CN100509710C - Method for preparing clean urea-sulfuricacid compound-mixed fertilizer - Google Patents
Method for preparing clean urea-sulfuricacid compound-mixed fertilizer Download PDFInfo
- Publication number
- CN100509710C CN100509710C CNB2005101060212A CN200510106021A CN100509710C CN 100509710 C CN100509710 C CN 100509710C CN B2005101060212 A CNB2005101060212 A CN B2005101060212A CN 200510106021 A CN200510106021 A CN 200510106021A CN 100509710 C CN100509710 C CN 100509710C
- Authority
- CN
- China
- Prior art keywords
- urea
- fertilizer
- slurry
- sulfuric acid
- solution
- 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 57
- SSBRSHIQIANGKS-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;hydrogen sulfate Chemical compound NC(N)=O.OS(O)(=O)=O SSBRSHIQIANGKS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 54
- 239000004202 carbamide Substances 0.000 claims abstract description 47
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims description 51
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 47
- 239000002002 slurry Substances 0.000 claims description 40
- 238000004519 manufacturing process Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000005469 granulation Methods 0.000 claims description 22
- 230000003179 granulation Effects 0.000 claims description 22
- 229940032330 sulfuric acid Drugs 0.000 claims description 22
- 239000012190 activator Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- WPLORVPXJOETTJ-UHFFFAOYSA-N [P].NC(N)=O Chemical compound [P].NC(N)=O WPLORVPXJOETTJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000005696 Diammonium phosphate Substances 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- 239000011573 trace mineral Substances 0.000 claims description 4
- 235000013619 trace mineral Nutrition 0.000 claims description 4
- 208000006558 Dental Calculus Diseases 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 2
- 235000015097 nutrients Nutrition 0.000 abstract description 11
- 239000002367 phosphate rock Substances 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011737 fluorine Substances 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 235000021049 nutrient content Nutrition 0.000 abstract 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract 1
- 230000002459 sustained effect Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 235000019691 monocalcium phosphate Nutrition 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 230000003381 solubilizing effect Effects 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 235000019731 tricalcium phosphate Nutrition 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- MAHJBKDUCDFDMU-UHFFFAOYSA-N [O-][N+]([P])=O Chemical compound [O-][N+]([P])=O MAHJBKDUCDFDMU-UHFFFAOYSA-N 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical class [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- GFIKIVSYJDVOOZ-UHFFFAOYSA-L calcium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Ca+2].[O-]P([O-])(F)=O GFIKIVSYJDVOOZ-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- 210000003608 fece Anatomy 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010871 livestock manure Substances 0.000 description 2
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- BTZJQYVYGCCNHY-UHFFFAOYSA-N calcium;urea Chemical compound [Ca].NC(N)=O BTZJQYVYGCCNHY-UHFFFAOYSA-N 0.000 description 1
- XQTIWHSAQUFHIT-UHFFFAOYSA-L calcium;urea;sulfate Chemical compound [Ca+2].NC(N)=O.[O-]S([O-])(=O)=O XQTIWHSAQUFHIT-UHFFFAOYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 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
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Landscapes
- Fertilizers (AREA)
Abstract
The invention belongs to a fertilizer, using urea water-reducing method, under the action of activating agent, using the producing process of using urea sulfuric acid solution to resolve phosphorite to prepare release- sustained N and P or N, P and K specialized composite fertilizers with different nutrient contents. And the process can shorten producing cycle, extremely simplify fluorine recovering system, implement no-'three wastes' discharge, raise producing efficiency and save constructional investment. And the product can reduce N loss by dissolving straining and volatilization, reduce P degradation and fixation, effectively raising nutrient utilization of fertilizer. And the process is a clean process according with cyclic economic requirements.
Description
Technical field the present invention relates to the manufacture method of a kind of, phosphorus nitrogenous with the clean explained hereafter or nitrogen, phosphorus, potassium composite fertilizer.
Specifically, this manufacturing process relates to by Phosphate Rock of China-calcium monofluorophosphate production composite fertilizer.
In the present composite fertilizer production technology of background technology, what extensively adopt is granulating method production particulate state fertilizer containing nitrogen.Be about to powdery, granuliform base fertilizer, under the effect of binding agent such as water, steam, fertilizer slurry, acid etc., in tablets press after the granulation, the series products that processes such as drying, screening, cooling are made.In the various product of its production, be that the acidolysis thing (superphosphate) of nitrogenous source, Rock Phosphate (72Min BPL) accounts for sizable ratio for the composite fertilizer in main phosphorus source with urea.The acidolysis thing of Rock Phosphate (72Min BPL) such as calcium superphosphate etc., traditional production process will be through the fragmentation supply of phosphorus ore, phosphorus ore and vitriolic mix, slip change into, cut and the slaking three of banking up goes on foot greatly, and general not being all 6～30 days according to phosphorus ore character and processing condition of curing time.Wherein effective P
2O
5Be 12～18%, moisture 11～15%.When being used as the raw material of composite fertilizer, must be through pre-treatment.
France Armines, big bus Hess chemical company on July 29th, 1992 open (publication number: 1063095A) preparation method of nitrogenous phosphorus product and the product that makes thereof.This invention is reacted with tricalcium phosphate and by sulfuric acid and the mixed reactant that gets of urea, produces compound manure.This nitrogen phosphorus product is soluble in neutral ammonium citrate, does not have a large amount of free urea to exist in the product, and urea mainly exists with calcium sulfate four urea salt chemical combination states.The ratio of sulfuric-urea mixture is a urea: sulfuric acid=(1～2): 1 or (3～4): 1.(contain P with Morocco's natural phosphate
2O
532%, CaO 52%, fineness: be raw material mean particle size＜100 μ m), (its proportioning is a urea: sulfuric acid: water=3.6: 1: 1) decompose Morocco's phosphoric acid salt, can obtain total nutrient (N+P with the reactant of urea sulfate
2O
5Be 31.65%) compound manure, wherein total N21.85%, effectively P
2O
59.80%.But it still will adopt breeze is raw material, and must use ore deposits such as high reactivity, high-grade Morocco.
" Phosphorus ﹠amp; Potassium " (No.191,1994) reported the exploitation of research department of France mining institute of Paris, FRA engineering corporation a kind of on the existing calcium superphosphate device production nitro phosphor complex technology.This technology is a reagent (urea: sulfuric acid: water=3.6: 1: 1) replace the decomposed solution of sulfuric acid as phosphorus ore (phosphorus ore is levigate to granularity 80%≤80 μ m) with the urea/sulphur acid reaction, phosphorus ore is through mixing with decomposed solution, change into slaking after, obtain the powdery nitro phosphor complex.Main nutrient exists with four urea sulfate calcium and a water monocalcium phosphate in the product.Manufacture experimently out total nutrient (N+P with Morocco's phosphorus ore
2O
5) granulated product greater than 30%, wherein contain total N 20.90%, effectively P
2O
59.70%, moisture 1%.Its critical relative humidity is 65～70% in the time of 20 ℃.But this technology is only applicable to the good phosphorus ore of reactive behavior such as Morocco's phosphorus ore, Jordan's phosphorus ore etc., and phosphorus ore all is to add with dry powder.
The Li Hui of Shanghai Chemical Research Inst jumps and equals to disclose April 25 calendar year 2001 (publication number CN1292367A) a kind of manufacture method that contains the granular nitrogen-phosphorus composite fertilizer of moderate-element.This technology adopts urea is dissolved in production ureasulfuric acid solution in the sulfuric acid, ground phosphate rock is added to react in the ureasulfuric acid solution again and makes fertilizer slurry, and fertilizer slurry is used in the neutralizing agent and the back granulation, makes nitro phosphor complex.The ureasulfuric acid solution ratio is a urea: sulfuric acid: water=(3.1～3.5): 1: (5.5～6.5), the fineness of ground phosphate rock be-100 orders (150 μ m) greater than 93% ,-200 orders (74 μ m) are greater than 78%.The proportioning of fertilizer slurry and neutralizing agent fused(calcium magnesium)phosphate is 1: (0.18～0.3) (weight ratio).Use one of best phosphorus ore of Chinese reactive behavior Kaiyang ground phosphate rock (P
2O
533.85% ,-100 orders (150 μ m), 93.6% ,-200 orders (74 μ m) 79.7%) manufactured experimently out total nutrient (N+P
2O
5) be 25.72% granulated product.Wherein contain total N 16.59%, effectively P
2O59.13%, water-soluble rate 46.55%.But its phosphorus ore must be a dry powder, and this method does not have the industrialization report so far.
The phosphorus ore 80% of China be a sedimentogeneous rock, 70% be in low-grade collophanite, reactive behavior is lower, when utilizing such technology, it is very slow at first can to run into reaction slurry curing, even does not solidify for a long time, product physicals extreme difference, problem that can't ordinary production.
At present, cover surplus the calcium superphosphate device 1000 of China, but the technology that the overwhelming majority adopts is the concentrated acid pulp process.When promptly producing, at first will be crushed to necessarily required Rock Phosphate (72Min BPL) adds a certain amount of water and (determines according to the character in ore deposit in ball mill, guarantee that the ore pulp certain fluidity is as the criterion, be finely ground to granularity＜0.15mm and reach and deliver to mixing tank respectively with sulfuric acid behind 95% ore pulp and react.And above-mentioned patent (claiming USP) technology all is to send into mixing tank with the dry powder phosphorus ore, and there is serious water imbalance problem in the water yield that water content is only brought into for reagent, can't obtain having mobile suitable ore pulp.
Summary of the invention clean urea of the present invention sulfuric acid multiple fertile (being called for short USC) manufacture method can be described below:
(1) preparation of urea sulfuric acid solution: the urea of aequum is divided into two parts in will preparing burden, wherein, a part is dissolved in and makes urea sulfuric acid solution in the sulphuric acid soln, and solution temperature remains on 75～85 ℃, and its ratio of components is a urea: sulfuric acid: water (mol ratio)=(0.5-1.8): 1: (0-0.5).
(2) preparation of urea ore pulp: with phosphorus ore, another part urea and water are prepared into urea phosphorus ore slurry (being called for short the phosphorus ore slurry, down together) by metering than the adding ball mill.Phosphorus ore: urea: water (mass ratio) is 1: (0.66-1.10): (0.12-0.24).
(3) preparation of activator solution: activator is mixed with the solution of 13～20% (mass ratioes), the consisting of of activator: polyoxyethylene 20 sorbitan monooleate: alkylbenzene sulfonate: tri-polyphosphate: carboxymethyl cellulose: ethylene glycol or polyoxyethylene glycol (mass ratio)=(5～20): (40～65): (2～10): (0～1): (0～4).
(4) preparation of fertilizer slurry: phosphorus ore slurry, urea sulfuric acid solution and activator solution are joined mixing reactor respectively make fertilizer slurry, the proportioning of each material is the phosphorus ore slurry: urea sulfuric acid solution: activator (mass ratio)=1: (0.34-0.70): (0.000952-0.00255), temperature of reaction is 68～78 ℃, and the reaction times is 8～10 minutes.
(5) dedicated fertilizer preparation: fertilizer slurry through changing into, is sent into the cutting of belt cutting machine and after the turning cooling, is broken for powdery, send granulation system to make binary or ternary compound fertilizer material.Change into time control 30～50 minutes, temperature fall time 1～3 day; Perhaps fertilizer slurry is continued reaction 25～35 minutes and make binary or ternary granulated shape composite fertilizer after be pumped into tablets press.
Composite fertilizer manufacture method of the present invention in described powdered fertilizer or the slurry pelleting process, adds the basic material of nitrogenous, phosphorus, potassium and trace element, finally can be made into particulate state tailored version composite fertilizer.
Composite fertilizer manufacture method of the present invention, the fineness of described phosphorus ore ore pulp are less than 0.15mm 〉=95%.
Composite fertilizer manufacture method of the present invention, the basic material of described nitrogenous, phosphorus, potassium and trace element is: Repone K, vitriolate of tartar, salt of wormwood, saltpetre, monoammonium phosphate, diammonium phosphate, double superhosphate, bicarbonate of ammonia, calcium sulfate, manganous sulfate, borax, copper sulfate etc.
The principle of composite fertilizer manufacture method of the present invention is:
The urea of allocating in the ball mill mainly is the character of utilizing urea solubleness big, under the condition that guarantees the ore pulp flowability, replaces water with urea, realizes diminishing; And the urea that is dissolved in the sulphuric acid soln generates urea sulfuric acid solution, and its chemical equation is:
xCO(NH
2)
2+H
2SO
4＝xCO(NH
2)·H
2SO
4 (x＝1、2、4)
Aborning, urea after the metering, water and sulfuric acid add in the urea sulfuric acid Preparation tank, urea and sulphuric acid soln solubilizing reaction generate urea sulfuric acid solution, and solution temperature is kept 75～80 ℃, and solution composition is: urea: sulfuric acid: water=(0.5～1.8): 1: (0～0.5) (mol ratio).
Urea sulfuric acid is the strongly-acid material, can its decomposing phosphate rock slurry.In urea sulfuric acid and phosphorus ore reaction process, the calcium monofluorophosphate (Ca in the phosphorus ore slurry
5F (PO
4)
3) overwhelming majority is converted into mono-calcium phosphate and Lin Suanergai, impurity in the phosphorus ore slurry such as carbonate, iron, aluminium salt etc. also participate in reaction, consumption acids.For guaranteeing the phosphorus ore slurry high rates of decomposing and transforming of trying one's best, adopt theoretical excessive slightly urea sulfuric acid solution in the technology.The chemical equation of urea sulfuric acid and calcium monofluorophosphate reaction can be expressed as follows:
Silicon-dioxide (SiO during urea sulfuric acid is starched with phosphorus ore simultaneously
2) effect, following reaction takes place:
4HF+SiO
2＝SiF
4+2H
2O
2HF+SiF
4＝H
2SiF
6
4CO(NH
2)
2+H
2SiF
6＝{[(NH
2)
2CO]
2H}
2SiF
6
Because silicofluoric acid urea { [(NH
2)
2CO]
2H}
2SiF
6Generation, reduced the vapour pressure of silicate fluoride solution system significantly, the more traditional reactive system of effusion rate of fluorine is reduced significantly, and (traditional technology fluorine effusion rate is about 40%, fluorine effusion rate≤7% in the technology of the present invention, under the optimal conditions≤3%), the irritating smell of on-the-spot imperceptible fluorochemical.
Composite fertilizer manufacture method of the present invention, tie up under the activator solution effect with the preparation of urea sulfuric acid solution decomposing phosphate rock slurry, the phosphorus ore slurry with the proportioning of urea sulfuric acid solution is: phosphorus ore slurry: urea sulfuric acid solution: activator=1: (0.34～0.70): (0.000952～0.00255) (mass ratio) temperature of reaction: 68～78 ℃, reaction times: 8～10 minutes, the fineness of phosphorus ore slurry: less than 0.15mm 〉=95%.
Required condition is when carrying out the particulate state production of compound fertilizer after cooling when the fertilizer slurry process changes into: change into the time: 30～50 minutes, and temperature fall time: 1～3 day;
When fertilizer slurry when changing into, after needing to prolong certain reaction times, use pumping tablets press degranulationization again.Prolong the reaction times: 25～35 minutes.
Composite fertilizer manufacture method of the present invention, add mixing reactor respectively when reacting at urea sulfuric acid solution and ore pulp, add activator solution simultaneously, activator is a kind of production process additive, can significantly improve the absorption in the reaction process, mass transfer, reaction, crystalline condition and foaming ventilation property, thus fast reaction speed is improved the physical behavior of product.The concentration of activator solution is 13～20%, and its add-on is: slip: activator=1: (0.0007～0.0015) (mass ratio).
The fertilizer slurry of being sent here by shurry pump or send in the tablets press through the cooled powdered fertilizer of lowering the temperature carries out granulation with the granulating raw material that enters tablets press after metering such as monoammonium phosphate, diammonium phosphate, Repone K, vitriolate of tartar, zinc sulfate, manganous sulfate, borax, copper sulfate etc. with returning charge.Prilling temperature: 45～65 ℃, granulation water: 3～5% or 4～7%.Granulated fertilizer is sent into the rotary shelf drier drying after the granulation, sends into sieve apparatus through discharging machine and conveyor, returns granulating system through return conveyer greater than the 4.75mm particle after crusher in crushing with less than the fine powder material of 1mm, and the particle of 1～4.75mm is as product.
The characteristics that the present invention has:
The present invention be to traditional Production of Single Superphosphate method and urea calcium superphosphate (USP) production technique perfect, improve and improve.Generally lower at Chinese phosphorus ore reactive behavior, the slip curing performance is relatively poor, domestic Production of Single Superphosphate is mainly ore pulp concentrated acid method, therefore adopt and add activator and two sections ways that add the urea diminishing, solved and used homemade phosphorus ore to adopt difficult curing and the unbalanced problem of water in the concentrated acid pulp process technological process, and can cancel in the Production of Single Superphosphate 6～30 days bank up the maturation period, shortened the production cycle, improve production efficiency, saved construction investment.
2. clean technology of the present invention has theoretical foundation, based on to the discovering of fluorine form, owing to added urea, the silicofluoric acid that discharges in urea and the phosphate rock-sulfuric acid process (impurity SiO in HF that generates in the reaction and the phosphorus ore in reactive system
2Resultant) thus generated the vapour pressure that the silicofluoric acid urea reduces silicofluoric acid significantly, the effusion rate that makes fluorine drops to below 7% (under the optimal conditions≤3%) by 40% of traditional technology, greatly simplified the fluorine recovery system, and reclaim all retrieval systems of liquid, realize three-waste free discharge, operational condition and environment obviously improve, and are a kind of clean technology that recycling economy requires that meets.
3. in the product that the present invention makes, nutrients ratio meets special-purpose fertile requirement.Wherein nitrogen is mainly with CaSO
44CO (NH
2)
2Form exist, and phosphorus is mainly with CaHPO
4And Ca (H
2PO
4)
2CO (NH
2)
2Exist, different ratios is quick-acting to be existed with the slow component, can effectively reduce the molten pouring and the volatilization loss of nitrogen, the degeneration of minimizing phosphorus and fixing, thus improve the fertilizer nutrient utilization ratio.And allocate each nutritive element into because having considered the physical condition of concrete crop, help the enforcement and the popularization of agriculture balance fertilizing.
Be exemplifying embodiment of the present invention below the embodiment, the percentage composition among the embodiment is mass percent.
Embodiment 1:
Sulfuric acid (98%, H
2SO
4) 59.68kg/h, granular urea 21.93kg/h adds respectively in the stirring reactor of band temperature regulating device uniformly, and urea and sulfuric acid generation solubilizing reaction generate urea sulfuric acid solution, 75 ℃ of solution temperatures, this solution overflow enters in the temperature control reactor of band whipping appts.Activator 300g/h, water 1700g/h join respectively in the dosing vessel of band whipping appts simultaneously, are made into concentration and are 15% solution, and 50 ℃ of solution temperatures are sent into rubber pipe pump in the temperature control reactor of band whipping appts.Contain P
2O
528.03% Baokang phosphorus ore 100kg/h, granular urea 109.61kg/h, water 18.59kg/h adds ball mill respectively uniformly and is prepared into urea phosphorus ore slurry (less than the particle of 0.15mm〉95%), this urea phosphorus ore slurry adds in the temperature control reactor of being with whipping appts simultaneously with the ore pulp pump, 45 minutes reaction times, 72 ℃ of temperature of reaction.The slip that reaction generates is evenly sent in the granulation machine with shurry pump, through disperseing after and mixing granulations such as the returning charge in the machine, additive.Prilling temperature is 55～65 ℃ in the granulation machine, and the granulation material is moisture 5.6%～6.6%, returning charge multiple 2.5.Granulating material drying machine drying, getting 1～4.75mm particle after the screening is product.The chemical analysis results of product NP compound fertilizer is as follows:
Total P
2O
59.32%
Effective P
2O
58.21%
Water-soluble P
2O
56.06%
Total N 19.69%
Total nutrient (N+P
2O
5) 27.90%
Embodiment 2:
Sulfuric acid (98%, H
2SO
4) 59.68kg/h, granular urea 109.61kg/h adds in the stirring reactor of band temperature regulating device respectively uniformly, urea and sulfuric acid generation solubilizing reaction generate urea sulfuric acid solution, 73 ℃ of solution temperatures, this solution overflow enter in the temperature control reactor of band whipping appts, activator 300g/h, water 1700g/h joins respectively in the dosing vessel of band whipping appts simultaneously, be made into concentration and be 15% solution, 50 ℃ of solution temperatures are sent into rubber pipe pump in the temperature control reactor of band whipping appts.Contain P
2O
