CN107617239A - A kind of method for removing catalyst fines in heavy catalytic cracking slurry oil - Google Patents
A kind of method for removing catalyst fines in heavy catalytic cracking slurry oil Download PDFInfo
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Abstract
The invention discloses a kind of method for removing catalyst fines in heavy catalytic cracking slurry oil, settling promotor is added in the slurry oil of preheating, carries out ultrasonic radiation processing after constant temperature is well mixed, then constant temperature settles, lower floor's water of separation and concentration catalyst fines, you can complete the removing of catalyst fines.Two kinds of means of this method combination settling promotor and ultrasonic radiation are handled slurry oil, the catalyst fines in slurry oil can be removed within a short period of time, removal efficiency and removal efficiency are high, and process simply need not be separated by filtration or centrifuge, and can realize continuous production.
Description
Technical field
The present invention relates to a kind of method for removing catalyst fines in heavy catalytic cracking slurry oil.
Background technology
Catalytic cracked oil pulp (abbreviation slurry oil, similarly hereinafter) is the unconverted of caused 350 DEG C of boiling point ＞ in catalytic cracking process
Hydro carbons, belong to oil refining accessory substance, wherein rich in aromatic hydrocarbons, colloid, asphalitine, there is the characteristics of viscosity is high, density is big, while also contain
There is substantial amounts of catalytic cracking catalyst powder.The processing method of slurry oil mainly has two kinds：(1) whole freshenings or part freshening；
(2) throwing away device outside turns into externally extracting oil.But document shows, under identical experimental enviroment, the aromatic hydrocarbons ratio in vacuum distillate
Aromatic hydrocarbons in reprocessed oil slurry is easier cracking, and the selectivity of wherein vacuum distillate aromatic hydrocarbons generation gasoline is reprocessed oil slurry aromatic hydrocarbons
1.6-1.7 times, only generate the 77%-89% of selective the latter of coke.Industrial practice then shows, a large amount of cracking
The very poor slurry oil of energy circulates freshening in catalytic cracking unit not only causes device disposal ability to decline, and the slurry oil of freshening is easy
Green coke causes system thermal discharge big on a catalyst, reduces the stability of device.Therefore, slurry oil freshening is not a good place
Reason method.It is each to refine oil unit increasing of having to and mix refining heavy oil, residual oil ratio so that above-mentioned contradiction is more with crude oil heaviness
It is prominent.In order to overcome or relax above-mentioned contradiction, the place of device is mostly improved using the method for partly or entirely getting rid of slurry oil outside
Reason ability, the amount of getting rid of is about the 4%-12% of feed oil outside.
Prior art China and foreign countries get rid of catalytic slurry be only used as heavy oil blend component or enter coking plant as produce it is general
The raw material of logical petroleum coke, added value be not high.It is valuable industrial chemicals in fact, containing a large amount of heavy aromatics in slurry oil.Slurry oil
In largely the condensed-nuclei aromatics with short-side chain be production carbon black, needle coke, carbon fiber, RX and rubber filling oil, plastics
The quality raw materials of the high value added products such as plasticizer, heavy duty road asphalt and conduction oil.However, the catalyst in slurry oil is consolidated
For body content of powder between 1000-18000ppm, average grain diameter only has more than ten microns or smaller, seriously constrains slurry oil conduct
Industrial chemicals or the further application of other devices charging, because：When it is as the raw material of production carbon black and needle coke
The necessary ＜ 500ppm of ash content, then require that its ash content must ＜ 200ppm when producing top grade product carbon black and needle coke；When it is as life
Require that its ash content must ＜ 500ppm when production RX and rubber filling oil, plastic plasticizer raw material；When it is as production
It is even more to require that ash content must ＜ 20ppm during carbon fiber material；If during as hydrocracking raw material, it is also necessary to make its ash content
Below 500ppm is dropped to, otherwise the catalyst fines of slurry oil entrainment can cause hydrogenation catalyst hole plug, pressure drop increase and urge
Agent inactivation etc.；Catalytic slurry is rich in heavy aromatics, and the heavy arene by solvent extraction concentrate is the preferable filling of rubber and plastic processing
Material, but operation and solvent recovery that the presence of catalyst fines then can be to extraction tower make troubles；In addition, even if when slurry oil is made
For heavy oil blend component when, if not purified, the catalyst solid powder in slurry oil can accelerate heating furnace nozzles grind
Damage, cause the problems such as the serious dust stratification in furnace tubing surface, the thermal efficiency decline, energy consumption increases.Therefore, the comprehensive utilization of slurry oil
First have to solve the problems, such as be, it is necessary to adopt an effective measure, efficiently, rapidly remove slurry oil in solid catalyst powder.
At present, the technical method of solid catalyst powder includes in removing slurry oil both at home and abroad：Natural sedimentation, it is separated by filtration
The methods of method, electrostatic separation method, centrifugal separation and auxiliary agent sedimentation separation method.
Natural sedimentation is the method used earliest, only by gravitational settling, although with equipment is simple, operating cost is low,
The features such as easy is operated, but because catalyst fines particle size range is between 0-80 μm, wherein less than 20 μm particle diameters account for quite
Proportion, slurry oil viscosity and proportion are all larger in addition, and the resin and asphalt in slurry oil also counteracts that the sedimentation of catalyst fines, i.e.,
Make rise settling temperature catalyst fines removal efficiency also not high, therefore the common disadvantage of this method is, sinking speed is slow, separation when
Between it is long, efficiency is low.For example, when temperature is 250 DEG C, sedimentation depth is 60cm, when making catalyst fines removal efficiency up to 85%,
The required sedimentation time about more than 20000 hour, is difficult to apply on industrial installation.
The method of being separated by filtration is to intercept the catalyst solid powder in slurry oil by filter medium to purify slurry oil to reach
Isolation technics.The core technology for being separated by filtration method is to select suitable filter medium and effective backwash mode.Filtering point
There is equipment and simple to operate, separative efficiency stabilization from method, but for the higher mink cell focus of colloid, asphalt content
During slurry, the problem of medium is difficult to selection is faced using high temperature filtration；Moreover, filtration method is very high there is also the requirement to equipment, if
Standby investment is excessive, and filter core is easily blocked, damaged and is not easy regeneration, it is necessary to continually backwash, and filtration resistance is big, it is impossible to removes micro-
The shortcomings of rice scaled powders.
Electrostatic separation technique cardinal principle be the slurry oil containing small catalyst fines when flowing through filling batch, particulate exists
Polarization and filled absorption, and then the purpose of slurry oil purification are produced under electric field action.After adsorption bed adsorption saturation, need
Backwashed with flushing liquor, prepared for next round absorption.Although electrostatic separation method has, flushing is easy, resistance is small, right
Nominal particle size powder has the advantages that preferable removal effect, once but slurry oil property be deteriorated, particularly handle raw material be heavy
During slurry oil, due to wherein containing substantial amounts of resin and asphalt, slurry oil can produce " competitive Adsorption " phenomenon in electrostatic separator,
Catalyst surface adsorbs the very strong material of one layer of polarity so that catalyst can not be separated well, reduce point of device
From efficiency；And equipment investment is big, apparatus structure is complicated, running cost is high, difficult in maintenance.
Centrifugal separation is segmented into centrifugal settling method and cyclonic separation method.Slurry oil is mainly put into height by centrifugal settling method
Its purification is realized in warm test tube type sedimentation centrifuge, equipment operating cost is high, Operation and Maintenance inconvenience, and equipment treating capacity is small.Rotation
Flow separation method is to make the motion of high-speed screw shape, catalyst solid after the slurry oil containing catalyst solid powder enters swirl-flow devices
Powder is operationally separated under caused centrifugal action, and this method has small equipment volume, simple in construction, operation and dimension
The advantages that shield is simple, energy consumption is small, but the shortcomings of separative efficiency is high, the solid content after separation in slurry oil is higher be present.The two mesh
It is preceding to be not carried out industrializing.
The shortcomings that for natural subsidence, auxiliary agent sedimentation separation method are a kind of emerging sedimentation methods the 1980s, existing
Increasingly it is being taken seriously.This method improves the sinking speed of catalyst fines and removing degree using chemical assistant.
Many document reports addition auxiliary agents accelerates the method that catalyst fines settles in slurry oil：
Abroad, it is mainly some United States Patent (USP)s, e.g., US5,481,059 disclose acrylic acid and phenolic resin alkoxy
Changing addition product and make settling aids, US5,593,572, which disclose the heteroatomic aliphatic polymer containing N, S, O etc., makees flocculant,
US5,681,451 disclose and make auxiliary agent with molecular weight 1500-5000 alkoxylated alkylphenol urea formaldehyde, and US6,316,685 is public
Open the unsaturated carboxylic acid polymer containing polyalcohol, alkoxide alkyl phenolic resin unit and make settling aids, and, WO97/
04042 discloses by the use of alkyl phenol ethoxy substratess and is used as flocculant, etc..
CN1297981A discloses a kind of method for removing catalyst powder in catalytic cracking oil slurry, is in cycle oil
Amine, fats, sulfonate surfactant are added in slurry as flocculant, flocculating setting 16~48 hours, is isolated
Layer clear liquid, lower floor's flocculation liquid are centrifuged obtaining centrifugal clear liquid, and above two clear liquid is as clarification oil product.The program claims energy
Solid content in slurry oil is removed to below 50ppm, the clarification oil yield after Removal of catalyst powder is up to more than 98% (weight).
The method that CN1958735A discloses two kinds of removing catalyst powder in catalytic cracking oil slurries：Processing proportion is less than water
Lightweight slurry oil be to mix the water containing demulsifier and flocculant with catalytic cracked oil pulp；Handle proportion and be more than or equal to water
Heavy slurry oil is in addition to demulsifier and flocculant is added in water, is also added into weighting agent.Method is disclosed in CN1958738A
Light solvent oil is mixed with catalytic cracked oil pulp, density is made into and is less than the miscella of water, then demulsifier and flocculant will be contained
Water mixed with light solvent oil/slurry oil miscella.And catalyst in the disclosed removing catalytic cracked oil pulps of CN101205472A
The composition and method of powder are by water and catalytic cracked oil pulp containing wetting agent, demulsifier, weighting agent and (or) flocculant
Mixing.The processing method of above three scheme is similar, i.e. is broken in case of heating using demulsification instrument or closed pressure vessel
Breast more than 1 hour, then the lower floor's moisture for being enriched catalyst fines is gone out.Demulsifier, flocculant used in 3 schemes,
Weighting agent is all similar：Demulsifier is alkoxylated alkylphenol urea formaldehyde, polyalcohol polyoxyethylene polyoxypropylene block copolymer, more
Ethylene polyamine polyoxyethylene polyoxypropylene block copolymer etc.；Flocculant is polymerization silicate, aluminium polychloride, polyacrylamide
Deng；Weighting agent be proportion be more than water and weak electrolyte or non-electrolyte miscible with water, as ammonium acetate, ammonium citrate, fructose,
Glucose, sorbierite or xylitol etc..Difference is：Light solvent oil described in CN1958738A is that boiling point is 100-200
DEG C solvent naphtha that can be miscible with catalytic cracked oil pulp；Wetting agent described in CN101205472A is APES, alkane
Base sulfonate etc..Above-mentioned 3 schemes claim, and 90% can be removed using catalyst fines highest in slurry oil after coagulation, if adopting
More than 95% is just can reach with two stage treatment highest removal efficiency.
CN101670199A discloses a kind of capturing settling agent and the method for removing catalyst solid powder in slurry oil.This kind
Capturing settling agent is made up of alkyl R quaternary ammonium salts, flocculant solution and polyalcohol.Capturing settling agent and catalytic cracked oil pulp is high
Shearing force is carried out after mixing twice, carries out the sedimentation of 4-24 hours, the capturing settling agent of lower floor's enriched catalytic agent solid powder is again
It is sent into horizontal centrifuge and carries out separation of solid and liquid.The program claims, and sedimentation rear catalyst solid powder removal efficiency is left 50% within 8 hours
The right side, up to 90% after sedimentation in 24 hours.
China is the big country of catalytic cracking in the world first.With the increase of China's refining capacity, annual caused slurry oil amount
Increase year by year, slurry oil annual production reaches as many as millions of tons, turns into a kind of very important resource.Therefore, in China, slurry oil
How comprehensive utilization removes the catalyst fines in slurry oil and is primarily solved as oil refining enterprise into the current matter of great urgency
Certainly the problem of.
As it was previously stated, natural subsidence, be separated by filtration, electrostatic separation and centrifuge the methods of all exist so or like that
The defects of, such as：Sinking speed is slow, inferior separating effect, equipment investment is excessive, running cost is high, is unable to continuous production, etc..It is existing
Some auxiliary agent sedimentation separation methods there is also the sedimentation separation time is longer, separating effect is preferable not to the utmost, need using demulsification instrument or
The deficiency of closed pressure vessel demulsification etc.；Moreover, slurry oil and the auxiliary agent of the container bottom of catalyst fines enrichment will also be through
The means such as it is separated by filtration or centrifuges and come Removal of catalyst powder and recovery slurry oil, these all has influence on treating capacity and place
Manage cost.
The content of the invention
It is an object of the invention to provide a kind of method for removing catalyst fines in heavy catalytic cracking slurry oil, this method
Slurry oil is handled with reference to two kinds of means of settling promotor and ultrasonic radiation, urging in slurry oil can be removed within a short period of time
Agent powder, removal efficiency and removal efficiency are high, and process simply need not be separated by filtration or centrifuge, and can realize continuous
Production.
The purpose of the present invention is achieved through the following technical solutions：Catalyst powder in one kind removing heavy catalytic cracking slurry oil
The method at end, settling promotor is added in the slurry oil of preheating, carries out ultrasonic radiation processing after constant temperature is well mixed, then constant temperature
Sedimentation, lower floor's water of separation and concentration catalyst fines, you can complete the removing of catalyst fines.It is heavy to be added into the slurry oil of preheating
The sedimentation that accelerator promotes catalyst fines is dropped, and ultrasonic radiation processing can then make powder coacervating large particle in slurry oil, more have
Beneficial to the sedimentation of catalyst fines.
Rich in aromatic hydrocarbons, resin and asphalt etc. in slurry oil, viscosity high density is big, hinders point of the settling promotor in slurry oil
Dissipate, to ensure mixed effect, select suitable mixing temperature and incorporation time etc. to be very important, suitable mixing temperature can
So that slurry oil has good mobility, be advantageous to the scattered and contact of settling promotor, and suitable incorporation time does not only have
Disperse beneficial to settling promotor in slurry oil, be more beneficial for fully contacting for settling promotor and slurry oil, play De-emulsification flocculent work
With.In the present invention, mixing temperature is 60-100 DEG C, preferably 80-100 DEG C；Incorporation time is 5-30 minutes, preferably 10-
20 minutes.
Ultrasonic radiation can promote the cohesion of powder particle, and different ultrasonic radiation conditions can influence removal efficiency, because
And select suitable ultrasonic radiation condition to shorten the removing time, improve removal efficiency.In the present invention, the ultrasonic radiation
Condition is：Temperature and temperature during sedimentation are similar, that is, control in the range of 70-100 DEG C, preferably 90-100 DEG C；Supersonic frequency is
10kHz-50kHz；Ultrasonic time 10-30min, preferably 20-30min.
Settling promotor of the present invention is mainly made up of demulsifier, flocculant, weighting agent and water.Further, with
Also include auxiliary demulsifying agent on the basis of upper composition, can directly add or use using auxiliary demulsifying agent to help containing demulsification
The demulsifier of agent increases auxiliary demulsifying agent in settling promotor.
In order to improve the removal effect of catalyst fines, select suitable additive and add agent order to be then key
One：(1) order of addition：Each component can add simultaneously in settling promotor, and powder removal efficiency can reach more than 77%.But
It is added portionwise by studying settling promotor, can greatly lifts powder removal efficiency.It is preferably in the present invention：First plus water and
Weighting agent, add demulsifier and auxiliary demulsifying agent and flocculant afterwards；Either first add demulsifier and auxiliary demulsifying agent and flocculant, Hou Jiashui
And weighting agent, both the above mode can make powder removal efficiency reach more than 98%.
In the present invention, flocculant is inorganic or organic polymer, including but not limited to polymerization silicate, polyaluminium
Aluminium, polyacrylamide, Sodium Polyacrylate, polyvinyl alcohol, viscous silicone fluid, calcium mahogany sulfonate, polyethylene glycol etc..Preferably,
Described flocculant is combination more than one or both of Sodium Polyacrylate, polyacrylamide and polyethylene glycol.And flocculate
The dosage of agent is the 300-1200ppm, preferably 800-1200ppm of slurry oil quality.The effect of demulsifier is by mixture
Water is separated, demulsifier can be alkoxylated alkylphenol urea formaldehyde, polyalcohol polyoxyethylene polyoxypropylene block copolymer,
Polyethylene polyamine polyoxyethylene polyoxypropylene block copolymer and its compound, etc..Demulsifier dosage is the 50- of slurry oil quality
1200ppm, preferably 300-800ppm.Auxiliary demulsifying agent is inorganic salts auxiliary demulsifying agent, and such as ammonium sulfate, its dosage is slurry oil matter
The 800-1000ppm of amount.Weighting agent is the material for the proportion that can increase water, i.e., proportion is more than water and light current miscible with water
Matter or non-electrolyte are solved, such as ammonium acetate, ammonium citrate, fructose, glucose, sucrose, sorbierite or xylitol, etc..Weighting agent
Dosage should make the water containing weighting agent proportion be more than slurry oil proportion.In the present invention, the dosage of water is slurry oil quality
5-30%, preferably 10-20%；The dosage of weighting agent is preferably the 2-6% of slurry oil quality.
The key of another removal effect that can improve catalyst fines of the present invention is settling temperature, in the present invention, is sunk
Cooling degree is suitable for control at 70-100 DEG C, preferably 90-100 DEG C.
Further, the present invention after carrying out first time processing to catalytic slurry, then can weigh to catalytic slurry two stage treatment
Complex phase biconditional operation carries out second to the catalytic slurry after coagulation and handled, and the first time processing is coagulation, described
Second of processing is two stage treatment.After coagulation, catalyst fines removal efficiency can reaches more than 98%, and two stage treatment
Catalyst fines content in slurry oil then can be further reduced, makes content of powder in slurry oil close to zero.
Further, the aqueous solution of discharge is separated after handling each time, through the catalyst powder for settling, being filtered to remove suspension
It is last, can reuse repeatedly, as the aqueous solution after coagulation is used in two stage treatment, the aqueous solution after two stage treatment is used
In the processing of next batch slurry oil, water, weighting agent and related auxiliaries are saved, reduce processing cost.
The present invention has advantages below：
1. the present invention is to provide a kind of " settling promotor-physics outfield " process integration removing heavy catalytic cracked oil
The method of catalyst fines in slurry, promotes the sedimentation of powder using settling promotor and ultrasonic radiation.It is very viscous with its processing
Thick heavy slurry oil, De-emulsification flocculent, Removal of catalyst powder significant effect, one-level removing processing can be by catalyst powder in slurry oil
End is removed to below 100ppm, removal efficiency from 5000ppm or so is more than 98%.Meanwhile substantially reduce water-oil separating and urge
The time of agent powder drop, shortening to only needs the 1/10~1/20 of the former sedimentation time.
2. this method technological process is simple, it is not necessary to carries out extra process and such as filters, centrifuges, and can realize continuous industry
Production；Ultrasonic radiation equipment and precipitation apparatus used are industrially with maturation, and be easy to mutually hold in the mouth with existing catalytic cracking unit
Connect, overall investment is not high, and processing cost is low.
3. the aqueous solution separated in technique can reuse repeatedly, both saved water, weighting agent and related auxiliaries, reduced again
The discharge of sewage, the pollution to environment is reduced, significantly reduces energy consumption and production cost, improves production efficiency and economy
Benefit.
Brief description of the drawings
Fig. 1 is present invention process flow chart.
Embodiment
Illustrate present invention in further detail by the following examples, but following embodiments are only intended to the present invention
Content be illustrated, rather than limitation is therefore any in the implication and scope suitable with claims of the present invention
Change, be all considered as being included within the scope of the claims.
Removal effect of the inventive method to catalyst fines in slurry oil is assessed from oil product ash determination.Ash content
Assay method see GB/T 508-1985《Oil product Ash determination method》, take de- preceding slurry oil to compare, calculated using following formula de-
Except rate (%)：
The technological process of the present invention：As shown in figure 1, enter blender after slurry oil is heated by heater；In blender
Middle slurry oil is well mixed with demulsifier, auxiliary demulsifying agent, flocculant, weighting agent, water；Slurry oil, water, agent mixture enter ultrasonic spoke
Emitter carries out radiation treatment, accelerates demulsification and catalyst flocculation process；Finally, slurry oil, water, the auxiliary agent radiation treatment crossed mix
Thing is transferred in static settler, constant temperature sedimentation, is purified slurry oil, and solid powder, the aqueous solution.
Embodiment 1
The property of handled slurry oil is shown in Table 1.Specific method is as follows：Take 100g slurry oils to add a beaker, be heated to 85 DEG C；Again
Demulsifier, auxiliary demulsifying agent ammonium sulfate and 10g water are added in slurry oil together, high-speed stirred 10min is well mixed, temperature control
At 85 DEG C or so；Then, a glass tube with a scale is poured the mixture into, the standing sedimentation 12h at 95 DEG C；Finally, observation is de-
Regimen condition, and take the oil sample of oil reservoir medium position to carry out ash analysis.A variety of commercially available domestic and importeds are have selected in experiment to break
It is public that emulsion A, B, C, D, E and F, A-F correspond to BP2040, AE8051, AR26, Baker company 168, PFA9311, Baker respectively
Department 150, result of the test is shown in Table 2.In single dose, demulsifier D and E effect is preferable, and profit layering is obvious, and water base instinct separates, wherein
The performance of demulsifier D Removal of catalyst powder is more preferable；By dehydration and Removal of catalyst powder property best two kinds of demulsifiers D, E
Compounding use, and auxiliary demulsifying agent is added, the effect of dehydration and Removal of catalyst powder improves to some extent；(demulsifier D
200ppm+ demulsifier E 200ppm+ be demulsified accelerator 800ppm) combination Removal of catalyst powder effect it is best, catalyst fines
Removal efficiency is 62.0%.
The catalytic cracked oil pulp property of table 1
The removal effect of 2 different demulsifiers of table
Embodiment 2
The property of handled slurry oil is shown in Table 1.Due to the density ratio water weight of slurry oil, the water that embodiment 1 is deviate from is in upper strata, this limit
The effect of Removal of catalyst powder is made.In order to which the water after demulsification is deposited into bottom, ammonium acetate, ammonium citrate, fruit have been selected
Sugar, glucose, sucrose etc. are used as weighting agent.Specific method is as follows：Take 100g slurry oils to add a beaker, be heated to 85 DEG C；Again will
Demulsifier (D 200ppm+E 200ppm), demulsification accelerator 800ppm, weighting agent and water 10g are added in slurry oil together, at a high speed
Stirring 10min is well mixed, and temperature control is at 85 DEG C or so；Then, a glass tube with a scale is poured the mixture into, at 95 DEG C
Lower standing sedimentation 12h；Finally, cases of dehydration is observed, and takes the oil sample of oil reservoir medium position to carry out ash analysis.Result of the test is shown in
Table 3.Comparative example 1, aqueous phase, which is deposited to bottom, strengthens the positive effect of Removal of catalyst powder；Add the de- of different weighting agents
Except difference on effect is little；But the dosage of weighting agent allows for making water be deposited to bottom, and otherwise effect is bad.
The removal effect of 3 different weighting agents of table
Embodiment 3
The property of handled slurry oil is shown in Table 1.Specific method is as follows：Take 100g slurry oils to add a beaker, be heated to 85 DEG C；Again
Flocculant is added into stirring 10min；Then by demulsifier (D 200ppm+E 200ppm), demulsification accelerator 800ppm, weighting agent
3g and water 10g are added in slurry oil together, and high-speed stirred 10min is well mixed, and temperature control is at 85 DEG C or so；Then, will be mixed
Compound pours into a glass tube with a scale, the standing sedimentation 12h at 95 DEG C；Finally, the oil sample of oil reservoir medium position is taken to carry out ash
Analysis.Result of the test is shown in Table 4.Water-soluble flocculant Sodium Polyacrylate and polyacrylamide are respectively provided with preferable Removal of catalyst
Powder effect, especially polyacrylamide are better；The removal effect of polyethylene glycol 2000 is also fine；Addition exists
Removal effect is optimal during 1000ppm.
The removal effect of 4 different flocculants of table
Embodiment 4
The property of handled slurry oil is shown in Table 1.Specific method is as follows：Take 100g slurry oils to add a beaker, be heated to 85 DEG C；Add
It is mixed to enter demulsifier (D 100ppm+E 200ppm), water 10g, weighting agent 3g, auxiliary demulsifying agent 800ppm, flocculant 1000ppm stirrings
Close uniform；Then the standing sedimentation 12h at 95 DEG C.Change charging sequence, result of the test is shown in Table 5.Various additives are together simultaneously
The effect for adding Removal of catalyst powder is worst；At first demulsifier and flocculant one add stirring 10min, then add water and increasing
Heavy prescription is stirred for 5min, and the Removal of catalyst powder effect of the order of addition is best；Next to that water and weighting agent first add stirring
5min, then add demulsifier and flocculant stirring 10min orders.
The removal effect of the different additive order of addition of table 5
Embodiment 5
The property of handled slurry oil is shown in Table 1.Specific method is as follows：Take 100g slurry oils to add a beaker, be heated to 85 DEG C；Add
It is equal to enter demulsifier (D 100ppm+E 200ppm), weighting agent 3g, auxiliary demulsifying agent 800ppm, flocculant 1000ppm and water mixing
It is even；Then the standing sedimentation 12h at 95 DEG C.Result of the test is shown in Table 6.When the addition of water reaches 10%, Removal of catalyst powder
End effect fruit has basically reached best, and catalyst fines removal efficiency is 97% or so.
The removal effect of the different water dosages of table 6
Embodiment 6
The property of handled slurry oil is shown in Table 1.Specific method is as follows：Take 100g slurry oils to add a beaker, be heated to 85 DEG C；Add
Enter demulsifier, water 10g, weighting agent 3g, auxiliary demulsifying agent 800ppm, flocculant 1000ppm to be well mixed；Then stood at 95 DEG C
Settle 12h.Result of the test is shown in Table 7.The dosage of demulsifier dehydration rate at 300ppm (D 100ppm+E 200ppm) just reaches
100%；Continue the amount of increase demulsifier, catalyst fines removal efficiency increase rate is limited.
The removal effect of the different demulsification dosage of table 7
Embodiment 7
The property of handled slurry oil is shown in Table 1.Specific method is as follows：Take 100g slurry oils to add a beaker, be heated to a constant temperature
Degree；Add demulsifier (D 100ppm+E 200ppm), water 10g, weighting agent 3g, auxiliary demulsifying agent 800ppm, flocculant 1000ppm
It is well mixed；Then the standing sedimentation 12h at 95 DEG C.Result of the test is shown in Table 8.The whipping temp that additive adds is to catalyst powder
The removal effect at end has a great influence, and preferable temperature is more than 80 DEG C.
The different additive of table 8 adds the removal effect of whipping temp
Embodiment 8
The property of handled slurry oil is shown in Table 1.Specific method is as follows：Take 200g slurry oils to add a beaker, be heated to 85 DEG C；Add
Enter demulsifier (D 100ppm+ oli oil 200ppm), flocculant 1000ppm, water 20g, weighting agent 4g, auxiliary demulsifying agent 800ppm to mix
Close uniform；Then settled under certain temperature and time.Result of the test is shown in Table 9.With settling temperature rise or sedimentation time
Increase, dehydration rate and catalyst fines removal efficiency improve；Water is removed into clean and catalyst fines removal efficiency and reaches preferable
Degree, settling temperature is suitable for control, and and the sedimentation time need to be in more than 12h more than 90 DEG C.
9 different sedimentation times of table, the removal effect of settling temperature
Embodiment 9
The property of handled slurry oil is shown in Table 1.Specific method is as follows：Take 200g slurry oils to add a beaker, be heated to 85 DEG C；Add
Enter demulsifier (D 100ppm+ oli oil 200ppm), (embodiment 4-6 is polyacrylamide sodium to flocculant 1000ppm, embodiment 7-9
For polyacrylamide), water 20g, weighting agent 4g (embodiment 3-5 is glucose, and embodiment 6-9 is sucrose), auxiliary demulsifying agent sulfuric acid
Ammonium 800ppm is well mixed；Slurry oil, water, agent mixture are transferred to ultrasonic radiator again ultrasonic radiation is carried out at 90 DEG C, surpassed
Acoustic frequency is 15kHz；Finally, the standing sedimentation 1h at 90 DEG C.Result of the test is shown in Table 10.Comparative example 8, in other conditions phase
With in the case of, radiation 20min sedimentation 1h effects are suitable with without radiation treatment sedimentation 12h effects；After radiating 30min sedimentations 1h
Effect then with without radiation treatment sedimentation 24h effect it is suitable.
The removal effect of the different ultrasonic radiation times of table 10
Claims (10)
1. a kind of method for removing catalyst fines in heavy catalytic cracking slurry oil, sedimentation promotion is added in the slurry oil of preheating
Agent, it is characterized in that, ultrasonic radiation processing is carried out after constant temperature is well mixed, then constant temperature settles, separation and concentration catalyst fines
Lower floor's water, you can complete the removing of catalyst fines.
2. the method for catalyst fines in removing heavy catalytic cracking slurry oil according to claim 1, it is characterized in that, it is described
Settling promotor be mainly made up of demulsifier, flocculant, weighting agent and water.
3. the method for catalyst fines in removing heavy catalytic cracking slurry oil according to claim 2, it is characterized in that, it is described
Settling promotor also include auxiliary demulsifying agent.
4. the method for catalyst fines in removing heavy catalytic cracking slurry oil according to claim 3, it is characterized in that, it is described
Each component can add simultaneously in settling promotor, or first add water and weighting agent, add demulsifier and auxiliary demulsifying agent and wadding afterwards
Solidifying agent, or first add demulsifier and auxiliary demulsifying agent and flocculant, add water and weighting agent afterwards.
5. the method for catalyst fines, its feature in the removing heavy catalytic cracking slurry oil according to Claims 2 or 3 or 4
It is that the dosage of the flocculant is the 300-1200ppm of slurry oil quality；The demulsifier dosage is the 50- of slurry oil quality
1200ppm；The dosage of the water is the 5-30% of slurry oil quality；The dosage of the weighting agent is the 2-6% of slurry oil quality.
6. the method for catalyst fines in the removing heavy catalytic cracking slurry oil according to Claims 2 or 3 or 4 or 5, it is special
Sign is that the flocculant is inorganic or organic polymer, including but not limited to polymerization silicate, aluminium polychloride, polyacrylamide
Group more than one or both of amine, Sodium Polyacrylate, polyvinyl alcohol, viscous silicone fluid, calcium mahogany sulfonate and polyethylene glycol
Close；The demulsifier includes but is not limited to alkoxylated alkylphenol urea formaldehyde, polyalcohol polyoxyethylene polyoxypropylene block copolymerization
Combination more than one or both of thing and polyethylene polyamine polyoxyethylene polyoxypropylene block copolymer and its compound；Institute
State one kind that weighting agent includes but is not limited in ammonium acetate, ammonium citrate, fructose, glucose, sucrose, sorbierite and xylitol or
Two or more combinations.
7. the method for catalyst fines in the removing heavy catalytic cracking slurry oil according to any one of claim 1 to 6, it is special
Sign is that the mixing temperature is 60-100 DEG C, and incorporation time is 5-30 minutes；The settling temperature is suitable for control in 70-100
℃。
8. the method for catalyst fines in the removing heavy catalytic cracking slurry oil according to claim 1 or 7, it is characterized in that,
The ultrasonic radiation condition is：Temperature control is in the range of 70-100 DEG C；Supersonic frequency is 10kHz-50kHz；Ultrasonic time 10-
30min。
9. the method for catalyst fines in removing heavy catalytic cracking slurry oil according to claim 8, it is characterized in that, to urging
Carburetion starches two stage treatment, i.e., after carrying out first time processing to catalytic slurry using the method described in claim 1, repeats identical
Operate and second of processing is carried out to the catalytic slurry after coagulation, the first time processing is coagulation, described second
Handle as two stage treatment.
10. the method for catalyst fines in the removing heavy catalytic cracking slurry oil according to any one of claim 1 to 9, its
It is characterized in, the aqueous solution of discharge is separated after handling each time, the catalyst powder through settling, being filtered to remove suspension is last, repeatedly
Reuse.
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