CN104415963A - Combined treatment method for acid sludge and desulfurization ash - Google Patents
Combined treatment method for acid sludge and desulfurization ash Download PDFInfo
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Abstract
The invention relates to the field of comprehensive utilization of industrial wastes and particularly relates to a combined treatment method of waste acid sludge in the lubricating oil recycling industry and desulfurization ash in the dry-process/semidry process flue gas desulfurization industry. The combined treatment method of the acid sludge and the desulfurization ash comprises the following steps: after pulping the desulfurization ash, mixing and aerating with the acid sludge, and performing phase separation by virtue of emulsion-breaking and neutralizing effects, wherein an oil phase is utilized as fuels, a water phase is returned to a desulfurization ash pulping system for recycling, and a solid phase is utilized as a building material. The combined treatment method disclosed by the invention is simple in process, environmentally friendly, and capable of realizing innocent treatment of harmful wastes and developing a new way for recycling the harmful wastes, and has good economic benefits and environmental benefits.
Description
Technical field
The present invention relates to trade waste field of comprehensive utilization, particularly relate to a kind of method that lubricant oil regeneration industry acid sludge and dry method/semi-dry process flue gas desulphurization industry Desulphurization combine disposal.
Background technology
At widely used lubricating oil in field such as steel rolling, machinery, electric power, transport, chemical industry, oil, in use for some time, waste oil is become because deterioration is rotten.In view of the severe situation of lack of energy and waste lubricating oil are to the pollution of environment, the regeneration of waste lubricating oil has caused the attention of various countries.
The regeneration technology of waste lubricating oil existing tens of kinds at present, mainly comprises sulfuric acid one carclazyte method, distills a pickling one carclazyte method, distills a solvent extraction process, furfural treatment, molecule rectifying, hydrofinishing etc.Wherein, sulfuric acid one carclazyte method because of small investment, simple to operate, constant product quality, applicability are strong and widely adopt at medium-sized and small enterprises, thereby produce a large amount of acid sludges.Produce the oil plant of lubricating oil 50,000 tons 1 year, as adopted sulfuric acid refining process to refine reclaimed oil, annual approximately generation 3000 tons of acid sludges.
The harmful substances such as sulfuric acid, organic acid, oils, sulfonated bodies, colloid, asphalitine, sulfide, nitride, high condensation product, heavy metal compound are contained due to acid sludge, acidity is high, corrosivity is strong, toughness is large, deposit and transport very difficult, arbitrarily abandon or landfill, severe contamination can be brought to soil, vegetation, air, surface water, underground water, current acid sludge is put into " National Hazard refuse register ", need properly dispose.Meanwhile, acid sludge is also resource, and hydrocarbon wherein and sulfuric acid can fully utilize, and produces value product.
At present, the main thought of acid sludge treatment is: 1) be separated organic and inorganic acids contained in acid sludge and oily substance, then process respectively according to its physico-chemical property; 2) directly to acid neutralisation treatment in acid sludge, then residue is disposed.Acid sludge comprehensive Utilization Ways is mainly produces fuel heavy oil or solid fuel, extraction acid (sulfuric acid and sulfonic acid, aphthenic acids) or SO
2, processing chemical products (white carbon, antirust oil, mould oil, malthoid, saltcake, sulphur ammonia etc.), prepare building materials (gypsum, sulfonated gilsonite, road asphalt etc.), solidification dispose etc.
Both at home and abroad from the sixties in last century, pay much attention to acid sludge pollution problem always, develop multiple technologies: as CN 1195564A have employed a kind of method adding neutralizer, acid sludge is processed, produces fuel heavy oil, industrial saltcake, the sulphur in fuel heavy oil is separated, but the heating and cooling repeatedly of process, improve process energy consumption, the wastewater flow rate of generation is comparatively large, and the saltcake obtained needs further purification just can meet industrial requirements; CN 1740295A and CN 101724281A first adds used oil and regulates material viscosity in acid sludge, then adds calcium hydroxide powder, is then stirred to boiling, and shortcoming is that mixing is uneven, and sulfur dioxide gas is overflowed again; After acid sludge is heated to 25-200 DEG C by CN 1330986A, calls in oily molten thing, neutralize through basic species, add people's defoamer, then drying, grinding obtain drilling well sulfonated gilsonite, but the more difficult control of process for sulfonation, easy generation autoxidation, over oxidation or condensation coking, even can not produce sulfonated gilsonite; During CN 98104751.3 and CN 200510037244.8 uses lime directly and acid sludge, but a large amount of calcium sulphate solid particles that reaction generates cannot be separated with residual oil, have a strong impact on the quality of fuel oil; CN 1454966A first uses alkali lye neutralization, negative pressure dehydration, then at 0.09-0.06 MPa, 115-145 DEG C, decomposes sulfonic acid species, reduce sulfur content in finishing slag, but energy consumption is very high; CN85102005A adopts ammoniacal liquor to be nertralizer, and make acid sludge be divided into oil reservoir and sulfate solution layer, but this method overflows ammonia aborning, operating environment is poor, is not suitable for the acid sludge treatment that gum level is larger; In CN1073965A, propose acid sludge fragmentation atomization to react as oxidant and organic matter the processing method generating boiler oil or pitch, when its shortcoming is to be atomized, energy consumption is comparatively large, and treating capacity is little, reaction is difficult to carry out completely, containing the strong sulfuric acid that is corrosive in final products; US 5288392, US 5470455 and US 5573656 add pH value adjusting agent in acid sludge, raise between acid sludge pH value to 3-7 and obtain the intermediate state dregs of fat, be used for producing maltha, pitch or modified pitch, emulsified asphalt etc., processing procedure needs the water of 5-10 times repeatedly to wash, and it is uneconomical, meanwhile, the acid intermediate state dregs of fat can produce sour gas in subsequent high temperature processing, cause secondary pollution; JP 49126701 adds appropriate waste oil or light oil in acid sludge, and washing with sulfuric acid a small amount of in limestone vegetation oil, is converted into light oil as heavy oil or after catalysis after being separated.It is more that this method produces waste water, and have calcium sulfate in oil without separation, and waste residue is mixed in wherein, and oil product is defective; JP 76002919 continues to add sulfuric acid in acid sludge, makes acid content reach 65-90%, is heated to high temperature and makes organic matter generation dehydrogenation and carburizing reagent, prepare acticarbon, and under this method high temperature, acid gas is seriously polluted, and sulfuric acid solution needs process further.
Analyze the acid sludge treatment technique reported, find in actual use, have that big or middle, the residual oil high with alkaline agent cost of investment is separated that practical application effect is not good all to a certain extent, deficiency in economic performance, there is the problems such as secondary pollution, innoxious degree are not thorough, still have room for improvement.
On the other hand, dry method/semidry method desulphurization technique, because of advantages such as its technological process is short, it is little to take up an area, reduced investment, control is simple, water consumption is few, chimney-free rain, is widely used in the medium and small Thermal generation unit of China and steel enterprise sintering factory flue-gas desulfurizing engineering at present.Its accessory substance dry method/semidry method desulphurization ash (hereinafter referred to as Desulphurization) is usually in greyish white, grey brown powder form, and alkalescence is strong, particle is thin, complicated component, and character is unstable, containing CaSO
42H
2o, CaSO
31/2H
2o, CaCO
3, f-CaO and Ca (OH)
2deng polycalcium based compound, high temperature easily decomposes, normal temperature is oxidizable, transport easy airborne dust, building materials easily burst, and therefore utilizes difficulty very large.
Desulphurization disposal and utilization technology is mainly around the construction material such as production non-burning brick, steamed brick, cement retarder, Binder Materials, dry-mixed mortar, roadbed material, pottery, plastering, combined wall board panel, building block, filling material, slag/flyash composite blending material, but unstable, the actual dosage of mixing of final because Desulphurization is little and cannot realize industrialization and produce.Also there are research and utilization Desulphurization thermal decomposition relieving haperacidity (CN200910180052.0), catalytic oxidation gypsum (CN200910263921.6), prepare nano-calcium carbonate (CN201110209483.2), prepare wet desulphurization agent (CN200910194833.5), produce the techniques such as K-Ca-Si-S compound fertilizer (CN200610123966.X) and desulfurization ash modification (CN201110072276.7), but because of reasons such as energy consumption are high, production cost is high, environment potential impact large, product purification is comparatively complicated, be only in conceptual design and laboratory research stage at present.
At present, Desulphurization there is no appropriate scale utilization ways, and most Desulphurization is stored up to be abandoned, and fine day airborne dust is boundless, and rainy day sewage crossing current, causes serious secondary pollution to environment, become flue gas desulfurization enterprise must faced by a difficult problem.
Summary of the invention
The object of the present invention is to provide a kind of acid sludge and Desulphurization associating method of disposal, the method technique is simple, environmental friendliness, the harmlessness disposing of two kinds of harmful wastes can be realized, and open new approach for its recycling, there is good economic benefit and environmental benefit.
In order to realize above-mentioned technical purpose, the present invention adopts following technical scheme:
A kind of acid sludge and Desulphurization associating method of disposal, comprise the following steps:
After Desulphurization slurrying, with acid sludge mixed aeration, through breakdown of emulsion, neutralization, be separated, oil phase is as fuel utilization, and aqueous phase returns Desulphurization pulping system and recycles, and solid phase utilizes as building materials;
Described Desulphurization slurrying, Desulphurization slurrying mass percent concentration is: 5%-30%;
Described mixed aeration, the acid sludge of mixed process, water, Desulphurization ratio are: 1: 5-20: 0.5-5, and controlling reaction tank plasm PH value is 4.0-5.5; Gas is compressed air, CaSO in air capacity and Desulphurization
3content is linearly correlated with, and both mol ratios are 4-10:1, and aeration time is 5-60 min;
Described breakdown of emulsion, demulsifier is commercially available petroleum-type demulsifier, and the interpolation mass percent of demulsifier is the 0.1-1% of mixed serum, and breakdown of emulsion process continues 10-60 min under agitation;
Described neutralization, nertralizer alkali lye is the one of NaOH, calcium hydroxide, potassium hydroxide, and concentration of lye is 10-30%, and after neutralization, the pH value of mixed serum is 6-9;
Describedly to be separated, to refer to that the mixed liquor after by neutralization carries out " Gu-water-oil " three phase separation.
Further, described Desulphurization comes from one or more accessory substances in recirculating fluidized bed, rotating spraying, gas suspension absorption, the activation of flue dry sorbent injection, in-furnace calcium spraying calcium oxide, novel all-in-one and lime stone gas cleaning dry method/semi-dry method flue gas desulfurization technique, CaSO in described Desulphurization
31/2H
2o, CaCO
3, f-CaO and Ca (OH)
2the gross mass mark of four kinds of materials is 50-95%.
Described acid sludge is the acid slag that the oily waste of waste lubricating oil, used oil, waste oil mud, petroleum distillate and intermediate product adopts regeneration of sulfuric acid technique to produce, for black paste, acidity is high, toughness is large, wherein sulfur content is 5%-30%, and all the other are the mixture of oils, colloid, asphalitine, heavy aromatics, mahogany acid, aphthenic acids, sulfuric ester, macromolecule condensation product, heavy metal compound, salt.
Further, described Desulphurization slurrying mass percent concentration is 10-15%.
Further, the mixed process of described mixed aeration controls reaction tank plasm PH value is 4.5-5.2.
Further, CaSO in the air capacity of described mixed aeration and Desulphurization
3the mol ratio of content is 6:1.
Described demulsifier is hydroxyl or the nonionic organic surface active agent containing alkyl, comprises the multiple organic compound of expoxy propane one polyacid polymer, alkyd resins, nitrobenzene compound, hydramine, hydroxylamine derivative and ethers.
Described phase disengagement method comprises natural subsidence, heating sedimentation, centrifugation, one in " filtration+separatory " and joint operation thereof.
Further, described natural subsidence, time of repose is 30-60 min, adopts multiple settling tank, rotation settling operation, namely after the sedimentation of a period of time leaves standstill, the material extracting different aspects utilizes respectively, and wherein, the oil phase of supernatant fluid utilizes as oil plant, the aqueous phase of mid-water liquid returns Desulphurization pulping system, and the solid phase of pitch calcium slag carries out recycling as building materials.
Described " filtration+separatory " mode, first by filter element, first separates the solid phase of pitch calcium slag, then adopts the form of separatory funnel to be separated oil phase and aqueous phase.
The present invention is the acid sludge of lubricant oil regeneration industry and the Desulphurization of dry method/semi-dry process flue gas desulphurization industry, provide simple, the eco-friendly associating method of disposal of a kind of technique, not only achieve the harmlessness disposing of two kinds of harmful wastes, also for its recycling opens new approach, thus there is good economic benefit and environmental benefit.The beneficial effect of technical scheme of the present invention is as follows:
(1) acid sludge is in acid, Desulphurization is in alkalescence, it is all difficult, unstable hazardous waste, the present invention is by both mixed aerations, Desulphurization, while stabilisation, impels the acidity of acid sludge fully to discharge, then through breakdown of emulsion, neutralize, the step such as to be separated obtains oil phase and solid phase respectively, be a kind of feasible innoxious and recycling treatment process, thoroughly can eliminate the environment hidden danger of two kinds of industrial wastes.
(2) the present invention is while dealing carefully with two kinds of industrial dangerous wastes, fully can recycle valuable resource wherein, really achieve the treatment of wastes with processes of wastes against one another, and full dose reclaims.
(3) dihydrate gypsum in solid phase mixing material has cementation, effectively improves the physical and chemical performance of pitch calcium slag, is easier to following resourceization and utilizes;
(4) the present invention is simple to operate, and cost of equipment is low, and the waste water that technical process produces can be recycled, and does not produce secondary pollution.
Accompanying drawing explanation
Fig. 1 is acid sludge of the present invention and Desulphurization associating method of disposal flow chart.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
A kind of acid sludge and Desulphurization associating method of disposal, comprise the following steps: see Fig. 1,
After Desulphurization slurrying, with acid sludge mixed aeration, through breakdown of emulsion, neutralization, be separated, oil phase obtains oil product as fuel utilization or further refining, and aqueous phase returns Desulphurization pulping system and recycles, and solid phase carries out recycling as building materials.
Described Desulphurization comes from one or more accessory substances in recirculating fluidized bed, rotating spraying, gas suspension absorption, the activation of flue dry sorbent injection, in-furnace calcium spraying calcium oxide, novel all-in-one and lime stone gas cleaning dry method/semi-dry method flue gas desulfurization technique.CaSO in Desulphurization
31/2H
2o, CaCO
3, f-CaO and Ca (OH)
2the gross mass mark of four kinds of materials is 50-95%.
Described acid sludge is the acid slag that the oily waste of waste lubricating oil, used oil, waste oil mud, petroleum distillate and intermediate product adopts regeneration of sulfuric acid technique to produce, for black paste, acidity is high, toughness is large, wherein sulfur content is 5%-30%, and all the other are the mixture of oils, colloid, asphalitine, heavy aromatics, mahogany acid, aphthenic acids, sulfuric ester, macromolecule condensation product, heavy metal compound, salt.
(1) Desulphurization slurrying
Desulphurization slurrying mass percent concentration is: 5%-30%, preferred 10-15%.
(2) mixed aeration
Described mixed process, the ratio of acid sludge, water, Desulphurization is: 1: 5-20: 0.5-5.
Described mixed aeration, controlling reaction tank plasm PH value is 4.0-5.5, and preferred pH value is 4.5-5.2, with this understanding, CaSO in Desulphurization
3be converted into Ca (HSO
3)
2and then be converted into CaSO
4process more thorough, be easier to the stabilisation of Desulphurization.
Described mixed aeration, gas is compressed air, has stirring action concurrently, and acid sludge and Desulphurization are fully mixed, CaSO in air capacity and Desulphurization
3content is linearly correlated with, and both mol ratios are 4-10:1, preferred 6:1.
Described mixed aeration, aeration time is 5-60 min.
(3) breakdown of emulsion
Described demulsifier is commercially available petroleum-type demulsifier, preferred hydroxyl or the nonionic organic surface active agent containing alkyl, as multiple organic compounds such as expoxy propane one polyacid polymer, alkyd resins, nitrobenzene compound, hydramine, hydroxylamine derivative and ethers.
The interpolation mass percent of demulsifier is the 0.1-1% of mixed serum.
Described breakdown of emulsion process, continues 10-60 min under agitation.
(4) neutralize
Described nertralizer alkali lye is the one of NaOH, calcium hydroxide, potassium hydroxide, preferred NaOH; Concentration of lye is 10-30%.
After neutralization, the pH value of mixed serum is 6-9.
The pH value of acid sludge is very low, is in most cases less than 1, and in the mixed aeration stage, the Desulphurization in alkalescence is by acid sludge preneutralization, and therefore, mixed liquor is 4.0-5.5 from pH value, then is increased to 6-9, and actual consumption alkali lye is limited.This step is necessary, because ensure that slag at the bottom of sedimentation is for neutral, comprehensive utilization can not etching apparatus, does not also have sour gas effusion.
(5) be separated
Describedly to be separated, to refer to that the mixed liquor after by neutralization carries out " Gu-water-oil " three phase separation.Concrete separation means is not particularly limited, and can take natural subsidence, heating sedimentation, centrifugation, the one in " filtration+separatory " and joint operation thereof.
As adopted natural subsidence, time of repose is 30-60 min, can adopt multiple settling tank, rotation settling operation, and namely after the sedimentation of a period of time leaves standstill, the material extracting different aspects utilizes respectively.Wherein, oil phase (supernatant fluid) utilizes as oil plant, and aqueous phase (mid-water liquid) returns Desulphurization pulping system, and solid phase (pitch calcium slag) carries out recycling as building materials.
As adopted " filtration+separatory " mode, first can pass through filter element, first solid phase (pitch calcium slag) being separated, then adopt the form of separatory funnel to be separated oil phase and aqueous phase.
(6) oil content utilizes
Described oil content, can be used as fuel heavy oil or mould oil, refining through bleaching earth adsorption, be in harmonious proportion after, also can obtain lube base oil, oil antirust agent or drilling well seizureproof agent.
(7) pitch calcium slag utilizes
Described pitch calcium slag, because wherein containing thermal source and calcium source, can be used as the auxiliary material of cement rotary kiln, also can be used as building materials raw material (it is high for replacing natural), asphalt material (road asphalt, building asphalt, activation pitch) or soil conditioner.
Technical scheme of the present invention has following features:
This programme, by after Desulphurization slurrying, with acid sludge mixed aeration, has following effect:
(1) acid-base neutralization, the treatment of wastes with processes of wastes against one another, kills two birds with one stone.Acidic materials in acid sludge fully can react with the alkaline matter in Desulphurization, and involved chemical reaction mainly comprises:
CaO + H
2SO
4→ CaSO
4+ H
2O
CaCO
3+ H
2SO
4→ CaSO
4+ CO
2+ H
2O
Ca(OH)
2+ H
2SO
4→ CaSO
4+ 2H
2O
CaSO
3+ H
2SO
4→ CaSO
4+ H
2O+SO
2
2ArSO
3H + CaCO
3→ Ca(ArSO
3)
2+ CO
2+ H
2O
2ArSO
3H + Ca(OH)
2→ Ca(ArSO
3)
2+ 2H
2O 。
(2) the Desulphurization character factors of instability are eliminated, f-CaO and CaSO
3be able to effective conversion.Involved chemical reaction comprises:
f-CaO + H
2O → Ca(OH)
2
SO
2+ H
2O → H
2SO
3
CaSO
3+ H
2SO
3→ Ca(HSO
3)
2
CaSO
3+ 1/2 O
2→ CaSO
4
Ca(HSO
3)
2+ Ca(OH)
2+ O
2→ 2CaSO
4+2H
2O
CaSO
4+ 2H
2O → CaSO
4·2H
2O 。
(3) acid-base neutralization is exothermic reaction, and along with the carrying out of reaction, reaction can maintain certain temperature, impels acid sludge and Desulphurization fully to dissolve; Compressed-air actuated intervention, has supplemental oxygen and the effect adding strong mixing concurrently, can improve reaction speed.
(4) traditional acid sludge is administered, generally first be hydrolyzed, breakdown of emulsion, after profit initial gross separation, carry out acid-base neutralization again, and the Desulphurization that technical scheme of the present invention adopts, except the raised gas to nertralizer effect, the release of serial hydration reaction of alkalescence enhances except the mixing effect of " oil-slag-water " three-phase, the multicomponent in Desulphurization, as, CaSO
4, CaCO
3, Ca (HSO
3)
2, Ca (OH)
2deng the effect also with inorganic demulsifier, while self transforms, also enhance the demulsification of acid sludge, decrease the consumption of follow-up breakdown of emulsion process demulsifier.
(5) effective conversion of acid sludge: acid sludge material can be divided into three parts substantially: mineral acid (sulfuric acid, sulfurous acid), organic acid (arene-sulfonic acids, long-chain carboxylic acid etc.) and neutral oil.Under the neutralization of Desulphurization suspension, the mineral acid in acid sludge first with alkaline matter generation neutralization, meanwhile, organic acid and water carry out the back reaction of sulfonation, are reduced into aromatic hydrocarbons colloid and sulfuric acid (ArSO
3h+H
2o=ArH+H
2sO
4), achieve organic acid in acid sludge and disengage initial gross separation with aromatic hydrocarbons and colloid (being generally referred to as " residual oil "), and in the breakdown of emulsion stage, oil phase is separated further with aqueous phase.
(6) after three phase separation, supernatant fluid can do fuel utilization, also can refine further and obtain oil product; Aqueous phase returns Desulphurization pulping system and recycles, and solid phase is mainly the mixture of gypsum, pitch, colloid, macromolecule organic, salt, can utilize as building resourceization.
Embodiment 1:
As shown in Figure 1, for a kind of lubricant oil regeneration acid sludge and dry method/semidry method desulphurization ash combine the method for disposal, comprise the following steps:
(1) Desulphurization and acid sludge
Desulphurization takes from circulating fluidized bed dry sintered flue gas desulfurization device, and main component is: CaSO
4h
2o, 16.7%, CaSO
31/2H
2o, 42.6%, f-CaO, 14.3%, Ca (OH)
2, 9.5%, CaCO
3, 6.5%, the gross mass percentage of rear four kinds of materials is 72.9%.
Acid sludge is the acid slag that waste lubricating oil adopts sulfuric acid-clay regeneration technique generation, and in black ointment shape, pH value <1, acid number is 1.025gKOH/g, SO
4 2-be 66.4%, oil content 85.6mg/g, poor fluidity, toughness are large, and sulfur content is 20%, mainly becomes the mixture of remaining sulfuric acid, oils, colloid, asphalitine, heavy aromatics, mahogany acid, aphthenic acids, sulfuric ester, macromolecule condensation product, heavy metal compound, salt.
Get acid sludge 200 g, Desulphurization 500 g, for subsequent use.
(2) Desulphurization slurrying and mixed aeration: by Desulphurization slurrying, mass percent concentration is 15%, Desulphurization suspension (containing Desulphurization 500g) after slurrying is mixed with 200g acid sludge, Desulphurization suspension slowly adds, to control mixed serum pH value be 4.5-5.2(because of control pH value therefore, Desulphurization suspension may cannot not add completely), carry out aeration agitation 45min, acid sludge and Desulphurization are fully mixed, CaSO in air capacity and Desulphurization
3the mol ratio of content is close to 6:1.
(3) breakdown of emulsion: add the commercially available petroleum-type demulsifier (model OX-932) of 0.2% in the slurries of mixed aeration, belong to the nonionic organic surface active agent of hydroxyl, breakdown of emulsion whipping process continues 20min.
(4) neutralize: after breakdown of emulsion completes, in mixed serum, add the NaOH of 20%, regulate the pH value of mixed serum, to 6-9, leave standstill 30 min.
(5) be separated: adopt natural subsidence, time of repose is 50min, draws the material of different aspects respectively.Obtain oil phase (supernatant fluid) about 15 g (Oil recovery rate is 87.6%), aqueous phase (mid-water liquid) about 2250 g, weigh after constant weight after solid phase (pitch calcium slag) 105 DEG C of dryings about 603g.
Oil phase is reddish brown, has transparent feel, and acid number is 45.5mgKOH/g, SO
4 2-be 1.4%, sulfur content is 1.25%, meet national standard fuel heavy oil sulfur content lower than 3% requirement.Therefore, the oil phase component after separation can be used as fuel heavy oil or mould oil, refining through bleaching earth adsorption, be in harmonious proportion after, also can obtain lube base oil, oil antirust agent or drilling well seizureproof agent.
Aqueous phase is taupe, has suspension, detects macroelement Ca, Na, Si, SO
4 2-, CO
3 2-deng, and contain the Pb of Zn, 2.6ppm of Fe, 1.5ppm of 25.6ppm, do not detect the heavy metal ion such as Ni, Cd, Cu, Hg, Ag, Cr.Aqueous phase returns Desulphurization slurrying and recycles, and eliminates secondary pollution.
Analyzed by X-ray diffraction, solid-phase component is with CaSO
42H
2o is main, and content is 82.6%, and asphalt colloid class organic matter is auxiliary, and content is 10.2%, and containing CaSO
31/2H
2o, 2.2%, f-CaO, 0.3%, Ca (OH)
2, 0, CaCO
30.2%, the gross mass percentage of rear four kinds of materials, be reduced under 3.0% from initial 72.9%, this illustrates, acid sludge is after neutralization, " Desulphurization " that be converted into dihydrate gypsum with the overwhelming majority forms proterties and stablizes, is convenient to the pitch calcium slag that utilizes, because wherein containing thermal source and calcium source, the auxiliary material of cement rotary kiln can be used as, also can be used as building materials raw material (it is high for replacing natural), asphalt material (road asphalt, building asphalt, activation pitch) or soil conditioner.
Experimentally resulting estimate, 1 ton of acid sludge, 2.5 tons of Desulphurizations, after combining disposal, can obtain about 75 kilograms of fuel heavy oils and 3 tons of pitch calcium slags.By technology path of the present invention, not only achieve the harmlessness disposing of two kinds of harmful wastes, also for its recycling opens new approach, thus there is good economic benefit and environmental benefit.
Embodiment 2:
As shown in Figure 1, for a kind of lubricant oil regeneration acid sludge and dry method/semidry method desulphurization ash combine the method for disposal, comprise the following steps:
(1) Desulphurization and acid sludge
Desulphurization takes from rotating spraying semidry method coal fired power plant flue gas desulfurization system, and main component is: CaSO
4h
2o, 26.5%, CaSO
31/2H
2o, 32.6%, f-CaO, 10.3%, Ca (OH)
2, 8.8%, CaCO
3, 4.5%, the gross mass percentage of rear four kinds of materials is 56.2%.
Acid sludge is the acid slag that used oil adopts sulfuric acid-clay regeneration technique generation, and in black ointment shape, pH value <1, acid number is 1.142 gKOH/g, SO
4 2-be 60.4%, oil content 75.8mg/g, poor fluidity, toughness are large, and sulfur content is 30%, mainly becomes the mixture of remaining sulfuric acid, oils, colloid, asphalitine, aphthenic acids, sulfuric ester, macromolecule condensation product, heavy metal compound, salt.
Get acid sludge 200 g, Desulphurization 1000 g, for subsequent use.
(2) Desulphurization slurrying and mixed aeration: by Desulphurization slurrying, mass percent concentration is 30%, Desulphurization suspension (containing Desulphurization 1000g) after slurrying is mixed with 200g acid sludge, Desulphurization suspension slowly adds, controlling mixed serum pH value is 4.8-5.5, carry out aeration agitation 60min, acid sludge and Desulphurization are fully mixed, CaSO in air capacity and Desulphurization
3the mol ratio of content is close to 10:1.
(3) breakdown of emulsion: add the commercially available petroleum-type demulsifier (model OX-932) of 1% in the slurries of mixed aeration, belong to the nonionic organic surface active agent of hydroxyl, breakdown of emulsion whipping process continues 30min.
(4) neutralize: after breakdown of emulsion completes, in mixed serum, add the potassium hydroxide of 10%, regulate the pH value of mixed serum, to 6-9, leave standstill 30 min.
(5) be separated: adopt natural subsidence, time of repose is 60min, draws the material of different aspects respectively.Obtain oil phase (supernatant fluid) about 12.5 g (Oil recovery rate is 82.4%), aqueous phase (mid-water liquid) about 3200g, weigh after constant weight after solid phase (pitch calcium slag) 105 DEG C of dryings about 1080g.
Oil phase is reddish brown, has transparent feel, and acid number is 48.2mgKOH/g, SO
4 2-be 0.9%, sulfur content is 1.82%, meet national standard fuel heavy oil sulfur content lower than 3% requirement.Therefore, the oil phase component after separation can be used as fuel heavy oil or mould oil, refining through bleaching earth adsorption, be in harmonious proportion after, also can obtain lube base oil, oil antirust agent or drilling well seizureproof agent.
Aqueous phase is taupe, has suspension, detects macroelement Ca, Na, Si, SO
4 2-, CO
3 2-deng, and Fe, the Zn of 2.5 ppm, the Pb of 3.6 ppm containing 10 ppm, do not detect the heavy metal ion such as Ni, Cd, Cu, Hg, Ag, Cr.Aqueous phase returns Desulphurization slurrying and recycles, and eliminates secondary pollution.
Analyzed by X-ray diffraction, solid-phase component is with CaSO
42H
2o is main, and content is 82.4%, and asphalt colloid class organic matter is auxiliary, and content is 8.1%, and containing CaSO
31/2H
2o, 1.8%, f-CaO, 0.8%, Ca (OH)
2, 0, CaCO
30.1%, the gross mass percentage of rear four kinds of materials, be reduced under 3.0% from initial 56.2%, this illustrates, acid sludge is after neutralization, " Desulphurization " that be converted into dihydrate gypsum with the overwhelming majority forms proterties and stablizes, is convenient to the pitch calcium slag that utilizes, because wherein containing thermal source and calcium source, the auxiliary material of cement rotary kiln can be used as, also can be used as building materials raw material (it is high for replacing natural), asphalt material (road asphalt, building asphalt, activation pitch) or soil conditioner.
Experimentally resulting estimate, 1 ton of acid sludge, 5 tons of Desulphurizations, after combining disposal, can obtain about 62.5 kilograms of fuel heavy oils and 5.5 tons of pitch calcium slags.By technology path of the present invention, not only achieve the harmlessness disposing of two kinds of harmful wastes, also for its recycling opens new approach, thus there is good economic benefit and environmental benefit.
Embodiment 3:
As shown in Figure 1, for a kind of lubricant oil regeneration acid sludge and dry method/semidry method desulphurization ash combine the method for disposal, comprise the following steps:
(1) Desulphurization and acid sludge
Desulphurization is taken from gas suspension and is absorbed dry method coal fired power plant flue gas desulfurization device, and main component is: CaSO
4h
2o, 15.8%, CaSO
31/2H
2o, 38.9%, f-CaO, 10.5%, Ca (OH)
2, 8.6%, CaCO
3, 4.3%, the gross mass percentage of rear four kinds of materials is 62.3%.
Acid sludge is the acid slag that waste oil mud adopts sulfuric acid-clay regeneration technique generation, and in black ointment shape, pH value <1, acid number is 2.15gKOH/g, SO
4 2-be 44.8%, oil content 65.4mg/g, poor fluidity, toughness are large, and sulfur content is 5%, mainly becomes the mixture of remaining sulfuric acid, oils, colloid, asphalitine, aphthenic acids, sulfuric ester, macromolecule condensation product, heavy metal compound, salt.
Get acid sludge 200 g, Desulphurization 100 g, for subsequent use.
(2) Desulphurization slurrying and mixed aeration: by Desulphurization slurrying, mass percent concentration is 5%, Desulphurization suspension (containing Desulphurization 100g) after slurrying is mixed with 200g acid sludge, Desulphurization suspension slowly adds, controlling mixed serum pH value is 4.5-5.5, carry out aeration agitation 30min, acid sludge and Desulphurization are fully mixed, CaSO in air capacity and Desulphurization
3the mol ratio of content is close to 4:1.
(3) breakdown of emulsion: add the commercially available petroleum-type demulsifier (model OX-932) of 0.1% in the slurries of mixed aeration, belong to the nonionic organic surface active agent of hydroxyl, breakdown of emulsion whipping process continues 10min.
(4) neutralize: after breakdown of emulsion completes, in mixed serum, add the NaOH of 10%, regulate the pH value of mixed serum, to 6-9, leave standstill 20 min.
(5) be separated: adopt natural subsidence, time of repose is 30min, draws the material of different aspects respectively.Obtain oil phase (supernatant fluid) about 10 g (Oil recovery rate is 76.4%), aqueous phase (mid-water liquid) about 2000 g, weigh after constant weight after solid phase (pitch calcium slag) 105 DEG C of dryings about 160g.
Oil phase is reddish brown, has transparent feel, and acid number is 38.2 mgKOH/g, SO
4 2-be 2.5%, sulfur content is 2.2%, meet national standard fuel heavy oil sulfur content lower than 3% requirement.Therefore, the oil phase component after separation can be used as fuel heavy oil or mould oil, refining through bleaching earth adsorption, be in harmonious proportion after, also can obtain lube base oil, oil antirust agent or drilling well seizureproof agent.
Aqueous phase is taupe, has suspension, detects macroelement Ca, Na, Si, SO
4 2-, CO
3 2-deng, and contain the Pb of Zn, 1.6ppm of Fe, 9.2ppm of 28.5 ppm, do not detect the heavy metal ion such as Ni, Cd, Cu, Hg, Ag, Cr.Aqueous phase returns Desulphurization slurrying and recycles, and eliminates secondary pollution.
Analyzed by X-ray diffraction, solid-phase component is with CaSO
42H
2o is main, and content is 78.8%, and asphalt colloid class organic matter is auxiliary, and content is 12.1%, and containing CaSO
31/2H
2o, 1.2%, f-CaO, 0.5%, Ca (OH)
2, 0, CaCO
30.2%, the gross mass percentage of rear four kinds of materials, be reduced under 3.0% from initial 62.3%, this illustrates, acid sludge is after neutralization, " Desulphurization " that be converted into dihydrate gypsum with the overwhelming majority forms proterties and stablizes, is convenient to the pitch calcium slag that utilizes, because wherein containing thermal source and calcium source, the auxiliary material of cement rotary kiln can be used as, also can be used as building materials raw material (it is high for replacing natural), asphalt material (road asphalt, building asphalt, activation pitch) or soil conditioner.
Experimentally resulting estimate, 2 tons of acid sludges, 1 ton of Desulphurization, after combining disposal, can obtain about double centner fuel heavy oil and 1.6 tons of pitch calcium slags.By technology path of the present invention, not only achieve the harmlessness disposing of two kinds of harmful wastes, also for its recycling opens new approach, thus there is good economic benefit and environmental benefit.
Claims (10)
1. acid sludge and a Desulphurization associating method of disposal, is characterized in that: comprise the following steps:
After Desulphurization slurrying, with acid sludge mixed aeration, through breakdown of emulsion, neutralization, be separated, oil phase is as fuel utilization, and aqueous phase returns Desulphurization pulping system and recycles, and solid phase utilizes as building materials;
Described Desulphurization slurrying, Desulphurization slurrying mass percent concentration is: 5%-30%;
Described mixed aeration, the acid sludge of mixed process, water, Desulphurization ratio are: 1: 5-20: 0.5-5, and controlling reaction tank plasm PH value is 4.0-5.5; Gas is compressed air, CaSO in air capacity and Desulphurization
3content is linearly correlated with, and both mol ratios are 4-10:1, and aeration time is 5-60 min;
Described breakdown of emulsion, demulsifier is commercially available petroleum-type demulsifier, and the interpolation mass percent of demulsifier is the 0.1-1% of mixed serum, and breakdown of emulsion process continues 10-60 min under agitation;
Described neutralization, nertralizer alkali lye is the one of NaOH, calcium hydroxide, potassium hydroxide, and concentration of lye is 10-30%, and after neutralization, the pH value of mixed serum is 6-9;
Describedly to be separated, to refer to that the mixed liquor after by neutralization carries out " Gu-water-oil " three phase separation.
2. acid sludge according to claim 1 and Desulphurization associating method of disposal, it is characterized in that: described Desulphurization comes from one or more accessory substances in recirculating fluidized bed, rotating spraying, gas suspension absorption, the activation of flue dry sorbent injection, in-furnace calcium spraying calcium oxide, novel all-in-one and lime stone gas cleaning dry method/semi-dry method flue gas desulfurization technique, CaSO in described Desulphurization
31/2H
2o, CaCO
3, f-CaO and Ca (OH)
2the gross mass mark of four kinds of materials is 50-95%.
3. acid sludge according to claim 1 and Desulphurization associating method of disposal, it is characterized in that: described acid sludge is the acid slag that the oily waste of waste lubricating oil, used oil, waste oil mud, petroleum distillate and intermediate product adopts regeneration of sulfuric acid technique to produce, for black paste, acidity is high, toughness is large, wherein sulfur content is 5%-30%, and all the other are the mixture of oils, colloid, asphalitine, heavy aromatics, mahogany acid, aphthenic acids, sulfuric ester, macromolecule condensation product, heavy metal compound, salt.
4. acid sludge according to claim 1 and Desulphurization associating method of disposal, is characterized in that: described Desulphurization slurrying mass percent concentration is 10-15%.
5. acid sludge according to claim 1 and Desulphurization associating method of disposal, is characterized in that: it is 4.5-5.2 that the mixed process of described mixed aeration controls reaction tank plasm PH value.
6. acid sludge according to claim 1 and Desulphurization associating method of disposal, is characterized in that: CaSO in the air capacity of described mixed aeration and Desulphurization
3the mol ratio of content is 6:1.
7. acid sludge according to claim 1 and Desulphurization associating method of disposal, it is characterized in that: described demulsifier is hydroxyl or the nonionic organic surface active agent containing alkyl, comprises the multiple organic compound of expoxy propane one polyacid polymer, alkyd resins, nitrobenzene compound, hydramine, hydroxylamine derivative and ethers.
8. acid sludge according to claim 1 and Desulphurization associating method of disposal, is characterized in that: described phase disengagement method comprises natural subsidence, heating sedimentation, centrifugation, one in " filtration+separatory " and joint operation thereof.
9. acid sludge according to claim 8 and Desulphurization associating method of disposal, it is characterized in that: described natural subsidence, time of repose is 30-60 min, adopts multiple settling tank, rotation settling operation, namely after the sedimentation of a period of time leaves standstill, the material extracting different aspects utilizes respectively, and wherein, the oil phase of supernatant fluid utilizes as oil plant, the aqueous phase of mid-water liquid returns Desulphurization pulping system, and the solid phase of pitch calcium slag carries out recycling as building materials.
10. acid sludge according to claim 8 and Desulphurization associating method of disposal, is characterized in that: described " filtration+separatory " mode, first by filter element, first the solid phase of pitch calcium slag separated, then adopt the form of separatory funnel to be separated oil phase and aqueous phase.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109593543A (en) * | 2018-12-28 | 2019-04-09 | 新疆天蓝水清环境服务有限公司 | A kind of comprehensive processing technique of refining slag |
| CN110860197A (en) * | 2019-10-23 | 2020-03-06 | 航天环境工程有限公司 | Desulfurization, dedusting and purification system and method for flue gas generated after combustion of oil-containing fuel and application |
| CN111252774A (en) * | 2020-01-19 | 2020-06-09 | 刘文治 | Method for producing silica sol by using desulfurized gypsum and fly ash through treating waste with waste |
| CN114105343A (en) * | 2020-08-26 | 2022-03-01 | 宝山钢铁股份有限公司 | Method for cooperatively treating desulfurization ash by desulfurization wastewater treatment system and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4261812A (en) * | 1980-01-17 | 1981-04-14 | Cities Service Company | Emulsion breaking process |
| US5759409A (en) * | 1994-05-30 | 1998-06-02 | Basf Aktiengesellschaft | Separation of water from crude oil and oil demulsifiers used for this purpose |
| CN1607044A (en) * | 2003-10-16 | 2005-04-20 | 石鸿颖 | Acid sludge handling method |
| CN101323458A (en) * | 2008-06-03 | 2008-12-17 | 南京师范大学 | Method for comprehensively processing petroleum acid slag and alkaline residue |
| CN102140252A (en) * | 2010-02-02 | 2011-08-03 | 新疆金源石油化工有限公司 | Process for preparing cationic emulsified asphalt by petroleum sulfonate acid residue |
| CN102295982A (en) * | 2011-08-03 | 2011-12-28 | 江苏雕皇集团有限公司 | Refining and regenerating method of black-brown used lubricating oil |
-
2013
- 2013-08-28 CN CN201310380609.1A patent/CN104415963A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4261812A (en) * | 1980-01-17 | 1981-04-14 | Cities Service Company | Emulsion breaking process |
| US5759409A (en) * | 1994-05-30 | 1998-06-02 | Basf Aktiengesellschaft | Separation of water from crude oil and oil demulsifiers used for this purpose |
| CN1607044A (en) * | 2003-10-16 | 2005-04-20 | 石鸿颖 | Acid sludge handling method |
| CN101323458A (en) * | 2008-06-03 | 2008-12-17 | 南京师范大学 | Method for comprehensively processing petroleum acid slag and alkaline residue |
| CN102140252A (en) * | 2010-02-02 | 2011-08-03 | 新疆金源石油化工有限公司 | Process for preparing cationic emulsified asphalt by petroleum sulfonate acid residue |
| CN102295982A (en) * | 2011-08-03 | 2011-12-28 | 江苏雕皇集团有限公司 | Refining and regenerating method of black-brown used lubricating oil |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109593543A (en) * | 2018-12-28 | 2019-04-09 | 新疆天蓝水清环境服务有限公司 | A kind of comprehensive processing technique of refining slag |
| CN110860197A (en) * | 2019-10-23 | 2020-03-06 | 航天环境工程有限公司 | Desulfurization, dedusting and purification system and method for flue gas generated after combustion of oil-containing fuel and application |
| CN111252774A (en) * | 2020-01-19 | 2020-06-09 | 刘文治 | Method for producing silica sol by using desulfurized gypsum and fly ash through treating waste with waste |
| CN114105343A (en) * | 2020-08-26 | 2022-03-01 | 宝山钢铁股份有限公司 | Method for cooperatively treating desulfurization ash by desulfurization wastewater treatment system and application |
| CN114105343B (en) * | 2020-08-26 | 2023-06-13 | 宝山钢铁股份有限公司 | Method for cooperatively treating desulfurization ash by desulfurization wastewater treatment system and application |
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