CN103601165B - Additive is utilized to change the method for crystal morphology of ammonium dihydrogen phosphate - Google Patents
Additive is utilized to change the method for crystal morphology of ammonium dihydrogen phosphate Download PDFInfo
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- CN103601165B CN103601165B CN201310578292.2A CN201310578292A CN103601165B CN 103601165 B CN103601165 B CN 103601165B CN 201310578292 A CN201310578292 A CN 201310578292A CN 103601165 B CN103601165 B CN 103601165B
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Abstract
A kind of method utilizing additive to change crystal morphology of ammonium dihydrogen phosphate, raw material primary ammonium phosphate purity more than 95%, by primary ammonium phosphate: water mixes in the ratio of ratio of quality and the number of copies 30-85:100, add organic carboxyl acid or carboxylate salt additive, stir, solution is heated to 45-65 DEG C of dissolving, adopts crystallisation by cooling method, be cooled to 5-35 DEG C; Through washing, filtration, drying, obtain the ammonium dihydrogen phosphate crystal of rod-like morphology.The rod-like morphology ammonium dihydrogen phosphate crystal utilizing the inventive method to prepare, two ends are tetrapyamid shape, crystal average radial granularity 0.6 ~ 1.2mm, axial granularity 3 ~ 5mm, product purity more than 99.5%, crystal product intensity is high, good fluidity, be easy to filter and drying, improve the using value of primary ammonium phosphate product.
Description
Technical field
The invention belongs to chemical engineering industrial crystallization technical field, be specifically related to the additive and the method that change crystal morphology of ammonium dihydrogen phosphate.
Background technology
Primary ammonium phosphate, English name is ammonium dihydrogen phosphate, is also called monoammonium phosphate, is a kind of crystal of white; Molecular formula is NH
4h
2pO
4, relative molecular weight is 115.03, and heating can resolve into ammonium metaphosphate (NH
4pO
3), available ammoniacal liquor and phosphatase reaction are made.Primary ammonium phosphate is soluble in water, is slightly soluble in ethanol, is insoluble to acetone.Primary ammonium phosphate is mainly used as the fireproofing agent of fertilizer and timber, paper, fabric, also for pharmacy and ruminant feed supplement.
Document Physica B-Condensed Matter404 (2009) 8-11:1611-1616 mentions, in the saturated aqueous solution (37.4g/100g water) of monoammonium phosphate, the oxalic acid of concentration 1%-5% is added at 20 DEG C, slow evaporation 20 days under static condition, autonomous growth obtains crystal, and product is the monoammonium phosphate crystal 3-5 grain obtaining about granularity 3mm in 250mL solution.The method is crystalline growth under the static conditions of laboratory, and rely on the spontaneous evaporation of moisture, its vaporator rate is affected by the external environment greatly, and vaporator rate is slow, and preparation cycle is oversize, and product crystalline form is imperfect, and process yield is low, is not easy to large-scale application.
Patent CN101654235B proposes agricultural monoammonium phosphate pure water to dissolve, add oxygenant, discoloring agent and biological flocculant, filter post-heating and concentrate 180 ~ 240 minutes to 70-80 DEG C, until there is micro-crystallization to occur, then natural cooling crystallization cools to 25 DEG C, obtain monoammonium phosphate crystal after drying, granular size is only about 0.2mm.This raw materials technology is second-rate, and the complex operation step time is longer, and product is in small, broken bits.
Chinese patent 200910263800.1 naturally cools to room temperature after reacting with phosphoric acid and ammonia neutralization, obtains crystal, higher to the purity requirement of raw material phosphoric acid, and preparation process equipment is complicated, relates to neutralization reactor, tubular reactor, neutralizing well, spray granulating machine.Chinese patent 200910102880.2 utilizes phosphoric acid by wet process neutralization reaction, and by second-heating concentrated phosphoric acid one ammonium slip, granulation, drying, crushing and screening become granular monoammonium phosphate product.Yielding poorly of the method, product is the agglomerate of crystal, and low in glossiness, easily contains impurity, and purity only about 98%, only uses as agrochemical.Production process energy consumption is comparatively large, and equipment is complicated.Patent CN101538027A adopts single tube one step neutralization-rotary drum prilling process production granular monoammonium phosphate, the method need more equipment and also High Temperature High Pressure energy consumption larger.Patent CN1174812A selects phosphoric acid by wet process to be raw material, and spraying dry obtains monoammonium phosphate particle.Because spray process evaporation is incomplete, cause particle water content up to 3%.
Primary ammonium phosphate crystalline product form commercially available is at present irregular, sees accompanying drawing 1, its main granularity 0.2 ~ 0.4mm, and crystal is in small, broken bits, surface irregularity, and crystal face is imperfect, thus affects the performance such as purity, bulk density, mobility of product.When primary ammonium phosphate is used as fertilizer, because the granularity of powdery product is little, bulk density is low, easily dispels with the wind after being sprinkled into field, reduce effect of fertilizer.In order to improve its granularity and proportion, being suitable for agricultural, generally using agglomeration technique, be processed into the spherical agglomerate particles that proportion is larger, but granulation itself does not change the crystal habit of primary ammonium phosphate, does not improve product purity.When primary ammonium phosphate is used as timber, the fireproofing agent of fabric and pharmaceutical industry, its crystal habit of general requirement, comprises crystal outward appearance, granularity, mobility, purity etc., to play better effect.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of method utilizing additive to change crystal morphology of ammonium dihydrogen phosphate, further cost and the operation easier reducing preparation, adopt additive to obtain the rhabdolith form of primary ammonium phosphate, crystal size is large, form rule, any surface finish, crystal face is complete, easily filters, and product purity reaches more than 99.5%.
The present invention utilizes additive to change the method for crystal morphology of ammonium dihydrogen phosphate, raw material primary ammonium phosphate purity more than 95%, by primary ammonium phosphate: water mixes in the ratio of ratio of quality and the number of copies 30-85:100, add organic carboxyl acid or carboxylate salt additive, stir, solution is heated to 45-65 DEG C of dissolving, adopts crystallisation by cooling method, be cooled to 5-35 DEG C; Through washing, filtration, drying, obtain the ammonium dihydrogen phosphate crystal of rod-like morphology.
Described organic carboxyl acid additive is selected from Dicarboxylic Acids, organic ternary carboxylic acid or organic quaternary carboxylic acid.
Described Dicarboxylic Acids is selected from the one in succinic acid or propanedioic acid, and organic ternary carboxylic acid is selected from the one in citric acid or nitrilotriacetic acid(NTA), and organic quaternary carboxylic acid is selected from the one in ethylenediamine tetraacetic acid (EDTA) or pyromellitic acid.
Described carboxylate salt additive is selected from carboxylic acid sodium salt or carboxylic acid potassium salt.
Described carboxylic acid sodium salt is selected from the one in disodium ethylene diamine tetraacetate, Trisodium Citrate or propanedioic acid disodium, and carboxylic acid potassium salt is selected from the one in pyromellitic acid potassium, nitrilotriacetic acid(NTA) potassium or Tripotassium Citrate.
The add-on of described organic carboxyl acid or carboxylate salt additive is 500-10000ppm.
Described rate of temperature fall is 2-20 DEG C/h.
Micro-organic carboxyl acid or carboxylate salt additive is added in primary ammonium phosphate crystallisation by cooling process, change the physics of its crystal growth, chemical environment, especially the surface charge of crystal distributes and solid-liquid interfacial tension, thus affect the growth velocity of different crystal face, reduce the overall growth velocity of crystal, tetrahedron PO in crystal
4be connected to N-H-O key and NH
4group, unnecessary hydrogen bond distortion NH
4the lattice of ion, thus the pattern controlling crystal.The growth velocity of present method major control (101) crystal face and (100) crystal face, promotes crystal transverse growth, suppresses longitudinal growth, obtains sturdy bar-shaped ammonium dihydrogen phosphate crystal.
The invention provides the method being changed crystal morphology of ammonium dihydrogen phosphate by additive, crystal product form is bar-shaped, crystal two ends are tetrapyamid shape, crystal average radial granularity 0.6-1.2mm, axial granularity 3-5mm, crystal habit rule, any surface finish, crystal face is complete, and product purity reaches more than 99.5%, process single mass yield 36% ~ 69%.The ammonium dihydrogen phosphate crystal particle obtained is large, is easy to filter and drying, and decrease mother liquor and carry secretly and remain, crystal purity is high, and glossiness is good, good fluidity, and crystal intensity is high, is convenient to packaging, transport, improves the using value of primary ammonium phosphate product.
Accompanying drawing explanation
Fig. 1: commercially available ammonium dihydrogen phosphate crystal amplifies 40 times of electromicroscopic photographs;
Fig. 2: embodiment 1 ammonium dihydrogen phosphate crystal amplifies 30 times of electromicroscopic photographs;
Fig. 3: embodiment 2 ammonium dihydrogen phosphate crystal amplifies 30 times of electromicroscopic photographs.
Embodiment
Following embodiment describes the present invention:
Embodiment 1:
Get purity 98% primary ammonium phosphate 30g, deionized water 100g, adds 500ppm ethylenediamine tetraacetic acid (EDTA), stirs.Solution is heated to 45 DEG C of dissolvings, adopt crystallisation by cooling method, rate of temperature fall is 2 DEG C/h, is cooled to 5 DEG C.Through washing, filtration, drying, obtain the ammonium dihydrogen phosphate crystal of rod-like morphology.Procedure quality yield 35.8%, product purity reaches 99.9%, and crystal average radial granularity 0.84mm, axial granularity 4.15mm, product electromicroscopic photograph as shown in Figure 2.
Embodiment 2:
Get purity 97.2% primary ammonium phosphate 70g, deionized water 100g, adds 10000ppm nitrilotriacetic acid(NTA), stirs, and is continued by solution to be heated to 60 DEG C, and adopt crystallisation by cooling method, rate of temperature fall is 6 DEG C/h, is cooled to 20 DEG C.Through washing, filtration, drying, obtain the ammonium dihydrogen phosphate crystal of rod-like morphology.Procedure quality yield 62.42%, product purity reaches 99.7%, crystal average radial granularity 1.00mm, axial granularity 3.18mm.Product electromicroscopic photograph as shown in Figure 3.
Embodiment 3:
Get purity 96% primary ammonium phosphate 60g, deionized water 100g, adds 2000ppm succinic acid, stirs.Solution is heated to 58 DEG C of dissolvings, adopt crystallisation by cooling method, rate of temperature fall is 12 DEG C/h, is cooled to 10 DEG C.Through washing, filtration, drying, obtain the ammonium dihydrogen phosphate crystal of rod-like morphology.Procedure quality yield 69.13%, product purity reaches 99.6%, crystal average radial granularity 0.64mm, axial granularity 4.03mm.
Embodiment 4:
Get purity 95.5% primary ammonium phosphate 70g, deionized water 100g, add 5000ppm pyromellitic acid potassium, stir, continued by solution to be heated to 65 DEG C, adopt crystallisation by cooling method, rate of temperature fall is 20 DEG C/h, is cooled to 30 DEG C.Through washing, filtration, drying, obtain the ammonium dihydrogen phosphate crystal of rod-like morphology.Procedure quality yield 55.72%, product purity 99.5%, crystal average radial granularity 1.16mm, axial granularity 4.85mm.
Embodiment 5:
Get purity 95% primary ammonium phosphate 85g, deionized water 100g, adds 8000ppm Trisodium Citrate, stirs, and is continued by solution to be heated to 65 DEG C, and adopt crystallisation by cooling method, rate of temperature fall is 10 DEG C/h, is cooled to 35 DEG C.Through washing, filtration, drying, obtain the ammonium dihydrogen phosphate crystal of rod-like morphology.Procedure quality yield 60.78%, product purity reaches 99.6%, crystal average radial granularity 1.00mm, axial granularity 3.44mm.
The present invention's employing additive that is open and that propose changes the preparation method of crystal morphology of ammonium dihydrogen phosphate, and those skilled in the art are by using for reference present disclosure, and the links such as appropriate change raw material, processing parameter realize.Method of the present invention and product are described by preferred embodiment, person skilled obviously can not depart from content of the present invention, spirit and scope method as herein described and product are changed or suitably change with combination, realize the technology of the present invention.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (1)
1. the method utilizing additive to change crystal morphology of ammonium dihydrogen phosphate, it is characterized in that: raw material primary ammonium phosphate purity more than 95%, by primary ammonium phosphate: water mixes in the ratio of ratio of quality and the number of copies 30 ~ 85:100, add organic carboxyl acid or carboxylate salt additive, stir, solution is heated to 45 ~ 65 DEG C of dissolvings, adopts crystallisation by cooling method, be cooled to 5 ~ 35 DEG C; Rate of temperature fall is 2 ~ 20 DEG C/h; Through washing, filtration, drying, obtain the ammonium dihydrogen phosphate crystal of rod-like morphology; The ammonium dihydrogen phosphate crystal of rod-like morphology, two ends are tetrapyamid shape, crystal average radial granularity 0.6 ~ 1.2mm, axial granularity 3 ~ 5mm; Described organic carboxyl acid additive is selected from the one in succinic acid, propanedioic acid, citric acid, pyromellitic acid; Carboxylate salt additive is selected from the one in Trisodium Citrate, propanedioic acid disodium, pyromellitic acid potassium or Tripotassium Citrate; The add-on of described additive is 500 ~ 10000ppm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4269814A (en) * | 1978-08-30 | 1981-05-26 | Central Glass Company, Limited | Process for preparing crystalline ammonium dihydrogen phosphate |
| CN101654235A (en) * | 2009-09-19 | 2010-02-24 | 宜昌瑞特精细化工有限公司 | Method for producing food grade monoammonium phosphate by using agricultural monoammonium phosphate |
| CN101811684A (en) * | 2009-11-23 | 2010-08-25 | 瓮福（集团）有限责任公司 | Method for co-production of granular monoammonium phosphate by using powdery monoammonium phosphate production device |
-
2013
- 2013-11-14 CN CN201310578292.2A patent/CN103601165B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4269814A (en) * | 1978-08-30 | 1981-05-26 | Central Glass Company, Limited | Process for preparing crystalline ammonium dihydrogen phosphate |
| CN101654235A (en) * | 2009-09-19 | 2010-02-24 | 宜昌瑞特精细化工有限公司 | Method for producing food grade monoammonium phosphate by using agricultural monoammonium phosphate |
| CN101811684A (en) * | 2009-11-23 | 2010-08-25 | 瓮福（集团）有限责任公司 | Method for co-production of granular monoammonium phosphate by using powdery monoammonium phosphate production device |
Non-Patent Citations (2)
| Title |
|---|
| P.Rajesh et al..Effect of oxalic acid on the optical,thermal,dielectric and mechanical behaviour of ADP crystals.《Physica B》.2009,第404卷(第8-11期),第1611-1616页. * |
| 汤秀华等.磷酸二氢铵结晶动力学研究.《无机盐工业》.2007,第39卷(第6期),第28-30页. * |
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