Digitala Vetenskapliga Arkivet

Endre søk
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf
Study of the Synthesis of ZSM-5 from Inexpensive Raw Materials
Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.ORCID-id: 0000-0002-8637-0461
2014 (engelsk)Licentiatavhandling, med artikler (Annet vitenskapelig)
Abstract [en]

ZSM-5 is an aluminosilicate with high silica ratio with suitable properties for catalysis, ion exchange, adsorption and membrane applications. ZSM-5 is usually produced industrially from concentrated systems in which there is formation of an amorphous gel phase. Typical syntheses of ZSM-5 require sources of silicon and aluminium, a mineralizer and an organic molecule as so-called templating agent. The silicon and aluminum sources widely used for the synthesis are pure reagent chemicals and in particular quaternary ammonium compounds like tetrapropyl ammonium hydroxides (TPA-OH), are employed as templating agents. Unfortunately, these compounds are rather expensive. Demand for inexpensive sources of aluminosilicates for the synthesis of ZSM-5 has increased during the last two decades. Natural raw materials such as kaolin clay and diatomaceous earth (diatomite) are two potential inexpensive sources of silica and alumina. Moreover, the molecule n-butylamine (NBA) has been reported as a low-cost templating agent to replace the quaternary ammonium compounds. The aim of this work was to show for the first time that leached metakaolinite or diatomite in combination with sodium hydroxide and n-butylamine could be used as inexpensive raw materials for the synthesis of ZSM-5 without using an additional source of silica. After synthesis optimization, both sources of aluminosilicate were found to behave differently during the course of synthesis and led to slightly different products. The chemical composition of the raw materials and the products were determined using inductively coupled plasma-sector field mass spectrometry (ICP-SFMS). Crystallinity was examined by X-ray diffractometry (XRD), the morphology was studied by extreme-high-resolution scanning electron microscopy (XHR-SEM) and the specific surface area was estimated from nitrogen adsorption data by the BET method. The chemical composition of individual crystals was determined by energy dispersive spectrometry (EDS). Dealumination of the raw materials by acid leaching made it possible to reach appropriate SiO2/Al2O3 ratios and reduced the amount of impurities. The final ZSM-5 products had a SiO2/Al2O3 ratio in the range 20 – 40. The use of leached diatomite allowed reaching higher yield of ZSM-5 crystals within comparable synthesis times. However, low amounts of mordenite were formed, which was related to the high calcium content of diatomite. Another considerable advantage of diatomite over kaolin is that diatomite does not require heat treatment at high temperature to convert the kaolin to reactive metakaolin. Further characterization of the system by XHR-SEM and EDS at low voltage was carried out in order to understand the nucleation and early growth of the ZSM-5 zeolite crystals. The observations with unprecedented detail strongly suggest that nucleation and the succeeding growth occurs on the gel surface. The growth rates in the various crystallographic directions already at an early stage are such that the shape of the growing crystals resembles that of the final crystals. However, as the early growth is interface mediated, the growth rate along the gel particles is high and the gel particles will become partially embedded inside the growing crystals at an early stage. The Si and Al nutrients are probably transported along the solid/liquid interface and possibly through the liquid in the form of nanoparticles detaching from the gel. The organic template was initially contained in the liquid. However, it remains unclear at which stage the template becomes incorporated in the solid material. EDS at low voltage was also used to gain compositional information about the sodium/calcium ion exchanged products and extraneous phases when kaolin and Bolivian montmorillonite clay were used for the synthesis of zeolite A by alkali fusion. In order to evaluate the cation exchange capacity (CEC) of the synthesized zeolite, ICP-SFMS and EDS were compared. The EDS method used in this work resulted in (Na,Ca)/Al ratios in equivalent moles very close to 1.0 as expected and was therefore found more reliable than ICP-SFMS to measure cation exchange capacity for zeolite A. To summarize, the present work shows that it was possible to synthesize well-crystallized ZSM-5 zeolite from inexpensive raw materials such as leached metakaolin or leached diatomite, sodium hydroxide and n-butyl amine. Furthermore, the crystallization mechanism evidenced in this system might be more general and also apply for other concentrated systems, e.g. those using TPA as structure-directing. Finally, this work displays that EDS at low voltage can provide valuable local compositional information in the field of zeolite synthesis.

sted, utgiver, år, opplag, sider
Luleå: Luleå tekniska universitet, 2014.
Serie
Licentiate thesis / Luleå University of Technology, ISSN 1402-1757
HSV kategori
Forskningsprogram
Kemisk teknologi
Identifikatorer
URN: urn:nbn:se:ltu:diva-16976Lokal ID: 0f9e91ac-8b6a-4d54-94f4-316093ee211aISBN: 978-91-7439-964-6 (tryckt)ISBN: 978-91-7439-965-3 (digital)OAI: oai:DiVA.org:ltu-16976DiVA, id: diva2:989968
Presentation
2014-06-19, C305, Luleå tekniska universitet, Luleå, 14:00
Opponent
Tilgjengelig fra: 2016-09-29 Laget: 2016-09-29 Sist oppdatert: 2023-11-29bibliografisk kontrollert

Open Access i DiVA

fulltekst(6392 kB)929 nedlastinger
Filinformasjon
Fil FULLTEXT01.pdfFilstørrelse 6392 kBChecksum SHA-512
8a9444118a9553463903d97322e49f3e80b36a59b0e46eb2fad1bfa65a1fe43eccd6caf258789957a6417b603e79325133fde1f0f4bdb2a0bc57b93a60589aa6
Type fulltextMimetype application/pdf

Søk i DiVA

Av forfatter/redaktør
Aguilar, Wilson
Av organisasjonen

Søk utenfor DiVA

GoogleGoogle Scholar
Totalt: 937 nedlastinger
Antall nedlastinger er summen av alle nedlastinger av alle fulltekster. Det kan for eksempel være tidligere versjoner som er ikke lenger tilgjengelige

isbn
urn-nbn

Altmetric

isbn
urn-nbn
Totalt: 1814 treff
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf