WO2006049465A1 - Pulp sludge ash composition for producing building materials - Google Patents
Pulp sludge ash composition for producing building materials Download PDFInfo
- Publication number
- WO2006049465A1 WO2006049465A1 PCT/KR2005/003736 KR2005003736W WO2006049465A1 WO 2006049465 A1 WO2006049465 A1 WO 2006049465A1 KR 2005003736 W KR2005003736 W KR 2005003736W WO 2006049465 A1 WO2006049465 A1 WO 2006049465A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pulp sludge
- sludge ash
- composition
- sodium silicate
- building materials
- Prior art date
Links
Classifications
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/01—Waste products, e.g. sludge
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- 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
Definitions
- the present invention relates to a pulp sludge ash composition for producing building materials. More particularly, the present invention relates to a pulp sludge ash composition for producing building materials, which comprises pulp sludge ash obtained by incineration of pulp sludge generated from a paper manufacturing process after a wastewater treatment step, and further comprises modified sodium silicate having an acidic group.
- the pulp sludge ash composition according to the present invention allows fast curing with no need for additional baking or sintering. Additionally, the above pulp sludge ash composition further comprising a polymer emulsion shows excellent strength and water resistance.
- pulp sludge is generated from a paper manufacturing process after a wastewater treatment step, in a great amount. Most of the pulp sludge has been discarded in a landfill. However, pulp sludge itself is not suitable to be discarded as landfill because it is not solidified with ease due to its high water content. Therefore, a recent tendency has been for pulp sludge to be dumped in the sea.
- Pulp sludge ash generated from such incineration has been thought to have low industrial applicability, and thus has been utilized in limited use (for example, a supplementary additive for cement).
- Korean Patent Publication No. 1989-0002566 discloses a method for producing building materials using ash generated from the incineration of paper-manufacturing sludge. More particularly, the method comprises adding slaked lime, asbestos, paper-manufacturing sludge, or the like to the pulp sludge ash, further adding sodium silicate thereto to accomplish preliminary bonding, and curing the resultant product with steam under high temperature and high pressure conditions to provide building materials. The method permits the initial molding work to be performed quickly due to the curing reaction of metal oxides and sodium silicate added to the pulp sludge ash.
- the present invention has been made iri view of the above-mentioned problems. It is an object of the present invention to provide a pulp sludge ash composition for producing building materials, wherein the pulp sludge ash composition comprises pulp sludge ash and modified sodium silicate having an acidic group added thereto, allows fast curing with no need for additional baking or sintering, and shows excellent strength and water resistance.
- a pulp sludge ash composition for producing building materials which is obtained by mixing pulp sludge ash with modified sodium silicate having an acidic group.
- a pulp sludge ash composition for producing building materials which is obtained by mixing pulp sludge ash with modified sodium silicate having an acidic group, combined with a polymer emulsion.
- the modified sodium silicate having an acidic group is obtained by mixing sodium silicate with any one selected from the group consisting of: aqueous sodium sulfate, copper sulfate, iron sulfate, aluminum, sulfate, magnesium sulfate, potassium bicarbonate, chrome alum, sulfuric acid and hydrochloric acid solutions; and mixtures thereof; and then adding caustic soda thereto as a catalyst.
- the modified sodium silicate having an acidic group is obtained by introducing sodium silicate and each aqueous solution of copper sulfate, sodium sulfate, caustic soda and chrome alum into ' an agitator, followed by agitation.
- the modified sodium silicate having an acidic group is obtained by introducing sodium silicate, 10% aqueous sodium lauryl sulfate solution, caustic soda and aqueous sulfuric acid solution into an agitator, followed by agitation.
- the polymer emulsion is any one selected from the group consisting of latex, silicone resin, gum arabic, acrylic resins and epoxy resins.
- the pulp sludge ash composition according to the present invention the pulp sludge ash and the modified sodium silicate having an acidic group are mixed in a ratio of 1: 1.2—2.
- the pulp sludge ash composition may further comprise any one selected from the group consisting of- dust, fly ash, sand, slag, gypsum, lime and molding sand.
- the pulp sludge ash composition may further comprise any one light-weight additive selected from the group consisting of wood powder, pearlite, vermiculite, Styrofoam particles and a foaming agent.
- any one light-weight additive selected from the group consisting of wood powder, pearlite, vermiculite, Styrofoam particles and a foaming agent.
- organic bentonite or methyl cellulose is further added thereto in order to accomplish a uniform distribution.
- the pulp sludge ash composition may further comprise any one selected from the group consisting- of wire mesh, waste fiber and fiber.
- the cement-like composition according to the present invention which comprises pulp sludge ash and the modified sodium silicate, shows excellent water resistance and strength, and thus is useful for various industrial fields as a building material, etc.
- the composition may further comprise various kinds of additives, if desired, to conform to the particular use thereof. Additionally, it is possible to transform various kinds of industrial wastes into the composition according to the present invention. Therefore, the present invention contributes to recycling of wastes and the protection of environment, and is cost-efficient and time-efficient.
- FIG. 1 is a photograph showing various building materials obtained from the pulp sludge ash compositions according to preferred embodiments of the present invention.
- modified sodium silicate to improve the strength of a pulp sludge ash composition, wherein the modified sodium silicate is obtained by adding sodium silicate to an acidic solution, such as an aqueous solution of sodium sulfate, copper sulfate, iron sulfate, aluminum sulfate, magnesium sulfate, potassium bicarbonate, chrome alum, sulfuric acid or hydrochloric acid solutions.
- caustic soda sodium hydroxide
- modified sodium silicate 1 and modified sodium silicate 2 as described hereinafter so as to improve the water resistance to the highest degree.
- Modified sodium silicate 1 having an acidic group is obtained by introducing sodium silicate, copper sulfate, sodium sulfate and chrome alum into an agitator in a mixing ratio of 30:4:3:20, further introducing caustic soda into the agitator in the same proportion as chrome alum, and agitating the resultant mixture for 30 minutes.
- Modified sodium silicate 2 having an acidic group is obtained by adding 10% aqueous sodium lauryl sulfate solution and caustic soda to sodium silicate, agitating the resultant mixture for 30 minutes, and further adding aqueous sulfuric acid solution thereto with stirring.
- sodium silicate, 10% aqueous sodium lauryl sulfate solution, caustic soda and aqueous sulfuric acid solution are mixed in a ratio of 10:3:10:3.
- the modified sodium silicate having an acidic group, obtained as described above, is added to pulp sludge ash to provide the composition for producing building materials according to the present invention.
- the pulp sludge ash has a fine size of 150 mesh or less, and the mixing ratio of pulp sludge ash to the modified sodium silicate is 1: 1.2—2, on the weight basis.
- the cement-like composition according to the present invention comprising pulp sludge ash and the modified sodium silicate having an acidic group, may further comprise various additives, so as to improve the water resistance, to prevent deformation such as shrinkage, to increase the strength, to reduce the specific gravity, or to improve the bending strength.
- the composition optionally further comprises a polymer emulsion selected from the group consisting of latex, silicone oil, gum arabic, acrylic resins and epoxy resins, in addition to the modified sodium silicate having an acidic group.
- a polymer emulsion selected from the group consisting of latex, silicone oil, gum arabic, acrylic resins and epoxy resins, in addition to the modified sodium silicate having an acidic group.
- ⁇ 4i> For example, 3—25 g of latex, as a polymer emulsion, may be further added to 100 g of the above Modified sodium silicate 1 having an acidic group with stirring, and then the resultant combination may be added to pulp sludge ash. However, addition of the latex in an amount of 25 g or more inhibits fast curing.
- silicone oil as a polymer emulsion, may be further added to 100 g of the above Modified sodium silicate 1 having an acidic group with stirring, and then the resultant combination may.be added to pulp sludge ash.
- addition of the silicone oil in an amount of 15 g or more inhibits fast curing.
- the cement-like composition comprising pulp sludge ash and the modified sodium silicate having an acidic group, may further comprise calcium carbonate, lime, a metal oxide such as magnesium oxide or zinc oxide, or the like.
- the cement-like composition comprising pulp sludge ash and the modified sodium silicate having an acidic group
- the cement-like composition, comprising pulp sludge ash and the modified sodium silicate having an acidic group may further comprise light-weight aggregate, such as wood powder, pearlite, vermiculite or Styrofoam particles, or may be provided with air bubbles obtained from pressurized air with a vegetable foaming agent.
- a thickening agent such as organic bentonite or methyl cellulose may be further added thereto so as to accomplish uniform blending.
- the cement- like composition comprising pulp sludge ash and the modified sodium silicate having an acidic group, may further comprise wire mesh, waste fiber, fiber, or the like.
- the pulp sludge ash composition was injected into a cylindrical mold having a diameter of 50mm and a depth of 100 mm. Then, a bar having a weight of lkg and a diameter of 10mm was placed on the mold at different times, and determined the initial curing completion time, when the molded product showed no physical changes in its surface and permitted demolding and handling.
- the composition removed from the mold was cured naturally for 7 days. Then, the composition was measured for its weight and strength. Additionally, the composition was dipped into a water bath for 24 hours and removed from the water bath. Then, the composition was dried for 1 hour, and then was measured for its weight and strength to determine the water absorptivity and strength of the composition. The results are shown in the following Table 1.
- ⁇ 6i> First, 60 parts of pulp sludge ash were provided. Next, 85 parts of modified sodium silicate were prepared by mixing 1,50Og of sodium silicate with an aqueous acidic solution with stirring. The acidic solution was obtained by introducing 20Og of copper sulfate, 15Og of sodium sulfate, 1,00Og of caustic soda and 1,00Og of chrome alum into an agitator, each in the form of an aqueous solution, and agitating the materials for 30 minutes. Further, 3Og of silicone oil were added to l,000g of the acidic solution. Then, 60 parts of pulp sludge were mixed with 85 parts of the modified sodium silicate to obtain a cement-like composition.
- a composition was prepared by adding 100 parts of non-modified sodium silicate solution to 60 parts of pulp sludge ash.
- the compositions comprising pulp sludge ash and the modified sodium silicate having an acidic group are capable of fast curing within 1 hour, thereby providing products that can be demolded, transported and loaded with ease. Such compositions are amenable to mass production.
- addition of a polymer emulsion can provide the compositions with excellent water resistance, as compared to the sample free from a polymer emulsion, which shows a relatively high water absorptivity and a relatively low strength.
- the sample according to the above Comparative Example comprising non-modified sodium silicate, is not capable of fast curing and causes cracking and deformation on the surface during drying.
- the comparative sample shows such poor water resistance that the sample may be dissolved in the water bath dipping test, thereby making it impossible to measure the strength after dipping. Therefore, it can be seen that the sample according to the above Comparative Example has no industrial applicability.
- the final composition was injected into a cylindrical mold having a diameter of 100mm and a depth of 200 mm. Then, a bar having a weight of lkg and a diameter of 10mm was placed on the mold at different times, and determined the initial curing completion time, when the molded product showed no physical changes in its surface and permitted demolding and handling.
- the composition removed from the mold was cured naturally for 3 days. Then, the composition was measured for its weight and strength. Additionally, the composition was dipped into a water bath for 24 hours and removed from the water bath, and then was measured for its weight and strength to determine the water absorptivity and strength of the composition. The results are shown in the following Table 3.
- a cement-like composition was prepared by mixing 60 parts of pulp sludge ash with 120 parts of the modified sodium silicate having an acidic group, obtained in the same manner as described in Example 6. Then, 100 parts of dust generated from a steel-manufacturing process was added to the composition. The composition was tested according to the method as described in Example 6. The results are shown in the following Table 3.
- Example 8 Composition Further Comprising Iron Powder ⁇ 86>
- a cement-like composition was prepared by mixing 60 parts of pulp sludge ash with 120 parts of the modified sodium silicate having an acidic group, obtained in the same manner as described in Example 6. Then, 300 parts of iron powder generated after a surface treatment process for iron panels was added to the composition. The composition was tested according to the method as described in Example 6. The results are shown in the following Table 3.
- Example 9 Composition Further Comprising Copper Slag ⁇ 88>
- a cement-like composition was prepared by mixing 60 parts of pulp sludge ash with 120 parts of the modified sodium silicate having an acidic group, obtained in the same manner as described in Example 6. Then, 170 parts of copper slag generated during a copper refining process was added to the composition. The composition was tested according to the method as described in Example 6. The results are shown in the following Table 3.
- Example 10 Composition Further Comprising Waste Molding Sand ⁇ 90> A cement-like composition was prepared by mixing 60 parts of pulp sludge ash with 120 parts of the modified sodium silicate having an acidic group, obtained in the same manner as described in Example 6. Then, 100 parts of waste molding sand with a size of 7 mm or less, generated during a molding process, was added to the composition. The composition was tested according to the method as described in Example 6. The results are shown in the following Table 3.
- each composition according to Examples 6—10 conform to the constitution of the cement-like composition according to the present invention due to the presence of the modified sodium silicate in addition to pulp sludge ash.
- - addition of fly ash results in a slightly delayed curing time. Therefore, it can be seen that addition of fly ash controls the curing time.
- addition of steel- manufacturing dust and other aggregate contributes to realization of fast curing and improved strength.
- industrial wastes such as steel-manufacturing dust containing a large amount of heavy metals can be incorporated into the composition according to the present invention, it is -possible to recycle various types of harmful wastes into curable cement.
- compositions according to the present invention via a pressurized molding process by incorporating aggregate into the composition.
- the following Examples 11—13 illustrates the compositions further comprising light-weight aggregate for the purpose of weight-down.
- Example 11 Composition Further Comprising Wood Powder ⁇ 96>
- a composition was prepared by mixing 80 parts of pulp sludge ash with 100 parts of the modified sodium silicate having an acidic group, obtained in the same manner as described in Example 6. Then, 60 parts (based on the weight of the above composition) of wood powder (sawdust), as light-weight aggregate, was added to the composition, and 1.5 parts (based on the weight of the above composition) of organic bentonite was further added thereto, so that the light-weight aggregate can be distributed and blended uniformly in the resultant mortar.
- the final composition was injected into a cylindrical mold with a diameter of 50mm and a depth of 100mm. Then, the composition was measured for its demoldable strength and initial curing time. Additionally, the composition was cured naturally for 3 days and was measured for its specific gravity. Also. The composition was measured for its weight before and after dipping it into a water bath for 12 hours. The results are shown in the following Table 4.
- Example 12 Composition Further Comprising Pearlite ⁇ 98>
- a composition was prepared by mixing 80 parts of pulp sludge ash with 130 parts of the modified sodium silicate having an acidic group, obtained in the same manner as described in Example 6. Then, 40 parts (based on the weight of the above cement-like composition) of pearlite, as light-weight aggregate, was added to the composition, and 1.5 parts (based on the weight of the above composition) of organic bentonite was further added thereto. The final composition was measured in the same manner as described in Example 11. The results are shown in the following Table 4.
- Example 13 Composition Further Comprising Styrofoam Particles
- a composition was prepared by mixing 80 parts of pulp sludge ash with 130 parts of the modified sodium silicate having an acidic group, obtained in the same manner as described in Example 6. Then, light-weight aggregate, comprising l,000cc of Styrofoam particles with a size of 3mm or less and 1.2 parts (based on the weight of the above cement-like composition) of methyl cellulose, was added to the composition. The final composition was measured in the same manner as described in Example 11. The results are shown in the following Table 4.
- each composition further comprising light-weight aggregate to reduce the weight also allows fast curing. Moreover, a greater amount of light aggregate may be used to reduce the weight to a higher degree, so that the composition is amenable to pressurized molding. Additionally, it can be seen that use of a thickening agent such as organic bentonite or methyl cellulose permits uniform blending of light-weight aggregate.
- the composition according to the following Example 14 comprises air bubbles for the purpose of weight-down.
- Example 12 Composition Further Comprising Air Bubbles ⁇ 106>
- a pulp sludge ash composition was prepared by mixing 80 parts of pulp sludge ash, containing 1.5 parts of methyl cellulose added thereto, with 100 parts of the modified sodium silicate having an acidic group, obtained in the same manner as described in Example 6. Then, l,000cc of air bubbles, obtained from pressurized air with a vegetable foaming agent, were added to the composition with stirring to provide a final composition. The final composition was injected into a cylindrical mold with a diameter of 50mm and a depth of 100mm. Then, the composition was measured for its demo1dabIe strength and initial curing time. Additionally, the composition was cured naturally for 3 days and was measured for its specific gravity. Also. The composition was measured for its weight before and after dipping it into a water bath for 12 hours. The results are shown in the following Table 5.
- the modified sodium silicate having an acidic group can provide a cement-like composition, which is capable of fast curing, and has excellent strength and water resistance.
- the composition according to the present invention may further comprise fly ash, aggregate, light-weight aggregate and air bubbles, it is possible to provide a cost-efficient composition that can be used in various industrial fields, as a building material, a civil engineering material, an interior material, a filler for a safe, or the like.
- the pulp sludge ash composition is useful for solidifying harmful industrial wastes promptly.
- the composition may further comprise wire mesh, waste fiber, fiber or pulp sludge in order to improve the bending strength.
- the composition may further comprise a dye, a pigment, an additional waterproofing or water-repel1ant agent for Portland cement, or the like, if desired.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05820588A EP1809809A4 (en) | 2004-11-05 | 2005-11-05 | Pulp sludge ash composition for producing building materials |
JP2007540258A JP2008518878A (en) | 2004-11-05 | 2005-11-05 | Pulp sludge ash composition for building material manufacture |
US11/667,032 US20080006383A1 (en) | 2004-11-05 | 2005-11-05 | Pulp Sludge Ash Composition for Producing Building Materials |
CA002586809A CA2586809A1 (en) | 2004-11-05 | 2005-11-05 | Pulp sludge ash composition for producing building materials |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2004-0090032 | 2004-11-05 | ||
KR20040090032A KR100588488B1 (en) | 2004-11-05 | 2004-11-05 | Pulp Sludge Ash Composition for Construction Materials |
Publications (1)
Publication Number | Publication Date |
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WO2006049465A1 true WO2006049465A1 (en) | 2006-05-11 |
Family
ID=36319427
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2005/003736 WO2006049465A1 (en) | 2004-11-05 | 2005-11-05 | Pulp sludge ash composition for producing building materials |
Country Status (7)
Country | Link |
---|---|
US (1) | US20080006383A1 (en) |
EP (1) | EP1809809A4 (en) |
JP (1) | JP2008518878A (en) |
KR (1) | KR100588488B1 (en) |
CN (1) | CN101057031A (en) |
CA (1) | CA2586809A1 (en) |
WO (1) | WO2006049465A1 (en) |
Cited By (3)
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CN107915433A (en) * | 2017-11-22 | 2018-04-17 | 陈波霖 | A kind of preparation method of concrete |
EP3322491A4 (en) * | 2015-07-13 | 2019-02-27 | Mason Greenstar, Inc. | Method of fabrication of a lightweight aggregate and product formed from paper mill sludge |
CN111620529A (en) * | 2020-06-05 | 2020-09-04 | 广东工业大学 | Curing agent for sludge road and preparation method thereof |
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NL2035284B1 (en) * | 2023-07-06 | 2025-01-13 | Hauge Kapitael B V | Product and a method for producing the product |
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2004
- 2004-11-05 KR KR20040090032A patent/KR100588488B1/en not_active Expired - Fee Related
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2005
- 2005-11-05 US US11/667,032 patent/US20080006383A1/en not_active Abandoned
- 2005-11-05 JP JP2007540258A patent/JP2008518878A/en active Pending
- 2005-11-05 CA CA002586809A patent/CA2586809A1/en not_active Abandoned
- 2005-11-05 WO PCT/KR2005/003736 patent/WO2006049465A1/en active Application Filing
- 2005-11-05 CN CNA2005800381248A patent/CN101057031A/en active Pending
- 2005-11-05 EP EP05820588A patent/EP1809809A4/en not_active Withdrawn
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3322491A4 (en) * | 2015-07-13 | 2019-02-27 | Mason Greenstar, Inc. | Method of fabrication of a lightweight aggregate and product formed from paper mill sludge |
CN107915433A (en) * | 2017-11-22 | 2018-04-17 | 陈波霖 | A kind of preparation method of concrete |
CN107915433B (en) * | 2017-11-22 | 2020-09-15 | 霸州市隆浩鼎混凝土有限公司 | Preparation method of concrete |
CN111620529A (en) * | 2020-06-05 | 2020-09-04 | 广东工业大学 | Curing agent for sludge road and preparation method thereof |
CN111620529B (en) * | 2020-06-05 | 2022-08-16 | 广东工业大学 | Curing agent for sludge road and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN101057031A (en) | 2007-10-17 |
KR20060040434A (en) | 2006-05-10 |
EP1809809A1 (en) | 2007-07-25 |
JP2008518878A (en) | 2008-06-05 |
US20080006383A1 (en) | 2008-01-10 |
KR100588488B1 (en) | 2006-06-09 |
CA2586809A1 (en) | 2006-05-11 |
EP1809809A4 (en) | 2010-12-29 |
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