CN104250001A - Production method of special tobacco fertilizer serving as byproduct of preparation of monopotassium phosphate - Google Patents
Production method of special tobacco fertilizer serving as byproduct of preparation of monopotassium phosphate Download PDFInfo
- Publication number
- CN104250001A CN104250001A CN201410478386.7A CN201410478386A CN104250001A CN 104250001 A CN104250001 A CN 104250001A CN 201410478386 A CN201410478386 A CN 201410478386A CN 104250001 A CN104250001 A CN 104250001A
- Authority
- CN
- China
- Prior art keywords
- potassium
- tobacco
- fertilizer
- product
- production method
- 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.)
- Granted
Links
Landscapes
- Fertilizers (AREA)
Abstract
The invention relates to the technical field of chemical engineering, in particular to a production method of special tobacco fertilizer serving as a byproduct of preparation of monopotassium phosphate. The special tobacco fertilizer serving as the byproduct prepared from waste liquid obtained by preparation of the monopotassium phosphate by a wet method is produced by detecting and analyzing the element content of the special tobacco fertilizer and an effective absorption form and an effective absorption amount of tobaccos to nitrogen, phosphorus and potassium elements and adjusting and matching the element content in a technical production process; the matching contents of a large quantity of nutritional elements such as nitrogen, phosphorus and potassium are adjusted, so that excessive nutritional elements are prevented from being introduced into soil, and the environmental pollution caused by solidification of composite fertilizer and blocking of the soil is avoided; furthermore, the phenomenon that the composite tobacco fertilizer is extremely high in production cost due to element mis-matching is also avoided; the production method is obvious in environment-friendly value and high in economical benefit.
Description
Technical field
The present invention relates to chemical technology field, especially a kind of production method preparing potassium primary phosphate by-product fertilizer special for tobacco.
Background technology
Nitrogen, phosphorus, potassium are the requisite important nutritive elements of plant-growth.Root system of plant to the absorption of nitrogen mainly with the [NH of inorganic states
4 +] and [NO
3 -]; Phosphorus is mainly with [H
2pO
4 -] form be absorbed by plants; Potassium is dissociated in water [K
+], absorbed by root system of plant.Urea is organic nitrogenous fertilizer, need urase effect in soil, after being hydrolyzed into volatile salt or bicarbonate of ammonia, and could utilization absorbed by crops.
Meanwhile, potassium primary phosphate is that one can the field such as applicable industry, agricultural, and tool has been widely used.As in the production of industrial aspect mainly as chemical raw material, agriculturally be mainly used in the interpolation of feed and chemical fertilizer, in addition, potassium primary phosphate can also be used for food to be added as raw material, improve food mouthfeel and quality, supplement the trace elements such as potassium element for human body.But, production method at present for potassium dihydrogen phosphate product mainly contains thermal phosphoric acid and phosphoric acid by wet process, and thermal phosphoric acid cost is larger, unsuitable as extensively promoting, therefore, Wet-process Phosphoric Acid Production potassium dihydrogen phosphate product becomes main method, , phosphoric acid by wet process is prepared in the process of potassium dihydrogen phosphate product, also there is more defect, difficulty such as when carrying out potassium primary phosphate and purifying is larger, in production process, equipment requirements is relatively high, raw material difficulty is asked, the technique extracting the phosphorus in Rock Phosphate (72Min BPL) is comparatively complicated, technical process is long, and then cause production cost high, meanwhile, a large amount of waste and old wastes can be produced in production process, cause the pollution of environment.
For this reason, this investigator in early stage from waste and old waste and high to equipment requirements, raw material difficulty such as to ask start with at the technical problem, after Ureaphil intermediate is formed to potassium dihydrogen phosphate product employing phosphoric acid and urea reaction, be that potassium hydroxide etc. contains potassium raw material reaction, and urea is prepared in reacted Recycling Mother Solution use, or directly proceed to chemical fertilizers production line and produce chemical fertilizer, make abundant raw material source, the extent of corrosion of equipment is reduced, reduce the discharge of waste gas and waste liquid, reduce potassium dihydrogen phosphate product production cost, preparation for potassium dihydrogen phosphate product provides a kind of new approaches.
The improvement of above technology still also exists larger problems, generate in the process of Ureaphil as adopted phosphoric acid and urea reaction, its process regulation is bad, then can not form simple replacement(metathesis)reaction in next step reaction, and then cause the also not necessarily contained in stock liquid to be urea raw material, meanwhile, in whole production technique, also have a large amount of waste and old mass emissions, be difficult to the zero release problem of address contamination; And, potassium dihydrogen phosphate product is also difficult to separate out completely in the process of crystallization, but be in the saturated solution of state of saturation all the time, then content is larger in the solution to make potassium primary phosphate, if degree of depth crystallization, the purity of the potassium dihydrogen phosphate product then obtained is poor, affects the quality of potassium dihydrogen phosphate product.Based on this, by carrying out research and discussion to potassium primary phosphate as the character of fertilizer, and in conjunction with a large amount of reports, potassium primary phosphate has the character that can be absorbed by plants and reach more than 98%, and it is reported that common phosphate fertilizer utilization ratio absorbed by crops only can reach 10-25%, common potash fertilizer only absorbed by cropsly can utilize 45-60%, and the nitrogenous fertilizer such as urea, carbon ammonium only absorbed by cropsly can utilize 20-46%; As can be seen here, potassium primary phosphate utilization ratio absorbed by crops is apparently higher than common azophoska.
But, what the current application for azophoska mainly adopted is the nitrogen fertilizers such as urea, Repone K etc. contain phosphatization fertilizer containing potassium fertilizer and phosphate fertilizer etc., composite and obtain according to the demand of farm crop, form the composite fertilizer of a large amount of mixed states, and then the element heterogeneity causing in fertilizer, and be difficult to be absorbed completely as much as possible by plant, cause element pollution environment, affect the soil property of soil, for this reason, there is investigator from the composite fertilizer of composite state, composite fertilizer is prepared into the composite fertilizer of chemical combination state, and then make the collocation between element and element suitable, again during a kind of element absorbed by crops, another element can be made to be balanced in soil, element is not caused to be wasted and contaminate environment, and the cost reduced in composite heat transfer process,
If the patent No. is 200710048214.6, " co-production of a kind of potassium primary phosphate, S-based compound fertilizer and polymerize aluminum chloride " discloses the co-production produced and produce S-based compound fertilizer and polymerize aluminum chloride in potassium primary phosphate process, and what improve that phosphoric acid by wet process prepares impurity in potassium dihydrogen phosphate product process affects problem.
And for example the patent No. be 200810197992.6 " a kind of production method of magnesium ammonium phosphate composite fertilizer " disclose a kind of composite fertilizer containing magnesium ion, ammonium radical ion and phosphate anion mixed state, reduce wet phosphoric acid refining cost, prevent the waste of resource.
Simultaneously, also the technology of preparing carrying out mixing composite fertilizer for crop is had, but do not see having and anyly carry out element collocation about by composite fertilizer's preparation process for the demand of crop, and the technical scheme being made into the composite fertilizer of chemical combination state exists, particularly for this comparatively special cash crop of tobacco; Also not finding that there is document prepares in potassium dihydrogen phosphate product process for phosphoric acid and urea reaction, the waste of a large amount of potassium dihydrogen phosphate product that potassium primary phosphate crystallization is incomplete caused, and potassium primary phosphate crystallization is excessively again with a large amount of impurity, then make the purity of potassium dihydrogen phosphate product inadequate, and the technical problem that a large amount of waste liquid transforms difficulty and gets rid of solve.
For this reason, investigator of the present invention is from a large amount of prior art documents and Exploration & stu dy for many years, and the component content of traditional fertilizer special for tobacco and the absorbing state of tobacco are studied, effective discussion is out suitable for the special of Tobacco and flies Hefei, then in production potassium dihydrogen phosphate product process, adjust whole production technique and processing parameter thereof, by-product is suitable for the new exclusive efficient compound fertilizer of Tobacco.
Summary of the invention
In order to solve the above-mentioned technical problem existed in prior art, the invention provides a kind of production method preparing potassium primary phosphate by-product fertilizer special for tobacco, it has that production technique is short, equipment requirements is low, the purity of potassium dihydrogen phosphate product is high, fully can be absorbed by crop without the fertilizer special for tobacco of waste gas and waste liquid discharge, by-product, and the nutritive element collocation in fertilizer is proper, element-free is wasted, production cost is low, has the features such as the significant value of environmental protection and economic benefit.
Be achieved particular by following technical scheme:
A kind of production method preparing potassium primary phosphate by-product fertilizer special for tobacco, phosphoric acid is adopted to be (1.2-1.6) with carboxamide according to mol ratio: 1 mixes, and be that 5 DEG C/min is warming up to 80-160 DEG C with heat-up rate, stirring reaction 4-5h, obtains intermediate slip, this intermediate slip is adopted to mix with 1.1-1.3mol alkaline potassium salt again, after reaction terminates, obtain nitrogenous, phosphorus, the slip of potassium, and by nitrogenous, phosphorus, the slip of potassium is placed in cooling crystallizer and carries out decrease temperature crystalline filtration treatment, make filtrate circulation crystallization process in cooling crystallizer, and detect analysis filtrate, when the content of nitrogen component is 15-18%, Vanadium Pentoxide in FLAKES component content is 1.5-4.5%, when potassium oxide component content is 8.1-14.4%, stop crystallization and filter, the filter cake obtained is potassium dihydrogen phosphate product, in filtrate, add other trace compounds be adjusted to chemical combination state composite fertilizer just finished product.And first finished product is placed in baker, adopt heat-up rate to be that 3 DEG C/min is warming up to 45-55 DEG C, after dry 0.5-1h, adjustment moisture content is 3-4%, can obtain fertilizer special for tobacco.
Described phosphoric acid and carboxamide react, and are phosphoric acid solution and carboxamide solid reaction.
Described phosphoric acid and carboxamide react, and are phosphoric acid solution and carboxamide liquid reactions.
Described phosphoric acid and carboxamide react, and are phosphoric acid solid and carboxamide liquid reactions.
Described alkaline potassium salt is potassium hydroxide; Described trace compound is CaSO
4, MgSO
4, Fe
2+inner complex, H
3bO
3in one or more mixtures.
Described composite fertilizer's chemical combination state just finished product, wherein nitrogen component content is 16.5%, Vanadium Pentoxide in FLAKES component content is 3%, potassium oxide component content is 11-13%.
It is by the nitrogen contained in filtrate, phosphorus, potassium three kinds of macroelement that filtrate is analyzed in described detection, determination method traditionally, its content is adjusted, its content is reached when nitrogen component is 16%, Vanadium Pentoxide in FLAKES composition is 3.5%, potassium oxide composition is 12%, stop the crystallization treatment step to filtrate.
Described fertilizer special for tobacco is chemical combination state Chemical Mixed Fertilizer.
Described chemical combination state Chemical Mixed Fertilizer, containing following N P and K chemical combination state structural formula in its composition:
wherein, the dotted line between carbon atom and Sauerstoffatom represents to there is coordinate bond between C atom and O atom.
Urea and phosphoric acid are reacted under heat-up rate is the temperature environment of 5 DEG C/min, generates Ureaphil, and along with the progressively rising of temperature, and then make the coordinate bond dialysis between Ureaphil and form two kinds of ion like materials, be namely exactly
when
ion is in phosphoric acid environment, will be close with phosphoric acid, and then carries out ionic polymerization under temperature environment when the dialysis of Ureaphil coordinate bond, makes
ion and phosphoric acid generate
intermediate-ion, make containing a large amount of dihydrogen phosphates in solution, when adding potassium ion compound, dihydrogen phosphate and potassium ion react and generate potassium primary phosphate, and in succession reach capacity simultaneously; When potassium content is excessive, will reacts with the ammonium radical ion in intermediate-ion, further make intermediate-ion chelating become
intermediate-ion, and with positive charge, and then when participating in other electronegative ions or compound in solution, compound salt will be formed with this ion, further enriching the nutritive ingredient in product.
As added potassium sulfate in solution, the Determination of Potassium in adjustment solution, then can generate sulfenyl double salt chemical combination state composite fertilizer.
As added saltpetre in solution, the Determination of Potassium in adjustment solution and nitrogen element content, then can generate nitrate compound salt composite fertilizer.
Meanwhile, when in solution containing a large amount of affect the element of fertilizer impurity time, it not easily generates colloid, and then makes the character of fertilizer unaffected:
In process as Wet-process Phosphoric Acid Production potassium dihydrogen phosphate product, the elements such as a large amount of iron, magnesium, aluminium can produce colloid in the solution, and then affect the technique ease of potassium dihydrogen phosphate product preparation process, make in potassium dihydrogen phosphate product preparation process, removal of impurities cost is larger; Iron ion, magnesium ion, aluminum ion are positively charged gas ions, and then interference can not be formed to intermediate-ion, solution and another formation with elements such as iron, magnesium, aluminium of intermediate-ion easily decompose intermediate-ion body on the contrary, make fully to be absorbed by crop.
Compared with prior art, the technique effect of technical scheme of the present invention is embodied in:
1, by the constituent content in fertilizer special for tobacco and tobacco the effective absorbed dose to n-p-k element carry out detection analyze, and carry out regulating to the constituent content in production process and arrange in pairs or groups, make the composite fertilizer of the chemical combination state prepared can meet the demand of crop to greatest extent, and reduce in composite heat transfer because element mismatch, the high cost caused, further avoid too much element to drop among soil, cause solidifying of composite fertilizer and contaminate environment.
2, by controlling the processing condition of producing, make in fertilizer special for tobacco preparation process, highly purified potassium dihydrogen phosphate product can be produced, compensate for removal of impurities cost when traditional wet phosphoric acid prepares potassium dihydrogen phosphate product, the purity of the potassium dihydrogen phosphate product prepared is made to reach more than 95%, production cost reduces 93%, has significant economic benefit.
3, by production process, the mol ratio of raw material, in crystallisation step, the accurate analysis of filtrate and detection, make the quality of the tobacco compound fertilizer produced be guaranteed, and with adjusting the mode of filtrate component content, using the raw material of the waste liquid in Chemicals production process as composite heat transfer, avoid the discharge of waste liquid, reduce composite heat transfer cost, there is the significant value of environmental protection and economic benefit.
Choosing and control 4, by raw materials for production, avoids adding of chlorine element, and then avoids the impact of chlorine element on tobacco plants, ensure that the quality of fertilizer special for tobacco.
5, by technical parameter in chemical combination state compound fertilizer production technology, namely be exactly temperature, the control of material concentration and proportioning, after making phosphoric acid and urea reaction, generate Ureaphil product, Ureaphil product itself has stronger acidity, and between phosphoric acid and urea, be the chemical combination state double salt be combined together to form by the mode of coordinate bond, also be fertile as crop in conventional art, and crop is to the specific absorption comparison urea of this chemical combination state double salt, volatile salt, the unitary such as ammonium nitrate, binary fertilizer specific absorption is a kind of chemical combination state composite fertilizer all preferably, but, under the environment that this chemical combination state double salt exists at phosphoric acid, at the temperature of 80-250 DEG C, complicated decomposition polyreaction can be there is, Ureaphil is made to form (H
2pO
4)
-(H
2nCONH
3)
+two ions, (H
2nCONH
3)
+ion and phosphoric acid close, and be under the environment of 80-160 DEG C in temperature, formed
intermediate-ion and dihydrogen phosphate, and coordinate bond is formed between C and O, this intermediate-ion can form multielement intermediate-ion with centering element compound chelating, and then the compound electronegative with other can be continued or ion forms inner complex, improve constituent content in double salt, and then the nutrient content that can adjust in the double salt of this ion existence, simultaneously, this inner complex can be hydrolyzed again and by crop, and then fertilizer efficiency can be provided for crop effectively for a long time, simultaneously, in conjunction with the mensuration of constituent content in the solution existed this ion, and then each constituent content during formation of adjustment double salt, dry and obtain chemical combination state double salt composite fertilizer, and by avoiding adding of chlorine element, while making the quality product of chemical combination state double salt composite fertilizer can meet the requirement of tobacco nutritive ingredient, avoid the infringement that fertilizer brings tobacco, reduce tobacco planting cost and improve tobacco quality.
Embodiment
Below in conjunction with concrete embodiment, further restriction is done to technical scheme of the present invention, but claimed scope is not only confined to done description.
Principle illustrates:
The present invention carries out research and discussion by the mechanism of reacting phosphoric acid and carboxamide, and arrives in conjunction with prior art literature, and phosphoric acid and carboxamide react and generate Ureaphil, and its molecular formula is: CO (NH
2)
2.H
3pO
4under the environment of comparatively high temps, the chemical bond meeting dialysis between H and O in phosphoric acid, hydrogen ion is combined the ionic state formed containing positive charge with urea, the ion double salt making Ureaphil form a kind of positive and negative charge to attract mutually, its mechanism structural response following expression: CO (NH
2)
2.H
3pO
4→ (H
2pO
4)
-. (H
2nCONH
3)
+
Further, under the environment that Ureaphil ion double salt exists at phosphoric acid, (H wherein
2nCONH
3)
+positive ion and phosphoric acid close, form the intermediate-ion of C → O coordinate bond, be (CO
5pN
2h
8)
+, and then make in Ureaphil intermediate containing a large amount of (H
2pO
4)-and (CO
5pN
2h
8)
+ion, when adding excessive and appropriate potassium ion, dihydrogen phosphate and potassium ion form potassium dihydrogen phosphate crystal and are precipitated, unnecessary potassium ion and (CO
5pN
2h
8)
+ionic reaction, and displace part NH
4 +, make in solution containing (CO
5pNH
4k)
+double salt ion, and analyze by detecting and control the content of N in solution, P, K element, the chemical combination state composite fertilizer containing N, P, K element can be obtained at heat drying.
Its concrete reaction principle will carry out further instruction by following reaction structure formula and reaction mechanism:
Reaction formula one:
CO(NH
2)
2+H
3PO
4→CO(NH
2)
2.H
3PO
4
Reaction formula two:
Reaction formula three:
Wherein, the dotted line between carbon atom and Sauerstoffatom represents to there is coordinate bond between C atom and O atom.
Reaction formula four:
Wherein, the dotted line between carbon atom and Sauerstoffatom represents to there is coordinate bond between C atom and O atom.
Noun illustrates:
Ureaphil (Ureaphosphate, UP), No. CAS is 4861-19-2, and molecular formula is CH
7n
2o
5p, can be expressed as CO (NH
2)
2h
3pO
4:
It is a kind of fine chemical product being widely used in the fields such as livestock industry, industry, agricultural, its solid is white crystals or crystalline powder, and soluble in water and alcohol is insoluble to ethers, toluene and tetracol phenixin, the aqueous solution, in acid, start during melting to decompose and releases carbonic acid gas and ammonia.
Embodiment: with concrete operation embodiment, the present invention is further elaborated below.
Phosphoric acid is prepared in potassium dihydrogen phosphate product process in a wet process, to be combined with urea by phosphoric acid and react, after obtained Ureaphil intermediate, adopt intermediate with carry out containing the compound of potassium element reacting prepare potassium dihydrogen phosphate product processing step based on, adjusting process parameter, its temperature is made to reach the temperature of reaction of 80-160 DEG C, and adopt the heat-up rate of 5 DEG C/min to carry out the process of intensification stirring reaction, stirring velocity controls at 120-210r/min, and then make temperature-controllable in reaction process, and regulate pH value, make the product state in reaction process controlled, and by crystallisation process, the control of the amount of potassium dihydrogen phosphate product, the impurity in filtrate is made to be difficult to be crystallized out, and then purifying potassium dihydrogen phosphate product, and in conjunction with Addition ofelements adjustment filtrate structure in filtrate, make in filtrate, to form a kind of Chelating state compound, and by after drying, obtain the special efficient composite fertilizer being suitable for Tobacco.
Embodiment 1
Prepare a production method for potassium primary phosphate by-product fertilizer special for tobacco, comprise the following steps:
(1) raw material preparation mixing: be that 1.2:1 is in stirring-type reactor according to mol ratio by phosphoric acid and carboxamide, be that 5 DEG C/min is warming up to 160 DEG C with heat-up rate, the stirring velocity controlling stirring tank is that 100r/min is uniformly mixed reaction 4h, obtains Ureaphil intermediate slip;
(2) KH is prepared
2pO
4: again the potassium hydroxide 3h of 1.3mol is at the uniform velocity added containing in steps 1) in the reactor of obtained Ureaphil intermediate slip, and employing stirring speed is 160r/min stirring reaction 30min, obtains containing potassium Ureaphil slip;
(3) circulation crystallization filters: by step 2) obtain and be placed in cooling crystallizer be cooled to temperature 20 DEG C containing potassium Ureaphil slip, down cycles crystallization filtration treatment, and detect the nutrient content analyzed in filtrate, when content until nitrogen component is 18%, Vanadium Pentoxide in FLAKES component content is 4.5%, potassium oxide component content is 14.4%, stop crystallization and filter, acquisition filter cake is potassium primary phosphate, and adds the CaSO of 0.5% in filtrate
4be adjusted to chemical combination state composite fertilizer just finished product;
(4) filtrate dries: by step 3) the chemical combination state composite fertilizer that obtains just finished product be placed in baker, adopt heat-up rate to be that 3 DEG C/min is warming up to 45 DEG C, after dry 1h, adjustment moisture content is 4%, detects packaging, can obtain fertilizer special for tobacco.
Embodiment 2
Prepare a production method for potassium primary phosphate by-product fertilizer special for tobacco, comprise the following steps:
(1) raw material preparation mixing: by concentration be 48% phosphoric acid solution and concentration be 35% carbon amide solution be that 1:1.3 is in stirring-type reactor according to mol ratio, be that 5 DEG C/min is warming up to 90 DEG C with heat-up rate, the stirring velocity controlling stirring tank is that 100r/min is uniformly mixed reaction 4.2h, obtains Ureaphil intermediate slip;
(2) KH is prepared
2pO
4: again the potassium hydroxide solution 3h of 1.1mol is at the uniform velocity added containing in steps 1) in the reactor of obtained Ureaphil intermediate slip, and employing stirring speed is 205r/min stirring reaction 70min, obtains containing potassium Ureaphil slip;
(3) circulation crystallization filters: by step 2) obtain and be placed in cooling crystallizer be cooled to temperature 18 DEG C containing potassium Ureaphil slip, down cycles crystallization filtration treatment, and detect the nutrient content analyzed in filtrate, until nitrogen component content be 17%, Vanadium Pentoxide in FLAKES component content is 4%, potassium oxide component content is 14% time, stop crystallization and filter, acquisition filter cake is potassium primary phosphate, and adds the CaSO of 0.2% in filtrate
4, 0.05% MgSO
4, 0.02% Fe
2+inner complex, 0.05% H
3bO
3be adjusted to chemical combination state composite fertilizer just finished product;
(4) filtrate dries: by step 3) the chemical combination state composite fertilizer that obtains just finished product be placed in baker, adopt heat-up rate to be that 3 DEG C/min is warming up to 55 DEG C, dry 0.9h, adjustment moisture content is 4%, detects packaging, can obtain fertilizer special for tobacco.
Embodiment 3
Prepare a production method for potassium primary phosphate by-product fertilizer special for tobacco, comprise the following steps:
(1) raw material preparation mixing: be that 1.6:1 is in stirring-type reactor according to mol ratio by phosphoric acid and carboxamide, be that 5 DEG C/min is warming up to 80 DEG C with heat-up rate, the stirring velocity controlling stirring tank is that 210r/min is uniformly mixed reaction 5h, obtains Ureaphil intermediate slip;
(2) KH is prepared
2pO
4: again the potassium hydroxide 2h of 1.1mol is at the uniform velocity added containing in steps 1) in the reactor of obtained Ureaphil intermediate slip, and employing stirring speed is 205r/min stirring reaction 70min, obtains containing potassium Ureaphil slip;
(3) circulation crystallization filters: by step 2) obtain and be placed in cooling crystallizer be cooled to temperature 19 DEG C containing potassium Ureaphil slip, down cycles crystallization filtration treatment, and detect the nutrient content analyzed in filtrate, when content until nitrogen component is 15%, Vanadium Pentoxide in FLAKES component content is 4.5%, potassium oxide component content is 8.1%, stop crystallization and filter, acquisition filter cake is potassium primary phosphate, and adds the CaSO of 0.2% in filtrate
4, 0.03% MgSO
4, 0.01% H
3bO
3be adjusted to chemical combination state composite fertilizer just finished product;
(4) filtrate dries: by step 3) the chemical combination state composite fertilizer that obtains just finished product be placed in baker, adopt heat-up rate to be that 3 DEG C/min is warming up to 50 DEG C, after dry 0.5h, adjustment moisture content is 3%, detects packaging, can obtain fertilizer special for tobacco.
Embodiment 4
Prepare a production method for potassium primary phosphate by-product fertilizer special for tobacco, comprise the following steps:
(1) raw material preparation mixing: by concentration be 48% phosphoric acid solution and carboxamide be that 1:1.5 is in stirring-type reactor according to mol ratio, be that 5 DEG C/min is warming up to 150 DEG C with heat-up rate, the stirring velocity controlling stirring tank is that 210r/min is uniformly mixed reaction 4.8h, obtains Ureaphil intermediate slip;
(2) KH is prepared
2pO
4: again the potassium hydroxide 2h of 1.3mol is at the uniform velocity added containing in steps 1) in the reactor of obtained Ureaphil intermediate slip, and employing stirring speed is 160r/min stirring reaction 30min, obtains containing potassium Ureaphil slip;
(3) circulation crystallization filters: by step 2) obtain and be placed in cooling crystallizer be cooled to temperature 17 DEG C containing potassium Ureaphil slip, down cycles crystallization filtration treatment, and detect the nutrient content analyzed in filtrate, until nitrogen component content be 16%, Vanadium Pentoxide in FLAKES component content is 2%, potassium oxide component content is 9% time, stop crystallization and filter, acquisition filter cake is potassium primary phosphate, and adds the MgSO of 0.05% in filtrate
4, 0.02% Fe
2+inner complex, 0.02% H
3bO
3be adjusted to chemical combination state composite fertilizer just finished product;
(4) filtrate dries: by step 3) the chemical combination state composite fertilizer that obtains just finished product be placed in baker, adopt heat-up rate to be that 3 DEG C/min is warming up to 48 DEG C, dry 0.8h, adjustment moisture content is 3%, detects packaging, can obtain fertilizer special for tobacco.
Embodiment 5
Prepare a production method for potassium primary phosphate by-product fertilizer special for tobacco, comprise the following steps:
(1) raw material preparation mixing: by concentration be 48% phosphoric acid solution and concentration be 35% carbon amide solution be that 1:1.4 is in stirring-type reactor according to mol ratio, be that 5 DEG C/min is warming up to 120 DEG C with heat-up rate, the stirring velocity controlling stirring tank is that 160r/min is uniformly mixed reaction 4.5h, obtains Ureaphil intermediate slip;
(2) KH is prepared
2pO
4: again the potassium hydroxide solid 2.5h of 1.2mol is at the uniform velocity added containing in steps 1) in the reactor of obtained Ureaphil intermediate slip, and employing stirring speed is 190r/min stirring reaction 50min, obtains containing potassium Ureaphil slip;
(3) circulation crystallization filters: by step 2) obtain and be placed in cooling crystallizer be cooled to temperature 25 DEG C containing potassium Ureaphil slip, down cycles crystallization filtration treatment, and detect the nutrient content analyzed in filtrate, until nitrogen component content be 16.5%, Vanadium Pentoxide in FLAKES component content is 3%, potassium oxide component content is 11.5% time, stop crystallization and filter, acquisition filter cake is potassium primary phosphate, and adds the Fe of 0.02% in filtrate
2+inner complex, 0.03% H
3bO
3be adjusted to chemical combination state composite fertilizer just finished product;
(4) filtrate dries: by step 3) the chemical combination state composite fertilizer that obtains just finished product be placed in baker, adopt heat-up rate to be that 3 DEG C/min is warming up to 54 DEG C, dry 0.85h, adjustment moisture content is 3.5%, detects packaging, can obtain fertilizer special for tobacco.
Embodiment 6
Prepare a production method for potassium primary phosphate by-product fertilizer special for tobacco, comprise the following steps:
(1) raw material preparation mixing: get 150g massfraction be 64.88% phosphoric acid join 500ml be with whipping appts beaker in, regulating thermostatic water-bath is to 100 DEG C, start and stir, rotating speed 0.15kr/min, slowly adds the CO (NH that 120g massfraction is 60%
2)
2.After reaction 2h, Temperature fall crystallization 24h under mixing speed 0.1kr/min, pour out washing crystal after mother liquor, suction filtration, filter cake is put into thermostatic drying chamber and be dried to constant weight at 50 DEG C, intermediate H
3p0
4cO (NH
2)
2;
(2) potassium primary phosphate is prepared: the concentration of getting 100g is the H of 62.5%
3p0
4cO (NH
2)
2crystal joins in the beaker of 500ml band whipping appts and dissolves, and puts into thermostat water bath, is adjusted to 120 DEG C and constant temperature, start and stir, rotating speed 0.10kr/min, dissolve.After reaction 15min dissolves solution to be moved in 25 DEG C of thermostat water baths and rotating speed is adjusted to 0.20kr/min, slowly adding the potassium hydroxide solution that 53g concentration is 40%;
(3) circulation crystallization filters: after dripping, regulate mixing speed circulation crystallization 15min to 0.18kr/min and at 20 DEG C, after pouring out mother liquor, suction filtration, filter cake is put into thermostatic drying chamber and be dried to constant weight at 50 DEG C, obtains potassium primary phosphate and filtrate, adds appropriate zinc phosphate, borax, ferrous sulfate trace element and mineralized material additive, the content of adjustment solution N P and K, recording N:P2O5:K2O is: 15-18%:1.5-4.5%:8.1-14.4%;
(4) filtrate dries: dry cooling, obtains the special nitrogen-phosphorus-potassium compound fertilizer of efficient tobacco.
Test example: the technique effect of technical scheme of the present invention and product performance are described further below in conjunction with specific embodiment content.
Test example 1 potassium dihydrogen phosphate product production cost and quality product test experience
By carrying out the cost compare in potassium dihydrogen phosphate product production process according to the production method of embodiments of the invention 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 and embodiment 6 and traditional Methods For The Manufacture of Potassium Dihydrogen Phosphate; And according to GBT278-1997 " People's Republic of China's chemical industry standard " feed grade potassium primary phosphate test experience method, detect the quality of the product that embodiments of the invention 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 are produced, its result is as shown in table 1.
The quality examination of table 1 traditional method and embodiments of the invention production potassium dihydrogen phosphate product and the comparative result of its cost:
| ? | Purity >=% | Moisture≤% | As≤％ | Pb≤％ |
| Tradition | 97 | 0.4 | 0.0009 | 0.0019 |
| Embodiment 1 | 98.1 | 0.3 | 0.0008 | 0.0017 |
| Embodiment 2 | 99.2 | 0.35 | 0.0007 | 0.0018 |
| Embodiment 3 | 97.5 | 0.45 | 0.00085 | 0.0014 |
| Embodiment 4 | 97.3 | 0.5 | 0.0009 | 0.0017 |
| Embodiment 5 | 96.9 | 0.61 | 0.00095 | 0.0016 |
| Embodiment 6 | 99.1 | 0.29 | 0.00081 | 0.0015 |
| Standard | 98 | 0.5 | 0.001 | 0.002 |
Note: the conventional art adopted in table refers to that the employing patent No. is " co-production of a kind of potassium primary phosphate, S-based compound fertilizer and polymerize aluminum chloride " of 200710048214.6
As can be seen from table, the standard of the potassium dihydrogen phosphate product that technical scheme of the present invention is produced can close to feed grade potassium dihydrogen phosphate product, and the purity of product is also higher, has significant progressive.
Test example 2 tobacco plants specific absorption and impact experiment
Adopt cultivation technique without soil to be grouped into three groups respectively, often organize three basin crops, often organizing label is respectively A, B, C, and each each basin organized respectively label is A1, A2, A3; B1, B2, B3; C1, C2, C3; And in each basin, plant a tobacco respectively, and three basins of composite fertilizer of the prior art to A group are adopted to adopt 0.1kg, 0.2kg, 0.4kg to carry out fertilizer treatment respectively; Adopt the patent No. be 200710048214.6 " co-production of a kind of potassium primary phosphate, S-based compound fertilizer and polymerize aluminum chloride " S-based compound fertilizer three basins to B group of obtaining adopt 0.1kg, 0.2kg, 0.4kg to carry out fertilizer treatment respectively; Adopting embodiment 1 of the present invention, embodiment 2, embodiment 6 to obtain three basins of composite fertilizer to C group adopts 0.25kg to carry out fertilizer treatment; Cultivate after 1 month, and detect the n-p-k element in the nutrient solution in three groups respectively, and observe the growth conditions of tobacco, its result is as shown in table 2 below:
Table 2 tobacco plants on the specific absorption of azophoska and azophoska on the impact of tobacco
| ? | Nitrogen % | Phosphorus % | Potassium % | Upgrowth situation |
| A1 | 11％ | 10％ | 9％ | Blade yellowing is serious |
| A2 | 9％ | 8％ | 10％ | Plant strain growth unshapeliness |
| A3 | 10％ | 11％ | 8％ | Blade yellowing |
| B1 | 8％ | 9％ | 6％ | Yellowing |
| B2 | 6％ | 8％ | 7％ | Plant unshapeliness |
| B3 | 7％ | 7％ | 8％ | Normally |
| C1 | 4％ | 3％ | 2％ | Normally |
| C2 | 2％ | 3％ | 2％ | Normally |
| C3 | 3％ | 4％ | 2％ | Normally |
As can be seen from the above table, tobacco special efficient composite fertilizer of the present invention, fully can be absorbed by tobacco, utilization ratio is higher, and the content of each element of N P and K is comparatively balanced, can maintain the normal demand of tobacco, has significant economic benefit.
Claims (10)
1. prepare the production method of potassium primary phosphate by-product fertilizer special for tobacco for one kind, it is characterized in that, adopt phosphoric acid to be (1.2-1.6) with carboxamide according to mol ratio: 1 mixes, and is that 5 DEG C/min is warming up to 80-160 DEG C with heat-up rate, stirring reaction 4-5h, obtains intermediate slip, this intermediate slip is adopted to mix with 1.1-1.3mol alkaline potassium salt again, after reaction terminates, obtain nitrogenous, phosphorus, the slip of potassium, and by nitrogenous, phosphorus, the slip of potassium is placed in cooling crystallizer and carries out decrease temperature crystalline filtration treatment, make filtrate circulation crystallization process in cooling crystallizer, and detect analysis filtrate, when the content of nitrogen component is 15-18%, Vanadium Pentoxide in FLAKES component content is 1.5-4.5%, when potassium oxide component content is 8.1-14.4%, stop crystallization and filter, the filter cake obtained is potassium dihydrogen phosphate product, in filtrate, add trace compound be adjusted to chemical combination state composite fertilizer just finished product, and first finished product is placed in baker, adopt heat-up rate to be that 3 DEG C/min is warming up to 45-55 DEG C, after dry 0.5-1h, adjustment moisture content is 3-4%, can obtain tobacco special chemical combination state composite fertilizer.
2. prepare the production method of potassium primary phosphate by-product fertilizer special for tobacco as claimed in claim 1, it is characterized in that, comprise the following steps:
(1) raw material preparation mixing: be (1.2-1.6) according to mol ratio by phosphoric acid and carboxamide: 1 in stirring-type reactor, be that 5 DEG C/min is warming up to 80-160 DEG C with heat-up rate, the stirring velocity controlling stirring tank is that 100-210r/min is uniformly mixed reaction 4.2-4.8h, obtains intermediate slip;
(2) KH is prepared
2pO
4: again the alkaline potassium salt 2-3h of 1.1-1.3mol is at the uniform velocity added containing in steps 1) in the reactor of obtained intermediate slip, and employing stirring speed is 160-205r/min stirring reaction 30-70min, obtains nitrogenous, phosphorus, potassium slip;
(3) circulation crystallization filters: by step 2) obtain nitrogenous, phosphorus, potassium slip and be placed in cooling crystallizer and be cooled to temperature≤20 DEG C, down cycles crystallization filtration treatment, and detect the nutrient content analyzed in filtrate, until nitrogen component content be 16-17%, Vanadium Pentoxide in FLAKES component content is 2-4%, potassium oxide component content is 9-14% time, stop crystallization and filter, acquisition filter cake is potassium primary phosphate, and in filtrate, add other trace compounds adjustment fertilizer structure becomes chemical combination state composite fertilizer just finished product;
(4) filtrate dries: by step 3) the chemical combination state composite fertilizer that obtains just finished product be placed in baker, adopt heat-up rate to be that 3 DEG C/min is warming up to 45-55 DEG C, dry 0.8-0.9h, adjustment moisture content is 3-4%, detect packaging, tobacco special chemical combination state composite fertilizer can be obtained.
3. prepare the production method of potassium primary phosphate by-product fertilizer special for tobacco as claimed in claim 1 or 2, it is characterized in that, described phosphoric acid and carboxamide react, and are phosphoric acid solution and carboxamide solid reaction.
4. prepare the production method of potassium primary phosphate by-product fertilizer special for tobacco as claimed in claim 1 or 2, it is characterized in that, described phosphoric acid and carboxamide react, and are phosphoric acid solution and carboxamide liquid reactions.
5. prepare the production method of potassium primary phosphate by-product fertilizer special for tobacco as claimed in claim 1 or 2, it is characterized in that, described phosphoric acid and carboxamide react, and are phosphoric acid solid and carboxamide liquid reactions.
6. prepare the production method of potassium primary phosphate by-product fertilizer special for tobacco as claimed in claim 1 or 2, it is characterized in that, described alkaline potassium salt is potassium hydroxide; Described trace compound is CaSO
4, MgSO
4, Fe
2+inner complex, H
3bO
3in one or more mixtures.
7. prepare the production method of potassium primary phosphate by-product fertilizer special for tobacco as claimed in claim 1 or 2, it is characterized in that, described composite fertilizer's chemical combination state just finished product, wherein nitrogen component content is 16.5%, Vanadium Pentoxide in FLAKES component content is 3%, potassium oxide component content is 11-13%.
8. prepare the production method of potassium primary phosphate by-product fertilizer special for tobacco as claimed in claim 1 or 2, it is characterized in that, it is by the nitrogen contained in filtrate, phosphorus, potassium three kinds of macroelement that filtrate is analyzed in described detection, determination method traditionally, its content is adjusted, its content is reached when nitrogen component is 16%, Vanadium Pentoxide in FLAKES composition is 3.5%, potassium oxide composition is 12%, stop the crystallization treatment step to filtrate.
9. prepare the production method of potassium primary phosphate by-product fertilizer special for tobacco as claimed in claim 1 or 2, it is characterized in that, described fertilizer special for tobacco is chemical combination state Chemical Mixed Fertilizer.
10. prepare the production method of potassium primary phosphate by-product fertilizer special for tobacco as claimed in claim 9, it is characterized in that, described chemical combination state composite fertilizer, containing following N P and K chemical combination state structural formula in its composition:
wherein, the dotted line between carbon atom and Sauerstoffatom represents to there is coordinate bond between C atom and O atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410478386.7A CN104250001B (en) | 2014-09-19 | 2014-09-19 | A kind of production method preparing potassium primary phosphate by-product fertilizer special for tobacco |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410478386.7A CN104250001B (en) | 2014-09-19 | 2014-09-19 | A kind of production method preparing potassium primary phosphate by-product fertilizer special for tobacco |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104250001A true CN104250001A (en) | 2014-12-31 |
| CN104250001B CN104250001B (en) | 2016-03-16 |
Family
ID=52185292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410478386.7A Expired - Fee Related CN104250001B (en) | 2014-09-19 | 2014-09-19 | A kind of production method preparing potassium primary phosphate by-product fertilizer special for tobacco |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104250001B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060648A (en) * | 1990-10-08 | 1992-04-29 | 邢新华 | Polybasic fertilizer |
| CN101215202A (en) * | 2007-12-27 | 2008-07-09 | 山东大学 | Leaf vegetable release-controlling fertilizer |
| CN104003362A (en) * | 2014-05-20 | 2014-08-27 | 贵阳中化开磷化肥有限公司 | Production method of dipotassium phosphate |
| CN104016322A (en) * | 2014-05-20 | 2014-09-03 | 贵阳中化开磷化肥有限公司 | Production method for diammonium hydrogen phosphate |
-
2014
- 2014-09-19 CN CN201410478386.7A patent/CN104250001B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060648A (en) * | 1990-10-08 | 1992-04-29 | 邢新华 | Polybasic fertilizer |
| CN101215202A (en) * | 2007-12-27 | 2008-07-09 | 山东大学 | Leaf vegetable release-controlling fertilizer |
| CN104003362A (en) * | 2014-05-20 | 2014-08-27 | 贵阳中化开磷化肥有限公司 | Production method of dipotassium phosphate |
| CN104016322A (en) * | 2014-05-20 | 2014-09-03 | 贵阳中化开磷化肥有限公司 | Production method for diammonium hydrogen phosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104250001B (en) | 2016-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104261374B (en) | A kind of production method preparing primary ammonium phosphate by-product Radix Astragali special fertilizer | |
| CN104250001B (en) | A kind of production method preparing potassium primary phosphate by-product fertilizer special for tobacco | |
| CN104261377B (en) | A kind of production method preparing potassium primary phosphate by-product shepherd's purse special fertilizer | |
| CN104261375B (en) | Production method for preparing ammonium dihydrogen phosphate and byproduct special fertilizer for radix scutellariae | |
| CN104261378B (en) | A kind of production method preparing potassium dihydrogen phosphate by-product Fructus Lycii special fertilizer | |
| CN104276558B (en) | A kind of production method preparing calcium hydrogen phosphate by-product Fructus Piperis special fertilizer | |
| CN104276561B (en) | A kind of production method preparing calcium hydrogen phosphate by-product Pericarpium Zanthoxyli special fertilizer | |
| CN104291304B (en) | A kind of production method preparing calcium hydrogen phosphate by-product calabash special fertilizer | |
| CN104261381B (en) | A kind of production method preparing monocalcium phosphate by-product chili special-purpose fertilizer | |
| CN104291294B (en) | A kind of production method preparing tripotassium phosphate by-product Specialized fertilizer for litchi | |
| CN104261938B (en) | Production method for preparation of calcium dihydrogen phosphate and by-production of special fertilizer for cauliflowers | |
| CN104310331B (en) | A kind of production method preparing ammonium phosphate by-product Arillus Longan special fertilizer | |
| CN104250000B (en) | Method for co-producing fertilizer special for white paeony root during preparation of monopotassium phosphate | |
| CN104310346B (en) | A kind of production method preparing dipotassium hydrogen phosphate by-product spinach special fertilizer | |
| CN104276556A (en) | Production method of monopotassium phosphate with byproduct fertilizer specially used for towel gourd | |
| CN104291303B (en) | A kind of method preparing potassium dihydrogen phosphate coproduction Semen Sesami composite fertilizer special | |
| CN104310349B (en) | A kind of production method preparing tripotassium phosphate by-product Caulis et Folium Lini special fertilizer | |
| CN104291308A (en) | Production method for preparing tricalcium phosphate and coproducing special fertilizer for rye | |
| CN104291296B (en) | A kind of production method preparing dipotassium hydrogen phosphate by-product tomato special fertilizer | |
| CN104310352B (en) | A kind of production method preparing dipotassium hydrogen phosphate by-product Caulis et Folium Lactucae sativae special fertilizer | |
| CN104310340B (en) | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for beet as byproduct | |
| CN104291287A (en) | Producing method for preparing ammonium dihydrogen phosphate byproduct as special fertilizer for white gourd | |
| CN104276557A (en) | Production method for preparing tripotassium phosphate and byproduct special fertilizer for sunflowers | |
| CN104291302B (en) | A kind of production method preparing tripotassium phosphate by-product special fertilizer for Chinese goosebeery | |
| CN104276550A (en) | Production method for preparing special fertilizer for dasheen from diammonium hydrogen phosphate by-products |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160215 Address after: No. 237 Jinyang City Kailin Lake District Road 550009 Guizhou city of Guiyang Province Applicant after: GUIZHOU KAILIN GROUP Co.,Ltd. Applicant after: GUIZHOU KEXIN METALLURGICAL Co.,Ltd. Applicant after: Guizhou University Address before: Xifeng County in Guizhou Province, Guiyang city town 551109 Applicant before: GUIYANG SINOCHEM KAILIN FERTILIZER Co.,Ltd. Applicant before: GUIZHOU KEXIN METALLURGICAL Co.,Ltd. Applicant before: Guizhou University |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160316 Termination date: 20210919 |