CN101278033B - 由生物质产生甲烷和/或甲烷水合物的方法 - Google Patents
由生物质产生甲烷和/或甲烷水合物的方法 Download PDFInfo
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- CN101278033B CN101278033B CN2006800368375A CN200680036837A CN101278033B CN 101278033 B CN101278033 B CN 101278033B CN 2006800368375 A CN2006800368375 A CN 2006800368375A CN 200680036837 A CN200680036837 A CN 200680036837A CN 101278033 B CN101278033 B CN 101278033B
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- methane
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- gas
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 106
- 239000002028 Biomass Substances 0.000 title claims abstract description 77
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 title claims description 22
- 230000008569 process Effects 0.000 title abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 27
- 238000002309 gasification Methods 0.000 claims abstract description 26
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- 238000000926 separation method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
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- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 206010061876 Obstruction Diseases 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
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- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
本发明涉及一种由生物质产生甲烷的方法,其具有下列方法步骤:a)由生物质制备整备成最佳干物质含量的生物质浆料,b)使该生物质浆料处于压力下,c)在压力下加热该生物质浆料以液化该生物质浆料的固体有机成分,d)将该处于压下的和经加热的生物质浆料再加热到至少该混合物特有的临界温度,e)在压力和高温下从残余流体相中分离出沉积的固体,f)在压力和提高温度下用反应器使至少一部分残余流体相气化成富甲烷气体。以此方式提供一种具有非常高效率的方法,因为大部分干扰催化气化的物质,特别是盐,通过在超临界条件下的沉积可从该混合物中分离。以此方法使催化气化产生高的甲烷产率和高的反应速率,同时还达到高的催化剂的使用寿命。
Description
本发明涉及一种由生物质产生甲烷和/或甲烷水合物的方法。
术语“生物质”意指植物的或动物的物质。例如可列举木材、粪肥、污泥(Gülle)、植物茎、草、藻类、污水过滤后产生的淤泥和宰牲废物。
但是本方法也适用于其它含有机组分的物质如:塑料废物、废水、垃圾、废轮胎、废纸、废油、有机溶剂、化石生物质(泥炭、煤,石油)。
