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CN115636739A - A kind of method of synthetic gas one-step process acetone - Google Patents

A kind of method of synthetic gas one-step process acetone Download PDF

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CN115636739A
CN115636739A CN202211179244.1A CN202211179244A CN115636739A CN 115636739 A CN115636739 A CN 115636739A CN 202211179244 A CN202211179244 A CN 202211179244A CN 115636739 A CN115636739 A CN 115636739A
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acetone
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methanol
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CN115636739B (en
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康金灿
黄欣宇
刘志铭
张庆红
王野
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Xiamen University
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Abstract

一种合成气一步法制丙酮的方法,以合成气(CO/H2)为原料,在多功能复合催化剂上,CO加氢反应一步法制备丙酮为主的产物。其中,多功能复合催化剂中具有甲醇合成、甲醇羰基化、乙酸酮基化制备丙酮的催化功能。包括以下步骤:1)将催化剂置于反应器内,进行预处理;2)通入合成气,进行催化反应,得到丙酮。催化剂由合成气制甲醇功能的金属氧化物、甲醇羰基化制乙酸功能的沸石分子筛和乙酸酮基化制丙酮的负载型金属氧化物复合而成。本发明利用接力催化,缩短反应步骤,提高了催化效率,实现目标产物丙酮的选择性高达90%以上;无需分离中间产物,整体工艺能量消耗较少,成本低,具有良好的应用前景。A one-step method for producing acetone from synthesis gas, using synthesis gas (CO/H 2 ) as a raw material, and preparing acetone-based products through CO hydrogenation reaction on a multifunctional composite catalyst in one step. Among them, the multifunctional composite catalyst has the catalytic function of methanol synthesis, methanol carbonylation, and acetic acid ketonylation to prepare acetone. The method comprises the following steps: 1) placing a catalyst in a reactor for pretreatment; 2) feeding synthesis gas for catalytic reaction to obtain acetone. The catalyst is compounded by the metal oxide with the function of producing methanol from syngas, the zeolite molecular sieve with the function of producing acetic acid from methanol carbonylation, and the supported metal oxide which can produce acetone from the ketoylation of acetic acid. The invention utilizes relay catalysis, shortens the reaction steps, improves the catalytic efficiency, realizes the selectivity of the target product acetone as high as 90% or more; does not need to separate intermediate products, consumes less energy in the overall process, has low cost, and has good application prospects.

Description

一种合成气一步法制丙酮的方法A kind of method of synthetic gas one-step process acetone

技术领域technical field

本发明涉及化工领域,尤其涉及合成气一步法制丙酮的方法,特别在多功能复合催化剂上CO加氢一步法制丙酮。The invention relates to the field of chemical industry, in particular to a method for producing acetone by one-step synthesis gas, in particular to one-step production of acetone by CO hydrogenation on a multifunctional composite catalyst.

背景技术Background technique

发展非石油基碳基资源制备液体燃料以及高价值化学品意义重大,其中,煤、生物质、天然气、页岩气经过蒸汽重整或者二氧化碳还原得到合成气,合成气通过催化转化可实现制备液体燃料以及高价值化学品。然而除甲醇、甲烷外,合成气转化反应产物的碳数分布均较宽,因此需要聚焦于如何调控特定碳数范围的产物甚至实现单一产物的生成。The development of non-petroleum-based carbon-based resources to produce liquid fuels and high-value chemicals is of great significance. Among them, coal, biomass, natural gas, and shale gas are steam reformed or carbon dioxide reduced to obtain synthesis gas, and synthesis gas can be produced through catalytic conversion. fuels and high value chemicals. However, except for methanol and methane, the carbon number distribution of the synthesis gas conversion reaction products is relatively wide, so it is necessary to focus on how to regulate the products in a specific carbon number range or even realize the formation of a single product.

近年来研究表明,通过设计双功能催化剂可以将合成气高选择性催化转化为汽油、柴油、航空煤油、低碳烯烃、芳烃、C2+含氧化合物,突破了合成气转化的选择性局限,实现了特定碳数范围产物的高选择性合成。为实现单一产物高选择性生成,研究者们提出接力催化的思路,由合成气出发一步法高选择性制C2化学品如乙醇(Nat.Commun.,2020,11:827-837)、乙烯(Angew.Chem.Int.Ed.,2018,57:12012-12016)、乙酸(CN109908947A)以及C3化学品如乙酸甲酯(CN108774130A)等。Studies in recent years have shown that syngas can be converted to gasoline, diesel, aviation kerosene, light olefins, aromatics, and C2 + oxygenates with high selectivity by designing dual-functional catalysts, breaking through the selectivity limitation of syngas conversion. The highly selective synthesis of products in a specific carbon number range has been achieved. In order to achieve high selectivity of a single product, researchers have proposed the idea of relay catalysis, starting from syngas to produce C2 chemicals such as ethanol (Nat. Commun., 2020, 11:827-837) and ethylene ( Angew.Chem.Int.Ed., 2018,57:12012-12016), acetic acid (CN109908947A), and C3 chemicals such as methyl acetate (CN108774130A), etc.

丙酮作为一种重要的C3化学品,广泛应用于塑料、纤维、橡胶、喷漆等行业作为溶剂,亦可作为生产双酚A、烯酮、甲基丙烯酸甲酯等高值产品的重要原料,并且丙酮还可以用于芯片表面清洗和液相色谱洗脱剂。由合成气直接法制丙酮,仅可实现13.5%的丙酮选择性 (Catal.Commun.,2009,10:468-471),其余副产物选择性高。2014年中国专利公开了关于一种合成气制丙酮的工艺(CN104193606A),该工艺为多步法的间接过程,包括合成气制甲醇、甲醇均相羰基化和乙酸转化为丙酮,在多个反应器上进行。此工艺中,甲醇羰基化反应催化剂为均相催化剂,涉及贵金属及碘化物,导致成本较高以及会对设备产生腐蚀。另一方面,该间接法过程,需要用到不同的反应器,并且中间产物均需要分离,导致设备能源消耗大、成本高。As an important C3 chemical, acetone is widely used as a solvent in industries such as plastics, fibers, rubber, and spray paint, and can also be used as an important raw material for the production of high-value products such as bisphenol A, ketene, and methyl methacrylate. Acetone can also be used for chip surface cleaning and liquid chromatography eluent. The direct method of producing acetone from synthesis gas can only achieve acetone selectivity of 13.5% (Catal. Commun., 2009, 10: 468-471), and the selectivity of the remaining by-products is high. In 2014, a Chinese patent disclosed a process for producing acetone from syngas (CN104193606A). on the device. In this process, the methanol carbonylation reaction catalyst is a homogeneous catalyst involving noble metals and iodides, resulting in higher costs and corrosion to equipment. On the other hand, the indirect method needs to use different reactors, and all intermediate products need to be separated, resulting in large energy consumption and high cost of equipment.

发明内容Contents of the invention

本发明的目的在于解决现有技术中的上述问题,提供合成气一步法制丙酮的方法,利用接力催化,缩短反应步骤,提高催化效率,实现目标产物丙酮的选择性高达90%以上;无需分离中间产物,整体工艺能量消耗较少,成本低,具有良好的应用前景。The purpose of the present invention is to solve the above-mentioned problems in the prior art, to provide a method for producing acetone from syngas in one step, using relay catalysis, shortening the reaction steps, improving the catalytic efficiency, and realizing the selectivity of the target product acetone as high as 90% or more; no need to separate intermediate The product, the energy consumption of the overall process is less, the cost is low, and it has a good application prospect.

为达到上述目的,本发明采用如下技术方案:To achieve the above object, the present invention adopts the following technical solutions:

一种合成气一步法制丙酮的方法,将复合型催化剂置于反应器内,进行预处理,然后通入合成气,进行催化反应,得到丙酮;所述复合型催化剂采用多床层方式进行复合,接力催化反应,其中,合成气制甲醇的金属氧化物催化剂置于第一床层,甲醇羰基化制乙酸的沸石分子筛置于第二床层,乙酸酮基化制丙酮的负载型金属氧化物置于第三床层。A method for producing acetone from synthesis gas in one step, comprising placing a composite catalyst in a reactor for pretreatment, and then feeding synthesis gas to carry out a catalytic reaction to obtain acetone; the composite catalyst is composited in a multi-bed manner, Relay catalytic reaction, in which, the metal oxide catalyst for syngas to methanol is placed in the first bed, the zeolite molecular sieve for methanol carbonylation to acetic acid is placed in the second bed, and the supported metal oxide for ketone ketone to acetone is placed in the second bed. Third bed.

所述复合型催化剂中,合成气制甲醇的金属氧化物、甲醇羰基化制乙酸的沸石分子筛和乙酸酮基化制丙酮的负载型金属氧化物的质量比为1:(0.5~4):(0.5~4)。In the composite catalyst, the mass ratio of the metal oxide for the production of methanol from synthesis gas, the zeolite molecular sieve for the production of acetic acid by carbonylation of methanol, and the supported metal oxide for the production of acetone by ketoylation of acetic acid is 1:(0.5~4):( 0.5~4).

所述合成气制甲醇的金属氧化物选自Cu-ZnO-Al2O3、Pd-ZnO-Al2O3、ZnO-Cr2O3-Al2O3、 ZnO-Cr2O3、ZnO-ZrO2、CeO2-ZrO2、ZnO-Al2O3、ZnO-Ga2O3、ZnO-Fe2O3、In2O3-ZnO、In2O3-Al2O3中的至少一种。The metal oxides for methanol production from syngas are selected from Cu-ZnO-Al 2 O 3 , Pd-ZnO-Al 2 O 3 , ZnO-Cr 2 O 3 -Al 2 O 3 , ZnO-Cr 2 O 3 , ZnO -At least one of ZrO 2 , CeO 2 -ZrO 2 , ZnO-Al 2 O 3 , ZnO-Ga 2 O 3 , ZnO-Fe 2 O 3 , In 2 O 3 -ZnO, In 2 O 3 -Al 2 O 3 A sort of.

所述甲醇羰基化制乙酸的沸石分子筛选自具有八元环拓扑结构的MOR、FER、IWW、MEL型沸石分子筛中的至少一种。The zeolite molecular sieve for the carbonylation of methanol to acetic acid is selected from at least one of MOR, FER, IWW, and MEL zeolite molecular sieves with an eight-membered ring topology.

所述沸石分子筛具有微孔结构,其中微孔的孔径为0.2~0.8nm,微孔的孔容为0.05~0.5 cm3/g。The zeolite molecular sieve has a microporous structure, wherein the pore diameter of the micropores is 0.2-0.8 nm, and the pore volume of the micropores is 0.05-0.5 cm 3 /g.

所述乙酸酮基化制丙酮的负载型金属氧化物记为x wt.%MOx/Y,其中x的范围为5%~ 50%,M为Ce、Mn、Zr、La、Pr、Nd中的至少一种,Y为H-MOR、H-ZSM-5、Al2O3、SiO2、 TiO2、MgO、CaCO3中的至少一种。The supported metal oxide for the preparation of acetone from acetic ketone is denoted as x wt.% MO x /Y, wherein the range of x is 5% to 50%, and M is Ce, Mn, Zr, La, Pr, Nd Y is at least one of H-MOR, H-ZSM-5, Al 2 O 3 , SiO 2 , TiO 2 , MgO, and CaCO 3 .

所述复合型催化剂预处理的方法为:在固定床、流化床或移动床反应器上装好催化剂后,通入氢气或氢气与惰性气体的混合气,以1~10℃/min速率升温至200~500℃,并保持0.5~ 10h,然后切换成惰性气体吹扫0.1~5h。The pretreatment method of the composite catalyst is as follows: after the catalyst is installed on the fixed bed, fluidized bed or moving bed reactor, hydrogen gas or a mixture of hydrogen gas and inert gas is introduced, and the temperature is raised to 200~500℃, and keep it for 0.5~10h, then switch to inert gas purging for 0.1~5h.

所述催化反应的方法如下:复合型催化剂经预处理后,温度降低至30~200℃,通入合成气,其中H2与CO的体积比为1:(0.2~3),然后升温至反应温度为200~400℃,反应压力为0.5~7MPa,合成气空速为500~15000h-1,合成气经过催化剂床层反应得到产物丙酮The method of the catalytic reaction is as follows: After the composite catalyst is pretreated, the temperature is lowered to 30-200° C., and the synthesis gas is introduced, wherein the volume ratio of H and CO is 1: (0.2-3), and then the temperature is raised to the reaction temperature. The temperature is 200-400°C, the reaction pressure is 0.5-7MPa, the space velocity of the synthesis gas is 500-15000h -1 , and the synthesis gas is reacted through the catalyst bed to obtain the product acetone

相对于现有技术,本发明技术方案取得的有益效果是:Compared with the prior art, the beneficial effects obtained by the technical solution of the present invention are:

1、本发明为直接法新工艺,可通过合成气一步法得到丙酮,工艺简单,利用接力催化保证反应的可控进行,无需分离中间产物,整体工艺能源消耗少,大幅减少设备,降低成本,可大规模生产;1. The present invention is a new process of direct method. Acetone can be obtained by one-step method of synthesis gas. The process is simple. Relay catalysis is used to ensure the controllable progress of the reaction. There is no need to separate intermediate products. The overall process consumes less energy, greatly reduces equipment, and reduces costs. Can be mass-produced;

2、本发明利用接力催化,耦合了合成气制甲醇、甲醇多相羰基化制乙酸和乙酸酮基化制丙酮,其中合成甲醇的金属氧化物主要活化CO加氢生成甲醇中间体,多级孔沸石分子筛负责催化中间产物甲醇进一步生成乙酸,乙酸在负载型金属氧化物上进一步高选择性转化为丙酮;2. The present invention utilizes relay catalysis to couple syngas to methanol, methanol heterogeneous carbonylation to acetic acid, and acetic acid ketoylation to acetone, wherein the metal oxides used to synthesize methanol are mainly activated by CO hydrogenation to generate methanol intermediates, with hierarchical pores Zeolite molecular sieves are responsible for catalyzing the intermediate product methanol to further generate acetic acid, which is further converted to acetone with high selectivity on the supported metal oxide;

3、本发明中,合成气高选择性转化制丙酮的催化剂具有较佳的反应性能,在较优的反应条件下,丙酮的选择性高于90%;3. In the present invention, the catalyst for highly selective conversion of synthesis gas to acetone has better reaction performance, and under better reaction conditions, the selectivity of acetone is higher than 90%;

4、本发明合成气高选择性转化制丙酮的催化剂稳定性良好,价格低廉,产品附加值高,具有良好的经济效益,具有潜在的应用前景。4. The catalyst of the present invention for producing acetone through highly selective conversion of synthesis gas has good stability, low price, high added value of the product, good economic benefits, and potential application prospects.

具体实施方式Detailed ways

为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚、明白,以下结合实施例,下面进一步详细说明本发明提供的合成气接力催化高选择性制丙酮的催化剂及其应用,但本发明并不因此而受到任何限制。In order to make the technical problems to be solved by the present invention, technical solutions and beneficial effects clearer and clearer, below in conjunction with embodiment, the catalyst and the application thereof of synthesis gas relay catalysis highly selective acetone system provided by the present invention are further described below, but this The invention is not limited thereby.

实施例1Example 1

称取0.5g Cu-ZnO-Al2O3(Cu/Zn/Al摩尔比为6:3:1)催化剂、1.0g H-ZSM-35(Si/Al= 12)和1.0g 10wt.%ZrO2/Al2O3,装入石英管中,其中10wt.%ZrO2/Al2O3在下层,H-ZSM-35 在第二层,Cu-ZnO-Al2O3在顶层。通入10%H2-Ar混合气,以5℃/min速率升温至260℃处理1h,后切换为N2吹扫1h,降温至200℃,随后进行催化反应,反应条件如下:反应温度为230℃,反应压力为4MPa,合成气空速为3000h-1,合成气中H2与CO的体积比为2。反应原料及产物经管路保温进入气相色谱在线分析,具体催化反应性能如表1所示。Weigh 0.5g Cu-ZnO-Al 2 O 3 (Cu/Zn/Al molar ratio is 6:3:1) catalyst, 1.0g H-ZSM-35 (Si/Al=12) and 1.0g 10wt.%ZrO 2 /Al 2 O 3 , loaded into a quartz tube, with 10wt.% ZrO 2 /Al 2 O 3 in the lower layer, H-ZSM-35 in the second layer, and Cu-ZnO-Al 2 O 3 in the top layer. Introduce 10% H 2 -Ar mixed gas, heat up to 260°C at a rate of 5°C/min for 1 hour, then switch to N 2 purge for 1 hour, cool down to 200°C, and then carry out catalytic reaction. The reaction conditions are as follows: The reaction temperature is 230°C, the reaction pressure is 4MPa, the space velocity of the synthesis gas is 3000h -1 , and the volume ratio of H 2 to CO in the synthesis gas is 2. The raw materials and products of the reaction were analyzed by gas chromatography through pipeline insulation. The specific catalytic performance is shown in Table 1.

