CA1269859A - Ammonium thiosulfate-containing fertilizers - Google Patents
Ammonium thiosulfate-containing fertilizersInfo
- Publication number
- CA1269859A CA1269859A CA000499118A CA499118A CA1269859A CA 1269859 A CA1269859 A CA 1269859A CA 000499118 A CA000499118 A CA 000499118A CA 499118 A CA499118 A CA 499118A CA 1269859 A CA1269859 A CA 1269859A
- Authority
- CA
- Canada
- Prior art keywords
- nitrogen
- ammonium
- urea
- source
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003337 fertilizer Substances 0.000 title claims abstract description 43
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 title claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 80
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 40
- 239000004202 carbamide Substances 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002689 soil Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 9
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 5
- 230000002401 inhibitory effect Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000006193 liquid solution Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims 3
- 150000003839 salts Chemical class 0.000 claims 3
- 239000011236 particulate material Substances 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 12
- 235000015097 nutrients Nutrition 0.000 abstract description 12
- 108010046334 Urease Proteins 0.000 abstract description 5
- 229940048910 thiosulfate Drugs 0.000 abstract description 4
- 239000004615 ingredient Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000007605 air drying Methods 0.000 abstract description 2
- CSGLCWIAEFNDIL-UHFFFAOYSA-O azanium;urea;nitrate Chemical compound [NH4+].NC(N)=O.[O-][N+]([O-])=O CSGLCWIAEFNDIL-UHFFFAOYSA-O 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 abstract 1
- 229960005419 nitrogen Drugs 0.000 description 23
- 241000196324 Embryophyta Species 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 11
- 239000003112 inhibitor Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 238000007738 vacuum evaporation Methods 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 3
- DHMYGZIEILLVNR-UHFFFAOYSA-N 5-fluoro-1-(oxolan-2-yl)pyrimidine-2,4-dione;1h-pyrimidine-2,4-dione Chemical compound O=C1C=CNC(=O)N1.O=C1NC(=O)C(F)=CN1C1OCCC1 DHMYGZIEILLVNR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 244000228957 Ferula foetida Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- DCUJJWWUNKIJPH-UHFFFAOYSA-N nitrapyrin Chemical compound ClC1=CC=CC(C(Cl)(Cl)Cl)=N1 DCUJJWWUNKIJPH-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000014786 phosphorus Nutrition 0.000 description 2
- HOLQXBRPSSZJMZ-FGRXCANLSA-N (2s)-n-[(2s)-1-[[(2s)-6-amino-1-[[(2s)-1-[[(2s)-1-[[(2s)-1-[[(2s)-1-[[(2s)-1-[[(2s)-1-[[(2s)-6-amino-1-[[(2s)-1-[[(2s)-1-[[(2s)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-1-oxopropan-2-yl]amino]-1-oxohexan-2-yl]amino]-1-oxop Chemical compound CC[C@H](C)[C@H](N)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](C)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](C)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](C)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O HOLQXBRPSSZJMZ-FGRXCANLSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 101100371682 Caenorhabditis elegans cyk-3 gene Proteins 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 102100026933 Myelin-associated neurite-outgrowth inhibitor Human genes 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- PPBAJDRXASKAGH-UHFFFAOYSA-N azane;urea Chemical compound N.NC(N)=O PPBAJDRXASKAGH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 244000239634 longleaf box Species 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000021049 nutrient content Nutrition 0.000 description 1
- -1 phenyl phosphorodiamidate potassium Chemical compound 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
AMMONIUM
THIOSULFATE-CONTAINING
FERTILIZERS
ABSTRACT
A fertilizer material , particularly in a solid particulate form, incorporating anmonium thio-sulfate with a source of nitrogen, such as urea, urea ammonium nitrate, ammonium phosphate, ammonium nitrate, calcium nitrate or ammonium sulfate, and a process for preparation thereof. The fertilizer supplies necessary nutrients to the soil, and in addition inhibits urease and nitrification losses from the soil. The solid fertilizer is prepared by mixing the liquid ingredients at elevated temperature, and then flash cooling the liquid mixture under vacuum at elevated temperature.
Drying may be completed by air drying under ambient conditions or in a vacuum oven.
THIOSULFATE-CONTAINING
FERTILIZERS
ABSTRACT
A fertilizer material , particularly in a solid particulate form, incorporating anmonium thio-sulfate with a source of nitrogen, such as urea, urea ammonium nitrate, ammonium phosphate, ammonium nitrate, calcium nitrate or ammonium sulfate, and a process for preparation thereof. The fertilizer supplies necessary nutrients to the soil, and in addition inhibits urease and nitrification losses from the soil. The solid fertilizer is prepared by mixing the liquid ingredients at elevated temperature, and then flash cooling the liquid mixture under vacuum at elevated temperature.
Drying may be completed by air drying under ambient conditions or in a vacuum oven.
Description
5~3 BACKGROUND OF THE INVEN~ION
-Thi~ invention rel~tes to agricultural ferti-lizer ~aterials~ and, more particularly to a ~ertilizer containing ammon~um thiosulf~te.
Fertilizer~ are used in agri~ulture to supply macro and mi~ro nu~rien~ ~o the ~oil and thence to the growing plants. Most fertilizer~ ~upply one or more of nitrogen, phosphoru , potassium~ and ~ulfur, and in addition may ~upply elements needed by the plants in trace amounts, ~u~h as iron, copper, ~inc, and o~her nutrients. A farmer obtains a 80il analysis for his fields~ compare~ the available nutrient content with that required to grow the desired crops, and ~hen either purchases a ready-made fertilizer or o~tains a custom-blended fertilizer to meet the soil needs.
Many ~ertilizers may be produced in ei~her a liquid or a solid form. The $anmer ~elects the liquid or 601id form for purchase based on several factors, including avallability, the type of fertilizer applica-tion equipment that the ~armer u6es, and th0 objectives of the fertilization progr~m. It 1~ there~ore highly desirable to manufacture partioular fertilizer~ in both ~olid and liquid forms, to increase the available market and convenience to the consumerO
;25 Fertilizers are ~ypically prepared in the llquid form to achieve homogeneous mia~tures and reac tions where nece~ry. ~olid ~erki~izer~ are then prepared from ~he liquid fert~lizer material~ In some ~nstance~O the preparation of the solid ~ertilizer is 3~ 6imple ~nd ~traightforward, ~uch as by dehydrating the liquid fer~ er to a 601id particulat@D and ~hen cru~hing and granulating the particula~e. In other ;~
i9 instances ~ the dehydrating operatiorl m~y cau~e un-desirable reaction~ in the fertilizer, Qu~h ~8 the lo~
of one ~r more con6tituents, as by volatilizatis:~n or precipit~tion. The inabili~cy to prepare a par'cicular fertilizer in ~olid form is ~ seriou~ di5~dvantage both for the farmer and for the fertil lzer producer .
Although fertilizer8 ~re used to augmen~ and lncrease the natural level~ of nutrient~ in the ~oil ~o ~upport high volume agriculture~ the application of fertil izers repre~ent~ only one p~rt o~ the complex chemistry of the soil and the growing plant. Once the nutrient~ are placed into the s~il either naturally or by a fer~cilizerc a portion of the nutrien~s is converted in~o a form ~hat may be utillzed by the plant and ing~sted into the plant, while anc~ther portion of the nutrients may be lost from the soil and thence -unavailable ~o the plant. Such nutrlent los~es are undesirable, ~ince they drain the 80il of it~ naturally occurriny nutrient material ~nd in addition deprive the plants of a portion of the nutrients pro~ided in the fertilizer. Nutrienk lo~ses may occur ~n many dl~Perent ways, including leaching by water ~rom th2 ~oil, vola-tile lose to the ~ir, ~nd chemical and biological reactions in the soil which promote and accelerate other loss me~:hanisms or ~onvert the nutrients to ~ ~orm unusable by the plant~.
One of the ~ingle most important and univer-~ally required nutrient~ i~ ni~rogen9 provided in a form which may be utilized by the plant. ~itrog~n is ~ypi~
~ally suppl ied as ammoni~ or urea, or ~ compound there-of v whic~h may be conven;ently Islanufactured and tran~-pl~rted, and 9 wben appl ied i~ read ily util ~zed by 'che plants, Although nitrogen 1~ required by the plants and , i9~r ~
i~ readily provided in f~rtil ~z~rs, unfortunately the rate of nitrogen lc~ss from the ~oil prior to up'c~ke by ~he pl~n~ci c~n be large., Ilt i~ e~timated tha~ as much as 109~ - 65~6 of the ni~rogen IDay be lo~t before i~
re~che~ th~ pl~n'c, by leaching, vol~tlll~ation~ and, p~rticularly, by bacteri~l re~ction~ in ~he I~C~ilo ~itrogen 10E~;6 OCCUrB prlncipally by ~wo mechani~m~. In ~he ~ir~t, nitrogen 1n the forlD of ammoni~ xidized ln a nitrific~tion reaction by t~cter$a $n the . oil ~co form a v~latile or leachable n~L~rate., In the ~scond, nitrogen in the fonn of ure~ i~ hydroly2ed ~o Amlaonia gas, a reaction ~ccelerated by the ~re~ence of ure~se enzymeO Nitrifi~t~on and urease inhibltors are ~here~c~re ~esirable fertil~2~er ~ddit$ons~ ~ince they improve fertllizer ei~ficieney, r~duee ~rounæ water pollut1on by ni~r~tes, increa e ~rop yield~ and allow ~he farmer to more effectively ~anage his ~ime by ~pplying ~ertili2er at his ~onvenience.
~ qreat deal o~ effort h~s been devot~d ~o finding w~y~ to inhlbit nitrogen 1088 ~rom the 80il.
Exlsting technique~ ~re generally too expen~iv~ ~or wide~pread ~gricultural use, u~e vol~t~le inhibitors ~o that ~pplication procedure~ are limited~ ~nd ~ay d~pend upon the u6e of d~ngerous~ envlronmen~Ally damaging~
chemicalsO ~nown nltriflc2tion inhibi~or~ h~ving varying degrees of eff~ctiveness ~n~lude ~rbon di-sulfide, ~odium tr$~hio~arbonat~ d~m~thyl diæulfide, ~ulfa drugs such ~s sulfathi~zole~ thiourea~ dicyandi~-mide, phenyl phosphorodiamidate potassium ~thyl ~anthate, t2 ~hlor~6~tr1~hloro~et~yl) pyridine or n~rapyr$n], and 15-etho~y-3-(trichloromethyl)-l~2~-thiadi~ole]. ~he latter tw~ ~hemical~ are re pe~iv~ly marketed under ~he name~ o~ N-Serve* (by Dow C~emical Co.) and Dwell (by Olin Corporation)~
* Trademark , .
- 12~;9B'~
N-Serve ~nd Dwell are used primarily with liquid fertilizer~, but in mos'c ca6es the fertili2er must be incorporated into the ~oil ~mmediately after the inhibitor addition to avoid decomposition and volatili-zation o the inhibitor" When the~e inbibitors are used with ~olld fertili2ers ~uch ~s granular urea, the in-hibitor i~ typically sprayed onto the granule immedi-ately before application, but volatilization losses are high due to the larget porous surf~e c>f the granules~
There have been attempts to incorporate nitrifi~:ation inhibitor~ into solid fertil~zer~ ~uch as urea by cogranula~ion proceduresO Solid urea is usually prepared by concen~crating aqueous urea solution at temperatures rea~hing 280F - 300~F~, followed by 9ranulation. Any inhibitor added to the ~olution must therefore be ~table at these temperatures. Tests have shown that dicyandi~nide, thiourea ~nd phenyl phosphoro-diarnidate, may be thus cogranulated with urea to form a solid fertilizer9 but u~e of these inhibitor~ has drawbacks such a~ high coæt, easy volatilization, and possible carcinogerlic charact~r.
There therefore exists an ongoing need for improved fertilizer materials, which provide important nutrient~ in u~able ~orm ~nd may be manufac~ured as
-Thi~ invention rel~tes to agricultural ferti-lizer ~aterials~ and, more particularly to a ~ertilizer containing ammon~um thiosulf~te.
Fertilizer~ are used in agri~ulture to supply macro and mi~ro nu~rien~ ~o the ~oil and thence to the growing plants. Most fertilizer~ ~upply one or more of nitrogen, phosphoru , potassium~ and ~ulfur, and in addition may ~upply elements needed by the plants in trace amounts, ~u~h as iron, copper, ~inc, and o~her nutrients. A farmer obtains a 80il analysis for his fields~ compare~ the available nutrient content with that required to grow the desired crops, and ~hen either purchases a ready-made fertilizer or o~tains a custom-blended fertilizer to meet the soil needs.
Many ~ertilizers may be produced in ei~her a liquid or a solid form. The $anmer ~elects the liquid or 601id form for purchase based on several factors, including avallability, the type of fertilizer applica-tion equipment that the ~armer u6es, and th0 objectives of the fertilization progr~m. It 1~ there~ore highly desirable to manufacture partioular fertilizer~ in both ~olid and liquid forms, to increase the available market and convenience to the consumerO
;25 Fertilizers are ~ypically prepared in the llquid form to achieve homogeneous mia~tures and reac tions where nece~ry. ~olid ~erki~izer~ are then prepared from ~he liquid fert~lizer material~ In some ~nstance~O the preparation of the solid ~ertilizer is 3~ 6imple ~nd ~traightforward, ~uch as by dehydrating the liquid fer~ er to a 601id particulat@D and ~hen cru~hing and granulating the particula~e. In other ;~
i9 instances ~ the dehydrating operatiorl m~y cau~e un-desirable reaction~ in the fertilizer, Qu~h ~8 the lo~
of one ~r more con6tituents, as by volatilizatis:~n or precipit~tion. The inabili~cy to prepare a par'cicular fertilizer in ~olid form is ~ seriou~ di5~dvantage both for the farmer and for the fertil lzer producer .
Although fertilizer8 ~re used to augmen~ and lncrease the natural level~ of nutrient~ in the ~oil ~o ~upport high volume agriculture~ the application of fertil izers repre~ent~ only one p~rt o~ the complex chemistry of the soil and the growing plant. Once the nutrient~ are placed into the s~il either naturally or by a fer~cilizerc a portion of the nutrien~s is converted in~o a form ~hat may be utillzed by the plant and ing~sted into the plant, while anc~ther portion of the nutrients may be lost from the soil and thence -unavailable ~o the plant. Such nutrlent los~es are undesirable, ~ince they drain the 80il of it~ naturally occurriny nutrient material ~nd in addition deprive the plants of a portion of the nutrients pro~ided in the fertilizer. Nutrienk lo~ses may occur ~n many dl~Perent ways, including leaching by water ~rom th2 ~oil, vola-tile lose to the ~ir, ~nd chemical and biological reactions in the soil which promote and accelerate other loss me~:hanisms or ~onvert the nutrients to ~ ~orm unusable by the plant~.
One of the ~ingle most important and univer-~ally required nutrient~ i~ ni~rogen9 provided in a form which may be utilized by the plant. ~itrog~n is ~ypi~
~ally suppl ied as ammoni~ or urea, or ~ compound there-of v whic~h may be conven;ently Islanufactured and tran~-pl~rted, and 9 wben appl ied i~ read ily util ~zed by 'che plants, Although nitrogen 1~ required by the plants and , i9~r ~
i~ readily provided in f~rtil ~z~rs, unfortunately the rate of nitrogen lc~ss from the ~oil prior to up'c~ke by ~he pl~n~ci c~n be large., Ilt i~ e~timated tha~ as much as 109~ - 65~6 of the ni~rogen IDay be lo~t before i~
re~che~ th~ pl~n'c, by leaching, vol~tlll~ation~ and, p~rticularly, by bacteri~l re~ction~ in ~he I~C~ilo ~itrogen 10E~;6 OCCUrB prlncipally by ~wo mechani~m~. In ~he ~ir~t, nitrogen 1n the forlD of ammoni~ xidized ln a nitrific~tion reaction by t~cter$a $n the . oil ~co form a v~latile or leachable n~L~rate., In the ~scond, nitrogen in the fonn of ure~ i~ hydroly2ed ~o Amlaonia gas, a reaction ~ccelerated by the ~re~ence of ure~se enzymeO Nitrifi~t~on and urease inhibltors are ~here~c~re ~esirable fertil~2~er ~ddit$ons~ ~ince they improve fertllizer ei~ficieney, r~duee ~rounæ water pollut1on by ni~r~tes, increa e ~rop yield~ and allow ~he farmer to more effectively ~anage his ~ime by ~pplying ~ertili2er at his ~onvenience.
~ qreat deal o~ effort h~s been devot~d ~o finding w~y~ to inhlbit nitrogen 1088 ~rom the 80il.
Exlsting technique~ ~re generally too expen~iv~ ~or wide~pread ~gricultural use, u~e vol~t~le inhibitors ~o that ~pplication procedure~ are limited~ ~nd ~ay d~pend upon the u6e of d~ngerous~ envlronmen~Ally damaging~
chemicalsO ~nown nltriflc2tion inhibi~or~ h~ving varying degrees of eff~ctiveness ~n~lude ~rbon di-sulfide, ~odium tr$~hio~arbonat~ d~m~thyl diæulfide, ~ulfa drugs such ~s sulfathi~zole~ thiourea~ dicyandi~-mide, phenyl phosphorodiamidate potassium ~thyl ~anthate, t2 ~hlor~6~tr1~hloro~et~yl) pyridine or n~rapyr$n], and 15-etho~y-3-(trichloromethyl)-l~2~-thiadi~ole]. ~he latter tw~ ~hemical~ are re pe~iv~ly marketed under ~he name~ o~ N-Serve* (by Dow C~emical Co.) and Dwell (by Olin Corporation)~
* Trademark , .
- 12~;9B'~
N-Serve ~nd Dwell are used primarily with liquid fertilizer~, but in mos'c ca6es the fertili2er must be incorporated into the ~oil ~mmediately after the inhibitor addition to avoid decomposition and volatili-zation o the inhibitor" When the~e inbibitors are used with ~olld fertili2ers ~uch ~s granular urea, the in-hibitor i~ typically sprayed onto the granule immedi-ately before application, but volatilization losses are high due to the larget porous surf~e c>f the granules~
There have been attempts to incorporate nitrifi~:ation inhibitor~ into solid fertil~zer~ ~uch as urea by cogranula~ion proceduresO Solid urea is usually prepared by concen~crating aqueous urea solution at temperatures rea~hing 280F - 300~F~, followed by 9ranulation. Any inhibitor added to the ~olution must therefore be ~table at these temperatures. Tests have shown that dicyandi~nide, thiourea ~nd phenyl phosphoro-diarnidate, may be thus cogranulated with urea to form a solid fertilizer9 but u~e of these inhibitor~ has drawbacks such a~ high coæt, easy volatilization, and possible carcinogerlic charact~r.
There therefore exists an ongoing need for improved fertilizer materials, which provide important nutrient~ in u~able ~orm ~nd may be manufac~ured as
2~ either a liquid or a ~table ~olid. Such fertilizers would preferably inhibi'c nitrogen lo~s from the ~oil by a ~afe approach u~ing an inhibitor incorporated into the ~oil. In particular, there has exi~ted a need for such a fer~ilizer which ~upplie~ ni~rogen and ~ulfur ~o ~che ~oil, sin~e these elemen~s are sometin~es required to meet parti~ular nutrierlt needs. The pre~ent invention f ul f il l ~ th i ~ need, and f urther prov ide$ rel ated advan~
tages O
9~5~`~
SUMMARY OF THE INVENTION
The present invention provid~s a fertilizer con'caining ulfur and nitrog~n in biologi~lly usabl*
form, and a procesæ :IEor preparing a ~olid particulate f~rtilizer which prevents volatilization and lo~s of sulfur during prepara~ion~, Th~ fertil~zer material is found ~o inhibit urease and nitrifica~ion lo~es from the soil~ ~hus improving the efficiency of ~he fer-tilizer addi~ion as well as improvisg the overall ~fficiency of the soil in prs~v~ding nutrients to the pl an'cs.
In accordance with lthe invention, a fertil izer material co~nprises a ~ubstan~ially uniform mixture of ~mmonium thiosulfate and at least one ~ource Qf nitro-gen, preferably 6elected rom the group consisting of urea~ urea ammonium ni1:rate, ammoniwn phosphate, am-mc~ni~n nitrate, calcium nitrate~ and Ammoni~n sulfate.
In its solid particulate ~orm" each particle comprise~ a substantially uniform mixture of ammoniwn thio~ulfate and the nitrogen ~ource. ~he rativ o the nitrogen source and the thiosulf~te is not critical ~ bu~ pre-ferably the ammonium thiosulfate is pregent in an amount of at least 5% by weight of the inal produc~. As 1 ittle as 0~ 2~6 ammoni~n thiosulfa'ce is effective in inhlbi'cing urease and nitrification lo~es, but such ~mall ~mount~
are agriculturally not pra~tical ~ lf ~ufur is being added as ~ nutrient.
In anoth~r a6pec'c o$ the invention, a solid fertili~er material may b~ prepared by mixing together ~nmoni~n thiosulf~te and the ~ource oiE nitrogen to form ~ liquid ~olution~ at a temperature of no greater than about lBO~F; and ~hen applylng a va~uum ~o the liquid ~olu'cion to remove ~a'cer th~re~rom~ ~t ~ temperature of no gre~ter than about 180F, to form a ~ol id par'cicu-late. At temperature6 greater than about 180 F, the ammonium thio~ulfate decompo~es. Opt$onally, ~mall amount of water may ~e added to a8si8t in forming a liquid mixture when the ammonium thlosul~ate and the source of nitrogen are mixed ~oge~her at eleva~ed temperature. Agitation and continued mixing during vacuum evaporation ac~elerate the production of ~he æolid. The last ~tages of the vacuum evapora~ion of wa~er proceed relatively slowly, and it i~ preferred to complete the drying by ambient air dry~ng or at elevated temp~ratures in a vacuum dryer~ The final drying should not be accomplished at elevated tempera~ure in air~
since sulfur i6 precitated from the fertilizer material.
Finally~ the dried particulate solid i~ crushed and ~creened to produce granules of a desired size distri-bu~ion~
It will now be appreciated that the present invention represents an advance in the field of ferti-lizer manufacture and utilization. A fertilixer con-taining nitrogen and ~ulfur in usable form, ~nd suppli~d by relatively inexpens1ve ingredient~, may be prepared a~ either a liqu$d or solid, without a ~ubstantial loss or precipit~tion of sul~ur during manufacture~ When applied, the fertili~er material inhibits ni~rogen loss from the ~oil, to achieve in~re~sed efficie~cyc O~her features and advantages of the present invention will become ~pparen~ from ~he followin~ more detailed des-cription~ which illustrate6, by way of e~ample, the principles of the invention 7 B';,~
DETAILED DESCRIPTION OF TH~ PREFERRED ~MBODIMENT
__________ ____ The raw materials ut~lized in the ~ertilizer process and material of the preferred embodiment~ of the present 1nvention are readily obtained commercially.
Ammoniwn thio~ulfate having a nominal c~mpo~ition of grade (12~û-0 26 ~ ~as obt~ined ~rom J. R. Simplot Companyc 8randon, Mani'coba, Canada., The conYentional N-P ~ X agriculturaî notation ~ ~; used herein 9 where N
denotes nitrogen, P deno~e~ phosphorus, R denotes potassi~Dn7 and X represent~ other elements, here ~ufur.) The commercial product was found to contain about 57 weight percent ammonium thiosulfate9 38 weight percent wa~er, 2"~ weight percent ammonium sul~a~e, and 2.5 weight percent ammonium sulfite. Urea-anunonl~n r itrate csf grade (28-0-0) wa~ obtained ~rom J.. R. Simplot Company, Brandon, ~anitoba, Canada. Solid pure urea was obtained from J. R. Simplot Company, Pocatello, Idaho.
Operabil ity of the present invention does not re~uire the use o~ ingredients of high purlty or other ~pecial characteristic~.
In accordance with one aspect of the inven-tion9 the liquid ammonium thiosulfate and the source of nitrogent preferably ure~ or urea-æmmonium nitrate, ~re mixed together to form a substantially uniform mixed 2~ solution at a temperature of no greater than about 180~o ~n pr~paring ~he mixed ~olution, no observable chemical reaction oc~ur~O Th~re is no known limita~ion on the ratios of the ammonium thiosulPate ~nd the ~ource of nitrogen in the solution~ but a typical ~olution is prepared by mi~ng abou~ 100 part~ by ~eight o~ the liquid ammonium thiosulfate ~slution with about 950 parts by weight of urea. Sin~e the ~mmonium thio~ulfate 801ution contain~ about 57 weight percent ammonium thio~ulfate~ the r~sulting uniform ~ised ~olution contains about 950 parts urea, 57 parts ammoni~n thlo~ul-fate, 38 parts water, and 5 parts impurit~es. Th~
ooncerltration amount of ammonil2m tlhiosulfate i~ found to be effective in inhibiting nitrification reactions in ~j 80il~, as will be de~cribed more fully belowO Other ratios of ammonium 'chiosulfate have varying effects, but all ratios examined have been ~ound effective in inhib-iting nitrifica~ion of soil~ ~o which the fertilizer material i5 addedO
In accordan~e ~ith another aspec~ of the invention, a ~olid fertilizer includes particles each comprising ~ sub tantially uniform mix~ure of ammonium thiosulfate ~nd ~ sour~e of nitrogen,, the source of nitrogen preferably being urea. ~uch ~olld mixtures have been previously in~pos~ible to prepare ~ due to volatilization and loss of ~ulfur during dehydra~ion and drylng of a 1 iquid mixture of ~he lngred ien'cs to form a sol id . In a process for preparing the pre~erred am-moni~n thiosulfate-urea fertilizer material~ the desired portion~ of ammon~ um thiosulfate ~nd urea are mixed to~ether to form a 1 iquid solution at a temp~rature of no greater than about 180F~ and then a vacuum i~
appl ied to the liquid ~olutlorl ~o evaporate water thererom, while maint~ining a temperature of no greater 'chan about 180P.
No limi~ations are known on the ratios of the ammonium thlo~ulfate ~nd ~he urea in the ~olu tion. For example, ~he pr~viously described liquid solution of 950 parts urea, 57 parts ammoni~n 'chio~ul~
fate 9 38 part~ water and 5 parts impur~ 5 maS7 he vacuum evaporated to yield ~ ~olid particulate having 950 part~ urea, 57 parts ammoni~n thiosulf~e9 and 5 part~ impuritie~ (by wei~ht3, s~r ~ htl~r less than 95~6 by weight urea.
Urea and ~nmonium th~o~ulfate aqueous solutiLon have 1 imited mu~cual sQlubil ~ty at elevated tempera-~ures. When more ~han abou'c 95% by we~ght urea $s utilized, a minor amount of water may b~ add~d to ass~st ~n preparing a liguid 801lJt~Oll ~t a temperature of no ~rea~cer than abou~ 180F. Typically, no ~dded water is needed ~or a solution containing 9096 Iby weigh~ urea, while 5% water by weight i8 added to achieve solubiliza-~ion for a mixtu~e containing 54 by weight ammonium 10 thiosulfat~ 801ution and 90% by wei~ht urea,. The excess water i8 present only ~o aid in forming the solutiorl at elevated temperatures, and is evaporated in forming the solid. Mixing can occur in any suitable container, such as a metal or plastic vessel.
