Synthetic Clinoptilolite: Seeding and Cultivating Pure Zeolite Crystals in a Controlled Environment

What is Synthetic Zeolite?  

In regards to zeolites, the term “synthetic” describes the process of carefully cultivating zeolite crystals in a clean lab environment. Cultivating crystals by seeding and growing them in a clean lab is the best way to produce zeolite crystals free from impurities and contaminants. The term “synthetic” in regards to crystallization does not mean that there are unnatural or man-made components in the end-product; it simply means that the crystals were not found in the wild, but developed in a controlled environment.   

In the cultivation of synthetic zeolites, controlling the temperature and the basic components of the zeolite crystals allows us to also control the quality of the mineral product. (1) Synthesized zeolite molecules are more uniform than natural, are free of the contaminants found in nature, and can be harvested at extremely small sizes, increasing the surface area exponentially, which also vastly increases the ability of the zeolites to detoxify on a cellular level. (1)  

“Although the mining of clinoptilolite from natural resources has been popular for many years, its artificial creation has been investigated in the last decades by many scientists due to the demand for high quality and purity of clinoptilolite. Consequently, there is a significant number of studies focused on the synthesis of clinoptilolite. Literature [18–32] demonstrates the efforts to synthesize from various sources of chemicals and different techniques to obtain clinoptilolite with different compositions….” (1) 

What is Modified Zeolite?

Scientists have been exploring the vast synthetic zeolite possibilities by modifying zeolite crystals.  Modification can include the use of surfactants as well as organic and inorganic substances. Modified zeolites have unique properties and can be used in a variety of applications. These modifications allow scientists to expand the potential applications of zeolites.. Modified zeolite applications include use in agriculture/horticulture as slow releasing carriers of fertilizers, antibacterial agents, growth stimulators, fertilizers, and pest control. (1) Modified zeolites are also frequently used for environmental purposes, such as the removal of heavy metals, dyes, and surfactants as well as the elimination of toxic gases. Modified Clinoptilolite has also been used for biomedical applications like antidiarrheals, antivirals, anticancer agents and drug carriers. (1)

“Clinoptilolite is used not only in its initial form but also in its modified form. In recent years, numerous studies [15,17,32–50] have contributed to the issue of clinoptilolite modification. It was pointed out that the area of application could be intensively expanded by the functionalization of external as well as internal surfaces of clinoptilolite. The modification can be conducted by various chemical reagents such as surfactants, organic compounds [33–43], and inorganic substances [51–62]. The modification process can be single steps like cation exchanging [51,61] or multiple steps including cation exchanging, oxidizing, or reducing [55,58,59]…” (1) 

 All modified zeolites are synthetic, but not all synthetic zeolites are modified. The zeolites in TRS are synthetic, but are NOT considered to be “modified.”  

Natural vs Synthetic 

Natural zeolites detoxify the environment around them, deftly locking heavy metals, pesticides, fluoride, radiation particles, carcinogens, and plastic residues in the crystalline cages, essentially removing and sequestering toxins from everything they “touch”. These toxins are almost impossible to remove completely from the zeolite cage once they have been absorbed/adsorbed. Even crystal “washing” techniques like Vitamin C flushes will only remove up 85-90% of toxins from the zeolite, the rest of the contaminants remain.

Natural zeolite crystals are most often micronized/powdered through industrial grinding processes, which breaks the zeolite molecule and releases the remaining 10-15% of contaminants into the zeolite product. Natural zeolites are NOT recommended for human and animal ingestion due to this contamination. Natural zeolite products are better suited for wastewater decontamination, soil conditioning, swimming pool filtration, and other agricultural/environmental uses. 

Unfortunately, natural zeolites are very cheap to mine and produce/micronize, so a lot of very cheap zeolite powders are available on the market. Beware of these products! Read the ingredient labels for any zeolite product you consider using. If you find a list of “humic” or “fulvic acid”, this includes a long list of heavy metals and other minerals found in nature, and is a clue that the zeolite product is NOT pure.  

Synthetic zeolites are more expensive to produce, requiring a clean laboratory environment to be cultivated, and so are not the most commonly found zeolites on the market. You have to search diligently to find a pure product, and TRS is the only product out there that has lab-cultivated, pure crystals as its active ingredient. 

Here is the USGS’ official stance on synthetic vs natural zeolites: 

“There is little competition between natural zeolites and synthetic zeolites. The high cost of synthetic zeolites precludes their use for most natural zeolite applications. Conversely, stringent product specifications prevent the large-scale use of natural zeolites for most synthetic zeolite applications”  (2)

How are Zeolite Crystals Synthesized in the Lab?

Raw materials & Si/Al ratio: 

The Clinoptilolite in TRS has been synthesized with silica, aluminum, and alkali sourced from potassium and/or calcium minerals. A third-party Certificate of Analysis on TRS measured the amount of Silica (Si) in TRS at 1.73 mg/L while the amount of Alumina (Al) ions in TRS equals 0.299 mg/L. Taking these amounts into consideration, the ratio is almost 6:1, or, to be accurate, 5.7:1. A high ratio of silica to alumina produces a stable, nearly indestructible zeolite molecule, thus ensuring it will be a very effective and safe chelation agent in vivo.

“The raw materials used in synthesizing of clinoptilolite include silica, alumina, and alkali sources. Silica source may be colloidal silica [19,21,24,26,28–30], silica gel [18,20], fumed silica [24], and amorphous silica [24], from among in which colloidal silica is the most frequently used. The influence of silica sources on the formation of clinoptilolite has not much been in question. In the contribution reported by Williams [24], the authors supposed that the colloidal silica stabilized by ammonium ion was expedient for the synthesis of clinoptilolite. The raw materials providing alumina are varied. They can be aluminum hydroxide [18,21,23,27–30,32], sodium aluminate [20,22,23,29,30], aluminum [24,29,30], and aluminum salts [19,22]. The use of aluminum hydroxide was the most common way to produce pure clinoptilolite that could be obtained, while the use of aluminum salts was not preferred because it produced impurities. The most commonly used alkali source was a hydroxide form including sodium and potassium hydroxides. The alkali source could contain single or multiple alkali elements….” (1)

“The influence of Si-Al ratio on the formation of clinoptilolite was disclosed by Zhao et al. (1997) and it was found that pure clinoptilolite could only be synthesized from gels having Si/Al ratios of 3.0–5.0 [25]…. In addition, clinoptilolite with good yield was obtained when Si/Al ratio was in a range from 5.0 to 6.0 [29]…. According to the above background, the ratio alkali:alumina:silica in the raw material is extremely significant for the synthesis of pure clinoptilolite. The most expedient ratio was described in the research of Chi et al. [21]….” (1)

Temperature:

The temperature of the clean lab must be strictly controlled to produce a stable Clinoptilolite molecule. Clinoptilolite (like TRS) requires a high temperature of 180+ ◦C.

“Generally, clinoptilolite was synthesized under a hydrothermal condition, so the reaction temperature played an important role…. It can be supposed that Na-clinoptilolite can be synthesized at a range of temperatures from 100 to 140 ◦C, while K-clinoptilolite is formed at a higher temperature—about 195 ◦C. When both Na and K are present in the reaction system, the temperature for synthesizing of pure (Na,K)-clinoptilolite is in the range from 140 to 180 ◦C, as shown in the” graphic below… (1) 

Seeding:

The process of “seeding” is an important part of synthesizing zeolites. To cultivate a Clinoptilolite zeolite, one must use a minute amount of Clinoptilolite crystal grains in order to jump-start the process of reproduction/cultivation.  Without this, the crystals produced would be a form of zeolite called Mordenite, and not Clinoptilolite.  Using Clinoptilolite “seeds” ensures that the end result will be Clinoptilolite zeolite. 

“The role of seeding in the synthesis of clinoptilolite was firstly described in the study by Hawkins [19]. The author supposed that adding a few grains of clinoptilolite into the reactants was necessary for the reproducible synthesis of all the clinoptilolites, while in the absence of clinoptilolite seeds mordenite was the main product. In the contribution [21], pure clinoptilolite was obtained when clinoptilolite seeds were added into the starting material mixtures….” (1)

Time: 

Depending on the desired result, zeolites are synthesized anywhere from hours to days before they are harvested. The zeolite molecules in TRS are on a nano-sized scale, so the process takes less time to produce than zeolite crystals of larger molecular sizes. 

“Based on the literature, the period for synthesizing pure clinoptilolite varies from several hours to more than one thousand hours as shown in” this graphic: (1)

 

Conclusion

Synthesizing zeolites is a fascinating process that has been scientifically studied for over a decade. Synthetic Clinoptilolite is far superior to naturally mined sources due to their purity, molecular size, and overall quality.  The synthesizing of Clinoptilolite allows scientists to control the components of the zeolite crystals, selecting particular minerals for optimal cultivation and stability.  Synthesizing zeolites has also significantly broadened the possible applications of zeolites in biomedical, environmental, and agricultural arenas.  The Clinoptilolite in TRS has a high ratio of Si/Al, which produces a very stable and effective zeolite for detoxification in the human body.  

 

References:

(1) http://www.mdpi.com/1420-3049/22/7/1107/pdf

“Clinoptilolite is a natural mineral with exceptional physical characteristics resulting from its special crystal structure, mainstreamed into a large zeolite group called heulandites. An overall view of the research related to the synthesis, modification and application of synthetic clinoptilolite is presented. A single phase of clinoptilolite can be hydrothermally synthesized for 1–10 days in an autoclave from various silica, alumina, and alkali sources with initial Si/Al ratio from 3.0 to 5.0 at a temperature range from 120 to 195 ◦C. Crystallization rate and crystallinity of clinoptilolite can be improved by seeding….”

(2) https://minerals.usgs.gov/mineralofthemonth/zeolites.pdf