CN108367338B - Foundry sand containing binder and method for producing same - Google Patents
Foundry sand containing binder and method for producing same Download PDFInfo
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- CN108367338B CN108367338B CN201680061396.8A CN201680061396A CN108367338B CN 108367338 B CN108367338 B CN 108367338B CN 201680061396 A CN201680061396 A CN 201680061396A CN 108367338 B CN108367338 B CN 108367338B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/2246—Condensation polymers of aldehydes and ketones
- B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
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Abstract
A binder-containing foundry sand comprising an aggregate derived from artificial sand and/or natural sand, a binder, if necessary, a curing agent, and an anti-blocking agent, wherein the anti-blocking agent is a fatty acid amide.
Description
Technical Field
The present invention relates to a foundry sand containing a binder and a method for producing the same. More particularly, the present invention relates to a binder-containing foundry sand that prevents a decrease in mold strength even after repeated use, and a method for manufacturing the binder-containing foundry sand.
Background
One method used in the casting industry for making molds is the shell mold method. The method comprises the following steps: the preheated metal mold is filled with sand (resin-coated sand, RCS; binder-containing foundry sand) coated with a binder, if necessary, a curing agent, and then baked to manufacture a mold.
Today, there are a variety of aggregates of foundry sand (including silica sand) containing binders used in methods of making molds (such as shell molding). The foundry sand containing a binder comprises an aggregate derived from artificial sand or natural sand, a binder, and, if necessary, a curing agent and an antiblocking agent. As the binder, for example, a thermosetting resin (e.g., a phenol resin) can be used, and if necessary, a curing agent (e.g., hexamethylenetetramine) can also be used.
The anti-blocking agent is used for preventing blocking of products or promoting molding of foundry sand containing a binder into a desired mold shape. A commonly used anti-blocking agent in the field of the casting industry is calcium stearate. For example, the use of calcium stearate as an anti-blocking agent is described in Japanese unexamined patent publication No. 2006-334612 (patent document 1).
List of cited documents
Patent document
Patent document 1: japanese unexamined patent publication No. 2006-334612
Disclosure of Invention
In the field of the foundry industry, attempts have also been made to reduce the amount of waste molding sand by reusing waste molding sand (waste mold sand) for foundry due to resource consumption and regulation of industrial waste.
The waste molding sand contains carbides and inorganic substances derived from an anti-blocking agent or a binder component. The waste molding sand is generally recycled as aggregate (hereinafter referred to as recycled sand) by performing thermal reclamation in a temperature range of 400 to 1000 ℃ to obtain thermally reclaimed sand and then performing dry-polishing (dry-polishing) on the thermally reclaimed sand. When recycled sand is used, the mold has insufficient strength. Therefore, there is a need to provide binder-containing foundry sand that can provide sufficient mold strength even when the sand is recycled.
The inventors of the present invention studied the cause of the decrease in the strength of the mold made of recycled binder-containing foundry sand and found that the mold strength is related to the amount of elution of calcium ions from the recycled sand into water. Specifically, the inventors found that when the elution of calcium ions is high, the mold strength decreases. The inventors found that, from the viewpoint that calcium ions are derived from calcium stearate used as an anti-blocking agent, the decrease in mold strength can be suppressed by examining the type of the anti-blocking agent. The inventors have thus completed the present invention.
Accordingly, the present invention provides a binder-containing foundry sand comprising an aggregate derived from artificial sand and/or natural sand, a binder, if necessary, a curing agent, and an anti-blocking agent, wherein the anti-blocking agent is a fatty acid amide.
Further, the present invention provides a method for manufacturing a binder-containing foundry sand, the method comprising the steps of:
performing thermal regeneration on waste molding sand generated after casting at the temperature of 400-1000 ℃ to obtain thermally regenerated sand, and then performing dry polishing on the thermally regenerated sand to recycle the thermally regenerated sand as aggregate;
mixing the aggregate with a binder and a curing agent if necessary; and
mixing a mixture of aggregate, a binder and, if necessary, a curing agent with an anti-blocking agent,
wherein the anti-blocking agent is fatty acid amide.
According to the recycling method of the present invention, it is possible to provide a binder-containing foundry sand that can provide a sufficient mold strength even after being recycled. The inventors of the present invention recognized that calcium ions were unexpectedly associated with a decrease in the mold strength in the field of the casting industry, and recognized that fatty acid amides have hardly been used as an antiblocking agent in this field.
Further, it is possible to provide a binder-containing foundry sand that can provide more sufficient mold strength even after being recycled, in any of the following cases:
(a) the anti-blocking agent is fatty acid amide with the melting point of more than 90 ℃;
(b) the fatty acid amide is selected from ethylene bis-stearamide (ethylene bis-stearamide), ethylene bis-behenamide (ethylene bis-behenamide), ethylene bis-lauramide (ethylene bis-lauramide), ethylene bis-capramide (ethylene bis-capramide), and methylene bis-stearamide (ethylene bis-stearamide);
(c) the anti-blocking agent is contained in an amount of 0.01 to 10.0 parts by weight relative to 100 parts by weight of the total weight of the aggregate, the binder and the curing agent.
(d) An anti-blocking agent is contained in an amount such that the blocking rate is 15% or less; and
(e) the binder-containing foundry sand comprises: aggregate from artificial sand, a binder, a curing agent if necessary, and an anti-blocking agent, wherein the anti-blocking agent is a fatty acid amide, and
the artificial sand meets the following conditions:
(1) the artificial sand comprises synthetic mullite and/or synthetic corundum as main components, wherein the synthetic mullite and/or synthetic corundum contains 40-90 wt% of alumina and 60-10 wt% of silica; and
(2) a solution obtained by thermally regenerating the binder-containing foundry sand at 600 ℃ for 1 hour and stirring the binder-containing foundry sand in a 0.05M HCl aqueous solution for 1 hour after subjecting the binder-containing foundry sand to a dry polishing step showed calcium ion elution of more than 0.25mg/L and less than 51.11 mg/L.
Drawings
FIG. 1 is a schematic view of a thermal regeneration furnace used in the examples.
Fig. 2 is a schematic view of a rotary regenerator used in the examples.
Fig. 3 is a graph showing the relationship between the number of times the binder-containing foundry sand of the first example was recycled and the bending strength and calcium ion elution thereof.
Fig. 4 is a graph showing the relationship between the number of times the binder-containing foundry sand of the first example was recycled and the bending strength and calcium ion elution thereof.
Fig. 5 is a graph showing the relationship between the number of times the binder-containing foundry sand of the first example was recycled and the bending strength and calcium ion elution thereof.
Fig. 6 is a graph showing the relationship between the number of times the binder-containing foundry sand of the first example was recycled and the bending strength and calcium ion elution thereof.
Fig. 7 is a graph showing the relationship between the number of times the binder-containing foundry sand of the first example was recycled and the bending strength and calcium ion elution thereof.
Fig. 8 is a graph showing the relationship between the bending strength of the binder-containing foundry sand of the first example when fresh sand is used and the bending strength of the sand of the fifth recovery.
Fig. 9 is a graph showing the relationship between the amount of methylene bis stearamide added to the binder-containing foundry sand of example two and the blocking rate.
Fig. 10 is a graph showing the relationship between the number of times the binder-containing foundry sand of example three was recycled and the bending strength and calcium ion elution thereof.
Fig. 11 is a graph showing the relationship between the number of times the binder-containing foundry sand of example three was recycled and the bending strength and calcium ion elution thereof.
Fig. 12 is a graph showing the relationship between the bending strengths of the binder-containing foundry sand of the third example when fresh sand is used and when it is recycled for the fifth time.
Detailed Description
(foundry sand containing a Binder)
The foundry sand containing the binder comprises aggregate, a binder and an anti-blocking agent.
(1) Anti-blocking agent
The anti-blocking agent is fatty acid amide.
Fatty acid amides having 6 to 24 carbon atoms may be used as the fatty acid amide. Examples of the higher fatty acid include saturated fatty acids such as capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, and lignoceric acid, and unsaturated fatty acids such as oleic acid and linoleic acid.
The fatty acid amide preferably has a melting point of 90 ℃ or higher. More preferably, the melting point is 120 ℃ or higher. The melting point can be measured according to JIS K0064-1992.
Preferred examples of the fatty acid amide include ethylene bis stearamide, ethylene bis behenamide, ethylene bis lauramide, ethylene bis capramide, and methylene bis stearamide.
The anti-blocking agent includes a fatty acid amide as a main component, and may be used in combination with other anti-blocking agents as long as the bending strength is not decreased in the case where heat-regenerated in a temperature range of 400 to 1000 ℃ to obtain heat-regenerated sand, and binder-containing foundry sand is manufactured by using aggregate obtained by dry-polishing the heat-regenerated sand. The term "main component" means, for example, 50% by weight or more, 70% by weight or more, 90% by weight or more, or 100% by weight.
The fatty acid amide as described above is preferably on the outermost surface of the aggregate from artificial sand and/or natural sand coated with a binder and, if necessary, a curing agent.
The content of the fatty acid amide is preferably such an amount that the blocking rate becomes 15% or less. If the blocking ratio is within the above range, the content of the fatty acid amide in the binder-containing foundry sand may be judged to be suitable for casting. In the case where the blocking ratio is higher than 15%, the mold may not be properly manufactured, and the surface of the molded article may be rough due to insufficient fluidity. Furthermore, binder-containing foundry sand may stick when stored in flexible shipping bags.
The specific content of the fatty acid amide may be 0.1 to 10.0 parts by weight relative to 100 parts by weight of the total weight of the aggregate, the binder and the curing agent, from the viewpoint of blocking prevention. The content is more preferably 0.02 to 5.0 parts by weight, and further preferably 0.03 to 1.0 part by weight.
The type of the antiblocking agent constituting the binder-containing foundry sand can be determined, for example, by the following procedure.
That is, first, the anti-blocking agent was sampled from the surface of the foundry sand containing the binder by using a micromanipulator (e.g., micromanipulator system MMS-77 manufactured by shimadzu corporation). Infrared spectroscopic analysis (e.g., Spectrum one FT-IR/MultiScope microscope Infrared microscopy System: available from PerkinElmer) was performed on the obtained samples to obtain IR maps. The obtained IR map was compared with IR maps of known fatty acid amides to determine the type of antiblocking agent.
Further, the amount of the anti-blocking agent constituting the binder-containing foundry sand can be determined by separating the anti-blocking agent using an appropriate solvent and analyzing the separated substance by a known method such as spectroscopic analysis, gas chromatography, or liquid chromatography.
(2) Aggregate material
The aggregate is from artificial sand and/or natural sand. The artificial sand and the natural sand are not particularly limited, and examples thereof include alumina sand, silica sand, zircon sand, chromite sand, MgO/SiO-containing sand2And mixed sands thereof.
The alumina sand may contain Al2O3Other than, e.g. SiO2、Fe2O3、Cr2O3、CrO2、MgO、CaO、K2O and TiO2. Further, the alumina sand may be artificial sand containing synthetic corundum and/or synthetic mullite containing Al2O3And SiO2。
The synthetic mullite and the synthetic corundum can be made of 40-90 wt% of alumina (Al)2O3) And 60 to 10% by weight of Silica (SiO)2) And (4) forming. In addition, the proportions of alumina and silica may be 60 to 90 wt% and 40 to 10 wt%, respectively. The synthetic mullite and synthetic corundum may contain other components besides alumina and silica, for example Fe2O3、Cr2O3、CrO2、MgO、CaO、K2O and TiO2. The synthetic mullite and/or synthetic corundum may account for more than 50% by weight of the synthetic sand.
Further, the surface area per unit volume (cm) of the aggregate2/cm3) Is 6 × 104/d～1.8×106D (where d is the average particle diameter (. mu.m) of the spherical particles). The following description is given for an aggregate of, for example, 300-425 μm. When it is assumed that the aggregate has 362.An average particle size of 5 μm (intermediate between 300 μm and 425 μm), a surface area of 165.5 to 4965.5cm2/cm3When the surface area is 1.8 × 106/d(cm2/cm3) Here, the surface area is used by measuring the specific surface area per gram with a specific surface area analyzer (BELSORP 28SA automatic gas adsorption apparatus: available from BEL Japan, Inc.) and multiplying the specific surface area by the true density.the surface area is preferably 1.6 × 106A value of 1.45 × 10 or less, more preferably 1.45 ×6A value of 1.3 × 10 or less, more preferably 1.3 d or less6D or less, particularly preferably 1.1 × 106Number/d is less than or equal to.
The aggregate preferably has a round particle shape. Specifically, the particle shape coefficient (circularity index) is preferably 1.2 or less, more preferably 1.1 or less. When the particle shape factor is 1.2 or less, the filling rate of the aggregate in the mold can be improved, and the permeability of the resulting mold can be improved. Also, due to the almost spherical shape, the amount of waste that may be generated due to contact between the aggregate particles can be reduced.
The particle shape factor as used herein refers to a value calculated with a sand specific surface analyzer (available from George Fischer Ltd.). Therefore, the particle shape coefficient refers to a value obtained by dividing the actual surface area of 1g of aggregate by the theoretical surface area. Theoretical surface area refers to the surface area assuming that all aggregates are spherical. Therefore, a value of the particle shape factor closer to 1 means that the shape of the material is closer to spherical.
The aggregate has a particle size distribution of 30 to 1180 μm. When the particle size distribution is less than 30 μm, the permeability of the resulting mold may be reduced. When the particle size distribution is higher than 1180 μm, the surface of the resulting casting may be rough. As preferable particle size distributions, for example, 212 to 1180 μm (corresponding to JIS # 10 and #14), 150 to 820 μm (corresponding to JIS # 20 and #28), 106 to 600 μm (corresponding to JIS #35 and #48), 75 to 425 μm (corresponding to JIS #65 and #100), and 53 to 300 μm (corresponding to JIS #150 and #200) can be included. The particle size distribution can be appropriately selected depending on casting conditions such as the type of iron or steel casting (iron casting, ordinary steel casting, stainless steel casting, high Mn steel casting, aluminum alloy casting, copper alloy casting, etc.), the casting size, or the casting thickness. The aggregate may contain sand of less than 30 μm in an amount (for example, 25% by weight or less) not to impair the effects of the present invention.
The particle size distribution refers to a value measured according to a method for determining the particle size of foundry sand (JIS Z2601). The method is briefly described. For example, a sieve with a nominal size of 30 μm is overlaid on a sieve of 1180 μm. The raw material is placed on a 1180 μm sieve and sieved on a sieve shaker such as Ro-tap. The material remaining between the two screens is referred to as sand with a particle size distribution of 30 to 1180 μm.
The aggregate and the binder-containing foundry sand have almost the same surface area per unit volume, particle shape factor and particle size distribution.
The aggregate containing synthetic mullite and/or synthetic corundum having the above-mentioned surface area can be obtained by melting raw materials of synthetic mullite and/or synthetic corundum containing alumina and silica, and blowing air into the molten material. Thereby, the molten material is ground into particles having a predetermined particle size distribution by blowing air, and an aggregate having a predetermined surface area is provided by the surface tension of the molten particles. The melting method is not particularly limited, and an electric arc furnace, a crucible furnace, an induction furnace (high frequency furnace, low frequency furnace, etc.), a resistance furnace, a reverberatory furnace, a rotary furnace, a vacuum melting furnace, or a cupola furnace can be used. Among them, an arc furnace which is relatively easy to handle is preferable.
The particle size distribution, appearance and the like of the aggregate containing synthetic mullite and/or synthetic corundum can be adjusted by the raw material composition of synthetic mullite and synthetic corundum, the melting temperature, the air speed when air is blown in, and the contact angle of the melted material and air. The melting temperature is preferably in the range of 1600 to 2200 ℃. The air speed is preferably 80-120 m/s. The contact angle is preferably 60-90 degrees.
Preferably, water cooling is performed after the air is blown in.
(2) Binder
The binder is not particularly limited, and examples thereof include furan resin, phenol resin, oil-modified urethane resin, phenol urethane resin, alkaline phenol resin, sodium silicate, bentonite, and the like. The adhesive may be cured with a curing agent according to the type of adhesive. Examples of the curing agent for furan resin include inorganic acids such as sulfuric acid, phosphoric acid esters, and pyrophosphoric acid, and organic acids such as xylene sulfonic acid, toluene sulfonic acid, and benzene sulfonic acid. Examples of curing agents for alkaline phenolic resins include lactones (e.g. propiolactone) and organic esters such as ethyl formate, methyl formate and triacetin. Examples of the curing agent for the phenolic resin include hexamethylenetetramine and the like. Examples of the curing agent for the phenolic urethane resin include triethylamine and a pyridine-containing compound. Examples of the curing agent for sodium silicate include carbon dioxide gas, dicalcium silicate, and organic esters.
The content of the binder is preferably in the range of 0.4 to 10 parts by weight per 100 parts by weight of the aggregate. When the content is less than 0.4 parts by weight, the binding of the aggregate may be insufficient, thus resulting in a decrease in the mold strength. When the content is more than 10 parts by weight, components from the binder may adhere to the surface of the casting, or the time required for recycling the waste molding sand may increase. The content is more preferably 0.2 to 2.0 parts by weight, and still more preferably 0.4 to 3 parts by weight.
The aggregate having a surface area per unit volume in the range of 60000/d to 1800000/d (d is the average particle diameter (μm) of the spherical material) can reduce the content of the binder to 0.2 to 2.0 parts by weight. The application of the present invention is particularly useful because the effect of calcium ions on the reduction of the mold strength increases as the amount of the binder is reduced.
(4) Method for producing foundry sand containing binder
The binder-containing foundry sand may be produced by a known method. For example, while the aggregate is heated and mixed in the mixer, the binder is charged into the mixer to obtain a mixture of the binder and the aggregate. In the case where the binder is a binder cured by a curing agent, the curing agent is also mixed at this time. Subsequently, the anti-blocking agent was charged into the mixer. This allows the antiblocking agent to be present on the outermost surface of the aggregate coated with the binder and, if necessary, the curing agent. It is believed that all or a portion of the surface of the aggregate is coated with a binder and a curing agent. It is also believed that all or a portion of the surface of the aggregate coated with the binder and curing agent is coated with an antiblocking agent.
It was confirmed that the amount of the anti-blocking agent charged was approximately the same as the amount of the anti-blocking agent in the binder-containing foundry sand.
In the case where recycled sand from waste molding sand generated after casting is used by using casting sand containing a binder containing a fatty acid amide as an anti-blocking agent, the waste molding sand can be converted into recycled sand by, for example, going through the following thermal regeneration step and polishing step.
(i) Thermal regeneration step
The thermal regeneration step may be performed at a temperature of 400 to 1000 ℃. By subjecting the waste molding sand to a thermal regeneration process, the components of the anti-blocking agent and the binder from the waste molding sand are carbonized and eliminated by burning. The remaining part of the surface of the aggregate is removed in a subsequent grinding (attrition) process, so that recycled sand can be obtained. Here, the calcium component from calcium stearate, which is used as a conventional anti-blocking agent, accumulates on the surface of the sand. Even if subjected to a milling process, such calcium components cannot be completely removed.
When the temperature in the thermal regeneration step is lower than 400 ℃, carbonization may not be sufficiently performed, resulting in a decrease in the strength of the mold obtained with recycled binder-containing foundry sand (recycled sand). When the temperature is higher than 1000 ℃, although sufficient carbonization may be performed, sand particles may be aggregated due to melting of the surface of the recycled sand caused by inorganic components contained in the recycled sand. The temperature range is more preferably 400 to 800 ℃, and further preferably 500 to 800 ℃.
The heat regeneration time may be, for example, 0.5 to 2.5 hours. When the thermal regeneration time is less than 0.5 hours, sufficient carbonization may not be performed, resulting in a decrease in the strength of the mold obtained by recycling the sand. The reason why the upper limit of the heat-regenerating time is 2.5 hours is that, even when the waste molding sand is heat-regenerated for a longer time, an increase in the heat-regenerating effect is not expected, and the recycling cost rises with the consumption of fuel. The thermal regeneration time is more preferably 1.5 to 2.5 hours, and still more preferably 1.75 to 2.25 hours.
The atmosphere in which the thermal regeneration step is performed is not particularly limited as long as the binder in the waste molding sand can be carbonized, and is usually an atmosphere containing oxygen (for example, in air).
The thermal regenerator (roasting furnace) may have any structure without particular limitation so long as it can regenerate the waste molding sand. The waste molding sand in the thermal regenerator may be fluidized or not; however, in order to obtain uniform thermally reclaimed sand, it is preferable that the waste molding sand be fluidized. The thermal regenerator may be batch or continuous. In view of treatment efficiency, it is preferable to use a continuous fluidized thermal regenerator.
There are various known configurations of continuous fluidized thermal regenerators. Examples thereof include a thermal regenerator in which the flow direction of sand intersects with the flow direction of air for fluidizing the sand, and a thermal regenerator in which the flow direction of sand is opposite to and parallel to the flow direction of air for fluidizing the sand. The latter thermal regenerator is more preferable in view of thermal efficiency. In particular, a thermal regenerator in which the flow direction of sand is the same as the direction of gravity and the flow direction of air is opposite to the direction of gravity is preferable because it has high thermal efficiency, so that the amount of fuel for thermal regeneration can be reduced.
In the thermal regenerator in which the flow direction of the sand is the same as the gravity direction, the waste molding sand is thrown into the thermal regenerator from the upper part of the thermal regenerator and falls into the thermal regenerator. The falling sand stays at a predetermined position as a fluidized bed for a predetermined time by means of air blown upward from the lower portion of the thermal regenerator. The sand staying at a specific location is thermally regenerated for a predetermined time by means of a heating device such as a burner. Since the sand is charged from the upper portion of the fluidized bed, the sand at the lower portion of the fluidized bed gradually falls down and falls to the bottom of the heat recovery apparatus as thermally regenerated sand. This type of thermal regenerator is characterized by high thermal efficiency because the heat of the thermally regenerated sand can be used to heat up the waste molding sand to be input.
(ii) Grinding process
The grinding step is performed on the thermally reclaimed sand obtained in the thermal reclamation step. In the grinding process, surface residues of the thermally reclaimed sand are removed, whereby the waste molding sand can be recycled as aggregate used as a mold raw material.
The milling may be dry milling, wet milling, or a combination thereof.
Examples of dry methods include: a method using a sand regenerator in which sand is ground by means of collision and friction between sand particles generated by raising sand with a high-speed air flow and allowing the sand to collide with a collision plate; a method of using a high-speed rotating regenerator in which sand is ground by means of collision between shot sand generated by centrifugal force obtained by loading sand on a rotor rotating at high speed and dropped sand; and a method of using a stirring mill in which sand is ground by friction between sand particles.
Examples of the wet method include a method using a groove mill device in which sand is ground by means of friction between sand particles in grooves including, for example, rotating blades.
Preferably, the milling is performed by a dry process. The dry method enables the production of binder-containing foundry sand even in water-deficient places. Further, the dry method does not require a drainage step, and thus can suppress the influence on the environment.
When conventional binder-containing foundry sand containing calcium stearate as an anti-blocking agent is recycled from waste molding sand by dry grinding, the mold strength is disadvantageously reduced. The inventors of the present invention measured the calcium content in the recycled sand, found that the calcium content increased with the increase in the number of recycling times, and that the content correlated with the mold strength. Therefore, the present inventors have found that by using a fatty acid amide containing no calcium as an anti-blocking agent, even when grinding is performed by a dry method, a decrease in mold strength can be prevented because accumulation of calcium in recycled sand is suppressed.
The conditions of the dry grinding are not particularly limited as long as the dry grinding can remove carbides existing on the surface of the hot sand.
(iii) Other embodiments
(1) The waste molding sand may be treated with a pulverizer before the thermal regeneration process. By processing with the crusher, the aggregate of the waste molding sand can be crushed, whereby the yield of the recycled sand from the waste molding sand can be increased.
(2) The waste molding sand may be treated with a magnetic separator before the thermal regeneration process. By the treatment with the magnetic separator, the casting residue in the waste molding sand can be removed, whereby the yield of the reclaimed sand from the waste molding sand can be increased.
(3) Preferably, the thermally reclaimed sand obtained from the thermal reclamation process is subjected to a cooling step before being subjected to the grinding process. By passing through the cooling step, the chipping of the thermally reclaimed sand due to sudden temperature change can be prevented, whereby the yield of reclaimed sand from the waste molding sand can be increased. The cooling step may be performed while fluidizing the thermally reclaimed sand, thereby uniformly cooling the thermally reclaimed sand.
(4) The sand after the grinding process may be subjected to a classification step to classify the recycled sand according to a desired particle size distribution.
Examples
Example one
As the anti-blocking agent, calcium stearate, ethylene bis stearamide, ethylene bis behenamide, ethylene bis lauramide, and ethylene bis capramide were used to produce foundry sand containing a binder, respectively. The binder-containing foundry sand was manufactured by the following procedure, and the flexural strength and calcium ion elution thereof were measured.
(1) Production of foundry sand containing binder
As the aggregate, Espearl #60 (available from Shanchuan industries, Ltd., unit volume surface area: 3300 cm) which had never been used as a binder-containing foundry sand was used2/cm3The particle size distribution: 53-600 μm, particle shape coefficient: 1.03; the total content of alumina and silica was 94 wt% (77 wt%: 23 wt%) and contained 40 wt% of synthetic mullite and 10 wt% of synthetic corundum. This Espearl # 60 will be referred to as new sand. Adding the aggregateHeated to 160 ℃ and placed in a mixer (purchased from Enshu Tekko k.k., model NSC-1) to maintain the temperature of the aggregate at 150 ℃. The aggregate was stirred for about 60 seconds while adding 0.8 parts by weight of a binder HP-333N (a phenol novolac resin available from hitachi chemical industries) relative to 100 parts by weight of the aggregate to coat the binder on the aggregate. While stirring, 15 parts by weight of hexamethylenetetramine (curing agent) was added with respect to 100 parts by weight of the binder, and 1.3 parts by weight of water (dispersion medium of the curing agent) was added with respect to 100 parts by weight of the aggregate, and stirring was performed for about 45 seconds to coat the mixture of the binder and the curing agent on the aggregate. While stirring the mixture of the binder, the curing agent and the aggregate, 0.06 parts by weight of the antiblocking agent was added with respect to 100 parts by weight of the mixture of the binder, the curing agent and the aggregate, and stirring was performed for about 15 seconds to obtain binder-containing foundry sand (RCS). The resulting RCS was sieved on a sieve having a mesh size of 1180 μm to remove lumps.
The bending strength of the obtained RCS was measured according to the following procedure. The flexural strength represents the mold strength.
(2) Measurement of bending Strength
(a) Sample preparation
The bending strength of the test piece was tested according to JACT test method SM-1 (test method for bending strength (corresponding to JIS K6910)). Specific measurement conditions are as follows.
A lower mold having 5 recesses each having a depth of 10mm, a width of 10mm and a length of 60mm and an upper mold serving as a cap of the lower mold were prepared. The lower and upper molds were heated to 250 ℃ ± 3 ℃, and then the recesses were filled with about 50g of foundry sand containing a binder. The upper surface of the binder-containing foundry sand filled in the concave portion was scraped off by a sample scraper. The lower and upper molds were then combined and baked for 60 seconds. After baking, the upper mold is removed and the baked part is filed so that the upper surface of the baked part is flush with the upper surface of the lower mold. The baked piece was then removed from the lower mold to obtain a sample. The time from opening the upper mold to taking out the sample from the lower mold was set to 30 seconds.
The obtained sample was cooled to room temperature (about 25 ℃) in a desiccator and kept until the flexural strength was measured.
Three samples were prepared, thereby obtaining 15 samples of each binder-containing foundry sand.
(b) Measurement of bending Strength
Pairs of parts or convex members (Apair or projected members) each having a tip angle of 60 °, a tip cone curvature of 1.5R, and a length of 10mm or more were placed on the specimen mount at intervals of 50mm so that the parts were parallel in the longitudinal direction. The sample is mounted on the sample mounting stage so that the surface of the sample to be filed is not placed on the stage or on the opposite side (top side) of the stage.
The load was applied to the center of the upper surface of the specimen with a load wedge having a tip angle of 60 ° and a tip curvature of 1.5R. The amount of loading applied at the time of specimen break was recorded. The load test was performed on each of 15 test pieces.
The bending load is calculated from the measured load value according to the following equation.
σfb＝3×l×P/2×W×h2
Wherein σ fb is bending load (kgf/cm)2) L is the distance (5cm) between a pair of convex members on the specimen mount table, P is the load value (kgf), W is the width (1cm) of the specimen, and h is the height (1cm) of the specimen.
Flexural strength (kgf/cm)2) Obtained as the average of the bending loads of 15 specimens.
(3) Recycling of foundry sand containing binder
The sample after the flexural strength is measured as described above is pulverized, and then the pulverized raw material is recycled as an aggregate by subjecting it to a thermal regeneration step and a dry grinding step.
In a JFE Pipe Fitting thermal regenerator (JFE Pipe Fitting Mfg. thermal regenerator, model JTR-G-1, available from JFE Pipe Fitting Co., Ltd.) shown in FIG. 1, a thermal regeneration process was performed under the conditions of a thermal regeneration temperature of 600 ℃, a differential flow pressure in the thermal regenerator of 4.5MPa, and an input sand amount of 2.5 t/hr. Under the above conditions, the actual processing time of the waste molding sand was about 1 hour. In fig. 1, 1 denotes a thermal regenerator, 2 denotes a pulverized material inlet, 3 denotes a burner, 4 denotes a fluidized bed, 5 denotes a heat exchanger, 6 denotes an air inlet for fluidizing sand, 7 denotes a cooling air inlet, 8 denotes a fluidizing cooler, 9 denotes a sand discharge valve, 10 denotes an air nozzle, 11 denotes a differential flow gauge, and 12 denotes an exhaust port.
The dry grinding is continuously carried out under the conditions of a load current of 20-40A and an input sand amount of 2-3 t/h by using an S-type rotary regenerator (available from Nippon Chuzo K.K.) shown in FIG. 2. In fig. 2, 21 denotes an orifice, 22 denotes a shelf, 23 denotes a shelf ring, 24 denotes a rotary drum, 25 denotes a fan, 26 denotes a motor, and 27 denotes a cover.
(4) Measurement of bending Strength of recycled RCS
The manufacture of RCS in the same manner as in step (1), the measurement of bending strength in the same manner as in step (2), and the recycling of RCS in the same manner as in step (3) were carried out 5 times, respectively. The bending strengths obtained are shown in table 1.
Table 1 also shows calcium ion (Ca) of fresh sand and recycled aggregate2+Ions) to elute.
(elution of calcium ion)
(1) Preparation of internal standard solution and Standard solution
Internal standard solution (Y: 50mg/L)
An yttrium standard solution (Y: 1000mg/L for atomic absorption analysis: 25mL) purchased from Kanto chemical Co., Ltd was charged into a 500-mL volumetric flask, and pure water was added to the marked line.
Standard solution (Ca: 100mg/L)
A standard solution IV (Ca: 1000mg/L, 10mL) for ICP emission spectrometry, which was purchased from Kanto chemical Co., Ltd, was charged in a 100-mL volumetric flask, and pure water was added to the marked line.
Standard solution (Ca: 10mg/L)
The standard solution (Ca: 100mg/L, 10mL) was added to a 100-mL volumetric flask and purified water was added to the marked line.
Standard solution (Ca: 1mg/L)
The standard solution (Ca: 10mg/L, 10mL) was added to a 100-mL volumetric flask and purified water was added to the marked line.
Standard solution (Ca: 0.1mg/L)
The standard solution (Ca: 1mg/L, 10mL) was added to a 100-mL volumetric flask and purified water was added to the marked line.
Standard solution (Ca: 0.01mg/L)
The standard solution (Ca: 0.1mg/L, 10mL) was added to a 100-mL volumetric flask and purified water was added to the marked line.
(2) Preparation of calibration Curve (measurement Range: Ca: 0 to 10mg/L)
An internal standard solution (Y: 50mg/L, 20mL) was added to a 100-mL volumetric flask, and a standard solution (Ca: 10mg/L), a standard solution (Ca: 1mg/L), a standard solution (Ca: 0.1mg/L) and a standard solution (Ca: 0.01mg/L) were added to the marked line, respectively. As a blank control, an internal standard solution (Y: 50mg/L, 20mL) was added to a 100-mL volumetric flask and pure water was added to the marked line to prepare a standard solution. The above solution was measured by an ICP emission spectrometer (ICPS-8100) from Shimadzu corporation to prepare a calibration curve showing the relationship between the calcium ion concentration and the indicated value.
(3) Preparation of sample solution
A sand sample (50g) was placed in a 300-mL polyethylene beaker, 50mL of pure water and 50mL of a 0.1mol/L hydrochloric acid solution were added, and the mixture was stirred on a magnetic stirrer for 1 hour. After stirring, it was passed through a glass fiber filter according to JISP 3801 filter paper (for chemical analysis) to filter the mixture. After filtration, the solution was again vacuum-filtered through a membrane filter (pore size: 0.45 μm) purchased from ADVANTEC to obtain a sample solution (pure). As a blank, 50mL of pure water and 50mL of 0.1mol/L hydrochloric acid solution were added to a 300-mL polyethylene beaker and the same procedure was followed.
(4) Determination of sample solutions
The internal standard solution (Y: 50mg/L, 10mL) was charged into a 50mL volumetric flask, the sample solution (pure) was added to the reticle, and the mixed solution was measured by an ICP emission spectrometer (ICPS-8100) from Shimadzu corporation. The difference between the determined calcium ion concentration and the concentration obtained from the blank control test was calculated as calcium ion elution. When the measured calcium ion concentration exceeds the measurement range of the standard curve, the sample solution is diluted with pure water (pure) to obtain a sample solution within the measurement range (dilution). The internal standard solution (Y: 50mg/L, 10mL) was added to a 50-mL volumetric flask, the sample solution (dilution) was added to the reticle, and the mixed solution was measured again with an ICP emission spectrometer (ICPS-8100) from Shimadzu corporation to determine the calcium ion concentration. When the sample solution was measured (diluted), the calcium elution was calculated by subtracting the concentration obtained from the blank control test from the product of the measured calcium concentration and the dilution factor.
TABLE 1
For each antiblocking agent, the number of recyclings (horizontal axis), flexural strength and Ca based on Table 12+The relationship between the ion elution (vertical axis) is shown in fig. 3 to 7. Fig. 3 shows the results when calcium stearate was used as an antiblocking agent. FIG. 4 shows the results when ethylene bis stearamide was used as an antiblocking agent. Figure 5 shows the results when ethylene bis behenamide was used as an antiblock agent. Figure 6 shows the results when ethylene dilauramide was used as an antiblock agent. Fig. 7 shows the results when ethylene bisdecylamide was used as an antiblocking agent. In addition, the relationship between the bending strength when fresh sand was used and the bending strength when recycled for the fifth time was extracted for each anti-blocking agent and summarized in fig. 8. In FIG. 8, Ca-St represents calcium stearate, StA represents ethylene bis-stearamide, BeA represents ethylene bis-behenamide, LaA represents ethylene bis-lauramide, and CpA represents ethylene bis-decanamide.
As can be seen from Table 1 and FIGS. 3 to 7, the flexural strength of calcium stearate was reduced at each recycling, and little change was observed in the fatty acid amide. As can be seen from fig. 3, the tendency is that the bending strength decreases with increasing calcium ions, which are divalent ions attached to the aggregate. Thus, it can be concluded that calcium ions may adversely affect the binder (e.g., increase viscosity due to chelation of calcium ions with the binder). Meanwhile, in fig. 4 to 7, it can be assumed that the reason why the fatty acid amide does not have such an adverse effect is that the fatty acid amide does not include calcium.
From fig. 8 showing the effect of each antiblocking agent on the reduction in flexural strength, it can be clearly understood that the fatty acid amide exhibits a significant superiority when used as an antiblocking agent.
It is believed that the calcium ions detected in fig. 4-7 are from the calcium ions contained in the binder. The amount of calcium ions detected in these figures can be further reduced by using a binder that does not contain calcium.
Example two
The effect of the amount of added ethylene bis stearamide on blocking rate was confirmed by the following procedure.
(1) Production of foundry sand containing binder
Espearl #60 (available from Shanchuan industries, Ltd.) which had never been used as a binder-containing foundry sand was used as an aggregate. The aggregate was heated to 160 ℃ and placed in a mixer (purchased from Enshu Tekko k.k., model NSC-1) to maintain the temperature of the aggregate at 150 ℃. The aggregate was stirred for about 60 seconds while adding 0.8 parts by weight of a binder HP-333N (a phenol novolac resin available from hitachi chemical industries) relative to 100 parts by weight of the aggregate to coat the binder on the aggregate. While stirring, 24 parts by weight of hexamethylenetetramine (curing agent) was added with respect to 100 parts by weight of the binder, and 1.6 parts by weight of water (dispersion medium of the curing agent) was added with respect to 100 parts by weight of the aggregate, and stirring was performed for about 45 seconds to coat the mixture of the binder and the curing agent on the aggregate. While stirring the mixture of the binder, the curing agent and the aggregate, various amounts of ethylene bis stearamide as shown in table 2 were added relative to 100 parts by mass of the mixture of the binder, the curing agent and the aggregate, and then stirring was performed for about 15 seconds to obtain RCS. The resulting RCS was sieved on a sieve having a mesh size of 1180 μm to remove lumps.
(2) Measurement of blocking Rate
The adhesion rate was measured according to the following procedure based on the adhesion test method of JACT test method C-3.
100g of RCS was charged in a 50ml glass beaker to obtain a sample. The mixture was heated in a thermostatic chamber (obtained from AS ONE, ONW-450S) maintained at 45 to 50 ℃ for 60 minutes. The humidity in the thermostatic chamber is maintained at 40-60% by placing an aluminum bucket containing about 1L of water in the thermostatic chamber.
After 60 minutes, the heated RCS was sieved over a 6 mesh sieve. The amount of RCS remaining on the sieve was measured and its percentage in the total amount of RCS was calculated as the blocking rate.
The results are shown in Table 2. The results of table 2 are graphically represented in fig. 9.
TABLE 2
| Amount of ethylene bis stearamide added (parts by weight per sand) | Adhesion Rate (%) |
| 0.00 | 69.1 |
| 0.01 | 13.4 |
| 0.02 | 13.8 |
| 0.03 | 7.4 |
| 0.06 | 6.9 |
| 0.08 | 3.9 |
| 0.10 | 3.3 |
| 0.12 | 4.3 |
| 0.14 | 2.2 |
| 0.16 | 2.0 |
| 0.20 | 0.3 |
| 0.24 | 1.6 |
| 0.30 | 0.4 |
| 0.50 | 0.1 |
| 0.70 | 5.6 |
| 1.00 | 7.5 |
| 2.00 | 0.6 |
| 5.00 | 3.0 |
| 10.00 | 0.6 |
As can be seen from table 2 and fig. 9, when the amount of ethylene bis stearamide added is in the range of 0.01 to 10.0 parts by weight with respect to 100 parts by weight of the mixture of binder, aggregate and curing agent, the binding rate can be reduced to 15% or less as compared with the case where ethylene bis stearamide is not added.
EXAMPLE III
Flexural strength was measured in the same manner as in example one, except that calcium stearate and ethylene bis stearamide were used as an anti-blocking agent, respectively, silica sand (fracturing sand (フラタリ - サソド); particle size distribution: 75 to 600 μm, particle shape factor: 1.43) which had never been used as binder-containing foundry sand was used as an aggregate, and the amount of the binder used was set to 1.0 part by weight per 100 parts by weight of the aggregate. The measurement results for each lubricant are shown in fig. 10 and 11. Fig. 10 corresponds to the results when calcium stearate was used as the antiblocking agent, and fig. 11 corresponds to the results when ethylene bis stearamide was used as the antiblocking agent. In addition, for each anti-blocking agent, the bending strength when fresh sand was used and the bending strength when recycled for the fifth time were extracted and summarized in fig. 12.
As shown in fig. 10 to 12, it can be seen that, in the case of calcium stearate, even in the case of using silica sand as an aggregate, the flexural strength was reduced every time it was repeatedly recycled, while almost no change was seen in the case of ethylene bis-stearamide.
Description of the reference numerals
1: thermal regenerator, 2: pulverized material inlet, 3: burner, 4: fluidized bed, 5: heat exchanger, 6: air inlet for fluidized sand, 7: cooling air inlet, 8: fluidized cooler, 9: sand discharge valve, 10: air nozzle, 11: differential flow gauge, 12: exhaust port, 21 port, 22 shelf, 23: shelf ring, 24: drum, 25: fan, 26: motor, 27: cover for portable electronic device
Claims (6)
1. A binder-containing foundry sand comprising: aggregate from artificial sand, a binder, and an anti-blocking agent, wherein the anti-blocking agent is a fatty acid amide;
in the case where the binder is a binder cured by a curing agent, the binder-containing foundry sand contains a curing agent;
the artificial sand meets the following conditions:
(1) the artificial sand comprises synthetic mullite and/or synthetic corundum as main components, wherein the synthetic mullite and/or synthetic corundum contains 40-90 wt% of alumina and 60-10 wt% of silica; and
(2) a solution obtained by thermally regenerating the binder-containing foundry sand at 600 ℃ for 1 hour and stirring the binder-containing foundry sand in a 0.05M HCl aqueous solution for 1 hour after subjecting the binder-containing foundry sand to a dry polishing step showed calcium ion elution of more than 0.25mg/L and less than 51.11 mg/L.
2. The binder-containing foundry sand of claim 1, wherein the antiblocking agent is a fatty acid amide having a melting point of 90 ℃ or higher.
3. The binder-containing foundry sand of claim 1 wherein the fatty acid amide is selected from the group consisting of ethylene bis-stearamide, ethylene bis-behenamide, ethylene bis-lauramide, ethylene bis-decanamide, and methylene bis-stearamide.
4. The binder-containing foundry sand of claim 1, wherein the anti-blocking agent is contained in an amount of 0.01 to 10.0 parts by weight, relative to 100 parts by weight of the total weight of the aggregate, the binder and the curing agent.
5. The binder-containing foundry sand according to claim 1, wherein the anti-blocking agent is contained in an amount such that the blocking rate is 15% or less.
6. A method for manufacturing the binder-containing foundry sand of any one of claims 1 to 5, which comprises:
thermally regenerating the waste molding sand generated after casting at the temperature of 400-1000 ℃ to obtain thermally regenerated sand, and then performing dry polishing on the thermally regenerated sand to recycle the thermally regenerated sand as aggregate;
mixing the aggregate with a binder, and in the case where the binder is a binder cured by a curing agent, further mixing a curing agent to prepare a mixture; and
mixing the mixture with an anti-blocking agent,
wherein the anti-blocking agent is fatty acid amide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2015206590A JP5933800B1 (en) | 2015-10-20 | 2015-10-20 | Mold-containing binder-containing sand and its production method |
| JP2015-206590 | 2015-10-20 | ||
| PCT/JP2016/004644 WO2017068785A1 (en) | 2015-10-20 | 2016-10-20 | Binder-containing foundry sand and method of manufacturing the same |
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| JP (1) | JP5933800B1 (en) |
| KR (1) | KR20180099639A (en) |
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| JP6564837B2 (en) * | 2017-12-19 | 2019-08-21 | 山川産業株式会社 | Binder-containing sand for mold, raw material sand for its production, mold and method for producing raw material sand |
| CN116239346A (en) * | 2023-03-28 | 2023-06-09 | 安徽科博建材科技有限公司 | Method for preparing cement cementing material fine aggregate by using foundry waste sand |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2943068A (en) * | 1957-08-23 | 1960-06-28 | Monsanto Chemicals | Shell molding compositions |
| US3278316A (en) * | 1960-03-21 | 1966-10-11 | Minerals & Chem Philipp Corp | Foundry sand composition |
| JPH10216895A (en) * | 1997-02-06 | 1998-08-18 | Kao Corp | Binder composition for casting mold |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51140823A (en) * | 1975-05-30 | 1976-12-04 | Komatsu Mfg Co Ltd | Method of regenerating and processing casting sand |
| JPS57209741A (en) * | 1981-06-18 | 1982-12-23 | Hitachi Chem Co Ltd | Production of resin coated sand for casting |
| JPS59178150A (en) * | 1983-03-26 | 1984-10-09 | Sumitomo Deyurezu Kk | Coated sand for shell mold |
| JPS6149740A (en) * | 1984-08-18 | 1986-03-11 | Hitachi Chem Co Ltd | Production of resin-coated sand for casting |
| JPH06154941A (en) * | 1992-11-20 | 1994-06-03 | Kurimoto Ltd | Reconditioning method for molding sand and production of casting mold |
| JP4688575B2 (en) | 2005-05-31 | 2011-05-25 | 山川産業株式会社 | Mold aggregate |
| CN102448637A (en) * | 2009-07-23 | 2012-05-09 | 旭有机材工业株式会社 | Phenol resin composition for shell molding, resin-coated sand for shell molding, and shell molding die obtained using the same |
-
2015
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- 2016-10-20 MY MYPI2018701421A patent/MY194119A/en unknown
- 2016-10-20 KR KR1020187014150A patent/KR20180099639A/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2943068A (en) * | 1957-08-23 | 1960-06-28 | Monsanto Chemicals | Shell molding compositions |
| US3278316A (en) * | 1960-03-21 | 1966-10-11 | Minerals & Chem Philipp Corp | Foundry sand composition |
| JPH10216895A (en) * | 1997-02-06 | 1998-08-18 | Kao Corp | Binder composition for casting mold |
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| WO2017068785A1 (en) | 2017-04-27 |
| MY194119A (en) | 2022-11-14 |
| JP5933800B1 (en) | 2016-06-15 |
| CN108367338A (en) | 2018-08-03 |
| JP2017077571A (en) | 2017-04-27 |
| KR20180099639A (en) | 2018-09-05 |
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