CN103708964B - Instant chelated solid water-soluble fertilizer - Google Patents
Instant chelated solid water-soluble fertilizer Download PDFInfo
- Publication number
- CN103708964B CN103708964B CN201310738398.4A CN201310738398A CN103708964B CN 103708964 B CN103708964 B CN 103708964B CN 201310738398 A CN201310738398 A CN 201310738398A CN 103708964 B CN103708964 B CN 103708964B
- Authority
- CN
- China
- Prior art keywords
- soluble fertilizer
- water
- sulfate
- chelated
- instant
- 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 - Fee Related
Links
- 239000003337 fertilizer Substances 0.000 title claims abstract description 64
- 239000007787 solid Substances 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 31
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 11
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 11
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 11
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 11
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 11
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 11
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000003352 sequestering agent Substances 0.000 claims description 31
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 16
- 239000001110 calcium chloride Substances 0.000 claims description 16
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 15
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000292 calcium oxide Substances 0.000 claims description 15
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 15
- 239000011591 potassium Substances 0.000 claims description 15
- 229910052700 potassium Inorganic materials 0.000 claims description 15
- 150000001413 amino acids Chemical class 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000013522 chelant Substances 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 229920001661 Chitosan Polymers 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 229920001529 polyepoxysuccinic acid Polymers 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 239000002738 chelating agent Substances 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract 4
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 abstract 3
- 239000002426 superphosphate Substances 0.000 abstract 3
- 238000004176 ammonification Methods 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 229940099596 manganese sulfate Drugs 0.000 abstract 1
- 239000011702 manganese sulphate Substances 0.000 abstract 1
- 235000007079 manganese sulphate Nutrition 0.000 abstract 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 abstract 1
- 235000019796 monopotassium phosphate Nutrition 0.000 abstract 1
- 235000015097 nutrients Nutrition 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 239000011684 sodium molybdate Substances 0.000 abstract 1
- 235000015393 sodium molybdate Nutrition 0.000 abstract 1
- 239000011573 trace mineral Substances 0.000 description 19
- 235000013619 trace mineral Nutrition 0.000 description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 11
- 239000001632 sodium acetate Substances 0.000 description 11
- 229960004249 sodium acetate Drugs 0.000 description 11
- 235000017281 sodium acetate Nutrition 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 229960002337 magnesium chloride Drugs 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- CCVYRRGZDBSHFU-UHFFFAOYSA-N (2-hydroxyphenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1O CCVYRRGZDBSHFU-UHFFFAOYSA-N 0.000 description 2
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000003973 irrigation Methods 0.000 description 2
- 230000002262 irrigation Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical class O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000002374 bone meal Substances 0.000 description 1
- 229940036811 bone meal Drugs 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical class OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940073589 magnesium chloride anhydrous Drugs 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000011785 micronutrient Substances 0.000 description 1
- 235000013369 micronutrients Nutrition 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Fertilizers (AREA)
Abstract
The invention relates to an instant chelated solid water-soluble fertilizer, particularly a chelated water-soluble fertilizer capable of heating a solution, belonging to the field of crop fertilizers. The water-soluble fertilizer comprises 25-40% of urea, 10-20% of potassium dihydrogen phosphate, 10-25% of double superphosphate, 10-25% of potassium sulfate, 2-6% of magnesium chloride, 0.5-3% of zinc sulfate, 0.5-3% of manganese sulfate, 0.5-4% of sodium molybdate, 0.5-2% of ferrous sulfate, 2-8% of chelator and 4-10% of heating agent. The preparation method of the water-soluble fertilizer comprises the following steps: carrying out ammonification pretreatment on double superphosphate for later use, chelating microelements with a chelator to obtain a chelated mixture, thoroughly mixing the treated double superphosphate, chelated mixture, macroelements and heating agent, pulverizing and packaging to obtain the instant chelated solid water-soluble fertilizer. The water-soluble fertilizer contains abundant microelements and overall nutrients; and the heating agent can increase the dissolution temperature, thereby enhancing the solubility of the components, increasing the dissolution rate and reducing the water consumption. The microelements are chelated by the chelator, thereby promoting the absorption and utilization of plants for macroelements and microelements; and thus, the fertilizer is suitable for various crops.
Description
Technical field
The invention belongs to the fertilizer field of farm crop, more precisely relate to the instant sequestering solid Water soluble fertilizer of a kind of water-saving chelating.
