CN100396653C - Rare earth additive, rare earth superphosphate and preparing method thereof - Google Patents
Rare earth additive, rare earth superphosphate and preparing method thereof Download PDFInfo
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- CN100396653C CN100396653C CNB2006100571056A CN200610057105A CN100396653C CN 100396653 C CN100396653 C CN 100396653C CN B2006100571056 A CNB2006100571056 A CN B2006100571056A CN 200610057105 A CN200610057105 A CN 200610057105A CN 100396653 C CN100396653 C CN 100396653C
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- rare earth
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Abstract
This invention relates to a rare earth additive, rare earth acid phosphate containing said additive and its preparation method, in which, the main composition of said additive is rare earth, dolomite powder, zeolite powder, citric acid or citrate, the secondary composition includes magnesia powder and bentonite, the preparation method includes: putting the compositions into a mill in weight proportion and mixing them uniformly, and the preparation method of rare earth acid phosphate includes: adding a rare earth additive into phosphorite powder uniformly in proportion in the process of ball-milling phosphorite stones or pulping powder then to be reacted, solidified and aged in a formation chamber to generate rare earth acid phosphate.
Description
Technical field
The invention belongs to fertilizer field.
Technical background
Phosphate fertilizer is one of three large chemical fertilizers.Since the 1950's, 50 short years, China's phosphate fertilizer industry experienced grow out of nothing, evolution from small to large.Successively developed high-concentration phosphate compound fertilizerses such as fused(calcium magnesium)phosphate, coarse whiting, phosphorus ammonium, nitrogen phosphorus potassium, nitrophosphate fertilizer, the production process of phosphate fertilizer is ripe.Except that ammonium phosphate salt fertilizer, great majority are calcium phosphate fertilizer, as normal superphosphate, double superhosphate and fused(calcium magnesium)phosphate etc. in the kind of phosphate fertilizer.For calcium superphosphate and coarse whiting, higher because of the free acid composition, the water-soluble rate of its phosphorus is also high, easily causes water-soluble phosphorus loss, simultaneously, combines the formation insoluble compound with calcium, iron and manganese, and the utilization ratio of phosphorus reduces.And the major ingredient of fused(calcium magnesium)phosphate is a tricalcium phosphate, and because of not containing water-soluble phosphorus, fertilizer efficiency is slow, can not satisfy the demand to phosphorus in plant-growth early stage.How to improve the available phosphorus of phosphate fertilizer, the researchist has carried out number of research projects.As adding a certain proportion of carbon ammonium with neutralization part free acid in the production process of normal superphosphate, tricalcium phosphate is administered in the acid soil, and these measures just improve the fertilizer efficiency of calcium superphosphate to a certain extent.
For the application of rare earth in agricultural, as far back as Chinese scholar Qian Chongshu in 1917 and American W.J. Ao Sitante (Ostenhout) joint research the special physiological effect of barium, strontium, cerium to the water silk floss.Rare-earth phosphate fertilizer has carried out relevant research as a new research field.Discover that compare with normal superphosphate, rare-earth phosphate fertilizer does not change the content of available phosphorus and free acid, but because of rare earth and phosphorus interaction have promoted plant-growth, therefore, the research of carrying out rare-earth phosphate fertilizer preparation technology there is certain realistic meaning.
Current, the rare-earth phosphate fertilizer on the market utilizes ree distribution pattern liquid to produce additive and be added in the ground phosphate rock changing into chamber reaction, curing, slaking and forms.No matter be Guanghan, Sichuan rare-earth phosphate fertilizer, Yumen, Gansu rare-earth phosphate fertilizer, or Guangdong cloud sulphur rare-earth phosphate fertilizer, on different regions, Different Crop, carried out biological test, all obtain in comparatively ideal effect.As cumin volume increase 23.4%, hops volume increase 11% in Gansu, α acid increases by 0.5 percentage point.Simultaneously, the saltings wheat increase yield 13.4% of yellow Hua County, soybean yield-increasing 12.6%～14.2%, sorghum yield increasing 14.2%～15.8%, cotton volume increase 19.3% in Hebei.But also there are certain defective in the production of this kind phosphate fertilizer and effect.At first, the production process of production process middle-weight rare earths additive is more numerous and diverse.Allow a Production of Single Superphosphate enterprise or other enterprises begin to produce rare earth addition from rare earth ore concentrate and relate to a plurality of steps, production cost is higher.Secondly, go wrong, can cause radiocontamination if remove the whereabouts of radioelement thorium link and thorium.Once more, add this kind additive and make the physico-chemical property that rare earth calcium superphosphate compares with normal superphosphate in soil and can not change, also the indissoluble phosphorus in can not activating soil.These all are the defectives of this kind calcium superphosphate additive, need improvement and perfect.
By discovering, there are substantial connection in the formation of Lupinus albus row root and the secretion and the plant adaptability of organic substance, and particularly coercing down at phosphorus, the formation and the organic acid secretion of row's root are the keys of phosphorus attainment branch being coerced adaptation reaction.This result of study provides scientific basis for biotic potential, the degeneration-resistant new variety of seed selection nutrition efficient type of excavating the utilization of soil phosphorus nutrition efficient.Simultaneously, this achievement in research discloses, if in the preparation process of calcium superphosphate, adds an amount of citric acid and salt thereof, rare earth and ground dolomite, and phosphorus hard to tolerate in the activating soil and raising fertilizer efficiency are played an important role.
Summary of the invention
The present invention is based on above technical background, prepare a kind of rare earth addition and a kind of rare earth calcium superphosphate, wherein the major ingredient of rare earth addition is at least a in rare earth, ground dolomite, zeolite powder, citric acid and the Citrate trianion, and less important composition is magnesia and wilkinite; Comprise rare earth (material object) 10%～30%, ground dolomite 10%～60%, zeolite powder 10%～40%, citric acid or Citrate trianion 1%～10%, magnesia 5%～10%, swollen wilkinite 5%～10%, rare earth calcium superphosphate and normal superphosphate are relatively, available phosphorus, free acid and moisture content do not change, and its dispersiveness has improved.
The preparation method of rare earth addition adds stirrer to several compositions to mix by weight percentage: comprise rare earth 10%～30%, ground dolomite 10%～60%, zeolite powder 10%～40%, citric acid or Citrate trianion 1%～10%, magnesia 5%～10%, wilkinite 5%～10% are made powder rare earth calcium superphosphate additive.
Rare earth is at least a in the rare earth nitrate, rare earth chloride, carbonated rare earth, rare earth oxalate, citric acid rare earth, rare earth hydrate, acetic acid rare earth of at least a preparation in 15 kinds of ion lanthanums, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the yttrium;
Citric acid or Citrate trianion are that Citric acid monohydrate Food grade, Citric Acid, usp, Anhydrous Powder, Citrate trianion comprise: at least a in Tripotassium Citrate, Trisodium Citrate, citrate of lime, zinc citrate, ironic citrate, the manganese citrate.
The major ingredient of ground dolomite is lime carbonate and magnesiumcarbonate, its granularity 〉=80 orders; The major ingredient of zeolite powder is silicon oxide, aluminum oxide, its granularity 〉=80 orders.
The preparation method of rare earth calcium superphosphate is that rare earth addition evenly joins in the ground phosphate rock with ratio 0.1%～5% in ball milling Rock Phosphate (72Min BPL) or breeze pulping process.Except that adding the 98% required vitriol oil of ground phosphate rock reaction, add the vitriol oil of 1～50 kilogram of breeze per ton in addition, generate a kind of rare earth calcium superphosphate through changing into chamber reaction, curing, final ripening.The rare earth calcium superphosphate middle-weight rare earths content (oxide compound) of final preparation is 0.03～1%.
One of purpose of the present invention is a kind of calcium superphosphate additive of preparation.
Another purpose of the present invention is to utilize a kind of rare earth calcium superphosphate of this kind additive preparation.
Another purpose of the present invention is the processing method of a kind of rare earth calcium superphosphate of preparation.
Characteristics of the present invention are:
1, a kind of method for preparing the calcium superphosphate additive of simple, safe, remarkably productive, with low cost and suitable scale operation is provided.
2, the preparation rare earth calcium superphosphate that provides of this invention is with plant phosphorus to be coerced to adapt to and regulation mechanism is a foundation, makes the rare earth calcium superphosphate utilization ratio of preparation higher.
3, this invention has also further been expanded rare earth in the application of transforming the conventional fertilizers field.
The used method of all embodiments of the present invention does not limit the content of claims, all is as the criterion with claims.
Embodiment
The preparation technology of rare earth calcium superphosphate additive:
The preparation of example 1:1000g rare earth addition: add abundant mixing in the stirrer with 250g Europium trichloride (45%REO), 10g Citric acid monohydrate Food grade, 440g ground dolomite, 200g zeolite powder, 50g magnesia, 50g wilkinite, can make the rare earth addition of 1kg, wherein the granularity of rare earth chloride is 〉=8 orders, and the granularity of other compositions is 〉=80 orders.
The preparation of example 2:20kg rare earth addition: add abundant mixing in the stirrer, the rare earth addition of the 20kg that can make with 6kg (60%REO) carbonated rare earth, 1kg Citric acid monohydrate Food grade, 6kg ground dolomite, 5kg zeolite powder, 1kg magnesia, 1kg wilkinite.The granularity of its middle-weight rare earths and other compositions is 〉=80 orders.
The preparation of example 3:500g rare earth addition: add abundant mixing in the stirrer with 75g (32%REO) citric acid rare earth, 25g zinc citrate, 250g ground dolomite, 100g zeolite powder, 25g magnesia, 25g wilkinite, can make the rare earth addition of 500g, wherein the granularity of citric acid rare earth is 〉=8 orders, and the granularity of other compositions is 〉=80 orders.
The preparation of example 4:500g rare earth addition: add abundant mixing in the stirrer with 80g (78%REO) lanthanum hydroxide, 25g Tripotassium Citrate, 170g ground dolomite, 100g zeolite powder, 50g magnesia, 75g wilkinite, can make the rare earth addition of 500g, wherein the granularity of lanthanum hydroxide is 〉=8 orders, and the granularity of other compositions is 〉=80 orders.
The preparation of example 5:500g rare earth addition: add abundant mixing in the stirrer with 150g (38%REO) ytterbium nitrate, 25g citrate of lime, 100g ground dolomite, 100g zeolite powder, 50g magnesia, 75g wilkinite, can make the rare earth addition of 500g, wherein the granularity of rare earth nitrate is 〉=8 orders, and the granularity of other compositions is 〉=80 orders.
The preparation of example 6:1000g rare earth addition: add abundant mixing in the stirrer with 350g (30%REO) rare earth oxalate, 50g citrate of lime, 300g ground dolomite, 200g zeolite powder, 50g magnesia, 50g wilkinite, can make the rare earth addition of 1000g, wherein the granularity of rare earth oxalate is 〉=8 orders, and the granularity of other compositions is 〉=80 orders.
The preparation of example 7:1000g rare earth addition: add abundant mixing in the stirrer with 300g (45%REO) lanthanum acetate, 50g Trisodium Citrate, 300g ground dolomite, 200g zeolite powder, 100g magnesia, 50g wilkinite, can make the rare earth addition of 1000g, wherein the granularity of lanthanum acetate is 〉=8 orders, and the granularity of other compositions is 〉=80 orders.
Rare earth addition prepares the technology of rare earth calcium superphosphate:
Example 8: in the process of the pulping process that calcium superphosphate prepares, breeze per ton adds 20 kilograms of rare earth additions, stirs, except that adding the required sulfuric acid of breeze per ton, the vitriol oil that also additionally adds 13 kilogram 98% generates rare earth calcium superphosphate after the chamber of changing into reaction and slaking.Available phosphorus (the P of the rare earth calcium superphosphate that is generated
2O
5) content 〉=12%, free acid content [H
+]≤5.5%, moisture content≤15%, rare earth (RE
2O
3) content is 0.18%.
Example 9: in the process of the pulping process that calcium superphosphate prepares, breeze per ton adds 30 kilograms of rare earth additions, stirs, except that adding the required sulfuric acid of breeze per ton, the vitriol oil that also additionally adds 19 kilogram 98% generates rare earth calcium superphosphate after changing into chamber reaction, curing and slaking.Available phosphorus (the P of the rare earth calcium superphosphate that is generated
2O
5) content 〉=12%, free acid content [H
+]≤5.5%, moisture content≤15%, rare earth (RE
2O
3) content is 0.25%.
Claims (8)
1. rare earth addition, it is characterized in that: the major ingredient of this additive is rare earth, ground dolomite, zeolite powder, and is at least a in citric acid or the Citrate trianion, less important composition is magnesia and wilkinite; By weight percentage, ratio is rare earth 10%～30%, ground dolomite 10%～60%, zeolite powder 10%～40%, citric acid or Citrate trianion 1%～10%, magnesia 5%～10%, wilkinite 5%～10%.
2. according to the described a kind of rare earth addition of claim 1, it is characterized in that: described rare earth is at least a in rare earth nitrate, rare earth chloride, carbonated rare earth, rare earth oxalate, citric acid rare earth, rare earth hydrate, the acetic acid rare earth.
3. according to the described a kind of rare earth addition of claim 2, it is characterized in that: described rare earth is at least a in 15 kinds of ion lanthanums, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, the yttrium.
4. according to the described a kind of rare earth addition of claim 1, it is characterized in that: the major ingredient of described ground dolomite is lime carbonate and magnesiumcarbonate, its granularity 〉=80 orders.
5. according to the described a kind of rare earth addition of claim 1, it is characterized in that: the major ingredient of described zeolite powder is silicon oxide, aluminum oxide, its granularity 〉=80 orders.
6. according to the preparation method of the described rare earth addition of claim 1, it is characterized in that: several compositions are added stirrer by weight percentage mix: comprise that rare earth 10%～30%, ground dolomite 10%～60%, zeolite powder 10%～40%, citric acid or Citrate trianion 1%～10%, magnesia 5%～10%, wilkinite 5%～10% make.
7. containing right requires the preparation method of the rare earth calcium superphosphate of 1 rare earth addition it is characterized in that, in ball milling Rock Phosphate (72Min BPL) or breeze pulping process, evenly join in ground phosphate rock with ratio 0.1%～5% rare earth addition, except that adding the 98% required vitriol oil of ground phosphate rock reaction, breeze per ton adds in addition 1～50 kilogram the vitriol oil, generates a kind of rare earth calcium superphosphate through changing into chamber reaction, curing, final ripening.
8. according to the preparation method of the described a kind of rare earth calcium superphosphate of claim 7, it is characterized in that: the rare earth calcium superphosphate middle-weight rare earths content of final preparation is 0.03～1%.
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| CNB2006100571056A CN100396653C (en) | 2006-03-09 | 2006-03-09 | Rare earth additive, rare earth superphosphate and preparing method thereof |
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| CN100396653C true CN100396653C (en) | 2008-06-25 |
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| CN101172891B (en) * | 2007-10-23 | 2011-05-18 | 北京有色金属研究总院 | Fertilizer additive agent for sustained-releasing rare earth and method for producing the same |
| CN104956872A (en) * | 2015-06-10 | 2015-10-07 | 安徽翔华农林有限公司 | Planting method for jasmine trees grown on high mountains |
| CN105145628A (en) * | 2015-08-17 | 2015-12-16 | 佛山市顺德区今日景艺生物科技有限公司 | Inducer and inducing method for promoting flower bud differentiation of Dendrobium loddigesii Rolfe |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113934A (en) * | 1994-05-24 | 1995-12-27 | 四川联合大学 | Solid composite containing sulfuric acid and its application |
| CN1318298A (en) * | 2000-04-20 | 2001-10-24 | 刘秀娟 | Plant growth promoter |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113934A (en) * | 1994-05-24 | 1995-12-27 | 四川联合大学 | Solid composite containing sulfuric acid and its application |
| CN1318298A (en) * | 2000-04-20 | 2001-10-24 | 刘秀娟 | Plant growth promoter |
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Free format text: FORMER OWNER: GRIREM ADVANCED MATERIALS CO., LTD. Effective date: 20130912 Owner name: GRIREM ADVANCED MATERIALS CO., LTD. Free format text: FORMER OWNER: BEIJING CENTRAL INST.OF THE NONFERROUS METAL Effective date: 20130912 |
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Effective date of registration: 20130912 Address after: 100088, 2, Xinjie street, Beijing Patentee after: Grirem Advanced Materials Co., Ltd. Address before: 100088, 2, Xinjie street, Beijing Patentee before: General Research Institute for Nonferrous Metals Patentee before: Grirem Advanced Materials Co., Ltd. |
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Granted publication date: 20080625 Termination date: 20180309 |