WO2024093786A1 - 一种制备无碱无氯无氟早强型液体速凝剂的方法 - Google Patents

一种制备无碱无氯无氟早强型液体速凝剂的方法 Download PDF

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WO2024093786A1
WO2024093786A1 PCT/CN2023/126785 CN2023126785W WO2024093786A1 WO 2024093786 A1 WO2024093786 A1 WO 2024093786A1 CN 2023126785 W CN2023126785 W CN 2023126785W WO 2024093786 A1 WO2024093786 A1 WO 2024093786A1
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free
stirring
aluminum sulfate
diethanolamine
alkali
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PCT/CN2023/126785
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English (en)
French (fr)
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元强
田义
杨乾
胡朝龙
陈雷
余志武
谈隧
Original Assignee
中南大学
高速铁路建造技术国家工程研究中心
中铁十局集团有限公司
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Publication of WO2024093786A1 publication Critical patent/WO2024093786A1/zh

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    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention relates to the technical field of building materials, and in particular to a method for preparing an alkali-free, chlorine-free, and fluorine-free early-strength liquid accelerating setting agent.
  • Shotcrete is a special type of concrete widely used for support and reinforcement in tunnel engineering. Accelerators are essential admixtures for their rapid coagulation and hardening. According to the state of the accelerator, it is divided into powder accelerators and liquid accelerators. Powder accelerators are mainly used in dry spraying construction processes, which will produce a large amount of dust, which will not only cause great harm to the health of workers, but also cause serious environmental pollution. Therefore, liquid accelerators suitable for wet spraying processes have become the main development direction, especially early-strength accelerators.
  • the China Railway Group Standard Q/CR807-2020 “Liquid Alkali-free Accelerators for Tunnel Shotcrete” requires that when the liquid accelerator is added to cement at a dosage of 6% to 8%, the mortar formed needs to reach a 6h strength of 1.0MPa or more (including 1.0MPa).
  • the main quick-setting component of the liquid quick-setting agent is aluminum sulfate.
  • the applicant used a single-component test to determine that the dosage of aluminum sulfate should be 4.5%. (percentage of cement mass) or more.
  • the dosage of liquid accelerator is 8%, the concentration of aluminum sulfate is required to exceed 56%.
  • the solubility of aluminum sulfate at room temperature is only 36g/100g water, which means that the liquid accelerator will crystallize and cause poor stability. Therefore, solving the contradiction between the early strength type and stability of liquid accelerator has become the key to the development of alkali-free liquid accelerator.
  • alkali metals In order to solve the problem of rapid setting and early strength, adding alkali metals to promote cement hydration is a technical approach.
  • the addition of alkali metals not only brings about a corrosive environment, but is also not conducive to the development of the later strength of concrete. More importantly, it brings the risk of alkali-aggregate reaction. Therefore, the application prospects of high-alkali liquid accelerators are relatively limited.
  • researchers also considered adding chloride ions, but the risk of steel corrosion it brings is also difficult to avoid.
  • the effective content of aluminum ions in the accelerator is the main factor in promoting the coagulation and hardening of cement concrete.
  • the use of complexing technology is an important technical approach to increase the effective content of aluminum ions.
  • the complexing agents currently used are mainly fluoride ions, but they also bring certain environmental problems. Therefore, from the perspective of durability and environmental protection, the accelerator is required to be alkali-free, chlorine-free, and fluorine-free.
  • the purpose of the present invention is to provide a method for preparing an alkali-free, chlorine-free, and fluorine-free early-strengthening liquid accelerator.
  • a pH regulator and a complexing agent By combining a pH regulator and a complexing agent with specific components, the concentration of effective aluminum ions in the liquid accelerator can be increased, thereby achieving a 6-hour early-strengthening effect of the liquid accelerator; at the same time, the use of a suitable amount of stabilizer can improve the stability of the liquid accelerator.
  • the specific technical scheme is as follows:
  • the present application provides a method for preparing an alkali-free, chlorine-free, and fluorine-free early-strength liquid accelerating setting agent. The following steps are involved:
  • Step S1 mixing water, a pH regulator and a complexing agent and adding them into a reaction kettle, heating the reaction kettle to 70° C.-80° C., and keeping the temperature;
  • Step S2 adding aluminum sulfate into the reactor and stirring until completely dissolved;
  • Step S3 adding diethanolamine into the reactor to obtain a premix, and stirring the premix until it is in a liquid state;
  • Step S4 adding Tween 20 to the liquid premix to obtain a full mix, then stopping the heat preservation of the reactor, stirring and cooling the full mix to obtain the alkali-free, chlorine-free, and fluorine-free early-strength liquid accelerator;
  • the pH adjuster includes any one of tartaric acid and formic acid
  • the complexing agent includes any one of aspartic acid and methylglycine.
  • the aluminum sulfate meets the requirements of HG/T2225-2018 "Industrial Aluminum Sulfate”.
  • the diethanolamine meets the requirements of HG/T2916-1997 "Diethanolamine for Industrial Use”.
  • step S2 the following stirring parameters are adopted for aluminum sulfate: stirring time is not less than 30 min; stirring rate is not less than 300 rpm.
  • the stirring parameters adopted for the premix are a stirring time of 30-60 min and a stirring rate of not less than 300 rpm.
  • the stirring parameters adopted for the whole mixture are a stirring time of not less than 30 min and a stirring rate of not less than 300 rpm.
  • the preparation method of the alkali-free, chlorine-free and fluorine-free early-strength liquid accelerator described in the present invention uses tartaric acid or formic acid as a pH regulator to increase the solubility of aluminum sulfate and improve the aluminum ion content; at the same time, aspartic acid or methylglycine is used as a complexing agent to improve the blocking performance of dissolved aluminum ions, thereby effectively increasing the concentration of complexed aluminum ions, preventing aluminum ion crystal precipitation, and is beneficial to increasing the 6h early strength performance of the liquid accelerator; using a suitable amount of stabilizer can improve the stability of the liquid accelerator; using a suitable amount of diethanolamine can reduce the setting time of the mortar slurry, and at the same time, can improve the 6h early strength performance.
  • the present invention uses a pH regulator and a complexing agent of specific ingredients in the raw material components, and does not use alkali metals, chloride ions and fluoride ions, so that the prepared liquid accelerator can achieve the effects of alkali-free, chlorine-free and fluorine-free while ensuring the effects of rapid setting, early strength and stability.
  • the preparation method of the alkali-free, chlorine-free, and fluorine-free early-strength liquid accelerator of the present invention comprises the following steps: step S1 is used to ensure that the pH regulator and the complexing agent are heated in the reactor to achieve the best dissolution and complexing conditions for aluminum sulfate; step S2 is used to add aluminum sulfate into the reactor to ensure that the aluminum sulfate is fully dissolved and complexed; step S3 is used to add diethanolamine to facilitate the preparation of a liquid premix, and at the same time, it is also convenient to prepare an alkali-free, chlorine-free, and fluorine-free early-strength liquid accelerator with good stability after adding a stabilizer Tween 20 in step S4. In addition, the use of Tween 20 in step S4 can also improve the solubilization effect of each component.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • An alkali-free, chlorine-free, and fluorine-free early-strength liquid accelerator comprises the following raw material components in percentage by mass: 56% aluminum sulfate; 5.5% diethanolamine; 0.7% pH regulator; 1.3% complexing agent; 0.8% stabilizer; the balance is water;
  • the pH adjusting agent is tartaric acid
  • the complexing agent is aspartic acid.
  • the stabilizer is Tween 20.
  • the aluminum sulfate meets the requirements of HG/T2225-2018 "Industrial Aluminum Sulfate”.
  • the diethanolamine meets the requirements of HG/T2916-1997 "Diethanolamine for Industrial Use”.
  • a method for preparing the alkali-free, chlorine-free and fluorine-free early-strength liquid accelerator comprises the following steps:
  • Step S1 mixing water, pH regulator and complexing agent and adding them into a reaction kettle, heating the reaction kettle to 70° C. and keeping the temperature;
  • Step S2 adding aluminum sulfate into the reactor and stirring until completely dissolved;
  • Step S3 adding diethanolamine into the reactor to obtain a premix, and stirring the premix until it is in a liquid state;
  • Step S4 adding a stabilizer to the liquid premix to obtain a full mix, then stopping the heat preservation of the reactor, stirring and cooling the full mix to obtain the alkali-free, chlorine-free, and fluorine-free early-strength liquid accelerator.
  • step S2 the following stirring parameters are adopted for aluminum sulfate: stirring time 30 min; stirring rate not less than 300 rpm.
  • step S3 the stirring parameters adopted for the premix are a stirring time of 30-60 min and a stirring rate of not less than 300 rpm.
  • step S4 the stirring parameters adopted for the whole mixture are a stirring time of 30 minutes and a stirring rate of not less than 300 rpm.
  • the present invention also makes Examples 2-10 and Comparative Examples 1-10. Different from Example 1, Examples 2-10 and Comparative Examples 1-10 make adjustments in raw material composition and dosage, see Table 1 for details.
  • Each alkali-free, chlorine-free, and fluorine-free early-strength liquid accelerator prepared by Examples 1-10 is marked as implementation sample 1-10.
  • Each liquid accelerator prepared by Comparative Example 1-10 is marked as comparative sample 1-10.
  • the implementation samples 1-10 and comparative samples 1-10 are tested for their corresponding properties according to the test methods for density, pH value, solid content, stability, chloride ion content, and alkali content of accelerators specified in GB/T 35159-2017 "Accelerators for Shotcrete”, and the implementation samples 1-10 and comparative samples 1-10 are tested for their corresponding fluoride ion content according to the test method for fluoride ion content specified in Q/CR807-2020 "Liquid alkali-free accelerators for tunnel shotcrete".
  • Table 2 The above test results are detailed in Table 2.
  • the chloride ion content and alkali content in the implementation samples 1-10 prepared by the present invention are lower than the requirements of the national standard GB/T35159-2017, and the fluoride ion content is also lower than the requirements of Q/CR807-2020, and the sample stability is good. Therefore, the present invention can prepare alkali-free, chlorine-free, and fluorine-free liquid rapid
  • the implementation samples 1-10 prepared by the present invention meet the requirements of 1d compressive strength, 28d strength ratio and 90d strength retention value specified in the national standard GB/T35159-2017, and the 6h strength is much higher than the requirements specified in Q/CR807-2020, showing excellent early strength performance.
  • Comparative Sample 2 the content of aluminum sulfate was increased, resulting in the phenomenon of crystal precipitation, which reduced the stability. At the same time, the crystallized aluminum sulfate failed to participate in the hydration reaction of cement, that is, the effective aluminum phase content in Comparative Sample 2 was reduced, so the setting time of the pure paste was prolonged, and the 6h compressive strength was reduced, which did not meet the requirements of the early strength and accelerator.
  • the alkali-free, chlorine-free, and fluorine-free early-strength liquid accelerator prepared by the present invention meets the requirements of GB/T 35159-2017 and Q/CR807-2020 for the setting time of the pure paste and the compressive strength of the mortar with different cements, showing good adaptability.
  • the present invention also made comparative examples 11-13 on the basis of embodiment 1, and the specific scheme is as follows:
  • the stirring speed in steps S2-S4 is 250 rpm.
  • reaction kettle is heated to 60° C. in step S1.
  • Example 2 Different from Example 1, the required amounts of water, pH regulator, complexing agent, aluminum sulfate, diethanolamine and Tween 20 are added into the reaction kettle at one time.
  • Example 11 Compared with Example 1, in Comparative Example 11, reducing the stirring rate will result in the prepared liquid accelerating agent having a bottom sediment of 20 ml at 28 days and a 6-hour mortar compressive strength of 0.7 MPa. That is, the prepared liquid accelerating agent has poor stability and does not meet the requirements of early strength.
  • Example 2 Compared with Example 1, in Comparative Example 12, the heating temperature was lowered, and the dissolution rate of aluminum sulfate was reduced, so that the prepared liquid accelerating agent had a bottom precipitation of 24 ml at 28 days, and the 6h mortar compressive strength was 0.6 MPa. That is, the prepared liquid accelerating agent had poor stability and reached Not meeting the requirements of early strength.
  • Example 13 Compared with Example 1, in Comparative Example 13, the one-time feeding makes it impossible for the components to be evenly dispersed and dissolved in time, and the accelerating setting agent is in a paste state after stirring, which does not meet the requirements of a liquid accelerating setting agent.
  • the present invention also made a comparative example 14 on the basis of Example 2, and the specific scheme is as follows:
  • Example 2 The difference from Example 2 is that the complexing agent aspartic acid is replaced by an equal weight of glutamic acid.
  • the liquid quick-setting agent prepared in Comparative Example 14 had a bottom sedimentation of 18 ml at 28 days, and a 6-hour mortar compressive strength of 0.8 MPa.
  • the prepared liquid quick-setting agent had poor stability and could not meet the requirements of early strength.
  • the present invention can prepare an alkali-free, chlorine-free, and fluorine-free early-strength liquid accelerating setting agent, and the 6h compressive strength of the mortar can reach 1.7MPa, which has good early strength performance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

本发明提供了一种制备无碱无氯无氟早强型液体速凝剂的方法，以质量百分含量计，以硫酸铝、二乙醇胺、pH调节剂、络合剂、吐温20和水的用量之和为基准，硫酸铝的用量为56％～58％，二乙醇胺的用量为5％～6％，pH调节剂的用量为0.7％～0.8％，络合剂的用量为1.3％～1.4％，吐温20的用量为0.6％～0.8％，余量为水；该制备方法包括将水、pH调节剂和络合剂混匀后加入反应釜中，并加热反应釜；将硫酸铝加入所述反应釜中搅拌至完全溶解；将二乙醇胺加入所述反应釜中得到预混料；向所述预混料中加入吐温20制得液体速凝剂。本发明所制备的液体速凝剂在保证速凝、早强和稳定性的效果下，也实现了无碱无氯无氟的效果。

Description

一种制备无碱无氯无氟早强型液体速凝剂的方法
相关申请的交叉引用
本申请要求2022年11月04日提交的中国专利申请202211377410.9的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及建筑材料技术领域，具体涉及一种制备无碱无氯无氟早强型液体速凝剂的方法。
背景技术
喷射混凝土是一种广泛应用于隧道工程中的支护和加固作用的特种混凝土，其中，速凝剂是使其快速凝结硬化必不可少的外加剂。根据速凝剂存在的状态，将其分为粉体速凝剂和液体速凝剂。粉体速凝剂主要应用于干喷施工工艺，该工艺会产生大量的粉尘，不仅对工人的身体健康危害较大，同时也会产生严重的环境污染。因此，适用于湿喷工艺的液体速凝剂成为了主要发展方向，尤其是早强型速凝剂。为此，国铁集团标准Q/CR807-2020《隧道喷射混凝土用液体无碱速凝剂》要求液体速凝剂在水泥中的掺量为6％～8％时，所形成的砂浆需要达到6h强度1.0MPa以上(含1.0MPa)。
液体速凝剂的主要速凝组分为硫酸铝，为了使砂浆达到6h强度1.0MPa以上，申请人采用单组分试验确定了硫酸铝的掺量需在4.5％ (与水泥质量的百分比)以上。当液体速凝剂的掺量为8％时，即要求硫酸铝的浓度超过56％。然而，常温下硫酸铝的溶解度仅为36g/100g水，意味着此时液体速凝剂将会结晶导致稳定性不良的问题。因此，解决液体速凝剂早强型和稳定性的矛盾成为了开发无碱液体速凝剂的关键。
为了解决速凝与早强的问题，掺入碱金属促进水泥的水化是一种技术途径。然而碱金属的掺入不仅带来了腐蚀的环境，还不利于混凝土后期强度的发展，更重要的是带来碱骨料反应的风险。因此高碱型液体速凝剂的应用前景比较有限。此外，研究人员还考虑掺入氯离子，然而其带来的钢筋锈蚀的风险也难以避免。速凝剂中铝离子的有效含量是促进水泥混凝土凝结硬化的主要因素，采用络合技术是增加铝离子有效含量的一种重要技术途径。目前采用的络合剂主要是氟离子，然而其同样会带来一定的环保问题。因此，从耐久性及环保角度出发，要求速凝剂中无碱、无氯、无氟。
发明内容
本发明目的在于提供一种制备无碱无氯无氟早强型液体速凝剂的方法，通过组合使用特定成分的pH调节剂和络合剂，能够增加液体速凝剂中有效铝离子的浓度，进而达到液体速凝剂6h早强效果；同时，采用适宜用量的稳定剂，能够提升液体速凝剂的稳定性效果。其具体技术方案如下：
本申请提供了一种制备无碱无氯无氟早强型液体速凝剂的方法， 包括以下步骤：
步骤S1、将水、pH调节剂和络合剂混合后加入反应釜中，加热所述反应釜至70℃-80℃，并保温；
步骤S2、将硫酸铝加入所述反应釜中搅拌至完全溶解；
步骤S3、将二乙醇胺加入所述反应釜中得到预混料，将所述预混料搅拌至液体状；
步骤S4、向液体状的所述预混料中加入吐温20制得全混料，然后停止对所述反应釜保温，将全混料经搅拌冷却后制得所述无碱无氯无氟早强型液体速凝剂；
以质量百分含量计，以硫酸铝、二乙醇胺、pH调节剂、络合剂、吐温20和水的用量之和为基准，硫酸铝的用量为56％～58％，二乙醇胺的用量为5％～6％，pH调节剂的用量为0.7％～0.8％，络合剂的用量为1.3％～1.4％，吐温20的用量为0.6％～0.8％，余量为水；
其中，所述pH调节剂包括酒石酸和甲酸中的任意一种；
所述络合剂包括天冬氨酸和甲基甘氨酸中的任意一种。
可选的，所述硫酸铝满足HG/T2225-2018《工业硫酸铝》的要求。
可选的，所述二乙醇胺满足HG/T2916-1997《工业用二乙醇胺》的要求。
可选的，在步骤S2中，对硫酸铝采用以下搅拌参数：搅拌时间不小于30min；搅拌速率不小于300rpm。
可选的，在步骤S3中，所述预混料采用的搅拌参数为搅拌时间30-60min，搅拌速率不小于300rpm。
可选的，在步骤S4中，所述全混料采用的搅拌参数为搅拌时间不小于30min，搅拌速率为不小于300rpm。
应用本发明的技术方案，至少具有以下有益效果：
(1)本发明中所述无碱无氯无氟早强型液体速凝剂的制备方法，采用酒石酸或甲酸作为pH调节剂，能够增加硫酸铝的溶解度，提高铝离子含量；同时，采用天冬氨酸或甲基甘氨酸作为络合剂，能够提高对溶解的铝离子的封锁性能，进而有效的增加络合铝离子的浓度，防止铝离子结晶沉淀，有利于增加液体速凝剂的6h早强性能；采用适宜用量的稳定剂，能够提升液体速凝剂的稳定性；采用适宜用量的二乙醇胺，能够减少对砂浆的净浆凝结时间，同时，能够提高6h早强性能。此外，本发明在原料组分中组合使用特定成分的pH调节剂和络合剂，未使用碱金属、氯离子和氟离子，从而使得所制备的液体速凝剂在保证速凝、早强和稳定性的效果下，也实现了无碱无氯无氟的效果。
(2)本发明中所述无碱无氯无氟早强型液体速凝剂的制备方法，采用步骤S1确保pH调节剂和络合剂在反应釜中被加热以达到对硫酸铝最佳的溶解和络合条件；采用步骤S2将硫酸铝加入反应釜中，确保对硫酸铝充分溶解和络合；采用步骤S3加入二乙醇胺便于制得液体状预混料，同时，也便于在步骤S4中加入稳定剂吐温20后制得稳定性良好的无碱无氯无氟早强型液体速凝剂。此外，在步骤S4中使用吐温20还能够提高各组分的增溶效果。
具体实施方式
下面将结合本发明实施例对本发明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。基于本发明中的实施例，本领域普通技术人员所获得的所有其他实施例，都属于本发明保护的范围。
实施例1：
一种无碱无氯无氟早强型液体速凝剂，包括以下质量百分比的原料组分：硫酸铝56％；二乙醇胺5.5％；pH调节剂0.7％；络合剂1.3％；稳定剂0.8％；余量为水；
其中，所述pH调节剂为酒石酸；
所述络合剂为天冬氨酸。
所述稳定剂为吐温20。
所述硫酸铝满足HG/T2225-2018《工业硫酸铝》的要求。
所述二乙醇胺满足HG/T2916-1997《工业用二乙醇胺》的要求。
一种所述的无碱无氯无氟早强型液体速凝剂的制备方法，包括以下步骤：
步骤S1、将水、pH调节剂和络合剂混匀后加入反应釜中，加热所述反应釜至70℃，并保温；
步骤S2、将硫酸铝加入所述反应釜中搅拌至完全溶解；
步骤S3、将二乙醇胺加入所述反应釜中得到预混料，将所述预混料搅拌至液体状；
步骤S4、向液体状的所述预混料中加入稳定剂制得全混料，然后停止对所述反应釜保温，将全混料经搅拌冷却后制得所述无碱无氯无氟早强型液体速凝剂。
在步骤S2中，对硫酸铝采用以下搅拌参数：搅拌时间30min；搅拌速率不小于300rpm。
在步骤S3中，所述预混料采用的搅拌参数为搅拌时间30-60min，搅拌速率为不小于300rpm。
在步骤S4中，所述全混料采用的搅拌参数为搅拌时间30min，搅拌速率为不小于300rpm。
本发明还做了实施例2-10和对比例1-10。与实施例1不同的是，实施例2-10和对比例1-10在原料组成和用量上做了调整，详见表1。
表1

由实施例1-10所制备的各无碱无氯无氟早强型液体速凝剂对应标记为实施样品1-10。由对比例1-10所制备的各液体速凝剂对应标记为对比样品1-10。将实施样品1-10和对比样品1-10均按照GB/T 35159-2017《喷射混凝土用速凝剂》中规定的速凝剂密度、pH值、固含量、稳定性、氯离子含量和碱含量测试方法测试对应的性能，且将实施样品1-10和对比样品1-10均根据Q/CR807-2020《隧道喷射混凝土用液体无碱速凝剂》中规定的氟离子含量测试方法测试对应的氟离子含量。上述测试结果详见表2。
表2
续表2
根据国标GB/T 35159-2017《喷射混凝土用速凝剂》规定的检测方法，采用P.I.42.5基准硅酸盐水泥和厦门艾思欧生产的标准砂对实施样品1-10和对比样品1-10进行净浆凝结时间和砂浆抗压强度测试，测试结果详见表3。
表3
续表3
由表1-表3数据知：
本发明所制备的实施样品1-10中的氯离子含量和碱含量均低于国家标准GB/T35159-2017的要求，氟离子含量也低于Q/CR807-2020的要求，且样品稳定性良好。故本发明能够制备无碱无氯无氟液体速 凝剂。本发明所制备的实施样品1-10符合国家标准GB/T35159-2017中规定的1d抗压强度、28d强度比及90d强度保留值的要求，并且6h强度远高于Q/CR807-2020中规定要求，表现出了优异的早强性能。
对比样品1中减少了硫酸铝的含量，其表现出了较好的稳定性，其pH值、稳定性、氯离子含量、碱含量、氟离子含量和凝结硬化性能也满足GB/T 35159-2017《喷射混凝土用速凝剂》的要求，但是6h强度仅为0.7MPa，不符合Q/CR807-2020《隧道喷射混凝土用液体无碱速凝剂》的要求，早强性能不足。
在对比样品2中，增加了硫酸铝的含量，导致其产生结晶沉淀的现象，使得稳定性下降。同时，结晶沉淀的硫酸铝未能参加水泥的水化反应，即对比样品2中有效的铝相含量降低，从而净浆凝结时间延长，6h抗压强度降低，不符合早强速凝剂的要求。
在对比样品3中，降低了二乙醇胺的含量，虽然其表现出良好的稳定性，但净浆凝结时间延长，6h强度为0.4MPa，不符合早强速凝剂的要求。
在对比样品4中，增加了二乙醇胺的含量，二乙醇胺含量的增加将对水泥的凝结硬化带来负面的影响，导致净浆凝结时间延长，6h强度降低，不符合早强速凝剂的要求。
在对比样品5中，pH调节剂由酒石酸换成磷酸，因为磷酸对硫酸铝的溶解性较差，导致对比样品5中产生结晶物质，使得稳定性变差，净浆凝结时间延长，早期强度降低。
在对比样品6中，pH调节剂由酒石酸换成了硫酸，此时相当于 在硫酸铝饱和溶液中增加硫酸根的浓度，同样导致对比样品6中硫酸铝结晶，使得稳定性变差，净浆凝结时间延长，早期强度降低。
在对比样品7中，降低了天冬氨酸的含量，即络合剂用量不足时，铝离子不能均匀分散，导致对比样品7出现稳定性不良的问题。硫酸铝的结晶沉淀导致参与反应的硫酸铝的量降低，使得净浆凝结时间延长，早期强度降低。
在对比样品8中，增加了天冬氨酸的含量，使得对比样品8的pH值降低，延缓了水泥的水化，导致净浆凝结时间延长，6h抗压强度仅0.4MPa，不符合早强速凝剂的要求。
在对比样品9中，降低了吐温20的含量，导致硫酸铝结晶沉淀，引起稳定性不良的问题，且净浆凝结时间延长，早期强度降低。
在对比样品10中，吐温20换成吐温40，同样出现稳定性不良的问题，且净浆凝结时间延长，6h强度为0.7MPa，达不到早强的要求。
为了验证本发明所制备的无碱无氯无氟早强型液体速凝剂与不同水泥的适应性，分别选取了贵州西南水泥、山东杨春水泥、河北冀东水泥、广东金洋水泥和江西万年青水泥企业生产的42.5级普通硅酸盐水泥，采用实施样品2对上述各企业水泥分别进行净浆凝结时间和砂浆抗压强度测试，测试方法参考参照国标GB/T 35159-2017《喷射混凝土用速凝剂》规定的标准实施，实施样品2掺量为8％，测试结果详见表4。
表4
由表4知，本发明所制备的无碱无氯无氟早强型液体速凝剂对不同水泥的净浆凝结时间和砂浆抗压强度均满足GB/T 35159-2017和Q/CR807-2020的要求，表现出良好的适应性。
本发明在实施例1的基础上还做了对比例11-13，具体方案如下：
对比例11：
与实施例1不同的是，在步骤S2-S4中各搅拌速率均为250rpm。
对比例12：
与实施例1不同的是，在步骤S1中加热所述反应釜至60℃。
对比例13：
与实施例1不同的是，将所需用量的水、pH调节剂、络合剂、硫酸铝、二乙醇胺和吐温20一次性加入所述反应釜中。
相比于实施例1，在对比例11中，降低搅拌速率会导致所制备的液体速凝剂在28d时底部沉淀为20ml，6h砂浆抗压强度为0.7MPa。即，所制备的液体速凝剂稳定性不良，且达不到早强的要求。
相比于实施例1，在对比例12中，降低加热温度，硫酸铝溶解速率降低，使得所制备的液体速凝剂在28d时底部沉淀24ml，6h砂浆抗压强度为0.6MPa。即，所制备的液体速凝剂稳定性不良，且达 不到早强的要求。
相比于实施例1，在对比例13中，一次性投料使得各组分不能及时均匀分散和及时溶解，搅拌结束后速凝剂为膏状，达不到液体速凝剂的要求。
本发明在实施例2的基础上还做了对比例14，具体方案如下：
对比例14：
与实施例2不同的是，将络合剂天冬氨酸替换为等重量的谷氨酸。
相比于实施例2，在对比例14中制备的液体速凝剂在28d时底部沉淀18ml，6h砂浆抗压强度为0.8MPa。所制备的液体速凝剂稳定性不良，且达不到早强的要求。
综上所述，本发明能够制备一种无碱无氯无氟早强型液体速凝剂，并且砂浆6h抗压强度可达到1.7MPa，具有较好的早强性能。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。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。

Claims (6)

  1. 一种制备无碱无氯无氟早强型液体速凝剂的方法，其特征在于，包括以下步骤：
    步骤S1、将水、pH调节剂和络合剂混合后加入反应釜中，加热所述反应釜至70℃-80℃，并保温；
    步骤S2、将硫酸铝加入所述反应釜中搅拌至完全溶解；
    步骤S3、将二乙醇胺加入所述反应釜中得到预混料，将所述预混料搅拌至液体状；
    步骤S4、向液体状的所述预混料中加入吐温20制得全混料，然后停止对所述反应釜保温，将全混料经搅拌冷却后制得所述无碱无氯无氟早强型液体速凝剂；
    以质量百分含量计，以硫酸铝、二乙醇胺、pH调节剂、络合剂、吐温20和水的用量之和为基准，硫酸铝的用量为56％～58％，二乙醇胺的用量为5％～6％，pH调节剂的用量为0.7％～0.8％，络合剂的用量为1.3％～1.4％，吐温20的用量为0.6％～0.8％，余量为水；
    其中，所述pH调节剂包括酒石酸和甲酸中的任意一种；
    所述络合剂包括天冬氨酸和甲基甘氨酸中的任意一种。
  2. 根据权利要求1所述的方法，其特征在于，所述硫酸铝满足HG/T2225-2018《工业硫酸铝》的要求。
  3. 根据权利要求1所述的方法，其特征在于，所述二乙醇胺满足 HG/T2916-1997《工业用二乙醇胺》的要求。
  4. 根据权利要求1-3中任意一项所述的制备方法，其特征在于，在步骤S2中，对硫酸铝采用以下搅拌参数：搅拌时间不小于30min；搅拌速率不小于300rpm。
  5. 根据权利要求1-3中任意一项所述的制备方法，其特征在于，在步骤S3中，所述预混料采用的搅拌参数为搅拌时间30-60min，搅拌速率不小于300rpm。
  6. 根据权利要求1-3中任意一项所述的制备方法，其特征在于，在步骤S4中，所述全混料采用的搅拌参数为搅拌时间不小于30min，搅拌速率为不小于300rpm。
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