CN115286266B - Carbon-negative clinker prepared from phosphogypsum and preparation method of carbon-negative clinker - Google Patents
Carbon-negative clinker prepared from phosphogypsum and preparation method of carbon-negative clinker Download PDFInfo
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- CN115286266B CN115286266B CN202211001671.0A CN202211001671A CN115286266B CN 115286266 B CN115286266 B CN 115286266B CN 202211001671 A CN202211001671 A CN 202211001671A CN 115286266 B CN115286266 B CN 115286266B
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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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
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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
- C04B7/00—Hydraulic cements
- C04B7/02—Portland cement
- C04B7/04—Portland cement using raw materials containing gypsum, i.e. processes of the Mueller-Kuehne type
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- 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
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Abstract
The invention provides a negative carbon clinker utilizing phosphogypsumA material and a preparation method thereof. The negative carbon clinker comprises the following chemical components in percentage by mass: caO:40 to 55 percent; siO 2 2 ：30～45％；Al 2 O 3 ：3～10％；Fe 2 O 3 ：2～8％；P 2 O 5 :1.8 to 5 percent, and CaO/SiO 2 The molar ratio of (A) to (B) is 1.0 to 1.5. The molar ratio of Ca/Si of the clinker is 1.0-1.5, and the lower molar ratio of Ca/Si ensures that the clinker is mainly low-calcium silicate minerals and low-melting-point phase calcium sulfosilicate and the like can not appear. The liquid phase that appears during firing consists mainly of the molten gypsum phase; the liquid phase can accelerate the reduction decomposition reaction rate of the phosphogypsum and CO; the highly active liquid phase CaO generated by reduction can promote the mineralization of tricalcium disilicate and monocalcium silicate which mainly contribute to the strength. Therefore, the simultaneous occurrence of an ore-forming reaction and a phosphogypsum decomposition reaction is completed in a rotary kiln by a one-step method, but the completion in the conventional process can be completed by a two-step method.
Description
Technical Field
The invention relates to the technical field of inorganic materials, in particular to a negative carbon clinker utilizing phosphogypsum and a preparation method thereof.
Background
Phosphogypsum is a solid waste produced in the process of preparing phosphoric acid by an industrial wet method, and 4-5 tons of phosphogypsum are produced per ton of phosphoric acid produced. Due to the impurities such as soluble phosphorus, fluorine and the like, the phosphogypsum and natural gypsum have difference in physical and chemical properties, thereby limiting the resource utilization of the phosphogypsum. Most of the unused phosphogypsum is disposed in a stacking mode, occupies a large amount of land and causes serious pollution to the ecological environment.
The copper tailings refer to solid waste discharged after mining copper ore resources as main resources and separating useful components in ores through mineral separation process treatment. The copper tailings in China have large amount, so that the huge copper tailing resources cannot be obviously consumed by recycling valuable components through secondary utilization, and the target requirements of efficient resource utilization and tail-free discharge are difficult to achieve. The problems of land resource waste, enterprise operation cost increase, easy initiation of serious disasters, serious waste of available resources and the like caused by copper tailing stacking are solved, and great challenges are brought to the sustainable and healthy development of economy, environmental improvement, resource protection and the like in China.
Billions of tons of natural resources such as limestone, natural clay and the like are consumed by the cement industry every year, and the industry is utilized on a large scaleThe solid waste burned cement is very important for ecological civilization construction and sustainable development of building material industry. The main chemical component of the phosphogypsum is CaSO 4 While containing a small amount of SiO 2 (ii) a The main chemical component of the copper tailings is SiO 2 While containing a small amount of Al 2 O 3 、Fe 2 O 3 . The industrial solid waste phosphogypsum is used as a calcareous raw material, and the copper tailings are used as siliceous raw materials to calcine the cement clinker, so that the CO is obviously reduced 2 Release, and also produce sulfuric acid to create additional revenue.
China has developed a large amount of research on co-production of cement by producing sulfuric acid from phosphogypsum, and the material system of the research is mainly ordinary portland cement clinker (Ca/Si molar ratio)>2.0 And a low calcium cement clinker system (2.0)>Molar ratio of Ca/Si>1.5). However, the reduction atmosphere required by the pre-decomposition of the phosphogypsum is incompatible with the cement mineralizing and oxidizing atmosphere, the pre-decomposition furnace cannot be applied due to large liquid phase amount during the decomposition of the phosphogypsum, the economic benefit of cement burning by the pre-decomposition two-step method is not obvious, the generation of tricalcium silicate is inhibited due to the solid solution of phosphorus impurities to stabilize the dicalcium silicate structure, a large amount of free CaO is generated, and the like, so that the technology is difficult to be applied on a large scale. The first problem is that the reducing atmosphere required by the pre-decomposition of the phosphogypsum is incompatible with the oxidizing atmosphere of the silicate cement clinker tetracalcium aluminoferrite (ferric ion) mineralization, and a two-step process adopting pre-decomposition-remineralization sintering is researched and proposed. The second problem, the decomposition temperature of the phosphogypsum is about 1100 ℃, the rapid decomposition temperature is about 1200 ℃, and when the Ca/Si molar ratio of the clinker is more than about 1.5, the temperature is close to the temperature at which a low-melting phase such as calcium sulfosilicate (Ca/Si molar ratio is 2.0) forms a liquid phase in the clinker sintering process; a large amount of generated liquid phase flows in the pre-decomposition furnace, so that the pre-decomposition furnace is blocked, and the pre-decomposition furnace cannot be suitable for pre-decomposition furnace equipment; and a large amount of liquid phase is easy to wrap undecomposed phosphogypsum, so that the contact between the phosphogypsum and CO is prevented, and the decomposition rate of the phosphogypsum is reduced. The third problem is that calcium oxide generated in the phosphogypsum predecomposition process is generally large in particle due to the occurrence of liquid phase; if the calcium carbonate is directly used for cement batching, the cooling, crushing and grinding are necessary, otherwise, the calcium component in the raw material is not uniformly distributed. The processes of cooling, crushing and grinding waste the heat value of calcium oxide which is generated by pre-decomposition and is close to 1200 ℃,significantly increasing energy costs and CO 2 And the discharge has no obvious economic benefit and ecological value. The fourth problem is that when the molar ratio of Ca/Si of the clinker is more than 2.0, phosphorus impurities in the phosphogypsum can enter a dicalcium silicate structure through solid solution, the reaction activity of tricalcium silicate generated through the reaction of dicalcium silicate and calcium oxide is reduced, tricalcium silicate is inhibited from being generated, a large amount of free calcium oxide is left in the clinker, and the burning quality of portland cement is reduced.
Therefore, the development of the clinker which has large phosphogypsum consumption and large impurity containing rate of phosphorus, fluorine and the like in the phosphogypsum is urgently needed, and the preparation process is compatible with the conditions of temperature, atmosphere and the like of phosphogypsum decomposition and clinker mineralization.
Disclosure of Invention
The invention provides a negative carbon clinker utilizing phosphogypsum and a preparation method thereof for solving the technical problems.
In order to achieve the purpose, the invention adopts the technical scheme that:
the negative carbon clinker comprises the following chemical components in percentage by mass: caO:40 to 55 percent; siO 2 2 ：30～45％；Al 2 O 3 ：3～10％；Fe 2 O 3 ：2～8％；P 2 O 5 :1.8 to 5 percent, and CaO/SiO 2 The molar ratio of (A) to (B) is 1.0 to 1.5.
Preferably, the phase composition of the negative carbon clinker comprises the following components in percentage by mass: calcium silicate: 50 to 75 percent; 10 to 30 percent of tricalcium disilicate; dicalcium aluminosilicate: 10 to 25 percent; 3% -20% of glass phase, and the sum of the contents of free calcium oxide and residual gypsum phase is not more than 5%.
Preferably, the raw material composition of the negative carbon clinker comprises the following components in percentage by mass: 65-80% of phosphogypsum, 5-15% of coal powder, 0-5% of iron correcting material, 0-20% of copper tailings, 0-20% of clay and 0-20% of sandstone; wherein, the copper tailings, the clay and the sandstone do not take 0 value at the same time.
The preparation method of the negative carbon clinker comprises the following steps:
crushing and grinding all the raw materials in sequence, wherein the particle size is less than 100 microns;
premixing raw materials, feeding the raw materials into a rotary kiln, and simultaneously performing ardealite decomposition and one-step calcination of clinker mineralization;
and (4) quenching the sintered clinker.
Preferably, the cooling rate of the quenching is 500-800 ℃/min.
Preferably, the calcining temperature is 1100-1250 ℃, and the calcining time in the rotary kiln is 0.5-2 h.
Preferably, the method also comprises the step of recovering the tail gas of the kiln head of the rotary kiln to prepare the sulfuric acid.
Preferably, SO in the tail gas 2 The concentration is not less than 6%.
Preferably, the tail gas is subjected to waste heat recovery and electrostatic dust removal in sequence, enters a reaction tower, and is oxidized into SO by a catalyst 3 Then the sulfuric acid is prepared by absorption.
The beneficial effects of the invention are as follows:
1. the clinker Ca/Si molar ratio is 1.0-1.5, and tricalcium silicate is not contained, so that a large amount of free calcium oxide generated by phosphorus impurities is avoided. Meanwhile, phosphorus impurities enter the structures of alpha-calcium metasilicate and tricalcium disilicate in a solid solution mode, the carbonization activity of the clinker is increased, and the development of the strength of the clinker is facilitated.
2. The clinker does not contain silicon-aluminum raw materials such as tetracalcium aluminoferrite, clay and the like and iron elements introduced by an iron correction material, and divalent iron ions are formed after the calcination under the reducing atmosphere and exist in a glass phase, so that the strength development is not influenced.
3. The molar ratio of Ca/Si of the clinker is 1.0-1.5, and the lower molar ratio of Ca/Si ensures that the clinker is mainly low-calcium silicate minerals and low-melting phase calcium sulfosilicate (the molar ratio of Ca/Si is 2.0) and the like can not appear. The main composition of the liquid phase occurring during the firing process is the molten gypsum phase; the liquid phase can accelerate the reduction decomposition reaction rate of the phosphogypsum and CO; the highly active liquid phase CaO generated by reduction can promote the mineralization of tricalcium disilicate and monocalcium silicate which mainly contribute to the strength. Therefore, the simultaneous occurrence of an ore-forming reaction and a phosphogypsum decomposition reaction is completed in a rotary kiln by a one-step method, while the conventional process can be completed by a two-step method.
4. Clinker phase of monocalcium silicate, tricalcium disilicate and diasphonic acidCalcium has CO 2 Driving the mineralization and hardening capacity, and CO in the tail gas 2 Reacting to generate calcium carbonate and silica gel to form the strength. CO of clinker 2 Absorption capacity of up to 0.2g CO 2 Per gram of clinker. And the clinker negative carbon preparation is really realized through carbon emission calculation.
Drawings
FIG. 1 is the XRD pattern of the clinker in example 1;
FIG. 2 is an XRD pattern of the clinker in comparative example 1;
figure 3 is the XRD pattern of the clinker in comparative example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Examples 1-4 the ingredients for preparing negative carbon clinker using phosphogypsum and other raw materials and steel slag as iron calibration material are shown in table 1, and the chemical compositions thereof are shown in table 2.
TABLE 1 (unit: wt%)
| Phosphogypsum | Copper tailings | Sandstone | Clay | Iron correction material | Pulverized coal | |
| Example 1 | 75.7 | 12.3 | 2.5 | -- | 1.5 | 8 |
| Example 2 | 74.6 | -- | 13.1 | 2.8 | 1.5 | 8 |
| Example 3 | 72.5 | 5.1 | -- | 13.6 | 1.8 | 7 |
| Example 4 | 73.2 | 3.8 | 11.1 | -- | 0.9 | 11 |
Table 2 (unit: wt%), wherein F represents the impurity fluorine in the clinker.
The invention also provides a preparation method of the negative carbon clinker, which comprises the following steps:
all the raw materials in the table 1 are sequentially crushed, ground and premixed according to the proportioning design, so that the particle size of the raw materials is less than 100 mu m;
and (3) feeding the raw material into a rotary kiln for burning, wherein the burning temperature is 1180 ℃, and the burning time is 90min. The rotating speed of the rotary kiln is 0.2-1.2rpm;
quenching the sintered clinker;
the collected tail gas is sequentially subjected to waste heat recovery and electrostatic dust collection, enters a sulfuric acid preparation system for treatment after entering a grate cooler, and is oxidized into SO by a catalyst 3 Then the sulfuric acid is prepared by absorbing with concentrated sulfuric acid.
The specific surface area of the negative carbon clinker sintered in the examples 1 to 4 after ball milling for 1h is more than 400m 2 The mineral phase composition of the carbon-bearing clinker in examples 1 to 4, which is less than 5% in 75 μm sieve residue and meets the requirements of national standards, is obtained by quantitative XRD analysis as shown in Table 3. Wherein f-CaO is determined according to the method for chemical analysis of Cement (GB/T176-2017), caSO 4 Measured according to the method for chemical analysis of Gypsum (GB/T5484-2012).
Mixing the negative carbon clinker with mixing water at a mixing ratio of 0.15 and a forming pressure of 4MPa, and placing the mixture in CO at 0.2MPa 2 Carbonizing and curing are carried out under the atmosphere, the compressive and flexural strength and the carbon fixing amount are tested and shown in the table 4,
table 3 (unit:%)
| CS | C 3 S 2 | C 2 AS | f-CaO | CaSO 4 | Glass phase | |
| Example 1 | 59.8 | 10.8 | 14 | 0.5 | 0.9 | 8.3 |
| Example 2 | 58.7 | 13.5 | 10.3 | 0.7 | 1.4 | 9.7 |
| Example 3 | 53.1 | 15.9 | 17 | 0.8 | 1.7 | 8.5 |
| Example 4 | 56.8 | 13.6 | 13.2 | 0.4 | 1.8 | 7.4 |
Table 4 (unit:%)
Comparative examples 1 to 4
To further illustrate CaO/SiO 2 The influence of the molar ratio on the one-step method for firing the phosphogypsum into the negative carbon clinker is realized by increasing the dosage of the phosphogypsum in the raw material and reducing the dosage of the siliceous raw material on the basis of the examples 1 to 4 to realize CaO/SiO 2 The molar ratio was increased as in comparative examples 1 to 4, respectively. The comparative example mainly considers the influence of the calcium-silicon ratio on clinker sintering, and the added small amount of aluminum and iron does not change the performance greatly. In which CaO/SiO of comparative examples 1-2 2 CaO/SiO in a molar ratio of 1.5 to 2, comparative examples 3 to 4 2 The molar ratio is greater than 2, and the other conditions are in accordance with the examples. The ingredients of the comparative example are shown in Table 5, the chemical composition is shown in Table 6, the mineral phase composition of the calcined clinker is shown in Table 7, and the properties are shown in Table 8.
Table 5 (unit:%)
| Phosphogypsum | Copper tailings | Sandstone | Clay | Iron correction material | Pulverized coal | |
| Comparative example 1 | 79.8 | 3.0 | 6.7 | -- | 1.5 | 9 |
| Comparative example 2 | 78.7 | 5.7 | -- | 6.5 | 1.1 | 8 |
| Comparative example 3 | 85.9 | 2.0 | 4.1 | -- | 1.0 | 7 |
| Comparative example 4 | 85.1 | 5.1 | -- | 1.6 | 1.2 | 7 |
Table 6 (unit:%)
The results, taken in conjunction with comparative examples 1-2 and examples 1-4, show that the clinker CaO/SiO 2 When the molar ratio is 1.5-2.0, the decomposition temperature of the gypsum is close to the appearance temperature of a liquid phase; a large amount of liquid phase wraps the undecomposed gypsum particles, thus blocking the diffusion of CO gas molecules, making the reduction reaction of gypsum difficult, leading to a large amount of gypsum residue in clinker, and producing a large amount of calcium sulfosilicate (C) without carbonization reaction activity and strength 5 S 2 S) phase, and can participate in carbonization reaction to generate monocalcium silicate (CS) and tricalcium disilicate (C) with strength 3 S 2 ) And dicalcium aluminosilicate (C) 2 AS) content is lower (AS shown in fig. 2). Therefore, the clinker has lower strength and carbon fixation amount, and does not meet the performance requirement of the negative carbon clinker.
Similarly, the results of the combination of comparative examples 3-4 and examples 1-4 show that the clinker CaO/SiO 2 When the molar ratio is more than 2.0, a large amount of liquid phase wraps undecomposed gypsum particles, so that the diffusion of CO gas molecules is hindered, the reduction reaction of gypsum is extremely difficult, and the content of residual gypsum in clinker reaches 50%; and can participate in carbonization reaction to generate calcium monosilicate (CS) and tricalcium disilicate (C) 3 S 2 ) And dicalcium aluminosilicate (C) 2 AS) content is even less than 20% (AS shown in figure 3). Therefore, the clinker has lower strength and carbon fixation amount, and does not meet the performance requirement of the negative carbon clinker.
Table 7 (unit:%)
| CS | C 3 S 2 | C 5 S 2 S | SiO 2 | C 2 AS | f-CaO | CaSO 4 | Glass phase | |
| Comparative example 1 | 6.9 | 8.7 | 28.2 | 1.9 | 8.8 | 3.3 | 21.8 | 18.3 |
| Comparative example 2 | 5.2 | 10.1 | 28.3 | 2.6 | 11.1 | 1.7 | 20.4 | 17.8 |
| Comparative example 3 | 10.2 | -- | -- | 6.8 | 5.4 | 1.2 | 47.2 | 27.7 |
| Comparative example 4 | 9.8 | -- | -- | 6.5 | 6.1 | 1.1 | 50.7 | 23.3 |
Table 8 (unit:%)
The above embodiments are only examples for clearly illustrating the present invention and are not intended to limit the present invention. Other variants and modifications will be apparent to those skilled in the art in light of the foregoing description, which are not necessarily exhaustive of all embodiments and are therefore intended to be within the scope of the invention.
Claims (7)
1. The negative carbon clinker utilizing the phosphogypsum is characterized by comprising the following chemical components in percentage by mass: caO:40 to 55 percent; siO 2 2 ：30～45％；Al 2 O 3 ：3～10％；Fe 2 O 3 ：2～8％；P 2 O 5 :1.8 to 5 percent, and CaO/SiO 2 The molar ratio of the carbon-negative clinker is 1.0-1.5, and the phase composition of the carbon-negative clinker comprises the following components in percentage by mass: calcium silicate: 50 to 75 percent; 10 to 30 percent of tricalcium disilicate; dicalcium aluminosilicate: 10 to 25 percent; 3% -20% of a glass phase, the sum of the contents of free calcium oxide and residual gypsum phase is not more than 5%, and the negative carbon clinker comprises the following raw materials in percentage by mass: 65-80% of phosphogypsum, 5-15% of coal powder, 0-5% of iron correcting material, 0-20% of copper tailings, 0-20% of clay and 0-20% of sandstone; wherein, the copper tailings, the clay and the sandstone do not take 0 value at the same time.
2. The method for preparing negative carbon clinker according to claim 1, comprising the steps of:
crushing and grinding all the raw materials in sequence, wherein the particle size is less than 100 microns;
premixing raw materials, feeding the raw materials into a rotary kiln, and simultaneously performing ardealite decomposition and one-step calcination of clinker mineralization;
and (4) quenching the sintered clinker.
3. The method of claim 2, wherein the quench cooling rate is 500-800 ℃/min.
4. The method of claim 2, wherein the calcining temperature is 1100 to 1250 ℃ and the calcining time in the rotary kiln is 0.5 to 2 hours.
5. The method as claimed in claim 2, further comprising the step of recovering tail gas from the kiln head of the rotary kiln to produce sulfuric acid.
6. The method of claim 5, wherein SO in the tail gas is 2 The concentration is not less than 6%.
7. The preparation method according to claim 5, wherein the tail gas is subjected to waste heat recovery and electrostatic dust removal in sequence, enters a reaction tower, and is oxidized into SO by a catalyst 3 Then absorbing to prepare sulfuric acid.
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