CN1962523A - Method for consolidating heavy metal zinc of cement base material and suppressing its slow coagulation effect - Google Patents

Method for consolidating heavy metal zinc of cement base material and suppressing its slow coagulation effect Download PDF

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CN1962523A
CN1962523A CNA2005101103330A CN200510110333A CN1962523A CN 1962523 A CN1962523 A CN 1962523A CN A2005101103330 A CNA2005101103330 A CN A2005101103330A CN 200510110333 A CN200510110333 A CN 200510110333A CN 1962523 A CN1962523 A CN 1962523A
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heavy metal
sulfide
cement
ion
zinc
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CN100434385C (en
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施惠生
施慧聪
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Tongji University
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Tongji University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/60—Methods for eliminating alkali metals or compounds thereof, e.g. from the raw materials or during the burning process; methods for eliminating other harmful components
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Toxicology (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a consolidating method of heavy-metal zinc in the cement base material and inhibiting method of deferred action, which is characterized by the following: adding sulfate in the cement base material at additive pattern; releasing enough sulphur ion in the solution or cement slurry; dissolving sulfate in the water; adding proportional sulphur ion and kinds of heavy metal as standard; making sulphur ion excess according to the influence of waste material kinds and other impurity ion; converting other metal ion into zinc ion according to atom quantity when the solubility bulk of sulphate is less than ZnS; affirming the total amount of needed sulphate with industrial slag of sodium sulphate.

Description

The method of heavy metal zinc and its delayed coagulation of inhibition in a kind of solid cement sill
Technical field
The invention belongs to utilization of waste as resource and material of construction manufacturing technology field, relate to the offal treatment technology.
Background technology
Utilize various wastes to be considered to a kind of recycling economy pattern of Sustainable development rationally and effectively, under this background, the recycling of waste is the key of current social Sustainable development.Therefore, the safety issue of utilization of waste as resource also more and more comes into one's own, and it is particularly thorny that one of numerous safety issues that heavy metal contamination control problem solves as urgent need show, and becomes a lot of solid waste and reclaims the obstacle that resource utilizations are utilized again.Usually, the content of heavy metal in general solid waste is lower, adopt special technology that it is reclaimed, all very difficult technically and economically, and, even still exist a large amount of solid waste need dispose utilization after heavy metal reclaimed, and the minimizing of its quantity is very little; On the other hand, a spot of heavy metal just can produce serious harm to human ecological environment.At present, taking stabilization/solidified mode to carry out landfill disposal often to the processing mode of the solid waste that contains heavy metal, promptly mainly is harmless treatment.Relatively commonly used have cement solidification, a bituminization etc.Be the waste that the curing technology of basic material is suitable for inorganic type most with cement, especially contain the waste of heavy metal contaminants.Because the high alkalinity that cement had, though can make nearly all heavy metal form insoluble oxyhydroxide or carbonate form and be fixed in the cured body, but the intensity of its cured body is lower usually, assist measure during technology such as cement solidification can only be disposed as landfill, and, the landfill of waste is actually the great waste to resource
Quite a few solid waste of discharging in the current industrial society all contains the material with gelation activity, as many industrial residues and burning city domestic garbage lime-ash etc., through being used for the production of cement-based material after the suitable processing as complementary gelling material, but because these solid waste all contain heavy metal substance more or less, thereby fail so far to be utilized effectively.
Zinc is more common and heavy metal element that content is higher in some solid waste, studies show that much there is adverse influence in zinc to cement-based material, the unbodied zinc hydroxide that Zn forms can be deposited on the cement clinker mineral particle surface, delay the aquation of cement and condense, and further form unbodied CaZn with hydrated cementitious product calcium hydroxide reaction 2(OH) 62H 2O hinders the reaction of water and other ion and cement clinker, produces serious retardation phenomenon, and the ultimate compression strength of reduction hardening of cement slurry etc.Therefore, when containing the zinc waste, recycling also must consider the detrimental actions such as slow setting of effective inhibition zinc to cement-based material.
Summary of the invention
The object of the present invention is to provide heavy metal zinc and the method that suppresses its delayed coagulation in a kind of solid cement sill.
For achieving the above object, solution of the present invention is: the method for heavy metal zinc and its delayed coagulation of inhibition in a kind of solid cement sill, form with admixture in cement-based material is added sulfide, and this sulfide can discharge enough reacting thiourea ions in the aqueous solution or cement slurry.
Further, be that sulfide is dissolved in the water distribution, the ratio of interpolation realizes that with sulfonium ion and each heavy metal species complete reaction is that benchmark is determined.
Make sulfonium ion excessive according to the kind of waste and the influence of other foreign ions.
The excess of sulfur ion that the target heavy metal ion is had 10%-30%.
Employed sulfide adds in such a way: sulfide is dissolved in the mixing water, adds cement-waste mixture with mixing water then and stir.
Employed sulfide adds in such a way: after allowing sulfide be dissolved in the stirring water, after the adding waste stirs earlier, add cement and stir.
Zinc content is mass percent 2% when following in waste, and the addition of sulfide is 4.2～5.2 times of zinc content in the waste that utilizes in the material.
For other metal ion that contains, the sulfide solubility product situation littler than ZnS that itself and sulfonium ion form then according to the reaction precedence relationship, is converted into zine ion to other metal ion according to the nucleidic mass ratio, and then definite total amount that needs the sulfide of interpolation.
Employed sulfide is sodium sulphite.
Employed sulfide is the industrial residue of Containing Sulfur sodium.
Owing to adopted such scheme, the present invention has developed recycling economy, realizes the recycling of solid wastes utilization when solid waste is handled.
Embodiment
Present embodiment by in the cement-based material with alkali metalsulphide (Na 2S) form is added sulfonium ion, make its with waste in the heavy metal zinc ionic bond, formation heavy metal zinc sulphide because in solution to Zn 2+The ionic solubility product is 1.0 * 10 -23, and Zn 2+Ion and OH -The ionic solubility product is 1.0 * 10 -17Obviously, ZnS and Zn (OH) 2All be the indissoluble material, because the former solubility product is much smaller than the latter, so in theory, for S in the cement slurry 2-And OH -Ion is as long as the former concentration is greater than the latter's 1 * 10 -6The time, make Zn 2+Ion and S 2-In conjunction with producing the ZnS precipitation.But with different in water, each ion can not reach the free state in the aqueous solution in cement slurry, therefore need take suitable technical measures, and regulate the volume that adds control agent, and above-mentioned reaction is carried out, illustrate in the concrete method of calculation example below.On the other hand, sodium sulphite is extensive in industrial use, abundant raw material, and low price, therefore, the control method of this heavy metal species of the present invention also has very high economic and practical.
The addition manner of sodium sulphite is: sodium sulphite is dissolved in the mixing water, adds cement-waste mixture with mixing water then and stir; Or after allowing sodium sulphite be dissolved in the stirring water, after the adding waste stirs earlier, add cement and stir.The effect of two kinds of addition manners is identical.
The addition of sodium sulphite: according to the combination reaction relation of sodium sulphite and zine ion, and the influence of considering other compositions in foreign ion and the gelling material, zinc content is 2% (mass percent in waste, as follows) when following, the addition of sodium sulphite is 4.2～5.2 times of zinc content in the waste that utilizes in the material, promptly when the zinc content of waste is a, the volume of waste in cement-based material is b (generally can be 1%～30% in the practical application), and then the addition of sodium sulphite is (4.2～5.2) *a *B.Usually, the content of zinc is all much smaller than 2%, if the processing that should extract metallic zinc above 2% in the waste.The independent admixture of sodium sulphite is to the example of cement performance influence:
Cement is PII42.5 level silicate cement, and cement normal consistency water consumption, time of coagulation test according to national standard (GB/T1346-2001).The consumptive use of water normal consistence that test records this cement is 25.4%, and initial set, final setting time are respectively 135min and 198min; Intensity test piece is mixed the cement paste preparation of making 2cm * 2cm * 2cm by consumptive use of water normal consistence.Form removal behind the 24h, a ℃ following sealed maintenance is respectively tested its ultimate compression strength after 3 days, 7 days, 28 days in (20 ± 2); The ultimate compression strength of plain cement 3 days, 7 days and 28 days is respectively 86.1MPa, 93.2MPa and 101.5MPa.The leaching situation of heavy metal zinc in each hardenite when the test specimen of mixing waste is also tested 28 days respectively.Wherein the heavy metal zinc leaching test carries out according to GB5086.2-1997 " solid waste leaches the horizontal succusion of toxicity leaching method ", leach medium and simulated common physical environment (neutrality, pH=7) and severe environment (acidity, pH=3) two kinds of different conditions, filtrate is carried out assay determination with directly sucking atomic absorption spectrophotometry (AAS).
Under not zinciferous situation, sodium sulphite sees Table 1 to the influence of cement physical properties.
Table 1 sodium sulphite is to the influence of cement paste time of coagulation and ultimate compression strength
Specimen coding Sodium sulphite volume/% Presetting period/min Final setting time/min 3 days intensity/MPa 7 days intensity/MPa 28 days intensity/MPa
N01 0.02 136 200 85.5 92.1 100.8
N02 N03 0.3 1.2 136 133 197 195 84.9 85.2 92.0 93.4 98.6 99.9
As shown in Table 1, sodium sulphite exerts an influence hardly to cement setting time, and the presetting period of cement and final setting time are constant substantially behind the admixture sodium sulphite.Behind the admixture sodium sulphite cement each in length of time sky intensity and the ultimate compression strength of plain cement basic identical, the amount of strength of cement and added sodium sulphite is irrelevant, there is no the visible trend with the quantitative changeization of added sodium sulphite.The compound admixture of zinc and sodium sulphite is to cement performance influence example:
Example 1:
Heavy metal ion zinc is the form adding cement slurry with zinc nitrate in this example, and the content of zinc element is 0.06% of cement amount, and the addition content of sodium sulphite sees Table 2.The addition manner of sodium sulphite is: sodium sulphite is dissolved in the mixing water, adds in the cement admixture with mixing water then and stir; Or after allowing sodium sulphite be dissolved in to stir in the water, earlier with contain the zinc thing and stir after, add cement and stir.
Table 2 contains zinc thing A-cement material ML-1, ML-2, ML-3 test proportioning table
Specimen coding Zinc content/% Sodium sulphite addition/% The ratio of sodium sulphite and zinc Water consumption/g Cement consumption/g
ML-0 ML-1 ML-2 ML-3 0.06 0.06 0.06 0.06 0 0.252 0.276 0.312 -4.2 times 4.6 times 5.2 times 127 127 127 127 500 500 500 500
Table 3 sodium sulphite is to the time of coagulation that contains the zinc gelling material and the influence of ultimate compression strength
Specimen coding Presetting period/min Final setting time/min 3 days intensity/MPa 7 days intensity/MPa 28 days intensity/MPa
ML-0 ML-1 ML-2 ML-3 335 160 150 143 389 197 190 184 77.2 80.5 76.0 73.8 81.0 86.4 80.3 78.5 99.8 101.1 99.5 96.1
Table 4 sodium sulphite is to containing the leaching control of Toxicity of zinc gelling material
Specimen coding Neutral leach liquor concentration/(mgL -1) Leaching yield (%) Acid leaching solution concentration/(mgL -1) Leaching yield (%)
ML-0 ML-1 ML-2 ML-3 0.042 0.022 0.027 0.029 0.070 0.037 0.045 0.048 0.080 0.040 0.046 0.045 0.133 0.067 0.077 0.075
The interpolation of sodium sulphite has produced supression preferably to the delayed coagulation of zinc, can shorten about 50% time of coagulation, almost completely can offset the delayed coagulation of zinc to cement, close substantially with the time of coagulation of plain cement, and this is desirable when also to be the cement-based material recycling contain the zinc waste.In leaching toxicity test, sodium sulphite has produced control preferably to the leaching of zine ion, and as known from Table 4, leaching yield has reduced about 50%.
Example 2:
Heavy metal ion zinc is the form adding cement slurry with zinc nitrate in this example, and the volume of zinc element is 0.30%.Proportioning sees Table 5, and sodium sulphite addition manner and example 1 are together.
Table 5 contains zinc thing B-cement material MH-1, MH-2, MH-3 test proportioning table
Specimen coding Zinc content/% Sodium sulphite addition/% The ratio of sodium sulphite and zinc Water consumption/g Cement consumption/g
MH-0 MH-1 MH-2 MH-3 0.3 0.3 0.3 0.3 0 1.26 1.38 1.56 -4.2 times 4.6 times 5.2 times 127 127 127 127 500 500 500 500
Table 6 sodium sulphite is to the time of coagulation that contains the zinc gelling material and the influence of ultimate compression strength
Specimen coding Presetting period/min Final setting time/min 3 days intensity/MPa 7 days intensity/MPa 28 days intensity/MPa
MH-0 MH-1 MH-2 MH-3 462 160 126 137 615 194 188 198 46.6 66.8 67.2 64.3 57.5 76.5 75.9 72.4 77.6 89.5 87.3 84.4
Table 7 sodium sulphite is to containing the leaching control of Toxicity of zinc gelling material
Specimen coding Neutral leach liquor concentration/(mgL -1) Leaching yield (%) Acid leaching solution concentration/(mgL -1) Leaching yield (%)
MH-0 MH-1 MH-2 MH-3 0.062 0.030 0.028 0.025 0.021 0.010 0.009 0.008 0.131 0.056 0.053 0.048 0.043 0.018 0.018 0.016
The interpolation of sodium sulphite has produced control preferably to the delayed coagulation of zinc, and along with the increase of zinc content, its influence to the ultimate compression strength of hardened paste increases, though when zinc content is high strength of cement is had tangible detrimental action (comparing as can be known with example 1), but sodium sulphite also embodies active effect to being controlled at of zinc on the intensity, and cement intensity is with respect to the sample of not mixing sodium sulphite even also improve to some extent behind the admixture sodium sulphite.In leaching toxicity test, sodium sulphite to the control of zine ion can apparent in view ground as seen from Table 7, leaching yield reduces greater than 50%, the leaching yield under the acidic conditions has only and does not mix 41% of sodium sulphite sample.
Example 3:
Usually can contain various heavy in the solid waste, concerning some outer wastes that also contain other heavy metals that dezincify, also should consider other ionic influence when considering the sodium sulphite addition, be 3269mgkg as the zinc content of certain waste C -1, foreign ion copper content is 563.2mgkg -1, because the Standard Solubility Product constant of CuS is 6.0 * 10 -36, the Standard Solubility Product constant of ZnS is 1.0 * 10 -23So, show as the preferential and cupric ion reaction of sulfonium ion on the molecular balance.Sulfide solubility product all like this and sulfonium ion formation the metal ion littler than ZnS all need calculate according to following method and take in, promptly when calculating the sodium sulphite addition, can be earlier according to the reaction precedence relationship, copper (or the metal in other above-mentioned scopes) ion is converted into zine ion according to the nucleidic mass ratio, and then calculates the total amount of the sodium sulphite that adds.Be calculated as follows:
Heavy metal element: Cu～Zn
Nucleidic mass: 64 65
Content: 563.2 x
Calculating can obtain x=572 (mgkg -1)
So the equivalent of zinc is in this waste: 3269mgkg -1+ 572mgkg -1=3.8gkg -1=0.38%
When this kind waste of admixture in cement 20%, cement-waste mixture (GB/T1346-89) is carried out the test of standard consistency according to national standard " cement normal consistency water consumption, time of coagulation the method for inspection ", consumptive use of water normal consistence be P=26%.So, by the aforesaid sodium sulphite adding proportion of the present invention, the sodium sulfide amount of interpolation should for:
4.2*0.38％*20％＝0.32％
4.6*0.38％*20％＝0.35％
5.2*0.38％*20％＝0.40％
Table 8 waste C-cement testing proportioning table
Specimen coding Waste C volume/% Sodium sulphite addition/% Water consumption/g Cement consumption
F20 F20N-42 F20N-46 F20N-52 20 20 20 20 0 0.32 0.35 0.40 130 130 130 130 400 400 400 400
Table 9 sodium sulphite is to the cement slurry time of coagulation of mixing waste C and the influence of ultimate compression strength
Specimen coding Presetting period/min Final setting time/min 3 days intensity/MPa 7 days intensity/MPa 28 days intensity/MPa
F20 F20N-42 F20N-46 F20N-52 137 130 136 134 220 210 224 200 38.1 39.6 40.7 40.3 51.4 52.3 57.4 56.5 65.0 65.7 66.4 62.3
To carrying out leaching test after the broken sampling of the cement of maintenance after 28 days-waste hardened paste test block, leach medium simulated common physical environment (neutrality, pH=7) and severe environment (result is as shown in table 10 for acidity, condition pH=3).
The leaching of table 10 zinc in neutral and sour environment
Specimen coding Neutral leach liquor concentration/(mgL -1) Leaching yield (%) Acid leaching solution concentration/(mgL -1) Leaching yield (%)
F20 F20N-42 F20N-46 F20N-52 0.050 0.034 0.030 0.032 0.078 0.053 0.047 0.050 0.085 0.046 0.044 0.043 0.133 0.072 0.069 0.067
As can be seen from the results, though owing to contain some in this waste cement is promoted the agglomerative component, so after mixing waste cement setting time is influenced not quite, sodium sulphite here more has been the effect that the control heavy metal oozes out.Add under the sodium sulphite addition at three kinds, the zine ion of cement-waste hardened paste leaches concentration all will obviously be reduced with respect to the sample that does not add sodium sulphite, under acidic conditions, sodium sulphite is more remarkable to the stabilization of heavy metal, and its rate of release has reduced near about 50%.
Employedly also not necessarily be defined in alkali metalsulphide, if the material of the sulfonium ion that can dissociate, and this positively charged ion does not have a negative impact to the performance of cement-based material; Further, consider to use extensively abundant raw material, low price, the industrial residue of preferred sodium sulphite and Containing Sulfur sodium.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.

Claims (10)

1, heavy metal zinc and suppress the method for its delayed coagulation in a kind of solid cement sill, it is characterized in that: the form with admixture in cement-based material is added sulfide, and this sulfide can discharge enough reacting thiourea ions in the aqueous solution or cement slurry.
2, heavy metal zinc and suppress the method for its delayed coagulation in the solid cement sill according to claim 1, it is characterized in that: be that sulfide is dissolved in the water distribution, the ratio of interpolation realizes that with sulfonium ion and each heavy metal species complete reaction is that benchmark is determined.
3, heavy metal zinc and suppress the method for its delayed coagulation in the solid cement sill according to claim 1 is characterized in that: make sulfonium ion excessive according to the kind of waste and the influence of other foreign ions.
4,, it is characterized in that: the target heavy metal ion is had 10%～30% excess of sulfur ion according to heavy metal zinc in the solid cement sill described in the claim 3 with suppress the method for its delayed coagulation.
5, heavy metal zinc and suppress the method for its delayed coagulation in the solid cement sill according to claim 1, it is characterized in that: employed sulfide adds in such a way: sulfide is dissolved in the mixing water, adds cement-waste mixture with mixing water then and stir.
6, heavy metal zinc and suppress the method for its delayed coagulation in the solid cement sill according to claim 1, it is characterized in that: employed sulfide adds in such a way: after allowing sulfide be dissolved in the stirring water, after the adding waste stirs earlier, add cement and stir.
7, according to heavy metal zinc in claim 5 or the 6 described solid cement sills with suppress the method for its delayed coagulation, it is characterized in that: zinc content is mass percent 2% when following in waste, and the addition of sulfide is 4.2～5.2 times of zinc content in the waste that utilizes in the material.
8, heavy metal zinc and suppress the method for its delayed coagulation in the solid cement sill according to claim 7, it is characterized in that: for other metal ion that contains, the sulfide solubility product situation littler that it forms with sulfonium ion than ZnS, then according to the reaction precedence relationship, other metal ion is converted into zine ion according to the nucleidic mass ratio, and then definite total amount that needs the sulfide of interpolation.
9, according to heavy metal zinc in arbitrary described solid cement sill in the claim 1 to 6,8 with suppress the method for its delayed coagulation, it is characterized in that: employed sulfide is sodium sulphite.
10, according to heavy metal zinc in arbitrary described solid cement sill in the claim 1 to 6,8 with suppress the method for its delayed coagulation, it is characterized in that: employed sulfide is the industrial residue of Containing Sulfur sodium.
CNB2005101103330A 2005-11-11 2005-11-11 Method for consolidating heavy metal zinc of cement base material and suppressing its slow coagulation effect Expired - Fee Related CN100434385C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100579931C (en) * 2007-11-02 2010-01-13 浙江工业大学 Super slow-setting cement
CN109867467A (en) * 2019-04-16 2019-06-11 福建圣永业能源科技有限公司 A kind of enhanced high-efficiency grinding aid of slow setting and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100579931C (en) * 2007-11-02 2010-01-13 浙江工业大学 Super slow-setting cement
CN109867467A (en) * 2019-04-16 2019-06-11 福建圣永业能源科技有限公司 A kind of enhanced high-efficiency grinding aid of slow setting and preparation method thereof

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