A high-strength cement with rapid setting and environmental protection and a preparation process thereof

Abstract

The application relates to the technical field of cement, in particular to a quick-setting environment-friendly high-strength cement and a preparation process thereof. Step 1: limestone, high-silica soil, iron material, aluminum material and phosphorus slag are ground and mixed to obtain raw material; the raw material is calcined and cooled to obtain cement clinker; step 2: the cement clinker, limestone, clay, modified phosphorus slag, a quick-setting agent and an additive are ground and mixed to obtain high-strength cement. The quick-setting agent comprises aluminum sulfate and calcium carbonate with a mass ratio of (2.4-3.2):(0.6-0.8); the additive comprises modified fiber and cyclodextrin MOF with a mass ratio of 8-10:1-2. In the scheme, the phosphorus slag is introduced into the cement to realize waste utilization, the phosphorus slag is modified by using silica sol, and the quick-setting agent and the additive are introduced to effectively solve the defects of the phosphorus slag, so that the quick-setting property and the mechanical strength of the cement are enhanced.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of cement, in particular to a quick-setting and environment-friendly high-strength cement and a preparation process thereof. BACKGROUND

[0002] Cement, as an inorganic cementing material, is widely used in the fields of construction, water conservancy, transportation, national defense, etc. At present, the acceleration of the construction process of modern railway infrastructure promotes the demand for basic raw materials such as cement, and the performance requirements for basic raw materials such as cement are gradually increasing. Among them, the cement used in railways generally requires low alkalinity, and the main material is generally clinker after calcination, which generally needs to be promoted to coagulate by a quick-setting agent. However, the quick-setting agent is generally introduced to improve the hydration performance, but the compressive and flexural strength after quick-setting is generally low, so it is necessary to further improve the mechanical properties of this type of cement and enhance its practical applicability.

[0003] On the other hand, the accumulation of phosphorus slag has been increasing in recent years, but the comprehensive utilization rate is not high, which is not conducive to environmental protection. Among them, the main component of phosphorus slag is calcium substance, which can be used as a mixed material in cement to promote waste utilization and enhance environmental protection. However, its direct introduction into cement will affect the quick-setting property and mechanical properties of cement, and further optimization of its practical applicability is needed.

[0004] In view of the above, it is of great application value to solve the above problems and prepare a quick-setting and environment-friendly high-strength cement. SUMMARY

[0005] The present application aims to provide a quick-setting and environment-friendly high-strength cement and a preparation process thereof to solve the problems raised in the background.

[0006] In order to solve the above technical problems, the present application provides the following technical scheme:

[0007] A preparation process of a quick-setting and environment-friendly high-strength cement, comprising the following steps:

[0008] Step 1: grind and mix limestone, high-silica soil, iron material, aluminum material and phosphorus slag to obtain raw material; calcine the raw material and cool it to obtain cement clinker;

[0009] Step 2: grind and mix the cement clinker, modified phosphorus slag, quick-setting agent, additive and azobis isobutyronitrile to obtain high-strength cement.

[0010] More preferably, the process parameters for calcination are as follows: increase the temperature to 800-1000℃ at a rate of 40-50℃ / min, calcine for 10-30 minutes; increase the temperature to 1150-1250℃ at a rate of 20-30℃ / min, continue to calcine for 10-15 minutes.

[0011] More preferably, the raw materials of the cement clinker include the following components: 78-82 parts of limestone, 10-13 parts of high-silica soil, 2-5 parts of iron material, 1.5-3 parts of aluminum material, 3-4 parts of phosphorous slag by weight.

[0012] More preferably, the high-strength cement includes the following raw materials: 72-80 parts of cement clinker, 10-15 parts of modified phosphorous slag, 2-3 parts of accelerator, 8-10 parts of additive, 0.05-0.06 parts of azobisisobutyronitrile by weight.

[0013] More preferably, the preparation method of the modified phosphorous slag is as follows: the yellow phosphorous slag is added to the silica sol, the mercapto silane coupling agent solution is added, and stirring is performed at 50-60℃ for 1-2 hours; filtration and drying are performed to obtain the modified phosphorous slag.

[0014] In the preparation method, the silica content in the silica sol is 30-32%, the concentration of the mercapto silane coupling agent solution is 4-5wt%, and the mass ratio of the yellow phosphorous slag, the silica sol, and the mercapto silane coupling agent solution is 1.5:0.5:1.

[0015] More preferably, the accelerator includes aluminum sulfate and calcium carbonate in a mass ratio of (1.5-2.2):(0.5-0.8), and the additive includes modified fiber and cyclodextrin MOF in a mass ratio of (7.5-9):(0.5-1).

[0016] More preferably, the preparation method of the modified fiber is as follows: polyvinyl alcohol is dissolved in deionized water, hydrochloric acid is used to adjust the pH to 3±0.2 at room temperature, the temperature is raised to 70-75℃, glutaraldehyde is slowly added dropwise, and stirring is performed for 4-5 hours; the temperature is lowered to 60-65℃, 3-amino-1-propanol vinyl ether and 3-aminocarbonyl phenylboric acid are added, and stirring is performed for 6-8 hours; amino-modified glass fiber is added, and the reaction is continued for 5-6 hours, and then filtration, washing, and drying are performed to obtain the modified fiber.

[0017] More preferably, the raw materials of the modified fiber include the following components: 10-12 parts of polyvinyl alcohol, 20-30 parts of glutaraldehyde, 3-6 parts of 3-amino-1-propanol vinyl ether, 1-2 parts of 3-aminocarbonyl phenylboric acid, and 10-12 parts of amino-modified glass fiber by weight.

[0018] More preferably, the preparation method of the cyclodextrin MOF is as follows: β-cyclodextrin, mercapto-β-cyclodextrin, and zinc chloride in a molar ratio of 0.8:0.2:8 are sequentially added to a 20-25wt% methanol aqueous solution, mixed uniformly, and subjected to hydrothermal reaction at 60-65℃ for 5-7 days, and then filtration, washing, and drying are performed to obtain the cyclodextrin MOF.

[0019] The application relates to a preparation process of a high-strength cement with rapid setting and environmental protection.

[0020] Compared with the prior art, the application has the following beneficial effects:

[0021] (1) In the scheme, the phosphorous slag is used as a mineralizer, is mixed with limestone, high-silica soil, iron material and aluminum material, and is calcined to obtain low-alkalinity cement clinker; the introduction of the phosphorous slag reduces the piling and environmental pollution of industrial waste slag. Meanwhile, the addition of the phosphorous slag can reduce the calcination heat consumption of the clinker, improve the calcination rate and the clinker yield, and the phosphorous slag has the function of a crystal seed, can promote the formation of C3S, and improves the strength of the clinker.

[0022] (2) In the scheme, the phosphorous slag is modified by using a silica sol and is mixed with the clinker to further improve the utilization rate of waste resources. The direct addition of the phosphorous slag can reduce the hydration heat, which is not conducive to the rapid setting and mechanical strength; the modification by using the silica sol can effectively inhibit the delayed influence of P2O5, F and other elements contained in the phosphorous slag on C3A hydration; meanwhile, the modified silica sol can promote the hydration rate, and the silicon dioxide on the surface of the silica sol fills in the pores to improve the compactness. However, the introduction amount of the silica sol should not be too much, otherwise, secondary hydration will be caused, calcium silicate gel will be generated, harmful pores will be increased, the compactness will be reduced, and the impermeability will be adversely affected.

[0023] In addition, in the modification process, a mercapto silane coupling agent is introduced, the surface of the modified silica sol contains mercapto groups, the modified silica sol can be crosslinked with modified fibers and cyclodextrin MOF in subsequent additives in the presence of an initiator AIBN by using the hydration heat (the hydration heat of the cement can reach 60-80 DEG C), and the mechanical strength such as the bending strength of the cement after solidification is improved.

[0024] (3) In the scheme, aluminum sulfate and calcium carbonate are mixed to serve as a rapid setting agent to promote the rapid setting performance. However, the rapid setting performance is often accompanied by weak mechanical performance, therefore, in the scheme, modified fibers and cyclodextrin MOF are further added as additives to internally solidify and enhance the strength of the cement.

[0025] The preparation process of the modified fiber is as follows: the hydroxyl group in polyvinyl alcohol reacts with the aldehyde group of glutaraldehyde to graft, the aldehyde group of glutaraldehyde is used to graft 3-amino-1-propanol vinyl ether and 3-aminocarbonyl phenylboronic acid, and the interface of the amino-modified glass fiber is compounded to obtain the modified fiber. The reaction of the hydroxyl group and the aldehyde group produces N ether bonds, and a propanol vinyl ether segment is introduced at the same time. The organic ether segment can effectively make up for the insufficient strength caused by the introduction of aluminum sulfate, effectively enhance the bending strength and compressive strength. At the same time, glass fiber is a common cement reinforcing material, and direct modification can effectively enhance the dispersibility. In addition, the vinyl group of propanol vinyl ether can produce crosslinking with the modified phosphorous slag; the boric acid contained in 3-aminocarbonyl phenylboronic acid can produce cementation between the calcium carbonate in the accelerator; it can also act as a water reducing agent to reduce the viscosity and surface tension; promote early strength, reduce late damage and cracks, and improve impermeability.

[0026] The cyclodextrin MOF is a porous framework material with hydrophilicity, which can improve the fluidity of cement and improve the mid-late strength. At the same time, it has a unique framework structure, which makes it have excellent internal curing efficiency, excellent volume stability and better interface compatibility with the cement matrix; can prevent the formation of voids and cracks at the interface between the modified fiber and the cement clinker. In addition, the cyclodextrin MOF can produce nano C-S-H gel, thereby increasing the seeding effect, which can promote the formation of hydration products, thereby benefiting the density of the microstructure, so as to enhance the mechanical strength. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present application will be described below. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0028] It should be noted that the purchase manufacturer of all raw materials involved in the present application has no special restriction, and exemplary includes: in the following embodiments, the part is mass part; the silica sol is a sol with 30% silica content; the diameter of the glass fiber is 9-13 um, and the brand is Sunyang; the CAS number of 3-amino-1-propanol vinyl ether is 66415-55-2; the CAS number of 3-aminocarbonyl phenylboric acid is 351422-73-6; the CAS number of beta-cyclodextrin is 7585-39-9; the CAS number of mercapto-beta-cyclodextrin is 81644-55-5; all are commercially available. In addition, in the related raw materials, the quality requirements of limestone are CaO≥49.0, MgO≤2.5%, and alkali content≤0.6%; the quality requirements of high-silica soil are SiO2≥70%, and alkali content≤1.5%; the iron material is non-ferrous metal slag, and the quality requirements are Fe2O3≥50%, and alkali content≤1.5%; the aluminum material is clay, and the quality requirements are Al2O3≤20.0, and alkali content≤1.5%; the phosphorus slag is yellow phosphorus slag, and the quality requirements are CaO≥43%.

[0029] Example 1: A preparation process of a rapid-setting and environment-friendly high-strength cement, comprising the following steps:

[0030] Preparation: (1) The preparation method of the modified phosphorus slag is: the yellow phosphorus slag is added to the silica sol, 5wt% KH-580 aqueous solution is added, and stirring is carried out at 60℃ for 1 hour; filtration, drying, and the modified phosphorus slag is obtained; wherein the mass ratio of the yellow phosphorus slag, the silica sol and the KH-580 aqueous solution is 1.5:0.5:1;

[0031] (2) The preparation method of the modified fiber is: the glass fiber and KH-551 with a mass ratio of 1:0.2 are sequentially added to 10wt% ethanol aqueous solution, stirring is carried out at 60℃ for 2 hours, filtration, drying, and the amino-modified glass fiber is obtained; 10 parts of polyvinyl alcohol are dissolved in 100 parts of deionized water, at room temperature, 0.6mol / L hydrochloric acid solution is used to adjust the pH to 3.1; the temperature is increased to 70℃, 22 parts of glutaraldehyde are slowly added dropwise, and stirring is carried out for 4 hours; the temperature is decreased to 60℃, 4.5 parts of 3-amino-1-propanol vinyl ether and 1.5 parts of 3-aminocarbonyl phenylboric acid are added, and stirring is carried out for 6 hours; 10 parts of the amino-modified glass fiber is added, and the reaction is continued for 6 hours, filtration, washing, drying, and the modified fiber is obtained;

[0032] (3) The preparation method of the cyclodextrin MOF is: the beta-cyclodextrin, the mercapto-beta-cyclodextrin and the zinc chloride with a molar ratio of 0.8:0.2:8 are sequentially added to 25wt% methanol aqueous solution, mixed uniformly, and hydrothermal reaction is carried out at 60℃ for 6 days, filtration, washing, drying, and the cyclodextrin MOF is obtained;

[0033] Step 1: 80 parts of limestone, 12 parts of high-silica clay, 3 parts of iron material, 2 parts of aluminum material, and 3 parts of phosphorus slag are ground and mixed to obtain raw material; the raw material is heated at a rate of 50℃ / min to 900℃, calcined for 30 minutes; heated at a rate of 20℃ / min to 1200℃, continue to calcine for 10 minutes, cool down to obtain cement clinker;

[0034] Step 2: 76.5 parts of cement clinker, 12 parts of modified phosphorus slag, 2.5 parts of accelerator (2:0.5 of aluminum sulfate and calcium carbonate), 9 parts of additive (8.4:0.6 of modified fiber, cyclodextrin MOF), 0.05 parts of azobisisobutyronitrile are ground and mixed to obtain high-strength cement.

[0035] Example 2: A preparation process of a quick-setting and environmentally friendly high-strength cement, comprising the following steps:

[0036] Preparation: (1) The preparation method of the modified phosphorus slag is: the yellow phosphorus slag is added to the silica sol, 5wt% KH-580 aqueous solution is added, and stirred at 60℃ for 1 hour; filter, dry to obtain modified phosphorus slag; wherein the mass ratio of yellow phosphorus slag, silica sol, KH-580 aqueous solution is 1.5:0.5:1;

[0037] (2) The preparation method of the modified fiber is: glass fiber and KH-551 with a mass ratio of 1:0.2 are sequentially added to 10wt% ethanol aqueous solution, stirred at 60℃ for 2 hours, filtered, dried to obtain amino-modified glass fiber; 10 parts of polyvinyl alcohol is dissolved in 100 parts of deionized water, at room temperature, 0.6mol / L hydrochloric acid solution is used to adjust the pH to 3.1; heated to 70℃, slowly add 22 parts of glutaraldehyde, and stir for 4 hours; cool down to 60℃, add 4.5 parts of 3-amino-1-propanol vinyl ether and 1.5 parts of 3-aminocarbonyl phenylboronic acid, and stir for 6 hours; add 10 parts of amino-modified glass fiber, continue to react for 6 hours, filter, wash, dry to obtain modified fiber;

[0038] (3) The preparation method of the cyclodextrin MOF is: β-cyclodextrin, mercapto-β-cyclodextrin and zinc chloride with a molar ratio of 0.8:0.2:8 are sequentially added to 25wt% methanol aqueous solution, mixed uniformly, hydrothermal reaction at 60℃ for 6 days, filter, wash, dry to obtain cyclodextrin MOF;

[0039] Step 1: 78 parts of limestone, 13 parts of high-silica clay, 2 parts of iron material, 3 parts of aluminum material, and 4 parts of phosphorus slag are ground and mixed to obtain raw material; the raw material is heated at a rate of 50℃ / min to 900℃, calcined for 30 minutes; heated at a rate of 20℃ / min to 1200℃, continue to calcine for 10 minutes, cool down to obtain cement clinker;

[0040] Step 2: 80 parts of cement clinker, 15 parts of modified phosphorus slag, 3 parts of accelerator (2.2:0.8 of aluminum sulfate and calcium carbonate), 10 parts of additive (9:1 of modified fiber, cyclodextrin MOF), 0.05 parts of azobisisobutyronitrile are ground and mixed to obtain high-strength cement.

[0041] Example 3: A preparation process of a quick-setting and environmentally friendly high-strength cement, comprising the following steps:

[0042] Preparation: (1) The preparation method of the modified phosphorus slag is: adding yellow phosphorus slag into silica sol, adding 5wt% KH-580 aqueous solution, stirring at 60°C for 1 hour; filtering, drying to obtain modified phosphorus slag; wherein the mass ratio of yellow phosphorus slag, silica sol and KH-580 aqueous solution is 1.5:0.5:1;

[0043] (2) The preparation method of the modified fiber is: glass fiber and KH-551 with a mass ratio of 1:0.2 are sequentially added into 10wt% ethanol aqueous solution, stirring at 60°C for 2 hours, filtering, drying to obtain amino-modified glass fiber; 10 parts of polyvinyl alcohol are dissolved in 100 parts of deionized water, at room temperature, using 0.6mol / L hydrochloric acid solution to adjust the pH to 3.1; heating to 70°C, slowly adding 22 parts of glutaraldehyde, stirring for 4 hours; cooling to 60°C, adding 4.5 parts of 3-amino-1-propanol vinyl ether and 1.5 parts of 3-aminocarbonyl phenylboronic acid, stirring for 6 hours; adding 10 parts of amino-modified glass fiber, continuing to react for 6 hours, filtering, washing, drying to obtain modified fiber;

[0044] (3) The preparation method of the cyclodextrin MOF is: β-cyclodextrin, mercapto-β-cyclodextrin and zinc chloride with a molar ratio of 0.8:0.2:8 are sequentially added into 25wt% methanol aqueous solution, mixing uniformly, hydrothermal reaction at 60°C for 6 days, filtering, washing, drying to obtain cyclodextrin MOF;

[0045] Step 1: 80 parts of limestone, 10 parts of high-silica soil, 5 parts of iron material, 1.5 parts of aluminum material, 3.5 parts of phosphorus slag are ground and mixed to obtain raw material; the raw material is heated at a rate of 50°C / min to 900°C, calcined for 30 minutes; heated at a rate of 20°C / min to 1200°C, continue to calcine for 10 minutes, cool to obtain cement clinker;

[0046] Step 2: 80 parts of cement clinker, 15 parts of modified phosphorus slag, 3 parts of accelerator (2.2:0.8 of aluminum sulfate and calcium carbonate), 10 parts of additive (9:1 of modified fiber, cyclodextrin MOF), 0.05 parts of azobisisobutyronitrile are ground and mixed to obtain high-strength cement.

[0047] Comparative Example 1: Refer to Example 1, use yellow phosphorus slag directly instead of modified phosphorus slag, the rest is the same as Example 1; the specific steps are as follows:

[0048] Preparation: (1) The preparation method of the modified fiber is: 1:0.2 mass ratio of glass fiber and KH-551 is added to 10wt% ethanol aqueous solution in turn, stirred at 60℃ for 2 hours, filtered, dried to obtain amino modified glass fiber; 10 parts of polyvinyl alcohol is dissolved in 100 parts of deionized water, at room temperature, using 0.6mol / L hydrochloric acid solution to adjust pH to 3.1; heated to 70℃, slowly add 22 parts of glutaraldehyde, stir for 4 hours; cool to 60℃, add 4.5 parts of 3-amino-1-propanol vinyl ether, 1.5 parts of 3-aminocarbonyl phenylboric acid, stir for 6 hours; add 10 parts of amino modified glass fiber, continue to react for 6 hours, filter, wash, dry to obtain modified fiber;

[0049] (2) The preparation method of cyclodextrin MOF is: 0.8:0.2:8 molar ratio of β-cyclodextrin, mercapto-β-cyclodextrin, zinc chloride is added to 25wt% methanol aqueous solution in turn, mixed uniformly, hydrothermal reaction at 60℃ for 6 days, filtered, washed, dried to obtain cyclodextrin MOF;

[0050] Step 1: 80 parts of limestone, 12 parts of high silica, 3 parts of iron material, 2 parts of aluminum material, 3 parts of phosphorus slag are ground and mixed to obtain raw material; the raw material is heated to 900℃ at a rate of 50℃ / min, calcined for 30 minutes; heated to 1200℃ at a rate of 20℃ / min, continue to calcine for 10 minutes, cool to obtain cement clinker;

[0051] Step 2: 76.5 parts of cement clinker, 12 parts of yellow phosphorus slag, 2.5 parts of accelerator (2:0.5 aluminum sulfate and calcium carbonate), 9 parts of additive (8.4:0.6 modified fiber, cyclodextrin MOF), 0.05 parts of azobisisobutyronitrile are ground and mixed to obtain high strength cement.

[0052] Comparative Example 2: Refer to Example 1, replace the modified fiber with amino modified glass fiber, the rest is the same as Example 1; the specific steps are as follows:

[0053] Preparation: (1) The preparation method of modified phosphorus slag is: the yellow phosphorus slag is added to the silica sol, 5wt% KH-580 aqueous solution is added, stirred at 60℃ for 1 hour; filter, dry to obtain modified phosphorus slag; wherein the mass ratio of yellow phosphorus slag, silica sol, KH-580 aqueous solution is 1.5:0.5:1;

[0054] (2) The preparation method of the amino-modified glass fiber is: glass fiber and KH-551 with a mass ratio of 1:0.2 are sequentially added to 10wt% ethanol aqueous solution, stirred at 60°C for 2 hours, filtered and dried to obtain the amino-modified glass fiber;

[0055] (3) The preparation method of the cyclodextrin MOF is: β-cyclodextrin, mercapto-β-cyclodextrin and zinc chloride with a molar ratio of 0.8:0.2:8 are sequentially added to 25wt% methanol aqueous solution, uniformly mixed, and hydrothermally reacted at 60°C for 6 days; filtered, washed and dried to obtain the cyclodextrin MOF;

[0056] Step 1: 80 parts of limestone, 12 parts of high-silica clay, 3 parts of iron material, 2 parts of aluminum material and 3 parts of phosphorus slag are ground and mixed to obtain raw material; the raw material is heated at a rate of 50°C / min to 900°C, calcined for 30 minutes; heated at a rate of 20°C / min to 1200°C, and continued to calcine for 10 minutes, and then cooled to obtain cement clinker;

[0057] Step 2: 76.5 parts of cement clinker, 12 parts of modified phosphorus slag, 2.5 parts of accelerator (2:0.5 of aluminum sulfate and calcium carbonate), 9 parts of additive (8.4:0.6 of amino-modified glass fiber and cyclodextrin MOF), and 0.05 parts of azobisisobutyronitrile are ground and mixed to obtain high-strength cement.

[0058] Comparative Example 3: According to Example 1, the modified fiber does not graft 3-amino-1-propanol vinyl ether and 3-aminocarbonyl phenylboronic acid, and the rest is the same as Example 1; the specific steps are as follows:

[0059] Preparation: (1) The preparation method of the modified phosphorus slag is: yellow phosphorus slag is added to silica sol, and 5wt% KH-580 aqueous solution is added, stirred at 60°C for 1 hour; filtered, dried to obtain the modified phosphorus slag; wherein the mass ratio of yellow phosphorus slag, silica sol and KH-580 aqueous solution is 1.5:0.5:1;

[0060] (2) The preparation method of the modified fiber is: glass fiber and KH-551 with a mass ratio of 1:0.2 are sequentially added to 10wt% ethanol aqueous solution, stirred at 60°C for 2 hours, filtered and dried to obtain the amino-modified glass fiber; 10 parts of polyvinyl alcohol is dissolved in 100 parts of deionized water, at room temperature, 0.6mol / L hydrochloric acid solution is used to adjust the pH to 3.1; heated to 70°C, slowly drop 22 parts of glutaraldehyde, stirred for 4 hours; cooled to 60°C, added 10 parts of amino-modified glass fiber, continued to react for 8 hours, filtered, washed and dried to obtain the modified fiber;

[0061] The preparation method of the cyclodextrin MOF is: 0.8:0.2:8 molar ratio of β-cyclodextrin, mercapto-β-cyclodextrin and zinc chloride is sequentially added into 25wt% methanol aqueous solution, mixed uniformly, hydrothermal reaction is carried out at 60℃ for 6 days, filtration, washing and drying are carried out, and the cyclodextrin MOF is obtained;

[0062] Step 1: 80 parts of limestone, 12 parts of high-silica clay, 3 parts of iron material, 2 parts of aluminum material and 3 parts of phosphorus slag are ground and mixed to obtain raw material; the raw material is heated at a rate of 50℃ / min to 900℃, calcined for 30 minutes; heated at a rate of 20℃ / min to 1200℃, continue to calcine for 10 minutes, and cool to obtain cement clinker;

[0063] Step 2: 76.5 parts of cement clinker, 12 parts of modified phosphorus slag, 2.5 parts of accelerator (2:0.5 of aluminum sulfate and calcium carbonate), 9 parts of additive (8.4:0.6 of modified fiber, cyclodextrin MOF), 0.05 parts of azobisisobutyronitrile are ground and mixed to obtain high-strength cement.

[0064] Comparative Example 4: referring to Example 1, no cyclodextrin MOF is introduced, and the rest is the same as Example 1; the specific steps are as follows:

[0065] Preparation: (1) the preparation method of the modified phosphorus slag is: the yellow phosphorus slag is added into the silica sol, 5wt% KH-580 aqueous solution is added, stirring is carried out at 60℃ for 1 hour; filtration, drying are carried out, and the modified phosphorus slag is obtained; wherein, the mass ratio of the yellow phosphorus slag, the silica sol and the KH-580 aqueous solution is 1.5:0.5:1;

[0066] (2) the preparation method of the modified fiber is: 1:0.2 mass ratio of glass fiber and KH-551 is sequentially added into 10wt% ethanol aqueous solution, stirring is carried out at 60℃ for 2 hours, filtration, drying are carried out, and the amino-modified glass fiber is obtained; 10 parts of polyvinyl alcohol is dissolved in 100 parts of deionized water, at room temperature, 0.6mol / L hydrochloric acid solution is used to adjust the pH to 3.1; heating to 70℃, 22 parts of glutaraldehyde is slowly added dropwise, and stirring is carried out for 4 hours; cooling to 60℃, 4.5 parts of 3-amino-1-propanol vinyl ether and 1.5 parts of 3-aminocarbonyl phenylboronic acid are added, and stirring is carried out for 6 hours; 10 parts of the amino-modified glass fiber is added, and the reaction is continued for 6 hours, filtration, washing and drying are carried out, and the modified fiber is obtained;

[0067] Step 1: 80 parts of limestone, 12 parts of high-silica clay, 3 parts of iron material, 2 parts of aluminum material and 3 parts of phosphorus slag are ground and mixed to obtain raw material; the raw material is heated at a rate of 50℃ / min to 900℃, calcined for 30 minutes; heated at a rate of 20℃ / min to 1200℃, continue to calcine for 10 minutes, and cool to obtain cement clinker;

[0068] Step 2: 76.5 parts of cement clinker, 12 parts of modified phosphorus slag, 2.5 parts of accelerator (2:0.5 aluminum sulfate and calcium carbonate), 9 parts of modified fiber, 0.05 parts of azobisisobutyronitrile are ground and mixed to obtain high-strength cement.

[0069] Performance test: the high-strength cement prepared in the examples and comparative examples is subjected to relevant performance tests; wherein the initial setting time and final setting time are detected according to the relevant standards of GB / T1346; the 3-day and 28-day compressive strength is detected according to the relevant standards of GB / T17671; the obtained data are shown in the following table:

[0070] Sample Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Initial setting time (min) 82 93 91 87 86 Final setting time (min) 321 413 387 348 365 3d compressive strength (MPa) 28.2 24.3 24.9 25.6 25.9 28d compressive strength (MPa) 56.7 48.0 49.1 50.7 50.3

[0071] Conclusion: from the data in the above table, it can be seen that: through the pre-modification process of the silicon sol of yellow phosphorus slag, the specific grafting segment of the modified fiber, and the introduction of cyclodextrin MOF, etc. Characteristic limitation; and using the heat generated during the hydration process to initiate the cross-linking structure-effect relationship of the related materials, on the basis of ensuring the cement setting performance, the mechanical strength such as compressive strength is effectively enhanced. At the same time, in the scheme, the waste of phosphorus slag is effectively utilized, the resource utilization rate is increased, and the environmental protection is improved.

[0072] Finally, it should be pointed out that: the above only describes the preferred embodiments of the present application and is not used to limit the present application, although the present application has been described in detail with reference to the foregoing embodiments, for those skilled in the art, the technical solutions recorded in the foregoing embodiments can still be modified, or some technical features can be replaced. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A process for the preparation of an environment-friendly high strength cement with rapid setting, characterized in that: The preparation method comprises the following steps: Step 1: limestone, high-silica soil, iron material, aluminum material and phosphorus slag are ground and mixed to obtain raw meal; the raw meal is calcined and cooled to obtain cement clinker; Step 2: the cement clinker, modified phosphorus slag, accelerator, additive and azobisisobutyronitrile are ground and mixed to obtain high-strength cement; The preparation method of the modified phosphorus slag is as follows: the yellow phosphorus slag is added into silica sol, a mercapto silane coupling agent solution is added, and stirring is conducted at 50-60 DEG C for 1-2 hours; filtration and drying are conducted to obtain the modified phosphorus slag. The content of silicon dioxide in the silica sol is 30-32%, the concentration of the mercapto silane coupling agent solution is 4-5 wt%, and the mass ratio of the yellow phosphorus slag, silica sol and mercapto silane coupling agent solution is 1.5:0.5:

1. The additive comprises modified fiber and cyclodextrin MOF in a mass ratio of (7.5-9):(0.5-1). The preparation method of the modified fiber is as follows: polyvinyl alcohol is dissolved in deionized water, hydrochloric acid is used to adjust the pH to 3±0.2 at room temperature; The temperature is increased to 70-75 DEG C, and glutaraldehyde is slowly added dropwise, and stirring is conducted for 4-5 hours; the temperature is decreased to 60-65 DEG C, 3-amino-1-propanol vinyl ether and 3-aminocarbonyl phenylboric acid are added, and stirring is conducted for 6-8 hours; amino-modified glass fiber is added, and the reaction is continued for 5-6 hours, and then filtration, washing and drying are conducted to obtain the modified fiber.

2. A process for the preparation of an instant setting environment friendly high strength cement as claimed in claim 1, wherein: The process parameters of the calcination are as follows: the temperature is increased to 800-1000 DEG C at a rate of 40-50 DEG C / min, and the calcination is conducted for 10-30 minutes; the temperature is increased to 1150-1250 DEG C at a rate of 20-30 DEG C / min, and the calcination is continued for 10-15 minutes.

3. The preparation process of a fast-setting, environmentally friendly, high-strength cement according to claim 1, characterized in that: The raw material of the cement clinker comprises the following components: 78-82 parts of limestone, 10-13 parts of high-silica soil, 2-5 parts of iron material, 1.5-3 parts of aluminum material and 3-4 parts of phosphorus slag.

4. The preparation process of a fast-setting, environmentally friendly, high-strength cement according to claim 1, characterized in that: The high-strength cement comprises the following raw materials: 72-80 parts of cement clinker, 10-15 parts of modified phosphorus slag, 2-3 parts of accelerator, 8-10 parts of additive and 0.05-0.06 parts of azobisisobutyronitrile.

5. The preparation process of a fast-setting, environmentally friendly, high-strength cement according to claim 1, characterized in that: The accelerator comprises aluminum sulfate and calcium carbonate in a mass ratio of (1.5-2.2):(0.5-0.8).

6. The preparation process of a fast-setting environmentally friendly high-strength cement according to claim 5, characterized in that: The raw material of the modified fiber comprises the following components: 10-12 parts of polyvinyl alcohol, 20-30 parts of glutaraldehyde, 3-6 parts of 3-amino-1-propanol vinyl ether, 1-2 parts of 3-aminocarbonyl phenylboric acid and 10-12 parts of amino-modified glass fiber.

7. The preparation process of a fast-setting, environmentally friendly, high-strength cement according to claim 5, characterized in that: The preparation method of the cyclodextrin MOF is as follows: beta-cyclodextrin, mercapto-beta-cyclodextrin and zinc chloride in a molar ratio of 0.8:0.2:8 are sequentially added into 20-25 wt% methanol aqueous solution, uniformly mixed, and subjected to hydrothermal reaction at 60-65 DEG C for 5-7 days, and then filtration, washing and drying are conducted to obtain the cyclodextrin MOF.

8. The high-strength cement prepared by the preparation process of the environment-friendly high-strength cement with rapid setting according to any one of claims 1-7.