CN100415364C - 非均相吸附剂及其在扩散分离方法中的应用 - Google Patents

非均相吸附剂及其在扩散分离方法中的应用 Download PDF

Info

Publication number
CN100415364C
CN100415364C CNB038185385A CN03818538A CN100415364C CN 100415364 C CN100415364 C CN 100415364C CN B038185385 A CNB038185385 A CN B038185385A CN 03818538 A CN03818538 A CN 03818538A CN 100415364 C CN100415364 C CN 100415364C
Authority
CN
China
Prior art keywords
adsorbent
zeolite
homogeneous
heart layer
layer
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.)
Expired - Fee Related
Application number
CNB038185385A
Other languages
English (en)
Other versions
CN1671469A (zh
Inventor
E·若利迈特尔
L·鲁洛
O·迪克勒
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of CN1671469A publication Critical patent/CN1671469A/zh
Application granted granted Critical
Publication of CN100415364C publication Critical patent/CN100415364C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3028—Granulating, agglomerating or aggregating
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3223—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating by means of an adhesive agent
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3238—Inorganic material layers containing any type of zeolite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3295—Coatings made of particles, nanoparticles, fibers, nanofibers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)

Abstract

描述了一种非均相吸附剂，由心层和至少一个连续的外层形成，其中所述吸附剂的心层具有代表吸附剂体积至少35%的体积吸附量，外层具有大于5的扩散选择性。该吸附制用于气体分离方法或液体分离方法中。

Description

非均相吸附剂及其在扩散分离方法中的应用
技术领域
本发明涉及在扩散分离方法中使用的由至少一种晶体构成的非均相吸附剂，该晶体由心层(core)和至少一个连续的外层形成。扩散分离方法利用了通过不同化学成分的固体内部的扩散动力学差异而将两种分子分离的特性。
背景技术
进行大规模的分离，如分离空气中的氧和氮，从氮和氧分离氩，分离单支链和二支链的石蜡，最佳的吸附剂必须一方面具备所要分离的分子间的相当大的扩散动力学差异，另一方面具有良好的吸附量。
均相吸附剂，即完全由相同的化学成分构成的吸附剂，在现有技术是已知的；这些均相吸附剂一般具有良好的分离性能，但只有较低的吸附量，特别是MFI结构型的硅沸石(silicalite)，或者具有良好的吸附量，但不能进行理想的分离。
由心层和外层构成的非均相吸附剂在现有技术中也是已知的(FR-A1-2794993，EP-A1-1080771)。上述非均相吸附剂的中心部分如果是吸附剂也只是弱的吸附剂，且至少部分地被吸附剂周围层所覆盖，一般是沸石。上述吸附剂的制剂不能提高分离方法中有关吸附量的性能，只能降低被吸附到吸附剂微粒上的种类间的扩散阻力，以便具有高动力学的吸附剂微粒。在该例子中，是热力学分离的问题，其中周围层的选择性是使用热力学的。本发明提供了新的非均相吸附剂，其相对于均相吸附剂和中心部分不用作吸附剂的非均相吸附剂来说，吸附量明显提高。
发明概述
本发明的非均相吸附剂由至少一种晶体构成，该晶体由心层和至少一个连续的外层形成，特征在于所述吸附剂的心层具有代表吸附剂体积至少35％的体积吸附量，外层具有大于5的扩散选择性。所述的非均相吸附剂由结合为颗粒的晶体构成，每个晶体具有上文所定义特征的心层和至少一个连续的外层。优选地，心层的晶体大小为0.1μm-0.4mm，连续外层的厚度为0.01-100μm。
发明的有用性
本发明的非均相吸附剂由吸附剂心层和晶体内连续的和选择性的外层构成的事实使获得具有高的吸附量而仍然确保良好选择性的吸附剂成为可能。因此，由于非均相吸附剂的吸附量是高的，其中使用了非均相吸附剂的分离方法的成本显著地降低，因为对于特定分离所需吸附剂的质量与吸附量成反比。因此，本发明可能降低为了进行分离而所用吸附剂的量。
发明内容
本发明的吸附剂是由至少一种晶体构成的非均相吸附剂，该晶体由心层或中央核和至少一个化学成分或晶体结构不同于心层的外层构成。所述的吸附剂特别地适合于流体的扩散分离，最基本的是吸附剂的至少一个外层在吸附剂心层的表面上是连续的，使所述的心层不与所要分离的流动相直接接触。本发明吸附剂的心层保证了该吸附剂的良好的吸附量，而吸附剂心层表面的至少一个连续的外层则确保了良好的扩散选择性。因此，本发明涉及由心层和至少一个连续的外层形成的非均相吸附剂，特征在于该吸附剂的心层具有代表吸附剂体积35％的体积吸附量，外层具有大于5的扩散选择性。吸附量，在本发明范围内用体积％表示，可视为在某一温度每单位体积的吸附剂易接近可被吸附的分子的吸附剂体积。连续的外层必须被理解为在吸附剂心层表面的厚度一致的均相覆盖物。所述的连续外层覆盖整个心层，特征在于与进行理想分离相对的相当大的扩散选择性。因此，可以说是连续的和选择性的外层。因此，它具有相当大的扩散阻力，例如只允许要分离的混合物中存在的一些分子通过，即最快扩散的受到最小阻碍的分子。所述连续的外层，具有大于5的扩散选择性，具有小于本发明吸附剂心层的吸附量。心层，完全被具有强的扩散选择性的所述连续外层覆盖，具有小于所述外层的扩散选择性。本发明吸附剂的心层和连续的外层都没有催化活性。它们不含有催化活性的金属以避免与吸附剂接触的分子的任何反应和/或转化。
更精确地，本发明吸附剂由颗粒构成，每个颗粒由晶体构成。根据本发明，每个晶体由代表吸附剂体积至少35％的体积吸附量的心层和扩散选择性大于5的连续外层形成。根据本发明，晶体心层的成分不同于该相同晶体的连续外层。本发明吸附剂的非均相性因此位于晶体中(微米级)，每个晶体整体上具有非均相成分。
本发明吸附剂可具有多个外层以形成多层吸附剂。根据本发明，上述层中至少一个完全包住心层，以在心层表面形成连续的外层，使其具有大于5的扩散选择性。本发明吸附剂有利地含有单个连续外层。
吸附剂心层的体积吸附量优选为吸附剂体积的至少40％，更优选为吸附剂体积的至少45％。覆盖整个吸附剂心层的连续外层的扩散选择性优选大于10，再优选大于50，更优选大于100，甚至更优选大于175。
根据本发明的实施方案，吸附剂的心层部分地或全部是空的。在心层完全空的例子中，心层的体积吸附量为吸附剂体积的100％。该方案特别适合于液体混合物的分离。
根据本发明的另一实施方案，体积吸附量为吸附剂体积至少35％的吸附剂心层由孔直径为0.1-20nm的结晶微孔性固体或孔直径为20-500nm的结晶中孔性固体构成的吸附剂材料形成。从结晶的微孔性固体中，可选择例如陶瓷、粘土、柱粘土、活性炭、硅石、氧化铝、硅铝、沸石如属于FAU结构型的沸石(X沸石，Y沸石)，属于BEA结构型的沸石(β沸石)。在结晶中孔性固体中，MCM-41和MCM-48固体是特别优选的。通常，任何多孔的异质结构均适于形成吸附剂的心层，该异质结构是结晶或无定形的，具有0.1nm-500nm的孔大小和占吸附剂体积至少35％，优选吸附剂体积的至少40％，非常优选吸附剂体积的至少45％的体积吸附量。构成本发明吸附剂心层的晶体的大小有利地为0.1μm-0.4mm，更有利地0.2-50μm，甚至更有利地0.5-5μm。吸附剂的心层具有可以忽略的扩散阻力。
不受心层化学性质的限制，即不受部分或完全空的心层或由结晶固体形成的心层的限制，扩散选择性大于5的连续外层由孔直径0.1-20nm，优选0.1-10nm，甚至更优选0.1-5nm的结晶微孔性固体构成。例如活性炭、硅石、氧化铝、铝磷酸盐、与不同阳离子交换或非交换的沸石、表面处理或表面淀积(有机金属型)的沸石，金属硅酸盐如铝硅酸盐、硼硅酸盐和钛硅酸盐，和金属磷酸盐如铝磷酸盐、镓磷酸盐和锌磷酸盐。扩散选择性大于5并完全包围吸附剂心层的连续外层的厚度可根据吸附剂而变化，且对一个特定吸附剂而言也是要分离分子以及试验条件的函数，该试验条件特别是温度、压力、流体的循环速率。优选地，所述外层的厚度为0.01-100μm，更优选0.1-10μm。特别有利的是如果心层的尺寸为0.2-50μm，至少一个连续外层为0.01-100μm厚，得到本发明非均相吸附剂晶体的最大尺寸150μm。有利地，吸附剂的心层为本发明非均相吸附剂总体积的至少10％且最多99％，它优选地为所述吸附剂总体积的20-90％，更优选40-85％。在吸附剂是球形或圆柱形的例子中，心层的半径为吸附剂总半径的至少40％，更有利地为至少60％，甚至更有利地为吸附剂总半径的至少70％。优选地，本发明的吸附剂是球形的。
根据本发明，有利地，构成吸附剂心层的固体的孔大小比构成连续外层的固体的大。
对于本发明吸附剂的方案，优选使用沸石固体作为心层和连续外层。所述的沸石固体在它们的结构型和/或它们的结晶构架的化学成分和/或补偿阳离子的性质方面是不同的。优选地，用作吸附剂心层组分的沸石为FAU结构型的沸石，特别是Y沸石和X沸石，BEA结构型的沸石，特别是β沸石，EUO结构型的沸石，特别是EU-1沸石，和TON结构型的沸石，特别是ZSM-22沸石。用作连续外层组分的沸石优选为MFI结构型的沸石，特别是硅沸石。形成心层/连续外层组合的沸石固体组合非常有利地为Y沸石/硅沸石、X沸石/硅沸石、β沸石/硅沸石、Y沸石/EU-1沸石、X沸石/EU-1沸石、Y沸石/ZSM-22沸石和X沸石/ZSM-22沸石组合。
包含在本发明吸附剂中的每一种晶体的形状对于所述吸附剂的应用不是决定参数；它们尤其是球形、圆柱形或椭球形。
本发明非均相吸附剂的制备由以下步骤组成，即在构成本发明吸附剂心层的具有高吸附量的固体上或在有机支持材料上，该有机支持材料易于由热或化学处理分解，因而分解后得到非常大的孔体积，形成一个或多个固体层，其中该固体层至少一个是连续的和选择性的。所述的有机支持材料可例如为聚苯乙烯。所述层中的至少一个完全包围吸附剂的心层以便形成连续的和选择性的扩散选择性大于5的外层。该连续和选择性的外层由结晶的微孔性固体构成，例如MFI结构型的沸石。吸附剂的心层可由上文所述材料的一种构成。
本发明的非均相吸附剂可通过例如以下方法来制备，包括：
a)选择性沸石的纳米晶体粘着在构成心层的固体晶体上，任选地使用化学(接枝剂)或静电(表面电荷反转剂)粘合剂．该粘合可通过一种或多种操作完成，例如在搅拌的和含水介质中，例如在用化学或静电粘合剂预处理构成心层的固体后，
b)选择性沸石的生长，任选地伴随着具有核作用的纳米晶体的淀积或预先形成，扩使得能够放入晶种、易于生长和被例如上述方法粘住。该生长可通过一种或多种操作来进行，例如在水热条件下搅拌的和含水介质中，用沸石结晶所需的元素原料，例如在所要沸石的纳米晶体沉积后。
沸石纳米晶体可通过V.Valtchev等人在文章中描述的被称作“清液”的方法来合成(J.Mater.Chem，2002，12，1914-1918)。静电粘合剂可以是阳离子聚合物如V.Valtchev等人所描述的那些，特别是Rediflock
Figure C0381853800071
(AKZO Nobel)和Berocell
Figure C0381853800072
(AKZO Nobel)(Zeolites and Mesoporous Materials at the Dawn of the 21stCentury，Proceedings of the 13th International ZeoliteConference，Montpellier，法国，2001年7月8-13日，Studies inSurface Science and Catalysis，vol 135，p.298)。
构成心层的固体可任选的在层淀积之前进行多种处理．对于中孔性的沸石和材料，可设想进行本领域技术人员已知的标准热和化学改性处理，特别是为了消除例如有机结构剂的煅烧操作和为了将沸石转化为所要的阳离子形式的离子交挟操作。为了抽提出对该层的形成有害的元素，为了促进心层的反应性或该层晶体的锚定，可任选的进行表面处理。上述处理也可包括特定电荷反转或接枝剂的吸附以确保该层晶体的粘合。
在层形成后，为了分解例如结构剂，或有机粘合剂，或如果使用的话有机支持材料，和为了将沸石转化为所要的阳离子形式，可进行热和化学改性操作。
非均相吸附剂可通过本领域技术人员已知的方法利用粘合剂来成型，特别是造粒或挤出。有利地，成型之后进行干燥和煅烧。上述成型的固体在用于吸附方法前可进行热和化学处理，如上文所描述。
对构成吸附剂心层的固体进行选择以赋予本发明吸附剂所需的尺寸。连续和选择性外层的厚度通过控制粘合条件，特别是阶段的数目来保证。
本发明的吸附剂可用于以下所有的分离方法中，利用扩散选择性作为分离的原动力和使用通过本领域技术人员公知的吸附分离技术，通过压力效果(PSA或Pressure Swing Adsorption)，温度效果(TSA或Temperature Swing Adsorption)，温度和压力两种效果的组合(PTSA或Pressure and Temperature Swing Adsorption)，真空效果(VSA或Vaccum Swing Adsorption)或在SCC(模拟逆流)，反应性SCC中进行。
本发明吸附剂有利地用于气体或蒸汽分离方法中。它也可成功地用于液体分离方法中。它优选地用于根据分枝程度(正常、单、二、三支链的种类)分离石蜡异构体，非常优选地用于从二支链石蜡分离单支链石蜡。
实施例
实施例1：制备本发明的非均相吸附剂
制备非均相吸附剂，其心层由X沸石(八面沸石结构型)构成，外层由硅沸石-1(MFI结构型)构成。
硅沸石-1层通过硅沸石-1纳米晶体粘合后生长在X沸石晶体上形成。
X沸石的合成：
X沸石根据R.W.Thompson等人所述的方法进行合成(Zeolites，1993，vol 13，645-653)。根据制剂4.76Na2O-1.0Al2O3-3.5SiO2-454H2O-2TEA，凝胶由硅酸钠、铝酸钠和三乙醇胺的溶液来制备。
铝酸钠溶液通过将苏打(Aldrich)和铝丝(Aldrich)溶解于置换水中来制备。为了使之稳定，将三乙醇胺(Aldrich)加入到该溶液中。钠硅酸盐溶液通过在置换水(permutated water)中稀释非水合的硅酸钠(Fischer)而获得。将两种溶液充分混合以形成凝胶。
凝胶在自压下加入到125ml的高压釜中，在115℃经过24小时以确保结晶。过滤回收固体，用置换水在过滤器中充分地洗涤，大气下60℃烘箱干燥12小时。该固体是X沸石晶体型(FAU型)，根据X射线衍射分析纯度为95％。晶体的平均大小大约为6μm。
硅沸石-1纳米晶体的合成：
硅沸石-1纳米晶体通过V.Valtchev等人在文章中所述的所谓的“清液”方法来合成(J.Mater.Chem，2002，12，1914-1918)。
根据制剂9TPAOH-25SiO2-480H2O-100EtOH，凝胶由原硅酸四乙酯、氢氧化四丙基铵的溶液来制备。
原硅酸四乙酯(Merck)在置换水中稀释。该溶液与氢氧化四丙基铵的溶液(Merck，20重量％)充分混合，环境温度下放置14小时，伴随着搅拌，以促进硅源的水解，产生乙醇(EtOH)。
所获得的凝胶加入到125ml的高压釜中，在60℃经过3周以确保结晶。该固体通过超速离心法回收，然后在氢氧化铵溶液(0.1MNH3，pH＝9.5)中通过多重分散进行洗涤，以沸石的2重量％分散在该溶液中。该固体是硅沸石-1沸石晶体型(MFI型)，根据X射线衍射分析纯度为99％，根据透射电子显微镜，大小为100nm数量级。
硅沸石-1晶体在X沸石晶体上的吸附和生长：
根据V.Valtchev在文章中所描述的方法(Zeolites andMesoporous Materials Conference，Montpellier，法国，2001年7月8-13日，Studies in Surface Science and Catalysis，vol 135，p.298)，硅沸石-1纳米晶体通过X沸石与阳离子聚合物的电荷反转粘着在X沸石上。
电荷反转聚合物(Rediflock 4150，Akzo)吸附在含水溶液中的沸石上。硅沸石-1纳米晶体的分散液与吸附在阳离子聚合物上的X沸石的分散液混合。
硅沸石-1晶体的生长于125ml含有产生硅沸石-1纳米晶体凝胶的高压釜中通过95℃24小时的三步水热操作来进行。每步水热操作之后，悬浮的固体过滤回收，并用置换水滤器充分洗涤。三步水热操作所获得的固体在60℃烘箱干燥12小时，并进行煅烧处理以提取在硅沸石-1的孔中和其形成所需的有机结构剂。为了限制层的变坏，在含有5体积％O2的气体氮-氧混合物下，在500℃煅烧处理2小时。
根据X-射线衍射，如此获得的产物具有两个硅沸石-1和X沸石相，且由位于X沸石晶体上的连续的和选择性的厚度为1μm的硅沸石-1纳米晶体外层构成，直径为6μm。
实施例2：分离单/二支链的石蜡。用于分离3-甲基戊烷(3-MP)和2，2-二甲基丁烷(22DMB)
为了分离3-甲基戊烷(3-MP)和2，2-二甲基丁烷(22DMB)，测验的均相吸附剂的性能值，与实施例1制备的非均相吸附剂所获得的性能值进行比较，基测验用于分离相同的分子。均相吸附剂完全由硅沸石构成，球形，半径R＝1μm。
想要分离的分子，即3-甲基戊烷(3-MP)和2，2-二甲基丁烷(22DMB)在所研究的两种吸附剂上的主要的吸附和扩散特性记录在表1中。
表1：3MP和22DMB在X沸石和硅沸石中的吸附和扩散特性
     X沸石      硅沸石
在200℃的吸附量(体积％)      45.0      18.1
在200℃3MP的扩散系数(m<sup>2</sup>/s)      8*10<sup>-10</sup>      5*10<sup>-14</sup>
在200℃22DMB的扩散系数(m<sup>2</sup>/s)      2*10<sup>-10</sup>      2*10<sup>-16</sup>
扩散选择性      4      250
表1清楚地显示，X沸石对想要分离的分子具有非常良好的吸附量，但是扩散选择性较小。相反，硅沸石对两种石蜡具有非常良好的扩散选择性，但是比X沸石的吸附量小3倍多。最后，3MP和22DMB在X沸石中的扩散系数远高于硅沸石。
非均相吸附剂的吸附量通过以下公式计算
Figure C0381853800101
其中qsx和qs硅沸石分别是X沸石和硅沸石在200℃的吸附量，Rcx和Rc 硅沸石分别是X沸石和硅沸石的半径。
在该实施例中，吸附剂心层的半径为非均相吸附剂总半径的75％，得到了吸附剂体积29.4％的体积吸附量，即与硅沸石相比，吸附量增加了62.7％。因此，非均相吸附剂的吸附量比均相吸附剂大1.627倍。
扩散特性的计算：
表2显示了3MP和22DMB在由硅沸石(不是本发明)构成的均相吸附剂和由X沸石心层和硅沸石外层(根据本发明)构成的非均相吸附剂中的特征扩散时间。上述特征时间在球形的例子中定义为公式Rc 2/D，其中Rc为球体的半径，D为扩散系数，表示分子经过所研究固体的特征距离所需的平均时间。
表2：3MP和2，2-DMB在所研究的两种吸附剂中的特征扩散时间。
以上显示在两种吸附剂中，3MP和22DMB的特征扩散时间是相同的。上述分子在X沸石中的扩散是非常迅速的，该固体在非均相吸附剂中的存在所引起的扩散阻力是可以忽略的。因此两种吸附剂对于分离的扩散选择性是相同的。因此，本发明的非均相吸附剂保持了扩散选择特性，但是得到了双倍于均相吸附剂的吸附量。由吸附剂材料构成的心层加入到吸附剂的结构中形成非均相吸附剂，因此在吸附量上得到了明显的提高，非均相吸附剂保持了非常令人满意的扩散选择特性。

Claims (13)

1. 由至少一种晶体构成的非均相吸附剂，该晶体由心层和至少一个连续的外层形成，其特征在于所述吸附剂的心层具有占该吸附剂体积至少35％的体积吸附量，该外层具有大于5的扩散选择性；并且该心层的晶体大小为0.2μm-50μm，该连续外层的厚度为0.01-100μm.
2. 根据权利要求1的非均相吸附剂，其特征在于该心层的体积吸附量占吸附剂体积的至少40％.
3. 根据权利要求1或2的非均相吸附剂，其特征在于所述扩散选择性大于10.
4. 根据权利要求1或2的非均相吸附剂，其特征在于该心层的吸附量大于该连续外层的吸附量.
5. 根据权利要求1或2的非均相吸附剂，其特征在于该心层是部分或完全空的.
6. 根据权利要求1或2的非均相吸附剂，其特征在于该心层含有结晶的微孔性或中孔性固体.
7. 根据权利要求1或2的非均相吸附剂，其特征在于该连续的外层含有结晶的微孔性固体.
8. 根据权利要求1或2的非均相吸附剂，其特征在于该连续外层的厚度为0.1-10μm.
9. 根据权利要求1或2的非均相吸附剂，其特征在于所述的心层和连续外层是沸石固体.
10. 根据权利要求1或2的非均相吸附剂，其特征在于其为球形或圆柱形.
11. 根据权利要求1或2的非均相吸附剂，其特征在于该心层的半径为吸附剂总半径的至少40％.
12. 权利要求1-11之一的非均相吸附剂在气体或蒸汽分离方法中的应用.
13. 权利要求1-11之一的非均相吸附剂在液体分离方法中的应用.
CNB038185385A 2002-08-01 2003-07-11 非均相吸附剂及其在扩散分离方法中的应用 Expired - Fee Related CN100415364C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR02/09841 2002-08-01
FR0209841A FR2843049B1 (fr) 2002-08-01 2002-08-01 Adsorbant non homogene et son utilisation dans des procedes de separation diffusionnelle

Publications (2)

Publication Number Publication Date
CN1671469A CN1671469A (zh) 2005-09-21
CN100415364C true CN100415364C (zh) 2008-09-03

Family

ID=30129629

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB038185385A Expired - Fee Related CN100415364C (zh) 2002-08-01 2003-07-11 非均相吸附剂及其在扩散分离方法中的应用

Country Status (8)

Country Link
US (1) US7435699B2 (zh)
EP (1) EP1531917A2 (zh)
JP (1) JP2005534479A (zh)
KR (1) KR100969638B1 (zh)
CN (1) CN100415364C (zh)
AU (1) AU2003271806A1 (zh)
FR (1) FR2843049B1 (zh)
WO (1) WO2004012835A2 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7947182B2 (en) * 2008-08-29 2011-05-24 Conocophillips Company Naphthenic acid removal process
US9132410B2 (en) 2013-12-31 2015-09-15 Algenol Biotech LLC Compositions, systems and methods for separating ethanol from water and methods of making compositions for separating ethanol from water
AU2015370085B2 (en) * 2014-12-23 2018-10-04 Exxonmobil Research And Engineering Company Adsorbent materials and methods of use
CN111699036B (zh) * 2018-02-15 2022-12-20 普莱克斯技术有限公司 优异的碳吸附剂
US20220258124A1 (en) 2019-06-26 2022-08-18 China Petroleum & Chemical Corporation Composite layer agglomerating adsorbent and preparation process thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4420419A (en) * 1981-03-10 1983-12-13 Mizusawa Kagaku Kogyo Kabushiki Kaisha Abrasion-resistant granular zeolite and process for preparation thereof
FR2794993A1 (fr) * 1999-06-18 2000-12-22 Air Liquide Utilisation d'un adsorbant particulaire non homogene dans un procede de separation de gaz
EP1182246A1 (fr) * 2000-08-25 2002-02-27 Institut Francais Du Petrole Procédé de séparation de paraffines multibranches utilisant un adsorbant zeolithique de structure mixte

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3827989A (en) * 1972-11-13 1974-08-06 Atomic Energy Commission Impregnated chemical separation particles
US4283583A (en) * 1979-06-29 1981-08-11 The Standard Oil Company Alkylation of aromatic hydrocarbons in the presence of coated zeolite catalysts
JPS5916832A (ja) * 1982-07-20 1984-01-28 Agency Of Ind Science & Technol 複合ゼオライト及びそれを触媒として用いる炭化水素の製造方法
JP2680823B2 (ja) * 1987-12-09 1997-11-19 水澤化学工業株式会社 白色球状吸着剤及びその製法
JP2587328B2 (ja) * 1991-06-13 1997-03-05 株式会社荏原製作所 有機塩素化合物の吸着剤および吸着処理法
AU2600295A (en) * 1994-05-23 1995-12-18 Tda Research, Inc. Support for chemical sorbents
GB9502342D0 (en) * 1995-02-07 1995-03-29 Exxon Chemical Patents Inc Hydrocarbon treatment and catalyst therefor
JPH0957095A (ja) * 1995-08-25 1997-03-04 Tetsujiro Minagawa クリストバル石、鱗珪石及びその混成材等を原材料とする吸着剤に関する製造方法
US6284021B1 (en) 1999-09-02 2001-09-04 The Boc Group, Inc. Composite adsorbent beads for adsorption process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4420419A (en) * 1981-03-10 1983-12-13 Mizusawa Kagaku Kogyo Kabushiki Kaisha Abrasion-resistant granular zeolite and process for preparation thereof
FR2794993A1 (fr) * 1999-06-18 2000-12-22 Air Liquide Utilisation d'un adsorbant particulaire non homogene dans un procede de separation de gaz
EP1182246A1 (fr) * 2000-08-25 2002-02-27 Institut Francais Du Petrole Procédé de séparation de paraffines multibranches utilisant un adsorbant zeolithique de structure mixte

Also Published As

Publication number Publication date
AU2003271806A1 (en) 2004-02-23
FR2843049B1 (fr) 2005-03-25
CN1671469A (zh) 2005-09-21
US7435699B2 (en) 2008-10-14
KR100969638B1 (ko) 2010-07-14
EP1531917A2 (fr) 2005-05-25
WO2004012835A3 (fr) 2004-07-22
AU2003271806A8 (en) 2004-02-23
JP2005534479A (ja) 2005-11-17
WO2004012835A2 (fr) 2004-02-12
US20050250641A1 (en) 2005-11-10
KR20050026051A (ko) 2005-03-14
FR2843049A1 (fr) 2004-02-06

Similar Documents

Publication Publication Date Title
Tosheva et al. Nanozeolites: synthesis, crystallization mechanism, and applications
CN103011189B (zh) 一种含贵金属的微孔-介孔分子筛、制备方法及用于对硝基苯酚的催化还原
US7378076B2 (en) Process for production of macrostructures of a microporous material
US7094390B2 (en) Macrostructures of porous inorganic material and process for their preparation
US20160375427A1 (en) Process for modifying the physical and chemical properties of faujasite y-type zeolites
US8258071B2 (en) Catalyst in the form of grains comprising an acidic porous core surrounded by a uniform outer layer
CN103265050A (zh) 一种制备多级孔沸石分子筛微球的方法
CN100586855C (zh) 一种多级孔道贯流型沸石材料的制备方法
CN100415364C (zh) 非均相吸附剂及其在扩散分离方法中的应用
EP3397383A1 (de) Zeolithische partikel mit nanometerdimensionen und verfahren zu deren herstellung
CN102794193B (zh) 一种微孔分子筛外表面修饰的方法
EP2980019B1 (en) Method for producing ddr type zeolite crystals and method for producing ddr type zeolite membrane
CN109046456B (zh) 负载型锰-金属有机框架复合材料的制备方法及其应用
EP3838843A1 (en) Hierarchical zeolites and preparation method therefor
NL9201940A (nl) Katalysatorsysteem van het gestructureerde type.
KR101912719B1 (ko) 메조기공 및 미세기공을 갖는 y 제올라이트로 개질된 알루미나 멤브레인 제조방법
CN105460952B (zh) 一种zsm-5分子筛材料的制备方法及该方法制备而得的zsm-5分子筛材料
CN102500408B (zh) 微孔-介孔催化材料及其制备方法
CN1295149C (zh) Mcm－41分子筛与钛纳米复合材料及其制备方法
US20200038850A1 (en) Composite material
RU2781191C2 (ru) Композиционный материал
US20210094025A1 (en) Composite Material
JP3489904B2 (ja) メチルアミン類の製造方法
Zhang et al. Zeolite Nanocrystals: Hierarchical Assembly and Applications
Tsitsishvili et al. Formation of Highly Dispersed Faujasites in Natural Aluminosilicate Gels

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080903

Termination date: 20110711