CN1100119C - Catalytic process for modifying poor-quality diesel oil - Google Patents
Catalytic process for modifying poor-quality diesel oil Download PDFInfo
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Abstract
The present invention relates to a method for catalytically modifying poor-quality diesel oil, which is characterized in that the fraction of preheated diesel oil is filled in a lifting pipe or a fluidized-bed reactor and is contacted and reacts with catalysts of which the coke content is <=0.3 wt. % and the temperature is below 600 DEG C, wherein the reaction temperature is from 250 DEG C to 550DEG. C, the weight space velocity is from 1 to 120 hour <-1>, the weight ratio of the catalysts to the diesel oil fraction is from 2 to 20, the weight ratio of steam to the diesel oil fraction is from 0.01 to 0.15, and the reaction pressure is from 130 to 450KPa; reaction products are separated from spent catalysts which are returned to the reactor to be circularly used after air stripping and regeneration. The present invention has the advantage that the cetane value of diesel oil is obviously improved by using the method. The present invention has certain effects to reduce impurity contents such as sulfur, nitrogen, etc.
Description
The invention belongs to the catalysis conversion method of petroleum hydrocarbon under the situation that does not have hydrogen, more particularly, is a kind of method of utilizing catalytic conversion process to improve the poor ignition quality fuel quality.
Along with the development trend of crude oil heaviness, poor qualityization, heavy oil deep-processing process such as catalytic cracking, delayed coking, viscosity breaking are being brought into play more and more important effect in the production of oils.Yet, the vapour that said process is produced, the inferior quality of diesel product, directly using as fuel oil can serious environment pollution.
In order to satisfy environmental requirement, many countries have all formulated a series of fuel oil standard, various content of harmful in strict restriction vapour, the diesel oil.For example, developed country's requirements such as America and Europe, the sulphur content of diesel oil less than 20 body %, promptly requires to use the diesel product of low-sulfur, low aromatic hydrocarbons less than 0.05 heavy %, aromaticity content.China is relatively loose to the requirement of diesel quality at present, and sulphur content does not also propose the requirement to aromaticity content for not being higher than 0.2 heavy %.But along with the reinforcement gradually of environmental protection consciousness, will inevitably increasingly stringent to the requirement of fuel oil quality.
The poor ignition quality fuel that processes such as catalytic cracking in the prior art,, delayed coking, viscosity breaking are produced is mainly handled by hydrofining or hydrocracking.By hydrotreatment, under hydrogen pressure, realize the catalytic reforming of diesel oil, reach desulfurization, denitrogenation, alkene is saturated, aromatic hydrocarbons is saturated purpose, to improve diesel quality, satisfy environmental requirement.The upgrading of this method is effective, but cost is higher.Some at present domestic oil refining enterprises lack the means of hydrofining or hydrocracking, even possess the means of hydrotreatment, also exist problems such as working ability deficiency, shortage hydrogen source.Therefore, need the Technology of the effectively suitable China's national situation of research and development, to solve the diesel quality problem.
The catalytic process for modifying that the purpose of this invention is to provide a kind of poor ignition quality fuel non-hydrogen.
The objective of the invention is to realize by following scheme: in the diesel oil distillate injecting reactor after the preheating, be lower than 600 ℃ catalyzer with heavy % in coke content≤0.3 and temperature and contact and react, temperature of reaction is 250～550 ℃, and weight hourly space velocity is 1～120 o'clock
-1, the weight ratio of catalyzer and diesel oil distillate is 2～20, and the weight ratio of water vapour and diesel oil distillate is 0.01～0.15, and reaction pressure is 130～450Kpa; Reaction product isolated and spent agent, spent agent has at least a part to cool off earlier after stripping, regeneration, and Returning reactor recycles then.
Concrete implementation step of the present invention is as follows: in the diesel oil distillate injecting lift pipe or fluidized-bed reactor after the preheating, being in or be not in water vapor exists down and to be lower than 600 ℃ catalyzer with heavy % in coke content≤0.3 and temperature and to contact and react, temperature of reaction is 250～550 ℃, be preferably 320～530 ℃, weight hourly space velocity is 1～120 o'clock
-1, be preferably at 10～100 o'clock
-1, the weight ratio of catalyzer and diesel oil distillate (hereinafter to be referred as agent-oil ratio) is 2～20, is preferably 3～18, the weight ratio of water vapour and diesel oil distillate (hereinafter to be referred as water-oil ratio) is 0～0.15, be preferably 0.02～0.10, reaction pressure is 130～450KPa, is preferably 200～400KPa; The spent agent of reaction product isolated and reaction back carbon deposit, reaction product is separated into diesel oil, a spot of gasoline, liquefied gas and dry gas through subsequent separation system, spent agent is sent in the revivifier behind the water vapor stripping, coke burning regeneration under the effect of oxygen-containing gas, the high temperature regeneration agent after the regeneration partly or entirely after cooling off Returning reactor recycle.
The hydrocarbon raw material that the present invention is suitable for is a diesel oil distillate.This diesel oil distillate can be full cut, for example, and the cut about 200 ℃ to 380 ℃; Also can be part narrow fraction wherein, for example, 270～360 ℃ cut.Described diesel oil distillate can be the time processing diesel oil distillate, and for example straight-run diesel oil also can be the secondary processing diesel oil cut, and for example catalytic diesel oil, coker gas oil, viscosity breaking diesel oil etc. can also be the mixtures of above-mentioned more than one diesel oil distillates.
Catalyzer used in the present invention can be any solid acid catalyst that is applicable to catalytic cracking process, and its active ingredient is selected from one or more in Y type or HY type zeolite, the ultrastable Y that contains or do not contain rare earth and/or phosphorus, the ZSM-5 type zeolite that contains or do not contain rare earth and/or phosphorus or the supersiliceous zeolite with five-membered ring structure, β zeolite, the ferrierite.
In the present invention, the coke content of the catalyzer that contacts with diesel oil distillate is answered≤0.3 heavy %, preferably≤0.25 heavy %.Under the identical operations condition, the coke content of the catalyzer that contacts with diesel oil distillate is low more, and the effect of diesel oil catalytic reforming is good more.The described catalyzer that contacts with diesel oil distillate can be regenerator, half regenerator or their mixture.
Riser tube that the present invention is used or fluidized-bed reactor can be conventional riser tube or fluidized-bed reactors, also can be other reaction zones that is applicable to catalytic cracking process, for example, downflow reactor, etc. linear speed reactor etc.
The present invention implements separately on can catalytic cracking unit, also can with the catalytic cracking unit Joint Implementation of the conventional catalytically cracked material of processing.When the present invention implements separately, basic identical with conventional catalytic cracking process, only need diesel oil distillate as stock oil, after preheating in the injecting reactor, contact and react with catalyzer and get final product.When the catalytic cracking unit Joint Implementation of the present invention with the conventional catalytically cracked material of processing, need the catalytic cracking unit of routine is slightly done transformation, diesel oil distillate and conventional catalytically cracked material are reacted in reactor separately respectively, and the stripping process of the separation of the separating of reaction oil gas and catalyzer, reaction product and reaction back band Pd/carbon catalyst can above-mentioned two bursts of reactant flow carry out separately separately, also two bursts of reactant flow can be lumped together jointly and carry out, but the regenerative process of spent agent is carried out jointly, a promptly shared cover regeneration system rapidly.
Enumerate five kinds of concrete embodiments below and further specify catalytic process for modifying provided by the invention, but the present invention is not limited to any embodiment hereinafter.
Embodiment A: for riser fluid catalytic cracking, the cracking stock of routine can be replaced by diesel oil distillate, and increase a catalyst cooler in the downstream of revivifier, and regenerated catalyst is cooled to 300～600 ℃, contact with diesel oil distillate then and react.Reaction product, water vapor and reclaimable catalyst carry out gas solid separation, and reaction product further is separated into diesel oil, a spot of gasoline, liquefied gas and dry gas in subsequent separation system.Spent agent is transported to the revivifier coke burning regeneration behind the water vapor stripping, the high temperature regeneration agent Returning reactor after cooling off after the regeneration recycles.
Embodiment B:, need a newly-built riser reactor for the catalytic cracking unit of single riser reactor.The shared original settling vessel of newly-built riser reactor and original riser reactor, stripper, subsequent separation system and regeneration system rapidly.The raw material of newly-built reactor is a diesel oil distillate, and this reactor is called the diesel oil riser reactor; The raw material of original reactor is conventional cracking stock, and this reactor is called the stock oil riser reactor.Diesel raw material and conventional cracking stock react in reactor separately respectively, and reacted oil gas and mixture of catalysts enter settling vessel and subsequent separation system jointly.Isolated diesel product can partly return the raw material as the diesel oil riser tube.Spent agent is regenerated behind stripping, and the catalyzer after the regeneration is divided into two portions, and wherein a part is returned the stock oil riser tube, and another part returns the diesel oil riser tube after the catalyst cooler cooling.
Embodiment C: for the catalytic cracking unit of single riser reactor, need a newly-built fluidized-bed reactor that has or do not have riser tube, this reactor can have or not have stripping stage.Newly-built reactor and original reactor common regenerator.The raw material of newly-built reactor is a diesel oil distillate, and this reactor is called the diesel oil reactor; The raw material of original reactor still is conventional cracking stock, and this reactor is called the stock oil riser reactor.Diesel oil distillate and conventional cracking stock react in reactor separately respectively; Enter subsequent separation system after the reaction oil gas that reaction oil gas that diesel oil distillate generates and conventional cracking stock generate mixes, perhaps enter subsequent separation system separately respectively, isolated diesel product can partly return the raw material as the diesel oil riser tube.Spent agent is regenerated behind stripping, and the catalyzer after the regeneration is divided into two portions, and wherein a part is returned the stock oil riser tube, and another part returns the diesel oil reactor after the water cooler cooling.
Embodiment D: method provided by the invention can also be implemented on the machinery that is made of a kind of novel riser reactor and conventional catalytic cracking unit.Described novel riser reactor has been that CN1237477A, denomination of invention are open for the patent application of " a kind of riser reactor that is used for fluidized catalytic conversion " at publication number.This reactor vertically is followed successively by from bottom to up: co-axial each other pre lift zone, first reaction zone, enlarged-diameter second reaction zone, reduced outlet area, be connected with one section level pipe at the outlet area end.The combining site of first and second reaction zone is a truncated cone-shaped, and the apex angle of its longitudinal section isosceles trapezoid is 30～80 °; The combining site of second reaction zone and outlet area is a truncated cone-shaped, and the base angle β of its longitudinal section isosceles trapezoid is 45～85 °.In order to implement the present invention, need on original catalytic cracking unit, add an aforesaid novel riser reactor and a catalyst cooler.Original riser reactor as the diesel oil riser reactor, is used for the upgrading of diesel oil distillate; Novel riser reactor is used for the conventional catalytically cracked material of cracking as the stock oil riser reactor.Diesel oil distillate reacts in the diesel oil riser tube, and the reaction oil gas of generation and mixture of catalysts are introduced second reaction zone of stock oil riser tube as the cold shock medium.Reaction oil gas in the stock oil riser tube enters settling vessel with spent agent by its outlet area to be separated.Reaction oil gas is introduced subsequent separation system, and isolated diesel product can partly return the raw material as the diesel oil riser tube.Spent agent is divided into two portions after stripping, regeneration, wherein a part is returned the stock oil riser tube, and another part returns the diesel oil riser tube after cooling.
Embodiment E: adopt and the essentially identical device type of embodiment D.In order to implement the present invention, need on original catalytic cracking unit, add an aforesaid novel riser reactor and a catalyst cooler.Original riser reactor as the diesel oil riser reactor, is used for the conversion of diesel oil distillate; Novel riser reactor is used for the conventional catalytically cracked material of cracking as the stock oil riser reactor.Diesel oil distillate reacts in the diesel oil riser tube, and the reaction oil gas of generation and mixture of catalysts are introduced second reaction zone of stock oil riser tube as the cold shock medium.Reaction oil gas in the stock oil riser tube and reclaimable catalyst enter settling vessel by its outlet area; Reaction oil gas enters subsequent separation system to be separated, and isolated diesel oil can partly return the raw material as the diesel oil riser tube.Reclaimable catalyst is regenerated behind stripping.Half regenerated catalyst in first revivifier is divided into two portions, and wherein a part enters second revivifier and continues to burn coke residual on the catalyzer, and another part half regenerated catalyst enters catalyst cooler, returns the diesel oil riser tube after the cooling; And the regenerated catalyst in second revivifier returns the stock oil riser tube
Further specify the cited above-mentioned embodiment of the present invention below in conjunction with accompanying drawing, understand the present invention better to help those skilled in the art, but it should be interpreted as limitation of the present invention.
Fig. 1 is the schematic flow sheet of embodiment A.As shown in Figure 1, diesel oil distillate after the preheating enters riser tube 2 bottoms through pipeline 1, give birth to reaction with the regenerator hybrid concurrency from regenerator sloped tube 17, reactant flow enters the settling vessel 7 that has or do not have the dense fluidized bed bioreactor, and reaction oil gas and water vapor enter subsequent separation system through pipeline 8.Spent agent enters stripper 3, by the entrained reaction oil gas of water vapor stripping spent agent from pipeline 4, spent agent behind the stripping enters revivifier 13 through inclined tube 5 to be generated, oxygen-containing gas is introduced revivifier through pipeline 14, spent agent is coke burning regeneration under the effect of oxygen-containing gas, regenerated flue gas is drawn revivifier through pipeline 12, the pyritous regenerator enters catalyst cooler 16 through pipeline 15, cooled regenerator returns the riser tube bottom cycle by regenerator sloped tube 17 and uses, and loosening wind enters catalyst cooler 16 through pipeline 18.
Fig. 2 is the schematic flow sheet of embodiment B.As shown in Figure 2, diesel oil distillate after the preheating enters riser tube 2 bottoms through pipeline 1, contact with regenerator from regenerator sloped tube 17 and react, reactant flow enters the settling vessel 27 that has or do not have the dense fluidized bed bioreactor, the separating of realization response oil gas and catalyzer.Simultaneously, the pre-medium that promotes enters through the bottom of pipeline 20 from stock oil riser tube 22, the high temperature regeneration agent enters the bottom of riser tube 22 through regenerator sloped tube 19, promote by pre-lifting medium, conventional cracking stock after the preheating is through pipeline 21 injecting lift pipes 22, mix with the high temperature regeneration agent and react, reactant flow enters the settling vessel 27 that has or do not have the dense fluidized bed bioreactor, the separating of realization response oil gas and catalyzer.Reaction oil gas enters subsequent separation system through pipeline 28, realizes the separation to dry gas, liquefied gas, gasoline, diesel oil and heavy oil.Spent agent enters stripper 23, by the entrained reaction oil gas of water vapor stripping spent agent from pipeline 24, spent agent behind the stripping enters revivifier 13 by inclined tube 25 to be generated, oxygen-containing gas is introduced revivifier through pipeline 14, spent agent is coke burning regeneration under the effect of oxygen-containing gas, regenerated flue gas is drawn revivifier through pipeline 12, the high temperature regeneration agent is divided into two portions, wherein, part regenerator enters catalyst cooler 16 through pipeline 15, and cooled regenerator returns diesel oil riser tube bottom cycle by regenerator sloped tube 17 and uses; Another part regenerator returns stock oil riser tube 22 through regenerator sloped tube 19.The loosening wind of catalyst cooler enters through pipeline 18.
Fig. 3 is the schematic flow sheet of embodiment C.As shown in Figure 3, diesel oil distillate after the preheating enters diesel oil riser tube 2 bottoms through pipeline 1, contact with regenerator from regenerator sloped tube 17 and react, reactant flow enters the settling vessel 7 that has or do not have the dense fluidized bed bioreactor, the separating of realization response oil gas and catalyzer.Reaction oil gas and water vapor enter separation system 9 through pipeline 8, and gas and gasoline products are drawn through pipeline 10, and diesel product is then drawn through pipeline 11; Meanwhile, promote medium in advance and enter through the bottom of pipeline 20 from stock oil riser tube 22, the pyritous regenerated catalyst enters the bottom of riser tube 22 through regenerator sloped tube 19, is promoted by pre-lifting medium; Conventional cracking stock after the preheating enters the bottom of riser tube 22 through pipeline 21, and reacts after the pyritous regenerated catalyst mixes, and reactant flow enters the settling vessel 27 that has or do not have the dense fluidized bed bioreactor; The reaction oil gas and the water vapor of conventional cracking stock enter subsequent separation system through pipeline 28, realize the separation to dry gas, liquefied gas, gasoline, diesel oil and heavy oil.Also can will mix with reaction oil gas and water vapour through pipeline 32 from the reaction oil gas of diesel oil riser tube and water vapor from the stock oil riser tube, enter subsequent separation system through pipeline 28 together, realize separation dry gas, liquefied gas, gasoline, diesel oil and heavy oil.Reclaimable catalyst from the diesel oil riser tube enters stripper 3, behind the water vapor stripping from pipeline 4, enters revivifier 13 by inclined tube 5 to be generated; The reclaimable catalyst of stock oil riser tube enters stripper 23, by the water vapor stripping from pipeline 24; Catalyzer behind the stripping enters revivifier 13 by inclined tube 25 to be generated; Perhaps stripper 3,23 is linked to each other by pipeline 33, make above-mentioned two kinds of reclaimable catalysts in stripper 23, finish stripping process jointly.Air enters revivifier 13 through pipeline 14, and reclaimable catalyst is coke burning regeneration in air, and regenerated flue gas is drawn by pipeline 12.The pyritous regenerator is divided into two portions, and wherein a part is returned stock oil riser tube 22 through regenerator sloped tube 19; Another part enters water cooler 16 through pipeline 15, after the cooling, returns diesel oil riser tube 2 by regenerator sloped tube 17 and recycles according to a conventional method.Loosening medium enters catalyst cooler 16 through pipeline 18.
Fig. 4 is the schematic flow sheet of embodiment D.As shown in Figure 4, the diesel raw material after the preheating enters the bottom of diesel oil riser tube 2 through pipeline 1, reacts with cooled regenerator from regenerator sloped tube 17, and the reactant flow that is generated is injected the second reaction zone c of novel material oil riser 22.Meanwhile, promote medium in advance and enter through the bottom of pipeline 20 from novel riser tube 22, the high temperature regeneration agent enters the pre lift zone a of riser tube 22 through regenerator sloped tube 19, is promoted by pre-lifting medium; Conventional cracking stock after the preheating is through pipeline 21 incoming stock oil risers 22, mixes with high temperature regeneration agent in this riser tube, and reacts at the first reaction zone b of this riser tube; The reactant flow that is generated enters the second reaction zone c, and mixes from the reactant flow of diesel oil riser tube 2 and carries out secondary reaction.Above-mentioned reactant flow enters settling vessel 27 through outlet area d, the level pipe e of riser tube 22, and reaction oil gas is separated with catalyzer; Reaction oil gas enters subsequent separation system through pipeline 28, realizes the separation to dry gas, liquefied gas, gasoline, diesel oil and heavy oil.Spent agent falls into stripper 23 by settling vessel 27, behind the water vapor stripping from pipeline 24, sends into revivifier 13 by inclined tube 25 to be generated.Spent agent is coke burning regeneration in revivifier, and regeneration air is introduced revivifier through pipeline 14, and regenerated flue gas is drawn through pipeline 12.The high temperature regeneration agent is divided into two portions, and wherein a part is transported to riser tube 22 through regenerator sloped tube 19 and recycles; Another part enters catalyst cooler 16 through pipeline 15, and cooled regenerator returns diesel oil riser tube 2 by regenerator sloped tube 17 and recycles.The loosening medium of catalyst cooler 16 is introduced by pipeline 18.
Fig. 5 is the schematic flow sheet of embodiment E.As shown in Figure 5, diesel oil distillate after the preheating enters the bottom of diesel oil riser tube 2 through pipeline 1, cooled half regenerated catalyst enters, reacts with diesel oil distillate through the bottom of half regenerator sloped tube 17 by riser tube 2, and reactant flow enters the second reaction zone c of novel material oil riser 22.Meanwhile, promote medium in advance and enter through the bottom of pipeline 20 by novel material oil riser 22, the pyritous regenerated catalyst is promoted by pre-lifting medium through the pre lift zone a of regenerator sloped tube 19 incoming stock oil risers 22.Conventional cracking stock after the preheating is through pipeline 21 incoming stock oil risers 22, mixing the back with high-temperature regenerated catalyst reacts at the first reaction zone b of stock oil riser tube 22, reactant flow enters the second reaction zone c of riser tube 22, and mixes from the reactant flow of diesel oil riser tube 2.Reaction oil gas and reclaimable catalyst enter settling vessel 27 through outlet area d, the level pipe e of riser tube 22, and reaction oil gas and water vapor enter subsequent separation system through pipeline 28, realize the separation to dry gas, liquefied gas, gasoline, diesel oil and heavy oil.Reclaimable catalyst enters stripper 23, by the water vapor stripping from pipeline 24; Catalyzer behind the stripping enters first revivifier 13.1 by inclined tube 25 to be generated.Air enters first revivifier 13.1 and second revivifier 13.2 through pipeline 14, and reclaimable catalyst is coke burning regeneration in air, and regenerated flue gas is drawn first revivifier 13.1 and second revivifier 13.2 by pipeline 12.Half regenerated catalyst of heat is divided into two portions, and wherein a part enters second revivifier 13.2 and carries out holomorphosis, and regenerated catalyst returns stock oil riser tube 22 through regenerator sloped tube 19; Another part enters water cooler 16 through pipeline 15, returns diesel oil riser tube 2 by half regenerator sloped tube 17 after the cooling according to a conventional method and recycles.Loosening wind enters water cooler 16 through pipeline 18.
Compared with prior art, the advantage of catalytic process for modifying poor-quality diesel oil provided by the invention is mainly reflected in the following aspects:
1. catalytic process for modifying poor-quality diesel oil provided by the invention is applicable to the diesel oil distillate that hydrocarbon processing processes such as air distillation, catalytic cracking, coking, viscosity breaking are produced, complete no matter be cut, still part narrow fraction wherein can be as raw material of the present invention.
2. above-mentioned diesel oil distillate is behind catalytic reforming, and its aniline point and cetane value index obviously improve, and be depression of the freezing point, and gum level reduces, and sulphur, nitrogen content all have decline in various degree.Therefore, poor ignition quality fuel both can be used as the blending component of commercial Dissel oil behind upgrading of the present invention, also can be used as the raw material of unifining process, with the processing condition of optimizing hydrogenation process, create favorable conditions for further improving diesel quality.
3. the present invention has adopted device type more flexibly, both can implement separately, again can with existing catalytic cracking unit Joint Implementation.In numerous oil refining enterprises, the phenomenon that has the above catalytic cracking unit of two covers is very general.Yet, for the problem that solves that there is lack of raw materials or in order to reduce cost, to form certain process scale, increase economic efficiency, many refineries all left unused a cover or two cover catalytic cracking unit.Therefore, can utilize existing, the idle catalytic cracking unit in refinery to implement the present invention.Adopt the mode of Joint Implementation also smaller to the transformation of existing catalytic cracking unit, can with the shared settling vessel of existing catalytic cracking unit, stripper, subsequent separation system and regeneration system rapidly etc., only need to increase the riser reactor or the fluidized-bed reactor of a diesel oil distillate.Therefore, construction investment required for the present invention is less.
4. adopt method provided by the invention to handle poor-quality diesel-oil by cut fraction, in resulting material balance, diesel yield accounts for about 90 heavy %, and the productive rate of diesel oil+liquefied gas+gasoline is more than the 95 heavy %, rest part is dry gas and coke, and the aromaticity content of gained diesel product is less than 26 heavy %.
5. the present invention under the condition of non-hydrogen, realizes the catalytic reforming of poor ignition quality fuel based on sophisticated catalytic cracking process method.Therefore, the present invention is a kind of simple and effective technical scheme, and its economic benefit and social benefit all are conspicuous.
Fig. 1 is the schematic flow sheet of embodiment A provided by the invention.
Fig. 2 is the schematic flow sheet of embodiment B provided by the invention.
Fig. 3 is the schematic flow sheet of embodiment C provided by the invention.
Fig. 4 is the schematic flow sheet of embodiment D provided by the invention.
Fig. 5 is the schematic flow sheet of embodiment E provided by the invention.
The following examples will give further instruction to the present invention, but not thereby limiting the invention.Employed catalyzer of embodiment and raw material oil properties are listed in table 1 and table 2 respectively.Four kinds of listed in the table 1 catalyzer are by Qilu Petrochemical company of China PetroChemical Corporation catalyst plant industrial production.
The present embodiment explanation: dissimilar catalytic cracking catalysts all is suitable for catalytic process for modifying poor-quality diesel oil provided by the invention.
Listed diesel oil B is a raw material with table 2, uses the listed four kinds of dissimilar catalyzer of table 1, carries out the test of poor ignition quality fuel catalytic reforming in the small-sized fluidized bed reactor of successive reaction regenerative operation.Testing sequence is summarized as follows: diesel oil distillate B mixes with high-temperature water vapor laggardly to go in the fluidized-bed reactor, is 350 ℃ in temperature of reaction, and reactor head pressure is 0.2 MPa, and weight hourly space velocity is 10 hours
-1, agent-oil ratio is 6, water-oil ratio is to contact with catalyzer under 0.05 the condition to carry out catalytic conversion reaction.Reaction product, water vapor and reclaimable catalyst separate in settling vessel, reaction product isolated, and spent agent enters stripper, is gone out the hydrocarbon product that adsorbs on the spent agent by the water vapor stripping.Catalyzer behind the stripping enters into revivifier, contacts with the air that heated and regenerates, and the catalyzer after the regeneration uses through cooling off, turn back to reactor cycles.The character of test conditions, test-results and diesel product is all listed in table 3.
As can be seen from Table 3, behind catalytic reforming, the yield of diesel product is that 86.68～90.85 heavy %, diesel-fuel cetane number index can improve 6～10 units, and depression of the freezing point 8～18 ℃, gum level reduces, and sulphur, nitrogen content reduce.Therefore, adopt dissimilar catalyzer to implement the present invention and all can reach certain upgrading effect.
The present embodiment explanation: poor ignition quality fuel of different nature adopts catalytic process for modifying provided by the invention can receive certain upgrading effect.
The three kind diesel oil distillates listed with table 2 are raw material, contact with the listed catalyst A of table 1 in the small-sized fluidized bed reactor of successive reaction regenerative operation, carry out the catalytic reforming test.Concrete testing sequence is identical with embodiment 1.The character of test conditions, test-results and diesel product is listed in table 4.
As can be seen from Table 4, above-mentioned three kinds of poor ignition quality fuels are behind catalytic reforming, and the yield of diesel product is that 89.35～92.12 heavy %, its zero pour obviously reduce, and gum level reduces the heavy % in 50 heavy %～71, nitrogen content reduces the heavy % in 50 heavy %～61, and the amplitude that sulphur content reduces is less; In addition, the cetane value index of diesel oil distillate A and B has increased by 5～10 units, and the cetane value index of diesel oil distillate C has only increased by 1.2 units.As seen, for poor-quality diesel-oil by cut fraction of different nature, the effect of its catalytic reforming is slightly different.
The present embodiment explanation: in the process of poor ignition quality fuel catalytic reforming, reaction conditions has certain influence to the upgrading effect; In the scope of reaction conditions of the present invention, all can receive good upgrading effect.
With the diesel oil distillate A in the table 2 is raw material, adopts the catalyst A in the table 1, in the small-sized fluidized bed reactor of successive reaction regenerative operation, carries out the catalytic reforming test.Main operational condition is: temperature of reaction is that 300～450 ℃, reactor head pressure are that 0.2 MPa, weight hourly space velocity are 5～10 hours
-1, agent-oil ratio is 6～10, water-oil ratio is 0.05.Concrete testing sequence is identical with embodiment 1.The character of test conditions, test-results and diesel product is listed in table 5.
As can be seen from Table 5, under the identical situation of other reaction conditions, along with the rising of temperature of reaction, the yield of diesel product reduces, and its aniline point, cetane value index, zero pour all are downward trend, and gum level and sulphur, nitrogen content are in rising trend.Therefore, temperature of reaction raises, and reaction can bring disadvantageous effect to the diesel oil catalytic reforming.In like manner, present embodiment has also been investigated the influence of carbon contents different on agent-oil ratio, weight hourly space velocity and the catalyzer to the upgrading effect.By the testing data in the table 5 as can be seen: the variation of agent-oil ratio, weight hourly space velocity is not obvious to the influence of upgrading effect; And the carbon content on the catalyzer is to the obvious effect of upgrading effect, and carbon content is low more, and the upgrading effect is good more.
Present embodiment is the test-results of method provided by the invention on medium-sized riser fluid catalytic cracking, can be used to further specify implementation result of the present invention.
Present embodiment is to carry out on the catalytic cracking middle-scale device of double lifting leg, and the flow process of this device as shown in Figure 3.The test catalyst system therefor is the catalyst A shown in the table 1, with the raw material B in the table 2 as the pre-diesel oil distillate of upgrading, with raw material D as catalytically cracked stock.
Testing sequence is summarized as follows: as shown in Figure 3, diesel oil distillate B after the preheating enters diesel oil riser tube 2 bottoms through pipeline 1, contact with regenerator and react from regenerator sloped tube 17, reactant flow enters in the settling vessel 7 that has the dense fluidized bed bioreactor, the separating of realization response oil gas and catalyzer.Reaction oil gas and water vapor enter separation system 9 through pipeline 8, and gas and gasoline products are drawn through pipeline 10, and diesel product is then drawn through pipeline 11; Meanwhile, promote medium in advance and enter through the bottom of pipeline 20 from stock oil riser tube 22, the pyritous regenerated catalyst enters the bottom of riser tube 22 through regenerator sloped tube 19, is promoted by pre-lifting medium; Cracking stock after the preheating enters the bottom of riser tube 22 through pipeline 21, and reacts after the pyritous regenerated catalyst mixes, and reactant flow enters settling vessel 27; The reaction oil gas and the water vapor of conventional cracking stock enter subsequent separation system through pipeline 28, realize the separation to dry gas, liquefied gas, gasoline, diesel oil and heavy oil.Reclaimable catalyst from the diesel oil riser tube enters stripper 3, behind the water vapor stripping from pipeline 4, enters revivifier 13 by inclined tube 5 to be generated; The reclaimable catalyst of stock oil riser tube enters stripper 23, by the water vapor stripping from pipeline 24; Catalyzer behind the stripping enters revivifier 13 by inclined tube 25 to be generated; Air enters revivifier 13 through pipeline 14, and reclaimable catalyst is coke burning regeneration in air, and regenerated flue gas is drawn by pipeline 12.The pyritous regenerator is divided into two portions, and wherein a part is returned stock oil riser tube 22 through regenerator sloped tube 19; Another part enters water cooler 16 through pipeline 15, after the cooling, returns diesel oil riser tube 2 by regenerator sloped tube 17 and recycles according to a conventional method.
Main reaction conditions and test-results are referring to table 6.As can be seen from Table 6, the yield of diesel product is 92.02 heavy %, and its cetane value index increases by 7 units, and depression of the freezing point 11 ℃, colloid reduces by 45 heavy %, and nitrogen content reduces by 45.64 heavy %, and the sulphur content fall is less.Therefore, when adopting the Joint Implementation mode, the catalytic reforming effect of poor ignition quality fuel is still apparent in view.
Table 1
| The catalyzer numbering | A | B | C | D |
| Trade names | CRC-1 | RHZ-200 | ZCM-7 | RAG-1 |
| Zeolite type | REY | REHY | USY | REY-USY-ZRP |
| Chemical constitution, heavy % | ||||
| Aluminum oxide | 26.5 | 33.0 | 46.4 | 44.6 |
| Sodium oxide | 0.19 | 0.29 | 0.22 | 0.13 |
| Ferric oxide | 0.09 | 1.1 | 0.32 | / |
| Apparent density, kilogram/rice 3 | 450 | 560 | 690 | 620 |
| Pore volume, milliliter/gram | 0.41 | 0.25 | 0.38 | 0.36 |
| Specific surface area, rice 2/ gram | 132 | 92 | 164 | 232 |
| Abrasion index is when weighing % -1 | 4.2 | 3.2 | / | 2.5 |
| Size composition, heavy % | ||||
| 0～40 micron | 7.3 | 15.2 | 4.8 | 13.1 |
| 40～80 microns | 43.7 | 55.1 | 47.9 | 54.9 |
| ＞80 microns | 49.0 | 29.7 | 47.3 | 32.0 |
| Micro-activity MA | 70 | 68 | 69 | 66 |
Table 2
| The raw material numbering | A | B | C | D |
| Material name | Catalytic diesel oil | Catalytic diesel oil | Catalytic diesel oil | Long residuum |
| Density (20 ℃), kilogram/rice 3 | 880.8 | 891.7 | 911.6 | 900.5 |
| Refractive index (20 ℃) | 1.4993 | 1.5138 | / | / |
| Aniline point, ℃ | 25.7 | ＜20 | 38.6 | / |
| Colloid, mg/100ml | 66.0 | 376 | 455 | / |
| Zero pour, ℃ | ＜-15 | 0 | -3 | / |
| The cetane value index | 29.5 | 22 | 29 | / |
| 10% carbon residue, heavy % | 0.11 | 0.97 | / | (6.9 carbon residue) |
| Basic nitrogen, ppm | 119 | 114 | / | 1700 |
| Sulphur, ppm | 1160 | 1200 | 10267.6 | / |
| Nitrogen, ppm | 682 | 769 | 878.7 | / |
| Carbon, heavy % | 88.24 | 88.71 | 87.68 | 86.00 |
| Hydrogen, heavy % | 11.48 | 11.09 | 10.80 | 12.59 |
| Boiling range, ℃ | ||||
| Initial boiling point | 191 | 184 | 195 | 279 |
| 10％ | 208 | 202 | 234 | 363 |
| 30％ | 226 | 209 | 267 | 425 |
| 50％ | 247 | 237 | 298 | 484 |
| 70％ | 277 | 269 | 328 | / |
| 90％ | 324 | 341 | 358 | / |
| Final boiling point | 361 | 366 | 374 | / |
| Group composition, heavy % | ||||
| Alkane | 25.6 | 26.7 | 20.3 | / |
| Naphthenic hydrocarbon | 17.0 | 12.7 | 16.8 | / |
| Mononuclear aromatics | 22.7 | 21.5 | 22.2 | / |
| Double ring arene | 28.8 | 30.9 | 33.2 | / |
| Thrcylic aromatic hydrocarbon | 5.20 | 7.6 | 6.9 | / |
Table 3
| Catalyzer | A | B | C | D | |
| Catalyzer coke content, heavy % | 0.05 | 0.05 | 0.05 | 0.05 | |
| Temperature of reaction, ℃ | 350 | 350 | 350 | 350 | |
| Weight hourly space velocity, hour -1 | 10 | 10 | 10 | 10 | |
| Agent-oil ratio | 6 | 6 | 6 | 6 | |
| Water-oil ratio | 0.05 | 0.05 | 0.05 | 0.05 | |
| Product distributes, heavy % | |||||
| Dry gas | 0.28 | 0.34 | 0.45 | 0.63 | |
| Liquefied gas | 1.00 | 1.76 | 2.10 | 3.50 | |
| Gasoline | 4.25 | 5.00 | 5.56 | 5.78 | |
| Solar oil | 90.85 | 89.38 | 88.45 | 86.68 | |
| Coke | 3.57 | 3.50 | 3.42 | 3.39 | |
| Loss | 0.05 | 0.02 | 0.02 | 0.02 | |
| Diesel oil character | Feedstock property | ||||
| Density, kilogram/rice 3 | 891.7 | 876.8 | 875.0 | 876.0 | 879.0 |
| Zero pour, ℃ | 0 | -13 | -8 | -15 | -18 |
| Aniline point, ℃ | ＜20 | 36.5 | 33.2 | 33.0 | 32.0 |
| The | 22 | 32 | 31 | 29 | 28 |
| Colloid, milligram/100 milliliters | 376 | 188 | 125 | 125 | 125 |
| Sulphur, ppm | 1200 | 1100 | 1100 | 1150 | 1180 |
| Nitrogen, ppm | 769 | 321 | 369 | 390 | 410 |
| Alkane | 26.7 | 28.1 | 27.4 | 27.2 | 27.0 |
| Naphthenic hydrocarbon | 12.7 | 8.3 | 8.4 | 8.0 | 7.9 |
| Mononuclear aromatics | 21.5 | 22.5 | 22.8 | 23.0 | 23.4 |
| Double ring arene | 30.9 | 32.9 | 33.3 | 33.8 | 33.7 |
| Thrcylic aromatic hydrocarbon | 7.6 | 7.9 | 7.9 | 8.0 | 8.0 |
Table 4
| Stock oil | A | B | C |
| Temperature of reaction, ℃ | 350 | 350 | 350 |
| Weight hourly space velocity, hour -1 | 10 | 10 | 10 |
| Agent-oil ratio | 6 | 6 | 6 |
| Water-oil ratio | 0.03 | 0.03 | 0.03 |
| Product distributes, heavy % | |||
| Dry gas | 0.43 | 0.28 | 0.29 |
| Liquefied gas | 1.63 | 1.00 | 0.73 |
| Gasoline | 4.87 | 4.25 | 3.54 |
| Solar oil | 89.35 | 90.85 | 92.12 |
| Coke | 3.70 | 3.57 | 3.30 |
| Loss | 0.02 | 0.05 | 0.02 |
| Diesel oil character | |||
| Density, kilogram/rice 3 | 870.6 | 876.8 | 895.4 |
| Zero pour, ℃ | -31 | -13 | -21 |
| Aniline point, ℃ | 38.2 | 36.5 | 32.5 |
| The cetane value index | 34.4 | 32 | 30.2 |
| Colloid, mg/ | 20 | 188 | 225.0 |
| Sulphur, ppm | 1206 | 1100 | 8097 |
| Nitrogen, ppm | 339 | 321 | 303.8 |
| Alkane | 31.0 | 28.1 | 23.9 |
| Naphthenic hydrocarbon | 8.4 | 8.3 | 12.5 |
| Mononuclear aromatics | 22.4 | 22.5 | 24.2 |
| Double ring arene | 31.7 | 32.9 | 32.9 |
| Thrcylic aromatic hydrocarbon | 6.3 | 7.9 | 6.2 |
Table 5
| Operational condition | |||||||
| Temperature of reaction, ℃ | 300 | 350 | 450 | 350 | 350 | 350 | |
| Weight hourly space velocity, hour -1 | 10 | 10 | 10 | 10 | 5 | 10 | |
| Agent-oil ratio | 6 | 6 | 6 | 10 | 6 | 6 | |
| Water-oil ratio | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | |
| The catalyzer carbon content, heavy % | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.25 | |
| Product distributes, heavy % | |||||||
| Dry gas | 0.35 | 0.43 | 0.58 | 0.43 | 0.41 | 0.32 | |
| Liquefied gas | 1.07 | 1.63 | 4.67 | 1.07 | 1.58 | 1.08 | |
| Gasoline | 3.65 | 4.87 | 7.65 | 3.98 | 4.55 | 3.23 | |
| Solar oil | 91.59 | 89.35 | 82.76 | 89.62 | 89.28 | 92.24 | |
| Coke | 3.32 | 3.70 | 4.32 | 4.88 | 4.15 | 3.12 | |
| Loss | 0.02 | 0.02 | 0.02 | 0.02 | 0.03 | 0.01 | |
| Diesel oil character | Raw material | ||||||
| Density, kilogram/rice 3 | 880.8 | 870.5 | 870.6 | 879.9 | 870.6 | 871.5 | 878.7 |
| Zero pour, ℃ | -15 | -20 | -31 | -40 | -36 | -29 | -17 |
| Aniline point, ℃ | 25.7 | 40.2 | 38.2 | 33.4 | 34.7 | 36.3 | 30.7 |
| The cetane value index | 29.5 | 35.1 | 34.6 | 32.6 | 33.2 | 33.4 | 30.9 |
| Colloid, mg/100ml | 66.0 | 15.0 | 20.0 | 20.0 | 10.0 | 12.7 | 34 |
| Sulphur, ppm | 1160 | 1140 | 1206 | 1216 | 1122 | 1170 | 1180 |
| Nitrogen, ppm | 682 | 308 | 339 | 420 | 268.7 | 338.5 | 421 |
| Alkane | 25.6 | 31.5 | 31.0 | 28.0 | 30.3 | 30.1 | 29.6 |
| Naphthenic hydrocarbon | 17.0 | 8.7 | 8.4 | 6.4 | 6.8 | 8.2 | 10.8 |
| Mononuclear aromatics | 22.7 | 22.2 | 22.4 | 24.4 | 23.1 | 23.2 | 22.2 |
| Double ring arene | 28.8 | 31.2 | 31.7 | 34.0 | 32.9 | 31.9 | 31.0 |
| Thrcylic aromatic hydrocarbon | 5.2 | 6.2 | 6.3 | 7.0 | 6.8 | 6.4 | 6.0 |
Table 6
| Operational condition | The diesel oil riser tube | The cracking stock riser tube | |
| The riser tube temperature out, ℃ | 360 | 515 | |
| Reaction pressure, MPa | 0.2 | 0.18 | |
| Weight hourly space velocity, hour -1 | 50 | / | |
| Agent-oil ratio | 10 | 5.8 | |
| Water-oil ratio | 0.03 | / | |
| Product distributes, heavy % | |||
| Dry gas | 0.20 | 5.01 | |
| Liquefied gas | 0.95 | 11.69 | |
| Gasoline | 3.25 | 36.78 | |
| Diesel oil | 92.02 | 30.71 | |
| Heavy oil | / | 3.90 | |
| Coke | 3.56 | 11.87 | |
| Loss | 0.02 | 0.04 | |
| Diesel oil character | Raw material B | ||
| Density, kilogram/rice 3 | 891.7 | 877.6 | / |
| Zero pour, ℃ | 0 | -11 | / |
| Aniline point, ℃ | ＜20 | 33.4 | / |
| The | 22 | 29 | / |
| Colloid, m% | 376 | 207 | / |
| Sulphur, ppm | 1200 | 1050 | / |
| Nitrogen, ppm | 769 | 351 | / |
| Alkane | 26.7 | 29.1 | / |
| Naphthenic hydrocarbon | 12.7 | 9.3 | / |
| Mononuclear aromatics | 21.5 | 21.8 | / |
| Double ring arene | 30.9 | 31.9 | / |
| Thrcylic aromatic hydrocarbon | 7.6 | 7.7 | / |
Claims (10)
1. catalytic process for modifying poor-quality diesel oil, it is characterized in that in the diesel oil distillate injecting reactor after the preheating, be lower than 600 ℃ catalyzer with heavy % in coke content≤0.3 and temperature and contact and react, temperature of reaction is 250～550 ℃, and weight hourly space velocity is 1～120 o'clock
-1, the weight ratio of catalyzer and diesel oil distillate is 2～20, and the weight ratio of water vapour and diesel oil distillate is 0.01～0.15, and reaction pressure is 130～450Kpa; Reaction product isolated and spent agent, spent agent has at least a part to cool off earlier after stripping, regeneration, and Returning reactor recycles then.
2. in accordance with the method for claim 1, it is characterized in that described diesel oil distillate is selected from: more than one mixture in time processing diesel oil distillate, secondary processing diesel oil cut or the above-mentioned diesel oil distillate; Described diesel oil distillate can be full cut, also can be the part narrow fraction.
3. in accordance with the method for claim 2, it is characterized in that described diesel oil distillate is selected from: one or more in straight-run diesel oil, catalytic diesel oil, coker gas oil, the viscosity breaking diesel oil.
4. in accordance with the method for claim 1, it is characterized in that described reactor is riser reactor or fluidized-bed reactor.
5. in accordance with the method for claim 1, it is characterized in that the described catalyzer that contacts with diesel oil distillate is any solid acid catalyst that is applicable to catalytic cracking process, its active ingredient is selected from: contain or do not contain Y type or HY type zeolite, the ultrastable Y that contains or do not contain rare earth and/or phosphorus, the ZSM-5 type zeolite of rare earth and/or phosphorus or have in the supersiliceous zeolite, β zeolite, ferrierite of five-membered ring structure one or more.
6. in accordance with the method for claim 1, it is characterized in that the described catalyzer that contacts with diesel oil distillate is selected from: regenerator, half regenerator or their mixture.
7. according to claim 5 or 6 described methods, it is characterized in that the heavy % in coke content≤0.25 of the described catalyzer that contacts with diesel oil distillate.
8. in accordance with the method for claim 1, it is characterized in that described reaction process can be on catalytic cracking unit implements separately, also can with the catalytic cracking unit Joint Implementation of the conventional catalytically cracked material of processing.
9, in accordance with the method for claim 8, it is characterized in that when with processing conventional catalytically cracked material the catalytic cracking unit Joint Implementation time, diesel oil distillate and conventional catalytically cracked material react in reactor separately respectively; Settling vessel, stripper and subsequent separation system can be shared, also can be independent separately; Catalyst regeneration system is shared.
10. in accordance with the method for claim 1, it is characterized in that the reaction conditions of described diesel oil distillate is: temperature of reaction is 320～530 ℃, and weight hourly space velocity is 10～100 o'clock
-1, the weight ratio of catalyzer and diesel oil distillate is 3～18, the weight ratio 0.02～0.10 of water vapour and diesel oil distillate, reaction pressure 200～400Kpa.
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| CN00122844A CN1100119C (en) | 2000-08-30 | 2000-08-30 | Catalytic process for modifying poor-quality diesel oil |
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|---|---|---|---|
| CN00122844A CN1100119C (en) | 2000-08-30 | 2000-08-30 | Catalytic process for modifying poor-quality diesel oil |
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| CN1100119C true CN1100119C (en) | 2003-01-29 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080313A (en) * | 1992-03-05 | 1994-01-05 | 中国石化洛阳石油化工工程公司 | Catalytic upgrading-aromatization process of poor gasoline |
| CN1253576A (en) * | 1997-05-05 | 2000-05-17 | 菲利浦石油公司 | Process for conversion of hydrocarbons to olefins and aromatics |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080313A (en) * | 1992-03-05 | 1994-01-05 | 中国石化洛阳石油化工工程公司 | Catalytic upgrading-aromatization process of poor gasoline |
| CN1253576A (en) * | 1997-05-05 | 2000-05-17 | 菲利浦石油公司 | Process for conversion of hydrocarbons to olefins and aromatics |
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