WO2022242731A1 - 一种生物质转化制备对二甲苯的方法 - Google Patents
一种生物质转化制备对二甲苯的方法 Download PDFInfo
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- WO2022242731A1 WO2022242731A1 PCT/CN2022/094003 CN2022094003W WO2022242731A1 WO 2022242731 A1 WO2022242731 A1 WO 2022242731A1 CN 2022094003 W CN2022094003 W CN 2022094003W WO 2022242731 A1 WO2022242731 A1 WO 2022242731A1
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- Prior art keywords
- molecular sieve
- scm
- reaction
- catalyst
- alpo
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/865—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an ether
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- 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
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates (APO compounds)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/08—Xylenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/50—Diels-Alder conversion
- C07C2/52—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/88—Growth and elimination reactions
Abstract
Description
套用次数 | 甲基呋喃转化率/% | 甲苯选择性/% |
1 | 90 | 96 |
2 | 89 | 96 |
3 | 88 | 95 |
4 | 86 | 94 |
Claims (28)
- 从取代或未取代的呋喃制备取代或未取代的单环芳烃的方法,其特征在于,包括:将含有作为原料的取代或未取代的呋喃的有机相和乙烯与分子筛催化剂接触反应,制得取代或未取代的单环芳烃,其中所述的分子筛催化剂包含任选掺杂有元素A的SCM-X分子筛,所述元素A选自Sn、Zr和Al中的至少一种,X为14或者15。
- 根据权利要求1所述的方法,其特征在于,所述SCM-X分子筛具有如式“mSiO 2·nGeO 2”所示的示意性化学组成:其中,1≤m/n≤30,优选0.5≤m/n≤20,还优选2≤m/n≤10。
- 根据权利要求1或2所述的方法,其特征在于,所述有机相包含有机溶剂,其选自正己烷、正庚烷、正辛烷、四氢呋喃、1,4-二氧六环、环己烷和甲基异丁基酮。
- 根据权利要求1或2所述的方法,其特征在于所述取代或未取代的呋喃为甲基呋喃,所述取代或未取代的单环芳烃为甲苯。
- 根据权利要求5所述的方法,其中所述分子筛催化剂为A-SCM-X分子筛,该A-SCM-X分子筛中的A选自Sn、Zr和Al中的至少一种,X为14或者15。
- 根据权利要求6所述的方法,其特征在于所述A-SCM-X分子筛中A组分以氧化物计的含量不小于0.5wt%,优选为0.8wt%-3.5wt%, 更优选为1.2-3.2wt%;和/或所述A-SCM-X分子筛的Lewis酸量为30-500μmol·g-1,优选为50-300μmol·g-1,更优选为83-292μmol·g-1;和/或所述A-SCM-X分子筛的Lewis/Bronst酸比例为0.5-10,优选为0.6-5,更优选为0.6-2.1;和/或所述A-SCM-X分子筛为Sn-SCM-14、Sn-SCM-15、Zr-SCM-14、Zr-SCM-15、Al-SCM-14或者Al-SCM-15分子筛。
- 根据权利要求6所述的方法,其中,所述A-SCM-X分子筛具有如式“mSiO 2·nGeO 2·pAO 2”所示的示意性化学组成:其中,1≤m/n≤30,优选2≤m/n≤10,更优选3.5≤m/n≤8.7;20≤m/p≤200,优选30≤m/p≤150,更优选30≤m/p≤96;和/或A组分位于分子筛的骨架中。
- 根据权利要求5所述的方法,其中,所述接触反应的条件包括:反应温度为180-300℃,优选反应温度为210-270℃;和/或反应时间为4-72h,优选反应时间为10-50h;和/或反应压力为1-8MPa,优选反应压力为2-5MPa。
- 根据权利要求5所述的方法,其中,所述接触在有机溶剂存在下进行,所述有机溶剂选自正庚烷、正辛烷、四氢呋喃、甲基异丁基酮和环己烷中的一种或多种;和/或所述甲基呋喃与催化剂质量比为0.2-8∶1,优选为0.5-6∶1,优选为0.8-2∶1;和/或有机溶剂与甲基呋喃质量比为10-80∶1,优选为20-50∶1;和/或乙烯采用稀乙烯,在反应体系中充入稀乙烯,稀乙烯浓度为10v%-25v%,稀乙烯的其他气体为惰性气体。
- 根据权利要求1或2所述的方法,其特征在于所述取代或未取代的呋喃为2,5-二甲基呋喃,所述取代或未取代的单环芳烃为对二甲苯。
- 根据权利要求11所述的方法,其中所述分子筛催化剂为没有掺杂元素A的SCM-X分子筛;优选所述SCM-X分子筛为SCM-14分子筛,其具有如式 “SiO 2·1/nGeO 2”所示的示意性化学组成,其中n≤30,优选0.5≤n≤20,更优选1≤n≤10,更优选2≤n≤8。
- 根据权利要求11所述的方法,其特征在于,所述接触反应的条件包括:压力为0.5-8MPa,优选为1-5MPa;反应温度为160-340℃,优选为200-300℃;和/或,反应时间为6-64h,优选为8-48h。
- 根据权利要求11所述制备方法,其特征在于,所述接触在有机溶剂存在下进行,所述的有机溶剂包括正己烷、正庚烷、正辛烷、四氢呋喃、1,4-二氧六环和环己烷中的一种或几种;所述原料与催化剂的质量比为0.5-20.0∶1,优选为1.0-8.0∶1;和/或所述有机溶剂与原料质量比为5-50∶1,优选为10-20∶1。
- 一种制备对二甲苯的方法,其特征在于,包括:将含2,5-己二酮的有机相和乙烯与分子筛催化剂接触反应,制得对二甲苯,其中所述的分子筛催化剂包含SCM-X分子筛,X为14或者15;优选所述SCM-X分子筛为SCM-14分子筛,其具有如式“SiO 2·1/nGeO 2”所示的示意性化学组成,其中n≤30,优选0.5≤n≤20,更优选1≤n≤10,更优选2≤n≤8。
- 根据权利要求15所述方法,其特征在于,乙烯压力为0.5-5MPa,优选为1-4MPa;和/或,反应温度为160-340℃,优选为200-300℃;和/或,反应时间为6-64h,优选为12-48h。
- 一种生物质转化制备对二甲苯的方法,其特征在于,包括:(1)在包含有机溶剂相和水溶液相的双相溶剂体系中,以氢气为氢源,生物质原料与疏水性加氢催化剂接触反应,所得产物经分离得到含2,5-己二酮的有机相;其中所述水溶液相的pH为大约6.5-8.5,优选7-8;(2)使用权利要求15或16所述的方法,将含2,5-己二酮的有机相和乙烯与分子筛催化剂接触反应,制得对二甲苯。
- 根据权利要求17所述方法,其特征在于,步骤(1)中所述水 溶液相包含溶解于其中的无机盐,该无机盐中的阴离子和阳离子分别来自第VIIA族元素和第IA族元素;优选地,所述第VIIA族元素选自Cl和Br中的至少一种,和/或所述第IA族元素选自Li、Na和K中的至少一种。
- 根据权利要求17或18所述方法,其特征在于,步骤(1)中所述有机溶剂相的有机溶剂为1,2-二氯乙烷、1,4-二氧六环、甲基异丁基酮、四氢呋喃、γ-戊内酯、甲苯中的一种或者几种的混合物,优选为1,4-二氧六环、四氢呋喃中的一种或两种;和/或,所述有机溶剂与生物质原料的质量比为4-60,优选为10-40。
- 根据权利要求17或18所述方法,其特征在于,所述有机溶剂相的有机溶剂的质量与无机盐和水的质量之和的比值为2-16,优选为3-10;和/或,无机盐的质量与水的质量的比值为0.10-0.70,优选为0.20-0.70,进一步优选为0.40-0.70。
- 根据权利要求17所述方法,其特征在于,步骤(1)中生物质原料与加氢催化剂的质量比为0.2-4∶1,优选为0.5-2∶1;和/或,步骤(1)中反应温度为160-250℃,优选为180-230℃;反应时间为4-36小时,优选为6-20小时;和/或,步骤(1)反应体系中,氢气压力为0.2-5MPa,优选为0.5-3MPa。
- 根据权利要求17所述方法,其特征在于,步骤(1)中所述疏水性加氢催化剂包括加氢活性组分和载体;所述载体选自具有疏水性的活性炭和石墨烯中的一种或多种;所述加氢活性组分选自钌、铂、钯中的一种或几种,优选为铂和/或钯;优选地,步骤(1)中所述加氢催化剂与水的接触角大于50°,优选为55°-90°;优选地,以加氢催化剂的质量为基准,加氢活性组分以金属原子计的质量含量为0.5%-10%,优选为2%-6%。
- 根据权利要求17所述方法,其特征在于,步骤(1)中生物质原料是纤维素、菊糖、纤维二糖、蔗糖、葡萄糖、果糖、玉米秸秆、玉米芯、松木、杨木和桦木中一种或多种,优选为纤维素和/或葡萄糖。
- 根据权利要求17所述方法,其特征在于,步骤(2)中所述分子筛催化剂所包含SCM-14分子筛全部或部分替换为磷铝分子筛催化 剂为M-AlPO分子筛催化剂,其中M为金属,选自Co、Mg、Zn和Sn中的至少一种,所述AlPO分子筛选自AlPO-17、AlPO-5、AlPO-8、AlPO-11或AlPO-18中的至少一种,优选为AlPO-17、AlPO-5中的至少一种;优选地,M-AlPO分子筛中金属含量不小于0.2wt%,优选为0.2wt%-2.0wt%。
- 根据权利要求24所述方法,其特征在于,所述的M-AlPO分子筛具有如式“mP 2O 5·nAl 2O 3·pMO x”所示的示意性化学组成,其中:0.5≤m/n≤2,20≤m/p≤300;优选为0.8≤m/n≤1.2,40≤m/p≤200,x为满足M化合价所需的氧原子总数。
- 根据权利要求24或25所述方法,其特征在于,所述的M-AlPO分子筛的性质如下:总酸量为100-500μmol·g -1,优选为150-400μmol·g -1,进一步优选为250-400μmol·g -1,其中弱酸含量≥55%,优选为60%-80%,进一步优选为60%-75%,强酸含量≤35%,优选为5%-30%,进一步优选为10%-25%。
- 根据权利要求17所述方法,其特征在于,步骤(2)中分子筛催化剂与步骤(1)中生物质原料的质量比为0.1-5,优选为0.2-3。
- 根据权利要求17所述的方法,其特征在于,在步骤(1)过程中,不向所述反应体系中加入酸,以及优选不加入酸性盐。
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