CN105586081B - Processing method by shale oil through catalytic cracking - Google Patents
Processing method by shale oil through catalytic cracking Download PDFInfo
- Publication number
- CN105586081B CN105586081B CN201410558881.9A CN201410558881A CN105586081B CN 105586081 B CN105586081 B CN 105586081B CN 201410558881 A CN201410558881 A CN 201410558881A CN 105586081 B CN105586081 B CN 105586081B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oil
- catalytic cracking
- shale oil
- zone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a processing method by shale oil through catalytic cracking. The method is characterized in that a turbulent fluidized bed reactor is divided into an adsorption zone and a cracking zone, under non-hydrogen atmosphere, shale oil is introduced into the adsorption zone of the turbulent fluidized bed reactor with low temperature, impurity such as a basic nitride, colloid and heavy metal can be absorbed and removed, and then the shale oil is introduced into the cracking zone of the turbulent fluidized bed reactor and is contacted with a regeneration agent with high temperature and high activity for performing a catalytic cracking reaction. The invention provides the method for producing a lightweight product by the shale oil through direct catalytic cracking, and has the advantages of high shale oil conversion capability, low dry gas and coke, and high liquid yield.
Description
Technical field
The present invention relates to the processing method of shale oil catalytic cracking, turbulent fluidized bed is used more specifically to one kind
The method of the impurity of reactor elder generation adsorbing and removing shale oil catalytic cracking again, increases substantially shale oil conversion ratio and reduces dry
Gas and coke yield, so as to realize the efficient method for utilizing of shale oil resource.
Background technology
Shale oil be oil shale after hot-working, the product that its organic matter is thermally decomposed to generate, be similar to natural oil, but
Contain more unsaturated hydrocarbons than natural oil, and the non-hydrocarbons organic compound such as nitrogenous, sulphur, oxygen.Whole world oil shale reserves
400,000,000,000 tons of shale oil are approximately equivalent to, considerably beyond natural oil gross reserves；And China's oil shale resources very abundant, reserves are about
It is 16,000,000,000 tons, occupies the 4th, the world.Shale oil industry is an important component of energy industry, is also the one of natural oil
Plant the supplement energy.However, unsaturated hydro carbons and non-hydrocarbons organic compound influence the diesel colour and peace of shale oil in shale oil
The secondary operation that qualitative and higher nitrogen content has an effect on shale heavy oil is utilized, therefore the efficient of shale oil is existed using key
The heteroatomic compounds such as nitrogen, sulphur, oxygen in how removing shale oil.Current shale oil in addition to a small amount of production chemicals,
Major part is sold without secondary operation directly as fuel oil, it is therefore necessary to develop the skill of more efficient utilization shale oil
Art.
Because the heteroatomic compound content such as nitrogen, sulphur, oxygen is higher in shale oil, especially nitrogen content is general in 1%-
3%, it is impossible to the lighting of shale oil is carried out directly as catalytically cracked material.It is primarily due to nitride particularly alkali nitride
Thing during catalytic cracking reaction can and acidity of catalyst central role and reduce catalyst activity and selectivity, show product
It is that coking yield increases in thing distribution, slurry oil increases, and yield of light oil declines.ARCO companies point out, most of catalytic cracking units
It is resistant to 2000 μ g/g total nitrogens and 1000 μ g/g alkali nitrogen.By the anti-nitrogen cracking catalysis using peracid center density, rare earth containing zeolite
Agent such as RHZ-200, LC-7, CCC-1, RHZ-300, or with acid additive as nitrogen catcher, catalytic cracking unit
The charging of below the μ g/g of nitrogen content 3000 can only be processed.Patent CN200410082968.X disclose one kind 5-15% containing ferrous iron,
The hydrocarbon cracking catalyzer of aluminium dihydrogen phosphate 5-20% and balance of clay, alkali resistance nitrogen performance is good, cracking activity is high, it is adaptable to
Fluid bed riser processes the catalyst and cracking of hydrocarbon containing ferrous iron of nitrogenous shale oil high and high wax content oil.
US 4342641 discloses a kind of method for processing shale oil, and full cut shale oil first is carried out into hydrotreating, obtains
The cut less than 249 DEG C directly as jet fuel, the cut more than 249 DEG C for obtaining is hydrocracked again, with produce
Jet fuel；Wherein hydrotreating is carried out in two steps, and first carries out prerefining with the low catalyst of Ni-Mo contents, then contained with M-Mo
Amount catalyst high is further refined.
CN 1067089A, CN102453546A and CN201110074546.8 disclose a kind of hydrogenation of shale oil fractionation,
The processing method of hydrogenation heavy oil catalytic pyrolysis again, as described in CN 1067089A, shale oil first passes through hydrotreating and obtains hydrogenation life
Into oil, hydrogenated oil be separated into hydrogenation heavy oil and light-end products, hydrogenation heavy oil obtained after catalytic cracking dry gas, liquefied gas,
Gasoline, diesel oil and catalytic heavy, diesel oil and heavy-cycle oil can return to hydrotreating step；The simply page of CN201110074546.8
Shale oil is hydrogenated with heavy oil and carries out catalytic cracking reaction using two riser reactors, and being hydrogenated to obtained by CN102453546A
It is oily to enter cat-cracker together with optional vacuum gas oil (VGO).In a word, shale oil carries out hydrofinishing, the weight being refining to obtain
Shale oil can be changed into light-end products by oil as the processing method of the raw material of existing catalytic cracking technology, but asking of existing
Topic is：Hydrogenation process is more, and hydrogen consumption is high, and operating cost is high, and construction investment is high.
Non- hydrotreating is mainly and uses acid-alkali refining, and such as patent CN201010520957.0, acid-alkali refining can not only be produced
Raw a large amount of reluctant acid sludges, pollute environment, and oil yield is low；Although some researchers explore and use Dan Rong in recent years
Agent or multi-solvent extracting and refining method, such as patent CN200510114740.9, but it is larger to still suffer from solvent consumption, and energy consumption grade high lacks
Owe.More importantly with the raising of environmental protection requirement, the discharge standard to fuel oil combustion tail gas is improved constantly both at home and abroad,
The limitation of sulphur, nitrogen and arene content to vehicle fuel oil is lower, so being extremely difficult to require using non-hydroprocessing process.
Therefore, in order to efficiently utilize shale oil resource, the demand of growing light-weight fuel oil is met, it is necessary to develop
A kind of processing method that shale oil raw material Efficient Conversion can be a large amount of lightweights and the fuel oil for cleaning.
The content of the invention
In order to the transformation efficiency for overcoming existing method for processing shale oil to exist is low and obtains the sulphur of fuel oil, nitrogen and virtue
Hydrocarbon content defect higher, there is provided it is a kind of can by shale oil raw material Efficient Conversion be a large amount of lightweights and cleaning fuel oil plus
Work method.
To achieve these goals, the invention provides a kind of processing method of shale oil catalytic cracking, wherein, the method
Comprise the following steps：
(1) with non-hydrogen fluidizing agent flow, make first shale oil into turbulent fluid bed reactor adsorption zone with draw
The first catalytic cracking catalyst entered to the adsorption zone is contacted, and carries out adsorption reaction；The condition of adsorption reaction is：Temperature is 250-
450 DEG C, pressure is 0.1-0.4MPa, and time of contact is -10 minutes 5 seconds, and agent weight of oil ratio is 4.5-10：1；
(2) as non-hydrogen fluidizing agent flows, the shale oil after being contacted through step (1) and the first catalyst is made to enter described
The zone of cracking in turbulent fluid bed reactor contacts together with the second catalytic cracking catalyst for being incorporated into the zone of cracking, is urged
Change cracking reaction；The condition of catalytic cracking reaction is：Temperature is 450-580 DEG C, and pressure is 0.1-0.4MPa, and time of contact is 2-
20 seconds, agent weight of oil ratio was 4-10：1；
(3) material after the catalytic cracking reaction of step (2) is carried out into finish separation, isolated oil gas enters separation
System carries out product separation, and isolated reclaimable catalyst is regenerated into regenerator；
Wherein, first catalytic cracking catalyst is the fresh catalyst Cracking catalyst of supplement, or is from described
The regenerated catalyst or semi regeneration catalyst through cooling of regenerator, or be being urged through the to be generated of cooling from the reactor
Agent；Second catalytic cracking catalyst is the regenerated catalyst from the regenerator.
The present inventor is had found by years of researches, including the inferior feedstock oil catalytic cracking including shale oil
Not the higher the better for conversion ratio, when high conversion rate to a certain extent, purpose product increases little, and the yield of dry gas and coke is big
Amplitude increases；Nitride in shale oil can be by adsorbing and removing, and catalytic cracking catalyst in itself can also be used as absorption
Agent, is 4.5-10 particularly in agent weight of oil ratio (the weight ratio of the first catalytic cracking catalyst and shale oil)：1 adsorption effect
It is best；In addition, with the inferior feedstock oil after Pd/carbon catalyst adsorbing and removing nitrogen, heavy metal, carbon residue etc., density is high, viscosity is big, if
Just long-play easily condenses in a device for non-cracking, causes device green coke high.
Based on above-mentioned discovery, the invention provides a kind of processing method of shale oil catalytic cracking, by turbulent fluidization
In bed reactor, by introducing cooling medium, turbulent fluid bed reactor is divided into turbulent fluid bed reactor adsorption zone with rapids
The fluidized bed reactor zone of cracking, absorption and catalytic cracking process are organically combined, and from the direct catalytic cracking of shale oil, and are carried
Shale oil conversion capability high, particularly controlling agent weight of oil ratio the weight ratio of shale oil (the first catalytic cracking catalyst with) are
4.5-10：1, green coke and dry gas can also be significantly reduced while adsorption efficiency is kept, so as to realize shale oil resource
Efficiently utilize.
The present invention has following technique effect compared with prior art：
(1) shale oil can be without refining and directly catalytic cracking, and flow is short, hydrogen-free consumes and realizes long period serialization
Production；
(2) " device two is anti-", i.e., both also served as shale oil and urged in a catalyst in reactor as nitride adsorbent
Change the catalyst of cracking, cooperate with completion shale oil absorption denitrification reaction anti-with shale oil hydrocarbon catalytic cracking in same reaction atmosphere
Should；Then while activity recovery in same regeneration atmosphere.
(3) shale oil first adsorbs recracking, and dry gas is low with coke yield, fluid product (liquefied gas+gasoline+diesel oil) yield
It is high；
(4) shale oil elder generation adsorbing and removing basic nitrogen compound, heavy metal and/or colloid isopolarity material recracking, shale oil
High conversion rate, reduces device green coke.
(5) turbulent fluid bed reactor, is giving full play to high, continuous operation of fluidized bed plant reactor volume utilization rate etc.
On the basis of advantage, strict control linear speed makes catalyst be in turbulent fluidization regimes, and the residence time is long, and be conducive to shale oil with
The counter current contacting of catalyst, absorption denitrification effect is good, is suitable to the processing of shale oil large scale of production, device and reuses and produce low
The market demand of carbon olefin.
Brief description of the drawings
Fig. 1 is the process flow diagram of one embodiment of the present invention；
Fig. 2 is the process flow diagram of another embodiment of the present invention.
Description of reference numerals
The absorbing-stabilizing system of 1 atomizing medium, 2 shale oil, 3 fractionating system 4
The oil gas of 5 cooling medium, 6 regeneration gas, 7 flue gas 8
The diesel oil of 9 dry gas, 10 liquefied gas, 11 gasoline 12
The regenerator of 13 slurry oil, 14 lifting system 15
The normal temperature raw catelyst of 16 feed-line 17
I reactor adsorption zones
The II reactors zone of cracking
Specific embodiment
The invention provides a kind of processing method of shale oil catalytic cracking, wherein, the method comprises the following steps：
(1) with non-hydrogen fluidizing agent flow, make first shale oil into turbulent fluid bed reactor adsorption zone with draw
The first catalytic cracking catalyst entered to the adsorption zone is contacted, and carries out adsorption reaction；The condition of adsorption reaction is：Temperature is 250-
450 DEG C, pressure is 0.1-0.4MPa, and time of contact is -10 minutes 5 seconds, and agent weight of oil ratio is 4.5-10：1；
(2) as non-hydrogen fluidizing agent flows, the shale oil after being contacted through step (1) and the first catalyst is made to enter described
The zone of cracking in turbulent fluid bed reactor contacts together with the second catalytic cracking catalyst for being incorporated into the zone of cracking, is urged
Change cracking reaction；The condition of catalytic cracking reaction is：Temperature is 450-580 DEG C, and pressure is 0.1-0.4MPa, and time of contact is 2-
20 seconds, agent weight of oil ratio was 4-10：1；
(3) material after the catalytic cracking reaction of step (2) is carried out into finish separation, isolated oil gas enters separation
System carries out product separation, and isolated reclaimable catalyst is regenerated into regenerator；
Wherein, first catalytic cracking catalyst is the fresh catalyst Cracking catalyst of supplement, or is from described
The regenerated catalyst or semi regeneration catalyst through cooling of regenerator, or be being urged through the to be generated of cooling from the reactor
Agent；Second catalytic cracking catalyst is the regenerated catalyst from the regenerator.
The present inventor, by years of researches it was unexpectedly observed that being urged including the inferior feedstock oil including shale oil
Not the higher the better to change the conversion ratio of cracking, when high conversion rate to a certain extent, purpose product increases little, dry gas and coke
Yield is but increased considerably；Nitride in shale oil can be by adsorbing and removing, and catalytic cracking catalyst in itself can also
Used as adsorbent, adsorption effect particularly at low temperature is best；In addition, band Pd/carbon catalyst adsorbing and removing nitrogen, heavy metal, carbon residue
Inferior feedstock oil Deng after, density is high, viscosity is big, and long-play easily condenses in a device if non-cracking, causes dress
Put green coke high, therefore, the present invention, by introducing cooling medium, reactor zone is divided into by turbulent fluid bed reactor
Adsorption zone and the zone of cracking, absorption and catalytic cracking process are organically combined, and from the direct catalytic cracking of shale oil, and improve shale
Oily conversion capability, particularly controlling agent weight of oil ratio (the weight ratio of the first catalytic cracking catalyst and shale oil) are 4.5-10：
1, green coke and dry gas can also be significantly reduced while adsorption efficiency is kept, so as to realize shale oil resource high-efficiency profit
With.It is highly preferred that in step (1), first catalytic cracking catalyst is 5-10 with the weight ratio of shale oil：1.
According to the present invention, the apparent average linear speed of oil gas can be 0.5-2.0 meter per seconds, the zone of cracking in the adsorption zone
The apparent average linear speed of middle oil gas can be 0.5-8.0 meter per seconds.
Under preferable case, the condition of the adsorption reaction is：Temperature is 250-300 DEG C, and pressure is 0.1-0.4MPa, contact
Time is -5 minutes 20 seconds, and agent weight of oil ratio is 5-10：1；The condition of the catalytic cracking reaction is：Temperature is 480-550 DEG C,
Pressure is 0.1-0.4MPa, and time of contact is 5-15 seconds, and agent weight of oil ratio is 5-9：1.
In the present invention, the definition of the shale oil is known to those skilled in the art, refers to the page based on shale
Contained petroleum resources in the system of rock stratum, including the hot worked product of oil shale and shale gas association oil, relative density is 0.8-
1.1, rich in alkane, aromatic hydrocarbons and some olefin, gum level is 20%-50%, and carbon hydrogen element weight ratio is 7-9, and nitrogen,
The non-hydrocarbons organic compound content such as sulphur, oxygen is higher, and nonhydrocarbon elemental nitrogen content is 0.3%-5%, and sulfur content is 0.4%-7%,
Oxygen content is 0.5%-10%.
In the present invention, the shale oil can first pass through preheating, and the temperature of the preheating can be 150-400 DEG C, preferably
It is 200-350 DEG C.
According to the present invention, in the turbulent fluid bed reactor, the flow direction of shale oil is anti-with the flowing of catalyst
To identical or opposite；But under preferable case, in the turbulent fluid bed reactor, the flow direction of shale oil is catalyzed with first
The flow direction of Cracking catalyst and the second catalysis is conversely, be so more beneficial for shale oil absorption denitrogenation.
In the turbulent fluid bed reactor, the non-hydrogen flow media can be air, N2Or vapor etc..
According to the present invention, the turbulent fluid bed reactor can be isodiametric turbulent fluid bed reactor, it is also possible to
It is the turbulent fluid bed reactor of reducing, the preferably turbulent fluid bed reactor of reducing.If turbulent fluid bed reactor is inhaled
Attached area is expanding, can strengthen the adsorbing and removing of nitride, colloid etc. in shale oil.
Under preferable case, the turbulent fluid bed reactor is the turbulent fluid bed reactor of reducing, the internal diameter of adsorption zone
Can be 1.1-4 times of zone of cracking internal diameter, preferably 1.5-3.0 times, the absorption section length of the turbulent fluid bed reactor can
Think the 5-40%, preferably 10-30% of the turbulent fluid bed reactor zone of cracking reactor effective length.
In the present invention, by the turbulent fluid bed reactor inject low temperature catalyst and/or cooling medium, with
Adsorption zone and the zone of cracking are formed in the turbulent fluid bed reactor.
According to the present invention, the low temperature catalyst can be fresh catalyst, regenerative agent, the semi regeneration agent by exchanging heat
And/or intermixtures more than spent agent and two kinds or two kinds of agent therein, by the fresh catalyst or fresh catalyst that exchange heat
Agent is stronger with the intermixture denitrogenation adsorption capacity of thermal regenerant, 250-550 DEG C of low temperature catalyst temperature, preferably 250-300 DEG C.
The cooling medium can be water, gasoline, diesel oil, recycle oil or fused salt etc.；Liquid cooling medium injection mode can
It is up together with shale oil to be directly injected into turbulent fluid bed reactor, it is also possible to by the cloth in turbulent fluid bed reactor
Put heat production coil pipe etc. and cause that the first catalytic cracking catalyst exchanges heat with cooling medium, so as to control adsorption zone temperature；When by
Injection cooling medium in the turbulent fluid bed reactor, to form adsorption zone and cracking in the turbulent fluid bed reactor
Qu Shi, preferably arranges heat production coil pipe in turbulent fluid bed reactor, and heat is taken as heat carrier using fused salt.
In the present invention, turbulent flow bed reactor can be arranged in parallel with regenerator, it would however also be possible to employ reactor and
Regenerator vertical direction arranged superposed, reactor can also be above regenerator below regenerator.
In the present invention, the shale oil and catalyst following current or counter current contacting, when shale oil and catalyst co-current contact,
Catalyst is up and shale oil under feed, catalyst is descending and shale oil upper feeding；When shale oil and catalyst counter current contacting,
Catalyst is descending and fed under shale oil, shale oil enters adsorption zone from turbulent fluid bed reactor bottom, as non-hydrogen is fluidized
Medium flows from bottom to top, reverse contact catalyst from top to bottom, on band C catalyst (the first catalytic cracking catalyst)
The impurity such as adsorbing and removing wherein basic nitrogen compound, the carbon content with C catalyst can be 0.2 weight %-2.0 weight %, preferably
0.3 weight %-1.0 weights %.
For example, as shown in figure 1, shale oil 2 and catalyst counter current contacting, catalyst is descending and shale oil feeds for 2 times, turbulence
Fluidized-bed reactor is disposed vertically with regenerator 15, reactor interlude injection cooling medium 5, and reactor is distinguished from the bottom to top
It is adsorption zone I and zone of cracking II, and turbulent fluid bed reactor hypomere is adsorption zone I, the area is using cooling medium cooling first
Catalytic cracking catalyst, shale oil 2 flows from bottom to top with atomizing medium 1, inversely contacts by gravity urging from top to bottom
Agent, carries out catalytic adsorption removing wherein basic nitrogen compound, sulfide, colloid in band charcoal agent (the first catalytic cracking catalyst)
And/or the impurity such as heavy metal；Shale oil 2 therewith on be advanced into zone of cracking II, progressively contact high temperature high activity regenerative agent (second
Catalytic cracking catalyst) carry out catalytic cracking reaction；The oil gas of generation is carried out into fractionating system 3 and absorbing-stabilizing system 4
Product is separated, and obtains the light-end products such as liquefied gas 10, gasoline 11, diesel oil 12, and slurry oil selects freshening or not freshening as needed.Treat
Raw catalyst and part oil gas strip oil gas of its internal absorption of removing into carrying out sedimentation separation in settler；After separation
The boosted system 14 of reclaimable catalyst is conveyed into regenerator 15, is connect with upstream regeneration gas in regenerator 15
Touch, realize regeneration；Regenerative agent after regeneration is recycled through the Returning reactor of feed-line 16.
In addition, as shown in Fig. 2 shale oil 2 and catalyst co-current contact, catalyst is up and shale oil under feed, turbulence
Fluidized-bed reactor is placed in parallel with regenerator 15, and turbulent fluid bed reactor hypomere is adsorption zone I, and the area comes except introducing
Normal temperature fresh catalyst 17 is also introduced so as to obtain the cold catalyst (first of high absorption capacity from the thermal regenerant of outer regenerator 15
Catalytic cracking catalyst), impurity such as basic nitrogen compound, heavy metal and colloid in adsorbing and removing inferior feedstock oil etc.；Subsequent page
Zone of cracking II contacts thermal regenerant (the second catalytic cracking catalyst) is advanced into shale oil 2 carries out catalytic cracking reaction.
(the second catalytic cracking is catalyzed the adsorbent (the first catalytic cracking catalyst) of the adsorption zone with zone of cracking catalyst
Agent), it is composition identical synthetic zeolite catalysts cracking catalyst, it is preferably suitable to the catalytic cracking catalyst of oxygen-containing atmosphere regeneration.
The activity of first catalytic cracking catalyst can be 40-70, preferably 45-60；Second catalytic cracking
The activity of catalyst can be 40-70, preferably 45-65.
The composition of first catalytic cracking catalyst and the second catalytic cracking catalyst can include：Zeolite, inorganic oxygen
Compound and optional clay；First catalytic cracking catalyst and the second catalytic cracking catalyst concrete composition and loadings,
Both shale oil nitrogen content and denitrogenation requirement had been depended on, and had been determined by cracking reaction condition, for example, first catalytic cracking is urged
The composition of agent and the second catalytic cracking catalyst can be：Each component accounts for total catalyst weight respectively：Zeolite 1-50 weights %, nothing
Machine oxide 5-99 weights %, clay 0-70 weights %.Wherein, zeolite can be mesopore zeolite and optional large pore zeolite, mesopore boiling
Stone accounts for 80-100 the weights %, preferably 90 weight %-100 weights % of zeolite gross weight；Large pore zeolite accounts for the 0-20 weight % of zeolite gross weight,
It is preferred that 0 weight %-10 weights %.The mesopore zeolite is selected from ZSM series zeolites and/or ZRP zeolites, and also above-mentioned mesopore zeolite can be used
The transition metal such as the nonmetalloids such as phosphorus and/or iron, cobalt, nickel is modified, relevant ZRP more describe in detail referring to
The record of US5,232,675；ZSM series zeolites can be selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-
38th, one or more the mixture among the zeolite of ZSM-48 and other similar structures, relevant ZSM-5 is more detailed
Description may refer to US3,702,886.The large pore zeolite can be selected from Y-series zeolite, including Rare Earth Y (REY), rare earth hydrogen Y
(REHY) super steady Y, silicon Y high that, distinct methods are obtained.
The inorganic oxide can be selected from silica (SiO as bonding agent2) and/or alundum (Al2O3) (Al2O3),
In terms of dry weight base, silica can account for the heavy % of 50 weight -90 in inorganic oxide, and alundum (Al2O3) can account for the heavy % of 10 weight -50.
The clay, can be de- selected from silica, kaolin and/or halloysite, illiteracy used as matrix (i.e. carrier)
One or more in soil, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.
In the turbulent fluid bed reactor, catalyst is in bubbling or turbulence state, i.e. catalyst are in turbulence
Fluidized state simultaneously relies on gravity fall simultaneously.For this reason, it may be necessary to ensure gas-solid adverse current turbulent flow condition, first catalytic cracking
Based on microspheroidal, diameter range is that can be respectively 0-200 microns, its average grain for catalyst and the second catalytic cracking catalyst
Footpath can be 40-150 microns, and its particle apparent density can be respectively 0.4-0.9g/cm3, wherein, 0-40 microns of fine grained
Account for 10-30 weight %.Finally, the apparent average linear speed of oil gas is controlled to 0.5-2.0 meter per seconds in making the adsorption zone, makes described splitting
The apparent average linear speed of oil gas is controlled to 0.5-8.0 meter per seconds in changing area.
According to the present invention, in step (3), isolated oil gas carries out product separation into piece-rate system, isolated
Reclaimable catalyst regenerated into regenerator；In the regenerative process, regeneration gas can be air, oxygen and oxygen-containing
In gas it is a kind of with it is various, regeneration temperature can be 550-700 DEG C, preferably 600-650 DEG C.The heat exchange of regenerated catalyst
Can be carried out using method well known to those of ordinary skill in the art, so as to control coke growing amount and finish Contact Temperature.
On the other hand, isolated oil gas carries out product (such as gasoline, diesel oil and propylene etc.) side into piece-rate system
Method is well known to those of ordinary skill in the art；The boiling range such as gasoline or diesel oil is adjusted according to actual needs, is not limited only to full stream
Journey gasoline or diesel oil.
This method is further described below by embodiment, but and is not so limited this method.
Raw material used is shale oil in embodiment, and its property is as shown in table 1.
Table 1
| Feedstock oil title | Shale oil | Shale oil |
| Feedstock oil is numbered | A | B |
| Density (20 DEG C), kg/m3 | 895 | 928 |
| 100 DEG C of kinematic viscosity, millimeter2/ the second | 11.2 | 9.03 |
| Carbon residue, weight % | 1.2 | 3.1 |
| Condensation point, DEG C | 33 | 24 |
| Asphalitine, weight % | 0.85 | 1.3 |
| Colloid, weight % | 42.1 | 35.7 |
| Element is constituted | ||
| Carbon, weight % | 85.40 | 83.28 |
| Hydrogen, weight % | 12.09 | 11.65 |
| Sulphur, weight % | 0.53 | 0.53 |
| Nitrogen, weight % | 1.27 | 2.34 |
| Oxygen, weight % | 0.71 | 2.2 |
| Tenor, ppm | ||
| Iron | 6.31 | 11.0 |
| Nickel | 2.95 | 6.6 |
| Vanadium | 0.48 | <0.1 |
| Sodium | 0.9 | 1.3 |
| Boiling range, DEG C | ||
| Initial boiling point | 221 | 305 |
| 30% | 321 | 410 |
| 50% | 384 | 510 |
(the second catalytic cracking is catalyzed adsorbent used (the first catalytic cracking catalyst) with cracking agent in following examples
Agent) it is same, its preparation method is summarized as follows：
(1) by 20gNH4Cl is dissolved in 1000g water, to addition 100g (butt) crystallization product ZRP-1 zeolites in this solution
(Qilu Petrochemical Company's catalyst plant production, SiO2/Al2O3=30, content of rare earth RE2O3=2.0 heavy %), exchange 0.5h at 90 DEG C
Afterwards, filter cake is filtered to obtain；Add 4.0gH3PO4(concentration 85%) and 4.5gFe (NO3)3It is dissolved in 90g water, with filter cake hybrid infusion
Drying；Then phosphorous and iron MFI structure mesopore zeolite, its elementary analysis are obtained within 2 hours in 550 DEG C of roasting temperature treatment
Learning composition is：0.1Na2O·5.1Al2O3·2.4P2O5·1.5Fe2O3·3.8RE2O3·88.1SiO2；
(2) 250kg decationized Y sieves water is used by 75.4kg halloysites (Suzhou china clay company industrial products, solid content
71.6m%) be beaten, add 54.8kg boehmites (Shandong Aluminum Plant's industrial products, solid content 63m%), with hydrochloric acid by its
PH is adjusted to 2-4, stirs, and aging 1 hour is stood at 60-70 DEG C, and holding PH is 2-4, cools the temperature to less than 60 DEG C, plus
Enter 41.5Kg Alumina gels (Qilu Petrochemical Company's catalyst plant product, Al2O3Content is 21.7m%), stir 40 minutes, mixed
Close slurries；
(3) the MFI structure mesopore zeolite (butt is 22.5 kg) of the phosphorous and iron for preparing step (1) and DASY boilings
Stone (Qilu Petrochemical Company's catalyst plant industrial products, lattice constant is 2.445-2.448nm, and butt is 2.0kg) is added to step
Suddenly in the mixed serum that (2) obtain, stir, and add extraordinary adhesive, structural promoter and pore creating material, after mixing and be put in
In bonder, suitable quantity of water is added, stirred, placed 4 hours in atmosphere, shaped with bowling machine spin and placed 24 hours
Afterwards, in drying box 120 DEG C drying 3 hours after, washed with ammonium dihydrogen phosphate (phosphorus content is 1m%), wash away free Na+,
Washing removes free Na+, catalyst is drying to obtain again is designated as CAT-2 (average grain diameter is in 2~4mm), the composition of the catalyst
MFI structure mesopore zeolite, 3 weight %DASY zeolites, 32 weight % boehmites, the 6 heavy % Alumina gels of and iron phosphorous for 15 weight %
And balance kaolin.Its property is listed in table 2.
Table 2
| Catalyst is numbered | CAT-4 |
| Zeolite type | Mesopore and large pore zeolite |
| Chemical composition, weight % | |
| Aluminum oxide | 36.0 |
| Sodium oxide molybdena | 0.29 |
| Iron oxide | 1.6 |
| Rare earth | 2.5 |
| Apparent density, kg/m3 | 1000 |
| Pore volume, ml/g | 0.35 |
| Specific surface area, rice2/ gram | 220~260 |
| Abrasion index, during weight %-1 | 1.5 |
| Screening composition, weight % |
| 0~40 micron | 0 |
| 40~80 microns | 72.0 |
| 80~120 microns | 20.2 |
| 120~160 microns | 6.8 |
| 160~200 microns | 1.0 |
Embodiment 1
Flow according to Fig. 1 is tested, shale oil A as catalytic cracking raw material, on turbulent fluid bed reactor
Tested, regenerator is arranged vertically with reactor for upper and lower, and regenerative agent from top to bottom runs, shale oil is with catalyst countercurrently
Contact, using CAT-4 catalyst, injects a small amount of water as the cooling medium (reaction of adsorption zone between adsorption zone and the zone of cracking
Device internal diameter is identical with the reactor inside diameter of the zone of cracking, the length of the adsorption zone be the length of the zone of cracking 40%).
Shale oil A through 240 DEG C of adsorption zone bottoms of the laggard fluidized bed reactor lower part of preheating, with vapor fluidizing agent from it is lower to
Upper flowing, be than 8, pressure with the weight of shale oil in 280 DEG C of adsorption temp, cold catalyst (the first catalytic cracking catalyst)
0.4MPa, adsorption time remove the impurity such as basic nitrogen compound, sulfide and heavy metal to carry out adsorption reaction under the conditions of 120s,
The apparent average linear speed of oil gas is 0.5 meter per second in the adsorption zone；Shale oil therewith on be advanced into the zone of cracking, at 500 DEG C (to split
Change area's middle portion temperature to be defined), the weight of shale oil is 0.4MPa, reaction time 15s condition than 5, pressure after catalyst and denitrogenation
Next generation catalytic cracking reaction, the apparent average linear speed of oil gas is 2 meter per seconds in the catalytic cracking zone；The oil gas of generation
Product separation is carried out into fractionating system and absorbing-stabilizing system, the light-end products such as liquefied gas, gasoline, diesel oil are obtained, slurry oil is returned
Refining is than being 0.1.Reclaimable catalyst and part oil gas strip removing its internal absorption into carrying out sedimentation separation in settler
Oil gas；Reclaimable catalyst uses air as the lifting boosted system of gas and is conveyed into regenerator after separation, in 600 DEG C of regeneration temperature
Under contacted with upstream regeneration air, realize regeneration；Regenerative agent after regeneration is followed through feed-line Returning reactor
Ring is used.Operating condition and product slates are listed in table 3.
Comparative example 1
Tested on catalytic cracking unit same as Example 1, be different from embodiment 1：Reactor does not draw
Enter the catalyst after cooling, and shale oil A and medium steam are directly injected into the zone of cracking (the i.e. shale oil of turbulent fluid bed reactor
A directly carries out catalytic cracking reaction without absorption), operating condition and product slates are listed in table 3.
Comparative example 2
Catalytic cracking is carried out according to apparatus and method same as Example 1, difference is agent weight of oil ratio in adsorption zone
It is 1：1, adsorption time is 1200s, and product slates are listed in table 3.
Table 3
| Embodiment 1 | Comparative example 1 | Comparative example 2 | |
| Feedstock oil | Shale oil A | Shale oil A | Shale oil A |
| Feeding manner | Adsorption zone feeds | The zone of cracking feeds | Adsorption zone feeds |
| Catalyst title | CAT-4 | CAT-4 | CAT-4 |
| Leveler activity (MAT) | 62 | 62 | 62 |
| Recycle ratio | 0.1 | 0.2 | 0.15 |
| Adsorption zone operating condition | |||
| Raw material preheating temperature, DEG C | 240 | 240 | 240 |
| Adsorption temp, DEG C | 280 | / | 280 |
| Adsorption time, s | 120.0 | / | 1200.0 |
| The weight ratio of catalyst/feed oil | 8.0 | / | 1.0 |
| Shale oil denitrification percent, weight % | 79 | 27 | |
| Zone of cracking operating condition | |||
| Zone of cracking temperature of lower, DEG C | 510 | 510 | 510 |
| Zone of cracking middle portion temperature, DEG C | 500 | 500 | 500 |
| Zone of cracking upper temp, DEG C | 490 | 490 | 490 |
| The weight ratio of catalyst/feed oil | 5.0 | 5.0 | 5.0 |
| Oil gas residence time, s | 15 | 15 | 15 |
| The weight ratio of vapor/total raw material | 0.5 | 0.5 | 0.5 |
| Product slates, weight % | |||
| Dry gas | 3 | 3.5 | 3.3 |
| Liquefied gas | 21.5 | 20.4 | 20.8 |
| Propylene | 10.2 | 9.8 | 10.0 |
| Gasoline | 38.5 | 34 | 36.2 |
| Diesel oil | 24.3 | 26.2 | 25.1 |
| Slurry oil | 4.2 | 6.1 | 5.3 |
| Coke | 8.5 | 9.8 | 9.3 |
| It is total | 100.0 | 100.0 | 100.0 |
| Shale oil conversion ratio, weight % | 71.5 | 67.7 | 69.6 |
| Total liquid yield, weight % | 84.3 | 80.6 | 82.1 |
From table 3 it can be seen that in embodiment 1, shale oil A first adsorbs catalytic cracking again, its absorption denitrification percent is 79 heavy %；
Catalytic cracking again after absorption, the conversion ratio (100%- diesel yields-slurry oil yield) of shale oil is 71.5 heavy %, slurry oil yield
4.2 heavy %, the heavy % of dry gas yied 3.0, the heavy % of coke yield 8.5, total liquid yield (receive by yield of liquefied gas+yield of gasoline+diesel oil
Rate) 84.3 heavy % are up to, wherein gasoline yield is up to 38.5 heavy %, and productivity of propylene is up to 10.2 heavy %.
In comparative example 1, shale oil A directly carries out catalytic cracking reaction without absorption, the heavy % of conversion ratio 67.7 of shale oil,
The heavy % of slurry oil yield 6.1, the heavy % of dry gas yied 3.5, the heavy % of coke yield 9.8, the wherein heavy % of total liquid yield 80.6, gasoline are produced
The heavy % of rate 34.0, productivity of propylene is up to 9.8 heavy %.
The shale oil A of embodiment 1 first adsorbs recracking compared with without the comparative example 1 for adsorbing direct catalytic cracking, and heavy oil turns
Change ability is high, heavy oil recycle ratio is low, and shale oil conversion ratio improves 3.8 percentage points, and 1.9 percentage points of slurry oil low yield,
And dry gas is low with coke yield, dry gas+coke yield is low 1.8 percentage points, and total liquid yield improves 3.7 percentage points.
In comparative example 2, shale oil A is through low oil ratio (1：1), Catalytic Cracking Unit of Measure is carried out again after absorption in (20 minutes) for a long time
Should, shale oil absorption denitrification percent is 27 heavy %, and shale oil conversion ratio is 69.6 heavy %, the heavy % of slurry oil yield 5.3, dry gas yied
3.3 heavy %, the heavy % of coke yield 9.3, the heavy % of total liquid yield 82.1, the wherein heavy % of gasoline yield 36.2, productivity of propylene reach
10.0 heavy %.
The shale oil A of embodiment 1 first adsorbs recracking and through low oil ratio (1：1), the contrast of absorption in (20 minutes) for a long time
Example 2 is compared, and shale oil conversion capability is high, and heavy oil recycle ratio is low, and shale oil conversion ratio improves 1.9 percentage points, and slurry oil yield
It is low 5.3 percentage points, and dry gas is low with coke yield, dry gas+coke yield is low 1.1 percentage points, and total liquid yield improves
2.2 percentage points.
Embodiment 2
Flow according to Fig. 2 is tested, shale oil B as catalytic cracking raw material, on turbulent fluid bed reactor
Tested, reactor and regenerator are arranged in juxtaposition for height, shale oil and catalyst co-current contact, using CAT-4 catalyst,
Normal temperature fresh catalyst is also introduced so as to obtain high absorption capacity except introducing the thermal regenerant from outer regenerator in adsorption zone
Cold catalyst (the first catalytic cracking catalyst).Shale oil B is through 300 DEG C of absorption of the laggard fluidized bed reactor lower part of preheating
Area bottom, as vapor fluidizing agent flows from bottom to top, in the weight of 400 DEG C of adsorption temp, cold catalyst and shale oil B
It is that 0.2MPa, adsorption time are to carry out adsorption reaction under the conditions of 120s than 5.0, pressure, removing basic nitrogen compound, sulfide and weight
Metal impurities, the apparent average linear speed of oil gas is 2 meter per seconds in the adsorption zone；Shale oil B therewith on be advanced into the zone of cracking, connect
Thermal regenerant is touched, is occurred together with the conditions of the weight of shale oil B after denitrogenation is than 5.0, reaction time 5s in 540 DEG C, catalyst
Catalytic cracking reaction, the apparent average linear speed of oil gas is 6 meter per seconds in the zone of cracking；The oil gas of generation enter fractionating system and
Absorbing-stabilizing system carries out product separation, obtains the light-end products such as liquefied gas, gasoline, diesel oil, and slurry oil recycle ratio is 0.15.It is to be generated
Catalyst and part oil gas strip oil gas of its internal absorption of removing into carrying out sedimentation separation in settler；Treated after separation
Raw catalyst uses air as the lifting boosted system of gas and is conveyed into regenerator, at 640 DEG C of regeneration temperature with sail against the current
Regeneration air contacted, realize regeneration；Regenerative agent after regeneration is recycled through feed-line Returning reactor.Operation bar
Part and product slates are listed in table 4.
Embodiment 3
Catalytic cracking is carried out according to method same as Example 2, difference is：Reactor bottom adsorption zone introduce with
The fresh catalyst of hot recycling catalytic cracking catalyst heat exchange is used as the first catalytic cracking catalyst, operating condition and product slates
It is listed in table 3.
Comparative example 3
Catalytic cracking is carried out according to apparatus and method same as Example 2, difference is：Reactor is not injected into cooling and is situated between
Matter and shale oil B are directly injected into the top of turbulent fluid bed reactor with fluidizing agent steam, and (i.e. shale oil B is suitable with catalyst
Stream and on, shale heavy oil without absorption directly carry out catalytic cracking reaction).Operating condition and product slates are listed in table 4.
Table 4
| Embodiment 2 | Embodiment 3 | Comparative example 3 | |
| Feedstock oil | Shale oil B | Shale oil B | Shale oil B |
| Feeding manner | Adsorption zone feeds | Adsorption zone feeds | The zone of cracking feeds |
| Catalyst title | CAT-4 | CAT-4 | CAT-4 |
| Leveler activity (MAT) | 58 | 58 | 58 |
| Recycle ratio | 0.15 | 0.15 | 0.25 |
| Adsorption zone operating condition | |||
| Raw material preheating temperature, DEG C | 300 | 300 | 300 |
| Adsorption temp, DEG C | 400 | 400 | / |
| Adsorption time, s | 120.0 | 120.0 | / |
| The weight ratio of catalyst/feed oil | 6.0 | 6.0 | / |
| Shale oil denitrification percent, weight % | 85 | 93 | |
| Zone of cracking operating condition | |||
| Zone of cracking temperature of lower, DEG C | 550 | 550 | 550 |
| Zone of cracking middle portion temperature, DEG C | 540 | 540 | 540 |
| Zone of cracking upper temp, DEG C | 520 | 520 | 520 |
| The weight ratio of catalyst/feed oil | 5.0 | 5.0 | 5.0 |
| Oil gas residence time, s | 5.0 | 5.0 | 5.0 |
| The weight ratio of vapor/total raw material | 0.5 | 0.5 | 0.5 |
| Product slates, weight % | |||
| Dry gas | 3.8 | 3.6 | 4.3 |
| Liquefied gas | 23.5 | 23.9 | 20.4 |
| Propylene | 11.2 | 11.4 | 8.5 |
| Gasoline | 30.4 | 30.9 | 27.4 |
| Diesel oil | 27.3 | 27.5 | 29.4 |
| Slurry oil | 4.8 | 4.3 | 6.3 |
| Coke | 10.2 | 9.8 | 12.2 |
| It is total | 100 | 100.00 | 100 |
| Shale oil conversion ratio, weight % | 67.9 | 68.2 | 64.3 |
| Total liquid yield, weight % | 81.2 | 82.3 | 77.2 |
From table 4, it can be seen that in embodiment 2, shale oil B first adsorbs catalytic cracking again, its absorption denitrification percent is 85 heavy %；
Catalytic cracking again after absorption, the conversion ratio of shale oil is 67.9 heavy %, the heavy % of slurry oil yield 4.8, the heavy % of dry gas yied 3.8, Jiao
The heavy % of charcoal yield 10.2, total liquid yield is up to 81.2 heavy %, and wherein gasoline yield is up to 30.4 heavy %, and productivity of propylene is up to
11.2 heavy %.
In embodiment 3, the fresh catalyst with the heat exchange of hot recycling catalytic cracking catalyst is introduced in reactor bottom adsorption zone
Agent adsorbs catalytic cracking again as the first catalytic cracking catalyst, shale oil B, and its absorption denitrification percent is 95 heavy %；Turbulence is adsorbed
Catalytic cracking again afterwards, the conversion ratio (100%- diesel yields-slurry oil yield) of shale oil is 68.2 heavy %, and slurry oil yield is 4.3
Weight %, dry gas yied is 3.6 heavy %, and coke yield is 9.8 heavy %, total liquid yield (yield of liquefied gas+yield of gasoline+diesel oil
Yield) 82.3 heavy % are up to, wherein gasoline yield is up to 30.9 heavy %, and productivity of propylene is up to 11.4 heavy %.
In comparative example 3, shale oil B directly carries out catalytic cracking reaction without absorption, and the conversion ratio of shale oil is 64.3
Weight %, the heavy % of slurry oil yield 6.3, the heavy % of dry gas yied 4.3, the heavy % of coke yield 12.2, the heavy % of total liquid yield 77.2, wherein
The heavy % of gasoline yield 27.4, productivity of propylene is up to 8.5 heavy %.
The shale oil B of embodiment 2 first adsorbs recracking compared with without the comparative example 3 for adsorbing direct catalytic cracking, and heavy oil turns
Change ability is high, heavy oil recycle ratio is low, and shale oil conversion ratio improves 3.6 percentage points, and 1.5 percentage points of slurry oil low yield,
And dry gas is low with coke yield, dry gas+coke yield is low 2.5 percentage points, and total liquid yield improves 4.0 percentage points.
Embodiment 3 (introduces the fresh catalyst with the heat exchange of hot recycling catalytic cracking catalyst in reactor bottom adsorption zone
As the first catalytic cracking catalyst) (the hot recycling catalytic cracking catalyst after cooling is used as the first catalytic cracking with embodiment 2
Catalyst) to compare, shale oil denitrification percent is high, and dry gas is low with coke yield, and dry gas+coke yield is low 0.5 percentage point, always
Liquid is received and improves 1.1 percentage points.
It can thus be seen that the method for processing shale oil that the present invention is provided, by turbulent fluid bed reactor, passing through
Low temperature catalyst is introduced, reactor zone is divided into turbulent fluid bed reactor adsorption zone and the turbulent fluid bed reactor zone of cracking,
Reaction absorption and catalytic cracking process are organically combined, from the direct catalytic cracking of shale oil, and shale oil conversion capability is improved,
Green coke and dry gas are reduced, so as to realize shale oil resources effective utilization.
Claims (7)
1. a kind of processing method of shale oil catalytic cracking, the method comprises the following steps：
(1) with non-hydrogen fluidizing agent flow, make first shale oil into turbulent fluid bed reactor adsorption zone be incorporated into
The first catalytic cracking catalyst contact of the adsorption zone, carries out adsorption reaction；The condition of adsorption reaction is：Temperature is 250-450
DEG C, pressure is 0.1-0.4MPa, and time of contact is -10 minutes 5 seconds, and agent weight of oil ratio is 4.5-10：1；
(2) as non-hydrogen fluidizing agent flows, the shale oil after being contacted through step (1) and the first catalyst is made to enter the turbulence
The zone of cracking in fluidized-bed reactor contacts together with the second catalytic cracking catalyst for being incorporated into the zone of cracking, carries out catalysis and splits
Change reaction；The condition of catalytic cracking reaction is：Temperature is 450-580 DEG C, and pressure is 0.1-0.4MPa, and time of contact is 2-20
Second, agent weight of oil ratio is 4-10：1；
(3) material after the catalytic cracking reaction of step (2) is carried out into finish separation, isolated oil gas enters piece-rate system
Product separation is carried out, isolated reclaimable catalyst is regenerated into regenerator；
Wherein, first catalytic cracking catalyst is the fresh catalyst Cracking catalyst of supplement, or is from the regeneration
The regenerated catalyst or semi regeneration catalyst through cooling of device, or be the catalysis to be generated through cooling down from the reactor
Agent；Second catalytic cracking catalyst is the regenerated catalyst from the regenerator；
Wherein, in the turbulent fluid bed reactor, the flow direction of shale oil and the first catalytic cracking catalyst and second
The flow direction of catalytic cracking catalyst is opposite；The turbulent fluid bed reactor is reducing turbulent fluid bed reactor, and
The internal diameter of the adsorption zone is 1.1-4 times of the zone of cracking internal diameter, and the length of the adsorption zone is the length of the zone of cracking
5-40%.
2. method according to claim 1, it is characterised in that the catalyst reactor is in bubbling or turbulence shape
State, wherein, the apparent average linear speed of oil gas is 0.5-2.0 meter per seconds in the adsorption zone, and oil gas is apparent average in the zone of cracking
Linear speed is 0.5-8.0 meter per seconds.
3. method according to claim 1, wherein, the condition of the adsorption zone is：Temperature is 250-300 DEG C, and pressure is
0.1-0.4MPa, time of contact is -5 minutes 20 seconds, and agent weight of oil ratio is 5-10：1.
4. method according to claim 1, wherein, the condition of the catalytic cracking reaction is：Temperature is 480-550 DEG C,
Pressure is 0.1-0.4MPa, and time of contact is 5-15 seconds, and agent weight of oil ratio is 5-9：1.
5. method according to claim 1 and 2, wherein, the catalyst particle size scope is in 0~200 micron, average grain diameter
40~150 microns, its particle apparent density is 0.8~1.5g/cm3。
6. method according to claim 1, wherein, first catalytic cracking catalyst and the second catalytic cracking catalyst
It is composition identical synthetic zeolite catalysts cracking catalyst, being to use includes zeolite, inorganic oxide and optional clay zeolite
Microballoon.
7. method according to claim 1, wherein, first catalytic cracking catalyst is the warp from the regenerator
Fresh catalyst after the regenerated catalyst of cooling or heat exchange.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410558881.9A CN105586081B (en) | 2014-10-20 | 2014-10-20 | Processing method by shale oil through catalytic cracking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410558881.9A CN105586081B (en) | 2014-10-20 | 2014-10-20 | Processing method by shale oil through catalytic cracking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105586081A CN105586081A (en) | 2016-05-18 |
| CN105586081B true CN105586081B (en) | 2017-05-24 |
Family
ID=55925992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410558881.9A Active CN105586081B (en) | 2014-10-20 | 2014-10-20 | Processing method by shale oil through catalytic cracking |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105586081B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109554192B (en) * | 2017-09-26 | 2021-10-08 | 中国石油化工股份有限公司 | Method for catalytic conversion of kerogen shale oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031148A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Catalytic conversion method for processing high-nitrogen raw material |
| CN103031147A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Catalytic conversion method for processing high-nitrogen raw material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7763163B2 (en) * | 2006-10-20 | 2010-07-27 | Saudi Arabian Oil Company | Process for removal of nitrogen and poly-nuclear aromatics from hydrocracker feedstocks |
-
2014
- 2014-10-20 CN CN201410558881.9A patent/CN105586081B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031147A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Catalytic conversion method for processing high-nitrogen raw material |
| CN103031148A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Catalytic conversion method for processing high-nitrogen raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105586081A (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107267211B (en) | A kind of processing method and system of inferior feedstock oil | |
| CN100487080C (en) | Chemical oil-refining method for preparing low carbon olefin and arene | |
| WO2020015603A1 (en) | Method, reactor and system for catalytic cracking of hydrocarbon oil | |
| CN107557067B (en) | A kind of catalysis conversion method and system of inferior feedstock oil | |
| CN105505455B (en) | A kind of processing method of shale oil catalytic cracking | |
| CN107267207B (en) | A kind of processing method and system of inferior feedstock oil | |
| CN113462429B (en) | Method for producing low-carbon olefin and aromatic hydrocarbon | |
| CN107557066B (en) | A kind of catalysis conversion method and system of inferior feedstock oil | |
| CN101204666B (en) | Catalytic cracking propylene-increasing catalyst and preparation method thereof | |
| CN107557063B (en) | A kind of catalysis conversion method of inferior feedstock oil | |
| CN105586081B (en) | Processing method by shale oil through catalytic cracking | |
| CN101204668B (en) | Propylene production increasing cracking catalyst and preparation method thereof | |
| CN105505454B (en) | A kind of shale oil fluidized catalytic cracking method | |
| CN102031138B (en) | Catalytic conversion method for productive diesel and propylene | |
| CN112745895B (en) | Method and device for continuously producing aromatic hydrocarbon by hydrocatalytically cracking FCC circulating oil | |
| CN111040807B (en) | Method and system for processing inferior oil by adopting double lifting pipes | |
| CN105586080B (en) | A kind of processing method of shale oil catalytic cracking | |
| CN107267208B (en) | A kind of processing method and system of inferior feedstock oil | |
| CN208869552U (en) | A kind of catalytic cracking system | |
| CN112745896B (en) | Method and device for continuously producing aromatic hydrocarbon by hydrocatalytically cracking FCC circulating oil | |
| CN111040809B (en) | Hydrogen process method and system for inferior oil | |
| CN102051227B (en) | Catalytic conversion method for producing diesel and propylene in high yield | |
| CN1142255C (en) | Process for catalytic cracking of heavy petroleum hydrocarbon | |
| CN107557061B (en) | A kind of catalysis conversion method and system of inferior feedstock oil | |
| CN115873623A (en) | Reaction system and method for producing low-carbon olefin and aromatic hydrocarbon by catalytic cracking |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |