CN101838094A - Resourceful treatment method and device for oil-containing sludge in oil fields by microwave pyrolysis - Google Patents
Resourceful treatment method and device for oil-containing sludge in oil fields by microwave pyrolysis Download PDFInfo
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- CN101838094A CN101838094A CN200910230249A CN200910230249A CN101838094A CN 101838094 A CN101838094 A CN 101838094A CN 200910230249 A CN200910230249 A CN 200910230249A CN 200910230249 A CN200910230249 A CN 200910230249A CN 101838094 A CN101838094 A CN 101838094A
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 37
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
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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
Abstract
The invention discloses a resourceful treatment method and a resourceful treatment device for oil-containing sludge in oil fields by microwave pyrolysis. The oil-containing sludge is conveyed into an enclosed reactor heated by microwaves, and is subjected to pyrolysis treatment at the temperature of between 200 and 900 DEG C; oil, gas and water generated by the pyrolysis treatment are recycled; the residue after the pyrolysis is used as a roadbed material or modified by nitric acid or NaOH alkali; and the modified residue is used as an adsorbing material. After the method and the device are implemented, over 75 percent of crude oil in the oil-containing sludge can be recycled, the pollution fee of 1,000 yuan/t can be saved, the social and economic benefits are obvious, and the method and the device have wide market application prospect.
Description
One, technical field
The present invention relates to a kind of oil field oil-containing mud microwave-heating recycling processing method and device, this method is applicable to that the oil field refinery is produced and minimizing, resource utilization and the harmless treatment of the refuses such as oily sludge that Sewage treatment systems produces.
Two, background technology
Along with continually developing of domestic oil field, the extraction sewage quantity sharply increases, by the sludge quantity of generation also sharply increase, its total amount has reached more than 1,000,000 tons/year, only the Shengli Oil Field sludge yield promptly reaches about 120,000 tons/year, these mud are oil-containing not only, and contain various oil by auxiliary component, the existence of these compositions causes cleaning, art breading effects such as biological degradation are relatively poor, decompose fully under the natural condition and need the years up to a hundred, not only directly land occupation and space, and severe contamination air, soil and underground water have restricted the development of domestic field produces to a certain extent.Along with the requirement of national environmental protection statutory standard improves constantly, the law enforcement for environmental protection dynamics continues to increase, and the pollution control and the recycling of oily sludge have become the difficult problem of puzzlement petroleum industry.Therefore, a kind of can to eliminate the technology that oily sludge can reclaim the energy and resource again to the harm of environment be pressing for of oil field in research and development.Along with the shortage of natural resource and the surge of solid waste discharge capacity, many countries actively develop comprehensive utilization to solid waste as " resource ", solid waste becomes developable " renewable resource " gradually, and the recycling sludge utilization also will be the fundamental way of its ultimate disposal from now on.
The treatment process of oily sludge is a lot, mainly is divided into physico-chemical processes and biological process.Physico-chemical processes is to make the process that greasy filth is handled or purified by physics or chemical action.Mainly comprise: burning method, concentrate mummification method, solidification/static stabilization method, flotation oil removal process, add the method for burying, hot melt glass method, supercritical methanol technology, isolation/control method, leaching irrigation, vaporizing extract process, chemical oxidization method, photodegradation method, solvent extration, solvent-sonic treatment method etc.
1. burning method
This method is mainly used in Europe, can realize thoroughly innoxiously, but working cost is very high, and the utilization ratio of crude resources is lower in the oily sludge.Though domestic refinery has built up several covering devices, all be difficult to normal operation.
2. biological process.
Biological treatment greasy filth process progressively is subjected to people's favor with superiority such as its ideal treatment effect, processing and running cost are lower.Because the various countries particularly U.S. find that this method of life-time service has potential danger to atmosphere, underground water, has limited use at present.This method is mainly adopted in domestic Daqing oil field, each oil field, northwest, also has cost height, the slow problem of decomposition rate.
3. concentrate the mummification method
This technology is a kind of traditional treatment process, is suitable for the higher oily sludge of water ratio.The advantage of this technology is that initial cost is few and running expense is low, simple to operate, therefore this technology is adopted in the present domestic oil field of high water-containing sludge more.
4. solidification/static stabilization method.
This method is to make oily sludge form the hard block with complete structure by adding chemical reagent, thereby strengthens the controllability of oily sludge, has reduced the effect of oily sludge to surrounding environment.The weak point of solidification/static stabilization is that the stacking place is excessive, and As time goes on, pollutent is contaminate environment once again.
5. pyrolysis method
5.1 Pintsch process
The Pintsch process technology is meant that oily sludge is being heated to certain temperature (be generally about 450 ℃, even higher) under the anoxybiotic condition, hydrocarbons is separated in the hydration of complexity and cracking reaction, and condensation is reclaimed.The RUGSGO company performance of Denmark is more outstanding, and its technology is in major oil companies' successful Application such as shell, BP.Along with the further strictness of various countries to oily sludge disposal index, this technology will become one of important way of oily sludge processing as thorough, the fireballing method for sludge treatment of a kind of disposal.
5.2 low temperature pyrogenation
Germany takes the lead in beginning the experimental study of sludge at low temperature pyrolysis oil preparation nineteen eighty-two.The sludge at low temperature pyrolysis is a new energy recovery type sludge treatment technology that is developing, and August first in 1999, cover sludge at low temperature pyrolysis oil preparation industrialized unit was in Australian successful operation.At present, external refinery has been developed many kinds of pyrolytic processes, mainly contains the oily sludge treatment process that comprises low temperature (107～204 ℃)-high temperature (357～510 ℃) heating evaporation-condensation (in a plurality of national applications in Europe patent) of exploitation such as Heuer.Norway one oil company and an investor cooperate, and have developed the TermTech pyrolytic process.
Three, summary of the invention
The purpose of this invention is to provide a kind of oil field oil-containing mud microwave-heating recycling processing method and device; the recycling treatment that is the oily sludge that refinery production of cost-effective solution oil field and Sewage treatment systems produce with utilize problem, for the environment protection and the cleaner production of oil field refinery production process provides the supporting technology support.
A kind of oil field oil-containing mud microwave-heating recycling processing method, it is characterized in that oily sludge is sent in the closed reactor of microwave heating, under temperature 200-900 ℃, carry out pyrolysis processing, the oil gas water that pyrolysis processing is produced reclaims, utilize again, residue roadbed material after the pyrolysis or utilize nitric acid or utilize NaoH alkali to carry out modification, the residue after the modification is done sorbing material.
Handle the residue oil domain under the 0.2%-0.29% state:
A, utilize nitric acid to make properties-correcting agent, concentration of nitric acid 45%, the quality proportioning of residue and nitric acid is 4.5-4.8: 1, soak time is 3.5h-4h, the absorption property of the residue Pyrogentisinic Acid after the modification is that saturated extent of adsorption is 60.12mg/g-64.3mg/g.
B, utilize alkali NaOH
3Make properties-correcting agent, alkali concn 30%-32%, the mass fraction proportioning of residue and alkali is 2-2.5: 140 ℃-150 ℃ of 1 activation temperatures, activity time 2.5h-3h, the residue Pyrogentisinic Acid after the modification and attached performance be that saturated extent of adsorption is 47.04-45mg/g.
A kind of oil field oil-containing mud microwave-heating processing equipment for recycling, mainly form by supervisory control desk, body of heater, ceramic crucible, microwave casing and equipment body, it is characterized in that equipment body is made as rectangle together, the main body middle and upper part is provided with the rectangle body of heater, rectangle body of heater middle part is provided with a rectangle microwave casing, be provided with several microwave feed-in mouths in the upper and lower of body of heater ring side face, be fixed with microwave source on the microwave feed-in mouth, microwave source links with the microwave power supply that is located at the below; Transversely being provided with several layers in the microwave casing week supports, be placed with several ceramic crucible in the support, be provided with the microwave Box Cover of band arched top in microwave casing upper end, connect with quick joint bolt between the two, cover at the microwave casing and to be provided with pressure transmitter, temperature sensor, decompression protection valve and air outlet, be provided with one and import the gas import at the bottom of microwave box, ingress is provided with a magnetic valve; The pilot circuit of microwave power supply, microwave source, magnetic valve, temperature sensor and pressure transmitter and supervisory control desk links.
The microwave casing is made by stainless steel, and interior table studs with quartz glass layer.
Housing partly adopts electric automatization PIC control, and control panel adopts the color touch screen.
After this technology implementation, can realize the utilization of oily sludge maximum resource and whole safe and harmlessization disposal, the Hazardous wastes effluent charge of 1000 yuan/t have at first been avoided, secondly can reclaim the crude oil more than 75%, thereby effectively solve the environmental pollution and the final problem of outlet that contain mud, economic results in society are remarkable, have wide market application prospect.
Four, description of drawings
Fig. 1-technical process block diagram of the present invention
Fig. 2-apparatus structure synoptic diagram of the present invention
Five, embodiment
For further disclosing technical scheme of the present invention, elaborate by embodiment below in conjunction with Figure of description:
A kind of oil field oil-containing mud microwave-heating recycling processing method and device, it is characterized in that oily sludge is sent in the closed reactor of microwave heating, under temperature 200-900 ℃, carry out pyrolysis processing, the oil gas water that pyrolysis processing is produced reclaims, utilize again, residue after the pyrolysis is done roadbed material or is utilized nitric acid or utilize NaoH alkali to carry out modification, and the residue after the modification is done sorbing material.
A kind of oil field oil-containing mud microwave-heating processing equipment for recycling, mainly form by supervisory control desk, body of heater, ceramic crucible 7, microwave casing 17 and equipment body 16, it is characterized in that equipment body 16 is made as rectangle together, the main body middle and upper part is provided with rectangle body of heater 13, rectangle body of heater middle part is provided with a rectangle microwave casing 17, be provided with several microwave feed-in mouths 14 in the upper and lower of body of heater ring side face, be fixed with microwave source on the microwave feed-in mouth, microwave source links with the microwave power supply that is located at the below; Transversely being provided with several layers in the microwave casing week supports, be placed with several ceramic crucible 7 in the support, be provided with the microwave Box Cover 2 of band arched top in microwave casing upper end, connect with quick joint bolt 5 between the two, cover at the microwave casing and to be provided with pressure transmitter 4, temperature sensor, decompression protection valve 3 and air outlet 1, be provided with one and import gas import 9 at the bottom of microwave box, ingress is provided with a magnetic valve; Microwave power supply 11, microwave source 15, magnetic valve 19, temperature sensor 18 and pressure transmitter 4 link with the pilot circuit of supervisory control desk.
Referring to Fig. 1; the present invention is the intermittent type microwave pyrolysis installation; oily sludge is put into the ceramic crucible that sandwich tape supports; integral installation is gone into microwave hearthstone English glass chamber; close the top bell; have red temperature sensor, unloading pressure protection valve, pressure transmitter, tensimeter and pyrolysis gas outlet pipeline on the bell, by the graphite grazing pad and compress the sealing quick joint bolt whole box body is sealed.Open power supply, carry out microwave exposure with heat, microwave source is started working, and microwave is through microwave feed-in mouth irradiation oily sludge and ceramic crucible, and when temperature was raised to 200 ℃, constant temperature fully dehydrated.Constant temperature is after for some time, and beginning feeds nitrogen through the shielding gas ingress pipe, continues to heat up; enter hydro carbons distillation and high temperature pyrolysis process section; make low molecule organic matter at first become gas by distillation and discharge, light component is produced in heavy hydrocarbon generation cracking, discharges from the top outlet.Temperature is controlled by PLC, can set parameters such as temperature rise rate, steady time.The drying process section aqueous vapor that discharge on top enters Sewage treatment systems after condensation, pyrolytic process section gas reclaims oil product through cooling, and the by-product non-condensable gas acts as a fuel.
Embodiment 1
Field joint stations is stacked the field, and water ratio is 8.0% dewatered sludge, and the dewatered sludge oil length is 22.9%:
1, dewatered sludge airtight reacting by heating (being pyrolysis) 4 hours under 550 ℃ of conditions, its residue oil length is 0.29%, the refiltered oil rate is 65.9%;
2, the nitric acid optimum activating condition is: concentration of nitric acid 45%, soak time 4h, mass fraction liquid-solid ratio 4.5: 1.Measure residue Pyrogentisinic Acid's absorption property, its saturated extent of adsorption is 60.12mg/g.
Field joint stations is stacked the field, and water ratio is 54.6% half-driedization mud, and half-driedization mud oil length is 12.3%:
1, dewatered sludge airtight reacting by heating (being pyrolysis) 4 hours under 600 ℃ of conditions, its residue oil length is 0.21%, the refiltered oil rate is 60.9%;
2, best alkali activation condition is as follows: activation temperature is that 150 ℃, soak time are that 3h, NaOH concentration are 30%, mass fraction alkali is admittedly than 2: 1.Measure residue Pyrogentisinic Acid's absorption property, its saturated extent of adsorption is 47.04mg/g.
The jar end mud of field joint stations slurry tank, water ratio is 65%, oil length is 10.8%:
1, dewatered sludge airtight reacting by heating (being pyrolysis) 4 hours under 600 ℃ of conditions, its residue oil length is 0.25%, the refiltered oil rate is 64.3%;
2, the nitric acid optimum activating condition is: concentration of nitric acid 45%, soak time 4h, mass fraction liquid-solid ratio 4.5: 1.Measure residue Pyrogentisinic Acid's absorption property, its saturated extent of adsorption is 51.96mg/g.
Claims (5)
1. oil field oil-containing mud microwave-heating recycling processing method, it is characterized in that oily sludge is sent in the closed reactor of microwave heating, under temperature 200-900 ℃, carry out pyrolysis processing, the oil gas water that pyrolysis processing is produced carries out recycling, residue after the pyrolysis is done roadbed material or is utilized nitric acid or utilize NaoH alkali to carry out modification, and the residue after the modification is done sorbing material.
2. oil field oil-containing mud microwave-heating recycling processing method according to claim 1 is characterized in that handling the residue oil domain under the 0.2%-0.29% state:
A, utilize nitric acid to make properties-correcting agent, concentration of nitric acid 45%, the mass fraction proportioning of residue and nitric acid is 4.5-4.8: 1, soak time is 3.5h-4h, the absorption property of the residue Pyrogentisinic Acid after the modification is that saturated extent of adsorption is 60.12mg/g-64.3mg/g.
B, utilize alkali NaOH
3Make properties-correcting agent, alkali concn 30%-32%, the mass fraction proportioning of residue and alkali is 2-2.5: 140 ℃-150 ℃ of 1 activation temperatures, activity time 2.5h-3h, the residue Pyrogentisinic Acid after the modification and attached performance be that saturated extent of adsorption is 47.04-45mg/g.
3. oil field oil-containing mud microwave-heating processing equipment for recycling, mainly form by supervisory control desk, body of heater, ceramic crucible, microwave casing and equipment body, it is characterized in that equipment body is made as rectangle together, the main body middle and upper part is provided with the rectangle body of heater, rectangle body of heater middle part is provided with a rectangle microwave casing, be provided with several microwave feed-in mouths in the upper and lower of body of heater ring side face, be fixed with microwave source on the microwave feed-in mouth, microwave source links with the microwave power supply that is located at the below; Transversely being provided with several layers in the microwave casing week supports, be placed with several ceramic crucible in the support, be provided with the microwave Box Cover of band arched top in microwave casing upper end, connect with quick joint bolt between the two, cover at the microwave casing and to be provided with pressure transmitter, temperature sensor, decompression protection valve and air outlet, be provided with one and import the gas import at the bottom of microwave box, ingress is provided with a magnetic valve; The pilot circuit of microwave power supply, microwave source, magnetic valve, temperature sensor and pressure transmitter and supervisory control desk links.
4. oil field oil-containing mud microwave-heating processing equipment for recycling according to claim 3 is characterized in that the microwave casing made by stainless steel, and interior table studs with quartz glass layer.
5. oil field oil-containing mud microwave-heating processing equipment for recycling according to claim 3 is characterized in that housing partly adopts electric automatization PIC control, and control panel adopts the color touch screen.
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