CN116024015A - Hydrocracking method for producing low-carbon light hydrocarbon and naphthene-rich product - Google Patents
Hydrocracking method for producing low-carbon light hydrocarbon and naphthene-rich product Download PDFInfo
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Abstract
The invention relates to a hydrocracking method for producing low-carbon light hydrocarbon and naphthene-rich products, which comprises the steps of mixing wax oil raw oil with a second hydrogen stream, sequentially entering a hydrogenation unit I and a hydrocracking unit for reaction, separating reaction effluent of the hydrocracking unit to obtain a first liquid-phase material and a second liquid-phase material, and allowing part or all of the obtained second liquid-phase material and first distillate oil to enter a hydrogenation unit II together with the first hydrogen stream for reaction, wherein the reaction products are respectively fractionated to obtain low-carbon light hydrocarbon, paraffin-rich light naphtha and naphthene-rich various products. The invention realizes the directional high-selectivity conversion of the wax oil raw material oil according to the chain structure and the ring structure on the whole, and can obtain the chemical raw material product rich in paraffin and the cycloalkyl special oil product rich in cyclic hydrocarbon.
Description
Technical Field
The invention relates to the technical field of hydrocarbon raw material treatment, in particular to a hydrocracking method for producing low-carbon light hydrocarbon and products rich in naphthenes.
Background
In the crude oil secondary processing technology, the hydrocracking technology has the advantages of strong raw material adaptability, flexible production operation and product scheme, good product quality and the like, can convert raw material oil into clean fuel and chemical raw materials, and is one of important processing technologies for the combination of product distribution and product quality adjustment and oiling of refining enterprises.
The hydrocracked feedstock is typically a wax oil, the wax oil feedstock consisting of paraffinic, naphthenic and aromatic hydrocarbon molecules and having a carbon number in the range of about 20 to 40. In the prior art, the conventional hydrocracking catalyst mainly takes a Y-type or beta-type molecular sieve as a catalytic material, and utilizes the acid function of the catalytic material to perform chain scission reaction, so that in the process of converting a wax oil raw material by the conventional hydrocracking technology, besides the ring opening cracking reaction of naphthenes, the chain scission reaction also occurs on long side chains of paraffins, aromatic hydrocarbons or naphthenes molecules, so that paraffins, naphthenes with side chains and aromatic hydrocarbons with side chains exist in all product fractions at the same time, the efficient enrichment of the paraffins is difficult to realize in the preparation of ethylene raw material (tail oil and light naphtha) by steam cracking in a hydrocracking product, and meanwhile, the efficient enrichment of the naphthenes and the aromatic hydrocarbons is difficult to realize in a reformate (heavy naphtha) in the product.
CN87105808A discloses an improved process for hydrodewaxing a hydrocracked lube base stock by passing the hydrocracked or solvent dewaxed lube base stock sequentially through a catalyst bed having dewaxing activity and a hydrofinishing catalyst bed to produce a lube base stock product having a reduced cloud point.
CN102959054a discloses a combined hydrocracking and dewaxing process for hydrocarbons, in which a feedstock is reacted sequentially through a hydrotreating and a first hydrocracking reaction zone, resulting in a first hydrocracking reaction effluent which is reacted in a first catalytic dewaxing reaction zone, the reaction effluent being separated and fractionated to give a naphtha fraction, a first diesel fraction and a bottoms fraction, wherein the bottoms fraction is reacted in a second hydrocracking or second catalytic dewaxing reaction zone, and the reaction effluent being separated and fractionated to give a second diesel fraction and a lube product fraction.
CN102311785a discloses a method for producing lubricating oil base oil by hydrogenation of naphthenic base distillate, which takes naphthenic base oil as a raw material, and adopts a hydrogenation pour point depressing catalyst containing beta-type molecular sieve, a hydrogenation pour point depressing catalyst containing ZSM-5 type molecular sieve and a hydrogenation refining method to produce a rubber filling oil product with a reduced pour point.
CN102971401B discloses a combined hydrocracking and dewaxing method for hydrocarbons, which comprises the steps of hydrotreating a raw oil, separating a hydrotreated product to obtain a liquid phase residue, performing catalytic dewaxing and hydrocracking reactions, and separating and fractionating a reaction effluent to obtain a diesel product fraction and a lubricant base oil product fraction.
