CN115466065B - Phosphorus-based II type anhydrous gypsum cementing material and activation method thereof - Google Patents
Phosphorus-based II type anhydrous gypsum cementing material and activation method thereof Download PDFInfo
- Publication number
- CN115466065B CN115466065B CN202211139758.4A CN202211139758A CN115466065B CN 115466065 B CN115466065 B CN 115466065B CN 202211139758 A CN202211139758 A CN 202211139758A CN 115466065 B CN115466065 B CN 115466065B
- Authority
- CN
- China
- Prior art keywords
- curing treatment
- phosphorus
- phosphogypsum
- activation method
- anhydrite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/05—Calcium sulfate cements obtaining anhydrite, e.g. Keene's cement
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a phosphorus-based II-type anhydrous gypsum cementing material and an activation method thereof, wherein the activation method comprises the following steps: calcining phosphogypsum, grinding, aging and forming in sequence, and performing two-stage curing treatment; the curing treatment comprises a first curing treatment and a second curing treatment. The prepared phosphorus-based II-type anhydrous gypsum cementing material has the flexural strength of 2-13MPa, the compressive strength of 5-40MPa and the hydration rate of more than or equal to 80 percent. According to the activation method provided by the invention, the phosphogypsum is subjected to calcination, grinding, aging and maintenance treatment in sequence to obtain the phosphorus-based II-type anhydrous gypsum cementing material with uniform particle size, high hydration rate and high strength; the hydration time of the anhydrous phosphogypsum can be further shortened through two-stage curing treatment of reducing the temperature section by section, the anhydrous phosphogypsum can be better excited, and the strength of the cementing material can be increased.
Description
Technical Field
The invention belongs to the technical field of gypsum activation, and particularly relates to a phosphorus-based II-type anhydrous gypsum cementing material and an activation method thereof.
Background
Phosphogypsum is solid waste generated in the wet-process phosphoric acid process, and the main component is CaSO 4 ·nH 2 O, not only contains soluble inorganic impurities such as: phosphoric acid, phosphate, silicate, fluoride, etc., and also contains a certain amount of organic matters, eutectic phosphorus, etc., as well as a plurality of harmful impurities. China is the country with the most phosphogypsum production, the annual discharge of the auxiliary yield of phosphogypsum is about 8000 ten thousand tons at present, but the utilization rate of phosphogypsum is less than 10 percent, a large amount of phosphogypsum is piled as solid waste, and the accumulated phosphogypsum exceeds 2 hundred million tons, thereby not only occupying a large amount of land, but also causing environmental pollution.
The traditional phosphogypsum has the advantages of quick setting and hardening, no shrinkage, light weight, heat preservation and the like, but the application range of the phosphogypsum is limited due to the disadvantages of low strength and poor water resistance. Phosphogypsum can generate II type anhydrous gypsum at high temperature, so that impurities in the gypsum become inert. CN104803651a discloses a gypsum-based cementing material, which comprises blast furnace slag powder, gypsum mixture, active admixture, alkali excitant, coagulant, lime, water reducer and early strength agent, wherein the weight ratio of each component is: 10-30% of blast furnace slag powder, 20-60% of gypsum mixture, 10-45% of active admixture, 4-15% of alkaline activator, 0-6% of coagulant, 0-1% of early strength agent, 0-1% of water reducer and 0-5% of lime; the cementing material is obtained by mixing the sulphoaluminate cement, the silicate cement and the gypsum in a certain proportion, has higher compressive strength and flexural strength, but has lower hydration rate.
CN106478041a discloses a preparation method of an early-strength phosphogypsum-based cementing material, which comprises the following steps: taking phosphogypsum as a raw material, drying, crushing, sieving, mixing with ammonia water, grinding, treating with sulfuric acid solution and other acids, standing for impurity removal, ball milling, filtering, drying and calcining to obtain pretreated phosphogypsum, and finally mixing the pretreated phosphogypsum with blast furnace slag, portland cement, polyaluminium chloride and other substances to obtain the early-strength phosphogypsum-based cementing material; the phosphogypsum-based cementing material has high strength and short initial and final setting time, but the preparation method thereof needs a large amount of acid-base solution, has high cost and is easy to cause environmental pollution.
At present, the process for preparing the II-type anhydrous gypsum cementing material by using phosphogypsum and the research for improving the hydration activity and strength are less, and the invention provides a novel method for activating the phosphorus-based II-type anhydrous gypsum cementing material in order to further popularize the use of phosphogypsum.
Disclosure of Invention
The invention aims to provide a phosphorus-based II-type anhydrous gypsum cementing material and an activation method thereof, wherein the activation method solves the problems of low hydration rate, low strength and the like in the excitation and activation application of the anhydrous gypsum material, and improves the comprehensive utilization rate of phosphogypsum; the phosphorus-based II-type anhydrous gypsum cementing material prepared by the method has the advantages of uniform particle size, high hydration rate, high strength, good volume stability and the like.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for activating a phosphorus-based type ii anhydrite cementitious material, the method comprising: calcining phosphogypsum, grinding, aging and curing in sequence;
the curing treatment comprises a first curing treatment and a second curing treatment.
According to the invention, the phosphogypsum is subjected to calcination, grinding, aging and curing in sequence to obtain the phosphorus-based II-type anhydrous gypsum cementing material with high hydration rate and high strength, and the curing treatment with gradually reduced temperature is performed at low temperature, so that the strength of the cementing material can be further increased.
In a preferred embodiment of the present invention, the calcination temperature is 800 to 950 ℃, for example, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃, 950 ℃ or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
Preferably, the calcination is carried out for a period of time ranging from 3 to 5 hours, for example, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, or 5 hours, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, the activating agent is mixed with calcined phosphogypsum before grinding. According to the invention, by mixing the activator and calcined phosphogypsum, not only can the grinding assisting effect be achieved, but also the contact specific surface area of the activator and calcined phosphogypsum can be increased, so that the unstable double salt generated by the activator and calcined phosphogypsum in the later stage can be decomposed to obtain dihydrate gypsum to be separated out in a crystal form, the dihydrate gypsum is used as a seed crystal in the hydration reaction of the dihydrate gypsum, and the hydration process is accelerated in the induction period.
Preferably, the mass ratio of the activator to calcined phosphogypsum is (0.002-0.03): 1, for example, 0.002:1, 0.005:1, 0.01:1, 0.015:1, 0.02:1, 0.025:1 or 0.03:1, etc., but not limited to the recited values, other non-recited values within the numerical range are equally applicable.
Preferably, the activator comprises any one or a combination of at least two of potassium oxalate, potassium aluminum sulfate, calcium sulfate dihydrate, calcium sulfate alpha-hemihydrate, calcium sulfate beta-hemihydrate, potassium sulfate, or aluminum sulfate, typical but non-limiting examples of which are: a combination of potassium oxalate and potassium aluminum sulfate, a combination of potassium aluminum sulfate and calcium sulfate dihydrate, a combination of alpha-calcium sulfate hemihydrate and beta-calcium sulfate hemihydrate, or a combination of potassium sulfate and aluminum sulfate, and the like.
In the invention, the calcium sulfate dihydrate is analytically pure calcium sulfate dihydrate; the alpha-calcium sulfate hemihydrate is prepared by heat preservation and pressure maintaining of calcium sulfate dihydrate at 140 ℃ and 0.2MPa for 2 hours; the beta-calcium sulfate hemihydrate is prepared by calcining calcium sulfate dihydrate at 150 ℃ for 4 hours.
In a preferred embodiment of the present invention, the grinding time is greater than 10min, for example, 15min, 20min, 25min, 30min, 40min, 50min or 60min, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the powder is ground to a specific surface area of not less than 500m 2 ·kg -1 For example, it may be 520m 2 ·kg -1 、550m 2 ·kg -1 、570m 2 ·kg -1 、600m 2 ·kg -1 、650m 2 ·kg -1 Or 700m 2 ·kg -1 And the like, but are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
In a preferred embodiment of the present invention, the aging temperature is 20 to 30℃and may be, for example, 20℃and 21℃and 22℃and 23℃and 24℃and 25℃and 26℃and 27℃and 28℃and 29℃or 30℃respectively, but the present invention is not limited to the values recited, and other values not recited in the numerical range are applicable.
The aging time is 4-8d, and may be, for example, 4d, 5d, 6d, 7d, or 8d, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the aging further comprises shaping.
In the invention, the powder and water are prepared into slurry according to the water demand of standard consistence, and the slurry is poured into a mould for molding treatment.
In a preferred embodiment of the present invention, the temperature of the first curing treatment is 15 to 30℃and may be, for example, 15℃17℃20℃22℃24℃26℃28℃30℃or the like, but not limited to the values listed, and other values not listed in the numerical range are equally applicable, preferably 20 to 25 ℃.
Preferably, the humidity of the first curing treatment is 30% -80%, for example, 30%, 40%, 50%, 60%, 70% or 80%, etc., but not limited to the recited values, and other non-recited values in the range of values are equally applicable, preferably 55% -65%.
Preferably, the time of the first curing treatment is 1-3d, for example, 1d, 1.5d, 2d, 2.5d, or 3d, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 1d.
Preferably, the temperature of the second curing treatment is 8 to 15 ℃ and does not include 15 ℃, for example, 8 ℃, 9 ℃, 10 ℃, 11 ℃, 12 ℃, 13 ℃ or 14 ℃, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable, and preferably 8 to 10 ℃.
Preferably, the humidity of the second curing treatment is 40% -60%, for example, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58% or 60%, etc., but not limited to the recited values, other non-recited values in the range of values are equally applicable, and preferably 45% -55%.
Preferably, the time of the second curing treatment is 2-28d, for example, 2d, 5d, 7d, 10d, 12d, 14d, 16d, 18d, 20d, 22d, 24d, 26d or 28d, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 2-6d.
In the invention, the second curing treatment is carried out until the specified age, and the second curing time is selected according to the test time.
According to the invention, two-stage curing treatment is adopted, so that the hydration time of the anhydrous phosphogypsum can be further shortened, the anhydrous phosphogypsum can be better excited, and the hydration rate of the phosphogypsum is improved; and meanwhile, the strength of the cementing material can be increased through the interaction between curing treatments with gradually reduced temperature.
As a preferable technical scheme of the invention, phosphogypsum is crushed before calcination.
Preferably, the particle size of the particles is not more than 2mm, for example, 0.5mm, 0.7mm, 1mm, 1.2mm, 1.5mm or 1.8mm, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) Crushing phosphogypsum to a particle size not larger than 2mm, calcining at 800-950 ℃ and preserving heat for 3-5h;
(2) Mixing the activator and calcined phosphogypsum in the step (1) according to the mass ratio of (0.002-0.03): 1, and grinding for more than 10min until the specific surface area is not less than 500m 2 ·kg -1 ；
(3) Aging the phosphogypsum ground in the step (2) for 4-8d at 20-30 ℃ to obtain a phosphorus-based II type anhydrous gypsum cementing material;
(4) And (3) forming the phosphorus-based II-type anhydrous gypsum cementing material, performing first curing treatment for 1-3d at 15-30 ℃ and humidity of 30% -80%, and performing second curing treatment for 2-28d at 8-15 ℃ and humidity of 40% -60% excluding 15 ℃.
In a second aspect, the invention provides a phosphorus-based type II anhydrite cementing material, which is prepared by the activation method in the first aspect.
As a preferable technical scheme of the invention, the flexural strength of the phosphorus-based II-type anhydrous gypsum cementing material is 2-13MPa, for example, 2MPa, 4MPa, 6MPa, 8MPa, 10MPa, 12MPa or 13MPa and the like can be adopted, but the phosphorus-based II-type anhydrous gypsum cementing material is not limited to the listed numerical values, and other non-listed numerical values in the numerical range are applicable.
Preferably, the compressive strength of the phosphorus-based type II anhydrous gypsum cementing material is 5-40MPa, for example, 5MPa, 10MPa, 15MPa, 20MPa, 25MPa, 30MPa, 35MPa or 40MPa, etc., but the compressive strength is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the hydration rate of the phosphorus-based type II anhydrite cementing material is more than or equal to 80%, for example, 80%, 82%, 84%, 86%, 88%, 90%, 92% or 95%, etc., but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the following beneficial effects:
according to the activation method provided by the invention, the phosphogypsum is subjected to calcination, grinding, aging and maintenance treatment in sequence to obtain the phosphorus-based II-type anhydrous gypsum cementing material with uniform particle size, high hydration rate and high strength; the hydration time of the anhydrous phosphogypsum can be further shortened through two-stage curing treatment of reducing the temperature section by section, the anhydrous phosphogypsum is better excited, the hydration rate is improved, and the strength of the cementing material can be increased.
Drawings
FIG. 1 is an XRD pattern of phosphogypsum raw material used in example 1 of the present invention;
FIG. 2 is an XRD pattern of the phosphorus-based type II anhydrite prepared in example 1 of the present invention;
FIG. 3 is a graph (200X) showing the crystal morphology of phosphogypsum feedstock used in example 1 of the present invention;
FIG. 4 is a graph (200X) showing the crystal morphology of the phosphorus-based type II anhydrite prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides an activation method of a phosphorus-based II-type anhydrous gypsum cementing material, which comprises the following steps:
(1) Crushing phosphogypsum to a particle size not larger than 2mm, calcining at 900 ℃ and preserving heat for 3h;
(2) Mixing potassium oxalate and phosphogypsum calcined in the step (1) according to the mass ratio of 0.02:1, and grinding for 20minTo a specific surface area of not less than 500m 2 ·kg -1 ；
(3) Aging the phosphogypsum ground in the step (2) for 5 days at 25 ℃ to obtain a phosphorus-based II-type anhydrous gypsum cementing material;
(4) And (3) after the phosphorus-based II-type anhydrous gypsum cementing material is molded, performing first curing treatment for 1d at 20 ℃ and humidity of 60%, and performing second curing treatment to a specified age at 10 ℃ and humidity of 50%.
As can be seen from FIGS. 1-4, the phosphorus-based type II anhydrite prepared in this example has a uniform particle size.
Example 2
The embodiment provides an activation method of a phosphorus-based II-type anhydrous gypsum cementing material, which comprises the following steps:
(1) Crushing phosphogypsum to a particle size not larger than 2mm, calcining at 800 ℃ and preserving heat for 4.5h;
(2) Mixing the calcium sulfate dihydrate and the phosphogypsum calcined in the step (1) according to the mass ratio of 0.002:1, and grinding for 20min until the specific surface area is not less than 500m 2 ·kg -1 ；
(3) Aging the phosphogypsum ground in the step (2) for 8 days at 20 ℃ to obtain a phosphorus-based II-type anhydrous gypsum cementing material;
(4) And (3) after the phosphorus-based II-type anhydrous gypsum cementing material is molded, performing first curing treatment for 2d at 24 ℃ and humidity of 40%, and performing second curing treatment to a specified age at 12 ℃ and humidity of 40%.
Example 3
The embodiment provides an activation method of a phosphorus-based II-type anhydrous gypsum cementing material, which comprises the following steps:
(1) Crushing phosphogypsum to a particle size not larger than 2mm, calcining at 950 ℃ and preserving heat for 3h;
(2) Mixing potassium sulfate, aluminum sulfate and phosphogypsum calcined in the step (1) according to the mass ratio of 0.02:0.01:1, and grinding for 30min until the specific surface area is not less than 500m 2 ·kg -1 ；
(3) Aging the phosphogypsum ground in the step (2) for 4d at 30 ℃ to obtain a phosphorus-based II-type anhydrous gypsum cementing material;
(4) And (3) after the phosphorus-based II-type anhydrous gypsum cementing material is molded, performing first curing treatment for 2d at 15 ℃ and humidity of 55%, and performing second curing treatment to a specified age at 8 ℃ and humidity of 45%.
Example 4
This example differs from example 1 only in that the calcination temperature in step (1) is 600 ℃; the remainder was the same as in example 1.
Example 5
This example differs from example 1 only in that the calcination temperature in step (1) is 1050 ℃; the remainder was the same as in example 1.
Example 6
This example differs from example 1 only in that the mass ratio of potassium oxalate to calcined phosphogypsum in step (2) is 0.001:1; the remainder was the same as in example 1.
Example 7
This example differs from example 1 only in that the mass ratio of potassium oxalate to calcined phosphogypsum in step (2) is 0.04:1; the remainder was the same as in example 1.
Example 8
This example differs from example 1 only in that potassium oxalate was not added except for step (2); the remainder was the same as in example 1.
Example 9
The difference between this example and example 1 is that the temperature of the first curing treatment in step (4) is 42 ℃; the remainder was the same as in example 1.
Example 10
The difference between this example and example 1 is that the temperature of the first curing treatment in step (4) is 36 ℃; the remainder was the same as in example 1.
Example 11
The difference between this example and example 1 is that the temperature of the second curing treatment in step (4) is 2 ℃; the remainder was the same as in example 1.
Example 12
The difference between this example and example 1 is that the temperature of the first curing treatment in step (4) is 10℃and the temperature of the second curing treatment is 20 ℃; the remainder was the same as in example 1.
Comparative example 1
The comparative example differs from example 1 only in that the ground phosphogypsum was not aged; the remainder was the same as in example 1.
Comparative example 2
The comparative example differs from example 1 only in that the curing treatment is carried out to a prescribed age at 20℃and 60% humidity in step (4); the remainder was the same as in example 1.
Comparative example 3
The comparative example differs from example 1 only in that the curing treatment is carried out to a prescribed age at 10℃and 60% humidity in step (4); the remainder was the same as in example 1.
The phosphorus-based type II anhydrous gypsum cementing materials prepared in the examples and the comparative examples are subjected to crystal water measurement according to GB/T17669.2-1999 'determination of the crystal water content of building gypsum', wherein the hydration rate is the percentage of the phosphorus-based type II anhydrous gypsum hydrated into dihydrate gypsum to the total amount of the original phosphorus-based type II anhydrous gypsum; the strength was measured according to GB/T28627-2012 plaster, and the hydration rate and the strength measurement result are shown in Table 1 and Table 2, respectively.
TABLE 1
TABLE 2
From tables 1 and 2, the following points can be found:
(1) The activation method provided by the embodiments 1-3 of the invention has the advantages that the obtained phosphorus-based II-type anhydrous gypsum cementing material has high hydration rate and high compressive and flexural strength, and is beneficial to the development and use of products;
(2) As is clear from comparison of examples 1 and examples 4 to 5, when the calcination temperature of phosphogypsum is too low, the residual part of harmful impurities, such as soluble phosphorus, fluorine, organic matters and eutectic phosphorus, cause slow setting and hardening of the gypsum, resulting in reduced hydration rate and strength; when the calcining temperature of phosphogypsum is too high, although the hydration rate and strength are not changed greatly, the energy consumption is increased, the gypsum structure is more compact, and the setting and hardening of the gypsum are slowed down;
(3) As is evident from comparison of examples 1 and examples 6 to 8, when the mass ratio of the activator to calcined phosphogypsum is too low, the reaction is insufficient due to the small contact area between the activator and anhydrite, resulting in insignificant excitation effect; when the mass ratio of the activator to calcined phosphogypsum is too high, the excitation effect is not provided; if no activator is added, the hydration rate and strength of the anhydrous gypsum are reduced due to slow dissolution and low hydration activity of the anhydrous gypsum;
(4) As can be seen from comparison of examples 1 and examples 9-12, when the first curing treatment temperature is too high, the anhydrous gypsum is firstly dissolved and then hydrated to be an exothermic reaction, and the hydration process is reduced due to slow dissolution of gypsum caused by too high temperature; when the second curing treatment temperature is too low, the energy consumption is increased, and the test block can be frosted and cracked after 28d curing;
(5) As is clear from the comparison of example 1 and comparative example 1, when no aging treatment is performed, gypsum performance is unstable due to large fluctuation in performance of the non-aged anhydrous gypsum;
(6) As is clear from comparison of example 1 with comparative examples 2 to 3, when curing treatment is carried out in only one stage, anhydrous phosphogypsum cannot be excited well, resulting in a decrease in the hydration rate of phosphogypsum.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (21)
1. A method for activating a phosphorus-based type ii anhydrite cementitious material, the method comprising: calcining phosphogypsum, grinding, aging and curing in sequence;
mixing an activating agent with calcined phosphogypsum before grinding; the activator comprises any one or a combination of at least two of potassium oxalate, aluminum potassium sulfate, calcium sulfate dihydrate, alpha-calcium sulfate hemihydrate, beta-calcium sulfate hemihydrate or aluminum sulfate;
the curing treatment comprises a first curing treatment and a second curing treatment;
the temperature of the first curing treatment is 15-30 ℃; the humidity of the first curing treatment is 30% -80%; the time of the first maintenance treatment is 1-3d;
the temperature of the second curing treatment is 8-15 ℃ and does not comprise 15 ℃; the humidity of the second curing treatment is 40% -60%; the time of the second curing treatment is 2-28d.
2. The activation process according to claim 1, characterized in that the calcination temperature is 800-950 ℃.
3. The activation process according to claim 1, characterized in that the incubation time for the calcination is 3-5h.
4. The method according to claim 1, wherein the mass ratio of the activator to calcined phosphogypsum is (0.002-0.03): 1.
5. The activation method according to claim 1, characterized in that the milling time is greater than 10min.
6. The activation method according to claim 1, wherein the powder is ground to a specific surface area of not less than 500m 2 ·kg -1 。
7. The activation process according to claim 1, characterized in that the aging temperature is 20-30 ℃.
8. The activation process according to claim 1, characterized in that the aging time is 4-8d.
9. The activation method of claim 1, wherein the aging further comprises shaping.
10. The activation method according to claim 1, wherein the temperature of the first curing treatment is 20-25 ℃.
11. The activation method according to claim 1, characterized in that the humidity of the first curing treatment is 55% -65%.
12. The activation method according to claim 1, wherein the temperature of the second curing treatment is 8-10 ℃.
13. The activation method according to claim 1, wherein the humidity of the second curing treatment is 45% -55%.
14. The activation method according to claim 1, wherein the time of the second curing treatment is 2-6d.
15. The activation method according to claim 1, characterized in that phosphogypsum is crushed before the calcination.
16. The activation method as claimed in claim 15, wherein the crushing is to a particle size of not more than 2mm.
17. The activation method according to claim 1, characterized in that it comprises the following steps:
(1) Crushing phosphogypsum to a particle size not larger than 2mm, calcining at 800-950 ℃ and preserving heat for 3-5h;
(2) Mixing the activator and calcined phosphogypsum in the step (1) according to the mass ratio of (0.002-0.03): 1, and grinding for more than 10min until the specific surface area is not less than 500m 2 ·kg -1 ；
The activator comprises any one or a combination of at least two of potassium oxalate, aluminum potassium sulfate, calcium sulfate dihydrate, alpha-calcium sulfate hemihydrate, beta-calcium sulfate hemihydrate or aluminum sulfate;
(3) Aging the phosphogypsum ground in the step (2) for 4-8d at 20-30 ℃ to obtain a phosphorus-based II type anhydrous gypsum cementing material;
(4) And (3) forming the phosphorus-based II-type anhydrous gypsum cementing material, performing first curing treatment for 1-3d at 15-30 ℃ and humidity of 30% -80%, and performing second curing treatment for 2-28d at 8-15 ℃ and humidity of 40% -60% excluding 15 ℃.
18. A phosphorus-based type ii anhydrite cementitious material prepared by the activation process of any one of claims 1-17.
19. The phosphorus-based type ii anhydrite cementitious material of claim 18, wherein the flexural strength of the phosphorus-based type ii anhydrite cementitious material is from 2MPa to 13MPa.
20. The phosphorus-based type ii anhydrite cementitious material of claim 18, wherein the compressive strength of the phosphorus-based type ii anhydrite cementitious material is from 5MPa to 40MPa.
21. The phosphorus-based type ii anhydrite cementitious material of claim 18, wherein the hydration rate of the phosphorus-based type ii anhydrite cementitious material is greater than or equal to 80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211139758.4A CN115466065B (en) | 2022-09-19 | 2022-09-19 | Phosphorus-based II type anhydrous gypsum cementing material and activation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211139758.4A CN115466065B (en) | 2022-09-19 | 2022-09-19 | Phosphorus-based II type anhydrous gypsum cementing material and activation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115466065A CN115466065A (en) | 2022-12-13 |
| CN115466065B true CN115466065B (en) | 2023-08-29 |
Family
ID=84333350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211139758.4A Active CN115466065B (en) | 2022-09-19 | 2022-09-19 | Phosphorus-based II type anhydrous gypsum cementing material and activation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115466065B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102278A (en) * | 2023-02-24 | 2023-05-12 | 安徽中铁工程材料科技有限公司 | Granite-based mineral admixture and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016134551A1 (en) * | 2015-02-26 | 2016-09-01 | 华智节能(香港)有限公司 | Inorganic cement material and manufacturing method thereof |
| CN106365578A (en) * | 2016-08-31 | 2017-02-01 | 韩涛 | Method for preparing building material by using phosphogypsum |
| CN110128045A (en) * | 2019-04-30 | 2019-08-16 | 江苏一夫科技股份有限公司 | II type anhydrous gypsum fast hydration exciting agent of one kind and fast hydration method |
| CN110803878A (en) * | 2019-11-25 | 2020-02-18 | 江苏一夫科技股份有限公司 | Device and method for producing II type anhydrous gypsum by using phosphogypsum |
| CN113735471A (en) * | 2021-10-12 | 2021-12-03 | 重庆杰博思石膏有限公司 | Phosphorus II type anhydrous gypsum, cementing material and preparation method thereof |
-
2022
- 2022-09-19 CN CN202211139758.4A patent/CN115466065B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016134551A1 (en) * | 2015-02-26 | 2016-09-01 | 华智节能(香港)有限公司 | Inorganic cement material and manufacturing method thereof |
| CN106365578A (en) * | 2016-08-31 | 2017-02-01 | 韩涛 | Method for preparing building material by using phosphogypsum |
| CN110128045A (en) * | 2019-04-30 | 2019-08-16 | 江苏一夫科技股份有限公司 | II type anhydrous gypsum fast hydration exciting agent of one kind and fast hydration method |
| CN110803878A (en) * | 2019-11-25 | 2020-02-18 | 江苏一夫科技股份有限公司 | Device and method for producing II type anhydrous gypsum by using phosphogypsum |
| CN113735471A (en) * | 2021-10-12 | 2021-12-03 | 重庆杰博思石膏有限公司 | Phosphorus II type anhydrous gypsum, cementing material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈燕等.《石膏建筑材料 第2版》.中国建材工业出版社,2012,第232页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115466065A (en) | 2022-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112723843B (en) | Preparation method of weak-base-excited nickel slag high-strength concrete | |
| CN108821671B (en) | Full-industrial solid waste high-strength ready-to-use foamed concrete material and preparation method thereof | |
| CN110104984B (en) | Phosphogypsum slag cement early strength coagulant based on modified composite dehydration phase | |
| CN110818297B (en) | Method for preparing alpha-type high-strength gypsum by microwave irradiation phosphogypsum crystal transformation under normal pressure | |
| CN114380518B (en) | Bayer process red mud-phosphogypsum baking-free cementing material and preparation method thereof | |
| CN108996939B (en) | Prehydrated mineral powder nanocrystal core early strength agent for steam-cured concrete and preparation method thereof | |
| CN115466065B (en) | Phosphorus-based II type anhydrous gypsum cementing material and activation method thereof | |
| CN112608047B (en) | Modified sulphoaluminate cement and preparation method and application thereof | |
| CN114988791B (en) | Flue grouting material doped with sulfur-rich lithium slag, and preparation method and application thereof | |
| CN112608048A (en) | Metal tailing cementing material and preparation method and application thereof | |
| CN112110661A (en) | Preparation method of phosphogypsum slag-based cement | |
| CN113880540B (en) | Method for preparing gypsum self-leveling material by using semi-dry method to oxidize desulfurized ash | |
| CN111978099A (en) | Aerated concrete and preparation method thereof | |
| CN115353361A (en) | Composite cementing material and preparation method and application thereof | |
| CN114605121A (en) | Tungsten tailing autoclaved aerated concrete and preparation method thereof | |
| CN114956642B (en) | Composite expanding agent based on regenerated micro powder and preparation method thereof | |
| CN114920475B (en) | Titanium gypsum mineral powder-based composite cementing material | |
| CN113929425B (en) | Building block and preparation method thereof | |
| CN114988835A (en) | Carbide slag-based high-solid-carbon-content non-autoclaved aerated concrete and preparation method thereof | |
| CN114890809A (en) | Steel slag-based high-carbon-fixation-quantity non-autoclaved aerated concrete and preparation method thereof | |
| CN113735545A (en) | Concrete product containing phosphogypsum fly ash cement and preparation method thereof | |
| CN1493541A (en) | Activated waste slay composite powder and its application in cement, concrete and bake free brick | |
| CN115772024B (en) | High-doping-amount lithium slag quick-setting and quick-hardening wallboard and manufacturing method thereof | |
| CN115093189B (en) | Gypsum-based self-leveling mortar and preparation method thereof | |
| CN111995282B (en) | Anti-cracking agent, preparation method thereof and preparation method of ultra-high performance concrete prefabricated part |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |