Synergist for solid waste-based gelling materials and preparation method thereof

Abstract

The present invention provides a synergist for solid waste-based cementitious materials and a preparation method thereof, which belongs to the technical field of solid waste recycling, and includes: an organic liquid phase component, an inorganic liquid phase component and an inorganic solid phase component. The organic liquid phase component is prepared by mixing triethanolamine and triisopropanolamine with maleic anhydride and ferric chloride hexahydrate respectively, and then heating the mixture, and then mixing the intermediate obtained by the reaction with sodium methacrylate and concentrated sulfuric acid respectively, and then heating the mixture, and finally mixing the mixture in a certain proportion to obtain the synergist; the inorganic liquid phase component is prepared by filtering the filtrate obtained by alkali melting and hydrothermal reaction of red mud and coal gangue powder; and the inorganic solid phase component is prepared by grinding the filter residue obtained by filtering the filter residue obtained by alkali melting and hydrothermal reaction of red mud and coal gangue powder. The present invention exerts a synergistic effect through the three components, which is beneficial to the generation of AFt and C-S-H, so that the strength is formed quickly, and the strength is continuously increased in the later stage of hydration, so as to achieve the effect of early strength and high strength of solid waste-based cementitious materials.

Description

Technical Field

[0001] The invention belongs to the technical field of solid waste recycling, and in particular relates to a synergist for solid waste-based gelling materials and a preparation method thereof. Background Art

[0002] As a substitute for cement, solid waste-based cementitious materials can effectively reduce CO2 emissions in the construction sector while improving the resource utilization rate of solid waste. This is in line with the dual carbon policy and has important practical significance for promoting sustainable green development.

[0003] At present, solid waste-based cementitious materials generally have problems such as long setting time, low early strength, weak later strength growth, and difficult construction. Summary of the invention

[0004] The embodiment of the present invention provides a synergist for solid waste-based cementitious materials and a preparation method thereof, which is prepared using red mud and coal gangue, and aims to solve the problem of low early strength and weak later strength growth of solid waste-based cementitious materials.

[0005] In the first aspect, in order to achieve the above-mentioned purpose, the technical solution adopted by the present invention is: to provide a synergist for solid waste-based cementitious materials, characterized in that, calculated by mass percentage, it includes: 10 to 25 parts of organic liquid phase components, 15 to 25 parts of inorganic liquid phase components and 50 to 70 parts of inorganic solid phase components.

[0006] In a second aspect, the present invention provides a method for preparing a synergist for solid waste-based cementitious materials, comprising the preparation of the organic liquid phase component, the preparation of the inorganic liquid phase component and the preparation of the inorganic solid phase component; wherein the organic liquid phase component is obtained by mixing triethanolamine and triisopropanolamine with maleic anhydride and ferric chloride hexahydrate in a certain proportion, heating and reacting, then modified with sodium methacrylate, and finally mixing in proportion; the inorganic liquid phase component is a filtrate obtained by filtering red mud and coal gangue powder after alkali melting and hydrothermal reaction; the inorganic solid phase component is obtained by grinding the filter residue obtained by filtering red mud and coal gangue powder after alkali melting and hydrothermal reaction.

[0007] In conjunction with the second aspect, in one achievable manner, the organic liquid phase component is prepared according to the following method:

[0008] Step 1, maleic anhydride, triethanolamine, and ferric chloride hexahydrate are mixed in a mass ratio of 1:1.2-2.0:0.05-0.2, and react to obtain liquid a;

[0009] Step 2, prepare three portions of deionized water, the mass of each portion of deionized water is 0.5 to 1.0 times the amount of maleic anhydride used, add sodium carbonate to one portion of deionized water until it is excessive, add sodium chloride to one portion of deionized water until it is excessive, add calcium chloride to one portion of deionized water until it is excessive, retain the excess sodium carbonate, sodium chloride, and calcium chloride to obtain a sodium carbonate solution, a sodium chloride solution, and a calcium chloride solution; wash the liquid a obtained by the reaction in step 1 with a sodium carbonate solution, a sodium chloride solution, and a calcium chloride solution in sequence, then dry it with sodium sulfate, and filter it to obtain an intermediate a;

[0010] Step 3, the intermediate a is mixed with sodium methacrylate and concentrated sulfuric acid in a three-necked flask in a mass ratio of 259:68-103:3-5, and heated to react at 70-95° C. During the reaction, 1-3 times the mass of the initial amount of sodium methacrylate is slowly added dropwise using a separatory funnel, and the addition time is controlled at 90-150 min; after the addition is completed, the reaction is continued at this temperature for 60-120 min to obtain an organic liquid phase component a, and the molecular formula of the organic liquid phase component a is:

[0011]

[0012] Step 4, mixing maleic anhydride, triisopropanolamine, and ferric chloride hexahydrate in a mass ratio of 1:1.5-2.5:0.05-0.2, and reacting to obtain liquid b;

[0013] Step 5, treating the liquid b after the reaction in step 4 according to step 2 to obtain an intermediate b;

[0014] Step 6, the intermediate b is mixed with sodium methacrylate and concentrated sulfuric acid in a three-necked flask in a mass ratio of 289:68-103:0.15-0.25, and heated to react at 70-95° C. During the reaction, 1-3 times the mass of the initial amount of sodium methacrylate is slowly added dropwise using a separatory funnel, and the addition time is controlled at 90-150 min; after the addition is completed, the reaction is continued at this temperature for 60-120 min to obtain an organic liquid phase component b, and the molecular formula of the organic liquid phase component b is:

[0015]

[0016] Step seven, mixing the organic liquid phase component a and the organic liquid phase component b in a mass ratio of 1:0.25-1.75 to obtain a finished organic liquid phase component.

[0017] In combination with the second aspect, in one achievable manner, in step 1, maleic anhydride, triethanolamine, and ferric chloride hexahydrate are mixed in proportion and reacted at 70-80° C. for 120-180 min to obtain liquid a.

[0018] In combination with the second aspect, in one achievable manner, in step 2, the sodium carbonate, sodium chloride, and calcium chloride are each in excess of 1 to 3 g in deionized water.

[0019] In combination with the second aspect, in one achievable manner, in step 4, maleic anhydride, triisopropanolamine, and ferric chloride hexahydrate are mixed according to a mass ratio and reacted at 70-80° C. for 120-180 min.

[0020] In conjunction with the second aspect, in one achievable manner, the molecular weight of the organic liquid phase component a is 7000-8000, and the molecular weight of the organic liquid phase component b is 7500-9000.

[0021] In conjunction with the second aspect, in one achievable manner, the inorganic liquid phase component and the inorganic solid phase component are prepared according to the following method:

[0022] Step 1: X-ray fluorescence spectroscopy was used to test the mass fraction of Al2O3 in coal gangue and red mud, which were recorded as oh 1 and oh 2. Crush the gangue to less than 0.30 mm to obtain gangue particles, and then calculate the feed mass of the gangue particles as follows: m 1. Red mud feed quality m 2:

[0023] (1) When oh 1 and oh 2 are not less than 20%, the gangue particles and red mud can be added in any mass ratio;

[0024] (2) When oh 1 and oh 2 If only one of them is not less than 20%, follow ( m 1 oh 1+ m 2 oh 2) / ( m 1+ m 2) The mass ratio range of coal gangue particles to red mud is calculated at a ratio of ≥20%;

[0025] (3) When oh 1 and oh 2 are less than 20%, in addition to coal gangue particles and red mud, a m 3. The mass ratio of sodium aluminate, coal gangue particles, red mud and sodium aluminate is as follows: m 1 oh 1+ m 2 oh 2+ m 3) / ( m 1+ m 2+m 3) ≥20% for calculation;

[0026] Mix the materials according to the calculation results to obtain mixed material a;

[0027] Step 2: Grind the mixed material a to 400~600 μm 2 / kg, and then mix the mixed material a and solid sodium hydroxide in a porcelain crucible in a mass ratio of 51:8-32, stir evenly and transfer to a muffle furnace, and roast at 550-750°C for 60-120min. After the roasting is completed, take out and dry in a dryer to room temperature to obtain a mixed material b;

[0028] Step 3, adding deionized water to the calcined mixed material b to obtain a slurry, wherein the added amount is the calcined mixed material b: deionized water mass ratio of 1:6-10, transferring the slurry to a three-necked flask, and performing a hydrothermal reaction at 105-125° C. for 90-150 min in a chemical microwave reactor under heating reflux conditions;

[0029] Step 4: Filter the slurry after the hydrothermal reaction, and the liquid obtained after filtration is the finished inorganic liquid phase component; grind the filter residue again to 400-600 μm. 2 / kg, and obtain the finished inorganic solid phase component.

[0030] In combination with the second aspect, in one achievable method, in step 2, after stirring evenly, the mixture is transferred to a muffle furnace and calcined at 550-750° C. for 60-120 min.

[0031] In combination with the second aspect, in one achievable manner, the triethanolamine, the triisopropanolamine, the maleic anhydride, the ferric chloride hexahydrate, and the sodium methacrylate are all industrially pure; and the sodium aluminate is analytically pure.

[0032] Compared with the prior art, the synergist for solid waste-based gelling materials and the preparation method thereof provided by the present invention have the following beneficial effects:

[0033] (1) AFt (also known as calcium sulfonate) is the main source of the initial strength of solid waste-based cementitious materials. The formation of AFt is inseparable from the Al element. When a synergist is added to the solid waste-based cementitious materials, red mud and coal gangue contain a large amount of Al phase, which can stimulate the hydration activity of the Al phase after the alkali melting-hydrothermal reaction. The inorganic liquid phase has a high alkalinity. Under the action of the inorganic liquid phase, this hydration activity can be further enhanced. At the same time, the inorganic liquid phase also contains a large amount of Al phase as a supplement, thereby promoting the formation of calcium sulfonate AFt in the early stage of hydration of solid waste-based cementitious materials.

[0034] (2) The alkali melting-hydrothermal reaction process can produce a part of zeolite-like phase, which, combined with the Si phase in the inorganic liquid phase, helps the formation of calcium silicate hydrate gel (CSH), thereby ensuring the subsequent strength growth.

[0035] (3) Since the inorganic solid phase components and solid waste-based gelling materials are fine in fineness and the raw materials contain coal gangue, the system after the two are combined is more likely to agglomerate, resulting in poor workability. The polymer macromolecules of the organic liquid phase component in the present invention contain negatively charged carboxylate groups, which can be adsorbed on the surface of the inorganic solid phase components and solid waste-based gelling materials to form an adsorption layer, which plays a role in dispersing the inorganic solid phase components and solid waste-based gelling materials; the steric hindrance effect generated by the long molecular chains of the organic liquid phase components a and b can also prevent the inorganic solid phase components and solid waste-based gelling materials from agglomerating ( Figure 2 , Figure 3 is the stretching direction of the chain links of the organic liquid phase components a and b in space); at the same time, the other ends of the two organic macromolecules, the organic liquid phase component a and the organic liquid phase component b, contain "N", which has strong polarity and hydrophilicity, and can form a layer of water film on the surface of the inorganic solid phase component and the solid waste-based cementitious material, which can play a lubricating role on the one hand, and can also make the inorganic solid phase component and the solid waste-based cementitious material better hydrated and improve the early strength.

[0036] (4) Since the organic liquid phase contains Na + When the carbon dioxide in the air reacts with the calcium hydroxide produced by the hydration of solid waste-based cementitious materials to form calcium carbonate, the OH remaining in the liquid phase - Can be with Na + The formation of NaOH continuously provides an alkaline environment for the enhancer, which is beneficial to the continuous growth of the enhancer's strength.

[0037] Therefore, the preparation method provided by the present invention can be used to prepare early-strength and high-strength solid waste-based cementitious materials; wherein the organic liquid phase component mainly plays the role of dispersing the solid waste-based cementitious materials and the inorganic solid phase components, and continuously provides an alkaline environment to provide power for the later strength growth; the inorganic liquid phase component mainly plays the role of providing an alkaline environment and improving the early strength, and the active components in the inorganic solid phase can react under the stimulation of the inorganic liquid phase component to improve the early strength. The three components play a synergistic role, which is conducive to the generation of AFt and CSH, so that they can quickly form strength, and the strength is continuously increased in the later stage of hydration, achieving the effect of early strength and high strength of solid waste-based cementitious materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 A process flow chart of a method for preparing a synergist for solid waste-based gelling materials provided by an embodiment of the present invention;

[0039] Figure 2A schematic diagram of the extension direction of the chain segments of the organic liquid phase component a in space provided in an embodiment of the present invention;

[0040] Figure 3 A schematic diagram of the extension direction of the chain segments of the organic liquid phase component b in space provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0041] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0042] As two typical bulk solid wastes, the large accumulation of red mud and coal gangue not only wastes land resources, but also threatens the ecological environment, harms human health, and restricts the sustainable development of related enterprises. The application of red mud and coal gangue in the synthesis of synergists for solid waste-based cementitious materials can achieve high-value and harmless utilization. It helps to reduce the damage of red mud and coal gangue to the environment, and at the same time improve the early strength and later growth strength of solid waste-based cementitious materials.

[0043] Combination Figure 1 It is understood that the preparation method of the synergist for solid waste-based gelling materials provided in the embodiment of the present invention is as follows:

[0044] Embodiment 1:

[0045] In this embodiment, the ratio of the synergist used for the solid waste-based gelling material is: 20 parts of organic liquid phase component, 25 parts of inorganic liquid phase component, and 55 parts of inorganic solid phase component by mass.

[0046] 1. The preparation process of organic liquid phase components is as follows:

[0047] Step 1: maleic anhydride, triethanolamine and ferric chloride hexahydrate are mixed in a mass ratio of 1:1.4:0.06, and reacted at 70° C. for 130 min to obtain liquid a.

[0048] Step 2, prepare three portions of deionized water, the mass of each portion of deionized water is 0.5 times the amount of maleic anhydride, add sodium carbonate to one portion until the excess is 1 g, add sodium chloride to one portion until the excess is 1 g, and add calcium chloride to one portion until the excess is 1 g, and retain the excess sodium carbonate, sodium chloride, and calcium chloride; the liquid a after the reaction in step 1 is passed through the above-mentioned sodium carbonate, sodium chloride and calcium chloride solutions in sequence, and then dried with sodium sulfate, and filtered to obtain intermediate a.

[0049] Step 3: Mix the intermediate a with sodium methacrylate and concentrated sulfuric acid in a three-necked flask at a mass ratio of 259:70:3, and heat to react at 75°C. During this period, slowly add sodium methacrylate in an amount of 1 times the mass of the initial amount of sodium methacrylate using a separatory funnel, and control the addition time to 100 min. After the addition is completed, continue to react at this temperature for 70 min to obtain an organic liquid phase component a.

[0050] Step 4: maleic anhydride, triisopropanolamine and ferric chloride hexahydrate are mixed in a mass ratio of 1:1.8:0.08, and reacted at 70° C. for 130 min to obtain liquid b.

[0051] Step 5, treating the liquid b after the reaction in step 4 according to step 2 to obtain intermediate b.

[0052] Step 6: Mix the intermediate b with sodium methacrylate and concentrated sulfuric acid in a three-necked flask at a mass ratio of 289:75:0.16, and heat to react at 75°C. During this period, slowly add sodium methacrylate in an amount of 1 times the mass of the initial amount of sodium methacrylate using a separatory funnel, and the addition time is controlled within 110 min. After the addition is completed, continue to react at this temperature for 60 min to obtain an organic liquid phase component b.

[0053] Step 7: Mix the organic liquid phase component a and the organic liquid phase component b in a ratio of 1:0.5 to obtain a finished organic liquid phase component.

[0054] 2. The preparation process of inorganic liquid phase components and inorganic solid phase components is as follows:

[0055] Step 1: X-ray fluorescence spectroscopy was used to measure the mass fractions of Al2O3 in gangue and red mud. oh 1 = 23.7% and oh 2=20.3%, both are not less than 20%, then the gangue particles and red mud can be mixed in any proportion. In this embodiment, the gangue particles and red mud are mixed in a mass ratio of 1:3 to obtain a mixed material a.

[0056] Step 2: Use a vertical mill to grind the mixed material a to 430 μm 2 / kg, and then mixed the mixed material a and sodium hydroxide in a porcelain crucible in a ratio of 51:12 by mass. After stirring evenly, the mixed material a was transferred to a muffle furnace and calcined at 600°C for 75min. After the calcination, the mixed material b was taken out and dried in a dryer to room temperature to obtain a mixed material b.

[0057] Step three, add deionized water to the calcined mixed material b to obtain a slurry, the added amount is the mass ratio of the calcined mixed material b to the deionized water is 1:7, the slurry is transferred to a three-necked flask, a small amount of zeolite is added, and a hydrothermal reaction is carried out at 105°C for 90 min under heating reflux conditions using a chemical microwave reactor.

[0058] Step 4: Filter the slurry after the hydrothermal reaction, and the liquid obtained after filtration is the finished inorganic liquid phase component; grind the filter residue again to 450 m 2 / kg, and obtain the finished inorganic solid phase component.

[0059] 3. The triethanolamine, triisopropanolamine, maleic anhydride, ferric chloride hexahydrate, and sodium methacrylate used in this embodiment are all industrial grade, and sodium aluminate is analytical grade.

[0060] Embodiment 2:

[0061] In this embodiment, the ratio of the synergist used for the solid waste-based gelling material is: 22 parts of organic liquid phase component, 16 parts of inorganic liquid phase component, and 62 parts of inorganic solid phase component by mass.

[0062] 1. The preparation process of organic liquid phase components is as follows:

[0063] Step 1: maleic anhydride, triethanolamine and ferric chloride hexahydrate are mixed in a mass ratio of 1:1.6:0.12, and reacted at 75° C. for 150 min to obtain liquid a.

[0064] Step 2, prepare three portions of deionized water, the mass of each portion of deionized water is 0.7 times the amount of maleic anhydride, add sodium carbonate to one portion until the excess is 2 g, add sodium chloride to one portion until the excess is 1 g, and add calcium chloride to one portion until the excess is 3 g, retaining the excess sodium carbonate, sodium chloride, and calcium chloride; the liquid a after the reaction in step 1 is passed through the above-mentioned sodium carbonate, sodium chloride and calcium chloride solutions in sequence, then dried with sodium sulfate, and filtered to obtain intermediate a.

[0065] Step 3: Mix the intermediate a with sodium methacrylate and concentrated sulfuric acid in a three-necked flask at a mass ratio of 259:86:4, and heat to react at 85°C. During this period, a separating funnel is used to slowly drop sodium methacrylate in an amount twice the mass of the initial amount of sodium methacrylate, and the dropping time is controlled within 110 min. After the dropwise addition is completed, continue to react at this temperature for 100 min to obtain an organic liquid phase component a.

[0066] Step 4: maleic anhydride, triisopropanolamine and ferric chloride hexahydrate are mixed in a mass ratio of 1:2.1:0.1, and reacted at 70° C. for 140 min to obtain liquid b.

[0067] Step 5, treating the liquid a after the reaction in step 4 according to step 2 to obtain an intermediate b.

[0068] Step 6: Mix the intermediate b with sodium methacrylate and concentrated sulfuric acid in a three-necked flask at a mass ratio of 289:85:0.19, and heat to react at 85°C. During this time, slowly add sodium methacrylate in an amount twice the mass of the initial amount of sodium methacrylate using a separatory funnel, and the addition time is controlled within 135 min. After the addition is completed, continue to react at this temperature for 90 min to obtain an organic liquid phase component b.

[0069] Step seven, mixing the organic liquid phase component a and the organic liquid phase component b in a ratio of 1:1.25 to obtain a finished organic liquid phase component.

[0070] 2. The preparation process of inorganic liquid phase components and inorganic solid phase components is as follows:

[0071] Step 1: X-ray fluorescence spectroscopy was used to measure the mass fractions of Al2O3 in gangue and red mud. oh 1 = 24.0% and oh 2=18.2%, only one is not less than 20%, according to ( m 1 oh 1+ m 2 oh 2) / ( m 1+ m 2) The mass ratio of the gangue particles to the red mud is calculated at a ratio of ≥20%. In this embodiment, the gangue particles and the red mud are mixed at a mass ratio of 3:1 to obtain a mixed material a.

[0072] Step 2: Use a vertical mill to grind the mixed material a to 500 μm 2 / kg, and then mixed the mixed material a and sodium hydroxide in a porcelain crucible in a ratio of 51:20 by mass. After stirring evenly, the mixed material a was transferred to a muffle furnace and calcined at 650°C for 95min. After the calcination, the mixed material b was taken out and dried in a dryer to room temperature to obtain a mixed material b.

[0073] Step three, add deionized water to the calcined mixed material b to obtain a slurry, the added amount is the mass ratio of the calcined mixed material b to deionized water is 1:8, the slurry is transferred to a three-necked flask, a small amount of zeolite is added, and a hydrothermal reaction is carried out at 115°C for 120 min under heating reflux conditions using a chemical microwave reactor.

[0074] Step 4: Filter the slurry after the hydrothermal reaction, and the liquid obtained after filtration is the finished inorganic liquid phase component; grind the filter residue again to 495 m 2 / kg, and obtain the finished inorganic solid phase component.

[0075] 3. The triethanolamine, triisopropanolamine, maleic anhydride, ferric chloride hexahydrate, and sodium methacrylate used in this embodiment are all industrial grade, and sodium aluminate is analytical grade.

[0076] Embodiment three:

[0077] In this embodiment, the ratio of the synergist used for the solid waste-based gelling material is: 13 parts of organic liquid phase component, 20 parts of inorganic liquid phase component, and 67 parts of inorganic solid phase component by mass.

[0078] 1. The preparation process of organic liquid phase components is as follows:

[0079] Step 1: maleic anhydride, triethanolamine and ferric chloride hexahydrate are mixed in a mass ratio of 1:2.0:0.16, and reacted at 80° C. for 170 min to obtain liquid a.

[0080] Step 2: prepare three portions of deionized water, each portion of which is 0.8 times the amount of maleic anhydride used, add sodium carbonate to one portion until an excess of 3 g, add sodium chloride to one portion until an excess of 3 g, and add calcium chloride to one portion until an excess of 2 g, retaining excess sodium carbonate, sodium chloride, and calcium chloride. Liquid a after the reaction in step 1 is sequentially passed through the above sodium carbonate, sodium chloride, and calcium chloride solutions, then dried with sodium sulfate, and filtered to obtain intermediate a.

[0081] Step 3, the intermediate a is mixed with sodium methacrylate and concentrated sulfuric acid in a three-necked flask in a mass ratio of 259:96:5, and heated to 90°C for reaction. During this period, sodium methacrylate in an amount 3 times the mass of the initial amount of sodium methacrylate is slowly added dropwise using a separatory funnel, and the addition time is controlled within 135 min; after the addition is completed, the reaction is continued at this temperature for 110 min to obtain an organic liquid phase component a.

[0082] Step 4: maleic anhydride, triisopropanolamine and ferric chloride hexahydrate are mixed in a mass ratio of 1:2.4:0.15, and reacted at 75° C. for 160 min to obtain liquid b.

[0083] Step 5, treating the liquid b after the reaction in step 4 according to step 2 to obtain intermediate b.

[0084] Step six, the intermediate b is mixed with sodium methacrylate and concentrated sulfuric acid in a three-necked flask in a mass ratio of 289:96:0.23, and heated to 95°C for reaction. During this period, sodium methacrylate in an amount twice the mass of the initial amount of sodium methacrylate is slowly added dropwise using a separatory funnel, and the addition time is controlled within 145 min; after the addition is completed, the reaction is continued at this temperature for 105 min to obtain an organic liquid phase component b.

[0085] Step seven, mixing the organic liquid phase component a and the organic liquid phase component b in a ratio of 1:1.55 to obtain a finished organic liquid phase component.

[0086] 2. The preparation process of inorganic liquid phase components and inorganic solid phase components is as follows:

[0087] Step 1: X-ray fluorescence spectroscopy was used to measure the mass fractions of Al2O3 in gangue and red mud. oh 1 = 17.7% and oh 2=19.1%, all less than 20%, a certain amount of sodium aluminate, coal gangue particles, red mud, sodium aluminate ( m 3) Mass ratio range according to ( m 1 oh 1+ m 2 oh 2+ m 3) / ( m 1+ m 2+ m In this embodiment, coal gangue particles, red mud, and sodium aluminate are mixed in a mass ratio of 1:3:0.3 to obtain a mixed material a.

[0088] Step 2: Use a vertical mill to grind the mixed material a to 530 μm 2 / kg, and then mixed the mixed material a and sodium hydroxide in a porcelain crucible in a ratio of 51:28 by mass. After stirring evenly, the mixed material a was transferred to a muffle furnace and calcined at 720°C for 110 min. After the calcination, the mixed material b was taken out and dried in a dryer to room temperature to obtain a mixed material b.

[0089] Step three, add deionized water to the calcined mixed material b to obtain a slurry, the added amount is the mass ratio of the calcined mixed material b to the deionized water is 1:9, the slurry is transferred to a three-necked flask, a small amount of zeolite is added, and a hydrothermal reaction is carried out at 120°C for 140 min under heating reflux conditions using a chemical microwave reactor.

[0090] Step 4: Filter the slurry after the hydrothermal reaction, and the liquid obtained after filtration is the finished inorganic liquid phase component; grind the filter residue again to 550 m 2 / kg, and obtain the finished inorganic solid phase component.

[0091] 3. The triethanolamine, triisopropanolamine, maleic anhydride, ferric chloride hexahydrate, and sodium methacrylate used in this embodiment are all industrial grade, and sodium aluminate is analytical grade.

[0092] The synergists in Example 1, Example 2, and Example 3 were used to prepare mortar test blocks, and compared with the blank group and the control group. Before preparing the mortar test blocks, the organic liquid phase component and the inorganic liquid phase component should be mixed with water, and the inorganic solid phase component should be mixed with the solid waste-based cementitious material, and then the strength and setting time should be tested in accordance with the relevant provisions of the current national standard "Test Method for Strength of Cement Mortar (IOS) Method" (GB / T17671) and "Test Method for Water Consumption, Setting Time, and Stability of Cement Standard Consistency" (GB / T 1346). The mortar test block ratio table and test results are shown in Tables 1 and 2.

[0093] Table 1 Mortar test block ratio table

[0094]

[0095] Table 2 Test results of mortar block strength and setting time

[0096]

[0097] It can be seen from Tables 1 and 2 that, compared with the solid waste-based cementitious materials without the synergist, the 3d strength of the solid waste-based cementitious materials after adding the synergist is increased by 26.7%-33.5%, the 28d strength is increased by 11.4%-16.4%, and the initial / final setting time is significantly shortened; compared with ordinary Portland cement, the strength and initial / final setting time are basically the same, indicating that the present invention has a significant effect on improving the performance of solid waste-based cementitious materials.

[0098] To explain, analytical grade (AR, red label secondary product): the purity is slightly lower than that of premium grade, and the impurity content is slightly higher than that of premium grade. It is suitable for important analysis and general research work, such as common reagents in general laboratories, research institutes, etc., and is often represented by AR.

[0099] The purity of chemical products refers to the purity of raw materials, and relatively speaking, it also refers to the degree of impurities in raw materials. Industrial purity is relatively low-level purity, suitable for non-rigorous laboratory work, such as rinsing, dissolution or as raw materials in production, with very low purity.

[0100] The purity of chemical products refers to the purity of raw materials, which also refers to the degree of impurities in raw materials. The higher the purity of raw materials, the fewer types and quantities of impurities they contain. Chemical raw materials can be divided into two categories according to their purity: industrial pure and reagent pure. And reagent pure raw materials can be divided into four levels according to their purity.

[0101] Super pure (GR, green label, first grade): The main component content and purity are very high, suitable for precise analysis and scientific research, and some can be used as reference materials;

[0102] Analytical grade (AR, red label, secondary product): The main component content is very high, the purity is high, and the interfering impurities are very low. It is suitable for general analysis and scientific research;

[0103] Chemically pure (CP, blue label, grade 3): high content of main components, high purity, with interfering impurities, suitable for general analysis and synthetic preparation in industry and teaching processes;

[0104] Experimental grade (LR, yellow or brown label): The main component content is high, the purity is poor, and the impurity content is not selected. It is only suitable for general chemical experiments and synthetic preparations.

[0105] Technical grade (TP reagent) has a purity lower than that of grade 4 products and is suitable for non-rigorous laboratory work, such as rinsing, dissolution or use as raw materials in production. Its purity is very low.

[0106] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described or recorded in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0107] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A synergist for solid waste-based cementitious materials, It is characterized in that Calculated by mass percentage, it includes: 10-25 parts of organic liquid phase component, 15-25 parts of inorganic liquid phase component and 50-70 parts of inorganic solid phase component; The preparation of the organic liquid phase component comprises: Step 1, maleic anhydride, triethanolamine, and ferric chloride hexahydrate are mixed in a mass ratio of 1:1.2-2.0:0.05-0.2, and react to obtain liquid a; Step 2, washing the liquid a obtained in the reaction in step 1 with a sodium carbonate solution, a sodium chloride solution and a calcium chloride solution in sequence, then drying with sodium sulfate, and filtering to obtain an intermediate a; Step 3, the intermediate a is mixed with sodium methacrylate and concentrated sulfuric acid in a three-necked flask at a mass ratio of 259:68-103:3-5, and heated to react at 70-95° C. to obtain an organic liquid phase component a. The molecular formula of the organic liquid phase component a is: Step 4, mixing maleic anhydride, triisopropanolamine, and ferric chloride hexahydrate in a mass ratio of 1:1.5-2.5:0.05-0.2, and reacting to obtain liquid b; Step 5, treating the liquid b after the reaction in step 4 according to step 2 to obtain an intermediate b; Step 6: Mix the intermediate b with sodium methacrylate and concentrated sulfuric acid in a three-necked flask at a mass ratio of 289:68-103:0.15-0.25, and heat to react at 70-95° C. to obtain an organic liquid phase component b. The molecular formula of the organic liquid phase component b is: ; Step 7, mixing the organic liquid phase component a and the organic liquid phase component b at a mass ratio of 1:0.25-1.75 to obtain a finished organic liquid phase component; The inorganic liquid phase component is a filtrate obtained by filtering red mud and coal gangue powder after alkali melting and hydrothermal reaction; the inorganic solid phase component is obtained by grinding the filter residue obtained by filtering red mud and coal gangue powder after alkali melting and hydrothermal reaction; the alkali melting is calcined at 550-750°C; and the hydrothermal reaction is carried out at 105-125°C.

2. A method for preparing a synergist for solid waste-based gelling materials, comprising preparing the synergist for solid waste-based gelling materials as claimed in claim 1, It is characterized in that The method comprises the preparation of the organic liquid phase component, the preparation of the inorganic liquid phase component and the preparation of the inorganic solid phase component; The organic liquid phase component is prepared according to the following method: Step 1, maleic anhydride, triethanolamine, and ferric chloride hexahydrate are mixed in a mass ratio of 1:1.2-2.0:0.05-0.2, and react to obtain liquid a; Step 2, prepare three portions of deionized water, the mass of each portion of deionized water is 0.5 to 1.0 times the amount of maleic anhydride used, add sodium carbonate to one portion of deionized water until it is excessive, add sodium chloride to one portion of deionized water until it is excessive, add calcium chloride to one portion of deionized water until it is excessive, retain the excess sodium carbonate, sodium chloride, and calcium chloride to obtain a sodium carbonate solution, a sodium chloride solution, and a calcium chloride solution; wash the liquid a obtained by the reaction in step 1 with a sodium carbonate solution, a sodium chloride solution, and a calcium chloride solution in sequence, then dry it with sodium sulfate, and filter it to obtain an intermediate a; Step 3, the intermediate a is mixed with sodium methacrylate and concentrated sulfuric acid in a three-necked flask in a mass ratio of 259:68-103:3-5, and heated to react at 70-95° C., during which 1-3 times the mass of the initial amount of sodium methacrylate is slowly added dropwise using a separatory funnel, and the addition time is controlled at 90-150 min; after the addition is completed, the reaction is continued at this temperature for 60-120 min to obtain an organic liquid phase component a; Step 4, mixing maleic anhydride, triisopropanolamine, and ferric chloride hexahydrate in a mass ratio of 1:1.5-2.5:0.05-0.2, and reacting to obtain liquid b; Step 5, treating the liquid b after the reaction in step 4 according to step 2 to obtain an intermediate b; Step 6, the intermediate b is mixed with sodium methacrylate and concentrated sulfuric acid in a three-necked flask in a mass ratio of 289:68-103:0.15-0.25, and heated to react at 70-95° C., during which 1-3 times the mass of the initial amount of sodium methacrylate is slowly added dropwise using a separatory funnel, and the addition time is controlled at 90-150 min; after the addition is completed, the reaction is continued at this temperature for 60-120 min to obtain an organic liquid phase component b; Step seven, mixing the organic liquid phase component a and the organic liquid phase component b in a mass ratio of 1:0.25-1.75 to obtain a finished organic liquid phase component.

3. The method for preparing the synergist for solid waste-based gelling materials according to claim 2, It is characterized in that In step 1, maleic anhydride, triethanolamine and ferric chloride hexahydrate are mixed in proportion and reacted at 70-80° C. for 120-180 min to obtain liquid a.

4. The method for preparing the synergist for solid waste-based gelling materials according to claim 2, It is characterized in that In step 2, the sodium carbonate, sodium chloride and calcium chloride are respectively added in excess of 1 to 3 g in deionized water.

5. The method for preparing the synergist for solid waste-based gelling materials according to claim 2, It is characterized in that In step 4, maleic anhydride, triisopropanolamine and ferric chloride hexahydrate are mixed according to a mass ratio and reacted at 70-80° C. for 120-180 min.

6. The method for preparing the synergist for solid waste-based gelling materials according to claim 2, It is characterized in that The molecular weight of the organic liquid phase component a is 7000-8000, and the molecular weight of the organic liquid phase component b is 7500-9000.

7. The method for preparing the synergist for solid waste-based gelling materials according to claim 2, It is characterized in that The inorganic liquid phase component and the inorganic solid phase component are prepared according to the following method: Step 1: Use X-ray fluorescence spectroscopy to test Al in coal gangue and red mud 2 O 3 The mass fractions of ω 1 and ω 2 ; Crush the gangue to less than 0.30 mm to obtain gangue particles, and then calculate the feeding mass of the gangue particles in the following way: m 1 The quality of red mud m 2 : (1) When ω 1 and ω 2 When both are not less than 20%, the gangue particles and red mud can be added in any mass ratio; (2) When ω 1 and ω 2 If only one of them is not less than 20%, follow ( m 1 ω 1 + m 2 ω 2 ) / ( m 1 + m 2 )≥20% to calculate the mass ratio range of gangue particles to red mud; (3) When ω 1 and ω 2 When the content of coal gangue particles and red mud is less than 20%, a m 3 The mass ratio of sodium aluminate, coal gangue particles, red mud and sodium aluminate is as follows: m 1 ω 1 + m 2 ω 2 + m 3 ) / ( m 1 + m 2 + m 3 ) ≥ 20% for calculation; Mix the materials according to the calculation results to obtain mixed material a; Step 2: Grind the mixed material a to 400~600 μm 2 / kg, and then mix the mixed material a and solid sodium hydroxide in a porcelain crucible in a mass ratio of 51:8-32, stir evenly and transfer to a muffle furnace, and roast at 550-750°C for 60-120min. After the roasting is completed, take out and dry in a dryer to room temperature to obtain a mixed material b; Step 3, adding deionized water to the calcined mixed material b to obtain a slurry, wherein the added amount is the calcined mixed material b: deionized water mass ratio of 1:6-10, transferring the slurry to a three-necked flask, and performing a hydrothermal reaction at 105-125° C. for 90-150 min in a chemical microwave reactor under heating reflux conditions; Step 4: Filter the slurry after the hydrothermal reaction, and the liquid obtained after filtration is the finished inorganic liquid phase component; grind the filter residue again to 400-600 μm. 2 / kg, and obtain the finished inorganic solid phase component.

8. The method for preparing the synergist for solid waste-based gelling materials according to claim 7, It is characterized in that In step 2, after being stirred evenly, the mixture is transferred to a muffle furnace and calcined at 550-750° C. for 60-120 min.

9. The method for preparing a synergist for solid waste-based gelling materials according to claim 7, It is characterized in that The triethanolamine, the triisopropanolamine, the maleic anhydride, the ferric chloride hexahydrate, and the sodium methacrylate are all of industrial grade; the sodium aluminate is of analytical grade.

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