CN106609803a discloses a catalyst for producing hydrocracking tail oil with high viscosity index and a preparation method thereof, the method comprises the steps of mixing macroporous alumina, modified USY molecules and modified ZSM-48 molecular sieves to prepare the catalyst, and adopting the catalyst to enable raw materials to undergo hydrogenation ring opening and hydroisomerization reaction to produce a lubricating oil base oil product with low alkane content, high isoparaffin content and high annual index.
From the prior art cited above, conventional hydrocracking techniques are mainly problematic: firstly, the conventional hydrocracking technology mainly adopts a hydrocracking catalyst containing a Y-type molecular sieve to convert the wax oil raw material oil into a product fraction with reduced distillation range, but the corresponding cracking reaction cannot be carried out according to the molecular structure composition, and the high-efficiency conversion of the wax oil raw material hydrocarbon molecules according to the hydrocarbon molecular structure type cannot be realized, so that the product quality and the added value are lower. Secondly, when the existing hydrocracking technology is used for producing high-added-value cycloalkyl special products, the existing hydrocracking technology is limited by adopting cycloalkyl wax oil raw materials only or realizing improvement of low-temperature fluidity of the products through a catalytic dewaxing reaction unit for converting normal paraffin into branched-chain-containing isoparaffin, and the existing hydrocracking technology has complex process flow and high device investment and operation cost.
Therefore, a carbon chain step conversion hydrocracking technology capable of meeting the requirement of respectively converting wax oil raw material molecules according to chain structures and ring structures is developed, and the method has important practical significance for realizing the efficient utilization of the wax oil raw material which is aromatic and alkene.
Disclosure of Invention
The invention aims to solve the problems of low added value of products and low utilization benefit of wax oil raw material molecules caused by indiscriminate conversion of wax oil raw material molecular structures in the existing hydrocracking technology.
The invention provides a hydrocracking method for producing low-carbon light hydrocarbon and naphthene-rich products, which comprises the following steps:
after being mixed with a second hydrogen material flow, wax oil raw oil enters a hydrogenation unit I to be sequentially contacted with a hydrogenation protective agent, an optional hydrodemetallization catalyst and a hydrofining catalyst I for reaction, the reaction effluent enters a hydrocracking unit without separation and is contacted with the hydrocracking catalyst for reaction, and the reaction effluent of the hydrocracking unit is subjected to gas-liquid separation by a separation unit I to obtain a first gas-phase material, a first liquid-phase material and a second liquid-phase material, wherein the cutting point of the first liquid-phase material and the second liquid-phase material is 250-320 ℃;
the obtained first liquid phase material enters a fractionating unit I to be fractionated to at least obtain low-carbon light hydrocarbon, light naphtha, heavy naphtha and first distillate;
mixing part or all of the obtained second liquid phase material and the first distillate oil with a first hydrogen stream, enabling the mixture to enter a hydrogenation unit II to contact with a hydrofining catalyst II for reaction, carrying out gas-liquid separation on a reaction effluent of the hydrogenation unit II through a separation unit II to obtain a second gas phase material and a third liquid phase material, and fractionating the obtained third liquid phase material in a fractionation unit II to obtain at least second distillate oil, middle distillate oil I, middle distillate oil II and tail oil;
the first hydrogen stream has a hydrogen purity of at least 95% by volume and the second hydrogen stream has a hydrogen purity of at least 85% by volume;
the reaction pressure of the hydrogenation unit II is 3.0MPa to 6.0MPa higher than that of the hydrogenation unit I.
In one embodiment of the invention, the initial distillation point of the wax oil raw oil is 300-350 ℃, and the wax oil raw oil is one or more selected from normal pressure wax oil, reduced pressure wax oil, hydrogenation wax oil, coking wax oil, catalytic cracking heavy cycle oil and deasphalted oil.
In one embodiment of the invention, the light hydrocarbon with low carbon is mainly C3-C4 component; the light naphtha has an initial boiling point of 20-30 ℃ and an end boiling point of 65-110 ℃ and the light naphtha has a paraffin mass fraction of at least 82%, preferably 85%.
In one embodiment of the invention, the heavy naphtha has an initial point of 65 ℃ to 100 ℃ and a final point of 155 ℃ to 175 ℃ and the sum of the mass fractions of naphthenes and aromatics in the heavy naphtha is at least 58%.
In one embodiment of the invention, the first distillate has an initial boiling point of 175-195 ℃; all the first distillate oil enters a hydrogenation unit II for reaction; or the part of the first distillate oil enters a hydrogenation unit II for reaction, and the rest part is sent to a fractionation unit II for fractionation.
According to different product schemes, the fractionating unit II has different cutting schemes, and the product can be cut into various naphthenic base special oil products such as large specific gravity jet fuel fractions, transformer oil base oil, refrigerator oil base oil and the like.
In one embodiment of the invention, the distillation range of the middle distillate I is 175-300 ℃, and the mass fraction of the naphthenes in the middle distillate I is 75-87%;
the distillation range of the middle distillate II is 300-370 ℃, and the mass fraction of the naphthenes in the middle distillate II is 70-80%;
the range of the tail oil is not less than 340 ℃ at the initial boiling point, and the mass fraction of the naphthenes in the tail oil is not less than 78%.
In one embodiment of the invention, the second distillate has a final distillation point of 175-195 ℃, and the second distillate is sent to a fractionation unit I for fractionation.
In order to improve the utilization value of hydrocarbon molecules in wax oil raw oil, the invention provides a hydrocracking method capable of realizing the characteristic based on the molecular structure of hydrocarbon, in the invention, after the wax oil raw oil and a second hydrogen material flow mixture with relatively low hydrogen purity are subjected to contact reaction by a hydrogenation unit I, a reaction effluent enters the hydrocracking unit to react with a hydrocracking catalyst, so that the selective conversion of chain structures in the wax oil raw oil is realized to obtain low-carbon light hydrocarbon and light naphtha rich in paraffin and a second liquid phase material rich in cyclic hydrocarbon (naphthene and aromatic hydrocarbon), and the second liquid phase material is mixed with a first hydrogen material flow with high hydrogen purity and then enters a hydrogenation unit II to mainly carry out aromatic saturation reaction, thereby obtaining middle distillate I, middle distillate II and tail oil rich in naphthene. In addition, the inventors of the present invention have intensively studied and found that, in the hydrogenation unit II, the use of the first hydrogen material having a low concentration of hydrogen sulfide and high purity free of ammonia impurities at a high pressure is advantageous in promoting the aromatic hydrocarbon saturation reaction of the second liquid phase material. The invention realizes the selective and efficient conversion of the wax oil raw oil according to the molecular chain structure and the ring structure type of the hydrocarbon on the whole, and respectively obtains the product fractions rich in paraffin and cyclic hydrocarbon.
In one embodiment of the invention, in the hydrogenation unit I, the hydrogenation protecting agent, the optional hydrodemetallization catalyst and the hydrofining catalyst I are respectively filled in the following volume fractions based on the whole catalyst of the hydrogenation unit I: 3% -10%; 0% -20%; 70% -90%.
The hydrogenation protective agent is a hydrogenation protective agent for processing heavy hydrocarbon oil products, which is conventional in the art, and is not limited to wax oil hydrogenation protective agents, residual oil hydrogenation protective agents or grading combinations thereof.
In a preferred case, the hydrogenation is carried outThe protective agent comprises a carrier and an active metal component loaded on the carrier, wherein the carrier is one or more of alumina, silica and titania, the active metal component is one or more of VIB group metal and VIII group non-noble metal, the weight of the active metal component is 0.1-15 wt% calculated by oxide based on the weight of the hydrogenation protective agent, the particle size of the hydrogenation protective agent is 0.5-50.0 mm, and the bulk density is 0.3-1.2 g/cm 3 A specific surface area of 50 to 300m 2 /g。
The hydrodemetallization catalyst is a hydrodemetallization catalyst for processing heavy hydrocarbon oil products, which is conventional in the art, and is not limited to wax oil hydrodemetallization catalysts, residual oil hydrodemetallization catalysts or grading combinations thereof.
In a preferred case, the hydrodemetallization catalyst comprises a carrier and an active metal component supported on the carrier, wherein the carrier is one or more of aluminum oxide, silicon oxide and titanium oxide, the active metal component is one or more of VIB group metal and VIII group non-noble metal, the weight of the hydrodemetallization catalyst is 3-30 wt% of the active metal component based on oxide, the particle size of the hydrodemetallization catalyst is 0.2-2.0 mm, and the bulk density is 0.3-0.8 g/cm 3 Specific surface area of 100-250 m 2 /g。
In the present invention, "optional" means that the corresponding step, catalyst or ingredient is optional, but not required, i.e., the step, catalyst or ingredient may or may not be present.
In one embodiment of the invention, the hydrofining catalyst I is a supported catalyst, the carrier is alumina and/or silica-alumina, and the active metal component is at least one selected from VIB group metal and/or at least one selected from VIII group metal; the VIII metal is selected from nickel and/or cobalt, the VIB metal is selected from molybdenum and/or tungsten, the content of the VIII metal is 1-15 wt% based on the total weight of the hydrofining catalyst, and the content of the VIB metal is 5-40 wt% based on oxide. In a preferred case, the active metal component of hydrofining catalyst I is selected from two or three of nickel, molybdenum and tungsten metals.
In one embodiment of the invention, the reaction conditions of hydrogenation unit I are: the reaction 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.
In a preferred embodiment, the aromatic hydrocarbon saturation ratio of the feedstock is controlled to 50% or less in the hydrogenation unit I. The inventor of the present invention has intensively studied and found that controlling a lower aromatic saturation rate in the hydrogenation unit I is advantageous for the hydrocracking unit to achieve conversion of chain hydrocarbons and enrichment of naphthenes. If the aromatic hydrocarbon saturation rate is too high, after the reaction effluent of the hydrogenation unit I enters the hydrocracking unit, the ring-opening cracking reaction of the naphthene in the hydrocracking reaction unit is increased, so that the effect of directional conversion reaction of the wax oil raw oil according to the chain structure and the ring structure is adversely affected.
In one embodiment of the invention, the reaction conditions of the hydrocracking unit are: the reaction 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.
In order to better realize the selective and efficient conversion of the wax oil raw oil according to the molecular chain structure and the ring structure type of hydrocarbon, in one embodiment of the invention, the fraction conversion control range of the hydrocracking reaction unit at the temperature of 350 ℃ is as follows:
from 100 (wt%/mass fraction of fraction >350 ℃ in the wax oil feedstock) to 100 (wt%/mass fraction of fraction >350 ℃ in the wax oil feedstock),
wherein A is the mass fraction of alkane in the wax oil raw oil, B is the sum of the mass fractions of alkane, naphthene and monocyclic arene in the wax oil raw oil,
wherein the hydrocracking reaction unit has a fraction conversion of >350 ℃ of =100% (fraction mass fraction of >350 ℃ in the wax oil feedstock-fraction mass fraction of >350 ℃ in the reaction product of the hydrocracking reaction unit)/fraction mass fraction of >350 ℃ in the wax oil feedstock.
In the invention, "mono-naphthene" in the wax oil raw material oil mainly refers to mono-naphthene with long side chains, and "mono-aromatics" in the wax oil raw material oil mainly refers to mono-aromatics with long side chains, wherein the carbon number of the long side chain hydrocarbons is more than 20.
If the hydrocracking reaction unit controls the fraction conversion rate of over low temperature of 350 ℃, the low-carbon light hydrocarbon and light naphtha yield is reduced, and the quality index of the product fraction can not meet the quality requirement of cycloalkyl special oil products. If the hydrocracking reaction unit controls the fraction conversion rate of higher than 350 ℃, the yield of the cycloalkyl special oil product is reduced, the hydrogen consumption of the device is greatly increased, and the product scheme of the device is uneconomical and reasonable.
In one embodiment of the invention, the hydrocracking catalyst comprises a carrier and an active metal component, wherein the carrier comprises a heat-resistant inorganic oxide and a molecular sieve, the heat-resistant inorganic oxide is selected from one or more of silicon oxide or aluminum oxide, and the active metal component is selected from at least two metal components of a group VIB metal and a group VIII metal; based on the whole hydrocracking catalyst and calculated by oxide, the weight of the VIB group metal is 10-35% and the weight of the VIII group metal is 2-8%;
10 to 75 weight percent of molecular sieve based on the carrier, and the balance of heat-resistant inorganic oxide;
the molar ratio of silicon to aluminum of the molecular sieve is 20-50, and the aperture is 0.4-0.58 nm.
Preferably, the molecular sieve is selected from one or more of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-48, ZSM-50, IM-5, MCM-22, EU-1 molecular sieves, and more preferably ZSM-5 molecular sieves.
In the invention, the reaction effluent of the hydrocracking unit is subjected to gas-liquid separation by a separation unit I to obtain a first gas-phase material, a first liquid-phase material and a second liquid-phase material, wherein the cutting points of the first liquid-phase material and the second liquid-phase material are 250-290 ℃; the obtained first liquid phase material enters a fractionating unit I for fractionating.
In one embodiment of the invention, the first gaseous material is subjected to desulfurization and deamination and then can be used as a second hydrogen stream.
In the hydrogenation unit II, in order to improve the aromatic hydrocarbon saturation rate of the second liquid phase material, part or all of the first distillate oil and the first hydrogen material with high hydrogen purity are mixed together to carry out reaction under the reaction pressure higher than that of the hydrogenation unit I. In one embodiment of the invention, the hydrogenation unit II reaction conditions are: the reaction pressure is 6.0 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.
In one embodiment of the invention, the hydrogenation unit II controls the hydrogenation depth such that the aromatic hydrocarbon content of the obtained tail oil is not more than 3%.
In one embodiment of the present invention, the hydrofining catalyst II is a supported catalyst, the carrier is alumina and/or silica-alumina, preferably the carrier is silica-alumina; the active metal component is at least one selected from VIB group metal and/or at least one selected from VIII group metal, the VIII group metal is selected from nickel and/or cobalt, the VIB group metal is selected from molybdenum and/or tungsten, the content of the VIII group metal is 1-15 wt% based on the total weight of the hydrofining catalyst II, and the content of the VIB group metal is 5-40 wt% based on oxide.
In the invention, the reaction effluent of the hydrogenation unit II is subjected to gas-liquid separation by a separation unit II to obtain a second gas-phase material and a third liquid-phase material, and the obtained third liquid-phase material enters a fractionation unit II to be fractionated to obtain at least second distillate, middle distillate I, middle distillate II and tail oil.
In one embodiment of the invention, the second vapor phase feed is a second hydrogen stream.
The invention discloses a hydrocracking method capable of realizing hydrocarbon molecular structure characteristics in order to improve the utilization value of hydrocarbon molecules in wax oil raw oil, which is characterized in that the wax oil raw oil can be selectively and efficiently converted according to hydrocarbon molecular chain structures and ring structure types, so that a product fraction rich in paraffin and a product fraction rich in cyclic hydrocarbon are respectively obtained, wherein the paraffin content of light naphtha rich in paraffin can meet less than or equal to 85 percent, and the light naphtha rich in paraffin can be used as a raw material of a high-quality steam cracking ethylene production device; the heavy naphtha rich in cyclic hydrocarbon meets the sum of the mass fractions of naphthenes and aromatics and can be used as a high-quality reforming material; in addition, the low aromatic naphthene product fraction rich in naphthenes can be used as a special oil product with high added value.
The method can realize the separate conversion of chain hydrocarbon and cyclic hydrocarbon (naphthene and arene) in the wax oil raw oil on the whole, and enriches the chain hydrocarbon and the cyclic hydrocarbon in each product fraction, and can directly obtain the low-carbon light hydrocarbon, the light naphtha rich in paraffin and the special oil rich in naphthene, which can be used as chemical raw materials, without additional processing, and has high added value, thereby having important significance for realizing the high-value utilization of the wax oil raw oil with low cost in refining enterprises.
Drawings
FIG. 1 is a schematic diagram of one embodiment of a hydrocracking process for producing light lower hydrocarbons and a naphthene-rich product provided in the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings, without thereby limiting the invention.
Fig. 1 is a schematic diagram of one embodiment of a hydrocracking method for producing light hydrocarbons with low carbon and products rich in naphthenes, as shown in fig. 1, wax oil raw oil 1 enters a hydrogenation unit I together with a second hydrogen stream 2 to be sequentially contacted with a hydrogenation protecting agent, an optional hydrodemetallization catalyst and a hydrofining catalyst I for reaction, a reaction effluent 3 directly enters the hydrocracking unit without separation for reaction, contacts the hydrocracking catalyst for reaction, and a reaction effluent 4 of the hydrocracking unit is subjected to gas-liquid separation by a separation unit I to obtain a first gas phase material 5, a first liquid phase material 6 and a second liquid phase material 11. The obtained first liquid phase material 6 enters a fractionating unit I to obtain low-carbon light hydrocarbon 7, light naphtha 8, heavy naphtha 9 and first distillate 10 after fractionation.
