CN110639604B - 一种黑液木质素氢解催化剂及其制备方法与应用 - Google Patents
一种黑液木质素氢解催化剂及其制备方法与应用 Download PDFInfo
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- CN110639604B CN110639604B CN201910845937.1A CN201910845937A CN110639604B CN 110639604 B CN110639604 B CN 110639604B CN 201910845937 A CN201910845937 A CN 201910845937A CN 110639604 B CN110639604 B CN 110639604B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 229920005610 lignin Polymers 0.000 title claims abstract description 72
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 20
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical compound [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
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- VNVQLDDPGAWSSB-UHFFFAOYSA-H iridium(3+);trisulfate Chemical compound [Ir+3].[Ir+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNVQLDDPGAWSSB-UHFFFAOYSA-H 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 7
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000852 hydrogen donor Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 238000011161 development Methods 0.000 description 3
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- GYPMBQZAVBFUIZ-UHFFFAOYSA-N 1,2-dimethoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1OC GYPMBQZAVBFUIZ-UHFFFAOYSA-N 0.000 description 2
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical compound COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
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- 239000012621 metal-organic framework Substances 0.000 description 2
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- PETRWTHZSKVLRE-UHFFFAOYSA-N 2-Methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC=C1O PETRWTHZSKVLRE-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
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- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种黑液木质素氢解催化剂及其制备方法与应用。所述催化剂包括HZSM‑5分子筛、二氧化钛和贵金属铱组分,铱在HZSM‑5上的负载量为1wt%~30wt%,二氧化钛在HZSM‑5上的负载量为10wt%~50wt%,催化剂微孔孔径为0.55~0.60 nm。该催化剂具有二氧化钛和铱分散度高、介孔分布均匀、尺寸均一的特性,与氢解后木素分子的尺寸相匹配,可以控制黑液木质素氢解产物的缩合。而且该催化剂的酸位和催化活性相适应,协同对黑液木质素氢解成分子量较低的木素单体,具对黑液木质素的转化率高和对产物选择性好的优点。
Description
技术领域
本发明涉及木质素氢解领域,具体涉及一种黑液木质素氢解催化剂及其制备方法与应用。
背景技术
由于化石燃料消耗量大、储量有限,所以寻求可替代的能源和化学原料是非常急需的。
木质素是自然界最丰富的芳香族聚合物。由于木质素含有大量的酚类化合物,因此被认为是生产各种聚合物和生物材料的替代原料。除了木质纤维素中的天然木质素外,世界各地每天都在生产大量的工业木质素。利用酸沉淀等方法从硫酸盐浆的制浆黑液中分离得到的木质素为黑液木质素,每年大约生产27,000吨硫酸盐木质素。然而,由于木质素结构复杂,黑液木质素的反应性远低于木质素片段,限制了它的应用,所以目前大部分木质素都是用来燃烧发电。大大降低了木质素的附加值。此外,黑液木质素还含有脂肪族硫醇基团,燃烧热值低,同时会产生硫化物和特殊的气味。因此,木质素的解聚可以提高木质素的利用率,并暴露出更多有利于进一步利用的活性位点。是实现木质素高效利用需要克服的关键问题之一。
脂肪族和芳香族羟基是黑液木质素的主要活性组分,也可直接用作聚氨酯的多元醇的生产,替代大约30%的石油基多元醇。与黑液木质素相比,解聚后的木质素片段可替代高达50%的石油基多元醇生产聚氨酯。
热解是研究木质素解聚最广泛的方法之一。木质素热解得到的最终产物大部分是液体或气体,这些产物含有大量的芳香单体。热解技术在将木质素转化领域展现出巨大潜相。然而,低选择性限制了其在特定化学品生产中的应用。另外,木质素热解反应条件苛刻,反应时间短,也给产品分离带来困难,同时也限制了研究者对其热解机理的研究。
针对以上问题,木质素选择性催化转化成为目前研究的热点和未来发展的趋势,木质素选择性催化转化的方法主要有选择性氢解和选择性加氢。通常大多数氢化反应研究中用高相氢气为氢源,这不仅存在潜在的安全隐患,也不好控制氢气的用量,导致过度还原。有机酸作为氢供体对设备的腐蚀严重。而以低碳醇类(甲醇、乙醇、丙醇)作为氢供体的木质素转化研究较少。利用醇类作为氢供体不仅安全性高、氢气的用量容易控制;而且这些氢供体可以从植物纤维原料中获得,因此,来源广泛。
木素氢解后的产物主要是木素单体,木素单体氢化或加氢脱氧是木质素向高品质燃油和平台化合物转化的关键。
在木素氢解反应中所使用的催化剂主要包括X/Z(X为贵金属,如:钯、铂、钌、铑、锇、铱、金、银等;Z为催化剂载体,如:活性炭、介孔碳、石墨烯、碳纳米管、分子筛、二氧化硅、碳化硅等)贵金属催化剂系列、双金属催化剂系列和金属有机框架(MOFs)催化剂系列等。在木质素转化过程中通常使用多种催化剂的协同特性,以提高木素的转化率、目标产物的选择性和催化剂的回收利用率。因此,负载型贵金属催化剂的研究已经引起越来越多研究者的关注。开发功能化的分子筛催化剂对木质素转化为生物油进而制备平台化合物的工业化应用更具有现实意义,同时符合可持续发展的战略要求。
发明内容
针对上述技术现状,本发明的目的是提供一种黑液木质素氢解催化剂及其制备方法与应用。
本发明可以解决使用贵金属铱催化黑液木质素氢解制备木素单体的问题。
本发明解决上述技术问题的技术方案如下。
一种黑液木质素氢解催化剂的制备方法,包括以下步骤:
(1)将铱源溶于无水乙醇中,然后加入HZSM-5分子筛,搅拌均匀;
(2)向步骤(1)所得混合液中加入钛酸四丁酯和盐酸溶液,用乙酰丙酮为引发剂,反应,再加入水和乙醇的混合溶液对钛酸四丁酯水解,生成凝胶后停止搅拌;
(3)将步骤(2)所得凝胶在室温下老化、干燥、焙烧,即得黑液木质素氢解催化剂。
在优选的实施方案中,所述的催化剂中二氧化钛和铱的分散度分别为15wt%~65wt%和40wt%~90wt%;所述催化剂的孔径尺寸为2-6nm。
在优选的实施方案中,所述的催化剂二氧化钛和铱的分散度分别为20wt%~60wt%和60wt%~80wt%;所述催化剂的孔径尺寸为3-4nm。
在优选的实施方案中,所述催化剂的组成以重量计为:HZSM-5为50%~99%,二氧化钛1%~50%,铱1%~30%。
在优选的实施方案中,所述催化剂的组成以重量计为:HZSM-5为60%~90%,二氧化钛10%~30%,铱1%~10%。
在优选的实施方案中,所述催化剂的ZSM-5分子筛的硅铝摩尔比为25~250。
在优选的实施方案中,所述催化剂的ZSM-5分子筛的硅铝摩尔比为100~150。
在优选的实施方案中,所述催化剂的铱源是醋酸铱、氯化铱、硝酸铱、硫酸铱中的一种或二种以上。
在优选的实施方案中,所述催化剂的铱源是醋酸铱或硝酸铱。
在优选的实施方案中,所述催化剂的二氧化钛源自钛酸四丁酯的水解生成。
在优选的实施方案中,所述反应的时间为1~4小时。
在优选的实施方案中,所述催化剂的真空干燥温度为90~110℃,焙烧温度为500~600℃。
在优选的实施方案中,所述催化剂的真空干燥温度为95~105℃,焙烧温度为525~575℃。
在优选的实施方案中,所述催化剂的真空干燥时间为8~12小时,焙烧时间为3-7小时。
在优选的实施方案中,所述催化剂的真空干燥时间为9~11小时,焙烧时间为4~6小时。
由以上所述的制备方法制得的一种黑液木质素氢解催化剂。
以上所述的催化剂应用于氢解黑液木质素,所述黑液木质素的氢解条件为:黑液木质素0.1~1g,催化剂用量为0.1~0.5g,异丙醇(反应溶剂和氢源)为40~60mL,反应温度为200~300℃,反应时间为1~8小时,反应相相为3.5~10MPa,转速为600~1000rpm。
在优选的实施方案中,所述黑液木质素的氢解条件为:黑液木质素0.5~0.8g,催化剂用量为0.2~0.4g,异丙醇(反应溶剂和氢源)为~50mL,反应温度为250~280℃,反应时间为2~6小时,反应相相为4~8MPa,转速为650~850rpm。
本发明通过浸渍的方法在HZSM-5分子筛上负载过渡金属铱,进一步在HZSM-5分子筛上通过溶胶凝胶的方法引入二氧化钛纳米粒子,制备具有活性物质分散均一、孔径与产物分子相匹配的氢解催化剂。所述催化剂在一定条件下催化黑液木质素发生氢解反应。
与现有技术相比,本发明具有如下优点:
1、本发明的催化剂具有尺寸均一的介孔,与氢解后木素分子的尺寸相匹配,可以控制黑液木质素氢解产物的缩合。
2、本发明涉及的催化剂为多孔催化剂,孔道内含有分布均一的B酸位点和L酸位点,具有对黑液木质素转化率高及产物选择性好的优点。
附图说明
图1为实施例1~3所得催化剂的吸附-脱附等温曲线图。
图2为实施例1~3所得催化剂的氨气-程序升温脱附(NH3-TPD)曲线图。
图3a、3c和3e分别为实施例1~3所得催化剂的透射电镜(TEM)图;图3b、3d和3f分别为实施例1~3所得催化剂的晶格条纹测试结果图。
图4为实施例1~3所得催化剂的X射线衍射(XRD)测试结果图。
具体实施方式
以下结合实例与附图对本发明的具体实施作进一步的说明,但本发明的实施方式不限于此。
实施例1
称取0.5g醋酸铱溶于10mL无水乙醇,然后加入10g HZSM-5分子筛。搅拌15分钟后逐滴加入2mL钛酸四丁酯和0.20mL0.5M盐酸溶液,用0.04mL乙酰丙酮作为引发剂,反应10分钟后加入5mL去离子水和乙醇的混合溶液(v:v=1:1)对钛酸四丁酯水解,生成凝胶后停止搅拌。在室温下老化12小时,然后在100℃真空干燥。干燥后的粉末在500℃焙烧5个小时即可获得负载10wt%二氧化钛和5wt%Ir的Ir/HZSM-5@TiO2催化剂。
实施例2
(1)称取0.1g醋酸铱溶于10mL无水乙醇,然后加入10g HZSM-5分子筛。搅拌15分钟后逐滴加入3mL钛酸四丁酯和0.20mL0.5M盐酸溶液,用0.04mL乙酰丙酮作为引发剂,反应10分钟后加入5mL去离子水和乙醇的混合溶液(v:v=1:1)对钛酸四丁酯水解,生成凝胶后停止搅拌。在室温下老化12小时,然后在100℃真空干燥。干燥后的粉末在550℃焙烧5个小时即可获得负载15wt%二氧化钛和1wt%Ir的Ir/HZSM-5@TiO2催化剂。
实施例3
