CN100418930C - SODMUrea and preparation method and application thereof - Google Patents
SODMUrea and preparation method and application thereof Download PDFInfo
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- CN100418930C CN100418930C CNB2006100018903A CN200610001890A CN100418930C CN 100418930 C CN100418930 C CN 100418930C CN B2006100018903 A CNB2006100018903 A CN B2006100018903A CN 200610001890 A CN200610001890 A CN 200610001890A CN 100418930 C CN100418930 C CN 100418930C
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- 238000002360 preparation method Methods 0.000 title claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 164
- 239000004202 carbamide Substances 0.000 claims abstract description 121
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 10
- 239000006200 vaporizer Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 6
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims description 4
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 claims description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 4
- 102000005741 Metalloproteases Human genes 0.000 claims description 4
- 108010006035 Metalloproteases Proteins 0.000 claims description 4
- 229960005261 aspartic acid Drugs 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- 102000019197 Superoxide Dismutase Human genes 0.000 claims description 3
- 108010012715 Superoxide dismutase Proteins 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000013110 organic ligand Substances 0.000 claims description 3
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- 101000836247 Aquifex pyrophilus Superoxide dismutase [Fe] Proteins 0.000 claims description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 2
- 229930195722 L-methionine Natural products 0.000 claims description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- 229940024606 amino acid Drugs 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 229960002989 glutamic acid Drugs 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
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- 235000021307 Triticum Nutrition 0.000 description 16
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
- 235000019750 Crude protein Nutrition 0.000 description 3
- 241000918585 Pythium aphanidermatum Species 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000009331 sowing Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
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- 238000013270 controlled release Methods 0.000 description 2
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- 239000010949 copper Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 210000002700 urine Anatomy 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 244000144730 Amygdalus persica Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 108010068370 Glutens Proteins 0.000 description 1
- 240000002024 Gossypium herbaceum Species 0.000 description 1
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- 244000178870 Lavandula angustifolia Species 0.000 description 1
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- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 229940090496 Urease inhibitor Drugs 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 150000003672 ureas Chemical class 0.000 description 1
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Abstract
The invention relates to a SODMUrea characterized by comprising SODMAnd urea, in which SOD is presentMTotal weight of urea, SODMThe content of (A) is 0.01-1.0 wt%, and the content of urea is 99-99.99 wt%; the invention also relates to SODMProcess for preparing urea from SODMDirectly adding into molten urea in urea production equipment, mixing and granulating, and its applicationMUse of urea in agriculture.
Description
Technical field
The present invention relates to a kind of Simulating SOD that includes (promptly simulates superoxide-dismutase, is called for short SOD
M) synergistic urea, and provide this SOD
MPreparation method of urea and application thereof.
Background technology
As everyone knows, the urea usage quantity accounts for 60% of whole nitrogenous fertilizer usage quantity, annual China has 3,000 ten thousand tons of urea to be used for farm crop, because crop has little time to absorb, quite a few urea volatilizees or loses with current, according to statistics, the urea utilization ratio is the highest at present only reaches 30%, 2/3rds urea runs off in farmland fertilization, not only cause the wasting of resources, also cause environmental pollution, in order to improve the urea utilization ratio, technician both domestic and external has done many research to urea-modified, for example developed polymer integument type urea, the bag Thio Urea, urine aldehyde urea, fertilizer is grand etc., these kinds, its exploitation purpose is to have increased nitrification inhibitor and urease inhibitor in urea, but there are problems in slow controlled release and stable urea technology, and not strong as controllability, intelligent degree is not high, do not possess the relatively stable controlled release time, have secondary pollution with the resene polymer capsule, the while, every kind of synergistic urea all can't keep the high nitrogen content of original urea, and is on the high side, at home and abroad possession share is very low in the urea market, is difficult to apply.
Plant is in environment stresses such as topsoil, low temperature, arid, salinity, high light radiation and senescence process, active oxygen produces ability greater than the removing ability in the plant materials, and excessive relatively active oxygen can be to microbial film and other biomacromolecule structure and function generation adverse influence.And SOD can remove active oxygen effectively, keep the active oxygen metabolism balance, prevent the plant cell membrane peroxidation, suppress base mutation, DNA splitting of chain and protein damage, thereby can improve plant immunization ability, resistance against diseases and prevent advantage such as deterioration of strains.
Yet but people also have suitable gap at aspects such as stability, membrane penetrating, biology availability and immunogenicities apart from practical application by extracting or express the natural SOD that obtains by genetically engineered from plant.Owing to the complex process of separating, purifying natural SOD, make resulting natural SOD cost an arm and a leg (natural SOD need tens of every gram even hundreds of dollar), thereby be difficult to industrialization production in addition, more be difficult on agricultural, carry out large-scale application.
Summary of the invention
At above-mentioned the deficiencies in the prior art, the object of the invention is to provide a kind of SOD
MUrea, it without any influence, is the unapproachable index of all synergistic ureas up to now to the nitrogen content of urea; It can prolong urea in soil time of releasing and do not give any pollution of soil; Can also improve the utilization ratio of urea significantly, reduce the fertilizer usage quantity significantly, can reach province's fertilizer about 20%; Can improve crop quality in addition, increase substantially crop yield, improve crop anti-adversity etc.
SOD of the present invention
MUrea is characterized in that: comprise SOD
MAnd urea, with SOD
MUrea gross weight meter, SOD
MContent be weight % O.01~1.0, content of urea is 99~99.99 weight %.Preferred SOD
MContent be 0.04~0.10 weight %.
SOD of the present invention
MUrea is characterized in that, SOD
MBe metalloprotease, wherein metal ion can be transition metal ion or alkaline-earth metal ions in the metalloprotease, and for example Mn, Fe, Ni also can be Cu, Zn, Mg, k and Na etc.Preferred SOD
MBe a metalloid protease, wherein organic ligand is artificial synthetic homology small peptide, and this homology small peptide is that L-aspartic acid, D.L-aspartic acid, L-L-glutamic acid or L-Methionin are polymerized separately by amino acid monomer.More preferably, SOD
MBe that to be that compositions such as organic ligand and manganese, copper, zinc, iron are a kind of with the homology small peptide have fine water miscible small molecules product, for example a Mn-SOD of synthetic
M, Cu-Zn-SOD
MAnd Fe-SOD
MOne or more mixture, above-mentioned SOD
MMolecular weight distribution is between 1000~2500.Above-mentioned SOD
MCan be synthetic according to disclosed method among the CN200510132464.9.
The present invention also provides above-mentioned SOD
MPreparation method of urea is characterized in that, SOD
MCarry out uniform mixing with fusing urea quantitatively in the solution mode, wherein urea and SOD
MThe mass ratio of solution is 1000: 1.5-2.5, carry out mist projection granulating then, and finally make SOD of the present invention
MUrea.This SOD
MSolution is the aqueous solution, with SOD
MAqueous solution total amount meter, SOD
MContent is 1~30 weight %.Usually can be in the common urea production process, with SOD
MSolution joins in the vaporizer, and this vaporizer is positioned at before the prilling tower of urea dirt product, in this vaporizer, and SOD
MCarry out uniform mixing with fusing urea.SOD of the present invention
MThe process flow sheet of preparation method of urea as shown in drawings.
With SOD
MSolution is imported the urine evaporation device with pump, and other processing condition are identical with the processing condition of common urea.
Because the SOD that the present invention uses
MBe polyelectrolyte, with fusing urea mixing process in, urea molecule-NH
2Can with the small peptide molecule-COO ' plays the hydrogen bond sequestering action, thereby make urea prolong time of releasing in soil, and do not give any pollution of soil.
The present invention also provides above-mentioned SOD
MThe application of urea on agricultural.With above-mentioned SOD
MUrea is applied to field crop, fruit tree and vegetables, and the result shows that it can promote crop that the reinforcement of major element and trace element is absorbed, and can make vegetables, grain, fruit crop yield, improves crop quality.SOD of the present invention
MUrea can be used for crop or fruit tree base manure and topdresses, and promotes plant growth, improves crop anti-adversity.SOD of the present invention
MUrea has also improved fertilizer utilization and absorption when promoting crop growth, and fertilizer utilization efficiency can improve about 20%.
SOD of the present invention
MUrea is a kind of white solid product, and particle is the size of national Specification
0.85~2.8mm.In order to distinguish common urea, available different colours dyestuff is with this SOD
MUrea is made other color, for example yellowish, pale green, lavender etc., but the color dye of adding must be nontoxic, free of contamination.
Description of drawings
Fig. 1 is SOD
MThe process flow sheet of preparation method of urea.
Embodiment
Following embodiment is only in order to further specify the present invention, rather than in order to limit the scope of protection of the invention.
Embodiment one
Used SOD in the present embodiment
MSyntheticly according to disclosed method among the CN200510132464.9 obtain this SOD
MCharacter is as follows:
SOD
MActive matter content 30%
SOD
MSpecific activity of enzyme 〉=4000IU/mg
SOD
MAqueous ph value: 8.0~10.5
SOD
MMolecular weight M
n: 1000~2500
SOD
M20 ℃ of the density of the aqueous solution: 1.20g/cm
3
Heat resisting temperature: 180 ℃
According to previously described SOD
MThe preparation method is with this SOD
MBe made into 30% aqueous solution, by volume pump with 70 kilograms/hour feed rate with SOD
MThe aqueous solution evenly joins in the vaporizer, at this moment urea and SOD
MThe mass ratio of component is 1000: (0.4~0.6), and in vaporizer, carry out liquid/liquid uniform mixing with fusing urea, the service temperature of this vaporizer is 140 ℃, the output with 40 tons/hour makes in prilling tower then
0.85mm the SOD of~2.8mm
MUrea utilizes developer and SOD simultaneously
MComponent produces the colour developing effect, measures SOD with spectrophotometry
MContent in urea, the SOD that makes
MThe urea specification sees the following form:
Comparative Examples: operation and device are with embodiment one, and just urea production process does not add Simulating SOD, produce gained urea specification see the following form (table 1):
Table 1:SOD
MUrea product and common urea quality index contrast table
Embodiment two:
The SOD that the present invention produces
MUrea is to the winter wheat manurial experiment, 4 mu in experimental plot, 1 mu of comparative group, soil base fertilizer sowing management process unanimity.
Test arrangement:
4 mu of wheats use the synthetic SOD of institute among the embodiment one
MUrea topdresses, and usage quantity is 25 kilograms/hour.1 mu of wheat paddock of control group is executed common urea and is topdressed, 35 kilograms/hour of usage quantitys.
Test-results:
Use SOD
MThe wheat paddock straw of urea is thick, the wheat head is long, wheat is big.Data see the following form (table 2):
Project | Plant height (centimetre) | The mu spike number | Grain number per spike | Thousand seed weight (gram) | The per mu yield kilogram | Stimulation ratio % | Save fertile rate % |
Use SOD MUrea | 95 | 379620 | 29 | 50 | 467.9 | 18.1 | 33 |
Use urea | 80 | 584210 | 21 | 38 | 396.3 |
As can be seen from Table 2, saved 10 kilograms of urea for every mu, can also improve the output about 18%, effect is very remarkable.
Embodiment three
Use the SOD among the embodiment one
MThe wheat that urea is gathered in the crops compares result such as following table (table 3) with using the common urea quality of wheat:
Interventions Requested | Use SOD MThe urea wheat | Use the common urea wheat |
Wet gluten weight % | 34.85 | 32.68 |
The unit weight grams per liter | 790 | 126 |
Crude protein (butt) weight % | 15.4 | 13.5 |
As can be seen from Table 3, use SOD
MThe crude protein of urea wheat has reached the highest level that wheat contains crude protein.
Embodiment four
SOD with embodiment one
MUrea is used for corn fertilizing.
Carried out following test in the corn field in flakes at 8 mu, wherein, soil, base fertilizer, sowing, management are all identical.Wherein 6 mu of corn fields use SOD
MUrea topdresses, and usage quantity is 25 kilograms of SOD
MUrea/mu; 2 mu of corn fields of control group use common urea to topdress, and usage quantity is 25 kilograms of urea/mus, result's following (table 4):
Test area | The kind of topdressing | Fertilising quantity (kilogram/mu) | Per mu yield (kilogram) | Percentage increases % | |
Test group | 6 | SOD MUrea | 25 | 738 | 23 |
Control group | 2 | Common urea | 25 | 600 |
Find out in the table and use SOD
MUrea topdresses and topdresses and compare with using common urea, and the quantity of topdressing is identical, and the kind difference is executed SOD
MThe robust plant of urea, resistant to lodging, heading in advance, premature ripening, full seed, bright in color, output increases by 138 kilograms for every mu, volume increase 23%.
Embodiment five
SOD with embodiment one
MUrea is used for cotton.
7 mu in flakes cotton Tanaka carried out following test, wherein, soil, base fertilizer, sowing, management are all identical.Wherein SOD is used in 5 mu of cotton fields
MUrea topdresses, and usage quantity is 25 kilograms of SOD
MUrea/mu; 2 mu of cotton fields of control group use common urea to topdress, and usage quantity is 25 kilograms of urea/mus.
Find that before not topdressing upright blight appears in the cotton field seedling, in the stage of 50~80 centimeters of cotton seedlings, 5 mu of experimental plots spray SOD
M100ppm solution is in the cotton blade face, and then fertilising, test-results such as following table (table 5):
Test area | The kind of topdressing | Fertilising quantity (kilogram) | The cotton plant height (centimetre) | Every mu of average knot peach number | Per mu yield (kilogram) | Percentage increases % | |
Test group | 5 | SOD MUrea | 25 | 90 | 35 | 350 | 40 |
Control group | 2 | Common urea | 25 | 80 | 25 | 250 |
The cotton seedling of discovery is partly caught damping-off at the beginning of 7 mu of cotton field tests, executes SOD for 5 mu
MUrea and spray SOD
MThe cotton seedling of synergistic agent, the cotton seedling of catching damping-off keeps full stand not have a strain death, and the cotton field of control group has been caught the cotton seedling of damping-off and have to be pulled out.
Embodiment six
SOD of the present invention
MUrea is to the influence of wheat leaf blade SOD level.
Test is to execute SOD
MThe wheatland that topdresses is gathered wheat leaf blade, also gathers the wheat leaf blade of comparative group wheatland simultaneously, and same extracting method is measured wheat leaf blade SOD enzyme activity level with the NBT photoreduction met hod, and the result is as follows:
Execute SOD MThe natural SOD specific activity of enzyme of urea | 1200IU/mg |
Execute the natural SOD specific activity of enzyme of common urea | 400IU/mg |
From above-mentioned embodiment as can be seen, SOD of the present invention
MUrea has following advantage:
1, product of the present invention contains urea and SOD
MEnzyme is introduced fertilizer with metalloenzyme, SOD
MUrea product has comprised urea national standard and SOD
MThe enzyme company standard increases substantially crop quality, output, and increases crop anti-adversity.
2, product of the present invention can improve utilization rate of fertilizer more than 20%, owing to reduce fertilizer amount, has reduced environmental pollution, has improved economic results in society.
3, SOD
MUrea does not contain any objectionable impurities.SOD
MCan degrade fully, soil is polluted without any cumulative bad, SOD
MIn soil, promote biological fungus grown, favourable to soil.
SOD
MUrea directly utilizes the common urea production line, to SOD in manufacturing processed
MUrea production equipment does not have particular requirement and input, is SOD
MUrea production provides favourable condition, SOD
MUrea makes powder dust minimizing in the production process, improves particle SOD
MThe urea yield makes SOD
MFactory that makes urea's economic benefit improves.
More than having narrated the preferred embodiment for the present invention, is not in order to limit the present invention.Those skilled in the art can not depart from the improvement and the variation of category of the present invention and spirit to embodiment disclosed herein.
Claims (8)
1. SOD
MUrea is characterized in that comprising SOD
MAnd urea, with SOD
MUrea gross weight meter, SOD
MContent be 0.01~1.0 weight %, content of urea is 99~99.99 weight %, wherein SOD
MBe metalloprotease, metal ion is transition metal ion or alkaline-earth metal ions in this metalloprotease; Organic ligand is artificial synthetic homology small peptide, and this homology small peptide is that L-aspartic acid, D.L-aspartic acid, L-L-glutamic acid or L-Methionin are polymerized separately by amino acid monomer.
2. SOD according to claim 1
MUrea is characterized in that SOD
MBe artificial synthetic Mn-SOD
M, CuZn-SOD
MAnd Fe-SOD
MIn one or more mixture.
3. SOD according to claim 1 and 2
MUrea is characterized in that with SOD
MUrea gross weight meter, SOD
MContent be 0.04~0.10 weight %.
4. SOD according to claim 1 and 2
MUrea is characterized in that SOD
MMolecular weight is 1000~2500.
5. SOD as claimed in claim 1 or 2
MPreparation method of urea is characterized in that, SOD
MCarry out uniform mixing with fusing urea quantitatively in the solution mode, wherein urea and SOD
MThe mass ratio of solution is 1000: 1.5-2.5, carry out mist projection granulating then.
6. preparation method according to claim 5 is characterized in that, wherein said SOD
MSolution is with SOD
MAqueous solution total amount meter, SOD
MContent is 1~30 weight %.
7. preparation method according to claim 5 is characterized in that, with wherein said SOD
MSolution joins in the vaporizer, and this vaporizer is positioned at before the prilling tower of urea production, SOD in this vaporizer
MCarry out uniform mixing with fusing urea.
8. SOD as claimed in claim 1 or 2
MThe application of urea on agricultural is characterized in that, with described SOD
MUrea is applied to field crop, fruit tree or vegetables.
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CN102050652B (en) * | 2010-09-01 | 2013-10-16 | 中国石油天然气股份有限公司 | SODM fruit tree compound special fertilizer |
CN102531764A (en) * | 2010-12-17 | 2012-07-04 | 山东远东国际生物化工股份有限公司 | Polypeptide compound fertilizer and preparation method thereof |
CN102746053A (en) * | 2011-04-20 | 2012-10-24 | 北京中农瑞利源高科技发展有限公司 | Formula of polypeptide compound fertilizer (polypeptide composite fertilizer), and application of fertilizer in agriculture |
CN102557798B (en) * | 2011-12-31 | 2013-04-03 | 山东宝源生物有限公司 | Organic-inorganic compound fertilizer added with SOD (Super Oxygen Dehydrogenise) analogue and production method thereof |
CN104250176B (en) * | 2013-06-28 | 2016-08-10 | 中国石油天然气股份有限公司 | Method for improving sand blown soil by using multi-element compound fertilizer |
CN103650944B (en) * | 2013-11-30 | 2015-10-14 | 福建省农业科学院农业生态研究所 | A kind of method of honeysuckle florescence control |
CN104150971B (en) * | 2014-08-27 | 2015-03-25 | 石家庄开发区德赛化工有限公司 | Calcium-reinforced SOD urea fertilizer, preparation method and application thereof |
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GB2278347A (en) * | 1993-05-25 | 1994-11-30 | Son Ui Sung | Medicinal fluid composition for trees |
CN1389442A (en) * | 2002-07-15 | 2003-01-08 | 任斌 | Proteinase biocatalyst and its prepn. |
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