WO2020011174A1 - 一种阻垢剂颗粒及其制备方法 - Google Patents

一种阻垢剂颗粒及其制备方法 Download PDF

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WO2020011174A1
WO2020011174A1 PCT/CN2019/095316 CN2019095316W WO2020011174A1 WO 2020011174 A1 WO2020011174 A1 WO 2020011174A1 CN 2019095316 W CN2019095316 W CN 2019095316W WO 2020011174 A1 WO2020011174 A1 WO 2020011174A1
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Prior art keywords
scale inhibitor
water
particles
weight
binder
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PCT/CN2019/095316
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English (en)
French (fr)
Inventor
肖国花
姚振虎
李水清
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艾欧史密斯(中国)热水器有限公司
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Priority claimed from CN201821076083.2U external-priority patent/CN209815789U/zh
Priority claimed from CN201810742893.5A external-priority patent/CN108821451B/zh
Application filed by 艾欧史密斯(中国)热水器有限公司 filed Critical 艾欧史密斯(中国)热水器有限公司
Publication of WO2020011174A1 publication Critical patent/WO2020011174A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
    • F24H9/00—Details

Definitions

  • the invention relates to a scale inhibitor particle and a preparation method thereof. Specifically, the present invention provides a scale inhibitor particle.
  • the scale inhibitor particle has a stable dissolution rate and can be used for a long period of time under the condition of meeting the scale inhibition effect.
  • the invention also relates to a water heater containing the scale inhibitor particles.
  • a scale inhibitor containing a scale inhibitor is usually provided before the water heater. Before the tap water enters the water heater, it is softened by the scale inhibitor, thereby improving the water quality and extending the service life of the water heater.
  • the scale inhibitor will occupy a certain space and affect the aesthetics of the room. Therefore, it is desirable to develop a new scale inhibitor.
  • the inventors hope to develop a scale inhibitor that can be used both outside and inside the water heater. If the scale inhibitor can be used inside the water heater, the above problems can be solved.
  • the scale inhibitor particles are placed in the liner of the water heater, which will occupy the water storage space of the liner.
  • the more the scale inhibitor particles are placed the longer the scale inhibitor life will be and the larger the space occupied by the liner. Therefore, it is desirable to install a sufficient amount of scale inhibitor particles in a tank as small as possible, but if the density of the scale inhibitor particles is too large, the water will not flow smoothly, and the scale inhibitor effect will also be affected;
  • the object of the present invention is to provide a scale inhibitor particle.
  • the purpose is to solve the above technical problems.
  • the scale inhibitor particles of the present invention can prevent the particles from being broken, thereby preventing the components of the scale inhibitor from being washed away by water flow.
  • the object of the present invention is also to improve the service life of the scale inhibitor particles.
  • the present invention also provides a scale inhibitor having a specific structure. By making the scale inhibitor of the present invention have a specific structure, the scale inhibitor of the present invention can be uniformly released from the scale inhibitor particles, the scale inhibition effect is improved, and the use time is prolonged.
  • the object of the present invention is also to provide a water heater, a scale inhibitor is built in the inner container, and scale inhibitor particles are contained in the scale inhibitor device.
  • the shape and structure of the scale inhibitor particles, the weight of the scale inhibitor, the adhesive are configured to ensure that the scale inhibitor particles in a unit area of the tank body equipped with the scale inhibitor particles have a better scale inhibition effect and a longer life and occupy less space.
  • the invention provides a scale inhibitor particle, the scale inhibitor particle comprises a scale inhibitor and a binder, and the content of the scale inhibitor is 60% to 98%, preferably 60% to 95%.
  • the content of the mixture is 2% to 40%, preferably 5% to 40%.
  • the solubility of the scale inhibitor in water below 90 ° C is less than 5g / 100g, and the adhesive is cured at a temperature below 90 ° C.
  • the solubility in water is lower than the solubility of the scale inhibitor, the swelling degree of the particles in water below 90 ° C is less than 12%, and the degree of hydrolysis in water below 90 ° C after curing of the adhesive is less than 1%.
  • the content of the scale inhibitor can be maximized by reducing the content of the binder, thereby extending the life of the scale inhibitor particles.
  • simply increasing the content of the scale inhibitor will result in insufficient strength of the scale inhibitor particles and easy fracture.
  • the inventors have discovered that by selecting a scale inhibitor with a solubility of less than 5g / 100g water, and further making the solubility of the binder lower than that of the scale inhibitor, while controlling the degree of swelling of the scale inhibitor particles in water below 90 ° C Less than 12%, and choose a binder with a degree of hydrolysis of less than 1% in water below 90 ° C after curing, so that when the scale inhibitor dissolves, the binder still maintains its skeleton structure, thereby extending the use of scale inhibitor particles time.
  • the inventors have also discovered that when a scale inhibitor having a specific polar group is used, it can interact with the binder and suppress the expansion rate of the scale inhibitor particles, thereby better solving the technical problem of the present invention.
  • the scale inhibitor may contain at least one of the following polar groups or salts thereof: a phosphate group, a phosphonic acid group, a phosphate group, a phosphoryl group, a carboxyl group, and a sulfonic acid group.
  • Scale inhibitors are preferably polyphosphates, organic phosphonates, maleic anhydride and polyaspartic acid.
  • the present invention also provides a method for preparing scale inhibitor particles and scale inhibitor particles having a specific structure.
  • the scale inhibitor particles of the present invention may be composed only of a scale inhibitor and a binder. Without affecting the technical effects of the present invention, the scale inhibitor particles of the present invention may contain other additives.
  • the ratio of the scale inhibitor to the binder decreases from the center to the outer surface.
  • the scale inhibitor content is small on the outer surface of the scale inhibitor particles, but the area where the scale inhibitor contacts water is large.
  • the scale inhibitor dissolves, the scale inhibitor particles become smaller, and the contact area of the scale inhibitor with water also becomes smaller, but the content of the scale inhibitor increases, thereby compensating for the smaller contact area between the scale inhibitor and water.
  • Reduced dissolution rate With this structure, the scale inhibitor can be dissolved out at a uniform rate, ensuring the scale inhibition effect and the service life of the scale inhibitor particles.
  • the scale inhibitor particles may have a core layer, an intermediate layer, and an outer layer.
  • the scale inhibitor of the core layer is 95% to 100% by weight, and the binder is 0 to 5% by weight.
  • the scale inhibitor of the layer is 90% to 95% by weight, and the content of the binder is 5% to 10% by weight; the scale inhibitor of the outer layer is 80% to 90% by weight, and the binder is 10%. % By weight to 20% by weight.
  • the invention also provides a water heater.
  • the water heater includes an inner tank and a scale inhibition device disposed in the inner tank.
  • the scale inhibition device contains the scale inhibitor particles.
  • the scale inhibitor particles of the present invention can play a long-term sustained release role. During the dissolution of the scale inhibitor, the scale inhibitor particles can still ensure that the particle skeleton is not broken. In particular, even if it is used in hot water, the scale inhibitor particles of the present invention can still be used for a long time while satisfying the scale inhibition effect.
  • Figure 1 is a photograph of the pure block of calcium citrate scale inhibitor at the beginning of soaking in water at room temperature (25 ° C), 40 ° C and 90 ° C;
  • Example 2 is a photo of the scale inhibitor particles of Example 1 after being soaked in water at room temperature (25 ° C), 40 ° C, and 90 ° C for 24 hours;
  • Figure 3 is a photo of a block-shaped pure scale inhibitor before and after 5 tons of water
  • Example 4 is a photograph of the scale inhibitor particles of Example 1 before and after 5 tons of water;
  • Example 5 is a schematic structural diagram of a scale inhibitor particle according to Example 5 of the present invention.
  • FIG. 6 is a schematic structural diagram of an inner container of a water heater according to the present invention.
  • the scale inhibitor particles of the present invention are made of the following components, based on the weight percent, by using a slightly soluble scale inhibitor: 60% -98%, preferably 60% -95%, Junking agent: 40% to 2%, preferably 5% to 40%.
  • the scale inhibitor is one or more of slightly soluble scale inhibitors such as calcium citrate, ethylenediamine tetramethylenephosphonic acid (EDTMPA), and the like;
  • the agent is at least one of epoxy resin, polyacrylates, polyurethane, polyvinyl alcohol, and a curing agent thereof.
  • the invention also provides a method for preparing a scale inhibitor.
  • the scale inhibitor particles can be formed by roll forming, extrusion rounding, screw extrusion and isostatic pressing.
  • the rolling step includes the steps of: mixing the scale inhibitor, the binder and the water at the above ratio and adding the scale inhibitor to a ball rolling machine to prepare a master ball. After the preparation of the cue ball is completed, it is placed in a ball rolling machine, and then sprays adhesive and water into the ball rolling machine, and then adds powder, and then reciprocates until the cue ball grows to the required size, then the preparation is stopped, and then Drying in an oven at 60-100 ° C for 4-12h will obtain the scale inhibitor particles of the present invention.
  • the above-mentioned mixed sample is kneaded in a kneader and mixed uniformly. Subsequently, a screw extruder is used for sample preparation, and dried in an oven at 60-100 ° C. for 4-12 h to obtain the scale inhibitor particles of the present invention.
  • the scale inhibitor particles can be stably existed in the water treatment process without being caused by excessive amounts of the binder and the scale inhibitor.
  • the dissolution causes the scale inhibitor particles to be washed away, and a long life cannot be achieved.
  • the inner liner 10 of the water heater of the present invention includes a scale inhibition device 20 disposed therein; the scale inhibition device 20 contains a certain amount of scale inhibitor particles.
  • the weight of each scale inhibitor particle is 0.1-300mg; the bulk density of the scale inhibitor device equipped with a group of scale inhibitor particles is within a range of 0.5-1.5g / cm 3 .
  • the scale inhibitor particles are preferably spherical with a diameter of 0.5-10 mm.
  • the scale inhibitor particles have a core layer and an outer layer covering the core layer, from the outer layer to the core layer, the scale inhibitor particles include a scale inhibitor and a binder, and the scale inhibitor
  • the weight-to-weight gradient of the binder increases, and the weight-to-weight gradient of the binder decreases; each scale inhibitor particle is consumed from the beginning to the end of consumption, and the surface area of the particles is from large to small.
  • the scale inhibitor is from the outer layer to the core layer, If the content is the same, the longer the time, the less the scale inhibitor content will be, and the scale inhibition effect will be reduced in different time periods.
  • the gradient structure of the scale inhibitor content is used to ensure that the scale inhibitors can be uniformly released in different time periods to ensure different The scale inhibition effect is consistent in the time period.
  • the scale inhibitor further comprises an intermediate layer between the core layer and the outer layer, the thickness of the core layer is 0.5-5 mm, the thickness of the intermediate layer is 0.5 mm-5 mm, and the thickness of the outer layer is 0.5 mm-5 mm.
  • the binder in the scale inhibitor particles preferably has a skeleton structure. After the scale inhibitor in the scale inhibitor particles is consumed, the binder can still remain in the scale inhibitor device to avoid contaminating the water in the liner.
  • the scale inhibitor particles placed in the liner of the water heater will occupy the water storage space of the liner.
  • the density of the scale inhibitor particles is too large, the water will not flow smoothly, and it will also affect the scale inhibition effect of the scale inhibitor.
  • the shape and structure of the scale inhibitor particles, the weight of the scale inhibitor, The weight and other parameters are configured to ensure that the scale inhibitor particles per unit area in the scale inhibition device have a better scale inhibition effect, and at the same time have a longer life and take up less space.
  • parameters such as the shape, structure, weight of the scale inhibitor, and the weight of the binder are designed to ensure that the scale inhibitor particles per unit area of the tank body is filled with scale inhibitor particles. Good anti-scaling effect and long life, and occupy less space.
  • the swelling degree of the scale inhibitor particles under different temperatures was tested according to the swelling balance method. Weigh 5 grams of filter material, place them in 100ml of water, and place them at different temperatures for standing. The scale inhibitor particles absorb water during immersion in water. After the water absorption equilibrium, the volume change of the scale inhibitor particles before and after water absorption was tested (V0 before water absorption and V1 after water absorption). The swelling degree is expressed by Q:
  • the change in diameter (D0 before water absorption and D1 after water absorption) can be directly used to confirm the swelling degree.
  • the swelling degree is expressed by Q:
  • the degree of hydrolysis was tested using the weightless method.
  • the adhesive used is individually cured according to the required ratio, and is not mixed with the powder. After curing, weigh a certain amount of adhesive as m1, soak it in a certain amount of water at 90 ° C, take it out and weigh it after a certain period of time until the weight remains the same, the experiment is over, and the weight is expressed as m2.
  • Formula to calculate the degree of hydrolysis :
  • a 10 g sample was placed in 100 ml of water, and the dissolution rate of the scale inhibitor particles was measured by measuring the concentration of calcium ions after soaking in water for 30 minutes and 24 hours, respectively.
  • a 100g sample was placed in a 10-inch filter bottle, and the water passing experiment was started. The water was passed at a flow rate of 5 L / Min. After passing 20 to 40 tons of water, the weight loss rate and static scale inhibition effect were tested to confirm the filter life.
  • scale inhibitor particles calcium citrate is used as the scale inhibitor, and the binder is AB type epoxy resin (Henkel, model: Loctite 7255).
  • Scale inhibitor: Binder 9: 1, and adding a certain amount of water
  • the solubility of calcium citrate in water at 25 ° C is 0.1 g / 100 g, and it is slightly soluble in water.
  • the samples were tested for swelling and hydrolysis at different temperatures. The test results are shown in Table 1. The dissolution of scale inhibitor particles at different temperatures is shown in Figures 1 and 2.
  • FIG. 1 is a photograph of the pure block of calcium citrate scale inhibitor at the beginning of soaking in water at room temperature (25 ° C), 40 ° C and 90 ° C, respectively. It can be seen from FIG. 1 that the pure block of calcium citrate is significantly dissolved.
  • FIG. 2 is a photo of the scale inhibitor particles of Example 1 after being immersed in water at room temperature (25 ° C.), 40 ° C., and 90 ° C. for 24 hours. Compared with FIG. 1, it can be seen that the scale inhibitor particles of the present application can be stably stored in an aqueous solution, thereby reducing waste of the scale inhibitor.
  • Table 1 shows the swelling rates of the scale inhibitor particles of Example 1 after soaking in water at room temperature (25 ° C), 40 ° C, and 90 ° C for 12 hours and 24 hours, respectively.
  • the inventors also tested the adhesive, which confirmed that the adhesive can be stably present in water at different temperatures, thereby achieving the effect that the scale inhibitor is well fixed and not washed away.
  • the test method is as follows: Mix and cross-link the A and B components of the epoxy resin. Weigh 1 g of each sample after the cross-linking and place it in a beaker, inject 200 ml of water, and then place it in room temperature water (ie, 25 ° C water) , 40 °C water and 90 °C water, left to stand for 24 hours, weighed, measured the weight of the glue, and the statistical results are shown in Table 2:
  • the adhesive can be stably present in water, and will not hydrolyze with immersion in water, thereby more stably maintaining the shape and performance of the particles.
  • the inventors also tested the dissolution rate of the calcium citrate powder and the scale inhibitor particles of Example 1. The test results are shown in Table 3. As can be seen from Table 3, the scale inhibitor particles of Example 1 can be stably present without being excessively dissolved.
  • the inventors not only studied the state of the scale inhibitor particles in a standing state, but also evaluated the dissolution life in a state of passing water.
  • Figure 3 is a photo of the block-type pure scale inhibitor before and after 5 tons of water. Weigh 10g each of the block scale inhibitor and the granular scale inhibitor to conduct the water test. With the increase of the water passing time, the amount of the block scale inhibitor is greatly reduced, and only a small amount is left in the end.
  • FIG. 4 is a photograph of the scale inhibitor particles of Example 1 before and after 5 tons of water. As can be seen from FIG. 4, after the scale inhibitor particles of Example 1 have passed 5 tons of water, the particles still remain intact and the shape is intact.
  • the life of the scale inhibitor particles of Example 1 can be more than twice that of the block-type pure scale inhibitor.
  • Ethylene diamine tetramethylene phosphonic acid was selected as the scale inhibitor in the scale inhibitor particles.
