CN101838159A - Titanium-complex-containing liquid fertilizer, preparation method thereof, and solid fertilizer containing the same - Google Patents
Titanium-complex-containing liquid fertilizer, preparation method thereof, and solid fertilizer containing the same Download PDFInfo
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Abstract
The invention relates to a preparation method of a titanium-complex-containing liquid fertilizer, which comprises the following steps: 1) dissolving titanyl sulfate or titanium sulfate in water; 2) adding a ligand A; 3) adding a ligand B; and 4) aging, wherein the ligand A and the ligand B are independently selected from tartaric acid, citric acid, malic acid, mandelic acid and lactic acid, and the ligand A and the ligand B are different; the ligand A, the ligand B and Ti (IV) meet the following relationship: 2 <= (the total mole number of the ligand A and the ligand B): the mole number of Ti (IV) <= 12. The invention also relates to the liquid fertilizer prepared by the method, and a solid fertilizer containing the liquid fertilizer. The titanium-complex-containing liquid fertilizer uses few ligands, has higher stability, and is still clear and transparent when being put for more than one year, and the concentration of titanium ion in a solution is almost unchanged, so the liquid fertilizer is of an excellent functional fertilizer.
Description
Technical field
The present invention relates to the chemical fertilizer field, particularly, the present invention relates to a kind of liquid fertilizer that contains titanium complex and preparation method thereof, contain the solid fertilizer of this liquid fertilizer.
Background technology
Existing at present a lot of research report about the application of element titanium in agricultural.Proved that now titaniferous fertilizer is the low functional fertilizer of a kind of broad spectrum, consumption, its some physiological activities to plant have good promoter action, can improve the specific absorption of plant to nutritive element, strengthen the disease-resistant anti-disaster ability of plant, obviously increase the output of crop, improve the quality of crop, so it is a kind of new-type fertilizer kind to be promoted that receives much attention in recent years.
Though the content of titanium in soil is not low, almost full form with oxide compound and insoluble salt exists, and embarrasses plant to utilize.The seventies in last century, Hungary I.Pais professor and co-worker thereof at first develop the Ti-Vc complex compound, confirm that through serial experiment it has the effect of obvious promotion plant-growth.After this decades, experiment or commodity titanium fertilizer adopt Pais professor's route basically, and this synthetic route is all with TiCl
4And Vc (xitix) wherein requires the Vc consumption must keep excessive 50-100 doubly for raw material processes.Obviously, the not ideal enough part of this synthetic route is that cost is too high, and introduces a large amount of chlorions.Through experiment, the inventor finds that Vc is used as ligand, and the synthetic product stability is poor, just occurs small amount of precipitate in the short period of time, just produces a large amount of insolubless about 3 months, not only influences the outward appearance of fertilizer, and has reduced the wherein content of effective titanium.Because the common circulation speed of fertilizer is slow, the currency is long, so stationary phase, too weak point will be to transporting and sell the very big problem of bringing.Also limited using of titanium fertilizer owing to contain a large amount of chlorions in addition.Therefore with TiCl
4With Vc be the product that raw material processes has many weak points, and this also need make great efforts to overcome just at present.The disclosed operational path of patent documentation CN1176954A and CN1337384A is all with TiCl
4With Vc be basic raw material.And in patent documentation CN101112200, also be with TiCl
4As the titanium source.Reference (" development and the application of novel chelating titanium fertilizer ", people such as Xu Liangzhong, " Shandong chemical industry ", 1996 the 1st phases, 16-17 page or leaf) discloses in the reaction of titanium sulfate and Vc and to have added the buffer reagent Citrate trianion and reduce by 80% Vc consumption.Cost is still very high though the consumption of Vc reduces significantly, and does not overcome product short defective stationary phase.This shows that good water solubility, the high titanium compound of stability are rare, can be applicable to that being easy to get of agricultural, cheap, nontoxic product are very rare.Therefore, very be necessary to seek a kind of novel low cost, good stability, no chlorion miscellaneous titanium fertilizer.
Summary of the invention
The object of the present invention is to provide a kind of liquid fertilizer that contains titanium complex.
The present invention also aims to provide a kind of preparation method who contains the liquid fertilizer of titanium complex.
The present invention also aims to provide a kind of solid fertilizer that contains described liquid fertilizer.
