Myths and the truth about zeolitic hemostatics

What is a zeolite?

Zeolites are alkali metal aluminosilicates with a tightly ordered crystal lattice structure. For basic alkaline metals, the zeolites receive a prefix of that same metal in the first part of their name (Ca, Na, K ), and the type of crystal lattice is reflected in the second part of the name (usually type A and type X (ex, not Xe). So the zeolites are called CaA, NaA, NaX, and their hybrid forms are called CaAX, NaCaAX, etc.

Many people mistakenly attribute it to the properties of its counterpart «natural mineral zeolite». This is not quite true, because in natural zeolite there is no possibility to create hybrid forms from different types of zeolite, it is impossible to have a stable product with a stable level of crystallinity, The chemical composition is the same and there is no guarantee of obtaining a product with the specified stereoregular structure. That is, it is impossible to influence the already existing properties of the finished mineral. The process of synthesis of zeolite crystals in the Earth’s crust takes thousands of years and the resulting type of zeolite is influenced by the specificity of the rock, climatic conditions and about a hundred other factors. Summary: natural zeolite is not the thing that can be used in specific products, including local hemostatic agents.

The term «synthetic zeolites» would be correct for zeolites. These are zeolites whose structure is artificially created in an industrial plant with well-planned and stable properties. Due to their unique properties in the tonnage industry, synthetic zeolites are used as various selective adsorbents in petrochemical and refining plants (basic adsorption processes in such plants have been around for more than 50 years).

Synthetic zeolites

Synthetic zeolites have come into the LHA (Local hemostatic agents) field relatively recently. The American company Z-medica in the early nineties discovered the possibility of using zeolites to stop massive bleeding. A large number of different tests (including clinical) were carried out and as a result, the series was launched in the zeolite LHA QuikLot (it is known as the first generation hemostat). Many members of the community of takmeds in the Russian Federation still consider the USA and the company Z-medica, in particular, the founders of all tactical medicine.

Thermal effect of first generation QuikLot hemostatic

The product effectively stopped bleeding, but had a pronounced thermal effect. The thermal effect, or «wetting heat effect» is a normal picture of the activity of zeolites. It is this effect that explains the informal name of zeolites «boiling stones». Zeolite comes into contact with a large amount of liquid and begins to actively absorb it, while the heating is not due to chemical reaction, as many think, but due to stress stresses in the crystalline lattice of zeolite. I.e. It’s a physical process. Often, when it comes to the zeolites of basic forms (CaA, NaA, NaX), it is the warm up that shows that the product is active and able to absorb a large amount of liquid. I.e. When contact with liquid zeolite warms – means active and can be used, does not warm – means lost activity and the liquid will not be absorbed.

After a large-scale trial of the QuikLot LHA, it was noted that to reduce the risk of burns, the safe application of LHA is only possible on massive bleeding where the actual volume of blood released from the wound is significantly greater (this is important!) the volume of the hemostatic used (i.e. when the thermal balance is shifted due to the inability of the LHA to heat up all the fluid and cause a burn).

Thus, the only possible direction in the use of such LHA remained military medicine. It was very important to follow a clear protocol for the use of this product. The product was effective, but the success of its use with mutual help was limited to a clear understanding of the specifics and the necessary qualification of the medium that this product applies. In this case, the forming factor of LHA itself assumed that it was possible to use LHA effectively within the framework of self-help due to its simplicity. Although to this simplicity of application was added the previously described circumstance in part of a clear evaluation of mass bleeding. I.e. the product is supposed to be easy to apply (opened, covered), but it is important to assess the degree and nature of bleeding to understand what force will be the final thermal effect, which is not an easy task in a stressful situation.

Characteristics of synthetic zeolite production in the USA

The only major producer of synthetic zeolites in the US is UOP, currently owned by HoneUWell. This company is often referred to as the parent of the entire global synthetic zeolite industry, which is a mistake. It was the UOP synthetic zeolites that were chosen for the QuikLot ICS.

In the international classification synthetic zeolite is called a molecular sieve. A in our aspect is the molecular sieve 5A, 4A, 13X and their derivatives (molecular sieve 5A, 4A, 13X). All synthetic zeolites of this company are produced by the so-called «traditional technology», which involves the use of a binder.

Production UOP looks like this: there are minute crystals of synthetic zeolite (crystal or 100% zeolite), they need to be mixed with a binder (most often it is an attapulgite clay or in other words palygorskite), then granulate and pour. The weak link in this technology is the crystal itself (100% zeolite powder), whose production is a very difficult issue in terms of process and ecology. That’s why an American company buys it in China.

UOP supplies synthetic zeolites to all petrochemical enterprises in the United States and to a number of countries where UOP is the basic process licensor (even on some refineries in the RF until 2022). The entire US petrochemical industry has been dependent on some Chinese powder for 20 years. In addition to this and the binder itself – it is also not an American product, but a clay binder from the field in Reggio (Italy). As a result, the world’s best-known brand UOP does not represent anything special in terms of development and production, but simply formulas granules from two components produced in China and mined in Italy. For the sake of fairness, let’s say that this approach is also used in production by a number of other world producers.

The main drawback of this approach is that it is not possible to combine properties of different types of zeolite in one product by changing the structure of the crystal lattice, and also the presence of a binder that is not zeolite and performs the role of so-called glue (this is essentially unnecessary ballast, which in the grain is about 30%). In the end, if you need to combine the properties of two or more types of zeolites, the maximum that can be expected is a mixture of different brands (for a successful improvement of the properties of the zeolite LHA (local hemostatic agent) , it was first necessary to be able to modify the crystal lattice, and UOP could not do this).

In terms of tonnage, the major volume of synthetic zeolites produced worldwide is in the field of petrochemicals and refineries. This is well known because the large-scale production of synthetic zeolites has been one of our main business lines for the past 20 years (it is a separate plant with more than 30,000 square meters of production area and more than 200 employees). Long before the events of 2022, we were able to successfully replace UOP’s products on almost all refineries in the Russian Federation, and subsequently secured success and permanently erased American products from the list of possible vendors. So we need to be more careful about the term «parent» in relation to US products and not glorify their dubious achievements.

So, Z-medica did not produce the zeolite itself, and the manufacturer was unable to modify the properties of the synthetic zeolite to change the properties of the final product and eliminate the spill.

The success of our company’s synthetic zeolites

The success of synthetic zeolites produced by our company is primarily due to their unique production technology. We don’t use a binder, and we can synthesize the zeolite structure and properties that we want with predicted characteristics. That is why we are the leading supplier of synthetic zeolites for petrochemical and oil refining plants in the Russian Federation (we ship more than 2,000 tons of synthetic zeolites annually).

Until 2009 we did not produce synthetic zeolites that would be used in LHA (local hemostatic agent), and started doing so only after receiving a task to develop the technology and obtain an analog of LHA QuikLot. We were able to achieve full identity with the original product from «parents» from the USA and after state registration in the Russian Federation this product was launched into a series. We produced only the basis, i.e. the synthetic zeolite itself, the necessary form and structure, and sterilization, final packaging and regulatory documentation were on the side of «partner company» (ie. the final manufacturer was this company).

We are the only manufacturer in Russia who, thanks to the right approach, was able to implement this development in a short time: the resulting product was identical to QuikLot and had similar properties in heating part (but it was as effective as hemostat). We, having the appropriate production and scientific resources, suggested that we start developing a modified zeolite LHA in order to get rid of the temperature effect first of all, without impairing its efficiency. Moreover, we have always had the opportunity to introduce into the structure of this product a special form of zeolite produced exclusively in our company. Our innovative approach was not supported by the «partner company» (the specific structure of this company and zero motivation were affected) and we left the initial formulation in the technology.

It should be said that even this product with the original recipe, as described in the original invention, can not be produced at any other plant for the production of zeolites. The «partner company» described above, with all its significant competence in the field of military medicine, has been very inactively involved in the process of studying the final application of the product (field trials, communication with the expert community, understanding of the characteristics of the work of LHA, etc.). In particular, in the product described so far it is not reflected in the instructions that this zeolite LHA can not be used with open head wounds (and, unfortunately, such cases were and the outcome is known to all). This attitude led to the community being poorly informed about the application of the product, and the producer’s attitude created a situation in which the product became extremely unpopular.

The main focus is the tonnage application of synthetic zeolites and our special development

The main application of synthetic zeolites is adsorption and purification of various hydrocarbon streams on NPP (i.e. in this case zeolite acts as an adsorbent, which is loaded into 10 to 100 ton adsorber machines).

In these processes, the adsorbent has the task of absorbing extremely low concentrations of water and drying to even smaller ones (less than 1 ppm, 1 part per million, one part per million, i.e. very little). In such conditions zeolite is not heated, because the water is small, but if there are emergency situations and a large amount of water enters the adsorber, then there is a sudden heating of the adsorbent and, subsequently, it can lead to an emergency. To solve this problem, zeolite producers usually use a so-called trap. I.e. On top of the adsorber there is a small amount of adsorbent, which does not heat up when in contact with water. Traditionally it is aluminum oxide (in particular, this makes the «parent» from the US), but this approach has a number of negative points.

For this purpose we developed a special form of synthetic zeolite – zeolite with a protective layer NaFH. It is a unique hydrogen form of zeolite, no longer produced by any manufacturer in the world. This zeolite is a hybrid form of zeolite type X and LTA structure, i.e. we have with the outer part of the structure one type of zeolite, and inside another. Yes, this type of zeolite does not test the degree of activity by contact with liquid (there are other methods to determine the activity), because it has minimal «heat effect wetting», but it is best suited for the basic structure of zeolite hemostatics. It is almost not heated.

Effective hemostatic «Hemofreeze»

The unique type of synthetic zeolite described above has a higher adsorption capacity, and is therefore more effective as a hemostat. It is also freely exchanged for calcium ions and forms a hybrid form of the desired zeolite.

This is the approach we chose for the product «Hemofreeze». Once again, we emphasize that the basic base and «Hemofreeze» and previously known zeolitic hemostatic can be produced only in our plant and these are completely different products.

Since 2022, we have decided to take care of the entire cycle of production, registration and promotion of LHA at the expense of our company’s resources. We see the advantages of this approach and are ready to follow it in the future. We do not ship the manufactured base to third-party manufacturers and produce products exclusively under our trademark.