实施例2Example 2

称取0.6g Pd-ZnO-Al2O3(Pd/Zn/Al摩尔比为1.5:5.5:3)催化剂、1.0g H-MOR(Si/Al= 13)和1.0g 20wt.%MnO2/H-MOR,装入石英管中,其中20wt.%MnO2/H-MOR在下层, H-MOR在第二层,Pd-ZnO-Al2O3在顶层。通入10%H2-Ar混合气,以5℃/min速率升温至 260℃处理1h,后切换为N2吹扫1h,降温至200℃,随后进行催化反应,反应条件如下:反应温度为280℃,反应压力为4MPa,合成气空速为3000h-1,合成气中H2与CO的体积比为2。反应原料及产物经管路保温进入气相色谱在线分析,具体催化反应性能如表1所示。Weigh 0.6g Pd-ZnO-Al 2 O 3 (Pd/Zn/Al molar ratio is 1.5:5.5:3) catalyst, 1.0g H-MOR (Si/Al=13) and 1.0g 20wt.%MnO 2 / H-MOR, loaded into a quartz tube, with 20wt.% MnO 2 /H-MOR in the lower layer, H-MOR in the second layer, and Pd-ZnO-Al 2 O 3 in the top layer. Introduce 10% H 2 -Ar mixed gas, heat up to 260°C at a rate of 5°C/min for 1 hour, then switch to N 2 purge for 1 hour, cool down to 200°C, and then carry out catalytic reaction. The reaction conditions are as follows: The reaction temperature is 280°C, the reaction pressure is 4MPa, the space velocity of the synthesis gas is 3000h -1 , and the volume ratio of H 2 to CO in the synthesis gas is 2. The raw materials and products of the reaction were analyzed by gas chromatography through pipeline insulation. The specific catalytic performance is shown in Table 1.

实施例3Example 3

称取0.6g ZnO-ZrO2(Zn/Zr摩尔比为1:4)催化剂、1.0g H-ZSM-35(Si/Al=12)和1.0 g 10wt.%La2O3/CaCO3,装入石英管中,其中10wt.%La2O3/CaCO3在下层,H-ZSM-35在第二层,ZnO-ZrO2在顶层。通入10%H2-Ar混合气,以5℃/min速率升温至260℃处理1h,后切换为N2吹扫1h,降温至200℃,随后进行催化反应,反应条件如下:反应温度为280℃,反应压力为4MPa,合成气空速为3000h-1,合成气中H2与CO的体积比为2。反应原料及产物经管路保温进入气相色谱在线分析,具体催化反应性能如表1所示。Weigh 0.6g ZnO-ZrO 2 (Zn/Zr molar ratio is 1:4) catalyst, 1.0g H-ZSM-35 (Si/Al=12) and 1.0 g 10wt.% La 2 O 3 /CaCO 3 , pack into a quartz tube with 10wt.% La 2 O 3 /CaCO 3 in the lower layer, H-ZSM-35 in the second layer, and ZnO-ZrO 2 in the top layer. Introduce 10% H 2 -Ar mixed gas, heat up to 260°C at a rate of 5°C/min for 1 hour, then switch to N 2 purge for 1 hour, cool down to 200°C, and then carry out catalytic reaction. The reaction conditions are as follows: The reaction temperature is 280°C, the reaction pressure is 4MPa, the space velocity of the synthesis gas is 3000h -1 , and the volume ratio of H 2 to CO in the synthesis gas is 2. The raw materials and products of the reaction were analyzed by gas chromatography through pipeline insulation. The specific catalytic performance is shown in Table 1.

实施例4Example 4

称取0.6g Cu-ZnO(Cu/Zn摩尔比为3:2)催化剂、1.0g H-ZSM-35(Si/Al=12)和1.0g 15wt.%La2O3/TiO2,装入石英管中,其中15wt.%La2O3/TiO2在下层,H-ZSM-35在第二层, Cu-ZnO在顶层。通入10%H2-Ar混合气,以5℃/min速率升温至260℃处理1h,后切换为N2吹扫1h,降温至200℃,随后进行催化反应,反应条件如下:反应温度为280℃,反应压力为4MPa,合成气空速为3000h-1,合成气中H2与CO的体积比为2。反应原料及产物经管路保温进入气相色谱在线分析,具体催化反应性能如表1所示。Weigh 0.6g Cu-ZnO (Cu/Zn molar ratio is 3:2) catalyst, 1.0g H-ZSM-35 (Si/Al=12) and 1.0g 15wt.% La 2 O 3 /TiO 2 , load In the quartz tube, 15wt.% La 2 O 3 /TiO 2 is in the lower layer, H-ZSM-35 is in the second layer, and Cu-ZnO is in the top layer. Introduce 10% H 2 -Ar mixed gas, heat up to 260°C at a rate of 5°C/min for 1 hour, then switch to N 2 purge for 1 hour, cool down to 200°C, and then carry out catalytic reaction. The reaction conditions are as follows: The reaction temperature is 280°C, the reaction pressure is 4MPa, the space velocity of the synthesis gas is 3000h -1 , and the volume ratio of H 2 to CO in the synthesis gas is 2. The raw materials and products of the reaction were analyzed by gas chromatography through pipeline insulation. The specific catalytic performance is shown in Table 1.

实施例5Example 5

称取0.6g ZnO-Al2O3(Zn/Al摩尔比为1:2)催化剂、1.0g经吡啶改性的H-MOR(Si/Al=13)表示为Py-H-MOR和1.0g 10wt.%ZrO2/MgO,装入石英管中,其中10wt.%ZrO2/MgO 在下层,Py-H-MOR在第二层,ZnO-Al2O3在顶层。通入10%H2-Ar混合气,以5℃/min速率升温至260℃处理1h,后切换为N2吹扫1h,降温至200℃,随后进行催化反应,反应条件如下:反应温度为280℃,反应压力为4MPa,合成气空速为3000h-1,合成气中H2与CO 的体积比为2。反应原料及产物经管路保温进入气相色谱在线分析,具体催化反应性能如表1 所示。Weigh 0.6g of ZnO-Al 2 O 3 (Zn/Al molar ratio is 1:2) catalyst, 1.0g of pyridine-modified H-MOR (Si/Al=13) is expressed as Py-H-MOR and 1.0g 10wt.% ZrO 2 /MgO, loaded into a quartz tube, where 10wt.% ZrO 2 /MgO is in the lower layer, Py-H-MOR is in the second layer, and ZnO-Al 2 O 3 is in the top layer. Introduce 10% H 2 -Ar mixed gas, heat up to 260°C at a rate of 5°C/min for 1 hour, then switch to N 2 purge for 1 hour, cool down to 200°C, and then carry out catalytic reaction. The reaction conditions are as follows: The reaction temperature is 280°C, the reaction pressure is 4MPa, the space velocity of the synthesis gas is 3000h -1 , and the volume ratio of H 2 to CO in the synthesis gas is 2. The raw materials and products of the reaction were analyzed by gas chromatography through pipeline insulation. The specific catalytic performance is shown in Table 1.

实施例6Example 6

称取0.6g ZnO-Fe2O3(Zn/Fe摩尔比为1:2)催化剂、1.0g经吡啶改性的H-MOR(Si/Al=13)表示为Py-H-MOR和1.0g 15wt.%CeO2/H-ZSM-5,装入石英管中,其中15wt.% CeO2/H-ZSM-5在下层,Py-H-MOR在第二层,ZnO-Fe2O3在顶层。通入10%H2-Ar混合气,以5℃/min速率升温至260℃处理1h,后切换为N2吹扫1h,降温至200℃,随后进行催化反应,反应条件如下:反应温度为280℃,反应压力为4MPa,合成气空速为3000h-1,合成气中H2与CO的体积比为2。反应原料及产物经管路保温进入气相色谱在线分析,具体催化反应性能如表1所示。Weigh 0.6g of ZnO-Fe 2 O 3 (Zn/Fe molar ratio is 1:2) catalyst, 1.0g of pyridine-modified H-MOR (Si/Al=13) is expressed as Py-H-MOR and 1.0g 15wt.% CeO 2 /H-ZSM-5, loaded into a quartz tube, where 15wt.% CeO 2 /H-ZSM-5 is in the lower layer, Py-H-MOR is in the second layer, ZnO-Fe 2 O 3 is in the top floor. Introduce 10% H 2 -Ar mixed gas, heat up to 260°C at a rate of 5°C/min for 1 hour, then switch to N 2 purge for 1 hour, cool down to 200°C, and then carry out catalytic reaction. The reaction conditions are as follows: The reaction temperature is 280°C, the reaction pressure is 4MPa, the space velocity of the synthesis gas is 3000h -1 , and the volume ratio of H 2 to CO in the synthesis gas is 2. The raw materials and products of the reaction were analyzed by gas chromatography through pipeline insulation. The specific catalytic performance is shown in Table 1.

实施例7Example 7

称取0.6g In2O3-ZrO2(In/Zr摩尔比为2:1)催化剂、1.0g经选择性脱铝的H-MOR(Si/Al =13)表示为H-MOR-DA-12MR和1.0g 10wt.%ZrO2/H-MOR,装入石英管中,其中10wt.%ZrO2/H-MOR在下层,H-MOR-DA-12MR在第二层,In2O3-ZrO2在顶层。通入10%H2-Ar混合气,以5℃/min速率升温至260℃处理1h,后切换为N2吹扫1h,降温至200℃,随后进行催化反应,反应条件如下:反应温度为280℃,反应压力为4MPa,合成气空速为3000h-1,合成气中H2与CO的体积比为2。反应原料及产物经管路保温进入气相色谱在线分析,具体催化反应性能如表1所示。Weigh 0.6g of In 2 O 3 -ZrO 2 (In/Zr molar ratio is 2:1) catalyst, 1.0g of selectively dealuminated H-MOR (Si/Al = 13) is expressed as H-MOR-DA- 12MR and 1.0g 10wt.% ZrO 2 /H-MOR, packed into a quartz tube, where 10wt.% ZrO 2 /H-MOR is in the lower layer, H-MOR-DA-12MR is in the second layer, In 2 O 3 - ZrO2 is in the top layer. Introduce 10% H 2 -Ar mixed gas, heat up to 260°C at a rate of 5°C/min for 1 hour, then switch to N 2 purge for 1 hour, cool down to 200°C, and then carry out catalytic reaction. The reaction conditions are as follows: The reaction temperature is 280°C, the reaction pressure is 4MPa, the space velocity of the synthesis gas is 3000h -1 , and the volume ratio of H 2 to CO in the synthesis gas is 2. The raw materials and products of the reaction were analyzed by gas chromatography through pipeline insulation. The specific catalytic performance is shown in Table 1.

