon-based solid acids reduces the cost of solid acid preparation, opens up a new way to improve the quality of fruit shells, and effectively improves the utilization of fruit shells, which is in line with the current sustainable development of the country. policy. Compared with the prior art, the reaction conditions for preparing carbon-based solid acid from condensed ring compounds are safe, the product has good color, and the prepared carbon-based solid acid has a large specific surface area and good catalytic effect.

附图说明Description of drawings

图1是本发明所述通过新鲜果壳制备碳基固体酸的方法的工艺流程图。Fig. 1 is the process flow diagram of the method for preparing carbon-based solid acid by fresh fruit shell of the present invention.

具体实施方式Detailed ways

为便于理解本发明,本发明列举实施例如下。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。In order to facilitate understanding of the present invention, the present invention enumerates the following examples. It should be clear to those skilled in the art that the embodiments are only for helping to understand the present invention, and should not be regarded as specific limitations on the present invention.

实施例1:Example 1:

新鲜果壳的预处理:Pretreatment of fresh husks:

取新鲜的河南信阳板栗壳(黄棕色),用水反复洗去板栗壳表面的灰尘及杂质,直至洗出的水清澈透明,然后把板栗壳放入120℃的烘箱中,干燥2h,去除板栗壳中的水分。在烘干的板栗壳中筛选品相较好的板栗壳,在破碎机中破碎至10-30目,称取200g,计为果壳1。Take fresh chestnut shells (yellow brown) from Xinyang, Henan, and repeatedly wash off the dust and impurities on the surface of the chestnut shells with water until the washed water is clear and transparent, then put the chestnut shells in an oven at 120°C, dry for 2 hours, and remove the chestnut shells moisture in. Screen the chestnut shells with better appearance from the dried chestnut shells, crush them in a crusher to 10-30 mesh, weigh 200g, and count them as shell 1.

实施例2:Example 2:

新鲜果壳的预处理:Pretreatment of fresh husks:

取新鲜的吉林通化松子壳(棕色),用水反复洗去松子壳表面的灰尘及杂质,直至洗出的水清澈透明,然后把松子壳放入120℃的烘箱中,干燥2h,去除松子壳中的水分。在烘干的松子壳中筛选品相较好的松子壳,在破碎机中破碎至10-30目,称取200g,计为果壳2。Take fresh Jilin Tonghua pine nut shells (brown), wash the dust and impurities on the surface of the pine nut shells repeatedly with water until the washed water is clear and transparent, then put the pine nut shells in an oven at 120°C, dry for 2 hours, and remove the pine nut shells of moisture. Screen the pine nut shells with better appearance from the dried pine nut shells, crush them in a crusher to 10-30 mesh, weigh 200g, and count them as shell 2.

实施例3:Example 3:

新鲜果壳的预处理:Pretreatment of fresh husks:

取新鲜的新疆库车核桃壳(黄褐色),用水反复洗去核桃壳表面的灰尘及杂质,直至洗出的水清澈透明,然后把核桃壳放入120℃的烘箱中,干燥2h,去除核桃壳中的水分。在烘干的核桃壳中筛选品相较好的核桃壳,在破碎机中破碎至10-30目,称取200g,计为果壳3。Take fresh Xinjiang Kuqa walnut shells (yellow brown), wash the dust and impurities on the surface of the walnut shells repeatedly with water until the washed water is clear and transparent, then put the walnut shells in an oven at 120°C and dry for 2 hours to remove the walnuts moisture in the shell. Screen the walnut shells with better appearance from the dried walnut shells, crush them in a crusher to 10-30 mesh, weigh 200g, and count them as shell 3.

实施例4:Example 4:

新鲜果壳的预处理:Pretreatment of fresh husks:

取新鲜的山东鲁花花生壳(黄褐色),用水反复洗去花生壳表面的灰尘及杂质,直至洗出的水清澈透明,然后把花生壳放入120℃的烘箱中,干燥2h,去除花生壳中的水分。在烘干的花生壳中筛选品相较好的花生壳,在破碎机中破碎至10-30目,称取200g,计为果壳4。Take fresh Shandong Luhua peanut shells (yellow brown), wash the dust and impurities on the surface of the peanut shells repeatedly with water until the washed water is clear and transparent, then put the peanut shells in an oven at 120°C, dry for 2 hours, and remove the peanut shells. moisture in the shell. Screen the peanut shells with better appearance from the dried peanut shells, crush them in a crusher to 10-30 mesh, weigh 200g, and count them as shell 4.

