CN1319893C - Composite grinding aid for cement , cement containing same and its production method - Google Patents
Composite grinding aid for cement , cement containing same and its production method Download PDFInfo
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- CN1319893C CN1319893C CNB2005101025007A CN200510102500A CN1319893C CN 1319893 C CN1319893 C CN 1319893C CN B2005101025007 A CNB2005101025007 A CN B2005101025007A CN 200510102500 A CN200510102500 A CN 200510102500A CN 1319893 C CN1319893 C CN 1319893C
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Abstract
The present invention relates to a composite grinding assistant for cement, and cement to which the composite grinding assistant is added and a production method thereof. The composite grinding assistant for cement comprises 5 to 30 wt% of unhydrous compound of ethanolamine, 10 to 50 wt% of slag and/or fly ash sieved with 300 meshes of screen mesh and 45 to 60 wt% of sodium sulfate. The composite grinding assistant for cement, obtained by the present invention, mainly has the following properties that the composite grinding assistant is directly added by 1 to 3% with various raw materials when cement is ground, and the composite grinding assistant is simple and easy and is convenient to be accurately metered and operated; under the condition of the same physical chemistry performance index, the catalyst can increase the production capacity of unit hour of a pulverizer by 10 to 20%, and the power consumption of cement production is lowered; under the condition of the same mixture ratio of various raw materials of cement, the catalyst can obviously increase the early strength of cement, and the strength for 28 days can be increased by 5 to 10MPa.
Description
Technical field
The present invention relates to a kind of cement additire that can improve the cement physical and chemical performance, especially a kind of cement composite grinding additive that can improve strength of cement, reduce ton cement ball consumption.The invention still further relates to the cement that added this cement grinding aid and the manufacture method of this cement grinding aid.
Background technology
Add together when carrying out grinding in the grinding machine at grog, auxiliary material when cement, because acutely and continually friction and bump between material and the material, between material and the grinding element, make material produce static, these materials that have electric charge can be adsorbed on the surface of steel ball and grinding element, cause cement mill serious bag ball, bag forging phenomenon to occur; When the humidity of the auxiliary material that adds is higher than 5%, can in grinding machine, produce a large amount of water vapour again, the humidity of abrasive is increased, can produce above-mentioned bag ball, bag forging phenomenon equally, cement output and quality are descended significantly.
In order to address this problem, the way that adds cement grinding aid is adopted in the cement mill more than 95% at present.Commercially available cement grinding aid mainly is by crude substance or the preparation of pure chemistry product, a kind of cement grinding aid that adopts talcum, molasses preparation is disclosed as CN 1089245A, its cost is low, source of goods foot, energy power saving 30%, but because molasses belong to sugar waste, the component complexity is subjected to the restriction in the place of production easily, and the quality of the finished product also is difficult to control; CN 1018387A discloses the cement grinding aid of preparation such as multiple employing urea and glycol ether, and these cement grinding aids or raw material sources are wide, unstable properties, perhaps cost height, and raw material is too expensive, does not all obtain excellent popularization and uses.
Purpose of the present invention will overcome above-mentioned shortcoming exactly, provides a kind of cost low, and product performance are stable, effective cement grinding aid.Simultaneously, because along with China's rapid development of economy, the present situation that various places are built thermal power plant and enlarged metallurgical scale causes the flyash quantity of slag, power plant emission of steel mill's discharging increasing, take the farmland, stop up rivers, contaminate environment for fear of these slags and flyash, in order effectively to promote slag and the application of flyash in building materials industry, we have carried out a large amount of research trials, have obtained the present invention finally.
Summary of the invention
According to an aspect of the present invention, the invention provides a kind of composite cement grinding aid, include the alcohol amine compound of 5～20wt%, the slag of 35～50wt% and/or flyash, the Sodium sulfate anhydrous.min(99) of 45～60wt%.Wherein, the water-free alcohol amine compound of further preferred employing, described alcohol amine compound preferably includes Monoethanolamine MEA BASF, diethanolamine and trolamine; Slag and/or flyash are slag and/or the flyash through the screening of 300 eye mesh screens.
