CN108689394A - 一种纳米磷酸氢钙的制备方法 - Google Patents

一种纳米磷酸氢钙的制备方法 Download PDF

Info

Publication number
CN108689394A
CN108689394A CN201710912734.0A CN201710912734A CN108689394A CN 108689394 A CN108689394 A CN 108689394A CN 201710912734 A CN201710912734 A CN 201710912734A CN 108689394 A CN108689394 A CN 108689394A
Authority
CN
China
Prior art keywords
calcium
nanometer
preparation
monohydrogen phosphate
phosphate
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
Application number
CN201710912734.0A
Other languages
English (en)
Other versions
CN108689394B (zh
Inventor
杨富巍
刘妍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianshui Normal University
Original Assignee
Tianshui Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tianshui Normal University filed Critical Tianshui Normal University
Priority to CN201710912734.0A priority Critical patent/CN108689394B/zh
Publication of CN108689394A publication Critical patent/CN108689394A/zh
Application granted granted Critical
Publication of CN108689394B publication Critical patent/CN108689394B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K10/00—Animal feeding-stuffs
    • A23K10/40—Mineral licks, e.g. salt blocks
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/24—Compounds of alkaline earth metals, e.g. magnesium
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/26—Compounds containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/16—Acids or salts thereof containing phosphorus in the anion, e.g. phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/325—Calcium, strontium or barium phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Animal Husbandry (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

本发明涉及一种纳米磷酸氢钙的制备方法。其制备步骤为先将磷酸酯、烷氧基钙、表面活性剂溶于多元醇和去离子水的混合溶剂中制成溶液，然后将该溶液加热至一定温度即可得到纳米磷酸氢钙。与传统的制备方法相比，本方法制得的产品粒径小且分布均匀，作为食品、饲料添加剂，医药载体更易于吸收，能有效提高磷、钙的利用率；作为骨水泥组成成分反应活性更高，可有效提高其强度。

Description

一种纳米磷酸氢钙的制备方法
技术领域
本发明涉及一种纳米磷酸氢钙的制备方法。
背景技术
纳米磷酸氢钙可用作高效食品强化剂，饲料添加剂，塑料稳定剂及高强骨水泥的组成成分。目前，纳米磷酸氢钙的制备通常采用均相法或非均相法。均相法通常采用氯化钙、硝酸钙与磷酸钾、磷酸钠等可溶盐为原料，通过原料之间的复分解反应制备磷酸氢钙。如蔡玉荣等公开了一种以氯化钙或硝酸钙为钙源，以磷酸氢钠或磷酸氢二钠为磷源的纳米磷酸氢钙制备技术[蔡玉荣等.一种水热法制备磷酸氢钙纳米线的方法，公开号：CN105314613A]。非均相法通常以石灰和磷酸为反应原料，以表面活性剂为改性剂，在高沸点醇中制备纳米磷酸氢钙。如陈苏等公开了一种利用纳米氢氧化钙为钙源，以磷酸为磷源，以span-80、tritonX-100、聚乙二醇或tween-60为分散剂，在正戊醇、正己醇或环戊醇等溶剂中制备纳米磷酸氢钙的技术[陈苏等.一种纳米氢氧化钙粉体的制备方法，公开号：CN201410070557.2]。基于复分解原理的均相法往往会副产氯化钾、硝酸钾或氯化钠、硝酸钠等可溶盐，得到的产品还要进行洗涤脱盐处理。由于磷酸氢钙的低溶解性，非均相法在采用氢氧化钙作为反应物时容易造成其与磷酸的反应不完全的情况。
发明内容
本发明提供了一种纳米磷酸氢钙的制备方法，即先将磷酸酯、烷氧基钙、表面活性剂、多元醇和去离子水按照一定比例在常温下混合均匀后制成澄清溶液，然后将该溶液加热升温至一定温度即可得到纳米级的磷酸氢钙。
附图说明
图1为纳米磷酸氢钙的制备方法流程图
即：
1、先将磷酸酯、烷氧基钙、表面活性剂、多元醇和去离子水按照质量比1∶0.9～1.7∶0.003～ 0.06∶9.8～49.1∶0.3～1.1在常温下混合溶解后制成澄清溶液。
2、然后将该溶液加热升温至80-120℃即可得到纳米级磷酸氢钙。
有益效果：与基于复分解原理的均相制备方法相比，本发明所述制备方法不副产氯化钾、硝酸钾或氯化钠、硝酸钠等可溶盐，得到的产品不须洗涤脱盐处理。与以氢氧化钙为原料的非均相制备方法相比，本发明所述制备方法反应彻底，制备的纳米磷酸氢钙纯度高，在97％以上。本发明所述制备方法所用设备及工艺条件简单、能耗小，产品粒径分布窄，在50～ 160nm之间。
具体实施方式
下面结合具体实施例对本发明做一详细说明：
实施例1.将磷酸二甲酯、甲氧基钙、曲拉通-100、乙二醇和去离子水按照质量比1∶0.9∶0.003∶ 9.8∶0.3在常温下混合均匀后制成澄清溶液，然后将溶液加热升温至85℃即可得到磷酸氢钙沉淀。经离心分离后，利用无水乙醇洗涤3次后即可得到白色粉末状纳米级磷酸氢钙，粒度范围为120～160纳米，纯度97％，可用于饲料添加剂。
实施例2.将磷酸二乙酯、乙氧基钙、tween-60、乙二醇和去离子水按照质量比1∶0.8∶ 0.006∶11∶0.4在常温下混合均匀后制成澄清溶液，然后将溶液加热升温至95℃即可得到磷酸氢钙沉淀。经离心分离后，利用无水乙醇洗涤3次后即可得到白色粉末状纳米级磷酸氢钙，粒度范围为100～135纳米，纯度97.6％，可用做塑料稳定剂。
实施例3.将磷酸二苯酯、乙氧基钙、OP-10、丙二醇和去离子水按照质量比1∶0.7∶0.01∶12∶0.5在常温下混合均匀后制成澄清溶液，然后将溶液加热升温至115℃即可得到磷酸氢钙沉淀。经离心分离后，利用无水乙醇洗涤3次后即可得到白色粉末状纳米级磷酸氢钙，粒度范围为90～110纳米，纯度98％，可用于高强骨水泥的活性组分。
注：烷氧基钙可由金属钙和相应的无水醇溶剂在加热回流下反应制得(也可直接购置)。

Claims (5)

1.一种纳米磷酸氢钙的制备方法，其特征在于：先将磷酸酯、烷氧基钙、表面活性剂、多元醇和去离子水按照质量比1∶0.9～1.7∶0.003～0.06∶9.8～49.1∶0.3～1.1在常温下混合溶解后制成澄清溶液，然后将该溶液加热升温至85℃-120℃即可得到纳米磷酸氢钙。
2.根据权利1要求所述的一种纳米磷酸氢钙的制备方法，其特征在于：所述磷酸酯为磷酸二甲酯、磷酸二乙酯、磷酸二苯酯中的一种。
3.根据权利1要求所述的一种纳米磷酸氢钙的制备方法，其特征在于：所述烷氧基钙为甲氧基钙、乙氧基钙中的一种。
4.根据权利1要求所述的一种纳米磷酸氢钙的制备方法，其特征在于：所述表面活性剂为曲拉通-100，tween-60或OP-10中的一种。
5.根据权利1要求所述的一种纳米磷酸氢钙的制备方法，所述多元醇为乙二醇、丙二醇、丁二醇中的一种。
CN201710912734.0A 2017-09-15 2017-09-15 一种纳米磷酸氢钙的制备方法 Active CN108689394B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710912734.0A CN108689394B (zh) 2017-09-15 2017-09-15 一种纳米磷酸氢钙的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710912734.0A CN108689394B (zh) 2017-09-15 2017-09-15 一种纳米磷酸氢钙的制备方法

Publications (2)

Publication Number Publication Date
CN108689394A true CN108689394A (zh) 2018-10-23
CN108689394B CN108689394B (zh) 2021-06-18

Family

ID=63844030

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710912734.0A Active CN108689394B (zh) 2017-09-15 2017-09-15 一种纳米磷酸氢钙的制备方法

Country Status (1)

Country Link
CN (1) CN108689394B (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4431630A (en) * 1981-05-08 1984-02-14 Colgate-Palmolive Company Dentifrice composition
JP2783565B2 (ja) * 1987-11-27 1998-08-06 株式会社神戸製鋼所 燐酸カルシウム化合物顆粒体およびその製造方法
CN1308017A (zh) * 2001-02-27 2001-08-15 天津化工研究设计院 一种生产大颗粒结晶饲料级磷酸氢钙工艺的杂质屏蔽方法
CN104220649A (zh) * 2012-04-09 2014-12-17 株式会社小糸制作所 磷灰石结晶
KR20160055253A (ko) * 2013-09-12 2016-05-17 할로자임, 아이엔씨 변형된 항-상피세포 성장인자 수용체 항체 및 이의 사용 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4431630A (en) * 1981-05-08 1984-02-14 Colgate-Palmolive Company Dentifrice composition
JP2783565B2 (ja) * 1987-11-27 1998-08-06 株式会社神戸製鋼所 燐酸カルシウム化合物顆粒体およびその製造方法
CN1308017A (zh) * 2001-02-27 2001-08-15 天津化工研究设计院 一种生产大颗粒结晶饲料级磷酸氢钙工艺的杂质屏蔽方法
CN104220649A (zh) * 2012-04-09 2014-12-17 株式会社小糸制作所 磷灰石结晶
KR20160055253A (ko) * 2013-09-12 2016-05-17 할로자임, 아이엔씨 변형된 항-상피세포 성장인자 수용체 항체 및 이의 사용 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KATALIN SINKÓ ET ALL.: "Effect of phosphorus precursors on the structure of bioactive calcium", 《MATERIALS SCIENCE AND ENGINEERING C》 *

Also Published As

Publication number Publication date
CN108689394B (zh) 2021-06-18

Similar Documents

Publication Publication Date Title
CN105503276B (zh) 一种全水溶性固体聚磷酸铵的制备方法
CN105400071A (zh) 一种防紫外线塑料编织袋用材料
CN103466701A (zh) 一种固相化学反应制备三氧化二铋纳米线的方法
CN104163449A (zh) 一种γ-碘化亚铜的制备方法
CN102408102B (zh) 一种纳米磷酸铁的制备方法
Xie et al. Shape-controlled synthesis of zinc phosphate nanostructures by an aqueous solution route at room temperature
CN103318954B (zh) 一种固相化学反应制备三钛酸钠纳米棒的方法
CN102580720A (zh) 可见光响应的纳米氧化锌-氧化铋复合光催化剂及其制备方法
CN105399128A (zh) 微米纺锤丝状结构球霰石碳酸钙的制备方法
CN107324363B (zh) 一种高Al13含量聚合氯化铝的简易制备方法
CN103806088B (zh) 一种利用三乙醇胺为助剂制备碳酸钙晶须的方法
CN108689394A (zh) 一种纳米磷酸氢钙的制备方法
CN110436512B (zh) 一种羟基氯化锌晶体及其制备方法
CN102557919B (zh) 一种用微波螯合工艺由新沉淀偏钛酸合成柠檬酸钛的方法
CN102603008B (zh) 纳米级黄铜矿的合成方法
CN106350870A (zh) 一种硫酸废液的处置利用方法
CN104418729A (zh) 一种可溶柠檬酸盐的制备方法
CN105543975A (zh) 基于羧甲基纤维素钠与氯化钾合成碳酸钙纳米晶须的方法
CN103318931B (zh) 一种微波水热合成过程中调控勃姆石形貌的方法
CN105776331B (zh) 一种以lrh为模版制备稀土钒酸盐的自牺牲模版合成方法
CN108689421A (zh) 一种单分散纳米氢氧化钙的制备方法
CN101367553B (zh) 合成钼酸锌或碱式钼酸锌的方法
CN104148668A (zh) 一种液相纳米银胶体的制备方法
CN106242705A (zh) 一种提高聚磷酸铵鳌合微量元素的方法
KR20120057189A (ko) 미네랄 수용액 제조방법 및 토양개량제 제조방법

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant