CN1342508A - 变温吸附法 - Google Patents
变温吸附法 Download PDFInfo
- Publication number
- CN1342508A CN1342508A CN01125282A CN01125282A CN1342508A CN 1342508 A CN1342508 A CN 1342508A CN 01125282 A CN01125282 A CN 01125282A CN 01125282 A CN01125282 A CN 01125282A CN 1342508 A CN1342508 A CN 1342508A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- air
- type
- zeolite
- removes
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/80—Water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/414—Further details for adsorption processes and devices using different types of adsorbents
- B01D2259/4141—Further details for adsorption processes and devices using different types of adsorbents within a single bed
- B01D2259/4145—Further details for adsorption processes and devices using different types of adsorbents within a single bed arranged in series
- B01D2259/4146—Contiguous multilayered adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/416—Further details for adsorption processes and devices involving cryogenic temperature treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0462—Temperature swing adsorption
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S95/00—Gas separation: processes
- Y10S95/90—Solid sorbent
- Y10S95/902—Molecular sieve
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Of Gases By Adsorption (AREA)
- Drying Of Gases (AREA)
Abstract
本发明提供一种在空气通过低温蒸馏分离出其氮和氧之前从空气中除去痕量杂质如氮氧化物和烃的变温吸附法。该方法使用三个吸附剂层;第一层主要除去水,第二层主要除去二氧化碳;第三层是组合吸附剂层,可除去空气中的氮氧化物和烃。另一个实施方案使用了两层吸附剂系统来除去杂质。另外,可以使用单层的组合吸附剂层,用于除去水、二氧化碳、氮氧化物和烃。
Description
发明领域
本发明涉及从空气中除去烃和氮氧化物的一种新颖变温吸附法(TSA)。具体而言,本发明涉及用于在低温蒸馏空气分离为氧和氮之前的预提纯装置(PPU)的一种TSA法。
发明背景
在通过蒸馏低温分离空气生产氧和氮之前,必须从原料空气中除去各种痕量杂质,避免在热交换设备中形成固体,以致在低温过程中产生高压和安全问题。必须除去的最明显的空气中痕量杂质包括二氧化碳(CO2)和水分(H2O)。有许多文献公开了在蒸馏低温分离空气为氧、氮和氩之前采用变压吸附(PSA)和变温吸附(TSA)的预提纯装置(PPU)中,从空气除去这些种类的杂质。
在空气进入空气低温分离装置之前从其中除去氮氧化物的重要性近年才为我们认识。由于一氧化二氮(N2O)(也被称作氧化亚氮)在大气中浓度增加,除去一氧化二氮特别重要。众所周知,一氧化二氮是一种温室气体,在过去的十年中,大气中N2O浓度(目前约0.3ppm)一直在稳步上升(每年上升约0.2-0.3%)。一氧化二氮气浓度上升的主要原因是人类活动以及各种化工厂的排放。在空气低温分离装置中若存在过量的N2O,会堵塞热交换器的管道并污染产品。N2O在空气中很稳定,在大气中的“寿命”大约150年,在空气预提纯装置除去N2O,无论在当前还是在未来都是必需的。设想在未来除去N2O会和除去水和CO2一样重要。由于空气中N2O浓度还在提高,PPU法目前的状况变得很不适应,因为采用现有的PPU法不易除去N2O。因此,明确需要研究一种适合在PPU装置中使用的有效吸附方法,不仅除去水和CO2,而且能除去痕量氮氧化物尤其是N2O,它们存在于送入空气低温分离装置的空气中。另外,应特别关注PPU方法,使其能从空气中除去痕量烃,例如低分子量烃气体如乙烷、丙烷、正丁烷、异丁烷、以及任何不饱和物质如乙炔、乙烯、丙烯、正丁烯异构体和异丁烯。同时在空气预提纯过程中同时除去烃和堵塞组分如N2O和CO2也很重要。堵塞组分的沉积物会为烃提供收集并集中在那些沉积物中的机会。本发明涉及这样一种解决方法,它具体是致力于同时高效地预提纯空气。
N2O不是环境空气中仅存在的有害痕量杂质。N2O属于通称为堵塞/沉积(plating)组分的一类有害杂质。水分和CO2是在PPU中除去的其余堵塞/沉积杂质。这些气体杂质在低温条件下会凝结,堵塞通道,沉积在冷表面上。环境空气还含有一些不可以和液态氧接触的烃杂质。通常,烃杂质进入冷箱,并在低压蒸馏塔再沸器的液态氧储槽中积累起来。空气分离过程还使这些杂质的浓度提高,致使它们在低压蒸馏塔中的浓度比PPU产物中的浓度高数倍。
当这些化合物在液氧中的浓度超过这些化合物在液氧中的溶解度和自燃极限时,这些化合物会燃烧,引起小的爆炸,在极端情况下,会引起蒸馏塔内部的燃烧。在热交换器和再沸器的通道内还会发生烃杂质的积累,引起和蒸馏塔内所发生的同样问题。热交换器通道内的积累由于存在堵塞/沉积组分而加重。沉积的N2O和CO2会形成静止液态氧的小穴,烃在其中积累并富集到超出自燃极限。
很清楚,堵塞组分和烃除了有各自的不良作用外,还造成对ASU安全的综合威胁。这些现象说明了在PPU过程中不仅除去N2O,而且除去烃的必要性。本发明涉及具体是致力于在变温吸附法中同时高效提纯空气的这样一个解决方案。
发明概述
本发明提供一种通过变温吸附从气流中除去杂质的新颖方法。该方法包括使含杂质的气流通过能从气流除去水的第一吸附剂层,然后通过能除去气体中二氧化碳的第二吸附剂层。最后,该气流通过能除去烃和氮氧化物的第三层。
第三吸附剂是一种组合吸附剂,它包含至少一种择优吸附氮氧化物和一系列烃的吸附剂即“除N2O吸附剂”和至少一种择优吸附已被第一吸附剂吸附至较低量的上述烃的吸附剂即“除烃吸附剂”。“除N2O吸附剂”较好的是CaLSX、CaMSX或CaX型沸石,“除烃吸附剂”较好的是CaA型沸石。
本发明的组合吸附剂可以理解为是至少两种吸附剂如上述沸石的初级颗粒(微粒)的物理混合物,这两种吸附剂是分别的,该混合物使用粘合剂通过挤压或造粒或其它已知方法形成最终类型的大颗粒。
本发明一个较好的实施方案中,提供的方法包括下列步骤:使含杂质的气流通过能从气流基本除去二氧化碳和水分的第一吸附剂层,然后通过能从该气流除去烃和氮氧化物的第二吸附剂层。这一实施方案中,第一层是沸石,第二层是组合吸附剂。
本发明的另一实施方案中,提供的方法包括下列步骤:使含杂质的气流通过能基本除去气流中水分的第一吸附剂层,然后通过能除去该气体中二氧化碳、烃和氮氧化物的第二吸附剂层。这一实施方案中,第一层是活化氧化铝,第二层是组合吸附剂。
本发明又一实施方案中,提供的方法包括下列步骤:使含杂质气流通过基本能除去水分、二氧化碳和烃以及氮氧化物的组合吸附剂。这一实施方案中,该组合吸附剂包含第一吸附剂和第二吸附剂。
本发明的优点在于与使用第四吸附剂层的方法相比比较简单。使用组合吸附剂将变温吸附预提纯装置成为不仅在气流进入空气低温分离装置之前除去气流中的水分和二氧化碳,而且能除去不合适的氮氧化物尤其是一氧化二氮以及饱和烃与不饱和烃的装置。这使得进入空气低温分离装置的气流基本上没有痕量杂质。进入空气低温分离装置的高度纯化的空气流使得装置的操作更安全,使空气分离装置生产出比过去更高质量的产品。
发明详细描述
本发明涉及通过变温吸附从气流中除去杂质的方法,该方法主要包括下列步骤:使气流依序通过能除去气流中水分的第一吸附剂层,能除去气流中二氧化碳的第二吸附剂层,能除去氮氧化物和烃的第三吸附剂层。
对本发明目的,“基本上”用于指“除去”杂质时定义为除去至少80%杂质。
通常,进入空气低温分离装置(ASU)的原料是含水蒸汽、二氧化碳和包括一氧化二氮、乙炔、乙烷、丙烷和其它烃等痕量杂质的大气空气。这种原料一般通过TSA预提纯装置除去水分和二氧化碳。目前的TSA-PPU设计装置适合这种除去,但不能完全充分地除去痕量杂质如氮的各种氧化物和/或烃。本发明方法涉及一种新颖的吸附剂和吸附剂在TSA-PPU中的排列,在空气原料进入ASU将氮(N2)和氧(O2)分离之前,除去空气原料中的水分和二氧化碳以及氮氧化物和烃。本发明的吸附剂和吸附剂排列也可用于变压吸附(PSA)-PPU装置。
第一吸附剂层是活化氧化铝(AA)或沸石NaX,但也可以使用任何常规的水吸附材料。
第二吸附剂层是沸石X材料,特别是NaLSX型沸石,它指的是硅铝原子比在0.9-1.1范围的沸石X。这种材料的晶体结构是八面沸石矿物的晶体结构,被Structure Commission of the International Zeolite Association表示为FAU。
第三吸附剂层是一组合吸附剂,它包含一种“除烃吸附剂”和一种“除氮氧化物吸附剂”,本文中也分别称作“烃吸附剂”和“N2O吸附剂”。烃吸附剂选自A型和X型沸石、硅胶和其它非沸石的吸附剂。N2O吸附剂选自A型、X型或Y型的沸石。较好的烃吸附剂是CaA型沸石,较好的N2O吸附剂是CaLSX、CaMSX或CaX型沸石。对本发明目的,根据气流中杂质的本性,组合吸附剂可以包含一种或多种烃吸附剂以及一种或多种N2O吸附剂。
本发明的组合吸附剂可理解为是至少两种吸附剂如上述沸石的初级颗粒(微粒)的物理混合物,这两种吸附剂是分别合成的,该混合物通过挤压出或造粒或其它已知方法,使用粘合剂形成最终类型的大颗粒。
下面描述形成本发明组合物的一些具体吸附剂配方。
CaLSX、CaMSX和CaX沸石是X型沸石(FAU沸石),其沸石相即无粘合剂的结晶相的硅与铝原子比范围分别约为0.9-1.1,1.1-1.15和1.16-3.0,按当量基准其可交换的阳离子包括约0-100%的钙离子和约100-0%的其它离子,这些其它离子选自IA族离子如锂、钠和钾,除钙外的IIA族离子,除金外的IB族离子,除汞外的IIB族离子和镧系离子,以及它们的混合物,然而,硅与铝的原子比较好为0.9-1.15;吸附剂的阳离子组成包括约50-100%的钙离子和约50-0%其它离子,这些其它离子选自IA族的阳离子如锂、钠和钾,除钙外的IIA族离子,除金外的IB族离子,除汞外的IIB族离子和镧系离子,以及它们的混合物,硅与铝的原子比更好的为0.95-1.05;阳离子组成包括约90-100%的钙离子和约10-0%的其它阳离子,这些其它离子选自IA族如锂、钠和钾,除钙外的IIA族离子,除金外的IB族离子,除汞外的IIB族离子和镧系离子,以及它们的混合物。硅与铝的原子比在0.9-1.15范围的FAU材料,和所述阳离子组成进一步称作钙低硅X型沸石(CaLSX型沸石)。
预期作为本发明“N2O吸附剂”的X型沸石组成中钙离子的作用,除了可以被前面段落中详细描述的IIA和IIB族金属代替外,还可以被其它两价金属离子,如镁、锶、锌和镉代替。
组合吸附剂包含约2-98%(重量)N2O吸附剂和约98-2%(重量)的烃吸附剂。该范围较好的是约50%(重量)N2O吸附剂和约50%(重量)的烃吸附剂。
气流较好是用空气,烃杂质是甲烷、乙炔、乙烯、丙烯、乙烷、丙烷、正丁烷、异丁烷、正丁烯异构体或异丁烯。氮氧化物杂质是一氧化二氮、氧化一氮、四氧化二氮或五氧化二氮。
在一较好的实施方案中,在空气PPU中,在空气低温分离装置前面进行本发明的TSA。
组合吸附剂较好的是一种粘合的材料,其中结晶沸石部分包括CaA型沸石以及CaLSX、CaMSX或CaX型沸石。就沸石部分而言组合物中各吸附剂的比例为约2-98%的烃吸附剂比约98-2%的N2O吸附剂。
本发明的组合吸附剂可以成形的颗粒(也称作次级颗粒(大颗粒))形式使用。这些次级颗粒可通过各种方法成形为各种几何形状如球形、挤出物和空心挤出物。在成形步骤之前,沸石结晶相中可加入无机粘合剂。这些粘合剂对颗粒机械强度是必需的,在成形的颗粒内部应形成传递用的粗孔系统它能对被吸附物质提供必需的有效传质性能。粘合剂含量根据使用的粘合剂类型和成形过程而不同,但一般约为最终产品的5-25%(重量)。
下面的一些实施例对本发明仅是代表性的,不构成对本发明的限制。
实施例
在TSA PPU中进行本发明方法的试验。除了CO2和H2O外,将下面的痕量杂质注入输入PPU的空气中:N2O、CH4、C2H4、C2H6、C3H6、C3H8、C2H2和nC4H10。各种情况下,TSA PPU产物中的CO2浓度为~1ppm。市售吸附剂产品即UOP级APG II的NaX沸石能够完全除去C2H2、CO2、C3H6、n-C4H10和H2O,但不能完全除去N2O、CH4、C2H4、C2H6和C3H8。BOC的NaLSX PPU吸附剂也获得同样的结果。
用TSA PPU进行试验的结果列于表1。
表I
TSA-PPU试验结果
原料压力=86-110psia原料温度=12-25℃
总床高=59英寸
原料杂质(浓度ppm) | 检测极限(ppm) | UPO APGII%除去 | BOCNaLSX%除去 | 本发明组合吸附剂%除去 |
水(饱和) | 1 | 100 | 100 | 100 |
CO2(400) | 0.001 | 100 | 100 | 100 |
N2O(0.3-0.35) | 0.005 | 35 | 45 | 100 |
CH4(2.2) | 0.01 | 0 | 0 | 0 |
C2H2(0.4-0.48) | 0.007 | 100 | 100 | 100 |
C2H4(1.4-1.6) | 0.01 | 35 | 40 | 100 |
C2H6(1.4) | 0.01 | 10 | 10 | 84 |
C3H6(0.4-0.48) | 0.01 | 100 | 100 | 100 |
C3H8(1.5-1.6) | 0.05 | 40 | 35 | 98 |
n-C4H10(1.6-1.8) | 0.02 | 100 | 100 | 100 |
*50%CaLSX和50%CaA。
由表I可知,50/50CaLSX/CaA组合物几乎可以除去所有的痕量杂质,包括N2O和烃。
虽用具体的实施方案描述了本发明,但本领域的技术人员可以理解本发明可有许多其它实施方案和变动。所附权利要求书和本发明一般应覆盖在本发明精神和范围之内的所有这样的实施方案和变动。
Claims (11)
1.一种通过变温吸附除去气流中杂质的方法,该方法依序包括下列步骤:使所述气流先通过能基本除去气流中水分的第一吸附剂层,然后通过能基本除去气流中CO2的第二吸附剂层,最后通过第三吸附剂层,所述第二吸附剂包括NaX、NaMSX或NaLSX型沸石,所述第三吸附剂包括包含除烃吸附剂和除氮氧化物的吸附剂的组合吸附剂。
2.如权利要求1所述的方法,其特征在于所述除烃吸附剂选自A型和X型沸石以及硅胶。
3.如权利要求1所述的方法,其特征在于所述除氮氧化物的吸附剂选自A型、X型和Y型沸石。
4.如权利要求3所述的方法,其特征在于所述除氮氧化物的吸附剂是CaLSX、CaMSX或CaX型沸石。
5.如权利要求4所述的方法,其特征在于所述CaLSX型沸石中,沸石相的硅与铝原子比值为0.95-1.05,阳离子组成包括约90-100%钙离子和约10-0%选自下列的阳离子:IA族离子、除钙外的IIA族离子、除金外的IB族离子、除汞外的IIb族离子、和镧系离子,以及它们的混合物。
6.如权利要求5所述的方法,其特征在于所述IA族离子选自锂、钠和钾。
7.如权利要求1所述的方法,其特征在于所述组合吸附剂的形式是成形的颗粒。
8.如权利要求7所述的方法,其特征在于所述组合吸附剂中还包含一种粘合剂。
9.如权利要求1所述的方法,其特征在于所述方法依序包括下列步骤:使所述气流先通过能基本除去气流中水分的第一吸附剂层,再通过第二吸附剂层,第二吸附剂包含除烃吸附剂和除氮氧化物吸附剂。
10.如权利要求1所述的方法,其特征在于所述方法包括使所述气流通过组合吸附剂,该组合吸附剂包含选自A型和X型沸石以及硅胶的第一吸附剂与选自A型、X型和Y型沸石的第二吸附剂。
11.如权利要求1所述的方法,其特征在于所述方法包括使所述气流通过包含CaA单元和CaX单元的沸石组合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/648,984 US6432171B1 (en) | 2000-08-28 | 2000-08-28 | Thermal swing adsorption process |
US09/648,984 | 2000-08-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1342508A true CN1342508A (zh) | 2002-04-03 |
Family
ID=24603015
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN01125282A Pending CN1342508A (zh) | 2000-08-28 | 2001-08-28 | 变温吸附法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US6432171B1 (zh) |
JP (1) | JP2002126436A (zh) |
CN (1) | CN1342508A (zh) |
AU (1) | AU775892B2 (zh) |
TW (1) | TW528613B (zh) |
ZA (1) | ZA200106649B (zh) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2800995B1 (fr) * | 1999-10-05 | 2002-01-04 | Ceca Sa | Adsorbants zeolitiques, leur procede d'obtention et leur utilisation pour la decarbonation de flux gazeux |
JP3545377B2 (ja) * | 2001-08-07 | 2004-07-21 | 日本酸素株式会社 | 空気液化分離用空気の精製装置および方法 |
US6719827B2 (en) * | 2002-03-01 | 2004-04-13 | Air Products And Chemicals, Inc. | Process for nitrous oxide removal |
US6638340B1 (en) * | 2002-03-27 | 2003-10-28 | Uop Llc | Composite adsorbents for air purification |
US6723155B2 (en) * | 2002-04-29 | 2004-04-20 | Air Products And Chemicals, Inc. | Purification of gas streams |
US20030221555A1 (en) * | 2002-05-31 | 2003-12-04 | Golden Timothy Christopher | Purification of gas streams using composite adsorbent |
AU2003248721A1 (en) | 2002-06-19 | 2004-01-06 | Georgia Tech Research Corporation | Adsorbents, methods of preparation, and methods of use thereof |
US6805728B2 (en) * | 2002-12-09 | 2004-10-19 | Advanced Technology Materials, Inc. | Method and apparatus for the abatement of toxic gas components from a semiconductor manufacturing process effluent stream |
US7364603B2 (en) * | 2002-12-09 | 2008-04-29 | Applied Materials, Inc. | Method and apparatus for the abatement of toxic gas components from a semiconductor manufacturing process effluent stream |
US6843830B2 (en) * | 2003-04-15 | 2005-01-18 | Advanced Technology Materials, Inc. | Abatement system targeting a by-pass effluent stream of a semiconductor process tool |
JP4512093B2 (ja) | 2004-03-30 | 2010-07-28 | 大陽日酸株式会社 | 空気液化分離装置の前処理精製装置、炭化水素吸着剤、及び原料空気の前処理方法 |
US20050252374A1 (en) * | 2004-05-12 | 2005-11-17 | Henzler Gregory W | Adsorbent bed and process for removal of propane from feed streams |
FR2877237B1 (fr) | 2004-10-29 | 2006-12-29 | Inst Francais Du Petrole | Procede de separation par adsorption selective sur un solide contenant une zeolithe de structure cristalline analogue a l'im-12. |
US7799117B1 (en) | 2006-09-27 | 2010-09-21 | Uop Llc | Gas treatment process by temperature swing adsorption |
CN102091502A (zh) * | 2009-12-10 | 2011-06-15 | 琳德股份公司 | 气体预纯化方法 |
FR2970184B1 (fr) * | 2011-01-07 | 2013-08-02 | Air Liquide | Composition zeolitique adaptee a l'epuration d'air |
CN103979692B (zh) * | 2014-05-19 | 2015-12-09 | 山东同源和环境工程有限公司 | 一种脱除焦化酚氰废水反渗透浓水中难降解有机物的工艺 |
CN104096472B (zh) * | 2014-06-27 | 2016-04-13 | 华中科技大学 | 一种二氧化碳/二氧化硫钙基吸收剂及其制备方法 |
FR3032130B1 (fr) * | 2015-02-02 | 2019-12-27 | Arkema France | Adsorbants zeolithiques de haute surface externe, leur procede de preparation et leurs utilisations |
Family Cites Families (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE43221C (de) | Firma Eisenwerke Gaggenau in Gaggenau | Zeitungs- und Rechnungshalter | ||
GB1051621A (zh) | ||||
US2882244A (en) | 1953-12-24 | 1959-04-14 | Union Carbide Corp | Molecular sieve adsorbents |
US2882243A (en) | 1953-12-24 | 1959-04-14 | Union Carbide Corp | Molecular sieve adsorbents |
US3012853A (en) | 1957-08-26 | 1961-12-12 | Union Carbide Corp | Crystalline zeolite |
US2996358A (en) | 1957-09-04 | 1961-08-15 | Union Carbide Corp | Crystalline zeolite f |
US3576901A (en) | 1968-09-20 | 1971-04-27 | Mobil Oil Corp | Method of modifying zeolite |
US3503901A (en) | 1969-01-13 | 1970-03-31 | Union Carbide Corp | Chemical reaction catalyst and its preparation |
DE2016838C3 (de) | 1970-04-09 | 1983-03-24 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von granulierten, abriebfesten, bindemittelfreien Molekularsiebzeolithen |
US3732326A (en) | 1970-05-19 | 1973-05-08 | Mobil Oil Corp | Selective sorption of less polar molecules with crystalline zeolites of high silica/alumina ratio |
US3723308A (en) | 1970-11-16 | 1973-03-27 | D Breck | Process for removal of ammonia from waste water streams |
US3885927A (en) | 1974-02-05 | 1975-05-27 | Union Carbide Corp | Process for removing carbon dioxide from gas streams |
US3985859A (en) | 1974-07-03 | 1976-10-12 | Ecodyne Corporation | Vacuum stripping of ammonia |
JPS51126987A (en) | 1975-04-30 | 1976-11-05 | Shokubai Kasei Kogyo Kk | Process for regenrating zeolite which has absorbed ammonical |
JPS538400A (en) | 1976-07-09 | 1978-01-25 | Mobil Oil | Process for preparing boujacite having low silica content |
DE2651485A1 (de) | 1976-11-11 | 1978-05-24 | Degussa | Kristallines zeolithpulver des typs a i |
US4173622A (en) | 1978-01-03 | 1979-11-06 | Fmc Corporation | Zeolite A crystals of uniformly small particle size and the manufacture thereof |
US4443422A (en) | 1978-12-20 | 1984-04-17 | J. M. Huber Corporation | Synthesis of zeolites of small and uniform size having a high magnesium exchange capacity |
US4556550A (en) | 1983-10-19 | 1985-12-03 | Union Carbide Corporation | Process for the preparation of high-level ion-exchanged forms of Zeolites F and Zeolite W |
US4606899A (en) | 1985-03-27 | 1986-08-19 | Air Products And Chemicals, Inc. | Synthesis of maximum aluminum X zeolites |
US4603040A (en) | 1985-03-27 | 1986-07-29 | Air Products And Chemicals, Inc. | Massive bodies of Maximum Aluminum X-type zeolite |
EP0196103A3 (en) | 1985-03-28 | 1988-07-13 | Air Products And Chemicals, Inc. | Maximum aluminum x-type zeolite adsorbents |
US4775396A (en) | 1987-11-05 | 1988-10-04 | Union Carbide Corporation | Selective adsorption of CO2 on zeolites |
DE3808742A1 (de) | 1988-03-16 | 1989-09-28 | Kernforschungsz Karlsruhe | Verfahren zur entfernung von iod und iodverbindungen aus gasen und daempfen mit silberhaltigem zeolith x |
US5075084A (en) | 1989-01-21 | 1991-12-24 | Bayer Aktiengesellschaft | Process for the removal of iodine and iodine compounds from hydrogen-containing gases and vapors |
US5174979A (en) | 1989-10-06 | 1992-12-29 | Uop | Mixed ion-exchanged zeolites and processes for the use thereof in gas separations |
US5451248A (en) * | 1990-07-19 | 1995-09-19 | The Boc Group Plc | Storage and transportation of goods under controlled atmospheres |
FR2669242B1 (fr) | 1990-11-16 | 1994-09-02 | Ceca Sa | Adsorbants industriels a base de zeolites x a basse teneur en silice pour la separation non cryogenique des gaz de l'air et leur procede de preparation. |
US5203887A (en) * | 1991-12-11 | 1993-04-20 | Praxair Technology, Inc. | Adsorbent beds for pressure swing adsorption operations |
US5152813A (en) | 1991-12-20 | 1992-10-06 | Air Products And Chemicals, Inc. | Nitrogen adsorption with a Ca and/or Sr exchanged lithium X-zeolite |
US6113671A (en) * | 1992-04-06 | 2000-09-05 | Garrett; Michael E. | Controlling atmospheres in containers |
US5354360A (en) | 1993-01-11 | 1994-10-11 | Air Products And Chemicals, Inc. | Magnesium A-zeolite for nitrogen adsorption |
US5464467A (en) | 1994-02-14 | 1995-11-07 | The Boc Group, Inc. | Adsorptive separation of nitrogen from other gases |
CA2148773C (en) | 1994-05-12 | 1999-08-17 | Scott Jeffrey Weigel | Gas separation with lithium-containing zsm-2 metallosilicates |
US5567407A (en) | 1994-05-12 | 1996-10-22 | Coe; Charles G. | Li-exchanged low silica EMT-containing metallosilicates |
US5531808A (en) | 1994-12-23 | 1996-07-02 | The Boc Group, Inc. | Removal of carbon dioxide from gas streams |
US5560763A (en) * | 1995-05-24 | 1996-10-01 | The Boc Group, Inc. | Integrated air separation process |
US5656064A (en) | 1995-10-04 | 1997-08-12 | Air Products And Chemicals, Inc. | Base treated alumina in pressure swing adsorption |
IT1284078B1 (it) | 1996-06-27 | 1998-05-08 | Condea Augusta Spa | Materiale cristallino microporoso, procedimento per la preparazione e uso in composizioni detergenti |
DE19647290A1 (de) | 1996-11-15 | 1998-05-28 | Bayer Ag | Verfahren zur Herstellung eines mit Lithium-Ionen ausgetauschten, bindemittelfreien Zeolithgranulats und dessen Verwendung zur adsorptiven Lufttrennung |
US6027548A (en) * | 1996-12-12 | 2000-02-22 | Praxair Technology, Inc. | PSA apparatus and process using adsorbent mixtures |
US5769928A (en) * | 1996-12-12 | 1998-06-23 | Praxair Technology, Inc. | PSA gas purifier and purification process |
US5916836A (en) | 1996-12-27 | 1999-06-29 | Tricat Management Gmbh | Method of manufacture of molecular sieves |
US5779767A (en) | 1997-03-07 | 1998-07-14 | Air Products And Chemicals, Inc. | Use of zeolites and alumina in adsorption processes |
FR2766475B1 (fr) | 1997-07-22 | 1999-09-03 | Ceca Sa | Procede pour l'obtention de corps granulaires en zeolite lsx a faible taux de liant inerte |
US5882625A (en) | 1997-08-08 | 1999-03-16 | Air Products And Chemicals, Inc. | Faujasite adsorbents with nonuniform Al distribution |
US6238460B1 (en) * | 1997-09-26 | 2001-05-29 | The Boc Group, Inc. | Air purification process |
US5906675A (en) * | 1997-09-30 | 1999-05-25 | The Boc Group, Inc. | Air purification process |
US5914455A (en) * | 1997-09-30 | 1999-06-22 | The Boc Group, Inc. | Air purification process |
US6099619A (en) * | 1997-10-09 | 2000-08-08 | Uop Llc | Purification of carbon dioxide |
US6074459A (en) * | 1998-01-05 | 2000-06-13 | Uop Llc | Ultra pure gases: removal of halocarbons, fluorocarbons, and sulfur compounds from gas streams |
FR2773499B1 (fr) * | 1998-01-14 | 2000-02-11 | Air Liquide | Procede de purification par adsorption de l'air avant distillation cryogenique |
CA2264418C (en) * | 1998-03-12 | 2002-05-14 | Adeola Florence Ojo | Removal of carbon dioxide from gas streams |
US6024781A (en) * | 1998-04-17 | 2000-02-15 | The Boc Group, Inc. | Separation of carbon dioxide and hydrocarbons |
US6106593A (en) | 1998-10-08 | 2000-08-22 | Air Products And Chemicals, Inc. | Purification of air |
FR2784599B1 (fr) * | 1998-10-20 | 2000-12-08 | Air Liquide | Procede de purification d'un flux gazeux en ses impuretes n2o |
US6143057A (en) | 1999-04-23 | 2000-11-07 | The Boc Group, Inc. | Adsorbents and adsorptive separation process |
-
2000
- 2000-08-28 US US09/648,984 patent/US6432171B1/en not_active Expired - Fee Related
-
2001
- 2001-08-03 TW TW090119047A patent/TW528613B/zh not_active IP Right Cessation
- 2001-08-13 ZA ZA200106649A patent/ZA200106649B/xx unknown
- 2001-08-21 AU AU63564/01A patent/AU775892B2/en not_active Ceased
- 2001-08-27 JP JP2001255728A patent/JP2002126436A/ja active Pending
- 2001-08-28 CN CN01125282A patent/CN1342508A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
TW528613B (en) | 2003-04-21 |
AU6356401A (en) | 2002-03-07 |
ZA200106649B (en) | 2002-02-13 |
AU775892B2 (en) | 2004-08-19 |
US6432171B1 (en) | 2002-08-13 |
JP2002126436A (ja) | 2002-05-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1342508A (zh) | 变温吸附法 | |
US6270557B1 (en) | Process for purifying air by adsorption before cryogenic distillation | |
EP0862936B1 (en) | The use of zeolites and alumina in adsorption processes | |
TW455505B (en) | Process and apparatus for removing water, carbon dioxide and nitrous oxide from a feed air stream, process and apparatus for air separation | |
EP1697042B1 (en) | Method of purifying a gas stream contaminated by co 2 and one or more hydrocarbons and/or nitrogen oxides by adsorption on an aggregated zeolitic adsorbent | |
AU773362B2 (en) | Temperature swing adsorption process | |
US6273939B1 (en) | Process for purifying a gas stream of its N2O impurities | |
US6358302B1 (en) | Purification of gases using multi-composite adsorbent | |
CN1123193A (zh) | 通过吸附膜进行氢气的回收 | |
CN1131053A (zh) | 气流中二氧化碳的去除 | |
US6658894B2 (en) | Process and adsorbent for the recovery of krypton and xenon from a gas or liquid stream | |
KR100501423B1 (ko) | 기체 또는 액체 스트림으로부터 크립톤 및 크세논을 회수하기 위한 공정 및 흡착제 | |
US6391092B1 (en) | Thermal swing adsorption process for the removal of dinitrogen oxide, hydrocarbons and other trace impurities from air | |
CN1031978C (zh) | 空气分离前的预净化 | |
CN1938081B (zh) | 空气液化分离装置的预处理精制装置、烃吸附剂、及原料空气的预处理方法 | |
EP1184067B1 (en) | Process for adsorptive purification of air | |
CN1406661A (zh) | 通过变压吸附的气体纯化 | |
CN1498669A (zh) | 从原料气流中吸附一氧化二氮的方法 | |
CN1319912C (zh) | 苯二取代物异构体在疏水硅沸石上复相吸附分离方法 | |
JP2005013832A (ja) | 空気液化分離装置用吸着剤及びそれを用いた空気の精製方法 | |
DE DK et al. | Verfahren zur adsorptiven Reinigung von Luft Procédé de purification d’air par adsorption |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |