NZ759837A - Fertilizer mixture containing nitrification inhibitor - Google Patents
Fertilizer mixture containing nitrification inhibitor Download PDFInfo
- Publication number
- NZ759837A NZ759837A NZ759837A NZ75983714A NZ759837A NZ 759837 A NZ759837 A NZ 759837A NZ 759837 A NZ759837 A NZ 759837A NZ 75983714 A NZ75983714 A NZ 75983714A NZ 759837 A NZ759837 A NZ 759837A
- Authority
- NZ
- New Zealand
- Prior art keywords
- dimethylpyrazole
- succinic acid
- aqueous solution
- fertilizer
- crystallization
- Prior art date
Links
- 239000003337 fertilizer Substances 0.000 title description 69
- 239000003112 inhibitor Substances 0.000 title description 32
- 239000000203 mixture Substances 0.000 title description 26
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000001384 succinic acid Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims abstract description 26
- 230000008025 crystallization Effects 0.000 claims abstract description 26
- VQTVFIMEENGCJA-UHFFFAOYSA-N 3,4-dimethyl-1H-pyrazole Chemical compound CC=1C=NNC=1C VQTVFIMEENGCJA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003085 diluting agent Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 12
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 12
- 239000011976 maleic acid Substances 0.000 claims abstract description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 claims abstract 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 235000021317 phosphate Nutrition 0.000 claims description 7
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 229920000388 Polyphosphate Polymers 0.000 claims description 5
- 239000001205 polyphosphate Substances 0.000 claims description 5
- 235000011176 polyphosphates Nutrition 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- XKVUYEYANWFIJX-UHFFFAOYSA-N 5-methyl-1h-pyrazole Chemical compound CC1=CC=NN1 XKVUYEYANWFIJX-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 25
- 239000011707 mineral Substances 0.000 description 25
- 235000010755 mineral Nutrition 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- NGLMYMJASOJOJY-UHFFFAOYSA-O azanium;calcium;nitrate Chemical compound [NH4+].[Ca].[O-][N+]([O-])=O NGLMYMJASOJOJY-UHFFFAOYSA-O 0.000 description 17
- 239000002689 soil Substances 0.000 description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 11
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- LXKCHCXZBPLTAE-UHFFFAOYSA-N 3,4-dimethyl-1H-pyrazole phosphate Chemical compound OP(O)(O)=O.CC1=CNN=C1C LXKCHCXZBPLTAE-UHFFFAOYSA-N 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 5
- 244000061456 Solanum tuberosum Species 0.000 description 5
- 235000002595 Solanum tuberosum Nutrition 0.000 description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 5
- 239000001095 magnesium carbonate Substances 0.000 description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 5
- 235000014380 magnesium carbonate Nutrition 0.000 description 5
- FGIFCVDSYXGMRG-UHFFFAOYSA-N 2-(3,4-dimethylpyrazol-1-yl)butanedioic acid Chemical compound CC1=CN(C(CC(O)=O)C(O)=O)N=C1C FGIFCVDSYXGMRG-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 230000004720 fertilization Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000001272 nitrous oxide Substances 0.000 description 4
- VQBSBAQOMFNIRC-UHFFFAOYSA-N 2-(2,3-dimethyl-3H-pyrazol-1-yl)butanedioic acid Chemical compound CN1N(C=CC1C)C(C(=O)O)CC(=O)O VQBSBAQOMFNIRC-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- DIOLOCSXUMYFJN-UHFFFAOYSA-N calcium;azane Chemical compound N.[Ca+2] DIOLOCSXUMYFJN-UHFFFAOYSA-N 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 150000003217 pyrazoles Chemical class 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000003419 tautomerization reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 240000007124 Brassica oleracea Species 0.000 description 2
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 2
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 2
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 239000012223 aqueous fraction Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- CSRWSPHRKUSDRE-UHFFFAOYSA-N 4-(chloromethyl)-1h-pyrazole Chemical class ClCC=1C=NNC=1 CSRWSPHRKUSDRE-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 240000007087 Apium graveolens Species 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 235000010591 Appio Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- YNGQHHUHCOYPKT-UHFFFAOYSA-L azanium;calcium;phosphate Chemical compound [NH4+].[Ca+2].[O-]P([O-])([O-])=O YNGQHHUHCOYPKT-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000001863 plant nutrition Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000723 toxicological property Toxicity 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Landscapes
- Fertilizers (AREA)
Abstract
The invention relates to a process for preparing 2-(N-3,4-dimethylpyrazole)succinic acid or a salt thereof by reaction of 3,4-dimethylpyrazole with maleic acid and/or maleic anhydride in the absence of organic solvents or diluents, and subsequent crystallization from the resulting reaction product in the absence of organic solvents or diluents.
Description
Fertilizer mixture containing nitrification inhibitor
This application is a onal of New Zealand Application No. 721123, filed on 12
December 2014, derives from 2014/077570, and claims priority to DE 10 2013 020
588.3, filed 13 December 2013, the contents of each of which are hereby incorporated by
reference in their entirety.
Description
The invention s to fertilizer mixtures comprising 2-(N-3,4-dimethylpyrazole)succinic
acid (isomer mixture of 2-(3,4-dimethyl-1H-pyrazolyl)succinic acid and 2-(2,3-dimethyl-1H-
pyrazolyl)succinic acid, in a ratio of preferably about 80 : 20, also referred to as DMPSA,
or one of the dual compounds) and based on m ammonium e (CAN) mineral
fertilizer, and also to a process for preparing DMPSA.
In order to provide plants in agriculture with the nitrogen they need, fertilizers comprising
ammonium compounds are frequently used.
Ammonium compounds are converted microbially to nitrate (nitrification) in the soil within a
vely short time. Nitrate, however, can be leached from the soil. The leached fraction is
no longer available for plant nutrition, and so for this reason rapid ication is undesirable.
In order to exploit the fertilizer more effectively, therefore, nitrification inhibitors are added to
it. One known group of nitrification inhibitors are pyrazole compounds.
One problem attending the use of le compounds as nitrification inhibitors is their high
volatility. When fertilizer preparations containing pyrazole compounds are stored, therefore,
there is a uous loss of active ingredient as a result of evaporation. For this reason the
pyrazole compounds must be formulated in a nonvolatile form by means of appropriate
measures.
EP-B-1 120 388 describes phosphoric acid addition salts of 3,4-dimethylpyrazole and 4-
chloromethylpyrazole for use as nitrification inhibitors. Through the salt form it is possible
for the lity to be significantly reduced.
WO 96/24566 relates to the use of low-volatility le derivatives having hydrophilic
groups as nitrification inhibitors. As an example, -methylpyrazole)succinic acid is
proposed as a nitrification inhibitor. Suitable mineral fertilizers cited are ammoniumcontaining
nitrates, sulfates or phosphates. The ty of this nitrification inhibitor makes it
more difficult to use, particularly at relatively high concentrations.
and describe nitrification inhibitors one of which is
DMPSA.
Nitrification inhibitors suitable for CAN fertilizers have not so far been disclosed, and so
to date CAN fertilizers have been used without nitrification inhibitor.
It is an object of the present invention to provide a CAN fertilizer mixture which results
in a low loss of nitrification inhibitor in the course of storage and application. A further
object of the present invention is to provide an effective nitrification inhibitor for CAN,
exhibiting a low lity during storage and during application in the soil, and also
corresponding CAN fertilizer mixtures. A further intention is to provide an improved
process for the preparation of 2-(N-3,4-dimethylpyrazole)succinic acid.
The object is achieved in accordance with the invention by means of a fertilizer mixture
comprising
A. calcium ammonium nitrate mineral izer which, besides ammonium nitrate and
calcium carbonate and/or ium ate and optionally water, may
contain up to 15 wt%, based on the calcium ammonium nitrate mineral fertilizer
without water, of further ingredients,
B. 100 to 10 000 ppm by , based on component A without water, of ,4-
dimethylpyrazole)succinic acid.
The water fraction in component A and in the fertilizer mixture is preferably not more
than 1.0 wt%, more ably not more than 0.5 wt%, more particularly not more than
0.3 wt%, and is therefore negligible in the balance of ties. Components A and B
preferably make up at least 90 wt%, more preferably at least 95 wt%, of the fertilizer
mixture.
Besides ammonium nitrate, the mineral fertilizer may comprise calcium carbonate or
ium carbonate, or a mixture of calcium carbonate with magnesium carbonate.
Here and in the text below, quantity figures, particularly of the nitrification inhibitor, are
based preferably on the solid mineral fertilizer A, even if water is additionally present,
such as in liquid formulations, for example.
The ion further relates to a process for producing a fertilizer mixture of this kind
by ucing 2-(N-3,4-dimethylpyrazole)succinic acid into the calcium ammonium
e mineral fertilizer and/or applying 2-(N-3,4-dimethylpyrazole)succinic acid to the
calcium ammonium e mineral fertilizer.
The invention further relates to a process for fertilizing soils exploited agriculturally or
ulturally, characterized in that a fertilizer e comprising
A. calcium um nitrate l fertilizer which, besides ammonium nitrate and
calcium carbonate and/or magnesium carbonate and optionally water, may
contain up to 15 wt%, based on the calcium ammonium nitrate mineral izer
without water, of further ingredients,
B. 100 to 10 000 ppm by weight, based on component A without water, of 2-(N-3,4-
dimethylpyrazole)succinic acid,
or components A and B separately, but within a period of 0 to 5 hours, preferably 0 to
1 hour, more preferably approximately at the same time, is d to the soils.
The invention further relates to a process for preparing 2-(N-3,4-
dimethylpyrazole)succinic acid by reaction of 3,4-dimethylpyrazole with maleic acid
and/or maleic ide in the absence of organic solvents or diluents, and subsequent
crystallization from the resulting reaction product in the absence of organic solvents or
diluents.