(1)称取1.0g醋酸铱溶于10mL无水乙醇,然后加入10g HZSM-5分子筛。搅拌15分钟后逐滴加入6mL钛酸四丁酯和0.20mL0.5M盐酸溶液,用0.04mL乙酰丙酮作为引发剂,反应10分钟后加入5mL去离子水和乙醇的混合溶液(v:v=1:1)对钛酸四丁酯水解,生成凝胶后停止搅拌。在室温下老化12小时,然后在100℃真空干燥。干燥后的粉末在600℃焙烧5个小时即可获得负载30wt%二氧化钛和10wt%Ir的Ir/HZSM-5@TiO2催化剂。
催化剂表征和催化性能测试:
(1)图1为实施例1~3所得催化剂的氮气吸附脱附等温曲线,从曲线表明该催化剂为微孔型吸附催化剂;图2为实施例1~3所得催化剂的氨气程序升温脱附曲线,从曲线表明实施例1、2和3所述催化剂分别在295、275和315℃具有较高的酸催化活性,大约在159、150和166℃分别为实施例1、2和3所得催化剂的弱酸位(B酸位点和L酸位点);图3a、3b、3c、3d、3e和3f为实施例1~3所得催化剂的透射电镜和晶格条纹测试结果,从图中表明该催化剂中含有Ir(111)、Ir(200)和Ir(220)的晶格形貌;图4为实施例1~3所得催化剂的X射线晶体衍射图,从中表明该催化剂具备二氧化钛和金属铱的晶型结构。
(2)称取0.1g上述实施例1~3制备的Ir/HZSM-5@TiO2催化剂,2g黑液木质素于反应容器中,加入50mL异丙醇作为溶剂和供氢体;将该反应器于超声分散器中分散1分钟,用氩气置换反应器中的空气后,拧紧气阀,设定反应温度为280℃,反应时间为5小时,搅拌转速为800rpm;反应结束后将反应器温度降至室温,过滤后取上清液,加入十二烷作为内标。用气相色谱-质谱联用联用仪5975自动进样检测。所用色谱柱为弹性石英毛细管柱HP-5ms(30m×0.25mm,厚度为0.25μm)。产物由四极质谱仪(型号HP 5973)进行分析,实施例1~3所述催化剂催化反应产物结果分析分别如表1~3所示。
表1木素降解产物结构和匹配度
表2木素降解产物结构和匹配度
表3木素降解产物结构和匹配度
由表1可以看出,木素的主要降解产物为长链烷烃、多碳酮、多碳醇、愈创木酚、紫丁香酚、邻苯二甲醚、对乙基苯酚、对甲基愈创木酚等。表2所示为实施例2催化剂对木素的催化降解产物,主要是多碳酮、多碳醇、环己醇结构单元、邻苯二甲醚和3,4-二甲氧基甲苯。表3为实施例3的催化剂对木素的降解产物,主要包括愈创木酚结构单元和邻苯二甲醚结构单元。
Claims (5)
1.一种黑液木质素氢解催化剂在氢解黑液木质素中的应用,其特征在于,所述黑液木质素的氢解条件为:黑液木质素0.1~1g,催化剂用量为0.1~0.5g,异丙醇为40~60mL,反应温度为200~300℃,反应时间为1~8小时,反应压力为3.5~10 MPa,转速为600~1000 rpm;
所述黑液木质素氢解催化剂的制备方法包括以下步骤:
(1)将铱源溶于无水乙醇中,然后加入HZSM-5分子筛,搅拌均匀;
(2)向步骤(1)所得混合液中加入钛酸四丁酯和盐酸溶液,用乙酰丙酮为引发剂,反应,再加入水和乙醇的混合溶液对钛酸四丁酯水解,生成凝胶后停止搅拌;
(3)将步骤(2)所得凝胶在室温下老化、干燥、焙烧,即得黑液木质素氢解催化剂;
所述催化剂的组成以重量计为:HZSM-5为50 wt%~99 wt%,二氧化钛1 wt%~50 wt%,铱1wt %~30 wt%;各组分之和为100 wt%;
步骤(3)所述焙烧的温度为500~600℃,时间为3-7小时;
所述催化剂中二氧化钛和铱的分散度分别为15%~65%和40%~90%;所述催化剂的孔径尺寸为2~6 nm。
2.根据权利要求1所述的应用,其特征在于,步骤(1)所述铱源是醋酸铱、氯化铱、硝酸铱、硫酸铱中的一种或二种以上;所述ZSM-5分子筛的硅铝摩尔比为25~250。
3.根据权利要求1所述的应用,其特征在于,步骤(2)所述反应的时间为1~4 小时。
4.根据权利要求1所述的应用,其特征在于,所述催化剂中二氧化钛和铱的分散度分别为20%~60%和60%~80%;所述催化剂的孔径尺寸为3~4 nm。
5.根据权利要求1所述的应用,其特征在于,所述催化剂的组成以重量计为:HZSM-5为60 wt%~90 wt%,二氧化钛10 wt%~30 wt%,铱1 wt%~10 wt%;各组分之和为100 wt%。
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