CN1477090A - Method for synthesizing dimethyl ether by adopting biomass indirect liquification one-step process - Google Patents

Method for synthesizing dimethyl ether by adopting biomass indirect liquification one-step process Download PDF

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Publication number
CN1477090A
CN1477090A CNA031265855A CN03126585A CN1477090A CN 1477090 A CN1477090 A CN 1477090A CN A031265855 A CNA031265855 A CN A031265855A CN 03126585 A CN03126585 A CN 03126585A CN 1477090 A CN1477090 A CN 1477090A
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China
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gas
synthesis
gasification
dimethyl ether
method
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CNA031265855A
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Chinese (zh)
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王铁军
常杰
吕鹏梅
祝京旭
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中国科学院广州能源研究所
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Publication of CN1477090A publication Critical patent/CN1477090A/en

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Abstract

The present invention relates to a method for synthesizing dimethyl ether by high-effectively cleanly utilizing biomass. It utilizes the gasified gas produced by catalytic gasification of biomass air-water vapor, and makes the gasified gas undergo the process of methane reformation to prepare synthetic gas, and utilizes the synthetic gas to directly synthesize clean fuel dimethyl ether.

Description

生物质间接液化一步法合成二甲醚的方法 Students one-step method of synthesis of dimethyl ether indirect liquefaction substance

所属技术领域 Those of skill

:本发明涉及生物质的高效洁净利用的一种新方法,进一步涉及利用沼气重整生物质气化气合成二甲醚的新方法。 : The present invention relates to a novel method for clean and efficient utilization of biomass, methane reformer further relates to new biomass gasification gas of dimethyl ether synthesis.

生物质气化是生物质热转化技术中历史最长、最具实用性的一种技术。 Biomass gasification thermal conversion of biomass is the oldest technology, the most practical technique. 但生物质气化气与煤气化、天然气气化以及重渣油气化等途径获得的合成气相比,存在最大的弱点,即气化气中H2/CO值较低,为提高生物质合成二甲醚的单程转化效率,减小因合成催化剂在贫氢条件下的积碳失活,必须设法提高合成气的H2/CO值。 However, the synthesis gas from biomass gasification and coal gasification gas, and heavy oil gasification gas and the like access to the gasifier as compared to the presence of the biggest weakness, i.e. H2 / CO values ​​lower gasification gas in order to improve biomass synthesis dimethyl ethers pass conversion efficiency, reduced carbon deposition synthesis catalyst due to deactivation of hydrogen under lean conditions, must try H2 / CO syngas value increased.

目前二甲醚的合成主要通过煤气化、天然气气化以及重渣油气化等途径获得的合成气来合成。 Currently DME synthesis primarily by coal gasification, synthesis gas and natural gas gasification of heavy oil gasification access to be synthesized. 由生物质空气-水蒸汽催化气化产生的气化气经甲烷重整制备合成气直接合成洁净燃料二甲醚,是一种新的绿色合成工艺,至今未见报道。 From biomass, air - water produced gasification gas by catalytic steam reforming of methane gasification produce syngas clean fuel direct synthesis of dimethyl ether, is used for synthesis of a new, so far not been reported. 发明的目的:本发明的目的是为实现能源的可持续发展而提供一种完全由生物质高效清洁利用合成燃料二甲醚的绿色合成方法。 OBJECT OF THE INVENTION: The object of the present invention is to achieve the sustainable development of green energy to provide a method for synthesizing a completely clean and efficient use of biomass fuels dimethyl ether synthesis.

本发明的工作气体为空气和水蒸汽,气化炉中催化气化的催化剂为自制的镍基催化剂,焦油采用催化裂解的方法净化,催化剂为镍/白云石双功能催化剂,生物质流化床气化炉中经空气-水蒸汽催化气化后得到富氢的气化气;甲烷来源于生物质产生的沼气。 The working gas of the present invention is air and water vapor, the catalytic gasifier in a gasification catalyst is made of nickel-based catalyst, catalytic cracking tar purification method, the catalyst is a nickel / dolomite bifunctional catalyst bed biomass the gasification furnace via an air - to obtain a hydrogen rich catalytic steam gasification of the gasification gas; methane produced from raw material gas.

富氢气化气经旋风分离、焦油裂解和水洗深度净化后用沼气中的甲烷进行催化重整得到H2∶CO为2∶1,且CO2含量小于5%的合成气;由合成气一步法合成燃料二甲醚,经分离精制后压缩成液化气使用。 Hydrogen rich gas by the cyclone of, washed with water and tar cracking deep purification process biogas obtained in the catalytic reforming of methane is 2:1 H2:CO, less than 5% and CO2 content of the synthesis gas; a synthetic fuel from syngas DME, was separated and purified liquefied compressed into use.

实施例:生物质杉木粉由螺旋进料器(4)进入流化床气化炉(2),空气经罗次风机由气化炉(2)下部吹入,水蒸汽发生器(3)产生的高温水蒸汽(400K)在气化炉(2)的不同高度进入,生物质在气化炉(2)中进行空气-水蒸汽催化气化,气化气中H2∶CO∶CO2∶N2为30∶10∶20∶30;从气化炉(2)出来的气化气经旋风分离器(5)除尘和焦碳后进入焦油裂解器(6)催化裂解焦油,焦油含量低于50mg/Nm3,水洗喷淋塔(7)对气化气深度净化;沼气发生器(8)产生的沼气净化后与气化气经混合器(9)混合后进入重整反应器(10)催化重整制取合成气,合成气中H2∶CO∶CO2∶N2为45∶25∶5∶20;合成气经一步法合成反应器(11)催化合成后经精馏装置(12)分离精制制得纯度大于90%的燃料二甲醚,二甲醚压缩为液化气运输和使用。 Example: fir flour biomass by the screw feeder (4) to the fluidized bed gasification furnace (2) through which air is blown from the lower portion of the fan views Luo gasification furnace (2), water vapor generator (3) to produce the high temperature water vapor (400K) at different heights gasification furnace (2) into the biomass air in the gasification furnace (2) - the catalytic steam gasification, gasification gas is H2:CO:CO2:N2 30:10:20:30; from the gasification furnace (2) out of the gasification gas by a cyclone (5) into the tar and coke dust cracker (6) catalytic pyrolysis tar, tar content below 50mg / Nm3 , water spray tower (7) for deep purification of gasification gas; biogas purification gas generator (8) with the gasification gas produced by the mixer (9) after mixing into the reforming reactor (10) catalytic reforming synthesis gas, the synthesis gas is 45:25:5:20 H2:CO:CO2:N2; syngas step synthesis reactor (11) after separation by distillation catalytic synthesis means (12) is greater than the purification was pure 90% of the fuel dimethyl ether, diethyl ether and compressed liquefied gas used.

本发明具有以下突出优点和积极效果1.在生物质空气-水蒸汽催化气化反应中,充分利用部分生物质燃烧产生的热量来提供气化所需的热量,实现自热反应;2.通过加入水蒸汽产生一系列水汽变换反应来克服生物质含氢量的不足,达到提高生物质潜在氢产量的目的;3.在生物质空气-水蒸汽催化气化反应中,利用自制的镍基催化剂实现了显著提高生物质潜在氢产量的目的;4.在富氢气化气的重整工序中采用由沼气提供的甲烷重整,使整个合成工艺全部采用可再生的生物质资源,实现了绿色的合成工艺路线;5.在甲烷重整工序,通过自制的重整催化剂实现了调整合成气比例,降低CO2含量的目的。 The present invention has the following outstanding advantages and positive effects of air biomass 1. - the catalytic steam gasification reaction, the biomass partially full use of heat produced by combustion to provide the heat required for gasification is achieved autothermal reaction; 2 via. water was added to produce a series of steam water gas shift reaction to overcome the disadvantages of the raw material hydrogen content, the purpose of increasing the yield of hydrogen potential biomass; 3 biomass air - catalytic steam gasification reaction, using a nickel-based catalyst homemade achieve a significantly improved object of potential production of hydrogen substance; 4 using methane reforming gas supplied from the hydrogen rich gas in the reforming step of fluidizing gas, so that the whole synthesis process in all renewable biomass resources, to achieve a green synthesis route; 5. methane reforming step, the reforming catalyst is made by adjusting the syngas ratio to achieve, the purpose of reducing the CO2 content.

Claims (6)

1.一种生物质间接液化一步法合成二甲醚的方法,包括如下的过程:原料生物质经螺旋进料器(4)进入流化床气化炉(2),空气经罗次风机由气化炉(2)下部吹入,水蒸汽发生器(3)产生的高温水蒸汽(400K)在气化炉(2)的不同高度进入,生物质在气化炉(2)中进行空气-水蒸汽催化气化;从气化炉(2)出来的气化气经旋风分离器(5)除尘和焦碳后进入焦油裂解器(6)催化裂解焦油,喷淋塔(7)对气化气深度净化;沼气发生器(8)产生的沼气与净化后的气化气经混合器(9)混合后进入重整反应器(10)催化重整制取合成气;合成气经二甲醚合成反应器(11)催化合成后经精馏装置(12)分离精制制得燃料二甲醚。 1. A method for dimethyl ether indirect liquefaction step synthesis of raw materials, including the following procedure: biomass feedstock via a screw feeder (4) to the fluidized bed gasification furnace (2) through which air from the blower views Luo gasifier (2) is blown into a lower, high-temperature water vapor (400K) steam generator (3) produced at different heights into the gasification furnace (2), the air in the biomass gasification furnace (2) - catalytic steam gasification; from the gasification furnace (2) out of the gasification gas by a cyclone (5) into the tar cracker (6) after the catalytic cracking of tar and coke dust, spray tower (7) for the gasification deep purge gas; gasification gas by mixer (9) after gas purification and gas generator (8) enters the reforming reactor generating (10) a catalytic reforming synthesis gas after mixing; syngas DME synthesis reactor (11) after separation and purification catalytic synthesis of dimethyl ether fuel was prepared by rectification plant (12).
2.根据权利要求1所述的一种生物质间接液化一步法合成二甲醚的方法,其特征在于工作气体为空气和水蒸汽。 2. According to a one-step indirect liquefaction of biomass according to a method of synthesis of dimethyl ether as claimed in claim, characterized in that the working gas is air and water vapor.
3.根据权利要求1所述的一种生物质间接液化一步法合成二甲醚的方法,其特征在于空气和水蒸汽催化气化的催化剂为自制的镍基催化剂。 3. According to a one-step indirect liquefaction of biomass according to a method of synthesis of dimethyl ether as claimed in claim, characterized in that the nickel-based catalyst and a catalytic air steam gasification catalyst is made of.
4.根据权利要求1所述的一种生物质间接液化一步法合成二甲醚的方法,其特征在于气化气中的焦油采用催化裂解的方法净化,催化剂为镍/白云石双功能催化剂。 4. According to a one-step indirect liquefaction of biomass according to a method of synthesis of dimethyl ether as claimed in claim, characterized in that the gasification gas in the catalytic cracking of the tar purification method, the catalyst is a nickel / dolomite bifunctional catalyst.
5.根据权利要求1所述的一种生物质间接液化一步法合成二甲醚的方法,其特征在于通过甲烷的水蒸汽和二氧化碳重整进行补氢和合成气比例调整;合成气的比例为:H2∶CO为2∶1,且CO2含量小于5%。 5. The method of claim 1. A one-step indirect liquefaction of biomass synthesis of dimethyl ether as claimed in claim, characterized in that the hydrogen for up scaling and synthesis gas by steam reforming of methane and carbon dioxide; the ratio of the synthesis gas : H2:CO is 2:1, and CO2 content of less than 5%.
6.根据权利要求1或5所述的一种生物质间接液化一步法合成二甲醚的方法,其特征在于所述的甲烷来源于生物质产生的沼气。 6. The biomass according to one of claim 1 or 5, a method for synthesizing dimethyl ether indirect liquefaction step process as claimed in claim, wherein the methane produced from raw material gas.
CNA031265855A 2003-05-16 2003-05-16 Method for synthesizing dimethyl ether by adopting biomass indirect liquification one-step process CN1477090A (en)

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