CN106316023A - Supercritical water gasification and recycling method and apparatus for steel mill high-oil-content iron-containing sludge - Google Patents
Supercritical water gasification and recycling method and apparatus for steel mill high-oil-content iron-containing sludge Download PDFInfo
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- CN106316023A CN106316023A CN201610837880.7A CN201610837880A CN106316023A CN 106316023 A CN106316023 A CN 106316023A CN 201610837880 A CN201610837880 A CN 201610837880A CN 106316023 A CN106316023 A CN 106316023A
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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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/03—Pressure
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/44—Time
Abstract
The invention relates to a supercritical water gasification and recycling method and apparatus for steel mill high-oil-content iron-containing sludge; steel mill high-oil-content iron-containing sludge is conditioned and then fed to and preheated in a heater using low-caloric blast furnace gas as a fuel, the preheated sludge is fed to a supercritical water gasification reactor and is subjected to supercritical water gasification before entering a gas-liquid separator, and separated mixed gas is separated to obtain high-caloric methane and hydrogen mixed gas; high-caloric fuel gas is produced by using low-caloric blast furnace gas and supercritical water gasification technique; after the iron-containing sludge is subjected to supercritical water gasification, iron matters therein are fully converted into ferriferous oxide; therefore, water-slag mixture separated from the gas-liquid separator can be simply dried and magnetically separated and then returned to a steel furnace as steelmaking material. The making method has high processing efficiency and short processing time, sludge and blast furnace gas are recycled, no secondary pollution is caused, and the method and apparatus are widely applicable to the recycling of steel mill sludge.
Description
Technical field
The invention belongs to chemical industry and technical field of ferrous metallurgy, particularly steel mill's mud and low combustion value furnace gas resource
Utilize field, relate to a kind of steel mill's height oil-containing iron containing sludge supercritical water gasification recycling processing method and device.
Background technology
During Rolling production, need directly to cool down in a large number water, rinse steel and equipment, substantial amounts of waste water can be produced,
Waste water mainly contains the ferrum oxide that the surface of spraying cooling rolling mill roll roller-way and rolled steel produces, the oil in plant equipment
Class material, solid impurity the like waste and mud etc., major pollutants be ferrum oxide that substantial amounts of granularity is different, lubrication oils and
Emulsion, wherein the grease concentration of the emulsion in cold rolling wastewater is high, emulsifying concentration is high, generally containing surfactant.According to statistics,
Steel mill of China the most often rolls 1 ton of steel plate and about discharges waste water 30-40m3.The about 5000mg/L Han iron scale in waste water, float
100-1250mg/L, residue 800-1500mg/L, oils 50-500mg/L.Steel industry the most all uses simple coagulating sedimentation
Process technique waste water of steel plants is processed, carry out burning or at landfill after the high oil-containing iron containing sludge dehydration produced after process
Reason.But for the mud of high-moisture, input and the operation cost of burning method treatment facility are higher, add the production of iron and steel
Cost.Additionally, high temperature incineration easily produces the noxious substances such as two English, nitrogen oxides, cause secondary pollution.Landfill method takes up an area face
Long-pending big, and sludge stabilization is poor, and can rot generation odour, the easy polluted underground water of Water deep leaching in mud.Additionally,
Steel mill's mud ferrum oxide Han high concentration, direct landfill can cause the wasting of resources, landfill disposal expense to increase the most year by year, and this is at iron and steel row
Industry goes, under the overall background of production capacity, to add the survival pressure of steel mill undoubtedly.Therefore a lot of scholars are seeking to some new techniques, new
Technique carries out recycling to mud.
Supercritical water gasification technology is the characteristic utilizing supercritical water, at temperature, pressure higher than the critical temperature of water and pressure
Under the conditions of power (374 DEG C, 22.1MPa), the density of water, viscosity and dielectric constant rapid decrease, cause supercritical water can with have
Machine thing and gas mix with arbitrary proportion, strengthen mass transfer.The most in the supercritical state, the ionic product of water is much smaller than 10-14, water
In chemical reaction mainly based on radical reaction, the Organic substance in mud can be quickly decomposed into carbon dioxide, water
With the material such as nitrogen, ferrum oxide is converted into the magnetic ferroso-ferric oxide of band, can be utilized by magnetic separation separation and recovery, or directly
Connect return converter recycling.But as a kind of emerging sludge disposal technology, supercritical water gasification technology is seldom applied
In steel mill's Treatment of Sludge, and conventional research finds, for reaching good Treatment of Sludge effect, system temperature must carry
Height, this adds the consumption of the energy undoubtedly.The by-product energy blast furnace gas produced in iron and steel enterprise's STEELMAKING PRODUCTION, due to calorific value relatively
Low, dust-laden water content is big, and the factors such as pressure oscillation is big are difficult in adapt to produce needs in iron and steel enterprise, and major part steel plant go out height
Outside stove air stove, coke oven and part are used in mixed way with coke-stove gas, remaining coal gas is diffused in vain, causes resource
Waste.And this part coal gas may be used for the heat supply of supercritical water gasification system, it is therefore necessary to excellent according to iron and steel enterprise self
Gesture and resource, research and development steel mill Treatment of Sludge processes the new technology disposed.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of steel mill height oil-containing iron containing sludge supercritical water gasification resource
Processing method and processing device, the method and device utilize supercritical water gasification technology to recycle steel mill height iron containing sludge, and fully
Utilize steel mill's low combustion value furnace gas as heater fuel, by supercritical water gasification technology, the oils and fats in mud is converted into
High heating value methane and hydrogen combustion gas.
For reaching above-mentioned purpose, the present invention provides following technical scheme:
A kind of steel mill height oil-containing iron containing sludge supercritical water gasification recycling processing method, the method comprises the following steps:
S1: steel mill's height oil-containing iron content is produced mud and carries out quenched pretreatment in pretreatment pool；
S2: by mud pretreated in step S1, be transported to heater by plunger displacement pump, carries out pre-add in the heater
Heat, the mud input supercritical water gasification reactor after preheating；
S3: after step S2 processes, carries out lowering the temperature and heat by heat exchanger by reacted for supercritical water gasification mud
Exchange processes；
S4: the mud after cooling enters gas-liquid separator, makes admixture of gas be sufficiently separated out from mud, separated
After process, obtain the air mixture of methane and hydrogen；And slag-water slurry enters in blowoff basin, blowoff basin adds flocculation
Agent, after standing 30-60min, supernatant is discharged into sewage treatment plant of steel mill and continues with, and pool bottom sludge carries out filter pressing, by filter pressing
After the waste heat that handed down by heat exchanger of mud carry out dewatered drying, the mud after drying is sent directly into converter, as refining
Steel raw material.
Further, in step sl, after modifier treatment, water/mud mass ratio is 5:1, and pH value is 6-10.
Further, in step s 2, the fuel used low combustion value furnace gas produced for steel mill of heater.
Further, in step s 2, the temperature of reactor controls at 600-700 DEG C, and Stress control, at 25-30MPa, stops
Time is 10-20min.
In step s 4, gas-liquid separation process after, the separated process of gaseous mixture of generation, the methane of the high heating value of generation and
Hydrogen air mixture can be as steel-making blast furnace combustion gas；Ironys all in mud are instead converted into four oxidations three by supercritical gasification
Ferrum, can be directly as steelmaking feed；Water after supercritical water gasification processes is directly discharged into sewage treatment plant of steel mill, it is not necessary to enter one
Step processes.
Present invention also offers a kind of steel mill height oil-containing iron containing sludge supercritical water gasification processing equipment for recycling, this device
Including the steel mill's sludge-tank 1 being sequentially connected, the quenched pond of mud 2, plunger displacement pump 3, heater 4, supercritical gasification reactor 5, heat exchange
Device 6, gas-liquid separator 7；
High oil-containing iron content in steel mill's sludge-tank 1 produces after mud carries out quenched pretreatment by the quenched pond of mud 2 to be passed through
Plunger displacement pump 3 is transported to heater 4, the mud input supercritical gasification reactor 5 after preheating in heater 4, passes through
The reacted mud of supercritical water gasification carries out lowering the temperature and heat exchange process by heat exchanger 6；Mud after cooling enters gas-liquid
Separator 7, makes admixture of gas be sufficiently separated out from mud；
After separated process, obtaining the air mixture of methane and hydrogen, air mixture subsequently enters gas storage holder 8 and gas divides
From system 9；Slag-water slurry enters in blowoff basin 10, adds flocculant in blowoff basin 10, after standing 30-60min, and supernatant
Being discharged into sewage treatment plant of steel mill to continue with, pool bottom sludge carries out filter pressing, and the mud after filter pressing is sent into waste residue drying system
11, the waste heat handed down by heat exchanger carries out dewatered drying, and the mud after drying is sent directly into converter, former as steel-making
Material.
The beneficial effects of the present invention is:
1) present invention makes full use of steel mill's height oil-containing iron containing sludge content of organic matter height, calorific value high, in conjunction with steel mill
Existing resource, such as a large amount of low-heat value gas, self-built sewage treatment plant of steel mill, high temperature converter etc., by steel mill's low heat value blast furnace coal
Gas, creates as the heating combustion gas of supercritical water gasification response system, oil-containing iron containing sludge after supercritical water gasification processes
The methane of high heating value and the air mixture of hydrogen, reached to utilize low combustion value furnace gas to combine supercritical water gasification technology, produces
The purpose of raw high heating value combustion gas.
2) present invention makes full use of self-built sewage treatment plant of steel mill, and the water after being processed by supercritical water gasification is directly discharged into steel
Sewage treatment plant of factory, it is not necessary to process further, technique is simple, workable.
3) present invention makes full use of the character of supercritical water, and iron containing sludge is after processing through supercritical water gasification, therein
Iron compound is fully converted to ferroso-ferric oxide, and after simple magnetic separation, the irony in waste residue returns converter, former as steel-making
Material, has reached the purpose that recycling sludge utilizes.
Accompanying drawing explanation
In order to make the purpose of the present invention, technical scheme and beneficial effect clearer, the present invention provides drawings described below to carry out
Illustrate:
Fig. 1 is system structure schematic diagram of the present invention, wherein: 1-steel mill sludge-tank, the quenched pond of 2-mud, 3-post
Plug pump, 4-heater, 5-supercritical gasification reactor, 6-heat exchanger, 7-gas-liquid separator, 8-gas storage holder, 9-gas segregative line
System, 10-blowoff basin, 11-waste residue drying system；
Fig. 2 is the XRD figure spectrum of the former mud of mud；
Fig. 3 is residue XRD spectra after mud SCW reaction.
Detailed description of the invention
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
Fig. 1 is system structure schematic diagram of the present invention, as it can be seen, this device includes that the steel mill being sequentially connected is dirty
The quenched pond of mud sump 1, mud 2, plunger displacement pump 3, heater 4, supercritical gasification reactor 5, heat exchanger 6, gas-liquid separator 7；
High oil-containing iron content in steel mill's sludge-tank 1 produces after mud carries out quenched pretreatment by the quenched pond of mud 2 to be passed through
Plunger displacement pump 3 is transported to heater 4, the mud input supercritical gasification reactor 5 after preheating in heater 4, passes through
The reacted mud of supercritical water gasification carries out lowering the temperature and heat exchange process by heat exchanger 6；Mud after cooling enters gas-liquid
Separator 7, makes admixture of gas be sufficiently separated out from mud；
After separated process, obtaining the air mixture of methane and hydrogen, air mixture subsequently enters gas storage holder 8 and gas divides
From system 9；Slag-water slurry enters in blowoff basin 10, adds flocculant in blowoff basin 10, after standing 30-60min, and supernatant
Being discharged into sewage treatment plant of steel mill to continue with, pool bottom sludge carries out filter pressing, and the mud after filter pressing is sent into waste residue drying system
11, the waste heat handed down by heat exchanger carries out dewatered drying, and the mud after drying is sent directly into converter, former as steel-making
Material.
Embodiment 1:
Steel mill's height oil-containing iron containing sludge is collected in the cold rolling sludge-tank of certain steel mill, and mud is black, has lubricating oil abnormal smells from the patient, oil-containing
Measure higher.The Industrial Analysis of mud and elementary analysis are as shown in table 1, and the inorganic elements composition of mud is as shown in table 2, mud
XRD crystal phase analysis is as shown in Figure 2:
Table 1 sludge industrial analysis and elementary analysis
M-moisture；A-ash；V-volatile matter, oil-oil content, solvent extraction measures.
* As-received
* subtractive calculates
Table 2 mud inorganic elements composition (wt.%, db)
| Fe2O3 | CaO | MgO | Al2O3 | SiO2 | SO3 | P2O5 | Na2O | TiO2 |
| 97.00 | 0.89 | 523ppm | 0.21 | 0.70 | 0.35 | 0.10 | - | - |
| Cr2O3 | MnO | CuO | K2O | MoO3 | Tb4O7 | ZnO | CuO | NiO |
| 777ppm | 0.45 | 472ppm | - | - | 123ppm | 516ppm | 472ppm | 397ppm |
It is 5 at water/sludge quality ratio, reaction temperature 660 DEG C, pressure 23.4 ± 0.4MPa, time of staying 20min condition
Under, adding the CaO of different quality, gaseous product composition and yield are as shown in Table 3 and Table 4.Owing to water gas shift reaction is carried out
The most complete, in gas, CO content is extremely low, gas-phase product based on hydrogen, carbon dioxide, methane and ethane, wherein hydrogen and
Methane respectively accounts for about 1/3rd.
Table 3 gas-phase product composition (vol.%)
Table 4 gas-phase product yield (ml/g dewatered sludge) and rate of gasification
After reaction, residue elementary analysis result is listed in table 5, and the efficiency of carbon con version in mud is 94.7%, is not added with CaO seasonal epidemic pathogens
Rate is close to 60%, and after adding CaO, rate of gasification reaches about 90%.
Residue elementary analysis (wt%, db) after reaction in table 5 supercritical water
| Sample | C | H | N | S | Efficiency of carbon con version (%) |
| After 2# sludge reaction | 0.547 | 0.043 | 0.003 | 0.021 | 94.7 |
Fig. 3 is the XRD spectra of residue after reaction, and after reaction, residue almost all is converted into magnetic iron ore, adds the residue of CaO
In have calcium carbonate, wherein Fig. 3 (a) is SCW reaction residues, Fig. 3 (b) be SCW add CaO reaction residues.
After mud reacts in supercritical water, in water, total organic carbon (TOC) and COD (COD) are listed in table 6.
Water quality after table 6 sludge reaction
| CaO/ sludge quality ratio | Ca/C mol ratio | TOC(mg/L) | COD(g/L) | |
| 1 | 0 | 0 | 307.5 | 0.66 |
| 2 | 0.33 | 0.78 | 2656.0 | 9.04 |
| 3 | 0.47 | 1.09 | 1264.0 | 5.18 |
Finally illustrate, preferred embodiment above only in order to technical scheme to be described and unrestricted, although logical
Cross above preferred embodiment the present invention to be described in detail, it is to be understood by those skilled in the art that can be
In form and it is made various change, without departing from claims of the present invention limited range in details.
Claims (5)
1. steel mill's height oil-containing iron containing sludge supercritical water gasification recycling processing method, it is characterised in that: the method includes
Following steps:
S1: steel mill's height oil-containing iron content is produced mud and carries out quenched pretreatment in pretreatment pool；
S2: by mud pretreated in step S1, be transported to heater by plunger displacement pump, preheat in the heater,
Mud input supercritical water gasification reactor after preheating；
S3: after step S2 processes, carry out lowering the temperature and heat exchange by heat exchanger by reacted for supercritical water gasification mud
Process；
S4: the mud after cooling enters gas-liquid separator, makes admixture of gas be sufficiently separated out from mud, separated process
After, obtain the air mixture of methane and hydrogen；And slag-water slurry enters in blowoff basin, blowoff basin adds flocculant, quiet
After putting 30-60min, supernatant is discharged into sewage treatment plant of steel mill and continues with, and pool bottom sludge carries out filter pressing, by the dirt after filter pressing
The waste heat that mud is handed down by heat exchanger carries out dewatered drying, and the mud after drying is sent directly into converter, as steelmaking feed.
A kind of steel mill the most according to claim 1 height oil-containing iron containing sludge supercritical water gasification recycling processing method, its
Being characterised by: in step sl, after modifier treatment, water/mud mass ratio is 5:1, and pH value is 6-10.
A kind of steel mill the most according to claim 1 height oil-containing iron containing sludge supercritical water gasification recycling processing method, its
It is characterised by: in step s 2, the fuel used low combustion value furnace gas produced for steel mill of heater.
A kind of steel mill the most according to claim 1 height oil-containing iron containing sludge supercritical water gasification recycling processing method, its
Being characterised by: in step s 2, the temperature of reactor controls at 600-700 DEG C, and Stress control in 25-30MPa, the time of staying is
10-20min。
5. steel mill's height oil-containing iron containing sludge supercritical water gasification processing equipment for recycling, it is characterised in that: this device includes
Steel mill's sludge-tank (1) of being sequentially connected, the quenched pond of mud (2), plunger displacement pump (3), heater (4), supercritical gasification reactor
(5), heat exchanger (6), gas-liquid separator (7)；
High oil-containing iron content in steel mill's sludge-tank (1) produces after mud carries out quenched pretreatment by the quenched pond of mud (2) to be passed through
Plunger displacement pump (3) is transported to heater (4), the mud input supercritical gasification reactor after preheating in heater (4)
(5), carry out lowering the temperature and heat exchange process by heat exchanger (6) through the reacted mud of supercritical water gasification；Mud after cooling
Slurry enters gas-liquid separator (7), makes admixture of gas be sufficiently separated out from mud；
After separated process, obtaining the air mixture of methane and hydrogen, air mixture subsequently enters gas storage holder (8) and separates with gas
System (9)；Slag-water slurry enters in blowoff basin (10), adds flocculant in blowoff basin (10), after standing 30-60min, on
Clear liquid discharging continues with to sewage treatment plant of steel mill, and pool bottom sludge carries out filter pressing, the mud after filter pressing is sent into waste residue and is dried
System (11), the waste heat handed down by heat exchanger carries out dewatered drying, and the mud after drying is sent directly into converter, as refining
Steel raw material.
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| CN201610837880.7A CN106316023A (en) | 2016-09-21 | 2016-09-21 | Supercritical water gasification and recycling method and apparatus for steel mill high-oil-content iron-containing sludge |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108328889A (en) * | 2018-02-28 | 2018-07-27 | 宝钢工程技术集团有限公司 | A kind of cold rolling wastewater dregs of fat innocuity disposal system and method |
| CN111792807A (en) * | 2020-07-20 | 2020-10-20 | 中国海洋石油集团有限公司 | Polymer-containing oil sludge treatment device and method based on supercritical water gasification process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108328889A (en) * | 2018-02-28 | 2018-07-27 | 宝钢工程技术集团有限公司 | A kind of cold rolling wastewater dregs of fat innocuity disposal system and method |
| CN108328889B (en) * | 2018-02-28 | 2021-03-09 | 宝武水务科技有限公司 | Cold rolling wastewater oil residue harmless treatment system and method |
| CN111792807A (en) * | 2020-07-20 | 2020-10-20 | 中国海洋石油集团有限公司 | Polymer-containing oil sludge treatment device and method based on supercritical water gasification process |
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Application publication date: 20170111 |