CN107177390A - A kind of reduction bone coal uses area's fluorine, the moulded coal of arsenic pollution - Google Patents

A kind of reduction bone coal uses area's fluorine, the moulded coal of arsenic pollution Download PDF

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CN107177390A
CN107177390A CN201710461750.2A CN201710461750A CN107177390A CN 107177390 A CN107177390 A CN 107177390A CN 201710461750 A CN201710461750 A CN 201710461750A CN 107177390 A CN107177390 A CN 107177390A
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coal
fluorine
bone
arsenic
powder
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赵超
雒昆利
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Institute of Geographic Sciences and Natural Resources of CAS
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
    • C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
    • C10L5/105—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with a mixture of organic and inorganic binders
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/10—Treating solid fuels to improve their combustion by using additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/02—Absorbents, e.g. in the absence of an actual absorbent column or scavenger
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/32—Molding or moulds

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

A kind of reduction bone coal uses area's fluorine, the moulded coal of arsenic pollution, and the invention provides the preparation method of a kind of solid fluorine for suitably using bone coal area, solid arsenic moulded coal.The moulded coal includes following components：1 sand charcoal（Or anthracite）, 2 common lump stone coals, 3 solid fluorine, arsenic additives, 4 clays.Wherein, additive is pulverized limestone and powder pureed bone coal.Through collecting evidence on the spot, scientific experiment, it is fluorine poisoning, the real source of arsenic poisoning to infer Southern Shaanxi room air pollution.Through door-to-door survey and questionnaire analysis, it have found and meet the moulded coal proportioning that people's lives needs reduce pollution that caused by coal burning again.The optimum proportion scheme of the present invention, fluorine, arsenic releasing factor averagely decline fluorine, sulfur dioxide, the concentration of ammonia in 45% and 72%, air and decline 34.1%, 96.47%, 92.51% respectively respectively.The moulded coal is directly manufactured successfully in moulded coal factory, and material is easily obtained, cheap, is easy to promote.In man of peasant household, experiment effect is good, in the Civil energy-saving cooking stove that can be widely applied to stone coal combustion area.

Description

A kind of reduction bone coal uses area's fluorine, the moulded coal of arsenic pollution
Technical field
The present invention relates to a kind of preparation method of clean type coal, consolidate more specifically to a kind of added with solid fluorine, arsenic performance Except agent, it is adaptable to which bone coal uses the manufacture method of the clean type coal in area.
Background technology
China is the area that coal-burning fluorosis and arsenic poisoning occurs in single report in the world.Coal-burning fluorosis is mainly related to And 12 provinces such as Guizhou, Yunnan, Sichuan, Hunan, Chongqing, Hubei, Shaanxi.China Health statistics is shown within 2014, place Property fire coal causes about 1453.72 ten thousand people to suffer from den tal fluorosis, and 188.19 ten thousand people suffer from fluorosis of bone., coal-smoke pollution type place in 2014 Property arsenic poisoning disease patient be 18628 people, relate generally to 8 counties of Southern Shaanxi and 4 counties with WESTERN GUIZHOU.Wherein, Shan Nan The 83% of total arsenic intoxication patients caused by coal number is accounted for, and there is the phenomenon of Fluoride arsenide poisoning.
For the coal-burning den tal fluorosis and fluorosis of bone of Yunnan Guizhou province, existing substantial amounts of research.As a result show, Yunnan-Guizhou Area's major part coal belongs to low fluorine coal（The μ g/g of ＜ 200）.Therefore in the absence of directly coal-fired caused fluorine poisoning.Through measure water fluorine, Oil repellent in the grain after coal clay fluorine, fresh grain and baking is mixed, specify that fluorine is in safe range in water fluorine and fresh grain It is interior, and the Oil repellent mixed in coal clay is up to more than 500 μ g/g, or even up to 2456 μ g/g.Resident is with this clay and Oil repellent Relatively low fine coal mixes lump coal, for drying substantial amounts of fresh corn and capsicum, and then causes to put down in this dried grain Equal Oil repellent increases by more than 10 times, considerably beyond food limit value.
Number of patent application be 03150300.4,200510000115.1,200610003468.1,200710195636.6, 200710302129.8th, 201110101974.5,201110105596.8 research, for reduction Yunnan-guizhou Area, burning pulverized coal and Mix during coal clay, fluorine, arsenic, the release of sulphur provide good technology and theory support.In addition, number of patent application 201110101988.7 also provide effective ways for fluorine content of pepper after the baking of reduction Yunnan-guizhou Area.
Southern Shaanxi, Sichuan, Chongqing and Hubei intersection, are located in Qinling Mountains Dabashan District, and height above sea level is 1500 to 2500 meters, The many folds of intermountain and tomography.Qin-ba Mountains coal resources are deficient, due to having inconvenient traffic, and the abundant coal resources in the north are difficult to be transported to In mountain.Shan Nan belongs to the continental monsoon climate of north subtropical, makes a clear distinction between the four seasons, vertical zonality weather is obvious.Winter solar radiancy Relatively low, sunshine is not enough, and weather is sombre, and March November to next year, temperature was relatively low, about 3-10 DEG C.Resident's warming ＆ cooking is, it is necessary to a large amount of raw Fuel living.Local strict limitation forest harvesting, therefore bury shallow, the bone coal easily exploited turns into important domestic energy.
Bone coal is the sapropelic material anthracite in Palaeozoic Strata, belongs to low calorie fuels, is not counted in national raw coal output.Shaanxi Southern bone coal expected reserves is up to 15.2 hundred million tons.With popular smokeless coal facies ratio, bone coal has high ash, high-sulfur, low-carbon, lower calorific value The characteristics of.Bone coal ash content is general in 40-80%, caloric value 1000-4500 cards/gram.According to mode of appearance, structure construction and thing Rationality energy, bone coal is divided into granular bone coal（Also known as sand charcoal）, lump stone coal（Also known as coal, common bone coal）, flakey bone coal and powder Pureed bone coal.Sand charcoal ash point are relatively low（40-50%）, caloric value is higher（3000-4500 cards/gram）, coal takes second place, powder pureed bone coal Caloric value is minimum（500-1200 cards/gram）.Because bone coal degree of metamorphism is higher, during burning, flame is short and few cigarette, therefore local occupies People's hobby excavates pit furnace indoors, and burning bone coal, which is warmed oneself by a fire, cooks.
Arsenic content is 8-277mg/kg in Qin_Ba mountain areas bone coal, and Oil repellent is 42-4532mg/kg, is Permo Carboniferous Coal 10-50 times（Luo K L. Arsenic and fluorine contents and distribution patterns of early Paleozoic stonelike coal in the Daba Fold Zone and Yangtze Plate, China. Energy Fuels. 2011, 25, 4479-4487;Luo Kunli, Su Wenzhi, Dumet profit, thunder good fortune Yao.Nan The micro- Xi'an Mining Technology Insts journal 1995,15 (2) of Qinling Mountains Eopaleozoic bone coal, 131-135;Yan Shishu, Appoint the occurrence status research Minerals And Rocks 1989,9 (3) of day training eastern Sichuan Basin bone coal fluorine, 109-112）.In bone coal Oil repellent and arsenic content have certain correlation with endemic disease illness rate.Shan Nan Ziyang, Langao and flat interest Area Inhabitants den tal fluorosis Illness rate is more than 50%, and some areas Dental fluorosis is more than 90%；Arsenic poisoning is related to flat interest, Langao, Zhenba, Zhenping etc. 8 Individual county.
Shaanxi Province comes into effect Oven improvement project in grave illness county within 1997.However, national health statistics in 2014 shows Show, Shan Nan still has the people of den tal fluorosis patient 17.65 ten thousand, the people of Patients With Skeletal Fluorosis 2.44 ten thousand；The people of arsenic poisoning 1.58 ten thousand., patent in 2016 Seminar where applicant, gos deep into Shan Nan counties, and 21 families of random searching, drop fluorine stove utilization rate only accounts for 24%, and pit furnace installs cigarette Chimney rate only 7%.Most resident's floor spaces are smaller, the larger drop fluorine stove of uncomfortable use floor space.Not only floor space is very for pit furnace It is small, and need not spend to purchase the chimney supporting with long term maintenance.In addition, warming up pin with pit furnace, warming oneself by a fire and all relatively drop fluorine stove more It is practical.
2016, the seminar where patent applicant, random searching 54 occupies the people in Shan Nan counties, and den tal fluorosis is ill Rate 89%.Resident is almost 0 to the awareness of the ill reason of fluorine poisoning, it is even contemplated that being local water quality inferiority, or eats self-produced corn It is caused.Factual survey shows that Shan Nan does not toast the custom of grain, is natural drying.Gather coal, soil, water, corn, capsicum, Potato, rice, Chinese cabbage, determine fluorine therein, arsenogen cellulose content（Table 1,2）.Except capsicum is slightly above national food element limit value （NY861-2004）In addition, remaining grain is in the range of safe edible.Fluorine and arsenic content are carried on the back higher than Chinese soil in soil Scape value, but Shan Nan is without using the custom for mixing coal clay, being mostly largely direct burning bone coal, therefore air is not constituted substantially Pollution.Fluorine and arsenic content in bone coal are 3.37 times and 18.65 times of CHINESE COAL average, are important pollution sources.
The Shan of table 1 south drinking water, corn, capsicum, potato, rice, Chinese cabbage, soil, the average content (mg/kg) of PAHs in coal
Drinking water Corn Capsicum Potato Rice Chinese cabbage Soil Bone coal
Fluorine 0.15(54)* 0.60(10) 1.15(6) 0.35(11) 0.50(9) 0.06(21) 907.49(113) 438.28(27)
Limit value 1 1 1 1.5 1 1 478 (Chinese soil backgrounds) 130 (CHINESE COAL averages)
* sample size is represented in bracket
The average content (mg/kg) of arsenic in the Shan of table 2 south drinking water, corn, capsicum, potato, rice, Chinese cabbage, soil, coal
Drinking water μ g/L Corn Capsicum Potato Rice Chinese cabbage Soil Bone coal
Arsenic 0.07 (39) 0.04 0.06(6) 0.01(11) 0.15(9) 0.00(21) 16.19(113) 70.49(27)
Limit value 10 0.2 0.05 0.2 0.15 0.05 11.2 (Chinese soil backgrounds) 3.78 (CHINESE COAL averages)
* sample size is represented in bracket
For reduce stone coal combustion during arsenic or fluorine release, number of patent application be 02153934.0,200310118291.6, 200310118292.0th, 200810231731.1 research, proposes the limestone or white clouds with 900-1000 DEG C of calcining 7 days of high temperature Rock is as admittedly except agent（Table 3）.This method is admittedly preferable except effect, but is not promoted so far in Shan Nan.First, exploitation of stone need through Government's examination ＆ approval are crossed, cost of winning is higher.Secondly, stone is taken to easily cause environmental pollution, ecological disruption, or even mountain blasting, mud occur Rock glacier, and the input of later stage ecological restoration and management fund, the regional pressure fallen behind for economic development are huge.In addition, high temperature connects Continuous calcining 7 days, challenge is proposed to the type coal field without calciner, and calcining needs a large amount of coals, exists to air Pollution hidden trouble.Therefore, although this method has preferably removes effect admittedly, multi-sector cooperation, abundant Evaluation Environment are stilled need It can just be promoted after effect.
The bone coal fluorine of table 3, arsenic pollution control patent
Application number It is open Time Most optimum materials are matched Advantage Admittedly except agent makes There is problem
02153934.0 2004 Fire natural white clouds Rock:Bone coal=50: 50 Gu fluorine rate 92% Natural dolomite is in 900- 1000 DEG C are calcined 7 days, plus Water cure Test indoor test, Proportioning can not be by stone Moulded coal is made in coal, lacks Few binding agent
200310118291.6 2004 Stone coal powder:Smokelessly Coal dust:Gu fluorine adds Plus agent (is fired white Cloud rock or limestone): Clay=30:45: 18:7 Gu fluorine rate 85%, air Fluoride removing rate 53% Natural dolomite or lime Rock burns at 900-1000 DEG C Burn 7 days, add water curing 8 families use new Coal, but without long-term Survey, resistance to burning Property and applicability are not Know.
200310118292.0 2004 Bone coal block:Curing Firing dolomite (or lime calcining Rock):Anthracite Powder:Clay=70: 12:12:6 Gu fluorine rate 75%, air Fluorine rate drops 85.7% Dolomite or limestone exist 900-1000 DEG C of calcination 7 My god, add water curing 8 families use parcel stone The solid fluorine fuel of coal, but It is not investigate length Phase practicality.It is uncomfortable For type coal field batch Amount production
200810231731.1 2009 Lime calcining rock: Stone coal powder:Clay: Bone coal block=12: 12:6:70 Air arsenic is dense Degree drops to 0.7μg/m3, Arsenic release rate It is down to 14.03% Natural limestone is in high temperature 900-1000 DEG C of calcining 7 My god, add water curing 15 families use bone coal Encapsulation fixed arsenic fuel. Imitated without being used for a long time Fruit monitors, and is not suitable for Make bone coal cleaning Moulded coal is promoted.
The national high-tech research development that 2006-2010, Luo Kunli researcher preside over（863）Plan " Zhaotong fluorine poisoning compartment Interior air sulphur, fluorine, arsenic pollution control technology ", Zhaotong County, Yunnan fluorosis area is compared for extensively removes material, including Early Permian Epoch admittedly Mao Kou groups dolomitic limestone, Early Permian Epoch Mao Kou group limestone, upper Ordovician series bottom limestone, the siliceous limestone of matter containing white clouds, siliceous ash Effect is removed admittedly after the protolith of rock and its calcining, and conclusion is the Early Permian Epoch Mao Kou group limestone after calcining（Main component is shown in Table 4） Gu fluorine best results, principle is that the carbonate rock after the calcination processing that siliceous content is lower, alkali metal is abundanter consolidates fluorine effect more It is good.Applicant seminar finds Middle Cambrian series hair Ba Guan group medium bed limestones in flakes on the southern type coal field periphery in Shan, however F with SiO2Content is higher（Table 4）, i.e., fluoride pollution easily is caused in calcination process, also because the solid fluorine effect of siliceous content height influence, no It is preferably to remove material admittedly.
Fluorine, arsenic content and the main physico-chemical property of the solid fluorine material of table 4
The siliceous content of pulverized limestone, fluorine and arsenic content are relatively low in the present invention, and calcareous content is high, and clay and powder pureed bone coal Middle alkali metal content is far above the Early Permian Epoch Mao Kou group limestone after the calcining of Zhaotong.In addition, common bone coal matter is hard, after crushing in It is granular, molding bonded is difficult, it is necessary to add binding agent；And because bone coal ash content is higher, the clay amount no more than 10% of addition, Otherwise the resistance to burning of moulded coal can be influenceed.Powder pureed bone coal is that matter is soft, a kind of high bone coal of viscosity, that is, is conducive to common bone coal to be bonded to Type, it may have certain combustibility, and its alkali metal content is higher, there is certain solid except effect to fluorine, arsenic, sulphur.Therefore, stone Ashes, lubrication coal, clay can be reached after being mixed with common bone coal preferably removes effect admittedly.Moreover, pulverized limestone and powder pureed stone Coal is easily bought in this region, cheap, non-secondary pollution, so being more easy to meet production at this stage and ecological requirements.
At present, stone coal combustion area is still faced with serious room air pollution, it would be highly desirable to develops and is adapted to local actual feelings The clean type coal of condition, simple and practical, the solid solid arsenic of fluorine.Long term accumulation of the invention according to seminar, in Shan Nan type coal field systems Clean type coal is made, has been used in peasant household's man's pit furnace and range of decrease stove, and continued observation one week, to calculate fluorine, arsenic releasing factor, simultaneously Fluorine, sulfur dioxide and ammonia concentration in room air are determined, finally provides and both meets the coal-fired needs of life, fluorine, arsenic can be reduced again The clean type coal preparation method of pollution.This method is simple and easy to apply, is adapted to, in the large scale investment production of Shan Nan moulded coals manufactory, have Important realistic meaning.
The content of the invention
It is an object of the invention to provide the manufacture method that a kind of bone coal uses the solid fluorine in area, solid arsenic moulded coal.The invention raw material It is easy to get, easy to use, cheap, better user experience, it is adaptable to the Civil energy-saving cooking stove for bone coal type fluorosis area of burning.
Clean type coal includes following components：
Sand charcoal（Or anthracite）Powder, common stone coal powder, Gu fluoride additive, clay
Preparation method and step
Wherein described solid fluoride additive is pulverized limestone and powder pureed bone coal.Sand charcoal（Anthracite）Powder, common stone coal powder, powder pureed Bone coal, pulverized limestone, the weight ratio of clay are 15-45: 27-64: 6: 6-15: 5-7；Preferably sand charcoal:Common bone coal:Powder Pureed bone coal:Lime:Clay=45: 27: 6: 15: 7；Or anthracite:Common bone coal:Powder pureed bone coal:Lime: Clay=15: 64: 6: 10: 5.
Wherein lime pulverizing is to 200 mesh, sand charcoal, anchracite duff, common bone coal, powder pureed bone coal, the powder particle diameter of clay Less than 2mm.It is well mixed, a small amount of water is added, clean type coal is pressed into standard briquette shaper.Current Ningxia anthratite is in Shan There is certain supply in south, the area for being difficult to buy in Ningxia anthratite, sand charcoal（The higher bone coal of calorific value content, such as wormwood artemisia level ground sand Charcoal）Anthracite can be replaced.
Sand charcoal, the main purpose of anchracite duff are the fuel values for improving solid fluorine fuel, it is to avoid common stone coal powder is with consolidating After fluoride additive, clay mixing, fuel value is relatively low.
Clay, the main purpose of powder pureed bone coal are to increase the mouldability and caking property of the solid fluorine fuel of moulded coal, prevent moulded coal Crush in combustion, cause to stop working, while there is certain solid fluorine effect, powder pureed bone coal also has certain combustibility.
The present invention has advantages below：
Effect preferably, is bonded, do not choke people during burning in terms of calorific intensity and smoke elimination.Resistance to burning property and resident's family expenses bone coal phase When continuing to monitor seven days, very hot oven furnace temperature is up to 1100 DEG C.
Pulverized limestone is added in bone coal, the fluoride that can be discharged with stone coal combustion reacts, and the calcirm-fluoride for producing infusibility is consolidated It is scheduled in cinder.The As that CaO discharges with coal combustion2O3Occur solid arsenic reaction, generate Ca3(AsO4)2Coal-fired ash is rested on solid phase In slag.According to optimum proportioning, fluorine, the more common bone coal of arsenic releasing factor averagely decline fluorine in 45% and 72%, air and declined respectively 39.01%。
Pulverized limestone is added in coal, sulphur, fixed nitrogen can also be consolidated, the release of oxysulfide and ammonia when reducing coal-fired.This is specially The clean type coal that profit is developed compared with the common bone coal of burning, in air sulfur dioxide, the concentration of ammonia decline 96.47% respectively, 92.51%。
Powder pureed bone coal, clay are added, the bonding force of bone coal can be improved, it is easy to be molded, solid fluorine effect is improved；Powder pureed Bone coal also has certain combustibility.
Sand charcoal or anchracite duff are added, makes the inflammable good burning of moulded coal, it is adaptable to Civil energy-saving cooking stove.
Material is easy to get, cheap（According to optimum proportioning, it is yuan one piece big that average sales price is equal to current commercial valency, i.e., 0.75 Honeycomb briquette）, it is easy to make, without special installation, it is easy to promote in honeycomb coal works.
Below by embodiment, the present invention will be further described, but is not meant to limitation of the present invention.
Embodiment
The preparation of moulded coal：
In Langao County honeycomb coal works, by lime grinds, sand charcoal（Or Ningxia anthratite）, it is common bone coal, powder pureed bone coal, glutinous Soil is crushed with honeycomb coal works pulverizer, and particle diameter is less than 2mm.In proportion（Table 5）Weigh sand charcoal（Or anchracite duff）, common bone coal, Powder pureed bone coal, lime, clay, plus suitable quantity of water, stir, are put into honeycomb briquet making making machine, honeycomb briquette is made.
Table 5 makes 8 kinds of different ratios (%) of clean type coal
Test family Wormwood artemisia level ground sand charcoal Common bone coal Powder pureed bone coal Lime Clay
1 19 64 6 6 5
2 25 58 6 6 5
3 15 64 6 10 5
4 45 27 6 15 7
Ningxia anthratite Common bone coal Powder pureed bone coal Lime Clay
5 19 64 6 6 5
6 25 58 6 6 5
7 15 64 6 10 5
8 45 27 6 15 7
Combustion of Mould Coal is tested：
Experiment point is carried out for 14 days, and the last week uninterruptedly uses traditional coal, and one week after is uninterruptedly using the clean type coal of the present invention.Choosing The family that 8 families normally use bone coal is selected, wherein, 6 families are pit furnace, and 2 families are drop fluorine stove.First week, using LTP method and fluorine Ion selective electrode method determines the air Funing tablet in each room.It is random repeatedly to determine SO in air2And NH3Concentration, and calculate average Value is used as indoor sulfur dioxide and ammonia concentration.Test the highest temperature of each household honeycomb briquette stove several times with hand-held fast thermocouple Degree.Bone coal, moulded coal that each family is usually used, and the cinder burnt are gathered, Oil repellent, arsenic content is determined, according to loss on ignition, meter Calculate fluorine, arsenic releasing factor.
Second week, 8 family residents use clean type coal, and it is dense that same method determines Funing tablet, sulfur dioxide and ammonia in air Degree.Furnace temperature is recorded, investigation user uses experience, including caking property, resistance to burning, smell etc..Gather clean type coal and its corresponding Cinder, calculates fluorine, arsenic releasing factor.The laboratory sample of all collections all delivers to Chinese Academy of Sciences's geographical science and the Study on Resources Tested.
Result of the test shows, reinforces except the Oil repellent reduction by 35% average than common bone coal of formulation coal, fluorine releasing factor averagely under Drop 45%（Table 6,7）；Reinforce except the arsenic content reduction by 40% average than common bone coal of formulation coal, arsenic releasing factor averagely declines 72%（Table 6,8）.Average fluoride removing rate 34.1% in air（Table 9）.The clean type coal sulphur removal of the present invention, nitrogen effect are preferable, with unguyed fluorine agent Common bone coal, honeycomb briquette are compared, and air desulphurizing ratio is 96.47%, except ammonia rate is 92.51%（Table 10）.
The satisfaction investigation of clean type coal is used according to experiment family, all 8 kinds of proportionings meet smokeless do not choke people, very hot oven The characteristics of temperature is up to 1100 DEG C.The caking property and resistance to burning for testing the clean type coal of family 3 and 7 are optimal, i.e. sand carbon content reaches 45% Preferably, this is higher relevant with sand charcoal calorific value for resistance to burning property；Ningxia anthratite content is not higher than 15%, caking property preferably, this with Ningxia without Bituminous coal is not blocking after burning, and the stove that easily collapses is relevant.
The resident of table 6 is often with bone coal and cinder fluorine, arsenic content and burning burst size
It is right Than Family Common bone coal is fluorine-containing Measure (mg/kg) Stone coal slag fluorine contains Measure (mg/kg) Fluorine release because Sub (mg/kg) Common bone coal contains arsenic Measure (mg/kg) Stone coal slag arsenic contains Measure (mg/kg) Arsenic release because Sub (mg/kg)
1 177.74 488.06 263.46 32.84 124.71 23.32
2 156.23 365.62 148.97 16.7 72.98 10.01
3 470.93 698.26 318.99 60.79 110.13 5.25
4 779.94 903.05 30.3 70.32 127.49 41.55
5 365.63 473.48 110.6 77.97 216.48 16.42
6 712.87 385.86 498.39 84.45 80.31 39.81
7 537.64 685.84 269.65 100.45 132.14 48.81
8 547.94 517.69 301.86 62.71 27.93 49.44
It is flat 468.62 564.73 242.78 63.28 111.52 29.33
The clean type coal of table 7 and cinder Oil repellent and burning burst size
Test family Reinforce and remove formulation coal fluorinated volume (mg/kg) Moulded coal slag Oil repellent (mg/kg) Fluorine releasing factor (mg/kg)
1 381.40 421.57 180.84
2 385.59 296.12 248.65
3 348.74 485.39 105.90
4 413.89 479.17 185.01
5 256.82 410.42 92.25
6 236.42 285.45 125.00
7 250.23 495.31 31.59
8 160.32 360.90 106.42
It is average 304.18 404.29 134.46
The clean type coal of table 8 and slag arsenic content and arsenic burst size
Test family Reinforce and remove formulation arsenic level in coal (mg/kg) Moulded coal slag arsenic content (mg/kg) Arsenic releasing factor (mg/kg)
1 46.98 73.17 12.17
4 50.19 103.67 0.67
6 33.53 66.96 8.28
7 37.36 60.55 9.32
8 20.54 57.96 10.72
It is average 37.72 72.46 8.23
Wherein, it is negative value that the experiment family of family 2,3,5, which calculates the arsenic releasing factor obtained, and reason is probably that arsenic burst size is very low, or Coal ash sample arsenic is contaminated, therefore unlisted.
Table 9 determines air fluorine and removing fluorine result
Test family It is unguyed to remove the common bone coal gas fluorine μ g/m of agent3 Reinforce and remove agent clean type coal gas fluorine μ g/m3 Fluoride removing rate %
1 6.09 4.27 29.91
2 12.33 7.26 41.13
3 9.32 6.63 28.94
4 3.90 3.47 11.13
5 11.16 7.37 33.93
6 17.89 10.91 39.01
7 24.21 16.18 33.17
8 16.23 7.21 55.60
It is average 12.64 7.91 34.10
Wherein, experiment family 5,6 use drop fluorine stove, use the Funing tablet in common bone coal, room air do not have significantly it is low In the family for using pit furnace.Reason is probably, family expenses drop fluorine stove in coal, cook during usually open bell, stone coal combustion The fluorine of release can be still discharged into room air.
The clean type coal sulphur removal of table 10, ammonia effect (ppm)
Test family Unguyed fluorine agent stone Coal air sulfur content Reinforce fluorine formulation coal empty Gas sulfur content Unguyed fluorine agent bone coal air Ammonia level Reinforce fluorine formulation coal air Ammonia level
1 1.8 0.25 9.1 1.47
2 9.1 0.13 15.55 0.2
3 3.67 0 6.23 0
4 11.95 0.88 5.43 1.12
5 2.5 0.07 2.43 0.23
6 5.2 0 3.4 0.24
7 0.15 0 2.97 0.24
8 6.25 0.1 4.37 0.21
It is average 5.08 0.18 6.18 0.46
Admittedly except rate 96.47% 92.51%
Measuring principle and method
The solid fluorine principle of technical solution of the present invention is：Calcium in lime at high temperature with the fluorine in coal, reaction of Salmon-Saxl, generation indissoluble The compounds such as calcirm-fluoride, calcium sulfate.The As that CaO discharges with coal combustion2O3Occur solid arsenic reaction, generate Ca3(AsO4)2It is deposited in ash In slag.In order to which bone coal is made into moulded coal, clay, powder pureed bone coal need to be added and improve caking property.During burning, fluorine in coal also can be with Aluminium, magnesium compound reaction, generation aluminum fluoride and magnesium fluoride in clay, so as to improve solid fluorine efficiency.
According to People's Republic of China (PRC) standard GB/T4633-1997 " assay method of PAHs in coal " and the People's Republic of China (PRC) Health industry standard（WS/T88-1996）, " coal and total fluorine assay method combustion hydrolytic-ion selective electrode method " is determined Fluorine in bone coal, clean type coal, cinder.Bone coal, clean type coal, cinder arsenic are determined with atomic fluorescence spectrum, instrument Use the full-automatic four lamp positions injecting type hydride-generation atomic fluorescence photometers of AFS-9780（Beijing Haiguang Instrument Co., Ltd.） As high performance hollow cathode lamps are equipped with to determine for total As.
Fluoride concentration is determined using lime filter paper-Fluoride ion selective electrode method in air.Indoor SO2And NH3Concentration is liked De Kesi ADKS-1 portable gas detectors are detected, are as a result directly displayed in units of ppm.TJ36-CAXL-18U-12 type hands The formula thermocouple of holding tests coal stove maximum temperature several times.
Issued according to State Administration for Quality Supervision and Inspection and Quarantine《Proximate analysis of coal（GB/T 212-2001）》In " slow-ashing method " determine samples of coal pulled product ash content.
Coal-fired fluorine, arsenic releasing factor calculation formula
In formula：E- fluorine（Arsenic）Releasing factor, mg/kg；C0Bone coal or clean type PAHs in coal before-heating（Arsenic）Content, mg/kg； C1Fluorine in residue after-heating（Arsenic）Content, mg/kg；The ash content of Ash- bone coals or clean type coal.
The specific assay method of fluorine, arsenic in coal, cinder
Weigh coal sample 0.2g（It is accurate to 0.0001g）With 0.5g silica flours in porcelain boat, mix, overlying 0.5g silica flours. Fluorine is converted into hydrogen fluoride or fluorine-containing waved in burning, hydrolysis, coal or coal ash in the air-flow of logical oxygen-vapor at 1000 DEG C Hair property compound, and absorbed by sodium hydroxide solution, determined with ion selective electrode method.With equipped with 15ml 0.2mol/L hydrogen-oxygens The colorimetric cylinder for changing sodium solution receives condensate liquid.Low-temperature space will be shifted before porcelain boat onto, stop 3 minutes, sample is gradually burnt.Then, Shift porcelain boat onto high-temperature region（1000℃）, wait 12 minutes.Then colorimetric cylinder is removed, porcelain boat is taken out.Add 1-2 drops in colorimetric cylinder Phenolphthalein indicator, neutrality is neutralized to 2mol/L nitric acid, adds 5ml ionic strength adjustors, 50ml is settled to deionized water, Shake up.Oil repellent is surveyed with ion-selective electrode.
The g of precise 0.0500 or so sample, is transferred in 100 mL glass beakers.Drawn respectively with glass pipet 10 mL HNO3, 2 mL HClO4It is transferred in beaker, is capped surface plate.Weak vibrations beaker, shakes scattered beaker bottom sample, puts Stood overnight on to electric hot plate.Next day, open heating board digestion sample.Electric hot plate surface temperature should be 180 DEG C, persistently clear up, when Emerged in beaker a large amount of HClO4During white dense smoke, the color of test solution and remaining sample in observation beaker.If test solution become it is transparent or Person's pale yellow transparent color, when remaining sample becomes white or canescence.Specimen eliminating is completed, cooling, and transfer is settled to 25ml examinations Pipe.The ascorbic acid solution of 1 mL2.5% thiocarbamides+2.5% is sequentially added into test tube, 1 mL concentrated hydrochloric acids are settled to examination with sub- boiling water Pipe graduation mark.Test tube is jumped a queue, and shakes up solution.40 minutes are stood, arsenic content is surveyed with atomic fluorescence spectrophotometer.

Claims (6)

1. a kind of reduction bone coal fluorine, the clean type coal of arsenic pollution, it is characterised in that this method comprises the following steps：
（1）Lime is clayed into power shape；
（2）Common block stone coal powder is broken；
（3）The higher sand charcoal of calorific value or anthracite are crushed；
（4）Powder pureed bone coal, clay are crushed；
（5）By sand charcoal（Anthracite）Powder:Common bone coal:Powder pureed bone coal:Lime:Clay is with 15-45: 27-64: 6: 6-15:5-7, is well mixed；
（6）A small amount of water is added in mixed coal powder, clean type coal is pressed into standard briquette shaper.
2. clean type coal according to claim 1, it is characterised in that described lime is powdered.
3. clean type coal according to claim 1, it is characterised in that described powder pureed bone coal is to be main by ferro-silico aluminium structure Into low heat value bone coal, matter is soft, toughness.
4. sand charcoal according to claim 1（Or anthracite）, common lump stone coal, powder pureed bone coal, clay, its feature exists In particle diameter is less than 2mm.
5. the moulded coal preparation method according to claim 1-3, it is characterised in that by sand charcoal（Anthracite）, common block stone Coal, powder pureed bone coal, lime are well mixed after crushed with clay, plus a small amount of water, are conventionally pressed into moulded coal.
6. clean type coal according to claim 1, it is characterised in that optimal proportion is sand charcoal:Common lump stone coal:Powder Pureed bone coal:Lime:Clay=45: 27: 6: 15: 7；Or anthracite:Common lump stone coal:Powder pureed bone coal: Lime:Clay=15: 64: 6: 10: 5.
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CN111026189B (en) * 2019-12-10 2021-02-26 山东科技大学 Smoking temperature rising device and method, smoking temperature rising detection method, control device and system

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Application publication date: 20170919