实施例5:Example 5:

选取经过预处理的新鲜果壳为原料进行活化剂溶液浸泡,然后保护气氛下碳化活化制备活性碳材料。Pretreated fresh fruit shells were selected as raw materials to be soaked in an activator solution, and then carbonized and activated under a protective atmosphere to prepare activated carbon materials.

在400mL烧杯中加入43g活化剂,向烧杯中倒入100mL蒸馏水,搅拌溶解,在活化剂溶液中加入预处理的新鲜果壳30g,搅拌5min,常温下浸渍8h。然后将浸渍好的样品放入110℃烘箱中烘干2h,去除水分。将烘干后的样品放在干锅中,放入管式电炉中,在氮气的保护气氛下,450℃下经碳化活化3h制备得活性碳。待管式电炉冷却后,取出其中的活性炭,研磨,用1mol/L的盐酸煮沸30min,然后用蒸馏水洗至PH为7左右,烘干即得活性炭材料。Add 43g of activator to a 400mL beaker, pour 100mL of distilled water into the beaker, stir to dissolve, add 30g of pretreated fresh fruit shells to the activator solution, stir for 5min, and soak for 8h at room temperature. Then put the impregnated sample in an oven at 110°C for 2 hours to remove moisture. The dried samples were placed in a dry pot, placed in a tube electric furnace, and activated carbon was prepared by carbonization and activation at 450°C for 3 hours under a nitrogen protective atmosphere. After the tube-type electric furnace is cooled, take out the activated carbon, grind it, boil it with 1mol/L hydrochloric acid for 30 minutes, then wash it with distilled water until the pH is about 7, and dry it to obtain the activated carbon material.

选取果壳1为原料,用氯化锌溶液作为活化剂浸渍,制得活性炭1;Choose fruit shell 1 as a raw material, impregnate it with zinc chloride solution as an activator, and prepare activated carbon 1;

选取果壳1为原料,用磷酸溶液作为活化剂浸渍,制得活性炭2;Choose fruit shell 1 as raw material, impregnate with phosphoric acid solution as activator, make activated carbon 2;

选取果壳2为原料,用氯化锌溶液作为活化剂浸渍,制得活性炭3;Selecting the fruit shell 2 as a raw material, impregnating it with a zinc chloride solution as an activator to obtain activated carbon 3;

选取果壳2为原料,用磷酸溶液作为活化剂浸渍,制得活性炭4;Select the fruit shell 2 as a raw material, impregnate it with a phosphoric acid solution as an activator, and obtain activated carbon 4;

选取果壳3为原料,用氯化锌溶液作为活化剂浸渍,制得活性炭5;Selecting the fruit shell 3 as a raw material, impregnating it with a zinc chloride solution as an activator to obtain activated carbon 5;

选取果壳3为原料,用磷酸溶液作为活化剂浸渍,制得活性炭6;Select the fruit shell 3 as a raw material, impregnate it with a phosphoric acid solution as an activator, and obtain activated carbon 6;

选取果壳4为原料,用氯化锌溶液作为活化剂浸渍,制得活性炭7;Choose fruit shell 4 as raw material, use zinc chloride solution as activator impregnation, make activated carbon 7;

实施例6:Embodiment 6:

选取活性炭1为原料制备碳基固体酸:Select activated carbon 1 as raw material to prepare carbon-based solid acid:

在250mL的四口烧瓶中加入活性碳10g,倒入浓硫酸(98%浓硫酸)100mL,将四口烧瓶放入油浴锅中,在四口烧瓶的一处接口接入氮气,另一接口作为氮气的出口,氮气出口接入水中。油浴升温至120℃,磺化8h。反应结束后,将混合液慢慢倒入冷水中,并不断搅拌,冷却后抽滤溶液,用蒸馏水洗涤黑色固体至中性,真空干燥5h,最终制得碳基固体酸。采用X线衍射(XRD)、红外光谱(FT-IR)的手段对产品进行表征,结果表明,碳基固体酸是由连接有磺酸基(-SO3H)的芳香碳片组成的无定形碳;通过氮气吸附BET法测得比表面积为1269m2/g,通过NaOH溶液滴定法测得酸密度为2.83mmol/L。Add 10g of activated carbon into a 250mL four-necked flask, pour 100mL of concentrated sulfuric acid (98% concentrated sulfuric acid), put the four-necked flask into an oil bath, connect nitrogen gas to one port of the four-necked flask, and As the nitrogen outlet, the nitrogen outlet is connected to the water. The oil bath was heated to 120°C for sulfonation for 8h. After the reaction, the mixture was slowly poured into cold water with constant stirring. After cooling, the solution was filtered with suction, the black solid was washed with distilled water until neutral, and dried in vacuum for 5 hours to finally obtain a carbon-based solid acid. The product was characterized by means of X-ray diffraction (XRD) and infrared spectroscopy (FT-IR). The results showed that the carbon-based solid acid is an amorphous form composed of aromatic carbon sheets connected with sulfonic acid groups (-SO 3 H). Carbon; the specific surface area measured by nitrogen adsorption BET method is 1269m 2 /g, and the acid density measured by NaOH solution titration method is 2.83mmol/L.

实施例7:Embodiment 7:

选取活性碳2为原料制备碳基固体酸:Select activated carbon 2 as raw material to prepare carbon-based solid acid:

在250mL的四口烧瓶中加入活性碳10g,倒入发烟硫酸135mL,将四口烧瓶放入油浴锅中,在四口烧瓶的一处接口接入氮气,另一接口作为氮气的出口,氮气出口接入水中。油浴升温至130℃,磺化8h。处理方法同实施例6,最终制得碳基固体酸。采用X线衍射(XRD)、红外光谱(FT-IR)的手段对产品进行表征,结果表明,碳基固体酸是由连接有磺酸基(-SO3H)的芳香碳片组成的无定形碳;通过氮气吸附BET法测得比表面积为1127m2/g,通过NaOH溶液滴定法测得酸密度为2.48mmol/L。Add 10g of activated carbon into a 250mL four-necked flask, pour 135mL of fuming sulfuric acid into it, put the four-necked flask into an oil bath, connect nitrogen to one port of the four-necked flask, and use the other port as the nitrogen outlet, The nitrogen outlet is connected to the water. The oil bath was heated to 130°C for sulfonation for 8h. The treatment method is the same as in Example 6, and finally a carbon-based solid acid is obtained. The product was characterized by means of X-ray diffraction (XRD) and infrared spectroscopy (FT-IR). The results showed that the carbon-based solid acid is an amorphous form composed of aromatic carbon sheets connected with sulfonic acid groups (-SO 3 H). Carbon; the specific surface area measured by nitrogen adsorption BET method is 1127m 2 /g, and the acid density measured by NaOH solution titration method is 2.48mmol/L.

实施例8:Embodiment 8:

选取活性碳3为原料制备碳基固体酸:Select activated carbon 3 as raw material to prepare carbon-based solid acid:

在250mL的四口烧瓶中加入活性碳10g,倒入浓硫酸(98%浓硫酸)150mL,将四口烧瓶放入油浴锅中,在四口烧瓶的一处接口接入氮气,另一接口作为氮气的出口,氮气出口接入水中。油浴升温至150℃,磺化9h。处理方法同实施例6,最终制得碳基固体酸。采用X线衍射(XRD)、红外光谱(FT-IR)的手段对产品进行表征,结果表明,碳基固体酸是由连接有磺酸基(-SO3H)的芳香碳片组成的无定形碳;通过氮气吸附BET法测得比表面积为1326m2/g,通过NaOH溶液滴定法测得酸密度为3.52mmol/L。Add 10g of activated carbon to a 250mL four-necked flask, pour 150mL of concentrated sulfuric acid (98% concentrated sulfuric acid), put the four-necked flask into an oil bath, connect nitrogen gas to one port of the four-necked flask, and As the nitrogen outlet, the nitrogen outlet is connected to the water. The oil bath was heated to 150°C for sulfonation for 9h. The treatment method is the same as in Example 6, and finally a carbon-based solid acid is obtained. The product was characterized by means of X-ray diffraction (XRD) and infrared spectroscopy (FT-IR). The results showed that the carbon-based solid acid is an amorphous form composed of aromatic carbon sheets connected with sulfonic acid groups (-SO 3 H). Carbon; the specific surface area measured by nitrogen adsorption BET method is 1326m 2 /g, and the acid density measured by NaOH solution titration method is 3.52mmol/L.

实施例9:Embodiment 9:

选取活性碳4为原料制备碳基固体酸:Select activated carbon 4 as raw material to prepare carbon-based solid acid:

在250mL的四口烧瓶中加入活性碳10g,倒入发烟硫酸80mL,将四口烧瓶放入油浴锅中,在四口烧瓶的一处接口接入氮气,另一接口作为氮气的出口,氮气出口接入水中。油浴升温至150℃,磺化9h。处理方法同实施例6,最终制得碳基固体酸。采用X线衍射(XRD)、红外光谱(FT-IR)的手段对产品进行表征,结果表明,碳基固体酸是由连接有磺酸基(-SO3H)的芳香碳片组成的无定形碳;通过氮气吸附BET法测得比表面积为1274m2/g,通过NaOH溶液滴定法测得酸密度为1.93mmol/L。Add 10g of activated carbon to a 250mL four-necked flask, pour 80mL of fuming sulfuric acid into it, put the four-necked flask into an oil bath, connect nitrogen to one port of the four-necked flask, and use the other port as the nitrogen outlet. The nitrogen outlet is connected to the water. The oil bath was heated to 150°C for sulfonation for 9h. The treatment method is the same as in Example 6, and finally a carbon-based solid acid is obtained. The product was characterized by means of X-ray diffraction (XRD) and infrared spectroscopy (FT-IR). The results showed that the carbon-based solid acid is an amorphous form composed of aromatic carbon sheets connected with sulfonic acid groups (-SO 3 H). Carbon; the specific surface area measured by nitrogen adsorption BET method is 1274m 2 /g, and the acid density measured by NaOH solution titration method is 1.93mmol/L.

实施例10:Example 10:

选取活性碳5为原料制备碳基固体酸:Select activated carbon 5 as raw material to prepare carbon-based solid acid:

在250mL的四口烧瓶中加入活性碳10g,倒入浓硫酸(98%浓硫酸)110mL,将四口烧瓶放入油浴锅中,在四口烧瓶的一处接口接入氮气,另一接口作为氮气的出口,氮气出口接入水中。油浴升温至160℃,磺化10h。处理方法同实施例6,最终制得碳基固体酸。采用X线衍射(XRD)、红外光谱(FT-IR)的手段对产品进行表征,结果表明,碳基固体酸是由连接有磺酸基(-SO3H)的芳香碳片组成的无定形碳;通过氮气吸附BET法测得比表面积为982m2/g,通过NaOH溶液滴定法测得酸密度为1.63mmol/L。Add 10g of activated carbon into a 250mL four-necked flask, pour 110mL of concentrated sulfuric acid (98% concentrated sulfuric acid), put the four-necked flask into an oil bath, connect nitrogen gas to one port of the four-necked flask, and As the nitrogen outlet, the nitrogen outlet is connected to the water. The temperature of the oil bath was raised to 160°C for sulfonation for 10 hours. The treatment method is the same as in Example 6, and finally a carbon-based solid acid is obtained. The product was characterized by means of X-ray diffraction (XRD) and infrared spectroscopy (FT-IR). The results showed that the carbon-based solid acid is an amorphous form composed of aromatic carbon sheets connected with sulfonic acid groups (-SO 3 H). Carbon; the specific surface area measured by nitrogen adsorption BET method is 982m 2 /g, and the acid density measured by NaOH solution titration method is 1.63mmol/L.

实施例11:Example 11:

选取活性碳6为原料制备碳基固体酸:Select activated carbon 6 as raw material to prepare carbon-based solid acid:

在250mL的四口烧瓶中加入活性碳10g,倒入发烟硫酸95mL,将四口烧瓶放入油浴锅中,在四口烧瓶的一处接口接入氮气,另一接口作为氮气的出口,氮气出口接入水中。油浴升温至180℃,磺化8h。处理方法同实施例6,最终制得碳基固体酸。采用X线衍射(XRD)、红外光谱(FT-IR)的手段对产品进行表征,结果表明,碳基固体酸是由连接有磺酸基(-SO3H)的芳香碳片组成的无定形碳;通过氮气吸附BET法测得比表面积为1073m2/g,通过NaOH溶液滴定法测得酸密度为2.47mmol/L。Add 10g of activated carbon into a 250mL four-necked flask, pour oleum 95mL, put the four-necked flask into an oil bath, connect nitrogen to one port of the four-necked flask, and use the other port as the nitrogen outlet. The nitrogen outlet is connected to the water. The oil bath was heated to 180°C for sulfonation for 8h. The treatment method is the same as in Example 6, and finally a carbon-based solid acid is obtained. The product was characterized by means of X-ray diffraction (XRD) and infrared spectroscopy (FT-IR). The results showed that the carbon-based solid acid is an amorphous form composed of aromatic carbon sheets connected with sulfonic acid groups (-SO 3 H). Carbon; the specific surface area measured by nitrogen adsorption BET method is 1073m 2 /g, and the acid density measured by NaOH solution titration method is 2.47mmol/L.

实施例12:Example 12:

选取活性碳7为原料制备碳基固体酸:Select activated carbon 7 as raw material to prepare carbon-based solid acid:

在250mL的四口烧瓶中加入活性碳10g,倒入浓硫酸(98%浓硫酸)120mL,将四口烧瓶放入油浴锅中,在四口烧瓶的一处接口接入氮气,另一接口作为氮气的出口,氮气出口接入水中。油浴升温至200℃,磺化9h。处理方法同实施例6,最终制得碳基固体酸。采用X线衍射(XRD)、红外光谱(FT-IR)的手段对产品进行表征,结果表明,碳基固体酸是由连接有磺酸基(-SO3H)的芳香碳片组成的无定形碳;通过氮气吸附BET法测得比表面积为856m2/g,通过NaOH溶液滴定法测得酸密度为1.68mmol/L。Add 10g of activated carbon into a 250mL four-necked flask, pour 120mL of concentrated sulfuric acid (98% concentrated sulfuric acid), put the four-necked flask into an oil bath, connect nitrogen gas to one port of the four-necked flask, and As the nitrogen outlet, the nitrogen outlet is connected to the water. The oil bath was heated to 200°C for sulfonation for 9h. The treatment method is the same as in Example 6, and finally a carbon-based solid acid is obtained. The product was characterized by means of X-ray diffraction (XRD) and infrared spectroscopy (FT-IR). The results showed that the carbon-based solid acid is an amorphous form composed of aromatic carbon sheets connected with sulfonic acid groups (-SO 3 H). Carbon; the specific surface area measured by nitrogen adsorption BET method is 856m 2 /g, and the acid density measured by NaOH solution titration method is 1.68mmol/L.

实施例13:Example 13:

将实例6中的碳基固体酸用于催化制备生物柴油,在250mL的三口烧瓶中加入大豆油和甲醇(摩尔比1:3),碳基固体酸加入量为大豆油和甲醇总质量的8%,在65℃下反应2h,生物柴油转化率达到93.6%。The carbon-based solid acid in Example 6 is used to catalyze the preparation of biodiesel, and soybean oil and methanol (molar ratio 1:3) are added to a 250mL three-necked flask. The amount of carbon-based solid acid added is 8% of the total mass of soybean oil and methanol. %, reacted at 65°C for 2 hours, and the conversion rate of biodiesel reached 93.6%.

实施例14:Example 14:

将实施例7中的碳基固体酸用于催化制备乙酸乙酯,在250mL的三口烧瓶中加入乙酸和乙醇(摩尔比1:1),碳基固体酸加入量为乙酸和乙醇总质量的8%,在65℃下反应2h,乙酸乙酯产率达到89.3%。The carbon-based solid acid in Example 7 was used to catalyze the preparation of ethyl acetate, and acetic acid and ethanol (molar ratio 1:1) were added to a 250mL three-necked flask. The amount of carbon-based solid acid added was 8% of the total mass of acetic acid and ethanol. %, reacted at 65°C for 2 hours, and the yield of ethyl acetate reached 89.3%.

实施例15:Example 15:

将实施例8中的碳基固体酸用于催化制备α-蒎烯异构化反应,催化剂:α-蒎烯=1:20(wt),在165℃下反应4h,α-蒎烯转化率达到94.87%。The carbon-based solid acid in Example 8 is used to catalyze the isomerization reaction of α-pinene, catalyst: α-pinene=1:20 (wt), react at 165°C for 4h, the conversion rate of α-pinene Reached 94.87%.

实施例16:Example 16:

将实施例12中的碳基固体酸用于催化制备环氧脂肪酸酯,在250mL的三口烧瓶中加入脂肪酸甲酯,恒速滴加占脂肪酸甲酯质量30%的双氧水,碳基固体酸加入量为脂肪酸甲酯质量的8%,在80℃下反应6h,环氧值达到4.4%。The carbon-based solid acid in Example 12 is used to catalyze the preparation of epoxy fatty acid esters, add fatty acid methyl esters in a 250mL three-necked flask, add hydrogen peroxide that accounts for 30% of the quality of fatty acid methyl esters dropwise at a constant rate, and add the carbon-based solid acids The amount is 8% of the mass of fatty acid methyl ester, reacted at 80°C for 6 hours, and the epoxy value reaches 4.4%.

本发明所述的通过新鲜果壳制备碳基固体酸的方法提供一种植物果壳的废物利用方法,所述方法制备得到的碳基固体酸的性能指标需要根据所应用的领域进行检测,检测合格后才能用于相关领域。本发明所述方法制备得到的碳基固体酸优选用于化工、洗涤剂、农牧业及纺织等行业,不推荐直接用于食品、医药、化妆品等领域。如需要将本发明制备得到的碳基固体酸应用于食品、医药、化妆品等领域,应严格遵守相关的法律法规,将碳基固体酸进行全面的检测,或进行进一步处理,消除其中对人健康不利的因素,才能用于这些领域。The method for preparing carbon-based solid acid from fresh fruit shells of the present invention provides a waste utilization method of plant fruit shells. The performance index of the carbon-based solid acid prepared by the method needs to be tested according to the field of application. Only after passing the qualification can it be used in related fields. The carbon-based solid acid prepared by the method of the present invention is preferably used in industries such as chemical industry, detergent, agriculture and animal husbandry, and textiles, and is not recommended to be directly used in fields such as food, medicine, and cosmetics. If it is necessary to apply the carbon-based solid acid prepared by the present invention to the fields of food, medicine, cosmetics, etc., relevant laws and regulations should be strictly followed, and the carbon-based solid acid should be fully tested or further processed to eliminate the harmful effects on human health. Unfavorable factors can be used in these fields.

Claims (1)

1. a preparation method for carbon-based solid acid, is characterized in that: described carbon-based solid acid utilizes fresh shell District, Xinyang Area, Henan Province chestnut shell to be prepared from for raw material, and obtained carbon-based solid acid specific area is 1127m 2/ g, acid number is 2.48mmol/L,
The concrete steps of described preparation method are,
(1) pretreatment of fresh shell: air-dry fresh shell District, Xinyang Area, Henan Province chestnut shell water is washed till repeatedly and does not have impurity, then the shell of wash clean is put into baking oven dry, remove moisture, the shell that screening product is compared, in disintegrating machine, be crushed to 10 ~ 30 orders for subsequent use;
(2) activation of shell: add 43g activator phosphoric acid in 400mL beaker, 100mL distilled water is poured in beaker, stirring and dissolving obtains activator solution, add through the pretreated fresh shell District, Xinyang Area, Henan Province chestnut shell 30g of step (1) in described activator solution, stir 5min, flood 8h under normal temperature, then the sample flooded is put into 110 DEG C of baking ovens and dry 2h, remove moisture;
(3) carbonization of shell: the shell obtained will be activated in step (2), 450 DEG C are heated under nitrogen protection atmosphere, carbonization 3h, prepare active carbon, by active carbon grind into powder, in the hydrochloric acid solution of 1mol/L, boil 30min, then suction filtration, obtain absorbent charcoal material with after distilled water rinsing, drying;
(4) sulfonation of absorbent charcoal material: by the absorbent charcoal material obtained in step (3), under 130 DEG C of conditions, through oleum sulfonation 8h, the solid-liquid ratio of absorbent charcoal material and sulfonating agent solution is 1:13.5g/mL, mixed liquor after sulfonation is gently poured in cold water and is also constantly stirred, and suction filtration, oven dry gained black solid powder are carbon-based solid acid.
CN201210547711.1A 2012-12-17 2012-12-17 Carbon-based solid acid and preparation method thereof Expired - Fee Related CN103084187B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210547711.1A CN103084187B (en) 2012-12-17 2012-12-17 Carbon-based solid acid and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210547711.1A CN103084187B (en) 2012-12-17 2012-12-17 Carbon-based solid acid and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103084187A CN103084187A (en) 2013-05-08
CN103084187B true CN103084187B (en) 2015-07-01

