PROJECT PLAN

Title of the Project: Determining the most suitable zeolite type for toilet types.

1. Aim and Extend: Choosing the right zeolite which can reduce the bad smell, humidity and dirtiness by making some changes in the structure of the tiles which are dirty, wet and smell bad.

2. Method and Equipment: Making a large scan of literature of zeolite, halloysite, diatomite, determining the areas of usage, determining the negative conditions of the toilets, taking samples of zeolite, halloysite and diamite, calculating the carbon dioxide absorbent with the help of QMC machine, comparing the results of experiment and determining the most suitable zeolite type.

3. Sources:

1-Barakat M.A, New trends in removing heavy metals from industrial wastewater: a review, Arabian Journal of Chemistry, in Press (2010)

2-Bogdanchikova N., Simakov A., Smolentseva E., Pestryakov A., Farias M.H., Diaz J.A., Tompos A., Avalos M., “Stabilization of catalytically active gold species in Femodified zeolites” Appl. Surf. Sci. 254 (2008) 4075–4083

3-Charkhia A., Kazemeinia M., Ahmadib S.J., Kazemian H., “Fabrication of granulated NaY zeolite nanoparticles using a new method and study the adsorption properties” Powder Technol. 231 (2012) 1–6.

4-Cincotti, A., Lai, N., Orru, R., Cao, G., “Sardinian natural clinoptilolites for heavy metals and ammonium removal: experimental and modeling”, Chemical Engineering Journal, 84: 275-282 (2001).

5-Devlet Planlama Teşkilatı (DPT), Madencilik Özel İhtisas Komisyonu Endüstriyel Hammaddeler Alt Komisyonu-Diğer Endüstri Mineralleri Çalışma Grubu Raporu, http://ekutup.dpt.gov.tr/madencil/sanayiha/oik480c1.pdf (1996).

6-DPT, 7. Beş Yıllık Kalkınma Planı, “Asbest, Bentonit, Fluorit, Diatomit (Kizelgur), Kalsit, Kıymetli ve Yarı-Kıymetli Taşlar (Süs Taşları), Lityum, Titanyum, Zirkonyum ve Hafniyum, Madencilik Özel İhtisas Komisyonu Raporu”, Cilt-2, DPT:2421-ÖİK: 480, Ankara, (1996).

7-Fathizadeh M., Aroujaliana A., Raisi A., “Effect of added NaX nano-zeolite into polyamide as a top thin layer of membrane on water flux and salt rejection in a reverse

8-Gao Y., Chen M., Zhang T., Zheng X., “A novel method for the growth of ZSM-5 zeolite membrane on the surface of stainless steel” Mater. Lett. 65 (2011) 2789–2792

9-Jiang N., Yang G., Zhang X., Wang L., Shi Ch., Tsubaki N., “A novel silicalite-1 zeolite shell encapsulated iron-based catalyst for controlling synthesis of light alkenes from syngas” Catal. Commun. 12 (2011) 951–954

10-Kurkina E.S., Tolstunova E.D., “The general mathematical model of CO oxidation reaction over Pd-zeolite catalyst” Appl. Surf. Sci. 182 (2001) 77–90

11-Malliou, E., Malamis, M., Sakellarides, P.O., “Lead and cadmium removal by ion exchange”, Water Science and Technology, 25(1): 133-138 (1992) .

12-ÖZGE C, Devrim B, Semra Ü, “Batch and column studies on heavy metal removal using a local zeolitic tuff”, Desalination 259 (2010) 17-21

13-Sue-aok N., Srithanratana T., Rangsriwatananon K., Hengrasmee S., “Study of ethylene adsorption on zeolite NaY modified with group I metal ions” Appl. Surf. Sci. 256 (2010) 3997–4002

14-Sun H., Lu L., Chen X., Jiang Z., “Surface-modified zeolite-filled chitosan membranes for pervaporation dehydration of ethanol”, Appl. Surf. Sci. 254 (2008) 5367–5374

15-Wang Y., Lei Z., Chen B., Guo Q., Liu N., “Adsorption of NO and N2O on Fe-BEA and H-BEA zeolites” Appl. Surf. Sci. 256 (2010) 4042–4047.

16-Zamzow M.J., Eichbaum B.R., Sandgren K.R., Shanks D.E., Removal of heavy metals and other cations from waste water using Zeolites Separation Science and Technology 25 (1990) 1555–1569.

17-Zamzow, M.J., Eichbaum, B.R., Sandgren, K.R., Shanks, D.E, “Removal of heavy metals and other cations from wastewater using zeolites”, Separation Science and Technology, 25(13-15): 1555-1569 (1990).

18-http://www.reade.com/products/12-minerals-clays/127-endellite-hydratedhalloysite-metahalloysite-halloysite-nano-clay-halloysite-nano-clayal2si2o5oh42h2osio2-hydrated-halloysite

4. Table of Job-Time:

Definition of the Job

Months

  JULY AUGUST SEPTEMBER OCTOBER NOVEMBER DECEMBER JANUARY

Literature Scanning X X X        

Collecting Data X X X X    

Experiment Phase

 

  X X X X  

Project Report         X X

Title of the Project: Determining the most suitable zeolite type for toilet tiles

Summary:

Zeolite , halloysite and diatomites are known for their characteristics of hallow structure, absorbent, clay mines. Besides, they are used very commonly in many construction materials fort heir being insulation of heat and electricity.

Those mines which are found in our country very abundantly used to have very limited field of usage until a few years ago and a large quantity of them also used to be sent abroad in a very low price.

We thought that using those mines, which are gas absorbent, heat insulator, anti-lime structured, and in the structure of hydrophilic, will bring great benefits as toilet floors are generally wet and dirty in addition to their bad smell which is produced with the mixture of ammoniac gas and air.

Thus, in order to choose the most suitable of this material, we have calculated the gas absorbent ratio with the help of QMC machine. We witnessed that zeolite kept carbon dioxide with the ratio of 20 %, which is pretty high.

Zeolite can keep not only carbon dioxide but also many gases and organic compound. At the same time, it has got the quality of solving the problem of flor wetness thanks to its being hydrophilic. Moreover, we saw that zeolite is not only a material of one-use (disposable) but renewable with the little loss as its pore can be opened completely.

Key Words: Zeolite, Halloysite, Diatomite, Bad Smell, Gas Absorbent

PROJECT REPORT

Determining the most suitable Zeolite type for toilet tiles

Contents:

1. INTRODUCTION1.1 ZEOLITE

1.1.1 AREAS OF USAGE OF ZEOLITE1.1.2 ZEOLITE SOURCES IN OUR COUNTRY

1.2. DIATOMITE

1.2.1 AREAS OF USAGE OF DIATOMITE

1.2.2. DIATOMITE SOURCES IN OUR COUNTRY

1.3 HALLOYSITE

1.3.1 AREAS OF USAGE OF HALLOYSITE

1.3.2 HALLOYSITE SOURCES IN OUR COUNTRY

2. MATERIAL AND METHOD

3. FINDINGS

3.1. DATA OF ZEOLITE

3.2 DATA OF HALLOYSITE

3.3 DATA OF DIATOMITE

4. RESULT AND ARGUMENT

5. SUGGESTIONS

6. BIBLIOGRAPHY

1. Introduction1.1 Zeolite

Zeolite, whizh are composed of many oxygen atoms[SiO4] and [A1O4] combining with tetrahedron in an network, is aluminosilicate. Structurally, they are made up of A13+ ions with negative charged state and Si4+ ions. These negative charges keeps alkali and alkaline-earth ions in balance.

Because of their ion change skills and hydrophilic characteristics, zeolite is used commonly for keeping away heavy metals from aqueous solution. In this way, many toxic heavy metals have been separated thank to zeolite.

The canals and blanks in the zelite structure are filled with water molecules and cations. Thanks to the negative charged ions, not only heavy metals but aşso organic compounds fill into the zeolite’s por structure. For that reason, it is not false to say that zeolite is used to clean dirtiness in many fields.

In recent years, zeolite, which has been synthesized in the nanometer scale, has attacted much attention since they are more useful and low-cost when compared with the equals in micron size. Zeolite is also used in many constitution structure because of its low densitiy and cost.

Naturally, zeolite group has more than 40 types. But of these types, since the chabazite, clinoptilotile, erinorite, phillipsite and analcime have the enough purity and quality, they are the ones used commonly.

Diagram1.1 The skeleton structure of Zeolite

1.1.1 The Areas of Usage of Zeolite

Below is the known and mostly used areas of Zeolite;

Cation Exchange Absorption and molecular Sieve Dehydration and rehydration Biological Reactivity Catalyst Zeolites

It is also used very commonly in medical application, consumers’ good and environmental applications. Some examples are;

Organic compound repellent Control of air-pollution Radioactive Substance repellent Heavy Metal Repellent Ammonium repellent Aquarium Stones

1.1.2 The Zeolite Sources im our Country

The Zeolites on the earth are found in Japan, America, Russia, East and West Europe and many other places. On the other hand, Turkey also has vast zeolite sources particularly in Central and West Anatolia. In the Western Anatolia Region, which can be considered rich in source of zeolite, in Balıkesir-Bigadiç and Manisa –Gördes, it is estimated that there are 500 million tons and 20 million tons of clinoptilotiles respectively. The total zeolite reserve of the country is estimated to be 50 billion tons.

Diagram 1.1 The Zeolite type and areas they are found in our country.

Zeolite Type The place it is foundAnalcime Bahçelik, Gölpazarı, Göynük, Ankara-Polatlı,

Mülk, Oğlakçı, Ayaş, Nallıhan, Çayırhan, Beypazarı, Mihalıççık

Clitonotilotil Kalecik, Şandır, Şabanözü, Hasayaz, Balıkesir-Bigadiç, Manisa-Gördes, emet, Yoncaağaç, Kütahya-Şaphane, Gediz, Hisarcık, İzmir-Urla, Amasya-Doğantepe

Chabazite and erionite Kayseri-Tuzköy

1.1. DiatomiteIt can be said that diatomites are sedimentary rocks which are formed of fossils of monocellular water palntsrhar include SiO2 (Sillissium Dioxide) in high levels. The large surface area of diatomites have given them the important characteristics such as high absorbing power, high permeability, small particle size, chemical stability, low heat conductivity, low mass density, having the quality of good grindabilty. Diatomites can absorb water three times more of their weight. Diatomites’ resistivity to electricity and high temperature and also their moving skeleton thanks to their porous structure have made them unique for adding into many construction material.

Diatomite is the mineral whose sources have been decreasing very fast in Europe and which can be found in our country plentifully. For that reason, their exportation and usage have great significance. Searching and examining the reserve of our country will play a key role in marketing. According to a study, even adding a very small amount of diatomite will provide pressure durability in a very large ratio. Besides, thanks to their characteristics of heat insulation, they have been solution to the problem of freezing and thawing.

1.1.1 The Areas of Usage of Diatomite

Diatomite is used in many processes in industry and their consumption areas can be listed as;

Material of filtration Material of heat, acoustic, electric insulation Catalyst carrier As a source of silica oil in production of many chemicals In the production of light construction material and production of refractory Backfill material Absorbent material Surface cleaner Production material of refractory As a carrier and preventive of earthling in the fertilizers

1.2.2 Diatomite Sources in our country

Afyon, Ankara, Aydın, Balıkesir, Bingöl, Çanakkale, Çankırı, Denizli, Eskişehir, Kayseri, Konya, Kütahya, Niğde, Sivas and are the main cities where there are diatomite reserves. Kayseri-Hırka is the biggest mineral deposit with 50 million tonnes. The total mineral deposit of Çankırı is approximately 25 million tonnes. It is also expressed that Erzurum-Tortum diatomite reserves are in good quality and its reserves could reach up to 50 million tonnes.

Diagram 1.2. Diatomite reserves in our country

1.2. HalloysiteThe halloysite is bilayering clay. The thickness of halloysite may reach up to 1.0nm by water’s entering into silicium layers and since these bonds are not strong, they may release water easily. The thickness of halloysite becomes back to 0.7 nm after releasing the water.

The halloysite is also known for their large surface area and adsoptivity like other zeolite types. The halloysite is known as nano type and it can be said to have been used instead of carbon nano tupes for their low-cost. The molecular structure of halloysite is Al2Si2O5(OH)4.nH2O

The halloysite, different from zeolite and diatomite, undergoes a change of no return with heat. And even if it means it has got smaller pores than the other types, we can still say it is in the state of hydrophilic since it contains less hydroxyl.

Diagram 1.3 Halloysite images. a) Raw Halloysite b) Grinded Halloysite c) TEM, d) SEM images and e) Halloysite’s Crystal Structure

Parameter Value/RangeLenght 0,2-2 umExternal Radius 40-70 nmInner Diameter 10-40 nmLenght-to-diameter ratio 10-50Elastic Modulus 140 GPa (230-340 GPa)Average Particle Size in Aqueous Solution 143 nmThe particle Size Range in Aqueous Solution 50-400 nmDensity 2.14-2,59 g/cm3Pore Diameter 79,7-100,2 ATemperature of Structural Water Releasing 400-600 C

1.3.2. The Areas of Usage of Halloysite

There are many areas of usage of the halloysite. Some important ones are listed below:1. In the tiles with high-quality2. On the glassy, bright surfaces3. In the paintings of octahedral and tetrahedral surfaces4. In the coating and Construction materials5. In agricultural Practises and plastics6. As a polymer booster with high performance7. In the process of releasing chemical and biological agents under control

1.3.2 Hallysite Sources in our Country

Turkey has got a considerable amount of hallosite sources. In North Anatolia, in Turkey, especially in Çanakkale and Balıkesir cities, there are halloysite reserves and 5000 tonnes of hallosite are unearthed and much of it has been exported. The hallosite extracted in Turkey has got high ratio of purity which makes Turkish halloysite much superior to the others extracted in the world.

Material and Method

Our aim was to find out which of these three types are the most keeping and compare their ability to keep carbon dioxide. First the samples were obtained and brought. For all of them, a common point was determined as 0.5 gr article and 50 ml alcohol. The samples were measured with precision scale and placed into glass jars. The jars were named as D, H, Z (diatomite, halloysite, zeolite)

Diagram 2.1 Precision Scale which can measure between 0 to 250 mg.

Diagram 2.2 The samples which were not mixed with 0,5 gram alcohol

Next, The samples were mixed up with 50ml alcohol with the help of precision drip cap since they are fast volatile substance and the jars were stirred in certain intervals.

Diagram 2.3 The samples which are mixed with alcohol.

After having solved adequately, the samples which were obtained with the help of precision drip cap were dripped onto QCM, a device called Quarts Crystal Microbalance, both sides of which are made up of golden plates. The frequency of device measured before the process. Later, they were left to dry in order to let the alcohol volatile (Duration of Drying is 90 minutes)

Diagram 2.4 QCMs which are left to dry

After approximately 90 minutes when the alcohol disappeared, the samples stuck on the golden plate. Then, the samples were placed to the QCM machine and the humidity and little alcohol kept by zeolite, diatomite and halloysite were cleaned with nitrogen as it is a passive gas. The new frequency was measured and noted down.

Diagram 2.5 The computer on which the QCM frequency were taken

Diagram 2.6 The nitrogen gas with which the samples were cleaned

Later, the period times and repetition numbers which have been specified before were entered to the computer( A period of 200 seconds and four periods). The intended gas was released to the reservoir. (Carbon Dioxide, Carbon Monoxide, Ammoniac). During the 200-second-period, zeolite, diatomite and halloysite kept the gas as much as they could and since their mass has increased by keeping the gas, the frequency has decreased. These decreases have been calculated and denominated as ‘ng’ 1 Hz=1.34 ng. In this way we were able to see how much carbon dioxide could a substance absorb and keep. Later on, we cleaned the gas kept in the samples by giving nitrogen gas in the specified periods of 200 seconds. When this period was over, carbon dioxide was released to the setting again. This process has been repeated four times and the results were noted down to the computer.

Diagram2.7- The device that QCM was placed on and released gas.

The tube device which makes the CO2 release

2. FINDINGS3.1 Zeolite DataFrequency change graphic of 562 ng Zeolite in 200 seconds. The first period should not be taken into consideration as the humidity was cleaned. That meant 107.2 ng CO2. Consequently, 562 ng zeolite kept 107.2 ng CO2, which means it kept 20% , that is, a very high value.Chart 3.1- Frequency/Time graphic of Zeolite

3.2.Halloysite DataBelow the graphic of 5968 ng halloysite’s change. The first period shouldn’t be taken into account as the humidity was cleaned. Hallysite went through a change of approximately 251 Hz in every period, which means 288 ng CO2. That is, 5698 ng halloysite kept 288 ng CO2, which means it has got %5 keeping ratio.

Chart 3.2. The frequency/Time Graphic of halloysite

3.3. Diatomite Data

Here is the change graphic of 1433,8 ng diatomite. First period shouldn’t be taken into account as humidity cleaning. Diatomite went through a change of 91Hz in every period, which means it keeps 121 ng CO2 that is, 8% of ratio.

Chart 3.3 The frequency/Time Graphic of diatomite

Table 3.1. Comparison of Zeolite, Halloysite and Diatomite

Material Frequency Value at the beginning

Frequency Value After Carbon Dioxide Release

Frequency Gap

Amount of Sample

Amount of kept Carbon Dioxide

Ratio of Carbon Dioxide Keeping

Zeolite 7.980.384 Hz

7.979.955 Hz 429 Hz 562,8 ng 107,2ng %20

Diatomite 7.997.098 Hz

7.996.028 Hz 1.070 Hz 1433,8 ng 121ng %8

Halloysite 7.978.454 Hz

7.974.000 Hz 4.454 Hz 5968 ng 288ng %5

4.Result and ArgumentConsequently, although its low density, zeolite has showed the most keeping characteristic thanks to its large surface area. On the other hand, its low cost, heat and electricity insulation make it unique for using in the toilet tiles. The toilet will be drier, and far from bad smell as zeolite will prevent bad smell(NH3), humidity, wetness, and dirtiness (thanks to its characteristic of keeping the organic compounds). What’s more, zeolite will perform this proceses again and again by opening its pores by passive gases.

Nitrogen is not the only gas that can be used to empty the pores of zeolite as done in the experiment. Because all the passive gases can break the bonds, zeolite can be ready to reuse in many ways.

There will not be problem of dirtiness as zeolite is passive in taking part reaction.

Zeolite will give to the floor flexibility and durability; therefore it will be difficult to break the tiles in the structure of porcelain. Thanks to its heat and electric insulation trait, it will prevent possible dangerous events and will keep the heat inside.

5. SuggestionsAs it can be seen zeolite is already being used in many fields. However, it is not demanded much in our country although it is very functional and can be found abundantly. It will be useful for the economy of our country to create an exportation market after searching zeolite sources and determining their traits.Besides, zeolite can also be used in different fields thanks to its trait of keeping many gases and heavy materials. We can enrich this usage fields.Changing the gases in experiments will enable us to find out other usage fields of zeolite.

BIBLIOGRAPHY

1-Barakat M.A, New trends in removing heavy metals from industrial wastewater: a review, Arabian Journal of Chemistry, in Press (2010)

2-Bogdanchikova N., Simakov A., Smolentseva E., Pestryakov A., Farias M.H., Diaz J.A., Tompos A., Avalos M., “Stabilization of catalytically active gold species in Femodified zeolites” Appl. Surf. Sci. 254 (2008) 4075–4083

3-Charkhia A., Kazemeinia M., Ahmadib S.J., Kazemian H., “Fabrication of granulated NaY zeolite nanoparticles using a new method and study the adsorption properties” Powder Technol. 231 (2012) 1–6.

4-Cincotti, A., Lai, N., Orru, R., Cao, G., “Sardinian natural clinoptilolites for heavy metals and ammonium removal: experimental and modeling”, Chemical Engineering Journal, 84: 275-282 (2001).

5-Devlet Planlama Teşkilatı (DPT), Madencilik Özel İhtisas Komisyonu Endüstriyel Hammaddeler Alt Komisyonu-Diğer Endüstri Mineralleri Çalışma Grubu Raporu, http://ekutup.dpt.gov.tr/madencil/sanayiha/oik480c1.pdf (1996).

6-DPT, 7. Beş Yıllık Kalkınma Planı, “Asbest, Bentonit, Fluorit, Diatomit (Kizelgur), Kalsit, Kıymetli ve Yarı-Kıymetli Taşlar (Süs Taşları), Lityum, Titanyum, Zirkonyum ve Hafniyum, Madencilik Özel İhtisas Komisyonu Raporu”, Cilt-2, DPT:2421-ÖİK: 480, Ankara, (1996).

7-Fathizadeh M., Aroujaliana A., Raisi A., “Effect of added NaX nano-zeolite into polyamide as a top thin layer of membrane on water flux and salt rejection in a reverse’’

8-Gao Y., Chen M., Zhang T., Zheng X., “A novel method for the growth of ZSM-5 zeolite membrane on the surface of stainless steel” Mater. Lett. 65 (2011) 2789–2792

9-Jiang N., Yang G., Zhang X., Wang L., Shi Ch., Tsubaki N., “A novel silicalite-1 zeolite shell encapsulated iron-based catalyst for controlling synthesis of light alkenes from syngas” Catal. Commun. 12 (2011) 951–954

10-Kurkina E.S., Tolstunova E.D., “The general mathematical model of CO oxidation

reaction over Pd-zeolite catalyst” Appl. Surf. Sci. 182 (2001) 77–90

11-Malliou, E., Malamis, M., Sakellarides, P.O., “Lead and cadmium removal by ion exchange”, Water Science and Technology, 25(1): 133-138 (1992) .

12-ÖZGE C, Devrim B, Semra Ü, “Batch and column studies on heavy metal removal using a local zeolitic tuff”, Desalination 259 (2010) 17-21

13-Sue-aok N., Srithanratana T., Rangsriwatananon K., Hengrasmee S., “Study of ethylene adsorption on zeolite NaY modified with group I metal ions” Appl. Surf. Sci. 256 (2010) 3997–4002

14-Sun H., Lu L., Chen X., Jiang Z., “Surface-modified zeolite-filled chitosan membranes for pervaporation dehydration of ethanol”, Appl. Surf. Sci. 254 (2008) 5367–5374

15-Wang Y., Lei Z., Chen B., Guo Q., Liu N., “Adsorption of NO and N2O on Fe-BEA and H-BEA zeolites” Appl. Surf. Sci. 256 (2010) 4042–4047.

16-Zamzow M.J., Eichbaum B.R., Sandgren K.R., Shanks D.E., Removal of heavy metals and other cations from waste water using Zeolites Separation Science and Technology 25 (1990) 1555–1569.

17-Zamzow, M.J., Eichbaum, B.R., Sandgren, K.R., Shanks, D.E, “Removal of heavy metals and other cations from wastewater using zeolites”, Separation Science and Technology, 25(13-15): 1555-1569 (1990).

18-http://www.reade.com/products/12-minerals-clays/127-endellite-hydratedhalloysite-metahalloysite-halloysite-nano-clay-halloysite-nano-clayal2si2o5oh42h2osio2-hydrated-halloysite