WO2016179974A1 - Two-step ethanol and 1-propanol preparation method using cellulose - Google Patents
Two-step ethanol and 1-propanol preparation method using cellulose Download PDFInfo
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Abstract
Provided is a two-step ethanol and 1-propanol preparation method using cellulose, comprising the following steps: (1) in an alcohol solvent system using cellulose as the raw material, reacting with alcohol under the effect of a first catalyst to produce glycolate and lactate; (2) adding a second catalyst to the mixed liquid product obtained from step (1), and performing hydrogenation by introducing hydrogen so as to obtain ethanol and 1-propanol. In the present invention, by means of the two-step reactions performed in alcohol, namely, esterification and hydrogenation, the cellulose conversion rate may reach 100% and the production rate for ethanol and 1-propanol may reach 70% or higher while reducing separation cost, thereby providing a new approach to comprehensive and highly effective cellulose usage.
Description
本发明涉及纤维素生产领域，特别是涉及一种纤维素两步法制备乙醇，正丙醇的方法。The invention relates to the field of cellulose production, in particular to a method for preparing ethanol and n-propanol by a two-step cellulose method.
木质纤维素生物质是世界上唯一可预测的能为人类提供物质和燃料的可持续资源，储量丰富、来源广泛，具有普遍性、易取性，能有效解决传统生物燃料“与人争粮”的问题。其中纤维素乙醇作为第二代生物燃料，被认为是最有发展前途的非粮生物燃料之一，具有广阔的发展前景。Lignocellulosic biomass is the only predictable sustainable resource that can provide humans with materials and fuels. It is rich in reserves, widely sourced, universal and easy to use, and can effectively solve traditional biofuels. The problem. Among them, cellulosic ethanol, as a second-generation biofuel, is considered to be one of the most promising non-food biofuels with broad development prospects.
目前，纤维素乙醇的生产方法主要是生物化学法，即将纤维素水解生成可发酵单糖，进而通过微生物发酵生成燃料乙醇的技术【文献1：Mohammad J,Enzyme-based hydrolysis processes for ethanol from lignocellulosic materials：A review.Bioresources，2(4):707-738.】而正丙醇主要由丙醛加氢得到【文献2：一种丙醛加氢制备正丙醇的清洁生产工艺，CN101774887A】，前者酶成本高且周期长，后者原料依赖于石油资源，且催化剂为贵金属，At present, the production method of cellulosic ethanol is mainly biochemical method, that is, the hydrolysis of cellulose to produce fermentable monosaccharides, and then the production of fuel ethanol by microbial fermentation [Document 1: Mohammad J, Enzyme-based hydrolysis processes for ethanol from lignocellulosic materials] :A review.Bioresources, 2(4): 707-738.] and n-propanol is mainly obtained by hydrogenation of propionaldehyde [Document 2: A clean production process for the preparation of n-propanol by hydrogenation of propionaldehyde, CN101774887A], the former The enzyme costs are high and the cycle is long. The latter raw materials depend on petroleum resources, and the catalyst is precious metal.
反应时间过长，均有一定的局限性。The reaction time is too long and has certain limitations.
本发明所设计的纤维素两步法制备乙醇，正丙醇的方法原料绿色可再生，过程分步可控，催化剂可分别回收，催化剂廉价且产物分离溶剂回收成本较低。The method for preparing ethanol by the two-step cellulose method of the invention is green, the raw material of the method is green renewable, the process is controllable step by step, the catalyst can be separately recovered, the catalyst is cheap, and the product separation solvent recovery cost is low.
发明内容Summary of the invention
本发明的目的在于提供一种纤维素制备乙醇，正丙醇的方法，首先将纤维素催化转化为乙醇酸酯，乳酸酯，然后进行加氢得到乙醇、正丙醇。The object of the present invention is to provide a method for preparing ethanol and n-propanol from cellulose. First, the cellulose is catalytically converted into glycolate, lactate, and then hydrogenated to obtain ethanol or n-propanol.
为实现上述目的，本发明采取的技术方案为：In order to achieve the above object, the technical solution adopted by the present invention is:
醇溶剂体系中以纤维素为原料，在第一催化剂作用下与醇在180-300℃反应0.5-3h生成乙醇酸酯，乳酸酯；向得到的液体混合产物加入第二催化剂，通入1-7MPa氢气于220-300℃下进行加氢1-3h得到乙醇和正丙醇的混合物。In the alcohol solvent system, cellulose is used as a raw material, and reacted with an alcohol at 180-300 ° C for 0.5-3 h under the action of the first catalyst to form a glycolate, a lactate; and a second catalyst is added to the obtained liquid mixed product, and the first catalyst is introduced. Hydrogenation of -7 MPa of hydrogen at 220-300 ° C for 1-3 h gives a mixture of ethanol and n-propanol.
醇溶剂为甲醇，正丙醇或异丙醇中的至少一种。第一催化剂为钨的氧化物，钨的硫化物，钨的氯化物，钨的碳化物，钨的氢氧化物，钨青铜，钨酸，钨酸盐，偏钨酸，偏钨酸盐，仲钨酸，仲钨酸盐，过氧钨酸，过氧钨酸盐，含钨杂多酸或含钨杂多酸盐中的至少一种。The alcohol solvent is at least one of methanol, n-propanol or isopropanol. The first catalyst is tungsten oxide, tungsten sulfide, tungsten chloride, tungsten carbide, tungsten hydroxide, tungsten bronze, tungstic acid, tungstate, metatungstic acid, metatungstate, secondary At least one of tungstic acid, paratungstate, peroxo-tungstic acid, peroxytungstate, tungsten-containing heteropolyacid or tungsten-containing heteropolyacid salt.
步骤(1)中产生的乙醇酸酯为乙醇酸甲酯、乙醇酸乙酯、乙醇酸丙酯、乙醇酸异丙酯中的至少一种，乳酸酯为乳酸甲酯，乳酸乙酯，乳酸丙酯或乳酸异丙酯中的至少一种。The glycolic acid ester produced in the step (1) is at least one of methyl glycolate, ethyl glycolate, propyl glycolate, and isopropyl glycolate. The lactate is methyl lactate, ethyl lactate, and lactic acid. At least one of propyl ester or isopropyl lactate.
第二催化剂采用二氧化硅为载体，以Cu为活性组分或主要活性组分，同时含有Ag,Mg,Ca,Ba,Zn,Zr,Co,Cr,Ni,Mn,Sn,Au,Pt,Pd,Ru或Re中的一种或多种作为助剂，其中Cu的质量分数为0.5-40％。助剂质量分数为0-5％，其余为载体。The second catalyst uses silica as a carrier, Cu as an active component or a main active component, and contains Ag, Mg, Ca, Ba, Zn, Zr, Co, Cr, Ni, Mn, Sn, Au, Pt, One or more of Pd, Ru or Re as an auxiliary agent, wherein the mass fraction of Cu is 0.5-40%. The additive mass fraction is 0-5%, and the rest is the carrier.
所述醇溶剂用量为纤维素质量的10-200倍，所述第一催化剂用量为纤维素质量的5％-50％，所述第二催化剂用量为纤维素质量的10-40％。The alcohol solvent is used in an amount of 10 to 200 times the mass of the cellulose, the first catalyst is used in an amount of 5% to 50% by mass of the cellulose, and the second catalyst is used in an amount of 10 to 40% by mass of the cellulose.
本发明具有如下优点：The invention has the following advantages:
1.相对于已有的乙醇，丙醇生产技术，本发明所涉及的两步法制备工艺反应原料绿色可再生，生产周期短，总体实现可持续。1. Compared with the existing ethanol and propanol production technology, the two-step preparation process of the present invention is green and renewable, the production cycle is short, and the overall realization is sustainable.
2.本发明所涉及的步骤(2)的催化剂主要活性中心为Cu,相对于已有的Ru,Ni
等贵金属相比，催化剂成本更低。2. The main active center of the catalyst of the step (2) according to the present invention is Cu, compared to the existing Ru, Ni
Compared to precious metals, the catalyst costs are lower.
3.本发明涉及的醇溶剂相对于已有的水解加氢技术中的水溶剂沸点更低，对于后续的产物分离及溶剂回收成本更低。3. The alcohol solvent of the present invention has a lower boiling point than the aqueous solvent in the existing hydrolyzed hydrogenation technology, and has lower cost for subsequent product separation and solvent recovery.
下面通过具体实施例对本发明进行详细说明，但这些实施例并不对本发明的内容构成限制。The invention is described in detail below by means of specific examples, but these examples are not intended to limit the scope of the invention.
实施例1Example 1
Cs2.5H0.5PW12O40催化剂的制备Preparation of Cs 2.5 H 0.5 PW 12 O 40 Catalyst
分别把2.5g CS2CO3和18.12g预处理得到的H3PW12O40·6H20配成0.1mol·L-1和0.08mol·L-1的溶液，0.1·mol·L-1的Cs2CO3溶液以1mL·min-1的速率在室温下滴加到0.08mol·L-1H3PW12040溶液中。滴加完毕，继续搅拌0.5h后，于室温下静置20h。然后在323K下缓慢蒸发水分，得白色固体，然后在110℃左右烘干，用前在300℃焙烧2h，比表面积为108m2g-1。Were put 2.5g CS 2 CO 3 and the resulting pretreated 18.12g H 3 PW 12 O 40 · 6H 2 0 0.1mol·L-1 and prepare a solution of 0.08mol·L -1, 0.1 · mol·L -1 The Cs 2 CO 3 solution was added dropwise to a solution of 0.08 mol·L -1 H 3 PW 12 0 40 at a rate of 1 mL·min -1 at room temperature. After the completion of the dropwise addition, stirring was continued for 0.5 h, and the mixture was allowed to stand at room temperature for 20 h. Then, the water was slowly evaporated at 323 K to obtain a white solid, which was then dried at about 110 ° C, and calcined at 300 ° C for 2 h before use, and had a specific surface area of 108 m 2 g -1 .
实施例2Example 2
W2C/AC的制备：称50g活性炭(AC),250mL 33wt％HNO3，置于500mL三口烧瓶中，80℃水浴处理24h,洗涤至中性，120℃烘干24h。将1g预处理过的AC倒入含0.588g偏钨酸铵的水溶液中，经120℃烘箱干燥后，将此催化剂前体于氢气中进行程序升温还原，具体反应过程为：由室温以8.8℃/min的升温速率升至550℃，然后以1℃/min的升温速率升温至900℃并保持1h，氢气流速为120mL/min。所制备的催化剂中W的理论担载量为30wt％。Preparation of W 2 C/AC: 50 g of activated carbon (AC), 250 mL of 33 wt% HNO 3 was weighed, placed in a 500 mL three-necked flask, treated in a water bath at 80 ° C for 24 h, washed to neutral, and dried at 120 ° C for 24 h. 1 g of the pretreated AC was poured into an aqueous solution containing 0.588 g of ammonium metatungstate, and after drying in an oven at 120 ° C, the catalyst precursor was subjected to temperature-programmed reduction in hydrogen, and the specific reaction process was: 8.8 ° C from room temperature. The heating rate of /min was raised to 550 ° C, and then the temperature was raised to 900 ° C at a heating rate of 1 ° C / min for 1 h, and the hydrogen flow rate was 120 mL / min. The theoretical loading of W in the prepared catalyst was 30% by weight.
实施例3Example 3
取0.3g SBA-15分散在30mL乙醇中，将0.13g磷钨酸溶解在10mL乙醇中，然后滴加至上述悬浮液，搅拌浸渍24h，蒸干溶剂，干燥，制备成负载量为30％的固载催化剂。其中SBA-15制备过程为：取2.0g P123溶解在15mL水中，然后滴加55mL盐酸，升温至40℃至少搅拌2-3h，滴加4.24g正硅酸四乙酯,在40℃下反应24h，然后转移至水热反应釜中，在100℃静置24h，用砂芯漏斗抽滤，水洗至中性，剩余固体先在60℃下烘干后再置于500℃下灼烧6h。0.3 g of SBA-15 was dispersed in 30 mL of ethanol, 0.13 g of phosphotungstic acid was dissolved in 10 mL of ethanol, and then added dropwise to the above suspension, and the mixture was stirred for 24 hours, and the solvent was evaporated to dryness to prepare a loading amount of 30%. Supported catalyst. The preparation process of SBA-15 is as follows: 2.0 g of P123 is dissolved in 15 mL of water, then 55 mL of hydrochloric acid is added dropwise, the temperature is raised to 40 ° C and stirred for at least 2-3 h, 4.24 g of tetraethyl orthosilicate is added dropwise, and the reaction is carried out at 40 ° C for 24 h. Then, it was transferred to a hydrothermal reaction kettle, allowed to stand at 100 ° C for 24 h, filtered with a sand core funnel, washed with water until neutral, and the remaining solid was first dried at 60 ° C and then placed at 500 ° C for 6 h.
实施例4Example 4
在室温下将7.56g Cu(NO3)2·3H2O溶于100mL去离子水中,加入浓氨水调节pH值至9.0,再加入8.0g SiO2。搅拌20min后,将混合物转移至冰水浴中,在搅拌下以15mL·min-1的速度加入去离子水,稀释至2L后过滤。用去离子水洗涤3次后,在120℃下干燥过夜,然后在450℃下焙烧4h。反应前在350℃下还原3h.得到20％-Cu/SiO2。7.56 g of Cu(NO 3 ) 2 ·3H 2 O was dissolved in 100 mL of deionized water at room temperature, concentrated aqueous ammonia was added to adjust the pH to 9.0, and 8.0 g of SiO 2 was further added. After stirring for 20 min, the mixture was transferred to an ice water bath, and deionized water was added at a rate of 15 mL·min -1 with stirring, diluted to 2 L, and filtered. After washing 3 times with deionized water, it was dried overnight at 120 ° C and then calcined at 450 ° C for 4 h. It was reduced at 350 ° C for 3 h before the reaction to obtain 20%-Cu/SiO 2 .
实施例5Example 5
将1.90g Cu(NO3)2·3H2O溶解于100mL去离子水中,向溶液中缓慢滴加11mL 28wt.％的氨水后室温下搅拌30min,向上述铜氨络合物溶液中加入含4.0g不同氧化铁(氧化镁，氧化钴)与二氧化硅比例的载体后,再剧烈搅拌2h,溶液初始pH＝11-12,然后升温至90℃蒸发过量的氨水和溶剂，使得铜物种在此过程中沉积到氧化铁和氧化硅载体上，至溶液呈中性时停止蒸发，离心，洗涤后在120℃下干燥12h,然后在450℃下焙烧4h。反应前在350℃下还原3h。如此制得5％Fe-15％Cu/SiO2，5％Mg-15％Cu/SiO2，5％Co-15％Cu/SiO2。1.90 g of Cu(NO 3 ) 2 ·3H 2 O was dissolved in 100 mL of deionized water, and 11 mL of 28 wt.% aqueous ammonia was slowly added dropwise to the solution, followed by stirring at room temperature for 30 min, and 4.0 was added to the above copper ammonia complex solution. g different iron oxide (magnesium oxide, cobalt oxide) and silica ratio carrier, and then vigorously stirred for 2h, the initial pH of the solution = 11-12, and then heated to 90 ° C to evaporate excess ammonia and solvent, so that copper species here During the process, it was deposited on the iron oxide and silica support, and when the solution was neutral, the evaporation was stopped, centrifuged, washed, dried at 120 ° C for 12 h, and then calcined at 450 ° C for 4 h. It was reduced at 350 ° C for 3 h before the reaction. Thus, 5% Fe-15% Cu/SiO 2 , 5% Mg-15% Cu/SiO 2 , 5% Co-15% Cu/SiO 2 were obtained .
实施例6Example 6
催化转化实验：将0.5g纤维素，0.2g第一催化剂H2WO4,和50ml甲醇加入到100ml反应釜中，以800转/min的速度进行搅拌，同时升温到260℃，反应2h。反应结束后，降至室温、5000rpm离心10min分离液体产物与催化剂。取0.2g第二催化剂
20％Cu/SiO2(加入到液体产物中，通入3MPa H2,升温至260℃反应2h，反应结束后，降至室温、5000rpm离心10min分离液体产物与催化剂。液体产物采用Agilent公司7890B气相色谱仪分析，配有氢火焰(FID)检测器，自动进样器。HP-INNOWAX毛细管柱(30m×250μm×0.5μm.)，载气为氮气，程序升温：45℃下停留3min，然后以5℃/min速率升至100℃，随后以12℃/min升至250℃停留3min。检测器温度270℃，氢气流量30ml/min，空气流量400ml/min，N2流量35ml/min。进样口温度220℃，进样量1μl，分流比20:1。Catalytic conversion experiment: 0.5 g of cellulose, 0.2 g of the first catalyst H 2 WO 4 , and 50 ml of methanol were placed in a 100 ml reaction vessel, stirred at a speed of 800 rpm, and simultaneously heated to 260 ° C for 2 h. After the reaction was completed, the liquid product and the catalyst were separated by dropping to room temperature and centrifuging at 5000 rpm for 10 minutes. Take 0.2g of the second catalyst 20% Cu/SiO 2 (added to the liquid product, pass 3MPa H 2 , heat up to 260 ° C for 2h, after the reaction is finished, drop to room temperature, centrifuge at 5000rpm for 10min to separate the liquid product and the catalyst. The product was analyzed by Agilent's 7890B gas chromatograph equipped with a hydrogen flame (FID) detector, autosampler, HP-INNOWAX capillary column (30m × 250μm × 0.5μm.), carrier gas was nitrogen, temperature programmed: 45 ° C Stay for 3 min, then raise to 100 ° C at 5 ° C / min, then rise to 250 ° C at 12 ° C / min for 3 min. Detector temperature 270 ° C, hydrogen flow rate 30 ml / min, air flow 400 ml / min, N 2 flow 35 ml/min. The inlet temperature was 220 ° C, the injection volume was 1 μl, and the split ratio was 20:1.
纤维素转化率由下式计算：The cellulose conversion rate is calculated by:
乙醇、正丙醇收率计算公式如下(其中反应物中纤维素含碳量由元素分析仪确定)：The formula for calculating the yield of ethanol and n-propanol is as follows (wherein the carbon content of the cellulose in the reactant is determined by an elemental analyzer):
其它液体产物及气体产物(CO，CO2，CH4等)未计算其收率。Other liquid products and gaseous products (CO, CO 2 , CH 4 , etc.) were not calculated for their yield.
实施例7Example 7
替换第一催化剂及第二催化剂的种类，其他反应条件同实施例6,比较各类含钨催化剂H2WO4，WO3，Na2WO4,AMT,W2C/AC,HPW/SBA-15,Cs2.5H0.5PW12O40及含铜催化剂20％Cu/SiO2，5％Fe-15％Cu/SiO2，5％Mg-15％Cu/SiO2，5％Co-15％Cu/SiO2催化下纤维素的催化转化结果，见表1。Replacing the types of the first catalyst and the second catalyst, the other reaction conditions are the same as in Example 6, comparing various types of tungsten-containing catalysts H 2 WO 4 , WO 3 , Na 2 WO 4 , AMT, W 2 C/AC, HPW/SBA- 15, Cs 2.5 H 0.5 PW 12 O 40 and copper-containing catalyst 20% Cu/SiO 2 , 5% Fe-15% Cu/SiO 2 , 5% Mg-15% Cu/SiO 2 , 5% Co-15% Cu The catalytic conversion results of cellulose catalyzed by /SiO 2 are shown in Table 1.
表1各种催化剂上纤维素催化转化性能的比较Table 1 Comparison of cellulose catalytic conversion performance on various catalysts
如表所示，纤维素能够在本发明中所涉及的各种含钨及含铜催化剂上高收率地转化为乙醇，正丙醇。其中，W2C/AC Fe-Cu/SiO2上能使乙醇，正丙醇收率达66.3％和7.8％。As shown in the table, cellulose can be converted to ethanol, n-propanol in high yield on various tungsten-containing and copper-containing catalysts involved in the present invention. Among them, W 2 C/AC Fe-Cu/SiO 2 can produce ethanol and n-propanol yields of 66.3% and 7.8%.
实施例8Example 8
替换溶剂种类，其他反应条件同实施例6，比较甲醇、正丙醇体系中纤维素催化转化结果，见表2。The solvent type was replaced, and other reaction conditions were the same as in Example 6. The results of cellulose catalytic conversion in methanol and n-propanol systems were compared, as shown in Table 2.
表2各种醇溶剂中纤维素催化转化性能的比较Table 2 Comparison of cellulose catalytic conversion performance in various alcohol solvents
如表所示，纤维素能在本发明所涉及的各类醇溶剂中有效转化为乙醇，正丙醇。As shown in the table, cellulose can be efficiently converted into ethanol and n-propanol in various alcohol solvents of the present invention.
实施例9Example 9
不同反应温度下纤维素催化转化性能的比较。见表3，除反应温度不同外，其他反应条件同实施例6。Comparison of catalytic conversion properties of cellulose at different reaction temperatures. See Table 3, except that the reaction temperature is different, the other reaction conditions are the same as in Example 6.
表3不同反应温度下纤维素催化转化性能的比较Table 3 Comparison of Catalytic Conversion Properties of Cellulose at Different Reaction Temperatures
从表中可以看出，在一定的温度范围内，纤维素均有优良的乙醇，正丙醇收率。It can be seen from the table that cellulose has excellent ethanol and n-propanol yield in a certain temperature range.
实施例10Example 10
不同反应时间下纤维素催化转化性能的比较。见表4，除反应时间不同外，其他反应条件同实施例6。Comparison of catalytic conversion properties of cellulose at different reaction times. See Table 4, except that the reaction time is different, the other reaction conditions are the same as in Example 6.
表4不同反应时间下纤维素催化转化性能的比较Table 4 Comparison of Catalytic Conversion Performance of Cellulose at Different Reaction Time
从表中可以看出，在一定的时间范围内，纤维素均有优良的乙醇，正丙醇收率。
It can be seen from the table that cellulose has excellent ethanol and n-propanol yield in a certain time range.
Claims (7)
- 一种纤维素两步法制备乙醇和正丙醇的方法，其特征在于，包括如下步骤：A method for preparing ethanol and n-propanol by a two-step cellulose method, comprising the steps of:(1)醇溶剂中加入纤维素，在第一催化剂作用下发生反应，得到混合产物；(1) adding cellulose to the alcohol solvent, and reacting under the action of the first catalyst to obtain a mixed product;(2)向步骤(1)得到的混合产物加入第二催化剂，通入氢气进行反应得到乙醇和正丙醇。(2) A second catalyst is added to the mixed product obtained in the step (1), and hydrogen is introduced to carry out a reaction to obtain ethanol and n-propanol.
- 如权利要求1所述的方法，其特征在于：步骤(1)中所述的醇溶剂为甲醇、正丙醇或异丙醇中的一种或二种或三种。The method according to claim 1, wherein the alcohol solvent in the step (1) is one or two or three of methanol, n-propanol or isopropanol.
- 如权利要求1所述的方法，其特征在于：步骤(1)中所述的第一催化剂为钨的氧化物、钨的硫化物、钨的氯化物、钨的碳化物、钨的氢氧化物、钨青铜、钨酸、钨酸盐、偏钨酸、偏钨酸盐、仲钨酸、仲钨酸盐、过氧钨酸、过氧钨酸盐、含钨杂多酸或含钨杂多酸盐中的一种或二种以上。The method according to claim 1, wherein the first catalyst in the step (1) is an oxide of tungsten, a sulfide of tungsten, a chloride of tungsten, a carbide of tungsten, a hydroxide of tungsten. , tungsten bronze, tungstic acid, tungstate, metatungstic acid, metatungstate, paratungstic acid, paratungstate, peroxytungstic acid, peroxytungstate, tungsten-containing heteropoly acid or tungsten-containing heteropoly One or more of the acid salts.
- 如权利要求1所述的方法，其特征在于：步骤(2)中所述的第二催化剂以二氧化硅为载体，以Cu为活性组分，同时其中不含有或含有Ag、Mg、Ca、Ba、Zn、Zr、Co、Cr、Ni、Mn、Sn、Au、Pt、Pd、Ru或Re中的一种或二种以上作为助剂，其中Cu的质量分数为0.5-40％，助剂质量分数为0-5％，其余为载体。The method according to claim 1, wherein the second catalyst in the step (2) uses silica as a carrier and Cu as an active component, and does not contain or contain Ag, Mg, Ca, One or more of Ba, Zn, Zr, Co, Cr, Ni, Mn, Sn, Au, Pt, Pd, Ru or Re as an auxiliary agent, wherein the mass fraction of Cu is 0.5-40%, auxiliary The mass fraction is 0-5% and the rest is the carrier.
- 如权利要求1所述的方法，其特征在于：步骤(1)中所述醇溶剂质量为纤维素质量的10-200倍，所述第一催化剂质量为纤维素质量的5％-50％，步骤(2)中所述第二催化剂质量为步骤(1)中纤维素质量的10-40％。The method according to claim 1, wherein the mass of the alcohol solvent in the step (1) is 10 to 200 times the mass of the cellulose, and the mass of the first catalyst is 5% to 50% of the mass of the cellulose. The second catalyst mass in the step (2) is 10 to 40% by mass of the cellulose in the step (1).
- 如权利要求1所述的方法，其特征在于：步骤(1)中所述的反应，反应温度为180-300℃，反应时间为0.5-3h。The method according to claim 1, wherein the reaction in the step (1) is carried out at a reaction temperature of from 180 to 300 ° C and a reaction time of from 0.5 to 3 hours.
- 如权利要求1所述的方法，其特征在于：步骤(2)中所述的反应，反应温度为220-300℃，反应时间为1-3h,氢气压力为1-7MPa。 The method according to claim 1, wherein the reaction in the step (2) has a reaction temperature of 220 to 300 ° C, a reaction time of 1-3 h, and a hydrogen pressure of 1 to 7 MPa.
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| CN107970932A (en) * | 2017-11-23 | 2018-05-01 | 黑龙江省能源环境研究院 | A kind of catalytic cellulose converts polynary alcohol catalyst and preparation method thereof and application method |
| CN109833884A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of methyl glycollate hydrogenolysis prepares catalyst of ethyl alcohol and its preparation method and application |
| CN108623436B (en) * | 2018-04-08 | 2021-02-19 | 华东师范大学 | Method for converting cellulose into bioethanol by one-pot method |
| CN110385131A (en) * | 2018-04-18 | 2019-10-29 | 中国科学院大连化学物理研究所 | A kind of catalyst of C2 acid esters preparation of ethanol by hydrogenating and its preparation and application |
| CN109289909B (en) * | 2018-10-16 | 2021-03-19 | 郑州大学 | Catalyst for preparing lactate by catalyzing conversion of complex sugar |
| CN111217672B (en) * | 2018-11-25 | 2021-08-17 | 中国科学院大连化学物理研究所 | Method for preparing ethanol from carbohydrate |
| CN115974646A (en) * | 2021-10-14 | 2023-04-18 | 中国科学院大连化学物理研究所 | Method for preparing ethanol by catalyzing carbohydrate with monatomic catalyst |
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