CN1301686A - Method for preparing dimethyl ether by methanol dewatering - Google Patents
Method for preparing dimethyl ether by methanol dewatering Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 196
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 30
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000018044 dehydration Effects 0.000 claims abstract description 27
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- DBUTVDSHVUGWOZ-UHFFFAOYSA-N [Si].[Ni].[Cr].[Ni] Chemical compound [Si].[Ni].[Cr].[Ni] DBUTVDSHVUGWOZ-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种以高岭土为原料,经硫酸改性后作为催化剂,用于甲醇脱水制二甲醚的方法。其特征在于,将高岭土缓慢加入水溶液中制成均匀浆液,加热的同时加入浓度为25%的硫酸,在60—100℃温度下处理3—9小时,反应完成后的浆液加水静置至pH=4左右,再经抽滤、水洗、干燥,冷却后筛分40—60目颗粒,得酸改性高岭土;经干燥的氢气带动甲醇汽化,两次汽化后的甲醇经100℃预热后进入反应器,进行甲醇脱水反应。该方法与现有生产方法比较,不仅能减少环境污染、腐蚀,而且,在常压下能够获得长期稳定的催化活性,提高甲醇转化率和二甲醚选择性,并且能较大地降低生产成本。A method of using kaolin as a raw material, modified by sulfuric acid, as a catalyst, and used for methanol dehydration to produce dimethyl ether. It is characterized in that kaolin is slowly added to the aqueous solution to form a uniform slurry, and sulfuric acid with a concentration of 25% is added while heating, and treated at a temperature of 60-100°C for 3-9 hours, and the slurry after the reaction is completed is added with water and left to stand until pH = 4 or so, then suction filtered, washed with water, dried, sieved after cooling, and sieved 40-60 mesh particles to obtain acid-modified kaolin; the dried hydrogen drives the vaporization of methanol, and the methanol vaporized twice enters the reaction after preheating at 100°C device for methanol dehydration. Compared with the existing production methods, the method not only can reduce environmental pollution and corrosion, but also can obtain long-term stable catalytic activity under normal pressure, improve methanol conversion rate and dimethyl ether selectivity, and greatly reduce production cost.
Description
本发明涉及甲醇脱水的醚化反应，具体涉及一种酸改性高岭土用于甲醇脱水制二甲醚的方法。The invention relates to the etherification reaction of methanol dehydration, in particular to a method for acid-modified kaolin used in methanol dehydration to prepare dimethyl ether.
二甲醚即甲醚，其结构式为CH3-O-CH3，具有无毒、安全、热值高等优点，是液化燃料气理想的代用品，也是一种重要的基本化工原料，在制药、染料、农药、制冷、日用化工等领域有着广泛的用途。早期，甲醇脱水制二甲醚采用的脱水剂是浓硫酸，反应在液相中进行，该工艺方法由于环境污染和腐蚀严重，因而急待改进；亦有用甲醇气相脱水制二甲醚的，传统的工业生产方法是把甲醇蒸汽在350-400℃和1.5MPa的压力下通过磷酸铝催化剂而制得,该方法温度偏高，转化率低：1981年，美国Mobil公司曾利用硅铝比比较高的HZSM-5型分子筛，其甲醇转化率可达70％，但由于催化剂制备较难，对于工业应用来说，其生产成本较高。1991年，日本三井东亚化学公司开发了具有特殊表面积和孔体积的γ-Al2O3作为甲醇脱水制二甲醚的催化剂，甲醇转化率可达80％。目前，国内外正在大力研究对高岭土进行改性及其催化活性的探索，应用研究集中在催化裂化反应上，而对高岭土进行酸改性用于甲醇脱水的醚化反应尚未见报导。Dimethyl ether is methyl ether, and its structural formula is CH 3 -O-CH 3 . It has the advantages of non-toxicity, safety, and high calorific value. It is an ideal substitute for liquefied fuel gas and an important basic chemical raw material. It is used in pharmaceuticals, It has a wide range of applications in the fields of dyes, pesticides, refrigeration, and daily chemicals. In the early days, the dehydrating agent used to produce dimethyl ether by methanol dehydration was concentrated sulfuric acid, and the reaction was carried out in the liquid phase. Due to the serious environmental pollution and corrosion, this process urgently needs to be improved; it is also used to produce dimethyl ether by methanol vapor phase dehydration, the traditional The current industrial production method is to pass methanol vapor through an aluminum phosphate catalyst at 350-400 ° C and a pressure of 1.5 MPa. The HZSM-5 type molecular sieve has a methanol conversion rate of up to 70%, but because the preparation of the catalyst is difficult, its production cost is relatively high for industrial applications. In 1991, Japan's Mitsui East Asia Chemical Company developed γ-Al 2 O 3 with special surface area and pore volume as a catalyst for methanol dehydration to dimethyl ether, and the conversion rate of methanol can reach 80%. At present, the modification of kaolin and the exploration of its catalytic activity are being vigorously studied at home and abroad. The applied research focuses on the catalytic cracking reaction, but the etherification reaction of acid modification of kaolin for methanol dehydration has not been reported yet.
本发明的目的旨在提供一种以便宜、易得的高岭土为原料，经硫酸改性后作为催化剂，用于甲醇脱水制二甲醚的方法，以解决：减少环境污染、腐蚀，在常压下能获得长期稳定的催化活性，提高甲醇转化率，使二甲醚选择性大于99％并且能较大降低生产成本等问题。The purpose of the present invention is to provide a method of using cheap and easy-to-get kaolin as a raw material, modified by sulfuric acid as a catalyst, and used for methanol dehydration to produce dimethyl ether, so as to solve: reduce environmental pollution, corrosion, Under the circumstances, long-term stable catalytic activity can be obtained, the conversion rate of methanol can be improved, the selectivity of dimethyl ether can be greater than 99%, and the production cost can be greatly reduced.
本发明是这样实现的，首先是酸改性高岭土的制备，在水溶液中，边搅拌边慢慢加入高岭土，制成均匀浆液，缓慢加热浆液，加入相对量为0.15-0.60、浓度为25％的H2SO4，继续升温，在60-100℃温度下，处理3-9小时，反应完成后的浆液加水静置至PH=4左右，经水泵抽滤、水洗、干燥，冷却后筛分40-60目颗粒即得酸改性高岭土；然后用于甲醇脱水制二甲醚的反应中，经干燥的氢气以流速20-130ml/min带动甲醇汽化，两次汽化后的甲醇经100℃预热后进入反应器，在常压、温度为220-320℃、甲醇液空速为0.62-8ml/h、催化剂装填量0.15g的条件下，进行甲醇脱水反应。下面详细叙述本发明。The present invention is realized in this way. Firstly, the preparation of acid-modified kaolin, in the aqueous solution, slowly add kaolin while stirring to make a uniform slurry, slowly heat the slurry, add a relative amount of 0.15-0.60, a concentration of 25% H 2 SO 4 , continue to heat up, and treat at 60-100°C for 3-9 hours. After the reaction is completed, add water to the slurry and let it stand until pH = 4. After pumping, filtering, washing, and drying, sieve after cooling for 40 -60 mesh particles to obtain acid-modified kaolin; then used in the reaction of methanol dehydration to dimethyl ether, the dried hydrogen drives the vaporization of methanol at a flow rate of 20-130ml/min, and the methanol after two vaporizations is preheated at 100°C After entering the reactor, the methanol dehydration reaction is carried out under the conditions of normal pressure, temperature 220-320°C, methanol liquid space velocity 0.62-8ml/h, and catalyst loading 0.15g. The present invention will be described in detail below.
本发明采用高岭土的组成是含有38％的氧化铝(Al2O3)和43％的二氧化硅(SiO2)。The composition of kaolin used in the present invention contains 38% of alumina (Al 2 O 3 ) and 43% of silicon dioxide (SiO 2 ).
(一)酸改生高岭土的制备(1) Preparation of acid-modified kaolin
在水溶液中，边搅拌边慢慢加入含有氧化铝(Al2O3)38％和二氧化硅(SiO2)43％的高岭土，制成均匀浆液，然后缓慢加热浆液，加入相对量为0.15-0.60、浓度为25％的H2SO4，继续升温，在60-100℃温度下，处理3-9小时，反应完成后的浆液加水静置至PH=4左右，经水泵抽滤、水洗、干燥，筛分40-60目颗粒，即得酸改性高岭土。In the aqueous solution, slowly add kaolin containing 38% aluminum oxide (Al 2 O 3 ) and 43% silicon dioxide (SiO 2 ) while stirring to make a uniform slurry, then slowly heat the slurry, and add a relative amount of 0.15- 0.60, H 2 SO 4 with a concentration of 25%, continue to heat up, and treat at 60-100°C for 3-9 hours. After the reaction is completed, add water to the slurry and let it stand until pH = 4. After pumping, filtering, washing, Dry and sieve 40-60 mesh particles to obtain acid-modified kaolin.
