CN110898850A - 一种用于木醋液及生物油提质催化剂的制备与应用方法 - Google Patents
一种用于木醋液及生物油提质催化剂的制备与应用方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 32
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
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- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C5/00—Production of pyroligneous acid distillation of wood, dry distillation of organic waste
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
以生物质为原料制备得到活性炭时，副产大量木醋液。木醋液中的油相组分，化学组成与生物油较为接近，含有50‑65%的有机成分（主要为有机酸，醛，酮类、呋喃类、酚类、愈创木酚、二甲氧基苯酚和糖类），15‑30 wt%的水分，20%的胶质成分。因此，对木醋液中油相组分进行加氢脱氧处理，能够有效提升其品质，得到液体燃料。本发明申请的方法，采用具有特殊结构、高效电子传输性能、稳定机械强度的载体，一步法与活性组分相结合，得到性能良好的加氢去氧催化剂。具有方法简便、载体和活性组分之间的协同效应好等优势。对木醋液油性组分进行催化加氢去氧后，大幅减少酸、醛、酮类等不稳定化合物，增加芳烃、醇、酯等产物，改进生物燃料品质。
Description
技术领域
本发明涉及一种新型贵金属-过渡金属/碳材料负载型催化剂的制备，及其在木醋液油相组分、生物油等物质中催化加氢去氧的应用方法。通过本发明的过程，将木醋液、生物原油进行精制，得到环烷烃、芳烃等化合物，广泛应用于燃料、化工平台分子和中间体。本方法不依赖于石油、煤炭等矿产资源，属于生物质化工技术领域。
背景技术
随着经济和社会的快速发展，造成能源供应较为紧张，尤其是对运输用燃料的需求更为迫切。大量使用化石燃料资源引发的环境问题、生态问题，使可再生能源和燃料的研发已经成为一个研究热点。生物质作为唯一可再生的碳资源，可以通过定向催化转化，制备可再生的能源。通过快速热解法，可将各类木材废渣、农作物秸秆、草本植物和木本植物热解为生物油。另外，以上述各类秸秆为原料，通过水蒸汽活化、化学活化等方法制备得到活性炭的同时，副产大量木醋液。木醋液中的油相组分，其化学组成与生物油较为接近。生物油和木醋液中油相组分含有50-65％的有机成分(主要为有机酸，醛，酮类、呋喃类、酚类、愈创木酚、二甲氧基苯酚和糖类)，15-30wt％的水分，20％的胶质成分。而这些化合物中含有大量的氧组分，会导致生物原油的性能较差，包括热值低、不稳定、高粘度和腐蚀性等。因此，去除生物油和木醋液中油相组分中多余的氧原子，是升级生物油品质的必经之路。对生物油和木醋液中油相组分进行加氢脱氧处理是一种有效提升质量的方法，在此过程中，催化剂是提质改性的关键。
目前已经公布的相关发明专利，主要包括：
发明专利CN201610284615.0对生物油加氢脱氧的方法及其所用的催化剂及其制备方法申请的催化剂，其活性组分至少含有VIB族金属中的一种或多种，VIII族金属中的一种或多种组成，以及VB族金属中的一种或多种(VIB族金属优选为Cr、Mo、W中的至少一种，所述VIII族金属优选为Fe、Co、Ni中的至少一种；所述VB族金属优选为钒、铌、钽中的至少一种)，在焙烧浸渍有活性组分的催化剂载体的过程中，使所述浸渍有活性组分的催化剂载体与含氧有机物接触，完成所述焙烧得到氧化态催化剂；
发明专利CN201610284189.0采用的活性组分与上述专利相同，制备方法调整为：取经过焙烧的浸渍有活性组分的催化剂载体，使其吸附含氧无机酸，并经高温干燥处理，之后进行硫化处理，即得产品；
发明专利CN201510165579.1公开了一种生物油基含氧化合物加氢脱氧催化剂及其制备方法，该催化剂包括载体为二氧化硅，活性组分为相互紧密接触的金属磷化物和贵金属，金属磷化物为磷化镍或磷化钼，贵金属为钯、铂或钌，金属磷化物5～15％，贵金属0.1～1.0％，余量为载体，该催化剂的反应条件温和，活性、选择性高；
发明专利CN201510779776.2公开了生物质热催化转化及精制制备航空燃料的工艺方法，包括航空燃料前驱体加氢脱氧制备符合航空燃料指标的生物航空燃料，催化剂分别为Pt/C与 Co-Mo/Al2O3混合物，Pt/C与Co-Mo/Al2O3的质量比为1:1，Pt与C的质量比为0.01:1，Co/Mo与Al2O3的质量比为0.02/0.03:1；反应器入口温度为120℃，出口温度为320℃，反应压力为5MPa，该方法具有原料来源广泛、充分考虑生物质原料特点、航空燃料收率高、品位高等优点；
发明专利CN201610700947.2以W2N/AC、Mo2N/AC、WP/AC或MoP/AC为催化剂，以生物质为原料，通过机械混合，在无氧条件下于300～600℃进行快速热解，催化剂催化热解生物质的过程中，具有催化加氢脱氧的效果，能够促进酚类及芳香烃类产物形成，并抑制酸类和醛类产物形成，由此获得的生物油品位较常规生物油有较大提升。上述催化剂制备工艺简单、价格低廉，有望替代贵金属催化剂使用，从而降低成本；
发明专利CN201380024393.3公开的催化剂，活性组分为包含Ni，单独或与至少一种选自Cr、 Mo、W、Fe、Co和Cu的金属组合；载体为至少一种选自单独或混合使用的活性炭、碳化硅、二氧化硅、过渡型氧化铝、二氧化硅-氧化铝、氧化锆、氧化铈、氧化钛和过渡金属铝酸盐；
发明CN201510373024.6公开了一种木质素高效解聚的方法，即以金属氯化物与贵金属为复合催化剂，以小分子有机溶剂为介质，在温和的条件下可实现木质素等难以利用的可再生能源的高效催化解聚，制备高附加值的酚类化学品和高热值生物油。金属氯化物催化剂选自 ZnCl2、MgCl2、AlCl3、CrCl3中的一种或两种，贵金属加氢催化剂选自Pd/C、Pt/C或Ru/C，具备工艺简单、条件温和、单酚收率高、产物可控、催化剂可实现循环使用等显著优点。可避免目前的生产方法中存在的设备要求高，能耗大，目标产物收率低，催化剂失活严重等不足；
发明专利CN201510102771.6提供了一种生物油脂催化加氢制备烷烃的催化剂。以含量为 10％～50％的非贵金属镍金属盐、钼金属盐、钴金属盐、钨金属盐作为活性组分，改性分子筛/氧化铝作为催化剂载体；将催化剂载体担载含量为10％～50％钼、镍、钴、钨中的一种或两种以上混合，获得生物油脂加氢精制催化剂前驱体；将该前驱体在300-600℃氢气气氛下活化2-6h，得到生物油脂催化加氢制备烷烃的催化剂，该非硫化生物油脂加氢精制催化剂，替代加氢脱氧反应的金属硫化物催化剂和贵金属催化剂，降低生产成本，有利于缓解石化能源短缺的危机。
上述专利公开了一系列生物油催化加氢脱氧催化剂的制备及应用，为生物燃料的制备提供了有价值的新方法。然而，上述发明专利的催化剂的性能尚未达到理想水平，制备方法和使用条件相对苛刻。本发明通过优化选择载体和制备方法，使催化剂的组成、晶体结构、离子价态、酸碱性质、比表面大小、机械强度及孔结构发生较大变化，从而产生良好的协同作用，在温和条件下使用亦能大幅提升催化剂活性。解决了生物油加氢去氧催化剂制备和作用的难点问题，大幅度降低了催化剂的成本，非常值得深入开发利用。目前未有专利或文献报道此类新型催化剂的制备与利用方法。
发明内容
本发明的关键是采用新型制备方法，将活性组分贵金属(包括但不限于Pd、Pt、Ru、Rh等)，与过渡金属(包括但不限于Mo、Cu、Ni、Co等)的单质及各类化合物，负载于高比表面积的g-C3N4、石墨烯、纳米二氧化硅等载体上，得到高分散、高比表面积的纳米催化剂。此类催化剂具有特殊的结构与性能，能够在相对温和的条件下，将生物油和木醋液中的含氧化合物进行催化加氢去氧，生成芳烃、环烷烃等化合物，得到高品质生物油。
本发明采用的技术方案包括：
1.催化剂的制备。活性组分为贵金属Pd、Pt、Au、Rh、Ir、Ru、Os、等，过渡金属Ni、Co、 Mo、W、Cu、Fe、Mn、等，载体为g-C3N4、纳米石墨烯、纳米氧化石墨烯、活性炭、碳纳米管等。本发明的制备方法特征，在于载体制备与活性组分负载同步完成，具体过程参见实施方式。
2.生物油、木醋液油相组分的催化加氢去氧。反应温度范围为60-360℃、氢气压力范围0.1-20MPa，反应时间0.5-20h，催化剂的用量范围为0.5-20％，使用十氢萘、十六烷、石油醚、三苯等溶剂，对生物油及木醋液中含氢化合物进行催化加氢去氧，生成芳烃、环烃等物质，得到高品质生物油。
3.催化剂、溶剂的分离与循环利用。通过离心、过滤等方法分离得到纳米催化剂，使用芳烃、环烃等溶剂洗涤、烘干后，催化剂可以重复循环利用。
本发明具有的优势：当前催化加氢去氧过程使用的催化剂，主要是负载于金属氧化物、活性碳等材料上，载体的电子传输能力较弱，与活性组分的协同效应较差；另外，活性组分在载体上的分散程度不高，进一步影响了与载体的协同效应。木醋液是生物基活性碳生产过程中大量副产的液体，生产1吨活性碳约形成10吨木醋液，目前还未见有木醋液催化加氢的专利。本发明申请的方法，以高分散高比表面积催化剂的制备为核心，采用具有特殊结构和高效电子传输性能、机械强度较高g-C3N4、石墨烯等材料为载体，充分发挥载体和活性组分之间的协同效应，对生物油或木醋液油性组分进行催化加氢去氧，得到芳醛、环烃等产物，制备得到高性能的燃料，避免石油路线获得能源，有利于减轻环境污染和生态破坏。
具体实施方式
实施例1
分别称取2.6g的(NH4)6Mo7O24·4H2O、2.9g的(NH4)2HPO4、5.8g的柠檬酸，0.15g的PdCl2，分别溶解于30mL HCl水溶液中，搅拌1小时后，将此溶液逐滴加入到12g超细 SiO2中。将此样品在120度下干燥过夜，在500度下煅烧5小时，然后在50度下用H2还原3小时，得到催化剂Pd/MoO3–P2O5/SiO2。
实施例2
分别称取2.6g的(NH4)6Mo7O24·4H2O、2.9g的(NH4)2HPO4、5.8g的柠檬酸，0.15g的PdCl2，分别溶解于30mL HCl水溶液中，搅拌1小时后，将此溶液逐滴加入到12g氧化石墨烯中(GO)。将此样品在120度下干燥过夜，在300度下煅烧5小时，然后在50度下用H2还原3小时，得到催化剂Pd/MoO3–P2O5/RGO。
实施例3
取棉杆热解后得到的生物油500g，加入50g催化剂，于110度，1Mpa H2反应2小时，原料和催化加氢产物经GC-MS分析，组分变化结果情况见表1。
表1生物油催化加氢后组成变化
由表1结果可知，生物油经催化加氢后，酚类、酮、醛、酸类物质的含量明显下降，而饱和醇和酯类物质的含量明显升高，pH值亦有明显升高。表明通过催化剂的催化加氢作用，生物油中性质不稳定的化合物含量大幅降低，转变成了含氢量较高和性质较为稳定的化合物，酸性也有明显下降，生物油的品质得到了明显提升。
实施例4
取棉杆快速热解得到的生物油500g，加入50g催化剂，在150度，1Mpa H2下反应15小时，原料和催化加氢产物经GC-MS分析，组分变化结果情况见表2。
表2生物油催化加氢后组成变化
表2结果说明，生物油经催化加氢后，酚类、酮类和糖类物质的含量明显下降，醛、酸类物质含量下降为零。饱和醇和酯类物质的含量明显升高，pH值明显升高。结果说明，通过催化剂的加氢去氧作用，生物油中酚、醛、酮等性质不稳定的化合物含量大幅降低，转变成了含氢量较高和性质较为稳定的醇、酯等化合物，酸性也有明显下降，生物油的品质得到了明显提升。
实施例5
以棉杆为原料，采用水蒸汽法制备活性炭，将副产的木醋液进行静置分层，取上层油相组分作为底物，进行催化加氢去氧。取木醋液500g，加入50g催化剂，在150度，1Mpa H2下反应15小时，原料和催化加氢产物经GC-MS分析，组分变化结果情况见表3。
表3木醋液催化加氢后组成变化
由表3可以看出，木醋液中酸类物质较多，经催化加氢后，酚类、酮、醛、酸类物质的含量明显下降，而饱和醇和酯类物质的含量明显升高，pH值明显升高。表明通过催化剂的催化加氢作用，木醋液中性质不稳定的化合物含量大幅降低，转变成了含氢量较高和性质较为稳定的化合物，酸性也有明显下降，木醋液的品质得到了明显提升。
Claims (5)
1.本发明的特征在于使用对象为木醋液油相组分或者生物油。
2.此类催化剂的特征在于采用活性组分与负载同步进行的方法，一步制得固载化的双金属催化剂。
3.此类催化剂的特征在于活性组分为贵金属Pd、Pt、Au、Rh、Ir、Ru、Os、等，过渡金属Ni、Co、Mo、W、Cu、Fe、Mn、等，载体为g-C3N4、纳米石墨烯、纳米氧化石墨烯、活性炭、碳纳米管等。
4.此类催化剂的特征在于反应温度范围为60-360℃、氢气压力范围0.1-20MPa，反应时间0.5-20h，催化剂用量范围为0.5-20％，使用十氢萘、十六烷、石油醚、三苯等溶剂，对生物油及木醋液中含氢化合物进行催化加氢去氧，生成芳烃、环烃等物质，得到高品质生物油。
5.此类催化剂的特征在于通过离心、过滤等方法分离得到纳米催化剂，经洗涤、烘干后，催化剂可以重复循环利用,有机溶剂通过蒸馏、精馏等方法可以分离并循环利用。
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| CN112691690B (zh) * | 2021-01-11 | 2023-06-20 | 南京师范大学 | 一种负载型双金属氮化物催化剂及其制备方法与应用 |
| CN113578352A (zh) * | 2021-09-01 | 2021-11-02 | 福州大学化肥催化剂国家工程研究中心 | 一种高稳定性固定床加氢脱氧催化剂及其制备方法和应用 |
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