CN101274131A - Comprehensive utilization technique of acid residuals of petroleum - Google Patents
Comprehensive utilization technique of acid residuals of petroleum Download PDFInfo
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- CN101274131A CN101274131A CNA2007100388125A CN200710038812A CN101274131A CN 101274131 A CN101274131 A CN 101274131A CN A2007100388125 A CNA2007100388125 A CN A2007100388125A CN 200710038812 A CN200710038812 A CN 200710038812A CN 101274131 A CN101274131 A CN 101274131A
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Abstract
The invention provides a technique for disposing petroleum acid sludge, which is characterized in that the technique comprises the steps as follows: step 1. water is pre-mixed with the acid sludge, mixed and crushed so as to lead the granularity of the mixture of water and acid sludge to achieve 1-50 Mum, and water-solubility acid in the acid sludge is dissolved in water phase, thus obtaining sour water and acid oil residue with pH value of 2-6; step 2. alkali is used for neutralizing the extracted acid oil residue with the pH value of 2-6, thus obtaining neutral oil residue or acid sludge with the pH value of 7-8. The process for disposing the acid sludge can reduce the cost of acid-removal, improve the acid-removal efficiency and improve the quality of recovered oil sludge.
Description
Technical field
The pollutant that the present invention relates in the petrochemical industry is handled and comprehensive utilization of resources, relates in particular to the recycling of the valuable organic matter in the acid residuals of petroleum.
Background technology
Acid residuals of petroleum (hereinafter to be referred as acid sludge) is that the petroleum distillate of oil plant adds the acid slag that produce man-hour in pickling, also produces acid slag with sulfuric acid treatment when used oil, waste lubricating oil recovery, and the general designation acid sludge is the pollutant of a class intractable.Wherein contain a large amount of sulfuric acid and harmful material,, can cause severe contamination environment if can not effectively handle.Simultaneously, acid sludge also is a resource, and hydrocarbon wherein and sulfuric acid can fully utilize, and produces value product.
Owing to use the technology of concentrated sulfuric acid acid treatment petroleum distillate and used oil simple, cost is low, at present, the acid-treated method of many employings when the middle-size and small-size oil refining enterprise of China, OIL IN LUBRICATING OIL PRODUCTION enterprise are produced lubricating oil with other relevant oil products is to remove harmful substance and colloid, asphalitines etc. such as wherein sulfur-bearing, nitrogen-containing compound.Acid-treated basic skills is that a certain amount of concentrated sulfuric acid (general concentration is 98% or 95%) is joined in petroleum distillate or the waste lubricating oil, and mixing and stirring at a certain temperature, after placing the regular hour, acid sludge and oil content layer that reaction generates, acid sludge is deposited in lower floor, with oil with obtain edible vegetable oil and acid sludge after acid sludge separates.In the acid sludge except also having colloid, asphalitine, heavy aromatics, mahogany acid, aphthenic acids, sulfuric ester, high condensation product, heavy metal compound outside the sulfuric acid (can reach 10%～60% of acid sludge quality) and being mixed in part light oil in the acid sludge usually 30%～50%.
The means of early time treatment acid sludge are to abandon and landfill.Because acid sludge can not be degraded by microorganisms, in the face of land and soil, vegetation goes to pot nuisance with long-term existence, the soil desertification, and sour water also can polluted underground water to underground infiltration.Acid sludge is poured rivers,lakes and seas into also can the severe contamination waters.Along with the reinforcement of environmental protection dynamics, will not allow to handle in this way again acid sludge both at home and abroad.
Reclaiming and utilize in the acid sludge technology of utility a lot, mainly is residual oil, sulfuric acid and sulfonic acid, the aphthenic acids of recycling wherein etc.The method of the open 03135906.X of Chinese patent 97103241.6 and Chinese patent is directly to add in the alkali and remove acid in the acid sludge, after the salt solution that neutralization reaction is produced is told, and the organic adjustable made fuel oil that obtains.Because contain a large amount of acid in the acid sludge, these acid that neutralize will consume a large amount of alkali, be NaOH or sodium carbonate price all than higher, the cost that acid sludge is handled is excessive.Chinese patent 98104751.3 and Chinese patent disclose 200510037245.2, the 200510037244.8 acid sludge treatment technologies that provide, be use lime directly in and the acid in the acid sludge.Though lime is cheap,, a large amount of calcium sulphate solid particles that reaction generates mix with the residual oil that obtains, and can't separate, and have a strong impact on the quality of fuel oil.The method of Chinese patent 03113311.8 be directly use in the water-soluble alkali and acid sludge in acid, do not separate the salt that neutralization reaction generates, directly the heating evaporation dehydration obtains fuel oil or pitch.Shortcoming is to have considerable sulfate to stay in the fuel oil, influences the quality of fuel oil.Same neutralizing acid will consume a large amount of alkali, has improved processing cost.
United States Patent (USP) 5,288,392,5,470,455 and 5,573,656 propose, in acid sludge, add pH and change agent (being actually water, liquid base or solid base), between pH value to 3～7 of rising acid sludge, oil obtains the intermediate state dregs of fat (the acid dregs of fat) afterwards with aqueous phase separation, is used for producing maltha, pitch or modified pitch, emulsified asphalt etc.According to these several patented technologies, if water changes agent as pH, produce pH at 3～7 the intermediate state dregs of fat, must use in a large number that the water of (5～10 times) repeatedly washs, this is uneconomic.In fact only wash with water and can not get the intermediate state dregs of fat that pH equals 7.More disadvantageously pH is acid at 3～7 the intermediate state dregs of fat, further can produce sour gas in the high temperature process afterwards, and not only the smell is awful, and contaminated environment, and giving further, processing makes troubles.
If directly handle acid sludge with water miscible alkali (mostly being the monovalence metal base), make its pH be raised to 3～7, then neutralization reaction is understood the more alkali of consumption rate, and the price height of these alkali has improved processing cost.If with solid lime treatment acid sludge, during its pH to 3 that raises～7 scopes, a large amount of calcium sulphate solid that is not dissolved in water of generation will be stayed in the dregs of fat, can't remove the asphalt quality of producing after this can have a strong impact on.Equally,, also can produce sour gas in the processing afterwards, make troubles to production technology with the incomplete acid slag of pH3～7 scopes of obtaining of neutralization of alkali.
In patented technology cited above, all do not provide the concrete process conditions of water or alkali treatment acid sludge.In fact, hybrid technique is very crucial in acid sludge is handled, and mixing uniformly fully can improve deacidification efficient greatly and reduce processing cost.Therefore mixing condition, mixing apparatus etc. directly influence efficient and the cost that acid sludge is handled in the hybrid technique.
Summary of the invention
The purpose of this invention is to provide a kind of washing and in and two-step method acid residuals of petroleum deacidification new technology, to reduce the deacidification cost, improve deacidification efficient and improve the quality that reclaims the dregs of fat.
Another object of the present invention provides a kind of effective utilization of acid sludge deacidification accessory substance sulfate and the method that waste water recycles.
The invention provides a kind of technology or method of handling acid residuals of petroleum, this technology or method may further comprise the steps:
The first step with water and acid sludge premixed, is mixed pulverizing then, make the granularity of water and acid sludge mixture reach 1-50 μ m, and make the water soluble acid in the acid sludge be soluble in the aqueous phase, thereby separation obtains acid water and pH is the acid dregs of fat of 2-6;
Second the step, with in the alkali with described extraction after pH be the acid dregs of fat of 2-6, thereby obtain the neutral dregs of fat or the residual oil of pH in 7～8 scopes.
In another preference, described technology also comprises step: the neutral dregs of fat that will obtain or residual oil are as feedstock production pitch or fuel oil.
In another preference, described acid residuals of petroleum comprises: lubricating oil acid sludge, diesel oil acid sludge or its combination.
In another preference, in the first step, described premixed is to use blender to mix continuously.
In another preference, premixed is used and is comprised static mixer, Venturi tube, and other equipment that maybe can mix continuously mix continuously.
In another preference, under heating condition, carry out described premixed.
In another preference, be heated to and carry out described premixed under 50-100 ℃ the condition and exist.
In another preference, use the blending tank that mechanical agitation and heater are housed to carry out premixed.
In another preference, in the first step, it is to carry out in the equipment of acid corrosion-resistant that described mixing is pulverized.
In another preference, the equipment that uses during described powerful mixing is pulverized is that equipment such as high shear mixing pulverizer with stator and rotor mechanism, colloid mill and other can make acid sludge be ground into the equipment of micron particles, and can reach acid sludge and fully mixes the equipment that contacts closely at a certain temperature with water.
In another preference, in the first step, the volume ratio of water and acid sludge is between 1: 1～4: 1.
In another preference, described water is fresh water or the very low salt solution of salt content, can also be weakly acidic water or the weakly alkaline water of pH in 5～9 scopes.
In another preference, when water and acid sludge premix, the temperature of described acid sludge is between 70～110 ℃, and/or the temperature of described water is between 60～100 ℃.
In another preference, the temperature of described acid sludge is between 80～110 ℃, and/or the temperature of described water is between 70～100 ℃.
In another preference, in second step, used alkali comprises the alkali of alkali metal base and/or alkaline-earth metal; And/or, also add demulsifier in second step.
In another preference, described alkali comprises saturated limewater, milk of lime.
In another preference, described alkali comprises solid bases such as lime (quick lime or white lime or milk of lime), agstone, dolomite dust, useless carbide slag.
In another preference, described alkali is the aqueous solution form of alkali.
In another preference, described demulsifier is selected from commercially available crude oil demulsifier or other can make water-in-oil type emulsion reach the demulsifier of water-oil separating.
In another preference, described technology also comprises the acid water that will obtain in the first step, neutralizes pH in 6～8 steps with alkali.
In another preference, the described alkali that is used to handle acid water is selected from calcium hydroxide, calcium oxide, calcium carbonate or its combination, and comprises reclaiming and generate calcium sulfate (for example, can be used as construction material).
In another preference, the described alkali that is used to handle acid water is selected from NaOH, sodium carbonate or its combination, and comprises reclaiming and generate sodium sulphate (for example, can be used as the raw material of producing saltcake).
In another preference, described technology also comprises step, absorbs with alkali lye handling the sour gas that produces in the acid sludge.
In another preference, used alkali lye is saturated limewater or milk of lime, also can be the aqueous solution of alkali metal base.
Description of drawings
Fig. 1 is technological process of the present invention.
Symbol description:
1: the acid sludge heating tank
2: the acid gas absorption tower
3: premixed equipment
4: hot-tub
5: the high shear mixing disintegrating apparatus
6: the mixture subsider
7: the sour water neutralization pond
8: the gypsum storage tank
9: acid dregs of fat neutralization chamber
10: lye tank (vat)
11: dregs of fat thermal dehydration groove
12: product dregs of fat storage tank
The specific embodiment
The inventor is through extensive and deep research, be surprised to find that, by water and the merging of acid sludge premix are broken to the degree that particle diameter reaches 1-50 μ m with the acid sludge mixed powder, can only use under the situation of water gaging seldom, just make the acid in the acid sludge remove very effectively, and obtain the neutral dregs of fat or the residual oil of pH in 7～8 scopes through neutralisation treatment by being soluble in the aqueous phase.This method step is simple effectively, help environmental protection (for example saving a large amount of water).
Particularly, the main points of acid sludge processing of the present invention and comprehensive utilization of resources new technology are as follows:
The first step of two-step method deacidification is that the powerful mixing of carrying out water and acid sludge premixed and pre-composition is earlier pulverized, and extracts water soluble acid.In certain temperature range, after acid sludge and water carried out premixed by premixing device, re-using acid sludge and the water of powerful mixing disintegrating apparatus such as high shear after with premix carries out powerful mixing and pulverizes, the fine particle of acid sludge is fully contacted with water, extract the water soluble acid (mainly being sulfuric acid) in the acid sludge, the pH value of acid sludge is elevated to more than 2 or 2 (2-6), obtains containing the acid dregs of fat of low amounts of water behind the discharge acid water.The acidity of the acid dregs of fat is mainly derived from remaining minute quantity water soluble acid and oil-soluble acid, i.e. mahogany acid and aphthenic acids.
Second step of two-step method is the acid dregs of fat of neutralization.The aqueous acidic dregs of fat that obtain after the extraction with water miscible alkali or the non-water-soluble alkali neutrality that neutralizes, make pH reach 7～8 scopes again, and heating is sloughed after the water, obtains the neutral dregs of fat.The neutral dregs of fat can not produce sour gas in the high temperature process process afterwards as the raw material of modulation fuel oil or preparing product pitch, have avoided environmental pollution.
The acid water that forms during water extraction acid sludge obtains calcium sulfate (gypsum) with the lime neutrality that neutralizes, by precipitation or filter back and moisture from, gypsum can be used as construction material and uses, neutral water can recycling be handled acid sludge.In and acid water can also select the alkali of other kinds for use, to reduce processing cost and convenient post-treatment, not produce that to pollute be principle.
The sour gas that produces in the acid sludge processing procedure can absorb fully with buck, does not have environmental pollution.
This shows that the present invention has following outstanding advantage: the water high efficiency extracts a large amount of water soluble acids in the acid sludge, has reduced processing cost.Water-insoluble acid in the acid dregs of fat is neutralized by alkali again, generates petroleum sulfonate and naphthenate, has improved the quality of the dregs of fat or material asphalt.The sour water that extraction produces neutralizes with lime, and the gypsum of generation is a construction material, does not have waste sludge discharge.Neutral water can also be used for handling acid sludge again, does not have discharge of wastewater.The sour gas that produces during the heating acid sludge can absorb with alkali, does not have toxic emission.So the present invention does not have three waste discharge can all reclaim the method for the low-cost processes acid sludge of useful resources again.
Said acid sludge mainly is the acid sludge that produces when handling base oil with the concentrated sulfuric acid in the OIL IN LUBRICATING OIL PRODUCTION process among the present invention, the acid sludge that produces in acid sludge that produces when also comprising sulfuric acid treatment diesel oil and the used oil recovered acid processing procedure.The characteristics of these acid sludges are at room temperature to be solid or semi-solid state, do not have flowability, even in the time of 90～100 ℃, the viscosity of its fluid is also very high.Wherein the content of acid (mainly being sulfuric acid) can account for 10%～60% of acid sludge quality, usually between 30%～50%.PH is between 0.2～1.0, and acidity is very strong, and very strong corrosivity is arranged.Content of organics in the acid sludge is between 40%～90%, and is most between 50%～70%.These organic matters comprise petroleum distillate, condensed-nuclei aromatics, high condensation product, sulfuric ester, mahogany acid, aphthenic acids, colloid, asphalitine, contain oxygen, sulfur-bearing, nitrogen-containing compound and heavy metal compound etc., and composition is very complicated.
The present invention removes the method for water soluble acid in the acid sludge (mainly being sulfuric acid), mainly is to adopt premixing device and powerful mixing disintegrating apparatus acid sludge and water to be carried out the extraction process of powerful mixing.
Under normal conditions, water is mixed with acid residuals of petroleum, rigidly connect at acid sludge and water touch, after the sulfuric acid in the acid sludge interface enters water, the organic matter layer that loses on the acid sludge interface of sulfuric acid hardens at once, form duricrust, the sulfuric acid that is not extracted is wrapped in organic facies inside, itself and water are separated.Because the affinity of organic matter layer and water is not strong, sulfuric acid and other water-soluble substanceses of wrapping in the organic layer inside of sclerosis are difficult to enter water again.So, acid sludge is fully mixed with water, fully removes sulfuric acid and be not easy.In the patented technology of quoting as proof, all do not provide the specific descriptions of acid sludge and water hybrid technique in the above, just point out prevailingly to make the two mixing, how undesirable actual effect is.With common churned mechanically method acid sludge is mixed with water, because impulsive force, shearing force are not enough, acid sludge can not be torn into small fragment by impact, contact insufficient with water, extraction efficiency is not high, and is consuming time very long, needs repeatedly hybrid extraction just can make the pH of acid sludge reach needed scope.For example, United States Patent (USP) 5,573,656 just propose acid sludge and water are joined in the blending tank, with the mechanical agitation method water are mixed with acid sludge, and water consumption big (being generally 5～10 times) need repeat repeatedly, just can make the pH of acid sludge reach 3～7 scopes.Use additive method such as cylinder to grind, add continuously water, continuous the drain method washing acid sludge of superfluous water though this patent also discloses, clean result is not described, according to its simple introduction, operation sequence is cumbersome.
Technological process of the present invention is referring to Fig. 1.In the methods of the invention, adopt basically washing and in and two-step method remove acid in the acid sludge.
The first step is to adopt premixed and powerful mixing disintegrating apparatus, realizes that the abundant mixing of water and acid sludge is pulverized, and removes the water soluble acid in the acid sludge substantially, mainly is sulfuric acid.Second step was to remove the acid dregs of fat that water soluble acid obtains later on the alkali neutralization, removes remaining water soluble acid and transforms oil-soluble acid, and be acylate as mahogany acid and aphthenic acids.
The method that adopts the premix powerful mixing to pulverize has overcome the shortcoming of common simple mechanical stirring means, the acid sludge of sclerosis can be ground into small particle, granularity can reach micron order (for example 1-50 micron), increase the surface area that acid sludge contacts with water greatly, guarantee that the water soluble acids such as sulfuric acid in the acid sludge fully contact with water, acid removes thoroughly.
Specifically, premixed that the present invention adopts and powerful mixing breaking method are earlier acid sludge and water to be carried out premixed in premixing device, adopt the high shear mixing disintegrating apparatus to carry out powerful mixing again and pulverize.Earlier acid sludge is heated to suitable temperature exactly, have certain fluidity after, with pump itself and water are sent in the premixing device simultaneously in definite ratio again, for example in the static mixer.Because the special construction of static mixer, make acid sludge and water in static mixer, form mixture relatively uniformly, to leave the acid sludge behind the static mixer and the mixture of water again sends in the high shear mixing pulverizer, make acid sludge wherein be ground into ultra-fine grain, particle diameter reaches micron order, increased the contact area of acid sludge and water greatly, made the water soluble acid in the acid sludge be easy to be extracted to aqueous phase.In the high shear mixing pulverizer, the ultra-fine grain of acid sludge is constantly broken again, constantly forms new interface and contacts with water, thereby improved extraction efficiency.
After mixture leaves High shear device, be admitted in the subsider (jar), in certain temperature range, leave standstill, layering, separation.
The volume ratio of water and acid sludge was controlled at 1: 1～4: 1 during premix, usually 2: 1～3: 1 scopes.The temperature of acid sludge is preferably in 95～105 ℃ of scopes 80～110 ℃ of scopes.The temperature of water is controlled at 70～100 ℃ of scopes, is preferably in 90～100 ℃ of scopes.
The premixed equipment that the present invention adopts can be static mixer, also can be to realize water and more mixed uniformly other equipment of acid sludge, as Venturi tube.Even still can adopt the blending tank that mechanical agitator is housed.But be more prone to adopt static mixer or Venturi tube, because can work continuously.Consider the severe corrosive of acid sludge, premixed equipment is wanted acid corrosion-resistant.
Being not particularly limited for pulverizing or abrasive method among the present invention, can be existing extra-fine grinding in this area or breaking method, as long as it can make the particle diameter of acid sludge and water reach required size.
Can be used for mixing disintegrating apparatus of the present invention and be not particularly limited, can adopt the existing mixing disintegrating apparatus in this area.Usually, described powerful mixing disintegrating apparatus can be the high shear mixing pulverizer with stator, rotor structure.The high shear mixing pulverizer can be single group stator and rotor sructure, can also have one group of above stator and rotor sructure.Powerful mixing disintegrating apparatus of the present invention can also be that colloid mill can be realized the equipment of powerful mixing pulverizing purpose with other.Equally, consider the severe corrosive of acid sludge, the high shear mixing disintegrating apparatus preferably can acid corrosion-resistant (for example inner bag adopts acidproof stainless steel material).Representational example includes, but are not limited to: Chinese patent application number: equipment such as disclosed rotary pulsive superfine powder mixing grinder in 01109394.3.
Adopting another advantage of powerful mixing equipment such as premixed equipment and high shear mixing pulverizer is the production efficiency height, because be that big flow is worked continuously, the time that material stops in mixing apparatus is very short, only be the several seconds to tens seconds, enter subsider (jar) after promptly leaving mixing apparatus.
In the present invention, acid sludge and water are joined according to a certain percentage mix in the disintegrating apparatus usually and mix extra-fine grinding, thereby make the grain diameter of mixture reach required size.
In most cases the volume mixture ratio of water and acid sludge is when 2: 1 to 3: 1 scopes, and 1 extraction can make the pH of the dregs of fat reach more than 2 or 2, and when very high or acid content was very high when the viscosity of acid sludge, re-extract also can make for 1 time the pH of the dregs of fat reach more than 2 or 2.
Used water in the extraction process of the present invention is fresh water, or the very low light salt brine of salt content, also can be that pH is at 5～9 faintly acid, weakly alkaline water, only otherwise influencing the acid sludge effect of extracting gets final product.
The dregs of fat after the water extraction and the mixture of acid water make the dregs of fat and acid water layering through leaving standstill in subsider.Time of repose was at 30 minutes to 2 hours, and this depends on the density and the viscosity of the dregs of fat.
In order to help water-oil separating, the temperature that keep mixture generally 70～100 ℃ of scopes, is preferably in 90～100 ℃ of scopes in suitable scope.Because the kind of acid sludge is different with the dregs of fat density of generation, after the profit layering, water is on the upper strata sometimes, and oil is in lower floor; Sometimes oil is on the upper strata, and water is in lower floor.But as a rule, the interface of profit layering is clear.Profit is separated, can moisture be gone out, also can water be got subsider with pump with the method for toppling over.
Subsider of the present invention can be a jar, also can be the groove that lid is arranged.Be equipped with heater and other annexes, carry and gas liquid discharge pipe line, temperature survey and liquid meter etc. as liquid.Acid corrosion also will be prevented in the inside of subsider.
Second step of depickling is to obtain the acid dregs of fat neutrality that neutralizes after the water extraction.The acid dregs of fat that neutralize use milk of lime or do not contain the saturated limewater of calcium hydroxide solid particle, and reaction temperature is controlled between 85 ℃～110 ℃, is preferably between 95 ℃～105 ℃, adopts mechanical stirring equipment to carry out.The addition of control saturated limewater or milk of lime, constantly the pH value of monitoring reaction mixture when pH reaches 7～8, stops to add alkali.Leave standstill, layering, the water of draining obtains containing the neutral dregs of fat of low amounts of water.
The acid dregs of fat that neutralize can also use water miscible alkali, as NaOH, sodium carbonate, sodium acid carbonate, potassium hydroxide etc.Usually, with in the water miscible alkali and the acid dregs of fat, the emulsifying mixture phenomenon can take place, must use an amount of demulsifier, can guarantee that just organic facies and water layering are clear, help water-oil separating.Demulsifier can be pre-mixed with alkali, adds again, also can add best and alkali premixed, better effects if after neutralization is finished again.The water of draining after the profit layering obtains containing the neutral dregs of fat of low amounts of water.Demulsifier described herein can be commercially available crude oil demulsifier, also can be other commercially available demulsifiers that can make the water-in-oil type emulsion breakdown of emulsion.
With depending on the requirement of product property and the control of production cost with the acid dregs of fat in the alkali of what type.
The neutral dregs of fat also will dewater.The neutral dregs of fat that obtain after the neutralization progressively are heated between 110～140 ℃ in drain sump, make the water evaporates that is present in the dregs of fat, obtain the substantially anhydrous dregs of fat.The dregs of fat that obtain thus can be used for modulating fuel oil or production maltha or further be processed into the modified pitch of oxidized asphalt and other kinds.
During the extraction of acid sludge water, form a large amount of acid water, mainly contain sulfuric acid.Sour water can be with lime pH6～8 scopes that neutralize.The calcium sulfate that neutralization generates can be used as construction material.In and the alkali of sour water can be quick lime, also can be white lime, also can be agstone, dolomite dust, can also be carbide slag etc.In a word, the oxide of divalent metal and hydroxide can use, and are advisable cheaply to be easy to get.
In and sour water also can use monoacidic base metal base such as NaOH, sodium carbonate, the sulfate of Sheng Chenging is water miscible like this, can sodium sulphate be separated with the method that is recrystallized, and obtains saltcake, saltcake is useful industrial chemicals.
In handling the acid sludge process, can produce a large amount of sour gas, especially the warm-up phase acid gas growing amount maximum before acid sludge is washed, this is that escaping gas mainly is the sulfur trioxide of sulfur dioxide and minute quantity because acid sludge sulfonic acid in heating process decomposes and concentrated sulfuric acid volatilization.Escaping gas is sent into by air-introduced machine in the device of Packed absorption tower or other types and is absorbed fully by buck.The alkali that absorbs sour gas can use limewash, also can use water miscible alkali, as NaOH, sodium carbonate etc.
In another preference, the subsider 6 among Fig. 1, neutralization chamber 9 and drench pit 11 can be same grooves, can save equipment like this, but can influence production efficiency.Be provided with respectively, can realize working continuously, enhance productivity.Subsider, neutralization chamber and drench pit can also adopt 2 covers mode in parallel, and blocked operation more can be enhanced productivity.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1
The used acid sludge of present embodiment is the lubricating oil acid sludge that lubricating oil enterprise forms during with the sulfuric acid treatment base oil, and pH is less than 1, and content of organics 71% is semi-solid state under the room temperature.
Referring to Fig. 1.In heating tank 1, the lubricating oil acid sludge is heated to about 100 ℃, the a large amount of sour gas that produce in the heating process are sent into the acid gas absorption tower 2 that filler is housed with air-introduced machine, simultaneously the saturated limewater in the lye tank (vat) 10 is sent into the acid gas absorption tower, from the cat head spray down, sour gas is absorbed fully, and the gas pH that discharges from the absorption tower is 7.
With acidproof screw pump the hot acid slag is sent in the premixed equipment SL type static mixer 3, flow-control is at 10 cubic metres/hour.With heat-exchanger pump 95 ℃ water is also sent in the same static mixer 3 with 30 cubic metres/hour flow in hot-tub 4 simultaneously, be in more uniform admixture by water behind the static mixer and acid sludge.The water and the acid sludge mixture that leave static mixer are admitted in the GZR type high shear mixing pulverizer 5 again.Before mixture enters the mixing pulverizer, start the pulverizer running earlier.Under the condition that powerful mixing is pulverized, the sulfuric acid in the acid sludge all enters aqueous phase basically, and the acid sludge that loses water soluble acid then changes into the dregs of fat that have certain acidity, and hardens.Raw material is sent into static mixer and high shear mixing pulverizer continuously, discharges from mixing disintegrating apparatus continuously, keeps and works continuously.Always having 2 cubic metres acid sludge and 6 cubic metres water mixes.Mixture is admitted in the subsider 6 after leaving High shear device.Keep the interior temperature of charge of settling tank about 95 ℃, static 60 minutes, demixing was clear, and acid water is on the upper strata, and the acid dregs of fat are in lower floor.After testing, the pH of the dregs of fat reaches 3.With pump the acid water in the subsider is entered in the sour water neutralization pond 7, the acid dregs of fat that contain low amounts of water are with being pumped in the dregs of fat neutralization chamber 9.Slowly add milk of lime under mechanical agitation in neutralization chamber, the dregs of fat then carry out neutralization reaction with the milk of lime that slowly adds in neutralization chamber, and the control reaction temperature constantly detects the pH of the dregs of fat simultaneously about 95～100 ℃, when reaching 7, stop to add milk of lime.Mixture left standstill 60 minutes, and oil and water stratification enter sour water neutralization pond 7 with water.With the neutral dregs of fat of remainder with being pumped in the thermal dehydration groove 11, and slowly substep is heated to 130 ℃, makes the residual water evaporation in the dregs of fat, up to there not being steam obviously to discharge, obtain the dregs of fat that dewater, and the dregs of fat after will dewatering with pump are sent into product holding vessel 12 in the time of 130 ℃.The neutral dregs of fat after the dehydration can be as the raw material of the pitch that manufactures a finished product, and for example waterproof roll, oxidized asphalt, emulsified asphalt etc. also can be used as the raw material of modulating fuel oil.
The acid water that water extraction acid sludge produces sour water neutralization pond 7 in milk of lime or the calcium lime powder neutrality (pH6～8) that neutralizes, the calcium sulfate (hydrated gypsum) that generates is sunken at the bottom of the pond, the neutral water on top is with being pumped into hot-tub 4, can be used further to extract acid sludge, the gypsum that is sunken to the bottom then is scavenged in the gypsum storage tank 8 and stores, and sell as gypsum dry back.
Embodiment 2
Raw material is identical with embodiment 1 with extraction process.The acid dregs of fat that obtain after the water extraction reach 7 with the 3% sodium hydrate aqueous solution pH that neutralizes.Mixture after the neutralization is the emulsion state, and profit can not layering, adds 0.2% demulsifier of amount of the mixture, leaves standstill after the stirring 90 minutes, and the profit layering is clear.Neutral water enters hot-tub and is used further to the acid sludge processing, and organic facies is sent in the dregs of fat drench pit and progressively is heated to 130 ℃ of dehydrations, obtains the neutral dehydration dregs of fat, sends into the product tank stores.Sour water in the sour water pond still with the quick lime neutralization, obtains neutral hydrated gypsum.
Raw material is the diesel oil acid sludge that obtains after the catalytic diesel oil of certain oil refining enterprise decolours through sulfuric acid treatment.The pH value is less than 1, and content of organics 45% at room temperature has certain flowability, but viscosity is very high.
In acid sludge groove 1, acid sludge is heated to 80 ℃, send into SL type static mixer 3 with acid-proof pump with 15 cubic metres speed per hour, simultaneously 80 ℃ hot water is also sent into blender 3 with 30 cubic metres speed per hour in the hot-tub, keeping the volume flow ratio of water and acid sludge is 2: 1, work continuously, make 5 cubic metres acid sludge and 10 cubic metres water pass through static mixer 3 altogether.After preliminary the mixing, mixture is admitted to GZR mixing pulverizer 5, sends into subsider 6 again by the mixture that mixes pulverizer.Keep the interior temperature of charge of subsider at 90 ℃, left standstill 60 minutes, the profit layering enters sour water neutralization pond 7 with acid water.The pH value that detects residual oil is less than 2.With the residual oil in the subsider 6, send into static mixer 3 again, also send into 80 ℃ hot water simultaneously to static mixer, still controlling water oil volume ratio is 2: 1, repeats above-mentioned extraction process.For the second time the residual oil pH that obtains after the extraction equals 3, equals 7 with the milk of lime pH that neutralizes, and obtains neutral residual oil.In drench pit, neutral residual oil is heated to 130 ℃ of dehydrations, obtain substantially anhydrous residual oil, can be used for modulating fuel oil, for example 200# or 250# fuel oil.
Embodiment 4
Raw material and extraction equipment, technology are identical with embodiment 3, but 3% sodium hydrate aqueous solution is adopted in the neutralization of the acid residual oil that obtains after the water extraction, and the oil water mixture that obtains after the neutralization is an emulsion.Add 0.2% demulsifier of emulsion total amount, stir, leave standstill, the profit layering obtains neutral residual oil after the separation, and the anhydrous dregs of fat that obtain behind the thermal dehydration can be used for modulating fuel oil, for example 200# or 250# fuel oil.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. a technology of handling acid residuals of petroleum is characterized in that, this technology may further comprise the steps:
The first step with water and acid sludge premixed, is mixed pulverizing then, make the granularity of water and acid sludge mixture reach 1-50 μ m, and make the water soluble acid in the acid sludge be soluble in the aqueous phase, thereby separation obtains acid water and pH is the acid dregs of fat of 2-6;
Second the step, with in the alkali with described extraction after pH be the acid dregs of fat of 2-6, thereby obtain the neutral dregs of fat or the residual oil of pH in 7～8 scopes.
2. technology as claimed in claim 1 is characterized in that, described acid residuals of petroleum comprises: lubricating oil acid sludge, diesel oil acid sludge or its combination.
3. technology as claimed in claim 1 is characterized in that, in the first step, described premixed is to use blender to mix continuously.
4. technology as claimed in claim 1 is characterized in that, in the first step, it is to carry out in the equipment of acid corrosion-resistant that described mixing is pulverized.
5. technology as claimed in claim 1 is characterized in that, in the first step, the volume ratio of water and acid sludge is between 1: 1～4: 1.
6. technology as claimed in claim 1 is characterized in that, when water and acid sludge premix, the temperature of described acid sludge is between 70～110 ℃, and/or the temperature of described water is between 60～100 ℃.
7. technology as claimed in claim 1 is characterized in that, in second step, used alkali comprises the alkali of alkali metal base and/or alkaline-earth metal; And/or in second step, also add demulsifier.
8. technology as claimed in claim 1 is characterized in that, comprises that also the acid water that will obtain in the first step neutralizes pH in 6～8 step with alkali.
9. technology as claimed in claim 8 is characterized in that, the described alkali that is used to handle acid water is selected from calcium hydroxide, calcium oxide, calcium carbonate or its combination, and comprises and reclaim the calcium sulfate that generates; Or
The described alkali that is used to handle acid water is selected from NaOH, sodium carbonate or its combination, and comprises and reclaim the sodium sulphate that generates.
10. technology as claimed in claim 1 is characterized in that, also comprises step, absorbs with alkali lye handling the sour gas that produces in the acid sludge.
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| CNA2007100388125A CN101274131A (en) | 2007-03-30 | 2007-03-30 | Comprehensive utilization technique of acid residuals of petroleum |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798522A (en) * | 2010-04-02 | 2010-08-11 | *** | Deacidification method of acid sludge oil |
| CN102002411A (en) * | 2010-09-20 | 2011-04-06 | 广东石油化工学院 | Method for producing solid fuel from oil refining acid sludge |
| CN101328428B (en) * | 2008-08-01 | 2012-03-21 | 潍坊百乐卫浴制品有限公司 | Processing process of sulfuric acid containing petrol |
| CN103589443A (en) * | 2013-10-31 | 2014-02-19 | 吴国存 | Pollution-free purifying and efficient using method for inferior organic wastes |
| CN107838169A (en) * | 2016-09-20 | 2018-03-27 | 朱岩安 | A kind of both economically and environmentally beneficial processing method of acid residuals of petroleum |
| CN108405552A (en) * | 2018-02-08 | 2018-08-17 | 兰州康顺石化有限责任公司 | Chemical industry acid sludge Neutralisation treatment method |
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2007
- 2007-03-30 CN CNA2007100388125A patent/CN101274131A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328428B (en) * | 2008-08-01 | 2012-03-21 | 潍坊百乐卫浴制品有限公司 | Processing process of sulfuric acid containing petrol |
| CN101798522A (en) * | 2010-04-02 | 2010-08-11 | *** | Deacidification method of acid sludge oil |
| CN101798522B (en) * | 2010-04-02 | 2013-05-01 | *** | Deacidification method of acid sludge oil |
| CN102002411A (en) * | 2010-09-20 | 2011-04-06 | 广东石油化工学院 | Method for producing solid fuel from oil refining acid sludge |
| CN103589443A (en) * | 2013-10-31 | 2014-02-19 | 吴国存 | Pollution-free purifying and efficient using method for inferior organic wastes |
| CN103589443B (en) * | 2013-10-31 | 2015-09-09 | 唐山山岛石油化学有限公司 | The nuisanceless purification of organic waste inferior and Efficient utilization method |
| CN107838169A (en) * | 2016-09-20 | 2018-03-27 | 朱岩安 | A kind of both economically and environmentally beneficial processing method of acid residuals of petroleum |
| CN108405552A (en) * | 2018-02-08 | 2018-08-17 | 兰州康顺石化有限责任公司 | Chemical industry acid sludge Neutralisation treatment method |
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