EP2099285A1 - Procédé et système d'irrigation pour des sols contenant de l'hydrogel - Google Patents

Procédé et système d'irrigation pour des sols contenant de l'hydrogel

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Publication number
EP2099285A1
EP2099285A1 EP07847638A EP07847638A EP2099285A1 EP 2099285 A1 EP2099285 A1 EP 2099285A1 EP 07847638 A EP07847638 A EP 07847638A EP 07847638 A EP07847638 A EP 07847638A EP 2099285 A1 EP2099285 A1 EP 2099285A1
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EP
European Patent Office
Prior art keywords
water
irrigation
hydrogel
soil
polymerization
Prior art date
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Application number
EP07847638A
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German (de)
English (en)
Inventor
Aloys HÜTTERMANN
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BASF SE
Original Assignee
BASF SE
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Publication date
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Publication of EP2099285A1 publication Critical patent/EP2099285A1/fr
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G25/00—Watering gardens, fields, sports grounds or the like

Definitions

  • the present invention relates to the field of irrigation systems and methods, in particular irrigation systems and methods used in hydrogel-containing soils.
  • hydrogels which make them interesting for use in soils, is their ability to store water. For this reason, it has already been proposed several times to use hydrogels also in arid or semi-arid areas. Areas of application include u.a. the cultivation of crops, but also lawns, especially golf courses.
  • a method for irrigating hydrogel-containing soils is proposed, characterized in that irrigation requirement with an amount of water per square meter of> 0.5 l / m 2 and ⁇ 15 l / m 2 at a rate of> 20 to ⁇ 50 l / h is watered.
  • Such a method in many applications within the present invention, by limiting the amount of irrigation per square meter, can prevent water from penetrating into deeper soil layers and being lost to the purpose otherwise associated with the presence of hydrogels in the soil
  • hydrogel-containing in the sense of the present invention means or comprises in particular that hydrogels have been incorporated into the soil prior to planting the soil.
  • hydrogel in the sense of the present invention means or comprises in particular optionally water-containing, but water-insoluble polymers whose molecules are chemically bonded, for example by covalent or ionic bonds, or physically, eg by looping of the polymer chains Three-dimensional network are linked and which are able to swell with the addition of water or aqueous solutions under volume increase.
  • An advantageous and insofar preferred embodiment of the present method involves irrigating with irrigation requirement with a quantity of water per square meter of> 1 l / m 2 and ⁇ 9 l / m 2 , still preferably ⁇ 5 l / m 2 and ⁇ 8 l / m 2 becomes. This has been found to be advantageous in many embodiments of the present invention.
  • An advantageous and therefore preferred embodiment of the present method involves irrigating at irrigation requirements at a rate of> 30 to ⁇ 40 l / h.
  • a method for irrigating hydrogel-containing soils is proposed, characterized in that in the presence of a suction pressure of> 200 mbar near the roots and / or a partial section in the range of> 5 to ⁇ 50 cm soil depth is irrigated at a rate of> 20 to ⁇ 50 l / h.
  • suction pressure in the sense of the present invention includes in particular the water potential of the soil measured with conventional potentiometers.
  • root proximity in the sense of the present invention comprises in particular the soil area which is penetrated by the roots of the above-ground growing plants.
  • a partial section in the range of> 5 to ⁇ 50 cm floor depth includes or comprises in particular at least one selected point in the range of> 5 to ⁇ 50 cm floor depth at which the suction pressure is measured.
  • a suction pressure of> 500 mbar preferably> 800 mbar near the root and / or a partial section in the range of ⁇ 5 to ⁇ 50 cm soil depth irrigated. This has proved to be advantageous for many applications within the present invention, since the absorption capacity of the plants for the water is thus increased again.
  • An advantageous and insofar preferred embodiment of the present method includes that when irrigation is terminated when the suction pressure drops below ⁇ 50 mbar. This has been the case for many applications within the present Invention found to be advantageous, since the water supply is often optimal and not unnecessarily water enters the deeper soil layers.
  • An advantageous and insofar preferred embodiment of the present method involves irrigating at irrigation requirements at a rate of> 30 to ⁇ 40 l / h.
  • An advantageous and insofar preferred embodiment of the present method includes that the suction pressure is measured continuously or at intervals of> 5s and ⁇ 10 min, preferably> 1 min and ⁇ 5 min.
  • An advantageous and therefore preferred embodiment of the present method involves irrigation being carried out when the suction pressure near the roots is> 50 mbar and ⁇ 200 mbar and the irrigation is terminated when the suction pressure is outside these limits. This has proved to be advantageous for many applications within the present invention, since so the water supply can often be optimized.
