CN102583451B - Method for preparing sodium sulfate and magnesium nitride compound fertilizer by processing astrakhanite - Google Patents

Method for preparing sodium sulfate and magnesium nitride compound fertilizer by processing astrakhanite Download PDF

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CN102583451B
CN102583451B CN 201210076190 CN201210076190A CN102583451B CN 102583451 B CN102583451 B CN 102583451B CN 201210076190 CN201210076190 CN 201210076190 CN 201210076190 A CN201210076190 A CN 201210076190A CN 102583451 B CN102583451 B CN 102583451B
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mgso
mother liquor
bloedite
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composition
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CN102583451A (en
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曹吉林
郭宏飞
张广林
李琳
杨璐
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Hebei University of Technology
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Hebei University of Technology
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Abstract

The invention relates to a process for preparing a sodium sulfate and magnesium nitride compound fertilizer by processing astrakhanite, which comprises the following steps of: mixing the astrakhanite, ammonium sulfate with water to form a mixed system; enabling the composition of the mixed system to be on the connecting line of an astrakhanite composition point and an ammonium sulfate composition point of an Na2SO4-MgSO4-(NH4)2SO4-H2O system phase diagram at the temperature of 25 DEG C; then, reacting at the constant temperature of 25 DEG C, and then, separating the magnesium nitride compound fertilizer by crystallization to obtain a mother solution B; then, adding Na2CO3 to the mother solution B; reacting at the room temperature to separate magnesium carbonate crystal by crystallization to obtain a mother solution C; performing cooling crystallization on the mother solution C at the temperature of 0 DEG C to separate Na2SO4.10H2O crystal by crystallization to obtain a mother solution D; adding the astrakhanite, the ammonium sulfate and the water to the mother solution D; and reacting at the temperature of 25 DEG C to separate the magnesium nitride compound fertilizer by crystallization. The compositions and the mass percent compositions of the mother solutions meet the composition range of the mother solution B, and the mother solutions can be circularly produced. The process for preparing the sodium sulfate and magnesium nitride compound fertilizer by processing the astrakhanite has the advantages that no waste liquor or waste residue or waste gas is discharged, generated little magnesium carbonate is also an important chemical raw material, and no environmental pollution is generated.

Description

A kind of by bloedite processing and preparing sodium sulfate and the multiple fertile method of nitrogen magnesium
Technical field
Technical scheme of the present invention relates to sodium sulfate and the multiple fertile preparation method of nitrogen magnesium, and is particularly a kind of by bloedite processing and preparing sodium sulfate and the multiple fertile technology of nitrogen magnesium.
Background technology
The bloedite ore deposit is salt lake, the common a kind of surficial deposit thing in playa lake area, be commonly called as nitre plate or ground mirabilite, extremely abundant in china natural resources, distributed more widely, only Yuncheng, Shanxi salt pond reserves are just more than 20,000,000 tons, and the ground such as Alashan League that are located in the Inner Mongol are a mass of tens tons bloedite ore deposit especially.Processing exploitation at this resource, people have just carried out a large amount of research before 30 years, yet because the bloedite ore deposit is the double salt that sodium sulfate and sal epsom are formed, processing separates relatively difficulty, and this resource realizes that never good industrialization exploitation utilizes at present.
Salt-water system equilibrium and phasor that more complete sal epsom and sodium sulfate have been arranged at present, from Phase Diagram Analysis as can be known the relatively more suitable method of separating of sal epsom and sodium sulfate be, elder generation's low temperature crystallization extracts sodium sulfate, high temperature evaporation concentration extraction sal epsom then, but Na 2SO 4-MgSO 4-H 2The double salt that sodium sulfate and sal epsom form in the O system is interval big, produces separating out of ice when freezing temp is lower than zero degree, just might obtain pure sodium sulfate so freezing temp and solution composition must be controlled in a very narrow and small scope; When the temperature of low temperature crystallization is higher, it is less relatively then to separate out the sodium sulfate amount, produces the mother liquor be rich in sal epsom in a large number, causes to extract sal epsom need evaporate a large amount of moisture from this mother liquor, and increased the difficulty that sodium sulfate separates with sal epsom, can only obtain a spot of sal epsom.For this reason, some new viewpoints have appearred in the utilization to the bloedite ore deposit, the yellow snow jasmine has carried out the research of bloedite and Repone K prepared in reaction vitriolate of tartar, Wang Linxiang has carried out alkaline process (sodium hydroxide or yellow soda ash) and has changed the sal epsom in the bloedite research of sodium sulfate into, but does not also have a good bloedite ore deposit exploitation machining process route so far.
Sal epsom is had many uses, and as fertilizer sources is a big field of its application.China's fertilizer grade sal epsom annual requirement is 520,000 t/a, amounts to magnesium sulfate monohydrate about 300,000 t/a, and the domestic sal epsom fertilizer of using at present estimates to have only several ten thousand t/a, only is about 10% of annual requirement.Ammonium sulfate can form MgSO as the widely used nitrogenous fertilizer of farm crop with sal epsom in the aqueous solution 4(NH 2) 2SO 46H 2O double salt, this double salt has the effect of fertiliser containing magnesium and nitrogenous fertilizer simultaneously.Therefore, the present invention is directed to bloedite processing and separate difficult characteristics, proposing with bloedite and ammonium sulfate is raw material direct production MgSO 4(NH 2) 2SO 46H 2O composite fertilizer and Na 2SO 4Novel process, this technology can realize easily that sodium sulfate separates with sal epsom in the bloedite, can overcome the shortcoming that traditional sal epsom production need be evaporated the large quantity of moisture highly energy-consuming, has the green energy conservation advantage.
