CN86107787A - The method of separating catalyst particulate in the charging of catalytic cracking always - Google Patents

Abstract

The present invention relates to use a method isolating the catalyzer minuteness particle in the filtration method charging of the hydrocarbon-containiproducts of catalytic cracking device always by inorganic barrier layer and filtering ring.

This method essence is: make described charging accept filtration by heat-stable and its porosity with the inorganic barrier layer (1) that the minimum diameter that need hold back particle adapts, porosity is usually included between 0.1～100 micron (μ m).

Description

The present invention relates to filtering technology, specially refers to method of separating catalyst minuteness particle in the charging of the hydrocarbon-containiproducts of catalytic cracking device always and for implementing a kind of filtering ring of this method.

As for the charging of hydrocarbon-containiproducts, in the main a kind of charging be made up of hydrocarbon polymer of hereinafter being meant of the application's book, it also can contain other atoms for example oxygen, sulphur etc. except containing carbon and hydrogen atom.This charging can be especially but not be to constitute by crude oil or through the product of refining crude oil gained uniquely that for example the residual oil that is called slurry oil through the catalytic cracking gained constitutes, and constitutes as the residual oil that will be known as slurry oil hereinafter.As will be described hereinafter, unless this selection can constitute any one restriction of the present invention.

Catalytic cracking is a widely method known to the people, and its essence is: when catalyzer exists the molecule that is contained in the hydrocarbon-containiproducts charging is smashed under the effect of heat, typically this technological process is finished at fluidized-bed.For this reason, catalyzer is made up of subparticle, and the mean sizes of its particle is about 70 microns, and wherein a part (minimum particle) can be pulled away with reaction product, and enrichment in the residual oil that take out the bottom of separation column.

This residual oil is used as thinner (low viscosity base) product in industry expense (fioul) difficult to understand is produced.

(stock size is included between 0～50 micron the minuteness particle of catalyzer, and can not be removed by traditional filtration method) existence can make product impure, for example make product can not be fit to some purposes [for example expense Austria (fioul) of ocean-do bunker oil], by combine the serious fouling that causes Industrial Boiler and stove with some heavy metals, these heavy metals comprise the vanadium that contains in other compositions (for example adhesive matrix of vacuum residuum type) of expense (fioul) difficult to understand.

Due to the fact that, this phenomenon gets over seriously, and promptly along with the increase of catalytic cracking capacity, the output of slurry oil also increases, and on the other hand along with the output reduction of adhesive matrix, the heavy metal concentration of these matrix also just improves simultaneously.

So the particulate of isolating catalyzer from cracking-residuum becomes a problem that must solve, people test various separation methods, recommend each refinery then.

In the whole bag of tricks of patent application formerly, should suitably quote as proof and be called the GIJLFTRONIC method, promptly by wet cyclone (hydrocyclone) and the separation method by electric current.

But be only to take out a part of particulate that slurry oil contains on these methodological principles, if seek higher efficient, the then very fast raising of expense.In addition, discharge isolating particulate like this and need an external fluid, be exactly cracker charging itself usually, this causes making the particulate recirculation of catalyzer in reactor, thereby above-mentioned phenomenon is continued, unless abandon this effluent liquid, but this will cause the value-added remarkable loss of crude oil.

And patent application person of the present invention has sought a kind of more effective separation method, it can eliminate those particles that its diameter surpasses so-called excision minimum diameter fully, these particles are enriched in the slurry oil itself, and this makes and can discharge particulate outside system with lower cost.

For this reason, be noticeable at hereinbefore described the sort of separation method, promptly filter the charging of hydrocarbon-containiproducts by having inorganic barrier layer that its porosity is adapted to hold back the minimum diameter (generally comprising between 0.1～100 micron) of particle.

These blocking layers that can on market, buy at present; be rendered as the variable tubular of internal diameter (generally comprising between 1～15 millimeter); constitute by inorganic materials; such as aluminum oxide (vanadine) or carbon; inner one deck (or several layers) metal oxide that covers is as protective layer; for more definite description; can be indicated in previous patent application; NO; 8011442(1980 May 22; with " Commissariat Energie Atomique " and Compagnie de Raffinage et de Disiribution Total France " name at French submit applications book), these blocking layers are specially adapted to oil salvage and handle.

Commercialization is realized by " French catalysis element company " (being called for short SFEC) in France in such blocking layer, the extensive stock label is arranged, consider simultaneously active substance is entered in the composition of internal layer or carrier internal layer or carrier layer, and have and relevant accurate physical features such as its porosity, mechanical life.

Forming is not open-and-shut used for various applications, can cause proposing various patent applications, producing application of the present invention thus is to consider such fact, the i.e. filtration of nonhomogeneous media as petroleum feeding, normally be difficult to, even can not realize by means of usual method.

According to one embodiment of the present invention, a filtering ring (shape thing) also comprises the means of measurement and dominant discharge, may also include measurement and the control device of concentrate, and additionally also include the means of concentrate of measuring in ring (shape thing) temperature inside in the speed of ring (shape thing) inner circulation.

According to another remodeling embodiment, the noticeable part of this ring (shape thing) also is: the flow of filtrate is controlled by a simple valve, and the flow of concentrate is adjusted to a prescribed value by a proportional valve.

Hereinafter contrast the description of accompanying drawing, be not construed as limiting and provide, but how to realize, and estimate energy of the present invention and scope better thus in order to understand the present invention better.On figure be:

Fig. 1 represents the section of a filter assemblies; And

Fig. 2 represents to be applied to the schematic diagram from the filter method of catalytic cracking residual oil (slurry oil) separating catalyst particulate.

In Fig. 1, depicted: by several inorganic barrier layers 2a, the 2b that are installed in parallel at cell body 3 ... a micro particle filtering assembly 1 of being formed.Connect by screw bolt and nut, one connects cone 4 cell body 3 and circulating line 5 is coupled together.Concentrate at ring (shape thing) internal recycle enters filter assemblies by pipeline 5, the 2 inner circulation on the blocking layer, and then through pipeline outflow (not providing this pipeline herein, because it is not a part of the present invention strictly speaking).Filtrate is the share of passing the charging on blocking layer 2 internally to the outside, and this is caused owing to having pressure difference these two zone institutes, and this pressure difference can reach, even surpasses ten individual crust.In order to guarantee that (inner institute forms by pipeline 5 and blocking layer in the high pressure area, as a side) and low pressure area (inner institute forms by the blocking layer, as the opposing party) between stopping property, must consider seal means, for example, select the annular or the cylinder-shaped link 7 of synthetic rubber (Uitom) or graphite system for use according to the temperature of the concentrate of circulation in ring (shape thing).

In Fig. 2, drawn the synoptic diagram of a catalytic cracking unit, this device comprises one according to filtering ring of the present invention.

The separation column of a catalytic cracking unit of mark 11 same expressions.

Such separation column and more generally catalytic cracking unit and its working conditions or adjusting condition do not remake in the application's book further and describe, because it is not a part of the present invention strictly speaking, can select practical relevant basic works that can reference for use, for example " WU I IH IER ", the I volume, the II chapter.Extract cracked residual oil from separation column 11, cracked residual oil is at first accepted stripping in tower 12, is sent to filtering ring 15 by reclaiming pump 13 and conduit 14 then, and filtering ring 15 is peculiar parts of the present invention.

As previously mentioned bright, the residual oil that extracts (or slurry oil) that is loaded with catalyst particles is to be introduced in filtering ring 15 by linking conduit 14, this ring is by a recycle pump 15, cover series connection-parallel connection (for example placed in-line 4 assemblies, each assembly has 250 blocking layers, installing like that as shown above) a blocking layer 17 and a circulation duct 18 are formed, the vent pipe of filtrate 19 and concentrate 20 is used as the charging that is recovered on the one hand in the hold tank 21 not with the hydrocarbon-containiproducts of catalyzer minuteness particle, can discharge concentrate on the other hand.At last, this filtering ring 15 also has to be measured and control device, such as flow director, be labeled as FC(" flow-comtrol "), temperature regulator, be labeled as TC(" temperature-control ") and also have the speed of circulation controller sometimes, be labeled as SC(" spead-control ").And between filtering ring and catalytic cracking unit, also exist the liquid level of controller to concern.Therefore, the control of flow of filtrate is the mensuration that is driven in liquid level in stripping columns 12, and same, filtrate is the measurements that are driven in the pressure difference (DPC) between the low pressure area of the high pressure area of filtering ring and filtrate outlet to the recirculation of main fractionating tower 11.In a word, the flow of concentrate is controlled by the flow of filtrate, so that passing ratio valve (FRRC) can make fixed ratio between these two flows to a set-point.

The inorganic barrier layer of using for the equipment filtering ring is characterised in that its penetration radius.These blocking layers are being supplied with its penetration radius value on the market, comprise: the first estate, between 2～100 millimicrons (mm) (in the case, just be called ultrafiltration), and second grade, between 0.1 micron (um) and 100 microns, and (be used for this type special purpose this just be called microfiltration).

The impurity that presents in the hydrocarbon-containiproducts charging of introducing filtering ring is held back by described blocking layer, so charging itself (wherein existing above-mentioned impurity, these impurity are in by different situations and suspend or solution state) is by constituting the sensitive layer of described blocking layer inwall.Therefore, the concentration of impurity is brought up in filtering ring and is reached equilibrium level, this is determined by the extraction flow of filtrate and concentrate, perhaps more properly determine by the ratio between these two flows, this ratio is called concentration ratio, and it is to regulate by means of the proportional valve that it is contained in the concentrate exit.So concentrate constantly is extracted at the inner circulation of filtering ring, so that inward flux (hydrocarbon-containiproducts charging, for example slurry oil) is equal with discharge flux (filtrate and concentrate).At last, such system washes down automatically, the concentrate of circulation is promoted (tangential speed is caused by recycle pump) by quite big tangential speed in filtering ring, so that this concentrate is always on the surface of the inner sensitive layer in washing blocking layer, and the impurity that can not pass this sensitive layer (one or more layers) is attracted.This regular washing can or seldom can not make sensitive layer degenerate, and shows that the blocking layer has long work-ing life (above 1 year) because the various tests that patent application person of the present invention carried out have been demonstrate,proved.When resulting in blockage owing to fault or unsuitable operational condition on whole blocking layers of a blocking layer or an assembly, just need stop up the removing operation at that time, and this is easy to finish, can adopt the way that to inside the blocking layer is applied counterpressure from the outside, or adopt and to make concentrate not extract the way of (using or do not use turbulent flow to promote device) at the filtering ring internal recycle, can also adopt the way that purifies loop and introduce suitable fluid to make it the round-robin way to filtering ring.These fluids that are used to remove obstruction can have various, generally depend on normally the charging at the blocking layer internal recycle: typically be solvent based, and can give an example as the catalysis lightnaphtha under the situation of utilizing the charging of being made up of silt oar oil.

Experimental test

Patent application person of the present invention has realized a test, and this is in their research centre, is being equipped with on the filtering test device of suitable barrier layer and is carrying out under the full-scale condition of this blocking layer work.

This testing apparatus is equipped with the assembly on one group of three blocking layer, and the filtration area that has is 0.066 square metre.This test duration has carried out 100 hours, and this carries out after concentration rate is stabilized in 20 and under following operational condition, that is:

Temperature: 330 ℃

The top hole pressure on blocking layer: 4.5 crust

Linear velocity 5 meter per seconds

The content of catalyst particles in charging filtrate and the concentrate (the mean diameter grain is 20 microns) be respectively 1500ppm(1,000,000/), be lower than 50ppm and 3%.These analysis on Content are undertaken by the PCAS118 filtration method.The yield of filtrate is about 95%.

Commerical test

It is enough inspirer that these results are considered to, and can provide argument so that can expand and safeguard easily for the object of patent application person's exploitation of the present invention at the exemplary filtering ring with pattern character of plant construction.

From top description, can be clear that: the professional and technical personnel can imagine and many remodeling and variant, and this does not surmount scope of the present invention, as determined in the appended claims.Especially, so a kind of method can be applicable to other types solid (coke, the coal that exists equally effectively in slurry ...), only depend on these solid granularities, consider that the porosity on employed blocking layer adapts with it.This method equally also is applicable to the charging of every other type, so that solid fraction (or major part of solid fraction) is separated with liquid fraction.

Claims (7)

1, isolates the method for catalyzer minuteness particle in the charging of the hydrocarbon-containiproducts of catalytic cracking device (11) always, it is characterized in that making described charging to accept filtration by heat-stable with the inorganic barrier layer (1) with the porosity that adapts with the minimum diameter that need hold back particle, its porosity generally comprises between 0.1～100 μ m (micron).

2, according to the separation method of claim 1, it is characterized in that described charging is sent to filtering ring (15), filtering ring contains the inorganic barrier layer of a cover series connection-parallel connection, makes the concentrate circulation in inside, blocking layer; Its feature also be to retrieve from these blocking layers remove the filtrate that its diameter surpasses the particle of above-mentioned minimum diameter, with and feature be to make a part of above-mentioned concentrate (contain in a large number these with like-particles) discharge again.

3, according to the separation method of claim 2, it is characterized in that quality according to the spendable charging quality and the filtrate of wish reclaiming, be used for changing ratio between amount of filtrate and the concentrate flow by Comparative Examples valve (FRRC).

4,, it is characterized in that by recycle pump (16) being used for change the circular velocity of concentrate in the described ring according to the separation method of one of claim 2 and 3.

5, filtering ring (15), for realizing method according to one of claim 1～4, it is characterized in that it contain one the cover series connection-parallel connection inorganic barrier layer (2), this inorganic barrier layer is made of the cylindrical tubes that the inorganic substance of suitable one deck of granularity (or several layers) oxide compound covering inwall are made, and cylindrical tubes is connected by a pipeline that is arranged to the ring form.In ring, can make the concentrate circulation; Comprise that the charging that makes that is under conduit (14) and fresh feed pump (13) form introduces the means of described filtering ring and the device for transferring of filtrate (19) and concentrate (20).

6, according to the filtering ring (15) of claim 5, it is characterized in that it also contains the mensuration and the control device of flow, and also contain the mensuration and the control device of the speed of circulation of concentrate in the ring, or the temperature survey means of concentrate in the ring are arranged.

7,, it is characterized in that the flow of filtrate is controlled by a simple valve, and the flow of concentrate is adjusted to a prescribed value by means of proportional valve according to the filtering ring (15) of claim 6.

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