WO2017161780A1 - 一种全氢芴或全氢芴烷基取代物的制备方法 - Google Patents

一种全氢芴或全氢芴烷基取代物的制备方法 Download PDF

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WO2017161780A1
WO2017161780A1 PCT/CN2016/089625 CN2016089625W WO2017161780A1 WO 2017161780 A1 WO2017161780 A1 WO 2017161780A1 CN 2016089625 W CN2016089625 W CN 2016089625W WO 2017161780 A1 WO2017161780 A1 WO 2017161780A1
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catalyst
compound
perhydrohydroquinone
alkyl substituent
metal
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French (fr)
Inventor
邹吉军
潘伦
张香文
王庆法
王莅
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Tianjin University
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Tianjin University
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Priority to US15/536,569 priority Critical patent/US10233135B2/en
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Definitions

  • the invention belongs to the field of high energy density fuel synthesis and relates to a preparation method of perhydroanthracene or perhydroalkylene alkyl substituent.
  • High-density fuel is a synthetic liquid hydrocarbon used as a fuel. Essentially, it can be applied to all kerosene fuels, such as petroleum-refined hydrocarbon fuels such as aviation kerosene Jet A and rocket kerosene RP-1. Aspirated engines and rocket engines for fuel. Compared with petroleum refining fuel, the density of high-density fuel is greatly improved, and the calorific value of mass combustion is basically the same. Therefore, it can also be called high-energy density fuel, and its volumetric calorific value is greatly improved. When the tank is of a certain volume, it can provide more propulsion power and significantly improve the range or carrying capacity of the aircraft.
  • High-density liquid hydrocarbon fuels such as RJ-4, RJ-5, and JP-10, are synthesized by diels-Alder addition and hydrogenation using biscyclopentadienyl compounds and acetylene as raw materials. These fuels are based on fossil resources such as oil and coal. Biomass feedstock can also be used to prepare high-density fuels.
  • the most widely used biomass resource is lignocellulose.
  • the platform compounds are phenol, anisole, guaiacol, cyclohexanone, cyclopentanone, acetone. ⁇ -valerolactone and furfural.
  • the high-density fuels prepared by these platform compound molecules are mainly long-chain alkanes, and the synthesis of polycyclic hydrocarbons is less.
  • Green Chemistry 2015, 17(8), 4473-4481 uses cyclohexanone to prepare a density of 0.887g. /ml of composite fuel, Scientific Reports 5, Article number: 9565 (2015) to prepare a fuel having a density of 0.91 g/ml with cyclopentanol.
  • Totally hydrogenated hydrazine is a tricyclic hydrocarbon which has a density of 1.012 g/ml at 20 ° C and can be used as an oil additive to increase the density of the oil.
  • the existing synthesis method is obtained by reducing hydrazine, and hydrazine can be obtained by alkylation of benzene and dichloromethane, or intramolecular cyclization of a diphenylmethane derivative containing a halogen or a boronic acid site.
  • Patent EP0911309A1 proposes a route for the conversion of a dibenzoylalkyl derivative to a mercapto compound on a metal support on an oxide support; the literature Angew. Chem. Int. Ed.
  • Patent CN102701897A obtains up to 32.8% of ruthenium in the process of hydrogenation of the washed oil fraction to produce cyclic hydrocarbon compounds, and the selectivity of perhydroanthracene is only 28.8%.
  • the literature Chem. Eur. J. 2009, 15, 6953-6963 uses isopropanol as solvent, Rh/C as catalyst, and 5 MPa of H 2 , the yield of hydrogenation to perhydrohydroquinone is only 80%.
  • Angewandte Chemie International Edition 2010, 49(16), 2909-2912 Ru is used to catalyze cross-coupling and intramolecular cyclization of 1,2-dihalobenzene and phenylboronic acid to obtain hydrazine;
  • Advanced Synthesis & Catalysis 2010, 352(18), 3267-3274 is palladium catalyzed 2 - Halo-2'-methyl-1,1'-biphenyl
  • hydrazine One method of mass production of hydrazine is the alkylation reaction of methylene chloride and benzene or biphenyl under the catalysis of aluminum trichloride, but this method introduces toxic benzene, and the introduced halogen is separated and recovered. Difficulties, high production costs, heavy environmental pollution, and the conditions for reducing hydrazine derivatives are harsh and the yield is low.
  • the method comprises the following steps:
  • the second catalyst is a mechanical mixture of a metal catalyst and an acid catalyst or a metal catalyst supported on an acid catalyst.
  • the first catalyst is selected from the group consisting of SiO 2 -Al 2 O 3 , HZSM-5, Al-MCM-41, H ⁇ , MMT-K10, SAPO-34, USY, H 3 O 40 PW 12 ⁇ xH 2 O
  • One or more of Amberlyst-15, Nafion, AlCl 3 , FeCl 3 , ZnCl 2 , CuCl 2 , metal modified HPW, Nb 2 O 5 , WO 3 or liquid phosphoric acid the amount of the first catalyst added is The benzyl compound is 0.5 to 26% by weight.
  • the metal modified HPW is Sn 0.5 TPA, HfTPA.
  • the metal catalyst is selected from one or more of Cu, W, Mo, Ni, Pd, Pt, Ru, Ir, Rh, Zn or PtNi, CoNi, CoMo, IrFe, PdPt, RuCu;
  • the acid catalyst is selected from the group consisting of SiO 2 -Al 2 O 3 , HZSM-5, Al-MCM-41, H ⁇ , MMT-K10, SAPO-34, USY, H 3 O 40 PW 12 ⁇ xH 2 O, Amberlyst-15, Nafion One or more of AlCl 3 , FeCl 3 , ZnCl 2 , CuCl 2 , metal modified HPW (Sn 0.5 TPA, HfTPA), Nb 2 O 5 , WO 3 or liquid phosphoric acid; When the acid catalyst is mechanically mixed, the mass ratio of the two is 0.02% or more, and when the metal catalyst is supported on the acid catalyst, the mass ratio of the two is 0.02 to 10%.
  • the phenolic compound is selected from the group consisting of phenol, guaiacol, 3-methylphenol, 2-methylphenol, 3-methoxyphenol, 4-ethylphenol, catechol, 4-vinyl Phenol, 3-methoxycatechol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-vinylphenol, 2,6-dimethoxyphenol, 4-methyl- 2,6-dimethoxy-phenol or 4-allyl-2,6-dimethoxyphenol;
  • the aromatic hydrocarbon compound is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, trimethylbenzene, and 2-ene Propyl benzene, 1-ethyl-2-methylbenzene, 1,2,4,5-tetramethylbenzene, naphthalene, 1-methylnaphthalene;
  • the aryl ketone compound is selected from the group consisting of benzophenone and phenylethyl a ketone,
  • the alkylation reaction conditions are as follows: a reaction temperature of 50 to 200 ° C, a reaction time of 0.5 to 24 h, a molar ratio of a phenolic compound or an aromatic hydrocarbon compound or an aryl ketone compound or an aryl ether compound to a benzyl compound 2:1 to 30:1;
  • the hydrogenation reaction conditions are as follows: the mass ratio of the second catalyst to the substituted or unsubstituted diphenylmethane is 0.01 to 23%, the hydrogen pressure is 3 to 8 MPa, and the reaction temperature is 120 to 250 ° C. The reaction time is 2 to 40 hours.
  • the proportion of metal catalyst in the second catalyst is increased to increase the selectivity of the perhydroindene and/or perhydroindole alkyl substituent.
  • the perhydrohydroquinone or perhydroindole alkyl substituent of the present invention can be used as a liquid jet fuel.
  • the present invention first uses an acid catalyst to catalyze the alkylation of a phenol or an aromatic hydrocarbon or an aryl ketone or an aryl ether compound to obtain a substituted or unsubstituted diphenylmethane, and then catalytic hydrogenation/deoxygenation using a metal catalyst.
  • a metal catalyst Intramolecular cyclization, the conversion of substituted or unsubstituted diphenylmethane to a high density fuel of perhydroanthracene or perhydroanthracene alkyl substituent.
  • the catalyst can be reused, providing a new practical method for the preparation of perhydroanthracene and its alkyl substituents.
  • the inventors have unexpectedly discovered that by controlling the ratio of metal catalyst to acid catalyst, the content of perhydroanthracene and its alkyl substituent in the fuel can be controlled.
  • the present invention uses a lignin-derived phenol or aromatic hydrocarbon or an aryl ketone or an aryl ether compound as a raw material, and obtains a class by a simple alkylation reaction, replacing a halogen with a natural oxygen-containing functional group.
  • Halogen substituted or unsubstituted diphenylmethane, raw material source is green, easy to scale production, low cost and environmentally friendly; for intramolecular cyclization and hydrazine and its derivatives difficult to hydrogenate, the method will be intramolecular
  • the cyclization and hydrogenation/deoxygenation are effectively combined to achieve one step to obtain a perhydroanthracene or an alkylate thereof.
  • the process conditions are mild and the product selectivity is controllable, which was first obtained by the inventors.
  • the invention synthesizes a tricyclic-containing perhydroanthracene and a perhydroalkylene alkyl-substituted biomass fuel from lignin, which can greatly increase the density of the biomass fuel and obtain a fuel of high energy density.
  • the selectivity of the perhydrohydroquinone and/or perhydroalkylene alkyl substituents is increased.
  • the inventors have also unexpectedly discovered that, in the case of fixing the lignin derivative and the corresponding amount of the catalyst, by continuously adding the benzyl compound while maintaining the molar ratio of the two to always be 30:1, Continuous conversion of lignin derivatives almost completely and with high selectivity.
  • the present invention will be a lignin derivative (i.e., some phenols or aromatic hydrocarbons or aryl ketones or aryl ether compounds selected from the group consisting of phenol, guaiacol, 3-methylphenol, 2-methylphenol , 3-methoxyphenol, 4-ethylphenol, catechol, 4-vinylphenol, 3-methoxycatechol, 4-ethyl-2-methoxyphenol, 2-methoxy -4-vinylphenol, 2,6-dimethoxyphenol, 4-methyl-2,6-dimethoxy-phenol or 4-allyl-2,6-dimethoxyphenol;
  • the aromatic hydrocarbon compound is selected from the group consisting of benzene, toluene, ethylbenzene, xylene, trimethylbenzene, 2-allylbenzene, 1-ethyl-2-methylbenzene, 1,2,4,5-tetramethylbenzene, Naphthalene, 1-methylnaphthalene;
  • the aryl ketone compound
  • the first step is the alkylation reaction.
  • Lignin derivatives and benzyl compounds in acidic catalysts (SiO 2 -Al 2 O 3 , HZSM-5, Al-MCM-41, H ⁇ , MMT-K10, SAPO-34, USY, H 3 O 40 PW 12 ⁇ xH 2 O (HPW), Amberlyst-15, Nafion, AlCl 3 , FeCl 3 , ZnCl 2 , CuCl 2 , metal modified HPW (such as Sn 0.5 TPA, HfTPA), Nb 2 O 5 , WO 3 and other metal oxides and Under the action of liquid phosphoric acid, and maintaining the molar ratio of the two reactants at 2:1 to 30:1, the alkylation reaction is carried out at a reaction temperature of 50 to 200 ° C to obtain a diphenylmethane derivative (substituted or not).
  • the lignin derivative is an oxygen-containing compound, which is a phenolic compound or an aryl ketone compound or an aryl ether compound obtained by thermal cracking of lignin or acid-catalyzed hydrolysis, or may be obtained by deoxidation of these phenolic compounds.
  • the condensation product is dibenzyl ether and the like.
  • the amount of the catalyst added is 0.5 to 26% by mass of the benzyl compound, and the reaction time is 0.5 to 24 hours. After completion of the reaction, the diphenylmethane derivative was isolated by distillation under reduced pressure.
  • the second step is a deoxy/cyclization/hydrogenation reaction of a diphenylmethane derivative (substituted or unsubstituted diphenylmethane).
  • acid catalysts SiO 2 -Al 2 O 3 , HZSM-5, Al-MCM-41, H ⁇ , MMT-K10, SAPO-34, USY, H 3 O 40 PW 12 ⁇ xH 2 O (HPW), Mechanical mixture of Amberlyst-15, Nafion, AlCl 3 , FeCl 3 , ZnCl 2 , CuCl 2 , metal modified HPW (eg Sn 0.5 TPA, HfTPA), Nb 2 O 5 ,
  • the product of alkylation of diphenylmethane derivatives was analyzed by gas chromatography.
  • the conversion of dibenzyl ether was 100%, the conversion of anisole was 15%, and the derivatives of diphenylmethane (ie, substituted or unsubstituted diphenylmethane).
  • the yield is 90%.
  • a mixture of pure diphenylmethane or a substituted diphenylmethane can be obtained after distillation under reduced pressure.
  • the lignin contains a benzene ring derivative and a benzyl compound (2-methylbenzyl alcohol, 4-methylbenzyl alcohol, isomer of 2-methylbenzyl alcohol, dehydration condensation product of benzyl alcohol and benzyl alcohol, dibenzyl ether, etc.
  • the lignin derivative (phenolic or aromatic hydrocarbon or aromatic ketone or aryl ether compound) may be in a molar ratio of 2:1 to 30:1 with the benzyl compound,
  • the temperature is in the range of 50 to 200 ° C, and the conversion rate is 6% or more.
  • the benzyl compound can be completely converted.
  • the lower the proportion of the benzyl compound the higher the yield of the bicyclic compound.
  • the ratio of the lignin derivative to the benzyl compound is 30:1, the alkylation product selectivity can reach 100%.
  • the higher the temperature the more readily the benzyl compound undergoes its own conversion, producing by-products. The same reaction can occur for all of the listed acidic catalysts.
  • lignin derivatives including phenolic or aromatic hydrocarbons or aromatic ketones or aryl ethers
  • benzyl compounds (2-methylbenzyl alcohol, 4-methyl) under the listed acidic catalysts.
  • An alkylation reaction occurs in benzyl alcohol, an isomer of 2-methylbenzyl alcohol, a dehydration condensation product of benzyl alcohol and benzyl alcohol, and the like.
  • the higher the acidity the shorter the reaction time, and the more susceptible the benzyl derivative is to side reactions.
  • the prepared fuel was analyzed by GC-MS analysis and the product was composed of two components (including a mixture of 35% dicyclohexylmethane and 65% perhydroanthracene).
  • a metal catalyst (Cu, W, Mo, Ni, Pd, Pt, Ru, Ir, Rh, Zn, etc.) or a bimetallic catalyst (PtNi, CoNi, CoMo, IrFe, PdPt, RuCu, etc.) and an acid catalyst (SiO 2 -Al 2 O 3 , HZSM-5, Al-MCM-41, H ⁇ , MMT-K10, SAPO-34, USY, H 3 O 40 PW 12 ⁇ xH 2 O (HPW), Amberlyst-15, Nafion Mechanical mixture of AlCl 3 , FeCl 3 , ZnCl 2 , CuCl 2 , metal modified HPW (eg Sn 0.5 TPA, HfTPA), Nb 2 O 5 , metal oxides such as WO 3 and liquid phosphoric acid, and metal-loaded An acidic catalyst (maintaining a mass ratio of the metal catalyst to the acidic catalyst of 0.02% or more and
  • the combination of the metal site and the acid site can catalyze the HDO process of the diphenylmethane derivative (ie, substituted or unsubstituted diphenylmethane) at a hydrogen pressure of 3-8 MPa and a temperature of 120.
  • a conversion of 100% can be achieved at -250 ° C, resulting in a mixture of saturated hydrocarbon derivatives of dicyclohexylmethane and perhydroanthracene and their alkyl substituents.
  • the formation of perhydroanthracene and its alkyl substituents is a special place.
  • the individual metal sites can catalyze the diphenylmethane derivative to obtain a pure perhydroanthracene saturated hydrocarbon derivative.
  • the diphenylmethane derivative will form a dicyclohexylmethane saturated hydrocarbon derivative under normal conditions, and the combination of the intramolecular cyclization and the HDO process gives a tricyclic compound, and the larger the proportion of the metal sites, the third of the products The greater the proportion of cyclic compounds.
  • the formation of tricyclic hydrocarbons further increases the density of the fuel.
  • Pure perhydro fluorenyl density can be achieved at 20 °C 1.012g.ml -1, density of pure methane dicyclohexyl achieved at 20 °C 0.8750g.ml -1.
  • the density was determined to be 0.9172 g.ml -1 according to the national standard GB2540-81 "Petroleum Density Determination Method”; according to the national standard GB2430-81 "jet fuel freezing point determination” The method measures the freezing point below -60 ° C; the dynamic viscosity is determined to be 10.41 mm 2 /s according to GB 265-88 "Kinematic viscosity measurement method and dynamic viscosity calculation method". It can be seen that the mixture after hydrodeoxygenation of dicyclohexylmethane is a good fuel or fuel additive.

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Abstract

一种全氢芴或全氢芴烷基取代物的制备方法，该方法包括如下步骤：(1)使酚类化合物或芳烃类化合物或芳酮类化合物或芳醚类化合物与苄基化合物在第一催化剂存在下发生烷基化反应，生成取代的或未取代的二苯甲烷；其中所述第一催化剂为酸性催化剂；(2)使所述取代的或未取代的二苯甲烷在第二催化剂的存在下与氢气进行加氢或加氢脱氧反应，得到全氢芴或全氢芴烷基取代物；其中所述第二催化剂为金属催化剂和酸催化剂的机械混合物或负载在酸催化剂上的金属催化剂。

Description

一种全氢芴或全氢芴烷基取代物的制备方法 技术领域
本发明属于高能量密度燃料合成领域，涉及全氢化芴或全氢化芴烷基取代物的制备方法。
背景技术
高密度燃料是人工合成的作为燃料使用的液体碳氢化合物，从本质上说，与石油炼制的碳氢燃料，如航空煤油Jet A、火箭煤油RP-1等相同，可应用于所有以煤油为燃料的吸气式发动机和火箭发动机。与石油炼制的燃料相比，高密度燃料的密度有很大程度的提高，而质量燃烧热值基本相当，因此也可以称为高能量密度燃料，其体积热值有很大的提高，在油箱体积一定的情况下，可以提供更多的推进动力，显著提高飞行器的航程或运载能力。
高密度液体碳氢燃料，如RJ-4,RJ-5,JP-10,都是以双环戊二烯基化合物、乙炔等为原料，通过Diels-Alder加成，加氢合成而来。这些燃料都是以石油和煤等的化石资源为基础得来的。生物质原料也可以用来制备高密度燃料，最广泛存在的生物质资源是木质纤维素，其平台化合物分子有苯酚、苯甲醚、愈创木酚、环己酮、环戊酮、丙酮、γ-戊内酯及糠醛等。目前，通过这些平台化合物分子制备的高密度燃料主要是一些长链烷烃，多环碳氢化合物的合成较少，Green Chemistry 2015,17(8),4473-4481采用环己酮制备密度为0.887g/ml的复合燃料，Scientific Reports 5,Article number:9565(2015)以环戊醇制备密度为0.91g/ml的燃料。
全氢化芴是一种三环碳氢化合物，其密度在20℃时可以达到1.012g/ml，可以作为油品添加剂提高油品的密度。现有的合成方法通过还原芴得到，而芴可以通过苯和二氯甲烷烷基化反应，或者含卤素或者硼酸位的二苯甲烷类衍生物分子内环化得到。专利EP0911309A1提出了金属负载在氧化物载体上将二苯甲烷基衍生物转化为芴基化合物的路线；文献Angew.Chem.Int.Ed.2012,51,5359-5362采用有机贵金属催化剂催化二苯甲烷衍生物脱氢环化制备芴；文献Angew.Chem.Int.Ed.2012,51,5359-5362；Org.Lett.,Vol.11,No.20,2009；J.AM.CHEM.SOC.9VOL.130,NO.48,2008，16159；Adv.Synth.Catal.2010,352,3267-3274采用钯基催化剂催化含卤素的芳烃分子内环化制备芴基化合物。将芴加氢为全氢化芴是一个相对较难的过程，专利CN102701897A在洗油馏分加氢制备环烃类化合物的方法中最高得到 32.8％的芴，且全氢化芴的选择性只有28.8％，文献Chem.Eur.J.2009,15,6953-6963采用异丙醇为溶剂，Rh/C为催化剂，5MPa的H2的条件下，芴加氢为全氢芴的收率只有80％。
现有制备全氢芴或全氢化芴烷基取代物的制备方法是芴或其烷基取代物加氢。其中芴的来源有两个：一是煤焦油，芴在高温焦油中约含1.0～2.0％，经过冷却，结晶，离心分离，得到粗芴，然后将工业芴溶于苯中，再经中和水洗，脱溶，将芴重新蒸馏，馏出物用汽油和乙醇重结晶得到95％的纯芴，此种方法耗能较大；二是通过含卤素或硼酸位的联环芳烃发生分子内或分子间的烷基化反应得到，例如，Angewandte Chemie International Edition 2012,51(22),5359-5362采用Ru活化2,2-二苯基乙酸的C-H，环化得到芴；Angewandte Chemie International Edition 2010,49(16),2909-2912用Ru催化1,2-二卤苯和苯硼酸发生交叉偶联和分子内的环化得到芴；Advanced Synthesis&Catalysis 2010，352(18),3267-3274用钯催化2-卤-2'-甲基-1,1'-联苯发生分子内的烷基化反应得到芴，但此方法成本高，难以实现工业化。芴的大批量生产的一种方法是二氯甲烷和苯或联苯在三氯化铝的催化作用下发生烷基化反应，但此种方法引入了具有毒性的苯，而且引入的卤素分离回收困难，生产成本高，环境污染重，同时还原芴的衍生物的条件较苛刻，收率较低。
发明内容
本发明的目的在于提供全氢化芴及全氢化芴烷基取代物的新的制备方法。该方法包括如下步骤：
(1)使酚类化合物或芳烃类化合物或芳酮类化合物或芳醚类化合物与苄基化合物在第一催化剂存在下发生烷基化反应，生成取代的或未取代的二苯甲烷；其中所述第一催化剂为酸性催化剂；
(2)使所述取代的或未取代的二苯甲烷在第二催化剂的存在下与氢气进行加氢反应或加氢脱氧反应，得到全氢芴或全氢芴烷基取代物；其中所述第二催化剂为金属催化剂和酸催化剂的机械混合物或负载在酸催化剂上的金属催化剂。
优选地，所述第一催化剂选自SiO2-Al2O3、HZSM-5、Al-MCM-41、Hβ、MMT-K10、SAPO-34、USY、H3O40PW12·xH2O、Amberlyst-15、Nafion、AlCl3、FeCl3、ZnCl2、CuCl2、金属改性的HPW、Nb2O5、WO3或液体磷酸中的一种或多种，第一催化剂的加入量为苄基化合物重量的0.5～26％。优选地，金属改性的HPW为Sn0.5TPA,HfTPA。
优选地，所述金属催化剂选自Cu、W、Mo、Ni、Pd、Pt、Ru、Ir、Rh、Zn或PtNi、 CoNi、CoMo、IrFe、PdPt、RuCu中的一种或几种；所述酸催化剂选自SiO2-Al2O3、HZSM-5、Al-MCM-41、Hβ、MMT-K10、SAPO-34、USY、H3O40PW12·xH2O、Amberlyst-15、Nafion、AlCl3、FeCl3、ZnCl2、CuCl2、金属改性的HPW(Sn0.5TPA,HfTPA)、Nb2O5、WO3或液体磷酸中的一种或多种；所述金属催化剂与所述酸催化剂机械混合时二者的质量比为0.02％以上，所述金属催化剂负载在所述酸催化剂上时二者的质量比为0.02～10％。
优选地，所述酚类化合物选自苯酚、愈创木酚、3-甲基苯酚、2-甲基苯酚、3-甲氧基苯酚、4-乙基苯酚、儿茶酚、4-乙烯基苯酚、3-甲氧基儿茶酚、4-乙基-2-甲氧基苯酚、2-甲氧基-4-乙烯基苯酚、2，6-二甲氧基苯酚、4-甲基-2，6-二甲氧基-苯酚或4-烯丙基-2，6-二甲氧基苯酚；所述芳烃类化合物选自苯、甲苯、乙苯、二甲苯、三甲苯、2-烯丙基苯、1-乙基-2-甲基苯、1,2,4,5-四甲基苯、萘、1-甲基萘；所述芳酮类化合物选自苯甲酮、苯乙酮、苯丙酮或3，4-二甲氧基-1-苯乙酮；所述芳醚类化合物选自苯甲醚、1-乙基-4-甲氧基苯；所述苄基化合物选自苯甲醇、2-甲基苯甲醇、4-甲基苯甲醇或二苄醚。
