WO2020140359A1 - 一种叶黄素载体用高吸附性二氧化硅的制备方法 - Google Patents

一种叶黄素载体用高吸附性二氧化硅的制备方法 Download PDF

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WO2020140359A1
WO2020140359A1 PCT/CN2019/085756 CN2019085756W WO2020140359A1 WO 2020140359 A1 WO2020140359 A1 WO 2020140359A1 CN 2019085756 W CN2019085756 W CN 2019085756W WO 2020140359 A1 WO2020140359 A1 WO 2020140359A1
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sulfuric acid
lutein
reaction
sodium silicate
silica
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PCT/CN2019/085756
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English (en)
French (fr)
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吴晓林
胡金星
高海明
徐红新
李祥凯
李品
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山东联科科技股份有限公司
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Priority to US16/766,729 priority Critical patent/US11439974B2/en
Publication of WO2020140359A1 publication Critical patent/WO2020140359A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3071—Washing or leaching
    • 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
    • A23K20/10—Organic substances
    • A23K20/179—Colouring agents, e.g. pigmenting or dyeing agents
    • 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
    • A23K20/28—Silicates, e.g. perlites, zeolites or bentonites
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K50/00—Feeding-stuffs specially adapted for particular animals
    • A23K50/70—Feeding-stuffs specially adapted for particular animals for birds
    • A23K50/75—Feeding-stuffs specially adapted for particular animals for birds for poultry
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K50/00—Feeding-stuffs specially adapted for particular animals
    • A23K50/80—Feeding-stuffs specially adapted for particular animals for aquatic animals, e.g. fish, crustaceans or molluscs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the invention relates to the field of preparation of silica, in particular to a preparation method of highly adsorbed silica for lutein carrier.
  • Lutein is mainly used in the coloring of poultry skin, shin, egg yolk, abdomen fat and aquatic animals such as yellow croaker, soft-shelled turtle, yellow catfish, catfish, shrimp, crab, etc. in feed.
  • the lutein sold on the market is mainly derived from the deep processing of marigold flowers, using low-temperature leaching processing technology, the product is a viscous oily liquid, using silica as a carrier, and then dispersed in feed in proportion.
  • Most silicas have the problems of poor adsorption, poor fluidity, and uneven distribution of adsorbed lutein. In the process of production and storage, they are easy to stick and block the processing machinery, which seriously affects the quality of lutein products. The finished product is not easily dispersed in the premix, which restricts the development of the industry.
  • the preparation methods of silica are mainly the precipitation method and the gas phase method. Because the raw materials used in the precipitation method are cheap and readily available, the production process and equipment are relatively simple, and the product prices are low, so they dominate.
  • the precipitation method mainly includes preparing a dilute solution with a certain concentration by using industrial water glass, and then adding an acid under certain conditions to precipitate the silica, and then preparing the silica after washing, filtering, drying and crushing.
  • the silica carriers used in the lutein industry are mostly in the form of fine powder, with a wide particle size distribution and poor fluidity.
  • the pore volume of the product is less than 0.7. After adsorption of lutein, the surface is sticky and easy to agglomerate. Therefore, it is necessary to prepare a highly-adsorbent silica that can be used as a lutein carrier with a narrow particle size distribution, good fluidity, large pore volume, good adsorption, and not easy to agglomerate.
  • the present invention discloses a method for preparing highly adsorbed silica for lutein carrier, which includes the following steps:
  • step (2) To the reaction solution B obtained in step (1), sulfuric acid and sodium silicate are simultaneously added for a synthesis reaction, and the reaction solution C is obtained;
  • step (3) Stop adding sodium silicate to the reaction solution C obtained in step (2), and add only sulfuric acid for post-acidification. After the pH value reaches 3.5-4.0, stop adding sulfuric acid. After curing, dilute slurry D is obtained;
  • step (4) The slurry obtained in step (4) is dried and packaged to obtain the high-absorption silica microspheres for the lutein carrier.
  • the sodium silicate in the steps (1)-(2) is a sodium silicate aqueous solution with a concentration of 30-40 Baume, and the modulus of the sodium silicate is 3.30-3.60.
  • the feeding amount of the sodium silicate is 4-8.0m 3 , the concentration of the sodium silicate in the reaction primer A is 15-20 Baume;
  • the sulfuric acid is a mass fraction of 15%-30% sulfuric acid aqueous solution, the feeding speed of the sulfuric acid is 15m 3 /h, the feeding time of the sulfuric acid is 10-30min;
  • the reaction temperature is 30-60°C; the stirring speed is 45-80rpm
  • the sulfuric acid is a sulfuric acid aqueous solution with a mass fraction of 93-99%, the feed rate of the sulfuric acid is 0.6m 3 /h, and the feed rate of the sodium silicate is 4-8m 3 / h, the feeding time of the sulfuric acid and sodium silicate is 30-60min; the reaction temperature is 75-95°C.
  • the sulfuric acid is a sulfuric acid aqueous solution with a mass fraction of 93-99%, and the feed rate of the sulfuric acid is 50-75% of the feed rate of sulfuric acid in the step (2); the feed time is 15 -30min, the reaction temperature is 75-95 °C; the aging time is 15-30min.
  • the slurry viscosity-reducing agent is a food-grade organic acid; preferably, the organic acid is citric acid; the conductivity of the drain water of the washing water during the washing process is 3.0-8.0ms/ cm.
  • the drying method is drying in a centrifugal drying tower at an atomizing speed; the inlet temperature of the centrifugal drying tower is 450-550°C, and the outlet temperature of the centrifugal drying tower is 110-150 °C, the pressure of the centrifugal drying tower is -150 ⁇ -50Pa; the rotation speed of the atomizer is 5000-9000rpm; the packaging is packaging using a vacuum packaging machine, the pressure of the packaging is -100 ⁇ -300Pa.
  • the highly-adsorbent silica for lutein carrier provided by the present invention can be prepared by controlling the process parameters in each step of the synthesis process, including the concentration of sodium silicate and sulfuric acid, the concentration of the primer, the synthesis time, etc.
  • the silica has large pore volume, high adsorption and stable structure.
  • the present invention uses food-grade organic acids, which not only ensures the safety of silica, but also makes the prepared silica have a certain hardness.
  • the drying method in the present invention is to dry in a centrifugal drying tower at a certain atomization speed.
  • the prepared product has a narrow particle size distribution.
  • vacuum Negative pressure packaging effectively removes fine dust in the product.
  • the present invention makes the highly-adsorbed silica for the lutein carrier prepared after adsorbing lutein strong in adsorption, good in dispersibility and fluidity.
  • Example 1 A method for preparing highly adsorbed silica for lutein carrier
  • step (2) To the reaction solution B obtained in step (1), sulfuric acid and sodium silicate are simultaneously added for a synthesis reaction, and the reaction solution C is obtained;
  • step (3) Stop adding sodium silicate to the reaction solution C obtained in step (2), and add only sulfuric acid for post-acidification, stop adding sulfuric acid after the pH value reaches 4.0, and obtain a thin slurry D after aging;
  • step (4) The slurry obtained in step (4) is dried and packaged to obtain the silica microspheres for the lutein carrier, and the silica microspheres for the lutein carrier are uniform coarse powder Silica products.
  • the sodium silicate in the steps (1)-(2) is an aqueous solution of sodium silicate with a concentration of 30 Baume, and the modulus of the sodium silicate is 3.30.
  • the feeding amount of the sodium silicate is 8.0m 3 , the concentration of sodium silicate in the reaction primer A is 20 Baume;
  • the sulfuric acid is sulfuric acid with a mass fraction of 30%
  • the feed rate of the sulfuric acid is 15 m 3 /h, and the feed time of the sulfuric acid is 25 min;
  • the reaction temperature in the step (1) is 60° C.; and the stirring speed is 72 rpm.
  • the sulfuric acid is an aqueous solution of sulfuric acid with a mass fraction of 98%, the feed rate of the sulfuric acid is 0.6 m 3 /h, and the feed rate of the sodium silicate is 8 m 3 /h, the The feeding time of sulfuric acid and sodium silicate is 60 min; the reaction temperature is 95°C.
  • the sulfuric acid is a sulfuric acid aqueous solution with a mass fraction of 98%, the feed rate of the sulfuric acid is 0.3m 3 /h; the feed time is 30min, the reaction temperature is 95°C; and the aging The time is 30min.
  • the slurry viscosity-reducing agent citric acid the addition amount of the citric acid is 8.0Kg, the pH of the slurry F is 6.5, and the drainage conductivity of the washing water is 3.0ms /cm.
  • the drying method is drying in a centrifugal drying tower at an atomizing speed; the inlet temperature of the centrifugal drying tower is 500°C, and the outlet temperature of the centrifugal drying tower is 120°C
  • the pressure of the centrifugal drying tower is -100 Pa; the rotational speed of the atomizer is 9000 rpm; the packaging is packaging using a vacuum packaging machine, and the pressure of the packaging is -100 Pa.
  • Example 2 A method for preparing highly adsorbed silica for lutein carrier
  • step (2) To the reaction solution B obtained in step (1), sulfuric acid and sodium silicate are simultaneously added for a synthesis reaction, and the reaction solution C is obtained;
  • step (3) Stop adding sodium silicate to the reaction solution C obtained in step (2), and add only sulfuric acid for post-acidification, stop adding sulfuric acid after the pH value reaches 4.0, and obtain a thin slurry D after aging;
  • step (4) The slurry obtained in step (4) is dried and packaged to obtain the silica microspheres for the lutein carrier, and the silica microspheres for the lutein carrier are uniform coarse powder Silica products.
  • the sodium silicate in the steps (1)-(2) is an aqueous solution of sodium silicate with a concentration of 38 Baume, and the modulus of the sodium silicate is 3.60.
  • the feeding amount of the sodium silicate is 8.0m 3 , the concentration of sodium silicate in the reaction primer A is 20 Baume;
  • the sulfuric acid is sulfuric acid with a mass fraction of 30% In an aqueous solution, the feed rate of the sulfuric acid is 15 m 3 /h, and the feed time of the sulfuric acid is 25 min;
  • the reaction temperature in the step (1) is 40° C.; and the stirring speed is 72 rpm.
  • the sulfuric acid is an aqueous solution of sulfuric acid with a mass fraction of 98%, the feed rate of the sulfuric acid is 0.6 m 3 /h, and the feed rate of the sodium silicate is 8 m 3 /h, the The feeding time of sulfuric acid and sodium silicate is 60 min; the reaction temperature is 85°C.
  • the sulfuric acid is an aqueous solution of sulfuric acid with a mass fraction of 98%, the feed rate of the sulfuric acid is 0.3m 3 /h; the feed time is 30min, the reaction temperature is 85°C; the aging The time is 30min.
  • the slurry viscosity reducer is citric acid; the added amount of the citric acid is 8.0Kg; the pH of the slurry F is 6.4, and the drainage conductivity of the washing water is 3.0 ms/cm.
  • the drying method is drying in a centrifugal drying tower at an atomizing speed; the inlet temperature of the centrifugal drying tower is 500°C, and the outlet temperature of the centrifugal drying tower is 140°C
  • the pressure of the centrifugal drying tower is -150 Pa; the rotation speed of the atomizer is 5500 rpm; the packaging is packaging using a vacuum packaging machine, and the pressure of the packaging is -200 Pa.
  • Example 3 A method for preparing highly adsorbed silica for lutein carrier
  • step (2) To the reaction solution B obtained in step (1), sulfuric acid and sodium silicate are simultaneously added for a synthesis reaction, and the reaction solution C is obtained;
  • step (3) Stop adding sodium silicate to the reaction solution C obtained in step (2), only add sulfuric acid for post-acidification, stop adding sulfuric acid after the pH reaches 3.8, and obtain a thin slurry D after aging;
  • step (4) The slurry obtained in step (4) is dried and packaged to obtain the silica microspheres for the lutein carrier, and the silica microspheres for the lutein carrier are uniform coarse powder Silica products.
  • the sodium silicate in the steps (1)-(2) is an aqueous solution of sodium silicate with a concentration of 30 Baume, and the modulus of the sodium silicate is 3.60.
  • the feeding amount of the sodium silicate is 9.0m 3 , the concentration of the sodium silicate in the reaction primer A is 17.0 Baume;
  • the sulfuric acid is sulfuric acid with a mass fraction of 60% In an aqueous solution, the feed rate of the sulfuric acid is 15 m 3 /h.
  • the feed time of the sulfuric acid is 25 min;
  • the reaction temperature in the step (1) is 50° C.; and the stirring speed is 47 rpm.
  • Said step (2) mass fraction of the sulfuric acid is 98% aqueous sulfuric acid, the sulfuric acid feed rate was 0.6m 3 / h, a feed rate of the sodium silicate was 7.0m 3 / h, the The feeding time of the sulfuric acid and sodium silicate is 55 min; the reaction temperature is 80°C.
  • the sulfuric acid is a sulfuric acid aqueous solution with a mass fraction of 98%, the feed rate of the sulfuric acid is 0.3m 3 /h; the feed time is 35min, the reaction temperature is 85°C; and the aging The time is 20min.
  • the slurry viscosity-reducing agent is citric acid; the amount of the citric acid added is 8.0 Kg; the pH of the slurry F is 6.3, and the drain water conductivity of the washing water is 4.0 ms/cm.
  • the drying method is drying in a centrifugal drying tower at an atomizing speed; the inlet temperature of the centrifugal drying tower is 500°C, and the outlet temperature of the centrifugal drying tower is 130°C
  • the pressure of the centrifugal drying tower is -100 Pa; the rotation speed of the atomizer is 7800 rpm; the packaging is packaging using a vacuum packaging machine, and the pressure of the packaging is -100 Pa.
  • Comparative Example 1 A method for preparing highly absorbent silica for lutein carrier
  • the preparation method is basically the same as Example 1, and the difference from Example 1 is that:
  • the modulus of the sodium silicate is 2.90.
  • Comparative Example 2 A method for preparing highly absorbent silica for lutein carrier
  • the preparation method is basically the same as Example 1, and the difference from Example 1 is that:
  • the slurry viscosity reducer is polyacrylic acid.
  • the lutein carrier prepared by the preparation methods in the above Examples 1-3 and Comparative Examples 1-2 was subjected to performance testing with highly adsorbent silica, and the test results are shown in the following table:
  • the highly-adsorbent silica for lutein carrier provided by the present invention has a large DBP absorption capacity, a small bulk specific gravity, and a high water absorption rate.

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Abstract

提供一种叶黄素载体用高吸附性二氧化硅的制备方法，包括：将硅酸钠加入到合成釜中，在搅拌下通入蒸汽升温，加水搅拌反应得到反应底料A，向其中加入硫酸进行酸化，至溶液pH为8.5-10.5，得到反应液B；向反应液B中同时加入硫酸和硅酸钠进行合成反应，得到反应液C；停止向其中加入硅酸钠，只加入硫酸，pH达到3.5-4.0后停止加酸，熟化后得稀浆料D；过滤、洗涤后得到滤饼E，转移至制浆机，加入浆料降粘剂，得浆料F；经干燥、包装，得二氧化硅微球产品。该方法通过对各工艺的精确控制使得到的叶黄素载体用二氧化硅在吸附叶黄素后仍具备吸附性强、分散性和流动性好的优点。

Description

一种叶黄素载体用高吸附性二氧化硅的制备方法 技术领域
本发明涉及二氧化硅的制备领域，特别涉及一种叶黄素载体用高吸附性二氧化硅的制备方法。
背景技术
随着人们对动物产品色泽的要求，营养学研究重点不仅要促进畜禽水产品生长，而且也有越来越多的研究集中在如何提高畜禽水产品的色、香、味、营养等商品的品质上，通过在饲料中添加叶黄素类着色剂以满足消费者需求即是其目标。叶黄素在饲料中主要用于禽类的皮肤、脚胫、禽蛋蛋黄、禽腹脂和水产动物如黄鱼、甲鱼、黄颡鱼、斑点叉尾鮰、虾、蟹等的着色。目前市场上所售叶黄素主要来源于万寿菊鲜花的深加工，采用低温浸出加工工艺，产品为粘稠油状液体，用二氧化硅做载体，然后按比例分散于饲料中。多数二氧化硅在使用中存在吸附性差，流动性差，吸附的叶黄素分布不均匀的问题，在生产和储存过程中易粘连结块，堵塞加工机械，严重影响叶黄素制品产品质量，制成品在预混料中不易分散，制约了该行业发展。以上缺陷导致二氧化硅载体的使用受到较大限制，只能依靠降低产品水分到装备极限来弥补吸附性和流动性差的不足，造成产品成本居高不下。目前，二氧化硅的制备方法主要是沉淀法和气相法，由于沉淀法所用原料便宜易得，生产工艺和设备较为简单，产品售价低，因此占主导地位。沉淀法主要包括是采用工业水玻璃配制成一定浓度的稀溶液，然后在一定条件下加入某种酸，使二氧化硅沉淀出来，再经清洗、过滤、干燥、粉碎后制备得到二氧化硅。目前叶黄素行业使用的二氧化硅载体外观多为细粉状，产品粒度分布宽，自身流动性差；产品孔容低于0.7，吸附叶黄素后，表面粘稠易团聚。因此，需要制备出一种粒径分布窄、流动性好、孔容大、吸附性好、不易团聚的可作为叶黄素载体用高吸附性二氧化硅。
发明内容
为解决上述技术问题，本发明公开了一种叶黄素载体用高吸附性二氧化硅的制备方法，包括以下步骤：
(1)：将硅酸钠加入到合成釜中，在搅拌的条件下通入蒸汽升温，加入水搅拌反应得到反应底料A，向得到的反应底料A中加入硫酸进行先酸化，至溶液pH为8.5-10.5，得到反应液B；
(2)：向步骤(1)得到的反应液B中同时加入硫酸和硅酸钠进行合成反应，反应得到反应液C；
(3)：步骤(2)得到的反应液C中停止加入硅酸钠，只加入硫酸进行后酸化，检测pH达到3.5-4.0后停止加入硫酸，熟化后得到稀浆料D；
(4)：将步骤(3)得到的稀浆料D经过过滤、洗涤后得到滤饼E，将得到的滤饼E转移至制浆机，加入浆料降粘剂，得到浆料F；
(5)：将步骤(4)得到的浆料经过干燥、包装，即得到所述的叶黄素载体用高吸附性二氧化硅微球。
所述步骤(1)-(2)中的硅酸钠为浓度为30-40波美度的硅酸钠水溶液，所述硅酸钠的模数为3.30-3.60。
所述步骤(1)中：所述硅酸钠的加料量为4-8.0m 3，所述反应底料A中硅酸钠的浓度为15-20波美度；所述硫酸为质量分数为15％-30％的硫酸水溶液，所述硫酸的加料速度为15m 3/h，所述硫酸的加料时间为10-30min；所述反应温度为30-60℃；所述搅拌速度为45-80rpm
所述步骤(2)中：所述硫酸为质量分数为93-99％的硫酸水溶液，所述硫酸的加料速度为0.6m 3/h，所述硅酸钠的加料速度为4-8m 3/h，所述硫酸和硅酸钠的加料时间为30-60min；所述反应温度为75-95℃。
所述步骤(3)中：所述硫酸为质量分数为93-99％的硫酸水溶液，所述硫酸的加料速度为步骤(2)中硫酸加料速度的50-75％；所述加料时间为15-30min，反应温度为75-95℃；所述熟化时间为15-30min。
所述步骤(4)中：所述浆料降粘剂为食品级有机酸；优选地，所述的有机酸为柠檬酸；所述洗涤过程中洗涤水的排水电导率为3.0-8.0ms/cm。
所述步骤(5)中：所述干燥方法为在离心干燥塔内，在雾化转速下进行干燥；所述离心干燥塔的进口温度为450-550℃，所述离心干燥塔的出口温度为110-150℃，所述离 心干燥塔的压力为-150～-50Pa；所述雾化器的转速为5000-9000rpm；所述包装为采用真空包装机进行包装，所述包装的压力为-100～-300Pa。
本发明的有益效果是：
(1)本发明提供的叶黄素载体用高吸附性二氧化硅通过控制合成过程中的各个步骤中的工艺参数，包括硅酸钠和硫酸浓度、底料浓度、合成时间等，使得制备得到的二氧化硅孔容大、吸附性高，结构稳定。
(2)本发明采用食品级有机酸，不仅保证了二氧化硅的安全性，并且使得制备得到的二氧化硅具有一定的硬度。
(3)本发明中的干燥方法为在离心干燥塔内，在一定的雾化转速下进行干燥，通过控制雾化器中的转速，使得制备得到的产品具有较窄的粒度分布，通过采用真空负压包装，有效去除了产品中的较细粉尘。
(4)本发明通过上述的各个工艺的精确控制，使得制备得到的叶黄素载体用高吸附性二氧化硅在吸附叶黄素后，其吸附性强、分散性和流动性好。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。
实施例1一种叶黄素载体用高吸附性二氧化硅的制备方法
包括以下步骤：
(1)：将硅酸钠加入到合成釜中，在搅拌的条件下通入蒸汽升温，加入水搅拌反应得到反应底料A，向得到的反应底料A中加入硫酸进行先酸化，至溶液pH为10.0，得到反应液B；
(2)：向步骤(1)得到的反应液B中同时加入硫酸和硅酸钠进行合成反应，反应得到反应液C；
(3)：步骤(2)得到的反应液C中停止加入硅酸钠，只加入硫酸进行后酸化，检测pH达到4.0后停止加入硫酸，熟化后得到稀浆料D；
(4)：将得到的稀浆料D经过过滤、洗涤后得到滤饼E，将得到的滤饼E转移至制浆机，加入浆料降粘剂，得到浆料F；
(5)：将步骤(4)得到的浆料经过干燥、包装，即得到所述的叶黄素载体用二氧化硅微球，所述叶黄素载体用二氧化硅微球为均匀粗粉状二氧化硅产品。
所述步骤(1)-(2)中的硅酸钠为浓度为30波美度的硅酸钠水溶液，所述硅酸钠的模数为3.30。
所述步骤(1)中：所述硅酸钠的加料量为8.0m 3，所述反应底料A中硅酸钠的浓度为20波美度；所述硫酸为质量分数为30％的硫酸水溶液，所述硫酸的加料速度为15m 3/h，所述硫酸的加料时间为25min；所述步骤(1)中的反应温度为60℃；所述搅拌速度为72rpm。
所述步骤(2)中：所述硫酸为质量分数为98％的硫酸水溶液，所述硫酸的加料速度为0.6m 3/h，所述硅酸钠的加料速度为8m 3/h，所述硫酸和硅酸钠的加料时间为60min；所述反应温度为95℃。
所述步骤(3)中：所述硫酸为质量分数为98％的硫酸水溶液，所述硫酸的加料速度为0.3m 3/h；所述加料时间为30min，反应温度为95℃；所述熟化时间为30min。
所述步骤(4)中：所述浆料降粘剂柠檬酸，所述柠檬酸的加入量为8.0Kg，所述浆料F的pH为6.5，所述洗涤水的排水电导率为3.0ms/cm。
所述步骤(5)中：所述干燥方法为在离心干燥塔内，在雾化转速下进行干燥；所述离心干燥塔的进口温度为500℃，所述离心干燥塔的出口温度为120℃，所述离心干燥塔的压力为-100Pa；所述雾化器的转速为9000rpm；所述包装为采用真空包装机进行包装，所述包装的压力为-100Pa。
实施例2一种叶黄素载体用高吸附性二氧化硅的制备方法
(1)：将硅酸钠加入到合成釜中，在搅拌的条件下通入蒸汽升温，加入水搅拌反应得到反应底料A，向得到的反应底料A中加入硫酸进行先酸化，至溶液pH为10.0，得到反应液B；
(2)：向步骤(1)得到的反应液B中同时加入硫酸和硅酸钠进行合成反应，反应得到反应液C；
(3)：步骤(2)得到的反应液C中停止加入硅酸钠，只加入硫酸进行后酸化，检测pH达到4.0后停止加入硫酸，熟化后得到稀浆料D；
(4)：将得到的稀浆料D经过过滤、洗涤后得到滤饼E，将得到的滤饼E转移至制浆机，加入浆料降粘剂，得到浆料F；
(5)：将步骤(4)得到的浆料经过干燥、包装，即得到所述的叶黄素载体用二氧化硅微球，所述叶黄素载体用二氧化硅微球为均匀粗粉状二氧化硅产品。
所述步骤(1)-(2)中的硅酸钠为浓度为38波美度的硅酸钠水溶液，所述硅酸钠的模数为3.60。
所述步骤(1)中：所述硅酸钠的加料量为8.0m 3，所述反应底料A中硅酸钠的浓度为20波美度；所述硫酸为质量分数为30％的硫酸水溶液，所述硫酸的加料速度为15m 3/h，所述硫酸的加料时间为25min；所述步骤(1)中的反应温度为40℃；所述搅拌速度为72rpm。
所述步骤(2)中：所述硫酸为质量分数为98％的硫酸水溶液，所述硫酸的加料速度为0.6m 3/h，所述硅酸钠的加料速度为8m 3/h，所述硫酸和硅酸钠的加料时间为60min；所述反应温度为85℃。
所述步骤(3)中：所述硫酸为质量分数为98％的硫酸水溶液，所述硫酸的加料速度为0.3m 3/h；所述加料时间为30min，反应温度为85℃；所述熟化时间为30min。
所述步骤(4)中：所述浆料降粘剂为柠檬酸；所述柠檬酸的加入量为8.0Kg；所述浆料F的pH为6.4，所述洗涤水的排水电导率为3.0ms/cm。
所述步骤(5)中：所述干燥方法为在离心干燥塔内，在雾化转速下进行干燥；所述离心干燥塔的进口温度为500℃，所述离心干燥塔的出口温度为140℃，所述离心干燥塔的压力为-150Pa；所述雾化器的转速为5500rpm；所述包装为采用真空包装机进行包装，所述包装的压力为-200Pa。
实施例3一种叶黄素载体用高吸附性二氧化硅的制备方法
(1)：将硅酸钠加入到合成釜中，在搅拌的条件下通入蒸汽升温，加入水搅拌反应得到反应底料A，向得到的反应底料A中加入硫酸进行先酸化，至溶液pH为9.0，得到反应液B；
(2)：向步骤(1)得到的反应液B中同时加入硫酸和硅酸钠进行合成反应，反应得到反应液C；
(3)：步骤(2)得到的反应液C中停止加入硅酸钠，只加入硫酸进行后酸化，检测pH达到3.8后停止加入硫酸，熟化后得到稀浆料D；
(4)：将得到的稀浆料D经过过滤、洗涤后得到滤饼E，将得到的滤饼E转移至制浆机，加入浆料降粘剂，得到浆料F；
(5)：将步骤(4)得到的浆料经过干燥、包装，即得到所述的叶黄素载体用二氧化硅微球，所述叶黄素载体用二氧化硅微球为均匀粗粉状二氧化硅产品。
所述步骤(1)-(2)中的硅酸钠为浓度为30波美度的硅酸钠水溶液，所述硅酸钠的模数为3.60。
所述步骤(1)中：所述硅酸钠的加料量为9.0m 3，所述反应底料A中硅酸钠的浓度为17.0波美度；所述硫酸为质量分数为60％的硫酸水溶液，所述硫酸的加料速度为15m 3/h所述硫酸的加料时间为25min；所述步骤(1)中的反应温度为50℃；所述搅拌速度为47rpm。
所述步骤(2)中：所述硫酸为质量分数为98％的硫酸水溶液，所述硫酸的加料速度为0.6m 3/h，所述硅酸钠的加料速度为7.0m 3/h，所述硫酸和硅酸钠的加料时间为55min；所述反应温度为80℃。
所述步骤(3)中：所述硫酸为质量分数为98％的硫酸水溶液，所述硫酸的加料速度为0.3m 3/h；所述加料时间为35min，反应温度为85℃；所述熟化时间为20min。
所述步骤(4)中：所述浆料降粘剂为柠檬酸；所述柠檬酸的加入量为8.0Kg；所述浆料F的pH为6.3，所述洗涤水的排水电导率为4.0ms/cm。
所述步骤(5)中：所述干燥方法为在离心干燥塔内，在雾化转速下进行干燥；所述离心干燥塔的进口温度为500℃，所述离心干燥塔的出口温度为130℃，所述离心干燥塔的压力为-100Pa；所述雾化器的转速为7800rpm；所述包装为采用真空包装机进行包装，所述包装的压力为-100Pa。
对比例1一种叶黄素载体用高吸附性二氧化硅的制备方法
其制备方法基本同实施例1，与实施例1的差别在于：
所述的硅酸钠的模数为2.90。
对比例2一种叶黄素载体用高吸附性二氧化硅的制备方法
其制备方法基本同实施例1，与实施例1的差别在于：
所述步骤(4)中浆料降粘剂为聚丙烯酸。
将上述实施例1-3及对比例1-2中的制备方法制备得到的叶黄素载体用高吸附性二氧化硅进行性能测试，测试结果如下表所示：
表1
Figure PCTCN2019085756-appb-000001
从上表可以看出，本发明提供的叶黄素载体用高吸附性二氧化硅具有较大的DBP吸收量，堆积比重小，吸水率高。
表2
Figure PCTCN2019085756-appb-000002
从表2可以看出，本发明实施例1-3制备得到的叶黄素载体用高吸附性二氧化硅的稳定性好，对叶黄素的吸收率高，高于对比例2。
表3
Figure PCTCN2019085756-appb-000003
从表3可以看出，本实施例1-3提供的叶黄素载体用高吸附性二氧化硅具有较大的比表面积和孔容积，二氧化硅含量高，并且分散性好，制备的二氧化硅不团聚。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。另外，各个实施例之间的技术方案可以相互结合，但是必须是以本领域普通技术人员能够实现为基础；当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在，也不在本发明要求的保护范围之内。

Claims (10)

  1. 一种叶黄素载体用高吸附性二氧化硅的制备方法，其特征在于，包括以下步骤：
    (1)：将硅酸钠加入到合成釜中，在搅拌的条件下通入蒸汽升温，加入水搅拌反应得到反应底料A，向得到的反应底料A中加入硫酸进行先酸化，至溶液pH为8.5-10.5，得到反应液B；
    (2)：向步骤(1)得到的反应液B中同时加入硫酸和硅酸钠进行合成反应，反应得到反应液C；
    (3)：步骤(2)得到的反应液C中停止加入硅酸钠，只加入硫酸进行后酸化，检测pH达到3.5-4.0后停止加入硫酸，熟化后得到稀浆料D；
    (4)：将步骤(3)得到的稀浆料D经过过滤、洗涤后得到滤饼E，将得到的滤饼E转移至制浆机，加入浆料降粘剂，得到浆料F；
    (5)：将步骤(4)得到的浆料F经过干燥、包装，即得到所述的叶黄素载体用高吸附性二氧化硅微球。
  2. 如权利要求1所述的叶黄素载体用高吸附性二氧化硅的制备方法，其特征在于，所述步骤(1)-(2)中的硅酸钠为浓度为30-40波美度的硅酸钠水溶液，所述硅酸钠的模数为3.30-3.60。
  3. 如权利要求2所述的叶黄素载体用高吸附性二氧化硅的制备方法，其特征在于，所述步骤(1)中：所述硅酸钠的加料量为4.0-8.0m 3，所述反应底料A中硅酸钠的浓度为15-20波美度；所述硫酸为质量分数为15-30％的硫酸水溶液，所述硫酸的加料速度为15m 3/h，所述硫酸的加料时间为10-30min；所述反应温度为30-60℃；所述搅拌速度为45-80rpm。
  4. 如权利要求2所述的叶黄素载体用高吸附性二氧化硅的制备方法，其特征在于，所述步骤(2)中：所述硫酸为质量分数为93-99％的硫酸水溶液，所述硫酸的加料速度为0.6m 3/h，所述硅酸钠的加料速度为4-8m 3/h，所述硫酸和硅酸钠的加料时间为30-60min；所述反应温度为75-95℃。
  5. 如权利要求4所述的叶黄素载体用高吸附性二氧化硅的制备方法，其特征在于，所述步骤(3)中：所述硫酸为质量分数为93-99％的硫酸水溶液，所述硫酸的加料速度为 步骤(2)中硫酸加料速度的50-75％；所述加料时间为30-60min，反应温度为75-95℃；所述熟化时间为15-30min。
  6. 如权利要求1所述的叶黄素载体用高吸附性二氧化硅的制备方法，其特征在于，所述步骤(4)中：所述浆料降粘剂为食品级有机酸。
  7. 如权利要求6所述的叶黄素载体用高吸附性二氧化硅的制备方法，其特征在于，所述有机酸为柠檬酸。
  8. 如权利要求1所述的叶黄素载体用高吸附性二氧化硅的制备方法，其特征在于，所述洗涤过程中洗涤水的排水电导率为3.0-8.0ms/cm，所述滤饼pH值为6-7。
  9. 如权利要求1所述的叶黄素载体用高吸附性二氧化硅的制备方法，其特征在于，所述步骤(5)中：所述干燥方法为在离心干燥塔内，在一定的雾化转速下进行干燥；所述离心干燥塔的进口温度为450-550℃，所述离心干燥塔的出口温度为110-150℃，所述离心干燥塔的压力为-150～-50Pa；所述雾化器的转速为5000-9000rpm。
  10. 如权利要求1所述的叶黄素载体用高吸附性二氧化硅，其特征在于，所述步骤(5)中的包装为采用真空包装机进行包装，所述包装的压力为-100～-300Pa。
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