CN102574114A - 活性受控的热解催化剂 - Google Patents
活性受控的热解催化剂 Download PDFInfo
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- CN102574114A CN102574114A CN2010800183360A CN201080018336A CN102574114A CN 102574114 A CN102574114 A CN 102574114A CN 2010800183360 A CN2010800183360 A CN 2010800183360A CN 201080018336 A CN201080018336 A CN 201080018336A CN 102574114 A CN102574114 A CN 102574114A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 121
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 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 description 11
- 241000209094 Oryza Species 0.000 claims description 9
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- 239000012018 catalyst precursor Substances 0.000 claims description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 5
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- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010949 copper Substances 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
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- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- 235000013339 cereals Nutrition 0.000 claims 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
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- 150000002738 metalloids Chemical class 0.000 abstract description 8
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- 239000000571 coke Substances 0.000 abstract description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 206010021143 Hypoxia Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229910052849 andalusite Inorganic materials 0.000 description 1
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
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- 239000012876 carrier material Substances 0.000 description 1
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- 238000006356 dehydrogenation reaction Methods 0.000 description 1
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
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- 239000001095 magnesium carbonate Substances 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910052664 nepheline Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
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- 238000012856 packing Methods 0.000 description 1
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- 235000019362 perlite Nutrition 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 239000010454 slate Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- YRWWOAFMPXPHEJ-OFBPEYICSA-K sodium L-ascorbic acid 2-phosphate Chemical compound [Na+].[Na+].[Na+].OC[C@H](O)[C@H]1OC(=O)C(OP([O-])([O-])=O)=C1[O-] YRWWOAFMPXPHEJ-OFBPEYICSA-K 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229940048058 sodium ascorbyl phosphate Drugs 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010435 syenite Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
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Abstract
本发明揭示了一种用于催化热解固体生物质材料的催化剂体系。该体系包含金属或类金属的氧化物、硅酸盐或碳酸盐。该体系的介观和宏观总比表面积在1-100米2/克的范围内。当用于催化过程时,该体系提供了高得油率和低产焦率。所得液体具有较低的含氧量。
Description
发明背景
1.发明领域
本发明一般涉及用于催化热解过程的催化剂,更具体地涉及在催化热解过程中用来转化固体生物质材料的催化剂。
2.背景技术
人们亟须找到将固体生物质材料转化为液体燃料的方法,将其作为一种途径,降低人类对原油的依赖性,扩大可再生能源的利用,减少地球大气中二氧化碳的积聚。
一般认为热解过程,尤其是急骤热解过程是将固体生物质材料转化为液体产品的最具潜力的途径,这种产品通常称作生物油或生物原油。除液体反应产物外,这些过程还产生气体反应产物和固体反应产物。气体反应产物包括二氧化碳、一氧化碳和量相对较少的氢气、甲烷和乙烯。
固体反应产物包括焦炭。
为了尽量提高液体产率而减少固体和气体反应产物,热解过程应快速加热生物质原料,缩短其在反应器中的停留时间,并快速冷却反应产物。近来的研究焦点是烧蚀反应器、旋风反应器和流化反应器,用来提供快速加热。流化反应器包括流化固定床反应器和输送反应器。
输送反应器给反应器进料供热的方式是向反应区注入热的粒状载热材料。该技术能对原料进行快速加热。原料的流化确保了热在反应器混合区内的均匀分布。
美国专利5961786披露了一种将木材颗粒转化为液体烟熏香味料产品的方法。该方法采用输送反应器,热量由热的传热颗粒提供。文献提到沙、沙/催化剂混合物和氧化硅-氧化铝催化剂作为有潜力的传热材料。所有实施例基于沙作为热载体,而比较例采用炭。文献报告较高的液体产率在50%-65%的范围内。液体反应产物的pH低(3左右),含氧量高。液体反应产物需要大规模的升级处理,以便用作液体运输燃料,如汽油替代品。
PCT/EP20009/053550披露了一种固体生物质材料的催化热解方法。用第一催化剂预处理固体生物质材料,然后在第二催化剂存在下,在输送床里转化。产物是经低总酸值(TAN)读数证实具有低含氧量的液体反应产物。反应器中存在两种催化剂增大了生物质原料和/或初级反应产物过度裂解的风险。在该过程的不同阶段使用两种催化剂需要复杂的催化剂回收系统。
因此,需要一种用于催化热解固体生物质材料的催化剂体系,能够产生得油率高而含氧量低的液体反应产物,同时降低生物质原料和/或初级反应产物过度裂解的风险。
单一催化剂体系是尤其需要的。
人们还需要这种催化剂体系能以低成本获得。
发明概述
本发明提供了一种用于催化热解固体生物质材料的催化剂体系,所述催化剂体系包含至少一种金属氧化物或类金属氧化物,其介观和宏观总比表面积在1-100米2/克的范围内,由此解决了上述问题。
本发明另一方面包括一种利用所述催化剂体系对固体生物质材料进行催化转化的方法。
具体实施方式
下面描述本发明的一些实施方式,这些实施方式仅仅是给出的示例。
生物质材料的热解可以通过加热进行,即不使用催化剂。加热热解过程的一个例子是将木材转化为木炭,其历史几乎与人类一样久远。应当记住,固体生物质材料本来就不可避免地至少包含一些矿物质,即“灰分”。一般认为,灰分的一些成分在“加热”热解过程中具有催化活性。尽管如此,若不添加催化剂,则热解过程视为加热热解。
制备木炭的过程涉及缓慢加热,产生气体产物和固体产物,后者就是木炭。可对热解过程加以改进,以产生较少的焦炭而产生较多的液体产物。一般地,要提高生物质热解过程的液体产率,就需要快速加热,缩短反应时间,急速冷却液体反应产物。
人们建议生物质热解过程使用流化床反应器和输送反应器,因为已经知道这两类反应器能提供快速加热。一般地,热量是通过向反应器内注入热的粒状传热介质提供的。
美国专利4153514披露了一种热解反应器,它用炭颗粒作为传热介质。
美国专利5961786披露了一种输送反应器型热解反应器,它用沙作为传热介质。虽然该专利提到用沙和催化剂颗粒或者氧化硅-氧化铝的混合物作为传热介质的可能性,但该专利中所有实施例均基于用沙作为唯一传热介质的实验。根据’786专利中的数据,用沙作为传热介质比用炭产生的结果更好。
’786专利方法制得的液体产物是液体烟熏香味料产品,意在为食品特别是肉类提供烟熏味或BBQ风味。该液体产物的特征是pH低(3左右),含氧量高。该专利特别提到该液体变成棕色的倾向,这是明显有利于烟熏香味料产品的性质。这三个特性(低pH、高含氧量和变色)对用作液体运输燃料或要升级为液体运输燃料的液体热解产物来说是非常不利的。因为pH低,这些液体产物不能在标准钢制设备甚至不锈钢设备中加工。它们的腐蚀性要求加工过程在玻璃或特种合金设备中进行。
由于含氧量高,要将这些液体升级为可接受的液体运输燃料或者可接受的液体运输燃料的混合原料,将要求在昂贵的设备中进行大规模的加氢处理,所述设备要能经受住这种过程涉及的高压。加氢处理要消耗大量昂贵的氢气。
PCT/EP2009/053550介绍了一种用固体碱作催化剂催化热解生物质材料的方法。固体粒状生物质材料用不同的催化剂预处理。所得液体热解产物具有低总酸值(TAN),证实其含氧量低。用Na2CO3或K2CO3作预处理催化剂,用水滑石(HTC)作固体碱催化剂,可以得到最佳结果。
尽管PCT/EP2009/053550报告的结果已在较大规模的反应器中得到验证,但使用两种不同的催化剂且在该过程的两个不同阶段加入它们,带来了固有的问题。这两种催化剂材料在反应器中不可避免地彼此混合。对于连续过程来说,这两种催化剂体系必须分离,使一种催化剂可循环回到预处理步骤,而另一种催化剂回到热解反应器。
还发现,该专利建议的催化剂体系的产焦率通常高于为该过程提供所需热量所需要的产焦率。任何超出该过程需要的焦都是原料中有价值的碳的损失。尽可能降低产焦率是很重要的。
我们还希望找到成本低于水滑石之类的材料的催化剂材料。
本发明通过提供用于催化热解固体生物质材料的催化体系解决了这些问题,所述催化体系包含至少一种金属或类金属的氧化物、硅酸盐或碳酸盐,其介观和宏观总比表面积在1-100米2/克的范围内。
可以认为,所述催化体系对固体生物质材料的热解和/或对热解反应产物的次级反应具有催化活性。不过,此催化活性经过适当削弱,避免过度成焦。在热解反应中采用本发明的催化体系,可以产生得油率较高而含氧量较低的液体热解产物,类似于或者优于PCT/EP2009/053550所披露的情况。与此同时,其产焦率则明显低于用PCT/EP2009/053550所披露的催化体系得到的产焦率。
本发明一方面是金属和类金属的氧化物、碳酸盐和/或硅酸盐的应用,它们与零价态或金属形式的金属有明显差异。氧化物、碳酸盐和硅酸盐的催化活性远不及零价态金属。在优选实施方式中,本发明的催化体系基本上不含元素态或零价态金属。
术语“类金属(metalloid)”源自希腊语“metallon”(=金属)和eidos(=类),指元素周期表中介于金属与非金属之间的元素。元素硼、硅、锗、砷、锑、碲和钋一般视为类金属。周期表中,除氢外,类金属左侧元素视为金属。由于丰度大而成本低,硅是本发明的催化体系中高度优选的类金属。
在金属当中,铝高度优选用于本发明的催化体系。其他优选的金属包括选自下组的金属:1)选自钙、钡和镁的碱土金属;2)选自铁、锰、铜和锌的过渡金属;以及3)选自铈和镧的稀土金属。
本发明另一方面是具有低比表面积至中等比表面积的这种材料的应用。本文所用术语“比表面积”指材料的中孔和大孔的表面积,用BET法测定,单位为米2/克。中孔孔隙至少约2纳米,最多至约10纳米,大孔孔隙至少约10纳米。参见James B.Condon于2006年发表的题为“通过物理吸附测定表面积和孔隙”的文章。在多相催化中,催化活性发生在固体催化剂与其周围液相或气相之间的界面上。固体催化剂的制备者通常会努力增大催化剂颗粒的比表面积,以图尽可能提高催化材料的催化活性。比表面积超过150米2/克或200米2/克的固体催化剂材料是常遇到的。即使比表面积超过300米2/克的材料也不是不常见。有鉴于此,本发明的催化体系一反催化领域的成见,不允许介观和宏观总比表面积超过100米2/克。优选的催化体系的介观和宏观总比表面积为60米2/克或更小,更优选的体系的比表面积为40米2/克或更小。
所述催化体系的介观和宏观总比表面积也应当足够高,以提供有用的催化活性,因为已经知道惰性材料产生含氧量高的液体热解产物。一般地,所述催化体系的介观和宏观总比表面积至少为1米2/克,优选至少5米2/克,更优选至少10米2/克。
本文所用术语“催化体系”指热解反应中使用的材料总体,用于提供催化和/或传热功能。因此,该术语涵盖惰性材料和催化颗粒的混合物。在此情况下,该体系的比表面积是这两种组分的混合物的代表性样品的比表面积。
术语“催化体系”还包括两种或更多种不同固体粒状催化材料的混合物。在此情况中,该体系的介观和宏观总比表面积是颗粒混合物的代表性样品的介观和宏观总比表面积。
术语“催化体系”还包括含有两种或更多种材料的复合颗粒。在此情况中,该体系的介观和宏观总比表面积是复合颗粒的代表性样品的介观和宏观总比表面积。
术语“催化体系”还包括由一种催化材料的颗粒组成的体系。在此情况中,该体系的介观和宏观总比表面积是颗粒的代表性样品的介观和宏观总比表面积。
一般地,催化体系优选其中每种组分单独使用时所具有的介观和宏观总比表面积为1-100米2/克,优选2-60米2/克,更优选3-40米2/克。
采自地壳的矿物可能适用于本发明的催化体系。例子包括金红石、镁氧、硅线石、红柱石、浮石、多铝红柱石、长石、氟石、铝矾土、重晶石、铬铁矿、锆石、菱镁矿、霞石、正长岩、橄榄石、钙硅石、锰矿、钛铁矿、叶腊石、珍珠岩、板岩、硬石膏等。这些矿物很少为纯物质形式,但也不需要为用于本发明的催化体系而进行提纯。这些材料中有很多成本低廉,其中一些可以毫不夸张说是“白菜价”。
一般地,刚采出的矿物不适合直接用于所述催化体系;这种物质在本文中称作“催化剂前体”,意思是它们可以通过某种预处理转化为催化剂体系所需的材料。预处理可包括干燥、提取、洗涤、煅烧或其组合。
在本发明背景下,煅烧是优选的预处理方式。它一般包括对材料进行短时加热(急骤煅烧),或者加热数小时甚至数天。它可在空气中进行,也可在特殊气氛如蒸汽、氮气或稀有气体中进行。
煅烧的目的可以多种多样。常用煅烧的方法除去所煅烧的材料中水合形式的水,从而产生孔结构。较佳的是,这样的煅烧在至少400℃的温度下进行。温和的煅烧可得到可重新水合的材料。将材料转化为不可重新水合的形式可能是适宜的,这要求煅烧温度至少为600℃。
在非常高的温度煅烧时,可导致所煅烧的材料发生化学和/或形态变化。例如,碳酸盐可转化为氧化物。一般地,催化剂制造商会尽力避免这种变化,因为它们涉及催化活性的损失。不过,出于本发明的目的,这种相变化是所希望的,因为可以得到具有所需低催化活性的材料。
以化学和/或形态变化为目的的煅烧过程一般要求煅烧温度较高,例如至少800℃,甚至至少1000℃。
煅烧后适用于本发明催化体系的材料的例子包括经过煅烧的硬硼酸钙石(coleminite)、经过煅烧的镁橄榄石(fosterite)、经过煅烧的白云石和经过煅烧的石灰。
煅烧也可用来使具有过高催化活性的污染物降低活性。例如,主要由氧化铝组成的矾土是来源丰富、具有所需催化活性分布的材料。但是,矾土中通常存在的铁氧化物会不利地提高矾土的催化活性。高温煅烧,例如在至少800℃煅烧,可以降低铁氧化物的活性,从而使该材料适用于催化体系,而不用通过花费很大的分离步骤除去铁氧化物。
从这个角度看,所谓的“红泥”是值得关注的材料。它是用所谓拜耳(Bayer)工艺处理矾土的副产物,在该工艺中,氧化铝溶解在苛性物(NaOH)中,形成铝酸钠。将不可溶的棕红色铁氧化物从铝酸盐溶液中分离。这种红泥是炼铝工业中比较麻烦的废物流,需要经过高成本中和处理(除去夹带的苛性物)之后,才能弃置于废物填埋场。因此,红泥只有负面经济价值。可是,经煅烧后,红泥可用于本发明的催化体系。其碱性是有益的,因为能俘获热解反应产物中酸性更强(因而腐蚀性更强)的成分。
蒸汽减活可视为一种特殊类型的煅烧。在蒸汽减活过程中,存在于处理气氛中的水分子固定住被煅烧的固体材料的组成原子,帮助其转化为热力学上更稳定的形式。这种转化可能包括孔结构坍塌(失去比表面积)、固体材料的表面组成发生变化或二者同时发生。蒸汽减活一般在至少600℃的温度下进行,有时温度还要高得多,如900℃或1000℃。
页硅酸盐矿物,尤其是粘土,构成一类特别有吸引力的催化剂前体材料。这些材料具有层状结构,水分子结合在层之间。它们容易转化为本发明的催化剂体系或者这种体系的组分。
一般过程可结合高岭土说明。该过程可用于任何页硅酸盐材料,尤其是其他粘土,如膨润土或蒙脱土型粘土。术语“高岭土”一般指这样的粘土,其主要矿物组成是高岭石、叙永石、珍珠陶土、地开石、富硅高岭石及其混合物。
在该过程中,将粉化水合粘土分散在水中,优选存在反絮凝剂。合适的反絮凝剂的例子包括硅酸钠和缩水磷酸钠盐如焦磷酸四钠。存在反絮凝剂就可以制备粘土含量更高的浆料。例如,不含反絮凝剂的浆料一般包含不超过40重量%-50重量%的粘土固体。利用反絮凝剂就有可能将固含量增至55重量%-60重量%。
在喷雾干燥器中干燥水性粘土浆料,形成微球。当用于流化床或输送反应器时,微球直径优选在20-150微米之间。喷雾干燥器优选在干燥条件下操作,从而除去浆料中的游离水分,但不会除去原粘土成分中水合形式的水。例如,顺流喷雾干燥器可在空气进气温度约为650℃时操作,采用的粘土进料流速足以产生120-315℃的出口温度。不过,喷雾干燥过程可视需要在更苛刻的条件下进行,从而使粘土原料部分或完全脱水。
可对经喷雾干燥的颗粒进行分选,选出所需的粒径范围。若需要,可将超出粒径范围的颗粒研磨后再循环至该过程中形成浆料的步骤。应当理解,若粘土原料在干燥步骤中未明显脱水,则粘土更容易再循环至浆料中。
微球颗粒在850-1200℃范围内的温度下煅烧足够长的时间,使粘土通过其放热曲线。利用Ralph E.Grim在《粘土矿物学》(Clay Minerology)[麦格劳-希尔公司(McGraw Hill)出版,1952年]中描述的技术,很容易通过差热分析(DTA)确定高岭土是否通过其放热曲线。
低温煅烧将水合高岭土转化为偏高岭土,其催化活性通常太高,不适用于本发明的催化体系。不过,导致水合高岭土部分转化为偏高岭土而余下部分通过放热曲线煅烧的煅烧条件,可得到适用于本发明的催化体系的材料;它包括但不限于含高岭土的新鲜商业催化剂或者用过的商业催化剂,所述用过的商业催化剂在商业应用中已经经受了至少500℃的温度。所述用过的催化剂体系的典型实例有FCC型、FCC/添加剂及其混合物。
通过上述过程得到的材料可作为制备沸石微球的反应物从商业渠道获得。出于本发明的目的,所述材料自煅烧过程得到之后即可使用,无须进一步转化为沸石。经煅烧的粘土微球的比表面积通常低于约15米2/克。
若需要,可在浆料中加入少量可燃烧的有机粘合剂,如PVA或PVP,用来提高喷雾干燥颗粒的生坯强度。所述粘合剂在煅烧步骤被烧掉。
可利用类似于本文所描述的转化高岭土的方法,由其他催化剂前体制备微球。合适的催化剂前体的例子包括水滑石和类水滑石材料;硅铝酸盐,尤其是沸石,如Y沸石和ZSM-5;氧化铝;氧化硅;以及混合金属氧化物。所述方法一般包括以下步骤:(1)制备前体的水性浆料;(2)喷雾干燥浆料,制备微球;(3)煅烧微球,产生所需比表面积。在此情况下应记住,本文所用术语“煅烧”包括蒸汽减活。对于高活性材料如沸石,蒸汽减活可能是优选的煅烧方法。
本发明另一方面是所述催化体系在固体粒状生物质材料的催化热解过程中的应用。
以下实施例用于进一步说明本发明,不应视为对本发明范围的限制。
实施例
对于下表所列各轮独立的反应,将粒径在约10微米-约1000微米范围内的木材装入热解反应器,使之接触几种具有不同的化学组成以及不同的介观和宏观总比表面积(MSA)的催化剂,反应器的温度在约850℉-约1100℉。
表
从上表可以看出,无论催化剂的化学组成如何,生物油产率的总体趋势是随着MSA增加而降低,直至得油率在商业上不是特别合理。
虽然已结合具体实施方式特别展示和描述了本发明,但本领域的技术人员应理解,只要不背离所附权利要求书限定的本发明的精神和范围,可对形式和细节作出各种改变。
Claims (29)
1.一种用于催化热解固体生物质材料的催化体系,所述催化体系包含至少一种金属氧化物或类金属氧化物,其介观和宏观总比表面积在1-100米2/克的范围内。
2.如权利要求1所述的催化体系,其特征在于,所述催化体系的介观和宏观总比表面积在2-60米2/克的范围内。
3.如权利要求1所述的催化体系,其特征在于,所述催化体系的介观和宏观总比表面积在3-40米2/克的范围内。
4.如权利要求1-3所述的催化体系,其特征在于,所述催化体系包含至少一种通过在至少600℃煅烧催化剂前体得到的组分。
5.如权利要求4所述的催化体系,其特征在于,所述催化体系包含至少一种通过在至少800℃煅烧催化剂前体得到的组分。
6.如权利要求4所述的催化体系,其特征在于,所述催化体系包含至少一种通过在至少900℃煅烧催化剂前体得到的组分。
7.如权利要求4所述的催化体系,其特征在于,所述催化体系包含至少一种通过在至少1000℃煅烧催化剂前体得到的组分。
8.如权利要求1-7中任一项所述的催化体系,其特征在于,所述催化体系包含至少一种通过在至少400℃对催化剂前体进行蒸汽减活得到的组分。
9.如权利要求8所述的催化体系,其特征在于,所述催化体系包含至少一种通过在至少600℃对催化剂前体进行蒸汽减活得到的组分。
10.如权利要求8所述的催化体系,其特征在于,所述催化体系包含至少一种通过在至少800℃对催化剂前体进行蒸汽减活得到的组分。
11.如权利要求1-10中任一项所述的催化体系,其特征在于,所述催化体系包含选自下组的金属:1)碱土金属,特别选自钙、钡、镁和铁;2)选自铁、锰、铜和锌的过渡金属;以及3)选自铈和镧的稀土金属。
12.如权利要求4-10中任一项所述的催化剂体系,其特征在于,所述催化剂前体包含页硅酸盐矿物。
13.如权利要求10所述的催化剂体系,其特征在于,所述页硅酸盐矿物是粘土矿物。
14.如权利要求11所述的催化剂体系,其特征在于,所述粘土矿物包含高岭石。
15.如权利要求14所述的催化剂体系,其特征在于,所述粘土矿物包含已经经受了至少500℃的温度的高岭土。
16.如权利要求14所述的催化剂体系,其特征在于,所述粘土矿物包含已经经受了至少500℃的温度的膨润土。
17.如权利要求14所述的催化剂体系,其特征在于,所述粘土矿物包含蒙脱石。
18.如权利要求4-10中任一项所述的催化剂体系,其特征在于,所述催化剂前体是水滑石或类似于水滑石的材料。
19.如权利要求4-10中任一项所述的催化剂体系,其特征在于,所述催化剂前体是硅铝酸盐。
20.如权利要求19所述的催化剂体系,其特征在于,所述硅铝酸盐是Y沸石、离子交换Y沸石和/或经端部处理或脱铝。
21.如权利要求20所述的催化剂体系,其特征在于,所述沸石是ZSM-5沸石。
22.如前述权利要求中任一项所述的催化剂体系,其特征在于,所述催化剂体系包含已经经受了至少500℃的温度的氧化铝。
23.如前述权利要求中任一项所述的催化剂体系,其特征在于,所述催化剂体系包含氧化铝。
24.如前述权利要求中任一项所述的催化剂体系,其特征在于,所述催化剂体系包含氧化硅。
25.如前述权利要求中任一项所述的催化剂体系,其特征在于,所述催化剂体系包含混合金属氧化物。
26.如前述权利要求中任一项所述的催化剂体系,其特征在于,所述催化剂体系是微球形式。
27.如权利要求26所述的催化剂体系,其特征在于,所述微球的平均粒径在20-200微米的范围内。
28.如权利要求26所述的催化剂体系,其特征在于,所述微球的平均粒径在40-100微米的范围内。
29.如前述权利要求中任一项所述的催化剂体系,其特征在于,所述催化剂体系还包含粘合剂。
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CN105419829B (zh) * | 2015-10-09 | 2018-05-11 | 青海威德生物技术有限公司 | 一种热解菊苣残渣制备生物质气的方法 |
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CN108855101A (zh) * | 2016-07-18 | 2018-11-23 | 山东省科学院能源研究所 | 利用铁基复合催化剂在线提质生物油的方法 |
CN108855101B (zh) * | 2016-07-18 | 2020-10-20 | 山东省科学院能源研究所 | 利用铁基复合催化剂在线提质生物油的方法 |
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Also Published As
Publication number | Publication date |
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WO2010124069A2 (en) | 2010-10-28 |
EP2421647A2 (en) | 2012-02-29 |
CA2754172A1 (en) | 2010-10-28 |
BRPI1014826A2 (pt) | 2016-04-05 |
EP2421647A4 (en) | 2013-03-20 |
CN102574114B (zh) | 2015-12-02 |
US20120142520A1 (en) | 2012-06-07 |
WO2010124069A3 (en) | 2012-05-24 |
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