CN117809777A - Prediction method of influence of phosphorus content on compatibility and strength of cement raw materials - Google Patents
Prediction method of influence of phosphorus content on compatibility and strength of cement raw materials Download PDFInfo
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- 239000004568 cement Substances 0.000 title claims abstract description 236
- 239000002994 raw material Substances 0.000 title claims abstract description 220
- 238000000034 method Methods 0.000 title claims abstract description 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000011574 phosphorus Substances 0.000 title claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 38
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 37
- 239000011707 mineral Substances 0.000 claims abstract description 37
- 235000013305 food Nutrition 0.000 claims abstract description 32
- 238000004364 calculation method Methods 0.000 claims description 36
- 239000010802 sludge Substances 0.000 claims description 26
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 239000002910 solid waste Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 150000004683 dihydrates Chemical class 0.000 claims description 5
- 239000010440 gypsum Substances 0.000 claims description 5
- 229910052602 gypsum Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 239000007858 starting material Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 9
- 235000019738 Limestone Nutrition 0.000 description 7
- 230000006870 function Effects 0.000 description 7
- 239000006028 limestone Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 238000005457 optimization Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 235000012054 meals Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000011278 co-treatment Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Abstract
The invention belongs to the field of cement, and discloses a method for predicting the influence of phosphorus content on compatibility and strength of cement raw materials, which comprises the following steps: determining the loss on ignition of each cement raw material and the oxide content; construction of a content matrix (W) 1 W 2 W 3 …W n ) T The method comprises the steps of carrying out a first treatment on the surface of the The operation is carried out to obtain the loss on ignition of the cement raw material and the matrix (L) of the oxide content in the raw material Raw materials C Raw materials S Raw materials A Raw materials F Raw materials P Raw materials M Raw materials ) T The method comprises the steps of carrying out a first treatment on the surface of the The operation is carried out to obtain an oxide content matrix (C) Cooked food S Cooked food A Cooked food F Cooked food P Cooked food M Cooked food ) The method comprises the steps of carrying out a first treatment on the surface of the Cement clinker is treated with the sum eta of the percentage by mass of mineral phases C3S and C2S in the clinker by the three values KH, SM and IM of the cement clinker C3S +η C2S And (3) taking 28-day pure slurry compressive strength P of clinker as a target, and planning and solving to obtain a cement raw material compatibility result.The invention establishes P in cement raw materials 2 O 5 The quantitative relation between the content of the mineral phase of the cement clinker and the net pulp strength can predict the content of the C3S, C2S mineral phase in the cement clinker and the net pulp strength of the cement after 28 days of curing.
Description
Technical Field
The invention belongs to the field of cement, and particularly relates to a prediction method of the influence of phosphorus content on the compatibility and strength of cement raw materials, which can be particularly used for solid waste treatment and disposal and recycling of solid waste in the preparation of cement.
Background
The Chinese patent (CN 115724603A) proposes a cement raw material compatibility method and system for cooperatively disposing solid waste in a cement kiln, wherein the conventional three-rate value is used for raw material compatibility, and the influence of phosphorus element on cement is not considered. The Chinese patent (publication No. CN 112598254A) discloses a method for preparing a cement kiln front dangerous waste material, wherein the method refers to the use of a linear regression algorithm for P in kiln front dangerous waste 2 O 5 Restriction is performed, but P is 2 O 5 The content is only a preset fixed value, and is used for screening the dangerous waste in warehouse;and this patent only gives P in the database 2 O 5 Upper limit of admission of content for controlling P in raw material or cement raw material 2 O 5 The content is lower than a preset value, and P is not established 2 O 5 Quantitative relation with clinker performance or mineral phase content cannot be based on P 2 O 5 The content predicts the clinker properties and therefore the clinker product design cannot be performed. Thus, there is a need for a method for quantitatively evaluating the effect of phosphorus on the mineral phase content and mechanical strength of cement clinker.
Disclosure of Invention
In view of the above-mentioned drawbacks or improvements of the prior art, an object of the present invention is to provide a method for predicting the effect of phosphorus content on compatibility and strength of cement raw materials, using oxides P in each raw material 2 O 5 Content (P) i And corresponding P in cement raw materials Raw materials Corresponding P in cement clinker Cooked food ) The cement clinker three-rate values KH, SM and IM which are concerned in the prior art are also calculated by eta by planning in combination with the loss on ignition and the content of other oxides C3S 、η C2S P is the target, P in cement raw materials is established 2 O 5 The quantitative relation between the content of mineral phase of cement clinker and the strength of net pulp is realized by cement raw material P 2 O 5 Content prediction of C3S, C S mineral phase content in cement clinker, cement paste strength after 28 days of curing, and readjustment of P in cement raw material in combination with prediction result 2 O 5 Until the clinker performance reaches the standard. According to the influence rule of the phosphorus content in the cement raw material on the mineral phase content of the cement clinker and the compressive strength of the 28-day clean slurry, the invention optimally designs the ingredients of the cement raw material, and provides support for the compatibility design of the existing cement kiln for cooperatively disposing the phosphorus-containing waste.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a cement raw material based on phosphorus content, comprising the steps of:
(S1) selecting a plurality of cement raw materials participating in the batching in advance, and measuring the mass loss rate of each cement raw material participating in the batching after calcining for 2 hours at the temperature of 1200 ℃ in the air atmosphere to obtainThe percentage reached is noted as loss on ignition; at the same time, the oxide CaO and SiO in each cement raw material participating in batching are measured 2 、Al 2 O 3 、Fe 2 O 3 、P 2 O 5 And SO 3 Is prepared from the following components in percentage by mass;
(S2) recording n kinds of cement raw materials participating in the batching, n being a natural number, and recording the mass fraction of the ith cement raw material in the cement raw material as W i The unit is that i is more than or equal to 1 and less than or equal to n; then, a matrix (W 1 W 2 W 3 … W n ) T And give an initial value to make0≤W i ≤100；
Meanwhile, the loss on ignition of the ith cement raw material is denoted as L i The unit is; oxide CaO and SiO in the ith cement raw material 2 、Al 2 O 3 、Fe 2 O 3 、P 2 O 5 And SO 3 The contents are respectively marked as C i 、S i 、A i 、F i 、P i And M i The units are all, and a matrix X is constructed i ＝(L i C i S i A i F i P i M i )；
(S3) A method of converting (X) 1 T X 2 T X 3 T … X n T ) And (W) 1 W 2 W 3 … W n ) T Multiplying the two matrices to obtain the matrix (L) of the loss on ignition of the cement raw material and the content of oxides in the cement raw material Raw materials C Raw materials S Raw materials A Raw materials F Raw materials P Raw materials M Raw materials ) T The unit of any element in the matrix is;
(S4) for the matrix (L Raw materials C Raw materials S Raw materials A Raw materials F Raw materials P Raw materials M Raw materials ) T Loss on ignition L in cement raw materials Raw materials Deducting and dividing each other matrix element by [ (100-L) Raw materials )/100]ObtainingMatrix of oxide content in cement clinker (C Cooked food S Cooked food A Cooked food F Cooked food P Cooked food M Cooked food ) The unit of any element in the matrix is;
(S5) taking the sum eta of the mass percentages of the mineral phases C3S and C2S in the cement clinker as the three values KH, SM and IM of the cement clinker C3S +η C2S The 28-day net paste compressive strength P of the cement clinker is used as a target, the target value is set, and the solution is planned and adjusted (W 1 W 2 W 3 … W n ) T The element of the matrix takes the value when meeting the following conditionsAnd W is more than or equal to 0 i Under the requirement of less than or equal to 100, the calculation result of the cement clinker three-rate values KH, SM and IM is equal to the target value, and the sum eta of the mass percent of the mineral phases C3S and C2S in the cement clinker C3S +η C2S The calculated result of the net pulp compressive strength P of the cement clinker for 28 days is more than or equal to a target value; planning the obtained (W 1 W 2 W 3 … W n ) T The matrix corresponds to the compatibility result of the cement raw materials, wherein,
the calculation results of the cement clinker three-rate values KH, SM and IM are calculated according to the following formula:
mass percentage eta of mineral phase C3S in cement clinker C3S Mass percentage eta of mineral phase C2S in cement clinker C2S The mass percentage eta of other mineral phases except the mineral phases C3S and C2S in the cement clinker Other phases ，η C3S 、η C2S 、η Other phases All three units are eta C3S 、η C2S 、η Other phases The calculation results of the three are calculated according to the following formula:
η C3S ＝-4.66×P raw materials +53.25
η C2S ＝5.97×P Raw materials +13.76
η Other phases ＝100-η C3S -η C2S
The unit of the net paste compressive strength P of the cement clinker for 28 days is MPa, and the calculation result of P is calculated according to the following formula:
P＝-11.49×P raw materials +96.21。
As a further preferred aspect of the present invention, in the step (S1), the plurality of cement raw materials participating in the batching include dried organic solid waste materials.
As a further preferred aspect of the present invention, in the step (S1), the plurality of cement raw materials participating in the batching include dried municipal sludge.
As a further preferred aspect of the present invention, in the step (S5), the step of adjusting (W 1 W 2 W 3 … W n ) T When the elements of the matrix are valued, the mass fraction W of the dry municipal sludge in the cement raw material Municipal sludge The value is kept unchanged and is a preset value.
In a further preferred aspect of the present invention, in the step (S5), the cement clinker three-rate values KH, SM, IM are respectively set to 0.92, 2.6, 1.4.
According to another aspect of the present invention, there is provided a method for predicting 28-day net paste compressive strength of cement clinker based on the above-mentioned cement raw material compounding method, characterized in that in step (S5), after planning and solving, the method uses the formula p= -11.49 xp Raw materials +96.21, it can be predicted that cement clinker and gypsum dihydrate are mixed in a mass ratio of 20:1 to form cement, water and cement are mixed in a mass ratio of 0.35 to form cement paste, and the cement paste has a compressive strength after standard curing for 28 days.
According to still another aspect of the present invention, there is provided a method for predicting 28-day dry pulp compressive strength of cement clinker based on compatibility of cement raw materials, comprising the steps of:
(1) According to a predetermined cement raw material compatibility scheme, determining the mass loss rate of each cement raw material participating in batching after calcining for 2 hours at the temperature of 1200 ℃ in air atmosphere, and recording the obtained percentage as loss on ignition; at the same time, the oxide CaO and SiO in each cement raw material participating in batching are measured 2 、Al 2 O 3 、Fe 2 O 3 、P 2 O 5 And SO 3 Is prepared from the following components in percentage by mass;
(2) According to a predetermined cement raw material compatibility scheme, n cement raw materials participating in the batching are recorded, n is a natural number, and the mass fraction of the ith cement raw material in the cement raw material is recorded as W i The unit is that i is more than or equal to 1 and less than or equal to n; then, a matrix (W 1 W 2 W 3 … W n ) T And according to a predetermined cement raw material compatibility scheme, W i Assigning a value; wherein,0＜W i ≤100；
meanwhile, the loss on ignition of the ith cement raw material is denoted as L i The unit is; oxide CaO and SiO in the ith cement raw material 2 、Al 2 O 3 、Fe 2 O 3 、P 2 O 5 And SO 3 The contents are respectively marked as C i 、S i 、A i 、F i 、P i And M i The units are all, and a matrix X is constructed i ＝(L i C i S i A i F i P i M i )；
(3) Will (X) 1 T X 2 T X 3 T … X n T ) And (W) 1 W 2 W 3 … W n ) T Multiplying the two matrices to obtain the matrix (L) of the loss on ignition of the cement raw material and the content of oxides in the cement raw material Raw materials C Raw materials S Raw materials A Raw materials F Raw materials P Raw materials M Raw materials ) T The unit of any element in the matrix is;
(4) Predicting the compressive strength P of the cement clinker for 28 days, which corresponds to a predetermined cement raw material compatibility scheme, wherein the unit of the P is MPa, and the calculation result of the P is calculated according to the following formula:
P＝-11.49×P raw materials +96.21
Thus, the cement clinker and the dihydrate gypsum are predicted to be mixed according to the mass ratio of 20:1 under the predetermined cement raw material compatibility scheme to form cement, water and the cement are mixed according to the mass ratio of 0.35 to form cement paste, and the compressive strength of the cement paste is maintained for 28 days in a standard manner.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The process according to the invention is based on the oxides P in the individual starting materials 2 O 5 Content (P) i And corresponding P in cement raw materials Raw materials Corresponding P in cement clinker Cooked food ) The mass percent eta of the mineral phase C3S in the cement clinker can be calculated and predicted by matching the loss on ignition and the contents of other oxides C3S Mass percentage eta of mineral phase C2S in cement clinker C2S And 28 days of net paste compressive strength P of cement clinker, wherein:
η C3S ＝-4.66×P raw materials +53.25
η C2S ＝5.97×P Raw materials +13.76
P＝-11.49×P Raw materials +96.21
Solving by using a planning method, and taking the sum eta of the mass percent ratio of mineral phases C3S and C2S in cement clinker as the three values KH, SM and IM of the cement clinker C3S +η C2S The compressive strength P of the cement clinker for 28 days is taken as a target, and the mass percentage ratio W of various raw materials obtained after planning and solving i Namely, the optimized cement raw material compatibility results are corresponded, so that the optimization of cement raw material compatibility is realized.
(2) The invention establishes a cementP in the material 2 O 5 The quantitative formula of the content and the C3S, C2S mineral phase content in the clinker and the 28-day net paste strength of the cement increases P on the basis of the three-rate value of the traditional cement ingredients 2 O 5 The content is used as one of the compatibility calculation variables, the constraint condition is established by the target value of clinker performance, and the P in the cement raw material is optimized 2 O 5 The content of the components is optimized to optimize the compatibility result, so that the scientificity and applicability of the compatibility result in the invention are superior to those of the traditional three-rate value compatibility method.
(3) The method can be especially used for organic solid wastes (such as municipal sludge and the like) with high phosphorus content, not only can obtain the allowable dosage proportion of the municipal sludge in the cement raw material under different targets, but also can obtain the mass fraction W of the municipal sludge in the cement raw material Municipal sludge Under the condition of meeting the preset requirement, optimizing and predicting the corresponding cement performance.
For example, P in cement raw materials 2 O 5 With known content, the cement clinker mineral phase content and 28-day net pulp strength can be predicted, so that the clinker performance can be designed according to practical application conditions, and as shown in the examples below, the sum of mineral phase content is predicted to have an absolute error of less than +/-5%, and the strength prediction has an absolute error of less than +/-2 MPa. Therefore, the invention provides a new idea and related data support for the cement kiln co-treatment of the phosphorus-containing organic waste.
(4) The coefficient of the formula (especially eta C3S 、η C2S 、η Other phases And a 28-day compressive strength P calculation formula), based on series of experimental data, experiments prove that phosphorus in the organic solid waste mainly exists in the form of inorganic phosphorus, and the inorganic phosphorus is not volatilized in the cement firing process and is completely reserved in a solid phase, so that the calculated phosphorus content is the same as the phosphorus content actually participating in the reaction; the experiment uses municipal sludge and other organic solid wastes as research objects, is the same as the national majority of cement kiln co-treatment objects, and eliminates the interference of other elements by single-factor experiments, so that the experimental design is fit with the engineering practice, and the reliability of experimental results is high.
(5) In the invention, P in each raw material, cement raw material and cement clinker 2 O 5 The content can be measured by using the existing XRF equipment of a cement plant, and no additional detection equipment is needed; the related calculation process in the invention can be realized by common office software without additional learning cost. Therefore, the invention has the characteristics of simple operation and easy implementation.
Drawings
FIG. 1 is a schematic flow chart of a cement raw material compatibility process in an embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Overall, the method of the invention is based on phosphorus content, and enables optimization of cement raw material compatibility and prediction of strength impact. In actual operation, the method can be carried out according to the following steps:
(S1) determining the mass loss rate of cement raw materials participating in the batching after calcining for 2 hours at 1200 ℃ in an air atmosphere, and recording the mass loss rate as loss on ignition; determination of CaO and SiO in Cement raw materials 2 、Al 2 O 3 、Fe 2 O 3 、P 2 O 5 And SO 3 Is contained in the composition.
(S2) designing and mixing different cement raw materials into cement raw materials, wherein the ith cement raw material is marked as X i The mass fraction of the ith cement raw material in the cement raw material is recorded as W i In "%", given W i Initial values (values can be preset) form a matrix (W 1 W 2 W 3 … W n ) T ，0≤W i Less than or equal to 100, n is the number of kinds of cement raw materials. I-th cement raw material loss on ignition and oxide CaO, siO 2 、Al 2 O 3 、Fe 2 O 3 、P 2 O 5 And SO 3 The contents are respectively marked as L i 、C i 、S i 、A i 、F i 、P i And M i The units are "%". Definition matrix X i ＝(L i C i S i A i F i P i M i )。
(S3) A method of converting (X) 1 T X 2 T X 3 T … X n T ) And (W) 1 W 2 W 3 … W n ) T Multiplying the two matrices to obtain the loss on ignition of the cement raw material and the oxide content in the cement raw material, wherein the unit is "%", which is denoted as (L) Raw materials C Raw materials S Raw materials A Raw materials F Raw materials P Raw materials M Raw materials ) T 。
(S4) loss on ignition L in cement raw materials Raw materials Deducting and dividing the oxide content by [ (100-L) Raw materials )/100]Obtaining the oxide content (C) in the cement clinker Cooked food S Cooked food A Cooked food F Cooked food P Cooked food M Cooked food ) The units are "%".
(S5) linking the matrices of steps (S1) to (S4) using software having a function calculation function.
(S6) calculating cement clinker three-rate values KH, SM and IM in the software described in the step (S5), wherein the numerical calculation formula is as follows:
(S7) calculating the content of the cement clinker mineral phase C3S, C2S and other mineral phases (other phases for short) in the software described in the step (S5), wherein the unit is "%", and the numerical calculation formula is as follows:
C3S＝-4.66P raw materials +53.25
C2S＝5.97P Raw materials +13.76
Other phase = 100-C3S-C2S
(S8) calculating the 28-day net paste compressive strength of the cement clinker in the software described in the step (S5), wherein the unit is 'MPa', and the numerical calculation formula is as follows:
28-day net pulp compressive strength= -11.49P Raw materials +96.21
(S9) setting the three values, the sum of the contents of C3S and C2S, and the target value of the 28-day net pulp compressive strength described in the steps (S6) to (S8) in the software described in the step (S5), setting constraint conditions with the target value according to the dosing purpose, and using a planning and solving function to solve the problem (W) described in the step (S3) 1 W 2 W 3 …W n ) T And (3) adjusting the matrix value to ensure that the calculated value of the three-value is equal to the target value, the sum of the contents of C3S and C2S and the calculated value of the 28-day net pulp compressive strength is greater than or equal to the target value.
The matrix input and calculation processes in the steps (S2) to (S9) may be implemented using Office software such as WPS or Office. The following examples take Excel software under Office as an example.
The sources of limestone, sandstone, shale, iron slag, and sludge in the following examples of the present invention are described below.
Limestone: the fineness of the mineral products purchased from Chuandong mineral products manufactured in the Ming county is 400 meshes.
Sandstone, shale, iron slag: samples were taken from the Huaxin cement yellow stone factory.
Sludge: and (3) conditioning the mud cake dehydrated by the plate frame by Fenton, and drying and grinding the mud cake to below 80 meshes.
The results of measuring the loss on ignition and the oxide content of each raw material are shown in Table 1. Both the loss on ignition and the oxide content were determined with reference to the national standard method for Cement chemistry analysis (GB/T176-2017), and the other element contents in the raw materials are not listed in the table. Due to errors in the measurements, the sum of the loss on ignition and the oxide content is not 100%, but the fluctuations often do not exceed + -5%.
Table 1 oxide content (wt%) of each raw material
Example 1
The purpose of this example was to design a clinker with 28 days net slurry strength above 95mpa and a sum of C3S and C2S mineral phase contents above 66% to give a cement raw meal formulation. The specific compatibility optimization and strength prediction process comprises the following steps:
(S1) measuring the mass loss rate of limestone, sandstone, shale, iron slag and sludge which participate in the batching after calcining for 2 hours at 1200 ℃, and recording the mass loss rate as loss on ignition; determination of CaO and SiO in Cement raw materials 2 、Al 2 O 3 、Fe 2 O 3 、P 2 O 5 And MgO, K 2 O、Na 2 O、SO 3 Is contained in the composition.
(S2) inputting the loss on ignition, the oxide content and the mass fraction of the cement raw materials into the Excel software to form a cement raw material batching calculation table shown in Table 2 (row numbers 1, 2 and … …, column numbers A, B and … … in the table are numbered for convenience in responding to the Excel software; the same applies below).
Table 2 cement raw material content table
(S3) the loss on ignition of the raw meal is calculated by a matrix [ B2: B6B 6] T And matrix [ L2: l6]The specific calculation function is SUMPRODUCT (B2:B6, $L3 $L6)/100, and by this, the oxide content of the raw meal is calculated, and the calculated data is filled in the 7 th row as shown in Table 3.
Table 3 cement raw materials calculation table
(S4) loss on ignition L in cement raw materials Raw materials Deducting and dividing the oxide content by [ (100-L) Raw materials )/100]Obtaining the oxide content (C) in the cement clinker Cooked food S Cooked food A Cooked food F Cooked food P Cooked food M Cooked food ) The units are "%", and the clinker calculation data is filled to line 8, as shown in table 4.
Table 4 cement clinker calculation table
(S5) calculating cement clinker three-rate values KH, SM and IM in the cement clinker calculation table in the step (S4), wherein the calculation formula is as follows:
(S6) calculating the contents of the cement clinker mineral phases C3S, C S and other mineral phases in the cement clinker calculation table in the step (S4), wherein the calculation formula is as follows:
C3S＝-4.66P raw materials +53.25
C2S＝5.97P Raw materials +13.76
Other phase = 100-C3S-C2S
(S7) calculating the 28-day net-pulp compressive strength of the cement clinker in the cement clinker calculation table in the step (S4), wherein the calculation formula is as follows:
28-day net pulp compressive strength= -11.49P Raw materials +96.21
The calculation results of steps (S5) to (S7) are filled in to the 9 th to 12 th rows as shown in table 5.
Table 5 cement clinker performance calculation table
(S8) using an Excel programming solving function, wherein the constraint conditions are that target values of KH, SM and IM are 0.92, 2.6 and 1.4, and the calculated value is equal to the target value; the sum of the calculated values of C3S and C2S is more than or equal to 66 percent; the compressive strength target value is 95MPa, and the calculated value is more than or equal to the target value; the sludge ratio was 0%. And a nonlinear solving mode is adopted.
The calculated raw material proportion of (S9) is 77.66% of limestone, 6.78% of sandstone, 11.24% of shale and 4.32% of iron slag. The calculated values of the clinker mineral phase content are 53.04% C3S, 14.02% C2S, 67.07% C3S and C2S, and 95.7MPa for compressive strength, as shown in Table 6.
Table 6 example 1 raw meal batch calculation table
After the cement raw materials are matched and burned into cement according to the calculation result of the step (S9), the phase content and the 28-day compressive strength of the burned cement clinker are actually measured, wherein the measured phase content of the cement clinker is that C3S accounts for 51.40%, C2S accounts for 18.90%, the sum of the C3S and C2S contents is 70.30%, and the compressive strength is 96.8MPa.
The actual measurement of the compressive strength (i.e., 28 day paste compressive strength) was obtained by mixing cement clinker and gypsum dihydrate at a mass ratio of 20:1 to form cement, mixing water and cement at a mass ratio of 0.35 to form paste, and standard curing the paste for 28 days.
Example 2
The purpose of this example is to mix sludge as cement raw material and to make the mixing amount of sludge as high as possible, and to require 28 days of clinker to have a net slurry strength higher than 90MPa, to obtain P in cement raw material 2 O 5 Is added into the raw cement material. Specific compatibility optimization and strength prediction process packageThe method comprises the following steps:
the raw material data input method is the same as steps (S1) to (S7) of embodiment 1, except that an Excel programming solution function is used in (S8), and the constraint condition is that the target values of KH, SM, IM are 0.92, 2.6, 1.4, and the calculated values are equal to the target values; the compressive strength target value is 90MPa, and the calculated value is more than or equal to the target value; the sludge ratio takes the maximum value. And a nonlinear solving mode is adopted.
(S9) the calculated raw material proportion is 71.19 percent of limestone, 10.17 percent of sandstone, 2.82 percent of shale, 15.82 percent of sludge and P 2 O 5 The admission content of the raw material is 0.44%, the experiment verification is carried out on the integral value of the sludge doping amount, the sludge doping amount is adjusted to 15.00%, the recalculated raw material proportion is 71.53% of limestone, 9.99% of sandstone, 3.26% of shale, 0.22% of iron slag and 15.00% of sludge, and at the moment, P in the raw material is P 2 O 5 The calculated value of the clinker mineral phase content is 51.28 percent of C3S, 16.29 percent of C2S, the sum of the C3S and C2S contents is 67.56 percent, and the calculated value of the compressive strength is 91.3MPa.
After the cement raw materials are matched and burned into cement according to the calculation result of the step (S9), the phase content and the 28-day compressive strength of the burned cement clinker are actually measured, wherein the measured phase content of the cement clinker is 49.60 percent of C3S, 20.80 percent of C2S, the sum of the C3S and C2S contents is 70.40 percent, and the compressive strength is 91.7MPa.
Example 3
The purpose of this example was to incorporate sludge as cement raw material with a sludge incorporation of 10% and to predict the mineral phase content of cement clinker and the 28 day dry pulp compressive strength. The specific compatibility optimization and strength prediction process comprises the following steps:
the raw material data input method is the same as steps (S1) to (S7) of embodiment 1, except that an Excel programming solution function is used in (S8), the constraint condition is that target values of KH, SM and IM are 0.92, 2.6 and 1.4, calculated values are equal to the target values, sludge ratio is 10%, and a nonlinear solution mode is adopted.
(S9) the calculated raw material proportion is 73.57 percent of limestone, 8.92 percent of sandstone, 5.92 percent of shale, 1.59 percent of iron slag and 10.00 percent of sludge,cement raw material P 2 O 5 The calculated value of the clinker mineral phase content is 51.87 percent of C3S, 15.53 percent of C2S, 67.40 percent of the sum of the C3S and C2S contents and 92.8MPa.
After the cement raw materials are matched and burned into cement according to the calculation result of the step (S9), the phase content and the 28-day compressive strength of the burned cement clinker are actually measured, wherein the measured phase content of the cement clinker is 53.90 percent of C3S, 17.20 percent of C2S, the sum of the C3S and C2S is 71.10 percent, and the compressive strength is 93.5MPa.
The above embodiment is merely an example, and the target value may be set according to the actual demand (for example, the 28-day net-slurry compressive strength P of the cement clinker may be set to another target value or the like). Has been verified to be 0.ltoreq.P Raw materials ≤3，KH、SM、IM、η C3S 、η C2S 、η Other phases And the calculation formula of the compressive strength P in 28 days has good prediction effect. In addition, the above embodiment uses Na 2 O、MgO、K 2 The content of the 3 oxides is included in the operation process, and the content of the 3 oxides is mainly considered to be a common detection index of the existing cement plant; the method of the invention (whether the method is a cement raw material compatibility method based on phosphorus content or a method for predicting the compressive strength of 28-day net paste of cement clinker) is not affected by Na 2 O、MgO、K 2 The effect of the O3 oxide content (whether high or low).
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The cement raw material compatibility method based on the phosphorus content is characterized by comprising the following steps of:
(S1) pre-selecting a plurality of cement raw materials participating in batching, measuring the mass loss rate of each cement raw material participating in batching after calcining for 2 hours at the temperature of 1200 ℃ in air atmosphere, and recording the obtained percentage as loss on ignition; as same asAt the time, the oxide CaO and SiO in each cement raw material participating in the batching are measured 2 、Al 2 O 3 、Fe 2 O 3 、P 2 O 5 And SO 3 Is prepared from the following components in percentage by mass;
(S2) recording n kinds of cement raw materials participating in the batching, n being a natural number, and recording the mass fraction of the ith cement raw material in the cement raw material as W i The unit is that i is more than or equal to 1 and less than or equal to n; then, a matrix (W 1 W 2 W 3 … W n ) T And give an initial value to make
Meanwhile, the loss on ignition of the ith cement raw material is denoted as L i The unit is; oxide CaO and SiO in the ith cement raw material 2 、Al 2 O 3 、Fe 2 O 3 、P 2 O 5 And SO 3 The contents are respectively marked as C i 、S i 、A i 、F i 、P i And M i The units are all, and a matrix X is constructed i ＝(L i C i S i A i F i P i M i )；
(S3) A method of converting (X) 1 T X 2 T X 3 T … X n T ) And (W) 1 W 2 W 3 … W n ) T Multiplying the two matrices to obtain the matrix (L) of the loss on ignition of the cement raw material and the content of oxides in the cement raw material Raw materials C Raw materials S Raw materials A Raw materials F Raw materials P Raw materials M Raw materials ) T The unit of any element in the matrix is;
(S4) for the matrix (L Raw materials C Raw materials S Raw materials A Raw materials F Raw materials P Raw materials M Raw materials ) T Loss on ignition L in cement raw materials Raw materials Deducting and dividing each other matrix element by [ (100-L) Raw materials )/100]Obtaining an oxide content matrix (C) Cooked food S Cooked food A Cooked food F Cooked food P Cooked food M Cooked food ) The unit of any element in the matrix is;
(S5) taking the sum eta of the mass percentages of the mineral phases C3S and C2S in the cement clinker as the three values KH, SM and IM of the cement clinker C3S +η C2S The 28-day net paste compressive strength P of the cement clinker is used as a target, the target value is set, and the solution is planned and adjusted (W 1 W 2 W 3 … W n ) T The element of the matrix takes the value when meeting the following conditionsAnd W is more than or equal to 0 i Under the requirement of less than or equal to 100, the calculation result of the cement clinker three-rate values KH, SM and IM is equal to the target value, and the sum eta of the mass percent of the mineral phases C3S and C2S in the cement clinker C3S +η C2S The calculated result of the net pulp compressive strength P of the cement clinker for 28 days is more than or equal to a target value; planning the obtained (W 1 W 2 W 3 … W n ) T The matrix corresponds to the compatibility result of the cement raw materials, wherein,
the calculation results of the cement clinker three-rate values KH, SM and IM are calculated according to the following formula:
mass percentage eta of mineral phase C3S in cement clinker C3S Mass percentage eta of mineral phase C2S in cement clinker C2S In cement clinkerThe mass percentage eta of the mineral phases other than the mineral phases C3S and C2S Other phases ，η C3S 、η C2S 、η Other phases All three units are eta C3S 、η C2S 、η Other phases The calculation results of the three are calculated according to the following formula:
η C3S ＝-4.66×P raw materials +53.25
η C2S ＝5.97×P Raw materials +13.76
η Other phases ＝100-η C3S -η C2S
The unit of the net paste compressive strength P of the cement clinker for 28 days is MPa, and the calculation result of P is calculated according to the following formula:
P＝-11.49×P raw materials +96.21。
2. The method of claim 1, wherein in step (S1), the plurality of cement raw materials involved in the formulation comprise dried organic solid waste materials.
3. The method of claim 1, wherein in step (S1), the plurality of cementitious materials involved in the formulation comprise dried municipal sludge.
4. A method according to claim 3, wherein in the step (S5), the cement raw material is mixed by adjusting (W 1 W 2 W 3 …W n ) T When the elements of the matrix are valued, the mass fraction W of the dry municipal sludge in the cement raw material Municipal sludge The value is kept unchanged and is a preset value.
5. The method according to claim 1, wherein in the step (S5), the cement clinker three-rate values KH, SM, IM are respectively set to 0.92, 2.6, 1.4.
6. Cement according to any one of claims 1-5The method for predicting the 28-day net paste compressive strength of the cement clinker by using the raw material compatibility method is characterized in that in the step (S5), after planning and solving, the formula P= -11.49 xP is utilized Raw materials +96.21, it can be predicted that cement clinker and gypsum dihydrate are mixed in a mass ratio of 20:1 to form cement, water and cement are mixed in a mass ratio of 0.35 to form cement paste, and the cement paste has a compressive strength after standard curing for 28 days.
7. The method for predicting the 28-day net paste compressive strength of the cement clinker based on the compatibility of the cement raw materials is characterized by comprising the following steps:
(1) According to a predetermined cement raw material compatibility scheme, determining the mass loss rate of each cement raw material participating in batching after calcining for 2 hours at the temperature of 1200 ℃ in air atmosphere, and recording the obtained percentage as loss on ignition; at the same time, the oxide CaO and SiO in each cement raw material participating in batching are measured 2 、Al 2 O 3 、Fe 2 O 3 、P 2 O 5 And SO 3 Is prepared from the following components in percentage by mass;
(2) According to a predetermined cement raw material compatibility scheme, n cement raw materials participating in the batching are recorded, n is a natural number, and the mass fraction of the ith cement raw material in the cement raw material is recorded as W i The unit is that i is more than or equal to 1 and less than or equal to n; then, a matrix (W 1 W 2 W 3 … W n ) T And according to a predetermined cement raw material compatibility scheme, W i Assigning a value; wherein,
meanwhile, the loss on ignition of the ith cement raw material is denoted as L i The unit is; oxide CaO and SiO in the ith cement raw material 2 、Al 2 O 3 、Fe 2 O 3 、P 2 O 5 And SO 3 The contents are respectively marked as C i 、S i 、A i 、F i 、P i And M i The units are all, and a matrix is constructedX i ＝(L i C i S i A i F i P i M i )；
(3) Will (X) 1 T X 2 T X 3 T … X n T ) And (W) 1 W 2 W 3 … W n ) T Multiplying the two matrices to obtain the matrix (L) of the loss on ignition of the cement raw material and the content of oxides in the cement raw material Raw materials C Raw materials S Raw materials A Raw materials F Raw materials P Raw materials M Raw materials ) T The unit of any element in the matrix is;
(4) Predicting the compressive strength P of the cement clinker for 28 days, which corresponds to a predetermined cement raw material compatibility scheme, wherein the unit of the P is MPa, and the calculation result of the P is calculated according to the following formula:
P＝-11.49×P raw materials +96.21
Thus, the cement clinker and the dihydrate gypsum are predicted to be mixed according to the mass ratio of 20:1 under the predetermined cement raw material compatibility scheme to form cement, water and the cement are mixed according to the mass ratio of 0.35 to form cement paste, and the compressive strength of the cement paste is maintained for 28 days in a standard manner.
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