Family

ID=48197616

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210547711.1A Expired - Fee Related CN103084187B (en) 2012-12-17 2012-12-17 Carbon-based solid acid and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103084187B (en)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104418423B (en) * 2013-08-23 2016-01-20 中国石油天然气股份有限公司 Method for treating reverse osmosis concentrated water by catalytic ozonation
CN103691483B (en) * 2013-12-16 2015-04-29 太原理工大学 Carbon-based solid acid catalyst and preparation method thereof
CN103709010B (en) * 2014-01-06 2016-01-20 河北工业大学 A kind of by tetrahydrobenzene, carboxylic acid and water Reactive Synthesis hexalin method
CN103990471B (en) * 2014-05-05 2016-05-18 江苏科技大学 A kind of preparation method of ramulus mori based solid acid
CN104475127A (en) * 2014-11-18 2015-04-01 成都理想财富投资咨询有限公司 Method for preparing solid acid catalyst
CN104399497B (en) * 2014-11-18 2017-03-01 马晓均 The acid catalyst of fry starch of konjak
CN104941663A (en) * 2015-04-09 2015-09-30 广东工业大学 Preparation method of high acid content solid acid catalyst
CN104815677B (en) * 2015-04-25 2017-05-03 哈尔滨工业大学 Preparation method of solid catalyst for cast nylon subcritical hydrolysis
CN105197929A (en) * 2015-09-30 2015-12-30 江苏通瑞环保科技发展有限公司 Method for preparing activated carbon with large specific surface area from sawdust
CN105195136A (en) * 2015-10-01 2015-12-30 常州市奥普泰科光电有限公司 Method for improving catalytic activity of palladium-carbon catalyst
CN106938196A (en) 2015-12-10 2017-07-11 财团法人工业技术研究院 Solid catalyst and preparation method of saccharide using the same
CN105618025B (en) * 2016-01-14 2018-04-17 北京道顺国际技术开发有限责任公司 A kind of method that low-temperature catalyzed organic waste of sulfonation charcoal prepares biomass carbon
CN105771891B (en) * 2016-03-24 2018-12-25 宁波德纳希环保科技有限公司 It is a kind of for adsorbing the modified activated carbon preparation method of dioxin
CN105771576B (en) * 2016-03-24 2018-09-11 宁波德纳希环保科技有限公司 A kind of technique removing bioxin using modified activated carbon
CN106380394B (en) * 2016-08-26 2018-11-06 南京工业大学 Preparation method of carbon-silicon solid acid catalyst and application of carbon-silicon solid acid catalyst in extraction of organic acid in fermentation liquor
CN106492839A (en) * 2016-08-29 2017-03-15 中国科学院西双版纳热带植物园 A kind of magnetic catalyst prepared as carbon source carrier with Jatropha curcus shell and its application
CN106861719B (en) * 2017-03-07 2019-07-23 湖南师范大学 A kind of preparation method of superelevation sulfonic acid density biomass carbon solid acid
CN107876100B (en) * 2017-10-24 2020-07-28 安徽省福泰精细化工有限责任公司 Preparation method of solid acid catalyst for preparing methylal
CN108097312A (en) * 2017-12-19 2018-06-01 河南金土地科技服务有限公司 A kind of preparation method and applications of lignocellulosic based solid acid catalyst
CN108793157B (en) * 2018-08-24 2020-04-24 山东大学 Method for preparing activated carbon from wetland fruit shells and hydrolyzed feather meal mixed base carbon precursor
CN109225275A (en) * 2018-11-06 2019-01-18 绍兴文理学院 A kind of preparation method of carbon-based solid acid
CN109603905B (en) * 2018-12-05 2022-03-25 福州大学 Pennisetum hydridum porous carbon-based solid catalyst and preparation method thereof
CN110846194A (en) * 2019-11-21 2020-02-28 广西民族大学 Method for improving quality of white spirit by using carbon-based solid acid
CN118579780B (en) * 2024-07-12 2024-12-17 江苏乾汇和环保再生有限公司 Preparation method and preparation device of supported activated carbon

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101298566A (en) * 2008-06-27 2008-11-05 大连理工大学 Method for preparing biocarbon solid acid catalyst and biodiesel
CN101618341A (en) * 2009-07-27 2010-01-06 西北农林科技大学 Carbon-based solid acid catalyst and preparation method thereof
CN101670299A (en) * 2009-10-16 2010-03-17 青岛生物能源与过程研究所 Preparation method of nanometer carbon-based solid acid

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5528036B2 (en) * 2008-09-12 2014-06-25 公益財団法人神奈川科学技術アカデミー Carbon-based solid acid and method for producing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101298566A (en) * 2008-06-27 2008-11-05 大连理工大学 Method for preparing biocarbon solid acid catalyst and biodiesel
CN101618341A (en) * 2009-07-27 2010-01-06 西北农林科技大学 Carbon-based solid acid catalyst and preparation method thereof
CN101670299A (en) * 2009-10-16 2010-03-17 青岛生物能源与过程研究所 Preparation method of nanometer carbon-based solid acid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
由生物质木粉制备高比表面积炭基固体酸催化剂的研究;黄苗;《西北农林科技大学硕士学位论文》;20111231;第14-18页第2.5-2.7节以及第20-25页第3.4节 *

Also Published As

Publication number Publication date
CN103084187A (en) 2013-05-08

Similar Documents

Publication Publication Date Title
CN103084187B (en) Carbon-based solid acid and preparation method thereof
CN103657689B (en) A kind of solid acid catalyst and preparation method thereof and at catalyzed conversion biomass-making for the application in lactic acid
CN100467372C (en) Preparation method of biomass high specific surface area microporous carbon material
CN107099314B (en) A method for preparing long-chain fatty acids and nitrogen-doped carbon from agricultural and forestry waste
CN100491244C (en) A method for preparing activated carbon from wheat straw
CN102275917A (en) Preparation method of high-specific surface area mangosteen shell active carbon rich in mesopores
CN104724699A (en) Method for preparing biomass graphene employing cellulose as raw material
CN102583311A (en) Method for preparing biomass carbon by utilizing agricultural and forestry waste
CN108516548A (en) A kind of preparation method of high mesoporous rate activated carbon and its activated carbon of acquisition
EP3587431B1 (en) Method for preparing levoglucosenone by catalytic pyrolysis of biomass
CN102145280A (en) Method for preparing rice hull active carbon/silicon dioxide/titanium dioxide composite material
CN114308132B (en) Protonated CdS-COF-366-M composite photocatalyst and preparation method thereof
WO2022134443A1 (en) Carbon-based solid acid catalyst, and method for preparing same and method for applying same to biomass hydrothermal conversion
CN104998686A (en) Preparing method and application of nitro phthalocyanine zinc/sulfur-containing carbon nitride composite catalyst
CN102381703A (en) Method for preparing activated carbon by using flax straws
CN102583367A (en) Preparation technology of mesopore-rich active carbon with high specific surface area
CN106744915A (en) A kind of cellulose base graphitized material and preparation method thereof
CN107892291A (en) A kind of method that grapheme material is prepared using discarded object coconut husk as raw material
CN112023924A (en) Preparation method and application of copper-based catalyst loaded with rubber seed shell porous activated carbon
CN111408349A (en) Preparation method of straw-based magnetic porous biochar
CN110586131A (en) Preparation method of sulfonated coconut shell activated carbon solid acid catalyst
CN108043407A (en) A kind of Co/ sepiolites catalyst and its preparation method and application
CN104383927B (en) The Catalysts and its preparation method of a kind of methane and CO 2 reformation preparing synthetic gas
CN106423214A (en) Method for preparing carbon-based solid acid with high specific surface area and high acid content from corncob hydrolysis residues
CN112844409B (en) Preparation method and application of biomass straw-based magnetic solid acid catalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20201201

Address after: 215000 No. 8 Jinfeng Road, hi tech Zone, Suzhou, Jiangsu, Suzhou

Patentee after: Suzhou science and Technology City Biomedical Technology Development Co.,Ltd.

Address before: Unit 2414-2416, main building, no.371, Wushan Road, Tianhe District, Guangzhou City, Guangdong Province

Patentee before: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd.

Effective date of registration: 20201201

Address after: Unit 2414-2416, main building, no.371, Wushan Road, Tianhe District, Guangzhou City, Guangdong Province

Patentee after: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd.

Address before: 213164 Jiangsu city of Changzhou province Changzhou University Wujin District Gehu Lake Road No. 1

Patentee before: CHANGZHOU University

CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: 215000 No.8, Jinfeng Road, science and Technology City, Suzhou high tech Zone, Suzhou City, Jiangsu Province

Patentee after: Suzhou Medical Device Industry Development Co.,Ltd.

Address before: 215000 No.8, Jinfeng Road, science and Technology City, Suzhou high tech Zone, Suzhou City, Jiangsu Province

Patentee before: Suzhou science and Technology City Biomedical Technology Development Co.,Ltd.

Address after: 215000 No.8, Jinfeng Road, science and Technology City, Suzhou high tech Zone, Suzhou City, Jiangsu Province

Patentee after: Suzhou Medical Device Industry Development Group Co.,Ltd.

Address before: 215000 No.8, Jinfeng Road, science and Technology City, Suzhou high tech Zone, Suzhou City, Jiangsu Province

Patentee before: Suzhou Medical Device Industry Development Co.,Ltd.

CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150701