CN111375449A - 一种脱氢催化剂及其在二乙苯脱氢制备二乙烯苯中的应用 - Google Patents
一种脱氢催化剂及其在二乙苯脱氢制备二乙烯苯中的应用 Download PDFInfo
- Publication number
- CN111375449A CN111375449A CN202010222268.5A CN202010222268A CN111375449A CN 111375449 A CN111375449 A CN 111375449A CN 202010222268 A CN202010222268 A CN 202010222268A CN 111375449 A CN111375449 A CN 111375449A
- Authority
- CN
- China
- Prior art keywords
- diethylbenzene
- dehydrogenation
- catalyst
- dehydrogenation catalyst
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 4
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000012159 carrier gas Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- -1 tris-epoxy phenyl-p-aminophenol Chemical compound 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- PBGVMIDTGGTBFS-UHFFFAOYSA-N but-3-enylbenzene Chemical compound C=CCCC1=CC=CC=C1 PBGVMIDTGGTBFS-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明属于催化化学领域，尤其涉及一种脱氢催化剂及其在二乙苯脱氢制备二乙烯苯中的应用。该催化剂包含重量份数如下的组分：20–40份镧系元素改性的杂多酸盐，10–20份大孔交联聚合物负载纳米α‑Fe2O3；40–70份CeO2、MnO2、ZrO2、WO3氧化物中的一种或者几种。本发明将上述负载型催化剂应用于二乙苯脱氢反应中，通过调节杂多酸盐中组分，能够有效优化产物分布。反应过程中无需加入水蒸气，反应速率快、选择性高，产物体系分离简单、工艺过程安全环保，适用于工业化生产。
Description
技术领域
本发明属于催化化学领域，尤其涉及一种脱氢催化剂及其在二乙苯脱氢制备二乙烯苯的应用。
背景技术
近年来，随着高分子材料迅速发展，二乙烯苯作为功能型单体，其应用领域不断扩大。二乙烯苯分子中含有两个乙烯基，形成邻、间、对三种异构体。精制二乙烯苯，提高混合物中间、对位体的含有率，获得不同纯度等级的产品成为市场价格的主要控制因素。低纯度二乙烯苯可以直接用作功能性化学交联剂，广泛应用于胶粘剂、专业塑料、和弹性体中。二乙烯苯与苯乙烯交联聚合制造离子交换树脂，也用作聚酯树脂、聚苯乙烯树脂改性及各种特殊用途的高分子多孔微球与工程塑料。高端光学材料(如透镜、隐形眼镜、光学仪器等)制备过程要求原料中邻二乙烯苯含量低至1％，这样可以有效避免杂质生成，保证树脂的光学性能。
二乙烯苯的制备方法众多，工业上主要采用二乙苯脱氢法制备。原料二乙苯(邻位、间位和对位混合物)在催化剂的作用下，生成目标产物二乙烯苯，同时大量副产乙烯基甲苯和乙烯基乙苯，以及杂质萘等。二乙烯苯的纯度等级受到影响，严重制约其在高端光学材料中的应用。此外，这一传统脱氢工艺采用氧化铁为主催化剂，存在单程转化率低、产物选择性低等突出问题。在实际生产中，催化剂诱导期较长，在生产中后期容易发生催化效率降低、表面结焦等现象，反应中需要持续加入大量水蒸气进行催化剂的再生，造成高能耗。
专利CN1915941公开了在Fe–K–Ce–Mo催化体系中添加稀土元素化合物催化二乙苯脱氢反应，催化剂具有较高抗积碳能力，但是副产物乙基苯乙烯的选择性较高。专利CN10779282A公开了以一种含有Fe2O3、K2O、CeO2、MoO3、CaO、Na2O等成分以及选自MnO2、TiO2、Pr2O3的至少一种或者几种的复合催化剂，用于二乙苯脱氢反应，生成的产物具有单双烯比值低的特点，但是反应温度较高，且必须加入水蒸气对催化剂进行再生。
现有生产工艺的催化性能和生产需求以及产品质量不匹配，成为高选择性二乙烯苯生产的发展瓶颈和技术壁垒。因此，寻求制备二乙烯苯的新工艺和合适的催化剂来提高二乙苯脱氢催化剂的活性是首要研究目标。
发明内容
本发明涉及一种脱氢催化剂及其在二乙苯脱氢制备二乙烯苯的应用。即采用气固相反应，以镧系元素改性的杂多酸盐、大孔交联聚合物负载纳米α-Fe2O和金属氧化物的混合物作为催化剂，在固定床反应器中直接催化二乙苯选择性脱氢制备二乙烯苯。
一种脱氢催化剂，包含重量份数如下的组分：
(a)20–40份镧系元素改性的杂多酸盐，
(b)10–20份大孔交联聚合物负载纳米α-Fe2O3；
(c)40–70份CeO2、MnO2、ZrO2、WO3、氧化物中的一种或者几种。
所述催化剂中，组分a为K13[X(SiW9Mo2O39)2]·nH2O或K11[X(PW9Mo2O39)2]·nH2O，X为La、Pr、Nd、Pm、Sm中的一种。
所述催化剂中，组分b的制备方法如下：以1-乙基-2-甲基咪唑乙酸酯EA为固化剂，引发环氧树脂DGEBA或者三环氧苯基对氨基苯酚TGAP形成大孔交联聚合物作为载体，负载纳米α-Fe2O3。其中纳米α-Fe2O3优选粒径10–20nm的球形粒子。
本发明所述的脱氢催化剂的制备方法，包括以下步骤：将a、b、c组分按比例和水混合均匀，经过挤出、干燥、氮气氛围中焙烧得到催化剂。
所述干燥温度为40–100℃，焙烧温度为200–400℃。
本发明所述的脱氢催化剂在二乙苯脱氢制备二乙烯苯中的应用，具体操作为：在固定床反应器中装入脱氢催化剂，以二乙苯为原料，反应温度为380–500℃，二乙苯的体积空速为2.5–5h–1，氮气作为载气。
本发明的有益效果为：
(1)与传统的Fe2O3系列催化剂相比，本发明的催化剂能在相对低的温度下进行(380–500℃)，反应速率快，催化剂活性和选择性高。
(2)本发明的反应过程直接采用二乙苯为原料，无需引入水蒸气，催化剂能够有效固定钾组分，延缓在二乙苯脱氢反应过程中的流失，明显改善了催化剂在低水比条件下的稳定性。
具体实施方式
下面结合具体实施例对本发明做进一步说明，但并不因此而限制本发明。
实施例1
将40g镧系元素改性的杂多酸盐K13[La(SiW9Mo2O39)2]·nH2O、20g粒径为10–20nm的大孔交联聚合物负载纳米α-Fe2O3、40g CeO2在捏合机搅拌1.5小时，加入占催化剂原料总重24.6％的去离子水，搅合0.5小时，取出挤条造粒，在80℃下干燥4小时，然后置于氮气气氛箱式炉中，在300℃下焙烧2小时得到成品催化剂。
在固定床连续流动反应装置中装入催化剂10mL,直接催化二乙苯选择性脱氢制备二乙烯苯。氮气作为载气，预热器温度为200℃，反应温度为450℃，二乙苯的体积空速为3h–1，反应结果如表1。
表1
实施例2-5
催化剂及反应条件同实施例1，仅改变反应温度，反应时间为1天，反应结果如表2。
表2
实施例6-8
催化剂及反应条件同实施例1，仅改变体积空速，反应时间为1天，反应结果如表3。
表3
实施例9
将20g镧系元素改性的杂多酸盐K13[Nd(SiW9Mo2O39)2]·nH2O、10g粒径为10–20nm的大孔交联聚合物负载纳米α-Fe2O3、70g MnO2在捏合机搅拌1.5小时，加入占催化剂原料总重24.6％的去离子水，搅合0.5小时，取出挤条造粒，在100℃下干燥4小时，然后置于氮气气氛箱式炉中，在400℃下焙烧2小时得到成品催化剂。
在固定床连续流动反应装置中装入催化剂10mL,直接催化二乙苯选择性脱氢制备二乙烯苯。氮气作为载气，预热器温度为200℃，反应温度为450℃，二乙苯的体积空速为3h–1，反应时间为1天，二乙苯的转化率为58.1％，二乙烯苯的选择性为95.3％。
实施例10
将30g镧系元素改性的杂多酸盐K11[Pm(PW9Mo2O39)2]·nH2O、15g粒径为10–20nm的大孔交联聚合物负载纳米α-Fe2O3、55g WO3在捏合机搅拌1.5小时，加入占催化剂原料总重24.6％的去离子水，搅合0.5小时，取出挤条造粒，在40℃下干燥4小时，然后置于氮气气氛箱式炉中，在350℃下焙烧2小时得到成品催化剂。
在固定床连续流动反应装置中装入催化剂10mL,直接催化二乙苯选择性脱氢制备二乙烯苯。氮气作为载气，预热器温度为200℃，反应温度为450℃，二乙苯的体积空速为3h–1，反应时间为1天，二乙苯的转化率为68.8％，二乙烯苯的选择性为75.6％。
实施例11
将25g镧系元素改性的杂多酸盐K11[Pr(PW9Mo2O39)2]·nH2O、20g粒径为10–20nm的大孔交联聚合物负载纳米α-Fe2O3、20g MnO2、35g ZrO2在捏合机搅拌1.5小时，加入占催化剂原料总重24.6％的去离子水，搅合0.5小时，取出挤条造粒，在90℃下干燥4小时，然后置于氮气气氛箱式炉中，在200℃下焙烧2小时得到成品催化剂。
在固定床连续流动反应装置中装入催化剂10mL,直接催化二乙苯选择性脱氢制备二乙烯苯。氮气作为载气，预热器温度为200℃，反应温度为450℃，二乙苯的体积空速为3h–1，反应时间为12小时，二乙苯的转化率为70.4％，二乙烯苯的选择性为90.4％。
实施例12
将40g镧系元素改性的杂多酸盐K11[Sm(PW9Mo2O39)2]·nH2O、10g粒径为10–20nm的大孔交联聚合物负载纳米α-Fe2O3、20g CeO2、20g MnO2、10g ZrO2在捏合机搅拌1.5小时，加入占催化剂原料总重24.6％的去离子水，搅合0.5小时，取出挤条造粒，在60℃下干燥4小时，然后置于氮气气氛箱式炉中，在380℃下焙烧2小时得到成品催化剂。
在固定床连续流动反应装置中装入催化剂10mL,直接催化二乙苯选择性脱氢制备二乙烯苯。氮气作为载气，预热器温度为200℃，反应温度为450℃，二乙苯的体积空速为3h–1，反应时间为4小时，二乙苯的转化率为68.8％，二乙烯苯的选择性为85.8％。
Claims (7)
1.一种脱氢催化剂，其特征在于，包含重量份数如下的组分：
(a)20–40份镧系元素改性的杂多酸盐，
(b)10–20份大孔交联聚合物负载纳米α-Fe2O3；
(c)40–70份CeO2、MnO2、ZrO2、WO3、氧化物中的一种或者几种。
2.根据权利要求1所述的一种脱氢催化剂，其特征在于，所述催化剂中，组分a为K13[X(SiW9Mo2O39)2]·nH2O或K11[X(PW9Mo2O39)2]·nH2O，X为La、Pr、Nd、Pm、Sm中的一种。
3.根据权利要求1所述的一种脱氢催化剂，其特征在于，所述催化剂中，组分b大孔交联聚合物负载纳米α-Fe2O3的制备方法如下：以1-乙基-2-甲基咪唑乙酸酯EA为固化剂，引发环氧树脂DGEBA或者三环氧苯基对氨基苯酚TGAP形成大孔交联聚合物作为载体，负载纳米α-Fe2O3；其中纳米α-Fe2O3优选粒径10–20nm的球形粒子。
4.根据权利要求1所述的脱氢催化剂的制备方法，其特征在于，包括以下步骤：将a、b、c组分按比例和水混合均匀，经过挤出、干燥、氮气氛围中焙烧得到脱氢催化剂。
5.根据权利要求4所述的制备方法，其特征在于，所述干燥温度为40–100℃，所述焙烧温度为200–400℃。
6.根据权利要求1所述的脱氢催化剂的用途，其特征在于，所述脱氢催化剂在二乙苯脱氢制备二乙烯苯中的应用。
7.根据权利要求6所述的用途，其特征在于，在固定床反应器中装入脱氢催化剂，以二乙苯为原料，反应温度为380-500℃，二乙苯的体积空速为2.5-5h–1，氮气作为载气。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010222268.5A CN111375449B (zh) | 2020-03-26 | 2020-03-26 | 一种脱氢催化剂及其在二乙苯脱氢制备二乙烯苯中的应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010222268.5A CN111375449B (zh) | 2020-03-26 | 2020-03-26 | 一种脱氢催化剂及其在二乙苯脱氢制备二乙烯苯中的应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111375449A true CN111375449A (zh) | 2020-07-07 |
| CN111375449B CN111375449B (zh) | 2023-03-21 |
Family
ID=71213787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010222268.5A Active CN111375449B (zh) | 2020-03-26 | 2020-03-26 | 一种脱氢催化剂及其在二乙苯脱氢制备二乙烯苯中的应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111375449B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113509935A (zh) * | 2021-04-22 | 2021-10-19 | 江苏常青树新材料科技股份有限公司 | 一种复合脱氢催化剂及其制备方法与应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1260240A (zh) * | 1999-12-17 | 2000-07-19 | 大庆石油管理局天然气公司新世纪精细化工有限公司 | 甲烷直接芳构化的阳离子型沸石催化剂及其应用 |
| CN1915941A (zh) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | 二乙苯脱氢制备二乙烯苯的方法 |
| CN101624334A (zh) * | 2008-07-11 | 2010-01-13 | 中国科学院大连化学物理研究所 | 一种甘油制备甘油醚的方法 |
| CN107790148A (zh) * | 2016-09-06 | 2018-03-13 | 中国石油化工股份有限公司 | 二乙苯脱氢制二乙烯苯的催化剂及其制备方法和应用 |
-
2020
- 2020-03-26 CN CN202010222268.5A patent/CN111375449B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1260240A (zh) * | 1999-12-17 | 2000-07-19 | 大庆石油管理局天然气公司新世纪精细化工有限公司 | 甲烷直接芳构化的阳离子型沸石催化剂及其应用 |
| CN1915941A (zh) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | 二乙苯脱氢制备二乙烯苯的方法 |
| CN101624334A (zh) * | 2008-07-11 | 2010-01-13 | 中国科学院大连化学物理研究所 | 一种甘油制备甘油醚的方法 |
| CN107790148A (zh) * | 2016-09-06 | 2018-03-13 | 中国石油化工股份有限公司 | 二乙苯脱氢制二乙烯苯的催化剂及其制备方法和应用 |
Non-Patent Citations (3)
| Title |
|---|
| HEBA M. GOBARA等: "A novel route for synthesis of α-Fe2O3–CeO2 nanocomposites for ethanol conversion", 《J MATER SCI》 * |
| 李小海: "Cu掺杂磷钼杂多酸催化剂的低温SCR脱硝性能", 《化工进展》 * |
| 杨水金 等: "合成丁酸丁酯的催化剂", 《化学推进剂与高分子材料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113509935A (zh) * | 2021-04-22 | 2021-10-19 | 江苏常青树新材料科技股份有限公司 | 一种复合脱氢催化剂及其制备方法与应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111375449B (zh) | 2023-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112973761B (zh) | 一种石墨相氮化碳复合材料及制备方法和应用 | |
| CN111375449B (zh) | 一种脱氢催化剂及其在二乙苯脱氢制备二乙烯苯中的应用 | |
| CN115646501B (zh) | 熔融盐法合成的钴单原子催化剂及其应用 | |
| CN111423298B (zh) | 一种乙苯和乙醇为原料一步法制备二乙烯苯的方法 | |
| CN113976179B (zh) | 一种空心结构催化剂及其制备方法和用途 | |
| CN113426437A (zh) | 一种镓基丙烷脱氢制丙烯的催化剂及其制备方法 | |
| CN104549339B (zh) | 一种甲烷选择性氧化催化剂及其制备方法和应用 | |
| CN103769150B (zh) | 低水比乙苯脱氢的催化剂及其方法 | |
| CN103028421A (zh) | 低水比乙苯脱氢催化剂 | |
| CN113198521B (zh) | 一种usy分子筛催化剂的制备方法、及该催化剂在制备二乙烯苯中的应用 | |
| CN113185378B (zh) | 一种乙醇和乙苯为原料制备二乙烯苯的方法 | |
| CN108855205B (zh) | 一种乙醇脱水制乙烯用分子筛催化剂及其制备方法和应用 | |
| CN110614108B (zh) | 载体为具有三维立方笼状孔道分布结构的介孔分子筛的异丁烷脱氢催化剂及制法和应用 | |
| CN106866336A (zh) | 一种制备汽油组分及丁二烯的方法 | |
| CN106492862A (zh) | 一种用于制备顺酐的催化剂及其制备方法 | |
| CN109569637B (zh) | 低水比乙苯脱氢催化剂及制备方法 | |
| CN110694675A (zh) | 一种低碳烃择形芳构化高效合成对二甲苯的催化剂 | |
| CN110496629B (zh) | 异丁烷脱氢催化剂及其制备方法以及异丁烷脱氢制异丁烯的方法 | |
| CN110813284A (zh) | 载体为硅胶的异丁烷脱氢催化剂及其制备方法和应用 | |
| CN110614107A (zh) | 载体为空心球状介孔分子筛硅胶复合材料的异丁烷脱氢催化剂及其制备方法和应用 | |
| CN110694680A (zh) | 合成气与2-甲基萘一步制备2,6-二甲基萘的催化剂 | |
| CN113198533B (zh) | 一种超交联聚合物负载分子筛和Fe催化剂的制备方法及其在生产二乙烯苯的应用 | |
| CN114192184B (zh) | 一种裂解催化剂及其制备方法和应用 | |
| CN110496631B (zh) | 异丁烷脱氢催化剂及其制备方法以及异丁烷脱氢制异丁烯的方法 | |
| CN111905758B (zh) | 一种金基催化剂、其制备方法和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |