CN103917532A - 用于生产烃的方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
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Abstract
本发明涉及用于通过糠醛或糠醇在固体催化剂存在情况下的气相氢化生产γ-戊内酯(GVL)的方法。糠醛或糠醇向GVL的转化在一个单一的步骤中进行。
Description
本发明涉及用于从生物质衍生糖生产烃、特别是液体烃的方法。更特别地，本发明涉及通过糠醛和糠醇的非均相催化氢化生产γ-戊内酯(GVL)，糠醛和糠醇可从五碳糖衍生。糠醛和糠醇向GVL的转化在气相中并且在一个单一步骤中进行。
γ-戊内酯(GVL)是生物质转化领域中最引人关注的平台化学品之一，这是因为已经证明其例如可以以良好的收率转化为烃，并且与根据已建立的基于石油的方法所生产的烃的质量相同。这使得更接近有效并经济地从生物质生产燃料、特别是液体燃料例如汽油和柴油这一目标。
糠醛是C5-糖的直接脱水产物，从1920年代以来已经从富含戊糖的底物例如玉米芯和向日葵以工业规模生产(近来~280.000 t/年)。
当前存在商业上可行的从其中生产糠醛的生物质转化工厂。一个这样的方法为所谓的Biofine方法，根据该方法将大量木质纤维素转化为化学产物例如乙酰丙酸、甲酸(C6-糖的产物流)、糠醛(C5-糖的产物流)和木质炭。
现有技术致力于使用糠醛作为底物，主要涉及糠醛选择性氢化成为糠醇或2-甲基呋喃。生产的糠醛的大部分(~60%)被转化为糠醇，后者具有多种用途，包括转化为乙酰丙酸。
从C6-糖生产GVL也为人所知。根据该途径，GVL从5-(羟甲基)糠醛(HMF)而非糠醛(一个C5-糖衍生物)衍生。HMF首先转化为乙酰丙酸和甲酸。乙酰丙酸可接着经由催化氢化转化为GVL。
专利申请WO-A-2010151343公开了其中分解纤维素产生包含乙酰丙酸和甲酸的产物混合物然后乙酰丙酸/甲酸溶液经Ru/C-催化剂转化为GVL的方法。GVL可进一步转化为正丁烯混合物，后者可经受异构化和低聚反应以产生汽油、煤精和柴油燃料范围内的烯烃。
专利申请WO-A-08151269公开了用于在氢存在情况下经包含Ru或Pd的催化剂转化生物油(其定义为生物质快速热解的产物液体并且其可为单相或多相液体)的方法。此处通过提供包含糠醛、愈创木酚或取代的愈创木酚的液体，提供氢并使它们在包含Ru或Pd的催化剂上反应，公开了用于糠醛氢化的液相方法。糠醛转化为i.a.四氢呋喃-甲醇(THF-MeOH)和2-甲基-四氢呋喃(MTHF)。糠醛较小程度地转化为GVL。因此，该引用公开了糠醛在液相中通过使用贵金属催化剂向GVL的转化。
一个已知的从糠醛、从而从C5-糖制造GVL的多步骤途径为通过将糠醛转化为糠醇，然后在醇溶剂例如丁醇中使用酸性催化剂将糠醇转化为乙酰丙酸丁酯，最后在氢化步骤中将乙酰丙酸丁酯还原为GVL。
上述糠醇至乙酰丙酸酯中间体的转化必须在液相中在合适的均相或固体酸性催化剂的帮助下进行。还原乙酰丙酸形成GVL可随后在液相或气相中完成。
目前我们已经发现用于从糠醛或糠醇获得GVL的选择性和直接途径，其通过在气相中并使用非-贵金属氢化催化剂将糠醛和/或糠醇直接转化为GVL。本发明如下列与本公开内容的权利要求1-14相对应的特征所述。
发明特征：
1. 用于通过在非均相催化剂存在的情况下在气相中转化包含糠醛的气流或包含糠醇的气流生产γ-戊内酯(GVL)的方法，所述催化剂包含铜和铝。
2. 特征1的方法，其中所述包含糠醛的气流或包含糠醇的气流与水共进给。
3. 特征1或2的方法，其中所述铜铝催化剂为铜-铝(Cu-Al)尖晶石形式。
4. 特征3的方法，其中所述铜-铝尖晶石为沉淀的理想配比的Cu-Al尖晶石(CuAl2O4)。
5. 特征1-4中任一项的方法，其中所述催化剂通过包括使用Cu和Al溶液的共沉淀方法制备。
6. 特征5的方法，其中Cu和Al溶液中原子比Cu2+/Al3+在1/9-7/3的范围内，并且共沉淀与碱性溶液一起进行。
7. 特征1-6中任一项的方法，其中所述方法在100-300℃、优选100-200℃、更优选120-190℃、最优选160-180℃范围内的反应温度下进行。
8. 特征1-7中任一项的方法，其中反应压力在1-30 atm、优选10-25 atm、更优选20 atm的范围内。
9. 特征1-8中任一项的方法，其中糠醛衍生自C5-糖。
10. 特征1-9中任一项的方法，进一步包括将GVL转化为液体烃。
11. 根据特征1-19中任一项产生的GVL用于生产液体烃的用途。
12. 包含铜和铝的固体催化剂用于通过糠醛或糠醇的气相氢化生产γ-戊内酯(GVL)的用途。
13. 特征12的用途，其中糠醛或糠醇与水共进给。
14. 特征12或13的用途，其中所述催化剂为Cu-Al尖晶石，优选理想配比的Cu-Al尖晶石。
在本发明的第一个方面，提供了如特征1-10所述的用于生产GVL的方法和GVL用于生产液体烃的用途，与权利要求1-10相对应。
将理解的是，气相中的转化在氢存在情况下进行。
优选地，所述方法在固定床反应器中进行。
特征1的一般实施方案中的任一气流均可包含糠醛和糠醇。
所述包含糠醛的气流优选包含至少5 wt%的糠醛，更优选5-10 wt%的糠醛，甚至更优选20-90 wt%糠醛。该气流的其它组分可包括糠醇或水。糠醛气流的合适组成为例如100 wt%糠醛，然后在穿过非均相催化剂时其以蒸气(气体)形式使用。另一个合适的组成为水中包含5-10 wt%糠醛、例如水中含7 wt%糠醛的气流，然后在穿过非均相催化剂时其以蒸气(气体)形式使用。
所述包含糠醇的气流优选包含至少10 wt%的糠醇，更优选20-90 wt%的糠醇。该气流的其它组分可包括糠醛或水。
包含糠醛或糠醇的气流中的水量优选至多95 wt%的水，更优选50-70 wt%的水。特别地，我们还发现用糠醛和水的共沸混合物进行该方法是合乎需要的。因此，在本发明一个与上文或下文实施方案之一有关的特别的实施方案中，包含糠醛的气流中水的量包括65 wt%水和35 wt%糠醛。此为糠醛和水的共沸组合物。
根据本发明，氢化催化剂为铜铝催化剂。所述催化剂优选为Cu-Al尖晶石，更优选理想配比的Cu-Al尖晶石。理想配比的Cu-Al尖晶石意指具有35.0 wt% Cu和29.7 wt% Al、剩余为氧的组成的CuAl2O4。
铜铝(Cu-Al)催化剂优选通过共沉淀方法制备。更优选Cu-Al溶液中原子比Cu2+/Al3+在1/9 - 7/3范围内并且共沉淀与碱性溶液例如包含NaOH和Na2CO3的溶液一起进行。特别地，其中催化剂为Cu-Al尖晶石时，Cu-Al溶液中原子比Cu2+/Al3+为1/2。
在本发明一个优选实施方案中，所述方法采用糠醛原料流在200℃反应温度、20 atm反应压力和1 g糠醛/g催化剂/h的WHSV (重量小时空速)下进行。这使得糠醛能够直接转化为包含10 wt% GVL的产物。
在本发明另一个优选实施方案中，所述方法采用糠醛原料流在180℃反应温度、1 atm反应压力和0.08-0.09 g糠醛/g催化剂/h的WHSV (重量小时空速)下进行。这使得糠醛能够直接转化为包含21 wt% GVL的产物。
根据本发明，糠醛或糠醇氢化成为GVL在一个单一步骤中进行，不需要首先分离烷基乙酰丙酸酯/乙酰丙酸。
不被任何理论束缚，认为根据本发明GVL通过糠醇异构化然后氢化/脱氢获得。
本发明还使得能够较便宜地生产GVL和由此下游产物例如液体烃，这是因为在GVL生产步骤中避免了使用贵金属催化剂例如钯。进一步地，所述转化通过在气相中进行的非均相催化实施，而不是诉诸于均相催化或液相反应。
当前GVL可从C6-糖的产物乙酰丙酸产生。作为C5-糖的产物，糠醛因此使得能够大大简化下游的产物升级，这是因为C5和C6-糖二者的GVL产物均可进一步作为一种单一组合气流处理或整体出售。生物质转化方法，例如Biofine方法的经济意义因此显著增加。
本发明第二个方面还包括催化剂的使用。相应地，如特征13-15中所述，本发明包括铜铝催化剂形式的固体催化剂用于通过糠醛或糠醇气相氢化生产γ-戊内酯(GVL)的用途。
优选地，糠醛或糠醇与水共进给。该混合物接着以其蒸气(气体)形式通过非均相催化剂。
如上所述，所述催化剂优选为Cu-Al尖晶石，更优选理想配比的的Cu-Al尖晶石。理想配比的Cu-Al尖晶石意指具有35.0 wt.% Cu和29.7 wt.% Al、剩余为氧的组成的CuAl2O4。
铜铝催化剂优选通过共沉淀方法制备。更优选Cu-Al溶液中原子比Cu2+/Al3+在1/9 - 7/3范围内，并且共沉淀与碱性溶液例如包含NaOH和Na2CO3的溶液一起进行。特别地，其中催化剂为Cu-Al尖晶石时，Cu-Al溶液中原子比Cu2+/Al3+为1/2。
实施例1
将4.0 g铜铝催化剂(34 wt% Cu、28 wt% Al、Na和低于0.5 wt%的其它杂质，氧作为剩余直至100 wt%)的细分颗粒(0.3-0.7 mm)装入固定床反应器中。更特别地，催化剂为通过共沉淀方法制备的理想配比的Cu-Al尖晶石(P.A. Kumar等, Journal of Molecular Catalysis A: Chemical 291 (2008) 66-74)：从2 M NaOH和1 M Na2CO3制备碱性溶液(溶液1)，并制备Cu(II)和Al(III)硝酸盐的水性溶液(溶液2)。把溶液放入单独的漏斗中，然后在剧烈搅拌下逐滴加入包含1000 mL蒸馏水的烧杯中。将所得溶液在剧烈搅拌下在60-70℃熟化1小时。然后用蒸馏水洗涤几次以达到中性pH。然后将溶液过滤，所得沉淀烘干12小时，并随后在静态空气中在835℃焙烧5小时。
催化剂在370℃通过在5% H2和95% N2中还原活化5小时。使用0.5℃/min的加热坡道。
使用200 ml/min的氢气流在20 bar压力(约20 atm)下将反应器加热至200℃。然后将糠醛蒸气通过催化剂(0.08 ml/min，WHSV为约1.0 g/g/h)。产物蒸气使用在线-GC系统定量，还收集液体样品并通过GC-MS分析以鉴定产物组分。发现该产物由10 wt% GVL、10 wt% 2-甲基四氢呋喃、5 wt% 1-戊醇和75 wt% 2-甲基呋喃组成。
实施例2
将4.0 g实施例1中使用的同种铜铝催化剂的细分颗粒(0.3-0.7 mm)装入固定床反应器中。催化剂在370℃通过在5% H2和95% N2中还原活化5小时。使用0.5℃/min的加热坡道。
使用200 ml/min的氢气流在环境压力下将反应器加热至180℃。使水中包含7 wt.% 糠醛的溶液气化并通过催化剂(0.08 ml/min，WHSV为约0.084 g/g/h)。产物蒸气使用在线-GC系统定量。该产物由21 wt% GVL、73 wt% 2-甲基呋喃以及剩余为3 wt% 2-甲基四氢呋喃和3 wt% 1-戊醇组成。
Claims (14)
1.用于通过在非均相催化剂存在的情况下在气相中转化包含糠醛的气流或包含糠醇的气流生产γ-戊内酯(GVL)的方法，所述催化剂包含铜和铝。
2.权利要求1的方法，其中所述包含糠醛的气流或包含糠醇的气流与水共进给。
3.权利要求1或2的方法，其中所述铜铝催化剂为铜-铝(Cu-Al)尖晶石形式。
4.权利要求3的方法，其中所述铜-铝尖晶石为沉淀的理想配比的Cu-Al尖晶石(CuAl2O4)。
5.权利要求1-4中任一项的方法，其中所述催化剂通过包括使用Cu和Al溶液的共沉淀方法制备。
6.权利要求5的方法，其中Cu和Al溶液中原子比Cu2+/Al3+在1/9-7/3的范围内，并且共沉淀与碱性溶液一起进行。
7.权利要求1-6中任一项的方法，其中所述方法在100-300℃、优选100-200℃、更优选120-190℃、最优选160-180℃范围内的反应温度下进行。
8.权利要求1-7中任一项的方法，其中反应压力在1-30 atm、优选10-25 atm、更优选20 atm的范围内。
9.权利要求1-8中任一项的方法，其中糠醛衍生自C5-糖。
10.权利要求1-9中任一项的方法，进一步包括将GVL转化为液体烃。
11.根据权利要求1-19中任一项产生的GVL用于生产液体烃的用途。
