WO2019218490A1 - 一种合成气直接制备二甲醚的方法 - Google Patents

一种合成气直接制备二甲醚的方法 Download PDF

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WO2019218490A1
WO2019218490A1 PCT/CN2018/098069 CN2018098069W WO2019218490A1 WO 2019218490 A1 WO2019218490 A1 WO 2019218490A1 CN 2018098069 W CN2018098069 W CN 2018098069W WO 2019218490 A1 WO2019218490 A1 WO 2019218490A1
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reaction
dimethyl ether
synthesis gas
spinel oxide
zinc
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English (en)
French (fr)
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倪友明
朱文良
刘中民
刘勇
刘红超
马现刚
刘世平
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中国科学院大连化学物理研究所
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Priority to US17/054,894 priority Critical patent/US11247959B2/en
Priority to EP18918803.0A priority patent/EP3795556A4/en
Priority to EA202092622A priority patent/EA202092622A1/ru
Publication of WO2019218490A1 publication Critical patent/WO2019218490A1/zh

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Definitions

  • the invention relates to a method for directly preparing dimethyl ether from syngas.
  • Dimethyl ether (CH 3 OCH 3 , DME) is a non-toxic, harmless, non-corrosive chemical. Due to its high cetane number, no nitrogen and sulfur, and good compatibility with diesel, dimethyl ether is a very potential clean diesel additive. The physicochemical properties of dimethyl ether and liquefied petroleum gas are very close, and it has a broad application space in the field of household fuel.
  • the synthesis gas can be directly converted into dimethyl ether in one step.
  • the methanol synthesis catalyst is generally used below 250 ° C.
  • the solid acid catalyst used for the methanol dehydration reaction needs to be higher than this temperature to exert good performance, so the composite catalyst generally has an operating temperature of 250 to 300 ° C.
  • the stability of the composite catalyst is deteriorated, and CuZnAlO x can not be regenerated.
  • the synthesis gas is passed through a reaction zone carrying the catalyst, and reacted under reaction conditions sufficient to convert at least a portion of the feedstock to provide a reaction effluent comprising dimethyl ether;
  • the catalyst is a zinc aluminum spinel oxide.
  • the reaction zone contains a fixed bed reactor, or a plurality of fixed bed reactors in series and/or in parallel.
  • the reaction conditions include: a reaction temperature of 300 to 450 ° C, a reaction pressure of 0.5 to 10.0 MPa, a molar ratio of hydrogen to carbon monoxide in the synthesis gas of 1:9 to 9:1, and 1000 to 20000 h. Syngas volume hourly space velocity in the standard state of -1 .
  • the present invention provides a process for the direct preparation of dimethyl ether from syngas, the process comprising:
  • the synthesis gas is passed through a reaction zone carrying the catalyst, and reacted under reaction conditions sufficient to convert at least a portion of the feedstock to provide a reaction effluent comprising dimethyl ether;
  • the catalyst is a zinc aluminum spinel oxide.
  • the catalyst used in the process of the invention is a zinc aluminum spinel oxide.
  • the zinc aluminum spinel oxide has a zinc aluminum spinel crystal size of less than or equal to 30 nm.
  • the zinc aluminum spinel oxide further contains at least one other element selected from the group consisting of chromium, zirconium, copper, manganese, indium, gallium, and silicon.
  • the other elements may be added to the zinc aluminum spinel oxide by impregnation and/or coprecipitation of a brine solution of at least one other element.
  • the mass fraction of the other element in the zinc aluminum spinel oxide is less than or equal to 10%, such as 1%, 3%, 5%, 7%, 9% or 10%.
  • the zinc aluminum spinel oxide is prepared by a precipitation-calcination process.
  • the zinc aluminum spinel oxide is prepared by a method comprising the steps of: formulating a zinc salt and an aluminum salt into a mixed metal salt aqueous solution; contacting the mixed metal salt aqueous solution with an aqueous solution of a precipitating agent to make The metal ions in the mixed metal salt aqueous solution are coprecipitated; aged; and the precipitate is washed, dried, and calcined to obtain the zinc aluminum spinel oxide.
  • precipitating agents include, but are not limited to, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, aqueous ammonia, sodium hydroxide, potassium hydroxide, and mixtures thereof.
  • the temperature during the coprecipitation is from 20 ° C to 95 ° C
  • the pH during the coprecipitation is from 7.0 to 9.0
  • the aging time is not less than 1 hour
  • the calcination temperature is from 450 ° C to 800 ° C.
  • the zinc aluminum spinel oxide is prepared by dissolving a zinc salt and an aluminum salt in any ratio in deionized water to prepare a mixed metal salt aqueous solution having a concentration of the mixed metal salt aqueous solution.
  • the room temperature can be completely dissolved in any concentration of deionized water; the precipitating agent is dissolved in deionized water to prepare an aqueous solution of a precipitating agent, and the concentration of the aqueous solution of the precipitating agent is completely soluble in any concentration of deionized water at room temperature;
  • the mixed metal salt aqueous solution is contacted with the aqueous solution of the precipitating agent, and coprecipitated at 20 to 95 ° C.
  • the pH of the mixed metal salt aqueous solution and the aqueous solution of the precipitating agent is controlled during the precipitation to control the pH between 7.0 and 9.0.
  • the mixture is aged at 20 to 95 ° C for 1 to 24 hours, then centrifuged, washed with deionized water, dried at 100 ° C for 24 hours, and finally calcined at 450 to 800 ° C for 2 to 10 hours to obtain zinc aluminum spinel oxide.
  • the kinds of the salts of the zinc salt, the aluminum salt and at least one other element are not particularly limited as long as they are water-soluble, for example, have a water solubility of more than 1 g/L at 25 °C.
  • Examples of salts of the zinc salt, aluminum salt, and at least one other element include, but are not limited to, hydrochloride, sulfate, and nitrate.
  • the manner of contacting the mixed metal salt aqueous solution with the aqueous solution of the precipitating agent is not particularly limited.
  • the contacting can be accomplished by cocurrent, feed or reverse feed.
  • the syngas is contacted with the catalyst in the reaction zone under reaction conditions sufficient to convert at least a portion of the feed to provide a dimethyl ether containing reaction effluent.
  • synthesis gas refers to a mixture of hydrogen and carbon monoxide.
  • the molar ratio of hydrogen to carbon monoxide in the syngas feed may be from 1:9 to 9:1, preferably from 1:9 to 1:1.
  • the synthesis gas in the process of the present invention may further contain carbon dioxide, and the molar concentration of carbon dioxide in the synthesis gas is 1.0 to 20.0%, for example, 1%, 3%, 5%, 8%, 10%, 13%. , 15%, 17% and 20%.
  • the reaction zone may be one or more fixed bed reactors.
  • the fixed bed reactor can be operated in a continuous mode.
  • the plurality of reactors can be in series, parallel, or a combination of series and parallel.
  • the reaction conditions include: a reaction temperature of 300 to 450 ° C, a reaction pressure of 0.5 to 10.0 MPa, a molar ratio of hydrogen to carbon monoxide in a synthesis gas of 1:9 to 9:1, and 1000 to Syngas volume hourly space velocity in the standard state of 20000 h -1 .
  • the reaction conditions include: a reaction temperature of 310 to 360 ° C, a reaction pressure of 1.0 to 4.0 MPa, a molar ratio of hydrogen to carbon monoxide in the synthesis gas of 3:1 to 6:1, and 3000. Syngas volume hourly space velocity in the standard state of ⁇ 8000h -1 .
  • the separation of the dimethyl ether product from the reaction effluent comprising dimethyl ether can be carried out according to methods known per se.
  • the method of the invention realizes the synthesis of dimethyl ether in one step of the synthesis gas, and reduces the problem of a large amount of energy consumption brought by the stepwise production.
  • Example 1 is an XRD chart of material A in Example 1 of the present application.
  • Example 2 is a TEM image of material A in Example 1 of the present application.
  • automated analysis was performed using an Agilent 7890 gas chromatograph with a gas autosampler, a TCD detector connected to a TDX-1 packed column, and an FID detector connected to a PLOT-Q capillary column.
  • Carbon monoxide conversion [( moles of carbon monoxide carbon in the feed) - (molar carbon monoxide carbon in the discharge)] ⁇ (moles of carbon monoxide in the feed) ⁇ 100%
  • Dimethyl ether selectivity (molar dimethyl ether carbon number in the discharge) ⁇ (sum of all hydrocarbon products in the discharge, methanol, dimethyl ether) ⁇ 100%
  • Methanol selectivity (mole of methanol carbon in the discharge) ⁇ (sum of all hydrocarbon products in the discharge, carbon moles of methanol, dimethyl ether) ⁇ 100%
  • Hydrocarbon selectivity (carbon moles of all hydrocarbon products in the discharge) ⁇ (sum of all hydrocarbon products in the discharge, methanol, dimethyl ether) ⁇ 100%
  • Carbon dioxide selectivity (molar carbon dioxide carbon produced by the reaction) ⁇ (molar carbon monoxide carbon converted) ⁇ 100%.
  • the product was analyzed by gas chromatography, and the results are shown in Table 1.
  • Example 7 The catalyst deactivated in Example 7 was treated with a mixture of a volume fraction of 2% oxygen and 98% nitrogen at 550 ° C for 10 h to cause the catalyst to regenerate for one round and reacted under the conditions of Example 7. Five rounds were regenerated in the same manner, and the catalytic activity data after 500 hours of each reaction was selected for comparison. The results are shown in Table 2.

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Abstract

本发明公开了一种合成气直接制备二甲醚的方法，该方法包括：使合成气通过载有催化剂的反应区，在足以转化至少部分原料的反应条件下反应，以得到包含二甲醚的反应流出物；和从所述反应流出物中分离所述二甲醚，其中所述催化剂为锌铝尖晶石氧化物。本发明中只使用一种锌铝尖晶石氧化物催化剂，能使合成气高选择性生成二甲醚，催化剂稳定性好，催化剂可以重生。本发明的方法实现了合成气一步生成二甲醚，降低了分步生产带来的大量能耗问题。

Description

一种合成气直接制备二甲醚的方法 技术领域
本发明涉及一种合成气直接制备二甲醚的方法。
背景技术
二甲醚(CH 3OCH 3，DME)是一种无毒、无害、无腐蚀性的化学品。由于十六烷值高，不含氮硫，与柴油互溶性好等优点，二甲醚是一种非常有潜力的清洁柴油添加剂。二甲醚与液化石油气的物理化学性质非常接近，在家用燃料领域具有广阔的应用空间。近年来，“煤制乙醇”技术一直是“煤化工”领域研究热点，例如，“煤转化为二甲醚，然后经过羰化、加氢反应制取无水乙醇”的技术，因此二甲醚未来在合成燃料乙醇技术中具有广泛的用途。目前，二甲醚主要通过甲醇在固体酸催化剂上的脱水反应进行工业生产。我们知道，甲醇主要由合成气在铜锌铝(CuZnAlO x)甲醇合成催化剂上进行合成。为了节约固定投资，降低能耗，人们希望能够将合成气直接一步转化为二甲醚。在大量关于合成气直接制取二甲醚的报道中，基于CuZnAlO x/固体酸(酸性分子筛或γ-Al 2O 3)复合催化剂的研究最多。甲醇合成催化剂一般在250℃以下使用，然而用于甲醇脱水反应的固体酸催化剂需要高于此温度才能发挥良好的性能，故复合催化剂一般操作温度为250～300℃。在高温反应条件下，复合催化剂稳定性变差，而且CuZnAlO x不能重生，这些因素导致了合成气直接制取二甲醚技术至今没有实现工业化。
发明内容
为了克服现有技术中存在的问题，本发明人进行了勤勉的研究。结果发现，锌铝尖晶石氧化物非常适合作为由合成气直接制备二甲醚方法的催化剂，使用该催化剂、由合成气直接制备二甲醚的方法能使合成气高选择性生成二甲醚，催化剂不仅稳定性好而且可以重生，并且降低了分步生产 带来的大量能耗问题。本发明人在上述发现基础上完成了本发明。
因此，本发明的一个目的是提供一种由合成气直接制备二甲醚的方法，该方法包括：
使合成气通过载有催化剂的反应区，在足以转化至少部分原料的反应条件下反应，以得到包含二甲醚的反应流出物；和
从所述反应流出物中分离所述二甲醚，
其中所述催化剂为锌铝尖晶石氧化物。
在一个实施方案中，所述反应区含有一个固定床反应器，或串联和/或并联的多个固定床反应器。
在一个实施方案中，所述反应条件包括：300～450℃的反应温度，0.5～10.0MPa的反应压力，1∶9～9∶1的合成气中氢气与一氧化碳的摩尔比，和1000～20000h -1的标准状态下合成气体积小时空速。
优选实施方案的描述
本发明提供了一种由合成气直接制备二甲醚的方法，该方法包括：
使合成气通过载有催化剂的反应区，在足以转化至少部分原料的反应条件下反应，以得到包含二甲醚的反应流出物；和
从所述反应流出物中分离所述二甲醚，
其中所述催化剂为锌铝尖晶石氧化物。
用于制备二甲醚的催化剂
如上所述，本发明方法中使用的催化剂为锌铝尖晶石氧化物。
本发明的锌铝尖晶石氧化物中Zn/Al摩尔比为任意比例，优选Zn/Al＝1∶9～1∶1，例如1∶1，1∶2，1∶4.5或1∶9。
在一些实施方案中，所述锌铝尖晶石氧化物中锌铝尖晶石晶体尺度小于或等于30nm。
在一些实施方案中，所述锌铝尖晶石氧化物中还含有选自铬、锆、铜、锰、铟、镓和硅中的至少一种其它元素。所述其它元素可以通过浸渍和/或共沉淀至少一种其它元素的盐水溶液添加到锌铝尖晶石氧化物中。优选地，所述其它元素在锌铝尖晶石氧化物中的质量分数小于或等于10％，例 如1％，3％，5％，7％，9％或10％。
在一个实施方案中，所述锌铝尖晶石氧化物是通过沉淀-煅烧方法制备的。例如，所述锌铝尖晶石氧化物是通过包括如下步骤的方法制备的：将锌盐与铝盐配成混合金属盐水溶液；使所述混合金属盐水溶液和沉淀剂水溶液接触，以使所述混合金属盐水溶液中的金属离子共沉淀；老化；和将沉淀物洗涤、干燥后煅烧，制得所述锌铝尖晶石氧化物。所述的沉淀剂的实例包括但不限于碳酸钠、碳酸钾、碳酸铵、碳酸氢钠、碳酸氢钾、碳酸氢铵、氨水、氢氧化钠、氢氧化钾和它们的混合物。
在一个实施方案中，所述共沉淀过程中温度为20℃至95℃，共沉淀过程中pH值为7.0至9.0，老化时间不低于1小时，煅烧温度为450℃至800℃。
在一个具体实施方案中，所述锌铝尖晶石氧化物如下制备：将任意比例的锌盐和铝盐溶于去离子水中，配制成混合金属盐水溶液，所述混合金属盐水溶液的浓度为室温可完全溶解于去离子水的任意浓度；将沉淀剂溶于去离子水中，配制成沉淀剂水溶液，所述沉淀剂水溶液的浓度为室温可完全溶解于去离子水的任意浓度；使所述混合金属盐水溶液与所述沉淀剂水溶液进行接触，在20～95℃下共沉淀，沉淀过程中通过控制混合金属盐水溶液与沉淀剂水溶液的流量来控制pH值为7.0～9.0之间。共沉淀完毕后，在20～95℃下老化1～24h，然后离心分离，去离子水洗涤，100℃下干燥24h，最后450～800℃下煅烧2～10h获得锌铝尖晶石氧化物。
在本发明中，对所述锌盐、铝盐和至少一种其它元素的盐的种类没有特殊的限制，只要它们是水溶性的，例如在25℃下具有大于1g/L的水溶解度。所述锌盐、铝盐和至少一种其它元素的盐的实例包括但不限于盐酸盐、硫酸盐和硝酸盐。
在本发明方法中，对所述混合金属盐水溶液与所述沉淀剂水溶液的接触方式没有特殊的限制。在一个具体的实施方案中，所述接触可以采取并流加料、正加料或反加料的方式完成。
由合成气制备二甲醚的方法
如前所述，在本发明的方法中，使合成气与催化剂在反应区中在足以 转化至少部分原料的反应条件下接触，以得到包含二甲醚的反应流出物。
不希望局限于任何具体理论，据信合成气直接制取二甲醚的反应包括一系列的反应过程，例如：
1)甲醇合成反应：
CO+2H 2＝CH 3OH
2)甲醇脱水制二甲醚反应：
2CH 3OH＝DME+H 2O
3)水煤气变换反应：
CO+H 2O＝CO 2+H 2
本文中使用的术语“合成气”是指氢气与一氧化碳的混合气。在所述合成气原料中，氢气与一氧化碳的摩尔比可以为1∶9-9∶1，优选为1∶9-1∶1。
由于合成气直接制取二甲醚反应中主要的副反应为水煤气变换反应，此反应为典型的平衡反应，加入二氧化碳有利于抑制水煤气变换反应，提高一氧化碳的利用效率。所以，本发明方法中的所述合成气中还可以含有二氧化碳，二氧化碳在合成气中的摩尔浓度为1.0～20.0％，例如，1％，3％，5％，8％，10％，13％，15％，17％和20％。
在本发明的方法中，所述反应区可以为一个或多个固定床反应器。所述固定床反应器可以采用连续模式操作。当采用多个固定床反应器时，所述多个反应器可以呈串联、并联、或者串联与并联相结合的构型。
在本发明的方法中，所述反应条件包括：300～450℃的反应温度，0.5～10.0MPa的反应压力，1∶9～9∶1的合成气中氢气与一氧化碳的摩尔比，和1000～20000h -1的标准状态下合成气体积小时空速。
在一个优选的实施方案中，所述反应条件包括：310～360℃的反应温度，1.0～4.0MPa的反应压力，3∶1～6∶1的合成气中氢气与一氧化碳的摩尔比，和3000～8000h -1的标准状态下合成气体积小时空速。
反应流出物的分离
在本发明的方法中，从所述包含二甲醚的反应流出物中分离二甲醚产物可以按照本质上已知的方法进行。
本发明能产生的有益效果包括：
1)本发明中只使用一种锌铝尖晶石氧化物催化剂，能使合成气高选择性生成二甲醚，催化剂稳定性好，催化剂可以重生。
2)通过加入二氧化碳，能有效抑制水煤气变换反应，一氧化碳利用效率高。
3)本发明的方法实现了合成气一步生成二甲醚，降低了分步生产带来的大量能耗问题。
附图说明
图1为本申请实施例1中材料A的XRD图。
图2为本申请实施例1中材料A的TEM图。
具体实施方式
下面结合实施例详述本发明，但本发明并不局限于这些实施例。
除非另外指明，本发明的实施例中的原料均通过商业途径购买。
在实施例中，利用带有气体自动进样器、连接TDX-1填充柱的TCD检测器以及连接PLOT-Q毛细管柱的FID检测器的Agilent7890气相色谱仪进行自动分析。
在实施例中，转化率和选择性均基于碳摩尔数进行计算：
一氧化碳转化率＝[(进料中的一氧化碳碳摩尔数)-(出料中的一氧化碳碳摩尔数)]÷(进料中的一氧化碳碳摩尔数)×100％
二甲醚选择性＝(出料中的二甲醚碳摩尔数)÷(出料中所有烃类产物、甲醇、二甲醚的碳摩尔数总和)×100％
甲醇选择性＝(出料中的甲醇碳摩尔数)÷(出料中所有烃类产物、甲醇、二甲醚的碳摩尔数总和)×100％
烃类选择性＝(出料中的所有烃类产物碳摩尔数)÷(出料中所有烃类产物、甲醇、二甲醚的碳摩尔数总和)×100％
二氧化碳选择性＝(反应生成的二氧化碳碳摩尔数)÷(已转化的一氧化碳碳摩尔数)×100％。
锌铝尖晶石氧化物制备
实施例1
将95g Zn(NO 3) 26H 2O与80g Al(NO 3) 39H 2O溶于200ml去离子水中，配制成盐溶液。将25g碳酸铵溶于200ml去离子水中，配制成碱溶液。将盐溶液与碱溶液分别用两个蠕动泵并流混合共沉淀，沉淀反应温度控制在60℃，pH值为7.2，并在此温度下老化4h，过滤、洗涤后100℃干燥24h，500℃煅烧4h，得到锌铝尖晶石氧化物，编号为A。X射线荧光光谱分析(XRF)显示A中Zn/Al(摩尔比)＝1∶1，XRD图如图1所示，TEM图如图2所示。
实施例2
将48g Zn(NO 3) 26H 2O与80gAl(NO 3) 39H 2O溶于200ml去离子水中，配制成盐溶液。将25g氨水(含25％NH 3)溶于200ml去离子水中，配制成碱溶液。将盐溶液与碱溶液分别用两个蠕动泵并流混合共沉淀，沉淀反应温度控制在70℃，pH值为7.5，并在此温度下老化6h，过滤、洗涤后100℃干燥24h，500℃煅烧4h，得到锌铝尖晶石氧化物，编号为B。XRF显示B中Zn/Al(摩尔比)＝1∶2。
实施例3
将10.6g Zn(NO 3) 26H 2O与80g Al(NO 3) 39H 2O溶于200ml去离子水中，配制成盐溶液。将25g碳酸钠溶于200ml去离子水中，配制成碱溶液。将盐溶液与碱溶液分别用两个蠕动泵并流混合共沉淀，沉淀反应温度控制在80℃，pH值为7.8，并在此温度下老化6h，过滤、洗涤后100℃干燥24h，500℃煅烧6h，得到锌铝尖晶石氧化物，编号为C。XRF显示C中Zn/Al(摩尔比)＝1∶9。
实施例4
将10.6g Zn(NO 3) 26H 2O与40g Al(NO 3) 39H 2O溶于200ml去离子水中，配制成盐溶液。将15g碳酸钾溶于200ml去离子水中，配制成碱溶液。将盐溶液与碱溶液分别用两个蠕动泵并流混合共沉淀，沉淀反应温度控制在70℃，pH值为7.1，并在此温度下老化6h，过滤、洗涤后100℃干燥24h，500℃煅烧4h，得到锌铝尖晶石氧化物，编号为D。XRF显示D中Zn/Al(摩尔比)＝1∶4.5。
实施例5
取7.7g Cr(NO 3) 39H 2O溶于15ml去离子水中，然后室温24h浸渍20g催化剂B，100℃干燥24h，500℃煅烧4h，得到5％(质量分数)铬改性的锌铝尖晶石氧化物，编号为E。
实施例6
取4.7g Zr(NO 3) 45H 2O溶于15ml去离子水中，然后室温24h浸渍20g催化剂B，100℃干燥24h，500℃煅烧4h，得到5％(质量分数)锆改性的锌铝尖晶石氧化物，编号为F。
催化剂性能测试
实施例7
将催化剂A破碎筛分成0.4～0.8mm颗粒，取2g装入内径为8mm的不锈钢反应管内，用50ml/min氢气在300℃下活化1h，在以下条件进行反应：反应温度(T)＝320℃，反应压力(P)＝4.0MPa，合成气中氢气与一氧化碳的摩尔比为(H 2∶CO)＝3∶1；标准状况下合成气体积小时空速(GHSV)＝6000h -1。反应500h后，用气相色谱分析产物，反应结果见表1。
实施例8-12
反应条件和反应结果见表1。其他操作同实施例7。
实施例13
将催化剂G破碎筛分成0.4～0.8mm颗粒，取2g装入内径为8mm的不锈钢反应管内，用50ml/min氢气在300℃下活化1h，在以下条件进行反应：反应温度(T)＝320℃，反应压力(P)＝4.0MPa，合成气中氢气、一氧化碳、二氧化碳的摩尔比为(H 2∶CO∶CO 2)＝3∶1∶0.04(即CO 2在合成气中含量为1％)；标准状况下合成气体积小时空速(GHSV)＝6000h -1。反应500h后，用气相色谱分析产物，反应结果见表1。
实施例14
将催化剂G破碎筛分成0.4～0.8mm颗粒，取2g装入内径为8mm的不锈钢反应管内，用50ml/min氢气在300℃下活化1h，在以下条件进行反应：反应温度(T)＝320℃，反应压力(P)＝4.0MPa，合成气中氢 气、一氧化碳、二氧化碳的摩尔比为(H 2∶CO∶CO 2)＝3∶1∶0.2(即CO 2在合成气中含量为4.8％)；标准状况下合成气体积小时空速(GHSV)＝6000h -1。反应500h后，用气相色谱分析产物，反应结果见表1。
实施例15
将催化剂G破碎筛分成0.4～0.8mm颗粒，取2g装入内径为8mm的不锈钢反应管内，用50ml/min氢气在300℃下活化1h，在以下条件进行反应：反应温度(T)＝320℃，反应压力(P)＝4.0MPa，合成气中氢气、一氧化碳、二氧化碳的摩尔比为(H 2∶CO∶CO 2)＝3∶1∶1(即CO 2在合成气中含量为20％)；标准状况下合成气体积小时空速(GHSV)＝6000h -1。反应500h后，用气相色谱分析产物，反应结果见表1。
表1实施例7-15中的催化反应结果
Figure PCTCN2018098069-appb-000001
催化剂重生性能测试
实施例16
将实施例7中失活后的催化剂利用体积分数为2％氧气和98％氮气的混合气，在550℃处理10h，使得催化剂重生一轮，在实施例7的条件下反应。按照同样的方式重生五轮，选取每轮反应500h后的催化活性数据进行比较，结果见表2。
表2实施例16中的催化反应结果
Figure PCTCN2018098069-appb-000002
以上所述，仅是本发明的几个实施例，并非对本发明做任何形式的限制，虽然本发明以较佳实施例揭示如上，然而并非用以限制本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (11)

  1. 一种合成气直接制备二甲醚的方法，该方法包括：
    a)使合成气通过载有催化剂的反应区，在足以转化至少部分原料的反应条件下反应，以得到包含二甲醚的反应流出物；和
    b)从所述反应流出物中分离所述二甲醚，
    其中所述催化剂为锌铝尖晶石氧化物。
  2. 权利要求1所述的方法，其中所述锌铝尖晶石氧化物中Zn/Al摩尔比为Zn/Al＝1∶9～1∶1。
  3. 权利要求1或2所述的方法，其中所述锌铝尖晶石氧化物是通过包括如下步骤的方法制备的：将锌盐与铝盐配成混合金属盐水溶液；使所述混合金属盐水溶液和沉淀剂水溶液接触，以使所述混合金属盐水溶液中的金属离子共沉淀；老化；和将沉淀物洗涤、干燥后煅烧，制得所述锌铝尖晶石氧化物。
  4. 权利要求3所述的方法，其具有以下特征中至少之一：
    -所述锌盐和铝盐选自盐酸盐、硫酸盐和硝酸盐；
    -所述沉淀剂选自碳酸钠、碳酸钾、碳酸铵、碳酸氢钠、碳酸氢钾、碳酸氢铵、氨水、氢氧化钠、氢氧化钾和它们的混合物；
    -所述共沉淀在20℃至95℃下进行；
    -所述共沉淀过程中pH值为7.0至9.0；
    -所述老化时间不低于1小时；
    -所述煅烧在450℃至800℃下进行。
  5. 权利要求1所述的方法，其中所述锌铝尖晶石氧化物中还含有选自铬、锆、铜、锰、铟、镓和硅中的至少一种其它元素，所述其它元素在锌铝尖晶石氧化物中的质量分数小于或等于10％。
  6. 权利要求5所述的方法，其中所述至少一种其它元素是通过浸渍和/或共沉淀至少一种其它元素的盐水溶液添加到锌铝尖晶石氧化物中的。
  7. 权利要求6所述的方法，其中所述至少一种其它元素的盐选自盐酸盐、硫酸盐和硝酸盐。
  8. 权利要求1所述的方法，其中所述反应区包括一个固定床反应器， 或者以串联和/或并联方式连接的多个固定床反应器。
  9. 权利要求1所述的方法，其中所述反应条件包括：300～450℃的反应温度，0.5～10.0MPa的反应压力，1∶9～9∶1的合成气中氢气与一氧化碳的摩尔比，和1000～20000h -1的标准状态下合成气体积小时空速。
  10. 权利要求9所述的方法，其中所述反应条件为：310～360℃的反应温度，1.0～4.0MPa的反应压力，3∶1～6∶1的合成气中氢气与一氧化碳的摩尔比，和3000～8000h -1的标准状态下合成气体积小时空速。
  11. 权利要求1所述的方法，其中所述合成气中还含有二氧化碳，二氧化碳在合成气中的摩尔浓度为1.0～20.0％。
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