CN116262882A - Hydrocracking method for producing naphtha, light ethylene material and high-quality tail oil - Google Patents
Hydrocracking method for producing naphtha, light ethylene material and high-quality tail oil Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of processing raw oil under high-pressure hydrogen conditions, and discloses a hydrocracking method for producing naphtha, light ethylene and high-quality tail oil. The method comprises the following steps: raw oil and hydrogen are mixed and then reacted in a hydrofining reaction zone to obtain a part of refined effluent, the part of refined effluent enters a hydrocracking reaction zone I, the reaction effluent is separated and fractionated into light naphtha fraction, heavy naphtha fraction, middle distillate and tail oil fraction I by a fractionating tower I, the other part of refined effluent, middle distillate and hydrogen are mixed and then enter a hydrocracking reaction zone II for continuous reaction, the reaction effluent is sent to a fractionating tower II for separation and fractionation, the obtained tower top material is sent to the fractionating tower I for further separation, and the tail oil fraction II is separated from the tower bottom. The method provided by the invention can be used for efficiently converting the raw oil into chemical raw materials including naphtha, light ethylene material, high-quality tail oil and the like in a large proportion.
Description
Technical Field
The invention relates to the field of processing raw oil under high-pressure hydrogen conditions, in particular to a hydrocracking method for producing chemical raw materials including naphtha, light ethylene material, high-quality tail oil and the like.
Background
The continuous development of the economy in China brings about the continuous increase of the chemical raw material demand. The hydrocracking process can convert different types of raw oil into light naphtha, heavy naphtha, middle distillate and tail oil, wherein the heavy naphtha can be used as a catalytic reforming raw material to produce aromatic hydrocarbon or low-sulfur low-alkene high-octane gasoline blending component, and the tail oil fraction can be used as a raw material for preparing ethylene by a steam cracking device or a raw material for preparing ethylene by catalytic cracking, and is one of important processing technologies for refinery oiling combination.
However, the main products of the prior single-stage once-through hydrocracking device in China are naphtha, middle distillate and tail oil, and the yield of the middle distillate is higher and is about 40-65%. For the hydrocracking device which does not need to produce middle distillate, the conversion of the middle distillate to the chemical raw material is realized, and the method has important practical significance for product structure adjustment and diving synergy of refining enterprises.
CN104611019a, CN104611046a, CN105001909a and CN105018137a disclose a low energy hydrocracking process to produce high quality jet fuels. The method mainly produces heavy naphtha and aviation kerosene by a catalyst grading method, and specifically comprises the steps of mixing raw oil and hydrogen, sequentially passing through a hydrofining and hydrocracking reaction zone, controlling the conversion rate of a cracking reaction to be about 70% to obtain a reaction effluent, and separating to obtain a product.
CN10461102a and CN104611026a disclose a low energy hydrocracking process for producing high quality chemical materials. The method is characterized in that the hydrocracking reaction zone is filled with at least two hydrocracking catalysts, the upstream of the hydrocracking reaction zone is filled with 30% -70% of modified Y molecular sieve of catalyst I, the catalyst II contains 15% -50% of modified Y molecular sieve, and the modified Y molecular sieve in the catalyst I is 10% -30% higher than the catalyst II. The loading volume ratio of the hydrocracking catalyst I to the hydrocracking catalyst II is 1:5-5:1.
CN1854263a discloses a hydrocracking method for producing chemical raw materials in maximum quantity, which adopts a two-stage hydrocracking process, and realizes the maximum conversion of heavy raw materials into chemical raw materials by independently setting a middle distillate oil conversion reaction zone.
CN1955261a discloses a hydrocracking process for middle distillate recycle, which adopts a two-stage hydrocracking process, and can convert wax oil raw materials and catalytic diesel into naphtha and tail oil by adopting a Y-type molecular sieve in a single conversion zone of middle distillate.
CN103059986a discloses a hydrocracking process for producing chemical raw materials, which employs a two-stage hydrocracking process, wherein the conversion of heavy raw materials into naphtha and tail oil is achieved by employing a hydrocracking catalyst with a reduced metal loading in the second cracking reaction zone.
From the above, the existing single-stage once-through hydrocracking technology still has the following problems in maximizing the production of chemical raw materials (naphtha and tail oil):
firstly, under the existing single-stage once-through hydrocracking technology, the naphtha yield can be improved to a certain extent by modulating the conversion depth, but the tail oil yield is correspondingly reduced, and middle distillate oil (jet fuel and diesel oil) with higher proportion also exists, so that the total yield of naphtha and chemical raw materials is insufficient.
Secondly, in the hydrocracking technology for the maximum production of chemical raw materials (naphtha and tail oil) by the existing two-stage method, although the conversion of middle distillate into naphtha can be realized by adding a cracking reaction zone and recycling middle distillate into a second cracking reaction zone for reaction, the cracking reaction zone is easy to generate operation fluctuation under the condition of processing low-sulfur and low-nitrogen middle distillate, and the selectivity and the safe operation of the device products are unfavorable.
Thirdly, for a refinery enterprise with limited load of the reforming device and short supply of raw materials of the cracking device, a middle distillate oil conversion reaction zone is arranged to completely convert middle distillate oil, so that on one hand, the selectivity of the middle distillate oil is reduced, and on the other hand, the yield of naphtha fraction is overhigh and the yield of ethylene is insufficient, which contradicts the supply and demand balance requirements of materials of a refinery.
Disclosure of Invention
The invention aims to solve the problems that the hydrocracking device in the prior art has insufficient yield of chemical raw materials (naphtha and tail oil), or the middle distillate reaction zone of the hydrocracking device for producing the chemical raw materials in a full-cycle way by using the prior two-stage middle distillate is easy to generate operation fluctuation, the middle distillate conversion product has poor flexibility and the like.
In order to achieve the above object, the present invention provides a hydrocracking process for producing naphtha, light ethylene and high quality tail oil, the process comprising:
(1) Raw oil and hydrogen are mixed and then enter a hydrofining reaction zone for hydrofining reaction to obtain refined effluent, wherein the density of the raw oil is 0.84g/cm 3 ～0.98g/cm 3 The nitrogen content is 200 mu g/g-1800 mu g/g, the final distillation point is 360 ℃ to 560 ℃, and the aromatic hydrocarbon content is 25wt% to 65 wt%;
(2) Introducing at least part of the refined effluent into a hydrocracking reaction zone I for reaction, and separating the reaction effluent through a fractionating tower I to obtain light naphtha, heavy naphtha, middle distillate and high-quality tail oil I; in the hydrocracking reaction zone I, controlling the conversion depth of the reaction to be 45% -80%, wherein the conversion depth of the reaction=100% -the fraction yield of the reaction effluent in the hydrocracking reaction zone I is more than 350 ℃;
(3) Mixing a straight-run diesel oil raw material or the optional residual refined effluent, middle distillate oil and hydrogen, introducing the mixture into a hydrocracking reaction zone II for reaction, separating the reaction effluent by a fractionating tower II, introducing the obtained tower top material into the fractionating tower I for continuous separation, and obtaining a tower bottom material which is tail oil II capable of being used as a light ethylene material; controlling the cracking conversion rate in the hydrocracking reaction zone II to be 70-90% based on 100% of the mass of middle distillate in the step, wherein the cracking conversion rate=100% -the fraction yield of the reaction effluent in the hydrocracking reaction zone II at the temperature of >175 ℃;
the mass ratio of the straight-run diesel oil or the refined effluent which is introduced into the hydrocracking reaction zone II is 0.5 to 25 percent by weight based on 100 percent of the refined effluent mass of the hydrofining reaction zone;
the difference between the content of the Y-type molecular sieve of the hydrocracking catalyst I filled in the hydrocracking reaction zone I and the content of the Y-type molecular sieve of the hydrocracking catalyst II filled in the hydrocracking reaction zone II is 5 to 15 weight percent based on 100 percent of the mass of the carrier.
The technology provided by the invention realizes the efficient and flexible conversion of raw oil into chemical raw materials comprising naphtha, light ethylene material, high-quality tail oil and the like.
Drawings
FIG. 1 is a schematic flow diagram of a hydrocracking process for producing naphtha, light ethylene and premium tail oil according to a preferred embodiment of the present invention.
Description of the reference numerals
1. Raw oil
2. Hydrofining reaction zone
3. Hydrocracking reaction zone I
4. Thermal high pressure separation zone I
5. Thermal low pressure separation zone I
6. Cold high pressure separation zone I
7. Cold low pressure separation zone I
8. Fractionating tower I
9. Light hydrocarbon
10. Light naphtha fraction
11. Heavy naphtha fraction
12. Middle distillate
13. Tail oil fraction I
14. Hydrocracking reaction zone II
15. Cold high pressure separator II
16. Cold low pressure separator II
17. Fractionating tower II
18. Overhead material
19. Tail oil fraction II
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As previously described, the present invention provides a hydrocracking process for producing naphtha, light ethylene and premium tail oil, the process comprising:
(1) Raw oil and hydrogen are mixed and then enter a hydrofining reaction zone for hydrofining reaction to obtain refined effluent, wherein the density of the raw oil is 0.84g/cm 3 ～0.98g/cm 3 The nitrogen content is 200 mu g/g-1800 mu g/g, the final distillation point is 360 ℃ to 560 ℃, and the total aromatic hydrocarbon content is 25wt% -65 wt%;
(2) Introducing at least part of the refined effluent into a hydrocracking reaction zone I for reaction, and separating the reaction effluent through a fractionating tower I to obtain light naphtha, heavy naphtha, middle distillate and high-quality tail oil fraction I; in the hydrocracking reaction zone I, controlling the conversion depth of the reaction to be 45% -80%, wherein the conversion depth of the reaction=100% -the fraction yield of the reaction effluent in the hydrocracking reaction zone I is more than 350 ℃;
(3) Mixing a straight-run diesel oil raw material or the optional residual refined effluent, middle distillate oil and hydrogen, introducing the mixture into a hydrocracking reaction zone II for reaction, separating the reaction effluent by a fractionating tower II, introducing the obtained tower top material into the fractionating tower I for continuous separation, and obtaining a tower bottom material which is tail oil II capable of being used as a light ethylene material; controlling the cracking conversion rate in the hydrocracking reaction zone II to be 70-90% based on 100% of the mass of middle distillate in the step, wherein the cracking conversion rate=100% -the fraction yield of the reaction effluent in the hydrocracking reaction zone II at the temperature of >175 ℃;
the mass ratio of the straight-run diesel oil or the refined effluent which is introduced into the hydrocracking reaction zone II is 0.5 to 25 percent by weight based on 100 percent of the refined effluent mass of the hydrofining reaction zone;
the difference between the content of the Y-type molecular sieve of the hydrocracking catalyst I filled in the hydrocracking reaction zone I and the content of the Y-type molecular sieve of the hydrocracking catalyst II filled in the hydrocracking reaction zone II is 5 to 15 weight percent based on 100 percent of the mass of the carrier.
Preferably, the cut point between the light naphtha and the heavy naphtha is 65-80 ℃; preferably, the cut point between the heavy naphtha and the middle distillate is 165-175 ℃; preferably, the cutting point between the middle distillate and the high-quality tail oil fraction I is 330-350 ℃; preferably, the initial point of the tail oil II which can be used as light ethylene material is 165-175 ℃.
Preferably, the middle distillate recycle amount is 40 to 50% based on 100% by mass of the raw oil in step (1).
According to the process of the present invention, the feedstock is preferably straight run feedstock and/or secondary process oil.
Preferably, the straight-run raw oil is at least one selected from straight-run diesel raw oil, straight-run wax oil raw oil and wide-fraction oil; the secondary processing oil is at least one selected from deasphalted oil, coal tar, coal direct liquefied oil, coal indirect liquefied oil, catalytic cracking light diesel oil, catalytic cracking heavy diesel oil, residual oil diesel oil and residual oil hydrogenated wax oil.
Preferably, more than two catalyst beds are disposed in the hydrofining reaction zone.
Preferably, in each of the hydrofining reaction zones, a hydrogenation protecting catalyst, a hydrodemetallization catalyst and a hydrofining catalyst are sequentially packed along the flow direction of the reaction liquid phase.
The present invention is not particularly limited by the specific types of the hydrogenation protecting catalyst and the hydrodemetallization catalyst, and those skilled in the art can select from the hydrogenation protecting catalyst and the hydrodemetallization catalyst of the types known in the art, and the present invention is not described herein in detail, and should not be construed as limiting the present invention.
Preferably, the hydrofining catalyst is a supported catalyst, the carrier is alumina and/or silica-alumina, and the active metal component is at least one of non-noble metal elements of the VIB group and non-noble metal elements of the VIII group.
Preferably, in the hydrofining catalyst, the group VIII non-noble metal element is nickel and/or cobalt, and the group VIB non-noble metal element is molybdenum and/or tungsten.
According to a preferred embodiment, the content of the non-noble metal element of group VIII in terms of oxide is 1wt% to 15wt%, the content of the non-noble metal element of group VIB in terms of oxide is 5wt% to 40wt%, based on the total weight of the hydrofining catalyst, the balance being the carrier.
Preferably, the conditions of the hydrofinishing reaction zone are at least: the hydrogen partial pressure is 3.0 MPa-20.0 MPa, the reaction temperature is 280-400 ℃ and the liquid hourly space velocity is 0.5h -1 ～6h -1 The volume ratio of hydrogen to oil is 300-2000.
Preferably, at least two catalyst beds are independently provided in each of the hydrocracking reaction zone I and the hydrocracking reaction zone II.
Preferably, the hydrocracking catalyst I packed in the hydrocracking reaction zone I is selected from at least one of catalysts having the following characteristics:
the catalyst contains an active metal component, an acidic component serving as a carrier and a heat-resistant inorganic oxide;
the heat-resistant inorganic oxide is selected from at least one of silicon oxide and aluminum oxide; the acidic component is a Y-type molecular sieve or the acidic component is a Y-type molecular sieve and an amorphous silicon-aluminum material;
the active metal component is at least two metal elements selected from a group VIB metal element and a group VIII metal element; based on the total weight of the catalyst, the content of the VIB group metal element calculated by oxide is 22-35 wt%, the content of the VIII group metal element calculated by oxide is 2-8 wt%, and the rest is a carrier;
the content of the Y-type molecular sieve is 5-35 wt% based on 100% of the carrier mass, and the content of the amorphous silicon-aluminum material is 0-40 wt%.
Preferably, in the hydrocracking reaction zone II, a hydrocracking catalyst II is filled, or a hydrofining catalyst is also filled, wherein the volume ratio of the hydrofining catalyst is 0% to 30% based on 100% of the volume of the hydrocracking reaction zone II, and the balance is the hydrocracking catalyst II.
According to a preferred embodiment, the hydrocracking catalyst II is selected from at least one of the catalysts having the following characteristics:
the catalyst contains active metal components, a Y-type molecular sieve serving as a carrier and a heat-resistant inorganic oxide;
the heat-resistant inorganic oxide is selected from at least one of silicon oxide and aluminum oxide;
the active metal component is at least two metal elements selected from a group VIB metal element and a group VIII metal element; based on the total weight of the catalyst, the content of the VIB group metal element calculated by oxide is 11-29 wt%, the content of the VIII group metal element calculated by oxide is 2-8 wt%, and the rest is a carrier;
the content of the Y-type molecular sieve is 5-35 wt% based on the total weight of the carrier, and the balance is heat-resistant inorganic oxide.
Preferably, the hydrocracking reaction zone I conditions at least satisfy: the hydrogen partial pressure is 11 MPa-16 MPa, the reaction temperature is 360-430 ℃, and the liquid hourly space velocity is 0.9h -1 ～2.0h -1 The volume ratio of the hydrogen oil is 1000-1200.
Preferably, the hydrocracking reaction zone II conditions at least satisfy: the hydrogen partial pressure is 11 MPa-16 MPa, the reaction temperature is 360-430 ℃, and the liquid hourly space velocity is 2.0h -1 ～4.0h -1 The volume ratio of the hydrogen to the oil is 800-1600.
The process provided below in connection with fig. 1 provides a hydrocracking process for producing chemical feedstock according to a preferred embodiment of the present invention.
In fig. 1, raw oil 1 is mixed with hydrogen and then enters a hydrofining reaction zone 2 for hydrofining reaction to obtain a refined effluent; at least part of refined effluent enters a hydrocracking reaction zone I3 for reaction to obtain a first reaction effluent, the first reaction effluent is introduced into a thermal high-pressure separation zone I4 for gas-liquid separation, and the obtained liquid phase is separated by a thermal low-pressure separation zone I5 and then sent into a fractionating tower I8 for further fractional cutting; the gas phase effluent obtained in the hot high pressure separation zone I4 is further separated into gas phase and liquid phase in a cold high pressure separation zone I6, the liquid phase is sent to a fractionating tower I8 for fractional cutting after being separated in a cold low pressure separation zone I7, the gas phase obtained in the cold high pressure separation zone is circularly utilized after hydrogen sulfide and ammonia gas are removed, the fractionating tower cuts to obtain light hydrocarbon 9, light naphtha fraction 10, heavy naphtha fraction 11, middle distillate 12 and tail oil fraction I13, the straight-run diesel oil or the residual refined reaction effluent is mixed with middle distillate 12 and hydrogen gas and then enters a hydrocracking reaction zone II 14 for reaction to obtain second reaction effluent, the second reaction effluent is sent to a cold high pressure separation zone II 15 for gas-liquid separation, the obtained liquid phase is sent to a fractionating tower II 17 for further fractional cutting after being separated in a cold low pressure separation zone II 16, the obtained gas phase is circularly utilized, a tower top material 18 obtained through fractional cutting is sent to the fractionating tower I for further separation, and a tail oil fraction II 19 is separated at the bottom.
The invention will be described in detail below by way of examples. In the following examples of the method of the present invention,
separating and fractionating a product obtained in the hydrocracking reaction zone to obtain light naphtha, heavy naphtha, middle distillate and high-quality tail oil, wherein the cutting end point of the heavy naphtha or the cutting initial point of the middle distillate is 175 ℃.
The yield of the heavy naphtha fraction is defined as: the weight percentage of the heavy naphtha fraction and the raw oil cut by the whole fraction product through a fractionating tower, wherein the end point of the heavy naphtha cut is 175 ℃;
the yield of the tail oil fraction is defined as: the total fraction product is prepared by cutting the tail oil fraction and the raw oil by a fractionating tower, wherein the tail oil is used as the raw material of a device for preparing ethylene by steam cracking, and the initial cutting point is 350 ℃.
In the example, the hydrogenation protecting catalyst and the hydrogenation demetallizing catalyst are the same, the commodity marks of the hydrogenation protecting catalyst are RG-30A and RG-30B, and the commodity mark of the hydrogenation demetallizing catalyst is RAM-100; the hydrofining catalysts used in the examples are the same and have the trade mark of RN-32V, and the hydrogenation protecting catalyst, the hydrodemetallization catalyst and the hydrofining catalyst are all produced by the company Changling of China petrochemical Co.
The types of the catalysts filled in the hydrofining reaction zone in the example are the same, the hydrofining reaction zone is sequentially filled with a hydrogenation protecting catalyst, a hydrodemetallization catalyst and a hydrofining catalyst along the flow direction of the reaction liquid phase, and the filling volume ratio of RG-30A, RG-30B, RAM-100 to RN-32V in the hydrofining reaction zone is 7 percent: 7%:6%:80%.
The properties of the raw materials used in the examples are shown in Table 1.
TABLE 1
Examples 1 to 2
In example 1 and example 2, the following hydrocracking catalysts were used.
In example 1, the hydrocracking catalyst I in the hydrocracking reaction zone I is hydrocracking catalyst 1, and the hydrocracking catalyst II in the hydrocracking reaction zone II is hydrocracking catalyst a.
Composition of hydrocracking catalyst 1: w is 27.5 wt% and Ni is 4.7 wt% based on oxide, and the rest is carrier; the mass fraction of the Y-type molecular sieve is 25% based on the carrier, and the balance is alumina.
Composition of hydrocracking catalyst a: based on oxide, W is 26.5 wt%, ni is 4.7 wt%, and the rest is a carrier; the content of the Y-type molecular sieve is 13% by weight based on the carrier, and the balance is alumina.
In example 2, the hydrocracking catalyst I in the hydrocracking reaction zone I is hydrocracking catalyst 2, and the hydrocracking catalyst II in the hydrocracking reaction zone II is hydrocracking catalyst B.
Composition of hydrocracking catalyst 2: based on oxide, W is 26.5 weight percent, ni is 4.3 weight percent, and the rest is a carrier; based on the carrier, the mass fraction of the Y-type molecular sieve is 15%, the mass fraction of amorphous silicon aluminum is 15%, and the balance is aluminum oxide.
Composition of hydrocracking catalyst B: based on oxide, W is 28.5 weight percent, ni is 4.5 weight percent, and the rest is a carrier; the mass fraction of the Y-type molecular sieve is 20% based on the carrier, and the balance is alumina.
TABLE 2
As can be seen from the data in Table 2, in examples 1 and 2, the reaction was carried out by using the raw oil and the method as claimed in the present invention, the light naphtha yields were 8.0% and 8.9%, the heavy naphtha yields were 39.1% and 42.2%, the tail oil fraction II yields as light ethylene materials were 7.7% and 9.5%, the tail oil fraction I yields were 41.5% and 34.5%, and the BMCI values as tail oil fraction II as light ethylene materials were 11.2 and 12.0, respectively, and as a high-quality steam cracking ethylene plant feedstock; the hydrogen content of the tail oil fraction I is 13.8%, and the tail oil fraction I can be used as a raw material of a high-quality catalytic cracking device.
It is known that the hydrocracking method of the invention can be used for efficiently obtaining the light naphtha, heavy naphtha fraction, light ethylene material and high-quality tail oil chemical raw materials in large proportion.
Example 3, example 4 and comparative example 1
In example 3, hydrocracking reaction zone I was a hydrocracking catalyst 3, and hydrocracking reaction zone II was charged with a hydrocracking catalyst C.
Composition of hydrocracking catalyst 3: based on oxide, W is 26.5 wt%, ni is 4.7 wt%, and the rest is a carrier; based on the carrier, the mass fraction of the Y-type molecular sieve is 35%, and the balance is alumina.
Composition of hydrocracking catalyst C: based on oxide, W is 26.5 weight percent, ni is 5.2 weight percent, and the rest is a carrier; the mass fraction of the Y-type molecular sieve is 28 percent based on the carrier.
In example 4, hydrocracking reaction zone I used hydrocracking catalyst 4 and hydrocracking reaction zone II used hydrocracking catalyst D.
Composition of hydrocracking catalyst 4: based on oxide, W is 26.5 weight percent, ni is 4.3 weight percent, and the rest is a carrier; based on the carrier, the mass fraction of the Y-type molecular sieve is 12 percent, the mass fraction of amorphous silicon aluminum is 15 percent, and the balance is aluminum oxide.
Composition of hydrocracking catalyst D: based on oxide, W is 26.5 weight percent, ni is 4.5 weight percent, and the rest is a carrier; the mass fraction of the Y-type molecular sieve is 17% based on the carrier, and the balance is alumina.
In comparative example 1, the same hydrocracking catalyst as in example 3 was used.
In example 3, example 4 and comparative example 1, raw materials 1, 2 and 4 are respectively mixed with hydrogen and then sequentially pass through a hydrofining reaction zone, part of effluent of the hydrofining reaction zone enters a hydrocracking reaction zone I to react to obtain a first reactant flow, the first reactant flow is separated and fractionated by a fractionating tower I to obtain light naphtha, heavy naphtha, middle distillate and tail oil fraction I, the other part of effluent of the refining reaction zone, middle distillate of the cyclic reaction and hydrogen enter a hydrocracking reaction zone II to react to obtain a second reaction effluent, the second reaction effluent is separated and fractionated by a fractionating tower II to obtain a material at the top of the fractionating tower I to be continuously separated, the light ethylene material tail oil fraction II is obtained at the bottom of the fractionating tower, and the technological condition parameters, product distribution and product property data of the reaction are listed in Table 3.
TABLE 3 Table 3
As can be seen from the data in Table 3, examples 3 and 4 were conducted by using the feed oil and the process of the present invention, the light naphtha rates of the products were 11.0% and 7.7%, the heavy naphtha rates of the products were 53.2% and 44.7%, the yields of the tail oil fraction II at >175℃were 9.4% and 12.3%, the yields of the tail oil fraction I were 23.0% and 32.0%, the BMCIs of the tail oil fraction I were 11.3 and 10.2, and the BMCIs of the tail oil fraction II were 11.5 and 11.0, respectively, and they could be used as raw materials for high-quality steam cracking ethylene plants.
It is known that the cracking method of the invention can be used for efficiently obtaining the light naphtha fraction, the heavy naphtha fraction, the light ethylene and the high-quality tail oil of chemical raw material components in large proportion.
As is also apparent from the data in Table 3, the hydrocracking reaction system provided by the present invention, but not the feedstock required by the present invention, the yields of light naphtha, heavy naphtha, light ethylene material tail oil fraction II and tail oil fraction I obtained in comparative example 1 were 9.8%, 54.9%, 9.6% and 20.0%, respectively, and the chemical feedstock obtained also had higher yields, but the BMCI value of the obtained tail oil fraction I was 15.4, and the BMCI of the tail oil fraction II was 13.5, which could not be used as the feedstock for high-quality steam cracking ethylene plant, and the reaction conditions of the hydrofining reaction zone and the hydrocracking reaction zone I were too severe, which was disadvantageous for long-period operation of the plant.
Example 5, comparative example 2 and comparative example 3
In example 5, comparative example 2 and comparative example 3, the same hydrocracking catalyst as in example 4 was used, and in example 5, the upper portion of the hydrocracking catalyst II was further charged with 20% by volume of the hydrotreating catalyst RN-32V based on 100% by volume of the hydrocracking reaction zone II.
In example 5, raw material 2 and hydrogen are mixed and then pass through a hydrofining reaction zone, all effluent of the refining reaction zone enters a hydrocracking reaction zone I to react to obtain a first reactant flow, the first reactant flow is separated and fractionated by a fractionating tower I to obtain light naphtha, heavy naphtha, middle distillate and tail oil fraction I, part of raw material 5 straight-run diesel, middle distillate and hydrogen of cyclic reaction enter a hydrocracking reaction zone II to react to obtain a second reaction effluent, the second reaction effluent is separated and fractionated by the fractionating tower II to obtain a tower top material, the tower bottom material is sent to the fractionating tower I to be continuously separated, and the light ethylene material tail oil fraction II is obtained at the tower bottom, and the technological condition parameters, product distribution and product property data of the reaction are listed in table 4.
In comparative examples 2 and 3, the raw material 2 and hydrogen gas are mixed and sequentially pass through a hydrofining reaction zone, part of effluent of the refining reaction zone enters a hydrocracking reaction zone I to react to obtain a first reactant flow, the first reactant flow is separated and fractionated by a fractionating tower I to obtain light naphtha, heavy naphtha, middle distillate and tail oil fraction I, the other part of effluent of the refining reaction zone, middle distillate and hydrogen gas of the circulating reaction enter a hydrocracking reaction zone II to react to obtain a second reactant flow, the second reactant flow is separated and fractionated by the fractionating tower II to obtain a tower top material, and the tower bottom material is sent to the fractionating tower I to be continuously separated, wherein the refined oil mass ratio of the hydrocracking reaction zone II is controlled to be 0%, and the refined oil mass ratio of the hydrocracking reaction zone II is controlled to be 42% in comparative example 3, and the corresponding reaction process condition parameters, product distribution and product property data are listed in Table 4.
TABLE 4 Table 4
As can be seen from the data in Table 4, example 5, using the method of the present invention, yields of the light naphtha fraction, the heavy naphtha fraction, the light ethylene material tail oil fraction II and the tail oil fraction I are 6.8%, 45.1%, 10.6% and 35.0%, respectively, BMCI value of the light ethylene material tail oil fraction II is 10.3, BMCI value of the tail oil fraction I is 11.3, and the method can be used as a feed of a high-quality steam cracking ethylene production device, indicating that the method of the present invention can be used for producing light naphtha, heavy naphtha, light ethylene material and high-quality tail oil chemical raw materials in large proportion.
As is also evident from the data in Table 4, the mass ratios of the refined oils in the controlled dehydrocracking reaction zones II of comparative examples 2 and 3 were not within the scope of the present invention, and were 0 and 42.0%, respectively, the corresponding light naphtha yields were 17.7% and 16.4%, the heavy naphtha yields were 32.5% and 42.8%, respectively, the light ethylene tail II yields were 11.7% and 16.0%, the tail I yields were 30.0% and 17.4.0%, the BMCI values of the light ethylene tail II were 11.4 and 11.7, and the BMCI values of the tail I were 10.5 and 10.2, respectively.
Although the tail oil in comparative example 2 and comparative example 3 can be used as high-quality ethylene material, the cracking catalyst in comparative example 3 is sensitive in activity, which results in reduced selectivity of cracking catalyst products, increased yields of light naphtha and liquefied gas, unstable temperature operation in the reaction zone, and easy occurrence of runaway risk. The severity of the cracking reaction in comparative example 4 is increased, so that the selectivity of the product is reduced at high temperature, and the yields of the light tail oil fraction II and the tail oil fraction I which can be used as ethylene materials are too low, so that the process is uneconomical and reasonable.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A hydrocracking process for producing naphtha, light ethylene and premium tail oil, the process comprising:
(1) Raw oil and hydrogen are mixed and then enter a hydrofining reaction zone for hydrofining reaction to obtain refined effluent, wherein the density of the raw oil is 0.84g/cm 3 ～0.98g/cm 3 The nitrogen content is 200 mu g/g-1800 mu g/g, the final distillation point is 360 ℃ to 560 ℃, and the aromatic hydrocarbon content is 25wt% to 65 wt%;
(2) Introducing at least part of the refined effluent into a hydrocracking reaction zone I for reaction, and separating the reaction effluent through a fractionating tower I to obtain light naphtha, heavy naphtha, middle distillate and high-quality tail oil fraction I; in the hydrocracking reaction zone I, controlling the conversion depth of the reaction to be 45% -80%, wherein the conversion depth of the reaction=100% -the fraction yield of the reaction effluent in the hydrocracking reaction zone I is more than 350 ℃;
(3) Mixing a straight-run diesel oil raw material or the optional residual refined effluent, middle distillate oil and hydrogen, introducing the mixture into a hydrocracking reaction zone II for reaction, separating the reaction effluent by a fractionating tower II, introducing the obtained tower top material into the fractionating tower I for continuous separation, and obtaining a tower bottom material which is tail oil II capable of being used as a light ethylene material; controlling the cracking conversion rate in the hydrocracking reaction zone II to be 70-90% based on 100% of the mass of middle distillate in the step, wherein the cracking conversion rate=100% -the fraction yield of the reaction effluent in the hydrocracking reaction zone II at the temperature of >175 ℃;
the mass ratio of the straight-run diesel oil or the refined effluent which is introduced into the hydrocracking reaction zone II is 0.5 to 25 percent by weight based on 100 percent of the refined effluent mass of the hydrofining reaction zone;
the difference between the content of the Y-type molecular sieve of the hydrocracking catalyst I filled in the hydrocracking reaction zone I and the content of the Y-type molecular sieve of the hydrocracking catalyst II filled in the hydrocracking reaction zone II is 5 to 15 weight percent based on 100 percent of the mass of the carrier.
2. The method of claim 1, wherein the feedstock is a straight run feedstock and/or a secondary process oil;
preferably, the straight-run raw oil is at least one selected from straight-run diesel raw oil, straight-run wax oil raw oil and wide-fraction oil; the secondary processing oil is at least one selected from deasphalted oil, coal tar, coal direct liquefied oil, coal indirect liquefied oil, catalytic cracking light diesel oil, catalytic cracking heavy diesel oil, residual oil diesel oil and residual oil hydrogenated wax oil.
3. The process of claim 1 or 2, wherein more than two catalyst beds are disposed in the hydrofinishing reaction zone.
4. The process of claim 3 wherein each of said hydrofinishing reaction zones is charged with a hydroprotecting catalyst, a hydrodemetallization catalyst and a hydrofinishing catalyst in sequence along the direction of the reactant liquid phase stream.
5. The method according to claim 4, wherein the hydrofining catalyst is a supported catalyst, the carrier is alumina and/or silica-alumina, and the active metal component is at least one of non-noble metal elements of group VIB and non-noble metal elements of group VIII;
preferably, in the hydrofining catalyst, the non-noble metal element of the VIII group is nickel and/or cobalt, and the non-noble metal element of the VIB group is molybdenum and/or tungsten.
6. The process according to claim 5, wherein the content of the group VIII non-noble metal element in terms of oxide is 1wt% to 15wt%, the content of the group VIB non-noble metal element in terms of oxide is 5wt% to 40wt%, and the balance is a carrier, based on the total weight of the hydrofining catalyst.
7. The process of any of claims 1-6, wherein the hydrofinishing reaction zone conditions are at least: the hydrogen partial pressure is 3.0 MPa-20.0 MPa, the reaction temperature is 280-400 ℃ and the liquid hourly space velocity is 0.5h -1 ～6h -1 The volume ratio of hydrogen to oil is 300-2000.
8. The process according to claim 1, wherein in the hydrocracking reaction zone I and the hydrocracking reaction zone II, at least two catalyst beds are each independently provided.
9. The process according to claim 1, wherein the hydrocracking catalyst I packed in the hydrocracking reaction zone I is selected from at least one of the catalysts having the following characteristics:
the catalyst contains an active metal component, an acidic component serving as a carrier and a heat-resistant inorganic oxide;
the heat-resistant inorganic oxide is selected from at least one of silicon oxide and aluminum oxide; the acidic component is a Y-type molecular sieve or the acidic component is a Y-type molecular sieve and an amorphous silicon-aluminum material;
the active metal component is at least two metal elements selected from a group VIB metal element and a group VIII metal element; based on the total weight of the catalyst, the content of the VIB group metal element calculated by oxide is 22-35 wt%, the content of the VIII group metal element calculated by oxide is 2-8 wt%, and the rest is a carrier;
the content of the Y-type molecular sieve is 5-35 wt% based on 100% of the carrier mass, and the content of the amorphous silicon-aluminum material is 0-40 wt%.
10. The process according to claim 1, wherein in the hydrocracking reaction zone II, a hydrocracking catalyst II is packed or a hydrofining catalyst is also packed, the hydrofining catalyst is packed in a volume ratio of 0% to 30% based on 100% of the volume of the hydrocracking reaction zone II, and the balance is the hydrocracking catalyst II.
11. The process according to claim 10, wherein the hydrocracking catalyst II is selected from at least one of the following catalysts:
the catalyst contains active metal components, a Y-type molecular sieve serving as a carrier and a heat-resistant inorganic oxide;
the heat-resistant inorganic oxide is selected from at least one of silicon oxide and aluminum oxide;
the active metal component is at least two metal elements selected from a group VIB metal element and a group VIII metal element; based on the total weight of the catalyst, the content of the VIB group metal element calculated by oxide is 11-29 wt%, the content of the VIII group metal element calculated by oxide is 2-8 wt%, and the rest is a carrier;
the content of the Y-type molecular sieve is 5-35 wt% based on the total weight of the carrier, and the balance is heat-resistant inorganic oxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1854263A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Hydrogenation cracking method of mass production of chemical materials |
| US20170335208A1 (en) * | 2015-02-11 | 2017-11-23 | Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. | Method of hydrotreatment of fischer-tropsch synthesis products |
| CN112725027A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrocracking method for producing heavy naphtha |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1854263A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Hydrogenation cracking method of mass production of chemical materials |
| US20170335208A1 (en) * | 2015-02-11 | 2017-11-23 | Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. | Method of hydrotreatment of fischer-tropsch synthesis products |
| CN112725027A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrocracking method for producing heavy naphtha |
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