CN101504143B - Technique for using leather products industrial waste as fuel - Google Patents
Technique for using leather products industrial waste as fuel Download PDFInfo
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- CN101504143B CN101504143B CN2009100196213A CN200910019621A CN101504143B CN 101504143 B CN101504143 B CN 101504143B CN 2009100196213 A CN2009100196213 A CN 2009100196213A CN 200910019621 A CN200910019621 A CN 200910019621A CN 101504143 B CN101504143 B CN 101504143B
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
The invention discloses a technological method for using a leather product industrial waste as a fuel. The method comprises the following steps of: a. throwing the leather product industrial waste and coal in a proportion of between 1 to 1 and 1 to 3 into a pre-combustion area of an industrial boiler for mixing to form a mixed fuel; b, incinerating the mixed fuel in the industrial boiler by using the third-order 'thermal decomposition type' incinerating process; c, recovering and converting the heat generated after the incinerating by a heat recovery device; and d, changing chromium salt generated after the incinerating into water-soluble chromate by an alkaline roasting method, and carrying out recovery by water leaching. The technological method not only can provide combustion heat and recover a toxic chromium element, but also can effectively reduce the content of harmful gases, such as SOx, NOx and the like generated during burning the fuel.
Description
Technical field
The present invention relates to a kind of process with using leather products industrial waste as fuel.
Background technology
Along with the adjustment of world's industrial structure, leather industry is shifted to developing country by developed country.There are widely human resources in China, and abundant rawhide resource, enough production capacity and certain technical merit are occupied in the world 1/5th large market simultaneously, the labor-intensive leather industry of suitable development.According to data, China at present leather enterprise has reached family more than 1.6 ten thousand, and number of employees reaches about 2,000,000 people.Yet, development of China leather industry is in fast development, also brought serious environmental pollution, wherein the Leather Solid Waste annual emissions is more than 1,400,000 ton, comprises mainly that waste wool is sent out, scrap leather bits, chrome leather shaving shavings, deburring material, useless two layers, severing bits the like waste.From environmental benefit, the placement of the leather leftover that annual tannery is a large amount of, if untimely processing, the chromium element in the shavings has very large harm to water quality and soil, and places the aesthetic property that a large amount of shavingss had not only taken a large amount of areas but also affected environment.
According to statistics, 1 ton of wet salted hide only produces the finished product leather (account for raw material tare weight 20%) of 200kg, but will produce the above solid waste of 600kg (surpass former tare weight 60%).Except the NCPs such as a small amount of hair, meat slag were arranged, major part was raw hide edge-trimming corner material, grey skin graft, the chromium-containing collagen discarded object that produces such as chromium-containing collagen and Lan Pi shaving, deburring not such as the bits of peeling in these solid waste.It is reported the annual solid waste that produces 150,000 tons of India; The chromium discarded object that contains that generation whenever is only by the U.S. just reaches 60,000 tons; China approximately produces more than 140 ten thousand tons leather corner discarded object (comprise and contain the chromium leather castoff) every year.These solid waste are to cause one of with serious pollution key factor of leather industry.
Industrial, the recovery of Leather Factory's solid waste and circulation comprehensive utilization all are the subject matter that people pay close attention to all the time.These solid waste comprise in salt, process hides useless skin, hair, grease and the process hides process not by the chemical material of full consumption.Be exactly skin, the leather slag bits that produce in the onal piece of deburring and split, shaving or the buffing process in addition.If these Leather Solid Wastes directly discharge, the one, contaminated environment, the 2nd, the waste of resource must be carried out treatment and comprehensive utilization to it.
Natural leather brings new pollution element-chromium element after the tanning stage.The pollution of chromium element also is the subject matter in the leather industry, and the toxicity of chromium exists form that much relations are arranged with it, it is generally acknowledged that chromic toxicity is higher approximately 100 times than trivalent chromium.
Extensive use inorganization burning method is processed the shavings discarded object at present, and the leftover bits and pieces of process hides is directly put into stove and burned, and collagen decomposition becomes the little molecular product such as carbon dioxide, water to be removed, and chromium then remains with the form of inorganic salts and oxide.The ridge village is great, once studied burning time, temperature etc. to the impact of product with common electric furnace in " effectively utilizing the research overview of leather about Japan ", finds that the condition that the shaving shavings burnouts fully is: 800～1000 ℃, and 30min; 700～800 ℃, 60min; 400～500 ℃, 180min.Pig leather waste material incineration temperature and time have a significant effect to chromate content in the product, and chromate is less below 500 ℃, begins to increase more than 600 ℃, and 800 ℃ reach maximum, burn 180min under this temperature, and 1/3 chromium becomes sexavalence.In special electric furnace, minute two sections burnings of low and high temperature, and it is combustion-supporting to add kerosene, fully burns, and can prevent chromic formation.Dispersing of the hexavalent chromium compound that may occur when preventing from burning, the great pressurized aqueous combustion of having studied again in ridge village, in the titanium liner autoclave, shavings in acid or alkaline medium, high-pressure constant temp oxidation, decomposes collagen.Under the alkalescence bar, the chromium 98% or more becomes chromic acid and burns chrome leather scrap and body refuse in alkalescence, under the cryogenic conditions, and discovery also only has 25% chromium to become sexavalence, has also produced a large amount of SO
x, NO
xDeng pernicious gas, be unfavorable for environmental protection.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of process with using leather products industrial waste as fuel, calory burning can either be provided, poisonous elemental chromium is reclaimed, and can effectively reduce the SO that produces in the fuel combustion again
x, NO
xDeng pernicious gas content.
For solving the problems of the technologies described above, the present invention includes following steps:
A, with using leather products industrial waste with coal-fired according to 1: 1-1: 3 ratio drops into respectively the preignition zone mixing formation fuel combination of Industrial Boiler;
B, in Industrial Boiler, adopt three grades of " thermal decomposition type " burning process to burn above-mentioned fuel combination;
C, utilize heat reclamation device that the heat that burns rear generation is reclaimed and thermal power transfer;
D, the chromic salts that burns rear generation is become water-soluble chromium acid salt by the basic roasting method with it, reclaim with flooding.
Below be the further improvement to technical solution of the present invention:
Three grades of " thermal decomposition type " burning process in the above-mentioned B step comprise following three steps:
1), at first in preignition zone, fuel combination placed under 550～650 ℃ the temperature and carry out the anoxic baking;
2), then the flue gas that produces after the fuel combination baking is placed further gasification under 1150～1250 ℃ temperature in the combustion zone;
3), the flue gas after will gasifying at last carries out all-oxygen combustion in burning-out zone.
As another kind of prioritization scheme, the Industrial Boiler in the B step comprises body of heater, is provided with preignition zone, combustion zone and burning-out zone in body of heater, and the shell wall of described body of heater is made of inwall and shell, is the water leg that is filled with recirculated water between inwall and the shell.
On the one hand, recirculated water absorbs inwall steel plate heat, reduces the inwall steel billet temperature, prolongs the inner-wall material life-span, guarantees that skin temperature reaches designing requirement; On the other hand, recirculated water can be used as follow-up waste heat boiler water.
As another kind of prioritization scheme, the heat reclamation device in the C step is heat exchanger.
As another kind of prioritization scheme, the chromic salts roasting is reclaimed and is carried out in the following manner:
2Cr
2O
3+4Na
2CO
3+3O
2＝4Na
2CrO
4+4CO
2
As another kind of prioritization scheme, the chromic salts roasting is reclaimed and also can be carried out in the following manner:
Cr
2O
3+2CaCO
3+3O
2＝2CaCrO
4+2CO
2
As another kind of prioritization scheme, during roasting, temperature is controlled at 900 ℃, then is incubated 1 hour.
As another kind of prioritization scheme, during lixiviate, Gu: liquid volume ratio=1: 5, extraction time 15～30min, temperature is controlled at 70 ℃.
Have following advance owing to having adopted above-mentioned technical scheme, the present invention to compare with original technology:
(1) energy-conservation:
Amount of heat is emitted in process hides and the burning of leather goods leftover bits and pieces, its fuel value quite or be higher than common burning of coal value, calory burning is collected utilization, the effectively use of fuel savings coal, can save 50,000 tons of common coals in namely 1 year, the annual fuel funds that can save 4,000 ten thousand yuan, economic benefit and social benefit are remarkable.
(2) reduce discharging:
If utilize the tanning waste of annual discharging, both reduced the pollution to environment and soil, energy savings again, its environmental and social benefits highly significant, can reduce SO every year
xDischarge capacity is more than 1500 tons.
(3) technique is simple and easy to control, easy to operate.
(4) pollution is few:
The residue rate only is 4%～6% after the burning of process hides and leather goods leftover bits and pieces, has substantial degradation than the residue rate (25%-30%) of coal, and 1 year can reduce by more than 10,000 ton waste residue, belong to process for cleanly preparing.
(5), economic benefit:
Commercially available coal price lattice: 1050 yuan/t, 250 yuan/t of leather leftover price.The total flow of the annual coal of factory is 100,000 tons, now uses 50,000 tons leather leftover to substitute 50,000 tons coal, and the annual escapable cost of factory is 4,000 ten thousand yuan like this.
Description of drawings
The present invention is further illustrated below in conjunction with the drawings and specific embodiments:
Accompanying drawing is the temperature correction figure of the experiment of Determination of Combustion Heat in the embodiment of the invention.
The specific embodiment
A, with using leather products industrial waste and the coal-fired preignition zone mixing formation fuel combination that drops into respectively Industrial Boiler according to 1: 1 ratio;
B, above-mentioned fuel combination is burned in Industrial Boiler.This Industrial Boiler comprises body of heater, is divided into preignition zone, combustion zone and burning-out zone in the described body of heater, and the shell wall of described body of heater is made of inwall and shell, is the water leg that is filled with recirculated water between inwall and the shell.
At first in preignition zone, fuel combination placed under 550～650 ℃ the temperature and carry out the anoxic baking; Then the flue gas that produces after the fuel combination baking is placed in the combustion zone and under 1150～1250 ℃ temperature, gasify; Flue gas after will gasifying at last carries out all-oxygen combustion in burning-out zone.
C, utilize heat reclamation device that the heat that burns rear generation is reclaimed and thermal power transfer;
D, the chromic salts that burns rear generation is reclaimed by the basic roasting method, this chromic salts is distributed in the slag, and the chromic salts roasting is reclaimed and carried out in the following manner:
2Cr
2O
3+4Na
2CO
3+3O
2＝4Na
2CrO
4+4CO
2
The chromic salts roasting is reclaimed and can also be carried out in the following manner:
Cr
2O
3+2CaCO
3+3O
2＝2CaCrO
4+2CO
2
During roasting, temperature is controlled at 900 ℃, then is incubated 1 hour, and it is become water-soluble chromium acid salt, reclaim with flooding, and during lixiviate, Gu: liquid volume ratio=1: 5, extraction time 15～30min, temperature is controlled at 70 ℃.
The below is the measuring to using leather products industrial waste:
1, selecting instrument is medicine
ZR-3R combustion heat experiments of measuring device (integrated), Nanjing helps development in science and technology Co., Ltd more; Beckman thermometer (Beijing Glass Institute), JA2003 electronic analytical balance, Shanghai Precision Scientific Apparatus Co., Ltd.
Benzoic acid, analyze pure, Shanghai development chemical industry three factories; The leather bits, ignition wire.
2, experimental procedure
A, calorimeter water equivalent (W
Water) mensuration
Weigh approximately 0.6g left and right sides benzoic acid in the balance, with the weight m of one section ignition wire of the accurate weighing of electronic analytical balance (approximately 15cm)
Silk, with the benzoic acid sample with the iron wire compressing tablet, more accurately iron wire and benzoic quality behind the weighing compressing tablet.The quality of removing iron wire is the benzoic quality m that participates in burning.Behind the device oxygen bomb device, can ignition measure temperature.Before and after the igniting, every 30 seconds, record one time temperature approach.Repeat 3 times and measure pending data.
B, leather bits measuring burning heat
The dried leather of weighing and skin, above-mentioned same method carries out the mensuration of fuel value.Record data.After the burning its residual residue is taken out, drying is weighed.Repeat 3 times and measure pending data.
The mensuration of c, moisture and volatile matter content
The mensuration of moisture and volatile matter content content generally adopts national standard Law (being Oven Method) in the leather.
Instrument: have the flat measuring cup of ground lid, high approximately 8cm, diameter 4～5cm; Baking oven; Drier; Assay balance.
Step: with baking oven little dry to constant weight of clean measuring cup in (102 ± 2) ℃, accurately take by weighing again sample 3～5g, accurately to 0.001g.Add baking oven, at (102 ± 2) ℃ oven dry 6h, take out measuring cup, lid is built, be placed on weighing behind the cooling 30min in the drier.Whenever dry by the fire again later on 1h, cooling 30min weighing once, until the difference of front and back two inferior qualities be no more than sample heavy 0.1% be constant weight.But must not surpass 8h total drying time.
Calculate: the content X (%) of moisture and volatile matter content is calculated according to the following formula.
M in the formula
0The quality of-dry front sample, g;
m
1The quality of-dry rear sample, g.
The mensuration of d, total ash
After the calcination of leather sample through high temperature (600～800 ℃), organic substance is completely decomposed of volatile, and remaining mineral matter residue is total ash.Ash content is the general name of noncombustibles matter in the shavings.Be convenient processing to residue, the composition of ash content (residue) and content all need to measure.The existence of shavings ash content can reduce its calorific value, has also increased smoke contamination and has gone out the quantity of slag, thereby affected the thermal efficiency.
Instrument: high temperature furnace, temperature is controlled, can keep temperature to reach 800 ℃; Crucible, glazy 30mL porcelain crucible.
Measure: in advance with crucible 800 ℃ of lower calcinations, cooling is weighed, calcination is to constant weight again.Take by weighing sample 2～3g, be accurate to 0.001g, be placed in the crucible of constant weight, will cover crack.First with crucible on electric furnace with flammule heating, make slowly charing of sample, to avoid the charcoal ball or with the phenomenon of crucible bond vitrified.When treating without the charcoal cigarette, thoroughly moistening with 1mol/L sulfuric acid.Low-temperature heat is to the cigarette disappearance of sulfur trioxide, heat intensive.Then be placed in 800 ℃ of high temperature furnaces calcination complete to ashing.In drier, cool off and weigh.Repeat-heating, cooling, weighing to twice 1mg that is not more than of poor quality, are namely made constant weight.
Calculate: total ash X (%) is calculated as follows.
M in the formula
1The quality of-crucible and ash content, g;
The quality of m-crucible, g;
m
0The quality of-sample, g.
E, chromium content
In the tannery of natural leather, must add the chromic salts tanning, this has just increased pollution sources-chromium element.Chromium is all toxic to human body and animals and plants and microorganism.The mensuration of chromium content also is the necessary test that shavings acts as a fuel.The method of chromium content generally is to adopt AAS in traditional mensuration leather.The below introduces main experimental procedure.
Key instrument and reagent: 752N type spectrophotometer (Shanghai Precision Scientific Apparatus Co., Ltd); PHS-25 type acidometer (Shanghai Precision Scientific Apparatus Co., Ltd), cation exchange column.
0.5mgL
-1Cr
2O
7 2-Standard liquid: take by weighing benchmark K
2Cr
2O
7Being mixed with mass concentration is 1.0mgL
-1Solution, this solution being diluted to one by one mass concentration again is 0.5mgL
-1Working solution;
0.5gL
-1Arsenazo (III) solution: take by weighing 0.25g arsenazo (III) and be dissolved in the 500mL water.
Experimental technique: get a certain amount of chromium (VI) standard liquid in the 25mL volumetric flask, add successively arsenazo (III) solution 5.5mL, nitric acid 25% solution 4mL is diluted to scale with intermediate water, shakes up.In boiling water bath, heat 10min, take out and be cooled to rapidly room temperature, on spectrophotometer, in wavelength 520nm place, use the 1cm cuvette, make reference with water, measure respectively the absorbance A of reagent blank
1Absorbance A with the solution that fades
2, and calculate Δ A=A
1-A
2
Accurately take by weighing again through the oven dry leather sample in the 100mL beaker, add the 0.5mL red fuming nitric acid (RFNA), heating and decompose on electric furnace.Add the 0.2mL red fuming nitric acid (RFNA) after the cooling, 0.1mL perchloric acid continues heating and decompose to emitting white dense smoke, takes off cooling, add the water-soluble thing that parses of 20mL, boiled several minutes, cooling, dripping concentration is the NaOH solution adjusting pH ≈ 6 of 0.1mol, use quick Filter paper filtering, filtrate is collected in the 500mL volumetric flask, and constant volume shakes up.Draw this test solution 2.5mL and on cation exchange column, exchange separation, remove cationic interference.Exchange current fluid and washing lotion constant volume are in the 250mL volumetric flask, and be to be measured.Draw this solution 1mL in the 25mL volumetric flask, below press the poor Δ A of absorbance of experimental technique time-and-motion study solution, and calculate the content of chromium.Experiment shows that the amount of chromium (VI) meets law of Beer in 0～0.05mg/L, and molar absorption coefficient is 3.7 * 10
6, the results are shown in Table 3.
Chromium recovery after f, the burning
Leather bits leftover bits and pieces is directly put into stove and is burned, and collagen decomposition becomes CO
2, H
2The little molecule such as O is removed, and chromium then remains with the form of inorganic salts and oxide.Chromium recovery also is an important aspect after burning.Burn the chromium after reclaiming, can continue to serve as the chrome tanning preparation in the leather processing.Through experiment, final choice sodium carbonate is that additive carries out basic roasting, and chromic salts (trivalent chromium) is oxidized to chromate (Cr VI), becomes water-soluble sodium salt, uses flooding.Equation is as follows:
2Cr
2O
3+4Na
2CO
3+3O
2＝4Na
2CrO
4+4CO
2
The experimental principle of g, Determination of Combustion Heat
The combustion heat refers to that 1mol material and oxygen carry out the fuel factor of complete oxidation.If the combustion heat that records is called the constant volume combustion heat, use Q under the constant volume condition
vExpression.Measure the constant volume combustion heat basic principle be with certain test substance sample completing combustion in the oxygen bomb device of sufficient oxygen, liberated heat makes the temperature rising of calorimeter itself and oxygen bomb surrounding medium (this experimental water).According to the changing value of measuring fuel value front and back temperature, can ask the constant volume combustion heat of calculating this sample.Its relational expression is suc as formula shown in (1).
M is the quality (g) of test substance in the formula, and M is the molal weight of test substance, Q
vBe the constant volume combustion heat of test substance, Q
SilkThe combustion heat (1400Jg for the unit mass ignition wire
-1), m
SilkBe the quality of ignition wire, W
WaterThe thermal capacitance that represents instrument for the weight of the water equivalent-water of calorimeter (comprising medium) means the heat of once required absorption of every rising, is converted into the heat that constant weight water absorbs.The water equivalent of calorimeter can be by reference material (benzoic acid, its Q of the known constant volume combustion heat
v=-26.460KJg
-1) demarcate.After the water equivalent of known calorimeter, can utilize formula (2) to measure by experiment the isochoric combustion heat of a certain amount of determinand.
Q
v=W
WaterΔ T-|Q
Silk| m
Silk(2)
Because in the measuring process, scattering and disappearing of heat can't be avoided fully, this can be owing to environment advances heat to the calorimeter radiation its temperature to be raise, and also can be owing to calorimeter goes out heat to environmental radiation the calorimeter temperature to be reduced.Because the changing value Δ T of temperature before and after the burning can not directly measure accurately, to proofread and correct and must pass through graphing method, the method for correction is as follows.
After an amount of test substance burning, the water temperature in the calorimeter raises 1.5～2.0 ℃.The all previous water temperature of observing before and after the burning is recorded, and mapping, abcd line (as shown in drawings) be linked to be.The point that the b point is equivalent to take fire in the way, the maximum temperature reading point of c point for observing, since calorimeter and extraneous exchange heat, usually run-off the straight of curve ab and cd.Get the corresponding temperature T of b point
1, the temperature T that the c point is corresponding
2, its mean temperature is (T
1+ T
2)/2 are T, make the parallel lines TO of abscissa through the T point, meet at the O point with broken line, then cross the O point and make vertical line, and the extended line of this line and ab line and cd line meets at E, F 2 points, and then E point and the represented temperature difference of F point are the lift-off value Δ T that wants to ask temperature.The heat that EE ' expression environmental radiation is come in and cause the rising of calorimeter temperature, this part is to deduct, and FF ' expression calorimeter goes out heat and causes the reduction of calorimeter temperature to environmental radiation, therefore this part is to add, and has represented because the numerical value that sample combustion raises the calorimeter temperature through the temperature difference after proofreading and correct like this.
H, calorimeter water equivalent (W
Water) mensuration
Be reference material with benzoic acid, carry out 3 times and measure, process by upper table, obtain the temperature difference between E point and the F point, namely Δ T=1.223K according to formula (1), can calculate W again
Water=13.14kJK
-1
I, leather bits fuel value measurement result
With industrial shavings oven dry, weigh, after the burning its residual residue to be taken out, drying is weighed.Use the same method, respectively the calorific value of artificial leather and natural skin carried out mensuration 3 times, the data obtained as shown in Table 1 and Table 2.
The measuring burning heat data of table 1 leather
Annotate: m
LeatherFor removing the quality behind the residue, m after the oven dry
SilkQuality for the ignition wire of Actual combustion
The measuring burning heat data of the natural skin of table 2
Annotate: m
SkinFor removing the quality behind the residue, m after the oven dry
SilkQuality Δ T for the ignition wire of Actual combustion
The above results as can be known, the right burning value of artificial leather is 5220Kcalkg
-1(21830kJkg
-1), the right burning value of natural skin is 6132Kcalkg
-1(25650kJkg
-1).Document announcement, the fuel value of charcoal is 8100Kcalkg
-1, the fuel value of standard coal is 7000Kcalkg
-1Compare with standard coal, the fuel value of leather bits, approaching or suitable with the right burning value of standard coal.Coal is power fuel as a kind of fuel energy that extensive use is arranged, and is again the raw material of chemical industry and the burnt ironmaking of system, have the title of " industrial grain ".Yet, in recent years, along with the shortage of coal resources and the rise of coal price, bring certain pressure for industrial production and people's life.Find out that from measurement result the leather bits very large potentiality that act as a fuel can substitute or be mixed together as industrial fuel with coal and use.
J, as a kind of fuel, table 3 and table 4 have been listed respectively leather bits and coal industrial analysis data.
Industrial Analysis and the elementary analysis data of table 3 leather bits
As can be seen from Table 3, the gas componant after the moisture evaporation thing of synthetic shavings and natural shavings, total ash, the completing combustion is seemingly closer, and difference is that a small amount of chromium content is arranged in the natural scurf.
Table 4 coal industrial analysis and elementary analysis data
K, shavings are mixed determining of use optimal proportion with coal
Leather bits and coal, difference 3: 1 in mass ratio, 2: 1,1: 1,1: 2,1: 3 ratio adopted the measuring burning heat method to measure.Then, make ratio and fuel value graph of a relation, the ratio when finding the maximum combustion value, thus definite shavings is mixed the ratio when using with coal.And mensuration residue composition this moment and content.The result is as shown in table 5.
Table 5 leather bits are determined with the coal combustion optimal proportion
| Leather bits and coal ratio | 3∶1 | 2∶1 | 1∶1 | 1∶2 | 1∶3 |
| Fuel value/kcal/kg | 5640 | 6235 | 6450 | 6470 | 6500 |
[0112]Can find out, along with reducing of leather bits and coal ratio, fuel value increases gradually, when ratio during greater than 1: 1, increases the amount of coal again, and the increasing degree of fuel value is slow.The optimal proportion of determining thus shavings and coal is 1: 1.
SO
xAnd NO
xComposition changes (it is rear that coal, coal add the leather burning)
Measure respectively the gas composition analysis after coal, leather bits and coal leather bits respectively account for 50% fuel combustion, the results are shown in Table 6.
SO after three kinds of fuel combustions of table 6
xAnd NO
xMensuration (the mg/Nm of content
3)
| Fuel | SO x | NO x |
| Coal | 916 | 147 |
| Leather bits coal (1: 1) | 376 | 162 |
| The leather bits | 146 | 171 |
Adopt leather bits to act as a fuel fully, the SO that discharges in the atmosphere
xContent with respect to Discharged form Coal Combustion SO
xContent much lower, only have Discharged form Coal Combustion SO
x15.9% of content, and NO
xThe content increasing degree only has 16.3%.The coal of the weight such as employing and shavings are used as fuel, the SO that discharges in the atmosphere
xContent also than Discharged form Coal Combustion SO
xContent much lower, only have Discharged form Coal Combustion SO
x41.0% of content can reduce poisonous SO greatly
xComposition is to the pollution of atmosphere with to the infringement of people's health.
Chromium recovery after m, the burning
Selecting sodium carbonate is that additive carries out basic roasting, and chromic salts (trivalent chromium) is oxidized to chromate (Cr VI), becomes water-soluble sodium salt, uses flooding.Equation is as follows:
2Cr
2O
3+4Na
2CO
3+3O
2＝4Na
2CrO
4+4CO
2
Inquired into the impact on conversion ratio of additive amount, sintering temperature and time, and the relation of extraction time, temperature, solid-to-liquid ratio and extraction rate.Determined that finally optimum process condition is: the soda ash consumption is 105%～110% of theoretical amount, 900 ℃ of sintering temperatures, insulation 1h; Extracting condition: Gu: liquid volume ratio=1: 5, extraction time 15～30min, temperature 70 C.Under the above-mentioned condition, the chromium recovery rate is greater than 95%.The chromium that reclaims can continue to serve as tanning agent.
The chromic salts roasting is reclaimed and can also be carried out in the following manner in above-described embodiment, can reach same effect:
Cr
2O
3+2CaCO
3+3O
2＝2CaCrO
4+2CO
2。
Claims (7)
1. the process of a using leather products industrial waste as fuel is characterized in that: may further comprise the steps:
A, with using leather products industrial waste and the coal-fired preignition zone mixing formation fuel combination that drops into respectively Industrial Boiler according to the ratio of 1:1-1:3;
B, in Industrial Boiler, adopt three grades of " thermal decomposition type " burning process to burn above-mentioned fuel combination;
C, utilize heat reclamation device that the heat that burns rear generation is reclaimed and thermal power transfer;
D, the chromic salts that burns rear generation is become water-soluble chromium acid salt by the basic roasting method with it, reclaim with flooding;
Three grades of " thermal decomposition type " burning process in the above-mentioned b step comprise following three steps:
1), at first in preignition zone, fuel combination placed under 550～650 ℃ the temperature and carry out the anoxic baking;
2), then with the flue gas further gasification under 1150～1250 ℃ temperature in the combustion zone that produces after the fuel combination baking;
3), the flue gas after will gasifying at last carries out all-oxygen combustion in burning-out zone.
2. the process of using leather products industrial waste as fuel according to claim 1, it is characterized in that: the Industrial Boiler in the b step comprises body of heater, in body of heater, be provided with preignition zone, combustion zone and burning-out zone, the shell wall of described body of heater is made of inwall and shell, is the water leg that is filled with recirculated water between inwall and the shell.
3. the process of using leather products industrial waste as fuel according to claim 1, it is characterized in that: the heat reclamation device in the c step is heat exchanger.
4. the process of using leather products industrial waste as fuel according to claim 1 is characterized in that: the chromic salts roasting is reclaimed and is carried out in the following manner:
2Cr
2O
3 + 4Na
2CO
3 + 3O
2 ＝ 4Na
2CrO
4 + 4CO
2
5. the process of using leather products industrial waste as fuel according to claim 1 is characterized in that: the chromic salts roasting is reclaimed and is carried out in the following manner:
Cr
2O
3 + 2CaCO
3 + 3O
2 ＝ 2CaCrO
4 + 2CO
2
6. according to claim 4 or the process of 5 described using leather products industrial waste as fuel, it is characterized in that: during roasting, temperature is controlled at 900 ℃, then is incubated 1 hour.
7. the process of using leather products industrial waste as fuel according to claim 6 is characterized in that: during lixiviate, Gu: liquid volume ratio=1:5, extraction time 15～30min, temperature is controlled at 70 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1024684C (en) * | 1991-04-09 | 1994-05-25 | 司徒其奖 | Chromium slag leaching and smelting detoxication method |
| CN1087064A (en) * | 1992-11-19 | 1994-05-25 | 林翠惠 | Process for chromium trioxide and device are extracted in chrome tanning leather leftover, angle |
| CN1027597C (en) * | 1992-01-30 | 1995-02-08 | 司徒其奖 | Method for comprehensive utilization of chrome slag by back-melting |
| CN2216637Y (en) * | 1995-05-19 | 1996-01-03 | 北京市机电研究院环境保护技术研究所 | Coal-combustion industrial noxious gas incinerator |
-
2009
- 2009-03-04 CN CN2009100196213A patent/CN101504143B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1024684C (en) * | 1991-04-09 | 1994-05-25 | 司徒其奖 | Chromium slag leaching and smelting detoxication method |
| CN1027597C (en) * | 1992-01-30 | 1995-02-08 | 司徒其奖 | Method for comprehensive utilization of chrome slag by back-melting |
| CN1087064A (en) * | 1992-11-19 | 1994-05-25 | 林翠惠 | Process for chromium trioxide and device are extracted in chrome tanning leather leftover, angle |
| CN2216637Y (en) * | 1995-05-19 | 1996-01-03 | 北京市机电研究院环境保护技术研究所 | Coal-combustion industrial noxious gas incinerator |
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