CN103059993A - 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 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 yield of low carbon olefins such as propylene and butylene 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 catalysis 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 the regeneration fume from catalytic cracking _XDischarging does not meet environmental requirement, and the sulphur content in gasoline and the diesel product all can not meet the 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 the 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 that adopts Hydrofining Technology to improve the catalytically cracked material quality, and the temperature of reaction of this hydro-refining unit is lower than 390 ℃, and reaction pressure more than 10.0MPa, is preferably in more than the 12.0MPa at least.Be conducive under the processing condition of aromatic saturation, improving the cracking performance of catalytic cracking unit raw material by hydrofining, thereby improving the transformation efficiency of catalytic cracking unit, producing high-octane gasoline blend component.CN101684417A discloses a kind of hydrogenation-catalytic cracking combination process of optimization, the wax oil raw material reacts at the hydrotreatment reaction zone, the hydrogenation wax oil that obtains is as catalytically cracked stock, directly enter catalytic cracking unit without fractionation, catalysis heavy cycle oil loops back the hydrotreatment reaction zone, the light circulation of high pressure hot separator top gaseous stream and catalysis enters the hydro-upgrading reaction zone with the gas oil of choosing wantonly, carry out the hydro-upgrading reaction, resultant of reaction obtains hydrotreated naphtha and hydrogenated diesel oil after fractionation.The public hydrogen gas system of hydrotreating unit and hydro-upgrading unit reduces appliance arrangement investment and process cost.Products scheme is flexible, can produce simultaneously high-quality low-sulfur gasoline, fine-quality diesel oil and reformer feed.

Usually, the 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 the hydrotreatment process, is unfavorable for voluminous gasoline and propylene.In addition, the catalytic cracking process of maximizing iso-paraffins (MIP) is to processing catalytically cracked stock, especially the hydrogenation wax oil of high-quality, cause content of olefin in gasoline on the low side, iso-butylene content in the 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 at present nearly 50 cover catalytic cracking unit, obtains huge economic benefit and social benefit.See ZL99105904.2, ZL99105905.0 and ZL99105903.4 about the liquefied gas that is rich in Trimethylmethane and the MIP technology detailed description that is rich in isoparaffin gasoline.

Along with environmental regulation requires increasingly stringent to catalytic cracking production process and quality product, even hydrogenation wax oil, the SO in the regeneration fume from catalytic cracking are processed in catalytic cracking _XDischarging also is difficult to meet environmental requirement, still needs to increase the regenerated flue gas treatment unit.Process the SO of lower aq when the regenerated flue gas treatment unit _XDuring flue gas, its processing efficiency will decrease.In addition, lower even content of sulfur in gasoline is produced in the cracking of hydrogenation wax catalysis, but still be difficult to the sulphur content in the gasoline is reduced to that 10 micrograms/below the gram, gasoline still needs aftertreatment.When adopting the lower gasoline of S-Zorb technical finesse sulphur content, S-Zorb is difficult to keep its balancing run because the sulphur content in the gasoline is excessively low, needs to replenish from the external world other sulfide, causes S-Zorb device utilization benefit to reduce.

Summary of the invention

The catalysis conversion method that the purpose of this invention is to provide 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 may further comprise the steps:

(1) the high-sulfur wax oil contacts in the bottom of catalytic cracking unit reactor with the hot regenerated catalyst that contains large pore zeolite and mesopore zeolite and cracking reaction occurs, the oil gas that generates and contain that the catalyzer of charcoal is up, and optionally hydrogen transfer reactions and isomerization reaction occur under certain reaction environment, reaction product isolated, reclaimable catalyst recycles after stripping, regeneration;

(2) from the wax oil of the catalytic wax oil of step (1) and optional other secondary processing stock oil as hydroeracking unit, enter the 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 the diesel fuel desulfurization device;

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

Catalysis conversion method provided by the invention is such implementation:

(1), catalytic cracking unit

(a), the high-sulfur inferior feedstock oil of preheating enters reactor and contacts with the hot regenerated catalyst that contains large pore zeolite and mesopore zeolite and cracking reaction occurs, temperature of reaction is 430 ℃～620 ℃, be preferably 490 ℃～600 ℃, reaction times is 0.2 second～2.0 seconds, be preferably 0.3 second～1.5 seconds, the weight ratio of catalyzer and stock oil (hereinafter to be referred as agent-oil ratio) is 2～15: 1, is preferably 3～12: 1;

(b), the oil gas and the used catalyst that generate are up, optionally hydrogen transfer reactions and isomerization reaction occur under certain reaction environment, temperature of reaction is 420 ℃～550 ℃, be preferably 460 ℃～500 ℃, 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 of stock oil (hereinafter to be referred as water-oil ratio) are 0.03～0.3: 1, be preferably 0.05～0.3: 1, pressure is 130kPa～450kPa;

(c), reaction product isolated obtains being rich in moderate gasoline, diesel oil, catalytic wax oil and other product of liquefied gas, olefin(e) centent of propylene, reclaimable catalyst enters revivifier through stripping, recycles behind coke burning regeneration.

(d), catalytic wax oil is installed or water distilling apparatus enters hydroeracking unit after removing a small amount of granules of catalyst after filtration.

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

Method provided by the invention can the equal diameter riser tube, etc. carry out in linear speed riser tube or the 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 the linear speed riser tube basic identical.The equal diameter riser tube, etc. the linear speed riser reactor be followed successively by from bottom to up pre lift zone, the first reaction zone, second reaction zone, 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 the equal diameter riser tube, etc. when linear speed riser tube or fluidized-bed reactor, establish one or more cold shocks medium inlet in the second reaction zone bottom, 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 respectively temperature and the reaction times of each reaction zone.The cold shock medium is one or more the mixture of arbitrary proportion that is selected from half regenerated catalyst of the regenerated catalyst of cold shock agent, cooling and cooling.Wherein the cold shock agent is one or more the mixture of arbitrary proportion that is selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or the water; The regenerated catalyst of cooling and half regenerated catalyst of cooling are that reclaimable catalyst cools off after two-stage regeneration and one section regeneration respectively and obtains, the regenerated catalyst carbon content is below the 0.1 heavy %, be preferably below the 0.05 heavy %, half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7.

Method provided by the invention also can be carried out in the compound reactor that is made 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 respectively temperature and the reaction times of each reaction zone.Establish one or more cold shocks medium inlet in the bottom of fluidized-bed, 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 respectively temperature and the reaction times of each reaction zone.The cold shock medium is one or more the mixture of arbitrary proportion that is selected from half regenerated catalyst of the regenerated catalyst of cold shock agent, cooling and cooling.Wherein the cold shock agent is one or more the mixture of arbitrary proportion that is selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or the water; The regenerated catalyst of cooling and half regenerated catalyst of cooling are that reclaimable catalyst cools off after two-stage regeneration and one section regeneration respectively and obtains, the regenerated catalyst carbon content is below the 0.1 heavy %, be preferably below the 0.05 heavy %, half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 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, is generally 0.02 meter～5 meters, and it highly accounts for 5%～10% of total reactor height.The effect of pre lift zone is in the presence of the pre-lift medium regenerated catalyst to be moved upward and accelerate, and used identical of used pre-lift medium 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 be slightly large than pre lift zone, the diameter of the first reaction zone and the diameter ratio of pre lift zone are 1.0～2.0: 1, it highly accounts for 10%～30% of total reactor height.Cracking reaction under higher temperature of reaction and agent-oil ratio, short residence time (being generally 0.5 second～2.5 seconds), mainly occurs in stock oil and catalyzer after this district is mixed.

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 flow velocity and the temperature of reaction that reduces oil gas and catalyzer.Reduce the method for this district's temperature of reaction, can be from the combining site injection cold shock medium of this district with the first reaction zone, and/or by in this district heat collector being set, take the part heat away to reduce this district's temperature of reaction, suppress the purpose that secondary cracking reacts, increases isomerization reaction and hydrogen transfer reactions thereby reach.The cold shock medium is one or more the mixture of arbitrary proportion that is selected from half regenerated catalyst of the regenerated catalyst of cold shock agent, cooling and cooling.Wherein the cold shock agent is one or more the mixture of arbitrary proportion that is selected from liquefied gas, raw gasline, stable gasoline, diesel oil, heavy gas oil or the water; The regenerated catalyst of cooling and half regenerated catalyst of cooling are that reclaimable catalyst cools off after two-stage regeneration and one section regeneration respectively and obtains, the regenerated catalyst carbon content is below the 0.1 heavy %, be preferably below the 0.05 heavy %, half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7.If heat collector is set, 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 can stop certain hour in this district, to suppress cracking reaction and heat cracking reaction, improves rate of flow of fluid.

