CN115210180A - 制备柠檬烯的方法和含有柠檬烯的组合物 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/31—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of rings
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
提出了一种生产柠檬烯的连续方法,其特征在于在酸催化剂存在下在滴流床反应器中将β‑蒎烯或含β‑蒎烯的起始原料异构化。
Description
技术领域
本发明属于萜烯化合物领域并且涉及将β-蒎烯催化重排为柠檬烯的方法。
背景技术
柠檬烯是单环萜烯类的一种天然物质,存在两种对映异构体
(R)-(+)-柠檬烯(也简称为D-(+)-柠檬烯或(+)-柠檬烯)和(S)-(-)-柠檬烯[也简称为L-(-)-柠檬烯或(-)-柠檬烯或]。两种对映异构体的外消旋体也称为二戊烯。
柠檬烯是植物中最常见的单萜。(R)-(+)-柠檬烯尤其存在于苦橙皮油、香菜油、莳萝油、芫荽子油、柠檬油(约65%)和橙油(通常>90%)中。它有一种类似橙子的香味。相比之下,(S)-(-)-柠檬烯存在于高大冷杉和薄荷油中,并散发出松节油的气味。外消旋柠檬烯尤其存在于松油、西伯利亚松针油、橙花油、肉豆蔻油和樟脑油中。
柠檬烯的生物合成起始于香叶基焦磷酸酯(GPP)。
柠檬烯是香料工业的重要原料,也是多种应用和产品的起始原料。特别是最近它也被用作“绿色”溶剂,并且是有环境问题的BTX溶剂的替代品。
虽然β-蒎烯是生产柠檬烯的现成来源,但β-蒎烯的酸催化异构化的困难在于通过为实现高柠檬烯选择性而必须避免的一系列平衡反应形成双环、三环和单环萜广泛产品谱的潜力。可能的产品范围选择如下所示。
相关现有技术最早的相关出版物包括1973年的两个产权U.S.3,780,124(DAVIS)和U.S.3,780,125(TAKACS),它们提出将碘应用于沸石以重排α-蒎烯。
U.S.4,508,930(WIDEMANN)公开了在高温下在负载碱金属硫化物催化剂存在下萜烯重排为柠檬烯。
在沸石存在下蒎烯异构化为柠檬烯和其他副产物已从U.S.3,270,075(GLIDDEN)获知。该反应在65℃至110℃的液相中进行。催化剂一般描述为Mex/n[(AlO2)x(SiO2)y]*zH2O并特别提到:Na86[(AlO2)86(SiO2)106]*267 H2O.
大连大学的两项中国专利CN 102126904B和cN 102343277B同样描述了在多相酸催化剂存在下将蒎烯异构化为柠檬烯。所用的催化剂是酸性分子筛,它已经用卤化物和碱进行了后处理。
还参考了Ma等人的MICROPOROUS AND MESOPOROUS MATERIAL 237,pp.180-188(2017)和Golets等人的CHEM.REV.115,s.3141-3196(2017)两篇论文。
缺点是现有技术中已知的方法在产率或选择性方面并不是经济上可行的替代方案。这些方法通常也在非常高的温度下操作,需要使用有毒溶剂,不能连续进行,而且催化剂使用寿命也不足。此外,反应产物通常含有不希望的副产物,例如特别是萜品烯,其含量会对产品质量产生不利影响。
发明目的
因此,本发明的第一个目的是提供一种将β-蒎烯连续异构化为柠檬烯的方法,其产率和选择性至少为65%,优选至少为75%,并且作为副产品大部分(即约15%至20重量%)产生莰烯。特别地柠檬烯应以L异构体的形式获得(>90重量%)。
本发明的另一个目的是运行该方法,如果可能的话完全避免或至少部分地避免使用有毒溶剂,特别是来自BTX系列的有毒溶剂。该反应还应可以在低于100℃的温度下进行,并且催化剂应具有足够长的使用寿命,以使其无需后处理即可多次使用和回收。
发明内容
本发明首先提供了一种生产柠檬烯的连续方法,其特征在于,在酸催化剂存在下,在滴流床反应器中将β-蒎烯或含β-蒎烯的起始原料异构化。
特别要求一种方法,包括或由以下步骤组成:
(a)提供β-蒎烯或含β-蒎烯的起始材料;
(b)提供配有催化剂固定床的滴流床反应器;
(c)用多相酸催化剂填充反应器固定床;
(d)在反应器顶部施加起始材料并将起始材料通过催化剂固定床;
(e)在反应器出口排出柠檬烯或富含柠檬烯的馏分。
令人惊讶地发现,使用配有集成固定催化剂床的滴流床反应器进行该方法可以实现β-蒎烯连续异构化为柠檬烯,选择性大于65%。流化床反应器中的过程管理允许通过在催化剂床中建立最佳停留时间对选择性进行动力学控制。这避免了例如在间歇过程中的平衡建立,导致形成热力学上更稳定但不希望的异构体。这也可以在很大程度上避免连续反应产生低聚或甚至聚合副产物,否则会导致催化剂过早失活。与传统的固定床反应器相比,流化床反应器总体上实现了更高的催化剂使用寿命。
值得注意的是,β-蒎烯可以两种对映体形式存在,即(S,S)和(R,R)。因此,在本发明的上下文中,术语“β-蒎烯”应理解为包括其两种形式或其混合物。优选的起始材料是(1S,5S)β-蒎烯,也称为(-)-β-蒎烯同时,特别优选(1R,5R)-β-蒎烯,也称为(+)-β-蒎烯,因为这可以获得对映纯的D-柠檬烯。
催化剂
根据本发明,异构化在固体酸的存在下进行;使用的多相催化剂优选为或Lewis酸。特别适合此目的的是沸石,尤其是选自Y、H-β、ZSM-5和MMW类型的那些。MCM-22或PSH-3型MWW沸石是特别优选的。
术语“MWW”被理解为是指如下图中生产的沸石类型(参见pubs.acs.org/doi/abs/10.1021/jp972319k):
沸石由两个相互分离的十环孔系统组成。变体A和B之间存在区别,其中腔体分别线性和正弦连接。
优选使用已经提前被煅烧和/或酸活化的MWW沸石。特别优选的沸石是符合下式的MCM-22或PSH-3型沸石
M2/nO*Al2O3*(20-150)SiO2
并且例如从EP0064205B1(BAYER)已知。优选在使用前对MMW沸石进行煅烧和/或通过酸处理活化。
煅烧可以优选在约400℃至约1000℃,特别是400℃至600℃的温度下煅烧约1至约10小时,优选4至6小时,硝酸特别适用于酸活化。非常特别优选预先用煅烧和硝酸活化的MCM-22沸石。
滴流床反应器和反应管理
滴流床反应器基本上已知于废水处理。同样在根据本发明的方法中,起始材料由反应器顶部引入,然后滴流通过催化固定床,在此发生异构化。进一步证明有利的是在惰性气体,特别是氮气的存在下进行反应,惰性气体以并流但优选以逆流的方式流动,因为这可以避免氧化分解反应并增加催化剂的使用寿命。
根据本发明的方法可以在有或没有溶剂的情况下进行。然而,溶剂的使用提高了选择性并提高了催化剂的使用寿命,因此是优选的。合适的溶剂是非质子溶剂,例如C6-C8-烷烃,特别是庚烷、1,4-二恶烷或乙酸C1-C4-烷酯,尤其是乙酸乙酯。溶剂与β-蒎烯的质量比优选在90∶10和50∶50之间,优选约80∶20的比例。
已证明在温和条件下进行该方法是可能并有利的,即在从50℃到120℃,特别是在约70℃到80℃的温度范围内和在1至10bar,特别是约2至4bar的压力下。
溶剂制剂
本发明进一步提供了可通过本方法获得的溶剂组合物,其由以下成分组成
(a)约70%至约80重量%的柠檬烯
(b)约15%至约20%重量的莰烯
前提是所报告的量,任选地与蒎烯、萜品烯和萜品油烯,总和为100重量%。
工业应用性
本发明最后还提供了MMC-22沸石,任选地在煅烧和/或酸活化之后,作为催化剂用于将β-蒎烯在如上所述的方法中重排成柠檬烯的用途。
实施例
实施例1至11
β-蒎烯的连续异构化
一种市售的、由钛制成的长度为60cm的连续1″流通式反应器装置(ParrInstruments)并配有两区加热套和内部温度感应器,用于实验。分别通过HPLC泵和质量流量控制器将液体和氩气计量加入反应器顶部。温度、压力和流量通过随附的软件进行监测和调整。将粒状催化剂填充到反应器管的中部。催化剂床上方和下方的空置反应器体积填充惰性刚玉颗粒。将5克固体酸催化剂(粒径0.3-0.7毫米)放置在刚玉颗粒床之间的反应器中间。将109.6克市售β-蒎烯溶解在400克溶剂中,然后使用HPLC泵在所需温度下将其泵送至催化剂床层上。同时在2bar的压力下以50ml/分钟的速度将氩气流计量加入反应器中。产物混合物减压后,在反应器出口下游定期取样并通过离线气相色谱法进行分析。其他实施例的其他实验条件由表1可见。沸石Y催化剂获自Zeolyst,缩写TOS代表运行时间。
也可以直接使用β-蒎烯作为进料而无需溶剂(实施例10)。
在长期测试(实施例11,图1)中,MCM-22催化剂的活性和选择性在两种不同的泵速(见图2)下监测了总共225小时。在225小时后测定,在97%的转化率下,柠檬烯的产率为67%。
Claims (15)
1.一种生产柠檬烯的连续方法,其特征在于在酸催化剂存在下在滴流床反应器中将β-蒎烯或含β-蒎烯的起始原料异构化。
2.根据权利要求1所述的方法,包括或由以下步骤组成:
(a)提供β-蒎烯或含β-蒎烯的起始材料;
(b)提供配有催化剂固定床的滴流床反应器;
(c)用多相酸催化剂填充反应器固定床;
(d)在反应器顶部施加起始材料并将起始材料通过催化剂固定床;
(e)在反应器出口排出柠檬烯或富含柠檬烯的馏分。
4.根据权利要求1至3至少一项所述的方法,其特征在于使用的催化剂是沸石。
5.根据权利要求4所述的方法,其特征在于沸石选自Y、H-β、ZSM-5和MMW类型。
6.根据权利要求5所述的方法,其特征在于使用的MWW沸石是MCM-22或PSH-3沸石。
7.根据权利要求4至6任一项所述的方法,其特征在于使用已经提前被煅烧和/或酸活化的沸石。
8.根据权利要求4至7任一项所述的方法,其特征在于使用已经提前被煅烧和硝酸活化的MCM-22沸石。
9.根据权利要求1至8任一项所述的方法,其特征在于反应在非质子溶剂的存在下进行。
10.根据权利要求9所述的方法,其特征在于使用的溶剂选自C6-C8-烷烃、1,4-二恶烷或乙酸C1-C4-烷酯。
11.根据权利要求9或10所述的方法,其特征在于使用的β-蒎烯和溶剂的重量比为约90∶10至50∶50。
12.根据权利要求1至11至少一项所述的方法,其特征在于反应在50℃到120℃的温度范围内进行。
13.根据权利要求1至12至少一项所述的方法,其特征在于反应在1至10bar的压力下进行。
14.一种通过根据权利要求1所述的方法得到的溶剂组合物,其由以下成分组成
(a)约70%至约80重量%的柠檬烯
(b)约15%至约20%重量的莰烯
前提是所报告的量,任选地与蒎烯、萜品烯和萜品油烯,总和为100重量%。
15.MMC-22沸石,任选地在煅烧和/或酸活化之后,在权利要求1所述的方法中作为催化剂的用途。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN86105408A (zh) * | 1986-08-26 | 1988-03-16 | 中国科学院广州化学研究所 | 天然丝光沸石催化合成单萜基醚 |
CN102126904A (zh) * | 2011-01-20 | 2011-07-20 | 大连理工大学 | 一种α-蒎烯异构化方法 |
CN102343277A (zh) * | 2011-06-30 | 2012-02-08 | 大连理工大学 | 一种高性能α-蒎烯异构化催化剂及应用 |
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US3270075A (en) | 1965-02-16 | 1966-08-30 | Glidden Co | Catalytic terpene isomerization process |
US3780125A (en) | 1972-12-18 | 1973-12-18 | E Takacs | Isomerization of alpha-pinene-containing feed by zeolite |
US3780124A (en) | 1973-02-26 | 1973-12-18 | Arizona Chem | Molecular sieve 13x catalyzed isomerization of alpha-pinene-improvement of catalyst activity by iodine |
DE3117135A1 (de) | 1981-04-30 | 1982-11-18 | Bayer Ag, 5090 Leverkusen | Kristallines alumosilicat, verfahren zu dessen herstellung sowie dessen verwendung zur katalytischen umwandlung von methanol und/oder dimethylether in kohlenwasserstoffe |
US4508930A (en) | 1984-07-20 | 1985-04-02 | The Goodyear Tire & Rubber Company | Process for the conversion of terpenes to limonene |
CN104496741A (zh) | 2014-12-16 | 2015-04-08 | 上海华谊(集团)公司 | 蒎烯异构化生成莰烯和三环烯的方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN86105408A (zh) * | 1986-08-26 | 1988-03-16 | 中国科学院广州化学研究所 | 天然丝光沸石催化合成单萜基醚 |
CN102126904A (zh) * | 2011-01-20 | 2011-07-20 | 大连理工大学 | 一种α-蒎烯异构化方法 |
CN102343277A (zh) * | 2011-06-30 | 2012-02-08 | 大连理工大学 | 一种高性能α-蒎烯异构化催化剂及应用 |
Non-Patent Citations (2)
Title |
---|
E.L FOLETTO等: "Gas phase β-pinene isomerization over acid-activated bentonite", 《LATIN AMERICAN APPLIED RESEARCH》, pages 141 - 144 * |
XUETAO MA等: "Highly selective isomerization of biomass b-pinene over hierarchically acidic MCM-22 catalyst", 《MICROPOROUS AND MESOPOROUS MATERIALS》, pages 180 - 188 * |
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