In order to realize purpose of the present invention, the invention provides a kind of preparation method who contains the liquid fertilizer of titanium complex, this method comprises:
1) under 30 ℃ to 90 ℃, titanyl sulfate or titanium sulfate are dissolved in the water, thereby obtain the aqueous solution of titanyl sulfate or titanium sulfate;
2) under 30 ℃ to 90 ℃, in the aqueous solution of above-mentioned titanyl sulfate or titanium sulfate, add ligand A and reacting 1～3 hour;
3) add down ligand B and reacted 1～3 hour at 30 ℃ to 90 ℃; And
4) 30 ℃ to 90 ℃ following ageings 2 to 5 days,
Wherein, described ligand A and described ligand B are selected from tartrate, citric acid, oxysuccinic acid, mandelic acid and lactic acid independently of one another, and described ligand A and described ligand B are inequality, and
Described ligand A, described ligand B and Ti (IV) satisfy the following relationship formula:
Mole number≤12 of 2≤(total mole number of described ligand A and described ligand B): Ti (IV).
In described step 1), the weight ratio of titanyl sulfate or titanium sulfate and water is preferably 1: 2～and 20.
Preferably, this method also comprises the step of filtering and filtered liquid being diluted to desired concn.
For reaction is more successfully carried out, described step 1), 2) and 3) preferably when stirring, carry out.More preferably, described stirring is to carry out under rotating speed is the condition of 50rpm to 100rpm.Do not limit for whipping appts, can use conventional whipping appts (for example mechanical stirrer) to stir.
The present invention also provides a kind of liquid fertilizer that contains titanium complex, and described liquid fertilizer makes by aforesaid method.
Wherein, and compare by the liquid fertilizer that contains titanium complex that uses a kind of ligand to form, the stability of liquid fertilizer of the present invention is higher.In this article, described " stability " be meant by under identical condition (for example identical temperature, identical humidity, identical illumination condition, identical air-proof condition etc.), each sample begins to occur that the sedimentary time determines.
The present invention also provides a kind of solid fertilizer that contains titanium complex, and it comprises:
The above-mentioned liquid fertilizer that contains titanium complex; And carrier.
Wherein, described carrier preferably includes: 1. inertia ore powder: zeolite, kaolin, pyrophyllite, wilkinite etc.; 2. nutritious inorganic salt: potassium primary phosphate, phosphorus ammonium, borax etc.; 3. other: gac, humic acids, xanthohumic acid, wood charcoal powder, agricultural byproducts tankage (as dry powder such as depleted agricultural-food stem, leaves) etc.
Contain the multiple titanium complex of being represented by formula Ti (IV) AiBj in the liquid fertilizer that contains titanium complex of the present invention, wherein, A and B are selected from tartrate, citric acid, oxysuccinic acid, mandelic acid and lactic acid independently of one another, and inequality; I and j have following several possibility: i=j=1 respectively; I=1, j=0 or i=2, j=0; I=0, j=1 or i=0, j=2.
In described titanium complex water solution system, there has been a lot of interdependences chemical equilibrium of mutual restriction again:
Ti(IV)+A＝Ti(IV)A
Ti(IV)A+A＝Ti(IV)A
2
Ti(IV)+2A＝Ti(IV)A
2
Ti(IV)+B＝Ti(IV)B
Ti(IV)B+B＝Ti(IV)B
2
Ti(IV)+2B＝Ti(IV)B
2
Ti(IV)A+B＝Ti(IV)AB
Ti(IV)A
2+B＝Ti(IV)AB+A
Ti(IV)B+A＝Ti(IV)BA
Ti(IV)B
2+A＝Ti(IV)B?A+B
In the present invention, temperature of reaction is preferably 30 ℃ to 90 ℃, helps like this reacting fully fast.With lactic acid is example, and the fusing point of L-(+) lactic acid is about 53 ℃, more favourable to reaction when temperature of reaction is higher than 53 ℃; But temperature should not be too high, otherwise reaction system easily generates the titanium oxide precipitation, reduced the concentration of effective titanium in the sintetics.
In the present invention, described ligand A and described ligand B are selected from tartrate, citric acid, oxysuccinic acid, mandelic acid and lactic acid independently of one another, and described ligand A and described ligand B and inequality.In addition, described ligand A, described ligand B and Ti (IV) satisfy the following relationship formula:
Mole number≤12 of 2≤(total mole number of described ligand A and described ligand B): Ti (IV).
With respect to the consumption of ligand in the prior art, the consumption of ligand of the present invention reduces greatly.When described ligand A, described ligand B and Ti (IV) satisfied the above-mentioned relation formula, the liquid fertilizer that contains titanium complex that makes was very bright, and stability is high.
The following inventor will describe mechanism of the present invention in detail.In agricultural titaniferous liquid fertilizer, titanium is positive 4 valency ions, and its outer electronic structure is d
0s
0, any symmetric form complexed all can't obtain ligand field stabilization energy (LFSE), and this is the basic reason that stable titanium complex is not prone to.Improve the stability of titanium complex, can only select from the ligand aspect.At first, the geometrical shape of ligand molecule, size and electronic structure are suitable, can fully occupy the ligancy that Ti (IV) ion can provide; Secondly, in the titanium complex that contains two ligands, to have between the ligand molecule to be similar to the such contact of hydrogen bond, so just can improve the chemical compatibility between the ligand molecule, make complex compound more stable.Because this extra stabilization energy just can impel the complex compound greater than a ligand molecule preferentially to form in multiple ligand coexistence system, comprising the complex compound that contains two kinds of different ligands.Consider that from the degree of Entropy Changes this complex compound that contains two different ligands is entropy increase bigger than the complex compound that contains two identical ligands, so it is bigger probability to occur, its stability is also higher.
In the present invention, preferably used tartrate, citric acid, oxysuccinic acid, mandelic acid and lactic acid as ligand.Can form hydrogen bond between hydroxyl between their differing moleculars and carboxyl, hydroxyl and hydroxyl, carboxyl and the carboxyl, and on agricultural, be easy to get, inexpensive, nontoxic, free from environmental pollution, do not bring latent dangerous factor to crop.
The inventor also finds, with Vc is the material of ligand, no matter be single Vc or Vc and the common ligand of forming of other joint compound, the stability of the product that forms with titanium is not high, a large amount of black precipitates just appearred about three months, along with the prolongation throw out of time little by little increases, titanium ion concentration descends thereupon.Compare with the product that contains single ligand, more stable by the product that two kinds of ligands and titanium form.The liquid fertilizer that contains titanium complex of the present invention is placed more than 1 year still clear, and titanium ion concentration is almost constant in the solution.
Embodiment
The invention will be further described below by the description of specific examples, but this is not to be limitation of the present invention, and those skilled in the art can make various modifications or improvement according to basic thought of the present invention, but only otherwise break away from basic thought of the present invention, all within the scope of the present invention.
Embodiment 1
Under 60 ℃ 24 kilograms of titanium sulfates being dissolved in 300 kg of water, adding 28 kilograms of lactic acid, is to stir 1 hour under the condition of 60rmp at 60 ℃, rotating speed.Adding 38 kilograms in tartrate then, is to stir 1 hour under the condition of 60rmp at 50 ℃, rotating speed.60 ℃ of following ageings 2 days.(lactic acid+tartaric total mole number): the mole number of Ti (IV) is 5.64.Filter, it is that 1 quality % (can carry out according to the method described in the following document: " graphite furnace atomic absorption spectrometry is measured trace amount Ti in the metallurgical material " by the mensuration of titanium ion concentration that filtrate water is diluted to titanium ion concentration, " assay office ", Vol.5, No.11, the 16-18 page or leaf, Zheng Yi etc.), thereby make sample 1.
Under 60 ℃ 24 kilograms of titanium sulfates being dissolved in 300 kg of water, adding 28 kilograms of lactic acid, is to stir 1 hour under the condition of 60rmp at 60 ℃, rotating speed.60 ℃ of following ageings 2 days.Filter, it is 1 quality % that filtrate water is diluted to titanium ion concentration, thereby makes sample 2.
Under 60 ℃ 24 kilograms of titanium sulfates being dissolved in 300 kg of water, adding 38 kilograms in tartrate, is to stir 1 hour under the condition of 60rmp at 50 ℃, rotating speed.60 ℃ of following ageings 2 days.Filter, it is 1 quality % that filtrate water is diluted to titanium ion concentration, thereby makes sample 3.
Measure the sample 1,2 and 3 of 2ml respectively, be diluted with water to 1000ml (be in every duplicate samples titanium ion concentration be 20ppm), preserve at the room temperature environment lower seal then, observe and the sedimentary time occurs.Sample 1 still kept the state of clear after 72 hours.After testing, wherein titanium ion concentration still is 20ppm.Sample 2 begins to occur precipitation after half hour, sample 3 began to occur precipitation after 26 hours.
This shows that with respect to the product that the effect of titanium sulfate and a kind of ligand (lactic acid or tartrate) obtains, the product that titanium sulfate and two kinds of ligand effects obtain is more stable.
Embodiment 2
Under 30 ℃, 80 gram Vc (xitix) are added in the 300ml water, be stirred to dissolving.In the Vc aqueous solution, add 6 gram TiCl then
4, be to stir 3 hours under the condition of 100rmp at rotating speed.Filter, collect filtrate, filtrate is brown solution, thereby obtains the Ti-Vc complex compound with sample as a comparison.
According to embodiment 1 in identical mode prepare sample 1.Adding water respectively in sample 1 and comparative sample and dilute, make that titanium ion concentration is 0.3 quality %, is 4 with acid with pH regulator simultaneously.Then, sample 1 after handling and comparative sample are preserved at the environment lower seal of room temperature lucifuge, observed the sedimentary time of appearance.Sample 1 still kept the state of clear after 1 year.After testing, wherein titanium ion concentration is 0.29 quality %, and is almost constant.A large amount of black precipitates appearred in comparative sample after 3 months.
This shows that in sour environment, fertilizer of the present invention is more stable than the fertilizer of prior art.
Embodiment 3
Under 60 ℃ 24 kilograms of titanium sulfates being dissolved in 300 kg of water, adding 28 kilograms of lactic acid, is to stir 1 hour under the condition of 100rmp at 60 ℃, rotating speed.Adding 38 kilograms in tartrate then, is to stir 1 hour under the condition of 100rmp at 50 ℃, rotating speed.60 ℃ of following ageings 2 days.(lactic acid+tartaric total mole number): the mole number of Ti (IV) is 5.64.Filter, it is 30ppm (sample 4), 15ppm (sample 5), 10ppm (sample 6) that filtrate water is diluted to titanium ion concentration, carries out field experiment then.
For studying thing: Thailand leaf of bamboo mater convolvulus, its seed is available from Yongan, Fujian seeds company
For trying soil: carry out in Yong'an City swallow South St Dao Maoping village, Fujian Province in August, 2009, experimental field is husky bottom ash mud field, and wherein the pH value is 4.6, the various main components of soil are as follows: organic 16.7g/kg, alkali-hydrolyzable nitrogen 109mg/kg, available phosphorus 209.2mg/kg, available potassium 219mg/kg.
Test design: establish 4 treatment zones, each regional area is 15 square metres, and repeat 3 times in each zone, totally 12 zones.Plantation Thailand leaf of bamboo mater convolvulus carried out spraying the first time at after planting the 16th day, foliage-spray sample 4,5,6 and etc. water gaging (blank).Sample or water 2kg are used in each zone.Carried out spraying the second time at after planting the 22nd day, foliage-spray sample 4,5,6 and etc. water gaging (blank).Sample or water 3kg are used in each zone.
Fertilising and management: in sowing on August 18th, 2009 Thailand leaf of bamboo mater convolvulus, gather in the crops the 27 days time of infertility September 14.Each regional bulk application (foreign rich composite fertilizer (14-16-15) is available from Hubei Yang Feng composite fertilizer factory) before the sowing) 0.75kg, after planting 18 days (September 5) each zone (foreign rich composite fertilizer (14-16-15)) 0.8kg that topdresses.The field management measure unanimity that each is regional.
Investigation method: gathering preceding 1 day, each arda sampling 10 strain measures that plant height, stem are thick, single-strain fresh weight, leaf is long, leaf is wide, single-strain blade number and biomass.Survey each regional output when gathering, convert out per mu yield (kg/667m
2).The results are shown in Table 1, wherein the data in the table 1 are mean value.
Table 1 different treatment mater convolvulus tree characteristics relatively
Table 2 different treatment mater convolvulus rate ratio
This shows that sample 4,5,6 all has a significant effect, wherein the effect of sample 4 is the most remarkable, and biomass and per mu yield are all the highest.Because the soil pH value in experiment field is 4.6, acidity is higher, and therefore the fertilizer efficiency of conventional titanium fertilizer under this environment is relatively poor, be not suitable for using, but the effect of sample 4,5,6 is satisfactory.
Embodiment 4
Under 60 ℃ 24 kilograms of titanium sulfates being dissolved in 300 kg of water, adding 13.4 kilograms of oxysuccinic acid, is to stir 3 hours under the condition of 100rmp at 65 ℃, rotating speed.Adding 15.2 kilograms of mandelic acids then, is to stir 3 hours under the condition of 100rmp at 65 ℃, rotating speed.63 ℃ of following ageings 3 days.The mole number of (total mole number of oxysuccinic acid+mandelic acid): Ti (IV) is 2.Filter, it is 1 quality % that filtrate water is diluted to titanium ion concentration.
20 kilograms of aforesaid liquids are adsorbed on 980 kilograms of gacs, with the solid fertilizer that obtains thus as sample 7.Carry out field experiment according to the mode identical with embodiment 3, difference is that applied amount is 50 kilograms every mu, spreads manuer in holes in plant root.The biomass of sample 7 is the 28.12g/ strain as a result, and per mu yield is 1524kg/667m
2
Embodiment 5
Under 60 ℃ 24 kilograms of titanium sulfates being dissolved in 300 kg of water, adding 179.6 kilograms of oxysuccinic acid, is to stir 2 hours under the condition of 100rmp at 65 ℃, rotating speed.Adding 115.2 kilograms of citric acids then, is to stir 2 hours under the condition of 100rmp at 65 ℃, rotating speed.62 ℃ of following ageings 3 days.The mole number of (total mole number of oxysuccinic acid+citric acid): Ti (IV) is 12.Filter, it is 30ppm that filtrate water is diluted to titanium ion concentration, as sample 8.
Carry out field experiment according to the mode identical with embodiment 3, the biomass of sample 8 is the 31.05g/ strain, and per mu yield is 1631kg/667m
2
Claims (9)
1. preparation method who contains the liquid fertilizer of titanium complex, this method comprises:
1) under 30 ℃ to 90 ℃, titanyl sulfate or titanium sulfate are dissolved in the water, thereby obtain the aqueous solution of titanyl sulfate or titanium sulfate;
2) under 30 ℃ to 90 ℃, in the aqueous solution of above-mentioned titanyl sulfate or titanium sulfate, add ligand A and reacting 1～3 hour;
3) add down ligand B and reacted 1～3 hour at 30 ℃ to 90 ℃; And
4) 30 ℃ to 90 ℃ following ageings 2 to 5 days,
Wherein, described ligand A and described ligand B are selected from tartrate, citric acid, oxysuccinic acid, mandelic acid and lactic acid independently of one another, and described ligand A and described ligand B are inequality, and
Described ligand A, described ligand B and Ti (IV) satisfy the following relationship formula:
Mole number≤12 of 2≤(total mole number of described ligand A and described ligand B): Ti (IV).
2. preparation method according to claim 1 is characterized in that, this method also comprises filtration and the step that filtrate is diluted.
3. preparation method according to claim 1 is characterized in that, described step 1), 2) and 3) be when stirring, to carry out.
4. preparation method according to claim 3 is characterized in that, described stirring is to carry out under rotating speed is the condition of 50rpm to 100rpm.
5. according to any described preparation method in the claim 1 to 4, it is characterized in that in described step 1), the weight ratio of titanyl sulfate or titanium sulfate and water is 1: 2～20.
6. a liquid fertilizer that contains titanium complex is characterized in that, described liquid fertilizer makes by any described method in the claim 1 to 5.
7. liquid fertilizer according to claim 6 is characterized in that, described liquid fertilizer is higher than the stability by using the liquid fertilizer that contains titanium complex that a kind of ligand forms.
8. solid fertilizer that contains titanium complex is characterized in that it comprises:
Claim 6 or the 7 described liquid fertilizers that contain titanium complex; And
Carrier.
9. solid fertilizer according to claim 8 is characterized in that, described carrier is inertia ore powder, inorganic salt, gac, humic acids, xanthohumic acid, wood charcoal powder or agricultural byproducts tankage.
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| CN105000935A (en) * | 2015-07-23 | 2015-10-28 | 合肥众月健康科技有限公司 | Liquid fertilizer improving crop photosynthesis and preparation method thereof |
| KR20200004886A (en) * | 2017-05-15 | 2020-01-14 | 인터매그 에스피. 지 오.오. | Formulations of Metal and Ascorbic Acid Complexes, Obtaining and Uses thereof |
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| CN107793262A (en) * | 2017-10-20 | 2018-03-13 | 日正九安科技（北京）有限公司 | A kind of water soluble fertilizer and preparation method thereof |
| CN112250478A (en) * | 2020-10-29 | 2021-01-22 | 四川龙蟒福生科技有限责任公司 | Full-water-soluble titanium fertilizer and preparation method thereof |
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