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

Described other secondary processing wax oil of step (2) is selected from CGO, DAO and composition thereof.

Described catalyzer comprises zeolite, inorganic oxide, clay.In butt, each component accounts for respectively total catalyst weight: about 5 weight of zeolite～about 50 % by weight, preferred about 10 weight～about 30 % by weight; About 0.5 weight of inorganic oxide～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 among Rare Earth Y, rare earth hydrogen Y, super steady Y, the high silicon Y, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and the ZSM series zeolite is selected from one or more among ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, the ZSM-48.

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

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

(2) hydrocracking unit

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

The wax oil of catalytic wax oil elder generation and/or other secondary processing mixes, then heating and mix with hydrogen, 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 successively.The tail oil cut 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 260 ℃ cut for initial boiling point, and hydrogen richness is not less than 10.5 heavy %.In a more preferred embodiment, described catalytic wax oil is that initial boiling point is not less than 330 ℃ cut, 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, 150～450 ℃ of temperature of reaction, volume space velocity 0.1～20h ^-1, hydrogen-oil ratio 100～2000v/v.Hydrogen-oil ratio among the present invention all refers to the volume ratio of hydrogen and catalytic wax oil.

Catalyst loading pattern in the described hydrotreatment fixed-bed reactor loads hydrogenation protecting agent, hydrodemetallation (HDM) sweetening agent and hydrotreating catalyst successively.Take the integer catalyzer volume as 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 load on unformed aluminum oxide or/and the group vib on the silica-alumina supports or/and VIII family non-precious metal catalyst; Described hydrocracking catalyst loads on group vib on the molecular sieve or/and VIII family non-precious metal catalyst for one or more.

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

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

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

(3) other auxiliary units

Gasoline hydrodesulfurizationmethod delivered to by the gasoline of catalytic cracking unit or the gasoline absorbing desulfurization device carries out gasoline desulfur, sees respectively patent CN101314734A or CN1658965A for details, and the diesel oil of catalytic cracking unit enters the 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 flue gas and processes the fume emission after the processing.

The invention has the advantages that:

1, improve different oil Refining Technologies utilization benefits, it is more reasonably integrated to strengthen oil Refining Technologies, cleans the new approach that provides for the oil refining production process cleans with refined oil product.

2, improve hydrocracking unit raw material character, improved the utilization ratio of hydrogen in the raw material, thereby can save petroleum resources.

3, improve diesel yield and diesel cetane-number.

4, increased low carbon olefine output such as propylene, butylene.

Description of drawings

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

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

Embodiment

Further specify 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 synoptic diagram.

High-sulfur wax oil raw material enters the catalytic cracking reaction unit and carries out catalytic cracking reaction, the catalytic cracking reaction unit is separated the catalytic wax oil cut obtain to be transported to the 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 preferred implementation of the present invention.Fig. 2 is the catalytic cracking of reducing riser reactor and the hydrocracking integrated technique schematic flow sheet of fixed-bed reactor, and the shape of equipment and pipeline, size are not subjected to the restriction of accompanying drawing, but determines as the case may be.

Each numbering is described as follows among Fig. 2:

1,3,4,6,11,13,17,18,21,22,23 all represents pipeline; 2 is the pre lift zone of riser tube; 5,7 the first reaction zone, the second reaction zones that are 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 the regenerated catalyst that contains large pore zeolite and mesopore zeolite of heat enters the riser tube pre lift zone through regenerator sloped tube 16 and promoted by pre-lift steam.Stock oil after the preheating enters from the riser tube pre lift zone by a certain percentage through pipeline 4 and atomizing steam from pipeline 3, and enters in the first reaction zone 5 after thermocatalyst mixes, and carries out under certain conditions cracking reaction.Reactant flow be mixed into second reaction zone 7 from the cold shock agent of pipeline 6 and/or the catalyzer (not marking among the figure) of cooling, carry out secondary reaction, reacted logistics enters outlet area 8, this reaction zone improves the linear speed of logistics, make reactant flow enter fast settling vessel 9, cyclonic separator 10 in the gas solid separation system, reaction product is gone separation system 19 through pipeline 11.Reclaimable catalyst with charcoal after the reaction enters stripper 12, after from the water vapor stripping of pipeline 13, enter revivifier 15 by inclined tube 14 to be generated, reclaimable catalyst is coke burning regeneration in from the air of pipeline 17, flue gas goes out revivifier through pipeline 18, and the regenerated catalyst of heat returns the 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 among the figure) and catalytic wax oil, wherein catalytic wax oil is delivered to hydroeracking unit 20 through pipeline 21.

From the catalytic wax oil of pipeline 21 with after new hydrogen and/or recycle hydrogen (not marking among the figure) mix, 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 and 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.Employed stock oil character is listed in table 1 in embodiment, the Comparative Examples, and the trade mark of catalytic cracking catalyst is CGP-1, and the CGP-1 catalyzer is through 800 ℃, and 100% steam aging 12 hours obtains activity level and be 62 CGP-1H catalyzer.The commercial trade mark of the catalyzer of filling is respectively RG-10A/RG-10B/RMS-1/RN-32V in the hydrotreatment fixed bed reaction district, the admission space ratio is 4: 4: 15: 77, the commercial trade mark of hydrocracking catalyst is RHC-1M, and above catalyzer is produced by Sinopec catalyzer branch office.。

Embodiment 1

Method provided by the invention is adopted in present embodiment explanation, raw material A after kitty cracker and medium-sized hydroeracking unit are processed products distribution and the situation of product property.

The raw material A of preheating is processed at kitty cracker first, 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 the pre lift zone diameter is 0.025 meter, and it highly is 1.5 meters; The first reaction zone diameter is 0.025 meter, and it highly is 4 meters; The second reaction zone diameter is 0.1 meter, and it highly is 6.5 meters; The diameter of outlet area is 0.025 meter, and it highly is 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 °.The listed raw material A of table 1 enters in this reactor, in the presence of water vapor, contact with the catalyst A of heat 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 recycles after burning.In certain test period, obtain the catalytic wax oil of some amount, for medium-sized hydrotreater is supplied raw materials.

Catalytic wax oil is carried out hydrocracking at medium-sized hydroeracking unit, and reaction product isolated obtains sour gas, a small amount of dry gas and liquefied gas, petroleum naphtha, hydrocracking diesel oil, hydrocracking tail oil after processing.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 at kitty cracker is fully identical with raw material A with catalyzer.The ratio that the gross product of three tests distributes in accordance with regulations sums up processing to three cover products distribution, catalytic gasoline character and catalytic diesel oil character ratio are in accordance with regulations mixed the medium-sized twice resulting gasoline of catalytic cracking and diesel oil and are converted, and then sample presentation is analyzed gained.The operational condition of test, product distribute and the character of product is listed in table 2 and table 3.

Comparative Examples 1

Adopt medium-sized tester and catalyzer and embodiment 1 identical, used stock oil also is the listed raw material A of table 1.Just raw material A is carried out hydrotreatment at medium-sized hydrotreater first, and reaction product isolated obtains sour gas, a small amount of dry gas, a small amount of liquefied gas, petroleum naphtha, hydrogenated diesel oil and hydrogenation catalyst wax oil after processing.In certain test period, obtain the hydrogenation catalyst wax oil of some amount, for kitty cracker is supplied raw materials.The operational condition that the hydrogenation wax oil is processed at kitty cracker, catalyzer, raw material are all identical.The products distribution ratio in accordance with regulations of two cover medium-sized testers is summed up calculating, obtain the total products distribution of twice test, its products distribution is listed in table 2.Catalytic gasoline, catalytic diesel oil and hydrogenated diesel oil character are to analyze resulting through sample presentation.Its character is listed in table 3.

Can find out from table 2 and 3, with respect to Comparative Examples 1, the hydrogen consumption of the present invention's processing is 0.46 heavy %, has reduced by 58.18%, liquid yield is 92.55 heavy %, increased by 2.59 percentage points, gasoline yield is increased to 47.09 heavy % from 39.74 heavy %, has increased by 7.35 percentage points, increasing degree is 18.50%, the catalytic diesel oil cetane value is increased to 29 from 28, increased by 1 unit, but the hydrogenated diesel oil cetane value is up to 67.The yield of propylene, butylene is respectively 7.26 heavy %, 3.16 heavy %, improves respectively 0.5,1.85 percentage point.

Table 1

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

Table 2

	Embodiment 1	Comparative Examples 1
			Operational condition
Catalytic unit
			Temperature of reaction, ℃
The first reaction zone/second reaction zone	550/500	550/500
			The residence time, second	5.5	5.5
The 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
			The hydrocracking unit
The hydrogen dividing potential drop, MPa	12.0	/
			The refining reaction temperature, ℃	376	/
The cracking reaction temperature, ℃	380	/
			Hydrogen to oil volume ratio, Nm 3/m 3	850	/
Hydrogenation unit
			The hydrogen dividing potential drop, MPa	/	8.0
Temperature of reaction, ℃	/	370
			The cumulative volume air speed, h -1	/	1.5
Hydrogen to oil volume ratio, Nm 3/m 3	/	500
			Product distributes, heavy %
Hydrogen sulfide	1.20	1.60
			Ammonia	0.06	0.12
Dry gas	1.74	1.90
			Liquefied gas	21.64	22.01
Propylene wherein	7.26	6.76
			Iso-butylene	3.16	1.31
Gasoline	47.09	39.74
			Hydrotreated naphtha wherein	7.80	0.77
Catalytic gasoline	39.29	38.97
			Solar oil	23.82	28.21
Hydrogenated diesel oil wherein	8.60	9.93
			Catalytic diesel oil	15.22	18.28
Heavy oil	0.18	1.77
			Coke	4.73	5.75
Add up to	100.46	101.10
			Liquid yield, heavy %	92.55	89.96
Chemistry consumption hydrogen, heavy %	0.46	1.10

Table 3

	Embodiment 1	Comparative Examples 1
			Catalytic gasoline character and composition
Octane value
			RON	94.2	93.6
MON	81.0	81.0
			Boiling range, ℃
Initial boiling point～do	38～200	37～200
			Sulphur content, μ g/g	1200	100
Group composition, volume %
			Alkene	31.6	12.3
Aromatic hydrocarbons	20.2	25.7
			Catalytic diesel oil character
Density (20 ℃), kg/m 3	900.0	905.0
			Sulphur content, heavy %	2.3	0.20
The boiling range scope, ℃	200～350	200～350
			Cetane value	29	28
Hydrogenated diesel oil character
			Density (20 ℃), kg/m 3	816.4	856.4
Sulphur content, μ g/g	＜20	240
			The boiling range scope, ℃	175～350	175～350
Cetane value	67	/

Claims (19)

1. the catalysis conversion method of a petroleum hydrocarbon is characterized in that the method may further comprise the steps:

(1) the high-sulfur wax oil contacts in the bottom of catalytic cracking unit reactor with the hot regenerated catalyst that contains large pore zeolite and mesopore zeolite and cracking reaction occurs, the oil gas that generates and contain that the catalyzer of charcoal is up, and optionally hydrogen transfer reactions and isomerization reaction occur under certain reaction environment, separating reaction oil gas obtains comprising the reaction product of liquefied gas, gasoline, diesel oil and catalytic wax oil, and reclaimable catalyst recycles after stripping, regeneration;

(2) enter the 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.

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

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

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 0.5 heavy %.

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

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

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

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

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

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

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

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

13. according to the method for claim 13, it is characterized in that the reducing riser tube, the diameter ratio of second reaction zone and the first reaction zone is 1.5～5.0: 1.

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

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

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

17. the method according to claim 16, it is characterized in that the composition of the described hydrocracking catalyst of step (2) by weight: the carrying alumina body burden is 20%～70%, molecular sieve content 10%～65%, the vib metal oxide content is that 10%～40%, VIII family metal oxide content is 1%～20%.

18. according to the method for claim 16 or 17, it is characterized in that described group vib base metal is molybdenum or/and tungsten, VIII family base metal is one or more in nickel, cobalt, the iron.

19. according to the method for claim 16 or 17, it is characterized in that in Y zeolite, beta molecular sieve, type ZSM 5 molecular sieve, SAPO Series Molecules sieve one or more of described molecular screening.

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