  • EDTMPA Ethylene diamine tetramethylene phosphonic acid
  • Spherical particle samples were prepared by roll forming, and the sample diameter was about 3 to 4 mm. The swelling degree and hydrolysis degree of the scale inhibitor particles of Example 2 at different temperatures were tested. The test results are shown in Table 4.
  • scale inhibitor calcium citrate was selected as the scale inhibitor.
  • Spherical particle samples were prepared by roll forming, and the sample diameter was about 3 to 4 mm. The swelling degree and hydrolysis degree of the scale inhibitor particles of Example 3 at different temperatures were tested. The test results are shown in Table 4.
  • EDTMPA was selected as the scale inhibitor in the scale inhibitor particles.
  • the selected adhesive is polyvinyl alcohol, and the required curing agent is simultaneously mixed, and a certain amount of water is added for mixing.
  • the swelling degree and hydrolysis degree of the scale inhibitor particles of Example 2 at different temperatures were tested. The test results are shown in Table 4.
  • the scale inhibitor particles were manufactured using the scale inhibitor and the binder in Example 1, except that, as shown in FIG. 5, the scale inhibitor particles were prepared as scale inhibitor particles having a multilayer structure.
  • the particle has a core layer 3, an intermediate layer 2 and an outer layer 1.
  • the scale inhibitor of the core layer 3 is 96% by weight, the binder is 4% by weight, and the thickness is 2mm.
  • the scale inhibitor of the intermediate layer 2 It is 90% by weight, the content of the adhesive is 10% by weight, and the thickness is 2mm; the scale inhibitor of the outer layer 1 is 85% by weight, the adhesive is 15% by weight, and the thickness is 2mm.
  • the above particles are prepared by first preparing a core layer 3, then an intermediate layer 2 and finally an outer layer 1.
  • the scale inhibitor particles of Example 5 have a more uniform release of the scale inhibitor. After 5 tons of water, the weight loss is 39.0%, which can further improve the service life of the scale inhibitor.
  • the scale inhibitor particles are placed in a scale inhibition tank in the inner liner of a water heater, and when used in a water heater, a good scale inhibition effect can still be maintained. After 5 tons of water at 70 ° C, the weight loss is 41.2%.
  • the amount of the scale inhibitor is 10 g, which can provide scale inhibition effect for about 10 tons of water.
  • the average user's annual water consumption of water heater is about 30-50 tons. If 100 g of the scale inhibitor of the present invention is used, a scale inhibition effect can be provided for about 100 tons of water. Therefore, the scale inhibitor of the present invention can be used for about 2 years or more, which greatly reduces the frequency of replenishing the scale inhibitor.

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Abstract

本发明提供一种阻垢剂颗粒及其制备方法，所述阻垢颗粒包含阻垢剂和粘合剂，所述阻垢剂的含量为60％～98％，所述粘合剂的含量为2％～40％，所述阻垢剂在90℃以下的水中的溶解度低于5g/100g，所述粘合剂固化后在90℃以下的水中的溶解度低于所述阻垢剂的溶解度，所述颗粒在90℃以下水中溶胀度低于12％，所述粘合剂固化后90℃以下水中的水解度低于1％。

Description

一种阻垢剂颗粒及其制备方法 技术领域
本发明涉及一种阻垢剂颗粒及其制备方法。具体而言，本发明提供了一种阻垢剂颗粒，该阻垢剂颗粒具有稳定的溶出率，能够在满足阻垢效果的情况下长期使用。本发明还涉及包含该阻垢剂颗粒的热水器。
背景技术
不同地区的水质不同。由于水中可能含有钙镁等离子，在使用中会形成水垢。尤其是在热水器领域，由于在使用时需要对水进行加热，更加容易形成水垢。为了防止水结垢，通常需要使用阻垢剂对水进行处理。为了延长阻垢剂的使用时间，现有技术中通常将阻垢剂与其他成分一起制备成块状或颗粒状。但是，现有技术的阻垢剂，通常存在阻垢剂颗粒或块容易破碎，导致阻垢剂被水冲走，使用寿命不足等问题。
发明内容
技术问题
在现有技术中，通常在热水器之前设置包含阻垢剂的阻垢器。自来水在进入热水器之前，先经阻垢剂软化，从而提高水质，延长热水器使用寿命。但是，阻垢器会占用一定的空间，且影响室内的美观性，因此希望开发新型阻垢剂。发明人着眼于此，希望开发出既能在热水器之外使用，又能在热水器内部使用的阻垢剂。如果阻垢剂可以在热水器内部使用，则可以解决上述问题。
但是，当阻垢剂在热水器内部使用时，会面临以下问题。即，大多数阻垢剂是在常温下使用，在高温下会快速损耗。因此，当在热水器中使用时，由于电热水器通常长时间保持在高温下，必须使用能够在高温下长期使用的阻垢剂。另外，由于阻垢剂内置在热水器中，普通用户难以自行更换阻垢剂，当阻垢剂耗尽时，必须由专业维修人员进行补充。这要求阻垢剂的使用寿命必须要长，以降低频繁补充阻垢剂给用户带来的不便。
其次阻垢剂颗粒放置在热水器的内胆内，会占用内胆的储水空间，阻垢剂颗粒的放置的量越多，则阻垢剂寿命就会越长，占用内胆的空间越大，所以希望在尽可能 小的罐体内装足够量的阻垢剂颗粒，但是阻垢剂颗粒堆积的密度过大，则会造成过水不通畅，同样也影响阻垢剂的阻垢效果；
本发明的目的是为了提供一种阻垢剂颗粒。其目的是解决上述技术问题。同时，本发明的阻垢剂颗粒可以防止颗粒破碎，从而避免阻垢剂成分被水流冲走。本发明的目的还在于提高阻垢剂颗粒的使用寿命。另外，本发明还提供了一种具有特定结构的阻垢剂。通过使本发明的阻垢剂具有特定结构，可以使本发明的阻垢剂从阻垢剂颗粒中均匀释放，提高阻垢效果，延长使用时间。
本发明的目的还提供一种热水器，在其内胆中内置阻垢装置，阻垢装置内装有阻垢剂颗粒，对阻垢剂颗粒的形状、结构、阻垢剂的重量、粘合剂的重量等参数进行了配置，保证了罐体装有阻垢剂颗粒区域单位面积的阻垢剂颗粒具有的较佳的阻垢效果和寿命并且占用空间较少。
技术方案
本发明提供了一种阻垢剂颗粒，所述阻垢颗粒包含阻垢剂和粘合剂，所述阻垢剂的含量为60％～98％，优选为60％～95％，所述粘合剂的含量为2％～40％，优选为5％～40％，所述阻垢剂在90℃以下的水中的溶解度低于5g/100g，所述粘合剂固化后在90℃以下的水中的溶解度低于所述阻垢剂的溶解度，所述颗粒在90℃度以下水中溶胀度低于12％，所述粘合剂固化后90度以下水中水解度低于1％。
在本发明的阻垢剂颗粒中，通过降低粘合剂的含量，可以最大限度的增大阻垢剂的含量，从而延长阻垢剂颗粒的寿命。但是，单纯增大阻垢剂的含量，会导致阻垢剂颗粒强度不足，易于破碎。为此，发明人发现，通过选择溶解度低于5g/100g水的阻垢剂，并且使得粘合剂的溶解度进一步低于阻垢剂的溶解度，同时控制阻垢剂颗粒在90℃以下水中溶胀度低于12％，并且选择固化后在90℃以下水中水解度低于1％的粘合剂，可以使得阻垢剂溶出时，粘合剂仍然保持其骨架结构，从而延长阻垢剂颗粒的使用时间。
发明人还发现，当使用具有特定极性基团的阻垢剂时，可以与粘合剂相互作用，抑制阻垢剂颗粒的膨胀率，从而更好地解决本发明的技术问题。所述阻垢剂可以含有以下至少一种极性基团或其盐：磷酸根、膦酸基、磷酸酯基、磷酰基、羧基和磺酸基。阻垢剂优选为聚磷酸盐、有机膦酸盐、马来酸酐和聚天冬氨酸。
另外，本发明还提供了阻垢剂颗粒的制备方法以及具有特定结构的阻垢剂颗粒。
本发明的阻垢剂颗粒可以仅由阻垢剂和粘合剂构成。在不影响本发明的技术效果的情况下，本发明的阻垢剂颗粒可以含有其他添加剂。
为了提高阻垢剂颗粒的使用寿命，在本发明的阻垢剂颗粒中，阻垢剂与粘合剂的配比自中心到外表面梯度减少。通过该结构，在阻垢剂颗粒的外表面，阻垢剂含量较少，但阻垢剂与水接触的面积较大。随着阻垢剂的溶出，阻垢剂颗粒变小，阻垢剂与水的接触面积也变小，但是阻垢剂的含量增大，由此补偿因阻垢剂与水接触面积变小而导致的溶出率的降低。通过该结构，可以使得阻垢剂以均匀的速率溶出，确保阻垢效果以及阻垢剂颗粒的使用寿命。
作为一个具体实例，阻垢剂颗粒可以具有芯层、中间层和外层，所述芯层的阻垢剂为95重量％～100重量％，粘合剂为0～5重量％，所述中间层的阻垢剂为90重量％～95重量％，粘合剂的含量：5重量％～10重量％；所述外层的阻垢剂为80重量％-90重量％，粘合剂为10重量％～20重量％。
本发明还提供了一种热水器，所述热水器包括内胆和设置于内胆内的阻垢装置，所述阻垢装置内装有上述阻垢剂颗粒。
技术效果
本发明阻垢剂颗粒可以起到长期缓释的作用，在阻垢剂溶出过程中，该阻垢剂颗粒仍然能够保证颗粒骨架不破碎。特别是，即使是在热水中使用，本发明的阻垢剂颗粒仍然能够在满足阻垢效果的情况下长期使用。
附图说明
图1是柠檬酸钙阻垢剂纯块分别在室温(25℃)、40℃和90℃下在水中浸泡开始时的照片；
图2是实施例1的阻垢剂颗粒分别在室温(25℃)、40℃和90℃下在水中浸泡24h后的照片；
图3为块状的纯阻垢剂在过水前和过水5吨后的照片；
图4为实施例1的阻垢剂颗粒在过水前和过水5吨后的照片；
图5为本发明实施例5的阻垢剂颗粒的结构示意图；
图6为本发明的热水器的内胆的结构示意图。
具体实施方式
下面结合具体实施例对本发明的具体实施方式做进一步说明。
本发明的阻垢剂颗粒，是通过采用自身微溶的阻垢剂，按照重量百分比计，其由以下组分制成：阻垢剂60％～98％，优选为60％～95％，粘结剂：40％～2％,优选为5％～40％。其中，所述阻垢剂为微溶阻垢剂，柠檬酸钙、亚乙基二胺四亚甲基膦酸(EDTMPA)等微溶阻垢剂中的一种或几种；所述粘合剂为环氧树脂、聚丙烯酸酯类、聚氨酯、聚乙烯醇及其固化剂中的至少一种。
本发明还提供了阻垢剂的制备方法。所述阻垢剂颗粒可采用滚制成型、挤出抛圆法、螺杆挤出法及等静压法成型。滚制成型制备步骤包括：将上述配比下阻垢剂、粘合剂和水混合后加入滚球机，制备母球。母球制备完成后，放置于滚球机，随后往滚球机中喷洒粘合剂、水，随后进行粉体添加，以此往复，直至母球生长至所需尺寸，则停止制备，随后在60-100℃烘箱中干燥4-12h既得本发明所述的阻垢剂颗粒。螺杆挤出法是将上述混合样品在捏合机进行捏合，混合均匀。随后采用螺杆挤出机进行样品制备，在60-100℃烘箱中干燥4-12h既得本发明所述的阻垢剂颗粒。
本发明通过采用自身微溶的阻垢剂，与可固化的粘合剂进行复配，可实现阻垢剂颗粒可在水处理过程中稳定存在，不会因为粘合剂和阻垢剂的过度溶解而引起阻垢剂颗粒被冲散，从而无法实现长寿命。
如图6所示，本发明的热水器的内胆10包括设置于其中的阻垢装置20；阻垢装置20内装有一定量的阻垢剂颗粒。每颗阻垢剂颗粒重量0.1-300mg；阻垢装置装有组垢剂颗粒区域单位体积的堆积密度在0.5-1.5g/cm 3范围内。阻垢剂颗粒优选为直径在0.5-10mm的球状。
优选的，阻垢剂颗粒具有芯层和包覆芯层的外层，自所述外层至所述芯层，所述阻垢剂颗粒包括组垢剂和粘合剂，所述阻垢剂的重量占比梯度增加，粘合剂的重量占比梯度减小；每颗阻垢剂颗粒从开始消耗到消耗结束，颗粒的表面积由大到小，如果阻垢剂由外层到芯层的含量一致，则时间越长阻垢剂含量越少，不同的时间段阻垢效果降低，本实施例利用阻垢剂含量的梯度结构保证不同时间段，阻垢剂都能够均量释放，保证不同时间阶段的阻垢效果一致。
优选的，阻垢剂还包括位于芯层和外层之间的中间层，所述芯层厚度为0.5-5mm，中间层厚度为0.5mm-5mm，外层厚度0.5mm-5mm。
所述阻垢剂颗粒中的粘合剂优选具有骨架结构，阻垢剂颗粒中的阻垢剂消耗完之后，粘合剂依然能够保留在阻垢装置内，避免污染内胆中的水。
阻垢剂颗粒放置在热水器的内胆内，会占用内胆的储水空间，阻垢剂颗粒的放置的量越多，则阻垢剂寿命就会越长，占用内胆的空间越大，所以希望在尽可能小的罐体内装足够量的阻垢剂颗粒。但是阻垢剂颗粒堆积的密度过大，则会造成过水不通畅，同样也影响阻垢剂的阻垢效果；对阻垢剂颗粒的形状、结构、阻垢剂的重量、粘合剂的重量等参数进行了配置，可以保证了阻垢装置内单位面积的阻垢剂颗粒具有的较佳的阻垢效果，同时具有较长的寿命并且占用空间较少。
本实施例阻垢剂颗粒的形状、结构、阻垢剂的重量、粘合剂的重量等参数进行了设计，保证了罐体装有阻垢剂颗粒区域单位面积的阻垢剂颗粒具有的较佳的阻垢效果和寿命并且占用空间较少。
实施例
溶胀度测试方法
按照溶胀平衡法测试阻垢剂颗粒在不同温度水下的溶胀度。称取5克滤料，分别放置于100ml水中，并将其置于不同温度下进行静置。阻垢剂颗粒在水中浸泡过程中会发生吸水。直至吸水平衡后，测试吸水前后的阻垢剂颗粒的体积变化(吸水之前为V0，吸水之后为V1)。溶胀度用Q表示：
Q＝(V1-V0)/V0*100％
而针对条状样品，可以直接采用直径变化(吸水之前直径为D0，吸水之后为D1)来确认溶胀度。溶胀度用Q表示：
Q＝(D1-D0)/D0*100％
水解度测试方法
水解度采用失重法进行测试。将所用粘合剂按照所需配比进行单独固化，不与粉体进行混合。固化后称取一定重量的粘合剂为m1，在一定水中于90℃下进行浸泡， 每隔一段时间后取出烘干称重，直至重量不变，实验结束，重量记为m2，则根据下式计算水解度：
水解度＝(m1-m2)/m1*100％
溶出速度测试方法
将10g的样品置于100ml的水中，通过测定在水中分别浸泡30分钟和24小时后钙离子的浓度，来测定阻垢剂颗粒的溶出速度。
过水溶出阻垢寿命测试方法
将100g样品放置于10寸滤瓶中，开启过水实验，采用5L/Min的流速进行过水，过水20吨、40吨后，测试失重率及静态阻垢效果，确认滤料寿命。
实施例1
阻垢剂颗粒中选用柠檬酸钙作为阻垢剂，粘合剂为AB型环氧树脂(汉高公司，型号为：乐泰7255)。阻垢剂：粘合剂＝9：1，并加入一定的水，阻垢剂：水＝1.5：1，采用螺杆挤出的方式制备条状颗粒样品，样品直径为1.5mm，长度为3-5mm。柠檬酸钙25℃下在水中的溶解度为0.1g/100g，微溶于水。对该样品进行不同温度下的溶胀度和水解度进行了测试，测试结果如表1所示。阻垢剂颗粒在不同温度下的溶解情况如图1和图2所示。图1是柠檬酸钙阻垢剂纯块分别在室温(25℃)、40℃和90℃下在水中浸泡开始时的照片。由图1可知，柠檬酸钙纯块发生了显著的溶解。图2是实施例1的阻垢剂颗粒分别在室温(25℃)、40℃和90℃下在水中浸泡24h后的照片。与图1相比，可以看出，本申请的阻垢剂颗粒可以稳定存在与水溶液中，从而可以减少阻垢剂的浪费。
在浸泡的同时，本申请对阻垢剂颗粒在不同温度下的稳定性也进行了测试。表1为实施例1的阻垢剂颗粒分别在室温(25℃)、40℃和90℃下在水中浸泡12小时和24小时后的溶胀率。
表1 实施例1的阻垢剂颗粒在不同温度和不同时间的溶胀率
温度(℃) 25 40 90
浸泡12小时的溶胀度(％) 0.58 0.65 0.65
浸泡24小时的溶胀度(％) 0.6 0.64 0.63
发明人还对粘合剂进行了测试，即确认粘合剂在不同温度下都能稳定存在于水中，从而实现阻垢剂被很好固定，不被冲走的效果。
测试方法如下：将环氧树脂A组分与B组分进行混合交联，对交联后样品各称取1g放置于烧杯中，注入200ml水，然后分别放置于室温水(即25℃水)、40℃水及90℃水中，静置24h后烘干称重，计量胶的重量，统计结果如表2所示：
表2 粘合剂固化后在不同温度下的水解度
温度(℃) 初始重量(g) 24h后重量(g) 水解度(％)
25 1.0051 1.0048 0.03
40 1.0032 1.0031 0.01
90 1.0029 1.0027 0.02
可以看出，该粘合剂经过AB组分发生交联后，可稳定存在于水中，不会随着在水中浸泡而发生水解，从而更加稳定地保持颗粒的形状与性能。
此外发明人还对柠檬酸钙粉末和实施例1的阻垢剂颗粒的溶出速度进行了测试，测试结果如表3所示。由表3可知，实施例1的阻垢剂颗粒可以稳定存在，不会过度溶出。
表3 阻垢剂颗粒与纯阻垢剂溶出速度对比
样品名称 块状阻垢剂 阻垢剂颗粒
浸泡30min溶解度(g/100g) 0.055 0.03
浸泡24h溶解度(g/100g) 0.065 0.03
发明人不仅对静置状态下的阻垢剂颗粒状态进行了研究，同时还对过水状态下的溶出寿命进行了评估。
图3分别为块状的纯阻垢剂在过水前和过水5吨后的照片。分别称取块状阻垢剂及颗粒状阻垢剂各10g进行过水实验。随着过水时间的延长，块状阻垢剂的量大幅减少，最终只有少量剩余。
图4为实施例1的阻垢剂颗粒在过水前和过水5吨后的照片。由图4可知，实施例1的阻垢剂颗粒在过水5吨后，颗粒仍然保持十分完整，形貌完好。
为更好的表征其寿命，发明人还对过水5吨后的样品进行计量称重，结果如下：
块状阻垢剂过水5吨后，重量为1.53g，失重为84.7％；而实施例1的阻垢剂颗粒过水5吨后，重量为5.89g，失重为41.1％。因此，实施例1的阻垢剂颗粒寿命可达块状纯阻垢剂的两倍以上。
实施例2
阻垢剂颗粒中选用亚乙基二胺四亚甲基膦酸(EDTMPA)作为阻垢剂。常温下EDTMPA为白色结晶性粉末，熔点215-217℃，微溶于水，在室温下溶解度小于5％。具有很强的螯合金属离子的能力，可以很好地阻止水垢的产生，此款阻垢剂吸水性较强。粘合剂为AB型环氧树脂(汉高公司，型号为乐泰7255)。阻垢剂：粘合剂＝9：1，并加入一定的水，使得阻垢剂：水＝1.5：1。采用滚制成型的方式制备球状颗粒样品，样品直径为3～4mm左右。对实施例2的阻垢剂颗粒在进行不同温度下的溶胀度和水解度进行了测试，测试结果如表4所示。
实施例3
阻垢剂颗粒中选用柠檬酸钙作为阻垢剂。粘合剂为AB型环氧树脂(汉高公司，型号为乐泰7255)。阻垢剂：粘合剂＝7：3，并加入一定的水，使得阻垢剂：水＝1.5：1。采用滚制成型的方式制备球状颗粒样品，样品直径为3～4mm左右。对实施例3的阻垢剂颗粒在进行不同温度下的溶胀度和水解度进行了测试，测试结果如表4所示。
实施例4
阻垢剂颗粒中选用EDTMPA作为阻垢剂。所选粘合剂为聚乙烯醇，同步混入所需固化剂，并加入一定的水进行混合。所选比例为：阻垢剂：粘合剂＝7：3，并加入一定的水，阻垢剂：水＝1.5：1，采用滚球法的方式制备球状颗粒样品，样品直径为1.5mm。对实施例2的阻垢剂颗粒在进行不同温度下的溶胀度和水解度进行了测试，测试结果如表4所示。
实施例5
采用实施例1中的阻垢剂和粘合剂制造阻垢剂颗粒，不同之处在于，如图5所示，将其制备成具有多层结构的阻垢剂颗粒。该颗粒具有芯层3、中间层2和外层1，所述芯层3的阻垢剂为96重量％，粘合剂为4重量％，厚度为2mm；所述中间层2的阻垢剂为90重量％，粘合剂的含量为10重量％，厚度为2mm；所述外层1的阻垢剂为85重量％，粘合剂为15重量％，厚度为2mm。上述颗粒采用先制备芯层3，再制备中间层2，最后制备外层1的方法来制备。与实施例1相比，实施例5的阻垢剂颗粒，阻垢剂释放更加均匀，过5吨水后失重为39.0％，可以进一步提高阻垢剂的使用寿命。将该阻垢剂颗粒放入热水器内胆中的阻垢罐内，在热水器中使用时，仍然能够保持良好的阻垢效果，在70℃过5吨水后失重为41.2％。
Figure PCTCN2019095316-appb-000001
由上表可知，当所述阻垢剂在90℃以下的水中的溶解度低于0.1g/100g，所述粘合剂固化后在90℃以下的水中的溶解度低于所述阻垢剂的溶解度，所述颗粒在90℃以下水中溶胀度低于12％，所述粘合剂固化后90℃以下水中的水解度低于1％时，阻垢剂过水5吨后的失重较小，具有更长的使用寿命。
在上述实验中，阻垢剂的用量为10g，可以为大约10吨水提供阻垢效果。普通用户年热水器用水量大约为30-50吨。如果使用100g本发明的阻垢剂，则可以为大约100吨水提供阻垢效果。因此，本发明的阻垢剂可以使用大约2年以上，大大降低了补充阻垢剂的频率。

Claims (16)

  1. 一种阻垢剂颗粒，所述阻垢颗粒包含阻垢剂和粘合剂，其特征在于：所述阻垢剂的含量为60％～98％，所述粘合剂的含量为2％～40％，所述阻垢剂在90℃以下的水中的溶解度低于5g/100g，所述粘合剂固化后在90℃以下的水中的溶解度低于所述阻垢剂的溶解度，所述颗粒在90℃以下水中溶胀度低于12％，所述粘合剂固化后90℃以下水中的水解度低于1％。
  2. 如权利要求1所述的阻垢剂颗粒，其特征在于，所述阻垢剂含有以下至少一种极性基团或其盐：磷酸根、膦酸基、磷酸酯基、磷酰基、羧基和磺酸基。
  3. 如权利要求2所述的阻垢剂颗粒，其特征在于，所述阻垢剂选自以下阻垢剂中的至少一种：柠檬酸盐、聚磷酸盐、有机膦酸盐、马来酸酐和聚天冬氨酸。
  4. 如权利要求1～3任一项所述的阻垢剂颗粒，其特征在于，在所述颗粒中，阻垢剂与粘合剂的配比自中心到外表面梯度减少。
  5. 如权利要求1～3任一项所述的阻垢剂颗粒，其特征在于，所述颗粒具有芯层和包覆芯层的外层，所述芯层的阻垢剂为85重量％～100重量％，粘合剂为0～15重量％，所述外层的阻垢剂为60重量％～95重量％，粘合剂为5重量％～40重量％。
  6. 如权利要求1～3任一项所述的阻垢剂颗粒，其特征在于，所述颗粒具有芯层、中间层和外层，所述芯层的阻垢剂为95重量％～100重量％，粘合剂为0～5重量％，所述中间层的阻垢剂为90重量％～95重量％，粘合剂的含量：5重量％～10重量％；所述外层的阻垢剂为80重量％-90重量％，粘合剂为10重量％～20重量％。
  7. 如权利要求5或6所述的阻垢剂颗粒，其特征在于，所述芯层厚度为0.5-5mm，所述中间层厚度为0.5mm-5mm，所述外层厚度为0.5mm-5mm。
  8. 如权利要求5或6所述的阻垢剂颗粒，其特征在于，所述粘合剂具有骨架结构。
  9. 一种如权利要求1所述的阻垢剂颗粒的制备方法，其特征在于，所述方法选自以下方法：
    将阻垢剂与水溶性粘合剂混合，加入交联剂，使交联剂与粘合剂反应，将组垢剂固定；
    将阻垢剂与热固性粘合剂混合并进行固化；或
    将阻垢剂、醇溶性粘合剂和醇溶剂进行混合后，再使醇溶剂挥发。
  10. 如权利要求9所述的方法，其特征在于，所述水溶性粘合剂选自聚乙烯醇、聚乙烯吡咯烷酮和羟乙基纤维素。
  11. 如权利要求9所述的方法，其特征在于，所述交联剂选自醛类、马来酸酐和硼酸。
  12. 如权利要求9所述的方法，其特征在于，所述热固性粘合剂选自环氧树脂、聚氨酯和酚醛树脂。
  13. 如权利要求9所述的方法，其特征在于，所述醇溶性粘合剂选自乙基纤维素、松香树脂和达玛树脂。
  14. 如权利要求9所述的方法，其特征在于，所述醇溶剂为乙醇。
  15. 一种热水器，所述热水器包括内胆和设置于内胆中的阻垢装置，所述阻垢装置内容纳有权利要求1-8任意一项所述的阻垢剂颗粒。
  16. 如权利要求15所述的热水器，所述阻垢剂颗粒为直径0.5-10mm的球状；每颗阻垢剂颗粒重量为0.1-300mg，所述阻垢装置中装有组垢剂颗粒的区域内单位体积的堆积密度为0.5-1.5g/cm 3。
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