528.03% Baokang phosphorus ore 100kg/h, granular urea 21.93kg/h, water 18.59kg/h adds ball mill respectively uniformly and is prepared into urea phosphorus ore slurry (less than the particle of 0.15mm〉95%), this urea phosphorus ore slurry adds in the temperature control reactor of being with whipping appts simultaneously with the ore pulp pump, 10 minutes reaction times, 71 ℃ of temperature of reaction.The slip that reaction generates changed into through 50 minutes, sent into tablets press after the cutting cooling, with mixing granulations such as returning charge in the machine, additives.Prilling temperature is 62～65 ℃ in the granulation machine, granulation material moisture 5.6%～6.6%.Granulating material drying machine drying, getting 1～4.75mm particle after the screening is product.The chemical analysis results of product NP compound fertilizer is as follows:
Total P
2O
59.32%
Effective P
2O
58.23%
Water-soluble P
2O
56.04%
Total N 19.70
Total nutrient (N+P
2O
5) 27.93%
Embodiment 3:
Sulfuric acid (98%, H
2SO
4) 59.68kg/h, granular urea 36.54kg/h adds in the stirring reactor of band temperature regulating device respectively uniformly, urea and sulfuric acid generation solubilizing reaction generate urea sulfuric acid solution, 78 ℃ of solution temperatures, this solution overflow enter in the temperature control reactor of band whipping appts, activator 320g/h, water 1810g/h joins respectively in the dosing vessel of band whipping appts simultaneously, be made into concentration and be 15% solution, 52 ℃ of solution temperatures are evenly sent into rubber pipe pump in the TR Thermal Reactor of band whipping appts.Contain P
2O
528.03% Baokang phosphorus ore 100kg/h, granular urea 51.16kg/h, water 18.59kg/h sends into the particle that is prepared in the wet-type ball mill less than 0.15mm respectively〉95% urea phosphorus ore slurry, with the ore pulp pump this urea ore pulp is added in the TR Thermal Reactor of being with whipping appts simultaneously, 50 minutes reaction times, 74 ℃ of temperature of reaction.The slip that makes of reaction is evenly delivered in the granulation machine with shurry pump, through disperseing after and additive, returning charge and Repone K mixing granulation, and 60～65 ℃ of prilling temperatures, granulation water 4.4%～5.4%, returning charge multiple 1.68.Repone K (K
2O:60%, granularity:＜0.45mm50%,＜1.6mm98.5%) 55kg/h.
Material drying machine drying after the granulation, getting 1～4.75mm particle after the screening is product.The chemical analysis results of product nitrogen PK compound fertilizer is as follows:
Total N 12.68%
Total P
2O
58.88%
Effective P
2O
57.81%
Water-soluble P
2O
55.76%
K
2O 10.48％
Total nutrient (N+P
2O
5+ K
2O) 30.97%
Embodiment 4:
Sulfuric acid (98%, H
2SO
4) 59.68kg/h, granular urea 65.77kg/h adds in the stirring reactor of band temperature regulating device respectively uniformly, urea and sulfuric acid generation solubilizing reaction generate urea sulfuric acid solution, 76 ℃ of solution temperatures, this solution overflow enter in the temperature control reactor of band whipping appts, activator 550g/h, water 3120g/h joins respectively in the dosing vessel of band whipping appts simultaneously, be made into concentration and be 15% solution, 53 ℃ of solution temperatures are evenly sent into rubber pipe pump in the TR Thermal Reactor of band whipping appts.Contain P
2O
528.03% Baokang phosphorus ore 100kg/h, granular urea 65.77kg/h, water 18.59kg/h adds ball mill respectively equably and is prepared into urea phosphorus ore slurry (less than the particle of 0.15mm〉95%), this urea phosphorus ore slurry adds in the TR Thermal Reactor of being with whipping appts simultaneously with the ore pulp pump, 48 minutes reaction times, 73 ℃ of temperature of reaction.The slip that reaction generates is evenly sent in the granulation machine with shurry pump, through disperseing after and returning charge, additive and base fertilizer mixing granulation in the machine, and prilling temperature: 63～65 ℃, granulation water: 4.0%～5.0%, returning charge multiple: 1.80.Base fertilizer comprises diammonium phosphate (N18%, P
2O
546% granularity :≤0.45mm77.5%,＜1.0mm98.0%) 115kg/h, Repone K (K
2O:60%, granularity:＜0.45mm80.1%,＜1mm98.8%=125kg/h, zinc sulfate (Zn30%, granularity :≤0.45mm98.8%) 2.0kg/h, borax (B10%, granularity :≤0.45mm90.5%) 4.0kg/h.
Material drying machine drying after the granulation, getting 1～4.75mm particle after the screening is product.The chemical analysis results of product nitrogen PK compound fertilizer is as follows:
Total N 14.78%
Total P
2O
514.72%
Effective P
2O
514.22%
Water-soluble P
2O
512.98%
K
2O 13.66％
Total nutrient (N+P
2O
5+ K
2O) 42.66%
Claims (3)
1, a kind of manufacture method of clean urea-sulfuricacid compound-mixed fertilizer is characterized in that: its production process is as follows:
(1) urea sulfuric acid solution preparation: the urea of aequum is divided into two parts in will preparing burden, wherein, part urea is dissolved in makes urea sulfuric acid solution in the sulphuric acid soln, solution temperature remains on 75～85 ℃, and its batching is urea in molar ratio: sulfuric acid: water=(0.5～1.8): 1: (0～0.5);
(2) urea phosphorus ore slurry preparation: is 1 with phosphorus ore, another part urea and water by mass ratio: (0.66～1.10): (0.12～0.24) adds ball mill and makes the phosphorus ore slurry, and the fineness of phosphorus ore slurry is less than 0.15mm 〉=95%;
(3) activator solution preparation: the composition of activator and mass ratio are polyoxyethylene 20 sorbitan monooleate: alkylbenzene sulfonate: tri-polyphosphate: carboxymethyl cellulose: ethylene glycol or polyoxyethylene glycol=(5～20): (40～65): (2～10): (0～1): (0～4), and activator is mixed with mass ratio is 13～20% solution;
(4) preparation of fertilizer slurry: is 1 with phosphorus ore slurry, urea sulfuric acid solution and activator solution by mass ratio: (0.34～0.70): (0.000952～0.00255) joins mixing reactor respectively and makes fertilizer slurry, 68～78 ℃ of temperature of reaction, 8～10 minutes reaction times;
(5) preparation of dedicated fertilizer: fertilizer slurry through changing into, is sent into the cutting of belt cutting machine and after the turning cooling, is broken for powdery, send granulation system to make binary or ternary granulated shape composite fertilizer, change into time control 30～50 minutes, temperature fall time 1～3 day; Perhaps fertilizer slurry is continued reaction 25～35 minutes and make binary or ternary granulated shape composite fertilizer after be pumped into tablets press.
2, the manufacture method of urea-sulfuricacid compound-mixed fertilizer according to claim 1, it is characterized in that: in described powdered fertilizer or slurry pelleting process, add the basic material of nitrogenous, phosphorus, potassium and trace element, finally can be made into particulate state tailored version composite fertilizer.
3, the manufacture method of urea-sulfuricacid compound-mixed fertilizer according to claim 2 is characterized in that: the basic material of wherein said nitrogenous, phosphorus, potassium and trace element is Repone K, vitriolate of tartar, salt of wormwood, saltpetre, monoammonium phosphate, diammonium phosphate, double superhosphate, bicarbonate of ammonia, zinc sulfate, manganous sulfate, borax, copper sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101060212A CN100509710C (en) | 2005-09-22 | 2005-09-22 | Method for preparing clean urea-sulfuricacid compound-mixed fertilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101060212A CN100509710C (en) | 2005-09-22 | 2005-09-22 | Method for preparing clean urea-sulfuricacid compound-mixed fertilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1935747A CN1935747A (en) | 2007-03-28 |
| CN100509710C true CN100509710C (en) | 2009-07-08 |
Family
ID=37953519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101060212A Expired - Fee Related CN100509710C (en) | 2005-09-22 | 2005-09-22 | Method for preparing clean urea-sulfuricacid compound-mixed fertilizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100509710C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508607B (en) * | 2009-03-20 | 2012-11-21 | 辽宁华锦化工（集团）有限责任公司 | Process for producing long-acting sustained-release complex fertilizer of urea sulfuric acid |
| CN102503719B (en) * | 2011-10-13 | 2013-07-31 | 贵州川恒化工有限责任公司 | Preparation method of strong-acidic water-soluble fertilizer special for alkaline soil |
| CN103130580B (en) * | 2013-03-22 | 2014-04-02 | 郑州大学 | Production method of urea sulfuric acid multi-nutrient functional compound fertilizer |
| CN105601385A (en) * | 2015-12-31 | 2016-05-25 | 中国科学院沈阳应用生态研究所 | Special novel efficient mixed fertilizer for alkali soil and applying method |