  • An advantageous and insofar preferred embodiment of the present method involves irrigation being carried out when the suction pressure near the roots is> 50 mbar and ⁇ 500 mbar, more preferably ⁇ 800 mbar, and irrigation is terminated when the suction pressure is outside this Borders lies.
  • An advantageous and insofar preferred embodiment of the present method includes that with an amount of water per square meter of> 0.5 l / m 2 and ⁇ 15 l / m 2 , preferably> 1 l / m 2 and ⁇ 9 l / m 2 , still preferably ⁇ 5 l / m 2 and ⁇ 8 l / m 2 is irrigated.
  • An advantageous and insofar preferred embodiment of the present method includes that sprinkler and / or drip irrigation is used.
  • the present invention also relates to an irrigation system for a method according to the invention.
  • the hydrogel content in Gew% is from> 0.05% to ⁇ 1% of the dry soil.
  • ⁇ 90% of the hydrogel is at a depth of> 5 to ⁇ 50 cm.
  • the soil comprises at least one superabsorbent hydrogel, preferably in at least partially swollen form.
  • superabsorbent hydrogel hereinafter also referred to simply as “superabsorber” in the context of the present invention also and in particular
  • suberabsorb Schlierendes hydrogel in the context of the present invention crosslinked hydrophilic polymers, especially polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable Graft, crosslinked cellulose or starch ethers, crosslinked carboxymethylcellulose, partially crosslinked polyalkylene oxide or natural products swellable in aqueous liquids, such as guar derivatives understood.
  • the at least one superabsorbent has a swelling capacity in distilled water of at least> 80 g / g, preferably at least ⁇ 120 g / g and in a particularly preferred form at least> 180 g / g and a CRC ("Centrifuge Retention Capacity") of at least> 40 g / g, preferably at least> 80 g / g and in a particularly preferred form at least ⁇ 100 g / g.
  • a swelling capacity in distilled water of at least> 80 g / g, preferably at least ⁇ 120 g / g and in a particularly preferred form at least> 180 g / g and a CRC ("Centrifuge Retention Capacity") of at least> 40 g / g, preferably at least> 80 g / g and in a particularly preferred form at least ⁇ 100 g / g.
  • the at least one superabsorber is preferably obtained by polymerization of a monomer solution containing
  • Suitable monomers a) are, for example, ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, or derivatives thereof, such as acrylamide, methacrylamide, acrylic esters and methacrylic esters. Particularly preferred monomers are acrylic acid and methacrylic acid. Very particular preference is given to acrylic acid.
  • Preferred hydroquinone half ethers are hydroquinone monomethyl ether (MEHQ) and / or tocopherols.
  • Tocopherol is understood in particular to mean compounds of the following formula
  • R 3 is hydrogen or methyl
  • R 4 is hydrogen or methyl
  • R 5 is hydrogen or methyl
  • R 4 is hydrogen or an acid radical having 1 to 20 carbon atoms.
  • Preferred radicals for R 6 are acetyl, ascorbyl, succinyl, nicotinyl and other physiologically acceptable carboxylic acids.
  • the carboxylic acids may be mono-, di- or tricarboxylic acids.
  • R 6 is particularly preferably hydrogen or acetyl. Especially preferred is RRR-alpha-tocopherol.
  • the monomer solution preferably contains at most 130 ppm by weight, more preferably at most 70 ppm by weight, preferably at least 10 ppm by weight, more preferably at least 30 ppm by weight, in particular by 50 ppm by weight, hydroquinone halide, in each case based on acrylic acid, wherein acrylic acid salts are taken into account as acrylic acid.
  • an acrylic acid having a corresponding content of hydroquinone half-ether can be used.
  • the crosslinkers b) are compounds having at least two polymerizable groups which can be incorporated in the polymer network by free-radical polymerization.
  • Suitable crosslinkers b) are, for example, ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane, di- and triacrylates, mixed acrylates which contain ethylenically unsaturated groups in addition to acrylate groups, or crosslinker mixtures.
  • Suitable crosslinkers b) are, in particular, N, N'-methylenebisacrylamide and N, N'-methylenebismethacrylamide, esters of unsaturated mono- or polycarboxylic acids of polyols, such as diacrylate or triacrylate, for example butanediol or ethylene glycol diacrylate or methacrylate, and trimethylolpropane triacrylate and allyl- compounds such as allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl esters, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine, allyl esters of phosphoric acid and Vinylphosphonkladehvate, as described for example in EP 343 427 A2.
  • crosslinkers b) are pentaerythritol di-, pentaerythritol tri- and pentaerythritol tetraallyl ethers, polyethylene glycol diallyl ether, ethylene glycol diallyl ether, glycidic and glycerol triallyl ethers, polyallyl ethers based on sorbitol, and ethoxylated variants thereof.
  • Di (meth) acrylates of polyethylene glycols can be used in the process according to the invention, the polyethylene glycol used having a molecular weight between 300 and 1000.
  • crosslinkers b) are di- and thacrylates of 3 to 15 times ethoxylated glycerol, of 3 to 15 times ethoxylated trimethylolpropane, of 3 to 15 times ethoxylated trimethylolethane, in particular di- and triacrylates of 2 to 6-times ethoxylated glycerol or trimethylolpropane, the 3-fold propoxylated glycerol or trimethylolpropane, and 3-times mixed ethoxylated or propoxylated glycerol or trimethylolpropane, 15-ethoxylated glycerol or trimethylolpropane, as well as 40-times ethoxylated glycerol, trimethylolethane or trimethylolpropane ,
  • Very particularly preferred crosslinkers b) are the polyethyleneglyoxylated and / or propoxylated glycerols esterified with acrylic acid or methacrylic acid to form di- or thacrylates.
  • Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol.
  • diacrylates or triacrylates of 1 to 5 times ethoxylated and / or propoxylated glycerol.
  • Most preferred are the triacrylates of 3 to 5 times ethoxylated and / or propoxylated glycerol.
  • acrylamide, methacrylamide, crotonic acid amide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate are monomers which can be copolymerized with the monomers a).
  • Suitable water-soluble polymers d) can be polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives, polyglycols, polymers which are formally wholly or partly made of vinylamine monomers, such as partially or completely hydrolyzed polyvinylamide (so-called "polyvinylamine”) or polyacrylic acids, preferably polyvinyl alcohol and starch.
  • Suitable polymerization regulators are, for example, thio compounds, such as thioglycolic acid, mercaptoalcohols, eg. B. 2-mercaptoethanol, mercaptopropanol and mercaptobutanol, dodecyl mercaptan, formic acid, ammonia and amines, eg. As ethanolamine, diethanolamine, triethanolamine, triethylamine, morpholine and piperidine.
  • thio compounds such as thioglycolic acid, mercaptoalcohols, eg. B. 2-mercaptoethanol, mercaptopropanol and mercaptobutanol, dodecyl mercaptan, formic acid, ammonia and amines, eg. As ethanolamine, diethanolamine, triethanolamine, triethylamine, morpholine and piperidine.
  • the monomers (a), (b) and optionally (c) are, optionally in the presence of water-soluble polymers d), in 20 to 80, preferably 20 to 50, in particular 30 to 45 wt .-% aqueous solution in the presence of polymerization initiators (co) polymerized with each other.
  • polymerization initiators it is possible to use all compounds which decompose into free radicals under the polymerization conditions, eg. As peroxides, hydroperoxides, hydrogen peroxide, persulfates, azover- compounds and the so-called redox initiators. Preference is given to the use of water-soluble initiators. In some cases, it is advantageous to use mixtures of different polymerization initiators, for.
  • Suitable organic peroxides are, for example, acetyl acetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perohexanoate, tert-butyl perisobutyrate, tert-butyl per-2-ethylhexanoate, tert Butyl perisononanoate, tert-butyl permaleate, tert-butyl perbenzoate, tert-butyl per-3,5,5-tri-methylhexanoate and tert-Amylperneodekanoat.
  • Suitable polymerization initiators are azo initiators, e.g. 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N-dimethylene) -isobutyramidine dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4,4'-azobis (e.g. 4-cyanovaleric acid).
  • azo initiators e.g. 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N-dimethylene) -isobutyramidine dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4,4'-azobis (e.g. 4-cyanovaleric acid).
  • the polymerization initiators mentioned are used in conventional amounts, for. B. in amounts of 0.01 to 5, preferably 0.1 to 2 mol%, based on the monomers to be polymerized.
  • the redox initiators contain as oxidizing component at least one of the abovementioned per compounds and a reducing component, for example ascorbic acid, glucose, sorbose, ammonium or alkali metal hydrogen sulfite, sulfite, thiosulfate, hyposulfite, pyrosulfite or sulfide, metal salts such as iron - ll-ions or silver ions or sodium hydroxymethylsulfoxylate.
  • reducing component of the redox initiator ascorbic acid or sodium pyrosulfite is preferably used.
  • Relative to the employed in the polymerization amount of monomers used 1 ⁇ 10 "5 and 1 mol% of the reducing component of the redox initiator and 1 • 10" 5 to 5 mol% of the oxidizing component.
  • the oxidizing component or in addition one can also use one or more water-soluble azo initiators.
  • a redox initiator consisting of hydrogen peroxide, sodium peroxodisulfate and ascorbic acid.
  • these components are in the concentrations of 1 ⁇ 1O 2 mol% hydrogen peroxide, 0.084 mol% sodium peroxodisulfate and 2.5 ⁇ 10- 3 mol% ascorbic acid based on the monomers used.
  • the aqueous monomer solution may contain the initiator dissolved or dispersed. However, the initiators can also be fed to the polymerization reactor separately from the monomer solution.
  • the polymerization inhibitors require dissolved oxygen for optimum performance.
  • the polymerization inhibitors may be prepared by inerting, i. Flow through with an inert gas, preferably nitrogen, to be freed of dissolved oxygen. This is done by means of inert gas, which can be introduced in cocurrent, countercurrent or intermediate inlet angles. Good mixing can be achieved, for example, with nozzles, static or dynamic mixers or bubble columns.
  • the oxygen content of the monomer solution before polymerization is reduced to less than 1 ppm by weight, more preferably less than 0.5 ppm by weight.
  • the monomer solution is optionally passed through the reactor with an inert gas stream.
  • the at least one superabsorbent is obtained by polymerization of an aqueous monomer solution and optionally subsequent comminution of the hydrogel.
  • Suitable preparation methods are e.g.
  • the reaction is preferably carried out in a kneader or on a belt reactor.
  • a particularly preferred process within the scope of this invention is continuous gel polymerization.
  • a monomer mixture is first prepared by the neutralizing agent, optional comonomers and / or other auxiliaries are added to the acrylic acid solution in temporally and / or spatially separate addition sequence, and the mixture is then transferred to the reactor, or is already presented in the reactor. The last addition is the metering of the initiator system to start the polymerization.
  • the reaction proceeds to the polymer gel (i.e., the polymer swollen to the gel in the solvent of the polymerization - usually water -) which, in the case of stirred polymerization, is already comminuted in advance.
  • the polymer gel is then dried, if necessary, also crushed and sieved and transferred for further surface treatment.
  • the acid groups of the resulting hydrogels are usually partially neutralized, generally at least> 25 mole%, preferably at least> 27 mole% and more preferably at least> 40 mole%, and generally at most ⁇ 85 mole%, preferably at most ⁇ 80 mol% and in a particularly preferred form at most ⁇ 75 mol%, to which the customary neutralizing agents can be used, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal bicarbonates and mixtures thereof.
  • alkali metal salts and ammonium salts can be used become.
  • Sodium and potassium are particularly preferred as alkali metals, but most preferably sodium hydroxide, sodium carbonate or sodium bicarbonate and mixtures thereof.
  • the neutralization is achieved by mixing the neutralizing agent as an aqueous solution or preferably as a solid.
  • the neutralizing agent for example, sodium hydroxide with a water content significantly below ⁇ 50 wt .-% may be present as a waxy mass with a melting point above> 23 ° C. In this case, a dosage as general cargo or melt at elevated temperature is possible.
  • the neutralization can be carried out after the polymerization at the hydrogel stage. However, it is also possible to carry out the neutralization to the desired degree of neutralization completely or partially before the polymerization.
  • partial neutralization before the polymerization generally at least> 10 mol%, preferably at least> 15 mol% and generally at most ⁇ 40 mol%, preferably at most ⁇ 30 mol% and in a particularly preferred form at most ⁇ 25 mol% % of the acid groups in the monomers used are neutralized before the polymerization by adding a part of the neutralizing agent already to the monomer solution.
  • the desired final degree of neutralization is in this case set only towards the end or after the polymerization, preferably at the stage of the hydrogel before it is dried.
  • the monomer solution is neutralized by mixing in the neutralizing agent.
  • the hydrogel can be mechanically comminuted in the neutralization, for example by means of a meat grinder or similar apparatus for comminuting gel-like masses, wherein the neutralizing agent is sprayed, sprinkled or poured over and then mixed thoroughly.
  • the gel mass obtained can be further gewolfft for homogenization.
  • the monomer solution is adjusted to the desired final degree of neutralization prior to polymerization by addition of the neutralizing agent.
  • the gels obtained from the polymerization are optionally some time, for example at least> 30 minutes, preferably at least> 60 minutes and more preferably at least> 90 minutes and generally at most ⁇ 12 hours, preferably at most ⁇ 8 hours and most preferably at most ⁇ 6 hours at a temperature of generally at least ⁇ 50 0 C and preferably at least> 70 0 C and generally at most ⁇ 130 0 C and preferably kept at most ⁇ 100 0 C, whereby their properties can often be improved.
  • the neutralized hydrogel is then dried with a belt or drum dryer until the residual moisture content is preferably less than 15% by weight, in particular less than 10% by weight, the water content being that recommended by EDANA (European Disposables and Nonwovens Association) Test Method No. 430.2-02 "Moisture Content" is determined.
  • the dry superabsorbent consequently contains up to ⁇ 15% by weight of moisture, preferably at most ⁇ 10% by weight.
  • v Preferably at least ⁇ 25 wt .-% and in a particularly preferred form at least ⁇ 30 wt .-% and generally at most ⁇ 90 wt .-%, preferably at most ⁇ 85 wt .-% and most preferably at most ⁇ 80 wt .-% is.
  • Particularly advantageous is the Vent the dryer with nitrogen or other non-oxidizing inert gas.
  • sufficient ventilation and removal of the water vapor also leads to an acceptable product.
  • Advantageous in terms of color and product quality is usually the shortest possible drying time.
  • the dried hydrogel (which is no longer a gel (even if so often called), but a dry polymer with superabsorbent properties, which falls under the term "superabsorbent”) is preferably ground and sieved, wherein for grinding usually roller mills, pin mills, hammer mills
  • the particle size of the screened, dry hydrogel is preferably below 1000 ⁇ m, more preferably below 900 ⁇ m, most preferably below 850 ⁇ m, and preferably above 800 ⁇ m, more preferably above 90 ⁇ m , most preferably over> 100 microns.
  • the superabsorbent polymers thus prepared are usually referred to as "base polymers" and are preferably subsequently postcrosslinked Surface crosslinking can be carried out in a manner known per se with dried, ground and screened polymer particles are usually applied in the form of a solution to the surface of the base polymer particles.
  • Di- or polyepoxides for example di- or polyglycidyl compounds, such as phosphonic acid diglycidyl esters, ethylene glycol diglycidyl ethers or bischlorohydrin ethers of polyalkylene glycols,
  • Alkoxysilyl compounds polyaziridines, compounds containing aziridine units based on polyethers or substituted hydrocarbons, for example bis-N-aziridinomethane,
  • Methyltriglycol polyethylene glycols having an average molecular weight Mw of 200-10,000, di- and polyglycerol, pentaerythritol, sorbitol, the oxethylates of these polyols and their esters with carboxylic acids or carbonic acid such as ethylene carbonate or propylene carbonate, carbonic acid derivatives such as urea, thiourea, guanidine, dicyandiamide, 2- oxazolidinone and its derivatives, bisoxazoline, polyoxazolines, di- and polyisocyanates,
  • di- and poly-N-methylol compounds such as methylenebis (N-methylol-methacrylamide) or melamine-formaldehyde resins, • compounds with two or more blocked isocyanate groups such as trimethylhexamethylene diisocyanate blocked with 2,2,3,6-tetramethyl -pipehdinon-fourth
  • acid catalysts such as p-toluenesulfonic acid, phosphoric acid, boric acid or ammonium dihydrogen phosphate may be added.
  • Particularly suitable postcrosslinkers are di- or polyglycidyl compounds such as ethylene glycol diglycidyl ether, the reaction products of polyamidoamines with epichlorohydrin, 2-oxazolidinone and N-hydroxyethyl-2-oxazolidinone.
  • the surface postcrosslinking (often only "postcrosslinking") is usually carried out in such a way that a solution of the surface postcrosslinker (often only “Nachvemetzer”) is sprayed onto the hydrogel or the dry base polymer powder.
  • the solvent used for the surface postcrosslinker is a conventional suitable solvent, for example water, alcohols, DMF, DMSO and mixtures thereof. Particularly preferred are water and water / alcohol mixtures such as water / methanol, water / isopropanol, water / 1, 2-propanediol and water / 1, 3-propanediol.
  • the spraying of a solution of the postcrosslinker is preferably carried out in mixers with moving mixing tools, such as screw mixers, paddle mixers, disk mixers, ploughshare mixers and paddle mixers.
  • moving mixing tools such as screw mixers, paddle mixers, disk mixers, ploughshare mixers and paddle mixers.
  • Vertical mixers are particularly preferred, plowshare mixers and paddle mixers are very particularly preferred.
  • Suitable and known mixers include for example Lödige ® - Bepex ® - Nauta ® - Processall® ® - and Schugi ® mixer. Very particular preference high-speed mixer, for example of the Schugi Flexomix ® or Turbolizer ®, are used.
  • a temperature treatment step essentially for carrying out the surface postcrosslinking reaction (yet usually only referred to as "drying"), may optionally follow, preferably in a downstream heated mixer ("dryer") at a temperature of Generally at least> 50 0 C, preferably at least> 80 0 C and in a particularly preferred form at least ⁇ 90 0 C and generally at most ⁇ 250 0 C, preferably at most ⁇ 200 0 C and in a particularly preferred form at most ⁇ 150 0 C.
  • dryer a downstream heated mixer
  • Die average residence time (ie the average residence time of the individual superabsorber particles) of the superabsorbent to be treated in the dryer is generally at least ⁇ 1 minute, preferably at least ⁇ 3 minutes and more preferably at least ⁇ 5 minutes and generally at most ⁇ 6 hours, preferably at most ⁇ 2 hours and more preferably ⁇ 1 hour at the most.
  • the thermal drying is carried out in conventional dryers, such as tray dryers, rotary kilns or heatable screws, preferably in contact dryers.
  • dryers in which the product is moved ie heated mixers, particularly preferably paddle dryers, most preferably disc dryers.
  • Suitable dryers include for example Bepex ® dryers and Nara ® dryers. Moreover, fluidized bed dryers can also be used. The drying can also be done in the mixer itself, by heating the jacket or blowing a preheated gas such as air. However, it is also possible, for example, to use an azeotropic distillation as the drying process. The crosslinking reaction can take place both before and during drying.
  • the hydrophilicity of the particle surface of the base polymers is modified by forming complexes.
  • the formation of the complexes on the outer shell of the particles is carried out by spraying solutions of divalent or polyvalent cations, wherein the cations can react with the acid groups of the polymer to form complexes.
  • divalent or polyvalent cations are polymers which are formally wholly or partly made up of vinylamine monomers, such as partially or completely hydrolyzed.
  • the polyvinylamide (so-called "polyvinylamine”), whose amine groups are always partially protonated to ammonium groups, even at very high pH values or metal cations such as Mg 2+ , Ca 2+ , Al 3+ , Sc 3+ , Ti 4+ , Mn 2+ , Fe 2+ / 3+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Y 3+ , Zr 4+ , La 3+ , Ce 4+ , Hf 4+ , and Au 3+ Preferred metal cations are Mg 2+ , Ca 2+ , Al 3+ , Ti 4+ , Zr 4+ and La 3+ , and particularly preferred metal cations, are Al 3+ , Ti 4+ and Zr 4+ The metal cations can be used both alone and mixed with one another.
  • metal cations can be used both alone and mixed with one another.
  • metal salts are suitable have a sufficient solubility in the solvent to be used.
  • metal salts with weakly complexing anions such as chloride, nitrate and Sulfate, hydrogen sulfate, carbonate, bicarbonate, nitrate, phosphate, Hydrogen phosphate, dihydrogen phosphate and carboxylate, such as acetate and lactate.
  • aluminum sulfate is used.
  • solvents for the metal salts water, alcohols, DMF, DMSO and mixtures of these components can be used. Particularly preferred are water and water / alcohol mixtures such as water / methanol,
  • the treatment of the base polymer with solution of a di- or polyvalent cation is carried out in the same way as with surface post-crosslinker, including the optional drying step.
  • Surface postcrosslinker and polyvalent cation can be sprayed in a common solution or as separate solutions.
  • the spraying of the metal salt solution onto the superabsorbent particles can be carried out both before and after the surface crosslinking.
  • the spraying of the metal salt solution is carried out in the same step by spraying the crosslinker solution, wherein both solutions are sprayed separately successively or simultaneously via two nozzles, or crosslinker and metal salt solution can be sprayed together via a nozzle ,
  • a drying step is carried out after the surface postcrosslinking and / or treatment with complexing agent, it is advantageous, but not absolutely necessary, to cool the product after drying.
  • the cooling can be continuous or discontinuous, conveniently the product is continuously conveyed to a dryer downstream cooler.
  • Any apparatus known for removing heat from powdered solids may be used for this purpose, in particular any apparatus mentioned above as a drying apparatus, unless it is supplied with a heating medium but with a cooling medium, such as cooling water, so that over the walls and depending on the construction No heat is introduced into the superabsorber via the stirring elements or other heat exchange surfaces, but is removed therefrom.
  • coolers in which the product is moved ie cooled mixers, for example, blade coolers, disk coolers or paddle coolers, for example Nara ® - or Bepex ® coolers.
  • the superabsorbent can also be cooled in the fluidized bed by blowing in a cooled gas such as cold air. The conditions of the cooling are adjusted so that a superabsorbent is obtained with the temperature desired for further processing.
  • a mean residence time in the cooler of generally at least ⁇ 1 minute, preferably at least ⁇ 3 minutes and more preferably at least ⁇ 5 minutes, and generally at most ⁇ 6 hours, preferably at most ⁇ 2 hours and most preferably at most ⁇ 1 Set hour and the cooling capacity so that the product obtained a temperature of generally at least ⁇ 0 0 C, preferably at least> 10 0 C and in a particularly preferred form at least ⁇ 20 0 C and generally at most ⁇ 100 ° C, preferably at most ⁇ 80 0 C and in a particularly preferred form at most ⁇ 60 0 C.
  • a further modification of the superabsorbents by admixing finely divided inorganic solids, such as silica, alumina, titanium dioxide and iron (II) oxide take place, whereby the effects of the surface treatment are further enhanced.
  • finely divided inorganic solids such as silica, alumina, titanium dioxide and iron (II) oxide
  • admixture of hydrophilic silica or alumina with an average size of the primary particles of> 4 to ⁇ 50 nm and a specific surface area of> 50 - ⁇ 450 m 2 / g.
  • the admixture of finely divided inorganic solids is preferably carried out after the surface modification by crosslinking / complex formation, but can also be carried out before or during these surface modifications.
  • superabsorber is provided with other common additives and excipients that affect storage or handling properties.
  • additives and excipients include stains, opaque additives to improve the visibility of swollen gel, which is desirable in some applications, additives to improve the flow behavior of the powder, surfactants or the like.
  • dedusting or dust binder is added to the superabsorbent.
  • Dedusting or dust binding agents are known, for example, polyether glycols such as polyethylene glycol having a molecular weight of> 400 to ⁇ 20,000 g / mol, polyols such as glycerol, sorbitol, neopentyl glycol or trimethylolpropane, which are optionally also ⁇ 7 to ⁇ 20-fold ethoxylated used , Even a finite water content of the superabsorbent can be adjusted by adding water, if desired.
  • polyether glycols such as polyethylene glycol having a molecular weight of> 400 to ⁇ 20,000 g / mol
  • polyols such as glycerol, sorbitol, neopentyl glycol or trimethylolpropane, which are optionally also ⁇ 7 to ⁇ 20-fold ethoxylated used .
  • the solids, additives and auxiliaries can each be added in separate process steps, but in most cases the most convenient method is to add them to the superabsorber in the cooler, for example by spraying a solution or adding it in finely divided solid or in liquid form.
  • the surface postcrosslinked superabsorbent is optionally ground and / or sieved in the usual way. Milling is typically not required here, but most often, the setting of the desired particle size distribution of the product, the screening of formed agglomerates or fine grain is appropriate. Agglomerates and fines are either discarded or preferably recycled to the process in a known manner and at a suitable location; Agglomerates after comminution.
  • the particle size of the superabsorbent particles is preferably at most ⁇ 1000 .mu.m, more preferably at most ⁇ 900 .mu.m, very preferably at most ⁇ 850 .mu.m, and preferably at least> 80 .mu.m, more preferably at least> 90 .mu.m, most preferably at least> 100 .mu.m.
  • Typical sieve cuts are, for example,> 106 to 850 ⁇ m or ⁇ 150 to ⁇ 850 ⁇ m.
  • the present invention also relates to a use of the method according to the invention and / or an irrigation system for
  • Fig. 1 A Besipiel for the distribution of water at today's usual irrigation
  • Fig. 2 is a graph of cumulative rainfall (in mm) against the
  • FIG. 3 shows a diagram of the water content for a hydrogel-containing test soil once irrigated according to an embodiment of the method according to the invention and once in a control experiment;
  • Fig. 4 is a diagram of the water content for a hydrogel-containing test soil two weeks after irrigation, once irrigated according to a
  • Fig. 1 shows the distribution of the water in the soil after today usual irrigation.
  • One tree - Hex europaeus - has been planted in a container filled with humus-rich brown earth. (Fig. 1).
  • BoldenMap Tensiometer are introduced, which measure the water content of the soil in the soil depths 20 cm (I), 60 cm (II), 110 cm (III) and 150 cm (IV)
  • the water contents are measured as negative water potentials, the higher the the absolute value of the water potentials is, the lower the water content in the soil.
  • the water distribution results from the curves according to an irrigation common today in horticultural practice:
  • Fig. 2 shows a graph of the accumulated rainfall (in mm) against infiltration rate in mm / h for three different hydrogel concentrations.
  • test soil containing no hydrogel was introduced. 2. The test soil was mixed with 0.4% hydrogel 3. The test soil was treated with 0.6% hydrogel.
  • FIG. 3 shows that in an irrigation according to the invention, the water does not penetrate into the lower, root-free, soil layers.
  • cylinders 1a and 1b were irrigated with 6 liters of water as usual in a nursery with a watering can, the application time took about one minute, the pot was provided with a commercial casting attachment. This corresponds to an application rate of 360 l per hour.
  • Fig. 3 shows that in the rapid irrigation almost half of the water is leaked into the lower soil layer, while in the slow irrigation by spraying almost all water remained in the upper - hydrogel inconveniencen - soil.
  • Fig. 4 shows that there was no balance in the water contents between the hydrogel-mixed and non-hydrogel soils. In all soils, the water content has decreased as a result of evaporation in the greenhouse, but the differences in water content measured directly after watering have remained.
  • CRC Centrifuge Retention Capacity
  • CRC Centrifuge Retention Capacity

Landscapes

  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Cultivation Of Plants (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne l'irrigation dirigée de sols contenant de l'hydrogel.
EP07847638A 2006-12-07 2007-12-03 Procédé et système d'irrigation pour des sols contenant de l'hydrogel Withdrawn EP2099285A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006058065A DE102006058065A1 (de) 2006-12-07 2006-12-07 Bewässerungsverfahren und -system für hydrogelhaltige Böden
PCT/EP2007/063126 WO2008068212A1 (fr) 2006-12-07 2007-12-03 Procédé et système d'irrigation pour des sols contenant de l'hydrogel

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EP2099285A1 true EP2099285A1 (fr) 2009-09-16

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US (1) US20100050506A1 (fr)
EP (1) EP2099285A1 (fr)
AU (1) AU2007329022B2 (fr)
DE (1) DE102006058065A1 (fr)
WO (1) WO2008068212A1 (fr)

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EP2178965A4 (fr) * 2007-07-31 2013-05-15 Shinewill Internat Ltd Composition et ses applications
US9850379B2 (en) * 2010-11-08 2017-12-26 Naihong Li Gels and hydrogels
CN104838976A (zh) * 2015-03-20 2015-08-19 甘肃农业大学 酿酒葡萄节水高产优质灌溉方法
KR20220044758A (ko) 2019-08-07 2022-04-11 바이엘 크롭사이언스 엘피 제자리 형성된 수분 흡수 히드로겔을 사용한 식물 건강의 개선

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US3680778A (en) * 1970-07-21 1972-08-01 Nelson Mfg Co Inc L R Improved water distribution in the operation of pivot move agricultural irrigation sprinkler systems
US3917166A (en) * 1974-06-17 1975-11-04 Andco Inc Drip irrigation method
FR2520582A1 (fr) * 1982-02-03 1983-08-05 Guisse Francis Procede d'irrigation controlee des terrains
IL70355A (en) * 1983-11-30 1988-05-31 Plassim Tech Plastics Works Irrigation emitter unit
US5185024A (en) * 1991-10-24 1993-02-09 Aqua Source Inc. Application of agricultural polyammonium acrylate or polyacrylamide hydrogels
EP1068279A1 (fr) 1998-03-26 2001-01-17 STOCKHAUSEN GmbH & CO. KG PROCEDE PERMETTANT D'AUGMENTER LE pH DANS LES SOLS ACIDES
DE19813425A1 (de) 1998-03-26 1999-09-30 Stockhausen Chem Fab Gmbh Verfahren zur Verminderung der Pflanzenverfügbarkeit von Schwermetallen sowie Verwendung von vernetzten Polyacrylaten in dem Verfahren
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AU2007329022B2 (en) 2012-09-06
US20100050506A1 (en) 2010-03-04
WO2008068212A1 (fr) 2008-06-12
AU2007329022A1 (en) 2008-06-12
DE102006058065A1 (de) 2008-06-19

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