CN102452858A - A kind of fertilizer composition and fertilizer and the preparation method of this fertilizer - Google Patents
A kind of fertilizer composition and fertilizer and the preparation method of this fertilizer Download PDFInfo
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- CN102452858A CN102452858A CN2010105191384A CN201010519138A CN102452858A CN 102452858 A CN102452858 A CN 102452858A CN 2010105191384 A CN2010105191384 A CN 2010105191384A CN 201010519138 A CN201010519138 A CN 201010519138A CN 102452858 A CN102452858 A CN 102452858A
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 177
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title description 12
- 239000002699 waste material Substances 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 239000000126 substance Substances 0.000 claims abstract description 43
- 239000011734 sodium Substances 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052593 corundum Inorganic materials 0.000 claims abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract 3
- 239000002245 particle Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000618 nitrogen fertilizer Substances 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 9
- 239000006012 monoammonium phosphate Substances 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 239000005696 Diammonium phosphate Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 7
- 239000002686 phosphate fertilizer Substances 0.000 claims description 7
- 229940072033 potash Drugs 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 235000015320 potassium carbonate Nutrition 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 239000002426 superphosphate Substances 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 239000004111 Potassium silicate Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 4
- 229910052681 coesite Inorganic materials 0.000 claims 2
- 229910052906 cristobalite Inorganic materials 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 229910052682 stishovite Inorganic materials 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- 239000011593 sulfur Substances 0.000 claims 2
- 229910052905 tridymite Inorganic materials 0.000 claims 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 239000001099 ammonium carbonate Substances 0.000 claims 1
- 235000012501 ammonium carbonate Nutrition 0.000 claims 1
- KMQAPZBMEMMKSS-UHFFFAOYSA-K calcium;magnesium;phosphate Chemical compound [Mg+2].[Ca+2].[O-]P([O-])([O-])=O KMQAPZBMEMMKSS-UHFFFAOYSA-K 0.000 claims 1
- 235000013877 carbamide Nutrition 0.000 claims 1
- 235000015097 nutrients Nutrition 0.000 abstract description 40
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002893 slag Substances 0.000 description 32
- 238000001035 drying Methods 0.000 description 24
- 238000005469 granulation Methods 0.000 description 20
- 230000003179 granulation Effects 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000012216 screening Methods 0.000 description 16
- 238000013467 fragmentation Methods 0.000 description 10
- 238000006062 fragmentation reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 208000006558 Dental Calculus Diseases 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000013268 sustained release Methods 0.000 description 4
- 239000012730 sustained-release form Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229960000892 attapulgite Drugs 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052625 palygorskite Inorganic materials 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 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
- 239000010908 plant waste Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- -1 rare-earth salts Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Landscapes
- Fertilizers (AREA)
Abstract
The fertilizer composition is characterized by comprising catalyst waste residue and a chemical fertilizer, wherein the content of the catalyst waste residue is 1-40 wt% and the content of the chemical fertilizer is 60-99 wt% based on the total weight of the fertilizer composition; in the catalyst waste residue, SiO is used2The silicon content is 20-80 wt.% calculated as Al2O3The content of aluminum is 10-70 wt%, and calculated as Na2The content of sodium in terms of O is 0.1 to 10% by weight. The fertilizer prepared from the fertilizer composition provided by the invention has the effect of slowly releasing fertilizer nutrients.
Description
Technical field
The fertilizer that the present invention relates to a kind of Ru 2006101161 and make, and the preparation method of this fertilizer by this Ru 2006101161.
Background technology
RFCC is important refining of petroleum technology, and in this technology, cracking catalyst is occupied critical role.The preparation of traditional cracking catalyst comprises: composite reactive component (generally being molecular sieve) at first, after modification, become catalyst component then with catalytic performance, and obtain product after again active ingredient and matrix being mixed making beating, spray drying forming.In the production process of cracking catalyst and active ingredient, can produce a large amount of waste water, sedimentation can take place under certain condition in the solid substance in the waste water, filters the back and forms a large amount of solid slags.Specifically comprise following three parts:
(1) waste residue in the sieve synthesis procedure.The synthetic whole process of molecular sieve is all carried out in liquid phase, and process is crystallization mother liquor and scrub raffinate to the discharge of environment.Contain identical alkaline matter-low modulus water glass (water glass) in these two kinds of waste liquids.Traditional production process all is that they are entered trench, gets into catalyzer sewage work and handles.This alkaline silicate precipitates after running into the sour water of other device discharge immediately.
(2) waste residue of molecular sieve modified process.Molecular sieve modified process comprises processes such as IX, drying and high-temperature roasting.Ion exchange process carries out under water or hygrometric state, and main effluent discharge is the waste liquid of ammonium salt-containing.Also discharge the waste liquid that contains rare-earth salts in some cases, waste liquid all is acid (pH is about 4), and the material form of processes such as drying and roasting is a pressed powder.These powder are discharged to sewage work with waste liquid, and the alkaline waste liquor that discharges in this acid waste liquid and the sieve synthesis procedure meets and promptly generates throw out.
(3) waste residue in the catalyst preparation process.The catalyzer manufacturing processed comprises into processes such as glue, spray drying forming, roasting, drying.Become the glue process almost not efflux thing; What spraying drying and roasting process mainly discharged is catalyst dust, hydrogenchloride, ammonium chloride etc.Contain a small amount of suspended substance and lower concentration ammonium salt in the waste liquid of catalyzer aftertreatment discharging, it is acid that this strand water shows, and after other waste water mixes, gets into sewage work.
If these waste residues directly adopt the method for landfill to handle, and not only can cause environmental pollution, but also can increase production cost.For this reason; A kind of A type prepare zeolite method is disclosed among the CN 1299778A; This method comprises: the catalyst plant waste residue of siliceous and/or aluminium is added the water making beating; Add or do not add other silicon source, to wherein adding silicate and mixing, the basicity that feeds intake with acid aluminium salt, acid or alkali adjustment again makes the mole composition of last gained reaction mixture meet (2.0-4.0) Na then
2O: Al
2O
3: (1.8-3.5) SiO
2: (80-200) H
2The proportioning of O, the wherein Al in the waste residue
2O
3Account for the total Al of mixture
2O
3The 0-45 weight % of amount, the SiO in the waste residue
2Account for the total SiO of mixture
2The 55-100 weight % of amount; Then the gained reaction mixture is pressed the ordinary method hydrothermal crystallizing.Yet because catalyst waste slag source more complicated, the component of waste residue is also unstable; And in preparation cracking catalyst process,, must prepare reaction mixture with certain proportioning for synthetic certain type molecular sieve; Obviously utilize the unsettled waste residue of component as the feedstock production zeolite; Can make the proportioning of reaction mixture unstable, therefore, be difficult to guarantee to reach industrial requirements according to the quality of the zeolite of method for preparing.
Chemical fertilizer plays crucial effects in human agriculture prodn, grain significantly increases production in recent years, and chemical fertilizer role therein accounts for 50% greatly.But the utilization ratio of China's chemical fertilizer is low, and the grain of unit chemical fertilizer raising the output is not as good as 1/2 of world standard, not as good as 1/3 of U.S.'s M.L..Most of chemical fertilizer fails to be fully utilized, and about 40-60% gets in the environment, causes the deterioration of the ecological environment; Cause the severe contamination of atmosphere, river and agricultural-food; Destroy the eubiosis, be detrimental to health.
The initial chemical fertilizer that uses single nutrient of China; Used the composite fertilizer of two kinds of nutrients afterwards; Develop into present multiple nutrient again, at present most popular is the composite fertilizer of nitrogenous, phosphorus, three kinds of nutrients of potassium, broad research and Development of New Generation composite fertilizer-slow-release fertilizer simultaneously.People such as U.S. K.G.Clart had synthesized the slowly-releasing urea-formaldehyde fertilizer in 1984, had found the new slow release fertilizer that improves chemical fertilizer utilization ratio.Slow release fertilizer can slowly discharge nutrient; Its compound release rate in soil control slow or that nutrient releasing speed can obtain to a certain degree that contains nutrient continues to absorb for crop; Can improve fertilizer utilization ratio to greatest extent, improve economic benefit, social benefit and the environmental benefit of fertilising.Use slow release fertilizer can reduce the loss in soil of fertilizer nutrient, particularly nitrogen; Fertilising operation number of times be can reduce, labour and expense saved; Can also avoid taking place the injury that causes owing to excessive fertilization to seed or seedling.Thereby slow-release fertilizer has become the focus of domestic and international fertilizer research.