Background technology
Water soluble fertilizer is a kind of water-soluble polyelement composite fertilizer, and be a kind of new-type fertilizer of rising in recent years, it can be dissolved in the water rapidly, more easily absorbed by farm crop, and absorption rate is relatively high, realize water-fertilizer integral, reach the effect that water-saving economizes fertile saving of labor.China is a large agricultural country, populous, water resources famine, occupancy volume per person is equivalent to world occupancy volume per person's 1/4, for the share of agriculture production also in continuous decline, has formed a very severe problem, agriculturally, greatly developing of water-saving fertilizer urgently can not be treated.
At present, China's Fertilizer Industry mainly with nitrogen, phosphorus, potassium for raw material production polyelement composite fertilizer, because this is the macroelement needed for farm crop, but the growth of farm crop is demand nitrogen, phosphorus, potassium element not only, go back the indispensable nutritive elements such as demand calcium, magnesium, sulphur, iron, zinc, manganese, copper, boron, molybdenum and chlorine simultaneously, they and nitrogen, phosphorus, potassium element have equal importance and irreplaceability, if once disappearance can have a strong impact on the yield and quality of farm crop in soil.Trace element can improve crop yield, negatively charged ion and positively charged ion is had in trace element, the mutual antagonistic action existed between zwitterion, and the interference of soil pH value and other foreign ions, seriously hinder the absorption of crop to trace element, therefore need suitable sequestrant, by trace element chelated, make it absorbed by crops and utilization to greatest extent.
Chinese invention patent publication number CN 102010267 A discloses a kind of preparation method of nitro-compound fertilizer.Fully mixed with each trace element by sequestrant in the method, granulation is dried and is formed, and wherein sequestrant used is diethylene triamine pentacetic acid (DTPA), ethylenediamine tetraacetic acid (EDTA), hydroxyethylethylene diamine tri-acetic acid or quadrol O-hydroxyphenylacetic acid, all belongs to ammonia carboxylic type compound.
Chinese invention patent publication number CN 102531776 A discloses a kind of composite microbiological fertilizer and preparation method thereof.Dry after fertilizer, inorganic fertilizer and medium trace element being mixed with sequestrant, microbiobacterial agent in the method and obtain.The method sequestrant used is one or more in amino acid, xanthohumic acid, molasses.Sequestrant used also belongs to ammonia carboxylic type compound.
Chinese invention patent publication number CN 102649657 A discloses the full Water soluble fertilizer production method of a kind of macroelement.The method sequestrant process raw phosphoric acid, make raw phosphoric acid form water soluble phosphorous fertilizer, then mix with water-soluble nitrogenous fertilizer, potash fertilizer, granulation, dry, cooling obtains.Sequestrant in this production method be following component by a certain percentage mixed preparing form: water, ethylene diamine tetra methylene phosphonic acid salt, diethylene triamine pentamethylene phosphonic salt, 8-hydroxyquinoline, the adjacent sodium of quadrol two, polypropylene acid sodium.
According to above-mentioned, the most sequestering Water soluble fertilizer of China all adds different sequestrants and carries out chelating to trace element, and these sequestrant major parts are ammonia carboxylic type compound.Chelant ties trace element, increases the specific absorption of crop to trace element.Above-mentioned China's major part chelating Water soluble fertilizer, the water requirement of dissolving Water soluble fertilizer does not still become, and the hydrolysis degree of Water soluble fertilizer does not also increase, and does not really reach water-fertilizer integral, the effect of water-saving.
Summary of the invention
The present invention, in order to overcome deficiency and the defect of above-mentioned technology, provides a kind of instant chelating solid Water soluble fertilizer.This instant chelating solid Water soluble fertilizer not by means of only interpolation chelant ties trace element, but also with the addition of the intensification agent of meeting water heat release, improves the temperature of solution, and then adds the solubleness of solid fertilizer, reach the effect of water-saving.Because element is absorbed by crops with the form of ion and utilizes, and solid fertilizer dissolves in water and be hydrolyzed into ion, but is not complete hydrolysis, by the concentration of salt, and the impact of solution temperature and pH value.Add intensification agent, solution temperature raises, and solid fertilizer hydrolysis degree increases, and solid fertilizer molecule just more easily and be more hydrolyzed into ionic species, just can be absorbed by crops faster, the utilization ratio of raising fertilizer and specific absorption.And the present invention's instant chelating solid Water soluble fertilizer color and luster and epigranular, short flow, cost is low, comprehensive nutrition, and fertilizer is solid, convenient storage and transport.
Invention further provides a kind of preparation method of instant chelating solid Water soluble fertilizer.By the pre-treatment to double superhosphate in the method, sequestrant is to trace element chelated, and both mix with nitrogenous source, potassium source, intensification agent again, dry, pulverize, and packs to obtain a kind of instant chelating solid Water soluble fertilizer.
A kind of instant chelating solid Water soluble fertilizer of the present invention, it is characterized in that each compositions in weight percentage proportioning is: urea 25% ~ 40%, potassium primary phosphate 10% ~ 20%, double superhosphate 10% ~ 25%, potassium sulfate 10% ~ 25%, magnesium chloride 2% ~ 6%, zinc sulfate 0.5% ~ 3%, manganous sulfate 0.5% ~ 3%, Sodium orthomolybdate 0.5% ~ 4%, ferrous sulfate 0.5% ~ 2%, sequestrant 2% ~ 8%, intensification agent 4% ~ 10%.
Sequestrant described above is following four kinds of mixtures: AMPS-polyacrylamide copolymer, AMPS-chitosan polymer, polyepoxysuccinic acid salt, amino acid powder, and ratio is: amino acid powder
:aMPS-chitosan polymer
:aMPS-polyacrylamide copolymer
:polyepoxysuccinic acid salt=10:2:2:1.Wherein said AMPS is AMPS.The sequestrant added can not only be water-soluble, and the title complex with ring texture can also be formed with trace element ion, in sequestrant there is conjugated double bond in each component molecular, make chelate structure more stable, the chelating number of rings that high molecular polymer and trace element ion are formed is more, chelate structure is more stable, therefore can make trace element ion can better be absorbed by crops, improves the utilization ratio of trace element.
Intensification agent described above consists of the one or more combination of following compound: calcium chloride, Magnesium Chloride Anhydrous, metal oxide, metal chloride, aluminium silicate salt, organic acid salt, limestone powder, bone meal.Water is met in intensification agent can release a large amount of heat, increases the temperature of solution.In Water soluble fertilizer of the present invention the solubility with temperature of each compound rising and increase, thus the required water requirement of dissolving the compound of equal quality just relatively reduces, and reaches the effect of water saving.The intensification agent added in the middle of the present invention is calcium chloride, calcium oxide and sodium-acetate, and the calcium chloride added, the ratio of calcium oxide and sodium-acetate is: calcium chloride: calcium oxide: sodium-acetate=6:2:2.Calcium chloride and sodium-acetate are dissolved in water can release heat, and calcium oxide can react with water, discharges a large amount of heat simultaneously, can elevate the temperature to more than 30 DEG C.Temperature raises, and the solubleness of solid Water soluble fertilizer increases, and the water requirement needed for dissolving just reduces, thus reach water saving effect moreover.And each compound hydrolysis degree also increases in Water soluble fertilizer, crop can be made to absorb faster and utilize each element.Moreover the intensification agent added equally can be soluble in water, can not produce other impurity.
A kind of instant chelating solid Water soluble fertilizer of the present invention, it is characterized in that, its preparation method comprises the following steps:
1) material pre-treatment: the double superhosphate of weight percent 10% ~ 25% is carried out predrying, then add the phosphoric acid with free state in a certain proportion of bicarbonate of ammonia, obtain the double superhosphate after neutralizing, pulverize, make its particle diameter be 80 ~ 200 orders, stand-by;
2) chelatropic reaction: by micro-magnesium chloride 2% ~ 6%, zinc sulfate 0.5% ~ 3%, manganous sulfate 0.5% ~ 3%, Sodium orthomolybdate 0.5% ~ 4%, ferrous sulfate 0.5% ~ 2% adds in chelating still, adds sequestrant, design temperature 55 DEG C ~ 70 DEG C, mixing speed 20r/min ~ 30r/min, churning time 30min ~ 50min, obtains chelate mix;
3) mix: by the double superhosphate after neutralization, urea 25% ~ 40%, potassium primary phosphate 10% ~ 20%, potassium sulfate 10% ~ 25%, chelate mix, intensification agent 4% ~ 10% joins in reactor and fully mixes, dry, pulverize, a kind of instant chelating solid Water soluble fertilizer.
In above-mentioned one instant chelating solid Water soluble fertilizer preparation method step 1), the amount of the bicarbonate of ammonia added is 1/10 of double superhosphate weight.Double superhosphate and urea mixing, generate 4CO (NH
2)
2ca (H
2pO
4)
2double salt, discharges crystal water simultaneously, causes mixture to become paste, increases the difficulty pulverized.Therefore add bicarbonate of ammonia pre-treatment, neutralization free state phosphoric acid wherein, changes its physics and chemistry character, but water-soluble P in product
2o
5content can not reduce.The add-on of bicarbonate of ammonia should control, and excessively can produce water-fast calcium phosphate salt as added.
Beneficial effect of the present invention:
1, the present invention first carries out predrying and ammoniated treatment to double superhosphate, in and double superhosphate in the middle of free state phosphoric acid, can not pasty state be become when making it mix with urea, it also avoid the reduction of effective constituent simultaneously.
2, the present invention is solid, convenient storage and transport, and this instant chelating solid Water soluble fertilizer solvability is good, owing to the addition of intensification agent, dissolution rate is fast, shortens 20% ~ 30% than conventional Water soluble fertilizer dissolution time, specific absorption can reach more than 90%, utilization ratio improves 10%, inclusion-free, is applicable to various irrigating facility.
3, N-P-K content of the present invention is even, compensate for the present situation that the few potassium of the many phosphorus of nitrogen lacks, and adding of amino acid powder, chelating can be carried out with trace element, improve crop to the specific absorption of trace element and utilization ratio, be applicable to various crop.
4, prevented from caking of the present invention, ensure that fertilizer efficiency, improves Soil structure, and crop increases income significantly, economizes fertile water-saving, reaches water-fertilizer integral, and the technological process of production is simple, and pollution-free generation in production process, energy consumption is low, is suitable for scale operation.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention
The outstanding feature of a kind of instant chelating solid Water soluble fertilizer of the present invention is:
1, sequestrant adopts high molecular weight water soluble polymer, wherein with the addition of amino acid powder, adding of amino acid powder, one energy chelated microelement, its two biological activity that can improve crop, it three can improve Soil structure, make each trace element can be better absorbed by crops and utilize, and high-molecular chelating agent, more five yuan and six-ring can be formed, chelate structure can be made more stable, improve specific absorption and the utilization ratio of trace element.
2, the intensification agent added in the middle of the present invention is calcium chloride, calcium oxide and sodium-acetate, and the ratio of the calcium chloride added and calcium oxide is: calcium chloride: calcium oxide: sodium-acetate=6:2:2.Calcium chloride and calcium acetate are dissolved in water can release a large amount of heat, and 5g calcium chloride can make the temperature of 1L water rise 1 DEG C; Calcium oxide can react with water, discharges a large amount of heat simultaneously, and 1g calcium oxide can make the temperature of 1L water rise 1.4 DEG C.The amount of the intensification agent added is 4% ~ 10%, and temperature can be made to rise to more than 30 DEG C, and temperature raises, and the solubleness of solid Water soluble fertilizer increases, and the water requirement needed for dissolving just reduces, thus reaches the effect of water saving.
3, the whole flow process prepared of the present invention is brief, and processing condition are easily controlled, non-pollution discharge, and raw material is easy to get, and energy consumption is low, is applicable to industrial production.This macroelement solid Water soluble fertilizer can be applicable to each kind of plant, sprinkling irrigation, drip irrigation, sprays, drenches Shi Jieke.
concrete case study on implementation
case study on implementation 1.a kind of instant chelating solid Water soluble fertilizer, its component and proportioning as follows, be all weight percentage:
Urea 25%, potassium primary phosphate 15%, double superhosphate 20%, potassium sulfate 20%, magnesium chloride 2%, zinc sulfate 1%, manganous sulfate 1%, Sodium orthomolybdate 1%, ferrous sulfate 1%, sequestrant 2%, intensification agent 10%.Wherein sequestrant composition and proportioning are: amino acid powder
:aMPS-chitosan polymer
:aMPS-polyacrylamide copolymer
:polyepoxysuccinic acid salt=10:2:2:1.Intensification agent composition and proportioning are: calcium chloride: calcium oxide: sodium-acetate=6:2:2.
Preparation method is as follows:
1) material pre-treatment: the double superhosphate of weight percent is carried out predrying, then add the phosphoric acid with free state in a certain proportion of bicarbonate of ammonia, obtain the double superhosphate after neutralizing, pulverize, make its particle diameter be 80 ~ 200 orders, stand-by;
2) chelatropic reaction: by micro-magnesium chloride 2%, zinc sulfate 1%, manganous sulfate 1%, Sodium orthomolybdate 1%, ferrous sulfate 1% adds in chelating still, adds sequestrant 2%, design temperature 55 DEG C ~ 70 DEG C, mixing speed 20r/min ~ 30r/min, churning time 30min ~ 50min, obtains chelate mix;
3) mix: by neutralization after double superhosphate, urea 25%, potassium primary phosphate 15%, potassium sulfate 20%, chelate mix, intensification agent 10% joins in reactor and fully mixes, and dry, pulverize, a kind of instant chelating Water soluble fertilizer.
case study on implementation 2.as described in case study on implementation 1, it is as follows unlike each feed composition, is all weight percentage:
Urea 30%, potassium primary phosphate 10%, double superhosphate 20%, potassium sulfate 20%, magnesium chloride 2%, zinc sulfate 1%, manganous sulfate 1%, Sodium orthomolybdate 1%, ferrous sulfate 1%, sequestrant 4%, intensification agent 8%.Wherein sequestrant composition and proportioning are: amino acid powder
:aMPS-chitosan polymer
:aMPS-polyacrylamide copolymer
:polyepoxysuccinic acid salt=10:2:2:1.Intensification agent composition and proportioning are: calcium chloride: calcium oxide: sodium-acetate=6:2:2.
case study on implementation 3.as described in case study on implementation 1, it is as follows unlike each feed composition, is all weight percentage:
Urea 35%, potassium primary phosphate 15%, double superhosphate 15%, potassium sulfate 15%, magnesium chloride 2%, zinc sulfate 1%, manganous sulfate 1%, Sodium orthomolybdate 1%, ferrous sulfate 1%, sequestrant 6%, intensification agent 6%.Wherein sequestrant composition and proportioning are: amino acid powder
:aMPS-chitosan polymer
:aMPS-polyacrylamide copolymer
:polyepoxysuccinic acid salt=10:2:2:1.Intensification agent composition and proportioning are: calcium chloride: calcium oxide: sodium-acetate=6:2:2.
case study on implementation 4.as described in case study on implementation 1, it is as follows unlike each feed composition, is all weight percentage:
Urea 40%, potassium primary phosphate 15%, double superhosphate 15%, potassium sulfate 10%, magnesium chloride 2%, zinc sulfate 1%, manganous sulfate 1%, Sodium orthomolybdate 1%, ferrous sulfate 1%, sequestrant 8%, intensification agent 4%.Wherein sequestrant composition and proportioning are: amino acid powder
:aMPS-chitosan polymer
:aMPS-polyacrylamide copolymer
:polyepoxysuccinic acid salt=10:2:2:1.Intensification agent composition and proportioning are: calcium chloride: calcium oxide: sodium-acetate=6:2:2.
case study on implementation 5.as described in case study on implementation 1, it is as follows unlike each feed composition, is all weight percentage:
Urea 40%, potassium primary phosphate 10%, double superhosphate 15%, potassium sulfate 15%, magnesium chloride 2%, zinc sulfate 1%, manganous sulfate 1%, Sodium orthomolybdate 1%, ferrous sulfate 1%, sequestrant 5%, intensification agent 7%.Wherein sequestrant composition and proportioning are: amino acid powder
:aMPS-chitosan polymer
:aMPS-polyacrylamide copolymer
:polyepoxysuccinic acid salt=10:2:2:1.Intensification agent composition and proportioning are: calcium chloride: calcium oxide: sodium-acetate=6:2:2.
In above five examples, the technical indicator that solid Water soluble fertilizer reaches is as follows:
1). micronutrient levels >=2%;
2). macroelement content >=40%;
3). water-insoluble≤3%;
4). moisture content≤2%.
Claims (3)
1. an instant chelating solid Water soluble fertilizer, it is characterized in that: the instant chelating solid Water soluble fertilizer containing intensification agent, composed of the following components, all be weight percentage: urea 25% ~ 40%, potassium primary phosphate 10% ~ 20%, double superhosphate 10% ~ 25%, potassium sulfate 10% ~ 25%, magnesium chloride 2% ~ 6%, zinc sulfate 0.5% ~ 3%, manganous sulfate 0.5% ~ 3%, Sodium orthomolybdate 0.5% ~ 4%, ferrous sulfate 0.5% ~ 2%, sequestrant 2% ~ 8%, intensification agent 4% ~ 10%, wherein said sequestrant is following four kinds of mixtures: AMPS-polyacrylamide copolymer, AMPS-chitosan polymer, polyepoxysuccinic acid salt, amino acid powder, the proportion of composing of four kinds of materials is: amino acid powder: AMPS-chitosan polymer: AMPS-polyacrylamide copolymer: polyepoxysuccinic acid salt=10:2:2:1, wherein said intensification agent is calcium chloride, calcium oxide, sodium-acetate form with part by weight 6:2:2.
2. the instant chelating solid of the one described in claim 1 Water soluble fertilizer, is characterized in that: preparation method comprises the following steps:
Chelatropic reaction: by micro-magnesium chloride 2% ~ 6%, zinc sulfate 0.5% ~ 3%, manganous sulfate 0.5% ~ 3%, Sodium orthomolybdate
0.5% ~ 4%, ferrous sulfate 0.5% ~ 2% adds in chelating still, adds sequestrant, design temperature 55 DEG C ~ 70 DEG C, and mixing speed 20r/min ~ 30r/min, churning time 30min ~ 50min, obtains chelate mix;
Mixing: by the double superhosphate 10-25% after neutralization, urea 25% ~ 40%, potassium primary phosphate 10% ~ 20%, potassium sulfate 10% ~ 25%, chelate mix, intensification agent 4% ~ 10% joins in reactor and fully mixes, dry, pulverize, a kind of instant chelating solid Water soluble fertilizer.
3. one according to claim 2 instant chelating solid Water soluble fertilizer, is characterized in that: the double superhosphate after described neutralization is the double superhosphate neutralized by bicarbonate of ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310738398.4A CN103708964B (en) | 2013-12-30 | 2013-12-30 | Instant chelated solid water-soluble fertilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310738398.4A CN103708964B (en) | 2013-12-30 | 2013-12-30 | Instant chelated solid water-soluble fertilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103708964A CN103708964A (en) | 2014-04-09 |
| CN103708964B true CN103708964B (en) | 2015-04-08 |
Family
ID=50402357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310738398.4A Expired - Fee Related CN103708964B (en) | 2013-12-30 | 2013-12-30 | Instant chelated solid water-soluble fertilizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103708964B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817355A (en) * | 2015-04-22 | 2015-08-05 | 于书强 | High-energy thermal fertilizer |
| CN105819951A (en) * | 2016-03-14 | 2016-08-03 | 山东植丰农化集团有限公司 | Water soluble fertilizer and preparation method thereof |
| CN106146217B (en) * | 2016-07-05 | 2019-10-25 | 金正大生态工程集团股份有限公司 | A kind of alkalescent solid Water soluble fertilizer and preparation method thereof improveing acid soil |
| CN107082716B (en) * | 2017-03-22 | 2021-01-08 | 深圳市芭田生态工程股份有限公司 | Value-added urea capable of activating soil and preparation method thereof |
| CN107188765A (en) * | 2017-07-13 | 2017-09-22 | 全椒县赤镇龙虾经济专业合作社 | It is a kind of to chelate the preparation method that diisocyanate is modified lobster shell powder liquid fertilizer |
| CN107673848A (en) * | 2017-10-26 | 2018-02-09 | 唐翔 | A kind of ecology volume increase strawberry fertilizer and preparation method thereof |
| CN107586209A (en) * | 2017-10-30 | 2018-01-16 | 成都云图控股股份有限公司 | A kind of instant chelating solid Water soluble fertilizer and preparation method thereof |
| CN107759414A (en) * | 2017-11-20 | 2018-03-06 | 安徽云峰农业发展有限公司 | A kind of Water soluble fertilizer containing a great number of elements |
| CN109369270A (en) * | 2018-11-26 | 2019-02-22 | 烟台富康生物科技有限公司 | A kind of environment-friendly fertilizer and its preparation process containing functional components of chlorella vulgaris |
| CN109369239A (en) * | 2018-12-25 | 2019-02-22 | 孟宪英 | Containing there are many Special compound fertilizer for corn of phosphorus element and preparation method thereof |
| CN109627117A (en) * | 2018-12-26 | 2019-04-16 | 龙蟒大地农业有限公司 | A kind of potassium acetate class Water soluble fertilizer preparation process and potassium acetate class Water soluble fertilizer |
| CN114874045A (en) * | 2022-04-21 | 2022-08-09 | 国投新疆罗布泊钾盐有限责任公司 | Instant potassium sulfate fertilizer containing chelated trace elements and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062846C (en) * | 1993-04-26 | 2001-03-07 | 郑州工学院 | Technology for production of modified calcium superphosphate compounded fertilizer |
| CN101003442B (en) * | 2006-12-31 | 2010-06-09 | 新疆惠森生物技术有限公司 | Microbial fertilizer of chelates of composite amino acid for spray irrigation, drop irrigation, and production method |
| CN102190591A (en) * | 2010-03-12 | 2011-09-21 | 陈郁 | Metal complex, preparation method and application thereof |
| CN101781151B (en) * | 2010-03-16 | 2013-06-26 | 北京中研美华生化研究所 | Amino acid chelated medium and trace element water-soluble fertilizer in and preparation method thereof |
| CN102267846B (en) * | 2011-07-08 | 2013-07-03 | 西北农林科技大学 | Sandy land fertilizer and preparation method thereof |
-
2013
- 2013-12-30 CN CN201310738398.4A patent/CN103708964B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103708964A (en) | 2014-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103708964B (en) | Instant chelated solid water-soluble fertilizer | |
| CN102153424B (en) | Novel method for preparing humic acid urea slow release fertilizer | |
| CN101333131B (en) | Double chelate compound fertilizer | |
| CN101215205B (en) | Synergistic foliage fertilizer and application method thereof | |
| US11787748B2 (en) | Polyphosphoric acid calcium magnesium fertilizer, polyphosphoric acid calcium magnesium fertilizer prepared by using phosphoric acid and phosphorus tailings as raw material and preparation method therefor | |
| CN102285830A (en) | Method for preparing high-tower organic-inorganic compound fertilizer | |
| CN103044144A (en) | Preparation method of organic chelate fertilizer | |
| CN106631578A (en) | Humic acid composite fertilizer and preparation method thereof | |
| CN108218568A (en) | A kind of garlic special synergistic chelating fertilizer and preparation method thereof | |
| CN102815991B (en) | Fertilizer special for peanuts | |
| CN102285822A (en) | Method for preparing environmental-friendly slow-release fertilizer | |
| CN102826882A (en) | Carbamide chelated controlled release fertilizer and its preparation method | |
| CN105110892B (en) | A kind of a great number of elements Water soluble fertilizer and preparation method thereof | |
| CN107226733A (en) | New multicomponent element ecology chelation fertilizer and its manufacture method | |
| CN104003787A (en) | Pear tree fertilizer composition for planting in saline-alkali land | |
| CN103193553A (en) | Production technology of water-soluble water retention drop irrigation slow release fertilizer | |
| CN103739406A (en) | Humic acid chelated boron, magnesium, zinc and iron fertilizer and preparation method thereof | |
| CN101696139B (en) | Method for producing compound fertilizer for fixing nitrogen, dissolving phosphor and dissolving potassium by using spray granulation process | |
| CN105523832A (en) | Special slow release water-soluble fertilizer for soybeans, and preparation method thereof | |
| CN102503626A (en) | Water-soluble fertilizer special for alkaline soil and its preparation method | |
| CN111689805A (en) | Production method of compound fertilizer | |
| CN110550988A (en) | Complexing product of mineral humic acid and inorganic salt fertilizer and preparation method thereof | |
| CN109111290A (en) | A kind of organic-inorganic special type water-soluble fertilizer | |
| CN103787780B (en) | A kind of compound organic and inorganic fertilizer and production method thereof containing chelated microelement | |
| CN115160052A (en) | High water-solubility chelate compound fertilizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170907 Address after: 404100 Chongqing Yongchuan satellite Lake Office Industrial Park Patentee after: CHONGQING SHIDUOSHOU TECHNOLOGY CO.,LTD. Address before: Qingyang District of Chengdu City, Sichuan province 610091 Dragon Industrial Port East Road 4 Patentee before: CHENDU NEW KELI CHEMICAL SCIENCE Co.,Ltd. CHINA |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150408 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |