A cement-based material activity activator and its preparation method and application

Abstract

The present invention provides a cement-based material activity stimulator and a preparation method and application thereof, which relate to the technical field of cement additives. The activity stimulator comprises the following raw materials by weight: 5 parts of polyether polyol, 3-10 parts of modified complex enzyme microcapsules, 2-8 parts of surfactants, and 3-5 parts of organic acids; the modified complex enzyme microcapsules comprise the following raw materials by weight: 10 parts of complex enzymes, 20-35 parts of chitosan, and 40-55 parts of fluorine-containing silicone ethers; wherein the complex enzymes comprise carbonic anhydrase and urease. The preparation method of the activity stimulator comprises mixing the raw materials. The cement-based material activity stimulator prepared by the present invention is applied to cement or concrete, which can reduce the consumption of clinker and improve the flexural strength and compressive strength of cement or concrete.

Description

Technical Field

[0001] The invention belongs to the technical field of cement additives, and in particular is a cement-based material activity activator and a preparation method and application thereof. Background Art

[0002] In the cement production process, the classification of admixtures mainly includes two categories: active admixtures and inactive admixtures. Adding admixtures to cement-based materials can not only reduce the proportion of clinker in cement, but also promote the comprehensive utilization of resources. However, in order to further stimulate the performance of admixtures, admixtures are often used in combination with active stimulants.

[0003] In the related art, the active activator is usually composed of hydroxyl, amino and carboxyl surfactants and inorganic salts with activating effects. However, the active activators in the prior art have certain limitations. They cannot fully activate the silicate and aluminate components in the admixture, which limits the improvement of cement strength and durability. Summary of the invention

[0004] In view of the limitations of the active stimulants in the prior art in improving the strength and durability of cement, the present invention proposes an active stimulant for cement-based materials, which can effectively improve the strength and durability of cement, thereby overcoming the deficiencies in the prior art.

[0005] The present invention solves the above technical problems through the following technical solutions.

[0006] The present invention provides a cement-based material activity stimulator, comprising the following raw materials in parts by weight: 5 parts of polyether polyol, 3 to 10 parts of modified complex enzyme microcapsules, 2 to 8 parts of surfactants, and 3 to 5 parts of organic acids;

[0007] The modified complex enzyme microcapsule comprises the following raw materials in parts by weight: 10 parts of complex enzyme, 20-35 parts of chitosan and 40-55 parts of fluorine-containing silicone ether;

[0008] Wherein, the complex enzyme comprises carbonic anhydrase and urease.

[0009] In the present invention, the cement-based material contains admixtures, wherein the admixtures include coal gangue, fly ash, slag or volcanic ash.

[0010] In the present invention, the polyether polyol is one of polyether diol, polyether triol and polyether tetraol, for example, at least one of NPE-108, PPG200 and PPG400.

[0011] In the present invention, the surfactant is sodium lignocellulose sulfonate or calcium lignosulfonate, preferably calcium lignosulfonate.

[0012] In the present invention, the organic acid is at least one of acetic acid, oleic acid and citric acid, preferably acetic acid.

[0013] In the present invention, the composite enzyme includes 50-68wt% carbonic anhydrase (CAS No.: 9001-03-0) and 32-50wt% urease (CAS No.: 9002-13-5) by mass percentage; for example, the composite enzyme includes 65wt% carbonic anhydrase and 35wt% urease. Urease decomposes urea into ammonia and carbon dioxide, and increases the environmental pH, which can promote carbonic anhydrase to catalyze the hydration reaction of carbonic acid to form carbonic acid, and the carbonic acid gradually ionizes carbonate ions, further accelerating the deposition of calcium carbonate.

[0014] Furthermore, the activity of the carbonic anhydrase is ≥2500u / mg, preferably ≥3000u / mg.

[0015] Furthermore, the activity of the urease is ≥2000u / mg.

[0016] In the present invention, the fluorine-containing silane ether is at least one of tridecafluorooctyltriethoxysilane (CAS No.: 51851-37-7), heptadecafluorooctyltrimethoxysilane (CAS No.: 85857-16-5) and heptadecafluorodecyltriethoxysilane (CAS No.: 83048-65-1). These fluorine-containing silane ethers release active low molecular weight silanols after hydrolysis to form a firm Si-O-Si or Si-O-Al structure, which can dissolve SiO2 and Al2O3 in the mixed material and improve the activity of the mixed material. Therefore, when preparing the modified composite enzyme microcapsules, the amount of fluorine-containing silane ether added can be appropriately increased to increase the content of fluorine-containing silane ether in the active stimulant system of the present invention.

[0017] In the present invention, the deacetylation degree of the chitosan (CAS No.: 9012-76-4) is ≥95%.

[0018] In the present invention, the chitosan Mw is between 30000 and 40000. Chitosan can wrap the complex enzyme to form a protective layer, which helps to prevent excessive wear of the complex enzyme during grinding; chitosan can also combine with water molecules to form a hydration film on the surface of cement particles, which helps the hydration reaction of cement; in addition, chitosan promotes the dissolution of SiO2 and Al2O3 in the mixed material through interaction with components such as fluorinated silicone ethers, thereby improving the activity of the mixed material.

[0019] In the present invention, the raw materials for preparing the cement-based material activity activator also include 10 to 18 parts of retarder, 20 to 30 parts of alkanolamine, 5 to 15 parts of inorganic salt and 30 to 55 parts of water.

[0020] In the present invention, the raw materials for preparing the cement-based material activity stimulator are composed of 5 parts of polyether polyol, 3-10 parts of modified complex enzyme microcapsules, 2-8 parts of surfactants, 10-18 parts of retarders, 3-5 parts of organic acids, 20-230 parts of alkanolamines, 5-15 parts of inorganic salts and 30-55 parts of water.

[0021] Furthermore, the preparation raw materials of the cement-based material activity activator are composed of 5 parts of polyether polyol, 5 to 8 parts of modified complex enzyme microcapsules, 4 to 6 parts of surfactants, 13 to 18 parts of retarders, 3 to 5 parts of organic acids, 25 to 27 parts of alkanolamines, 8 to 10 parts of inorganic salts and 32 to 50 parts of water.

[0022] Furthermore, the retarder comprises glycerol and molasses; preferably comprises 5 to 10 parts of glycerol and 5 to 8 parts of molasses.

[0023] Furthermore, the inorganic salt is at least one of sodium sulfate, potassium chloride and sodium acetate, preferably at least one of sodium sulfate and potassium chloride.

[0024] Furthermore, the alkanolamine is at least two of diethanol monoisopropylamine (CAS No.: 6712-98-7), diethanolamine (CAS No.: 111-42-2), triethanolamine (CAS No.: 102-71-6) and triisopropanolamine (CAS No.: 122-20-3).

[0025] The invention also provides a method for preparing a cement-based material activity stimulator, which comprises the following steps: mixing the preparation raw materials.

[0026] Furthermore, the preparation method of the cement-based material activity activator comprises the following steps: the polyether polyol and the modified composite enzyme microcapsule are mixed in advance to form a first mixture;

[0027] (1) adding an inorganic salt, a surfactant, and an organic acid to water and mixing the mixture to obtain a second mixture;

[0028] (2) adding alkanolamine and retarder to mix to obtain a third mixture;

[0029] (3) Add the first mixture into the third mixture.

[0030] In the present invention, what is added in step (3) is a first mixture formed by polyether and modified complex enzyme microcapsules. On the one hand, polyether polyol itself has good dispersibility, and its introduction can improve the fluidity of cement or concrete; on the other hand, polyether and modified complex enzyme microcapsules have good compatibility, so polyether can improve the dispersibility and solubility of modified complex enzyme microcapsules in the active stimulator system of the present invention, and the two can be more evenly filled in the concrete structure.

[0031] In the present invention, in steps (1), (2) and (3), the mixing time is independently 10 to 40 min, preferably 20 to 30 min; the mixing stirring speed is independently 10 to 80 rpm, preferably 20 to 50 rpm.

[0032] In the present invention, the preparation method of the modified composite enzyme microcapsule comprises the following steps:

[0033] Adding the complex enzyme and chitosan into water and stirring, adjusting the pH to 8-10, and drying to obtain the complex enzyme microcapsules;

[0034] The composite enzyme microcapsules and fluorine-containing silicon ether are added into an organic solvent for modification to obtain modified composite enzyme microcapsules.

[0035] Furthermore, the organic solvent is acetone or ether.

[0036] Furthermore, the amount of the organic solvent is 60 to 100 parts.

[0037] Furthermore, the pH value is 8-10, preferably 8-9.

[0038] Furthermore, the drying method may be freeze drying.

[0039] Furthermore, the water content of the complex enzyme microcapsule after drying is ≤0.5%.

[0040] Furthermore, the modification further includes a heating operation, the heating temperature being 50-70° C., wherein the heating is for volatilizing the solvent.

[0041] An application of the aforementioned cement-based material activity activator in cement or concrete.

[0042] On the basis of being in accordance with the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] 1. The cement-based material activity stimulator prepared in the present invention is applied to cement-based materials containing admixtures, which can effectively stimulate the activity of the admixtures and reduce the clinker consumption in cement, thereby achieving resource conservation and cost consumption.

[0045] 2. The present invention also includes a modified composite enzyme microcapsule, which can not only efficiently stimulate the activity of the mixed material, but also the design of the microcapsule can effectively protect the internal enzyme and prevent the enzyme from being inactivated due to heat release of cement, thereby ensuring the long-term stability and high efficiency of the active stimulant.

[0046] 3. From the perspective of short-term and long-term effects, the active stimulator of the present invention can significantly improve the compressive strength and flexural strength of cement or concrete containing admixtures when applied to the cement or concrete. DETAILED DESCRIPTION

[0047] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and carefully in combination with preferred embodiments below, but the protection scope of the present invention is not limited to the following specific embodiments.

[0048] Unless otherwise defined, all professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0049] "Scope" disclosed in the present invention is defined in the form of lower limit and upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a particular range. The scope defined in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a particular parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3,4 and 5 are listed, the following scope can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present invention, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0050] If not otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form a new technical solution.

[0051] Unless otherwise specified, all technical features and optional technical features of the present invention can be combined with each other to form a new technical solution.

[0052] If not otherwise specified, all steps of the present invention may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0053] If there is no special explanation, the "include" and "comprising" mentioned in the present invention represent open-ended or closed-ended expressions. For example, the "include" and "comprising" may represent that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0054] If not specifically stated, in the present invention, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0055] If the activity of carbonic anhydrase and urease is poor, it is necessary to inoculate and culture before use. Finally, the activity of carbonic anhydrase is above 2500u / mg, and the activity of urease is above 2000u / mg. The carbonic anhydrase (activity of 3000u / mg) used in the following examples and comparative examples was purchased from Nanjing Dulai, and the urease (activity ≥2000u / mg) was purchased from Shanghai Yingxin. Chitosan (deacetylation degree ≥95%, molecular weight (Mw) between 30000 and 40000) was purchased from Shanghai McLean, but not limited to the above company brands.

[0056] The active stimulant of the present invention is a special additive that can react with elements such as silicon and aluminum in the admixture to stimulate their potential activity, thereby improving the performance of cement. By adding an appropriate amount of active stimulant, the amount of admixture incorporated into cement can be increased to a certain extent, while ensuring the strength and durability of cement. In addition, the use of active stimulants can also significantly reduce the consumption of clinker in cement, reduce energy consumption in the cement production process, and improve production efficiency.

[0057] Example 1

[0058] 1. The modified composite enzyme microcapsules of this embodiment are prepared as follows:

[0059] 10 parts of complex enzyme (65wt% carbonic anhydrase and 35wt% urease) and 28 parts of chitosan were added to 30 parts of water and stirred, the pH was adjusted to 9, and freeze-dried to a water content of 0.5% to obtain complex enzyme microcapsules;

[0060] The prepared composite enzyme microcapsules and 47 parts of tridecafluorooctyltriethoxysilane were added to 88 parts of acetone for modification, and the modified composite enzyme microcapsules were obtained after heating to 55° C. to volatilize the acetone.

[0061] 2. The cement-based material activity activator of this embodiment includes, by mass, 26 parts of alkanolamine, 5 parts of polyether polyol, 8 parts of modified complex enzyme microcapsules, 4 parts of surfactant, 17 parts of retarder, 8 parts of inorganic salt, 3 parts of organic acid and 45 parts of water.

[0062] In this embodiment, the alkanolamine is 16 parts of diethyl monoisopropanolamine and 10 parts of diethanolamine.

[0063] In this embodiment, the polyether polyol is Jiangsu Haian polypropylene glycol PPG200.

[0064] In this embodiment, the surfactant is calcium lignin sulfonate.

[0065] In this embodiment, the retarder is 9 parts of glycerin and 8 parts of molasses.

[0066] In this embodiment, the inorganic salt is sodium sulfate.

[0067] In this embodiment, the organic acid is acetic acid.

[0068] 3. The preparation method of the cement-based material activity stimulator of this embodiment is as follows: prepare the raw materials according to the above ratio, wherein the polyether polyol and the modified complex enzyme microcapsule need to be mixed in advance to form a first mixture for standby use.

[0069] (1) An inorganic salt, a surfactant and an organic acid are added to water and mixed for 30 minutes to prepare a second mixture.

[0070] (2) Add alkanolamine and retarder to the second mixture and mix for 20 minutes to obtain a third mixture.

[0071] (3) Add the first mixture to the third mixture and mix for 30 minutes.

[0072] Example 2

[0073] 1. The modified composite enzyme microcapsules used in this example are the same as those in Example 1.

[0074] 2. The cement-based material activity activator of this embodiment includes, by mass, 27 parts of alkanolamine, 5 parts of polyether polyol, 6 parts of modified complex enzyme microcapsules, 6 parts of surfactant, 18 parts of retarder, 10 parts of inorganic salt, 3 parts of organic acid and 50 parts of water.

[0075] In this embodiment, the alkanolamine is 18 parts of diethyl monoisopropanolamine and 9 parts of diethanolamine.

[0076] In this embodiment, the polyether polyol is Jiangsu Haian polypropylene glycol PPG400.

[0077] In this embodiment, the surfactant is calcium lignin sulfonate.

[0078] In this embodiment, the retarder is 8 parts of glycerol and 10 parts of molasses.

[0079] In this embodiment, the inorganic salt is 8 parts of sodium sulfate and 2 parts of potassium chloride.

[0080] In this embodiment, the organic acid is acetic acid.

[0081] 3. The preparation method of this embodiment is the same as that of embodiment 1.

[0082] Example 3

[0083] 1. The modified composite enzyme microcapsules used in this example are the same as those in Example 1.

[0084] 2. The cement-based material activity activator of this embodiment includes, by mass, 26 parts of alkanolamine, 5 parts of polyether polyol, 6 parts of modified complex enzyme microcapsules, 5 parts of surfactant, 17 parts of retarder, 10 parts of inorganic salt, 4 parts of organic acid and 45 parts of water.

[0085] In this embodiment, the alkanolamine is 16 parts of diethyl monoisopropanolamine and 10 parts of triethanolamine.

[0086] In this embodiment, the polyether polyol is Ruhr Chemical Polyethylene Glycol NPE-108.

[0087] In this embodiment, the surfactant is calcium lignin sulfonate.

[0088] In this embodiment, the retarder is 9 parts of glycerin and 8 parts of molasses.

[0089] In this embodiment, the inorganic salt is 8 parts of sodium sulfate and 2 parts of potassium chloride.

[0090] In this embodiment, the organic acid is citric acid.

[0091] 3. The preparation method of this embodiment is the same as that of embodiment 1.

[0092] Example 4

[0093] 1. The modified composite enzyme microcapsules of this embodiment are prepared as follows:

[0094] 10 parts of complex enzyme (65wt% carbonic anhydrase and 35wt% urease) and 28 parts of chitosan were added to 30 parts of water and stirred, the pH was adjusted to 9, and freeze-dried to a water content of 0.5% to obtain complex enzyme microcapsules;

[0095] The prepared composite enzyme microcapsules and 52 parts of tridecafluorooctyltriethoxysilane were added to 88 parts of acetone for modification, and the modified composite enzyme microcapsules were obtained after heating to 55° C. to volatilize the acetone.

[0096] 2. The cement-based material activity activator of this embodiment includes, by mass, 26 parts of alkanolamine, 5 parts of polyether polyol, 8 parts of modified complex enzyme microcapsules, 4 parts of surfactant, 17 parts of retarder, 8 parts of inorganic salt, 3 parts of organic acid and 45 parts of water.

[0097] In this embodiment, the alkanolamine is 16 parts of diethyl monoisopropanolamine and 10 parts of diethanolamine.

[0098] In this embodiment, the polyether polyol is Jiangsu Haian polypropylene glycol PPG200.

[0099] In this embodiment, the surfactant is calcium lignin sulfonate.

[0100] In this embodiment, the retarder is 9 parts of glycerin and 8 parts of molasses.

[0101] In this embodiment, the inorganic salt is sodium sulfate.

[0102] In this embodiment, the organic acid is acetic acid.

[0103] 3. The preparation method of this embodiment is the same as that of embodiment 1.

[0104] Example 5

[0105] 1. The modified composite enzyme microcapsules of this embodiment, the composite enzyme in the preparation method thereof is composed of 52 wt % carbonic anhydrase and 48 wt % urease. The other steps and parameters are the same as those in Example 1.

[0106] 2. The cement-based material activity activator of this embodiment includes, by mass, 26 parts of alkanolamine, 5 parts of polyether polyol, 8 parts of modified complex enzyme microcapsules, 4 parts of surfactant, 17 parts of retarder, 8 parts of inorganic salt, 3 parts of organic acid and 45 parts of water.

[0107] In this embodiment, the alkanolamine is 16 parts of diethyl monoisopropanolamine and 10 parts of diethanolamine.

[0108] In this embodiment, the polyether polyol is polyether polyol Jiangsu Haian polypropylene glycol PPG200.

[0109] In this embodiment, the surfactant is calcium lignin sulfonate.

[0110] In this embodiment, the retarder is 9 parts of glycerin and 8 parts of molasses.

[0111] In this embodiment, the inorganic salt is sodium sulfate.

[0112] In this embodiment, the organic acid is acetic acid.

[0113] 3. The preparation method of this embodiment is the same as that of embodiment 1.

[0114] Example 6

[0115] 1. The modified composite enzyme microcapsules used in this example are the same as those in Example 1.

[0116] 2. The raw material formula for the preparation of this embodiment is the same as that of Example 1.

[0117] 3. The preparation method of this embodiment is as follows:

[0118] (1) An inorganic salt, a surfactant and an organic acid are added to water and mixed for 30 minutes to prepare a first mixture.

[0119] (2) Add alkanolamine and retarder to the first mixture and mix for 20 minutes to obtain a second mixture.

[0120] (3) First add the modified composite enzyme microcapsules into the second mixture and mix for 10 minutes, then add the polyether polyol and mix for 30 minutes.

[0121] Comparative Example 1

[0122] 1. This comparative example does not use the modified composite enzyme microcapsules of Example 1.

[0123] 2. The cement-based material activity activator of this comparative example includes, by mass, 26 parts of alkanolamine, 5 parts of polyether polyol, 4 parts of surfactant, 17 parts of retarder, 8 parts of inorganic salt, 3 parts of organic acid and 53 parts of water.

[0124] In this comparative example, the alkanolamine is 16 parts of diethyl monoisopropanolamine and 10 parts of diethanolamine.

[0125] In this comparative example, the polyether polyol is Jiangsu Haian polypropylene glycol PPG200.

[0126] In this comparative example, the surfactant is calcium lignin sulfonate.

[0127] In this comparative example, the retarder is 9 parts of glycerol and 8 parts of molasses.

[0128] In this comparative example, the inorganic salt is sodium sulfate.

[0129] In this comparative example, the organic acid is acetic acid.

[0130] 3. The preparation method of this comparative example is generally carried out with reference to Example 6, with the specific difference being that no modified composite enzyme microcapsules are added in step (3).

[0131] Comparative Example 2

[0132] 1. The modified composite enzyme microcapsules used in this comparative example are the same as those in Example 1.

[0133] 2. The cement-based material activity activator of this comparative example includes, by mass, 26 parts of alkanolamine, 8 parts of modified complex enzyme microcapsules, 4 parts of surfactants, 17 parts of retarders, 8 parts of inorganic salts, 3 parts of organic acids and 50 parts of water.

[0134] In this comparative example, the alkanolamine is 16 parts of diethyl monoisopropanolamine and 10 parts of diethanolamine.

[0135] In this comparative example, the surfactant is calcium lignin sulfonate.

[0136] In this comparative example, the retarder is 9 parts of glycerol and 8 parts of molasses.

[0137] In this comparative example, the inorganic salt is sodium sulfate.

[0138] In this comparative example, the organic acid is acetic acid.

[0139] 3. The preparation method of this comparative example is generally carried out in accordance with Example 6, except that no polyether polyol is added in step (3).

[0140] Comparative Example 3

[0141] 1. This comparative example does not use the modified composite enzyme microcapsules of Example 1.

[0142] 2. The cement-based material activity activator of this comparative example includes, by mass, 26 parts of alkanolamine, 4 parts of surfactant, 17 parts of retarder, 8 parts of inorganic salt, 3 parts of organic acid and 58 parts of water.

[0143] In this comparative example, the alkanolamine is 16 parts of diethyl monoisopropanolamine and 10 parts of diethanolamine.

[0144] In this comparative example, the surfactant is calcium lignin sulfonate.

[0145] In this comparative example, the retarder is 9 parts of glycerol and 8 parts of molasses.

[0146] In this comparative example, the inorganic salt is sodium sulfate.

[0147] In this comparative example, the organic acid is acetic acid.

[0148] 3. The preparation method of this comparative example is as follows:

[0149] (1) An inorganic salt, a surfactant and an organic acid are added to water and mixed for 30 minutes to prepare a second mixture.

[0150] (2) Add alkanolamine and retarder to the second mixture and mix for 20 minutes.

[0151] Comparative Example 4

[0152] 1. This comparative example does not use the modified composite enzyme microcapsules of Example 1, but directly adds 8 parts of composite enzyme (65wt% carbonic anhydrase and 35wt% urease).

[0153] 2. The cement-based material activity activator of this comparative example includes, by mass, 26 parts of alkanolamine, 5 parts of polyether polyol, 8 parts of complex enzyme, 4 parts of surfactant, 17 parts of retarder, 8 parts of industrial salt, 3 parts of organic acid and 45 parts of water.

[0154] In this comparative example, the alkanolamine is 16 parts of diethyl monoisopropanolamine and 10 parts of diethanolamine.

[0155] In this comparative example, the polyether polyol is Jiangsu Haian polypropylene glycol PPG200.

[0156] In this comparative example, the surfactant is calcium lignin sulfonate.

[0157] In this comparative example, the retarder is 9 parts of glycerol and 8 parts of molasses.

[0158] In this comparative example, the inorganic salt is sodium sulfate.

[0159] In this comparative example, the organic acid is acetic acid.

[0160] 3. The preparation method of the cement-based material activity activator of this comparative example is as follows: prepare the raw materials according to the above ratio, wherein the polyether polyol and the complex enzyme need to be mixed in advance to form a first mixture for standby use.

[0161] (1) An inorganic salt, a surfactant and an organic acid are added to water and mixed for 30 minutes to prepare a second mixture.

[0162] (2) Add alkanolamine and retarder to the second mixture and mix for 20 minutes to obtain a third mixture.

[0163] (3) Add the first mixture to the third mixture and mix for 30 minutes.

[0164] Comparative Example 5

[0165] 1. This comparative example does not use modified composite enzyme microcapsules, but modified enzyme microcapsules, and the preparation method thereof is as follows:

[0166] 10 parts of enzyme (carbonic anhydrase) and 28 parts of chitosan were added to 30 parts of water and stirred, and dried to a water content of 0.5% to obtain an enzyme protected by a chitosan layer, i.e., enzyme microcapsules;

[0167] The prepared enzyme microcapsules and 47 parts of tridecafluorooctyltriethoxysilane were added to 88 parts of acetone for modification, and the modified enzyme microcapsules were obtained after heating to 55° C. to volatilize the acetone.

[0168] 2. The cement-based material activity activator of this comparative example includes, by mass, 26 parts of alkanolamine, 5 parts of polyether polyol, 8 parts of modified enzyme microcapsules, 4 parts of surfactant, 17 parts of retarder, 8 parts of inorganic salt, 3 parts of organic acid and 45 parts of water.

[0169] In this comparative example, the alkanolamine is 16 parts of diethyl monoisopropanolamine and 10 parts of diethanolamine.

[0170] In this comparative example, the polyether polyol is Jiangsu Haian polypropylene glycol PPG200.

[0171] In this comparative example, the surfactant is calcium lignin sulfonate.

[0172] In this comparative example, the retarder is 9 parts of glycerol and 8 parts of molasses.

[0173] In this comparative example, the inorganic salt is sodium sulfate.

[0174] In this comparative example, the organic acid is acetic acid.

[0175] 3. The preparation method of the cement-based material activity activator of this comparative example is as follows: prepare the raw materials according to the above ratio, wherein the polyether polyol and the modified enzyme microcapsule need to be mixed in advance to form a first mixture for standby use.

[0176] (1) An inorganic salt, a surfactant and an organic acid are added to water and mixed for 30 minutes to prepare a second mixture.

[0177] (2) Add alkanolamine and retarder to the second mixture and mix for 20 minutes to obtain a third mixture.

[0178] (3) Add the first mixture to the third mixture and mix for 30 minutes.

[0179] Comparative Example 6

[0180] 1. This comparative example does not use the modified composite enzyme microcapsules of Example 1, but composite enzyme microcapsules, the preparation method of which is as follows:

[0181] 10 parts of complex enzyme (65 wt% carbonic anhydrase and 35 wt% urease) and 28 parts of chitosan were added to 30 parts of water, stirred, and freeze-dried to a water content of 0.5% to obtain complex enzyme microcapsules.

[0182] 2. The cement-based material activity activator of this comparative example includes, by mass, 26 parts of alkanolamine, 5 parts of polyether polyol, 8 parts of complex enzyme microcapsules, 4 parts of surfactant, 17 parts of retarder, 8 parts of inorganic salt, 3 parts of organic acid and 45 parts of water.

[0183] In this comparative example, the alkanolamine is 16 parts of diethyl monoisopropanolamine and 10 parts of diethanolamine.

[0184] In this comparative example, the polyether polyol is polyether polyol Jiangsu Haian polypropylene glycol PPG200.

[0185] In this comparative example, the surfactant is calcium lignin sulfonate.

[0186] In this comparative example, the retarder is 9 parts of glycerol and 8 parts of molasses.

[0187] In this comparative example, the inorganic salt is sodium sulfate.

[0188] In this comparative example, the organic acid is acetic acid.

[0189] 3. The preparation method of the cement-based material activity stimulator of this comparative example is as follows: prepare the raw materials according to the above ratio, wherein the polyether polyol and the complex enzyme microcapsule need to be mixed in advance to form a first mixture for standby use.

[0190] (1) An inorganic salt, a surfactant and an organic acid are added to water and mixed for 30 minutes to prepare a second mixture.

[0191] (2) Add alkanolamine and retarder to the second mixture and mix for 20 minutes to obtain a third mixture.

[0192] (3) Add the first mixture to the third mixture and mix for 30 minutes.

[0193] Effect implementation

[0194] A large-milling industrial test was conducted in a cement mill (with a roller press), and 0.03 parts of the active activator prepared in the above embodiment or comparative example was added to the following cement for raw grinding. The cement was composed of the following raw materials by weight: 63 parts of clinker, 34.5 parts of coal gangue and 5.5 parts of gypsum. The main components of some raw materials are shown in Table 1. The control group was a test group containing only cement without adding active activator;

[0195] .

[0196] f-CaO refers to free calcium oxide.

[0197] The test methods for compressive strength and flexural strength refer to the national standard GB175-2023.

[0198] Hourly output refers to the amount of cement that each grinding mill can produce per unit time (usually hour) during the cement production process.

[0199] The test results of the above embodiments and comparative examples are shown in Table 2;

[0200] .

[0201] Compared with Example 1, no modified composite enzyme microcapsules are added to the active stimulant formula of Comparative Example 1, no polyether is added to the active stimulant formula of Comparative Example 2, and no modified composite enzyme microcapsules and polyether are added to the active stimulant formula of Comparative Example 3. It can be seen from Comparative Examples 1 to 3 that modified composite enzyme microcapsules and polyether play a key role in improving the compressive strength and flexural strength of cement.

[0202] From the comparison between Comparative Example 1 and Example 1, it can be seen that not adding the modified composite enzyme microcapsules will significantly affect the compression and flexural properties of cement. From the comparison between Comparative Example 2 and Example 1, it can be seen that polyether plays an important role in improving the dispersibility and compatibility of the modified composite enzyme microcapsules in the active stimulant system due to its excellent physical dispersion properties, and also helps to improve the fluidity and density of the slurry. However, the results of Comparative Example 3 show that when the modified composite enzyme microcapsules and polyether are used at the same time, their effect on improving the compressive strength and flexural strength of cement is more significant.

[0203] In the early stage of research and development, an experiment of Comparative Example 4 was also carried out. Compared with Example 1, Comparative Example 4 directly used the composite enzyme in the active stimulant formula, and did not prepare it into modified composite enzyme microcapsules. The active stimulant prepared in Comparative Example 4 can improve the compression and flexural properties in a short period of time, but due to the inactivation of the enzyme, the compression and flexural properties tested after 28 days are not ideal.

[0204] In Comparative Example 5, only carbonic anhydrase was used to prepare microcapsules. The obtained modified enzyme (carbonic anhydrase) microcapsules had a slower precipitation rate of calcium carbonate because the pH of the enzyme microenvironment decreased after the carbonic anhydrase took effect.

[0205] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods. The specific embodiments described above further describe the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A cement-based material activity activator, characterized in that: The method comprises the following raw materials in parts by weight: 5 parts of polyether polyol, 3 to 10 parts of modified complex enzyme microcapsules, 2 to 8 parts of surfactants, and 3 to 5 parts of organic acids; The modified complex enzyme microcapsule comprises the following raw materials in parts by weight: 10 parts of complex enzyme, 20-35 parts of chitosan and 40-55 parts of fluorine-containing silicone ether; The fluorine-containing silane is at least one of tridecafluorooctyltriethoxysilane, heptadecafluorooctyltrimethoxysilane and heptadecafluorodecyltriethoxysilane; Wherein, the complex enzyme comprises carbonic anhydrase and urease; the complex enzyme comprises 50-68wt% carbonic anhydrase and 32-50wt% urease; The preparation method of the modified composite enzyme microcapsule comprises the following steps: Adding the complex enzyme and chitosan into water and stirring, adjusting the pH to 8-10, and drying to obtain the complex enzyme microcapsules; The composite enzyme microcapsules and fluorine-containing silicon ether are added into an organic solvent for modification to obtain modified composite enzyme microcapsules.

2. The cement-based material activity activator according to claim 1, characterized in that: The cement matrix contains mixed materials, wherein the mixed materials include coal gangue, fly ash, slag or volcanic ash.

3. The cement-based material activity activator according to claim 1, characterized in that: The preparation raw materials meet at least one of the following conditions ①-③: ① The polyether polyol is at least one of polyether diol, polyether triol and polyether tetraol; ② The surfactant is sodium lignocellulose sulfonate or calcium lignocellulose sulfonate; ③The organic acid is at least one of acetic acid, oleic acid and citric acid.

4. The cement-based material activity activator according to claim 1, characterized in that: The modified composite enzyme microcapsule satisfies at least one of the following conditions ①-④: ① The activity of the carbonic anhydrase is ≥2500u / mg; ② The activity of the urease is ≥2000u / mg; ③ The deacetylation degree of the chitosan is ≥95%; ④The chitosan Mw is between 30,000 and 40,000.

5. The cement-based material activity activator according to claim 1, characterized in that: The raw materials for preparing the cement-based material activity stimulator are composed of 5 parts of polyether polyol, 3-10 parts of modified complex enzyme microcapsules, 2-8 parts of surfactants, 10-18 parts of retarders, 3-5 parts of organic acids, 20-30 parts of alkanolamines, 5-15 parts of inorganic salts and 30-55 parts of water.

6. The cement-based material activity activator according to claim 5, characterized in that: The preparation raw materials meet at least one of the following conditions ①-③: ① The retarder comprises at least one of glycerol and molasses; ② The alkanolamine is at least two of diethanol monoisopropylamine, diethanolamine, triethanolamine and triisopropanolamine; ③The inorganic salt is at least one of sodium sulfate, potassium chloride and sodium acetate.

7. The method for preparing the cement-based material activity activator according to any one of claims 1 to 6, characterized in that: It includes the following steps: Mix the prepared ingredients.

8. The method for preparing the cement-based material activity activator according to claim 7, characterized in that: The preparation method of the modified composite enzyme microcapsule satisfies at least one of the following conditions ①-②: ① The organic solvent is acetone or ether; ② The water content of the composite enzyme microcapsule after drying is ≤0.5%.

9. Use of the cement-based material activity activator according to any one of claims 1 to 6 in cement or concrete.