CN103059994B - Catalytic conversion method of petroleum hydrocarbon - Google Patents

Abstract

The invention discloses a catalytic conversion method of petroleum hydrocarbon. High-sulfur wax oil is contacted with a heat regeneration catalyst at the lower portion of a catalytic cracking unit reactor and subjected to a cracking reaction, wherein the heat regeneration catalyst has relatively low activity and relatively uniform activity distribution, has a coarse particle size distribution and contains macropore zeolite and mesopore zeolite, the generated oil gas and a carbon-containing catalyst go up and are subjected to a selective hydrogen transfer reaction and an isomerization reaction under a certain reaction environment, the reaction oil gas is separated to obtain a reaction product containing liquefied gas, gasoline and catalytic wax oil, and the spent catalyst is recycled for use after stripping and regeneration, wherein the catalytic wax oil and optional other secondary processing wax oil are introduced into the hydrocracking unit for reaction, and preferably the hydrocracked tail oil is returned to the catalytic cracking unit. According to the method, the diesel oil yield and the cetane number of the diesel oil are increased, the mass percentages of low carbon olefins such as propylene and butylenes in the liquefied gas are increased, the hydrogen utilization rate of the raw materials is increased, and simultaneously the utilization rate of hydrogen in the raw materials is raised, so that the petroleum resource can be saved, and the method provides a novel approach for cleaning the refining process and the refined oil products.

Description

A kind of Catalytic conversion method of petroleum hydrocarbon

Technical field

The invention belongs to the catalysis conversion method of petroleum hydrocarbon, more particularly, relate to the catalysis conversion method of the integrated technique of a kind of faulty wax oil catalytic cracking and hydrocracking.

Background technology

Conventional catalytic cracking process processing high-sulfur faulty wax oil raw material not only makes the SO in regeneration fume from catalytic cracking _xdischarge does not meet environmental requirement, and the sulphur content in gasoline and diesel product all can not meet product specification requirement.Therefore, these high-sulfur faulty wax oil raw materials are first through hydrotreatment usually, and except desulfuration, nitrogen and metal impurities, the polycyclic aromatic hydrocarbons in saturated raw material, improves its catalytic cracking reaction performance, and then as the raw material of catalytic cracking, produce low-sulphur oil and diesel oil.

US4780193 discloses a kind of method adopting Hydrofining Technology to improve catalytically cracked material quality, the temperature of reaction of this hydro-refining unit lower than 390 DEG C, reaction pressure at least at more than 10.0MPa, preferably at more than 12.0MPa.Under the processing condition being conducive to aromatic saturation, improved the cracking performance of catalytic cracking unit raw material by hydrofining, thus improve the transformation efficiency of catalytic cracking unit, produce high-octane gasoline blending component.CN101684417A discloses a kind of hydrogenation-catalytic cracking combination process of optimization, wax oil raw material reacts in hydrotreatment reaction zone, the hydrogenation wax oil obtained is as catalytically cracked stock, directly catalytic cracking unit is entered without fractionation, catalysis heavy cycle oil loops back hydrotreatment reaction zone, the logistics of high pressure hot separator top gas phase and catalysis gently circulate and enter hydro-upgrading reaction zone with optional gas oil, carry out hydro-upgrading reaction, resultant of reaction obtains hydrotreated naphtha and hydrogenated diesel oil after fractionation.Hydrotreating unit and the public hydrogen gas system of hydro-upgrading unit, reduce appliance arrangement investment and process cost.Products scheme is flexible, can produce high-quality low-sulfur gasoline, fine-quality diesel oil and reformer feed simultaneously.

Usually, faulty wax oil raw material can improve its Catalytic Cracking Performance after hydrotreatment, but understands because boiling range lightens generating portion diesel oil, petroleum naphtha and lighter hydrocarbons in hydroprocessing processes, is unfavorable for voluminous gasoline and propylene.In addition, the catalytic cracking process (MIP) of maximizing iso-paraffins to the catalytically cracked stock of process high-quality, especially hydrogenation wax oil, cause content of olefin in gasoline on the low side, iso-butylene content in liquefied gas is on the low side, and products distribution is optimized not, and petroleum resources are underused.

MIP technique is widely used, has been applied to nearly 50 cover catalytic cracking unit at present, has obtained huge economic benefit and social benefit.ZL99105904.2, ZL99105905.0 and ZL99105903.4 is seen with the MIP technology detailed description being rich in isoparaffin gasoline about the liquefied gas being rich in Trimethylmethane.

Along with environmental regulation requires increasingly stringent to catalytic cracking production process and quality product, even if catalytic cracking process hydrogenation wax oil, the SO in regeneration fume from catalytic cracking _xdischarge is also difficult to meet environmental requirement, and still needing increases regenerated flue gas treatment unit.As the SO of regenerated flue gas treatment unit process lower aq _xduring flue gas, its processing efficiency will decrease.In addition, though the cracking of hydrogenation wax catalysis to produce content of sulfur in gasoline lower, but still be difficult to the sulphur content in gasoline to be reduced to 10 micrograms/gram below, gasoline still needs aftertreatment.When the gasoline adopting S-Zorb technical finesse sulphur content lower, S-Zorb because of the sulphur content in gasoline too low, be difficult to maintain its balancing run, other sulfide need be supplemented from the external world, cause S-Zorb device utilization benefit to reduce.

Summary of the invention

The object of this invention is to provide the Catalytic conversion method of the integrated technique of a kind of faulty wax oil catalytic cracking and hydrocracking.The first embodiment of the present invention is as follows:

Catalysis conversion method provided by the invention comprises the following steps:

(1) high-sulfur wax oil with heat regenerated catalyst catalytic cracking unit reactor lower contacts and there is cracking reaction, the oil gas generated and under certain reaction environment, optionally hydrogen transfer reactions and isomerization reaction occur containing the catalyzer of charcoal is up, reaction product isolated, reclaimable catalyst uses through stripping, regeneration Posterior circle, described catalyzer is containing large pore zeolite and mesopore zeolite, activity is lower and activity distribution is relatively uniform, in thick size distribution;

(2) from the catalytic wax oil of step (1) and the wax oil of other optional secondary processing as the stock oil of hydroeracking unit, enter Hydrocracking unit and carry out hydrocracking reaction;

(3) hydrocracking tail oil turns back to catalytic cracking unit, as the stock oil of catalytic cracking, or as the raw material of one or more unit in Hydrocracking unit, preparing ethylene by steam cracking unit, other hydro carbons processing unit.

The gasoline of step (1) enters gasoline sweetener, and diesel oil enters diesel fuel desulfurization device;

The regenerated flue gas of step (1) enters flue gas processing device, carries out fume treatment, the fume emission after process.

Catalysis conversion method provided by the invention is so concrete enforcement:

(1), catalytic cracking unit

A the high-sulfur inferior feedstock oil of (), preheating enters reactor and contacts with the regenerated catalyst of heat and cracking reaction occurs, temperature of reaction is 430 DEG C ~ 620 DEG C, be preferably 490 DEG C ~ 600 DEG C, reaction times is 0.2 second ~ 2.0 seconds, be preferably 0.3 second ~ 1.5 seconds, the weight ratio (hereinafter referred to as agent-oil ratio) of catalyzer and stock oil is 2 ~ 15: 1, be preferably 3 ~ 12: 1, described catalyzer is containing large pore zeolite and mesopore zeolite, activity is lower and activity distribution is relatively uniform, in thick size distribution;

B oil gas and the used catalyst of (), generation are up, optionally hydrogen transfer reactions and isomerization reaction is there is under certain reaction environment, temperature of reaction is 420 DEG C ~ 550 DEG C, be preferably 460 DEG C ~ 500 DEG C, reaction times is 1 second ~ 30 seconds, be preferably 2 seconds ~ 15 seconds, the weight ratio of catalyzer and stock oil is 2 ~ 18: 1, be preferably 3 ~ 15: 1, the water vapor of cracking reaction and hydrogen transfer reactions and the weight ratio (hereinafter referred to as water-oil ratio) of stock oil are 0.03 ~ 0.3: 1, be preferably 0.05 ~ 0.3: 1, pressure is 130kPa ~ 450kPa;

C (), reaction product isolated obtain being rich in the liquefied gas of propylene, olefin(e) centent moderate gasoline, diesel oil, catalytic wax oil and other products, reclaimable catalyst enters revivifier through stripping, uses through coke burning regeneration Posterior circle.

D (), catalytic wax oil after filtration device or water distilling apparatus enter hydroeracking unit after removing a small amount of granules of catalyst.

The reactor that the method is suitable for can be selected from equal diameter riser tube, etc. one of in linear speed riser tube, fluidized-bed or reducing riser tube, also can be the compound reactor be made up of equal diameter riser tube and fluidized-bed.

Method provided by the invention can equal diameter riser tube, etc. carry out in linear speed riser tube or fluidized-bed reactor, its intermediate diameters riser tube is identical with the catalyst cracker of refinery's routine, waits the linear speed of fluid in linear speed riser tube substantially identical.Equal diameter riser tube, etc. linear speed riser reactor be followed successively by pre lift zone, the first reaction zone, second reaction zone from bottom to up, fluidized-bed reactor is followed successively by the first reaction zone, second reaction zone from bottom to up, and the ratio of the height of the first reaction zone, second reaction zone is 10 ~ 40: 90 ~ 60.When use equal diameter riser tube, etc. linear speed riser tube or fluidized-bed reactor time, one or more cold shock medium inlet is established bottom second reaction zone, and/or heat collector is set in second reaction zone, the height of heat collector accounts for 50% ~ 90% of second reaction zone height.Control temperature and the reaction times of each reaction zone respectively.Cold shock medium is the mixture of one or more the arbitrary proportion be selected from cold shock agent, the regenerated catalyst of cooling and the semi regeneration catalyzer of cooling.Wherein cold shock agent is the mixture of one or more the arbitrary proportion be selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or water; The regenerated catalyst of cooling and the semi regeneration catalyzer of cooling are that reclaimable catalyst cools respectively and obtains after two-stage regeneration and one section of regeneration, regenerated catalyst carbon content is 0.1 heavy below %, be preferably 0.05 heavy below %, semi regeneration coke on regenerated catalyst is the 0.1 heavy % in heavy % ~ 0.9, and best carbon content is the 0.15 heavy % in heavy % ~ 0.7.

Method provided by the invention also can be carried out in the compound reactor be made up of equal diameter riser tube and fluidized-bed, the equal diameter riser tube of bottom is the first reaction zone, the fluidized-bed on top is second reaction zone, controls temperature and the reaction times of each reaction zone respectively.Establish one or more cold shock medium inlet in the bottom of fluidized-bed, and/or arrange heat collector in second reaction zone, the height of heat collector accounts for 50% ~ 90% of second reaction zone height.Control temperature and the reaction times of each reaction zone respectively.Cold shock medium is the mixture of one or more the arbitrary proportion be selected from cold shock agent, the regenerated catalyst of cooling and the semi regeneration catalyzer of cooling.Wherein cold shock agent is the mixture of one or more the arbitrary proportion be selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or water; The regenerated catalyst of cooling and the semi regeneration catalyzer of cooling are that reclaimable catalyst cools respectively and obtains after two-stage regeneration and one section of regeneration, regenerated catalyst carbon content is 0.1 heavy below %, be preferably 0.05 heavy below %, semi regeneration coke on regenerated catalyst is the 0.1 heavy % in heavy % ~ 0.9, and best carbon content is the 0.15 heavy % in heavy % ~ 0.7.

Method provided by the invention can also be carried out in a kind of Novel diameter reducing riser reactor, describes in detail and sees ZL99105903.4.The diameter of pre lift zone is identical with conventional equal diameter riser reactor, and be generally 0.02 meter ~ 5 meters, it highly accounts for 5% ~ 10% of total reactor height.The effect of pre lift zone is under the existence of pre-lift medium, make regenerated catalyst move upward and accelerate, and used identical of pre-lift medium used and conventional equal diameter riser reactor, is selected from water vapor or dry gas.

The similar of the first reaction zone is in the equal diameter riser reactor of routine, its diameter can be identical with pre lift zone, also can comparatively pre lift zone be slightly large, the diameter of the first reaction zone and the diameter ratio of pre lift zone are 1.0 ~ 2.0: 1, and it highly accounts for 10% ~ 30% of total reactor height.After the mixing of this district, at higher temperature of reaction and agent-oil ratio, under the shorter residence time (being generally 0.5 second ~ 2.5 seconds), mainly there is cracking reaction in stock oil and catalyzer.

Second reaction zone is thicker than the first reaction zone, and the diameter ratio of its diameter and the first reaction zone is 1.5 ~ 5.0: 1, and it highly accounts for 30% ~ 60% of total reactor height.Its effect is the flow velocity and the temperature of reaction that reduce oil gas and catalyzer.Reduce the method for this district's temperature of reaction, cold shock medium can be injected from the combining site of this district and the first reaction zone, and/or by arranging heat collector in this district, take partial heat away to reduce this district's temperature of reaction, thus reach the object suppressing secondary cracking reaction, increase isomerization reaction and hydrogen transfer reactions.Cold shock medium is the mixture of one or more the arbitrary proportion be selected from cold shock agent, the regenerated catalyst of cooling and the semi regeneration catalyzer of cooling.Wherein cold shock agent is the mixture of one or more the arbitrary proportion be selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or water; The regenerated catalyst of cooling and the semi regeneration catalyzer of cooling are that reclaimable catalyst cools respectively and obtains after two-stage regeneration and one section of regeneration, regenerated catalyst carbon content is 0.1 heavy below %, be preferably 0.05 heavy below %, semi regeneration coke on regenerated catalyst is the 0.1 heavy % in heavy % ~ 0.9, and best carbon content is the 0.15 heavy % in heavy % ~ 0.7.If arrange heat collector, then it highly accounts for 50% ~ 90% of second reaction zone height.Logistics can be longer in this reaction zone residence time, is 2 seconds ~ 30 seconds.

The similar of outlet area is in the equal diameter riser reactor top exit part of routine, and the diameter ratio of its diameter and the first reaction zone is 0.8 ~ 1.5: 1, and it highly accounts for 0 ~ 20% of total reactor height.Logistics Ke Gai district stops certain hour, to suppress cracking reaction and heat cracking reaction, improves rate of flow of fluid.

The high-sulfur wax oil that the method is suitable for is selected from atmospheric overhead, atmospheric tower is extracted out distillate, straight run decompressed wax oil, either shallow hydrogenation wax oil, wax tailings (CGO), deasphalted oil (DAO) and composition thereof, it is characterized by sulphur content and should be greater than 0.5 heavy %, more preferably greater than 1.0 heavy %.

Step (2) other secondary processing wax oil described is selected from CGO, DAO and composition thereof.

Described catalyzer comprises zeolite, inorganic oxide, clay.In butt, each component accounts for total catalyst weight respectively: zeolite about 5 weight ~ about 50 % by weight, preferably about 10 weight ~ about 30 % by weight; Inorganic oxide about 0.5 weight ~ about 50 % by weight; Clay 0 weight ~ about 70 % by weight.Its mesolite is lived as activity and is divided, comprise large pore zeolite and mesopore zeolite, described large pore zeolite accounts for 75 ~ 99 heavy % of zeolite gross weight, mesopore zeolite accounts for 1 ~ 25 heavy % of zeolite gross weight, large pore zeolite is selected from one or more in Rare Earth Y, rare earth hydrogen Y, super steady Y, high silicon Y, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and ZSM series zeolite is selected from one or more among ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48.

Inorganic oxide, as matrix, is selected from silicon-dioxide (SiO ₂) and/or aluminium sesquioxide (Al ₂o ₃).In butt, in inorganic oxide, silicon-dioxide accounts for about 50 weight ~ about 90 % by weight, and aluminium sesquioxide accounts for about 10 weight ~ about 50 % by weight.

Clay, as caking agent, is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, wilkinite.

The size composition of the catalyzer of described thick size distribution is: the particle being less than 40 microns accounts for the volume ratio of all particles lower than 10%, is preferably lower than 5%; The particle being greater than 80 microns accounts for the volume ratio of all particles lower than 15%, and be preferably lower than 10%, all the other are the particle of 40 ~ 80 microns.

The catalyzer that the activity that the method is suitable for is lower refers to that catalyst activity is 35 ~ 55, preferably 40 ~ 50.It is measured by measuring method of the prior art: the mat activity test method " Petrochemical Engineering Analysis method (RIPP test method) " of company standard RIPP 92-90--catalytic cracking, Yang Cui waits people surely, 1990, hereinafter referred to as RIPP 92-90.Described catalyst activity is represented by light oil microactivity (MA), and its calculation formula is the gasoline yield+gas yield+coke yield lower than 204 DEG C in MA=(lower than the gasoline production+gas yield+coke output of 204 DEG C in product)/charging total amount * 100%=product.The appreciation condition of light oil micro-reactor device (with reference to RIPP 92-90) is: become by catalyst breakage particle diameter to be the particle of 420 ~ 841 microns, loading amount is 5 grams, reaction raw materials to be boiling range the be straight distillation light diesel oil of 235 ~ 337 DEG C, temperature of reaction 460 DEG C, weight space velocity is 16 hours-1, agent-oil ratio 3.2.

