Technical Progress

1. Achievements between 9 November 1999 (starting date of the project) and 30 April 2002

• Physical-chemical properties of Hungarian zeolites were collected and determined
• Based on the properties two Hungarian natural zeolites were selected, the clinoptilolite contents of which varied between 50 and 65 %.
• It was found that rocks of highest zeolite content are quarried in the area of three Hungarian villages: Mád, Rátka and Bodrogkeresztúr. Clinoptilolite is mined mainly in the district of the first two villages while mordenite rich tuffs close to Bodrogkeresztúr.

  Two companies have mining operations in the above zeolite fields. They are:

  1. Zeotrade, Ltd., which produces between 20 - 25 thousand metric tons of clinoptilolite and mordenite containing rocks of different grain sizes annually.
     
  2. Geoproduct, Ltd. whichquarries clinoptilolite containing rocks in the villages of Rátka and Mád-Suba and mordenite in Bodrogkeresztúr.
     
• Natural zeolites of Zeotrade and Geoproduct companies were converted to H- and NH4-forms and modified with different cation active polymers (CAP) containing quaternary ammonium or amino groups
  
• Results of total organic carbon (TOC) measurements, Fourier transform infrared (IR) and microscopic examinations, as well as continuous biological degradability experiments showed that:
  • 1 - 4 mg of CAP expressed in TOC could be chemically attached to 1 g zeolite of H-form, natural zeolites could be modified using an acidic solution of CAP in a one step reaction.
  • there was a momentary interaction between modified zeolite particles and CAP molecules
  • positive effects of modified zeolite on (1) biological degradability of organic compounds and (2) sludge volume index (SVI) appeared instantly,
  • the interaction between zeolite particles and CAP molecules was stronger than a physical adsorption, i.e. the process of modification created chemical bonds
• The best biological degradability results belonged to natural zeolite (1) originating from Rátka, (2) pre-treated with aqueous HCl solution, (3) modified with polyacrylamine (4) of 50,000 molecule weight
• The relationship between the CAP content of modified zeolite (MZ) and the quality of treated water were determined.
• Three different types of zeolite modification methods were developed. They were:
  • Modification applying high water content
  • Modification applying low water content
  • “Dry” modification
• Industrial for the production of larger quantity of modified zeolite (MZ) using the “dry” method were developed
• Biodegradability tests of 9 end-users’ wastewater using modified zeolite were accomplished
• Pilot and full-scale experiments at wastewater treatment plants (WTP) of Szob as well as Pilisszentkereszt, Tét and Kunsziget were prepared, run and completed
• Patent specification of the technology of zeolite modification with cation active polymers (CAP) and the application of modified zeolite in wastewater treatment has been on the file with the Hungarian Patent Office and the international PCT Office in Brussels since 28 November 2000 and 27 November 2001, respectively.

At the request of Dr. Wispeleare, the NATO SfP Programme Director and Dr. Raynoud, the NATO Adviser, the project co-directors prepared a revised project plan in January 2002.

2. Achievements between 30 April and 31 October 2002

• Running and completion of industrial-scale experiments at the WTPs of Dorog, Mosonmagyaróvár and Dunakeszi
• Preparation of industrial-scale experiments at the WTPs of Dombóvár and Nagycenk
• Data evaluation of the industria-scale experiments carried out at the WTPs of Szob and Dunakeszi
• Development of an innovative equipment for the modification of large quantity of modified zeolite
• Industrial-scale production of modified zeolite
• Presentation of the paper titled “Improvement of the Biological Degradability of Wastewaters Using Modified Zeolites” in the Zeolite 02, 6th International Conference on the Occurrence Properties and Utilization of Natural Zeolites held in Greece in June 2002.