US 20140123717A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2014/0123717 A1 Muller (43) Pub. Date: May 8, 2014 (54) MIXTURES ON THE BASIS OF (30) Foreign Application Priority Data SULFUR-CROSSLINKED TRIGLYCERIDE, A METHOD FOR THE PRODUCTION Dec. 15, 2010 (EP) .................................. 101951 79.6 THEREOF, AND THE USE THEREOF AS FERTILIZER Publication Classification (75) Inventor: Helmut Muller, Kitzingen (DE) (51) Int. Cl. C05F II/00 (2006.01) (73) Assignee: RHEIN CHEMIERHEINAU GMBH, (52) U.S. Cl. Mannheim (DE) CPC ...................................... C05F II/00 (2013.01) USPC ................. 71/20: 71/11: 71/23: 71/15: 71/19 (21) Appl. No.: 13/993,728 s s s s (22) PCT Filed: Dec. 15, 2011 (57) ABSTRACT The present invention relates to novel mixtures based on (86). PCT No.: PCT/EP11/72937 Sulfur-crosslinked triglyceride, a process for their prepara S371 (c)(1), tion, and their use as fertilizers, in particular for promoting the (2), (4) Date: Jan. 15, 2014 growth of plants which require Sulfur. US 2014/O123717 A1 May 8, 2014 MIXTURES ON THE BASIS OF palm kernel oil, rapeseed oil (colza oil), castor oil, Sardine SULFUR-CROSSLINKED TRIGLYCERIDE, A oil, mustard seed oil, Soya oil, Sunflower oil, shea butter, METHOD FOR THE PRODUCTION grapeseed oil and/or walnut oil. THEREOF, AND THE USE THEREOF AS 0010 Colza oil, soya oil, sunflower oil and/or castor oil are FERTLIZER preferably employed. 0001. The present invention relates to novel mixtures 0011. In a further preferred embodiment of the invention, based on Sulfur-crosslinked triglyceride, a process for their mixtures of triglycerides are employed. In these cases, mix preparation, and their use as fertilizers, in particular for pro tures of colza oil, Soya oil, Sunflower oil and castor oil are moting the growth of plants which require Sulfur. preferred. In these cases, the ratio of the triglycerides to each 0002 Plant growth requires not only water, carbon dioxide other may be chosen as desired and is generally determined and Sunlight, but furthermore the macronutrients nitrogen, by the price of the raw materials. potassium and phosphate and secondary nutrients and trace 0012 All the abovementioned triglycerides are commer elements. Sulfur, too, is a vital secondary nutrient, especially cially available and thus available for example from Gustav in the plants protein synthesis, and is preferentially taken up Heess GmbH & Co. KG. by them via the root in the form of sulfate. 0013 The sulfur-crosslinked triglyceride for the purposes 0003. In the last one to two decades, sulfur depletion has of the invention preferably takes the form of those compounds been found in agriculture soils in some regions. This is caused which are obtainable by reacting at least one triglyceride with by reduced sulfur emissions as the result of the increased flue sulfur at temperatures of >150° C. gas desulfuration and reduction of the Sulfur content in fuels. 0014. The following preparation process is preferred in 0004. A multiplicity of mineral fertilizers is available for this context: sulfur fertilization. They differ mainly in their form (sulfate, 0015 The triglyceride or the mixture of several triglycer elemental 5) and hence the speed of action. In most sulfur ides is initially introduced into the reaction vessel, warmed to containing mineral fertilizers, Sulfur is present in Sulfate temperatures of at least 150°C., form. Sulfur in sulfate form is immediately available to the 0016 the sulfur, in the desired amount, is transformed into plants. Sulfur in elemental form (for example wettable sulfur) the liquid aggregate state by warming/melting and added, cannot be taken up directly by plants but must first be con preferably in portions, to the stirred triglyceride or mixture of verted into sulfate by thiobacteria, which, at soil temperatures several triglycerides; stirring is optionally continued to com of-10°C., may be a lengthy process. Moreover, sulfates have plete the reaction attemperatures of >150° C.; and the mix the disadvantage of being, as a rule, readily soluble in water, ture is poured into molds, where it is subjected to thermal and, as a result, are leached from the soil too rapidly, espe conditioning at >120° C. After cooling, it is preferred to cially in regions which receive a lot of rainfall, and is there comminute the Sulfur-crosslinked triglyceride. fore available to the plant only within a relatively short period. 0017 All customary commercially available cutting mills, 0005 DE 102007034278 A describes a mixture of ammo Such as, for example, a cutting mill from Pallmann nium sulfate as mineral sulfur fertilizer together with lime for Maschinenfabrik GmbH & Co. KG, may be employed for the avoiding the acidification of the soil as the result of sulfur comminution process. fertilizers. This, however, does not do away with the disad 0018. In this context, the sulfur is preferably employed in vantage of the sulfate being leached from the soil unduly elemental form, especially preferably in the form S8 sulfur. rapidly. Faktis, which is made with sulfur monochloride (see 0019. In a further preferred embodiment of the invention, DE 545375), in turn, has the disadvantage that it only com the sulfur content in the sulfur-crosslinked triglyceride prises short Sulfur bridges and, disadvantageously, has a high amounts to 10-30% by weight, especially preferably 10-20% chlorine content. Mercaptain-group-containing triglycerides, by weight, based on the triglyceride. as described, for example, in US 2006/0000252, are unsuit 0020. The content of sulfur-crosslinked triglyceride in the able for many applications due to the pronounced high odor. mixture preferably amounts to not more than 60%, based on 0006. The task was therefore to provide mixtures which the total mixture. Especially preferred is a content of 90.0% to can be employed as efficient fertilizers, are ecologically 99.9%, with the total of all components of the mixture being acceptable and are available to the plant at least over the entire 100%. growth period. 0021. The sulfur-crosslinked triglycerides are commer 0007 Surprisingly, it has now been found that mixtures cially available substances which are available for example based on sulfur-crosslinked triglyceride, obtainable by react from Rhein Chemie Rheinau GmbH under the RhenoprenR) ing at least one triglyceride and Sulfur at temperatures of aC. >150° C., further flow aids and optionally further additives 0022. The flow aids for the purposes of the invention are fulfill this task and are a highly effective fertilizer for plants release agents which are mixed with the comminuted Sulfur which require sulfur. crosslinked triglyceride to prevent clumping together of the 0008. An object of the present invention are mixtures, latter, mainly for the purposes of better suitability for comprising at least one Sulfur-crosslinked triglyceride, machines and dosability. obtainable by reacting at least one triglyceride and Sulfur at 0023 The flow aids employed for the purposes of the temperatures of 150°C., at least one flow aid based on silica, invention preferably take the form of fumed and/or precipi starch and/or metal oxides, and, if appropriate, further addi tated silica, obtainable from Evonik Degussa GmbH under tives. the names Sipernat(R) or Aerosil(R), polysaccharides composed 0009. In a preferred embodiment of the invention, the of C-D-glucose units as starch, obtainable from Sidstärke triglyceride is babussa oil, cottonseed oil, borage oil, thistle GmbH under the name Kartoffelstärke Superior, bentonite as oil (=safflower oil), groundnut oil, currant seed oil, hazelnut a mixture of different clay minerals such as montmorillonite, oil, herring oil, wood oil.jojoba oil, coconut oil, neatsfoot oil, quartZ, mica, spar, pyrite or else calcite, available from S&B bone oil, liver oil, linseed oil, corn oil, almond oil, olive oil, Industrial Minerals GmbH under the name IBECOR) US 2014/O123717 A1 May 8, 2014 AGROMONT and/or metal oxides of the elements Mg, Ca, 0040 Plants which require sulfur are preferably Cru obtainable from Rhein Chemie Rheinau GmbH under the ciferae Such as, for example, oilseed rape and mustard, cere name Rhenofit(R). als such as, for example, wheat, corn, Sorghum and millet, 0024. In this context, the mixtures according to the inven rye, oats and barley, Sugar beet, potatoes, fodder grass stems, tion may also comprise further additives and/or may also be cabbages, Liliaceae such as, for example, onions, garlic, leek, combined with customary nitrogen- and/or phosphorus-con chives, hyacinths, and Asparagaceae such as, for example, taining compounds such as, for example, ammonium nitrate Vegetable asparagus. and/or diammonium phosphate, or trace elements such as 0041. The scope of the invention extends to all of the boron, Zinc, copper, iron, molybdenum and/or manganese. definitions of radicals, indices, parameters and explanations 0025. These substances take the form of commercially in combination with each other which have been mentioned available compounds. hereinabove and mentioned hereinbelow in general terms or 0026. The content of each additive preferably amounts to in preferred ranges, that is to say that any combination from 0.0 to 10% of the mixture, with amounts from 0.0 to between the respective ranges and preferred ranges is also 1.0% of the mixture being preferred for the trace elements. possible. 0027. The flow aid content preferably amounts to from 0042. The examples which follow are intended to illustrate 0.1-40% by weight, especially preferably 1-5%. These flow the invention without having any limiting effect. aids preferably have a particle size of from 0.5-40.0 um, especially preferably a particle size of from 0.5-4.0 Lum. USE EXAMPLES 0028. In this context, the mixture according to the inven 10043. 1) Two comparison plots of in each case 1 m on a tion preferably has a particle size of from 0.3-20 mm.