优选地，所述烷基化反应条件如下：反应温度50～200℃，反应时间为0.5～24h，酚类化合物或芳烃类化合物或芳酮类化合物或芳醚类化合物与苄基化合物的摩尔比为2:1～30:1；
优选地，所述加氢反应条件如下：所述第二催化剂与所述取代的或未取代的二苯甲烷的质量比为0.01～23％，氢气压力3～8MPa、反应温度120～250℃，反应时间2～40h。
优选地，增加所述第二催化剂中的金属催化剂的比例，以提高全氢芴和/或全氢芴烷基取代物的选择性。
本发明的全氢芴或全氢芴烷基取代物可以用作液体喷气燃料的用途。
本发明的有益效果：
1、本发明首先采用酸催化剂，催化酚类或芳烃类或芳酮类或芳醚类化合物烷基化反应，得到取代的或未取代的二苯甲烷，然后采用金属催化剂催化加氢/脱氧/分子内环化，将取代的或未取代的二苯甲烷转化为全氢化芴或全氢化芴烷基取代物的高密度燃料。此过程无卤素和高毒性物质的引入，催化剂可以重复利用，为全氢化芴及其烷基取代物的制备提供了新的实用方法。本发明人意外发现，通过控制金属催化剂与酸性催化剂的比例，可以控制燃料中全氢化芴及其烷基取代物的含量。
2、合成全氢化芴及其烷基取代物的现有技术分两个阶段，首先得到芴的衍生物，然后再还原得到全氢化芴及其烷基取代物。得到芴的衍生物的过程或引入卤素或者需要制备含卤素或者硼酸位的二苯甲烷衍生物作为原料，操作流程复杂，污染重，并且第二个阶段还原芴 的衍生物的反应条件较苛刻，收率较低。针对第一阶段原料的问题，本发明以木质素来源的酚类或芳烃类或芳酮类或芳醚类化合物为原料，通过简单的烷基化反应，以天然的含氧官能团代替卤素得到类卤素的取代的或未取代的二苯甲烷，原料来源绿色，易规模化生产，成本低且环境友好；针对分子内的环化和芴及其衍生物难加氢的问题，本方法将分子内环化和加氢/脱氧有效地结合起来，实现一步得到全氢化芴或其烷基取代物。此工艺过程条件温和，且产品选择性可控，为本发明人首次得到。
3、针对大批量生产的生物质燃料密度低的问题，要得到更高密度(或高能量密度)的碳氢化合物，必须增加环数。本发明从木质素出发合成含有三环的全氢化芴及全氢化芴烷基取代物生物质燃料，可以大幅提高生物质燃料的密度，得到高能量密度的燃料。提高了全氢芴和/或全氢芴烷基取代物的选择性。
4、本发明人还意外发现，在固定木质素衍生物和相应的催化剂量的情况下，通过连续加入苄基化合物的方法，同时保持两者的摩尔比始终为30:1的情况下，可以连续的将木质素衍生物几乎完全转化，并且选择性很高。
附图说明
无。
具体实施方式
以下通过实施例来进一步说明本发明的实施。实施例仅仅是示例性的，而非限制性的。
本发明将木质素衍生物(即一些酚类或芳烃类或芳酮类或芳醚类化合物，所述酚类化合物选自苯酚、愈创木酚、3-甲基苯酚、2-甲基苯酚、3-甲氧基苯酚、4-乙基苯酚、儿茶酚、4-乙烯基苯酚、3-甲氧基儿茶酚、4-乙基-2-甲氧基苯酚、2-甲氧基-4-乙烯基苯酚、2，6-二甲氧基苯酚、4-甲基-2，6-二甲氧基-苯酚或4-烯丙基-2，6-二甲氧基苯酚；所述芳烃类化合物选自苯、甲苯、乙苯、二甲苯、三甲苯、2-烯丙基苯、1-乙基-2-甲基苯、1,2,4,5-四甲基苯、萘、1-甲基萘；所述芳酮类化合物选自苯甲酮、苯乙酮、苯丙酮或3，4-二甲氧基-1-苯乙酮；所述芳醚类化合物选自苯甲醚、1-乙基-4-甲氧基苯；所述苄基化合物选自苯甲醇、2-甲基苯甲醇、4-甲基苯甲醇或二苄醚等)和苄基化合物(2-甲基苯甲醇、4-甲基苯甲醇、2-甲基苯甲醇的异构体、苯甲醇以及苯甲醇的脱水缩合产物二苄醚等)进行烷基化反应得到二苯甲烷衍生物(取代的或未取代的二苯甲烷)，然后通过加氢/脱氧/分子内环化得到以全氢化芴或全氢化芴烷基取代物为主要成分的混合物及全氢化芴或全氢化芴烷基取代物 纯品。
此方法分为两步实现。第一步是烷基化反应。木质素衍生物与苄基化合物在酸性催化剂(SiO2-Al2O3、HZSM-5、Al-MCM-41、Hβ、MMT-K10、SAPO-34、USY、H3O40PW12·xH2O(HPW)、Amberlyst-15、Nafion、AlCl3、FeCl3、ZnCl2、CuCl2、金属改性的HPW(如Sn0.5TPA,HfTPA)、Nb2O5、WO3等金属氧化物及液体磷酸)的作用下，及保持两种反应物摩尔比2:1到30:1下，在反应温度50～200℃的范围，进行烷基化反应得到二苯甲烷衍生物(取代的或未取代的二苯甲烷)。木质素衍生物为含氧官能团的化合物，是木质素热裂解或者是酸性催化水解得到的一些酚类化合物或芳酮类化合物或芳醚类化合物，也可以是这些酚类化合物发生脱氧反应得到的芳烃，或烷基转移得到的一些烷基芳烃化合物，包括甲苯，二甲苯，三甲苯，乙苯，1-乙基-2-甲基苯，2-丙烯基苯1,2,4,5-四甲基苯，萘，1-甲基萘等；苄基化合物包括2-甲基苯甲醇，4-甲基苯甲醇，2-甲基苯甲醇的异构体，苯甲醇以及苯甲醇的脱水缩合产物二苄醚等。催化剂的加入量为苄基化合物质量的0.5～26％，反应时间0.5～24h。反应结束后，通过减压蒸馏的方式分离得到二苯甲烷衍生物。
第二步，二苯甲烷衍生物(取代的或未取代的二苯甲烷)的脱氧/环化/加氢反应。将一定量的二苯甲烷衍生物，在金属催化剂(Cu、W、Mo、Ni、Pd、Pt、Ru、Ir、Rh、Zn)或双金属催化剂(PtNi、CoNi、CoMo、IrFe、PdPt、RuCu等)和酸催化剂(SiO2-Al2O3、HZSM-5、Al-MCM-41、Hβ、MMT-K10、SAPO-34、USY、H3O40PW12·xH2O(HPW)、Amberlyst-15、Nafion、AlCl3、FeCl3、ZnCl2、CuCl2、金属改性的HPW(如Sn0.5TPA,HfTPA)、Nb2O5、WO3等金属氧化物及液体磷酸)机械混合物或负载在酸催化剂上的金属催化剂(保持金属催化剂和酸性载体的质量比例在0.02％以上，负载型的催化剂的负载量0.02～10％范围内)，氢气压力3～8MPa之间，温度120～250℃，反应时间2～40h，生成全氢化芴及其烷基取代物比例可以调控的混合物或纯品。
实施例1
将25.2g苯甲醚和3.08g二苄醚，0.1g MMT-K10加入容积为50mL的三口烧瓶中，磁力搅拌，温度110℃的条件下反应2小时；将上述反应混合物转移至蒸馏装置中减压蒸馏提纯，在-0.08MPa下收集温度为160～210℃的馏分，得到无色有机馏分6g。
用气相色谱对制备二苯甲烷衍生物烷基化反应产物进行分析，二苄醚转化率100％，苯甲醚转化率15％，二苯甲烷衍生物(即取代的或未取代的二苯甲烷)收率90％。经过减压蒸馏后可以得到纯二苯甲烷或有取代基的二苯甲烷混合物。
实施例2-18
同实施例1，SiO2-Al2O3、HZSM-5、Al-MCM-41、Hβ、MMT-K10、SAPO-34、USY、H3O40PW12·xH2O(HPW)、Amberlyst-15、Nafion、AlCl3、FeCl3、ZnCl2、CuCl2、金属改性的HPW(如Sn0.5TPA,HfTPA)、Nb2O5、WO3等金属氧化物及液体磷酸等都可以分别催化木质素含苯环衍生物与苄基化合物(2-甲基苯甲醇、4-甲基苯甲醇、2-甲基苯甲醇的异构体、苯甲醇以及苯甲醇的脱水缩合产物二苄醚等)的烷基化反应。现将催化剂及其用量、反应物转化率、反应物比例、反应温度、反应时间、以及二苯甲烷衍生物(即取代的或未取代的二苯甲烷)的收率的结果列于表1：
表1
Figure PCTCN2016089625-appb-000001
Figure PCTCN2016089625-appb-000002
由以上实施例1-18看出，木质素衍生物(酚类或芳烃类或芳酮类或芳醚类化合物)可以和苄基化合物在摩尔比在2:1至30:1的范围内，温度在50～200℃的范围内，达到6％以上的转化率。苄基化合物可以完全转化。苄基化合物的比例越低，双环化合物的收率越高。当木质素衍生物和苄基化合物的比例为30:1时，烷基化产物选择性可以达到100％。温度越高，苄基化合物越容易发生自身转化，生成副产物。对应于所有列出的酸性催化剂都可以发生相同的反应。对于所有的木质素衍生物(包括酚类或芳烃类或芳酮类或芳醚类化合物)都可以在所列出的酸性催化剂下与苄基化合物(2-甲基苯甲醇、4-甲基苯甲醇、2-甲基苯甲醇的异构体、苯甲醇以及苯甲醇的脱水缩合产物二苄醚等)发生烷基化反应。但是酸性越高，反应时间越短，苄基衍生物越容易发生副反应。
实施例19
将30g邻苄基苯甲醚，3.6g钯碳,3g HZSM-5催化剂加入容积为100mL的带搅拌的加压反应釜中，其中钯碳中钯的质量百分含量为5wt％，搅拌速率为680转/分钟，在氢气压力为6MPa、温度为200℃的条件下加氢反应10小时，离心分离得到26g无色有机液体。
用用GC-MS分析对制备的燃料进行分析，该产物是由两种组分组成(包括收率35％二环己基甲烷和65％全氢芴的混合物)。
实施例20-34
同实施例19，金属催化剂(Cu、W、Mo、Ni、Pd、Pt、Ru、Ir、Rh、Zn等)或双金属催化剂(PtNi、CoNi、CoMo、IrFe、PdPt、RuCu等)与酸催化剂(SiO2-Al2O3、HZSM-5、Al-MCM-41、Hβ、MMT-K10、SAPO-34、USY、H3O40PW12·xH2O(HPW)、Amberlyst-15、Nafion、AlCl3、FeCl3、ZnCl2、CuCl2、金属改性的HPW(如Sn0.5TPA、HfTPA)、Nb2O5、WO3等金属氧化物及液体磷酸)的机械混合物及以负载金属的酸性催化剂(保持金属催化剂和酸性催化剂的质量比例在0.02％以上，负载型的催化剂的负载量0.02～10％范围内)，都可以使二苯甲烷衍生物(即取代的或未取代的二苯甲烷)进行HDO(加氢、脱氧)和环化反应。催化剂及其用量、反应温度、反应压力、反应时间以及燃料收率变化总结入下表：
Figure PCTCN2016089625-appb-000003
Figure PCTCN2016089625-appb-000004
由实施例19-34可以看出，金属位和酸性位的结合可以催化二苯甲烷衍生物(即取代的或未取代的二苯甲烷)发生HDO过程，在氢气压力为3-8MPa,温度120-250℃的条件下可以达到100％的转化，生成了以二环己基甲烷饱和碳氢衍生物和全氢化芴及其烷基取代物的混合物。全氢化芴及其烷基取代物的生成是一个特别的地方。单独的金属位都可以催化二苯甲烷衍生物得到纯全氢化芴饱和碳氢衍生物。二苯甲烷衍生物在正常的情况下会生成二环己基甲烷饱和碳氢衍生物，而这里分子内的环化和HDO过程的结合得到了三环化合物，并且金属位比例越大，产物中三环化合物比例越大。三环碳氢化合物的生成使得燃料的密度进一步提高。
纯全氢芴的密度在20℃时可以达到1.012g.ml-1，纯二环己基甲烷的密度在20℃时可以达到0.8750g.ml-1。对于实施例得到的两者的混合物，如实施例19，依据国标GB2540-81“石油产品密度测定法”对其进行密度测定为0.9172g.ml-1；依据国标GB2430-81“喷气燃料冰点测定法”对其冰点进行测定，低于-60℃；依据国标GB265-88“石油产品运动粘度测定法和动力粘度计算法”对其动力学粘度进行测定为10.41mm2/s。由此看出二环己基甲烷加氢脱氧后的混合物是一种很好的燃料或燃料添加剂。

Claims (8)

  1. 一种全氢芴或全氢芴烷基取代物的制备方法，其特征在于，包括如下步骤：
    (1)使酚类化合物或芳烃类化合物或芳酮类化合物或芳醚类化合物与苄基化合物在第一催化剂存在下发生烷基化反应，生成取代的或未取代的二苯甲烷；其中所述第一催化剂为酸性催化剂；
    (2)使所述取代的或未取代的二苯甲烷在第二催化剂的存在下与氢气进行加氢反应或加氢脱氧反应，得到全氢芴或全氢芴烷基取代物；其中所述第二催化剂为金属催化剂和酸催化剂的机械混合物或负载在酸催化剂上的金属催化剂。
  2. 根据权利要求1所述的全氢芴或全氢芴烷基取代物的制备方法，其特征在于，所述第一催化剂选自SiO2-Al2O3、HZSM-5、Al-MCM-41、Hβ、MMT-K10、SAPO-34、USY、H3O40PW12·xH2O、Amberlyst-15、Nafion、AlCl3、FeCl3、ZnCl2、CuCl2、金属改性的HPW、Nb2O5、WO3或液体磷酸中的一种或多种，第一催化剂的加入量为苄基化合物重量的0.5～26％。
  3. 根据权利要求1所述的全氢芴或全氢芴烷基取代物的制备方法，其特征在于，所述金属催化剂选自Cu、W、Mo、Ni、Pd、Pt、Ru、Ir、Rh、Zn或PtNi、CoNi、CoMo、IrFe、PdPt、RuCu中的一种或几种；所述酸催化剂选自SiO2-Al2O3、HZSM-5、Al-MCM-41、Hβ、MMT-K10、SAPO-34、USY、H3O40PW12·xH2O、Amberlyst-15、Nafion、AlCl3、FeCl3、ZnCl2、CuCl2、金属改性的HPW、Nb2O5、WO3或液体磷酸中的一种或多种；所述金属催化剂与所述酸催化剂机械混合时二者的质量比为0.02％以上，所述金属催化剂负载在所述酸催化剂上时二者的质量比为0.02～10％。
  4. 根据权利要求2或3所述的全氢芴或全氢芴烷基取代物的制备方法，其特征在于，所述金属改性的HPW为Sn0.5TPA或HfTPA。
  5. 根据权利要求1所述的全氢芴或全氢芴烷基取代物的制备方法，其特征在于，所述酚类化合物选自苯酚、愈创木酚、3-甲基苯酚、2-甲基苯酚、3-甲氧基苯酚、4-乙基苯酚、儿茶酚、4-乙烯基苯酚、3-甲氧基儿茶酚、4-乙基-2-甲氧基苯酚、2-甲氧基-4-乙烯基苯酚、2，6-二甲氧基苯酚、4-甲基-2，6-二甲氧基-苯酚或4-烯丙基-2，6-二甲氧基苯酚；所述芳烃类化合物选自苯、甲苯、乙苯、二甲苯、三甲苯、2-烯丙基苯、1-乙基-2-甲基苯、1,2,4,5-四甲基苯、萘、1-甲基萘；所述芳酮类化合物选自苯甲酮、苯乙酮、苯丙酮或3，4-二甲氧基-1-苯乙酮；所述芳醚类化合物选自苯甲醚、1-乙基-4-甲氧基苯；所述苄基化合物选自苯甲醇、2-甲基苯甲醇、4-甲基苯甲醇或二苄醚。
  6. 根据权利要求1所述的全氢芴或全氢芴烷基取代物的制备方法，其特征在于，所述 烷基化反应条件如下：反应温度50～200℃，反应时间为0.5～24h，酚类化合物或芳烃类化合物或芳酮类化合物或芳醚类化合物与苄基化合物的摩尔比为2:1～30:1；所述加氢反应条件如下：所述第二催化剂与所述取代的或未取代的二苯甲烷的质量比为0.01～23％，氢气压力3～8MPa、反应温度120～250℃，反应时间2～40h。
  7. 根据权利要求1所述的全氢芴或全氢芴烷基取代物的制备方法，其特征在于，增加所述第二催化剂中的金属催化剂的比例，以提高全氢芴和/或全氢芴烷基取代物的选择性。
  8. 一种全氢芴或全氢芴烷基取代物用作液体喷气燃料的用途。
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