阅读说明：本技术 一种含氯氧镁水泥制品废料的氯氧镁水泥材料及制备方法 (Magnesium oxychloride cement material containing chlorine oxychloride cement product waste and preparation method thereof ) 是由 焦宝祥 孟长 韩俊哲 高宇航 邹翔 徐海笑 于 2021-08-30 设计创作，主要内容包括：本发明公开了一种含氯氧镁水泥制品废料的氯氧镁水泥材料,由如下重量份的组分制成：35～45份轻烧氧化镁,15～20份氯氧镁水泥制品废料,30～35份质量浓度为35％的氯化镁溶液,2～5份木粉,5～15份水,1～4份外加剂；所述外加剂由20～40％的磷酸盐、25～35％的减水剂、10～15％的助剂和25～30％的水组成。本发明将处理后的氯氧镁水泥制品废料作为填料,与外加剂、氯化镁溶液、轻烧氧化镁、木粉一起制备氯氧镁水泥材料,不仅实现了氯氧镁水泥制品废料的再利用,减少了环境污染,而且制得的氯氧镁水泥材料性能达到或超过原氯氧镁水泥性能,具有良好的社会效益和经济效益。(The invention discloses a magnesium oxychloride cement material containing chlorine oxychloride cement product waste, which is prepared from the following components in parts by weight: 35-45 parts of light-burned magnesium oxide, 15-20 parts of magnesium oxychloride cement product waste, 30-35 parts of 35% magnesium chloride solution, 2-5 parts of wood powder, 5-15 parts of water and 1-4 parts of an additive; the additive is composed of 20-40% of phosphate, 25-35% of a water reducing agent, 10-15% of an auxiliary agent and 25-30% of water. The invention takes the treated waste of the magnesium oxychloride cement product as the filler, and prepares the magnesium oxychloride cement material together with the additive, the magnesium chloride solution, the light-burned magnesium oxide and the wood powder, thereby not only realizing the reutilization of the waste of the magnesium oxychloride cement product and reducing the environmental pollution, but also leading the performance of the prepared magnesium oxychloride cement material to reach or exceed the performance of the original magnesium oxychloride cement, and having good social benefit and economic benefit.)

1. The magnesium oxychloride cement material containing the chlorine oxychloride cement product waste is characterized by being prepared from the following components in parts by weight: 35-45 parts of light-burned magnesium oxide, 15-20 parts of magnesium oxychloride cement product waste, 30-35 parts of 35% magnesium chloride solution, 2-5 parts of wood powder, 5-15 parts of water and 1-4 parts of an additive;

the additive is composed of 20-40% of phosphate, 25-35% of a water reducing agent, 10-15% of an auxiliary agent and 25-30% of water, and the percentages are weight percentages.

2. The magnesium oxychloride cement material containing magnesium oxychloride cement product waste of claim 1, wherein the phosphate salt is one of a monobasic phosphate salt or a dibasic phosphate salt.

3. The magnesium oxychloride cement material containing the waste of the magnesium oxychloride cement product as claimed in claim 1, wherein the water reducing agent is a polyether type polycarboxylic acid water reducing agent having a relative molecular weight of 40000-50000.

4. The magnesium oxychloride cement material containing the magnesium oxychloride cement product waste of claim 1, 2 or 3, wherein the auxiliary agent is one of an organosilicon surfactant or a polyether surfactant having a molecular weight of not more than 5000.

5. A process for the preparation of a magnesium oxychloride cement material containing magnesium oxychloride cement product waste as claimed in claim 1 or 2 or 3 or 4, which comprises the steps of:

(1) crushing the waste material of the magnesium oxychloride cement product into particles with the diameter less than 3cm, and then ball-milling to prepare the magnesium oxychloride cement product with the specific surface area of 2800-²A waste powder per gram;

(2) adding an additive and water into a magnesium chloride solution with the mass concentration of 35%, and uniformly stirring to obtain a mixture;

(3) and (2) adding light-burned magnesium oxide, the waste powder in the step (1) and wood powder into the mixture, and stirring and forming to obtain the magnesium oxychloride cement material.

6. The method for preparing a magnesium oxychloride cement material containing the waste of the magnesium oxychloride cement product as set forth in claim 5, wherein in the step (3), the stirring and forming method comprises: slowly stirring for 120s at the rotating speed of 62 +/-5 r/min, stopping for 15s, and quickly stirring for 120s at the rotating speed of 140 +/-10 r/min.

Technical Field

The invention belongs to the technology of treatment and application of magnesium oxychloride cement product waste, and particularly relates to a magnesium oxychloride cement material containing magnesium oxychloride cement product waste and a preparation method thereof.

Background

The magnesium oxychloride cement is a material with great potential, has the advantages of fast setting and hardening, high strength, corrosion resistance, simple forming process and the like, has wide market prospect, is widely concerned after years of development and application, and develops the product variety from simplification to diversification.

The magnesium oxychloride cement wood-like floor is a novel formaldehyde-free floor material and has good market prospect. However, in the processing process, about 10-25% of leftover materials are usually generated, and because the waste materials contain chloride ions and are difficult to treat, the waste materials are directly added into magnesium oxychloride cement, the problems of poor rheological property, low strength, poor durability, large surface adhesive absorption property, high speed and the like during floor preparation can be generated, the bottleneck for restricting the recycling of magnesium oxychloride cement products, particularly wood-like floor waste materials is formed, and if the waste materials are directly discarded, the serious influence is brought to the sustainable development of production enterprises, and potential danger is brought to the environment.

At present, little description is given in the art about the treatment of waste materials of magnesium oxychloride cement products. The inventor of the application discloses a method for solving the problem of magnesium oxychloride cement waste by adopting high-temperature calcination treatment, and the detailed scheme is shown in the Chinese patent application with the application number of 202110541744.4.

Disclosure of Invention

The invention aims to solve the defects existing in the prior art when the waste materials of the magnesium oxychloride cement product are recycled and reused, and provides a magnesium oxychloride cement material containing the waste materials of the magnesium oxychloride cement product and a preparation method thereof.

Technical scheme

A magnesium oxychloride cement material containing chlorine oxychloride cement product waste is prepared from the following components in parts by weight: 35-45 parts of light-burned magnesium oxide, 15-20 parts of magnesium oxychloride cement product waste, 30-35 parts of 35% magnesium chloride solution, 2-5 parts of wood powder, 5-15 parts of water and 1-4 parts of an additive;

the additive is composed of 20-40% of phosphate, 25-35% of a water reducing agent, 10-15% of an auxiliary agent and 25-30% of water, and the percentages are weight percentages.

The invention adopts the additive, reduces the porosity and the intercommunicating pores by reducing water, increases the fluidity and promotes the rodlike 5 MgO. MgCl.8H in the magnesium oxychloride cement₂O phase is generated, thereby improving the strength and the water resistance of the magnesium oxychloride cement material.

Further, the phosphate is dihydrogen phosphate or dihydrogen phosphate.

Further, the water reducing agent is a polyether type polycarboxylate water reducing agent (propenyl ether copolymer), and the relative molecular weight is 40000-50000.

Furthermore, the auxiliary agent is an organosilicon surfactant or a polyether surfactant with the molecular weight not more than 5000, and is used for reducing air holes of the waste magnesium oxychloride cement and improving the strength and the water resistance.

The preparation method of the magnesium oxychloride cement material containing the chlorine oxychloride cement product waste comprises the following steps:

(1) crushing the waste material of the magnesium oxychloride cement product into particles with the diameter less than 3cm, and then ball-milling to prepare the magnesium oxychloride cement product with the specific surface area of 2800-²A waste powder per gram;

(2) adding an additive and water into a magnesium chloride solution with the mass concentration of 35%, and uniformly stirring to obtain a mixture;

(3) and (2) adding light-burned magnesium oxide, the waste powder in the step (1) and wood powder into the mixture, and stirring and forming to obtain the magnesium oxychloride cement material.

Further, in the step (3), the stirring and forming method comprises the following steps: slowly stirring for 120s at the rotating speed of 62 +/-5 r/min, stopping for 15s, and quickly stirring for 120s at the rotating speed of 140 +/-10 r/min.

The invention has the beneficial effects that: the invention provides a method for recycling waste (grinding powder, leftover materials and the like) of a magnesium oxychloride cement product, which is used for activating the waste of the magnesium oxychloride cement product, so that high-temperature calcination and activation treatment are avoided, and the waste treatment process is simpler and more energy-saving; the treated waste material of the magnesium oxychloride cement product is used as a filler, and is used together with an additive, a magnesium chloride solution, light-burned magnesium oxide and wood powder to prepare the magnesium oxychloride cement material, so that the reutilization of the waste material of the magnesium oxychloride cement product is realized, the environmental pollution is reduced, the performance of the prepared magnesium oxychloride cement material reaches or exceeds the performance of the original magnesium oxychloride cement, and the method has good social benefit and economic benefit.

Detailed Description

The technical solution of the present invention is further illustrated by the following specific examples.

In the following examples, the waste material of magnesium oxychloride cement product used is from Zhejiang river science and technology ltd; the light-burned magnesium oxide, the potassium dihydrogen phosphate and the polyether type polycarboxylate superplasticizer are purchased from Shanghai minister and initiator chemical engineering science and technology Co., Ltd; the adopted organosilicon surfactant is a polysiloxane surfactant and is purchased from Shenzhen Jipeng silicon fluoride materials GmbH; the polyether surfactant is GP type glyceryl polyether surfactant, which is purchased from Jinhui, commerce and trade Co., Ltd, but is not limited thereto.

Example 1

A magnesium oxychloride cement material containing chlorine oxychloride cement product waste is prepared from the following components in parts by weight: 39 parts of light-burned magnesium oxide, 15.1 parts of magnesium oxychloride cement product waste, 30.2 parts of 35% magnesium chloride solution, 3 parts of wood powder, 9.3 parts of water and 3.4 parts of an additive;

the additive consists of 31.1 percent of monopotassium phosphate, 29.6 percent of polyether type polycarboxylate superplasticizer, 13.3 percent of polysiloxane surfactant and 26 percent of water, wherein the percentages are weight percentages.

The preparation method of the magnesium oxychloride cement material containing the chlorine oxychloride cement product waste comprises the following steps:

(1) crushing the waste material of the magnesium oxychloride cement product into particles with the diameter less than 3cm, and then ball-milling to prepare the magnesium oxychloride cement product with the specific surface area of 2800-²A waste powder per gram;

(2) adding an additive and water into a magnesium chloride solution with the mass concentration of 35%, and uniformly stirring to obtain a mixture;

(3) and (2) adding the light-burned magnesium oxide, the waste powder in the step (1) and the wood powder into the mixture, and stirring and forming (firstly slowly stirring for 120s at the rotating speed of 62 +/-5 r/min, pausing for 15s, and then quickly stirring for 120s at the rotating speed of 140 +/-10 r/min) to obtain the magnesium oxychloride cement material.

Example 2

A magnesium oxychloride cement material containing chlorine oxychloride cement product waste is prepared from the following components in parts by weight: 39.7 parts of light-burned magnesium oxide, 15.5 parts of magnesium oxychloride cement product waste, 30.9 parts of 35% magnesium chloride solution, 3 parts of wood powder, 7.8 parts of water and 3.1 parts of an additive;

the additive consists of 35 percent of monopotassium phosphate, 28.6 percent of polyether type polycarboxylate superplasticizer, 11 percent of polysiloxane surfactant and 25.4 percent of water, wherein the percentages are weight percentages.

The preparation of the magnesium oxychloride cement material containing the waste of the magnesium oxychloride cement product is the same as in example 1.

Example 3

A magnesium oxychloride cement material containing chlorine oxychloride cement product waste is prepared from the following components in parts by weight: 40.1 parts of light-burned magnesium oxide, 15.6 parts of magnesium oxychloride cement product waste, 31.2 parts of 35% magnesium chloride solution, 3 parts of wood powder, 7.8 parts of water and 2.3 parts of an additive;

the additive consists of 28 percent of monopotassium phosphate, 28.1 percent of polyether type polycarboxylate superplasticizer, 14.8 percent of GP type glycerol polyether surfactant and 29.1 percent of water, wherein the percentages are weight percentages.

The preparation of the magnesium oxychloride cement material containing the waste of the magnesium oxychloride cement product is the same as in example 1.

Example 4

A magnesium oxychloride cement material containing chlorine oxychloride cement product waste is prepared from the following components in parts by weight: 39.6 parts of light-burned magnesium oxide, 15.5 parts of magnesium oxychloride cement product waste, 30.8 parts of 35% magnesium chloride solution, 3 parts of wood powder, 8.1 parts of water and 3 parts of an additive;

the additive consists of 24.3 percent of monopotassium phosphate, 34.2 percent of polyether type polycarboxylate superplasticizer, 14.2 percent of GP type glycerol polyether surfactant and 27.3 percent of water, wherein the percentages are weight percentages.

The preparation of the magnesium oxychloride cement material containing the waste of the magnesium oxychloride cement product is the same as in example 1.

Comparative example 1

The magnesium oxychloride cement material is prepared from the following components in parts by weight: 49 parts of light-burned magnesium oxide, 38 parts of 35% magnesium chloride solution, 3.8 parts of wood powder and 8 parts of water.

The preparation method of the magnesium oxychloride cement material comprises the following steps: according to the above metering ratio, mixing the light-burned magnesium oxide, the magnesium chloride solution, the wood powder and the water, stirring and forming to obtain the magnesium oxychloride cement material.

Comparative example 2

The magnesium oxychloride cement material is prepared from the following components in parts by weight: 49 parts of light-burned magnesium oxide, 38 parts of 35% magnesium chloride solution, 3.8 parts of wood powder, 8 parts of water and 1.2 parts of monopotassium phosphate.

The preparation method of the magnesium oxychloride cement material comprises the following steps: according to the above metering ratio, mixing the light-burned magnesium oxide, the magnesium chloride solution, the wood powder, the water and the potassium dihydrogen phosphate, stirring and forming to obtain the magnesium oxychloride cement material.

Comparative example 3

The magnesium oxychloride cement material is prepared from the following components in parts by weight: 49 parts of light-burned magnesium oxide, 15.5 parts of magnesium oxychloride cement product waste, 38 parts of 35% magnesium chloride solution, 3.8 parts of wood powder, 8 parts of water and 1.2 parts of potassium dihydrogen phosphate.

The preparation method of the magnesium oxychloride cement material comprises the following steps: according to the above metering ratio, mixing the light-burned magnesium oxide, the magnesium chloride solution, the wood powder, the water and the potassium dihydrogen phosphate, stirring and forming to obtain the magnesium oxychloride cement material.

And (3) performance testing:

1. fluidity test

The magnesium oxychloride cement materials of examples 1-4 and comparative examples 1-3 were tested for fluidity, and the test standard is referred to GB/T8077-: and (3) quickly injecting the stirred cement paste into the truncated cone circular mould, leveling the cement paste by using a scraper, lifting the truncated cone circular mould in the vertical direction, starting a stopwatch to time, allowing the cement paste to flow on a glass plate for 30s, measuring the maximum diameter of the flowing part in two directions which are perpendicular to each other by using a ruler, and taking the average value as the fluidity of the cement paste. The results are shown in table 1 below:

TABLE 1

2. Testing of flexural strength, compressive strength, water absorption and softening coefficient

The magnesium oxychloride cement materials of the examples 1 to 4 and the comparative examples 1 to 3 are prepared into 20mm multiplied by 100mm test pieces, and the test pieces are subjected to the tests on the flexural strength, the compressive strength, the water absorption and the softening coefficient, wherein the test references for the flexural strength, the compressive strength and the water absorption are JC/T747 glass fiber magnesium cement corrugated tile and ridge tile; the test method of the softening coefficient refers to JC/T568 magnesium oxychloride cement plate, and the test method of the softening coefficient is as follows: and (3) maintaining the test block to be at the age of 28d, immersing the test piece into water, wherein the water temperature is 20 ℃ (± 2 ℃), the water surface is about 30mm higher than the test piece, the test pieces are not mutually attached, taking out the test piece after 24h (+/-2 h), wiping off the surface water by using a wringed wet towel, and immediately carrying out the flexural strength and compressive strength tests within 1 h. The results are shown in table 2 below:

TABLE 2

As can be seen from tables 1 and 2, the effect of modification by potassium dihydrogen phosphate is not good when the waste material is added in comparative example 3, and the properties of the magnesium oxychloride cement, such as strength, water resistance and fluidity, are improved when the magnesium oxychloride cement is modified by the admixture in comparison with the pure magnesium oxychloride cement test pieces (comparative examples 1 and 2). The fluidity of the magnesium oxychloride cement material in the example 4 can reach 16.1cm, and compared with the strength of the test piece in the example 2, the strength of the test piece in the example 2 can reach 52.3MPa in 28d, the compressive strength is improved by nearly 36 percent, the compression softening coefficient is improved by nearly 60 percent, the average water absorption of the test piece in the example 3 is 8.4 percent, and the average water absorption is further improved by 9.7 percent compared with the average water absorption of the pure chlorine oxygen magnesium cement test piece in the comparative example 1. Therefore, the additive is used for modifying the waste magnesium oxychloride cement, so that the water resistance and the strength are greatly improved, and the fluidity and the water absorption are further improved.

Therefore, the invention utilizes the additive to modify the waste-containing magnesium oxychloride cement, not only recycles the leftover materials, but also the modified waste-containing magnesium oxychloride cement has the characteristics of high strength, high fluidity, low water absorption and good water resistance. The method effectively solves the problem that the leftover materials of the magnesium oxychloride cement board are difficult to treat in production, not only recycles the leftover materials as the filler into the magnesium oxychloride cement product, but also further improves the performance of the magnesium oxychloride cement product containing waste materials through the modification of the additive compared with a comparative product, and is suitable for being applied to a production system of the magnesium oxychloride cement board product.