CN101671135B - Curing method of industrial waste gypsum - Google Patents
Curing method of industrial waste gypsum Download PDFInfo
- Publication number
- CN101671135B CN101671135B CN2009102722232A CN200910272223A CN101671135B CN 101671135 B CN101671135 B CN 101671135B CN 2009102722232 A CN2009102722232 A CN 2009102722232A CN 200910272223 A CN200910272223 A CN 200910272223A CN 101671135 B CN101671135 B CN 101671135B
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- gypsum
- curing
- industrial waste
- pressure
- curing agent
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000010440 gypsum Substances 0.000 title claims abstract description 98
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 98
- 239000002440 industrial waste Substances 0.000 title claims abstract description 22
- 238000001723 curing Methods 0.000 title description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000007921 spray Substances 0.000 claims abstract description 21
- 239000004568 cement Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003822 epoxy resin Substances 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 9
- 239000004814 polyurethane Substances 0.000 claims abstract description 6
- 239000002894 chemical waste Substances 0.000 claims abstract description 5
- 229920002635 polyurethane Polymers 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims description 10
- 239000011505 plaster Substances 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 7
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims description 7
- 239000011507 gypsum plaster Substances 0.000 claims description 7
- -1 hexafluorosilicic acid sodium Chemical compound 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 208000034189 Sclerosis Diseases 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- 239000006071 cream Substances 0.000 claims description 3
- 150000002118 epoxides Chemical class 0.000 claims description 3
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 239000011449 brick Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 description 16
- 239000000428 dust Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000006253 efflorescence Methods 0.000 description 6
- 206010037844 rash Diseases 0.000 description 6
- 239000010881 fly ash Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- YUJQZCDGMQSNKW-UHFFFAOYSA-N 5-(4-fluoro-3-nitrophenyl)-2h-tetrazole Chemical compound C1=C(F)C([N+](=O)[O-])=CC(C2=NNN=N2)=C1 YUJQZCDGMQSNKW-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明涉及一种工业废石膏的固化方法，利用液态固化剂喷淋或涂抹在压力成型机辊轮或压板的表面，将含有水分质量12％-20％的工业废石膏压制成型，成型石膏的表层吸附有固化剂，或者在成型后的石膏表面喷洒液体固化剂，通过液体固化剂的硬化即形成有坚硬壳体的固化石膏，其固化剂的量为石膏质量的0.3～1.0％。这种固化石膏可以用于水泥缓凝剂和建筑石膏的原材料。该方法可以用于磷石膏、脱硫石膏、黄石膏、盐田石膏和盐石膏等化工废石膏的固化。固化剂是水玻璃、酸酐类固化剂、环氧树脂、聚氨酯固化剂或有机硅固化剂。压力成型机可以是压力成球机、压力制砖机或压力成块、压力成条、成棒的设备。The invention relates to a solidification method of industrial waste gypsum, which uses a liquid solidifying agent to spray or smear on the surface of the roller or pressure plate of a pressure molding machine, and presses and molds the industrial waste gypsum containing 12%-20% of water mass to form the gypsum. The surface layer is adsorbed with a curing agent, or a liquid curing agent is sprayed on the surface of the formed gypsum, and the cured gypsum with a hard shell is formed through the hardening of the liquid curing agent, and the amount of the curing agent is 0.3-1.0% of the mass of the gypsum. This cured gypsum can be used as a raw material for cement retarders and building gypsum. The method can be used for curing chemical waste gypsum such as phosphogypsum, desulfurized gypsum, yellow gypsum, salt field gypsum and salt gypsum. The curing agent is water glass, acid anhydride curing agent, epoxy resin, polyurethane curing agent or silicone curing agent. The pressure forming machine can be a pressure ball forming machine, a pressure brick making machine or a pressure forming block, pressure forming bar, or bar forming equipment.
Description
Technical field
The invention belongs to the solid waste process field, is a kind of with industrial waste gypsum curing back making cement retardant or the raw-material method of plaster of Paris.
Background technology
The turnout of the phosphogypsum that China is annual surpasses 3,000 ten thousand tons, and annual desulfurated plaster reaches 1,000 ten thousand tons, and China also has the generation of other a large amount of chemical waste gypsums, and present utilization ratio is very low.Effective constituent CaSO in common these waste gypsums
4.2H
2O, CaSO
4.1/2H
2O and CaSO
4Content all be higher than the plaster of paris, can replace the usefulness of the plaster of paris fully as cement setting retarder or preparation plaster of Paris even high strength gypsum.But phosphogypsum, desulfurated plaster etc. be a kind of aqueous powder of paste normally; Water ratio is higher; Has higher viscosity again; It very easily is attached in course of conveying on the transportation equipment, in the process that its feeding is got into equipment such as grinding machine, occur easily stopping up and the influence metering stable with accurately, influence product quality stability.
Through the curing agglomeration technique of industrial waste gypsum, industrial waste gypsum is solidified into spherical, bulk or particulate state, can overcome above problem, multiple curing agglomeration technique had appearred in China in recent years, can be divided into 4 types substantially:
1, half water, two water laws: earlier gypsum dehydration is formed CaSO
4.1/2H
2O; Under the water spray condition, use pan-pelletizer to be spheroidal particle with semi-hydrated gypsum powder is body formed, utilize the gelling of semi-hydrated gypsum to be solidified into the spheroidal particle of certain intensity, its advantage is that balling ratio is high; Quick solidifying, intensity height, production are stablized; But its cost is high, energy consumption is high, and its product is compared with the plaster of paris, and price advantage is not obvious.
2, powder solidifying agent method: utilize both economical powder solidifying agent and the even mix of waste gypsum, adopt pressure to become the mode moulding of piece or balling-up.Its shortcoming is that insufficient strength is high, and the intensity height is then wanted too high solidifying agent volume if desired, influences economy, efflorescence easily behind the solidified waste gypsum in addition.
3, body solidifying agent method: adopt LCM and waste gypsum to mix, become the piece balling-up under the pressure effect.Be characterized in that solidifying agent is somewhat expensive usually, volume is low, so the bad assurance of the homogeneity of its mix, also efflorescence easily after waste gypsum solidifies.
4, lime fly ash solidification method: this be the applicant of this patent method of once inventing (Shen Weiguo, Nie Jiqiang, Zhou Mingkai. the research of ardealite setting retarder for cement. phosphate fertilizer and multiple fertile .2005; (5): 21-23); This method is that the solidifying agent cost is low; Form slowly but shortcoming is an intensity, some factory can not have lime fly ash and waste gypsum resource simultaneously, yet efflorescence easily after waste gypsum solidifies.
Waste gypsum solidified key is: the gypsum after the curing granulates in transportation and does not destroy, and does not produce dust pollution, therefore requires breakage rate and Pulverization ratio in 20～30%; Can keep globality and not efflorescence, play ash and airborne dust in that the effect of water is little.More than mix with waste gypsum through solidifying agent and to make the waste gypsum integrally curing, be formed with the cured body of certain intensity.Solidified is that the mix of solidifying agent is even at all, and solidifying agent must have suitable volume to form certain intensity.
The curing of waste gypsum does not need whole curing; If can will solidify the surface of gypsum is cured; Its inside can rely on the intergranular internal friction of waste gypsum and capillary adsorption and keep globality; Can save a large amount of solidifying agent like this, the solidifying agent usage quantity is about about 10～50%wt of integrally curing method hardener dose.Simultaneously, because solidifying agent mainly concentrates on the surface of spheroid, can guarantee also that therefore the surface can efflorescence not play ash, be a kind of curing of economical and efficient.
Summary of the invention
Technical problem to be solved by this invention; Be to the hardener dose that exists in the present curing high; The uneven problem of mix adopts the liquid curing-agent spray, spreads upon on the roller or pressing plate of pressure forming machine, and the waste gypsum material that will contain certain moisture is at forming under the pressure; Perhaps the gypsum surface after moulding is sprayed the certain amount of fluid solidifying agent; The surface attachment of waste gypsum type body has one deck solidifying agent like this, and has formed hard housing, and inner waste gypsum has also formed enough intensity under pressure.This curing gypsum is outer hard interior strong, and balling ratio is high, can reach more than 90%; Surface compact can be owing to solidifying agent adds the irregular efflorescence that forms; Good stability under the immersion of water.Use this technology to solidify waste gypsum, the yield rate of product is high, no airborne dust.
Technical scheme of the present invention is:
A kind of curing of industrial waste gypsum; It is characterized in that utilize LCM to spray or spread upon the surface of pressure forming machine running roller or pressing plate, will contain the moisture quality is the industrial waste gypsum compression moulding of 12%-20%; The top layer of molding of gypsum is adsorbed with solidifying agent; The perhaps gypsum surface spraying liquid solidifying agent after moulding promptly is formed with the curing gypsum of hard housing through the sclerosis of liquid curing-agent, and the amount of its solidifying agent is 0.3～1.0% of a gypsum quality.
The curing of aforesaid industrial waste gypsum for accelerating the curing progress, adopts the mode of spraying to spray into the intensity that gypsum is solidified in the hardening accelerator enhancing on the surface of solidifying gypsum, and this curing gypsum is used for the starting material of cement setting retarder or plaster of Paris.
Industrial waste gypsum of the present invention is a chemical waste gypsum: phosphogypsum, desulfurated plaster, Huangshi cream, saline gypsum or sugared gypsum.
LCM of the present invention is one or more compound in water glass, acid anhydride type curing agent (like H-167) or polyurethane curing agent (claiming PU solidifying agent or EPU solidifying agent again) or low viscosity epoxy resin 802,804 or 806.
In the curing of industrial waste gypsum of the present invention, described pressure forming machine is that pressure nodulizer or pressure become piece or pressure slivering or becomes excellent equipment.
Hardening accelerator of the present invention; It for LCM is water glass the hexafluorosilicic acid sodium solution; For LCM is epoxy resin any of curable epoxide promotor quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, or AC2001.
Embodiment
Further specify the present invention through embodiment below.
Following embodiment utilizes the LCM spray or spreads upon the surface of pressure forming machine running roller or pressing plate; To contain the moisture quality is the industrial waste gypsum compression moulding of 12%-20%; The top layer of molding of gypsum is adsorbed with solidifying agent; The perhaps gypsum surface spraying liquid solidifying agent after moulding promptly is formed with the curing gypsum of hard housing through the sclerosis of liquid curing-agent, and the amount of its solidifying agent is 0.3～1.0% of a gypsum quality.Its industrial waste gypsum is a chemical waste gypsum: phosphogypsum, desulfurated plaster, Huangshi cream, saline gypsum or sugared gypsum.LCM is one or more compound in water glass, acid anhydride type curing agent (like H-167) or polyurethane curing agent (claiming PU solidifying agent or EPU solidifying agent again) or low viscosity epoxy resin 802,804 or 806.LCM is that epoxy resin is any of curable epoxide promotor quadrol, hexanediamine, diethylenetriamine, triethylene tetramine, or AC2001.
Embodiment 1
Roller surface spray one deck water glass at the pressure nodulizer; Contain quality and be 12～18% phosphogypsum feeding pressure nodulizer, the pressure nodulizer is cured as spheroid with phosphogypsum, and the curing phosphogypsum balling ratio of preparation reaches 90%; Loose gypsum content does not have airborne dust less than 2% in the plant area.When the rainy day, curing was slow, can solidify the ball surface at phosphogypsum and spray a little hexafluorosilicic acid sodium solution with the mode of spraying, its amount is 0.005% of gypsum quality.Be made into concentration and be 10% solution and use, be sprayed onto the surface of solidifying ball with atomizer during use.Product is used for cement setting retarder.
Embodiment 2
One-tenth brick clamp surface spray one deck water glass at the pressure brick press; Contain quality and be 12～18% desulfurated plaster feeding brick pressing machine, brick pressing machine is cured as fragment of brick with desulfurated plaster, and the curing desulfurated plaster ratio of briquetting of preparation reaches 90%; Loose gypsum content does not have airborne dust less than 3% in the plant area.When the rainy day, curing was slow, can spray a little hexafluorosilicic acid sodium solution with the mode of spraying on the desulfurized gypsum brick surface, its amount is 0.002% of gypsum quality.
Embodiment 3
Roller surface spray one deck acid anhydride type curing agent (like H-167) at the pressure nodulizer; Contain quality and be 12～18% phosphogypsum feeding pressure nodulizer; The pressure nodulizer is cured as spheroid with phosphogypsum; The curing phosphogypsum balling ratio of preparation reaches 90%, and loose gypsum content does not have airborne dust less than 2% in the plant area.When the rainy day, curing was slow, can solidify the ball surface at phosphogypsum and spray a little toughener solution with the mode of spraying, its amount is 0.002% of gypsum quality.Product can be used for cement setting retarder.
Embodiment 4
Roller surface spray one deck epoxy resin 802 at the pressure nodulizer; In 804 or 806 one or more compound; Contain quality and be 12～18% phosphogypsum feeding pressure nodulizer, the pressure nodulizer is cured as spheroid with phosphogypsum, and the curing phosphogypsum balling ratio of preparation reaches 90%; Loose gypsum content does not have airborne dust less than 2% in the plant area.When the rainy day, curing was slow, can solidify the ball surface at phosphogypsum and spray a little epoxy resin cure accelerant A C2001 solution with the mode of spraying, its amount is 0.005% of gypsum quality.Product is used for cement setting retarder.
Embodiment 5
Roller surface spray one deck water glass at the pressure nodulizer; Contain quality and be 14～20% sugared gypsum feeding pressure nodulizer, the pressure nodulizer is cured as spheroid with phosphogypsum, and the curing sugar gypsum balling ratio of preparation reaches 90%; Loose gypsum content does not have airborne dust less than 2% in the plant area.When the rainy day, curing was slow, can solidify the ball surface at phosphogypsum and spray a little hexafluorosilicic acid sodium solution with the mode of spraying, its amount is 0.005% of gypsum quality.Product is used for cement setting retarder.
Embodiment 6
To contain quality and be 12～18% the phosphogypsum and the uniform mixture feeding of the mix pressure nodulizer of flyash; The pressure nodulizer is with phosphogypsum and the flyash fixed spheroid that turns to; At spherome surface spray one deck water glass, its amount is about 1% of gypsum weight, and the curing phosphogypsum balling ratio of preparation reaches 90%; Loose gypsum content does not have airborne dust less than 2% in the plant area.Solidify in the rainy day and can spray a little hexafluorosilicic acid sodium solution in the mode that phosphogypsum solidifies the ball surface spray in slow, its amount is 0.005% of gypsum quality.Product is used for cement setting retarder.
Claims (6)
1. the curing of an industrial waste gypsum; It is characterized in that utilize LCM to spray or spread upon the surface of pressure forming machine running roller or pressing plate, will contain the moisture quality is the industrial waste gypsum compression moulding of 12%-20%; The top layer of molding of gypsum is adsorbed with solidifying agent; The perhaps gypsum surface spraying liquid solidifying agent after moulding promptly is formed with the curing gypsum of hard housing through the sclerosis of liquid curing-agent, and the amount of its solidifying agent is 0.3～1.0% of a gypsum quality.
2. according to the curing of the described industrial waste gypsum of claim 1; It is characterized in that; For accelerating the curing progress, adopt the mode of spraying to spray into the intensity that gypsum is solidified in the hardening accelerator enhancing on the surface of solidifying gypsum, this curing gypsum is used for the starting material of cement setting retarder or plaster of Paris.
3. according to the curing of claim 1 or 2 described industrial waste gypsums, it is characterized in that described industrial waste gypsum is a chemical waste gypsum: phosphogypsum, desulfurated plaster, Huangshi cream, saline gypsum or sugared gypsum.
4. according to the curing of the described industrial waste gypsum of claim 1, it is characterized in that described LCM is a water glass, or polyurethane curing agent, or one or more compound in low viscosity epoxy resin 802,804 or 806.
5. according to the curing of the described industrial waste gypsum of claim 1, it is characterized in that described pressure forming machine is that pressure nodulizer or pressure become piece or pressure slivering or becomes excellent equipment.
6. according to the curing of the described industrial waste gypsum of claim 2; It is characterized in that; Described hardening accelerator; Being the hexafluorosilicic acid sodium solution for LCM is water glass, is any of curable epoxide promotor quadrol, hexanediamine, diethylenetriamine, triethylene tetramine for LCM is epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102722232A CN101671135B (en) | 2009-09-25 | 2009-09-25 | Curing method of industrial waste gypsum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102722232A CN101671135B (en) | 2009-09-25 | 2009-09-25 | Curing method of industrial waste gypsum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101671135A CN101671135A (en) | 2010-03-17 |
| CN101671135B true CN101671135B (en) | 2012-03-07 |
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|---|---|---|---|
| CN2009102722232A Expired - Fee Related CN101671135B (en) | 2009-09-25 | 2009-09-25 | Curing method of industrial waste gypsum |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622165A (en) * | 2014-11-07 | 2016-06-01 | 万峰石材科技股份有限公司 | Artificial stone rough block curing process |
| CN106083190B (en) * | 2016-06-22 | 2019-06-18 | 何宝成 | A kind of preparation method of plastering |
| CN107382252A (en) * | 2017-06-28 | 2017-11-24 | 常州市瑞泰物资有限公司 | A kind of reinforced plasterboard and preparation method thereof |
| CN110436805B (en) * | 2018-05-04 | 2021-09-21 | 北新集团建材股份有限公司 | Caulking gypsum powder, preparation method thereof and phosphogypsum harmless treatment method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2272363Y (en) * | 1996-11-05 | 1998-01-14 | 任志坚 | Composite plate made of metal and gypsum |
| CN101033128A (en) * | 2007-04-24 | 2007-09-12 | 福州大学 | Raw material formulation for ceramics polymer composite material and preparing method |
| CN101479209A (en) * | 2006-06-29 | 2009-07-08 | 吉野石膏株式会社 | Process for producing calcined gypsum and gypsum board |
-
2009
- 2009-09-25 CN CN2009102722232A patent/CN101671135B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2272363Y (en) * | 1996-11-05 | 1998-01-14 | 任志坚 | Composite plate made of metal and gypsum |
| CN101479209A (en) * | 2006-06-29 | 2009-07-08 | 吉野石膏株式会社 | Process for producing calcined gypsum and gypsum board |
| CN101033128A (en) * | 2007-04-24 | 2007-09-12 | 福州大学 | Raw material formulation for ceramics polymer composite material and preparing method |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2003-24900A 2003.01.28 |
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| CN101671135A (en) | 2010-03-17 |
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