After the liquid mi~ture o~ anmonium ~hiosul-fate and urea i5 prepared, it i~ processed to the æol id form by applying a vacuum to evapora~ce water ~rom the liquid mixture while controlling temperature to maintain the evaporating solution at ~ temperature of no greater 20 than sbout 180F. The evaporation is endothermic, and heat i8 typically added to maintain the temperature.
The vacuwm is pr~ferably applied by a barometric con-denser having a high ca~city ~o allow removal of ~he water vapor. The condenser i~ preferably sized ~o as to 25 maintain a vacuum of about 1-1/2 ~o about 4 incheæ
mercury above the evapor2ting solution. ~Higher or lower vacuums are operable but he ind i c~ted range is most commercially feasible to balance the cost of vacuum equipment requ~ red for higher v~cuums against the slower 30 evapora~clon lc~ne~is:6 of lower vacuums~,3 ~he vacuum evaporation i~ conducted in any ~uitable apparatus, such as ~ closed metal or plasti~ chanber.
The solution mixing and evapor~tion ~cempera-tures are preferably no greater than ~bou 1800F~ At ;q~5~3 --~o--temperatures above about 180~9 ~ulfur 18 precipll:ated from the thiosulfate, thereby producing an undesir~ble product. ~t tempera'cure~ below abou'c 180F,~ ~he evaporation rate of the water :Is reduced; al~hough the proce6s remains operableO The ~olution m~xing and evaporation temperature~ are therefore ~elec'ced to be no greater than abou'c 180F~ and preiEerably about lB0F.
At the ind icated temperature and ~acllum, the vacuum evaporation proceeds rapidlyO Preferably~ he mixture i8 agitated by a mechanical miacer or other means during Yacuum evaporation to accelerate the formation and drying of a solid. As an example, about 0.25 gal70n~ of a mixture of 4.6~ by wei~ht ammoni~n thiosul-fatP, 87~,9% by weight urea, and 7.,5~ by weight water was mixed together ~t about 180F. The liquid ~olution was transferred in~o a 0.33 gallon capacity vacuum chamber, and then a vacuum of about 1-1/2 $nches mercury was ~ppl ied by a vacuum pump. Heat was suppl ied to 'che vacuum chamber during vacuum evapora'cion by an electri-cal heater. Sufficient heat waR supplied to maintain the mixture at about 180F during the entire vacuum evaporation process. Af~er 6ubstantially all o~ the free liquid had evaporat~d, ~ clear particulate mass remained. It was observed that fis~al drying of this particulate mass to a ~ompl~tely dry ~lid occurs ~lowly, so that~ in a preferred approach, the particu-late ma~s was removed from the vacuum ~on~ainer and dried to complete dryness in ~mbient air. I~ was found that placing the parti~ulate mass into ~ low temperature drying oven in air re~ulted in decompo~ on and an undesirable precipitation of ~ulfur from the particulate ma~s. Therefore, use of an atmospheric pre~sure air drying oven to complete the dryin~ oper~tlon i~ to be avoided~ Drying may al50 be accompl~h2d ~n a low-temperature vacuum oven~
35'~
`
To complete the preparation of the ertilizer material ,, the particulate ma~s is preerably crushed and 8ized . Th~ ~ol id~ may be t:rushed ~ n ~ny convenient approach, ~;uch 1~ in a roll crusherO The crushed mixture i~ then graded by ~izing ~creen~ to produ~e the desired dis~ribution of granule~ for packa~ing. Par-ticula~e material having undesired product ~ize may be red issolved and recycled ~hrough ~he process ., It has been fs)und tha~ the fertilizer of the inventicn has a particularly beneficial effect on inhibiting nitrific~ation and urease rea~tions in soils.
That is, appl ication of the fertil izer reduces the loss of nitrogen from the soil, ma~ing more of the appl ied nitzogen ~vailable to the plants. In achieving this inhibition of nitrogen lo~s, the fertilizer of the present invention can replace ~ar more co~tly nitrifi-catis:~n inhibitor~ ~uch ~s dicyandiamide, thiourea~
phenyl phosphs~rodlamidate~ and potassiwn ethyl ~anthate~
It als~ avoids u~e of carbon disulfide and r~lated compounds ~ which are recognlzed as nitrlfication lnhibitor~, but which mav be objectional due to flama-bility, unavailabilityv toxictty, and odor. Becau~e of the very high volumes of ~ertilizer util~z~d, l~he C08t savings ba8ed on use of ammonium thio~ulfate are exten-~iv2.
In labora~ory ~ests~ 80il ~amples were pre-pared by mixing 50 grams of a Willi~ms I,oam soil wi~ch 10 milliliters of water ~n a bo~le. A 0.1 milliliter drop
tages O
9~5~`~
SUMMARY OF THE INVENTION
The present invention provid~s a fertilizer con'caining ulfur and nitrog~n in biologi~lly usabl*
form, and a procesæ :IEor preparing a ~olid particulate f~rtilizer which prevents volatilization and lo~s of sulfur during prepara~ion~, Th~ fertil~zer material is found ~o inhibit urease and nitrifica~ion lo~es from the soil~ ~hus improving the efficiency of ~he fer-tilizer addi~ion as well as improvisg the overall ~fficiency of the soil in prs~v~ding nutrients to the pl an'cs.
In accordance with lthe invention, a fertil izer material co~nprises a ~ubstan~ially uniform mixture of ~mmonium thiosulfate and at least one ~ource Qf nitro-gen, preferably 6elected rom the group consisting of urea~ urea ammonium ni1:rate, ammoniwn phosphate, am-mc~ni~n nitrate, calcium nitrate~ and Ammoni~n sulfate.
In its solid particulate ~orm" each particle comprise~ a substantially uniform mixture of ammoniwn thio~ulfate and the nitrogen ~ource. ~he rativ o the nitrogen source and the thiosulf~te is not critical ~ bu~ pre-ferably the ammonium thiosulfate is pregent in an amount of at least 5% by weight of the inal produc~. As 1 ittle as 0~ 2~6 ammoni~n thiosulfa'ce is effective in inhlbi'cing urease and nitrification lo~es, but such ~mall ~mount~
are agriculturally not pra~tical ~ lf ~ufur is being added as ~ nutrient.
In anoth~r a6pec'c o$ the invention, a solid fertili~er material may b~ prepared by mixing together ~nmoni~n thiosulf~te and the ~ource oiE nitrogen to form ~ liquid ~olution~ at a temperature of no greater than about lBO~F; and ~hen applylng a va~uum ~o the liquid ~olu'cion to remove ~a'cer th~re~rom~ ~t ~ temperature of no gre~ter than about 180F, to form a ~ol id par'cicu-late. At temperature6 greater than about 180 F, the ammonium thio~ulfate decompo~es. Opt$onally, ~mall amount of water may ~e added to a8si8t in forming a liquid mixture when the ammonium thlosul~ate and the source of nitrogen are mixed ~oge~her at eleva~ed temperature. Agitation and continued mixing during vacuum evaporation ac~elerate the production of ~he æolid. The last ~tages of the vacuum evapora~ion of wa~er proceed relatively slowly, and it i~ preferred to complete the drying by ambient air dry~ng or at elevated temp~ratures in a vacuum dryer~ The final drying should not be accomplished at elevated tempera~ure in air~
since sulfur i6 precitated from the fertilizer material.
Finally~ the dried particulate solid i~ crushed and ~creened to produce granules of a desired size distri-bu~ion~
It will now be appreciated that the present invention represents an advance in the field of ferti-lizer manufacture and utilization. A fertilixer con-taining nitrogen and ~ulfur in usable form, ~nd suppli~d by relatively inexpens1ve ingredient~, may be prepared a~ either a liqu$d or solid, without a ~ubstantial loss or precipit~tion of sul~ur during manufacture~ When applied, the fertili~er material inhibits ni~rogen loss from the ~oil, to achieve in~re~sed efficie~cyc O~her features and advantages of the present invention will become ~pparen~ from ~he followin~ more detailed des-cription~ which illustrate6, by way of e~ample, the principles of the invention 7 B';,~
DETAILED DESCRIPTION OF TH~ PREFERRED ~MBODIMENT
__________ ____ The raw materials ut~lized in the ~ertilizer process and material of the preferred embodiment~ of the present 1nvention are readily obtained commercially.
Ammoniwn thio~ulfate having a nominal c~mpo~ition of grade (12~û-0 26 ~ ~as obt~ined ~rom J. R. Simplot Companyc 8randon, Mani'coba, Canada., The conYentional N-P ~ X agriculturaî notation ~ ~; used herein 9 where N
denotes nitrogen, P deno~e~ phosphorus, R denotes potassi~Dn7 and X represent~ other elements, here ~ufur.) The commercial product was found to contain about 57 weight percent ammonium thiosulfate9 38 weight percent wa~er, 2"~ weight percent ammonium sul~a~e, and 2.5 weight percent ammonium sulfite. Urea-anunonl~n r itrate csf grade (28-0-0) wa~ obtained ~rom J.. R. Simplot Company, Brandon, ~anitoba, Canada. Solid pure urea was obtained from J. R. Simplot Company, Pocatello, Idaho.
Operabil ity of the present invention does not re~uire the use o~ ingredients of high purlty or other ~pecial characteristic~.
In accordance with one aspect of the inven-tion9 the liquid ammonium thiosulfate and the source of nitrogent preferably ure~ or urea-æmmonium nitrate, ~re mixed together to form a substantially uniform mixed 2~ solution at a temperature of no greater than about 180~o ~n pr~paring ~he mixed ~olution, no observable chemical reaction oc~ur~O Th~re is no known limita~ion on the ratios of the ammonium thiosulPate ~nd the ~ource of nitrogen in the solution~ but a typical ~olution is prepared by mi~ng abou~ 100 part~ by ~eight o~ the liquid ammonium thiosulfate ~slution with about 950 parts by weight of urea. Sin~e the ~mmonium thio~ulfate 801ution contain~ about 57 weight percent ammonium thio~ulfate~ the r~sulting uniform ~ised ~olution contains about 950 parts urea, 57 parts ammoni~n thlo~ul-fate, 38 parts water, and 5 parts impurit~es. Th~
ooncerltration amount of ammonil2m tlhiosulfate i~ found to be effective in inhibiting nitrification reactions in ~j 80il~, as will be de~cribed more fully belowO Other ratios of ammonium 'chiosulfate have varying effects, but all ratios examined have been ~ound effective in inhib-iting nitrifica~ion of soil~ ~o which the fertilizer material i5 addedO
In accordan~e ~ith another aspec~ of the invention, a ~olid fertilizer includes particles each comprising ~ sub tantially uniform mix~ure of ammonium thiosulfate ~nd ~ sour~e of nitrogen,, the source of nitrogen preferably being urea. ~uch ~olld mixtures have been previously in~pos~ible to prepare ~ due to volatilization and loss of ~ulfur during dehydra~ion and drylng of a 1 iquid mixture of ~he lngred ien'cs to form a sol id . In a process for preparing the pre~erred am-moni~n thiosulfate-urea fertilizer material~ the desired portion~ of ammon~ um thiosulfate ~nd urea are mixed to~ether to form a 1 iquid solution at a temp~rature of no greater than about 180F~ and then a vacuum i~
appl ied to the liquid ~olutlorl ~o evaporate water thererom, while maint~ining a temperature of no greater 'chan about 180P.
No limi~ations are known on the ratios of the ammonium thlo~ulfate ~nd ~he urea in the ~olu tion. For example, ~he pr~viously described liquid solution of 950 parts urea, 57 parts ammoni~n 'chio~ul~
fate 9 38 part~ water and 5 parts impur~ 5 maS7 he vacuum evaporated to yield ~ ~olid particulate having 950 part~ urea, 57 parts ammoni~n thiosulf~e9 and 5 part~ impuritie~ (by wei~ht3, s~r ~ htl~r less than 95~6 by weight urea.
Urea and ~nmonium th~o~ulfate aqueous solutiLon have 1 imited mu~cual sQlubil ~ty at elevated tempera-~ures. When more ~han abou'c 95% by we~ght urea $s utilized, a minor amount of water may b~ add~d to ass~st ~n preparing a liguid 801lJt~Oll ~t a temperature of no ~rea~cer than abou~ 180F. Typically, no ~dded water is needed ~or a solution containing 9096 Iby weigh~ urea, while 5% water by weight i8 added to achieve solubiliza-~ion for a mixtu~e containing 54 by weight ammonium 10 thiosulfat~ 801ution and 90% by wei~ht urea,. The excess water i8 present only ~o aid in forming the solutiorl at elevated temperatures, and is evaporated in forming the solid. Mixing can occur in any suitable container, such as a metal or plastic vessel.
After the liquid mi~ture o~ anmonium ~hiosul-fate and urea i5 prepared, it i~ processed to the æol id form by applying a vacuum to evapora~ce water ~rom the liquid mixture while controlling temperature to maintain the evaporating solution at ~ temperature of no greater 20 than sbout 180F. The evaporation is endothermic, and heat i8 typically added to maintain the temperature.
The vacuwm is pr~ferably applied by a barometric con-denser having a high ca~city ~o allow removal of ~he water vapor. The condenser i~ preferably sized ~o as to 25 maintain a vacuum of about 1-1/2 ~o about 4 incheæ
mercury above the evapor2ting solution. ~Higher or lower vacuums are operable but he ind i c~ted range is most commercially feasible to balance the cost of vacuum equipment requ~ red for higher v~cuums against the slower 30 evapora~clon lc~ne~is:6 of lower vacuums~,3 ~he vacuum evaporation i~ conducted in any ~uitable apparatus, such as ~ closed metal or plasti~ chanber.
The solution mixing and evapor~tion ~cempera-tures are preferably no greater than ~bou 1800F~ At ;q~5~3 --~o--temperatures above about 180~9 ~ulfur 18 precipll:ated from the thiosulfate, thereby producing an undesir~ble product. ~t tempera'cure~ below abou'c 180F,~ ~he evaporation rate of the water :Is reduced; al~hough the proce6s remains operableO The ~olution m~xing and evaporation temperature~ are therefore ~elec'ced to be no greater than abou'c 180F~ and preiEerably about lB0F.
At the ind icated temperature and ~acllum, the vacuum evaporation proceeds rapidlyO Preferably~ he mixture i8 agitated by a mechanical miacer or other means during Yacuum evaporation to accelerate the formation and drying of a solid. As an example, about 0.25 gal70n~ of a mixture of 4.6~ by wei~ht ammoni~n thiosul-fatP, 87~,9% by weight urea, and 7.,5~ by weight water was mixed together ~t about 180F. The liquid ~olution was transferred in~o a 0.33 gallon capacity vacuum chamber, and then a vacuum of about 1-1/2 $nches mercury was ~ppl ied by a vacuum pump. Heat was suppl ied to 'che vacuum chamber during vacuum evapora'cion by an electri-cal heater. Sufficient heat waR supplied to maintain the mixture at about 180F during the entire vacuum evaporation process. Af~er 6ubstantially all o~ the free liquid had evaporat~d, ~ clear particulate mass remained. It was observed that fis~al drying of this particulate mass to a ~ompl~tely dry ~lid occurs ~lowly, so that~ in a preferred approach, the particu-late ma~s was removed from the vacuum ~on~ainer and dried to complete dryness in ~mbient air. I~ was found that placing the parti~ulate mass into ~ low temperature drying oven in air re~ulted in decompo~ on and an undesirable precipitation of ~ulfur from the particulate ma~s. Therefore, use of an atmospheric pre~sure air drying oven to complete the dryin~ oper~tlon i~ to be avoided~ Drying may al50 be accompl~h2d ~n a low-temperature vacuum oven~
35'~
`
To complete the preparation of the ertilizer material ,, the particulate ma~s is preerably crushed and 8ized . Th~ ~ol id~ may be t:rushed ~ n ~ny convenient approach, ~;uch 1~ in a roll crusherO The crushed mixture i~ then graded by ~izing ~creen~ to produ~e the desired dis~ribution of granule~ for packa~ing. Par-ticula~e material having undesired product ~ize may be red issolved and recycled ~hrough ~he process ., It has been fs)und tha~ the fertilizer of the inventicn has a particularly beneficial effect on inhibiting nitrific~ation and urease rea~tions in soils.
That is, appl ication of the fertil izer reduces the loss of nitrogen from the soil, ma~ing more of the appl ied nitzogen ~vailable to the plants. In achieving this inhibition of nitrogen lo~s, the fertilizer of the present invention can replace ~ar more co~tly nitrifi-catis:~n inhibitor~ ~uch ~s dicyandiamide, thiourea~
phenyl phosphs~rodlamidate~ and potassiwn ethyl ~anthate~
It als~ avoids u~e of carbon disulfide and r~lated compounds ~ which are recognlzed as nitrlfication lnhibitor~, but which mav be objectional due to flama-bility, unavailabilityv toxictty, and odor. Becau~e of the very high volumes of ~ertilizer util~z~d, l~he C08t savings ba8ed on use of ammonium thio~ulfate are exten-~iv2.
In labora~ory ~ests~ 80il ~amples were pre-pared by mixing 50 grams of a Willi~ms I,oam soil wi~ch 10 milliliters of water ~n a bo~le. A 0.1 milliliter drop
3~ of a liquid fertilizer ~olution wa~ place~ on the ~oil surface ~nd ~llowed to in¢ubate for 28 day~,. Nitrogen los~ wa~ calculated and compared with nitrogen loss of a control ~ample, following the method de8e!r1t~ed by Bremner ~nd Bundy, 1974 ~ Inhi tion of Ni'crification in 3~ SoilR by Y~la~ile_Sulfur_Compounds9 Soil B~LO1. Biocheml.
~: 161-165.
$ ~26~38~
,, The liquid fertilizer~ ut~lized in the study all included about 90~ by volume urea ammonium nitrate~
and Ammonium thiosulfate in a range of 0~ 1, 2, 5, and 10 percent by volume. For those fertilizers c~ntain~ng le~s ~han 10~ by volume ammonium thiosulfa~e, the balance of th~ solution was water. Inhibition of nitrification af~er 28 days wa~ ~ound ~o be about 20%
for th* liquid fer il~zers conta~ning 1 and 2 perce~t ammonium ~hiosulf~te, abou~ 50~ for the fertilizer containing ~bout 5% ammonium thiosulfate9 ~nd about 60%
for the fertilizer containing about 10~ ammonium thio-sulfate. It is believed tha~ similar inhibition of nitrification result~ for solid fer~ilizers ~ontaining like a~unts of ammonium thiosulfate in ~ombination with the nitrogen sour~eO
The u~e of ammonium thiosulf~te in fertilizers rather than other ni~rifîcation inhibitors ~lso has impor~ant agricultural valueO ~he ammonium thiosulfate eventually decompo~es to nitrates and sulfates, which have fertilizer value in themselves, whereas decomposit-ion product~ of oth~r nitrification inhibitors typically have no ~uch ~ertil izer value ln 'themselve~.
A~ can now be appreciated, th~ fertllizer and process of the pre~ent invention provide impor~ant ~dvantage~ to the far~rO in th~ a fertilizer which inhibi~ nitrification ~ay be provided inexpensively~
and in either a liquid or solid form. The proce~s for preparing a 601id fer~ilizer from ammonium thiosulfate and a nitrogen source avoids the 10SB 0~ ~ulfur from ~he fertilizer by a vacuum evap~ration proce~ to remove water rom the liquid mixture to form ~ ~oli~, ~nd then further va~uum evapor~tion or ambient temperature drying to form a dry par~icula~Q. ~l~hough ~ par~icular embodiment of the invention has been described for purposes of illustratiorl, variou~ modificatic:~n~ may be m3de without departing from the ~pirit and ~cope of the invention. A~cordingly, the pre~ent invention i8 not to be limited except as by the appended claim~.
~: 161-165.
$ ~26~38~
,, The liquid fertilizer~ ut~lized in the study all included about 90~ by volume urea ammonium nitrate~
and Ammonium thiosulfate in a range of 0~ 1, 2, 5, and 10 percent by volume. For those fertilizers c~ntain~ng le~s ~han 10~ by volume ammonium thiosulfa~e, the balance of th~ solution was water. Inhibition of nitrification af~er 28 days wa~ ~ound ~o be about 20%
for th* liquid fer il~zers conta~ning 1 and 2 perce~t ammonium ~hiosulf~te, abou~ 50~ for the fertilizer containing ~bout 5% ammonium thiosulfate9 ~nd about 60%
for the fertilizer containing about 10~ ammonium thio-sulfate. It is believed tha~ similar inhibition of nitrification result~ for solid fer~ilizers ~ontaining like a~unts of ammonium thiosulfate in ~ombination with the nitrogen sour~eO
The u~e of ammonium thiosulf~te in fertilizers rather than other ni~rifîcation inhibitors ~lso has impor~ant agricultural valueO ~he ammonium thiosulfate eventually decompo~es to nitrates and sulfates, which have fertilizer value in themselves, whereas decomposit-ion product~ of oth~r nitrification inhibitors typically have no ~uch ~ertil izer value ln 'themselve~.
A~ can now be appreciated, th~ fertllizer and process of the pre~ent invention provide impor~ant ~dvantage~ to the far~rO in th~ a fertilizer which inhibi~ nitrification ~ay be provided inexpensively~
and in either a liquid or solid form. The proce~s for preparing a 601id fer~ilizer from ammonium thiosulfate and a nitrogen source avoids the 10SB 0~ ~ulfur from ~he fertilizer by a vacuum evap~ration proce~ to remove water rom the liquid mixture to form ~ ~oli~, ~nd then further va~uum evapor~tion or ambient temperature drying to form a dry par~icula~Q. ~l~hough ~ par~icular embodiment of the invention has been described for purposes of illustratiorl, variou~ modificatic:~n~ may be m3de without departing from the ~pirit and ~cope of the invention. A~cordingly, the pre~ent invention i8 not to be limited except as by the appended claim~.
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS.
1. A process for preparing a solid fertilizer material, comprising the steps of:
mixing together ammonium thiosulfate and a source of nitrogen to form a liquid solution, at a temperature of no greater than about 180°F, the source of nitrogen being a salt or organic compound containing nitrogen;
applying a vacuum to the liquid solution to evaporate water from the liquid mixture, at a temper-ature of no greater than about 180°F to prevent loss of ammonium thiosulfate, to form a solid particulate.
mixing together ammonium thiosulfate and a source of nitrogen to form a liquid solution, at a temperature of no greater than about 180°F, the source of nitrogen being a salt or organic compound containing nitrogen;
applying a vacuum to the liquid solution to evaporate water from the liquid mixture, at a temper-ature of no greater than about 180°F to prevent loss of ammonium thiosulfate, to form a solid particulate.
2. The process of claim 1, wherein the source of nitrogen is selected from the group consisting of urea, urea-ammonium nitrate, ammonium phosphate, ammonium nitrate, calcium nitrate, and ammonium sulfate.
3. The process of claim 1, wherein the source of nitrogen is urea.
4. The process of claim 1, wherein the ammonium thiosulfate is present in an amount of at least about 0.2% by weight of the solid.
5. The process of claim 1, wherein the ammonium thiosulfate is present in an amount of at least about 5% by weight of the solid.
6. The fertilizer process of claim 1, including the additional step of:
crushing the solid particulate remaining after evaporation to produce granules.
crushing the solid particulate remaining after evaporation to produce granules.
7. The process of claim 1, including the additional step, after said step of applying, of drying the solids remaining after evaporation in ambient temperature air.
8. A solid particulate fertilizer material, each particle comprising a substantially uniform mixture of ammonium thiosulfate and a source of nitrogen, the source of nitrogen being a salt or organic compound containing nitrogen.
9. The material of claim 8, wherein the source of nitrogen is selected from the group consisting of urea, urea-ammonium nitrate, ammonium phosphate, ammonium nitrate, calcium nitrate and ammonium sulfate.
10. The material of claim 8, wherein the ammonium thiosulfate is present in an amount of at least about 0.2% by weight of the solid.
11. The material of claim 8, wherein the ammonium thiosulfate is present in an amount of at least about 5% by weight of the solid.
12. The material of claim 8, wherein the source of nitrogen is urea.
13. A process for fertilizing and inhibiting nitrogen loss from soil, comprising the steps of:
preparing a solid particulate material, each particle comprising a substantially uniform mixture of ammonium thiosulfate and a source of nitrogen, the source of nitrogen being a salt or organic compound containing nitrogen; and applying the solid particulate material to the soil, whereby nitrogen and sulfur are provided to the soil, and nitrogen loss is inhibited.
preparing a solid particulate material, each particle comprising a substantially uniform mixture of ammonium thiosulfate and a source of nitrogen, the source of nitrogen being a salt or organic compound containing nitrogen; and applying the solid particulate material to the soil, whereby nitrogen and sulfur are provided to the soil, and nitrogen loss is inhibited.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US68964985A | 1985-01-08 | 1985-01-08 | |
US689,649 | 1985-01-08 |
Publications (1)
Publication Number | Publication Date |
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CA1269859A true CA1269859A (en) | 1990-06-05 |
Family
ID=24769361
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000499118A Expired - Lifetime CA1269859A (en) | 1985-01-08 | 1986-01-07 | Ammonium thiosulfate-containing fertilizers |
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CA (1) | CA1269859A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1298114A1 (en) * | 2000-05-15 | 2003-04-02 | Mitsui & Co., Ltd. | Fertilizers containing ammonium thiosulfate |
CN103483110A (en) * | 2013-09-06 | 2014-01-01 | 天津芦阳化肥股份有限公司 | Whole-process nutrient supply type composite fertilizer and preparation method thereof |
EP3626697A1 (en) * | 2018-09-19 | 2020-03-25 | Tessenderlo Kerley, Inc. | Stabilized fertilizer compositions and methods for preparing same |
EP3626696A1 (en) * | 2018-09-19 | 2020-03-25 | Tessenderlo Kerley, Inc. | Compositions comprising solid thiosulfates, polysulfides and/or (bi)sulfites and methods for preparing same |
-
1986
- 1986-01-07 CA CA000499118A patent/CA1269859A/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1298114A1 (en) * | 2000-05-15 | 2003-04-02 | Mitsui & Co., Ltd. | Fertilizers containing ammonium thiosulfate |
EP1298114A4 (en) * | 2000-05-15 | 2004-08-04 | Mitsui Bussan | Fertilizers containing ammonium thiosulfate |
CN103483110A (en) * | 2013-09-06 | 2014-01-01 | 天津芦阳化肥股份有限公司 | Whole-process nutrient supply type composite fertilizer and preparation method thereof |
EP3626697A1 (en) * | 2018-09-19 | 2020-03-25 | Tessenderlo Kerley, Inc. | Stabilized fertilizer compositions and methods for preparing same |
EP3626696A1 (en) * | 2018-09-19 | 2020-03-25 | Tessenderlo Kerley, Inc. | Compositions comprising solid thiosulfates, polysulfides and/or (bi)sulfites and methods for preparing same |
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