Summary of the invention
The objective of the invention is; Based on the market demand of slow release fertilizer and available technology adopting catalyst waste slag being difficult to satisfy the present situation of industrial requirements as the zeolite of feedstock production, a kind of Ru 2006101161 is provided, the fertilizer that makes by this Ru 2006101161 and the method for preparing this fertilizer.
The invention provides a kind of Ru 2006101161; Wherein, this Ru 2006101161 contains catalyst waste slag and chemical fertilizer, and is benchmark with the gross weight of said Ru 2006101161; The content of said catalyst waste slag is 1-40 weight %, and the content of said chemical fertilizer is 60-99 weight %; In said catalyst waste slag, with SiO
2The content of the silicon of meter is 20-80 weight %, with Al
2O
3The content of the aluminium of meter is 10-70 weight %, and with Na
2The content of the sodium of O meter is 0.1-10 weight %.
The present invention also provides a kind of fertilizer, and wherein, this fertilizer is with obtaining after said Ru 2006101161 uniform mixing provided by the invention and the granulation.
The present invention also provides a kind of preparation method of fertilizer, and wherein, this method comprises mixes said Ru 2006101161 provided by the invention and granulation.
Because Ru 2006101161 according to the present invention contains catalyst waste slag, make the fertilizer for preparing by this Ru 2006101161 have the effect of slow release fertilizer nutrient.
Embodiment
Ru 2006101161 according to the present invention contains catalyst waste slag and chemical fertilizer, is benchmark with the gross weight of said Ru 2006101161, and the content of said catalyst waste slag is 1-40 weight %, and the content of said chemical fertilizer is 60-99 weight %.Under preferable case; For making the fertilizer that makes by said Ru 2006101161 provided by the invention have better sustained release performance; And can enough nutrients be provided to soil; Gross weight with said Ru 2006101161 is a benchmark, and the content of said catalyst waste slag is 10-35 weight %, and the content of said chemical fertilizer is 65-90 weight %.Further under the preferable case, be benchmark with the gross weight of said Ru 2006101161, the content of said catalyst waste slag is 15-30 weight %, and the content of said chemical fertilizer is 70-85 weight %.
According to said Ru 2006101161 provided by the invention, in said catalyst waste slag, with SiO
2The content of the silicon of meter is 20-80 weight %, with Al
2O
3The content of the aluminium of meter is 10-70 weight %, and with Na
2The content of the sodium of O meter is 0.1-10 weight %.In the present invention, the waste residue that said catalyst waste slag produces in can the Catalyst Production process for various routines is as long as this catalyst waste slag has said components.Under the preferable case, said catalyst waste slag is the waste residue that produces in the cracking catalyst production process.
In order to make the fertilizer that makes by said Ru 2006101161 provided by the invention more nutrient is provided for soil; And the further sustained release performance that improves the fertilizer that makes by said Ru 2006101161 provided by the invention; Said catalyst waste slag preferably also contains calcium, sulphur and rare earth metal, and with SiO
2The content of the silicon of meter is 30-60 weight %, with Al
2O
3The content of the aluminium of meter is 14-30 weight %, with Na
2The content of the sodium of O meter is 3-7 weight %, is 0.1-20 weight % in the content of the calcium of CaO, with SO
3The content of the sulphur of meter is 0.1-25 weight %, with RE
2O
3The content of the rare earth metal of meter is 0.1-10 weight %.Under the preferred situation, with SiO
2The content of the silicon of meter is 30-40 weight %, with Al
2O
3The content of the aluminium of meter is 14-20 weight %, with Na
2The content of the sodium of O meter is 3-5 weight %, is 10-18 weight % in the content of the calcium of CaO, with SO
3The content of the sulphur of meter is 15-22 weight %, with RE
2O
3The content of the rare earth metal of meter is 7-9 weight %.
According to one embodiment of the present invention; Can also contain other composition that comprises in the conventional catalyst waste slag in the said catalyst waste slag; For example, fluorine, magnesium, phosphorus, chlorine, potassium, titanium and iron etc., and in said catalyst waste slag in the fluorine of F, in the magnesium of MgO, with P
2O
5The meter phosphorus, in the chlorine of Cl, with K
2The potassium of O meter, with TiO
2The meter titanium and with Fe
2O
3The total content of the iron of meter is 0.1-5 weight %, is preferably 1.5-4 weight %.
According to said Ru 2006101161 provided by the invention, said chemical fertilizer can be the chemical fertilizer of various routines, for example can be in nitrogenous fertilizer, phosphate fertilizer and the potash fertilizer at least a.In the present invention; Said nitrogenous fertilizer for example can be in urea, volatile salt, ammonium sulfate, ammonium chloride, nitrocalcite and an ammonium nitrate at least a; Said phosphate fertilizer for example can be in monoammonium phosphate, diammonium phosphate, superphosphate of lime, double superhosphate and the fused(calcium magnesium)phosphate at least a, what said potash fertilizer for example can be in Repone K, vitriolate of tartar, potassium silicate and the saltpetre is at least a.In the present invention; Said urea, volatile salt, ammonium sulfate, ammonium chloride, nitrocalcite, an ammonium nitrate, monoammonium phosphate, diammonium phosphate, superphosphate of lime, double superhosphate, Repone K, vitriolate of tartar, potassium silicate or saltpetre refer to the urea that usually uses as chemical fertilizer respectively, volatile salt is fertile, ammonium sulfate is fertile, ammonium chloride fertilizer, nitric acid calcareous fertilisers, an ammonium nitrate is fertile, monoammonium phosphate is fertile, diammonium phosphate is fertile, peroxophosphoric acid calcareous fertilisers, triple superphosphate fertilizer, potassium chloride fertilizer, potassium sulphate fertilizer, silicic acid potash fertilizer or kalium nitrate fertilizer, rather than the compound of pure urea, volatile salt, ammonium sulfate, ammonium chloride, nitrocalcite, an ammonium nitrate, monoammonium phosphate, diammonium phosphate, superphosphate of lime, double superhosphate, Repone K, vitriolate of tartar, potassium silicate or saltpetre.
A preferred embodiment of the invention, said chemical fertilizer are the mixture of nitrogenous fertilizer, phosphate fertilizer and potash fertilizer.In this case, the chemical fertilizer of being processed by said Ru 2006101161 can provide more comprehensive and competent nutrient to soil.Under the preferred situation, be benchmark with the gross weight of said chemical fertilizer, the content of said nitrogenous fertilizer is 10-60 weight %, and the content of phosphate fertilizer is 10-60 weight %, and the content of said potash fertilizer is 10-70 weight %.Further under the preferable case, be benchmark with the gross weight of said chemical fertilizer, the content of said nitrogenous fertilizer is 25-45 weight %, and the content of phosphate fertilizer is 15-40 weight %, and the content of said potash fertilizer is 20-55 weight %.
The present invention also provides a kind of fertilizer, and this fertilizer is for to carry out Ru 2006101161 to obtain after uniform mixing and the granulation, and said Ru 2006101161 is a Ru 2006101161 provided by the invention.
In the present invention, the particle diameter of said fertilizer is preferably the 1-4.75 millimeter.In this case, said fertilizer has sustained release performance preferably.
The present invention also provides a kind of preparation method of fertilizer, and this method comprises mixes Ru 2006101161 and granulation, and said Ru 2006101161 is a said Ru 2006101161 provided by the invention.
In the present invention, said process for granulating does not have special qualification, and the prilling process of various routines all can be used for the present invention.Under the preferable case, said method is carried out drying and screening after also being included in granulation, is the fertiliser granulates of 1-4.75 millimeter to obtain particle diameter.
According to one embodiment of the present invention; At the particle diameter of said catalyst waste slag and/or said chemical fertilizer when big (for example more than 20 millimeters); Said method can also be included in before the said mixing or after said mixing and before said granulation, and said catalyst waste slag and/or said chemical fertilizer are carried out fragmentation so that said catalyst waste slag and/or said chemical fertilizer are crushed to particle diameter less than 20 millimeters.The method of said fragmentation can adopt the mode of various routines to implement.