12.包含铜和铝的固体催化剂用于通过糠醛或糠醇的气相氢化生产γ-戊内酯(GVL)的用途。
13.权利要求12的用途，其中糠醛或糠醇与水共进给。
14.权利要求12或13的用途，其中所述催化剂为Cu-Al尖晶石，优选理想配比的Cu-Al尖晶石。
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| CN104557801A (zh) * | 2014-10-31 | 2015-04-29 | 华东理工大学 | 一种金属/固体酸催化剂上由糠醛制备γ-戊内酯的方法 |
| CN108976183A (zh) * | 2018-10-10 | 2018-12-11 | 江苏清泉化学股份有限公司 | 一种由糠醛气相加氢制备γ-戊内酯的方法 |
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| JP6479794B2 (ja) | 2013-11-12 | 2019-03-06 | ダウ シリコーンズ コーポレーション | ハロシランを製造する方法 |
| US11253841B2 (en) | 2016-05-31 | 2022-02-22 | Ptt Global Chemical Public Company Limited | Copper aluminium oxide catalyst for preparing furfuryl alcohol from furfural and a preparation of said catalyst |
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| US8148553B2 (en) | 2009-06-23 | 2012-04-03 | Wisconsin Alumni Research Foundation | Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities |
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| US2786852A (en) * | 1953-08-19 | 1957-03-26 | Quaker Oats Co | Process of preparing gammavalerolactone |
| EP1240941A2 (en) * | 1996-03-21 | 2002-09-18 | Engelhard Corporation | Copper-aluminum mixed oxide catalyst, its preparation and use thereof |
| CN101821358A (zh) * | 2007-06-06 | 2010-09-01 | 巴泰勒纪念研究所 | 生物油和有机化合物的钯催化氢化 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557801A (zh) * | 2014-10-31 | 2015-04-29 | 华东理工大学 | 一种金属/固体酸催化剂上由糠醛制备γ-戊内酯的方法 |
| CN104557801B (zh) * | 2014-10-31 | 2020-08-18 | 华东理工大学 | 一种金属/固体酸催化剂上由糠醛制备γ-戊内酯的方法 |
| CN108976183A (zh) * | 2018-10-10 | 2018-12-11 | 江苏清泉化学股份有限公司 | 一种由糠醛气相加氢制备γ-戊内酯的方法 |
| CN108976183B (zh) * | 2018-10-10 | 2023-03-10 | 江苏清泉化学股份有限公司 | 一种由糠醛气相加氢制备γ-戊内酯的方法 |
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