According to another aspect of the present invention, the invention provides a kind of employing cement of cement composite grinding additive as mentioned above, wherein the addition of cement composite grinding additive is 1～3wt%.
According to also aspect of the present invention, the invention provides a kind of manufacture method of cement composite grinding additive as mentioned above, comprise the following steps: to prepare various raw materials according to the proportioning and the specification requirement of above-mentioned composite cement grinding aid; They are joined in the mixing and blending machine successively stir; The pack discharging.
The cement composite grinding additive that obtains according to the present invention, it in use mainly has following performance:
1, when cement grinding, directly add 1～3% with various raw materials, simple, be convenient to accurately metering and operation.
2, under the identical condition of cement physical and chemical performance index, use this cement composite grinding additive can improve pulverizer unit hour output 10-20%, reduce the power consumption of manufacture of cement.
3, under the identical situation of the various raw material ratios of cement, use this cement composite grinding additive that cement early strength is significantly improved, and make 28 days intensity improve 5-10MPA.
Embodiment
One, the preparation of composite cement grinding aid
1, the dehydration of alcohol amine compound
The trolamine of 100 gram 98wt% content (is derived from Hua Feng chemical plant, Fushun, wherein contain a small amount of Monoethanolamine MEA BASF and diethanolamine, do not influence use) and 200 gram toluene inject 1000 milliliters of four-hole boiling flasks being placed on the heating jacket, four mouths of flask are plugged with the thermometer plug respectively, the opening for feed plug, stirring sleeve plug and water collector sleeve pipe, be connected with prolong on the water collector sleeve pipe again, in flask, add a small amount of zeolite, open water of condensation, raise the temperature to about 120 ℃, kept 5～10 hours, the oily water separation liquid level is no longer mobile in water collector, oil phase and water clarification, water and toluene liquid (oil phase) are collected respectively in the container, and the alcohol amine compound through processed in the flask is used for next step preparation manipulation.
The reason that alcohol amine compound is dewatered is because will prevent that the humidity that adds auxiliary material is higher than 5%, this may cause producing a large amount of water vapour in grinding machine, the humidity of abrasive is increased, thereby cause bag ball, bag forging phenomenon, cement output and quality are descended significantly.Simultaneously, according to the research of Lie Binjieer, contain suitable water in the cement process, can promote the reduction of cement particle surface energy, prevent the particulate reunion, thereby reduce the consumption of grinding machine electric energy, if but moisture too many, because water molecules all is a polar molecule, form spheroidal aggravation easily and between the cement granules, reunite to form macrobead gradually, and moisture also may cause bag ball, the cement problems such as inefficacy that harden.Owing to itself contain micro-moisture in the cement clinker, so should remove moisture in the raw material of synthetic water cement grinding aids as far as possible.
2, the pulverizing of slag/flyash
Slag
The present invention selects deslagging maximum, the more stable Shoudu Iron and Steel Co grain slag of performance for use.Concrete technical indicator satisfies: quality coefficient K 〉=1.2; Alkalescence coefficient Mo 〉=1.0; Reactivity coefficient Ma 〉=0.12.Its mineral composition, Chemical Composition and basicity see Table 1.
The mineral composition of table 1 grain slag, Chemical Composition and basicity (%)
| Numbering | C 3S | C 2S | RO | C 2F+CF | SiO 2 | Al 2O 3 | CaO | FeO | MgO | Fe 2O 3 | P 2O 5 | F-CaO | Basicity |
| 1 # | 39.70 | 18.20 | 27.30 | 1.20 | 11.40 | 3.13 | 43.13 | 9.71 | 9.86 | 10.37 | 0.35 | 1.29 | 3.54 |
Flyash
The present invention adopts the Yanshan Petrochemical dry discharge fly ash, detects through opticinstrument, wherein contains partial crystallization body, vitreum and a small amount of not most coal of alkene, and particle is thinner, and is active higher.Its Chemical Composition and loss on ignition see Table 2.
Table 2 flyash Chemical Composition and loss on ignition (%)
| Numbering | CaO | SiO 2 | Al 2O 3 | FeO | MgO | Na 2O | K 2O | f-CaO | Nnn |
| 1# | 3.98 | 46.90 | 31.13 | 11.52 | 0.75 | 0.28 | 1.44 | 4.35 | 3.17 |
5 kilograms of slags and 5 kilograms of flyash are packed into dispose in the ball mill of ceramic grinding ball, add a small amount of industrial spirit (70wt% purity is about 100 milliliters), stirred discharging, airing 2 days 24～48 hours, carry out dusting cover with 300 order mesh screens, will not pass through the thick slag ball milling use again of mesh screen.
The purpose of pulverizing is to make cement grinding aid be more suitable for the requirement of cement granularity, now in the high standard cement granules granularity to intensity play a decisive role generally about 3～35 microns, if the particle of cement grinding aid itself is too big or too little, all might increase the burden of cement ball-milling, have only the particle of cement grinding aid itself and particle that cement requires close, it is just the most satisfactory that both grind the result who obtains each other, so carry out dusting cover by 300 order mesh screens, can make the result of use of slag and flyash obtain the best.
3, the preparation of composite cement grinding aid
The chemical constitution of composite cement grinding aid
The chemical constitution of table 3 composite cement grinding aid (wt%)
| Trolamine * | Slag/flyash | Sodium sulfate anhydrous.min(99) ** | |
| Prescription 1 | 5 | 35 | 60 |
| Prescription 2 | 5 | 45 | 50 |
| Prescription 3 | 5 | 50 | 45 |
| Prescription 4 | 10 | 35 | 55 |
| Prescription 5 | 10 | 45 | 45 |
| Prescription 6 | 15 | 35 | 50 |
| Prescription 7 | 15 | 40 | 45 |
| Prescription 8 | 20 | 35 | 45 |
| Prescription 9 | 50 | 25 | 25 |
| Prescription 10 | 0 | 50 | 50 |
| Prescription 11 | 50 | 50 | 0 |
Annotate
*: this trolamine is above-mentioned technical grade trolamine through processed, wherein contains a spot of Monoethanolamine MEA BASF and diethanolamine (being less than 15wt%).
Annotate
*: the Sodium sulfate anhydrous.min(99) that the present invention uses is to derive from the technical grade Sodium sulfate anhydrous.min(99) that bright chemical plant is built in Shandong.
The preparation of composite cement grinding aid
Take by weighing the various embodiments described above proportion raw material successively, in pack into large-scale stirrer or the vibration mill, stirred 30 minutes, mix, pack standby.
4, composite cement grinding aid performance detection
Test water mud grog
In order to make result of the present invention have general applicability, when choosing starting material, fetch sample from the different manufacturers in Beijing and Hebei respectively.The mineral substance composition of various cement clinkers, Chemical Composition and rate value see Table 4.
Table 4 clinker mineral composition, Chemical Composition and rate value
| Numbering | Mineral composition (%) | Chemical Composition content (%) | The rate value | |||||||||||
| C 3S | C 2S | C 3A | C 4AF | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | SO 3 | nnn | KH | n | p | |
| 1 # 2 # | 58.19 51.32 | 12.10 19.70 | 9.54 6.85 | 10.51 15.31 | 19.30 18.51 | 6.07 6.71 | 3.85 2.78 | 63.01 62.15 | 3.58 2.78 | 1.86 1.40 | 0.37 0.50 | 0.93 0.85 | 1.94 1.81 | 1.51 1.49 |
Respectively prescription 1～5 is added in the cement clinker 1 when the cement grinding by 1% addition, prescription 6～11 is added in the cement clinker 2 when the cement grinding by 3% addition, and carry out following test.Can also add various blended materials (as phosphogypsum, slag, flyash etc.) in the cement clinker, to reduce cost.
Two, composite cement grinding aid physical and mechanical property test in manufacture of cement
1, the little mill experimental test in laboratory
Test by GB175-92, GB1344-92, GB1345-91 method, test-results sees Table 5.
The cement physical and mechanical property that table 5 adopts composite cement grinding aid of the present invention to produce
| Embodiment | Fineness (%) | (h:min) condenses | Stability | Anti-folding (MPa) | Resistance to compression (Mpa) | ||||
| 7d | 28d | 7d | 28d | ||||||
| The 1# grog | 1 2 3 4 5 6 | 7.5 7.4 6.9 7.1 7.2 7.6 | 1:15 1:30 1:51 1:49 1:54 0:45 | 3:10 3:23 3:40 3:45 3:51 2:56 | Qualified qualified | 6.1 5.6 5.7 5.6 5.5 6.2 | 8.9 6.9 6.8 6.7 6.5 7.4 | 45.7 31.5 32.4 34.7 31.4 42.7 | 63.2 51.2 49.7 49.2 49.4 59.3 |
| The 2# grog | 7 8 9 10 11 | 7.5 7.2 7.3 7.6 7.2 | 1:15 1:17 1:23 1:19 1:23 | 3:15 3:20 5:27 3:19 2:53 | Qualified defective defective | 5.7 5.8 2.5 1.7 2.6 | 6.9 7.2 3.8 3.2 3.8 | 30.2 29.1 19.8 18.4 17.4 | 49.6 48.9 19.1 18.8 17.6 |
2, laboratory test result analysis
By the data contrast as seen, adopt after the composite cement grinding aid of proportioning of the present invention, can improve the per-cent of blended material in cement ingredient, its concrete characteristics are as follows:
(1) behind the composite cement grinding aid of use proportioning of the present invention, the fineness of cement is constant substantially, and the presetting period is postponed about 30min, and 40min is postponed in final set, and stability obviously improves.
(2) as can be known from the test of 1# grog and 2# grog, adopt same grog, the increase of blending amount of mixture material slightly reduces the 7d intensity of cement behind the composite cement grinding aid of use proportioning of the present invention, but intensity does not change substantially, even the trend of raising being arranged. the composite cement grinding aid that proportioning of the present invention is described can make after to blended material catalysis the activity of blended material meet or exceed the activity of grog, produces the intensity close with grog.
(3) as can be known by the test of grog 1# and 2#, grog to different manufacturers, the cement intensity index is close with contrast sample intensity behind the composite cement grinding aid of use proportioning of the present invention, illustrates that the composite cement grinding aid of proportioning of the present invention all has extremely strong adaptability to various cement clinkers.
(4) under the identical condition of cement physical and chemical performance index, use the composite cement grinding aid of proportioning of the present invention can improve pulverizer unit hour output 10-20%, reduce the power consumption of manufacture of cement.
According to little mill test-results, we select 2# grog manufacturer to carry out with ratio of components industrialness production test, and concrete production method is identical with ordinary production, when discharging is stablized in test, extracted four groups of samples and detected, with the detected result comparison of comparative sample, data see Table 6.
Table 6 industrial production test result
| Project | Embodiment | Fineness (%) | (h:min) condenses | Stability | Anti-folding (MPa) | Resistance to compression (Mpa) | |||
| Initial set | Final set | 7d | 28d | 7d | 28d | ||||
| The present invention | 6 | 7.6 | 0:45 | 2:56 | Qualified | 6.2 | 7.4 | 42.7 | 59.3 |
| 7 | 7.5 | 1:15 | 3:15 | Qualified | 5.7 | 6.9 | 30.2 | 49.6 | |
| Original product | Do not add grinding aid | 6.1 | 1:35 | 3:31 | Qualified | 5.2 | 6.2 | 28.3 | 45.2 |
| 11 | 6.3 | 5:25 | 7:41 | Defective | 3.6 | 5.3 | 25.1 | 42.3 | |
According to table 6 testing data as can be known, because the improvement of production environment, blending dispersion gets more even, so effect is more better than little mill test.Cement fineness is close with the contrast sample, and 15-20min is postponed in initial set, and final set is postponed about 40min, and stability improves, and 7d intensity and 28d intensity all are better than the contrast sample.Therefore, the composite cement grinding aid of proportioning of the present invention is applied to can improve the volume of blended material, and product performance be reliable in the suitability for industrialized production of cement in enormous quantities.
More than by various specific embodiments the specific embodiment of the present invention and various performance have been carried out at large describing, but those skilled in the art should understand that, the present invention can make various modifications, change and recombinant in the scope of accompanying Claim, and without departing from the spirit and scope of the present invention.
Claims (4)
1. cement composite grinding additive, contain:
The water-free alcohol amine compound of 5～30wt%,
The slag of 10～50wt% and/or flyash,
The Sodium sulfate anhydrous.min(99) of 45～60wt%,
Wherein said slag and/or flyash are slag and/or the flyash through the screening of 300 eye mesh screens.
2. cement composite grinding additive as claimed in claim 1 is characterized in that described alcohol amine compound comprises Monoethanolamine MEA BASF, diethanolamine and trolamine.
3. cement that adopts cement composite grinding additive as claimed in claim 1, wherein the addition of cement composite grinding additive is 1～3wt%.
4. the manufacture method of a cement composite grinding additive as claimed in claim 1 comprises:
Proportioning and specification requirement according to composite cement grinding aid as claimed in claim 1 take by weighing various raw materials;
They are joined in the mixing and blending machine successively stir; And
The pack discharging.
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| CNB2005101025007A CN1319893C (en) | 2005-09-15 | 2005-09-15 | Composite grinding aid for cement , cement containing same and its production method |
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| CNB2005101025007A CN1319893C (en) | 2005-09-15 | 2005-09-15 | Composite grinding aid for cement , cement containing same and its production method |
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| CN1319893C true CN1319893C (en) | 2007-06-06 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337791B (en) * | 2008-08-13 | 2011-05-11 | 大庆石油管理局 | Grinding assistant modifier for complex cement including slag |
| BR112014030944A2 (en) * | 2012-06-25 | 2017-06-27 | Dow Global Technologies Llc | grinding aid composition for grinding cement slag, cement mixture and method for increasing grinding efficiency and improving specific surface area of a cement |
| CN112299738A (en) * | 2020-10-29 | 2021-02-02 | 南京永能新材料有限公司 | Grinding aid special for marine cement and preparation method thereof |
| CN112279552A (en) * | 2020-11-05 | 2021-01-29 | 南京永能新材料有限公司 | Grinding aid special for conductive cement and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1003511B (en) * | 1986-10-27 | 1989-03-08 | 国家建筑材料工业局建筑材料科学研究院水泥科学研究所 | Cement composite grinding aid |
| CN1351973A (en) * | 2000-11-15 | 2002-06-05 | 王先进 | Composite grinding aiding and reinforcing stabilizer for cement |
-
2005
- 2005-09-15 CN CNB2005101025007A patent/CN1319893C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1003511B (en) * | 1986-10-27 | 1989-03-08 | 国家建筑材料工业局建筑材料科学研究院水泥科学研究所 | Cement composite grinding aid |
| CN1351973A (en) * | 2000-11-15 | 2002-06-05 | 王先进 | Composite grinding aiding and reinforcing stabilizer for cement |
Non-Patent Citations (3)
| Title |
|---|
| 一种高性能复合水泥助磨剂的试验研究 丁向群等，水泥，第3期 2004 * |
| 多功能水泥复合助磨剂研究 江朝华等，河海大学学报(自然科学版)，第31卷第4期 2003 * |
| 多功能水泥复合助磨剂研究 江朝华等，河海大学学报(自然科学版)，第31卷第4期 2003;一种高性能复合水泥助磨剂的试验研究 丁向群等，水泥，第3期 2004 * |
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