Liquid cement raw material grinding aid and preparation method thereof
Through the combination of liquid cement raw material aids, containing raw materials such as phosphate and rare earth composition, the problems of high energy consumption and low grinding efficiency in cement production are solved, and the effect of improving grinding fineness and reducing harmful emissions is achieved. .
Patent Information
- Application Number
- CN202411300849.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-18
- Publication Date
- 2024-12-27
AI Technical Summary
The energy consumption is large and the energy utilization rate is low in the existing cement production process, and there are few researches on cement raw materials and admixtures, which affects grinding efficiency and exhaust gas emissions.
Liquid cement raw material grinding aids are used, which contain phosphate, rare earth composition, metal oxide, lignin sulfonate and organic grinding aids. They are prepared evenly by stirring to improve the fineness and sintering quality of raw material grinding. Reduce the firing temperature and harmful gas emissions.
The grinding fineness and firing quality of cement raw materials are improved, the firing temperature and harmful gas emissions are reduced, the oxidation atmosphere of clinker and the mineral decomposition speed are improved, and energy consumption is reduced.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of cement raw material processing, and in particular to a liquid cement raw material grinding aid and a preparation method thereof. Background Art
[0002] The cement production process consumes a lot of energy but the energy utilization rate is low. How to reduce energy consumption, improve energy utilization rate and reduce harmful waste gas emissions in the cement production process is the key to achieving sustainable development of the cement industry. The emergence of cement admixtures has balanced the social and economic benefits of the cement industry to a certain extent. However, the cement admixtures that are currently being studied more are cement clinker admixtures, which are used to improve the grinding efficiency of cement clinker, increase mill output, and improve cement strength. There is less research on cement raw material admixtures.
[0003] Cement raw material is the basic link in the whole cement production process. The quality and performance of cement raw material will have a direct impact on the subsequent burning, grinding and final clinker quality of the cement. Chinese patent CN110981238 proposes a granular cement raw material admixture, which improves the energy consumption of grinding to a certain extent and reduces the emission of waste gas. However, the contact degree between the granular admixture and the cement material is not high during use, so it is necessary to increase the amount of admixture added. Based on this, the present invention proposes a liquid cement raw material grinding aid. Summary of the invention
[0004] The invention provides a liquid cement raw meal grinding aid, which is characterized in that the raw materials of the cement raw meal grinding aid include phosphate, rare earth composition, metal oxide, lignin sulfonate, organic grinding aid component and water.
[0005] In a preferred embodiment, the organic grinding aid component is selected from at least one of polyols, cellulose ethers, acrylamide and its derivatives, polyamines and its derivatives.
[0006] In a preferred embodiment, the polyamine and its derivatives are ethylenediamine and its derivatives.
[0007] In a preferred embodiment, the ethylenediamine and its derivatives are at least one of hydroxyethylethylenediamine, N-(2-hydroxypropyl)ethylenediamine, N,N-diethylethylenediamine, N-ethylethylenediamine, and NN'-diethylethylenediamine.
[0008] In a preferred embodiment, the ethylenediamine and its derivatives are hydroxyethylethylenediamine.
[0009] In a preferred embodiment, the acrylamide and its derivatives are selected from at least one of N-hydroxymethyl acrylamide, N-(1-hydroxy-2,2-dimethoxyethyl)-2-acrylamide, N-(4-hydroxy-3,5-dimethylbenzyl) acrylamide, N-(tris(hydroxymethyl)methyl)acrylamide, N-(2-hydroxypropyl)-2-methyl-2-acrylamide, and N,N'-methylenebis[N-(hydroxymethyl)acrylamide].
[0010] In a preferred embodiment, the acrylamide and its derivatives are a composite substance of N-hydroxymethyl acrylamide and N-(1-hydroxy-2,2-dimethoxyethyl)-2-acrylamide.
[0011] In a preferred embodiment, the mass ratio of N-hydroxymethyl acrylamide to N-(1-hydroxy-2,2-dimethoxyethyl)-2-acrylamide is (3-6):1.
[0012] In a preferred embodiment, the mass ratio of N-hydroxymethyl acrylamide to N-(1-hydroxy-2,2-dimethoxyethyl)-2-acrylamide is 4.5:1.
[0013] In a preferred embodiment, the mass ratio of the composite material of hydroxyethylethylenediamine, N-hydroxymethylacrylamide and N-(1-hydroxy-2,2-dimethoxyethyl)-2-acrylamide is 2.5:1.
[0014] In a preferred embodiment, the rare earth composition is selected from at least one of rare earth nitrates, rare earth carbonates, rare earth sulfates, and rare earth hydrochlorides.
[0015] In a preferred embodiment, the rare earth nitrate is selected from at least one of lanthanum nitrate, zirconium nitrate, yttrium nitrate, neodymium nitrate and cerium nitrate.
[0016] In a preferred embodiment, the rare earth carbonate is selected from at least one of lanthanum carbonate, yttrium carbonate, cerium carbonate, zirconium carbonate and neodymium carbonate.
[0017] In a preferred embodiment, the rare earth composition is a composite material of cerium carbonate, cerium nitrate and lanthanum nitrate.
[0018] In a preferred embodiment, the mass ratio of the cerium carbonate, cerium nitrate and lanthanum nitrate is 1:5:3.
[0019] In a preferred embodiment, the metal oxide is selected from at least one of iron oxide, calcium oxide, manganese oxide, aluminum oxide, lanthanum oxide and yttrium oxide.
[0020] In a preferred embodiment, the metal oxide is iron oxide.
[0021] In a preferred embodiment, the phosphate is selected from at least one of sodium hexametaphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium dihydrogen phosphate, and potassium dihydrogen phosphate.
[0022] In a preferred embodiment, the phosphate is sodium hexametaphosphate.
[0023] In a preferred embodiment, the lignin sulfonate is selected from at least one of sodium lignin sulfonate, calcium lignin sulfonate, zinc lignin sulfonate and magnesium lignin sulfonate.
[0024] In a preferred embodiment, the lignin sulfonate is calcium lignin sulfonate.
[0025] In a preferred embodiment, the raw materials include, by mass percentage, 5-15% lignin sulfonate, 0.5-6% phosphate, 1-5% organic grinding aid component, 3.5-6% metal oxide, 8-15% rare earth composition, and the balance is made up of water.
[0026] In a preferred embodiment, the raw materials include, by mass percentage, 8-12% lignin sulfonate, 0.5-2% phosphate, 3-5% organic grinding aid component, 3.5-6% metal oxide, 8-15% rare earth composition, and water to make up the balance.
[0027] In a preferred embodiment, the mass ratio of the rare earth composition to the phosphate is (4-8):1.
[0028] In a preferred embodiment, the mass ratio of the rare earth composition to the phosphate is 6.5:1.
[0029] In a preferred embodiment, the raw materials include, by mass percentage, 12% lignin sulfonate, 1.8% phosphate, 3% organic grinding aid component, 4% metal oxide, 11.7% rare earth composition, and the balance is made up of water.
[0030] The applicant found in the experiment that the raw material grinding aid prepared by the present application can improve the fineness of raw materials in the grinding process, improve the quality of clinker burning, improve the burning atmosphere, and reduce the burning temperature of clinker. The applicant speculates that the possible reason is that the active substances contained in the grinding aid are thermally denatured during the grinding process of cement raw materials, which reduces the gaps between raw material particles in the initial grinding process and improves the grinding sufficiency of the initial raw material grinding. In the middle and late stages of grinding, the grinding aid prepared by the present application can also prevent grinding agglomeration to a certain extent and improve the fineness of raw materials; and in the process of raw material burning, the rare earth composition in the grinding aid of this system is thermally decomposed to release substances with catalytic activity, which improves the conversion of sulfur and nitrogen elements in the raw material calcination process, fixes sulfur elements in cement materials through minerals, and reduces the emission of harmful gases in the raw material combustion process. At the same time, the presence of rare earth elements participates in the decomposition of activated substances in the mineral decomposition process through the change of bond energy, accelerates the mineral decomposition rate, reduces the mineral decomposition temperature, and reduces energy consumption.
[0031] The second aspect of the present invention provides a method for preparing a liquid cement raw meal grinding aid, comprising the following steps: adding water into a stirrer, sequentially adding a grinding aid component, sulfate, rare earth salt, wood sulfonate, and metal oxide, and stirring evenly to obtain the raw meal grinding aid.
[0032] Compared with the prior art, the present invention has the following beneficial effects:
[0033] The cement raw material grinding aid prepared by the present invention has a simple preparation process and is easy to be promoted in industrialization. The added raw materials such as organic grinding aid components improve the fineness and uniformity of the cement raw material during the grinding process. At the same time, the addition of raw materials such as rare earth oxides improves the oxidizing atmosphere during the raw material calcination process, improves the quality of the clinker, and can also reduce the clinker calcination temperature and reduce the emission of sulfur elements during the cement raw material calcination process. DETAILED DESCRIPTION
[0034] Example 1
[0035] The first aspect of the present invention provides a liquid cement raw material grinding aid, the raw materials of which, by mass percentage, include: 12% calcium lignin sulfonate, 1.8% sodium hexametaphosphate, 3% organic grinding aid component, 4% iron oxide, 11.7% rare earth composition, and water to supplement the balance.
[0036] Among them, the organic grinding aid component is a composite material of hydroxyethylethylenediamine, N-hydroxymethylacrylamide and N-(1-hydroxy-2,2-dimethoxyethyl)-2-acrylamide, and the mass ratio of N-hydroxymethylacrylamide and N-(1-hydroxy-2,2-dimethoxyethyl)-2-acrylamide is 4.5:1; the mass ratio of the composite material of hydroxyethylethylenediamine, N-hydroxymethylacrylamide and N-(1-hydroxy-2,2-dimethoxyethyl)-2-acrylamide is 2.5:1.
[0037] The rare earth composition is a composite material of cerium carbonate, cerium nitrate and lanthanum nitrate, and the mass ratio of cerium carbonate, cerium nitrate and lanthanum nitrate is 1:5:3.
[0038] The second aspect of the present invention provides a method for preparing a liquid cement raw meal grinding aid, comprising the following steps: adding water into a stirrer, sequentially adding a grinding aid component, sulfate, rare earth salt, wood sulfonate, and metal oxide, and stirring evenly to obtain the raw meal grinding aid.
[0039] Example 2
[0040] The first aspect of the present invention provides a liquid cement raw meal grinding aid. The second aspect of the present invention provides a method for preparing the liquid cement raw meal grinding aid. The specific raw materials and implementation methods are the same as those in Example 1, except that the organic grinding aid component is hydroxyethylethylenediamine, and does not contain a composite substance of N-hydroxymethylacrylamide and N-(1-hydroxy-2,2-dimethoxyethyl)-2-acrylamide.
[0041] Example 3
[0042] The first aspect of the present invention provides a liquid cement raw meal grinding aid. The second aspect of the present invention provides a method for preparing the liquid cement raw meal grinding aid. The specific raw materials and implementation methods are the same as those in Example 1, except that the rare earth composition is a composite material of cerium nitrate and lanthanum nitrate, and no cerium carbonate is added; wherein the mass ratio of cerium nitrate to lanthanum nitrate is 5:3.
[0043] Example 4
[0044] The first aspect of the present invention provides a liquid cement raw meal grinding aid, and the second aspect of the present invention provides a method for preparing the liquid cement raw meal grinding aid. The specific raw materials and implementation methods are the same as those in Example 1, except that the rare earth composition is cerium carbonate and no iron oxide is added.
[0045] Performance Testing
[0046] The cement raw material grinding aid prepared in the embodiment was added to the cement raw material according to the grinding aid being 0.5% of the cement raw material mass, and the raw material was ground, and then the raw material was calcined. The sulfur dioxide emission during the 80 μm sieve residue after the raw material was ground and the raw material calcination process was tested. The data is recorded in Table 1.
[0047] 1.80μm sieve residue.
[0048] Refer to GB / T1345-2005 to determine the sieve residue.
[0049] 2. Sulfur dioxide emissions.
[0050] Determined by referring to the method described in GB / T37249-2018.
[0051] Table 1
[0052] 80μm sieve residue% Sulfur dioxide emissions kg / T Example 1 13.6 3.6 Example 2 18.3 3.7 Example 3 13.8 5.2 Example 4 14.3 4.3
Claims
1. A liquid cement raw meal grinding aid, characterized in that: The raw materials of cement raw material grinding aid include phosphate, rare earth composition, metal oxide, lignin sulfonate, organic grinding aid component and water.
2. The cement raw meal grinding aid according to claim 1, characterized in that: The organic grinding aid component is selected from at least one of polyols, cellulose ethers, acrylamide and its derivatives, polyamines and its derivatives.
3. The cement raw meal grinding aid according to claim 2, characterized in that: The polyamine and its derivatives are ethylenediamine and its derivatives.
4. The cement raw meal grinding aid according to claim 2, characterized in that: The acrylamide and its derivatives are selected from at least one of N-hydroxymethyl acrylamide, N-(1-hydroxy-2,2-dimethoxyethyl)-2-acrylamide, N-(4-hydroxy-3,5-dimethylbenzyl) acrylamide, N-(tris(hydroxymethyl)methyl) acrylamide, N-(2-hydroxypropyl)-2-methyl-2-acrylamide, and N,N'-methylenebis[N-(hydroxymethyl)acrylamide].
5. The cement raw meal grinding aid according to claim 1, characterized in that: The rare earth composition is selected from at least one of rare earth nitrates, rare earth carbonates, rare earth sulfates, and rare earth hydrochlorides.
6. The cement raw meal grinding aid according to claim 1, characterized in that: The metal oxide is selected from at least one of iron oxide, calcium oxide, silicon oxide, manganese oxide, aluminum oxide, lanthanum oxide and yttrium oxide.
7. The cement raw meal grinding aid according to any one of claims 1 to 6, characterized in that: The raw materials include, by mass percentage, 5-15% lignin sulfonate, 0.5-6% phosphate, 1-5% organic grinding aid component, 3.5-6% metal oxide, 8-15% rare earth composition, and the balance is supplemented by water.
8. The cement raw meal grinding aid according to claim 7, characterized in that: The raw materials include, by mass percentage, 8-12% lignin sulfonate, 0.5-2% phosphate, 3-5% organic grinding aid component, 3.5-6% metal oxide, 8-15% rare earth composition, and the balance is supplemented by water.
9. The cement raw meal grinding aid according to claim 8, characterized in that: The mass ratio of the rare earth composition to the phosphate is (4-8):
1.
10. A method for preparing a cement raw meal grinding aid according to claim 8, characterized in that: The method comprises the following steps: adding water into a stirrer, sequentially adding grinding aid components, sulfate, rare earth salt, wood sulfonate and metal oxide, and stirring evenly to obtain the raw material grinding aid.