(二)甲醇脱水制二甲醚(2) Dehydration of methanol to produce dimethyl ether
将上述方法制取的酸改性高岭土作催化剂用于甲醇脱水制二甲醚的反应中。甲醇气相催化的原理是将甲醇蒸汽通过固体酸催化剂，发生气固相催化反应，脱水生成二甲醚。The acid-modified kaolin prepared by the above method is used as a catalyst in the reaction of methanol dehydration to dimethyl ether. The principle of methanol gas-phase catalysis is to pass methanol vapor through a solid acid catalyst, a gas-solid phase catalytic reaction occurs, and dehydration produces dimethyl ether.
(1)、甲醇脱水生成二甲醚的化学反应式为：(1), the chemical reaction formula that methanol dehydration generates dimethyl ether is:
(2)、甲醇脱水制二甲醚及催化剂的活性评价在自组装的常压连续流动微反-色谱连用装置上进行(装置见附图1)。(2) The evaluation of methanol dehydration to dimethyl ether and the activity of the catalyst was carried out on a self-assembled normal pressure continuous flow micro-reflector-chromatographic device (see Figure 1 for the device).
参见图1，从H2钢瓶1出来的氢气经过干燥剂2干燥后进入甲醇饱和器5，用氢气鼓泡带动甲醇汽化，为使甲醇蒸汽达到饱和，采用两次汽化，同时，用皂末流量计将氢气流速控制在20-130ml/min范围内，两次汽化后的甲醇经过预热器6预热至100℃后进入微型反应管7中，在常压、温度220-320℃、甲醇液空速为0.62-ml/h、催化剂装填量0.15g的条件下，进行甲醇脱水反应。Referring to Fig. 1, the hydrogen from the H2
反应器为内径4mm的直型不锈钢管，置于恒温石英管中，反应炉温以702精密温度控制仪控制，镍铬-镍硅热电偶检测，恒温精度±0.5℃。The reactor is a straight stainless steel tube with an inner diameter of 4mm, which is placed in a constant temperature quartz tube. The temperature of the reaction furnace is controlled by a 702 precision temperature controller, detected by a nickel-chromium-nickel-silicon thermocouple, and the constant temperature accuracy is ±0.5°C.
将本发明的酸改性高岭土与现有催化剂比较(表1)。The acid-modified kaolin of the present invention was compared with existing catalysts (Table 1).
表1：
从表1中的对比数据可知：用酸改性高岭土作催化剂用于甲醇脱水制二甲醚反应，能够提高甲醇转化率，并使二甲醚选择性大于99％。从本发明的实验得出：From the comparative data in Table 1, it can be seen that using acid-modified kaolin as a catalyst for the reaction of methanol dehydration to dimethyl ether can increase the conversion rate of methanol and make the selectivity of dimethyl ether greater than 99%. Draw from experiment of the present invention:
1、高岭土用硫酸改性后用于甲醇脱水制二甲醚，催化活性较原土有很大提高。酸相对用量、处理时间、处理温度等条件对改性高岭土的催化性能有很大影响。当相对硫酸用量为0.30的MK-3催化剂活性最佳，反应温度300℃时甲醇转化率81.6％，二甲醚选择性＞99％，并且活性稳定性也很好。1. Kaolin modified with sulfuric acid is used for methanol dehydration to produce dimethyl ether, and its catalytic activity is greatly improved compared with the original soil. The relative amount of acid, treatment time, treatment temperature and other conditions have a great influence on the catalytic performance of modified kaolin. When the relative sulfuric acid dosage is 0.30, the activity of the MK-3 catalyst is the best, the conversion rate of methanol is 81.6% when the reaction temperature is 300°C, the selectivity of dimethyl ether is >99%, and the activity stability is also very good.
2、反应温度对甲醇脱水制二甲醚的转化率有很大影响。在一定停留时间下，随着反应温度升高，甲醇转化率提高，到320℃以后转化率基本保持不变。2. The reaction temperature has a great influence on the conversion rate of methanol dehydration to dimethyl ether. Under a certain residence time, the conversion rate of methanol increases with the increase of reaction temperature, and the conversion rate remains basically unchanged after 320°C.
因此，本发明的酸改性高岭土用于甲醇脱水制二甲醚的方法，不仅能减少环境污染、腐蚀，而且，在常压下能够获得长期稳定的催化活性，提高甲醇转化率和二甲醚选择性，并且能较大地降低生产成本。酸改性高岭土(1000元/吨)在工业上是一种优异的制取二甲醚的催化剂。Therefore, the acid-modified kaolin of the present invention is used in the method for methanol dehydration to produce dimethyl ether, which can not only reduce environmental pollution and corrosion, but also obtain long-term stable catalytic activity under normal pressure, improve methanol conversion rate and dimethyl ether Selectivity, and can greatly reduce production costs. Acid-modified kaolin (1000 yuan/ton) is an excellent catalyst for producing dimethyl ether in industry.
本发明的具体实施例如下：Specific embodiments of the present invention are as follows:
例1：在水溶液中，边搅拌边慢慢加入含有氧化铝(Al2O3)38％和二氧化硅(SiO2)43％的高岭土，制成均匀浆液，然后缓慢口热浆液，加入相对量为0.60、浓度为25％的H2SO4，继续升温至60℃，处理6小时，反应完成后的浆液加水静置至PH=4左右，经水泵抽滤、水洗、干燥，冷却后筛分40-60目颗粒，即得酸改性高岭土，记为MK-1。Example 1: In an aqueous solution, slowly add kaolin containing 38% of alumina (Al 2 O 3 ) and 43% of silicon dioxide (SiO 2 ) while stirring to make a uniform slurry, then slowly heat the slurry, and add the relative H 2 SO 4 with a concentration of 0.60 and a concentration of 25%, continue to heat up to 60°C, and treat for 6 hours. After the reaction is completed, the slurry is added with water and allowed to stand until PH = 4, filtered by a water pump, washed with water, dried, and sieved after cooling. Divide into 40-60 mesh particles to obtain acid-modified kaolin, which is denoted as MK-1.
将上述方法制备的酸改性高岭土按前述方法进行甲醇脱水制二甲醚反应，催化剂的活性以甲醇转化二甲醚的转化率表示，其测定结果如表2。The acid-modified kaolin prepared by the above method was subjected to methanol dehydration to dimethyl ether reaction according to the aforementioned method, and the activity of the catalyst was represented by the conversion rate of methanol into dimethyl ether, and the measurement results are shown in Table 2.
表2(注：二甲醚选择性均大于99％)
例2：制备方法同例1。酸的相对量为0.15，酸的处理时间为3小时，处理温度100℃，记为MK-2。Example 2: The preparation method is the same as Example 1. The relative amount of acid is 0.15, the acid treatment time is 3 hours, and the treatment temperature is 100°C, which is recorded as MK-2.
同前法进行甲醇脱水制二甲醚反应，其测定结果如表3。Carry out the reaction of methanol dehydration to dimethyl ether with the previous method, and the measurement results are shown in Table 3.
表3(注：二甲醚选择性均大于99％)
例3：制备方法同例1。酸的相对量为0.3，酸的处理时间为3小时，处理温度80℃，记为MK-3。Example 3: The preparation method is the same as Example 1. The relative amount of acid is 0.3, the acid treatment time is 3 hours, and the treatment temperature is 80°C, which is recorded as MK-3.
同前法进行甲醇脱水制二甲醚反应，其测定结果如表4。Carry out the reaction of methanol dehydration to dimethyl ether with the previous method, and the measurement results are shown in Table 4.
表4(注：二甲醚选择性均大于99％)
同时，对本实施例制备的催化剂进行了活性寿命试验，测初期最高甲醇转化率和500h内甲醇转化率，其结果如表5。At the same time, the catalyst prepared in this example was tested for activity life, and the highest methanol conversion rate at the initial stage and the methanol conversion rate within 500 hours were measured. The results are shown in Table 5.
表5
例4：制备方法同例1。酸的相对量为0.60，酸的处理时间为3小时，处理温度60℃，记为MK-4。Example 4: The preparation method is the same as Example 1. The relative amount of acid is 0.60, the acid treatment time is 3 hours, and the treatment temperature is 60°C, which is recorded as MK-4.
同前法进行甲醇脱水制二甲醚反应，其测定结果如表6。Carry out methanol dehydration to produce dimethyl ether with the previous method, and its measurement results are shown in Table 6.
表6 (注：二甲醚选择性均大于99/％)
同时，对本实施例制备的催化剂进行了活性寿命试验，测初期最高甲醇转化率和500h内甲醇转化率，其结果如表7。At the same time, the catalyst prepared in this example was tested for its active life, and the highest methanol conversion rate at the initial stage and the methanol conversion rate within 500 hours were measured. The results are shown in Table 7.
表7催化剂 温度(℃) 初期活性 120h 240h 360h 500hMK- 4 318-322 85.1 85.2 82.9 80.1 80.0Table 7 Catalyst Temperature (°C) Initial Activity 120h 240h 360h 500hMK- 4 318-322 85.1 85.2 82.9 80.1 80.0
例5：制备方法同例1。酸的相对量为0.60，酸的处理时间为9小时，处理温度60℃，记为MK-5。Example 5: The preparation method is the same as Example 1. The relative amount of acid is 0.60, the acid treatment time is 9 hours, and the treatment temperature is 60°C, which is recorded as MK-5.
同前法进行甲醇脱水制二甲醚反应，其测定结果如表8。Carry out the reaction of methanol dehydration to dimethyl ether with the previous method, and the measurement results are shown in Table 8.
表8 (注：二甲醚选择性均大于99％)
同时，对本实施例制备的催化剂进行了活陛寿命试验，测初期最高甲醇转化率年500h内甲醇转化率，其结果如表9。Simultaneously, the catalyst prepared by the present embodiment has been carried out live life test, and the maximum methanol conversion rate in the initial stage is measured within 500h of the methanol conversion rate, and the results are shown in Table 9.
表9
附图说明：图1为甲醇脱水制二甲醚反应装置图，图中：1-H2钢瓶；2-干燥剂；3-稳流阀；4-玻璃转子流量计；5-甲醇进料管；6-预热器；7-微反应管；8-六通阀；9-102G气相色谱仪；10-导池电源及氢焰离子放大器；11-精密温度控制器一台；12-微机处理系统；13-镍铬-镍硅精密控温仪；14-三通阀。Description of the drawings: Figure 1 is a diagram of the reaction device for methanol dehydration to dimethyl ether. In the figure: 1- H2 steel cylinder; 2-desiccant; 3-stabilizing valve; 4-glass rotameter; 5-methanol feed pipe ;6-preheater; 7-micro-reaction tube; 8-six-way valve; 9-102G gas chromatograph; 10-conducting pool power supply and hydrogen flame ion amplifier; 11-one precision temperature controller; System; 13-nickel-chromium-nickel-silicon precision temperature controller; 14-three-way valve.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366597C (en) * | 2006-07-21 | 2008-02-06 | 新奥新能(北京)科技有限公司 | Process for preparing dimethyl ether |
| US8304582B2 (en) | 2007-03-30 | 2012-11-06 | China Petroleum & Chemical Corporation | Fluidized catalytic process for production of dimethyl ether from methanol |
| US8541630B2 (en) | 2008-03-26 | 2013-09-24 | China Petroleum & Chemical Corporation | Process for producing dimethyl ether from methanol |
| WO2013166985A1 (en) * | 2012-05-11 | 2013-11-14 | Rhodia Operations | Preparation of an ether compound |
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1999
- 1999-12-24 CN CN 99122907 patent/CN1301686A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366597C (en) * | 2006-07-21 | 2008-02-06 | 新奥新能(北京)科技有限公司 | Process for preparing dimethyl ether |
| US8304582B2 (en) | 2007-03-30 | 2012-11-06 | China Petroleum & Chemical Corporation | Fluidized catalytic process for production of dimethyl ether from methanol |
| US8541630B2 (en) | 2008-03-26 | 2013-09-24 | China Petroleum & Chemical Corporation | Process for producing dimethyl ether from methanol |
| WO2013166985A1 (en) * | 2012-05-11 | 2013-11-14 | Rhodia Operations | Preparation of an ether compound |
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