阅读说明：本技术 一种无氟无碱液体速凝剂及其制备方法 (Fluoride-free alkali-free liquid accelerator and preparation method thereof ) 是由 曹玉林 李延华 于小雷 王金虎 焦汝强 杨斌 滕缙 宫长峰 沈修龙 陈延庆 于 2021-11-24 设计创作，主要内容包括：本发明涉及混凝土添加剂技术领域,具体地说,是一种无氟无碱液体速凝剂及其制备方法。制备方法包括如下步骤：将悬浮剂、分散剂、增稠剂加入水中搅拌制成改性悬浮液,将促凝剂和活性剂加入水中制成改性主剂,混合改性悬浮液和改性主剂,添加稳定剂和消泡剂搅拌即制得所述速凝剂。本发明的促凝剂可以降低在水泥中的添加量,满足混凝土的凝结时间要求,降低喷射混凝土的回弹量,并且不添加有害组分,绿色环保。(The invention relates to the technical field of concrete additives, in particular to a fluoride-free alkali-free liquid accelerator and a preparation method thereof. The preparation method comprises the following steps: adding a suspending agent, a dispersing agent and a thickening agent into water, stirring to prepare a modified suspension, adding a coagulant and an active agent into water to prepare a modified main agent, mixing the modified suspension and the modified main agent, adding a stabilizing agent and a defoaming agent, and stirring to prepare the accelerating agent. The coagulant can reduce the addition amount in cement, meet the setting time requirement of concrete, reduce the rebound amount of sprayed concrete, and is free from harmful components, green and environment-friendly.)

1. A preparation method of a fluorine-free alkali-free liquid accelerator is characterized by comprising the following steps:

s1: adding a suspending agent into deionized water, stirring for t1 time, adding a dispersing agent, stirring for t2 time, adding a thickening agent, and stirring for t3 time to prepare a modified suspension;

s2: adding a coagulant and an active agent into deionized water at the temperature of T1 to react for T4 time to prepare a modified main agent;

s4: adding the product modification suspension obtained in the step S1 into the product modification main agent obtained in the step S2, and stirring for t5 time;

s5: and adding a stabilizer and a defoaming agent into the product of the step S4, and stirring for t6 time to obtain the accelerator.

2. The method for preparing a porous material according to claim 1, wherein the steps between S2 and S4 further include a step S3: the modified main agent is placed in a vacuum environment to be degassed at the temperature T2.

3. The method according to claim 1, wherein the dispersant in step S1 comprises 35% by mass of a magnesium salt of naphthalene sulfonic acid, and the method for preparing the magnesium salt of naphthalene sulfonic acid comprises:

1) slowly adding inorganic acid into the dispersion liquid at the temperature of T3, and then heating to the temperature of T4 for sulfonation for T7;

2) after the sulfonation is finished, cooling to the temperature of T5, adding deionized water, continuously cooling to the temperature of T6, adding a fixing agent, and then heating to the temperature of T7 to react for T8 time;

3) and (3) adding deionized water and a transfer agent into the product obtained in the step 2), and stirring for t9 time to obtain the dispersing agent.

4. The method according to claim 1, wherein step S1 satisfies one or more of the following conditions:

a. the suspending agent comprises a silicon-containing magnesium salt;

preferably, the suspending agent comprises hydrous magnesium silicate and/or magnesium aluminum silicate;

b. the dispersing agent comprises 35% by mass of magnesium naphthalene sulfonate;

c. the thickener comprises one or more of xanthan gum, guar gum, xanthan gum and HPMC;

d. 5-15 parts by mass of a suspending agent, 100 parts by mass of deionized water, 5-60 parts by mass of a dispersing agent and 5-12 parts by mass of a thickening agent;

e. the t1 time is 1-2h, the t2 time is 20-30min, and the t3 time is 20-30 min;

f. the stirring is high-shear stirring with the linear speed of not less than 10 m/s.

5. The method according to claim 1, wherein step S2 satisfies one or more of the following conditions:

g. the coagulant comprises an aluminium salt;

preferably, the accelerator comprises iron-free aluminum sulfate;

h. the active agent comprises an organic alcohol amine;

preferably, the active agent comprises one or more of monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine;

i. the coagulant is 400-450 parts by mass, the deionized water is 280-320 parts by mass, and the activator is 35-65 parts by mass;

j. the temperature T1 is 55-65 ℃;

k. the t4 time is 30-60 min.

6. The method as claimed in claim 1, wherein the time t5 of step S4 is 30-60 min.

7. The method according to claim 1, wherein step S5 satisfies one or more of the following conditions:

the stabilizer comprises a lower alcohol;

preferably, the stabilizer comprises glycerol and/or ethylene glycol;

the defoamer comprises silicone defoamer 880B and/or polyether defoamer;

n, 15-45 parts of stabilizer and 0.5-0.8 part of defoamer by mass;

o. the t6 time is 30-60 min.

8. The method according to claim 2, wherein step S3 satisfies one or more of the following conditions:

p. the vacuum degree of the vacuum environment is (0.7-1.2) x 10^-3Pa；

q. the temperature of T2 is 50-60 ℃.

9. The method of claim 3, wherein the dispersant is prepared by one or more of the following conditions:

a) the inorganic acid comprises concentrated sulfuric acid;

b) the dispersion comprises liquid naphthalene;

c) the fixing agent comprises formaldehyde;

d) the transfer agent comprises magnesium oxide;

e) the molar mass ratio of the liquid naphthalene to the concentrated sulfuric acid to the formaldehyde to the magnesium oxide is 1:1.35:1.2: 0.6;

f) the temperature T3 is 140-150 ℃;

g) the temperature T4 is 165-170 ℃;

h) the T5 temperature is 120 ℃;

i) the T6 temperature is 105 ℃;

j) the temperature T7 is 110-115 ℃;

k) the t7 time is 2-3h

l) the time t8 is 4-5 h;

m) the time t9 is 30-40 min.

10. The fluorine-free alkali-free liquid accelerator prepared by the preparation method of claims 1-9, which is characterized in that the accelerator comprises the following components in parts by weight:

5-15 parts of suspending agent, 5-60 parts of dispersing agent, 5-12 parts of thickening agent, 450 parts of coagulant, 35-65 parts of active agent, 15-45 parts of stabilizing agent, 0.5-0.8 part of defoaming agent and 420 parts of deionized water.

Technical Field

The invention relates to the technical field of concrete additives, in particular to a fluoride-free alkali-free liquid accelerator and a preparation method thereof.

Background

The accelerator is an additive for quickly setting and hardening cement concrete, and is mainly applied to tunnel shotcrete construction and mortar rush-repair construction. The conventional accelerator is divided into an alkaline accelerator and an alkali-free accelerator, wherein the alkali-free accelerator is an accelerator with alkali content less than or equal to 1%, and the alkali-free accelerator is widely used due to the advantages of low alkali content, low injury to constructors, low rebound resilience, small dust amount, low later strength loss and the like.

The existing alkali-free accelerator usually adopts aluminum sulfate as a main agent, wherein aluminum ions are main accelerating components, but the solubility of the aluminum sulfate is limited, the concentration of the aluminum ions is generally less than 4.5 percent and unstable, and the aluminum ions can be crystallized and separated out after a long time, so that the mixing amount of the aluminum sulfate is generally larger (more than 8 percent) in order that the setting time of concrete can meet the construction requirement. In order to improve the effective concentration of aluminum ions, hydrofluoric acid and aluminum hydroxide are mostly adopted to generate complex aluminum fluoride, the concentration of the aluminum ions can be improved to more than 7 percent, the requirement of concrete setting time can be met, but the fluoride is a toxic substance, can burn skin and pollute the environment; and the sprayed concrete doped with the complexing aluminum fluoride has high resilience rate and poor adaptability in construction, the strength can not meet the requirement in 1 day, and the sprayed concrete can volatilize gas with stronger irritation and cause great damage to personnel operating in closed environments such as tunnels.

Disclosure of Invention

The invention aims to provide a fluoride-free alkali-free liquid accelerator which can reduce the addition amount of an accelerator in cement, meet the setting time requirement of concrete, reduce the rebound amount of sprayed concrete, does not add harmful components and is environment-friendly.

In order to achieve the above purpose, the technical scheme of the invention is as follows:

a preparation method of a fluorine-free alkali-free liquid accelerator comprises the following steps:

s1: adding 5-15 parts by mass of a suspending agent into 100 parts by mass of deionized water under high-shear stirring at an online speed of not less than 10m/s, stirring for 1-2h, then adding 5-60 parts by mass of a dispersing agent, stirring for 20-30min, then adding 5-12 parts by mass of a thickening agent, and stirring for 20-30min to prepare a modified suspension;

wherein the suspending agent comprises a silicon-containing magnesium salt;

preferably, the suspending agent comprises hydrous magnesium silicate and/or magnesium aluminum silicate;

the thickener comprises one or more of xanthan gum, guar gum, xanthan gum and HPMC;

the dispersing agent comprises 35% of naphthalene sulfonic acid magnesium salt by mass, and the preparation method of the naphthalene sulfonic acid magnesium salt comprises the following steps:

1) slowly adding inorganic acid into the dispersion liquid at the temperature of 140-150 ℃, and then heating to the temperature of 165-170 ℃ for sulfonation for 2-3 h;

2) cooling to 120 ℃ after sulfonation is finished, adding deionized water, continuously cooling to 105 ℃ to reinforce the fixing agent, and then heating to 110 ℃ and 115 ℃ for reaction for 4-5 h;

3) and (3) adding deionized water and a transfer agent into the product obtained in the step 2), and stirring for 30-40min to obtain the dispersing agent.

In the above method for preparing a magnesium salt of naphthalene sulfonic acid, the inorganic acid comprises concentrated sulfuric acid;

the dispersion comprises liquid naphthalene;

the fixing agent comprises formaldehyde;

the transfer agent comprises magnesium oxide;

the molar mass ratio of the liquid naphthalene to the concentrated sulfuric acid to the formaldehyde to the magnesium oxide is 1:1.35:1.2: 0.6.

In the conventional scheme, the thickening agent is generally added after pre-dissolving, the addition amount is very small, the addition amount is less than 1 KG/ton calculated by powder, the viscosity of the product cannot be used and the stability is not good, and a small amount of thickening agent cannot form an effective synergistic effect with a quick-setting component. In the step of the invention, the thickening agent is added when the modified suspension is prepared in the previous stage, the thickening component can exist in the material in a suspension state by virtue of the dispersing agent, the thickening agent and the coagulation accelerating component of the coagulant are mainly subjected to complexing action of aluminum ions, the content of the aluminum ions can be obviously improved after the modified main agent is prepared, the coagulation accelerating effect is obviously improved, the coagulation accelerating effect is also increased along with the increase of the dosage, the instantaneous agglomeration adhesion of the cement paste is increased, and the prepared coagulant has good stability for 90 days and has no obvious layering.

S2: adding 450 mass parts of coagulant and 35-65 mass parts of activator into 320 mass parts of ionized water at 55-65 ℃ for reaction for 30-60min to prepare a modified main agent;

wherein the coagulant is an aluminum salt;

preferably, the accelerator is iron-free aluminum sulfate;

the active agent is organic alcohol amine;

preferably, the active agent is one or more of monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine;

s4: adding the product modified suspension obtained in the step S1 into the product modified main agent obtained in the step S2, and stirring for 30-60 min;

s5: and (4) adding 15-45 parts by mass of a stabilizer and 0.5-0.8 part by mass of a defoaming agent into the product obtained in the step S4, and stirring for 30-60min to obtain the accelerator.

Wherein the stabilizer comprises a lower alcohol;

preferably, the stabilizer comprises glycerol and/or ethylene glycol;

the defoamer comprises a silicone defoamer 880B and/or a polyether defoamer.

The invention also provides a preparation method of the preferable fluoride-free alkali-free liquid accelerator, and particularly the method between the steps S2 and S4 further comprises the step S3: placing the product modification main agent obtained in the step S2 at a vacuum degree of (0.7-1.2). times.10^-3Degassing treatment is carried out in a vacuum environment of Pa at the temperature of 50-60 ℃.

The degassing treatment can remove water molecules on the active sites of the organic matter sites in the modified main agent, so that the organic matter is exposed to more active coordination, more binding coordination is provided for aluminum ions in the setting accelerator, the concentration of the aluminum ions in the product is improved, and the prepared setting accelerator can meet construction requirements such as setting time and the like only by doping a small amount of the setting accelerator into concrete.

The invention also provides a fluorine-free alkali-free liquid accelerator prepared by the preparation method, which comprises the following components in parts by weight:

5-15 parts of suspending agent, 5-60 parts of dispersing agent, 5-12 parts of thickening agent, 450 parts of coagulant, 35-65 parts of active agent, 15-45 parts of stabilizing agent, 0.5-0.8 part of defoaming agent and 420 parts of deionized water.

Compared with the prior art, the invention has the following advantages:

(1) the dosage of the thickening agent can be greatly increased under the action of the suspending agent and the dispersing auxiliary agent, the synergistic effect of thickening and quick-setting components can be more effectively exerted, the complexing effect with aluminum ions of the accelerating component is increased, the content of the aluminum ions in the quick-setting agent is effectively increased, and the construction requirement can be met when the cement doping amount is lower (6%).

(2) The use amount of the thickening agent is greatly increased, so that the instantaneous adhesiveness of the sprayed concrete is improved, and the rebound quantity of the sprayed concrete is greatly reduced.

Detailed Description

The terms as used herein:

"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).

The technical solutions of the present invention will be described in detail with reference to specific examples, but those skilled in the art will understand that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.

Example 1

A preparation method of a fluorine-free alkali-free liquid accelerator comprises the following steps:

preparing 35% naphthalene sulfonic acid magnesium salt dispersant, wherein the molar mass ratio of each material is as follows: sulfuric acid: formaldehyde: magnesium oxide 1:1.35:1.2:0.6

1) Slowly adding 108 parts by mass of concentrated sulfuric acid into 180 parts by mass of liquid naphthalene at 140 ℃, controlling the acid adding operation within 1h, and then heating to 165 ℃ for sulfonation for 2.5 h;

2) after sulfonation, cooling to 120 ℃, adding 55 parts by mass of deionized water, continuously cooling to 105 ℃, dropwise adding 80 parts by mass of formaldehyde, controlling the formaldehyde to be dropwise added within about 2 hours, and then heating to 110 ℃ for reaction for 4.5 hours;

3) 557 parts by mass of deionized water and 20 parts by mass of magnesium oxide are added into the product obtained in the step 2), and the mixture is stirred for 30min to obtain the naphthalenesulfonic acid magnesium salt dispersant with the mass fraction of 35%.

S1: adding 15 parts by mass of magnesium aluminum silicate into 100 parts by mass of deionized water under high-shear stirring at an online speed of not less than 10m/s, stirring for 1h, then adding 30 parts by mass of prepared 35% by mass of magnesium naphthalenesulfonate, stirring for 20min, adding 8 parts by mass of xanthan gum, and stirring for 20min to prepare a modified suspension;

s2: adding 450 parts by mass of anhydrous aluminum sulfate and 35 parts by mass of triethanolamine into 320 parts by mass of ionized water at 55 ℃ to react for 30min to prepare a modifying main agent;

s4: adding the product modified suspension obtained in the step S1 into the product modified main agent obtained in the step S2, and stirring for 30 min;

s5: and (4) adding 45 parts by mass of ethylene glycol and 0.5 part by mass of defoaming agent 880B into the product obtained in the step S4, and stirring for 30min to obtain the fluorine-free alkali-free liquid accelerator.

Example 2

A preparation method of a fluorine-free alkali-free liquid accelerator comprises the following steps:

preparing 35% naphthalene sulfonic acid magnesium salt dispersant, wherein the molar mass ratio of each material is as follows: sulfuric acid: formaldehyde: magnesium oxide 1:1.35:1.2:0.6

1) Slowly adding 108 parts by mass of concentrated sulfuric acid into 180 parts by mass of liquid naphthalene at 140 ℃, controlling the acid adding operation within 1h, and then heating to 165 ℃ for sulfonation for 2.5 h;

2) after sulfonation, cooling to 120 ℃, adding 55 parts by mass of deionized water, continuously cooling to 105 ℃, dropwise adding 80 parts by mass of formaldehyde, controlling the formaldehyde to be dropwise added within about 2 hours, and then heating to 110 ℃ for reaction for 4.5 hours;

3) 557 parts by mass of deionized water and 20 parts by mass of magnesium oxide are added into the product obtained in the step 2), and the mixture is stirred for 30min to obtain the naphthalenesulfonic acid magnesium salt dispersant with the mass fraction of 35%.

S1: adding 5 parts by mass of magnesium aluminum silicate and 10 parts by mass of hydrated magnesium silicate into 100 parts by mass of deionized water under high-shear stirring at an online speed of not less than 10m/s, stirring for 2 hours, then adding 50 parts by mass of prepared magnesium naphthalene sulfonate with a mass fraction of 35%, stirring for 30min, then adding 5 parts by mass of xanthan gum and 7 parts by mass of guar gum, and stirring for 30min to prepare a modified suspension;

s2: adding 423 parts by mass of anhydrous aluminum sulfate and 55 parts by mass of triethanolamine into 300 parts by mass of ionized water at 60 ℃ to react for 60min to prepare a modifying main agent;

s4: adding the modified suspension of the product obtained in the step S1 into the product obtained in the step S2, and stirring for 60 min;

s5: and (3) adding 30 parts by mass of glycerol and 0.8 part by mass of defoaming agent 880B into the product obtained in the step S4, and stirring for 30min to obtain the fluorine-free alkali-free liquid accelerator.

Example 3

A preparation method of a fluorine-free alkali-free liquid accelerator comprises the following steps:

preparing 35% naphthalene sulfonic acid magnesium salt dispersant, wherein the molar mass ratio of each material is as follows: sulfuric acid: formaldehyde: magnesium oxide 1:1.35:1.2:0.6

1) Slowly adding 108 parts by mass of concentrated sulfuric acid into 180 parts by mass of liquid naphthalene at 140 ℃, controlling the acid adding operation within 1h, and then heating to 165 ℃ for sulfonation for 2.5 h;

2) after sulfonation, cooling to 120 ℃, adding 55 parts by mass of deionized water, continuously cooling to 105 ℃, dropwise adding 80 parts by mass of formaldehyde, controlling the formaldehyde to be dropwise added within about 2 hours, and then heating to 110 ℃ for reaction for 4.5 hours;

3) and (3) adding 557 parts by mass of deionized water and 20 parts by mass of magnesium oxide into the product obtained in the step 2), and stirring for 40min to obtain the naphthalenesulfonic acid magnesium salt dispersant with the mass fraction of 35%.

S1: under high-shear stirring with the linear speed of not less than 10m/s, adding 15 parts by mass of hydrated magnesium silicate into 100 parts by mass of deionized water, stirring for 1h, then adding 60 parts by mass of prepared magnesium naphthalenesulfonate with the mass fraction of 35%, stirring for 45min, adding 7 parts by mass of guar gum, and stirring for 45min to prepare modified suspension;

s2: adding 400 parts by mass of anhydrous aluminum sulfate and 65 parts by mass of triisopropanolamine into 280 parts by mass of deionized water at 65 ℃ to react for 45min to prepare a modifying main agent;

s3: the modifying main agent is added under the vacuum degree of 1.2 multiplied by 10^-3Degassing for 2 hours at the temperature of Pa and 50 ℃ in a vacuum environment;

s4: adding the product modified suspension obtained in the step S1 into the product modified main agent obtained in the step S3, and stirring for 45 min;

s5: and (4) adding 10 parts by mass of glycerol, 5 parts by mass of ethylene glycol and 0.6 part by mass of defoaming agent polyether defoaming agent into the product obtained in the step (S4), and stirring for 30min to obtain the fluorine-free alkali-free liquid accelerator.

Test example 1

The fluorine-free alkali-free liquid setting accelerators prepared in examples 1 to 3 were added to cement mortar in an amount of 6% by weight of the cement to test the compressive strength thereof, in a manner according to the standard of GBT35159-2017 accelerating agent for shotcrete. The performance results of the tests are shown in table 1.

The proportion tested by the cement paste setting time is that of the standard cement: 400:140 parts of water;

the cement mortar is prepared from the following components in percentage by weight: standard sand: water 900:1350: 450.

Table 1 test performance results for examples 1-3

Serial number	Initial setting s	Final set s	1d compressive strength MPa	28d compressive strength ratio%
					Example 1	242	550	13.2	106
Example 2	150	386	11.3	99
					Example 3	195	438	12.4	102

Test example 2

The fluorine-free alkali-free liquid setting accelerator prepared in example 2 was added to cement mortar in an amount of 6% by weight of the cement to test the compressive strength thereof, specifically according to the standard test of GBT35159-2017 accelerating agent for shotcrete. The performance results for different brands of cement are shown in table 2.

The proportion tested by the setting time of the cement paste is as follows: 400:140 parts of water;

the cement mortar comprises the following components in percentage by weight: standard sand: water 900:1350: 450.

TABLE 2 Performance results for different brands of cement

Cement	Initial setting s	Final set s	1d compressive strength MPa	28d compressive strength ratio%
					Middle-linked PO42.5	208	490	11.2	101
Golden corner PO42.5	268	536	12.3	99
					Landscape PO42.5	187	417	9.4	93
Jinlong Po42.5	270	580	15.6	96

According to the analysis of the test results in tables 1 and 2, the performances of the fluorine-free and alkali-free liquid setting accelerators prepared in examples 1 to 3 all meet the requirements of GBT35159-2017 accelerating agent for sprayed concrete.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.