In this t, the ing processes may be excluded or excepted:
“In the first experiment, 41.608 mol of maleic anhydride with a purity of more than
99.5% were introduced and ved in 11 liters of distilled water. The temperature
rose here by 10°C. Then 41.608 mol of 80% strength aqueous 3,4-dimethylpyrazole
solution ding to NMR spectrum, the solution of 3,4-DMP used contained
approximately 2% of otherwise acterized impurities) were added, the
temperature rising by a further 12°C. After the end of the addition, the reaction mixture
was heated to an internal temperature of 100°C. When this temperature was reached,
the reaction mixture was stirred at 100°C for 24 hours and then cooled. When the
reaction mixture had cooled to 90°C, a sample was taken for NMR-spectroscopic
reaction monitoring, and the reaction mixture was subsequently seeded with 1 g of
product (crystals of 2-(N-3,4-dimethylpyrazole)succinic acid). At this temperature,
crystallization did not yet begin, but the added crystals also no longer dissolved. On
further cooling, crystallization began slowly from around 85°C. The major quantity of
the product only crystallized at just below 80°C, with an increase in temperature. For
complete crystallization, the reaction mixture was left to cool overnight with stirring. The
precipitated solid was filtered off on three 8 L G3 glass suction filters, using a suction
flask and membrane pump, under d pressure, and the solid product was washed
40 with a total of 8 liters of distilled water and then dried under reduced pressure at a bath
temperature of 60°C. The dry pr oduct thus obtained was placed into a container and
mixed thoroughly, and a sample thereof was analyzed by NMR spectroscopy. In the
subsequent experiments, instead of the led water, a corresponding amount of the
combined filtrates was employed as the reaction medium. The excess amount of the
combined filtrates was discarded.”
These excluded or excepted processes, however, may also be an inventive alternative
to the process of the invention with exclusion/exception.
The invention r s to an s solution of 2-(N-3, 4-dimethylpyrazole)
succinic acid having a pH of greater than 7.
2-(N-3,4-Dimethylpyrazole)succinic acid is preferably an isomer mixture of 2-(3,4-
dimethyl-1H-pyrazolyl)succinic acid and 2-(2,3-dimethyl-1H-pyrazolyl)succinic
acid, preferably in a molar ratio of 5 : 95 to 95 : 5, more preferably 50 : 50 to 95 : 5,
more particularly 70 : 30 to 90 : 10.
It may be present in the acid form or in wholly or partly neutralized form or wholly or
partly in salt form, as for example as alkali metal salt, such as potassium salt. The term
“2-(N-3,4-dimethylpyrazole)succinic acid” used in accordance with the invention also
es the partly or fully neutralized or salt form.
It has been found in ance with the invention that the combination of 2-(N-3,4-
dimethylpyrazole)succinic acid with calcium ammonium nitrate mineral fertilizers results
in an effective nitrification inhibitor which exhibits reduced volatility and a reduced loss
during storage and also after application to the soil.
Furthermore, 2-(N-3,4-dimethylpyrazole)succinic acid has been found as a particularly
effective nitrification inhibitor with low lity and low toxicity. The present invention
therefore relates ingly to the specific combination of ,4-
ylpyrazole)succinic acid with calcium ammonium nitrate fertilizers.
2-(N-3,4-Dimethylpyrazole)succinic acid may be ed by any suitable methods,
which are described for example in the general form in WO 96/24566. Preparation is
accomplished preferably by reaction of 3,4-dimethylpyrazole with maleic acid or maleic
anhydride. This reaction is typically carried out in an acidic environment. For the
preparation of 3,4-dimethylpyrazole, reference may be made to Noyce et al., Jour. of
Org. Chem. 20, 1955, pages 1681 to 1682. Reference may further be made to
EP-A-0 474 037, DE-A-3 840 342, and EP-A-0 467 707, and also to EP-B-1 120 388.
For the purification of the 3,4-dimethylpyrazole, reference may be made to
DE-A-10 2009 060 150.
The on is performed favorably at temperatures from 0 to 150°C, preferably 50 to
120°C, more particularly 70 to 105°C, under atmospheric pressure in the absence of a
solvent or, preferably, in an inert solvent, such as water, acetonitrile or dimethyl
sulfoxide. Other suitable ts are alcohols, ethers, ketones, water, and alkanes.
Reaction in an organic acid such as acetic acid may also be appropriate. The product
can be purified by recrystallization, by being taken up in diethyl ether, for example.
Maleic anhydride can be dissolved in water and reacted to give maleic acid. In that
case an aqueous solution of 3,4-dimethylpyrazole can be added. The reaction may
take place, for example, at temperatures of around 100°C, for example at 70 to 105°C.
Since 3,4-dimethylpyrazole undergoes tautomerization under the reaction ions in
which the reaction is customarily carried out, or the 3,5-tautomerism of the le
ring is eliminated by the substitution on the nitrogen, it is generally not possible to avoid
the presence of isomer mixtures of the resulting substituted succinic acid, these
es featuring structural isomers.
More preferably the 2-(N-3,4-dimethylpyrazole)succinic acid is prepared by reaction of
3,4-dimethylpyrazole with maleic acid, maleic anhydride or maleic acid/maleic
anhydride mixtures in the e of organic solvents or diluents, and subsequent
crystallization from the resulting reaction t in the absence of organic solvents or
diluents. Where the reaction product is not in solution after the reaction, it is dissolved
in a nonorganic solvent prior to crystallization.
In accordance with the ion it has been found that the product is obtained in high
yield and purity if the accompanying use of organic ts or diluents during the
preparation and crystallization is avoided.
The presence of small amounts of organic solvents or diluents during the reaction or
crystallization can be tolerated in this case. In accordance with the invention up to
wt%, more ably up to 5 wt%, more particularly up to 2.5 wt% of organic
solvents or diluents can be tolerated, based on nonorganic solvents or ts used in
the process. With particular preference no organic solvents or diluents at all are used in
the reaction and crystallization. As a result of this, the process becomes ularly
eco-friendly.
The reaction is carried out preferably in water as t, and the llization takes
40 place from the (dissolved) aqueous reaction product.
Here it is possible to react aqueous solutions or pastes of 3,4-dimethylpyrazole and/or
maleic acid and/or maleic anhydride. With particular preference both 3,4-
dimethylpyrazole and maleic acid (anhydride) are used as aqueous solutions or .
Certain compounds may also be used as solids. For e, 3,4-DMP may also be
used as a solid.
The crystallization ably takes place by cooling of the aqueous reaction product.
Here it is possible for seed crystals to be used as well, in order to initiate crystallization.
The reaction and crystallization may be carried out uously or tinuously.
One or more reactors and/or crystallizers may be used. For example, a cascade of
reactors and/or crystallizers may be used. Batchwise reaction is possible, as are
semicontinuous or continuous reaction and crystallization.
The 2-(N-3,4-dimethylpyrazole)succinic acid obtained after the crystallization preferably
has a purity of at least 99.7%, more preferably of at least 99.9%. This purity is
preferably achieved even after the first crystallization.
As a result of preparation in accordance with the invention, a high yield and a high
purity can be achieved with little cost and inconvenience. In particular, the use of
ive organic solvents and diluents which are potentially harmful to health and the
environment is unnecessary. Nor is there any need for solvents to be removed or
exchanged.
Through the use of the reaction product of 3,4-dimethylpyrazole with maleic acid, the
volatility of the 3,4-dimethylpyrazole can be greatly lowered.
Application of the 2-(N-3,4-dimethylpyrazole)succinic acid as nitrification inhibitor for
CAN fertilizer takes place according to the lly customary processes: the acid
may be d, for example, in solid form to the soil directly, in combination with CAN
fertilizers in the form of power or granules. Moreover, it may be added to liquid CAN
fertilizers, in a form, for example, in solution in water, also for the e of nitrogen
stabilization, or may be applied together with such fertilizers, in dissolved form. Also
possible is separate but closely timed application of DMPSA and CAN fertilizer.
It has proven ularly appropriate to use mixtures of 2-(N-3,4-
dimethylpyrazole)succinic acid with a CAN mineral fertilizer. Fertilizer mixtures of this
kind contain ably 100 to 10 000 ppm by weight, based on the mineral fertilizer, of
nitrification inhibitor (0.01 to 1 wt%), more preferably 0.03 to 0.5 wt%, more particularly
40 0.05 to 0.2 wt%.
The fertilizer mixtures may also include small amounts of water, as for example 0.1 to
0.5 wt%, based on the fertilizer mixture, including water. Large amounts of water in the
fertilizer e ought to be avoided.
Having proven particularly appropriate on account of their good long-term activity are
fertilizer es produced according to the following method:
granules of mineral fertilizers, preferably calcium ammonium nitrate mineral izers,
are coated or impregnated with 2-(N-3,4-dimethylpyrazole)succinic acid by being
sprayed with a solution of the nitrification inhibitor and dried again. The method is
known, for example, from 1 28 828, hereby referenced in full. The sealing of the
impregnated granules with a paraffin wax, which is an additional al in the latter
document, is lly unnecessary, owing to the substantially lower lity of the
nitrification inhibitor of the invention.
The 2-(N-3,4-dimethylpyrazole)succinic acid may also be added during the actual
tion of the mineral fertilizer, in the , for example.
If necessary, the mineral fertilizer may also be treated with polyacids, as described in
WO 98/05607/EP-B-0 971 526.
The nitrification inhibitors are customarily applied to the soil in s of 100 g/ha to
kg/ha.
Application in liquid fertilizer formulations may be accomplished, for example, by
ation with or without excess water, as described in DE-C-102 30 593.
In the context of its use as a nitrification inhibitor, the 2-(N-3,4-
dimethylpyrazole)succinic acid, which can be prepared in a simple way from
inexpensive starting products, is notable in particular for the fact that it effectively
inhibits the nitrification of ammonium nitrogen in the soil over a long period of time.
A further factor is that this compound possesses favorable toxicological properties, has
a low vapor pressure, and is sorbed well in the soil. A uence of this is that 2-(N-
3,4-dimethylpyrazole)succinic acid neither is emitted to the atmosphere by sublimation
to any significant extent, nor is easily leached by water. As a result, first of all,
economic advantages arise, such as high ability in view of the longer-lasting effect
of the nitrification inhibitor, and, moreover, environmental advantages such as a
reduction in the burdening of air (climate gas-reducing) and of surface waters and
40 groundwater. In the soil, the speed with which 2-(N-3,4-dimethylpyrazole)succinic acid
diffuses is similar to that of nitrate or ammonium, and it can therefore act optimally. In
the most general form, any desired suitable l fertilizers may be used in
accordance with the ion. These are fertilizers containing ammonium or urea.
Examples of such ammonium-containing fertilizers are NPK fertilizers, calcium
ammonium nitrate, ammonium e nitrate, ammonium sulfate, or ammonium
phosphate.
The quantity figures below relate to the mineral fertilizer, preferably without water.
ularly preferred in accordance with the ion is a combination of 2-(N-3,4-
dimethylpyrazole)succinic acid with calcium ammonium nitrate mineral izer. The
latter comprises ammonium nitrate and calcium carbonate and/or magnesium
carbonate as principal constituents, and water according to the degree of moisture. It is
possible in accordance with the invention for the calcium ammonium nitrate mineral
fertilizer to be able to contain up to 15 wt%, preferably up to 10 wt%, more preferably
up to 5 wt%, based on the calcium ammonium nitrate mineral fertilizer without water, of
further ingredients. Further ingredients are for example trace elements, r
ls, standardizers, binders, and so on.
The nitrogen content of component A (without water) is preferably 20 wt%, more
preferably at least 22 wt%, very preferably 25 to 29 wt%, more particularly 26 to
28 wt%. Calcium ammonium nitrate comprises frequently 26 to 27 wt% of en, in
which case, for example, there may be 13.5 wt% of fast-acting nitrate nitrogen and
13.5 wt% of slow-acting ammonium nitrogen.
The calcium content of component A (without water), when using calcium carbonate
and ammonium nitrate as ingredients, is preferably 6 to 15 wt%, more preferably 7 to
13 wt%, more particularly 7 to 11 wt%. imately 10 wt% is a typical content.
When magnesium is used instead of calcium in the carbonate, a corresponding amount
of Mg may preferably be present.
ing to one preferred embodiment, when using calcium carbonate and
um nitrate as ingredients, component A may se 0.5 to 7 wt%, preferably
1 to 5 wt%, more preferably 3 to 5 wt%, based on component A without water, of MgO
and/or Mg salt such as magnesium carbonate. Typically here MgO or MgCO3 is used.
Furthermore, according to one embodiment of the invention, based on component A
t water, component A may comprise 0.1 to 1 wt%, ably 0.1 to 0.5 wt%,
more particularly 0.15 to 0.3 wt% of boron as element and/or in the form of boron
40 compounds.
For a description of calcium ammonium nitrate, one possible reference source is the
tion in the EU Fertilizers Regulation 2003/2003.
Calcium ammonium nitrate is a white to gray solid which is normally odorless. The pH
of a 10% strength aqueous solution is typically more than 4.5. The g point is
situated typically in the range from 160 to 170°C, depending on moisture content. The
relative density is customarily 0.93 to 1.4 kg/l. The salt is hygroscopic and absorbs
atmospheric moisture.
Calcium um nitrate customarily has a water content of 0.1 to 0.5 wt%,
preferably 0.1 to 0.2 wt%, more particularly about 0.15 wt%. As a result of the
application of an aqueous solution of 2-(N-3,4-dimethylpyrazole)succinic acid to the
calcium ammonium nitrate l fertilizer, this water content may more than double.
It may consequently be necessary for the calcium ammonium nitrate mineral fertilizer
thus treated to be dried after the nitrification inhibitor has been applied or orated.
Preference is given to using the 2-(N-3,4-dimethylpyrazole)succinic acid as an aqueous
solution having a pH of greater than 7, more preferably greater than 10, more
particularly greater than 12. As a result of the basic pH, the ication inhibitor is
stabilized on the fertilizer mixture. The pH may be ed, for example, by addition of
a base, more particularly an alkali metal hydroxide, such as NaOH or KOH.
Furthermore, it has been found in accordance with the invention that an aqueous
solution of 2-(N-3,4-dimethylpyrazole)succinic acid having a pH of greater than 7, more
preferably greater than 10, more particularly greater than 12, is more stable, ng
the production of highly trated aqueous solutions. The fraction of ,4-
dimethylpyrazole)succinic acid, based on the aqueous solution, may thus amount
preferably to 20 to 40 wt%, more preferably 25 to 35 wt%, more particularly 27.5 to
32.5 wt%.
It has been further found in accordance with the invention that, by adding one or more
phosphates or osphates to the aqueous solution, the water fraction of the
aqueous solution can be reduced and the stability of the aqueous on of the
nitrification inhibitor can be further improved. Preferably, therefore, the aqueous
on contains 0.5 to 20 wt%, more preferably 1 to 10 wt%, more particularly 1.5 to
7 wt%, based on the aqueous solution, of one or more phosphates or polyphosphates.
Examples of ates contemplated are Na2HPO4, Na3PO4, K2HPO4, K3PO4,
diammonium phosphate or calcium ammonium phosphate.
The invention also relates to the above-described aqueous solutions of 2-(N-3,4-
dimethylpyrazole)succinic acid having a pH of greater than 7, and also to the red
solutions with the stated fraction of nitrification inhibitor and more preferably
phosphates or polyphosphates.
The invention is elucidated in more detail by the es below:
Examples
A. Preparation examples
Example 1
9.6 g of 3,4-dimethylpyrazole (0.1 mol) and 9.8 g of maleic anhydride (0.1 mol) were
heated to 100°C in 50 ml of 50% strength acetic acid. After 16 hours the reaction
mixture was evaporated to dryness. When the residue is taken up in diethyl ether, the
product (2-(N-3,4-dimethylpyrazole)succinic acid) is precipitated in pure form and is
isolated by filtration: white crystals in a yield of 92%. In the NMR spectrum there are a
number of methyl signals apparent, this being in agreement with the elimination of the
3,5-tautomerism as a result of the substitution on nitrogen.
Example 2: Preparation on the 200 kg scale
Starting materials used for the experiments were maleic anhydride from CVM with a
purity of more than 99.5%, and an 80% strength aqueous solution of 3,4-
dimethylpyrazole (3,4-DMP) from BASF SE. According to NMR spectrum, the solution
of 3,4-DMP used contained about 2% of otherwise uncharacterized impurities.
The experiments were first conducted in a 20 L reaction vessel, which in further
experiments was replaced by a 25 L reaction .
In the first experiment, 41.608 mol of maleic ide were uced and dissolved
in 11 liters of distilled water. The ature rose here by 10°C. Then 41.608 mol of
80% strength aqueous 3,4-dimethylpyrazole solution were added, the temperature
rising by a further 12°C. After the end of the addition, the on mixture was heated
to an internal temperature of 100°C. When this ature was reached, the reaction
mixture was stirred at 100°C for 24 hours and then cooled. When the reaction mixture
had cooled to 90°C, a sample was taken for NMR-spectroscopic reaction monitoring,
and the on mixture was subsequently seeded with 1 g of t als of 2-(N-
40 3,4-dimethylpyrazole)succinic acid). At this temperature, crystallization did not yet
begin, but the added crystals also no longer dissolved. On further cooling,
crystallization began slowly from around 85°C. The major quantity of the product only
crystallized at just below 80°C, with an increase in temperature. For te
crystallization, the reaction mixture was left to cool overnight with stirring. The
precipitated solid was filtered off on three 8 L G3 glass suction filters, using a suction
flask and membrane pump, under d pressure, and the solid product was washed
with a total of 8 liters of distilled water and then dried under reduced pressure at a bath
ature of 60°C. The dry product thus obtained was placed into a container and
mixed thoroughly, and a sample thereof was analyzed by NMR spectroscopy. In the
subsequent experiments, instead of the distilled water, a corresponding amount of the
combined filtrates was employed as the reaction medium. The excess amount of the
combined the bifiltrates was discarded.
NMR-spectroscopic reaction monitoring after 24 hours showed a relatively constant
conversion of around 92%, with a relatively constant P1/P2 (2-(3,4-dimethyl-1H-
pyrazolyl)succinic acid/2-(2,3-dimethyl-1H-pyrazolyl)succinic acid) isomer ratio of
around 3.3. Only at the start of the serial experiment was the ratio ly higher. That,
however, was also anticipated, since the use of the filtrate instead of the distilled water
as reaction medium introduced a greater amount of P2 (P1/P2 ratio in the filtrates is
around 1.0) into the subsequent experiments.
After just a few experiments, the composition of the on mixture after a reaction
time of 24 hours reached nt levels. By the same token, the compositions of the
isolated products from the individual experiments differ only slightly from one another.
The solids, obtained on average with a yield of 90.22%, possessed a purity of 99.9%
and on average an isomer ratio of 4.0 (2-(3,4-dimethyl-1H-pyrazolyl)succinic acid to
2-(2,3-dimethyl-1H-pyrazolyl)succinic acid). Impurities of 3,4-DMP, maleic acid, and
rac-malic acid were detectable in the 1H NMR spectra not at all or only in traces
(< 0.1%).
The carrier fertilizer used was calcium ammonium e with 27% N and 10% Ca. 2 g
of ,4-dimethylpyrazole)succinic acid and 46 g of KOH were dissolved in 133 g of
water. 20 kg of the r fertilizer in the form of granules were slowly sprayed in a
drum with 85 g of the formulation of the pyrazole compound.
Example 4
40 Example 3 was ed, using 111 g of water and 22 g of diammonium phosphate
instead of 133 g of water.
Comparative e
In y to example 3, 3,4-dimethylpyrazole phosphate (DMPP) was used instead of
,4-dimethylpyrazole)succinic acid.
B. Application examples
Example 1
Investigation of storage stability
Calcium ammonium nitrate (CAN) mineral fertilizer additized with 2-(N-3,4-
dimethylpyrazole)succinic acid (DMPSA) or with DMPP, in accordance with example 3
or comparative example, respectively, was investigated for storage stability in an
rated test, in which the nitrification-inhibited mineral izers were stored in an
open glass beaker (which, as a eap, mimics the storage situation in a large heap)
for 40 days at 30°C, 40% to 50% relative humidity and approximately 1.2 m/s air speed
in an aerated heating cabinet. The concentration of nitrification inhibitor on the mineral
fertilizer was determined before, during and after storage at two different depths in the
bed, and the loss of nitrification inhibitor was ascertained. In each case about 10 to
g of treated mineral fertilizer were stored. The concentration of DMPP at the start
was 1.028 g/kg fertilizer; for ,4-dimethylpyrazole)succinic acid, the figure was
1.244 g/kg fertilizer.
After 20 and 40 days, samples were taken from a surface region of the fertilizer bed (0
to 5 cm sampling depth and > 5 cm sampling depth).
The results are shown in table 1 below, where DMPSA denotes 2-(N-3,4-
dimethylpyrazole)succinic acid.
Table 1
Storage stability of DMPP and DMPSA on CAN
Analytical value
[g/kg]
DMPP on CAN
Value at start 1.028
d20, 0 – 5 cm 0.86
d20, > - 5 cm 0.91
d40, 0 – 5 cm 0.45
d40, > - 5 cm 0.68
DMPSA on CAN
Value at start 1.244
d20, 0 – 5 cm 1.15
d20, > - 5 cm 1.18
d40, 0 – 5 cm 1.21
d40, > - 5 cm 1.26
d = day
0 – 5 cm sampling depth
From the table it is clear that the loss is much lower for 2-(N-3,4-
dimethylpyrazole)succinic acid than for DMPP on storage over 20 to 40 days.
This is evidence of the advantages of the fertilizer of the invention.
Example 2
Verification of the biological (nitrification-inhibiting) effect of the 2-(N-3,4-
dimethylpyrazole)succinic acid
The biological activity of 2-(N-3,4-dimethylpyrazole)succinic acid was tested in a
number of field trials in different environments.
The field trials were set up, sampled, harvested, and evaluated in accordance with the
processes customary in agricultural trialing.
The plant and soil samples were analyzed by standard methods. The other productionrelated
measures, such as the crop protection, were in line with good agricultural
ce and were carried out mly.
Preferably, a distinguishing e of a biologically active nitrification inhibitor is that it
exhibits higher levels of NH4 nitrogen relative to the control (here, tized CAN
carrier fertilizer) within a period of up to 4 weeks and longer after application. As a
consequence of these conditions, the yield is increased and the nitrate content of the
plants is reduced.
The active ingredient was applied in analogy to e 3 to solid CAN fertilizers with
an application rate of 0.73% based on the reduced nitrogen. The active ingredient
exhibits a strong nitrification-inhibiting action in the soil after ation of the
fertilizers. In the CAN (calcium ammonium nitrate) + DMPSA, given by way of example
in table 2, there are still considerable amounts of reduced nitrogen both after 14 days
and after 28 days, in comparison to ted products; without nitrification inhibitor,
the entire reduced nitrogen has undergone nitrification and conversion to nitrate N after
no later than 28 days.
Table 2:
Inhibition of nitrification by DMPSA
Fertilizer % NH4 N (or NH2 N) of the fertilized N after
0 days 14 days 28 days
CAN 100 9.1 0.0
CAN + DMPSA 100 79.3 61.9
Example 3
Reduction in ouse gas emissions (N2O)
In addition to the protection of the hydrosphere, the maximum avoidance of release of
climate-relevant gases as a consequence of the agricultural tation of soils is also
a great challenge for agriculture.
The compilation of the measurements of nitrous oxide (N2O), an ely active
e gas (around 300 times stronger than CO2), both during the vegetation period of
winter wheat after fertilization, and after harvesting into the winter, gave a reduction by
28% (table 3) in comparison to conventional CAN when using CAN + DMPSA in
accordance with example 3.
Table 3:
Effect of fertilization with CAN with and without DMPSA on release of climate gas
during winter wheat culture
Without fertilization CAN CAN + DMPSA
g N2O N/ha tive March to December
1149 2690 1953
43% 100% 72%
Example 4
Effect on yield and quality of agricultural and ultural crops
Yields
In addition to possible consequences for the gentle treatment of soil, water, and air, the
effect on yield and quality is particularly important to the farmer. The compilation of the
weighed yields of various crops shows a consistently improved yield boost by the
fertilizers with DMPSA in accordance with example 3 than by the use of the respective
conventional fertilizers (table 4). Here there are virtually no differences between
agricultural crops and vegetable crops, or in terms of the respective climate
environments and ent soils. The reasons for the extra yields are firstly the reduced
losses as a result of leaching and the s losses through denitrification, and
secondly in the l ammonium nutrition of the plants, which is cial for the plant
metabolism by comparison with the customary nitrate nutrition with conventional
fertilizers.
Table 4:
Effect of fertilization with CAN with and without DMPSA on the yield of various
garden and agricultural crops
Yield Yield Extra
Region/ Fertilizer dt/ha dt/ha yield
Crop Country used without with [%]
Potato Hanover/D CAN 464 609 31
Potato Jutland/DK CAN 390 405 32
Potato Picardy/F CAN 642 667 4
Potato Orgiano/I CAN 531 582 9
Potato Galicia/E CAN 644 728 13
Celery* Palatinate/D CAN 563 595 5
* Palatinate/D CAN 756 781 3
Chinese Palatinate/D CAN 757 842 11
cabbage**
Chinese nate/D CAN 817 930 13
cabbage**
*weight/100 plants ** weight per head, g
Definitions of the specific embodiments of the ion as claimed herein follow.
According to a first embodiment of the invention, there is provided a process for
preparing 2-(N-3,4-dimethylpyrazole)succinic acid or a salt thereof by on of 3,4-
dimethylpyrazole with maleic acid and/or maleic anhydride in the absence of organic
solvents or diluents, and subsequent crystallization from the resulting reaction product
in the absence of organic solvents or diluents.
According to a second embodiment of the invention, there is ed an aqueous
solution of 2-(N-3,4-dimethylpyrazole)succinic acid or a salt thereof having a pH of
greater than 7.
According to a third embodiment of the ion, there is provided a di-alkali metal salt
of 2-(N-3,4-dimethylpyrazole)succinic acid.
Claims (15)
1. A s for preparing 2-(N-3,4-dimethylpyrazole)succinic acid or a salt thereof by reaction of methylpyrazole with maleic acid and/or maleic anhydride in the absence of organic solvents or diluents, and subsequent crystallization from the ing reaction product in the absence of organic solvents or diluents.
2. The s of claim 1, wherein the reaction takes place in water as solvent and the crystallization takes place from the aqueous reaction product.
3. The process of claim 1 or 2, wherein s ons or pastes of 3,4- dimethylpyrazole and/or maleic acid and/or maleic anhydride are reacted.
4. The process of any one of claims 1 to 3, wherein the crystallization takes place by cooling of the aqueous reaction product,
5. The process of claim 4, wherein the crystallization further comprises the accompanying use of seed crystals.
6. The process of any one of claims 1 to 5, wherein the 2-(N-3,4- dimethylpyrazole)succinic acid or salt thereof obtained after the crystallization has a purity of at least 99.7%,
7. The process of any one of claims 1 to 6, wherein the 2-(N-3,4- dimethylpyrazole)succinic acid or salt thereof obtained after the crystallization has a purity of at least 99.9%.
8. An aqueous solution of 2-(N-3,4-dimethylpyrazole)succinic acid having a pH of greater than 7.
9. The aqueous solution of claim 8, wherein the fraction of 2-(N-3,4- ylpyrazole)succinic acid or salt thereof, based on the aqueous solution, is 20 to 40 wt%.
10. The aqueous solution of claim 8 or claim 9, n the fraction of 2-(N-3,4- dimethylpyrazole)succinic acid or salt thereof, based on the aqueous solution, is 25 to 35 wt%.
11. The aqueous on of any one of claims 8 to 10, wherein the fraction of 2-(N- 3,4-dimethylpyrazole)succinic acid or salt thereof, based on the aqueous on, is 27.5 to 32.5 wt%.
12. The aqueous solution of any one of claims 8 to 11, wherein the aqueous solution contains 0.5 to 20 wt%, based on the aqueous solution, of one or more phosphates or polyphosphates.
13. The aqueous solution of any one of claims 8 to 12, n the aqueous solution contains 1 to 10 wt%, based on the aqueous solution, of one or more phosphates or polyphosphates.
14. The aqueous on of any one of claims 8 to 13, wherein the aqueous solution contains 1.5 to 7 wt%, based on the aqueous solution, of one or more phosphates or polyphosphates.
15. Di-alkali metal salt of 2-(N-3,4-dimethylpyrazole)succinic acid.
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