The relatively uniform catalyzer of the activity distribution that the method is suitable for refers to that joining catalytic cracking unit inner catalyst initial activity is no more than 80, preferably more than 75, more preferably no more than 70; The self regulation time of this catalyzer is 0.1 hour ~ 50 hours, preferably 0.1 ~ 30 hour, more preferably 0.1 ~ 10 hour.

Described catalyzer self regulation time refers to catalyzer aging time reached needed for equilibrium activity under 800 DEG C and 100% water vapor conditions (with reference to RIPP 92-90).

The relatively uniform catalyzer of described activity distribution such as can obtain through following 3 kinds for the treatment of processs:

Catalyst processing method 1:

(1), by live catalyst load fluidized-bed, preferred dense phase fluidized bed, contacts with water vapor, carry out under certain thermal and hydric environment aging after obtain active relatively uniform catalyzer;

(2), catalyzer relatively uniform for described activity is joined in corresponding reaction unit.

Treatment process 1 is such as so concrete enforcement:

Live catalyst is loaded in the preferred dense phase fluidized bed of fluidized-bed, water vapor is injected in the bottom of fluidized-bed, catalyzer realizes fluidisation under the effect of water vapor, water vapor carries out aging to catalyzer simultaneously, aging temperature is 400 DEG C ~ 850 DEG C, preferably 500 DEG C ~ 750 DEG C, be preferably 600 DEG C ~ 700 DEG C, the apparent linear velocity of fluidized-bed is 0.1 meter per second ~ 0.6 meter per second, be preferably 0.15 second ~ 0.5 meter per second, after aging 1 hour ~ 720 hours preferably 5 hours ~ 360 hours, obtain the catalyzer that described activity is relatively uniform, active relatively uniform catalyzer is by the requirement of full scale plant, join full scale plant, preferably join the revivifier of full scale plant.

Catalyst processing method 2:

(1), by live catalyst load the preferred dense phase fluidized bed of fluidized-bed, contact with the aging medium of moisture vapor, carry out under certain thermal and hydric environment aging after obtain active relatively uniform catalyzer;

(2), catalyzer relatively uniform for described activity is joined in corresponding reaction unit.

The technical scheme of Catalyst processing method 2 is such as so concrete enforcement:

Catalyzer is loaded in the preferred dense phase fluidized bed of fluidized-bed, the aging medium of moisture vapor is injected in the bottom of fluidized-bed, catalyzer realizes fluidisation under the aging medium effect of moisture vapor, simultaneously, the aging medium of moisture vapor carries out aging to catalyzer, aging temperature is 400 DEG C ~ 850 DEG C, preferably 500 DEG C ~ 750 DEG C, be preferably 600 DEG C ~ 700 DEG C, the apparent linear velocity of fluidized-bed is 0.1 meter per second ~ 0.6 meter per second, be preferably 0.15 second ~ 0.5 meter per second, the weight ratio of water vapor and aging medium is 0.20 ~ 0.9, be preferably 0.40 ~ 0.60, after aging 1 hour ~ 720 hours preferably 5 hours ~ 360 hours, obtain the catalyzer that described activity is relatively uniform, active relatively uniform catalyzer is by the requirement of full scale plant, join full scale plant, preferably join the revivifier of full scale plant.Described aging medium comprise the gas after air, dry gas, regenerated flue gas, air and dry combustion gas or air and combustion oil burn after gas or other gas as nitrogen.The weight ratio of described water vapour and aging medium is 0.2 ~ 0.9, is preferably 0.40 ~ 0.60.

Catalyst processing method 3:

(1), by live catalyst be input to the preferred dense phase fluidized bed of fluidized-bed, the hot regenerated catalyst of revivifier be transported to described fluidized-bed simultaneously, in described fluidized-bed, carry out heat exchange;

(2) live catalyst, after heat exchange contacts with water vapor or steam-laden aging medium, carry out under certain thermal and hydric environment aging after obtain active relatively uniform catalyzer;

(3), catalyzer relatively uniform for described activity is joined in corresponding reaction unit.

Technical scheme of the present invention is such as so concrete enforcement:

Live catalyst is transported in the preferred dense phase fluidized bed of fluidized-bed, the hot regenerated catalyst of revivifier is also transported to described fluidized-bed simultaneously, in described fluidized-bed, carry out heat exchange.The aging medium of water vapor or moisture vapor is injected in the bottom of fluidized-bed, live catalyst realizes fluidisation under the aging medium effect of water vapor or moisture vapor, simultaneously, the aging medium of water vapor or moisture vapor carries out aging to live catalyst, aging temperature is 400 DEG C ~ 850 DEG C, preferably 500 DEG C ~ 750 DEG C, be preferably 600 DEG C ~ 700 DEG C, the apparent linear velocity of fluidized-bed is 0.1 meter per second ~ 0.6 meter per second, be preferably 0.15 second ~ 0.5 meter per second, aging 1 hour ~ 720 hours, preferably 5 hours ~ 360 hours, when the aging medium of moisture vapor, the weight ratio of described water vapour and aging medium is for being greater than 0 ~ 4, be preferably 0.5 ~ 1.5, obtain at the relatively uniform catalyzer of described activity, active relatively uniform catalyzer is by the requirement of full scale plant, join full scale plant, preferably join the revivifier of full scale plant.In addition, water vapor after Aging Step enters reactive system (entering stripper, settling vessel, raw material nozzles, the pre lift zone in catalytic cracking unit as one or more in stripped vapor, anti-scorch steam, atomizing steam, lifting steam respectively) or regeneration system rapidly, and the aging medium of moisture vapor after Aging Step enters regeneration system rapidly, the regenerated catalyst after heat exchange turns back in this revivifier.Described aging medium comprise the gas after air, dry gas, regenerated flue gas, air and dry combustion gas or air and combustion oil burn after gas or other gas as nitrogen.

By above-mentioned treatment process, the distribution of the activity and selectivity of the catalyzer in industrial reaction device is more even, selectivity of catalyst be improved significantly, thus dry gas yied and coke yield significantly reduce.

(2) Hydrocracking unit

Hydrocracking unit comprises reactive system and fractionating system, and wherein reactive system generally includes refining reaction device and cracking case, the preferred fixed-bed reactor of reactive system, also can adopt other pattern reactor.

Catalytic wax oil wax oil that is first and/or other secondary processing mixes, then heat and mix with hydrogen, successively with Hydrobon catalyst and hydrocracking catalyst contact reacts, reaction generates oil gas and obtains gas, light naphthar, heavy naphtha, hydrocracking diesel oil and hydrocracking tail oil cut through fractionation.Tail oil fraction is directly as the raw material of catalytic cracking unit or the raw material of other unit.

Described catalytic wax oil (FGO) is not less than the cut of 260 DEG C for initial boiling point, and hydrogen richness is not less than 10.5 heavy %.In a more preferred embodiment, described catalytic wax oil is the cut that initial boiling point is not less than 330 DEG C, and hydrogen richness is not less than 10.8 heavy %.The wax oil of described secondary processing is wax tailings (CGO), deasphalted oil (DAO) and mixing raw material oil thereof.

The processing condition of described hydrocracking are: hydrogen dividing potential drop 3.0 ~ 20.0MPa, temperature of reaction 150 ~ 450 DEG C, volume space velocity 0.1 ~ 20h ^-1, hydrogen-oil ratio 100 ~ 2000v/v.Hydrogen-oil ratio in the present invention all refers to the volume ratio of hydrogen and catalytic wax oil.

Catalyst loading pattern in described hydrotreatment fixed-bed reactor loads hydrogenation protecting agent, hydrodemetallation (HDM) sweetening agent and hydrotreating catalyst successively.With integer catalyzer volume for benchmark, the admission space percentage ratio of hydrogenation protecting agent, hydrodemetallation (HDM) sweetening agent and hydrotreating catalyst is respectively 2 ~ 20 volume %, 0 ~ 20 volume %, 60 ~ 98 volume %.

Heavily % molybdenum oxides, surplus are alumina supporter to 0.5 ~ 5.0 heavy % nickel oxide, 2.0 ~ 10.0 that consists of of described hydrogenation protecting agent.

Described hydrodemetallation (HDM) sweetening agent consists of 2.0 ~ 7.0 heavy % cobalt oxides, 10.0 ~ 30.0, and heavily % molybdenum oxides, surplus are alumina supporter.

Described Hydrobon catalyst be one or more loads at unformed aluminum oxide or/and the group vib in silica-alumina supports is or/and VIII non-precious metal catalyst; Described hydrocracking catalyst is that one or more loads group vib is over a molecular sieve or/and VIII non-precious metal catalyst.

Described group vib base metal be molybdenum or/and tungsten, VIII base metal is one or more in nickel, cobalt, iron.

One or more in Y zeolite, beta molecular sieve, type ZSM 5 molecular sieve, SAPO Series Molecules sieve of the molecular screening of described hydrocracking catalyst load.

The composition of preferred hydrocracking catalyst is by weight: carrying alumina body burden is 20% ~ 70%, molecular sieve content 10% ~ 65%, and vib metal oxide content is 10% ~ 40%, and group VIII metal oxide content is 1% ~ 20%.

(3) other auxiliary units

Gasoline hydrodesulfurizationmethod delivered to by the gasoline of catalytic cracking unit or gasoline absorbing desulfurization device carries out gasoline desulfur, refers to patent CN101314734A or CN1658965A respectively, and the diesel oil of catalytic cracking unit enters diesel fuel desulfurization device and carries out diesel fuel desulfurization; The regenerated flue gas of catalytic cracking unit enters flue gas processing device, carries out fume treatment, the fume emission after process.

The invention has the advantages that:

1, improve different oil Refining Technologies utilization benefit, strengthening oil Refining Technologies is more reasonably integrated, provides a new approach for oil refining production process cleans to clean with refined oil product.

2, improve Hydrocracking unit feedstock property, improve the utilization ratio of hydrogen in raw material, thus can petroleum resources be saved.

3, diesel yield and diesel cetane-number is improved.

4, low-carbon alkene is improved as propylene, butylene massfraction in liquefied gas.

5, can products distribution be improved, reduce dry gas and coke yield, and suitably improve product property.Because granules of catalyst is more even, in regenerative process, the temperature distribution of local is also more even, and catalyst breakage tendency also correspondingly reduces.

Accompanying drawing explanation

Fig. 1 is catalytic cracking provided by the invention and hydrocracking integrated technology process principle process schematic diagram.

Fig. 2 is the schematic flow sheet of the preferred embodiment of the present invention.

Embodiment

Further illustrate method provided by the present invention below in conjunction with accompanying drawing, but the present invention is not therefore subject to any restriction.

Fig. 1 is catalytic cracking provided by the invention and hydrocracking integrated technology process principle process schematic diagram.

High-sulfur wax oil raw material enters catalytic cracking reaction unit and carries out catalytic cracking reaction, catalytic cracking reaction unit is separated the catalytic wax oil cut obtained to be transported to Hydrocracking unit and to react, obtain the products such as petroleum naphtha, hydrocracking diesel oil, hydrocracking tail oil, this hydrocracking tail oil can turn back to former catalytic cracking unit, also can be transported to other reaction member.

Fig. 2 is the schematic flow sheet of the preferred embodiment of the present invention.Fig. 2 is the catalytic cracking of reducing riser reactor and the hydrocracking integrated process flow schematic diagram of fixed-bed reactor, and shape, the size of equipment and pipeline not by the restriction of accompanying drawing, but are determined as the case may be.

In Fig. 2, each numbering is described as follows:

1,3,4,6,11,13,17,18,21,22,23 all pipeline is represented; 2 is the pre lift zone of riser tube; 5,7 the first reaction zone, the second reaction zone being respectively riser tube; 8 is the outlet area of riser tube; 9 is settling vessel, and 10 is cyclonic separator, and 12 is stripper, and 14 is inclined tube to be generated, and 15 is revivifier, and 16 is regenerator sloped tube, and 19 is separation system, and 20 is hydroeracking unit.

Pre-lift steam enters from riser tube pre lift zone 2 through pipeline 1, and containing large pore zeolite and mesopore zeolite, activity is lower and activity distribution is relatively uniform, regenerated catalyst in thick size distribution enters riser tube pre lift zone through regenerator sloped tube 16 and promoted by pre-lift steam.Stock oil after preheating enters from riser tube pre lift zone by a certain percentage through pipeline 4 and the atomizing steam from pipeline 3, enters in the first reaction zone 5, carry out cracking reaction under certain conditions with thermocatalyst after mixing.Reactant flow be mixed into second reaction zone 7 from the cold shock agent of pipeline 6 and/or the catalyzer (not marking in figure) of cooling, carry out secondary reaction, reacted logistics enters outlet area 8, the linear speed of logistics is improved in this reaction zone, make reactant flow enter settling vessel 9, cyclonic separator 10 in gas solid separation system fast, reaction product goes separation system 19 through pipeline 11.After reaction, the reclaimable catalyst of band charcoal enters stripper 12, through entering revivifier 15 from after the water vapor stripping of pipeline 13 by inclined tube 14 to be generated, reclaimable catalyst is coke burning regeneration in the air from pipeline 17, flue gas goes out revivifier through pipeline 18, and the regenerated catalyst of heat returns riser tube bottom cycle through regenerator sloped tube 16 and uses.

In separation system 19, isolate dry gas, liquefied gas, gasoline, diesel oil (not marking in figure) and catalytic wax oil, wherein catalytic wax oil delivers to hydroeracking unit 20 through pipeline 21.

After mixing with new hydrogen and/or recycle hydrogen (not marking in figure) from the catalytic wax oil of pipeline 21, enter hydroeracking unit 20 and carry out hydrocracking reaction, be isolated to isocrackate (comprising gas, light naphthar, heavy naphtha and hydrocracking diesel oil etc.) and hydrocracking tail oil to extract out through pipeline 22,23 respectively, wherein hydrocracking tail oil is mixed into riser reactor or other catalytic cracking unit through pipeline 23 and high-sulfur wax oil.

Embodiment

The following examples will be further described the present invention, but not thereby limiting the invention.The stock oil used in embodiment, comparative example and the character of catalyzer list in table 1 and table 2, the trade mark of catalytic cracking catalyst is CGP-1, CGP-1 catalyzer is through 800 DEG C, 100% water vapor aging 12 hours and 30 hours respectively, obtain CGP-1H and the CGP-1L catalyzer that activity level is respectively 62 and 50, wherein will carry out elutriation by part CGP-1L catalyzer, removing fine particle and the particle being greater than 100 microns, obtain the catalyzer CGP-1LA of thick size distribution, activity is 49, and its character lists in table 2.In hydrotreatment fixed bed reaction district, the catalyzer commercial grades of filling is respectively RG-10A/RG-10B/RMS-1/RN-32V, admission space ratio is 4: 4: 15: 77, hydrocracking catalyst commercial grades is RHC-1M, and above catalyzer is produced by Sinopec catalyzer branch office.

Embodiment 1

The present embodiment illustrates and adopts method provided by the invention, adopts the catalyzer of thick size distribution, the products distribution after kitty cracker and medium-sized hydroeracking unit process and the situation of product property.

The raw material A of preheating is first processed at kitty cracker, and the pre lift zone of the reactor of kitty cracker, the first reaction zone, second reaction zone, outlet area total height are 15 meters, and pre lift zone diameter is 0.025 meter, and it is highly 1.5 meters; First reaction zone diameter is 0.025 meter, and it is highly 4 meters; Second reaction zone diameter is 0.1 meter, and it is highly 6.5 meters; The diameter of outlet area is 0.025 meter, and it is highly 3 meters; The drift angle of the longitudinal section isosceles trapezoid of first and second reaction zone combining site is 45 °; The base angle of the longitudinal section isosceles trapezoid of second reaction zone and outlet area combining site is 60 °.Raw material A listed by table 1 enters in this reactor, in the presence of water vapor, contact with the thermocatalyst CGP-1LA (its catalyst activity is 49) of thick size distribution and react, reaction product isolated obtains sour gas, dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, catalytic wax oil and coke and can calculate its products distribution, reclaimable catalyst enters revivifier through stripping, and regenerated catalyst uses through burning Posterior circle.In certain test period, obtain the catalytic wax oil of some amount, for medium-sized hydrotreater is supplied raw materials.The CGP-1 catalyzer joined in medium-sized experimental installation is that fresh CGP-1 analyses the catalyzer after process through hydro-thermal and poplar, (catalyzer hydro-thermal treatment method adopts Catalyst processing method 1 of the present invention to process, dense phase fluidized bed, aging temperature 670 DEG C, the apparent linear velocity 0.30m/s of fluidized-bed, 100% water vapour, digestion time 28), its initial activity is 72, then mixes with the equilibrium catalyst in device, hydrothermal aging again in device, until the catalyst activity in device is 49.

Catalytic wax oil carries out hydrocracking on medium-sized hydroeracking unit, and after process, reaction product isolated obtains sour gas, a small amount of dry gas and liquefied gas, petroleum naphtha, hydrocracking diesel oil, hydrocracking tail oil.In certain test period, obtain the hydrocracking tail oil of some amount, for kitty cracker is supplied raw materials.The operational condition that hydrocracking tail oil is processed on kitty cracker is completely identical with raw material A with catalyzer.The gross product distribution of three tests sums up process in the ratio of regulation to three cover products distribution, the gasoline that catalytic gasoline character and catalytic diesel oil character obtain medium-sized twice catalytic cracking in the ratio of regulation and diesel oil carry out mixed converting, and then sample presentation analyzes gained.The character of the operational condition tested, product slates and product lists in table 3 and table 4.

Comparative example 1

Adopt medium-sized tester identical with embodiment 1, stock oil used is also the raw material A listed by table 1, just raw material A first carries out hydrotreatment on medium-sized hydrotreater, and the catalytic cracking catalyst adopted changes the CGP-1H catalyzer of conventional particle size distribution into by the CGP-1LA of thick size distribution.The operational condition that hydrogenation wax oil is processed on kitty cracker is identical with raw material A.The products distribution of two cover medium-sized testers is summed up calculating in the ratio of regulation, and obtain the products distribution that twice test is total, its products distribution lists in table 3.Catalytic gasoline, catalytic diesel oil and hydrogenated diesel oil character obtained through sample presentation analysis, and its character lists in table 4.

As can be seen from table 3 and 4, relative to the catalytic cracking catalyst CGP-1H of conventional particle size distribution, adopt the catalytic cracking catalyst CGP-1LA of thick size distribution, dry gas yied drops to 1.17 heavy % by 1.90 heavy %, coke yield drops to 3.57 heavy % by 5.75 heavy %, liquid yield rises to 94.60 heavy % by 89.96 heavy %, and catalytic diesel oil cetane value is increased to 35 by 28.In liquefied gas, the massfraction of propylene, butylene is respectively 34.85 heavy %, 15.38 heavy %, improves 4.14,9.43 percentage points respectively.

Table 1

Stock oil is numbered	A
		Stock oil title	High-sulfur wax oil
Density (20 DEG C), kg/m 3	907.7
		Kinematic viscosity, millimeter 2/ second
80℃	11.53
		100℃	7.02
Carbon residue, heavy %	0.30
		Condensation point, DEG C	37
Nitrogen, heavy %	0.12
		Sulphur, heavy %	1.80
Carbon, heavy %	85.49
		Hydrogen, heavy %	12.34
Boiling range, DEG C
		Initial boiling point	242
5％	349
		10％	377
50％	446
		70％	464
90％	498
		Final boiling point	511

Table 2

Catalyzer title	CGP-1LA	CGP-1H
			Grain type	Coarse grain footpath	Conventional particle size
Physical properties
			Specific surface, m 2/g	76	95
Pore volume, mL/g	0.20	0.23
			Size-grade distribution, volume %
0 ~ 40 micron	8.1	20.3
			40 ~ 80 microns	77.3	53.2
> 80 microns	14.6	26.5

Table 3

	Embodiment 1	Comparative example 1
			Operational condition
Catalytic unit
			Temperature of reaction, DEG C
First reaction zone/second reaction zone	550/500	550/500
			The residence time, second	5.5	5.5
First reaction zone/second reaction zone	2.0/3.5	2.0/3.5
			Agent-oil ratio	5.0	5.0
Water-oil ratio	0.1	0.1
			Hydrocracking unit
Hydrogen dividing potential drop, MPa	12.0	/
			Refining reaction temperature, DEG C	376	/
Cracking reaction temperature, DEG C	380	/
			Hydrogen to oil volume ratio, Nm 3/m 3	850	/
Hydrogenation unit
			Hydrogen dividing potential drop, MPa	/	8.0
Temperature of reaction, DEG C	/	370
			Cumulative volume air speed, h -1	/	1.5
Hydrogen to oil volume ratio, Nm 3/m 3	/	500
			Product slates, heavy %
Hydrogen sulfide	1.15	1.60
			Ammonia	0.06	0.12
Dry gas	1.17	1.90
			Liquefied gas	17.36	22.01
Wherein propylene massfraction	34.85	30.71
			Iso-butylene massfraction	15.38	5.95
Gasoline	44.30	39.74
			Wherein hydrotreated naphtha	12.20	0.77
Catalytic gasoline	32.10	38.97
			Solar oil	32.94	28.21
Wherein hydrogenated diesel oil	13.85	9.93
			Catalytic diesel oil	19.09	18.28
Heavy oil	0.19	1.77
			Coke	3.57	5.75
Add up to	100.74	101.10
			Liquid yield, heavy %	94.60	89.96
Chemistry consumption hydrogen, heavy %	0.74	1.10

Table 4

	Embodiment 1	Comparative example 1
			Catalytic gasoline character and composition
Octane value
			RON	94.1	93.6
MON	80.4	81.0
			Boiling range, DEG C
Initial boiling point ~ do	38～200	37～200
			Sulphur content, μ g/g	1020	100
Group composition, volume %
			Alkene	54.6	12.3
Aromatic hydrocarbons	18.0	25.7
			Catalytic diesel oil character
Density (20 DEG C), kg/m 3	889.8	905.0
			Sulphur content, heavy %	2.3	0.20
Boiling range scope, DEG C	200～350	200～350
			Cetane value	35	28
Hydrogenated diesel oil character
			Density (20 DEG C), kg/m 3	813.5	856.4
Sulphur content, μ g/g	＜20	240
			Boiling range scope, DEG C	175～350	175～350
Cetane value	68	/

Claims (25)

1. a Catalytic conversion method for petroleum hydrocarbon, is characterized in that the method comprises the following steps:

(1) high-sulfur wax oil with heat regenerated catalyst catalytic cracking unit reactor lower contacts and there is cracking reaction, the oil gas generated and under certain reaction environment, optionally hydrogen transfer reactions and isomerization reaction occur containing the catalyzer of charcoal is up, separating reaction oil gas obtains the reaction product comprising liquefied gas, gasoline, diesel oil and catalytic wax oil, reclaimable catalyst uses through stripping, regeneration Posterior circle, described catalyzer is containing large pore zeolite and mesopore zeolite, activity is lower and activity distribution is relatively uniform, and Catalyst Balance Activity is 35 ~ 60; In thick size distribution, described thick size distribution refers to that the size composition of catalyzer is that the particle being less than 40 microns accounts for the volume ratio of all particles lower than 10%;

(2) enter Hydrocracking unit from the catalytic wax oil of step (1) and other optional secondary processing wax oil and carry out hydrocracking reaction;

(3) hydrocracking tail oil turns back to catalytic cracking unit, as the stock oil of catalytic cracking, or as the raw material of one or more unit in Hydrocracking unit, preparing ethylene by steam cracking unit, other hydro carbons processing unit;

The sulphur content of described high-sulfur wax oil is greater than 0.5 heavy %.

2., according to the method for claim 1, it is characterized in that the gasoline of step (1) enters gasoline sweetener, diesel oil enters diesel fuel desulfurization device.

3., according to the method for claim 1, it is characterized in that the regenerated flue gas of step (1) enters flue gas processing device and processes, the fume emission after process.

4., according to the method for claim 1, it is characterized in that the sulphur content of described high-sulfur wax oil is greater than 1.0 heavy %.

5., according to the method for claim 1, it is characterized in that described high-sulfur wax oil is selected from atmospheric overhead, atmospheric tower is extracted out distillate, straight run decompressed wax oil, either shallow hydrogenation wax oil, wax tailings, deasphalted oil and composition thereof.

6., according to the method for claim 1, it is characterized in that other secondary processing wax oil described is selected from wax tailings, deasphalted oil and composition thereof.

7. according to the method for claim 1, it is characterized in that described cracking reaction condition is as follows: temperature of reaction is 430 DEG C ~ 620 DEG C, the reaction times is 0.2 second ~ 2.0 seconds, and the weight ratio of catalyzer and stock oil is 2 ~ 15: 1.

8. according to the method for claim 7, it is characterized in that described cracking reaction condition is as follows: temperature of reaction is 490 DEG C ~ 600 DEG C, the reaction times is 0.3 second ~ 1.5 seconds, and the weight ratio of catalyzer and stock oil is 3 ~ 12: 1.

9. according to the method for claim 1, it is characterized in that described hydrogen transfer reactions and isomerization reaction condition as follows: temperature of reaction is 420 DEG C ~ 550 DEG C, and the reaction times is 1 second ~ 30 seconds.

10. according to the method for claim 9, it is characterized in that described hydrogen transfer reactions and isomerization reaction condition as follows: temperature of reaction is 460 DEG C ~ 500 DEG C, and the reaction times is 2 seconds ~ 15 seconds.

11. according to the method for claim 1, it is characterized in that step (1) reactor used be selected from equal diameter riser tube, etc. one of in linear speed riser tube, fluidized-bed or reducing riser tube, or the compound reactor be made up of equal diameter riser tube and fluidized-bed.

12., according to the method for claim 11, is characterized in that the second reaction zone of described reducing riser tube and the diameter ratio of the first reaction zone are 1.5 ~ 5.0: 1.

13. according to the method for claim 1, it is characterized in that step (1) described large pore zeolite accounts for 75 ~ 99 heavy % of zeolite gross weight, mesopore zeolite accounts for 1 ~ 25 heavy % of zeolite gross weight, large pore zeolite is selected from one or more in Rare Earth Y, rare earth hydrogen Y, super steady Y, high silicon Y, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and ZSM series zeolite is selected from one or more among ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48.

14. according to the method for claim 1, it is characterized in that the size composition of the catalyzer of described thick size distribution is that the particle being less than 40 microns accounts for the volume ratio of all particles lower than 5%.

15. according to the method for claim 1 or 14, it is characterized in that the size composition of the catalyzer of described thick size distribution is that the particle being greater than 80 microns accounts for the volume ratio of all particles lower than 15%.

16. according to the method for claim 15, it is characterized in that the size composition of the catalyzer of described thick size distribution is that the particle being greater than 80 microns accounts for the volume ratio of all particles lower than 10%.

17. according to the method for claim 1, it is characterized in that step (1) Catalyst Balance Activity used is 40 ~ 55.

18. according to the method for claim 1, it is characterized in that the relatively uniform catalyzer of step (1) activity distribution used refers to that joining catalytic cracking unit inner catalyst initial activity is no more than 80, the self regulation time of this catalyzer is 0.1 hour ~ 50 hours.

19. according to the method for claim 14, it is characterized in that the relatively uniform catalyzer of step (1) activity distribution used refers to that joining catalytic cracking unit inner catalyst initial activity is no more than 75, the self regulation time of this catalyzer is 0.1 ~ 30 hour.

20. according to the method for claim 19, it is characterized in that the relatively uniform catalyzer of step (1) activity distribution used refers to that joining catalytic cracking unit inner catalyst initial activity is no more than 70, the self regulation time of this catalyzer is 0.1 ~ 10 hour.

21., according to the method for claim 1, is characterized in that the described hydrocracking reaction condition of step (2) is: hydrogen dividing potential drop 3.0 ~ 20.0MPa, temperature of reaction 150 ~ 450 DEG C, volume space velocity 0.1 ~ 20h ^-1, hydrogen-oil ratio 100 ~ 2000v/v.

22., according to the method for claim 1, is characterized in that step (2) described hydrocracking catalyst is that one or more loads group vib is over a molecular sieve or/and VIII non-precious metal catalyst.

23. according to the method for claim 22, it is characterized in that the composition of step (2) described hydrocracking catalyst by weight: carrying alumina body burden is 20% ~ 70%, molecular sieve content 10% ~ 65%, vib metal oxide content is 10% ~ 40%, and group VIII metal oxide content is 1% ~ 20%.

24. according to the method for claim 22 or 23, it is characterized in that described group vib base metal be molybdenum or/and tungsten, VIII base metal is one or more in nickel, cobalt, iron.

25. according to the method for claim 22 or 23, it is characterized in that one or more in Y zeolite, beta molecular sieve, type ZSM 5 molecular sieve, SAPO Series Molecules sieve of described molecular screening.