Summary of the invention
The invention provides and a kind of the associating produce sodium sulfate and the multiple fertile method of nitrogen magnesium, this method is raw material with bloedite and ammonium sulfate, can be mass-produced, when producing sodium sulfate, it is multiple fertile to produce nitrogen magnesium again, and it is simple to have production technique, equipment requirements is low, three-waste free discharge and energy-conservation characteristics.
Technical scheme of the present invention is:
A kind of by bloedite processing and preparing sodium sulfate and the multiple fertile technology of nitrogen magnesium, may further comprise the steps:
(1) with bloedite (MgSO 4Na 2SO 44H 2O), ammonium sulfate and water mixes and forms mixed system A, and the composition of mixed system A material is met at 25 ℃ of Na 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2Bloedite (the MgSO of O system phase diagram 4Na 2SO 44H 2O) form point and ammonium sulfate and form on the some line, wherein two of mixed system A end points are M 0And N 0, some M 0The quality proportioning of system consists of: bloedite: ammonium sulfate: water=1: 0.5565: 1.764, N 0The quality proportioning of system is: bloedite: ammonium sulfate: water=1: 0.725: 3.267; Then mixed system A is joined in the reactor, behind the mechanical stirring reaction 120min, nitrogen magnesium is fertilizer (MgSO again in 25 ℃ of thermostatic baths 4(NH 4) 2SO 46H 2O) will crystallization separate out, after the crystallization of whizzer centrifugal treating and the drying, just can get the multiple fertilizer product of nitrogen magnesium; Mother liquid obtained B; The composition of mother liquor B at E between the F, Na when E and F are 25 ℃ 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2The MgSO of O system phase diagram 4(NH 4) 2SO 46H 2O and Na 2SO 410H 2Point on the O two solid phase saturated lines, its mid point E are that mother liquor quality percentage composition is Na 2SO 4, 18.84%; MgSO 4, 0.3896%; (NH 4) 2SO 4, 7.536%; H 2O, 73.23%; Point F mother liquor quality percentage composition is Na 2SO 4, 10.76%; MgSO 4, 0.2817%; (NH 4) 2SO 4, 8.654%; H 2O, 80.30%.
(2) above-mentioned composition is joined in the reactor to the mother liquor B between the F at E, add Na again 2CO 3, its add-on be with mother liquor B in contained MgSO 4The amount of theoretical reaction, i.e. mass ratio MgSO 4: Na 2CO 3=1: 0.8811, mechanical stirring reaction at ambient temperature, through 30min, the magnesiumcarbonate crystal will be separated out in crystallization, the crystallization of whizzer centrifugal treating, 80 ℃ of dryings of solid phase can get magnesiumcarbonate; Mother liquid obtained C, C consists of at 0 ℃ of Na 2SO 4-(NH 4) 2SO 4-H 2The E of O system phase diagram 1And F 1On the straight line, E wherein 1Mother liquor quality percentage composition is: Na 2SO 4, 19.28%; (NH 4) 2SO 4, 7.531%; H 2O, 73.19%; F 1Mother liquor quality percentage composition is Na 2SO 4, 11.09%; (NH 4) 2SO 4, 8.650%; H 2O, 80.26%.
(3) (2) gained is formed at E 1To F 1Between mother solution C add in the reactor, mechanical stirring crystallisation by cooling in 0 ℃ of thermostatic bath, through 120min, Na 2SO 410H 2The O crystal will be separated out in crystallization; Through the whizzer centrifugal treating, solid phase is put into 60 ℃ of baking ovens and is carried out drying and can get white plates crystal product Na 2SO 410H 2O; The crystallization filtrate of gained is mother liquor D, and it is formed at 0 ℃ of Na 2SO 4-(NH 4) 2SO 4-H 2The E of O system phase diagram 2F 2On the straight line, E 2And F 2Na when being 0 ℃ 2SO 4-(NH 4) 2SO 4-H 2The Na of O system phase diagram 2SO 410H 2Point on the O saturated line, its mid point E 2Mother liquor quality percentage composition be: Na 2SO 4, 5.865%; (NH 4) 2SO 4, 11.61%; H 2O, 82.53%; Point F 2Mother liquor quality percentage composition be Na 2SO 4, 5.601%; (NH 4) 2SO 4, 10.09%; H 2O, 84.31%.
(4) the mother liquor D to (3) gained adds bloedite (MgSO 4Na 2SO 44H 2O), ammonium sulfate and water, form and be mixed into system W, make composition Na in the time of 25 ℃ of system W 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2The M of O system phase diagram 1N 1On the straight line, its mid point M 1Composition quality proportioning be: mother liquor E 2: bloedite (MgSO 4Na 2SO 44H 2O): ammonium sulfate: water=1: 0.5426: 0.208: 0.3585; N 1The quality proportioning be: mother liquor F 2: bloedite (MgSO 4Na 2SO 44H 2O): ammonium sulfate: water=1: 0.1634: 0.0610: 0.1075.Mechanical stirring reaction in 25 ℃ of thermostatic baths, through 120min, the multiple fertile (MgSO of nitrogen magnesium 4(NH 4) 2SO 46H 2O) will crystallization separate out, after the whizzer centrifugal treating drying, just can get the multiple fertilizer product of nitrogen magnesium; The mother liquid obtained Na that consists of 2SO 4, MgSO 4, (NH 4) 2SO 4And H 2O, and its quality percentage composition meets the compositing range that obtains mother liquor B in the step (1), can form to add according to (2), the required composition of (3) and (4) step successively to constitute cyclic production.
It is one of following that the composition quality proportioning of the mixture system A that adds in the described step (1) is specially:
Figure BDA0000145711550000031
It is one of following that the composition quality proportioning of the mixture system W that adds in the described step (4) is specially:
Figure BDA0000145711550000032
The reaction conditions gentleness that the present invention is used, easy to operate, more outstanding substantive distinguishing features is, is feedstock production nitrogen magnesium compound fertilizer (MgSO with the bloedite 4(NH 4) 2SO 46H 2O) and during sal glauberi, only need 25 ℃ of crystallizations of normal temperature and 0 ℃ of crystallisation by cooling sepn process of low temperature, do not exist the evaporation concentration of mother liquor just can realize stable circulation production, significantly reduced the separation tooling cost of bloedite, open defect such as separating difficulty is big when having overcome bloedite traditional mode of production sodium sulfate and sal epsom, the mother liquid evaporation energy consumption is big, low in economic efficiency.
Above-mentioned beneficial effect is embodied in:
Bloedite and ammonium sulfate are raw material production magnesium compound fertilizer (MgSO 4(NH 4) 2SO 46H 2O) and sal glauberi technology simple, the operational condition elastic range is big, only needs the construction equipments that routinize such as normal pressure mixing reactor and separating and filtering, do not need equipment such as evaporation concentration, this has not only reduced facility investment, and has saved production energy consumption, has improved economic benefit.In the stable circulation production process, no waste liquid, waste residue and exhaust gas emission, a small amount of magnesiumcarbonate of generation also is important industrial chemicals, does not have environmental pollution.
Description of drawings:
Fig. 1 is production process route figure of the present invention.
Fig. 1 technology is explained as follows: bloedite (MgSO 4Na 2SO 44H 2O), ammonium sulfate, water and circulation return mother liquor and be mixed to join by a certain percentage in the reactor, in 25 ℃ of thermostatic baths after the mechanical stirring reaction, the multiple fertile (MgSO of nitrogen magnesium 4(NH 4) 2SO 46H 2O) will crystallization separate out, isolate crystallization and drying with whizzer after, just can get the multiple fertilizer product of nitrogen magnesium; Mother liquid obtainedly contain a spot of sal epsom for E (F), add and MgSO 4The yellow soda ash amount of theoretical reaction will form the magnesiumcarbonate precipitation, the crystallization of whizzer centrifugal treating, and 80 ℃ of dryings of solid phase can get magnesiumcarbonate; Mother liquid obtained E 1(F 1) add in the reactor, mechanical stirring crystallisation by cooling in 0 ℃ of thermostatic bath just has Na 2SO 410H 2The O crystal will be separated out in crystallization, and through the whizzer centrifugal treating, solid phase is put into 60 ℃ of baking ovens and carried out drying, just can get white plates crystal product Na 2SO 410H 2O; The crystallization filtrate E of gained 2(F 2) be circulating mother liquor, can return and bloedite (MgSO 4Na 2SO 44H 2O), ammonium sulfate, water batching are carried out the multiple fertilizer of next nitrogen magnesium and Na 2SO 410H 2O produces.
Na when Fig. 2 gets 25 ℃ for contriver institute 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2The dried salt figure of O system
Na when Fig. 3 has 0 ℃ for document 2SO 4-(NH 4) 2SO 4-H 2The O system phase diagram
Embodiment:
Na when the contriver studies 25 ℃ that record 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2O system equilibrium (seeing Table 1)
Na during 25 ℃ in table 1 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2O system part equilibrium
Illustrate: S 10-Na 2SO 410H 2O; S H-NaNH 4SO 42H 2O; M N-MgSO 4(NH 4) 2SO 46H 2O; M 7-MgSO 47H 2O; M S-MgSO 4Na 2SO 44H 2O; N-(NH 4) 2SO 4
Mechanism of the present invention is: system consists of mass ratio M in accompanying drawing 2 1(MgSO 4: Na 2SO 4: (NH 4) 2SO 4: H 2O=1: 1.48: 1.660: 6.661) and N 1(MgSO 4: Na 2SO 4: (NH 4) 2SO 4: H 2O=1: 2.312: 2.752: 16.76) in the time of between, 25 ℃ down fully dissolving crystallized after, can get solid phase is MgSO 4(NH 4) 2SO 46H 2O, after the solid phase filtering separation corresponding residue mother liquor form point in accompanying drawing 2 E (the quality percentage composition is Na 2SO 4, 18.84%; MgSO 4, 0.3896%; (NH 4) 2SO 4, 7.536%; H 2O, 73.23%) (the quality percentage composition is Na for point and F 2SO 4, 10.76%; MgSO 4, 0.2817%; (NH 4) 2SO 4, 8.654%; H 2O, 80.30%) between the point, adds the yellow soda ash of 0.8811 times of its contained sal epsom quality in the system between E and the F respectively, can get the magnesiumcarbonate precipitation behind the stirring reaction.Mother liquor behind the filtering separation magnesiumcarbonate can be separated out the sal glauberi solid phase behind 0 ℃ of following crystallisation by cooling, mother liquor is formed the corresponding E in accompanying drawing 3 of point behind the filtering separation sal glauberi 2(the quality percentage composition is Na 2SO 4, 5.865%; (NH 4) 2SO 4, 11.61%; H 2O, 82.53%.) and F 2(the quality percentage composition is Na 2SO 4, 5.601%; (NH 4) 2SO 4, 10.09%; H 2O, 84.31%.) between.To mother liquor E 2And F 2Between system in add bloedite, ammonium sulfate and water and then can adjust mixed system again and form point at M 1And N 1Between.Can realize solid phase MgSO thus 4(NH 4) 2SO 46H 2The cyclic production of O and sal glauberi.
Material system M recited above 1And N 1Can by chemical feedstocks directly join or made by following method: bloedite and ammonium sulfate and water (are equivalent to M in accompanying drawing 2 by mass ratio at 1: 0.5565: 1.7638 0) or (be equivalent to N in accompanying drawing 2 at 1: 0.7246: 3.267 0) carry out mixed preparing, 25 ℃ down when solid phase bloedite and ammonium sulfate abundant dissolving crystallized after, can get solid phase is MgSO 4(NH 4) 2SO 46H 2O, after the solid phase filtering separation residue mother liquor form point corresponding in accompanying drawing 2 E or a F point, add the yellow soda ash of 0.8811 times of its contained sal epsom quality in E or the F system respectively, can get the magnesiumcarbonate precipitation behind the stirring reaction.Mother liquor behind the filtering separation magnesiumcarbonate can be separated out the sal glauberi solid phase behind the abundant crystallisation by cooling down at 0 ℃, and mother liquor is formed the corresponding E in accompanying drawing 3 of point behind the filtering separation sal glauberi 2Or F 2To mother liquor E 2Or F 2In add 0.5426 or 0.1634 times bloedite of quality, 0.208 or 0.061 times ammonium sulfate and 0.3585 or 0.1075 times respectively water then can adjust mixed system and form point and be M 1Or N 1
Fig. 2 is the Na that draws according to table 1 data 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2Phasor (dried salt figure) during 25 ℃ of O systems, among the figure: solid line is the crystallizing field boundary line, dotted line is the technological operation line; 3 of T, N and S represent pure MgSO respectively 4, (NH 4) 2SO 4And Na 2SO 4The composition point; D point and K point represented double salt MgSO respectively 4(NH 4) 2SO 46H 2O and bloedite (MgSO 4Na 2SO 44H 2O) composition point; Zone ABCK, KCEFQPSK, QGRP, GRN and BCEFQGND represent MgSO respectively 4(NH 4) 2SO 46H 2O, Na 2SO 410H 2O, NaNH 4SO 42H 2O, (NH 4) 2SO 4And MgSO 4(NH 4) 2SO 46H 2Single salt crystallizing field of O; The C point represents MgSO 4(NH 4) 2SO 46H 2O, Na 2SO 410H 2O and MgSO 4(NH 4) 2SO 46H 2Three salt of O are full point altogether, and the Q point represents MgSO 4(NH 4) 2SO 46H 2O, Na 2SO 410H 2O and NaNH 4SO 42H 2Three salt of O are full point altogether, G point representative (NH 4) 2SO 4, MgSO 4(NH 4) 2SO 46H 2O and NaNH 4SO 42H 2Three salt of O are full point altogether.
Fig. 3 is the Na that draws according to data in literature 2SO 4-(NH 4) 2SO 4-H 2Phasor during 0 ℃ of O system, among the figure: solid line is the crystallizing field boundary line, dotted line is the technological operation line; 3 of a, b and d represent pure Na respectively 2SO 4, (NH 4) 2SO 4And H 2The composition point of O; S 1Point and m point represent Na respectively 2SO 410H 2O and mistake double salt NaNH 4SO 42H 2The composition point of O; Zone S 1HfS 1, S 1Mh, mhe, meb and ebg represent Na respectively 2SO 410H 2The single salt crystallizing field of O, Na 2SO 410H 2O and NaNH 4SO 42H 2O two salt crystallizing fields, NaNH 4SO 42H 2The single salt crystallizing field of O, (NH 4) 2SO 4And NaNH 4SO 42H 2O two salt crystallizing fields and (NH 4) 2SO 4Single salt crystallizing field; The h point represents Na 2SO 410H 2O and NaNH 4SO 42H 2Two salt of O are full point altogether, and the e point represents NaNH 4SO 42H 2O and (NH 4) 2SO 4Two salt full point altogether.
From Fig. 2 and Fig. 3 as can be known: be raw material with bloedite and ammonium sulfate in the time of 25 ℃, water is mixed into them to be formed point and is the M among Fig. 2 0To N 0During system, just have double salt (MgSO 4(NH 4) 2SO 46H 2O) D separates out, and isolates the solid phase drying and is the multiple fertilizer of product nitrogen magnesium, and this moment, corresponding residue mother liquor point arrived F for E.In E and F system, add respectively and MgSO 4The yellow soda ash of theoretical reacting weight can get the magnesiumcarbonate precipitation behind stirring reaction, system composition point was the E among Fig. 3 after filtering separation was removed magnesiumcarbonate 1To F 1The point.E 1And F 1Mother liquor can be separated out the sal glauberi solid phase behind the abundant crystallisation by cooling down at 0 ℃, and mother liquor composition point corresponds to E behind the filtering separation sal glauberi in Fig. 3 and Fig. 2 2And F 2In accompanying drawing 2 to mother liquor E 2And F 2In add 0.5426 or 0.1634 times bloedite of quality, 0.208 or 0.061 times ammonium sulfate and 0.3585 or 0.1075 times water then can adjust mixed system and form point and be M 1And N 1From M 1And N 1Crystallization Separation goes out solid phase D (MgSO in the system 4(NH 4) 2SO 46H 2O) after, can obtain corresponding mother liquor E and F again, constitute the next nitrogen magnesium (MgSO that produces thus 4(NH 4) 2SO 46H 2O) circulation of multiple fertilizer and sodium sulfate.
Above-mentioned Phase Diagram Analysis proves, is the multiple fertile (MgSO of raw material production nitrogen magnesium with bloedite and ammonium sulfate 4(NH 4) 2SO 46H 2O) and the principle of sodium sulfate be feasible.
The process program of designing according to the present invention, specifically implement as follows:
Example 1 (operational path is seen Fig. 1)
(1) with the bloedite (MgSO of 100g 4Na 2SO 44H 2O), the water of the ammonium sulfate of 55.65g and the 176.38g system that is mixed into is formed M 0, join in the there-necked flask of 500ml, mechanical stirring reaction in 25 ℃ of thermostatic baths, through 120min, the multiple fertile (MgSO of nitrogen magnesium 4(NH 4) 2SO 46H 2O) will crystallization separate out, after 80 ℃ of dryings of whizzer centrifugal treating, just can get the multiple fertilizer product 105.1g of nitrogen magnesium.Mother liquid obtainedly be E 226.7g altogether, Na when mother liquor E is 25 ℃ 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2The MgSO of O system phase diagram 4(NH 4) 2SO 46H 2O and Na 2SO 410H 2Point on the O two solid phase saturated lines, recording E is that mother liquor quality percentage composition is Na 2SO 4, 18.84%; MgSO 4, 0.3896%; (NH 4) 2SO 4, 7.536%; H 2O, 73.23%.
(2) the E mother liquor with above-mentioned 226.7g joins in the there-necked flask of 500ml, adds the Na of 0.7782g again 2CO 3, mechanical stirring reaction at ambient temperature, through 30min, the magnesiumcarbonate crystal will be separated out in crystallization.The whizzer centrifugal treating, 80 ℃ of dryings of solid phase can get magnesiumcarbonate 0.619g; Mother liquid obtained is E 1Be total to 226.8g, mother liquor E 1Consist of at 0 ℃ of Na 2SO 4-(NH 4) 2SO 4-H 2The E of O system phase diagram 1And F 1On the straight line, F wherein 1Mother liquor quality percentage composition is Na 2SO 4, 11.09%; (NH 4) 2SO 4, 8.650%; H 2O, 80.26%; Record E 1Mother liquor quality percentage composition is: Na 2SO 4, 19.28%; (NH 4) 2SO 4, 7.531%; H 2O, 73.19%.
(3) with the mother liquor E of (2) gained 1Add in the there-necked flask of 500ml, mechanical stirring crystallisation by cooling in 0 ℃ of thermostatic bath, through 120min, Na 2SO 410H 2The O crystal will be separated out in crystallization.Through the whizzer centrifugal treating, solid phase is put into 60 ℃ of baking ovens and is carried out drying and can get white plates crystal product Na 2SO 410H 2O 83.04g.The filtrate that can get is E 2Be total to 147.1g, it is formed at 0 ℃ of Na 2SO 4-(NH 4) 2SO 4-H 2The E of O system phase diagram 2F 2On the straight line, E 2And F 2Na when being 0 ℃ 2SO 4-(NH 4) 2SO 4-H 2The Na of O system phase diagram 2SO 410H 2Point on the O saturated line, its mid point F 2Mother liquor quality percentage composition be Na 2SO 4, 5.601%; (NH 4) 2SO 4, 10.09%; H 2O, 84.31%, record E 2Mother liquor quality percentage composition be: Na 2SO 4, 5.865%; (NH 4) 2SO 4, 11.61%; H 2O, 82.53%.，
(4) with (3) gained 147.1g mother liquor E 2, 79.81g bloedite (MgSO 4Na 2SO 44H 2O) add the 500ml there-necked flask and in the water of the ammonium sulfate of 30.60g and 52.75g, mechanical stirring reaction in 25 ℃ of thermostatic baths, through 120min, the multiple fertile (MgSO of nitrogen magnesium 4(NH 4) 2SO 46H 2O) will crystallization separate out, after 80 ℃ of dryings of whizzer centrifugal treating, just can get the multiple fertilizer product 83.4g of nitrogen magnesium.Mother liquid obtained for E is total to 226.7g, record Na in the E mother liquor 2SO 4The quality percentage composition be 18.84%; MgSO 4The quality percentage composition be 0.3896%; (NH 4) 2SO 4The quality percentage composition be 7.536%; H 2The quality percentage composition of O is 73.23%, and it forms identical with the composition of mother liquor E in the preceding step (1).
(4) the E mother liquor that obtains can constitute cyclic production according to (2), (3) and (4) step successively.
Example 2 (operational path is seen Fig. 1)
(1) with the bloedite (MgSO of 100g 4Na 2SO 44H 2O), the water of the ammonium sulfate of 72.46g and the 326.7g system that is mixed into is formed N 0, join in the there-necked flask of 1000ml, mechanical stirring reaction in 25 ℃ of thermostatic baths, through 120min, the multiple fertile (MgSO of nitrogen magnesium 4(NH 4) 2SO 46H 2O) will crystallization separate out, after the whizzer centrifugal treating drying, just can get the multiple fertilizer product 104.5g of nitrogen magnesium.Mother liquid obtainedly be F 394.7g altogether, Na when mother liquor F is 25 ℃ 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2The MgSO of O system phase diagram 4(NH 4) 2SO 46H 2O and Na 2SO 410H 2Point on the O two solid phase saturated lines, recording F mother liquor quality percentage composition is Na 2SO 4, 10.76%; MgSO 4, 0.2817%; (NH 4) 2SO 4, 8.654%; H 2O, 80.30%;
(2) the F mother liquor with above-mentioned 394.7g joins in the there-necked flask of 1000ml, adds the Na of 0.980g again 2CO 3, mechanical stirring reaction at ambient temperature, through 30min, the magnesiumcarbonate crystal will be separated out in crystallization.The whizzer centrifugal treating, 80 ℃ of dryings of solid phase can get magnesiumcarbonate 0.7796g; Mother liquid obtained F 1Be 394.9g, mother liquor F 1Consist of at 0 ℃ of Na 2SO 4-(NH 4) 2SO 4-H 2The E of O system phase diagram 1And F 1On the straight line, E wherein 1Mother liquor quality percentage composition is: Na 2SO 4, 19.28%; (NH 4) 2SO 4, 7.531%; H 2O, 73.19%.Record F 1Mother liquor quality percentage composition is Na 2SO 4, 11.09%; (NH 4) 2SO 4, 8.650%; H 2O, 80.26%.
(3) with the mother liquor F of (2) gained 1Add in the there-necked flask of 500ml, mechanical stirring crystallisation by cooling in 0 ℃ of thermostatic bath, through 120min, Na 2SO 410H 2The O crystal will be separated out in crystallization.Through the whizzer centrifugal treating, solid phase is put into 60 ℃ of baking ovens and is carried out drying and can get white plates crystal product Na 2SO 410H 2O 56.27g.Can get filtrate is F 2Be total to 338.6g, it is formed at 0 ℃ of Na 2SO 4-(NH 4) 2SO 4-H 2The E of O system phase diagram 2F 2On the straight line, E 2And F 2Na when being 0 ℃ 2SO 4-(NH 4) 2SO 4-H 2The Na of O system phase diagram 2SO 410H 2Point on the O saturated line, its mid point E 2Mother liquor quality percentage composition be: Na 2SO 4, 5.865%; (NH 4) 2SO 4, 11.61%; H 2O, 82.53%; Record F 2Mother liquor quality percentage composition be Na 2SO 4, 5.601%; (NH 4) 2SO 4, 10.09%; H 2O, 84.31%.
(4) with (3) gained 338.6g mother liquor F 2, 55.34g bloedite (MgSO 4Na 2SO 44H 2O) add the 500ml there-necked flask and in the water of the ammonium sulfate of 20.65g and 36.42g, mechanical stirring reaction in 25 ℃ of thermostatic baths, through 120min, the multiple fertile (MgSO of nitrogen magnesium 4(NH 4) 2SO 46H 2O) will crystallization separate out, after the whizzer centrifugal treating drying, just can get the multiple fertilizer product 56.33g of nitrogen magnesium.Mother liquid obtained for F is 394.7g, record Na in the F mother liquor 2SO 4The quality percentage composition be 10.76%; MgSO 4The quality percentage composition be 0.2817%; (NH 4) 2SO 4The quality percentage composition be 8.654%; H 2The quality percentage composition of O is 80.30%.It forms identical with the composition of mother liquor F in the preceding step (1).
(4) the F mother liquor that obtains can constitute cyclic production according to (2), (3) and (4) step successively.
Example 3 (operational path is seen Fig. 1)
(1) with the bloedite (MgSO of 100g 4Na 2SO 44H 2O), the water of the ammonium sulfate of 63.70g and the 249.7g system that is mixed into is formed U 0, join in the there-necked flask of 1000ml, mechanical stirring reaction in 25 ℃ of thermostatic baths, through 120min, the multiple fertile (MgSO of nitrogen magnesium 4(NH 4) 2SO 46H 2O) will crystallization separate out, after the whizzer centrifugal treating drying, just can get the multiple fertilizer product 104.8g of nitrogen magnesium.Mother liquid obtainedly be Z 308.6g altogether, Na when mother liquor Z is 25 ℃ 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2The MgSO of O system phase diagram 4(NH 4) 2SO 46H 2O and Na 2SO 410H 2Point on the O two solid phase saturated lines, recording Z mother liquor quality percentage composition is Na 2SO 4, 13.85%; MgSO 4, 0.3242%; (NH 4) 2SO 4, 8.212%; H 2O, 77.61%.
(2) the Z mother liquor with above-mentioned 308.6g joins in the there-necked flask of 1000ml, adds the Na of 0.882g again 2CO 3, mechanical stirring reaction at ambient temperature, through 30min, the magnesiumcarbonate crystal will be separated out in crystallization.The whizzer centrifugal treating, 80 ℃ of dryings of solid phase can get magnesiumcarbonate 0.701g; Mother liquid obtained Z 1Be 308.8g, mother liquor Z 1Consist of at 0 ℃ of Na 2SO 4-(NH 4) 2SO 4-H 2The E of O system phase diagram 1And F 1On the straight line, E wherein 1Mother liquor quality percentage composition is: Na 2SO 4, 19.28%; (NH 4) 2SO 4, 7.531%; H 2O, 73.19%; F 1Mother liquor quality percentage composition is Na 2SO 4, 11.09%; (NH 4) 2SO 4, 8.650%; H 2O, 80.26%; Record Z 1Mother liquor quality percentage composition is Na 2SO 4, 14.22%; (NH 4) 2SO 4, 8.208%; H 2O, 77.57%.
(3) with the mother liquor Z of (2) gained 1Add in the there-necked flask of 500ml, mechanical stirring crystallisation by cooling in 0 ℃ of thermostatic bath, through 120min, Na 2SO 410H 2The O crystal will be separated out in crystallization.Through the whizzer centrifugal treating, solid phase is put into 60 ℃ of baking ovens and is carried out drying and can get white plates crystal product Na 2SO 410H 2O 68.46g.The filtrate that can get is Z 2Be total to 240.3g,, it is formed at 0 ℃ of Na 2SO 4-(NH 4) 2SO 4-H 2The E of O system phase diagram 2F 2On the straight line, E 2And F 2Na when being 0 ℃ 2SO 4-(NH 4) 2SO 4-H 2The Na of O system phase diagram 2SO 410H 2Point on the O saturated line, its mid point E 2Mother liquor quality percentage composition be: Na 2SO 4, 5.865%; (NH 4) 2SO 4, 11.61%; H 2O, 82.53%; Point F 2Mother liquor quality percentage composition be Na 2SO 4, 5.601%; (NH 4) 2SO 4, 10.09%; H 2O, 84.31%.Record Z 2Na in the mother liquor 2SO 4The quality percentage composition be 5.708%; (NH 4) 2SO 4The quality percentage composition be 10.55%; H 2The quality percentage composition of O is 83.74%.
(4) with (3) gained 240.3g mother liquor Z 2, 68.34g bloedite (MgSO 4Na 2SO 44H 2O) add the 500ml there-necked flask and in the water of the ammonium sulfate of 25.90g and 44.72g, mechanical stirring reaction in 25 ℃ of thermostatic baths, through 120min, the multiple fertile (MgSO of nitrogen magnesium 4(NH 4) 2SO 46H 2O) will crystallization separate out, after the whizzer centrifugal treating drying, just can get the multiple fertilizer product 70.68g of nitrogen magnesium.Mother liquid obtained for Z is total to 308.6g, record Na in the Z mother liquor 2SO 4The quality percentage composition be 13.85%; MgSO 4The quality percentage composition be 0.3242%; (NH 4) 2SO 4The quality percentage composition be 8.212%; H 2The quality percentage composition of O is 77.61%, and it forms identical with the composition of mother liquor Z in the preceding step (1).
(4) the Z mother liquor that obtains can constitute cyclic production according to (2), (3) and (4) step successively.
Embodiment 4,5,6,7,8,9,
Remove outside embodiment 1,2 and 3 used mixed system proportionings form, some other quality proportionings according to the mixture system W that adds in some other quality proportionings of the mixture system A that adds in the step that provides in the technical solution of the present invention (1) and the corresponding step (4), can copy embodiment 1, carry out the embodiment 4,5,6,7,8 and 9 of the cyclic production of the multiple fertilizer of bloedite processing and preparing sodium sulfate and nitrogen magnesium.(seeing Table 2,3)
Table 2: the quality proportioning of the mixture system A that adds in the step (1) is specially
Figure BDA0000145711550000091
Table 3: the quality proportioning of the mixture system W that adds in the step (4) is specially
Figure BDA0000145711550000092

Claims (3)

1. one kind by the multiple fertile method of bloedite processing and preparing sodium sulfate and nitrogen magnesium, it is characterized by may further comprise the steps:
(1) with bloedite (MgSO 4Na 2SO 44H 2O), ammonium sulfate and water mixes and forms mixed system A, and the composition of mixed system A material is met at 25 ℃ of Na 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2Bloedite (the MgSO of O system phase diagram 4Na 2SO 44H 2O) form point and ammonium sulfate and form on the some line, wherein two of mixed system A end points are M 0And N 0, some M 0The quality proportioning of system consists of: bloedite: ammonium sulfate: water=1:0.5565:1.764, N 0The quality proportioning of system is: bloedite: ammonium sulfate: water=1:0.725:3.267; Then mixed system A is joined in the reactor, behind the mechanical stirring reaction 120min, the multiple fertilizer of nitrogen magnesium will be separated out in crystallization in 25 ℃ of thermostatic baths, after the crystallization of whizzer centrifugal treating and the drying, just can get the multiple fertilizer product of nitrogen magnesium; Mother liquid obtained B; The composition of mother liquor B at E between the F, Na when E and F are 25 ℃ 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2The MgSO of O system phase diagram 4(NH 4) 2SO 46H 2O and Na 2SO 410H 2Point on the O two solid phase saturated lines, its mid point E are that mother liquor quality percentage composition is Na 2SO 4, 18.84%; MgSO 4, 0.3896%; (NH 4) 2SO 4, 7.536%; H 2O, 73.23%; Point F mother liquor quality percentage composition is Na 2SO 4, 10.76%; MgSO 4, 0.2817%; (NH 4) 2SO 4, 8.654%; H 2O, 80.30%; The multiple fertilizer of described nitrogen magnesium is MgSO 4(NH 4) 2SO 46H 2O;
(2) above-mentioned composition is joined in the reactor to the mother liquor B between the F at E, add Na again 2CO 3, its add-on be with mother liquor B in contained MgSO 4The amount of theoretical reaction, i.e. mass ratio MgSO 4: Na 2CO 3=1:0.8811, mechanical stirring reaction at ambient temperature, through 30min, the magnesiumcarbonate crystal will be separated out in crystallization, the crystallization of whizzer centrifugal treating, 80 ℃ of dryings of solid phase can get magnesiumcarbonate; Mother liquid obtained C; C consists of at 0 ℃ of Na 2SO 4-(NH 4) 2SO 4-H 2The E of O system phase diagram 1And F 1On the straight line, E wherein 1Mother liquor quality percentage composition is: Na 2SO 4, 19.28%; (NH 4) 2SO 4, 7.531%; H 2O, 73.19%; F 1Mother liquor quality percentage composition is Na 2SO 4, 11.09%; (NH 4) 2SO 4, 8.650%; H 2O, 80.26%;
(3) (2) gained is formed at E 1To F 1Between mother solution C add in the reactor, mechanical stirring crystallisation by cooling in 0 ℃ of thermostatic bath, through 120min, Na 2SO 410H 2The O crystal will be separated out in crystallization; Through the whizzer centrifugal treating, solid phase is put into 60 ℃ of baking ovens and is carried out drying and can get white plates crystal product Na 2SO 410H 2O; The crystallization filtrate of gained is mother liquor D, and it is formed at 0 ℃ of Na 2SO 4-(NH 4) 2SO 4-H 2The E of O system phase diagram 2F 2On the straight line, E 2And F 2Na when being 0 ℃ 2SO 4-(NH 4) 2SO 4-H 2The Na of O system phase diagram 2SO 410H 2Point on the O saturated line, its mid point E 2Mother liquor quality percentage composition be: Na 2SO 4, 5.865%; (NH 4) 2SO 4, 11.61%; H 2O, 82.53%; Point F 2Mother liquor quality percentage composition be Na 2SO 4, 5.601%; (NH 4) 2SO 4, 10.09%; H 2O, 84.31%;
(4) the mother liquor D to (3) gained adds bloedite (MgSO 4Na 2SO 44H 2O), ammonium sulfate and water, form and be mixed into system W, make composition Na in the time of 25 ℃ of system W 2SO 4-MgSO 4-(NH 4) 2SO 4-H 2The M of O system phase diagram 1N 1On the straight line, its mid point M 1Composition quality proportioning be: mother liquor E 2: bloedite (MgSO 4Na 2SO 44H 2O): ammonium sulfate: water=1:0.5426:0.208:0.3585; N 1The quality proportioning be: mother liquor F 2: bloedite (MgSO 4Na 2SO 44H 2O): ammonium sulfate: water=1:0.1634:0.0610:0.1075; Mechanical stirring reaction in 25 ℃ of thermostatic baths, through 120min, the multiple fertilizer of nitrogen magnesium will be separated out in crystallization, after the whizzer centrifugal treating drying, just can get the multiple fertilizer product of nitrogen magnesium; The mother liquid obtained Na that consists of 2SO 4, MgSO 4, (NH 4) 2SO 4And H 2O, and its quality percentage composition meets the compositing range that obtains mother liquor B in the step (1), can form to add according to (2), the required composition of (3) and (4) step successively to constitute cyclic production.
2. as claimed in claim 1 by the multiple fertile method of bloedite processing and preparing sodium sulfate and nitrogen magnesium, it is one of following that the composition quality proportioning that it is characterized by the mixture system A that adds in the described step (1) is specially:
Figure FDA0000313317491
。
3. as claimed in claim 1 by the multiple fertile method of bloedite processing and preparing sodium sulfate and nitrogen magnesium, it is one of following that the composition quality proportioning that it is characterized by the mixture system W that adds in the described step (4) is specially:
Figure FDA0000313317492
。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB190100276A (en) * 1901-01-04 1901-11-09 Gerhard Nicolaas Vis Improvements in the Purification of Brine
CN101563292A (en) * 2007-12-14 2009-10-21 派诺尔斯工业服务公司 Method for the production of sodium sulphate and magnesium hydroxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB190100276A (en) * 1901-01-04 1901-11-09 Gerhard Nicolaas Vis Improvements in the Purification of Brine
CN101563292A (en) * 2007-12-14 2009-10-21 派诺尔斯工业服务公司 Method for the production of sodium sulphate and magnesium hydroxide

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
Na2SO4-MgSO4-H2O体系的相图与两盐分离方法的研究;余杰等;《福建化工》;19941231(第2期);16-20 *
余杰等.Na2SO4-MgSO4-H2O体系的相图与两盐分离方法的研究.《福建化工》.1994,(第2期),16-20.
内蒙古某地芒硝矿选矿试验研究;王林祥等;《矿产保护与利用》;20060831(第4期);31-33 *
宋德镇等.四元交互体系Na+,NH4+||1/2SO42-,HCO3_H2O在10℃时的溶解度相图.《四川大学学报(自然科学版)》.1997,第34卷(第2期),118-120. *
托勒库勒湖生产无水硫酸钠的研究;李志强;《西部探矿工程》;20101231(第7期);136-138 *
李志强.托勒库勒湖生产无水硫酸钠的研究.《西部探矿工程》.2010,(第7期),136-138.
王林祥等.内蒙古某地芒硝矿选矿试验研究.《矿产保护与利用》.2006,(第4期),31-33.
西藏扎北盐湖夏季卤水自然蒸发实验研究;高峰等;《盐湖研究》;20111231;第19卷(第4期);21-27 *
高峰等.西藏扎北盐湖夏季卤水自然蒸发实验研究.《盐湖研究》.2011,第19卷(第4期),21-27.

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