Patent Application
20200392008
Naturally occurring zeolites, such as Clinoptilolite, have long been used to enhance plant growth for grains such as wheat, corn and rice. Typically, naturally occurring zeolites have been blended into the soil adjacent the seeds or roots of the seedlings so that the benefits of nutrients and moisture stored in the zeolites are available to the root system. Even though the benefits of using naturally occurring zeolites are substantial, particularly in view of the low cost, these naturally occurring zeolites suffer in three areas: moisture retention/release properties; ion exchange capacity; and external surface area. While synthetic zeolites can excel in these areas, their cost as, typically prepared, generally makes synthetic zeolites prohibitively expensive for use as plant growth promoters. In our experience the surface area of Clinoptilolite is generally less than about 10 m2/g.
This invention relates to low-cost synthetic zeolites that can be prepared from naturally occurring sources of aluminum and silicon, typically clay, preferably kaolin, more preferably delaminated calcined kaolin, that can yield dramatic improvements in those areas but can be manufactured at a cost which does not render its use economically prohibitive, at least for plants grown in pots or greenhouses, especially for high value plants. In particular, it is possible to double or even triple the ion exchange capacity of natural zeolites such as Clinoptilolite.
In these zeolites, it is preferred that the ratio of silicon to aluminum be reduced somewhat from those typically encountered. In most naturally occurring zeolites, the ratio of silicon to aluminum is far in excess of 1 to 1 which is generally considered to be the minimum attainable. However, as the ratio of silicon to aluminum is decreased, the exchange capacity and moisture retention and release ability is increased. As a general matter, the closer the approach to 1 to 1, the more these properties are increased. In general, silicon/aluminum ratios less than about 1.75 to 1 are suitable, with ratios of less than about 1.5 to 1 being more preferred, ratios of less than about 1.25 to 1 being even more preferred. Usually, in preparation of these zeolites, higher alkalinity results in lower silicon to aluminum ratios as the degree of polymerization of the silica chains in solution is decreased with increasing alkalinity.
In the practice of this invention, we produce synthetic zeolites, especially Zeolite A, chabazite and faujasite, from naturally occurring sources of silicon and aluminum, typically clay, preferably kaolin, preferably calcined kaolin, more preferably delaminated calcined kaolin by crystallizing the naturally occurring source of silicon and aluminum under alkaline conditions, typically over at least a pH of about 10; preferably over about 10.5, more preferably over 11.0, most preferably over 11.5, more preferably over at least about 12, and ideally between about 12.5 and 13.9 or even closely approaching 14. In these zeolites, it is preferred that the ratio of silicon to aluminum be reduced somewhat from those typically encountered. In most naturally occurring zeolites, the ratio of silicon to aluminum is far in excess of 1 to 1 which is generally considered to be the minimum attainable. However, as the ratio of silicon to aluminum is decreased, the exchange capacity and moisture retention and release ability is increased. As a general matter, the closer the approach to 1 to 1, the more these properties are increased. In general silicon/aluminum ratios less than about 1.75 to 1 are suitable, with ratios of less than about 1.5 to 1 being more preferred, ratios of less than about 1.25 being even more preferred. Usually, in preparation of these zeolites, higher alkalinity results in lower silicon to aluminum ratios as the degree of polymerization of the silica chains in solution is decreased with increasing alkalinity. Typically, we will prepare these zeolites at a pH of at least about 10, preferably at least about 10.5, more preferably at least about 11, still more preferably at least about 11.5 and most preferably at least about 12, with the most preferred range being over at least about 12.5 and closely approaching 14. In most cases, treatment under these conditions at about 50° C.-100° C., more usually between about 60° C. to about 95° C., more usually from about 65° C. to about 90° C. and most typically from about 70° C. to about 80° C. for about 1 to about 8 hours, more commonly from about 1½ to about 6 hours and most preferably from about 2 to 4 hours or so is sufficient to crystallize the naturally occurring source of silicon and aluminum depending upon the chosen alkalinity and temperature. After synthesis, the pH of the zeolite should be neutralized to between about 5.5 and 10, more preferably between about 6 and 9 and most preferably to between about 6.5 and 8.5. By following the Examples herein, it is possible to ensure that the Zeolite A will have: a moisture reserve capacity of at least about 20 wt %, more preferably at least about 25 wt %, most preferably approximately 30 wt %; an external surface area of at least about 10 m2/g and an ion exchange capacity of at least about 3.5 meq/g (weight of the zeolite being on a dry weight basis, i.e, anhydrous basis), preferably above about 4 meq/g, more preferably above about 5 meq/g, still more preferably above about 6 meq/g and even still more preferably approaching 7 meq/g, it being understood that when the term meg/g is used herein, it based on meq of additive per gram of weight of the anhydrous zeolite. A plant growth promoter chosen from the group consisting of copper and zinc will be included in an amount of at least about 0.04 meq/g, preferably at least about 0.1 meq/g; more preferably at least about 0.2 meq/g; still more preferably at least about 0.3 meq/g; yet again more preferably at least about 0.4 meq/g and even more preferably at least about 1.0 meq/g and most preferably from about 0.3 meq/g to about 1.5 meq/g with loadings of up to about 4 meq/g being advantageous when conditions disfavor the use of large amounts of the base zeolite. Additionally, ammonium, magnesium and/or potassium ions may be incorporated into the zeolite in amounts of at least 0.4 meq/g, between about 0.4 meq/g up to about 5 meq/g, more preferably between about 0.45 meq/g and about 5 meq/g and most preferably between 0.5 and 4 meq/g and most preferably between about 1 and 3 meq/g.
Our experience indicates that simply by virtue of having superior moisture uptake and release properties, platy surface morphology, and ion exchange capacity, the low cost Zeolite A that we produce is far more beneficial to plant growth than any of the common naturally occurring zeolites that can be purchased at prices making them suitable for use in agriculture and horticulture. When various plant nutrients are added to the Zeolite A, the benefits of use of the present invention are even more dramatic.
The file of this patent contains at least one drawing executed in color. Copies of this patent with color drawings will be provided by the Patent and Trademark Office upon request and payment of the necessary fee.
Conversion of Base Stock into Zeolite A:
Synthesis Method and Theory
The basics of the material synthesis of the materials of the present invention can be broken up into two parts:
The Conversion of Metakaolin Into a Platy Form of Zeolite A
The exchange of zeolite A, replacing the sodium ions inside of the material with a variety of minerals that promote plant growth.
Step 1 is roughly a 4 hours process, using various temperature points up to 80° C.
Step 2 is a two day process, using the platy material and the nutrient salts. This step is more time intensive and labor intensive however.
The finished material treated with zinc and copper will come out looking like a slightly green, sand like material that can then be mixed into the potting soil of the targeted plant, and will do its work from there.
Zeolite Production Procedure
A 12 Liter, stainless steel pot is placed into a water bath set to 50° C., and an overhead stirrer set to low is placed inside of it. Into the pot, is placed the following:
3308 g of RODI (Reverse Osmosis Deionized) water
520 g of NaOH pellets, added over the course of 2 minutes.
The two are allowed to mix for roughly 5 minutes, or until all of the NaOH pellets are observed to be dissolved.
At that point, 888 g of base stock metakaolin clay is added slowly over the course of another 5 minutes, to prevent clumping.
After all the reagents are added, the material is allowed to cook for 1 hour at 50° C. At that point, the temperature is increased to 80° C., and allowed to cook for another three hours.
Once completed, the material is washed in a Büchner funnel, and dried at 80° C. in a laboratory oven. In some cases, the exchanged zeolite was used without drying. In these cases, it was found that 10 g of undried zeolite was roughly equivalent to about 6 g of dried zeolite.
Neutralization and Incorporation of Plant Growth Nutrients
The following ingredients:
The above preparation was repeated except that the amounts of copper and zinc added were doubled. This composition was dubbed “Exchanged Zeolite high metals.”
In use, the platy high aluminum synthetic zeolite A of the present invention will typically be mixed with the soil the plant is to be grown in at a weight percentage of about 5% if the zeolite has been dried or 10% if undried. Beneficial results can be obtained with relatively small amounts of zeolite, desirably from 1 to about 20% by weight undried, preferably from about 2 to about 18%, more preferably from about 3 to about 15%, still more preferably from about 3.5 to 12%, and most preferably from about 4 to about 10%. In some cases, the root ball of seedlings still encased in the potting soil may be rolled in the zeolite or the root balls may be dusted with zeolite. Use of the platy high alumina synthetic zeolite A of the present invention will not only provide water uptake and release properties easing issues of watering but when nutrients are exchanged into the zeolite, extended supply of nutrients is extremely beneficial.
Activities were performed as set out in Appendix A below.
Potting soil was amended with about 5% dry weight or 10% undried (by weight) as indicated of:
the platy high aluminum synthetic zeolite A of the present invention exchanged with nutrients and growth promoting metals prepared as described above exchanged with 20 mmol Cu/300 g Zeolite A and 40 mmol Zn/300 g Zeolite A which is 0.067 mmol Cu/g Zeolite A and 0.133 mmol Zn/g Zeolite A or 0.4 wt % Cu and 0.83 wt % Zn referred to as: “Exchanged Zeolite regular metals”;
the platy high aluminum synthetic zeolite A of the present invention exchanged with nutrients and growth promoting metals prepared as described above but exchanged with 40 mmol Cu/300 g Zeolite A and 80 mmol Zn/300 g Zeolite A which is 0.134 mmol Cu/g Zeolite A and 0.266 mmol Zn/g Zeolite A or 0.8 wt % Cu and 1.66 wt % Zn, referred to as: “Exchanged Zeolite high metals”;
the platy high aluminum synthetic zeolite A of the present invention but without added nutrients and plant growth promoters; “raw platy high aluminum synthetic zeolite A”;
naturally occurring clinoptilolite; or
a control with no added zeolite.
In general, experiments were set up with four groups in mind:
Group 1—Soil with commercial fertilizer and 5% by dry weight of exchanged material of the present invention;
Group 2—Soil with commercial fertilizer and 2.5% by dry weight of exchanged material of the present invention;
Group 3—Soil with commercial fertilizer (Control 1);
Group 4—No fertilizers (Control 2).
Multiple plants were used per group to hedge against outliers. Where possible, pictures were taken every day, and plant material (flowers, buds, leaves) were counted once per week.
A series of pots were prepared for marigolds:
Conventional Miracle Grow potting soil enriched with 10 wt % of as produced (undried) Exchanged Zeolite, regular metals was placed in pot 1.
Conventional Miracle Grow potting soil enriched with 5 wt % of as produced (undried) Exchanged Zeolite, regular metals was placed in pot 2.
Conventional Miracle Grow potting soil enriched with 5 wt % of commercially available Clinoptilolite was placed in pot 3.
Conventional Miracle Grow potting soil enriched with Miracle Grow Plant Fertilizer was placed in pot 4—Control 1.
Marigolds seedlings were transplanted into the pots which were watered every other day and the plants were observed with the results being as presented in
Subjective looks aside, plants grown with materials of the present invention (
A second batch was done late in the growing season, starting in mid-August. This experiment had the same general set up as the first, only we tested growing the marigolds out of season, so see how the materials of the present invention would impact plant survivability.
Here some oddities were shown, as group 2 using exchanged zeolite material at lower ratio out performing everything. Group 4 with the highest level of exchanged zeolite fared the worst, though the grower was unsure if that was due to the conditions the plant saw, or simply it's positioning in the sun.
Group 2 however, faired very well, achieving a flower/bud ratio nearing 3:1 over the control.
In general, the material of the present invention—“platy zeolite A”, has consistently out-performed other forms of plant foods in terms of biomass attained, strength of plants, and number of seeds produced.
In summary, many items here can be generalized as follows subject to the understanding that not every plant will respond identically:
Multiple plants were used per group to hedge against outliers. Where possible, pictures were taken every day, and plant material (flowers, buds, leaves) were counted once per week.
Our first attempt at growing something with our material. This was done early in the growing season, mid May 2017, and served as our proof of concept. The flowers were broken up into 4 groups:
As expected over the course of the month, group 1 did better than 2, which did better than 3, which did better than 4.
For comparison
Subjective looks aside, plants grown with the material of the present invention had more leaves, buds and flowers over the course of the grow experiment than any of the other groups. With group 1 possessing a flower/bud ratio of 3:1 over the control group. This assessment could again be followed by group 1 being better than 2, which was better than 3, which was better than 4.
This second batch was done late in the growing season, starting in mid-August. This experiment had the same general set up as the first, only we tested growing the marigolds out of season, so see how our material would impact plant survivability.
Here some oddities were shown, as group 2, the group using our material but at a lower ratio than group 1, outperformed everything. Group 1 fared the worst, though our grower was unsure if that was due to the conditions the plant saw, or simply it's positioning in the sun.
Group 2 however, faired very well, achieving a flower/bud ratio nearing 3:1 over the control.
Similar to the second marigold group, this was a test to grow a plant far out of season, and see how it faired with our material. Here, violets were grown indoors between late November and December of 2017.
Here again, plants with our exchanged material mixed in was able to sustain all of its flowers, though no significant growth was noted. All other groups, without exchanged materials, saw significant (>50%) plant death, with the control plant being completely dead by the end of the month.
In Florida, on a property near Beach side, a grow experiment was performed on grass, to see how our material would work in a more distributed fashion, and in a high salt environment.
Similar to the above experiments, our material had a significant impact on the tested area. The grower reported that the grass grown with our material lightly, and evenly spread out over a patch of grass, grew faster, stronger and greener than all other groups.
8 squares 12 or 24 grams of additive was applied to each of 8 2′×2′ squares of St. Augustine grass, as follows:
The remainder of the lawn was untreated and can be considered the control.
After 2 months, boxes 3 and 1 appeared the most vigorous, followed by boxes 4 and 2, boxes 5-8 were only slightly improved over the control, if improved at all. It is not understood why square 1 should have such a positive appearance, except possibly that it was in a partially shaded region.
The test was done in 6 sets, each of 2 plants, all in small pots with combined soil, fertilizer and zeolite as follows (measurements in grams):
All plants were the same genetics using controlled feminized seeds. All plants had uniform watering that was the same in volume and timing. All plants shared the same light sources and their positions were rotated daily.
An aphid infestation caused the removal of plants 1A, 6B, 5A and 5B. Plants 4B and 1B went hermaphroditic, causing them to impregnate all of the remaining plants, including themselves.
Plant group “4” had the highest average seed count (34), a 17% improvement over the control competitor zeolite group “2”. Plant group “1” had a lower average seed count (20.5), a 29% decrease from the control competitor zeolite group “3”. Of course, due to the small size of this trial, the ability to draw statistically valid conclusions may be limited.
Though the trial had to be cut short due to hermaphroditic plants, there were encouraging signs. The test was tainted when 2 of the plants became hermaphroditic, but still yields useful insight on the effect of zeolite solution of the present invention. While it would be better to be able to look at the weight of “buds”, the amount of seeds present in each plant provides a useful indicator as seeds are indicative of the amount of energy and resources available to the plant which would amount to more “buds” per plant had they not been impregnated.
Although the test was imperfect, the data seems to suggest that zeolite has a positive effect on Cannabis Sativa plants and the ion-exchanged zeolite had an even greater impact. If it takes an amount of resources and energy to make more “buds” and seeds, then plants with the ion-exchanged zeolite of the present invention clearly had more available to it indicating that the results of this test are clearly positive.
This application claims priority of Provisional U.S. Patent Application Ser. No. 62/861,495 of the same title, filed Jun. 14, 2019 incorporated by reference hereto.
| Number | Date | Country | |
|---|---|---|---|
| 62861495 | Jun 2019 | US |
