CN113582642B - Phosphogypsum additive for 3D printing and application thereof - Google Patents

Phosphogypsum additive for 3D printing and application thereof Download PDF

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CN113582642B
CN113582642B CN202110575535.1A CN202110575535A CN113582642B CN 113582642 B CN113582642 B CN 113582642B CN 202110575535 A CN202110575535 A CN 202110575535A CN 113582642 B CN113582642 B CN 113582642B
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phosphogypsum
additive
temperature
printing
magnesia
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CN113582642A (en
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邢锋
寇世聪
崔棚
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Shenzhen University
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Shenzhen University
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    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/10—Lime cements or magnesium oxide cements
    • C04B28/105—Magnesium oxide or magnesium carbonate cements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/02—Selection of the hardening environment
    • C04B40/0231—Carbon dioxide hardening
    • 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
    • C04B9/00—Magnesium cements or similar cements
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses phosphogypsum additive for 3D printing and application thereof, wherein the phosphogypsum additive comprises the following raw materials in parts by weight: the invention uses phosphogypsum as a cementing material for 3D printing, further improves the technical level and efficiency of the resource utilization of phosphogypsum, simultaneously expands the utilization range of phosphogypsum, and solves the technical problems of complex processes, product dry cracking, high energy consumption, unstable performance and the like, such as cleaning, neutralization, drying, calcination, grinding and the like, required by the phosphogypsum to prepare the cementing material through the use of the magnesia and the dry ice, and has the advantages of simple production process, effective reduction of the production cost.

Description

Phosphogypsum additive for 3D printing and application thereof
Technical Field
The invention belongs to the field of building materials, and particularly relates to phosphogypsum additive for 3D printing and application thereof.
Background
With the development of agriculture in China, the demand for phosphate fertilizer is greatly increased, and the yield of the phosphate fertilizer in 2017 in China is 147% higher than that in 2000. Phosphoric acid is the most main chemical raw material for producing phosphate fertilizer, and 90% of the phosphoric acid in China is prepared by a wet process; every 1t of phosphoric acid produced by the process, 4.5-5 t of phosphogypsum is produced. Phosphogypsum is gray black and gray white solid waste particles with the diameter of 5-50 mu m, contains 20-25% of crystal water, mainly contains calcium sulfate dihydrate, and also contains incompletely decomposed phosphorite, residual phosphoric acid, fluoride, acid insoluble substances, organic matters and the like. A large amount of phosphogypsum is randomly discharged and piled up, so that land resource waste is caused, and underground water resource is seriously polluted. 2016. The annual issues of action plan for soil pollution control, clearly indicate the increase of treatment of industrial wastes such as phosphogypsum.
Phosphogypsum belongs to a strain softening material, the water permeability in a horizontal layer is poorer than that between layers, the solubility in water is extremely small, and the solubility is reduced along with the rise of temperature. Therefore, phosphogypsum has lower gelation property than natural gypsum, and has poorer viscosity and fluidity than natural gypsum, longer setting time and certain corrosiveness. Therefore, phosphogypsum is difficult to be directly used as building gypsum for recycling.
At present, one of the comprehensive utilization ways of phosphogypsum is to prepare a cementing material (such as patent CN101265068A, CN101138863A, CN102850081B, CN 110436869A) by using phosphogypsum, and the cementing material is used for producing building materials such as gypsum boards, plasters, cement retarders and the like. However, the following problems exist in the preparation of the cementing material by phosphogypsum: (1) Phosphogypsum is required to be cleaned, neutralized, dried, calcined and ground, and is required to be placed for 3-5 days, so that the production process is complex and the energy consumption is high; (2) phosphogypsum gel products are easy to crack; (3) Although 3D printed phosphogypsum products with complex shapes and no template support can be produced, a maintenance system matched with the phosphogypsum products is lacking.
Disclosure of Invention
The invention provides phosphogypsum additive for 3D printing and application thereof, and aims to at least solve the problems that phosphogypsum cannot be directly utilized in the prior art, and the preparation of a cementing material has complex production process, easy cracking of products, high energy consumption, lack of a method suitable for 3D printing additive maintenance of phosphogypsum and the like.
The invention discloses phosphogypsum additive for 3D printing, which comprises the following raw materials in parts by weight: 0 ≡100 parts of phosphogypsum, 100 parts of magnesia, 0.100 parts of phosphate, 0.4 part of magnesium salt, 0.5.5 parts of additive, 5.20 parts of dry ice, and the mass ratio of water to the total mass of phosphogypsum and magnesia is 1:1 ≡1:6.
Further, the magnesia is one or two of light-burned magnesia and heavy-burned magnesia, the average grain diameter of the magnesia is 65nm 190nm, and the specific surface area of the magnesia is 32m 2 /g 92m 2 /g。
Further, the magnesium oxide content in the light burned magnesium oxide is 88.6% 97.2%, and the active magnesium oxide content in the light burned magnesium oxide is 64.3% 76.0%.
The content of magnesium oxide in the re-burned magnesium oxide is 83.2 percent 98.0 percent, and the content of active magnesium oxide in the re-burned magnesium oxide is 8.3 percent 41.8 percent.
Further, the phosphate is one or two of potassium dihydrogen phosphate and ammonium dihydrogen phosphate;
the content of the phosphate is 98%;
the fineness of the phosphate is 45 μm and 90 μm.
Further, the magnesium salt is one or two of magnesium sulfate heptahydrate and magnesium chloride hexahydrate; the fineness of the magnesium salt is 48 mu m 75 mu m;
the content of the magnesium sulfate heptahydrate is 98%, and the content of the magnesium chloride hexahydrate is 44% to 46%.
Further, the additive is one or a combination of more than one of anhydrous citric acid, citric acid monohydrate, citric acid dihydrate, anhydrous sodium carbonate, anhydrous sodium citrate, sodium citrate dihydrate, borax, boric acid, oxalic acid and sodium oxalate.
Further, the dry ice is in the shape of rice grains, and the length of the dry ice is 5mm 15mm.
A method of preparing phosphogypsum additive for 3D printing, the method comprising the steps of:
s101, mixing phosphogypsum, phosphate, magnesium salt, additive and water uniformly;
s102, adding magnesia into the mixture of S101 and uniformly stirring;
and S103, adding dry ice into the mixture of the step S102, and stirring until the dry ice volatilizes to obtain phosphogypsum additive slurry for 3D printing.
An application for 3D printing phosphogypsum additive, the application comprising:
s201 printing: adding dry ice again before extruding the phosphogypsum additive by a 3D printing spray head, uniformly stirring, and printing;
s202, maintenance: s201 printing and additive curing comprises the following steps: the method comprises the steps of temperature control carbonization maintenance, humidity control carbonization maintenance and storage carbonization maintenance, wherein the humidity control carbonization maintenance is dry ice maintenance, and the temperature control carbonization maintenance and storage carbonization maintenance is carbon dioxide gas maintenance;
the carbon dioxide concentration is 50% during the temperature control carbonization maintenance, and the carbon dioxide gas pressure is 50 60kPa; the temperature is lower than 20 ℃ below zero;
the relative humidity of the humidity-controlled carbonization maintenance is 70 percent;
the carbon dioxide concentration during storage and maintenance is 50 percent, the temperature is 10 ℃ and the relative humidity is 80 percent.
Further, the specific steps of the curing in S202 are as follows:
s2021, preparing a reference sample, and embedding a temperature sensor in phosphogypsum additive before final setting; cutting the phosphogypsum additive, wherein a reference sample with a temperature sensor is a sample without the temperature sensor;
s2022, the temperature sensor of the reference sample is connected with a temperature controller, and the temperature controller adjusts the temperature of the sample according to the temperature of the reference sample, so as to perform temperature control carbonization maintenance;
s2023, when the surface temperature of the reference sample and the sample is reduced to the room temperature again, performing humidity-controlled carbonization maintenance on the reference sample and the sample.
S2024, storing, carbonizing and curing the reference sample and the sample cured by the step S2023 to obtain a finished product;
the carbon dioxide concentration of the temperature-controlled carbonization maintenance is 60%, the carbon dioxide gas pressure is 60kPa, and the temperature is minus 30 ℃; the relative humidity of the humidity-controlled carbonization maintenance is 80%; the carbon dioxide concentration of the storage carbonization maintenance is 88%, the temperature is 25 ℃, and the relative humidity is 92%.
According to the invention, phosphogypsum is used as a cementing material for 3D printing, the utilization range of phosphogypsum is enlarged, the resource utilization technical level and efficiency of phosphogypsum are further improved, and the technical problems of complex process, high energy consumption, inconvenient operation, easy cracking of products, unstable performance and the like of the phosphogypsum for preparing the cementing material are solved by using magnesia and dry ice, so that the phosphogypsum has the advantages of simple production process and effective reduction of production cost.
Drawings
FIG. 1 is a flow chart of phosphogypsum 3D printing and additive curing method;
FIG. 2 is a schematic diagram of a phosphogypsum 3D printer;
FIG. 3 is a schematic diagram of a special spray head for phosphogypsum 3D printing;
FIG. 4 is a schematic diagram of an phosphogypsum 3D printing additive identifier;
FIG. 5 is a schematic diagram of an phosphogypsum 3D printing additive temperature control carbonization chamber;
FIG. 6 is a schematic diagram of a phosphogypsum 3D printing additive controlled humidity carbonization chamber;
fig. 7 is a schematic diagram of phosphogypsum 3D printing additive storage curing room.
1, a spray head; a 2,3d printer holder; 3, a motor; 4, a motor control line; 5, a stirrer; 6, a hopper; 7, a nozzle; 8, a dry ice hopper; 9, a dry ice controller; 10,3d print drive control system; 11, supporting the rod; 12, spiral slices; 13, stirring the leaves; 14, a filter screen; 15, an exhaust groove; 16, dry ice; 17, a conveying device; 18, an identifier; 19, a temperature-controlled carbonization chamber; 20, a humidity-controlled carbonization chamber; 21, a storage maintenance room; 22, a print transfer device; 23, curing the conveying device; 24, a reference sample delivery device; 25, an additive transfer device; an image recognition device 26; 27, infrared volume measuring instrument; 28, a mass measurement device; 29, classifying and screening machine; 30, controlling a display; 31, a reference sample placement stage; 32, sample stage; 33, a temperature controller; 34, a cooling device; 35, a heating device; 36, a carbon dioxide gas bottle; 37, a carbon dioxide gas regulator; 38, a temperature controlled carbonization display; 39, a temperature sensor; 40, a dry ice storage room; 41, a dry ice regulator; 42, sample chamber; 43, a carbon dioxide gas pressure sensor; 44, a pressure relief valve; 45, a carbon dioxide gas concentration sensor; a relative humidity sensor 46; 47, relative humidity control; 48, a humidity controlled carbonization display; 49, sample storage rack; 50, a temperature and humidity regulating instrument; 51, storing and curing the display.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order.
Examples
The embodiment test method comprises the following steps: compression strength was measured for 3 days and 28 days at a loading rate of 2.4kN/s, and 3 cubic test blocks of 40mm were measured for each age, and the arithmetic average was taken as the compression strength value.
Example 1,3d printed phosphogypsum additive, the phosphogypsum additive ratio, test results are shown in table 1.
Table 13 d printed phosphogypsum additive ratios, test table 1
Figure BDA0003084171000000041
Wherein the light burned magnesia is an industrial grade raw material, the magnesia content is 93.8%, the active magnesia content is 66.2%, the average grain diameter is 190nm, and the specific surface area is 32m 2 And/g. The dry ice is in the shape of rice grains and has the length of 5mm.
When the preparation method is used, firstly, the weighed light-burned magnesium oxide is added into the weighed water and stirred uniformly; adding the weighed dry ice, and stirring until the dry ice is completely volatilized; and finally pouring the stirred slurry into a hopper of a 3D printer for 3D printing.
Example 2,3d printed phosphogypsum additive, the phosphogypsum additive ratio, test results are shown in table 2.
Table 23 d printed phosphogypsum additive ratios, test table 2
Figure BDA0003084171000000042
Wherein the light burned magnesia is an industrial grade raw material, the magnesia content is 93.8%, the active magnesia content is 66.2%, the average grain diameter is 190nm, and the specific surface area is 32m 2 And/g. The dry ice is in the shape of rice grains and has the length of 5mm.
Example 3,3d printed phosphogypsum additive, the phosphogypsum additive ratio, test results are shown in table 3.
Table 3d printed phosphogypsum additive ratios, test table 3
Figure BDA0003084171000000043
Figure BDA0003084171000000051
Wherein the light burned magnesia is an industrial grade raw material, the magnesia content is 97.2%, the active magnesia content is 76.0%, the average grain diameter is 118nm, and the specific surface area is 51m 2 /g; the anhydrous citric acid is chemically analytically pure; the dry ice is in the shape of rice grains and has the length of 15mm.
Example 4,3d printed phosphogypsum additive, the phosphogypsum additive ratio, test results are shown in table 4.
Table 43 d printed phosphogypsum additive ratios, test table 4
Figure BDA0003084171000000052
Wherein the light burned magnesia is an industrial grade raw material, the magnesia content is 88.6 percent, the active magnesia content is 64.3 percent, the average grain diameter is 135nm, and the specific surface area is 44m 2 /g; the citric acid monohydrate is chemically analytically pure; the dry ice is in the shape of rice grains and has the length of 10mm.
Example 5,3d printed phosphogypsum additive, the phosphogypsum additive ratio, test results are shown in table 5.
Table 5 3d printed phosphogypsum additive ratios, test table 5
Figure BDA0003084171000000053
Wherein the light burningThe magnesium oxide is industrial grade raw material, the magnesium oxide content is 93.8%, the active magnesium oxide content is 66.2%, the average particle diameter is 190nm, and the specific surface area is 32m 2 /g; the anhydrous sodium carbonate is chemically analytically pure; the dry ice is in the shape of rice grains and has the length of 10mm.
Example 6,3d printed phosphogypsum additive, the phosphogypsum additive ratio, test results are shown in table 6.
Table 63 d printed phosphogypsum additive ratios, test table 6
Figure BDA0003084171000000061
Wherein the light burned magnesia is an industrial grade raw material, the magnesia content is 95.3 percent, the active magnesia content is 74.7 percent, the average grain diameter is 65nm, and the specific surface area is 92m 2 And/g. The sodium citrate dihydrate is chemically analytically pure. The dry ice is in the shape of rice grains and has the length of 10mm.
Example 7,3d printed phosphogypsum additive, the phosphogypsum additive ratio, test results are shown in table 7.
Table 7 3d printed phosphogypsum additive ratios, test table 7
Figure BDA0003084171000000062
Wherein the re-burned magnesia is an industrial grade raw material, the magnesia content is 83.2 percent, the active magnesia content is 41.8 percent, the average grain diameter is 65nm, and the specific surface area is 32m 2 /g; the monopotassium phosphate is an industrial grade raw material, the content is 98%, and the fineness is 45 mu m; the magnesium chloride hexahydrate is an industrial grade raw material, the content is 44%, and the fineness is 48 mu m; the borax is chemically pure; the dry ice is in the shape of rice grains and has the length of 5mm.
The method for preparing the additive according to embodiments 2-7 comprises the steps of:
s101, mixing phosphogypsum, phosphate, magnesium salt, additive and water according to a certain proportion and stirring uniformly;
s102, adding magnesia into the mixture of S101 and uniformly stirring;
and S103, adding dry ice into the mixture of the step S102, and stirring until the dry ice volatilizes to obtain phosphogypsum additive slurry for 3D printing.
The phosphogypsum additive application of examples 1-8, as shown in figure 1, comprises:
s201 printing: adding dry ice again before extruding the phosphogypsum additive by a 3D printing spray head, uniformly stirring, and printing;
s202, maintenance: s201 printing and additive curing comprises the following steps: and (3) temperature-control carbonization maintenance, humidity-control carbonization maintenance and storage carbonization maintenance.
The special nozzle used for printing in the embodiment S201 includes: a motor, a hopper and a dry ice hopper; the dry ice hopper is connected with the hopper, a stirrer is arranged in the hopper, the bottom of the hopper is connected with the nozzle, and the stirrer is connected with the motor.
A dry ice controller is arranged between the dry ice hopper and the hopper; the dry ice controller is arranged at the bottom of the dry ice hopper; the upper part of the hopper is provided with a dry ice feeding hole, and the dry ice hopper is used for conveying dry ice for the hopper through the dry ice feeding hole.
The stirrer comprises a supporting rod and a spiral sheet, wherein the supporting rod is fixed at the bottom of the hopper, and the spiral sheet is spirally fixed on the supporting rod; the spiral sheet is provided with stirring blades, and at least one stirring blade is arranged on the spiral sheet.
When stirring leaf is a plurality of, be close to the stirring leaf terminal upward sloping of motor setting, stirring leaf is close to the nozzle setting, stirring leaf terminal downward sloping.
The stirring blade is in the shape of a folded sheet protruding outwards.
The middle lower part of the hopper is provided with an exhaust device which comprises an exhaust hole and an exhaust groove, and the exhaust groove is arranged at the lower part of the exhaust hole. The exhaust hole is a filter screen, and the exhaust groove ring hopper is arranged.
The dry ice 16 in the dry ice hopper is in a grain shape, and the length of the dry ice is 5mm 15mm.
The special spray head can realize that the slurry is added with dry ice again and uniformly stirred before being extruded by the printing spray head.
As shown in fig. 2 and 3, the phosphogypsum 3D printing special nozzle 1 is positioned on the 3D printer bracket 2, and the phosphogypsum 3D printing special nozzle comprises: the dry ice printing device comprises a motor 3, a motor control line 4, a stirrer 5, a hopper 6, a nozzle 7, a dry ice hopper 8 and a dry ice controller 9, wherein the motor 3 is connected with a 3D printing driving control system 10 through the motor control line 4, the stirrer 5 is positioned in the middle of the hopper 6, the hopper 6 is connected with the nozzle 7 through threads, the dry ice hopper 8 is connected with the dry ice controller 9, the dry ice controller 9 is connected with the hopper 6, and the dry ice controller 9 is connected with the motor control line 4; the motor 3 is fixed on the 3D printer support 2, the stirrer 5 is detachably connected with the motor 3 through a buckle, and the hopper 6 is detachably connected with the 3D printer support 2 through a buckle.
The stirrer 5 comprises a supporting rod 11, a spiral sheet 12 and a stirring blade 13, wherein the supporting rod 11 is connected with the motor 3, the spiral sheet 12 spirals downwards on the supporting rod 11, the stirring blade 13 is connected with the spiral sheet 12, the stirring blade 13 is in a folded sheet shape protruding outwards, one side of the stirring blade 13 protruding is 10mm away from the inner wall of the hopper, the stirring blade 13 is close to one end of the motor, the stirring blade 13 is upwards, the stirring blade 13 is close to one end of the nozzle, and the stirring blade 13 is downwards.
The middle part of the hopper 6 is provided with an exhaust groove 15 with a filter screen 14, the diameter of the mesh of the filter screen 14 is 35-74 mu m, the width of the exhaust groove 15 is 10mm, and the height is 20mm.
The dry ice controller 9 may set the rate at which dry ice 16 is added to the hopper by the dry ice 16 through the 3D printing control system 10.
Curing of this embodiment S202, as shown in fig. 4-7, a special curing system for phosphogypsum additive, includes: a conveying device 17, an additive identifier 18, a temperature control carbonization chamber 19, a humidity control carbonization chamber 20 and a storage maintenance chamber 21;
the conveyor 17 includes a print conveyor 22 and a maintenance conveyor 23; the maintenance conveyor 23 includes: a reference sample transfer means 24, an additive transfer means 25; the printing conveyor 22, the 3D printer, and the additive identifier 18 are connected by a track; the maintenance conveying device 23 is connected with the temperature control carbonization chamber 19, the humidity control carbonization chamber 20 and the storage maintenance chamber 21 through rails.
The additive identifier 18 includes: an image recognition device 26, an infrared volume measuring device 27, a mass measuring device 28, a sorting screening machine 29 and a control display 30.
The temperature-controlled carbonization chamber 19 includes: the device comprises a reference sample placing table 31, a sample table 32, a temperature controller 33, a cooling device 34, a heating device 35, a carbon dioxide bottle 36, a carbon dioxide regulator 37 and a temperature control carbonization display 38, wherein the cooling device 34 and the heating device 35 are positioned at the periphery of the sample table; the temperature controller 33 is connected with the sample table 32 through a temperature sensor 39, the temperature sensor 39 is embedded in the reference sample, the temperature controller 33 is connected with the reference sample through the temperature sensor 39, and the temperature reducing device 34 and the temperature increasing device 35 are connected with the temperature controller 33.
The humidity-controlled carbonization chamber 20 comprises a dry ice storage chamber 40, a dry ice regulator 41, a sample chamber 42, a carbon dioxide gas pressure sensor 43, a pressure release valve 44, a carbon dioxide gas concentration sensor 45, a temperature sensor 39, a relative humidity sensor 46, a relative humidity regulator 47 and a humidity-controlled carbonization display 48; the sample chamber 42 and the dry ice storage chamber 40 are connected through a pipeline with a valve; the sample chamber 42 is connected with the dry ice regulator 41 through a carbon dioxide gas concentration sensor 45, a carbon dioxide gas pressure sensor 43, a pressure relief valve 44 and a temperature sensor 39; the sample chamber 42 is connected to a relative humidity control instrument 47 via a relative humidity sensor 46.
The storage maintenance room 21 comprises a sample storage rack 49, a carbon dioxide regulator 37, a temperature and humidity regulator 50 and a storage maintenance display 51, wherein the carbon dioxide regulator 37 is connected with a carbon dioxide bottle 36 and a carbon dioxide concentration sensor 45.
S2021, preparing a reference sample, embedding a temperature sensor 39 in phosphogypsum additive before final setting, cutting the phosphogypsum additive into cubic test blocks with the dimensions of 40mm multiplied by 40mm, wherein the test blocks with the temperature sensor 39 are the reference sample, and the others are the test samples; is transferred to the identifier 18 by the print transfer device 22.
The image recognition device 26 comprises a camera with a photographing function and an image comparison recognition system, wherein the camera photographs the phosphogypsum 3D printing additive and transmits the photograph to the image comparison recognition system, and the image comparison recognition system determines the phosphogypsum 3D printing additive and the reference sample according to the color and the appearance by comparing the photograph photographed by the camera with a pre-stored additive standard photograph and a pre-stored reference sample photograph in the image comparison recognition system and transmits a recognition result to the control display 30.
The infrared volume measuring instrument 27 measures the external volume of phosphogypsum 3D printed additive and transmits the measurement result to the control display 30; the quality measuring device 29 weighs the phosphogypsum 3D printing additive and transmits the weighing result to the control display 30; the control display 30 automatically calculates the density of the phosphogypsum 3D printing additive according to the measured results of the infrared volume measuring instrument 27 and the quality measuring device 29, and combines the phosphogypsum 3D printing additive and the reference sample identified in the phosphogypsum pattern identifying device to carry out consistency judgment, and when the results are inconsistent, a prompt is sent out to request manual judgment.
If the results are consistent, the identified reference sample and the identified sample are transmitted to a temperature control carbonization chamber through a maintenance transmission device; after the temperature of the surface of the phosphogypsum 3D printing additive is reduced to the room temperature, the phosphogypsum is conveyed into the humidity-controlled carbonization chamber from the temperature-controlled carbonization chamber by the curing conveying device, and after a certain curing period, the phosphogypsum is conveyed into the storage curing chamber by the curing conveying device for storage carbonization curing.
Wherein S2022 is carbonized and maintained by temperature control, dry ice is arranged around phosphogypsum 3D printing additive in the temperature control carbonization chamber, and the dry ice is in a rice grain shape or a rod shape, and the length of the dry ice is 10mm and 40mm. Enabling the carbon dioxide concentration of the phosphogypsum 3D printing additive sample chamber to be 60% and the carbon dioxide pressure to be 60kPa; the temperature was-30 ℃. According to the embodiment, the reference sample placed on the reference sample placing table and the samples in the sample table are 3D printing test blocks in the same batch, the temperature controller controls the temperature change in the sample chamber through the temperature change of the temperature sensor in the reference sample, so that the hydration temperature of the inner center of phosphogypsum additive and the temperature in the sample chamber in the intelligent temperature control carbonization chamber are kept the same, and cracks of phosphogypsum 3D printing additive due to the fact that the hydration temperature is obviously higher than the ambient temperature are effectively avoided. Meanwhile, a low-temperature maintenance environment is created for phosphogypsum 3D printing and material adding with low cost and low energy consumption, and the method has obvious technical and economic advantages.
And S2023 is used for moisture-controlled carbonization maintenance, wherein a dry ice regulator in the moisture-controlled carbonization chamber controls the addition amount of dry ice in the sample chamber through a carbon dioxide gas concentration sensor, a carbon dioxide gas pressure sensor and a temperature sensor, and controls the relative humidity in the sample chamber through a relative humidity sensor and a relative humidity regulator, so that the relative humidity in the phosphogypsum 3D printing additive sample chamber is 80%. In the relative humidity environment of the embodiment, phosphogypsum 3D printing and additive carbonization effects are better.
Wherein, S2024 stores and carbonizes and cures, the carbon dioxide concentration in the storage curing chamber is 88% by the carbon dioxide regulator and the temperature and humidity regulator, the temperature is 25 ℃, and the relative humidity is 92%. Because the phosphogypsum 3D printing additive is hardened, specific carbon dioxide concentration, temperature and relative humidity are needed during storage maintenance, the storage maintenance room of the embodiment provides a continuous carbonization environment for the phosphogypsum 3D printing additive, so that the phosphogypsum is continuously carbonized.
Comparison of the test results from examples 1-8 shows that: according to the invention, phosphogypsum is used as a cementing material for 3D printing, and the magnesia enables the additive to be quickly solidified and early-strengthened, so that the material is fireproof and high-temperature resistant, and the cost is reduced; the addition of phosphate can accelerate the setting time of the cementing material and can obviously improve the early strength of the cementing material; the magnesium salt is doped to enhance the type of hydration product of the cementing material and improve the compressive strength of the cementing material; the comprehensive performance of the cementing material can be prepared by adding different additives, and the compression strength of the cementing material can be improved by adding anhydrous citric acid, citric acid monohydrate, citric acid dihydrate, anhydrous sodium carbonate, anhydrous sodium citrate, sodium citrate dihydrate, oxalic acid and sodium oxalate, so that the setting time can be adjusted, and less additives can be added; by effectively combining early carbonization of the cementing material and reduction of hydration heat by adding dry ice, the invention has important influence on hydration products and microstructures before solidification of the cementing material, improves the technical level and efficiency of phosphogypsum resource utilization, enlarges the utilization range of phosphogypsum and reduces the production cost; provides a new way for energy conservation and emission reduction in the building material industry, and has great economic and ecological benefits.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the specific embodiments of the present invention after reading the present specification, and these modifications and variations do not depart from the scope of the invention as defined by the appended claims.

Claims (8)

1. Phosphogypsum additive for 3D printing, which is characterized by comprising the following raw materials in parts by weight: 100 parts of phosphogypsum, 100 parts of magnesia, 100 parts of phosphate, 100 parts of magnesium salt, 10 parts of additive, 10 parts of dry ice and 40 parts of water;
the magnesia is one or two of light burned magnesia and heavy burned magnesia, the average grain size of the magnesia is 65 nm-190 nm, and the specific surface area of the magnesia is 32m 2 /g - 92 m 2 /g；
The additive is one or a combination of more of anhydrous citric acid, citric acid monohydrate, citric acid dihydrate, anhydrous sodium carbonate, anhydrous sodium citrate, sodium citrate dihydrate, borax, boric acid, oxalic acid and sodium oxalate.
2. The phosphogypsum additive for 3D printing of claim 1, wherein the magnesia content in the light burned magnesia is 88.6% -97.2%, and the active magnesia content in the light burned magnesia is 64.3% -76.0%;
the content of magnesium oxide in the re-burned magnesium oxide is 83.2% -98.0%, and the content of active magnesium oxide in the re-burned magnesium oxide is 8.3% -41.8%.
3. Phosphogypsum additive for 3D printing according to claim 1, wherein the phosphate is one or two of potassium dihydrogen phosphate and ammonium dihydrogen phosphate;
the content of the phosphate is 98%;
the fineness of the phosphate is 45-90 mu m.
4. The phosphogypsum additive for 3D printing of claim 1, wherein the magnesium salt is one or two of magnesium sulfate heptahydrate and magnesium chloride hexahydrate; the fineness of the magnesium salt is 48-75 mu m;
the content of the magnesium sulfate heptahydrate is 98%, and the content of the magnesium chloride hexahydrate is 44% -46%.
5. Phosphogypsum additive for 3D printing according to claim 1, characterized in that the dry ice is in the form of rice grains with a length of 5 mm-15 mm.
6. A method of preparing a phosphogypsum additive for 3D printing according to any one of claims 1 to 5, comprising the steps of:
s101, mixing phosphogypsum, phosphate, magnesium salt, additive and water uniformly;
s102, adding magnesia into the mixture of S101 and uniformly stirring;
and S103, adding dry ice into the mixture of the step S102, and stirring until the dry ice volatilizes to obtain phosphogypsum additive slurry for 3D printing.
7. Use of phosphogypsum additive for 3D printing according to any one of claims 1-5, comprising:
s201 printing: adding dry ice again to the phosphogypsum additive slurry before extrusion of a 3D printing spray head, uniformly stirring, and printing;
s202, maintenance: s201 printing and additive curing comprises the following steps: the method comprises the steps of temperature control carbonization curing, humidity control carbonization curing and storage carbonization curing, wherein the humidity control carbonization curing is dry ice curing, and the temperature control carbonization curing and storage carbonization curing is carbon dioxide gas curing;
the carbon dioxide concentration is 50-80% during the temperature control carbonization maintenance, and the carbon dioxide gas pressure is 50-60 kPa; the temperature is lower than minus 20 ℃;
the relative humidity during the humidity control carbonization maintenance is 70-90%;
the carbon dioxide concentration is 50-70%, the temperature is 10-30 ℃ and the relative humidity is 80-95% during storage and maintenance.
8. The use of phosphogypsum additive for 3D printing according to claim 7, wherein the specific steps of curing of S202 are as follows:
s2021, preparing a reference sample, and embedding a temperature sensor in phosphogypsum additive before final setting; cutting the phosphogypsum additive, wherein a reference sample with a temperature sensor is a sample without the temperature sensor;
s2022, the temperature sensor of the reference sample is connected with a temperature controller, and the temperature controller adjusts the temperature of the sample according to the temperature of the reference sample, so as to perform temperature control carbonization maintenance;
s2023, when the surface temperature of the reference sample and the sample is reduced to the room temperature again, performing humidity control carbonization maintenance on the reference sample and the sample;
s2024, storing, carbonizing and curing the reference sample and the sample cured by the step S2023 to obtain a finished product;
the carbon dioxide concentration of the temperature-controlled carbonization maintenance is 60%, the carbon dioxide gas pressure is 60kPa, and the temperature is minus 30 ℃; the relative humidity of the humidity-controlled carbonization maintenance is 80%; the carbon dioxide concentration of the storage carbonization maintenance is 88%, the temperature is 25 ℃, and the relative humidity is 92%.
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CN105731968A (en) * 2016-02-29 2016-07-06 同济大学 Glass fiber reinforced gypsum capable of being used for 3D printing
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CN110436869B (en) * 2019-07-29 2022-04-15 武汉理工大学 Gypsum-based 3D printing material and preparation method thereof
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