| CN106116784A (en) * | 2016-06-27 | 2016-11-16 | 陈启芬 | A kind of agricultural compound fertilizer |
| CN106220249A (en) * | 2016-07-12 | 2016-12-14 | 贵州芭田生态工程有限公司 | The preparation method of Quadrafos compound fertilizer |
| WO2019040427A1 (en) * | 2017-08-21 | 2019-02-28 | Lehigh University | Solvent free method of producing urea adduct |
| CN108689746B (en) * | 2018-05-25 | 2023-10-13 | 昌吉慧尔智联生态有限公司 | Liquid fertilizer production method and system |
| CN108558556A (en) * | 2018-07-04 | 2018-09-21 | 郑州大学 | A method of preparing particle urea groups composite fertilizer with urea-sulfuric acid decomposing rock phosphate with hydrogen |
| CN110256144B (en) * | 2019-06-19 | 2021-11-09 | 中北大学 | Preparation of biodegradable polymer sustained and controlled release organic nano fertilizer containing multiple nutrient elements |
-
2005
- 2005-09-22 CN CNB2005101060212A patent/CN100509710C/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| 尿素硫酸复肥生产新工艺研究. 候翠红，张宝林，王光龙，蒋登高.化工矿物与加工，第9期. 2002 |
| 尿素硫酸复肥生产新工艺研究. 候翠红，张宝林，王光龙，蒋登高.化工矿物与加工，第9期. 2002 * |
| 脲硫酸复肥新工艺减少氟逸出的研究. 候翠红，王光龙，张宝林，蒋登高.化工环保，第23卷第5期. 2003 |
| 脲硫酸复肥新工艺减少氟逸出的研究. 候翠红，王光龙，张宝林，蒋登高.化工环保，第23卷第5期. 2003 * |
| 脲硫酸复肥新技术的研究进展. 王光龙，候翠红，张宝林.化肥工艺，第29卷第6期. 2002 |
| 脲硫酸复肥新技术的研究进展. 王光龙，候翠红，张宝林.化肥工艺，第29卷第6期. 2002 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1935747A (en) | 2007-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100509710C (en) | Method for preparing clean urea-sulfuricacid compound-mixed fertilizer | |
| CN100389096C (en) | Process for producing slow releasing silicon potassium compound fertilizer by potassium feldspar | |
| CN102701256B (en) | Method for preparing granular ammonium sulfate and calcium carbonate by chemical gypsums via low-temperature transformation | |
| CN102765994A (en) | Method for preparing granular potash fertilizer | |
| 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 | |
| CN103130580B (en) | Production method of urea sulfuric acid multi-nutrient functional compound fertilizer | |
| CN109133995A (en) | A method of soluble potash fertilizer is prepared by decomposing of potassium feldspar | |
| CN103936524A (en) | Method for producing urea formaldehyde controlled-release compound fertilizer | |
| CN101508607B (en) | Process for producing long-acting sustained-release complex fertilizer of urea sulfuric acid | |
| CN108530175A (en) | A kind of granular compound fertilizer and its production method using the production of phosphoric acid slag acid | |
| CN101857513A (en) | Method for preparing long-acting slow-release compound fertilizers by one-step pulp spraying granulation | |
| CN100575316C (en) | Preparation technical method of urine sulfur radical composite fertilizer | |
| CN102557834A (en) | Method for producing composite fertilizer fillers by using phosphorite tailings | |
| CN102731186B (en) | Technology for continuously producing nitrocompound fertilizer by using low-grade phosphorus ore and dolomite | |
| CN1130321C (en) | Production method of granular nitrogen-phosphorus composite fertilizer containing secondary element | |
| CN104030765B (en) | A kind of method of molasses alcohol fermentation liquid comprehensive utilization | |
| CN101973790B (en) | Method for producing granular diammonium phosphate with low concentration of nutrients by tailings | |
| WO2023073697A1 (en) | A process for the production of a unified granule of polyhalite and an n-fertilizer | |
| Young et al. | Phosphate fertilizers and process technology | |
| CN1521151A (en) | Slow release high efficiency compound fertilizer of thio urea phosphor ammonium kalium and its preparing technology | |
| CN113860971A (en) | Continuous production process of one-step method slurry-melting chelating active humic acid compound fertilizer | |
| CN102001872A (en) | method for producing granular potash fertilizer and product thereof | |
| CN112979386A (en) | Low-polymerization-degree ammonium polyphosphate particle multi-component compound fertilizer and preparation method thereof | |
| CN102491858A (en) | Method for manufacturing urea-based nitrate slow-releasing compound fertilizer | |
| CN102408261A (en) | Ammonium sulfate phosphate compound fertilizer able to decompose phosphor and potassium in soil |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090708 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |