CN101935031A - Method for separating and recovering carbon from pyrolysis residue of sludge containing oil - Google Patents
Method for separating and recovering carbon from pyrolysis residue of sludge containing oil Download PDFInfo
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Abstract
The invention relates to a method for separating and recovering carbon from a pyrolysis residue of sludge containing oil, which is applied to the technical field of oil extraction waste water and oil sludge pollution treatment. The method comprises the following steps of: simultaneously adding the pyrolysis residue and an activating agent into a stirrer and uniformly stirring; then adding an obtained mixture into an activation furnace for treating for 1-4 hours; flushing the activated residue into a first reaction pot by utilizing a water replenishing system and adding a test solution A, wherein the mass ratio of the activated pyrolysis residue to the test solution A is (1:2)-(1:15); introducing into hydrogen and rinsing the residue with water for 3-8 times; flushing the residue into a second reaction pot 7 and adding a test solution B, wherein the mass ratio of the pyrolysis residue subjected to the treatment procedure of the test solution A to the test solution B is (1:3)-(1:12); introducing into steam; flushing the residue into a carbon storage slot, and starting a carbon storage slot stirrer to mix carbon and water; starting a centrifugal machine for dewatering; and adding the mixture into a dry ball mill to pulverize to 120-200 meshes. The invention has the advantages of good separation and recovery effects, small occupation area, convenient operation, economy, feasibility, no secondary pollution, carbon resource recovery, low energy consumption and low running cost.
Description
Technical field
The present invention relates to oil extraction waste water and greasy filth and pollute processing technology field, the method for carbon Separation and Recovery in particularly a kind of oily sludge pyrolysis residue.
Background technology
Oily sludge thermochemical treatment and resource utilization novel method are explored, and are representing the advanced direction and the development trend of field of treatment of solid waste.Oily sludge pyrolysis residue is that oil field oil-containing mud is handled the residual waste that the back produces by high temperature pyrolytic cracking (HTP), is commonly referred to the pyrolysis residue, is the pyrolysis residue that the present invention claims.Carbon content reaches about 40% in the pyrolysis residue, has higher Separation and Recovery to be worth.With the pyrolysis of oily sludge is to compare at organic composition wherein, and the recycling of pyrolysis residue mainly is the inorganic components that left behind with coke and cindery form at wherein, and these residues will cause secondary pollution if deal with improperly.Present technique is an object with oily sludge pyrolysis residue, principle according to " innoxious; minimizing; resource utilization ", self-characteristic at the pyrolysis residue, carry out new exploration from utilization of resources pattern, the separation and recovery technology of carbon in the research oily sludge pyrolysis residue, simultaneously by carbon residue and commodity carbon black to reclaiming, carburizing agent, the structure of activated carbon and characteristic comparative study, explore and reclaim carbon in metallurgical industry, carbon disulphide production, brick fuel is produced, tire, rubber, during printing ink is produced as additive and as sorbent material, discoloring agent, aspect possibility of its application such as support of the catalyst are for its commercial application and Pollution control technology provide necessary theoretical basis and scientific basis reliably.The research of carbon separation and recovery technology meets the theory of building a resource-conserving and environment-friendly society that country proposes in the oily sludge pyrolysis residue, has important environmental benefit, economic benefit, social benefit and certain academic significance.
At present, because pyrolytic technique is not extensive use of, so it is also less relatively for the research of oily sludge pyrolysis residue as resources utilization both at home and abroad, main also lay particular emphasis on the gas that produces in pyrolytic process research and the pyrolysis, solid, liquid product analytically, and, only mention the possibility that obtains carbon black one series products for solid residue.Chinese patent publication number: 101113067A, a kind of recycling processing method of oily sludge is disclosed: oily sludge is sent in the airtight carbonization decomposition stove carried out pyrolysis processing, pyrolysis processing was reacted 1～5 hour under 200～600 ℃ of conditions, refiltered oil, gas, water; Stoichiometric 1: 1～5 adding sulfuric acid or hydrochloric acid by aluminium salt or molysite in the pyrolysis residue of the mud that contains inorganic aluminate or molysite flocculation medicament carry out sour molten processing, and product is back to use Sewage treatment systems and makes the flocculation medicament, or the concentrated medicament of mud is made in reuse; Based on the pyrolysis residue of clay mineral directly as waste water and oil product decolorizing and absorbing material or be used as the sorbent material of lube oil finishing; This method is implemented in the oil field gathering and transportation treatment system, realizes the defeated treating processes mud " zero release " of collection.From the domestic and international related data of retrieval, the processing method that carbon reclaims in the reagent combination of carbon Separation and Recovery and the residue in the oily sludge pyrolysis residue that do not appear in the newspapers.
Summary of the invention
The objective of the invention is: the method for carbon Separation and Recovery in a kind of oily sludge pyrolysis residue is provided, and with carbon Separation and Recovery in the oily sludge pyrolysis residue, carbon purity reaches more than 95%.By physico-chemical process, remove other materials beyond the de-carbon in the pyrolysis residue.
The technical solution used in the present invention is: the device that the carbon separation and recovery method uses in the oily sludge pyrolysis residue, the device of use is made up of stirrer, activating reaction furnace, worm conveyor, retort, grug feeding jar, steam pipeline, screen plate, storage carbon groove, whizzer, drying machine, ball mill and waste liquid storage pool.The stirrer outlet is connected with the activating reaction furnace inlet, and the priming reaction outlet of still is equipped with worm conveyor; The outlet of worm conveyor connects the opening for feed of recycling bin, will activate the back residue by worm conveyor and be transported in the recycling bin.
Recycling bin is connected with water charging system, and recycling bin bottom discharge port has pipeline to be connected with the first retort top opening for feed, utilizes liquid level difference and by the water inlet of water charging system residue in the recycling bin is poured in the reaction container.On the pipeline between the recycling bin and first retort, be connected the outlet of grug feeding jar A with pipeline by threeway.The first retort bottom is connected with steam pipeline, can be for providing superheated vapour in first retort.The first retort inner bottom part has the screen plate A that filters waste liquid; On the first retort lower part outlet pipeline valve and pump are housed, pump outlet is connected with the import of waste liquid storage pool by pipeline, and waste liquid storage pool liquid outlet is connected with pump and pipeline, the fluid inlet UNICOM of pipeline and water charging system, grug feeding jar A and grug feeding jar B.In the first retort middle and lower part discharge port is arranged, discharge port has pipeline to connect the feeding mouth of second retort; On the pipeline between first retort and second retort, be connected the outlet of grug feeding jar B with pipeline by threeway.The second retort bottom also connects steam pipeline, and the second retort inner bottom part has the screen plate B that filters waste liquid; On the second retort lower part outlet pipeline valve and pump are housed, pump outlet is connected with the import of waste liquid storage pool by pipeline, and waste liquid storage pool liquid outlet is connected with pump and pipeline, the fluid inlet UNICOM of pipeline and water charging system, grug feeding jar A and grug feeding jar B.In the second retort middle and lower part discharge port is arranged, discharge port has pipeline to connect the inlet of storage carbon groove, and material is poured the storage carbon groove by water from second retort.In storage carbon groove agitator is housed, storage carbon groove lower part outlet pipeline is connected with the whizzer inlet line.The water outlet of whizzer is connected with pump and pipeline, the fluid inlet UNICOM of pipeline and water charging system, grug feeding jar A and grug feeding jar B.The liquid that whizzer is deviate from can return water charging system or grug feeding jar A or grug feeding jar and recycle.The discharge port of whizzer is connected with the rotary drying machine inlet capable, and wet carbon enters rotary dryer from whizzer.The discharge port of rotary dryer is connected with the dry ball opening for feed.
The method of carbon Separation and Recovery in the oily sludge pyrolysis residue:
A, pyrolysis residue and activator add stirrer simultaneously and stir, and the mass ratio of pyrolysis residue and activator is 1: 2～1: 4; Activator is the mixed solution of chloride soln and sulfide solution, and wherein muriate contains a kind of positively charged ion in ammonium, sodium, iron, aluminium, zinc, boron, magnesium, manganese or the calcium, preferred zinc chloride; Sulfide contains a kind of positively charged ion in sodium or the potassium, preferred potassium sulphide, and the volume ratio of chloride soln and sulfide solution is 1: 0.3～1: 0.45, the concentration of chloride soln and sulfide solution is 3mol/L.
B, then pyrolysis residue and activator are sent into activating reaction furnace and carry out activation treatment, heat-up rate: 5～10 ℃/min, the temperature of activation treatment is at 400～900 ℃, and the time of activation treatment is 1～4 hour, forms activation back pyrolysis residue in activating reaction furnace.
C, will activate back pyrolysis residue and be conveyed in the recycling bin, utilize the difference of altitude of recycling bin and first retort, and utilize the water of water charging system will activate the residue of pyrolysis afterwards and pour in first retort by worm conveyor.
D, utilize first grug feeding jar to add test solution A in first retort simultaneously, activation back pyrolysis residue and test solution A mass ratio are 1: 2～1: 15; Test solution A is one or both a mixture in sulphuric acid soln, hydrochloric acid soln, phosphoric acid solution and the hydrofluoric acid solution, and concentration is 1～8mol/L.
E, fed 120 ℃ of steam 20～60 minutes in first retort by steam pipeline; Open first retort bottom screen plate A and emit the interior waste liquid of first retort, with water rinse residue 3～8 times, with pump waste liquid and poaching wastewater are squeezed into the storage of waste liquid storage pool, the storage pool supernatant liquor returns the water charging system or first grug feeding jar or second grug feeding jar and re-uses.
F, with in first retort after test solution A treatment process pyrolysis residue water pour in second retort; Utilize second grug feeding jar to add test solution B simultaneously in second retort, the mass ratio of pyrolysis residue and test solution B is 1: 3～1: 12 after test solution A treatment process; Test solution B is a kind of in sodium hydroxide solution, the potassium hydroxide solution, and test solution B weight percent concentration is 1%～15%; Fed 120 ℃ of steam 20～40 minutes; Open second retort bottom screen plate B and emit the interior waste liquid of second retort, be neutral with water rinse residue 3～8 times to solution, with pump waste liquid and poaching wastewater are squeezed into the storage of waste liquid storage pool, the storage pool supernatant liquor returns the water charging system or first grug feeding jar or second grug feeding jar and re-uses.
G, with in second retort after test solution B treatment process the pyrolysis residue pour the storage carbon groove from second retort; Start the agitator in the storage carbon groove then, rinsing carbon is mixed with water.
H, rinsing carbon and water are entered whizzer by storage carbon trench bottom valve dewater, liquid returns the water charging system or first grug feeding jar or second grug feeding jar by pump and recycles.Wet carbon after the dehydration is conveyed into rotary dryer and carries out drying treatment.Dried carbon is sent into dry ball and is crushed to 120～200 orders.
The method of carbon Separation and Recovery in the oily sludge pyrolysis residue is by a series of physics and chemical process, removes other materials beyond the de-carbon in the pyrolysis residue, and carbon purity reaches more than 95% in the residue after treatment, has obtained the effect of good recovery carbon.The carbon that present technique reclaims is measured by electron-microscope scanning, energy spectrum analysis and iodine sorption value, on microtexture and characteristic, many similarities are arranged with commodity carbon black, activated carbon, the carbon that reclaims can use as the additive in carbon brick, tire, rubber, printing ink, the electrode production, also has its exploitation as aspect Application feasibility such as sorbent material, discoloring agent, support of the catalyst.For follow-up recycling creates conditions.
Beneficial effect of the present invention: the method for carbon Separation and Recovery in the oily sludge pyrolysis residue of the present invention,
1. Separation and Recovery is effective: the recovery reagent combination of independent development is added in the pyrolysis residue in certain sequence, after " activator activation, pyrolysis activation, fine purifiation, separation and drying " art breading, the carbon purity that reclaims reaches more than 95%, on microtexture and characteristic near commercial grade carbon black, activated carbon.
2. take up an area of little: carbon separating and reclaiming device floor space is less in the oily sludge pyrolysis residue, and suitability is strong in the environment protection of oil play oil-gas field.
3. simple in structure, easy to operate: process unit of the present invention is simple in structure, processes easy for installationly, and operation can realize automatization.
4. economically feasible: the present invention has non-secondary pollution, characteristics such as can reclaim carbon resource, energy consumption is low, and running cost is low, when realizing the harmless treatment of oily sludge pyrolysis residue, also laid good basis for the further recycling of carbon in the pyrolysis residue.
5. reclaiming the carbon that obtains measures through electron-microscope scanning, energy spectrum analysis and iodine sorption value, on microtexture and characteristic, many similarities are arranged with commodity carbon black, activated carbon, the carbon that reclaims can use as the additive in brick fuel, tire, rubber, printing ink, the electrode production, also has its exploitation as aspect Application feasibility such as sorbent material, discoloring agent, support of the catalyst.For follow-up recycling has been created condition.
Description of drawings
Fig. 1 is a carbon separating and reclaiming device structural representation in the oily sludge pyrolysis residue of the present invention.
Among the figure, 1. stirrer, 2. activating reaction furnace, 3. worm conveyor, 4. water charging system, 5. recycling bin, 6. first retort, 7. second retort, 8. screen plate A, 9. screen plate B, 10. storage charcoal groove, 11. agitators, 12. whizzer, 13. drying machines, 14. dry ball, 15. grug feeding jar A, 16. grug feeding jar B, 17. valves, 18. pump, 19. steam-pipes, 20. waste liquid storage pools.
Embodiment
With a processing power 30m
3The device of carbon Separation and Recovery is an example in the oily sludge pyrolysis residue of/d, and the present invention is described in further detail.
Consult Fig. 1.The device that the carbon separation and recovery method uses in the oily sludge pyrolysis residue, the device of use is made up of stirrer 1, activating reaction furnace 2, worm conveyor 3, retort, grug feeding jar, steam pipeline 19, screen plate, storage carbon groove 10, whizzer 12, drying machine 13, ball mill 14 and waste liquid storage pool 20.
Stirrer 1: dry-mix stirrer, model TDG-201, power 7.7kw;
Activating reaction furnace 2: rotary type, internal diameter 2m, power of motor 2.2kw;
Worm conveyor 3: diameter: 260mm, length is 6m;
Recycling bin 5: useful volume 20m
3
The useful volume of first retort 6 and second retort 7 is 60m
3, two interior screen plates of retort have unlatching, closing function, can controlledly filter.
Grug feeding jar A15 and grug feeding jar B16: useful volume 100m
3
Storage carbon groove 10: useful volume 20m
3
Agitator 11:XRD series, XR-Y aerofoil profile axial flow blade;
Whizzer 12: horizontal screw unloading filter centrifugal machine LW350 * 2000mm, rotating speed 2100～2500r/min, power of motor 15kw;
Drying machine 13: revolving drum drier internal diameter 1500mm, length 12000mm, treatment capacity 3t/h, driving power 7.5kw;
Dry ball 14: model internal diameter 1830mm, length is 3000mm, inlet amount 4～10t/h, power of motor 180kw;
Pump 18: model is MDH-425: flow 24m
3/ h, lift 25.5m, power 3.7kw.
Waste liquid storage pool 20: useful volume 300m
3
Stirrer 1 outlet is connected with activating reaction furnace 2 inlets, and activating reaction furnace 2 outlets are equipped with worm conveyor 3.The outlet of worm conveyor 3 connects the opening for feed of recycling bin 5.Recycling bin 5 is connected with water charging system 4 (claiming again: water feeding system, waterworks), and water charging system 4 adopts a water pot bottom to connect valve and water pipe.Recycling bin 5 bottom discharge ports have pipeline to be connected with first retort, 6 top opening for feeds.On the pipeline between the recycling bin 5 and first retort 6, be connected the outlet of grug feeding jar A15 with pipeline by threeway.First retort, 6 bottoms are connected with steam pipeline 19.First retort, 6 inner bottom parts have the screen plate A8 that filters waste liquid; On first retort, the 6 lower part outlet pipelines valve 17 and pump 18 are housed, the outlet of pump 18 is connected with 20 imports of waste liquid storage pool by pipeline, waste liquid storage pool liquid outlet is connected with pump and pipeline, the fluid inlet UNICOM of pipeline and water charging system 4, grug feeding jar A15 and grug feeding jar B16.In first retort, 6 outer wall middle and lower parts discharge port is arranged, the position of discharge port is at 5 millimeters places, top of screen plate A8.The discharge port of first retort 6 has pipeline to connect the feeding mouth of second retort 7; On the pipeline between first retort 6 and second retort 7, be connected the outlet of grug feeding jar B16 with pipeline by threeway.
Second retort, 7 bottoms also connect steam pipeline 19, the second retort 7 inner bottom parts the screen plate B9 that filters waste liquid; On second retort, the 7 lower part outlet pipelines valve and pump are housed, pump outlet is connected with 20 imports of waste liquid storage pool by pipeline, and waste liquid storage pool liquid outlet is connected with pump and pipeline, the fluid inlet UNICOM of pipeline and water charging system 4, grug feeding jar A15 and grug feeding jar B16.In second retort, 7 middle and lower parts discharge port is arranged, discharge port has pipeline to connect the inlet of storage carbon groove 10.In storage carbon groove 10 agitator 11 is housed, storage carbon groove 10 lower part outlet pipelines are connected with whizzer 12 inlet line.The water outlet of whizzer 12 is connected with pump and pipeline, the fluid inlet UNICOM of pipeline and water charging system 4, grug feeding jar A15 and grug feeding jar B16.The discharge port of whizzer 12 is connected with rotary dryer 13 opening for feeds.The discharge port of rotary dryer 13 is connected with dry ball 14 opening for feeds.
Preparing carbon with the method for carbon Separation and Recovery in five application oily sludge pyrolysis residues is example, and present method is elaborated.Consult Fig. 1.
The embodiment 1 of recovery method:
A, heat-obtaining are separated residue 60kg and activator 180kg and are added stirrer 1 simultaneously and stir, and the mass ratio of pyrolysis residue and activator is 1: 3; Activator is the mixing solutions of liquor zinci chloridi and potassium sulfide solution, and the composite volume ratio of liquor zinci chloridi and potassium sulfide solution is 1: 0.35, and liquor zinci chloridi and potassium sulfide solution concentration are 3mol/L.
B, then pyrolysis residue and activator are sent into activating reaction furnace 2 and carry out activation treatment, 10 ℃/min of heat-up rate; The temperature of activation treatment is 800 ℃; The time of activation treatment is 2 hours.In activating reaction furnace 2, form activation back pyrolysis residue.
C, will activate back pyrolysis residue and be conveyed in the recycling bin 5, utilize the difference of altitude of recycling bin 5 and first retort 6, and utilize the water of water charging system 4 will activate the residue of pyrolysis afterwards and pour in first retort 6 by worm conveyor 3.
D, utilize first grug feeding jar 15 to add hydrochloric acid soln 900kg when pouring in first retort 6, activation is pyrolysis residue and hydrochloric acid soln mass ratio 1: 15 afterwards.Concentration of hydrochloric acid solution is 5mol/L.
E, in first retort 6, fed 120 ℃ of steam 60 minutes by steam pipeline 19; Open first retort, 6 bottom screen plate A8 and emit waste liquid in first retort 6, with water rinse residue 7 times, with pump 18 waste liquid is squeezed into waste liquid storage pool 20 and store, the storage pool supernatant liquor returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 and re-uses.
F, with in first retort 6 after test solution A treatment process pyrolysis residue water pour in second retort 7; Utilize second grug feeding jar 16 to add test solution B90kg simultaneously in second retort 7, the mass ratio of pyrolysis residue and test solution B is 1: 3 after test solution A treatment process; Test solution B is a sodium hydroxide solution, and the sodium hydroxide solution weight percent concentration is 10%; Fed 120 ℃ of steam 40 minutes, open second retort, 7 bottom screen plate B9 and emit waste liquid in second retort 7, be neutral with water rinse residue 6 times to solution, with pump waste liquid is squeezed into waste liquid storage pool 20 and store, the storage pool supernatant liquor returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 and re-uses.
G, with in second retort 7 after test solution B treatment process the pyrolysis residue pour the storage carbon groove 10 from second retort 7; Start the agitator 11 in the storage carbon groove 10 then, rinsing carbon is mixed with water.
H, rinsing carbon and water are entered whizzer 12 by storage carbon groove 10 bottom valves dewater, liquid returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 by pump and recycles.Wet carbon after the dehydration is conveyed into rotary dryer 13 and carries out drying treatment.Dried carbon is sent into dry ball 14 and is crushed to 160 orders, obtains reclaiming carbon 24.7kg, and carbon purity reaches 96.7%.
The embodiment 2 of recovery method:
A, heat-obtaining are separated residue 30kg and activator 60kg and are added stirrer 1 simultaneously and stir, and the mass ratio of pyrolysis residue and activator is 1: 2; Activator is the mixing solutions of liquor zinci chloridi and sodium sulfide solution, and the composite volume ratio of liquor zinci chloridi and sodium sulfide solution is 1: 0.3, and liquor zinci chloridi and sodium sulfide solution concentration are 3mol/L.
B, then pyrolysis residue and activator are sent into activating reaction furnace 2 and carry out activation treatment, 10 ℃/min of heat-up rate; The temperature of activation treatment is 400 ℃; The time of activation treatment is 3 hours.In activating reaction furnace 2, form activation back pyrolysis residue.
C, will activate back pyrolysis residue and be conveyed in the recycling bin 5, utilize the difference of altitude of recycling bin 5 and first retort 6, and utilize the water of water charging system 4 will activate the residue of pyrolysis afterwards and pour in first retort 6 by worm conveyor 3.
D, utilize first grug feeding jar 15 to add phosphoric acid solution 180kg when pouring in first retort 6, activation is pyrolysis residue and phosphoric acid solution mass ratio 1: 6 afterwards.Phosphoric acid solution concentration is 8mol/L.
E, in first retort 6, fed 120 ℃ of steam 40 minutes by steam pipeline 19; Open first retort, 6 bottom screen plate A8 and emit waste liquid in first retort 6, with water rinse residue 8 times, with pump 18 waste liquid is squeezed into waste liquid storage pool 20 and store, the storage pool supernatant liquor returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 and re-uses.
F, with in first retort 6 after test solution A treatment process pyrolysis residue water pour in second retort 7; Utilize second grug feeding jar 16 to add test solution B105kg simultaneously in second retort 7, the mass ratio of pyrolysis residue and test solution B is 1: 7 after test solution A treatment process; Test solution B is a potassium hydroxide solution, and the potassium hydroxide solution weight percent concentration is 5%; Fed 120 ℃ of steam 20 minutes, open second retort, 7 bottom screen plate B9 and emit waste liquid in second retort 7, be neutral with water rinse residue 5 times to solution, with pump waste liquid is squeezed into waste liquid storage pool 20 and store, the storage pool supernatant liquor returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 and re-uses.
G, with in second retort 7 after test solution B treatment process the pyrolysis residue pour the storage carbon groove 10 from second retort 7; Start the agitator 11 in the storage carbon groove 10 then, rinsing carbon is mixed with water.
H, rinsing carbon and water are entered whizzer 12 by storage carbon groove 10 bottom valves dewater, liquid returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 by pump and recycles.Wet carbon after the dehydration is conveyed into rotary dryer 13 and carries out drying treatment.Dried carbon is sent into dry ball 14 and is crushed to 160 orders, obtains reclaiming carbon 12.8kg, and carbon purity reaches 95.7%.
The embodiment 3 of recovery method:
A, heat-obtaining are separated residue 90kg and activator 360kg and are added stirrer 1 simultaneously and stir, and the mass ratio of pyrolysis residue and activator is 1: 4; Activator is the mixing solutions of liquor zinci chloridi and potassium sulfide solution, and the composite volume ratio of liquor zinci chloridi and potassium sulfide solution is 1: 0.4, and liquor zinci chloridi and potassium sulfide solution concentration are 3mol/L.
B, then pyrolysis residue and activator are sent into activating reaction furnace 2 and carry out activation treatment, 7 ℃/min of heat-up rate; The temperature of activation treatment is 900 ℃; The time of activation treatment is 4 hours.In activating reaction furnace 2, form activation back pyrolysis residue.
C, will activate back pyrolysis residue and be conveyed in the recycling bin 5, utilize the difference of altitude of recycling bin 5 and first retort 6, and utilize the water of water charging system 4 will activate the residue of pyrolysis afterwards and pour in first retort 6 by worm conveyor 3.
D, utilize first grug feeding jar 15 to add sulphuric acid soln 630kg when pouring in first retort 6, activation is pyrolysis residue and sulphuric acid soln mass ratio 1: 7 afterwards.Sulphuric acid soln concentration is 3mol/L.
E, in first retort 6, fed 120 ℃ of steam 30 minutes by steam pipeline 19; Open first retort, 6 bottom screen plate A8 and emit waste liquid in first retort 6, with water rinse residue 6 times, with pump 18 waste liquid is squeezed into waste liquid storage pool 20 and store, the storage pool supernatant liquor returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 and re-uses.
F, with in first retort 6 after test solution A treatment process pyrolysis residue water pour in second retort 7; Utilize second grug feeding jar 16 to add test solution B270kg simultaneously in second retort 7, the mass ratio of pyrolysis residue and test solution B is 1: 6 after test solution A treatment process; Test solution B is a sodium hydroxide solution, and the sodium hydroxide solution weight percent concentration is 2%; Fed 120 ℃ of steam 40 minutes, open second retort, 7 bottom screen plate B9 and emit waste liquid in second retort 7, be neutral with water rinse residue 4 times to solution, with pump waste liquid is squeezed into waste liquid storage pool 20 and store, the storage pool supernatant liquor returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 and re-uses.
G, with in second retort 7 after test solution B treatment process the pyrolysis residue pour the storage carbon groove 10 from second retort 7; Start the agitator 11 in the storage carbon groove 10 then, rinsing carbon is mixed with water.
H, rinsing carbon and water are entered whizzer 12 by storage carbon groove 10 bottom valves dewater, liquid returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 by pump and recycles.Wet carbon after the dehydration is conveyed into rotary dryer 13 and carries out drying treatment.Dried carbon is sent into dry ball 14 and is crushed to 140 orders, obtains reclaiming carbon 40.1kg, and carbon purity reaches 96.1%.
The embodiment 4 of recovery method:
A, heat-obtaining are separated residue 20kg and activator 50kg and are added stirrer 1 simultaneously and stir, and the mass ratio of pyrolysis residue and activator is 1: 2.5; Activator is the mixing solutions of liquor zinci chloridi and potassium sulfide solution, and the composite volume ratio of liquor zinci chloridi and potassium sulfide solution is 1: 0.45, and liquor zinci chloridi and potassium sulfide solution concentration are 3mol/L.
B, then pyrolysis residue and activator are sent into activating reaction furnace 2 and carry out activation treatment, 5 ℃/min of heat-up rate; The temperature of activation treatment is 900 ℃; The time of activation treatment is 2 hours.In activating reaction furnace 2, form activation back pyrolysis residue.
C, will activate back pyrolysis residue and be conveyed in the recycling bin 5, utilize the difference of altitude of recycling bin 5 and first retort 6, and utilize the water of water charging system 4 will activate the residue of pyrolysis afterwards and pour in first retort 6 by worm conveyor 3.
D, utilize first grug feeding jar 15 to add hydrochloric acid and hydrofluoric acid mixing solutions 200kg when pouring in first retort 6, hydrochloric acid and hydrofluoric acid mixed liquor volume be than 15: 1, activated afterwards pyrolysis residue and hydrochloric acid and hydrofluoric acid mixing solutions mass ratio 1: 10.Concentration of hydrochloric acid solution is 7mol/L, and hydrofluoric acid solution concentration is 8mol/L.
E, in first retort 6, fed 120 ℃ of steam 50 minutes by steam pipeline 19; Open first retort, 6 bottom screen plate A8 and emit waste liquid in first retort 6, with water rinse residue 8 times, with pump 18 waste liquid is squeezed into waste liquid storage pool 20 and store, the storage pool supernatant liquor returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 and re-uses.
F, with in first retort 6 after test solution A treatment process pyrolysis residue water pour in second retort 7; Utilize second grug feeding jar 16 to add test solution B100kg simultaneously in second retort 7, the mass ratio of pyrolysis residue and test solution B is 1: 10 after test solution A treatment process; Test solution B is a sodium hydroxide solution, and the sodium hydroxide solution weight percent concentration is 3%; Fed 120 ℃ of steam 60 minutes, open second retort, 7 bottom screen plate B9 and emit waste liquid in second retort 7, be neutral with water rinse residue 8 times to solution, with pump waste liquid is squeezed into waste liquid storage pool 20 and store, the storage pool supernatant liquor returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 and re-uses.
G, with in second retort 7 after test solution B treatment process the pyrolysis residue pour the storage carbon groove 10 from second retort 7; Start the agitator 11 in the storage carbon groove 10 then, rinsing carbon is mixed with water.
H, rinsing carbon and water are entered whizzer 12 by storage carbon groove 10 bottom valves dewater, liquid returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 by pump and recycles.Wet carbon after the dehydration is conveyed into rotary dryer 13 and carries out drying treatment.Dried carbon is sent into dry ball 14 and is crushed to 200 orders, obtains reclaiming carbon 8.2kg, and carbon purity reaches 97.6%.
The embodiment 5 of recovery method:
A, heat-obtaining are separated residue 100kg and activator 350kg and are added stirrer 1 simultaneously and stir, and the mass ratio of pyrolysis residue and activator is 1: 3.5; Activator is the mixing solutions of ammonium chloride solution and sodium sulfide solution, and the composite volume ratio of ammonium chloride solution and sodium sulfide solution is 1: 0.3, and ammonium chloride solution and sodium sulfide solution concentration are 3mol/L.
B, then pyrolysis residue and activator are sent into activating reaction furnace 2 and carry out activation treatment, 10 ℃/min of heat-up rate; The temperature of activation treatment is 550 ℃; The time of activation treatment is 3 hours.In activating reaction furnace 2, form activation back pyrolysis residue.
C, will activate back pyrolysis residue and be conveyed in the recycling bin 5, utilize the difference of altitude of recycling bin 5 and first retort 6, and utilize the water of water charging system 4 will activate the residue of pyrolysis afterwards and pour in first retort 6 by worm conveyor 3.
D, utilize first grug feeding jar 15 to add hydrochloric acid and hydrofluoric acid mixing solutions 500kg when pouring in first retort 6, hydrochloric acid and hydrofluoric acid mixed aqueous solution volume ratio 15: 1 activated afterwards pyrolysis residue and hydrochloric acid and hydrofluoric acid mixing solutions mass ratio 1: 5.Concentration of hydrochloric acid solution is 6mol/L, and hydrofluoric acid solution concentration is 5mol/L.
E, in first retort 6, fed 120 ℃ of steam 50 minutes by steam pipeline 19; Open first retort, 6 bottom screen plate A8 and emit waste liquid in first retort 6, with water rinse residue 6 times, with pump 18 waste liquid is squeezed into waste liquid storage pool 20 and store, the storage pool supernatant liquor returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 and re-uses.
F, with in first retort 6 after test solution A treatment process pyrolysis residue water pour in second retort 7; Utilize second grug feeding jar 16 to add test solution B600kg simultaneously in second retort 7, the mass ratio of pyrolysis residue and test solution B is 1: 12 after test solution A treatment process; Test solution B is a sodium hydroxide solution, and the sodium hydroxide solution weight percent concentration is 1%; Fed 120 ℃ of steam 40 minutes, open second retort, 7 bottom screen plate B9 and emit waste liquid in second retort 7, be neutral with water rinse residue 3 times to solution, with pump waste liquid is squeezed into waste liquid storage pool 20 and store, the storage pool supernatant liquor returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 and re-uses.
G, with in second retort 7 after test solution B treatment process the pyrolysis residue pour the storage carbon groove 10 from second retort 7; Start the agitator 11 in the storage carbon groove 10 then, rinsing carbon is mixed with water.
H, rinsing carbon and water are entered whizzer 12 by storage carbon groove 10 bottom valves dewater, liquid returns the water charging system 4 or first grug feeding jar 15 or second grug feeding jar 16 by pump and recycles.Wet carbon after the dehydration is conveyed into rotary dryer 13 and carries out drying treatment.Dried carbon is sent into dry ball 14 and is crushed to 130 orders, obtains reclaiming carbon 37.9kg, and carbon purity reaches 95.1%.
Claims (2)
1. the method for carbon Separation and Recovery in the oily sludge pyrolysis residue is characterized in that:
A, pyrolysis residue and activator add stirrer (1) simultaneously and stir, and the mass ratio of pyrolysis residue and activator is 1: 2～1: 4; Activator is the mixed solution of chloride soln and sulfide solution, and wherein muriate contains a kind of positively charged ion in ammonium, sodium, iron, aluminium, zinc, boron, magnesium, manganese or the calcium, preferred zinc chloride; Sulfide contains a kind of positively charged ion in sodium or the potassium, preferred potassium sulphide, and the volume ratio of chloride soln and sulfide solution is 1: 0.3～1: 0.45, the concentration of chloride soln and sulfide solution is 3mol/L;
B, then pyrolysis residue and activator are sent into activating reaction furnace (2) and carry out activation treatment, heat-up rate: 5～10 ℃/min, the temperature of activation treatment is at 400～900 ℃, and the time of activation treatment is 1～4 hour, forms activation back pyrolysis residue in activating reaction furnace (2);
C, will activate back pyrolysis residue and be conveyed in the recycling bin (5), utilize the difference of altitude of recycling bin (5) and first retort (6), and utilize the water of water charging system (4) will activate back pyrolysis residue and pour in first retort (6) by worm conveyor (3);
D, utilize first grug feeding jar (15) to add test solution A in first retort (6) simultaneously, activation back pyrolysis residue and test solution A mass ratio are 1: 2～1: 15; Test solution A is one or both a mixture in sulphuric acid soln, hydrochloric acid soln, phosphoric acid solution and the hydrofluoric acid solution, and concentration is 1～8mol/L;
E, fed 120 ℃ of steam 20～60 minutes in first retort (6) by steam pipeline (19); Open first retort (6) bottom screen plate A (8) and emit the interior waste liquid of first retort (6), with water rinse residue 3～8 times, with pump (18) waste liquid and poaching wastewater are squeezed into waste liquid storage pool (20) storage, the storage pool supernatant liquor returns water charging system (4) or first grug feeding jar (15) or second grug feeding jar (16) and re-uses;
F, with in first retort (6) after test solution A treatment process pyrolysis residue water pour in second retort (7); Utilize second grug feeding jar (16) to add test solution B simultaneously in second retort (7), the mass ratio of pyrolysis residue and test solution B is 1: 3～1: 12 after test solution A treatment process; Test solution B is a kind of in sodium hydroxide solution, the potassium hydroxide solution, and test solution B weight percent concentration is 1%～15%; Fed 120 ℃ of steam 20～40 minutes; Open second retort (7) bottom screen plate B (9) and emit the interior waste liquid of second retort (7), be neutral with water rinse residue 3～8 times to solution, with pump waste liquid and poaching wastewater are squeezed into waste liquid storage pool (20) storage, the storage pool supernatant liquor returns water charging system (4) or first grug feeding jar (15) or second grug feeding jar (16) and re-uses;
G, with in second retort 7 after test solution B treatment process the pyrolysis residue pour the storage carbon groove (10) from second retort (7); Start the agitator (11) in the storage carbon groove (10) then, rinsing carbon is mixed with water;
H, rinsing carbon and water are entered whizzer (12) by storage carbon groove (10) bottom valve dewater, liquid returns water charging system (4) or first grug feeding jar (15) or second grug feeding jar (16) by pump and recycles; Wet carbon after the dehydration is conveyed into rotary dryer (13) and carries out drying treatment, and dried carbon is sent into dry ball (14) and is crushed to 120～200 orders.
2. the method for carbon Separation and Recovery in the oily sludge pyrolysis residue according to claim 1, it is characterized in that: the device of use is made up of stirrer (1), activating reaction furnace (2), worm conveyor (3), retort, grug feeding jar, steam pipeline (19), screen plate, storage carbon groove (10), whizzer (12), drying machine (13), ball mill (14) and waste liquid storage pool (20), stirrer (1) outlet is connected with activating reaction furnace (2) inlet, and activating reaction furnace (2) outlet is equipped with worm conveyor (3); The outlet of worm conveyor (3) connects the opening for feed of recycling bin (5);
Recycling bin (5) is connected with water charging system (4), recycling bin (5) bottom discharge port has pipeline to be connected with first retort (6) top opening for feed, is connected the outlet of grug feeding jar A (15) on the pipeline between recycling bin (5) and first retort (6) with pipeline by threeway; First retort (6) bottom is connected with steam pipeline (19), and first retort (6) inner bottom part has the screen plate A (8) that filters waste liquid; Valve (17) and pump (18) are housed on first retort (6) the lower part outlet pipeline, have pipeline to be connected between the outlet of pump (18) and the waste liquid storage pool (20); In first retort (6) middle and lower part discharge port is arranged, discharge port has pipeline to connect the feeding mouth of second retort (7); On the pipeline between first retort (6) and second retort (7), be connected the outlet of grug feeding jar B (16) with pipeline by threeway; Second retort (7) bottom also connects steam pipeline (19), and second retort (7) inner bottom part has the screen plate B (9) that filters waste liquid; On second retort (7) the lower part outlet pipeline valve and pump are housed, first retort (6) is connected with waste liquid storage pool (20) import by pipeline with second retort (7) lower part outlet pipeline pump outlet, waste liquid storage pool liquid outlet is connected with pump and pipeline, the fluid inlet UNICOM of pipeline and water charging system (4), grug feeding jar A (15) and grug feeding jar B (16); In second retort (7) middle and lower part discharge port is arranged, discharge port has pipeline to connect the inlet of storage carbon groove (10); In storage carbon groove (10) agitator (11) is housed, storage carbon groove (10) lower part outlet pipeline is connected with whizzer (12) inlet line; The water outlet of whizzer (12) is connected with pump and pipeline, the fluid inlet UNICOM of pipeline and water charging system (4), grug feeding jar A (15) and grug feeding jar B (16); The discharge port of whizzer (12) is connected with rotary dryer (13) opening for feed; The discharge port of rotary dryer (13) is connected with dry ball (14) opening for feed.
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| CN103112841A (en) * | 2013-02-22 | 2013-05-22 | 邹炎 | Process and system for manufacturing carbon product in clean and energy-saving manner |
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| CN104646051A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Catalyst for oily sludge pyrolysis process, preparation and application thereof |
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| CN103112841A (en) * | 2013-02-22 | 2013-05-22 | 邹炎 | Process and system for manufacturing carbon product in clean and energy-saving manner |
| CN103112841B (en) * | 2013-02-22 | 2015-08-26 | 邹炎 | A kind of clean energy-saving manufactures technique and the system of carbon product |
| CN104646051A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Catalyst for oily sludge pyrolysis process, preparation and application thereof |
| CN104307460A (en) * | 2014-10-21 | 2015-01-28 | 辽宁石化职业技术学院 | Method for preparing adsorbent from oily sludge and method for treating industrial wastewater containing organisms by using absorbent |
| CN106957714A (en) * | 2017-03-24 | 2017-07-18 | 中磁科技股份有限公司 | The reclaimer and method of neodymium iron boron cutting greasy filth |
| CN114149816A (en) * | 2021-11-29 | 2022-03-08 | 常州大学 | Method for preparing hydrogen-rich gas by catalyzing cracking of biomass tar by using aluminum smelting waste residues |
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