MXPA98010177A - Process for the formation of liquid agricultural biochemical products, stabilization - Google Patents

Abstract

The processes to form an agricultural, biochemical, liquid, stabilized product containing an extract with organic solvent of Reynoutria sachalinensis consist of: submit an extract with organic solvent of dry, particulate Reynoutria sachalinensis, to a first and second stages of concentration of the extract, and wherein before the second stage of concentration of the extract, the concentrated extract of said first stage of concentration of the extract is mixed with a liquid stabilizer, more preferably a fertilizer with liquid nitrogen content.

Description

PROCESS FOR THE FORMATION OF LIQUID, STABILIZED, AGRICULTURAL, BIOCHEMICAL PRODUCTS FIELD OF THE INVENTION The present invention generally describes the production of agricultural biochemical products. In preferred embodiments, the present invention describes a process for forming a concentrated extract of the plant Reynoutria sachalinensi s and the resulting biologically active product.

BACKGROUND AND COMPENDIUM OF THE INVENTION The plant Reynoutria sachalinensis (commonly known as "giant black centaurea", herein simply referred to as "Reysa") is known to possess fungicidal activity related to agriculture by evidence in U.S. Patent No. 4,861,734 de Po-mer et al (the entire contents of which is hereby expressly incorporated by reference). Considering this, it is known that Reysa can be extracted with an organic solvent, such as ethanol, and then subject to partial evaporation of the ethanol to obtain a Reysa extract in ethanol. However, there are several problems when extracting Reysa (or other plant materials) with an organic solvent. In this sense, when the materials of the plants, they are extracted with an organic solvent, such as ethanol, the resulting extract includes a complex mixture of materials that vary in terms of solubilities in water. The extraction of plant materials can, and often is, result in extracts containing chlorophyll, waxes and oils, in addition, water-soluble components. The less water soluble components are separated and agglomerated (also called "tar") by removing the organic solvent. The extracts and concentrates may also be susceptible to microbial decomposition once the ethanol has been removed, thereby rendering ineffective results. In a broad sense, the present invention is incorporated in a process for forming stable solvent-extracted Reysa formulations containing minimal residual organic solvent (if any) and the stable formulations thus obtained. In particular, the present invention involves subjecting an alcohol extract of Reysa to a primary concentration step (eg, via distillation, evaporation or the like) to remove a greater position of the organic solvent and to concentrate the Reysa in the resulting concentrated primary solution. Thereafter, an inorganic or organic liquid stabilizer (eg urea) is added to the primary concentrated solution which is then subjected to a concentration step secondary to remove all organic solvent, (example greater than 95% by weight). In such a manner, and consequently Reysa formulations are provided, which are stabilized against the microbial decomposition and the resultant reduced inefficiency.

DETAILED DESCRIPTION OF THE INVENTION The plant Reynoutria sachalinensi s ("Reysa") which can be used in the practice of the present invention includes not only the plant itself, but also parts of the plant such as rhizome, stem, leaves or a combination of the same. The dead Reysa plant, especially dry, is preferably used. It is particularly preferred that the plant and / or parts of the plant are initially air dried or dried with a slight application of heat, after which they are sprayed into a Reysa particulate powder. Particularly, Reysa plants grown in the field can be harvested, dried to a maximum moisture content of about 15% and then ground to thick sheets or flakes using a cutter. The dried Reysa pieces can then be subjected to extractions with organic solvent using techniques well known to those skilled in the art. More preferably, the organic solvent used to extract Reysa's active ingredient (s) is ethanol or denatured (ethyl) alcohol. Preferably at least about 0.5 liters of ethanol per kilogram (1 / kg) of Reysa is used, and more preferably at least about 0.75 1 / kg. However, particularly effective results are obtained if a significant excess of ethanol is used, for example up to about 6 liters of ethanol per kilogram of Reysa. This establishes a solvent ratio to Rs and the minimum extraction time recommended for the extraction "tea method". Usually, denatured ethanol is used because of the cost, pure ethanol is preferred, but not necessarily. Care must be taken, however, that the denaturing agents if concentrated in the final product are not phytotoxic. Normally such denaturing agents are extracted with ethanol in the distillation phase of this process. The extraction can be carried out under stirring conditions at ambient temperatures. The Soxhlet extraction is also suitable. The Reysa ethanol liquid extract is subsequently separated from the particulate plant material by filtration (eg, using a bag filter with a 250 micron pore size filter medium) and transferred to a distillation vessel. The material of the particulate silver that remains after the filtration can then be subjected to a second stage of extraction with new ethanol. Again it is preferred that an excess of ethanol be used, that is up to about 6 1 / kg. The liquid extract of Reysa in ethanol of the second stage is separated from the material of the dried plant and is preferably combined with the liquid extract from the extraction of the first stage in a distillation vessel. The material of the particulate plant, exhausted, will contain some residual ethanol can then be washed to recover ethanol or washed with water and discarded. An additional extract could be recovered using a centrifuge, filter press or compactor. An additional extract can also be recovered by steam stripping, direct heat distillation, vacuum distillation of the Rs solids containing ethanol. The combined extracts of Reysa in ethanol from the first and second stages of ethanol extractions can then be subjected to a first stage of the distillation process using conventional distillation techniques, to remove a larger portion of the ethanol as distillate, and to concentrate the amount of Reysa extract in the funds or waste. In this regard, the first distillation step is more preferably carried out until at least about 60% by volume, and more preferably, at least about 70% by volume of the ethanol is distilled from the Reysa extract. The first distillation step is preferably achieved under nitrogen for safety reasons. Commonly the distillation vessel is composed of a stainless steel jacketed vessel, heated by steam and capable of withstanding the vacuum. The connected condenser column is cooled by a glycol-based fluid kept below 40 ° F (4 ° C) until vacuum distillation (which is rapid and less destructive than distillation at 76 ° C) is achieved. Following the first distillation step, the concentrated Reysa extract (containing no more than about 40% by volume of ethanol and more preferably no more than about 30% by volume of ethanol) is mixed with a liquid stabilizer. This step is worked after the minimum practical volume is reached in the distillation vessel which is determined by the configuration of the vessel as well as the nature of the distillate residue fluid (bottoms). Almost any liquid stabilizer that is biologically compatible with the Reysa extract and has a boiling point that is significantly (i.e., at least about 10 ° C) higher than the boiling point of the organic solvent (eg, ethanol) can be employed in the practice of this invention. Plus preferably, the liquid stabilizer is one that has some biological benefits. Specifically, it is preferred that the liquid stabilizer be a fertilizer containing nitrogen, liquid. A liquid fertilizer that can be used satisfactorily in the practice of this invention is a salt solution with at least one nitrogen-containing compound selected from urea, ammonium nitrate, calcium nitrate and magnesium chloride in concentrations between 15 to about 60% (w / v) and more preferably between about 20 to about 40% (w / v). A preferred liquid fertilizer is a urea saline solution (25% w / v) with at least one ammonium nitrate (approximately 18% w / v), calcium nitrate (approximately 20% w / v) or magnesium chloride (approximately 10% p / v). A particularly preferred liquid fertilizer is commercially available from BASF Corporation with registered trademark fertilizer BASFoliar® 36. Distillation is continued to remove the largest portion of the remaining ethanol up to a maximum of approximately 5% w / w concentration of the residue. The quantity / weight of the residue distilled just before the addition of the liquid stabilizer, minus the solids content of the distilled residue, is the objective of the volume of additional distillation in this step of the process. The product is then cooled and mixed with a high-shear agitator (example for approximately 30 minutes), filtered (less than 100 microns) and packaged for use. Although a particularly preferred technique has been discussed above for extracting solid Rs with ethanol, skilled in the art can recognize that numerous equivalent extraction techniques can be employed in the practice of this invention. For example, it is possible to use countercurrent solvent extraction with a series of baskets containing Rs solids that are percolated with a solvent as they progressively pass through the extractor (eg, via a Crown extractor). Alternatively, a filter press can be charged with Rs solid through which a solvent is passed (eg, the "bag-tea" technique) or a Buchner filter can be loaded with Rs solids and solvent washes. Furthermore, it is literally possible that Soxhlet extraction can distill solvent cycles through the Rs solids contained in the basket filter where the extract is collected in a boiling vessel that provides solvent vapors to the previous condenser.

High-conditioned tubes, for example, with 10 US mesh filter plates can be filled with Rs solids. Then the solvent can be recycled from above to down until the saturation takes place. This process is repeated until the Rs can be exhausted. Then a piston can be used to press the solids Rs as much as to squeeze the solvent retained there, and finally to push out the spent Rs solids when the lower plate is removed. An extraction technique that can be used to eliminate the distillation is the spray drying of the extracted solids in the presence of an inert carrier to form a free flowing powder that can be suspended in an aqueous spray solution for foliar application.

EXAMPLES A better understanding of this invention will be apparent from the following non-limiting examples.

Example I - Preparation of a batch of Reysa formulations One drum (370 lbs) of denatured ethanol C-95 (ChemCentral Co.) was added to a 3-cylinder stainless steel and round bottom mixing kettle and 82.75 lbs of Reysa crushed dry were added with agitation. After 3 hours of stirring, the mixture was drained through a 250 micron filter bag, leaving the plant material in the kettle. 224.5 lbs of ethanoic extract [sic] (The) was then passed through a filter bag of 100 microns (1.52% solids by gravimetric analysis) and inside a distillation vessel. Filtration required one hour. One cylinder of ethanol (370 lbs) was added to the mixing kettle and 87.2 lbs of dry and crushed Reysa were added. After 3 hours of agitation, recovery was initiated via a 250 micron filter. The 268 lbs, or 72.4%, of extract (E3) recovered was transferred to the distillation vessel (stainless steel vessel, heated with steam, 100 gallons and with condenser) to recover the solvent. The filtration took 45 minutes. Another ethanol cylinder (370 lbs) was added to the Reysa remnant in the mixing kettle and after a short period of stirring, it was left overnight without stirring. Then the second extraction (E2) was filtered being the first extraction (El) distilled under vacuum (-22 inches Hg) in the distillation vessel at a temperature of 30 ° -38 ° C until reaching a solids content by weight of 13.93%. The E2 extraction produced a yield of 274 lbs of extract (0.72% solids) that was filtered through a 100 micron filter in the distillation vessel combined with the distillation El queues obtaining a loss of 241.5 lbs. of ethanol equal to approximately 33% of ethanol original loaded after absorption by the plant material. The residues of the Reysa plant from the first two extractions were suspended in water and filtered to remove excess ethanol. The filtrate and exhausted material of the Reysa plant was discarded. The washing process took an hour. Another cylinder of ethanol was added to the Reysa material in the mixing kettle, stirred and resting overnight. The filtration in the morning took an hour. The resulting extract (E4) had a solids content of 0.63% and a total weight of 357 lbs (99% recovered). Extracts E3 and E4 were combined in the distillation vessel and sampled yielding 625 lbs net weight (at 0.87% solids by weight). The combined extracts were then distilled at 47 ° C and 20 inches Hg. Approximately 100 pounds of the distillate was removed after 30 minutes. The distillation of combined extracts E3 and E4 continued for two hours to a final weight of 141 lbs (484 Ibs of distillate). Meanwhile, the El and E2 extracts were distilled, collecting 360 lbs of distillate from 490 lbs of extract, to 73% by weight reduction. The temperature started at 60 ° C and ended at 35 ° C when a vacuum of 22 inches of Hg was applied and the extract boiled. The tails of El and E2 made a total of 24 lbs and contained 26.11% solids.

The distillate from the combined extracts El and E2 (360 lbs) was added to the Reysa residue from the E4 extract and stirred for 2.5 hours. The E5 extract of 362 lbs (100% recovery) was recovered, sampled (0.28% solids) and added to the residues of extract E3 and E4 in kettle # 19. The net weight was 510 lbs at the restart of the distillation. Two hours of distillation at 46 ° C and 22 inches of Hg yielded the net weight in kettle # 19 of 91 lbs which had 6.5% solids (5.9 lbs) Tails from El to E5 were combined in the kettle # 1 to yield 12.04% solids. The vacuum distillation stirred 51.5 pounds of ethanol and then the product was cooled to room temperature overnight. BASFoliar® Extra liquid fertilizer (BASF Corporation) was added in an amount of 11.14 lbs / gal to kettle # 1 in two loads: 55.8 lbs + 55.0 lbs = 110.8 lbs = 37.65 liters (0.5 liters of liquid fertilizer per kilogram of extracted Reysa ). Then the vacuum distillation continued until a total of 58 lbs. Of distillate had been collected around a period of two hours. The temperature range is from 40 ° C to 56 ° C to 25 inches Hg. Based on the weights of the distillate, the theoretical final weight was 140 lbs, based on the solids content, the theoretical final weight could be 124 lbs. The actual collected weight for a sample of final product (BASF denomination 114 UBF) It was, however, 102.5 lbs. Evidently, some of the water in the formulation was distilled, there were losses in the transfer given that the liquid fertilizer loaded was 110 lbs and there were approximately 10-13 Ibs of solids.

Example II-Efficacy of the Greenhouse Ornamental Formulation Greenhouse tests were conducted to determine the efficacy of the Reysa formulation of Example I (BASF 114 UBF) for the control of powdery mold diseases in a variety of ornamental crops. These tests were concentrated on roses with additional tests in Easter flower, Begonia, Gerber daisy and Salvia. The test material was applied every 7-9 days in a protection program with sufficient volume of water for full coverage. These tests were performed with high propagation of the disease that usually does not exist in commercial greenhouses. As shown in Table 1 below, the efficacy of BAS 114 UBF according to the present invention was similar to that of the commercially available triadimefon products (STRIKE® triadimefon available commercially from Bayer Corporation) and piperalin (PIPRON® piperalin available in the Sepro Corporation trade). In addition, the efficacy of BAS 114 UBF according to this invention shows an efficacy similar to that of an ethanol extract (BAS 114 00S) prepared by an extraction or reflux using a mixture of ethanol and water (70-30) giving a final product (0.67 equivalents / ml of Reysa) containing 22% of ethanol used a ratio of 1.5% v / v. Table 1 Example III-Efficacy of the formulation in cucurbitaceae Tests for the control of powdery mold were made in cucumber, chayote, melon and squash. The test material was applied every 7-9 days in a protection program for a total of 4-6 applications. The formulation according to the present invention produced according to Example 1 above (BAS 114 UBF) was compared against a Reysa formulation (BAS 114 UAS +) consisting of a Reysa dust tank ground in a mill with air entrainment, mixed in with BASFoliar® liquid fertilizer (0.5% vol / vol). Other tests evaluate the effectiveness of BAS 114 UBF according to the present invention alone and in alternation with a decreased concentration of conventional fungicide (BAS 49002 S CYGNUS® fungicide commercially available from BASF Corporation) against the powdery mold of cucumber and chayote. Reysa's formulations were generally applied as a preventive spray in a 7-day program. The results appear in the tables below 2 and 3. The data show that, under conditions of low spread of the disease (test 1), both Reysa formulations provide excellent mold control, similar to the commercial standard, triadimefon (BAYLETON® fungicide commercially available by Bayer Corporation) in other tests (3 tests), there was high spread of the disease, both Reysa formulations averaged 60% disease control, but triadimefon was superior (77%). Alternating BAS 114 UBF with half the concentration of BAS 490 02F in a weekly spray interval provided excellent control of the disease which was similar to the total concentration of BAS 490 02F. This effect was observed under conditions of high and low spread of the disease and the usefulness of the Reysa formulations was demonstrated to reduce the use of conventional fungicides in a program integrated pest control. No phototoxicity was observed in any of the Reysa formulations.

Table 2 Control of dusty mold in cucurbits Average% mold severity Treatment Concentration1 Low Elevated All propagation propagation tests for the (n = 4) disease disease (n = = 1) (n = = 3) Untreated - 23.5 70.4 53.7 BAS 114 UBF 0.5 V 2.8 27.3 17.5 BAS 114 UBF 0.25 V 6.3 34.4 27.4 BAS 114 UAF + 0.25 P 5.5 28.0 22.4 BAS 114 UAF + 0.13 P 7.3 42.5 33.7 Bayleton 0.10 A 1.0 16.4 12.6 1V =% vol / vol, P -% p / vol, A- Ib ia / acre Table 3 Control of powdery mildew in curcubitáceas using the fomula of the invention alone and integrated to a conventional fungicidal program Treatment Concentration Interval Average% severity of (% or Ib) of dew mold Test no. 1 Test no. 2 (n = l) (n = 3) Untreated - - 20.0 39. BAS 114 UBF 0.50% 7 5.3 20.3 BAS 490 02F 0.05 Ib 14 5.5 7.2 BAS 490 02F 0.10 Ib 14 0.8 5.0 Alternating1 (see note 1) 7 1.0 2.1 Bayleton 0.25 7 0.0 - 0.05 Ib of BAS 490 02F alternated with 0.5% BAS 114 UBF Example IV - Effectiveness of the formulation in grapes BAS 114 UBF was tested for its effectiveness for control of powdery red-colored mold and varieties of Chardonnay grapes or propagation of severe and moderate disease, respectively. By means of comparative tests they were carried out separately using sprayable sulfur, a mixture of Reysa milled in dry with fertilizante liquid BASFoliar® (BAS 114 UAF +), and integrating the application of BAS 114 UBF together with myclobutanil (RALLY® myclobutanil commercially available from Rohm and Haas Co.) The results appear in Table 4 below. As can be seen from the data, BAS 114 UBF (0.5%) provided equal or superior control for the powdery mildew of the berries compared to sprayable sulfur and slightly less than myclobutanil, when applied by a 7-day spray program. BAS 114 UAF + (0.5% + 0.5%) was less effective than BAS 114 UBF (0.5%). The weekly applications of BAS 114 UBF (0.5% before the size of the berry, followed by three applications of myclobutanil (0.045 Ib. Ia / acre) during the classification or sizing and BAS 114 UBF for the rest of the season provided good control of the powdery mildew of the berry The level of control was similar to that of the sulfur used instead of BAS 114 UBF in the sequence, both treatments were superior to myclobutanil 0.075 Ib ia / acre) applied only in a 14 day program.

Table 4 Table 4 (Continued) classification of the disease taken at 13 DALT for leaves and 23 DALT for berries While the invention has been described in relation to what is currently considered the most practical and preferred embodiment, it should be understood that the invention is not limited to the described modality, but on the contrary is proposed to cover several modifications and equivalent arrangements included within the scope of the invention. spirit and scope of the appended claims.

Claims (27)

1. A process for preparing an agricultural biochemical product consisting of the sequence of steps of: (a) submitting Reynoutria sachalinensi s to an extraction with organic solvent; (b) concentrating the extract in a concentration process in a first step: (c) adding, to the concentrated extract, a liquid stabilizer to form a stabilized mixture thereof; and then (d) concentrating the stabilized mixture to remove a higher percentage of organic solvent remaining therein.

2. The process of claim 1, wherein the organic solvent is ethanol.

3. The process according to claim 1, wherein steps (a) and (c) include distillation to remove the organic solvent.

4. The process of claim 3, wherein said distillation is carried out under vacuum.

5. The process of claim 1, wherein the step (d) includes distillation to remove a larger portion of the remaining organic solvent.

6. The process of claim 1, wherein said Reynoutria sachalinensi s is in a dry, particulate form.

The process of claim 1, wherein step (a) includes the steps of: (i) submitting Reynoutria sachalinensi sa a primary extraction with organic solvent to form an extract with primary solvent, (ii) separating the extract with primary solvent of the Reynoutria sachalínensi s, and then (iii) submit the Reynoutria sachalinensi sa a second extraction with organic solvent to obtain a second extract in solvent.

The process of claim 7, wherein the extracts with primary and secondary solvent are combined and subjected to a first concentration step according to step (b).

9. The process of claim 7, wherein the organic solvent in the extractions with primary and secondary organic solvent is added to the Reynoutria sachalinensis in an amount of up to 6 liters of organic solvent per kilogram of Reynoutria sachalinensi s based on the dry weight .

The process of claim 1, wherein the liquid stabilizer has a boiling point of at least 10 ° C greater than the organic solvent.

11. The process of claim 1, wherein the liquid stabilizer is a fertilizer with nitrogen content.

The process of claim 11, wherein the nitrogen-containing fertilizer includes at least urea, ammonium nitrate, calcium nitrate or magnesium chloride.

The process of claim 12, wherein the fertilizer is a salt solution containing urea and at least ammonium nitrate, calcium nitrate or magnesium chloride.

The process of claim 1 or 11, wherein the liquid stabilizer is added in an amount of at least about 0.25 liters per kilogram of Reynoutria sachalinensis based on dry weight.

15. The process of claim 1 or 11, wherein the liquid stabilizer is added in an amount of at least about 0.50 liters per kilogram of Reynoutria sachalinensis based on dry weight.

16. The process of claim 1, wherein step (b) is practiced to remove at least 60 vol.% Of the organic solvent.

The process of claim 1, wherein step (d) is practiced until no more than about 10 vol.% Organic solvent remains.

18. A process for forming a stabilized liquid biochemical agricultural product containing an extract in an organic solvent of Reynoutria sachalinensi s, comprising the steps of: subjecting an extract in organic solvent of dry, particulate Reynoutria sachalinensis, to a first and second stage of concentration of the extract and before the second stage of concentration of the extract, mix the concentrated extract of the first stage of concentration of the extract with a liquid fertilizer.

19. The process of claim 18 wherein, before the first stage of extract concentration, the Reynoutria sachalinensis, particulate, is subjected to primary and secondary extractions with solvent to obtain extracts in primary and secondary solvent, which are combined before the first stage of concentration of the extract.

The process of claim 19, wherein said first and second solvent extracts are separated from Reynoutria sachalinensis by filtration.

The process of claim 18, wherein the liquid fertilizer is mixed with the concentrated extract of the first stage of concentration of the extract in an amount of at least about 0.25 liters of fertilizer per kilogram of Reynoutria sachalinensis based on dry weight .

22. The process of claim 21, wherein the liquid fertilizer is mixed in an amount of at least about 0.50 liters of fertilizer per kilogram of Reynoutria sachalinensis based on dry weight.

23. The process of claim 18, wherein the extract with organic solvent includes up to about 6 liters of organic solvent per kilogram of Reynoutria sachalinensis based on dry weight.

24. The process of claim 18, wherein the first step of concentrating the extract separates at least about 60 vol.% Of the organic solvent.

25. The process of claim 18 or 24, wherein the second step of concentrating the extract is practiced so that no more than about 10 vol.% Of the organic solvent remains.

26. The process of claim 18, wherein the fertilizer includes at least urea, ammonium nitrate, calcium nitrate or magnesium chloride. The process of claim 26, wherein the fertilizer is a salt solution containing urea and at least ammonium nitrate, calcium nitrate or magnesium chloride.