CN104003631B - Germanium tailings portland cement as primary raw material and preparation method thereof is carried with brown coal - Google Patents
Germanium tailings portland cement as primary raw material and preparation method thereof is carried with brown coal Download PDFInfo
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- CN104003631B CN104003631B CN201410265983.1A CN201410265983A CN104003631B CN 104003631 B CN104003631 B CN 104003631B CN 201410265983 A CN201410265983 A CN 201410265983A CN 104003631 B CN104003631 B CN 104003631B
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- brown coal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention discloses and a kind of carry germanium tailings portland cement as primary raw material and preparation method thereof with brown coal, the raw material components of this portland cement is that brown coal carry germanium tailings, solid exciting agent, Gypsum Fibrosum, filler, metakaolin；By brown coal are carried germanium tailings and solid exciting agent be dry mixed after be calcined, then be added thereto to Gypsum Fibrosum, filler and metakaolin, stirring, prepare brown coal after dry type ball milling and carry the portland cement that germanium tailings is primary raw material；Present invention process is simple, energy consumption is little, low cost, obtained portland cement hardened paste comprcssive strength high, excellent in durability.
Description
Technical field
The invention belongs to portland cement technical field, be specifically related to a kind of carry germanium mine tailing portland cement as primary raw material and preparation method thereof with brown coal.
Background technology
In recent years, along with China builds energetically, building trade quickly grows, and cement, as the pith in construction material, occupies very important effect.In research the most at home and abroad, more (the Li Ning of research of cement is prepared with mine tailing for raw material, Wei Lining. a kind of recycling cassiterite mine tailing is method [P] .CN103524059A that low-energy consumption cement prepared by raw material, 2013), but in this kind of research, mine tailing volume is less, fills limestone in a large number.And limestone is as a kind of commercially available raw material, price is also going up year by year.Currently propose, with brown coal, the research that germanium tailings prepares portland cement for primary raw material and have no report.
During carrying germanium, first by brown coal roasting, then use substantial amounts of acid-containing solution to process germanium-containing smoke dust, germanic therein transferred in solution, after filtration washing, filtering residue through in soda lime and after be brown coal and carry germanium tailings.Current brown coal carry germanium tailings and mainly take stacking to process, and easily cause occupation of land, pollute the problems such as environment, also result in the biggest potential safety hazard simultaneously.Therefore, how utilizing brown coal to carry germanium tailings becomes the important topic that we have to study, and building materials aspect is mainly prepared in current research.As: utilize brown coal to carry germanium tailings and prepare sintering ceramsite and baking-free ceramicite, and carry germanium tailings with brown coal and prepare the research of portland cement for raw material and have no and report for work.It is that substrate prepares portland cement that this research uses brown coal to carry germanium tailings, to realize secondary resource recycling and the purpose of environmental protection.Present invention process is simple, energy consumption is little, tailings utilization rate high.
Summary of the invention
It is contemplated that overcome existing technological deficiency, it is simple that purpose is to provide a kind of technique, the brown coal that energy consumption is less carry the portland cement that germanium tailings is primary raw material, and this portland cement constituent and percentage by weight thereof are that pretreatment brown coal carry germanium tailings 60wt% ~ 72wt%, solid exciting agent 5wt% ~ 10wt%, Gypsum Fibrosum 8wt% ~ 10wt%, filler 5wt% ~ 15wt%, metakaolin 5wt% ~ 14wt%；The percentage by weight sum of each component is 100%.
Wherein said solid exciting agent is the mixture (mixing in any proportion) that in sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, any two is mixed to prepare.
Described Gypsum Fibrosum is that industrial waste gypsum is crushed to the granularity material less than 0.074mm > 80%.
Described metakaolin is grinding gained after In Guangdong Province kaolinite is calcined 2～4h at 650～850 DEG C, and mean diameter is 3.8 μm, wherein Al2O3Content be 38.5% ~ 40%.
Described filler is a kind of in fine sand, agstone, calcium hydroxide, calcium oxide, and fine sand is conventional commercial products.
Another object of the present invention is to provide the preparation method carrying the germanium tailings portland cement as primary raw material with brown coal, and concrete operation step is as follows:
(1) brown coal carry germanium tailings, solid exciting agent obtain after being dry mixed 5～15min in pouring blender into stirring material；
(2) step (1) gained stirring material being placed in Muffle furnace calcination, temperature is 900 ~ 1100 DEG C, is incubated 20～40min, obtains calcination material；
(3) in step (2) gained calcination material, add Gypsum Fibrosum, filler and metakaolin, stir 5～15min, obtain compound；
(4) step (3) gained compound is placed in dry ball mill 10～20min, is i.e. able to brown coal and carries the portland cement that germanium tailings is primary raw material.Adding water in obtained portland cement, water is 1:(3～4 with the mass ratio of portland cement), limit is stirred, and marginal not is starched, and at room temperature forms hardened paste.
Heretofore described brown coal carry germanium tailings and refer to smelt adding chain furnace after the screening of germanic brown coal, coal briquette processed, whirlwind smoke collector, bagroom is used to be collected the germanium-containing smoke dust produced in stove, then 8～9mol/L hydrochloric acid solutions are used germanium-containing smoke dust to be heated leaching, heating-up temperature is for being 80 ~ 90 DEG C, extraction time 4h-8h, germanium is transferred in infusion solution with the form of germanium tetrachloride, is filtered by solution, and filtering residue fine sand is neutralized to neutrality through soda lime after washing and i.e. obtains brown coal and carry germanium tailings；It is relatively thin that the brown coal prepared put forward germanium tailings granularity, but forms bulk, the particle diameter tailings more than 3mm > 80%, need to be through grinding ability balling-up；Its plasticity index is 12% ~ 14%, and plasticity is medium；The smelting of germanic brown coal uses conventional method to carry out, as implemented with reference to method in application number 93121175.1.
Owing to have employed technique scheme, the present invention has a following beneficial effect:
The problems such as 1, the present invention carries germanium tailings with brown coal and prepares portland cement for raw material, solves the potential safety hazard that tailings impoundment causes, environmental pollution, it is achieved that the secondary resource comprehensive utilization of the waste materials such as mine tailing, have widened the raw material sources preparing portland cement；
2, in the present invention, brown coal put forward germanium tailings early stage and through acidleach and wash, and mineral surfaces is rougher, and therefore in these mineral, the silica containing activity of institute is higher, beneficially the carrying out of secondary polymerization reaction, therefore the portland cement product strength of preparation is higher；
3, the Gypsum Fibrosum in this preparation technology is from industrial waste gypsum, is effectively reduced cost, it is achieved the recycling of industrial waste.
Therefore, it is simple that the present invention has technique, and the advantage that energy consumption is little has widened the raw material sources of portland cement, has opened up brown coal and has put forward the new way of germanium tailings comprehensive utilization, and its product strength is high, superior in durability.
Detailed description of the invention
Being described in further detail the present invention below by embodiment, but protection scope of the present invention is not limited to described content, in the present embodiment, agents useful for same is if no special instructions, is conventional commercial reagent.
Brown coal described in embodiment carry germanium tailings and are all from Yunnan ore dressing company, it is by adding chain furnace smelting after the screening of germanic brown coal, coal briquette processed, whirlwind smoke collector, bagroom is used to be collected the germanium-containing smoke dust produced in stove, then 8～9mol/L hydrochloric acid solutions are used germanium-containing smoke dust to be heated leaching, heating-up temperature is for being 80 ~ 90 DEG C, extraction time 4h ~ 8h, germanium is transferred in infusion solution with the form of germanium tetrachloride, solution is filtered, is neutralized to neutrality through soda lime after residue washing and i.e. obtains brown coal and carry germanium tailings.
Embodiment 1 :Carry the germanium tailings portland cement constituent as primary raw material with brown coal and percentage by weight is: brown coal carry germanium tailings 60wt %, solid exciting agent (ratio of potassium hydroxide and sodium hydroxide 1:1 in mass ratio is mixed to prepare) 10wt%, Gypsum Fibrosum 10wt %, fine sand 15wt%, metakaolin 5wt%, wherein said metakaolin is to grind gained after somewhere, Guangdong kaolinite is calcined 4h at 650 DEG C, mean diameter is 3.8 μm, wherein Al2O3Content be 38.5%.
The preparation process that above-mentioned brown coal carry germanium tailings portland cement is as follows:
(1) brown coal carry germanium tailings, solid exciting agent obtain after 5min being dry mixed in pouring blender into stirring material；
(2) step (1) gained stirring material being placed in Muffle furnace calcination, temperature is 900 DEG C, is incubated 20min, obtains calcination material；
(3) in step (2) gained calcination material, add Gypsum Fibrosum, fine sand and metakaolin, stir 5min, obtain compound；
(4) step (3) gained compound is placed in dry ball mill 10min, is i.e. able to brown coal and carries the portland cement that germanium tailings is primary raw material.Adding water in obtained portland cement, water is 1:3 with the mass ratio of portland cement, and limit is stirred, and marginal not is starched, and at room temperature forms hardened paste.
Hardened paste prepared by the present embodiment, 3 days comprcssive strength of natural curing can reach more than 20Mpa, rupture strength can reach 4.8 more than Mpa, more than 28 days comprcssive strength 46.5Mpa of natural curing, rupture strength can reach 6.8 more than Mpa, there is good stability, and there is good later strength.
Embodiment 2 :Carry the germanium tailings portland cement constituent as primary raw material with brown coal and percentage by weight is: brown coal carry germanium tailings 72wt %, solid exciting agent (ratio of potassium hydroxide and sodium hydroxide 1:2 in mass ratio is mixed to prepare) 5wt%, Gypsum Fibrosum 8wt %, agstone 5wt%, metakaolin 10wt%, wherein said solid exciting agent is to grind gained after somewhere, Guangdong kaolinite is calcined 2h at 750 DEG C, mean diameter is 3.8 μm, wherein Al2O3Content be 38.5%.
The preparation process that above-mentioned brown coal carry germanium tailings portland cement is as follows:
(1) brown coal carry germanium tailings, solid exciting agent obtain after 10min being dry mixed in pouring blender into stirring material；
(2) step (1) gained stirring material being placed in Muffle furnace calcination, temperature is 1000 DEG C, is incubated 30min, obtains calcination material；
(3) in step (2) gained calcination material, add Gypsum Fibrosum, agstone and metakaolin, stir 10min, obtain compound；
(4) step (3) gained compound is placed in dry ball mill 15min, is i.e. able to brown coal and carries the portland cement that germanium tailings is primary raw material.Adding water in obtained portland cement, water is 1:4 with the mass ratio of portland cement, and limit is stirred, and marginal not is starched, and at room temperature forms hardened paste.
Hardened paste prepared by the present embodiment, 3 days comprcssive strength of natural curing can reach more than 28Mpa, rupture strength can reach more than 5.2Mpa, more than 28 days comprcssive strength 52.4Mpa of natural curing, rupture strength can reach 7.5 more than Mpa, there is good stability, and there is good later strength.
Embodiment 3 :Carry the germanium tailings portland cement constituent as primary raw material with brown coal and percentage by weight is: brown coal carry germanium tailings 61wt %, solid exciting agent (ratio of sodium silicate and potassium silicate 1:2 in mass ratio is mixed to prepare) 6wt%, Gypsum Fibrosum 9wt %, calcium hydroxide 10wt%, metakaolin 14wt%, wherein said solid exciting agent is to grind gained after somewhere, Guangdong kaolinite is calcined 2h at 750 DEG C, mean diameter is 3.8 μm, wherein Al2O3Content be 38.5%.
The preparation process that above-mentioned brown coal carry germanium tailings portland cement is as follows:
(1) brown coal carry germanium tailings, solid exciting agent obtain after 15min being dry mixed in pouring blender into stirring material；
(2) step (1) gained stirring material being placed in Muffle furnace calcination, temperature is 1100 DEG C, is incubated 40min, obtains calcination material；
(3) in step (2) gained calcination material, add Gypsum Fibrosum, calcium hydroxide and metakaolin, stir 15min, obtain compound；
(4) step (3) gained compound is placed in dry ball mill 20min, is i.e. able to brown coal and carries the portland cement that germanium tailings is primary raw material.Adding water in obtained portland cement, water is 1:4 with the mass ratio of portland cement, and limit is stirred, and marginal not is starched, and at room temperature forms hardened paste.
Hardened paste prepared by the present embodiment, 3 days comprcssive strength of natural curing can reach more than 35Mpa, rupture strength can reach 5.8 more than Mpa, more than 28 days comprcssive strength 54.6Mpa of natural curing, rupture strength can reach 7.8 more than Mpa, there is good stability, and there is good later strength.
Embodiment 4 :Carry the germanium tailings portland cement constituent as primary raw material with brown coal and percentage by weight is: brown coal carry germanium tailings 65wt %, solid exciting agent (ratio of potassium hydroxide and potassium silicate 1:2 in mass ratio is mixed to prepare) 8wt%, Gypsum Fibrosum 8wt %, calcium oxide 12wt%, metakaolin 7wt%, wherein said solid exciting agent is to grind gained after somewhere, Guangdong kaolinite is calcined 3h at 800 DEG C, mean diameter is 3.8 μm, wherein Al2O3Content be 38.5%.
The preparation process that above-mentioned brown coal carry germanium tailings portland cement is as follows:
(1) brown coal carry germanium tailings, solid exciting agent obtain after 12min being dry mixed in pouring blender into stirring material；
(2) step (1) gained stirring material being placed in Muffle furnace calcination, temperature is 950 DEG C, is incubated 35min, obtains calcination material；
(3) in step (2) gained calcination material, add Gypsum Fibrosum, calcium oxide and metakaolin, stir 12min, obtain compound；
(4) step (3) gained compound is placed in dry ball mill 10min, is i.e. able to brown coal and carries the portland cement that germanium tailings is primary raw material.Adding water in obtained portland cement, water is 1:3 with the mass ratio of portland cement, and limit is stirred, and marginal not is starched, and at room temperature forms hardened paste.
Hardened paste prepared by the present embodiment, 3 days comprcssive strength of natural curing can reach more than 30Mpa, rupture strength can reach more than 5.3Mpa, more than 28 days comprcssive strength 50.6Mpa of natural curing, rupture strength can reach 7.1 more than Mpa, there is good stability, and there is good later strength.
Claims (3)
1. one kind carries the germanium tailings portland cement as primary raw material with brown coal, it is characterised in that: its constituent and percentage by weight thereof be: brown coal carry germanium tailings 60wt% ~ 72wt%, solid exciting agent 5wt% ~ 10wt%, Gypsum Fibrosum 8wt% ~ 10wt%, filler 5wt% ~ 15wt%, metakaolin 5wt% ~ 14wt%；
Described solid exciting agent is the mixture that in sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, any two is mixed to prepare；
Described metakaolin is the material being ground to granularity after In Guangdong Province kaolinite calcines 2～4h at 650～850 DEG C less than 0.074mm > 80% gained, Al2O3Content be 38.5% ~ 40%；
Described filler is a kind of in fine sand, agstone, calcium hydroxide, calcium oxide.
The most according to claim 1 carry the germanium tailings portland cement as primary raw material with brown coal, it is characterised in that: Gypsum Fibrosum is that industrial waste gypsum is crushed to the granularity material less than 0.074mm > 80%.
3. the preparation method carrying the germanium tailings portland cement as primary raw material with brown coal according to any one of claim 1-2, it is characterised in that preparation process is as follows:
(1) brown coal are carried germanium tailings, solid exciting agent and after being dry mixed 5～15min, obtains stirring material；
(2) step (1) gained stirring material being placed in Muffle furnace calcining, temperature is 900 ~ 1100 DEG C, is incubated 20～40min, obtains calcining material；
(3) in step (2) gained calcining material, add Gypsum Fibrosum, filler and metakaolin, stir 5～15min, obtain compound；
(4) step (3) gained compound is placed in dry ball mill 10～20min, is i.e. able to brown coal and carries the portland cement that germanium tailings is primary raw material.
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| KR101638373B1 (en) * | 2014-09-16 | 2016-07-12 | 주식회사 마루치 | Hydraulic Binder Composition Having Ultra-rapid Hardening Property |
| CN105060742A (en) * | 2015-07-27 | 2015-11-18 | 中国科学院武汉岩土力学研究所 | Preparation method for low-grade manganese tailing-based binding material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1482088A (en) * | 2003-06-19 | 2004-03-17 | 中国建筑材料科学研究院 | Concrete slurry form finely-divided mineral admixture and and method for manufacturing the same |
| CN101492263A (en) * | 2008-06-04 | 2009-07-29 | 抚顺矿业集团有限责任公司 | Wax shale gray slag base polymer gelled material |
| CN103819174A (en) * | 2014-03-10 | 2014-05-28 | 临沧师范高等专科学校 | Sintered ceramsite adopting tailings generated during germanium extraction of lignite as main raw material and preparation method of sintered ceramsite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1482088A (en) * | 2003-06-19 | 2004-03-17 | 中国建筑材料科学研究院 | Concrete slurry form finely-divided mineral admixture and and method for manufacturing the same |
| CN101492263A (en) * | 2008-06-04 | 2009-07-29 | 抚顺矿业集团有限责任公司 | Wax shale gray slag base polymer gelled material |
| CN103819174A (en) * | 2014-03-10 | 2014-05-28 | 临沧师范高等专科学校 | Sintered ceramsite adopting tailings generated during germanium extraction of lignite as main raw material and preparation method of sintered ceramsite |
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