In most preferred embodiments, the preparation method of said fertilizer may further comprise the steps:
(1) catalyst waste slag and chemical fertilizer are carried out fragmentation respectively, so that catalyst waste slag and chemical fertilizer are crushed to particle diameter separately less than 20 millimeters;
(2) catalyst waste slag that obtains in the step (1) and chemical fertilizer are carried out proportioning with suitable amount, for example in stirrer, carry out uniform mixing then;
(3), carry out granulation through adding a spot of water and/or steam with mass transport to the granulating system (like rotary drum granulator) that obtains in the step (2);
(4) material that obtains in the step (3) is carried out drying;
(5) material that obtains in the step (4) is sent in the screening system (like vibratory screening apparatus); Sieve out the fertilizer of suitable particle size (1-4.75 millimeter); And oarse-grained fertilizer is back to carries out fragmentation in the step 1, short grained fertilizer is back in the step (3) carries out granulation.
Below through embodiment the present invention is described further, but protection scope of the present invention is not limited in this.
In following examples, the available nutrient (N+P of fertilizer
2O
5+ K
2O) content is measured according to the method for GB15063-2001; Method according to GB/T 8572-2001 is measured the total nitrogen content in the fertilizer; Method according to GB/T 8573-1999 is measured the phosphorus content in the fertilizer, measures the potassium content in the fertilizer according to the method for GB/T8574-2002; The burst size of the available nutrient of fertilizer is measured according to the method for HG/T3971-2007.
The catalyst waste slag that adopts among following examples 1-3 is all from the catalyst waste slag that produces in the cracking catalyst production process, and it forms as shown in table 1 respectively:
Table 1
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 4 |
| With SiO 2The silicon (weight %) of meter | 36.557 | 39.600 | 33.500 | 15.000 |
| With Al 2O 3The aluminium (weight %) of meter | 16.414 | 17.900 | 14.700 | 75.000 |
| With Na 2The sodium (weight %) of O meter | 3.527 | 4.440 | 3.070 | 9.286 |
| Calcium (weight %) in CaO | 14.200 | 11.800 | 16.200 | - |
| With SO 3The sulphur (weight %) of meter | 18.129 | 15.600 | 20.440 | - |
| With RE 2O 3The rare earth metal (weight %) of meter | 8.200 | 8.300 | 8.500 | - |
| Fluorine (weight %) in F | 0.493 | 0.299 | 0.551 | - |
| Magnesium (weight %) in MgO | 0.659 | 0.544 | 0.835 | - |
| With P 2O 5The phosphorus (weight %) of meter | 0.413 | 0.207 | 0.599 | 0.599 |
| Chlorine (weight %) in Cl | 0.901 | 0.813 | 1.090 | - |
| With K 2The potassium (weight %) of O meter | 0.117 | 0.109 | 0.115 | 0.115 |
| With TiO 2The titanium (weight %) of meter | 0.066 | 0.065 | 0.066 | - |
| With Fe 2O 3The iron (weight %) of meter | 0.324 | 0.323 | 0.334 | - |
Embodiment 1
Present embodiment is used to explain the preparation method of said Ru 2006101161 of the present invention and fertilizer and this fertilizer.
(it is formed as above shown in the table 1 with the urea of 26 weight parts, the monoammonium phosphate of 32 weight parts, the Repone K of 25 weight parts and the process exsiccant catalyst waste slag of 17 weight parts; Not moisture) use horizontal chained crusher (available from company of Shanghai Chemical equipment institute, model W-60) to carry out fragmentation respectively, be decreased to less than 20mm with particle diameter them; With they uniform mixing; And be added in the rotary drum granulator (available from the grand space drying plant of Dezhou City ltd, model HY15) with the water of 10 weight parts and carry out granulation, behind the granulating it is dropped into rotary drying cylinder (available from the logical heavy industry engineering works in Henan, Zhengzhou; Model HGJ0810) in; Drying is 20 minutes under 150 ℃, and dried material is sent into vibratory screening apparatus (Henan, Zhengzhou leads to heavy industry engineering works, model 2FZS35) sieve; Sieve out the fertiliser granulates that particle diameter is 1-4.75mm, thereby obtain fertilizer A1 provided by the invention; The particle diameter that will obtain after will sieving simultaneously carries out particle diameter that broken back obtains greater than the particle of 4.75mm and turns back to less than the particle of 1mm and carry out granulation again in the said rotary drum granulator after screening.
Main available nutrient (N+P among the said fertilizer A1
2O
5+ K
2O) massfraction is about 45 weight %, this fertilizer A1 is placed 24h with 1: 20 ratio of weight ratio in 25 ℃ of water after, the burst size that records the available nutrient in the said fertilizer is about 50 weight %; Place after 28 days, the burst size that records the available nutrient in the said fertilizer is about 95 weight %.
Comparative Examples 1
Use horizontal chained crusher (available from company of Shanghai Chemical equipment institute respectively in the urea of 26 weight parts, the monoammonium phosphate of 32 weight parts and the Repone K of 25 weight parts; Model W-60) carries out fragmentation; Be decreased to less than 20mm with particle diameter, be added to rotary drum granulator (available from the grand space drying plant of Dezhou City ltd then with the wilkinite and the 9 weight part attapulgite uniform mixing of they and 8 weight parts, and with the water of 10 weight parts with them; Model HY15) carries out granulation in; Behind the granulating it is dropped in the rotary drying cylinder (available from the logical heavy industry engineering works in Henan, Zhengzhou, model HGJ0810), drying is 20 minutes under 150 ℃; And dried material is sent into vibratory screening apparatus, and (Henan, Zhengzhou leads to heavy industry engineering works; Model 2FZS35) sieves, sieve out the fertiliser granulates that particle diameter is 1-4.75mm, thereby obtain fertilizer D1; The particle diameter that will obtain after will sieving simultaneously carries out particle diameter that broken back obtains greater than the particle of 4.75mm and turns back to less than the particle of 1mm and carry out granulation again in the said rotary drum granulator after screening.
Main available nutrient (N+P among the said fertilizer D1
2O
5+ K
2O) massfraction is about 45 weight %, this fertilizer D1 is placed 24h with 1: 20 ratio of weight ratio in 25 ℃ of water after, the burst size that records the available nutrient in the said fertilizer is about 95 weight %.
Embodiment 2
Present embodiment is used to explain the preparation method of said Ru 2006101161 of the present invention and fertilizer and this fertilizer.
(it is formed as above shown in the table 1 with the urea of 30 weight parts, the diammonium phosphate of 18 weight parts, the vitriolate of tartar of 30 weight parts and the process exsiccant catalyst waste slag of 22 weight parts; Not moisture) use horizontal chained crusher (available from company of Shanghai Chemical equipment institute, model W-60) to carry out fragmentation respectively, be decreased to less than 20mm with particle diameter them; With they uniform mixing; And be added in the rotary drum granulator (available from the grand space drying plant of Dezhou City ltd, model HY15) with the water of 12 weight parts and carry out granulation, behind the granulating it is dropped into rotary drying cylinder (available from the logical heavy industry engineering works in Henan, Zhengzhou; Model HGJ0810) in; Drying is 20 minutes under 150 ℃, and dried material is sent into vibratory screening apparatus (Henan, Zhengzhou leads to heavy industry engineering works, model 2FZS35) sieve; Sieve out the fertiliser granulates that particle diameter is 1-4.75mm, thereby obtain fertilizer A2 provided by the invention; The particle diameter that will obtain after will sieving simultaneously carries out particle diameter that broken back obtains greater than the particle of 4.75mm and turns back to less than the particle of 1mm and carry out granulation again in the said rotary drum granulator after screening.
Main available nutrient (N+P among the said fertilizer A2
2O
5+ K
2O) massfraction is about 40 weight %, this fertilizer A2 is placed 24h with 1: 20 ratio of weight ratio in 25 ℃ of water after, the burst size that records the available nutrient in the said fertilizer is about 45 weight %; Place after 28 days, the available nutrient that records in the said fertilizer discharges about 92 weight %.
Comparative Examples 2
Use chain crusher (available from company of Shanghai Chemical equipment institute, model W-60) to carry out fragmentation respectively the urea of 30 weight parts, the diammonium phosphate of 18 weight parts and the vitriolate of tartar of 30 weight parts, be decreased to less than 20mm with particle diameter with them; Then with the wilkinite and the 12 weight part attapulgite uniform mixing of they and 10 weight parts; And be added in the rotary drum granulator (available from the grand space drying plant of Dezhou City ltd, model HY15) with the water of 12 weight parts and carry out granulation, behind the granulating it is dropped into rotary drying cylinder (available from the logical heavy industry engineering works in Henan, Zhengzhou; Model HGJ0810) in; Drying is 20 minutes under 15 ℃, and dried material is sent into vibratory screening apparatus (Henan, Zhengzhou leads to heavy industry engineering works, model 2FZS35) sieve; Sieve out the fertiliser granulates that particle diameter is 1-4.75mm, thereby obtain fertilizer D2; The particle diameter that will obtain after will sieving simultaneously carries out particle diameter that broken back obtains greater than the particle of 4.75mm and turns back to less than the particle of 1mm and carry out granulation again in the said rotary drum granulator after screening.
Main available nutrient (N+P among the said fertilizer D2
2O
5+ K
2O) massfraction is about 40 weight %, this fertilizer D2 is placed 24h with 1: 20 ratio of weight ratio in 25 ℃ of water after, the burst size that records the available nutrient in the said fertilizer is about 92 weight %.
Embodiment 3
Present embodiment is used to explain the preparation method of said Ru 2006101161 of the present invention and fertilizer and this fertilizer.
(it is formed as above shown in the table 1 with the urea of 22 weight parts, the monoammonium phosphate of 20 weight parts, the vitriolate of tartar of 29 weight parts and the process exsiccant catalyst waste slag of 29 weight parts; Not moisture) use horizontal chained crusher (available from company of Shanghai Chemical equipment institute, model W-60) to carry out fragmentation respectively, be decreased to less than 20mm with particle diameter them; With they uniform mixing; And be added in the rotary drum granulator (available from the grand space drying plant of Dezhou City ltd, model HY15) with the water of 8 weight parts and carry out granulation, behind the granulating it is dropped into rotary drying cylinder (available from the logical heavy industry engineering works in Henan, Zhengzhou; Model HGJ0810) in; Drying is 20 minutes under 15 ℃, and dried material is sent into vibratory screening apparatus (Henan, Zhengzhou leads to heavy industry engineering works, model 2FZS35) sieve; Sieve out the fertiliser granulates that particle diameter is 1-4.75mm, thereby obtain fertilizer A3 provided by the invention; The particle diameter that will obtain after will sieving simultaneously carries out particle diameter that broken back obtains greater than the particle of 4.75mm and turns back to less than the particle of 1mm and carry out granulation again in the said rotary drum granulator after screening.
Main available nutrient (N+P among the said fertilizer A3
2O
5+ K
2O) massfraction is about 38 weight %, this fertilizer A3 is placed 24h with 1: 20 ratio of weight ratio in 25 ℃ of water after, the burst size that records the available nutrient in the said fertilizer is about 40 weight %; Place after 42 days, the burst size that records the available nutrient in the said fertilizer is about 90 weight %.
In addition, the particle diameter that obtains after the above-mentioned screening is mixed with weight ratio greater than the particle of 4.75mm and the particle diameter particle less than 1mm at 1: 1, obtain fertilizer A4.The amount that the available nutrient of this fertilizer of method test A4 of the amount that discharges according to the available nutrient of above-mentioned test fertilizer A3 discharges; The result places the release of the available nutrient after 24 hours in water amount is 60 weight %, and the amount of placing the release of the available nutrient after 42 days is 95 weight %.
Through the amount of the release of the available nutrient of fertilizer A3 and fertilizer A4 relatively can be found out, the particle diameter of fertilizer is controlled at obtains obviously the better effect of sustained release in the 1-4.75mm scope.
Comparative Examples 3
Use horizontal chained crusher (available from company of Shanghai Chemical equipment institute respectively the urea of 22 weight parts, the monoammonium phosphate of 20 weight parts and the vitriolate of tartar of 29 weight parts; Model W-60) carries out fragmentation; Be decreased to less than 20mm with particle diameter, be added to rotary drum granulator (available from the grand space drying plant of Dezhou City ltd then with the wilkinite and the 16 weight part attapulgite uniform mixing of they and 11 weight parts, and with the water of 15 weight parts with them; Model HY15) carries out granulation in; Behind the granulating it is dropped in the rotary drying cylinder (available from the logical heavy industry engineering works in Henan, Zhengzhou, model HGJ0810), drying is 20 minutes under 15 ℃; And dried material is sent into vibratory screening apparatus, and (Henan, Zhengzhou leads to heavy industry engineering works; Model 2FZS35) sieves, sieve out the fertiliser granulates that particle diameter is 1-4.75mm, thereby obtain fertilizer D3; The particle diameter that will obtain after will sieving simultaneously carries out particle diameter that broken back obtains greater than the particle of 4.75mm and turns back to less than the particle of 1mm and carry out granulation again in the said rotary drum granulator after screening.
Main available nutrient (N+P among the said fertilizer D3
2O
5+ K
2O) massfraction is about 38 weight %, this fertilizer D3 is placed 24h with 1: 20 ratio of weight ratio in 25 ℃ of water after, the burst size that records the available nutrient in the said fertilizer is about 90 weight %.
Comparative Examples 4
Method according to embodiment 3 prepares fertilizer, and different is that catalyst waste slag is as shown in table 1, thereby obtains fertilizer D4.
Main available nutrient (N+P among the said fertilizer D4
2O
5+ K
2O) massfraction is about 38 weight %, this fertilizer D4 is placed 24h with 1: 20 ratio of weight ratio in 25 ℃ of water after, the burst size that records the available nutrient in the said fertilizer is about 70 weight %; Place after 14 days, the burst size that records the available nutrient in the said fertilizer is about 90 weight %.
Comparative Examples 5
Method according to embodiment 3 prepares fertilizer, and different is, with the SiO of identical weight
2Replace catalyst waste slag, thereby obtain fertilizer D5.
Main available nutrient (N+P among the said fertilizer D5
2O
5+ K
2O) massfraction is about 38 weight %, this fertilizer D5 is placed 24h with 1: 20 ratio of weight ratio in 25 ℃ of water after, the burst size that records the available nutrient in the said fertilizer is about 90 weight %.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183572A (en) * | 2013-03-20 | 2013-07-03 | 中国农业大学 | Fertilizer used for acidizing soil |
| CN106831056A (en) * | 2017-02-27 | 2017-06-13 | 四川森迪科技发展股份有限公司 | A kind of Idesia polycarpa dedicated fertilizer and preparation method thereof |
| CN107094561A (en) * | 2017-02-24 | 2017-08-29 | 广西育运农业开发有限公司 | A kind of cultural method of granulated sugar tangerine |
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|---|---|---|---|---|
| KR0177793B1 (en) * | 1996-06-04 | 1999-03-20 | 장경천 | A method for producing persistent fertilizer using waste fluidized bed catalytic cracking catalyst |
| CN1299778A (en) * | 1999-12-13 | 2001-06-20 | 中国石油化工集团公司 | Preparation of A-type zeolite |
| CN1535939A (en) * | 2003-04-09 | 2004-10-13 | 陈大顺 | Fertilizer coating composite, its making method and multicomponent coated granular fertilizer |
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2010
- 2010-10-19 CN CN2010105191384A patent/CN102452858A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0177793B1 (en) * | 1996-06-04 | 1999-03-20 | 장경천 | A method for producing persistent fertilizer using waste fluidized bed catalytic cracking catalyst |
| CN1299778A (en) * | 1999-12-13 | 2001-06-20 | 中国石油化工集团公司 | Preparation of A-type zeolite |
| CN1535939A (en) * | 2003-04-09 | 2004-10-13 | 陈大顺 | Fertilizer coating composite, its making method and multicomponent coated granular fertilizer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183572A (en) * | 2013-03-20 | 2013-07-03 | 中国农业大学 | Fertilizer used for acidizing soil |
| CN103183572B (en) * | 2013-03-20 | 2014-12-17 | 中国农业大学 | Fertilizer used for acidizing soil |
| CN107094561A (en) * | 2017-02-24 | 2017-08-29 | 广西育运农业开发有限公司 | A kind of cultural method of granulated sugar tangerine |
| CN106831056A (en) * | 2017-02-27 | 2017-06-13 | 四川森迪科技发展股份有限公司 | A kind of Idesia polycarpa dedicated fertilizer and preparation method thereof |
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Application publication date: 20120516 |