CN106219941A - The method of resource of hydrogen is produced in municipal sludge deep dehydration and the pyrolysis of mud cake steam gasification - Google Patents
The method of resource of hydrogen is produced in municipal sludge deep dehydration and the pyrolysis of mud cake steam gasification Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
- C10J2300/0923—Sludge, e.g. from water treatment plant
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
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Abstract
The invention discloses a kind of municipal sludge deep dehydration and the method for resource of mud cake steam gasification pyrolysis product hydrogen, belong to municipal sludge dehydration and utilize technical field with pyrolysis, comprise the following steps: in mud, add composite conditioner conditioning improve the dewatering of mud, obtain nursing one's health mud, wherein, described composite conditioner includes oxidising agent and red mud, and described conditioning mud is carried out processed, obtains the deep dehydration mud cake that moisture content is 40～65%；By described deep dehydration mud cake natural drying and other treatment further, obtain the mummification deep dehydration mud cake that moisture content is 10～60%；Described mummification deep dehydration mud cake is carried out pyrolyzing sludge under protective gas atmosphere, obtains pyrolysis gas.The method makes pyrolytic process comprehensive energy consumption low, and pyrolysis gas yield and quality improves.
Description
Technical field
The invention belongs to municipal sludge dehydration and utilize technical field with pyrolysis, be specifically related to a kind of municipal sludge deep dehydration
And the method for resource of mud cake steam gasification pyrolysis product hydrogen.
Background technology
Municipal sludge is the by-product with sewage disposal process.The composition of mud is extremely complex, due to handled life
The water quality condition of sewage, process technique and the difference of coverage, the composition also phase of the mud that each sewage treatment plant produces
Difference is relatively big, but its moisture content is the highest, and the excess sludge moisture content of discharge is generally more than 99%, becomes restriction mud follow-up
Process the big factor disposed.In mud, content of organics is high simultaneously, is a kind of potential biomass resource.Therefore pyrolyzing sludge
Technology utilizes organic components in mud, and organic component in mud is converted into fuel gas, and the solid carbon-contg residue of residual can
Using as sorbent material, it is achieved resource and energy conversion, it it is the focus of current research.
At present, pyrolyzing sludge technology is mainly towards exploitation and the development of aerogenesis aspect of the gasification type of furnace.Chinese patent
CN101775315A is to develop in terms of the gasification type of furnace, improves sludge gasification efficiency.Chinese patent CN102557361A will add
Entering the layering of the sludge slurry after flocculant and ferment treatment, taking precipitate, as raw material, carries out gasification reaction, makes carbonaceous material face with super
Boundary's water generating gasification reaction, it is thus achieved that gaseous fuel, but this patent needs external adding water to obtain the steam participating in pyrolytic reaction.In
State's patent CN103396835A add during sludge conditioning have catalysis activity containing ferroxidant and calcio regulator, profit
Improve the growing amount of gaseous fuel in gasification by cooperative effect therebetween, but this patent also needs before to sludge crushing
It is carried out the heat drying of 5～30min, 45～200 DEG C so that pyrolytic process energy consumption increases.Chinese patent CN105293857A
With the dirty mud as a raw material that moisture content is 85%, by pyrolysis reactor by pyrolyzing sludge gaseous state product and moving-bed of catalyst
Layer counter current contacting, generates hydrogen-rich gaseous product.
Major part existing pyrolyzing sludge gasification technology all obtains with the conditioning of polyacrylamide (PAM) high polymer coagulant
The dirty mud as a raw material of moisture content more than 80%, also needs the step through heat drying, during this makes pyrolyzing sludge before pyrolysis
Heat drying stage moisture evaporation power consumption the highest, make capacity usage ratio reduce.The calorific value that even there is also pyrolysis gas cannot
Compensate heat drying and the predicament of pyrolysis energy consumption.In addition dirt is promoted frequently with by the method for extra catalyst such as Ni, dolomite etc.
Mud is pyrolyzed, but extra catalyst is difficult to be uniformly distributed in mud, it is also difficult to be fully contacted, the big discounting of effect making catalysis be pyrolyzed
Button, also makes hydrogen content in pyrolysis gas, pyrolysis gas quality relatively low.
To sum up, how to reduce municipal sludge moisture content, reduce the energy consumption of sludge heat drying part in pyrolytic process, and improve
In dehydrated sludge cake pyrolysis aerogenesis, the ratio of the high-quality fuel gas such as hydrogen becomes municipal sludge processed and mud cake pyrolysis
The important key technology of recycling, carry out being combined to mud by deeply dehydrating sludge technology and pyrolyzing sludge technology is harmless
Change processes significant with disposal.
Summary of the invention
Based on this, it is contemplated that in the place providing a kind of mud improving dehydrated sludge cake pyrolysis gas production and GAS QUALITY
Reason method.
The method of resource of hydrogen is produced in a kind of municipal sludge deep dehydration and the pyrolysis of mud cake steam gasification, including following step
Rapid:
In mud, add composite conditioner conditioning improve the dewatering of described mud, obtain nursing one's health mud, wherein, institute
State composite conditioner and include oxidising agent and red mud；
Described conditioning mud is carried out processed, obtains the deep dehydration mud cake that moisture content is 40～65%；
By described deep dehydration mud cake natural drying and other treatment further, obtain the mummification deep dehydration that moisture content is 10～60%
Mud cake；
Described mummification deep dehydration mud cake is carried out pyrolyzing sludge under protective gas atmosphere, obtains hydrogeneous pyrolysis gas
Body.
Wherein in an embodiment, red mud is the by-product produced during bauxite into alumina.
Wherein in an embodiment, oxidising agent includes containing Fe2+Aqueous solution and hydrogen peroxide.
Wherein in an embodiment, red mud contains the oxide of ferrum, the oxide of aluminum, titanyl compound and other ore deposits
Thing.
Wherein in an embodiment, in red mud, the oxide mass percentage composition of ferrum is 8%～42%, the oxide of aluminum
Weight/mass percentage composition is 12%～15%, and titanyl compound weight/mass percentage composition is 3%～12%, and other mineral quality percentages contain
Amount is 31%～77%.
Wherein in an embodiment, in composite conditioner, oxidising agent is 1:1～5 with the mass ratio of red mud.
Wherein in an embodiment, composite conditioner is 1:5～20 with the mass ratio of mud.
Wherein in an embodiment, at least one in nitrogen, argon of protective gas.
Wherein in an embodiment, the flow of protective gas is 0.1～0.2L/min.
Wherein in an embodiment, the pyrolysis temperature of pyrolyzing sludge is 700～900 DEG C, pyrolysis time be 25～
40min。
The method of resource of hydrogen is produced in above-mentioned municipal sludge deep dehydration and the pyrolysis of mud cake steam gasification, initially with oxidation
Mud is nursed one's health by the composite conditioner that reagent forms with red mud, and the dewatering of mud is improved, and passes through processed
It is substantially reduced moisture content of the cake, then by the natural mummification further of the mud cake after processed.At the red mud that the conditioning stage adds, make
Obtaining each catalyst component to be dispersed in sludge cake, catalysis pyrolysis is notable, and the moisture content that natural mummification regulates and controls mud cake can save
Going the heat drying step before pyrolyzing sludge, after saving energy consumption, and optimization, the moisture of residual participates in follow-up pyrolytic reaction, improves
Pyrolysis factor of created gase, in pyrolysis gas, hydrogen content improves so that pyrolysis gas quality improves.
Accompanying drawing explanation
Fig. 1 is municipal sludge deep dehydration and the method for resource of mud cake steam gasification pyrolysis product hydrogen of an embodiment
Process chart.
Fig. 2 is the iron oxides catalytic mechanism figure to coke tar cracking.
Fig. 3 is PAM conditioning heat drying mud and the combined cooker deep dehydration mud cake heat of different water cut under different temperatures
Solve the comparison diagram of aerogenesis total amount.
Fig. 4 is PAM conditioning heat drying mud and hydrogen output in combined cooker deep dehydration mud cake pyrolysis aerogenesis at 900 DEG C
Changes in contrast figure.
Detailed description of the invention
For the ease of understanding the present invention, below with reference to relevant drawings, the present invention is described more fully.In accompanying drawing
Give the preferred embodiment of the present invention.But, the present invention can realize in many different forms, however it is not limited to herein
Described embodiment.On the contrary, providing the purpose of these embodiments is to make the understanding to the disclosure more saturating
Thorough comprehensively.
Unless otherwise defined, all of technology used herein and scientific terminology and the technical field belonging to the present invention
The implication that technical staff is generally understood that is identical.The term used the most in the description of the invention is intended merely to describe tool
The purpose of the embodiment of body, it is not intended that in limiting the present invention.Term as used herein " and/or " include one or more phase
Arbitrary and all of combination of the Listed Items closed.
As it is shown in figure 1, the resource of hydrogen is produced in the municipal sludge deep dehydration of an embodiment and the pyrolysis of mud cake steam gasification
Change method, comprises the steps:
Step S110: add composite conditioner in mud and nurse one's health described mud, obtain nursing one's health mud.
Wherein, mud is the by-product separating with sewage disposal process or being retained down.
Wherein, composite conditioner includes oxidising agent and red mud.
Wherein, oxidising agent includes containing Fe2+Aqueous solution and hydrogen peroxide.Further, Fe2+Aqueous solution is selected from FeCl2
Aqueous solution, FeSO4At least one in aqueous solution, FeCl2Concentration of aqueous solution is 18～25mol/L, FeSO4Concentration of aqueous solution is 8
～15mol/L.The concentration of hydrogen peroxide is 8～12mol/L.Fe2+The volume ratio of aqueous solution and hydrogen peroxide is 1:1～5.
Wherein, the by-product produced during red mud is bauxite into alumina.
Wherein, red mud contains the oxide of ferrum, the oxide of aluminum, titanyl compound and other dirts.Further
In red mud, the oxide mass percentage composition of ferrum is 8%～42%, and the oxide mass percentage composition of aluminum is 12%～15%, titanium
Oxide mass percentage composition be 3%～12%, other mineral quality percentage compositions are 31%～77%.
Wherein, composite conditioner dosage is on the basis of mud butt.Further, composite conditioner and the quality of mud
Ratio is 1:5～20.
Wherein, in composite conditioner, oxidising agent is 1:1～5 with the mass ratio of red mud.
Wherein in an embodiment, mud is initially charged Fe2+Aqueous solution is also stirred, mixing speed be 120～
200rpm, mixing time is 2～4min, adds hydrogen peroxide and stirs, and mixing speed is 70～120rpm, and mixing time is 25
～40min, it is eventually adding red mud and stirs, mixing speed is 120～200rpm, and mixing time is 6～15min.
Step S120: conditioning mud is carried out processed, obtains the deep dehydration mud cake that moisture content is 40～65%.
Wherein, in this step, the barrier film machinery filtering equipment of pressure-variable is used to carry out mechanical dehydration process.Further
, the barrier film machinery filtering equipment of pressure-variable is filter press, and every 1～2min, dewatering pressure improves 0.1～0.3MPa,
And keep 25～30min, after repeating described operation 3～5 times, then under 0.9～1.5MPa, squeeze 8～10min.
Step S130: the natural mummification further of deep dehydration mud cake is obtained moisture content be 10～60% the mummification degree of depth take off
Pat of cement.
Wherein, mummification uses nature mummification, but is not limited to nature mummification, and the low temperature mummification reaching similar effect equally may be used
OK.
Wherein, drying time is 12～48h.
Step S140: mummification deep dehydration mud cake is carried out pyrolyzing sludge under protective gas atmosphere, obtains pyrolysis gas
Body.
Wherein, in this step, pyrolysis oven is used to carry out pyrolyzing sludge.Further, pyrolysis oven is selected from horizontal pipe warm
Solve at least one in stove, vertical tubular type pyrolysis oven.
Wherein, at least one in nitrogen, argon of protective gas.
Wherein, the flow of protective gas is 0.1～0.2L/min.
Wherein, pyrolysis temperature is 700～900 DEG C, and pyrolysis time is 25～40min.
Above-mentioned municipal sludge deep dehydration and the pyrolysis of mud cake steam gasification are produced the method for resource of hydrogen and are used oxidising agent
Nursing one's health mud with the composite conditioner of red mud composition, red mud used is the pair produced during bauxite into alumina
Product, based on oxides such as ferrum, aluminum, titaniums.Research shows, red mud can promote that Hydrocarbon decomposes, thus produces more
Hydrogen, improves pyrolysis gas quality, and iron oxides as the catalyst of tar consumption, can also change the component of aerogenesis, its
Mechanism is as in figure 2 it is shown, in steam gasification initial stage, with Fe3O4The Surface Fe (-Fe) being connected reacts with biomass coke tar, raw
Become CH4、C2H4、H2O, CO and H2.It follows that on the avtive spot of ferrum oxide, the CO of generation occurs steam to convert further
Reaction, changes into CO2And H2O, during pyrolyzing sludge gasifies, the catalyst that metal Fe also can consume as tar, by instead
Should (1) and the component of reaction (2) change aerogenesis.Metal-oxide in red mud is dispersed in sludge cake, it is possible to realize
Organic pyrolytic gasification in situ catalytic mud, catalytic effect is better than additional catalyst.Additionally, the moisture in mud can
Participating in the organic cracking reaction in mud, reaction equation is as shown in (3)～(6), thus promotes that in mud, organic matter pyrolysis produces
The yield of tolerance, especially hydrogen, improves the quality of pyrolysis gas.
Fe+CO2→FeO+CO(g) (1)
3Fe+4H2O→Fe3O4+4H2(g) (2)
Organics(g)+H2O(g)→CO(g)+H2(g) (3)
C(g)+H2O(g)→CO(g)+H2(g) (4)
CO+H2O→CO2(g)+H2(g) (5)
CH4+H2O→CO(g)+3H2(g) (6)
And simultaneously because the mud of above-mentioned processing method is by after combined cooker and processed, the thing of deep dehydration mud cake
Rationality matter there occurs the biggest change with the character of traditional 80% water content sludge obtained through PAM conditioning.Deep dehydration
Mud cake interior porosity increases, and maintains the passage of moisture evaporation, and dehydrated sludge cake easily, then is done by moisture evaporation the most naturally
Change so that dehydrated sludge cake moisture content is 10～60%, reduce further the moisture content of dehydrated sludge cake, before saving pyrolyzing sludge
Heat drying step, saves energy consumption.Additionally, residual moisture participates in follow-up heat in mummification deep dehydration mud cake after optimization moisture content
Solving reaction, improve pyrolysis factor of created gase, in pyrolysis gas, hydrogen content improves so that pyrolysis gas quality improves.
It it is below specific embodiment
Embodiment 1
The method of resource of hydrogen is produced in the municipal sludge deep dehydration of the present embodiment and the pyrolysis of mud cake steam gasification, by following
Step is carried out:
(1) adding in sludge conditioning tank by 30kg mud, adding the initial pH of sulfuric acid solution conditioning of mud is 5, then adds
8mol/LFeSO4Solution 2.41L is stirred, and mixing speed is 120rpm, and mixing time is 2min, adds 10mol/L double
Oxygen water 3L is stirred, and mixing speed is 70rpm, and mixing time is 25min, makes oxidising agent and mud that fully reaction to occur,
The last 8kg red mud that adds again, and quickly stirring is nursed one's health, mixing speed is 120rpm, and mixing time is 6min, wherein, red
In mud, the oxide mass percentage composition of ferrum is 8%, and the oxide mass percentage composition of aluminum is 12%, titanyl compound quality hundred
Dividing content is 3%, and silicon dioxide and other mineral quality percentage composition are 77%, finally obtains 41kg and nurses one's health mud.
(2) use filter press to carry out nursing one's health sludge dewatering treatment, first 32.5kg is nursed one's health mud pump and is driven into body
Amass the mud feedstock vessel for 50L, finally use air compressor machine to be pressed in barrier film sheet frame by the conditioning mud in feedstock vessel and take off
Water, the pressure of air compressor machine, every 1min, is gradually increased to 0.3MPa from 0, and keeps 25min, after being repeated 2 times, then at 0.9MPa
8min, the deep dehydration mud cake 11.84kg of final available moisture content 62% is squeezed under pressure.
(3) by 500g dehydrated sludge cake nature mummification, drying time is 24h, obtains the mummification of 364.85g moisture content 52.2%
Deep dehydration mud cake.
(4) using horizontal pipe pyrolysis oven to carry out deep dehydration mud cake pyrolysis, pyrolysis installation includes carrier gas device, pyrolysis dress
Put, condensing unit, gas knot screen and gas collector.The deep dehydration mud cake that 9.40g moisture content is 52.2% is made
For pyrolysis feed, first it is passed through the air in nitrogen discharge system with 0.1L/min, treats that horizontal pipe pyrolysis oven furnace temperature is increased to 900
After DEG C, the porcelain boat that will be equipped with deep dehydration mud cake is pushed into rapidly in horizontal pipe pyrolysis oven reaction zone, after pyrolysis 25min, logical
Crossing wet gas flow meter and recording aerogenesis cumulative volume is 0.24L/g DS.Use gas chromatographicanalyzer that the gas collected is entered
Row is analyzed.
The sludge conditioner of the present embodiment, pyrolysis temperature, pyrolysis time, moisture content, pyrolysis gas yield, pyrolysis hydrogen produce
Amount is shown in Table 1.
Embodiment 2
The method of resource of hydrogen is produced in the municipal sludge deep dehydration of the present embodiment and the pyrolysis of mud cake steam gasification, by following
Step is carried out:
(1) adding in sludge conditioning tank by 30kg mud, adding the initial pH of hydrochloric acid solution conditioning of mud is 7, then
20mol/LFeCl2Solution 0.96L is stirred, and mixing speed is 150rpm, and mixing time is 3min, adds 8mol/L double
Oxygen water 3.33L is stirred, and mixing speed is 100rpm, and mixing time is 30min, makes oxidising agent and mud occur the most anti-
Should, adding 6.87kg red mud the most again, and quickly stirring is nursed one's health, mixing speed is 150rpm, and mixing time is 10min,
Wherein, in red mud, the oxide mass percentage composition of ferrum is 40%, and the oxide mass percentage composition of aluminum is 13%, the oxidation of titanium
Thing weight/mass percentage composition is 11%, and silicon dioxide and other mineral quality percentage composition are 36%, finally obtains 38kg conditioning dirt
Mud.
(2) use filter press to carry out nursing one's health sludge dewatering treatment, first 30kg is nursed one's health mud pump and is driven into volume
For the mud feedstock vessel of 50L, finally use air compressor machine to be pressed in barrier film sheet frame by the conditioning mud in feedstock vessel and be dehydrated,
The pressure of air compressor machine, every 1min, is gradually increased to 0.4MPa from 0, and keeps 25min, after being repeated 2 times, then at 1.1MPa pressure
Lower squeezing 8min, the deep dehydration mud cake 12.85kg of final available moisture content 65%.
(3) 500g dehydrated sludge cake being entered nature mummification, drying time is 12h, obtains the dry of 488.23g moisture content 60.1%
Change deep dehydration mud cake.
(4) using horizontal pipe pyrolysis oven to carry out deep dehydration mud cake pyrolysis, pyrolysis installation includes carrier gas device, pyrolysis dress
Put, condensing unit, gas knot screen and gas collector.12.16g is cured to naturally the mummification that moisture content is 60.1%
Deep dehydration mud cake, as pyrolysis feed, is first passed through the air in nitrogen discharge system with 0.1L/min, treats that horizontal pipe is pyrolyzed
After stove furnace temperature is increased to 800 DEG C, the porcelain boat that will be equipped with deep dehydration mud cake is pushed into rapidly in horizontal pipe pyrolysis oven reaction zone,
After pyrolysis 30min, recording aerogenesis cumulative volume by wet gas flow meter is 0.17L/g DS.Use gas chromatographicanalyzer
The gas collected is analyzed.
The sludge conditioner of the present embodiment, pyrolysis temperature, pyrolysis time, moisture content, pyrolysis gas yield, pyrolysis hydrogen produce
Amount is shown in Table 1.
Embodiment 3
The method of resource of hydrogen is produced in the municipal sludge deep dehydration of the present embodiment and the pyrolysis of mud cake steam gasification, by following
Step is carried out:
(1) adding in sludge conditioning tank by 30kg mud, adding the initial pH of sulfuric acid solution conditioning of mud is 6, then adds
15mol/L FeSO4Solution 0.88L is stirred, and mixing speed is 200rpm, and mixing time is 4min, adds 12mol/L
Hydrogen peroxide 3L is stirred, and mixing speed is 120rpm, and mixing time is 40min, makes oxidising agent and mud occur the most anti-
Should, adding 7.5kg red mud the most again, and quickly stirring is nursed one's health, mixing speed is 100rpm, and mixing time is 15min, its
In, in red mud, the oxide mass percentage composition of ferrum is 42%, and the oxide mass percentage composition of aluminum is 15%, titanyl compound
Weight/mass percentage composition is 12%, and silicon dioxide and other impurity weight/mass percentage composition are 31%, obtains 39kg and nurses one's health mud.
(2) use filter press to carry out nursing one's health sludge dewatering treatment, first 30kg is nursed one's health mud pump and is driven into volume
For the mud feedstock vessel of 50L, finally use air compressor machine to be pressed in barrier film sheet frame by the conditioning mud in feedstock vessel and be dehydrated,
The pressure of air compressor machine, every 2min, is gradually increased to 0.5MPa from 0, and keeps 30min, after being repeated 3 times, then at 1.5MPa pressure
Lower squeezing 10min, the deep dehydration mud cake 7.75kg of final available moisture content 40%.
(3) by 100g dehydrated sludge cake nature mummification, drying time is 48h, obtains the mummification of 80.95g moisture content 10.6%
Deep dehydration mud cake.
(4) using vertical tubular type pyrolysis oven to carry out deep dehydration mud cake pyrolysis, pyrolysis installation includes carrier gas device, pyrolysis dress
Put, condensing unit, gas knot screen and gas collector.5.27g is cured to naturally the degree of depth that moisture content is 10.6%
Dehydrated sludge cake, as pyrolysis feed, first leads to the air in argon gas discharge system with 0.2L/min, treats horizontal pipe pyrolysis oven stove
Temperature rise to 700 DEG C until after, the porcelain boat that will be equipped with deep dehydration mud cake is pushed into rapidly in horizontal pipe pyrolysis oven reaction zone, heat
After solving 40min, recording aerogenesis cumulative volume by wet gas flow meter is 0.07L/g DS.Use gas chromatographicanalyzer pair
The gas collected is analyzed.
The sludge conditioner of the present embodiment, pyrolysis temperature, pyrolysis time, moisture content, pyrolysis gas yield, pyrolysis hydrogen produce
Amount is shown in Table 1.
Comparative example 1
The pyrolyzing sludge of comparative example 1 produces the method for hydrogen, sequentially includes the following steps:
(1) with certain sewage treatment plant through PAM conditioning and mechanical dehydration after dirty mud as a raw material, recording its moisture content is
85.15%.
(3) under the conditions of 120 DEG C, by 500g dehydrated sludge cake heat drying, drying time is 24h, obtains 212.87g moisture content
The heat drying mud of 65.1%.
(4) using horizontal pipe pyrolysis oven to carry out deep dehydration mud cake pyrolysis, pyrolysis installation includes carrier gas device, pyrolysis dress
Put, condensing unit, gas knot screen and gas collector.12.90g is cured to naturally the degree of depth that moisture content is 65.1%
Dehydrated sludge cake, as pyrolysis feed, is first passed through the air in nitrogen discharge system with 0.1L/min, treats horizontal pipe pyrolysis oven stove
After temperature rise to 700 DEG C, the porcelain boat that will be equipped with deep dehydration mud cake is pushed into rapidly in horizontal pipe pyrolysis oven reaction zone, pyrolysis
Reaction occurs immediately upon, and pyrolysis time is 40min.Recording aerogenesis cumulative volume by wet gas flow meter is 0.05L/g DS.
Use gas chromatographicanalyzer that the gas collected is analyzed.
The sludge conditioner of this comparative example, pyrolysis temperature, pyrolysis time, moisture content, pyrolysis gas yield, pyrolysis hydrogen produce
Amount is shown in Table 1.
Comparative example 2
The pyrolyzing sludge of comparative example 2 produces the method for hydrogen, sequentially includes the following steps:
(1) with certain sewage treatment plant through PAM conditioning and mechanical dehydration after dirty mud as a raw material, recording its moisture content is
85.15%.
(3) under the conditions of 120 DEG C, by 500g dehydrated sludge cake heat drying, drying time is 12h, obtains 371.79g moisture content
The heat drying mud of 80.5%.
(4) using horizontal pipe pyrolysis oven to carry out deep dehydration mud cake pyrolysis, pyrolysis installation includes carrier gas device, pyrolysis dress
Put, condensing unit, gas knot screen and gas collector.23.08g is cured to naturally the PAM that moisture content is 80.5%
Conditioning mud cake, as pyrolysis feed, is first passed through the air in nitrogen discharge system with 0.1L/min, treats horizontal pipe pyrolysis oven stove
After temperature rise to 800 DEG C, the porcelain boat that will be equipped with deep dehydration mud cake is pushed into rapidly in horizontal pipe pyrolysis oven reaction zone, pyrolysis
Reaction occurs immediately upon, and pyrolysis time is 30min.Recording aerogenesis cumulative volume by wet gas flow meter is 0.13L/g DS.
Use gas chromatographicanalyzer that the gas collected is analyzed.
The sludge conditioner of this comparative example, pyrolysis temperature, pyrolysis time, moisture content, pyrolysis gas yield, pyrolysis hydrogen produce
Amount is shown in Table 1.
Comparative example 3
The pyrolyzing sludge of comparative example 3 produces the method for hydrogen, sequentially includes the following steps:
(1) with certain sewage treatment plant through PAM conditioning and mechanical dehydration after dirty mud as a raw material, recording its moisture content is
85.15%.
(3) under the conditions of 120 DEG C, by 500g dehydrated sludge cake heat drying, drying time is 48h, obtains 124.48g moisture content
The heat drying mud of 40.4%.
(4) using horizontal pipe pyrolysis oven to carry out deep dehydration mud cake pyrolysis, pyrolysis installation includes carrier gas device, pyrolysis dress
Put, condensing unit, gas knot screen and gas collector.7.54g is cured to PAM that moisture content is 40.4% naturally adjust
Reason mud cake, as pyrolysis feed, is first passed through the air in argon discharge system with 0.2L/min, treats horizontal pipe pyrolysis oven furnace temperature
After being increased to 900 DEG C, the porcelain boat that will be equipped with deep dehydration mud cake is pushed into rapidly in horizontal pipe pyrolysis oven reaction zone, and pyrolysis is anti-
Should occur immediately upon, pyrolysis time is 25min.Recording aerogenesis cumulative volume by wet gas flow meter is 0.11L/g DS.Adopt
With gas chromatographicanalyzer, the gas collected is analyzed.
The sludge conditioner of this comparative example, pyrolysis temperature, pyrolysis time, moisture content, pyrolysis gas yield, pyrolysis hydrogen produce
Amount is shown in Table 1.
Table 1
From table 1 it follows that the dehydrated sludge cake moisture content of embodiment 1～3 is minimum is only 10.6%, pyrolysis gas yield
Minimum 0.07L/g DS, is pyrolyzed hydrogen output minimum 0.015L/g DS, and the dehydrated sludge cake moisture content of comparative example 1～3 is
Low is 40.4%, pyrolysis gas yield minimum 0.05L/g DS, is pyrolyzed hydrogen output minimum 0.009L/g DS, it is clear that real
Executing example 1～3 and have higher pyrolysis gas yield, higher pyrolysis hydrogen output, pyrolysis gas quality is the highest.Fig. 3 is not
The PAM conditioning heat drying mud of synthermal lower different water cut and the contrast of combined cooker deep dehydration mud cake pyrolysis aerogenesis total amount
Figure.Fig. 4 is PAM conditioning heat drying mud and hydrogen output contrast in combined cooker deep dehydration mud cake pyrolysis aerogenesis at 900 DEG C
Variation diagram.
Each technical characteristic of embodiment described above can combine arbitrarily, for making description succinct, not to above-mentioned reality
The all possible combination of each technical characteristic executed in example is all described, but, as long as the combination of these technical characteristics is not deposited
In contradiction, all it is considered to be the scope that this specification is recorded.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that, come for those of ordinary skill in the art
Saying, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the method for resource of hydrogen is produced in a municipal sludge deep dehydration and the pyrolysis of mud cake steam gasification, it is characterised in that bag
Include following steps:
In mud, add composite conditioner conditioning improve the dewatering of described mud, obtain nursing one's health mud, wherein, described multiple
Close conditioner and include oxidising agent and red mud；
Described conditioning mud is carried out processed, obtains the deep dehydration mud cake that moisture content is 40～65%；
By described deep dehydration mud cake natural drying and other treatment further, obtain the mummification deep dehydration mud that moisture content is 10～60%
Cake；
Described mummification deep dehydration mud cake is carried out pyrolyzing sludge under protective gas atmosphere, obtains hydrogeneous pyrolysis gas.
Is produced from the resource side of hydrogen in municipal sludge deep dehydration the most according to claim 1 and the pyrolysis of mud cake steam gasification
Method, it is characterised in that described red mud is the by-product produced during bauxite into alumina.
Is produced from the resource side of hydrogen in municipal sludge deep dehydration the most according to claim 1 and the pyrolysis of mud cake steam gasification
Method, it is characterised in that described oxidising agent includes containing Fe2+Aqueous solution and hydrogen peroxide.
Is produced from the resource side of hydrogen in municipal sludge deep dehydration the most according to claim 1 and the pyrolysis of mud cake steam gasification
Method, it is characterised in that described red mud contains the oxide of ferrum, the oxide of aluminum, titanyl compound and other mineralogical composition.
Is produced from the resource side of hydrogen in municipal sludge deep dehydration the most according to claim 1 and the pyrolysis of mud cake steam gasification
Method, it is characterised in that in described red mud, the oxide mass percentage composition of ferrum is 8%～42%, the oxide mass percentage of aluminum
Content is 12%～15%, and titanyl compound weight/mass percentage composition is 3%～12%, and other mineral quality percentage compositions are 31%
～77%.
Is produced from the resource side of hydrogen in municipal sludge deep dehydration the most according to claim 1 and the pyrolysis of mud cake steam gasification
Method, it is characterised in that in described composite conditioner, described oxidising agent is 1:1～5 with the mass ratio of described red mud.
Is produced from the resource side of hydrogen in municipal sludge deep dehydration the most according to claim 1 and the pyrolysis of mud cake steam gasification
Method, it is characterised in that described composite conditioner is 1:5～20 with the mass ratio of described mud.
Is produced from the resource side of hydrogen in municipal sludge deep dehydration the most according to claim 1 and the pyrolysis of mud cake steam gasification
Method, it is characterised in that at least one in nitrogen, argon of described protective gas.
Is produced from the resource side of hydrogen in municipal sludge deep dehydration the most according to claim 1 and the pyrolysis of mud cake steam gasification
Method, it is characterised in that the flow of described protective gas is 0.1～0.2L/min.
Is produced from the resource side of hydrogen in municipal sludge deep dehydration the most according to claim 1 and the pyrolysis of mud cake steam gasification
Method, it is characterised in that the pyrolysis temperature of described pyrolyzing sludge is 700～900 DEG C, pyrolysis time is 25～40min.
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