实施例8Example 8

称取0.6g ZnO-Ga2O3(Zn/Ga摩尔比为1:2)催化剂、1.0g经金属Mn修饰选择性脱铝的H-MOR(Si/Al=13)表示为1wt.%Mn/H-MOR-DA-12MR和1.0g 20wt.%CeO2/SiO2,装入石英管中,其中20wt.%CeO2/SiO2在下层,1wt.%Mn/H-MOR-DA-12MR在第二层, ZnO-Ga2O3在顶层。通入10%H2-Ar混合气,以5℃/min速率升温至260℃处理1h,后切换为N2吹扫1h,降温至200℃,随后进行催化反应,反应条件如下:反应温度为280℃,反应压力为4MPa,合成气空速为3000h-1,合成气中H2与CO的体积比为2。反应原料及产物经管路保温进入气相色谱在线分析,具体催化反应性能如表1所示。Weigh 0.6g of ZnO-Ga 2 O 3 (Zn/Ga molar ratio is 1:2) catalyst, 1.0g of H-MOR (Si/Al=13) decorated with metal Mn and selective dealumination, expressed as 1wt.%Mn /H-MOR-DA-12MR and 1.0g 20wt.% CeO 2 /SiO 2 , packed into a quartz tube, with 20wt.% CeO 2 /SiO 2 in the lower layer, 1wt.% Mn/H-MOR-DA-12MR In the second layer, ZnO- Ga2O3 is on top. Introduce 10% H 2 -Ar mixed gas, heat up to 260°C at a rate of 5°C/min for 1 hour, then switch to N 2 purge for 1 hour, cool down to 200°C, and then carry out catalytic reaction. The reaction conditions are as follows: The reaction temperature is 280°C, the reaction pressure is 4MPa, the space velocity of the synthesis gas is 3000h -1 , and the volume ratio of H 2 to CO in the synthesis gas is 2. The raw materials and products of the reaction were analyzed by gas chromatography through pipeline insulation. The specific catalytic performance is shown in Table 1.

实施例9Example 9

称取0.6g ZnO-ZrO2(Zn/Zr摩尔比为1:4)催化剂、1.0g经选择性脱铝的H-MOR(Si/Al =13)表示为H-MOR-DA-12MR和1.0g 15wt.%CeO2/TiO2,装入石英管中,其中15wt.%CeO2/TiO2在下层,H-MOR-DA-12MR在第二层,ZnO-ZrO2在顶层。通入10%H2-Ar混合气,以5℃/min速率升温至260℃处理1h,后切换为N2吹扫1h,降温至200℃,随后进行催化反应,反应条件如下:反应温度为310℃,反应压力为5MPa,合成气空速为2000h-1,合成气中H2与CO的体积比为2。反应原料及产物经管路保温进入气相色谱在线分析,具体催化反应性能如表1所示。Weigh 0.6g of ZnO-ZrO 2 (Zn/Zr molar ratio is 1:4) catalyst, 1.0g of selectively dealuminated H-MOR (Si/Al = 13) is expressed as H-MOR-DA-12MR and 1.0 g 15wt.% CeO 2 /TiO 2 , packed into a quartz tube, wherein 15wt.% CeO 2 /TiO 2 is in the lower layer, H-MOR-DA-12MR is in the second layer, and ZnO-ZrO 2 is in the top layer. Introduce 10% H 2 -Ar mixed gas, heat up to 260°C at a rate of 5°C/min for 1 hour, then switch to N 2 purge for 1 hour, cool down to 200°C, and then carry out catalytic reaction. The reaction conditions are as follows: The reaction temperature is 310°C, the reaction pressure is 5MPa, the space velocity of the synthesis gas is 2000h -1 , and the volume ratio of H 2 to CO in the synthesis gas is 2. The raw materials and products of the reaction were analyzed by gas chromatography through pipeline insulation. The specific catalytic performance is shown in Table 1.

实施例10Example 10

称取0.6g ZnO-Cr2O3(Zn/Cr摩尔比为3:2)催化剂、1.0g经金属Mn修饰选择性脱铝的H-MOR(Si/Al=13)表示为1wt.%Mn/H-MOR-DA-12MR和1.0g 20wt.%CeO2/Al2O3,装入石英管中,其中20wt.%CeO2/Al2O3在下层,1wt.%Mn/H-MOR-DA-12MR在第二层, ZnO-Cr2O3在顶层。通入10%H2-Ar混合气,以5℃/min速率升温至260℃处理1h,后切换为N2吹扫1h,降温至200℃,随后进行催化反应,反应条件如下:反应温度为310℃,反应压力为6MPa,合成气空速为1200h-1,合成气中H2与CO的体积比为3。反应原料及产物经管路保温进入气相色谱在线分析,具体催化反应性能如表1所示。Weigh 0.6g ZnO-Cr 2 O 3 (Zn/Cr molar ratio is 3:2) catalyst, 1.0g metal Mn-modified selective dealuminated H-MOR (Si/Al=13) expressed as 1wt.%Mn /H-MOR-DA-12MR and 1.0g 20wt.% CeO 2 /Al 2 O 3 , packed into a quartz tube with 20wt.% CeO 2 /Al 2 O 3 in the lower layer, 1wt.% Mn/H-MOR -DA-12MR on the second layer, ZnO- Cr2O3 on the top layer. Introduce 10% H 2 -Ar mixed gas, heat up to 260°C at a rate of 5°C/min for 1 hour, then switch to N 2 purge for 1 hour, cool down to 200°C, and then carry out catalytic reaction. The reaction conditions are as follows: The reaction temperature is 310°C, the reaction pressure is 6MPa, the space velocity of the synthesis gas is 1200h -1 , and the volume ratio of H 2 to CO in the synthesis gas is 3. The raw materials and products of the reaction were analyzed by gas chromatography through pipeline insulation. The specific catalytic performance is shown in Table 1.

表1实施例和对比例催化剂性能评价结果Table 1 embodiment and comparative example catalyst performance evaluation result

Figure BDA0003865941590000061
Figure BDA0003865941590000061

注:C2-4为C2-C4烃,C5+为碳数≥5的脂肪烃,DME为二甲醚,EtOH为乙醇,MA为乙酸甲酯,EA为乙酸乙酯,AA为乙酸。Note: C 2-4 is C 2 -C 4 hydrocarbon, C 5+ is aliphatic hydrocarbon with carbon number ≥ 5, DME is dimethyl ether, EtOH is ethanol, MA is methyl acetate, EA is ethyl acetate, AA is acetic acid.

对比例1Comparative example 1

称取0.6g ZnO-ZrO2(Zn/Al摩尔比为1:4)催化剂、0.2g经选择性脱铝的H-MOR(Si/Al =13)表示为H-MOR-DA-12MR和1.0g 15wt.%CeO2/TiO2,装入石英管中,其中15wt.%CeO2/TiO2在下层,H-MOR-DA-12MR在第二层,ZnO-ZrO2在顶层。通入10%H2-Ar混合气,以5℃/min速率升温至260℃处理1h,后切换为N2吹扫1h,降温至200℃,随后进行催化反应,反应条件如下:反应温度为310℃,反应压力为5MPa,合成气空速为2000h-1,合成气中H2与CO的体积比为2。反应原料及产物经管路保温进入气相色谱在线分析,具体催化反应性能如表1所示。Weigh 0.6g of ZnO-ZrO 2 (Zn/Al molar ratio is 1:4) catalyst, 0.2g of selectively dealuminated H-MOR (Si/Al = 13) is expressed as H-MOR-DA-12MR and 1.0 g 15wt.% CeO 2 /TiO 2 , packed into a quartz tube, wherein 15wt.% CeO 2 /TiO 2 is in the lower layer, H-MOR-DA-12MR is in the second layer, and ZnO-ZrO 2 is in the top layer. Introduce 10% H 2 -Ar mixed gas, heat up to 260°C at a rate of 5°C/min for 1 hour, then switch to N 2 purge for 1 hour, cool down to 200°C, and then carry out catalytic reaction. The reaction conditions are as follows: The reaction temperature is 310°C, the reaction pressure is 5MPa, the space velocity of the synthesis gas is 2000h -1 , and the volume ratio of H 2 to CO in the synthesis gas is 2. The raw materials and products of the reaction were analyzed by gas chromatography through pipeline insulation. The specific catalytic performance is shown in Table 1.

对比例2Comparative example 2

称取0.6g ZnO-ZrO2(Zn/Zr摩尔比为1:4)催化剂、1.0g经选择性脱铝的H-MOR(Si/Al =13)表示为H-MOR-DA-12MR和0.2g 15wt.%CeO2/TiO2,装入石英管中,其中15wt.%CeO2/TiO2在下层,H-MOR-DA-12MR在第二层,ZnO-ZrO2在顶层。通入10%H2-Ar混合气,以5℃/min速率升温至260℃处理1h,后切换为N2吹扫1h,降温至200℃,随后进行催化反应,反应条件如下:反应温度为310℃,反应压力为5MPa,合成气空速为2000h-1,合成气中H2与CO的体积比为2。反应原料及产物经管路保温进入气相色谱在线分析,具体催化反应性能如表1所示。Weigh 0.6g of ZnO-ZrO 2 (Zn/Zr molar ratio is 1:4) catalyst, 1.0g of selectively dealuminated H-MOR (Si/Al = 13) is expressed as H-MOR-DA-12MR and 0.2 g 15wt.% CeO 2 /TiO 2 , packed into a quartz tube, wherein 15wt.% CeO 2 /TiO 2 is in the lower layer, H-MOR-DA-12MR is in the second layer, and ZnO-ZrO 2 is in the top layer. Introduce 10% H 2 -Ar mixed gas, heat up to 260°C at a rate of 5°C/min for 1 hour, then switch to N 2 purge for 1 hour, cool down to 200°C, and then carry out catalytic reaction. The reaction conditions are as follows: The reaction temperature is 310°C, the reaction pressure is 5MPa, the space velocity of the synthesis gas is 2000h -1 , and the volume ratio of H 2 to CO in the synthesis gas is 2. The raw materials and products of the reaction were analyzed by gas chromatography through pipeline insulation. The specific catalytic performance is shown in Table 1.

本发明利用接力催化,耦合了合成气制甲醇、甲醇多相羰基化制乙酸和乙酸酮基化制丙酮,其中合成甲醇的金属氧化物主要活化CO加氢生成甲醇中间体,多级孔沸石分子筛负责催化中间产物甲醇进一步生成乙酸,乙酸在负载型金属氧化物上进一步高选择性转化为丙酮,丙酮的选择性高于90%;本发明合成气高选择性转化制丙酮的催化剂稳定性良好,价格低廉,产品附加值高,具有良好的经济效益,具有潜在的应用前景。The present invention uses relay catalysis to couple syngas to methanol, methanol heterogeneous carbonylation to acetic acid, and acetic acid ketonylation to acetone, wherein the metal oxides used to synthesize methanol are mainly activated to hydrogenate CO to generate methanol intermediates, and multi-stage pore zeolite molecular sieves It is responsible for catalyzing the intermediate product methanol to further generate acetic acid, and the acetic acid is further highly selectively converted into acetone on the supported metal oxide, and the selectivity of acetone is higher than 90%; the catalyst for the high-selective conversion of synthesis gas to acetone in the present invention has good stability, The price is low, the product has high added value, has good economic benefits, and has potential application prospects.

Claims (8)

1.一种合成气一步法制丙酮的方法,其特征在于:将复合型催化剂置于反应器内,进行预处理,然后通入合成气,进行催化反应,得到丙酮;所述复合型催化剂采用多床层方式进行复合,接力催化反应,其中,合成气制甲醇的金属氧化物催化剂置于第一床层,甲醇羰基化制乙酸的沸石分子筛置于第二床层,乙酸酮基化制丙酮的负载型金属氧化物置于第三床层。1. A method for syngas one-step system of acetone, characterized in that: the composite catalyst is placed in the reactor, pre-treated, then feeds the synthesis gas, carries out the catalytic reaction, and obtains acetone; the composite catalyst adopts multiple Composite in bed mode, relay catalytic reaction, in which, the metal oxide catalyst for syngas to methanol is placed in the first bed, the zeolite molecular sieve for methanol carbonylation to acetic acid is placed in the second bed, and the ketone for acetic acid to produce acetone The supported metal oxide is placed in the third bed. 2.如权利要求1所述的一种合成气一步法制丙酮的方法,其特征在于:所述复合型催化剂中,合成气制甲醇的金属氧化物、甲醇羰基化制乙酸的沸石分子筛和乙酸酮基化制丙酮的负载型金属氧化物的质量比为1:(0.5~4):(0.5~4)。2. the method for a kind of synthesis gas one-step method for producing acetone as claimed in claim 1, is characterized in that: in described composite catalyst, the metal oxide of synthesis gas production methanol, the zeolite molecular sieve and acetate ketone of methanol carbonylation production acetic acid The mass ratio of the supported metal oxides for the production of acetone is 1:(0.5-4):(0.5-4). 3.如权利要求1所述的一种合成气一步法制丙酮的方法,其特征在于:所述合成气制甲醇的金属氧化物选自Cu-ZnO-Al2O3、Pd-ZnO-Al2O3、ZnO-Cr2O3-Al2O3、ZnO-Cr2O3、ZnO-ZrO2、CeO2-ZrO2、ZnO-Al2O3、ZnO-Ga2O3、ZnO-Fe2O3、In2O3-ZnO、In2O3-Al2O3中的至少一种。3. A method for producing acetone from syngas in one step as claimed in claim 1, characterized in that: the metal oxides for the synthesis gas to methanol are selected from Cu-ZnO-Al 2 O 3 , Pd-ZnO-Al 2 O 3 , ZnO-Cr 2 O 3 -Al 2 O 3 , ZnO-Cr 2 O 3 , ZnO-ZrO 2 , CeO 2 -ZrO 2 , ZnO-Al 2 O 3 , ZnO-Ga 2 O 3 , ZnO-Fe At least one of 2 O 3 , In 2 O 3 -ZnO, and In 2 O 3 -Al 2 O 3 . 4.如权利要求1所述的一种合成气一步法制丙酮的方法,其特征在于:所述甲醇羰基化制乙酸的沸石分子筛选自具有八元环拓扑结构的MOR、FER、IWW、MEL型沸石分子筛中的至少一种。4. The method for producing acetone by one-step method of synthesis gas as claimed in claim 1, characterized in that: the zeolite molecules for the production of acetic acid by the carbonylation of methanol are selected from MOR, FER, IWW, MEL types with eight-membered ring topology At least one of zeolite molecular sieves. 5.如权利要求4所述的一种合成气一步法制丙酮的方法,其特征在于:所述沸石分子筛具有微孔结构,其中微孔的孔径为0.2~0.8nm,微孔的孔容为0.05~0.5cm3/g。5. A method for producing acetone from syngas in one step as claimed in claim 4, characterized in that: the zeolite molecular sieve has a microporous structure, wherein the pore diameter of the micropores is 0.2 to 0.8 nm, and the pore volume of the micropores is 0.05 nm. ~0.5 cm 3 /g. 6.如权利要求1所述的一种合成气一步法制丙酮的方法,其特征在于:所述乙酸酮基化制丙酮的负载型金属氧化物记为xwt.%MOx/Y,其中x的范围为5%~50%,M为Ce、Mn、Zr、La、Pr、Nd中的至少一种,Y为H-MOR、H-ZSM-5、Al2O3、SiO2、TiO2、MgO、CaCO3中的至少一种。6. the method for a kind of synthesis gas one-step method for producing acetone as claimed in claim 1, is characterized in that: the loaded metal oxide of described acetic acid ketoylation system acetone is marked as xwt.%MO x /Y, wherein x The range is 5% to 50%, M is at least one of Ce, Mn, Zr, La, Pr, Nd, Y is H-MOR, H-ZSM-5, Al 2 O 3 , SiO 2 , TiO 2 , At least one of MgO, CaCO 3 . 7.如权利要求1所述的一种合成气一步法制丙酮的方法,其特征在于,所述预处理的方法为:在固定床、流化床或移动床反应器上装好催化剂后,通入氢气或氢气与惰性气体的混合气,以1~10℃/min速率升温至200~500℃,并保持0.5~10h,然后切换成惰性气体吹扫0.1~5h。7. the method for a kind of synthetic gas one-step process acetone as claimed in claim 1, is characterized in that, the method for described pretreatment is: after installing catalyst on fixed bed, fluidized bed or moving bed reactor, pass into For hydrogen or a mixture of hydrogen and inert gas, the temperature is raised to 200-500°C at a rate of 1-10°C/min, and kept for 0.5-10h, and then switched to inert gas for 0.1-5h. 8.如权利要求1所述的一种合成气一步法制丙酮的方法,其特征在于,所述催化反应的方法如下:复合型催化剂经预处理后,温度降低至30~200℃,通入合成气,其中H2与CO的体积比为1:(0.2~3),然后升温至反应温度为200~400℃,反应压力为0.5~7MPa,合成气空速为500~15000h-1,合成气经过催化剂床层反应得到产物丙酮。8. A method for preparing acetone from syngas in one step as claimed in claim 1, characterized in that the catalytic reaction method is as follows: after the composite catalyst is pretreated, the temperature is reduced to 30-200° C. gas, wherein the volume ratio of H 2 to CO is 1:(0.2~3), and then the temperature is raised to a reaction temperature of 200~400°C, a reaction pressure of 0.5~7MPa, and a synthesis gas space velocity of 500~15000h -1 . The product acetone is obtained through catalyst bed reaction.
CN202211179244.1A 2022-09-27 2022-09-27 Method for preparing acetone by one-step method from synthesis gas Active CN115636739B (en)

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