阅读说明：本技术 一种尿素硫酸铵镁肥的制备方法及尿素硫酸铵镁肥产品 (A kind of preparation method and urea ammonium sulfate fertiliser containing magnesium product of urea ammonium sulfate fertiliser containing magnesium ) 是由 方进 顾春光 任光耀 黄德明 于 2019-08-01 设计创作，主要内容包括：本发明适用于化肥工业领域,公开了一种尿素硫酸铵镁肥的制备方法,包括以下步骤：对磷矿石依次进行脱钙、脱镁浸取处理,获得脱镁浸取液；将脱镁浸取液进行浓缩,冷却结晶,过滤得到硫酸铵镁晶体和结晶母液；将硫酸铵镁晶体与尿素合成得到尿素硫酸铵镁肥产品。本发明还公开了一种尿素硫酸铵镁肥产品,其成分包含：N≥16％、N<Sub>酰</Sub>9％～39％、N<Sub>铵</Sub>1％～15％、Ca<Sub>水</Sub>0.1％～0.3％、Mg<Sub>水</Sub>1％～5.5％、S2.5％～14％。本发明提供的一种尿素硫酸铵镁肥的制备方法及尿素硫酸铵镁肥产品,其含有适量的酰态氮、铵态氮、水溶镁、硫、钙,具有全水溶,肥效快的特点,可作追肥、基肥等,利于农作物生长和补充镁、硫、钙元素,且单位养分成本较低,产品售价易为市场所接受。(The present invention is suitable for chemical fertilizer industry field, discloses a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium, comprising the following steps: successively carries out decalcification, de-magging leaching processing to rock phosphate in powder, obtains de-magging leaching liquid；De-magging leaching liquid is concentrated, crystallisation by cooling, ammonium sulfate magnesium crystal and crystalline mother solution is obtained by filtration；Ammonium sulfate magnesium crystal and urea synthesizing are obtained into urea ammonium sulfate fertiliser containing magnesium product.The invention also discloses a kind of urea ammonium sulfate fertiliser containing magnesium products, and ingredient includes: N >=16%, N Acyl 9%~39%, N Ammonium 1%~15%, Ca Water 0.1%~0.3%, Mg Water 1%~5.5%, S2.5%~14%.The preparation method and urea ammonium sulfate fertiliser containing magnesium product of a kind of urea ammonium sulfate fertiliser containing magnesium provided by the invention, it contains suitable acyl state nitrogen, ammonium nitrogen, water soluble magnesium, sulphur, calcium, with complete water-soluble, the fast feature of fertilizer efficiency, it can make top dressing, base manure etc., conducive to crop growth and supplement magnesium, sulphur, calcium constituent, and cost is relatively low for unit nutrient, and product price is easily received by market.)

1. a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium, which comprises the following steps:

Decalcification, de-magging leaching processing are successively carried out to rock phosphate in powder, obtain de-magging leaching liquid；

The de-magging leaching liquid is concentrated, ammonium sulfate magnesium crystal and crystalline mother solution is obtained by filtration in crystallisation by cooling；

The ammonium sulfate magnesium crystal and urea synthesizing are obtained into urea ammonium sulfate fertiliser containing magnesium product.

2. a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium as described in claim 1, which is characterized in that taken off to rock phosphate in powder Calcium, de-magging leaching processing include:

S1, the temperature lower calcination by rock phosphate in powder at 850-1100 DEG C obtain burnt ore, and crush the burnt ore to obtain partial size Burnt ore particle less than 0.8mm；

S2, Xiang Suoshu burnt ore particle are added ammonium nitrate and leach decalcification, and filtering obtains leaching residue and leachate A；

S3, Xiang Suoshu leaching residue are added ammonium sulfate and leach de-magging, and filtering obtains phosphorus concentrate and the de-magging leaching liquid.

3. a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium as claimed in claim 2, which is characterized in that in step s 2, institute The reaction temperature for stating leaching decalcification is 10-40 DEG C.

4. a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium as claimed in claim 2, which is characterized in that in step s 2, right The leachate A is concentrated to give calcium ammonium nitrate crystal, and is added in urea melt and is synthesized, and is granulated and obtains urea nitric acid Ammonium calcium.

5. a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium as claimed in claim 2, which is characterized in that in step s3, institute The reaction temperature for stating leaching de-magging is 70-95 DEG C, reaction time 100-150min.

6. a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium as described in claim 1, which is characterized in that leach the de-magging Liquid is concentrated into crystal at 100-120 DEG C and is precipitated to obtain enriching slurry, and the ammonium hydroxide of 15%-25% is passed through to the enriching slurry Crystallisation by cooling is carried out, the crystallisation by cooling time is 2h-2.5h.

7. a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium as described in claim 1, which is characterized in that the ammonium sulfate magnesium is brilliant Body includes: to synthesize the urea melting at the ammonium sulfate magnesium crystal is added after urea melt with urea synthesis method.

8. a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium as described in claim 1, which is characterized in that the ammonium sulfate magnesium is brilliant The reaction temperature of body and urea synthesizing is 100-140 DEG C, reaction time 0.2-0.6h.

9. a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium as claimed in claim 8, which is characterized in that by the ammonium sulfate magnesium The step of crystal and urea synthesizing obtain urea ammonium sulfate magnesium products further includes granulation processing, and the granulation processing is made using high tower One of grain, rotary drum fluid-bed granulation, disc granulation, slurry-spraying pelletizing etc., and the prilling temperature is 80-100 DEG C.

10. a kind of urea ammonium sulfate fertiliser containing magnesium product, which is characterized in that use urea as claimed in any one of claims 1-9 wherein The preparation method of ammonium sulfate fertiliser containing magnesium is made, and the urea ammonium sulfate fertiliser containing magnesium product composition includes: N >=16%, N_Acyl9%~39%, N_Ammonium1%~15%, Ca_Water0.1%~0.3%, Mg_Water1%~5.5%, S 2.5%~14%.

Technical field

The invention belongs to chemical fertilizer industry field more particularly to a kind of preparation methods and urea sulfate of urea ammonium sulfate fertiliser containing magnesium Ammonium fertiliser containing magnesium product.

Background technique

China's phosphorus ore reserves occupy the second in the world, but compared with the countries concerned, the world, in ore quality, washability and phosphorus ore Stone exploitation etc. has larger gap, and the basic unit price for the rock phosphate in powder of processing and utilization is relatively low, and only 40.54 hundred million Ton, low-grade ore is more, wherein P₂O₅Rich ore of the mass fraction greater than 30% is only 11.08 hundred million tons, Chinese phosphorus ore P₂O₅Average quality Score is 17% or so, and most phosphorus ores are just able to satisfy phosphoric acid and high concentration phosphate fertilizer production requirement after must pass through enrichment, is pressed According to current exploitation rock phosphate in powder speed, if all being only capable of maintaining 10 years or so with the rich ore that mass fraction is 30%, economic reserve It is only capable of maintaining 40 years or so, future will be forced the phosphorus ore of the higher middle-low grade of cost of winning.

Above-mentioned mid low grade phosphate rock refers to P₂O₅Content is lower than 30% phosphorus ore, needs to obtain phosphorus concentrate powder by ore dressing. The purpose of ore dressing is the gangue mineral removed in phosphorus ore.Carbonate gangue is mainly dolomite (CaCO in phosphorus ore₃·MgCO₃), side Xie Shi (CaCO₃) and fluor-apatite (Ca₅F(PO₄)₃), reverse flotation is generally used in flotation of phosphate rock, which compares at present It is ripe, the tailing P of discharge₂O₅≤ 10%, MgO >=15%.If Patent No. CN201510224161 one kind is by mid low grade phosphate rock system The technique of standby phosphorus concentrate producing ammonium sulfate byproduct magnesium, calcium ammonium nitrate.The concrete technology scheme of the inventive method: mid low grade phosphate rock is forged It burns, filtered after digestion plus ammonium nitrate leaching, leachate concentration, which is granulated, produces calcium ammonium nitrate, after ammonium sulfate leaching is added in leached mud Filtering filters out slag drying and phosphorus concentrate is made, and filter liquor concentration, which is granulated, is made ammonium sulfate magnesium.

In order to which ammonium sulfate magnesium to be applied in fertilizer product, on this basis, urea and ammonium sulfate magnesium are synthesized, made Standby urea ammonium sulfate fertiliser containing magnesium new product a kind of out.

Summary of the invention

The present invention is directed at least solve one of above-mentioned technical problem, a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium is provided And urea ammonium sulfate fertiliser containing magnesium product, in the urea ammonium sulfate fertiliser containing magnesium product containing suitable acyl state nitrogen, ammonium nitrogen, water soluble magnesium, sulphur, Calcium nutrition, has complete water-soluble, and the fast feature of fertilizer efficiency can make top dressing, base manure etc., be conducive to crop growth and supplement magnesium, sulphur, calcium member Element, and cost is relatively low for unit nutrient, product price is easily received by market.

The technical scheme is that a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium, comprising the following steps:

Decalcification, de-magging leaching processing are successively carried out to rock phosphate in powder, obtain de-magging leaching liquid；

The de-magging leaching liquid is concentrated, ammonium sulfate magnesium crystal and crystalline mother solution is obtained by filtration in crystallisation by cooling；

The ammonium sulfate magnesium crystal and urea synthesizing are obtained into urea ammonium sulfate fertiliser containing magnesium product.

Optionally, decalcification is carried out to rock phosphate in powder, de-magging leaching processing includes:

S1, the temperature lower calcination by rock phosphate in powder at 850-1100 DEG C obtain burnt ore, and the burnt ore are crushed to obtain Partial size is less than the burnt ore particle of 0.8mm；

S2, Xiang Suoshu burnt ore particle are added ammonium nitrate and leach decalcification, and filtering obtains leaching residue and leachate A；

S3, Xiang Suoshu leaching residue are added ammonium sulfate and leach de-magging, and filtering obtains phosphorus concentrate and the de-magging leaching liquid.

Optionally, in step s 2, the reaction temperature of the leaching decalcification is 10-40 DEG C.

Optionally, in step s 2, concentration is carried out to the leachate A and obtains calcium ammonium nitrate crystal, and it is molten that urea is added It is synthesized in body, is granulated and obtains urea ammonium nitrate calcium.

Optionally, in step s3, the reaction temperature of the leaching de-magging is 70-95 DEG C, reaction time 100- 150min。

Optionally, the de-magging leaching liquid is concentrated at 100-120 DEG C crystal and is precipitated to obtain enriching slurry, and to institute The ammonium hydroxide progress crystallisation by cooling that enriching slurry is passed through 15%-25% is stated, the crystallisation by cooling time is 2h-2.5h.

Optionally, the ammonium sulfate magnesium crystal and urea synthesis method include: by the urea melting at urea melt after The ammonium sulfate magnesium crystal synthesis is added.

Optionally, the reaction temperature of the ammonium sulfate magnesium crystal and urea synthesizing is 100-140 DEG C, reaction time 0.2- 0.6h。

Optionally, the step of ammonium sulfate magnesium crystal being obtained urea ammonium sulfate magnesium products with urea synthesizing further includes making Grain processing, the granulation processing use one of high-tower granulation, rotary drum fluid-bed granulation, disc granulation, slurry-spraying pelletizing etc., and The prilling temperature is 80-100 DEG C.

The present invention also provides a kind of urea ammonium sulfate fertiliser containing magnesium products, using the preparation side of above-mentioned urea ammonium sulfate fertiliser containing magnesium Method is made, and the urea ammonium sulfate fertiliser containing magnesium product composition includes: N >=16%, N_Acyl9%~39%, N_Ammonium1%~15%, Ca_Water 0.1%~0.3%, Mg_Water1%~5.5%, S 2.5%~14%.

The preparation method and urea ammonium sulfate fertiliser containing magnesium product of a kind of urea ammonium sulfate fertiliser containing magnesium provided by the present invention, have with It is lower the utility model has the advantages that

1) it produces to obtain urea ammonium sulfate as raw material by urea and using de-magging leaching liquid caused by rock phosphate in powder chemical mineral processing Fertiliser containing magnesium product saves beneficiation cost；

2) urea ammonium sulfate fertiliser containing magnesium product obtained by preparation method of the present invention containing suitable acyl state nitrogen, ammonium nitrogen, water soluble magnesium and The ingredients such as sulphur also contain a small amount of water-soluble calcium, have the advantages that it is complete it is water-soluble, fertilizer efficiency is fast, top dressing, base manure etc. can be made, conducive to agriculture Plant growth and magnesium, sulphur, calcium constituent are supplemented for crops, and cost is relatively low for unit nutrient, and product price is easily received by market, Use easy to spread；

3) the urea ammonium sulfate fertiliser containing magnesium product that preparation method of the present invention is produced, can directly apply fertilizer use, also can be used as The raw material of fertilizer product, the additive of fertilizer product, chemical products additive, it is widely used.

Detailed description of the invention

It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached Figure.

Fig. 1 is a kind of flow chart of the preparation method of urea ammonium sulfate fertiliser containing magnesium provided in an embodiment of the present invention.

Specific embodiment

In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.

It should be noted that term " setting ", " connection " shall be understood in a broad sense, for example, it may be directly setting, connection, It can also be arranged indirectly by component placed in the middle, center configuration, be connected.

If in addition, have in the embodiment of the present invention " longitudinal direction ", " transverse direction ", " length ", " width ", " thickness ", "upper", "lower", The orientation or positional relationships of instructions such as "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom" "inner", "outside" Term is merely for convenience of to be based on the orientation or positional relationship shown in the drawings or conventional placement status or use state The description present invention and simplified description, rather than structure, feature, device or the element of indication or suggestion meaning must have specifically Orientation or positional relationship nor is it necessary that and be constructed and operated in a specific orientation, therefore is not considered as limiting the invention. In the description of the present invention, unless otherwise indicated, the meaning of " plurality " is two or more.

Described each particular technique feature and each embodiment in a specific embodiment, in the case of no contradiction, It can be combined in any appropriate way, such as can be with shape by different particular technique feature/embodiment combinations At different embodiments, in order to avoid unnecessary repetition, each the various of particular technique feature/embodiment can in the present invention No further explanation will be given for the combination of energy.

As shown in Figure 1, a kind of preparation method of urea ammonium sulfate fertiliser containing magnesium provided in an embodiment of the present invention, including following step It is rapid:

Decalcification, de-magging leaching processing are carried out to mid low grade phosphate rock stone, obtain de-magging leaching liquid；

The de-magging leaching liquid is concentrated, ammonium sulfate magnesium crystal and crystalline mother solution is obtained by filtration in crystallisation by cooling；

The ammonium sulfate magnesium crystal and urea synthesizing are obtained into urea ammonium sulfate fertiliser containing magnesium product.

Rock phosphate in powder in the present invention is preferably mid low grade phosphate rock stone, it is not limited to mid low grade phosphate rock stone.

According to above-mentioned method and step, mid low grade phosphate rock is calcined, low temperature leaches decalcification, high temperature leaching de-magging obtains De-magging leaching liquid is concentrated, crystallisation by cooling, is separated by filtration and can obtain ammonium sulfate magnesium crystal, then in proportion to ammonium sulfate magnesium Crystal is added urea and is synthesized, and is granulated, can be prepared by urea ammonium sulfate fertiliser containing magnesium product.

Optionally, to mid low grade phosphate rock stone carry out decalcification, de-magging leaching processing the following steps are included:

S1, the temperature lower calcination by mid low grade phosphate rock stone at 850-1100 DEG C obtain burnt ore, so that miscellaneous in phosphorus ore Matter dolomite and calcite decompose, and contain P₂O₅Compound do not decompose, and crush the burnt ore to obtain partial size and be less than The burnt ore particle of 0.8mm, by optimizing the partial size of burnt ore particle, so that the reaction process of burnt ore particle is uniformly quickly steady It is fixed；

S2, Xiang Suoshu burnt ore particle are added ammonium nitrate and leach decalcification, remove the calcium oxide in burnt ore particle, pass through Filter separation obtains leaching residue and leachate A；

S3, water washing is carried out to leaching residue, and ammonium sulfate is added to the leaching residue of washing and leaches de-magging, remove Magnesia in leaching residue obtains phosphorus concentrate and the de-magging leaching liquid by filtering.

Specifically, the calcination temperature of mid low grade phosphate rock stone can be 900-1000 DEG C.

Specifically, the calcination temperature of mid low grade phosphate rock stone can be 950 DEG C.

Specifically, the partial size of the burnt ore particle is smaller than 0.5mm, it is ensured that and reaction speed is fast when leaching decalcification, and Further ensure that the calcium constituent fully reacting in burnt ore particle.

Specifically, after ammonium sulfate leaching de-magging being added to leaching residue, filters pressing is carried out by filter press, de-magging leaching is discharged Liquid, the filters pressing filter cake left pass through water washing, drying and processing, phosphorus concentrate can be obtained.

In the present invention, burnt ore particle first passes through ammonium nitrate solution leaching, then is leaching to obtain through ammonium persulfate solution Calcium, magnesium elements in calcium oxide in burnt ore, magnesia can be separated effectively, improve P in phosphorus concentrate by phosphorus concentrate₂O₅Contain Amount.

Specifically, the concentration of the ammonium nitrate can be 25-30%, and the concentration of the ammonium sulfate can be 25-30%.

Optionally, in step s 2, the reaction temperature of the leaching decalcification is 10-40 DEG C, reaction time 45- 120min。

Specifically, the reaction temperature of the leaching decalcification is 20-30 DEG C, reaction time 60min.

Optionally, in step s 2, concentration is carried out to the leachate A and obtains calcium ammonium nitrate crystal, it is molten to add urea It is synthesized in body, is then granulated using technologies such as high tower, whitewashing, steel bands, obtain urea ammonium nitrate calcium.

In practical application, in step s 2, concentration granulation is carried out to the leachate A, can get calcium ammonium nitrate.

Optionally, in step s3, the reaction temperature of the leaching de-magging is 70-95 DEG C, reaction time 100- 150min。

Specifically, the reaction temperature of the leaching de-magging can be 80-90 DEG C, and the reaction time can be 100-120min.

It optionally, is that raw material is concentrated into crystal at a temperature of 100-120 DEG C and is precipitated and is concentrated by the de-magging leaching liquid Slurry send enriching slurry into cooler crystallizer, and carries out cooling knot to the ammonium hydroxide that the enriching slurry is passed through 15%-25% Crystalline substance, then concentrate feed after cooling will be sent to filter and be filtered separation, crystalline mother solution and ammonium sulfate magnesium crystal are obtained, In, the crystallisation by cooling time is 2h-2.5h.

In practical application, crystallisation by cooling operation can also be carried out to enriching slurry by the way of natural cooling crystallization.

Specifically, the ammonium sulfate that crystalline mother solution can be used in configuration step S3.

Optionally, the ammonium sulfate magnesium crystal and urea synthesis method include: ammonium sulfate magnesium crystal is sent into synth sink, and Urea into melting tank, which is passed through steam, which carries out heating, makes urea melting at urea melt, adds synth sink and ammonium sulfate magnesium is brilliant Body is synthesized, and urea ammonium sulfate magnesium is obtained.

Specifically, can be in urea: 1-4 parts, ammonium sulfate magnesium crystal: 1-4 parts of ratio be synthesized.

Optionally, the reaction temperature of the ammonium sulfate magnesium crystal and urea synthesizing is 100-140 DEG C, reaction time 0.2- 0.6h。

Specifically, the synthesis temperature of the ammonium sulfate magnesium crystal and urea synthesizing is 110-130 DEG C, and generated time is 0.25-0.5h。

Optionally, the step of ammonium sulfate magnesium crystal being obtained urea ammonium sulfate fertiliser containing magnesium product with urea synthesizing further include One in high-tower granulation, rotary drum fluid-bed granulation, disc granulation, slurry-spraying pelletizing etc. can be used in granulation processing, the granulation processing Kind, and the prilling temperature is 80-100 DEG C.During granulation, it is being granulated premise high material temperature, is making water after material balling-up It is point low, drying efficiency is improved convenient for being granulated.

The present invention also provides a kind of urea ammonium sulfate fertiliser containing magnesium products, using the preparation side of above-mentioned urea ammonium sulfate fertiliser containing magnesium Method is made, and the urea ammonium sulfate fertiliser containing magnesium product composition includes: N >=16%, N_Acyl9%~39%, N_Ammonium1%~15%, Ca_Water 0.1%~0.3%, Mg_Water1%~5.5%, S 2.5%~14%.The urea ammonium sulfate fertiliser containing magnesium product contains suitable acyl state Nitrogen, ammonium nitrogen, water soluble magnesium, sulphur, calcium also contain a small amount of water-soluble calcium, and complete water-soluble, fertilizer efficiency is fast, can make top dressing, base manure etc., be conducive to Crop growth and supplement magnesium, sulphur, calcium constituent.And the urea ammonium sulfate fertiliser containing magnesium product can be expired by adjusting nitrogen and sulphur ratio Sufficient different crops demand.

A kind of preparation method and urea ammonium sulfate fertiliser containing magnesium product of urea ammonium sulfate fertiliser containing magnesium provided by the embodiment of the present invention, It has the advantages that

1) it produces to obtain urea ammonium sulfate as raw material by urea and using de-magging leaching liquid caused by rock phosphate in powder chemical mineral processing Fertiliser containing magnesium product saves beneficiation cost；

2) urea ammonium sulfate fertiliser containing magnesium product obtained by preparation method of the present invention containing suitable acyl state nitrogen, ammonium nitrogen, water soluble magnesium and The ingredients such as sulphur also contain a small amount of water-soluble calcium, have the advantages that it is complete it is water-soluble, fertilizer efficiency is fast, can make top dressing, base manure etc., be conducive to work Object grows and supplements magnesium, element sulphur for crops, and cost is relatively low for unit of the product nutrient, and product price is easily received by market, Use easy to spread；

3) the urea ammonium sulfate magnesium granules fertilizer product that preparation method of the present invention is produced, can directly apply fertilizer use, can also As the raw material of fertilizer product, the additive of fertilizer product, chemical products additive, it is widely used.