近来,瑞士联邦能源局(BFE,瑞士)给大学的研究任务“Scheurer,K.;Baier,U.Biogene Güter in der Schweiz.Massen-undEnergieflüsse。Waedenswil大学,受BFE委托,生物质计划,总结报告,2001年2月”中,论证了污泥的巨大的远未被应用的能量潜力。全部庭院肥料废物(粪便+污泥)在1998/1999为2.283百万吨TS(干物质),其相应于37PJ的能量。在1998发酵4700t TS的庭院肥料可提供约48TJ的生物气形态的能量,这仅为庭院肥料的总能量潜力的约0.1%。此外,在发酵过程中还产生较大量的不可发酵的固体。木质类生物质实际上是不可发酵的。
下面的术语“水热的”意指在压力和高温下的含水体系,通常接近或高于水的临界点(374℃,221bar)。近临界或超临界的水形成一种对进行化学反应有利的反应介质。该介质特别适用于将生物质水解和转变成液态和气态产物。因为在压力下液态体系转变到超临界不发生真正的相变,所以在生物质中所含的水不必耗费蒸发焓,这与气相过程是不同的(如湿生物质的大气压下的气化)。因此水热过程具有高的热效率潜力。
将生物质转变成甲烷的最优选的反应可对木材示例性地用下面的化学计量描述:
CH1.52O0.64(s)+0.3H2O(g)→0.53CH4(g)+0.47CO2(g) (1)
在正常条件(低的水分压)下,生物质与水反应不按或不完全按式(1)进行,而产生副产物如焦油或固体碳(焦炭)。如果成功地反应条件的选择,使得反应(1)能完全进行,则可预计有高的热效率,因为反应(1)是轻微放热反应。理论上的最大可能的效率为95%(按木材的低热值Hu计)。本申请人对工业过程所进行的系统分析表明木材可实现的效率为70-80%。其详述于文献“Vogel,F.和F.Hildebrand,Catalytic HydrothermalGasification of Woody Biomass at High Feed Concentrations.Chem.Eng.Trans.2,2002,771-777”。这明显高于用于将木材转变成甲烷的其它方法的效率。
但总的看来,用于由生物质产生甲烷的目前已知方法在可达到的效率方面低于理论预计值,以致这些方法目前不能经济地应用。
因此,本发明的目的在于提供一种由生物质产生甲烷的方法,该方法可在水热条件下达到高的效率,该效率足以满足经济使用的要求。
本发明的目的是通过权利要求1的措施实现的。本发明的有利的实施方案列于其它权利要求中。
用于由生物质产生甲烷的本发明方法具有下列方法步骤:
a)由生物质制备调节到最佳干物质含量的生物质浆料,
b)使该生物质浆料处于压力下,
c)在压力下加热该生物质浆料以液化该生物质浆料的固体有机成分,
d)将该处于压力下和经加热的生物质浆料再至少加热到该混合物特有的临界温度,
e)在压力和提高温度下从流体相中分离出沉积的固体,和
f)在压力和提高温度下用催化反应器使至少一部分流体相气化成富甲烷气体。
以此方式提供了一种具有非常高效率的方法,因为大部分干扰催化气化的物质,特别是盐,通过在超临界条件下的沉积可从该混合物中分离。以此方法使催化气化产生高的甲烷产率和高的反应率,同时还达到高的催化剂的使用寿命。
在本发明的第一个扩展方案中,在催化气化后处于压力下的富甲烷气体与剩余的液相分离。该处于压力下的富甲烷气体的其后冷却导致形成固态的甲烷水合物,然后该水合物可与剩余的气体成分,特别是CO2和/或一氧化碳和氢分离。这样形成的甲烷水合物含有接近8CH4x46H2O的组成。由此该甲烷在约-15℃和1bar下可简单地以固体形式廉价地贮存和运输。因为甲烷优选贮存于水合物晶格中,所以该方法步骤也有利地用于分离甲烷和CO2以及其余气体成分如一氧化碳、氢气或更高级烃。为得到纯气态的甲烷,可加热该甲烷水合物,其导致分解成CH4和H2O。
在本发明的第二个扩展方案中,该在催化气化中产生的甲烷气可从处于压力下的富甲烷气中分离,优选利用该压力借助洗涤柱法、膜分离法或吸附器法与其余气体成分特别是CO2和/或一氧化碳和/或氢分离。在此方法步骤中,甲烷在合适的装置(如洗涤柱、膜分离器、吸附剂)中从气相中与其它成分,优选是CO2和一氧化碳分离,然后在高压(200-400bar)下提供使用。由此有利的是省去压缩步骤,所述压缩步骤用以将甲烷充于例如气瓶中、提供处于气罐中的动力燃料或将其供入天然气管网。也可考虑将压缩气直接用作燃气轮机过程中的燃料。
例如还可产生下列的优点:
i)在方法步骤a)中,优选可通过湿研磨调理以调节所需的干物质含量。该干物质含量特别可通过加入水或排出水调节到5-50质量%,优选约15-30质量%;
ii)为改进可泵送性,可在生物质中加入其它添加物,如淀粉或废油;
iii)在方法步骤b)中,将经调理的生物质浆料加压到200-400bar的高压,并按工序可连续或间歇地输送。为此可使用通常挤出机、高压偏心蜗轮泵、活塞膜式泵和/或固体泵。
接着将在压力下的生物质浆料加热到约200-350℃,以使生物质浆料的固体有机成分基本液化。
iv)为按步骤iii)的优点更好地加热和液化,还可考虑使用静态混合元件和/或催化剂如碳酸钾、碳酸钠、氢氧化钾、氢氧化钠或氧化锌;也可加酸(如硫酸)以改进液化。
v)在方法步骤d)中,有利的是温度超过各混合物的临界温度,例如纯水的临界温度在221bar为374℃。通过超过该混合物的临界点使盐和其它有机物质的溶解度大大下降。
vi)该较高的温度水平优选可通过如下方式达到:
-通过外部的热引入,例如通过具有燃烧器/催化燃烧器的热交换器,其由引回的产物气供料,或
-通过在冷的或也可经部分加热的生物质浆料中加入合适的氧化剂如氧、空气、过氧化氢、硝酸铵或其它硝酸盐,以使该生物质浆料的有机成分发生部分氧化。该氧化反应是放热的,并优选产生足以使生物质浆料达到所需温度的热。
-通过上两种方法的组合。
vii)所收集的沉积物,特别是大部分的盐,以及其余的固体可从工艺中连续或定期地有效排出。
viii)固体如上述的盐在催化气化前在所用反应器中于超临界条件下经沉积、分离和回收。富含元素N、P和K的盐例如特别适合用作制备农用肥料的基料。由此也可让生态物质循环闭合。
ix)在催化气化时,向反应器中加入可使气化主要产生二氧化碳、甲烷和氢的这种催化剂。这时可产生痕量的一氧化碳以及较高级的烃如乙烷、丙烷。
x)该反应器优选设计为流化层反应器、整体反应器、壁式反应器或管式反应器,其相关管或管束涂以催化剂。备选地,该管或反应器也可充填有经催化涂覆的金属板。也可用固定床反应器,但由于其较高的堵塞风险而不太有利。
下面用生物质(如木材或污泥固体)的气化附图详细阐明本发明:
附图简介:
图1示出按本发明第一实施方案的生物质催化水热气化的基本流程图,和
图2示出按本发明第二实施方案的生物质催化水热气化的基本流程图。
图1示出生物质催化水热气化的基本流程图。其中通过加入氧或变温(allotherm)方案(不加氧,从外部引入热)也可实现自热运行方式。在最后提及的方案中通过部分产物气的燃烧和通过间接热交换实现过热到400-500℃的温度。
依次运行下列工艺步骤:
步骤1:形成缓冲存储器,以接受在约20℃和1bar下的TM含量调节为5-50质量%的生物质(TM=干物质),
步骤2:在40℃和1bar下湿研磨该混含物,
步骤3:在80℃和300bar下压缩该经湿研磨的混合物,
步骤4:在300℃和300bar下预热(水解),
步骤5:任选加入氧(或其它氧化剂之一),
步骤6:在现有的大约450℃和300bar下,于超临界温度进行部分氧化,
步骤7:在约300℃下进行盐分离、冷却和盐水排出,其导致相对干净的盐浓缩物,为进行热回收,可将废热再返回到前面的预热步骤(步骤4)中,
步骤8:在约420℃和约300bar下气化和甲烷化成实际的富甲烷产物气,
步骤9:将富甲烷气体混合物冷却到约10℃,并总是还保持为约300bar,大部分的在这步中产生的废热可再返回到前面的预热步骤(步骤4)中,
步骤10:在约10℃和300bar下,固态的气体水合物在压力下从残余气相和液相中沉积和分离。将残余气相和液相减压到1bar,并使该气相和液相分离,
步骤11:通过进一步冷却到约-15℃和进一步减压到常压而得到固态的甲烷水合物。
此外,按图2的实施例需下列的方法步骤。
步骤9:将富甲烷气体混合物冷却到约50℃,并总是还保持为约300bar,大部分的在这步中产生的废热可再返回到前面的预热步骤(步骤4)中,
步骤12:在50℃和约300bar下进行气液分离,回收基本清洁的水,
步骤13:气体分离,例如通过在约30℃和280bar下通过高压洗涤,这时甲烷CH4与其它气体成分如CO2和氢分离并收集甲烷。
在整个工艺中由TM含量为5-50质量%的生物质产生固态甲烷水合物(TM=干物质)。一开始该生物质经湿研磨,并在约300bar下经泥浆泵送入反应器中。将该悬浮物预热到约300℃,使该生物聚合物(纤维素、木质素、蛋白质)经水解和裂解。在实际的催化气化和甲烷化之前引入氧原子(或其它氧化剂)。由此发生有机成分的部分氧化,其放出的热足以达到所需的400-500℃的反应温度(自热运行方式)。进入超临界范围(对纯水在300bar下约为402℃)时大部分盐呈固态沉淀出。由此可达到盐与催化剂床的分离。该水解的生物质成分经催化重整成CH4、CO2和副产物H2后,在压力下冷却该水-气混合物。选择在300bar下的约10℃冷却温度,从而形成甲烷水合物,但剩余的水未冷冻。在分离器中可将固态甲烷水合物与剩余的液相和气相分离。为得到在常压下呈亚稳态的甲烷水合物,在减压前必需将其冷却到至少约-15℃。优选地,该甲烷水合物预先与残留的粘附水分离。
图2中示出的方法从方法步骤9开始与图1所示方法不同。该冷却仅进行到25-50℃。在此范围内未形成甲烷水合物,而是该气体以溶于水相的形式存在。代替形成固态的甲烷水合物,是在步骤12中利用总是约300bar的压力的高压进行与液相和气相分离以及在下一步骤13中于高压洗涤器中进行与二氧化碳的分离。由此在此方法中该甲烷以高压气体的气态形式存在。
代替步骤13也可是使气体减压,并通过已知的分离方法(变压吸附、气体洗涤)分离成CH4/H2和CO2。但是,这提供了非高压下的甲烷气。
基于前述方式,与现有技术相比,利用本发明的方法可达到一系列的优点:
·该生物质的转化可在水中和与水一起进行。不需对潮的或湿的生物质进行干燥。由此可实现该方法的较高能量效率。
·该生物质在第一工艺阶段中经调理(即经破碎)和调节到所需的干物质含量(TM),优选是通过湿研磨进行。由此形成可泵送的浆料。为改进可泵送性,在该生物质中可加入其它添加剂(如淀粉、废油)。所需干物质含量为5-80质量%,优选约15-40质量%。如果该有机干物质含量约为20质量%或更高,则该方法可特别经济地操作。
·在第二工艺阶段中将经调理的生物质浆料升压到高压(200-400bar),并连续或间歇输送。挤出机、高压偏心蜗轮泵、活塞膜式泵和固体泵是合适的输送设备。
·在第三工艺阶段中将该生物质浆料在压力下加热到约200-350℃。使固体有机生物质成分基本液化。为了更好地加热和液化,该工艺阶段还可包括静态混合元件和/或催化剂(如氧化锌),
·在第四工艺阶段中使压力下的经加热和液化的生物质浆料在合适的设备(如旋风分离器、MODAR-分离器、过滤器)快速升高到较高的温度水平,优选达到或超过各混合物的临界温度。作为参照点是水的临界温度即374℃和221bar。这可通过外部引入热(如由引回的产物气供料的燃烧器/催化燃烧器)或通过加入合适的氧化剂(如氧、空气、过氧化氢、硝酸铵和其它硝酸盐)直接在第四工艺阶段(或前面工艺阶段1-3之一中)进行。由此大部分盐和其余的固体沉淀,并且可加以收集。作为变型方案,该所收集的沉淀物可连续或定期由工艺中排出。在催化气化反应器前在水热条件下的分离和回收固体以及可能加入盐类氧化剂(硝酸盐如硝酸铵)用于在水热条件下部分氧化该生物质可改进该方法的实施,并明显提高该方法的效率。由于原料特性是非常富含氮盐、磷盐和钾盐的,因此该排出的固体特别适于作为农用肥料。
·在第五工艺阶段中热生物质物流(现已与大部分固体分离)到达填充有合适催化剂的反应器,在此气化成甲烷、二氧化碳、氢和痕量的一氧化碳以及较高级的烃(乙烷、丙烷)。该催化剂优选含高的镍含量(如镍),并还可含钌、铬和/或铜。也可使用另一些基于Ni、Ru或Rh作为活性金属的催化剂。该反应器优选设计为流化层反应器、整体反应器或壁式反应器(涂催化剂的管或管束)。但也可使用其中引入经催化涂覆的金属薄板的管。
·在第六工艺阶段(A)中该产物物流按上述第一流程图在压力(200-400bar)下经冷却到约50℃,并在合适的设备中再冷却到0-20℃。这时形成固态的水-甲烷包合物(或甲烷水合物)。该白色固体的大致组成为8CH4x46H2O。由此甲烷可在约-15℃和1atm下作为固体廉价运输。该工艺步骤也可用于从CO2和其余的气体成分中分离甲烷。
该所述的由生物质制备的甲烷水合物以及形成用于简化甲烷分离的甲烷水合物具有高的效率。
·代替第六工艺阶段(A)可根据前述第二流程图选择第六工艺阶段(B)。在该工艺阶段中该产物物流经冷却到约50℃,并且该气相在压力下与液相分离。在合适的设备(洗涤柱、膜分离或吸附器)中该甲烷可从气相中与其余成分分离,并在高压(约200-400bar)下提供使用。由此可省去压缩步骤,该压缩步骤用于将甲烷充于气瓶中、提供处于气罐中的动力燃料或将其供入天然气管网。也可考虑将压缩气直接用作燃气轮机过程中的燃料。
由此按该第二方法从生物质制备处于适于天然气罐和/或引入天然气管网、适于充瓶或作为燃气轮机燃料应用的压力下的甲烷提供了特别经济的可行方案。
综上所述,本发明提供的部分技术方案如下:
1.一种用于由生物质产生甲烷的方法,其具有下列方法步骤:
a)由生物质制备调节到所需干物质含量的生物质浆料,
b)使该生物质浆料处于压力下,
c)在压力下加热该生物质浆料以液化该生物质浆料的固体有机成分,
d)将该处于压力下的和经加热的生物质浆料再至少加热到该混合物特有的临界温度,
e)在压力和升高温度下从流体相中分离出沉积的固体,和
f)在压力和升高温度下用反应器使至少一部分残余流体相气化成富甲烷气体。
2.技术方案1的方法,其特征在于,将处于压力下的富甲烷气从残余流体相中分离。
3.技术方案1或2的方法,其特征在于,该处于压力下的富甲烷气体经冷却,并使在此形成的固态甲烷水合物与剩余的气体成分,特别是CO2和/或一氧化碳和氢气,以及优选与残余水分离。
4.技术方案3的方法,其特征在于,该在气化中产生的甲烷从处于压力下的富甲烷气中分离,优选利用该压力借助洗涤柱法、膜分离法或吸附器法与剩余气体成分特别是CO2和/或一氧化碳和/或氢分离。
5.上述技术方案之一的方法,其特征在于,在方法步骤a)中该生物质经湿研磨破碎和经加入水或分离水将干物质含量调节到5-80质量%,优选15-40质量%。
6.技术方案5的方法,其特征在于,为改进生物质浆料的可泵送性,添加其它添加物,特别是淀粉或废油。
7.上述技术方案之一的方法,其特征在于,在方法步骤b)中,将生物质浆料加压到200-400bar。
8.技术方案7的方法,其特征在于,在方法步骤b)后将处于压力下的生物质浆料加热到200-400℃,优选250-350℃。
9.技术方案8的方法,其特征在于,为了更好地加热和液化,使用静态混合元件和/或催化剂如氧化锌。
10.上述技术方案之一的方法,其特征在于,在方法步骤d)中,较高的温度水平至少高于该混合物特有的临界温度。
11.技术方案10的方法,其特征在于,较高的温度水平以如下方式达到:
-通过外部引入热,如通过具有燃烧器/催化燃烧器的热交换器,其由返回的产物气供料,或
-通过加入合适的氧化剂如氧、空气、过氧化氢、硝酸铵或其它硝酸盐,以使该生物质浆料发生部分氧化。
12.技术方案10或11的方法,其特征在于,沉淀和收集盐和残余的固体,所收集的沉积物在气化前由工艺中连续或定期排出。
13.上述技术方案之一的方法,其特征在于,在方法步骤f)中使用催化剂以更快调节所需的产物气体组成。
14.技术方案13的方法,其特征在于,该催化剂含镍、钌或铑作为活性金属。
15.技术方案13或14之一的方法,其特征在于,该催化反应器优选设计为流化层反应器、整体反应器、壁式反应器或管式反应器,其相关管或管束涂以催化剂或在管中使用催化涂覆的分层板。
16.上述技术方案之一的方法,其特征在于,在超临界条件下进行催化气化。
Claims (21)
1.一种用于由生物质产生甲烷的方法,其具有下列方法步骤:
a)由生物质制备调节到所需干物质含量的生物质浆料,所需干物质含量为5-80质量%,
b)使该生物质浆料处于压力下,
其中在方法步骤b)中,将生物质浆料加压到200-400bar,
c)在压力下加热该生物质浆料到200-400℃以液化该生物质浆料的固体有机成分,
d)将该处于压力下的和经加热的生物质浆料再至少加热到该混合物特有的临界温度,
e)在压力和升高温度下从流体相中分离出沉积的固体,和
f)在压力和升高温度下用反应器使至少一部分残余流体相气化成富甲烷气体;
其中在超临界条件下进行催化气化,且
在方法步骤f)中使用催化剂以更快调节所需的产物气体组成。
2.权利要求1的方法,其特征在于,将处于压力下的富甲烷气从残余流体相中分离。
3.权利要求1的方法,其特征在于,该处于压力下的富甲烷气体经冷却,并使在此形成的固态甲烷水合物与剩余的气体成分分离。
4.权利要求1的方法,其特征在于,该处于压力下的富甲烷气体经冷却,并使在此形成的固态甲烷水合物与剩余的气体成分,也即:CO2和/或一氧化碳和/或氢气,分离。
5.权利要求1的方法,其特征在于,该处于压力下的富甲烷气体经冷却,并使在此形成的固态甲烷水合物与剩余的气体成分,也即:CO2和/或一氧化碳和/或氢气,以及与残余水分离。
6.权利要求3-5之一的方法,其特征在于,该在气化中产生的甲烷从处于压力下的富甲烷气中分离。
7.权利要求3-5之一的方法,其特征在于,该在气化中产生的甲烷从处于压力下的富甲烷气中分离,其中利用该压力借助洗涤柱法、膜分离法或吸附器法与剩余气体成分分离。
8.权利要求3-5之一的方法,其特征在于,该在气化中产生的甲烷从处于压力下的富甲烷气中分离,其中利用该压力借助洗涤柱法、膜分离法或吸附器法与剩余气体成分,也即:CO2和/或一氧化碳和/或氢,分离。
9.权利要求1或2的方法,其特征在于,在方法步骤a)中该生物质经湿研磨破碎和经加入水或分离水将干物质含量调节到5-80质量%。
10.权利要求1或2的方法,其特征在于,在方法步骤a)中该生物质经湿研磨破碎和经加入水或分离水将干物质含量调节到15-40质量%。
11.权利要求9的方法,其特征在于,为改进生物质浆料的可泵送性,添加其它添加物。
12.权利要求9的方法,其特征在于,为改进生物质浆料的可泵送性,添加其它添加物也即:淀粉或废油。
13.权利要求1的方法,其特征在于,在方法步骤b)后将处于压力下的生物质浆料加热到250-350℃。
14.权利要求1的方法,其特征在于,为了更好地加热和液化,使用静态混合元件和/或催化剂。
15.权利要求1的方法,其特征在于,为了更好地加热和液化,使用
静态混合元件
和/或
催化剂,也即氧化锌。
16.权利要求1的方法,其特征在于,在方法步骤d)中,使压力下的经加热和液化的生物质浆料在合适的设备快速升高到较高的温度水平,其中较高的温度水平至少高于该混合物特有的临界温度。
17.权利要求16的方法,其特征在于,较高的温度水平以如下方式达到:
-通过外部引入热,其由返回的产物气供料,或
-通过加入合适的氧化剂,以使该生物质浆料发生部分氧化。
18.权利要求16的方法,其特征在于,较高的温度水平以如下方式达到:
-通过外部引入热,也即通过具有燃烧器/催化燃烧器的热交换器,其由返回的产物气供料,或
-通过加入合适的氧化剂,以使该生物质浆料发生部分氧化,所述氧化剂选自氧、空气、过氧化氢、硝酸铵和其它硝酸盐。
19.权利要求16或17的方法,其特征在于,沉淀和收集盐和残余的固体,其中所收集的沉积物在气化前由工艺中连续或定期排出。
20.权利要求1的方法,其特征在于,该催化剂含镍、钌或铑作为活性金属。
21.权利要求1或20的方法,其特征在于,该催化反应器设计为流化层反应器、整体反应器、壁式反应器或管式反应器,其相关管或管束涂以催化剂或在管中使用催化涂覆的分层板。
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-
2005
- 2005-10-04 EP EP20050021601 patent/EP1772202A1/de not_active Withdrawn
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2006
- 2006-06-19 JP JP2008533877A patent/JP4977826B2/ja active Active
- 2006-06-19 CA CA2624510A patent/CA2624510C/en active Active
- 2006-06-19 CN CN2006800368375A patent/CN101278033B/zh active Active
- 2006-06-19 DK DK06754429.6T patent/DK1931753T3/en active
- 2006-06-19 EP EP06754429.6A patent/EP1931753B1/de active Active
- 2006-06-19 WO PCT/EP2006/005837 patent/WO2007038996A1/de active Application Filing
- 2006-06-19 US US11/992,812 patent/US8475549B2/en active Active
- 2006-06-19 BR BRPI0616850A patent/BRPI0616850B1/pt not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
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EP1931753A1 (de) | 2008-06-18 |
US8475549B2 (en) | 2013-07-02 |
CN101278033A (zh) | 2008-10-01 |
DK1931753T3 (en) | 2015-08-24 |
EP1931753B1 (de) | 2015-05-20 |
JP2009509759A (ja) | 2009-03-12 |
WO2007038996A1 (de) | 2007-04-12 |
BRPI0616850B1 (pt) | 2016-04-19 |
BRPI0616850A2 (pt) | 2011-07-05 |
JP4977826B2 (ja) | 2012-07-18 |
CA2624510A1 (en) | 2007-04-12 |
US20090126274A1 (en) | 2009-05-21 |
CA2624510C (en) | 2011-03-01 |
EP1772202A1 (de) | 2007-04-11 |
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