CN1037324A - Make the modification method of ardealite of cement setting retarder - Google Patents
Make the modification method of ardealite of cement setting retarder Download PDFInfo
- Publication number
- CN1037324A CN1037324A CN 88102607 CN88102607A CN1037324A CN 1037324 A CN1037324 A CN 1037324A CN 88102607 CN88102607 CN 88102607 CN 88102607 A CN88102607 A CN 88102607A CN 1037324 A CN1037324 A CN 1037324A
- Authority
- CN
- China
- Prior art keywords
- phosphogypsum
- cement
- ardealite
- retardant
- manufacture
- Prior art date
- 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.)
- Pending
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- 239000004568 cement Substances 0.000 title claims abstract description 23
- 238000002715 modification method Methods 0.000 title claims abstract description 7
- 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 34
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 6
- 239000011707 mineral Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 238000002329 infrared spectrum Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000009257 reactivity Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims 3
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000000979 retarding effect Effects 0.000 abstract description 3
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
- 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 description 5
- 239000011507 gypsum plaster Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- 235000012216 bentonite Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 bentonite modified phosphogypsum Chemical class 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000019580 granularity Nutrition 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators or shrinkage compensating agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a kind of modification method of ardealite of doing manufacture of cement with retardant.Add a kind of natural mineral or industrial residue with phosphogypsum, promptly can be used as the retardant of manufacture of cement after heating, insulation, cooling, this retardant can improve physicalies such as the retarding effect of cement and ultimate compression strength.Technology of the present invention is simple, and material-taking on-site reduces cost, utilization of waste material.
Description
The present invention relates to the modification method of ardealite of manufacture of cement with retardant.
The retardant that needs in the manufacture of cement mainly adopts the plaster of paris at present.Mainly containing pest in the by product phosphogypsum as liquid extraction production phosphoric acid is water-soluble phosphate and a small amount of organic impurity, soluble phosphate hinders hydrated cementitious, alkaline substance reaction in acid and the cement simultaneously, increase the excreting water phenomenon of cement, cause strength of cement on the low side, prolong time of coagulation.Making is used behind the phosphogypsum modification just can enlarge the raw material source of manufacture of cement retardant.Have some at present in the world to modification method of ardealite, mainly contain:
1. hydraulic cyclone method: washing phosphogypsum, get rid of the soluble acid thing, and organic impurity composition wherein, as Europe patent EU10,027, this method water loss is big, and has emission pollution problem, if carry out wastewater treatment, then to increase investment and cost, gypsum after the washing also will be dried, and energy consumption is bigger, and is less economical.
2. heating separating method: this method is first heating, separating impurity again, and as getting rid of calcium oxide etc., referring to U.S. Pat B366,402, this method sorting difficulty, the sorting amount is greatly also inadvisable.
3. heating neutralisation: see Japanese Patent 16,793/72, make the phosphogypsum heating earlier, destroy organic impurity, the phosphogypsum of firing mixes aquation with the slip that contains the neutrality material again, neutrality material such as Ca(OH)
2, Mg(OH)
2, Fe(OH)
3And water-granulated slag etc., purpose is the solubility objectionable constituent chemical combination that makes in neutrality material and the phosphogypsum, slip mixes evenly with heating back phosphogypsum, and fruit of better neutralization is just arranged.But it is 5% slip that this patent requires compound concentration, add water go into amount should strict control, otherwise will cause the phosphogypsum water content too much to influence its use, however water be difficult for again less mixing, influence neutralization unavoidably.Its neutralization is reflected at that to carry out neutralization reaction speed under the normal temperature slower in addition.
The object of the present invention is to provide a kind of can directly adopt natural mineral or/and industrial residue as the method for the properties-correcting agent of phosphogypsum.Reach and produce that modified ardealite technology is simple, cost reduces, the purpose of utilization of waste material.
The properties-correcting agent of phosphogypsum of the present invention is that chemical ingredients belongs to aluminosilicate, and the natural mineral (as: calcium-base bentonite) with chemical reactivity is or/and Chemical Composition belongs to aluminosilicate, and the industrial residue with chemical reactivity.
Wilkinite is rich in montmorillonite, main chemical is a hydrous alumino silicates, montmorillonite is replaced with picture because of the different valency matter of positively charged ion in the structural unit layer, make the electric charge in the structural unit layer not reach neutral condition, and have cationic exchange, and have multiple performances such as water-absorbent, cohesiveness, swelling property, stability.Under heating condition, the acid in the phosphogypsum has activated montmorillonite, and its cation exchange property is further improved, thus have stronger in and performance.Because bentonitic adding has also increased SO in the phosphogypsum
3Solubleness, improved retarding effect, cement-hydrate is formed fine and close crystal, thereby the resistance to compression degree of cement is that the intensity of retardant increases than the plaster of paris.Following table is modified ardealite, original state phosphogypsum, plaster of paris solubleness (the solvable CaSO in milk of lime
4Content):
| Lime milk concentration (%) | 2.0 | 4.0 | 6.0 | 8.5 | 10.0 |
| Natural day cream | 4.67 | 3.7 | 3.54 | 3.62 | 3.49 |
| Dried phosphogypsum | 7.37 | 6.54 | 5.56 | 6.55 | 4.96 |
| Modified ardealite SP 4 | 14.05 | 15.29 | 13.65 | 13.99 | 10.30 |
| Modified ardealite SP 5-2 | 7.62 | 5.05 | 5.78 | 5.17 | 6.26 |
When being the phosphogypsum modification agent with the water-granulated slag.Free acid reacts under heating condition in basic oxide in the slag and the phosphogypsum.Generate phosphoric acid salt, vitriol, organic composite salt etc. rapidly.Being added in when getting rid of acid of slag properties-correcting agent helps the carrying out of hydrated reaction of cement, thereby makes hydrate form fine and close crystallization, and strength of cement is significantly improved.
Belong to aluminosilicate with Chemical Composition, and have the natural mineral of chemical reactivity or/and industrial residue as properties-correcting agent, everyly can discharge a large amount of H during at normal temperatures with the phosphogypsum mixture
2S, SO
3, CO
2And H
2Gas and steam such as O, its infrared spectra is accompanying drawing 1, accompanying drawing 2 roughly the same.All belong to the category of the present invention as the phosphogypsum modification agent, all have above-mentioned characteristic with the phosphogypsum mix at normal temperatures as wilkinite or water-granulated slag, its infrared spectra is Fig. 1 and Fig. 2.
Concrete grammar is: the above-mentioned properties-correcting agent material, the thorough mixing that add weight and be phosphogypsum 10-30% in a original state phosphogypsum are even, with powdery or have definite shape dry material, be heated to 100-200 ℃, be incubated 0.5-1.5 hour, naturally cool to normal temperature then, promptly can be made into the qualified manufacture of cement retardant of every index, in above-mentioned modifying process, the solubility P in the phosphogypsum
2O
5Fully react with aluminosilicate with organic, form more stable compound.Phosphogypsum after treatment can replace the plaster of paris as retardant.Be directly used in manufacture of cement.
The present invention and Japanese Patent 16,793/73 are compared, and have following advantage:
1. properties-correcting agent can use pulverulent material, and consumption is the 10-30% of phosphogypsum, and mixed ratio is big, mixes easily.
2. neutralization reaction is carried out under heating condition, the reaction efficiency height.
3. increase with the solubleness of bentonite modified phosphogypsum in the caustic lime slurry, its retarding effect strengthens, thereby can reduce the come into operation amount of modified ardealite in cement.
4. technology is simple, is convenient to control.
Fig. 1 is the infrared spectra that produces gas under the wilkinite normal temperature during with the phosphogypsum mix.
Fig. 2 is the infrared spectra that produces gas under the slag normal temperature during with the phosphogypsum mix.
Fig. 3 is the phosphogypsum modification process flow diagram
Embodiment 1
In 85 parts of phosphogypsums, add 15 parts of calcium-base bentonites, be heated to 100 ℃ of insulations 1 hour, water-soluble P before and after handling
2O
5And SO
3Content is as follows:
Embodiment 2.
Adding 10 parts of granularities in 90 parts of phosphogypsums is 200 purpose water-granulated slag powder, is heated to 200 ℃, is incubated 1 hour, the water-soluble P of phosphogypsum before and after handling
2O
5And SO
3The content contrast is as follows:
Annotate: the grog that the serious bleeding 2.M of 1.ML.-factory produces is the grog that the phosphorus slag mineralizer is fired
Cement sample numbering implication explanation in the above-mentioned specification sheets table: (pressing Chinese phonetic alphabet lead-in)
As: KSP
1, MSP
5-2, KT
7
Wherein K.M.-is respectively the cement mill code
SP
4.SP
1-bentonite modified phosphogypsum
SP
5-2, SP
5-3-slag modified ardealite
T
5, T
6, T
7-the plaster of paris.
The unmodified dried phosphogypsum of L-.
Claims (3)
1, a kind of modification method of ardealite of making the manufacture of cement retardant, it is characterized in that with a phosphogypsum and weight being that the granularity 200 purpose properties-correcting agent powders of phosphogypsum 10-30% are fully mixed thoroughly, the material that becomes powdery or have definite shape, be heated to 100-200 ℃ then, be incubated 0.5-1.5 hour, naturally cool to normal temperature, promptly can be made into, make the qualified manufacture of cement retardant of every index through modification.
2, manufacture of cement as claimed in claim 1 is characterized in that with the modification method of ardealite of retardant employed properties-correcting agent is that Chemical Composition belongs to aluminum silicate and has the natural mineral of chemical reactivity or/and Chemical Composition belongs to the industrial residue of aluminum silicate.
3, as claim 1, the 2 described properties-correcting agent of making the phosphogypsum of cement setting retarder, it is characterized in that described properties-correcting agent: promptly Chemical Composition belongs to the natural mineral of aluminum silicate or/and industrial slag can discharge a large amount of H during at normal temperatures with the phosphogypsum mix
2S, CO
2, SO
3Gas and steam, its infrared spectra is accompanying drawing 1,2 roughly the same.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102607 CN1037324A (en) | 1988-04-30 | 1988-04-30 | Make the modification method of ardealite of cement setting retarder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102607 CN1037324A (en) | 1988-04-30 | 1988-04-30 | Make the modification method of ardealite of cement setting retarder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1037324A true CN1037324A (en) | 1989-11-22 |
Family
ID=4832222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88102607 Pending CN1037324A (en) | 1988-04-30 | 1988-04-30 | Make the modification method of ardealite of cement setting retarder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1037324A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065842C (en) * | 1997-09-24 | 2001-05-16 | 新密北方耐火工业有限公司 | Method for calcining and preparing fast hardening low-alkali cement using ardealite |
| CN100395207C (en) * | 2000-07-18 | 2008-06-18 | 拉法基石膏公司 | Adhesives for structural components, i.e. mortars, methods for their preparation and methods for making articles |
| CN108328956A (en) * | 2018-01-09 | 2018-07-27 | 解增信 | A kind of processing and treating method replacing the natural gypsum using ardealite |
| CN115286271A (en) * | 2022-08-03 | 2022-11-04 | 川恒生态科技有限公司 | Method for preparing cement retarder by modifying industrial byproduct phosphorus hemihydrate gypsum |
-
1988
- 1988-04-30 CN CN 88102607 patent/CN1037324A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065842C (en) * | 1997-09-24 | 2001-05-16 | 新密北方耐火工业有限公司 | Method for calcining and preparing fast hardening low-alkali cement using ardealite |
| CN100395207C (en) * | 2000-07-18 | 2008-06-18 | 拉法基石膏公司 | Adhesives for structural components, i.e. mortars, methods for their preparation and methods for making articles |
| CN108328956A (en) * | 2018-01-09 | 2018-07-27 | 解增信 | A kind of processing and treating method replacing the natural gypsum using ardealite |
| CN115286271A (en) * | 2022-08-03 | 2022-11-04 | 川恒生态科技有限公司 | Method for preparing cement retarder by modifying industrial byproduct phosphorus hemihydrate gypsum |
| CN115286271B (en) * | 2022-08-03 | 2023-09-19 | 川恒生态科技有限公司 | Method for preparing cement retarder by modifying industrial byproduct phosphogypsum |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
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