The second liquid phase material 11 obtained by separation and part or all of the first distillate oil 10 enter a hydrogenation unit II together with a first hydrogen material flow 12 to contact with a hydrofining catalyst II for reaction, a reaction effluent 13 of the hydrogenation unit II is subjected to gas-liquid separation by a separation unit II to obtain a second gas phase material 14 and a third liquid phase material 15, and the obtained third liquid phase material 15 enters a fractionation unit II to be fractionated to obtain a second distillate oil 16, a middle distillate oil I17, a middle distillate oil II 18 and a tail oil 19; the obtained second distillate 16 is sent to a fractionation unit I for fractionation.
The invention is further illustrated by the following examples, which are not intended to limit the invention in any way.
In examples and comparative examples, hydrocarbon composition data of wax oil raw oil and tail oil were obtained by SH/T0659 method for measuring hydrocarbon of saturated hydrocarbon fraction in gas oil (Mass Spectrometry).
The properties of the treated waxy oil feedstock are listed in table 1.
The physicochemical properties of the catalysts used in the examples and comparative examples of the present invention are shown in Table 2, and the catalysts having commercial grades are all produced by China petrochemical catalyst division, and the catalysts having no commercial grades are all obtained by adopting a conventional fixed bed supported hydrogenation catalyst preparation method.
The product quality index of various cycloalkyl specialty oils is set forth in table 5.
As can be seen from Table 1, the wax oil feedstock used in the present invention has a paraffin mass fraction (A) of 23.5 and the wax oil feedstock has a total mass fraction (B) of 52.3 of paraffins, mono-naphthenes and mono-ring aromatics.
The control range of fraction conversion of >350 ℃ for the hydrocracking reaction unit according to the invention is:
from 100 (wt%/mass fraction of fraction >350 ℃ in the wax oil feedstock) to 100 (wt%/mass fraction of fraction >350 ℃ in the wax oil feedstock),
wherein A is the mass fraction of alkane in the wax oil raw material oil, and B is the sum of the mass fractions of alkane, naphthene and monocyclic arene in the wax oil raw material oil.
Then, the fraction conversion rate of the hydrocracking reaction unit at the temperature of 350 ℃ is controlled to be 28.77-64.02 percent.
In the examples and comparative examples of the present invention, the low carbon light hydrocarbon yield, light naphtha yield, heavy naphtha yield, middle distillate I yield, middle distillate II yield and tail oil yield were all calculated based on the wax oil raw oil.
Example 1
After being mixed with a second hydrogen material flow, wax oil raw oil enters a hydrogenation unit I to be sequentially contacted with a hydrogenation protective agent (protective agent), a hydrodemetallization catalyst (demetallization agent) and a hydrofining catalyst I (refining agent I) for reaction, the reaction effluent is not separated and enters a hydrocracking unit to be contacted with a hydrocracking catalyst (cracking agent 1) containing a ZSM-5 molecular sieve for reaction, the reaction effluent of the hydrocracking unit is subjected to gas-liquid separation by a separation unit I to obtain a first gas phase material, a first liquid phase material and a second liquid phase material, and the cutting point of the first liquid phase material and the second liquid phase material is 290 ℃;
the obtained first liquid phase material enters a fractionating unit I for fractionating to obtain low-carbon light hydrocarbon, light naphtha, heavy naphtha and first distillate oil (with an initial distillation point of more than 175 ℃), and 5 wt% of the first distillate oil is sent to a fractionating unit II for fractionating. 95% by weight of the first distillate oil, and a second liquid phase material are mixed with a first hydrogen material flow, then enter a hydrogenation unit II together to contact with a hydrofining catalyst II (a refining agent II) for reaction, a reaction effluent of the hydrogenation unit II is subjected to gas-liquid separation by a separation unit II to obtain a second gas phase material and a third liquid phase material, the obtained third liquid phase material enters a fractionation unit II for fractionation to obtain a second distillate oil (the final distillation point is less than 175 ℃), middle distillate oil I, middle distillate oil II and tail oil, and the second distillate oil is sent to a fractionation unit I for fractionation. The specific reaction conditions and product properties are shown in table 3.
In the reaction process of this example, the aromatics saturation ratio of the hydrogenation unit I was controlled to 47.45% and the fraction conversion rate of the hydrocracking reaction unit at >350 ℃ was controlled to 44.26%.
As can be seen from Table 3, the light naphtha product has a paraffin content of 92.7% and can be used as a raw material for a high-quality ethylene production device by steam cracking; the content of naphthene and arene in the heavy naphtha product is 62.0%, and the heavy naphtha product can be used as a high-quality reforming material; the middle distillate I of the product meets the index requirement of No. 6 large specific gravity jet fuel; the aromatic hydrocarbon content of the middle distillate II of the product is less than 5%, so that the index requirement of industrial white oil can be met, the condensation point is lower than-50 ℃, and the index requirements of refrigerating machine oil and transformer oil can be met; the content of the tail oil alkane and the aromatic hydrocarbon of the product is 77.5%, the condensation point is-38 ℃, and the content of the aromatic hydrocarbon is less than 2%, so that the product can be used as high-quality environment-friendly refrigerating machine oil rich in naphthenes.
Comparative example 1
Comparative example 1 the same feed and process scheme as in example 1 was used, except that a Y-type molecular sieve cracker 2 was used in the hydrocracking reaction unit, as in example 1. The specific reaction conditions and product properties are shown in table 3.
As can be seen from Table 3, the light naphtha of comparative example 1 has a paraffin content of 54.9% and the product properties do not meet the requirements of the high quality steam cracking feedstock index; the content of naphthenes and aromatic hydrocarbons in the heavy naphtha product is 60.1%; the density of the middle distillate I is 0.8214g/cm 3 The product properties cannot meet the index requirements of No. 6 large specific gravity jet fuel; the condensation point of the middle distillate II of the product is-18 ℃, the aromatic hydrocarbon content is less than 5%, the product property can meet the index requirement of industrial white oil, but can not meet the index requirement of refrigerating machine oil or transformer oil; the content of naphthenes and aromatic hydrocarbons in the tail oil of the product is 54.0%, the condensation point is +28 ℃, and the index requirements of the base oil of the refrigerator oil cannot be met.
Comparative example 2
Comparative example 2 the same feed and process scheme as in example 1 was used, except that a beta-type molecular sieve cracking agent 3 was used in the hydrocracking reaction unit, unlike in example 1. The specific reaction conditions and product properties are shown in table 3.
As can be seen from Table 3, the paraffin content in the light naphtha of the comparative example 2 is 47.9%, and the product properties cannot meet the index requirements of high-quality steam cracking raw materials; the content of naphthenes and aromatic hydrocarbons in the heavy naphtha product is 58.6%; the density of the middle distillate I is 0.8140g/cm 3 Finger of No. 6 large specific gravity jet fuel with product property incapable of meetingStandard requirements; the condensation point of the middle distillate II of the product is-36 ℃, the aromatic hydrocarbon content is less than 5%, the product property can meet the index requirement of industrial white oil, but can not meet the index requirement of refrigerating machine oil or transformer oil; the content of naphthenes and aromatic hydrocarbons in the tail oil of the product is 68.2%, the condensation point is +8 ℃, and the index requirements of the base oil of the refrigerator oil cannot be met.
The results show that the high-efficiency selective conversion of the raw materials alkane and cycloalkane is difficult to realize by adopting the hydrocracking technology of the traditional Y-type or beta-type molecular sieve catalyst, and the directional conversion of the wax oil raw materials according to the chain structure and the ring structure can be realized by adopting the method of the invention, thereby realizing the production of high-quality chemical raw materials and low-arene environment-friendly high-added-value cycloalkane special oil products.
Example 2
After being mixed with a second hydrogen material flow, wax oil raw oil enters a hydrogenation unit I to be sequentially contacted with a hydrogenation protective agent (protective agent), a hydrodemetallization catalyst (demetallization agent) and a hydrofining catalyst I (refining agent I) for reaction, the reaction effluent is not separated and enters a hydrocracking unit to be contacted with a hydrocracking catalyst (cracking agent 1) containing a ZSM-5 molecular sieve for reaction, the reaction effluent of the hydrocracking unit is subjected to gas-liquid separation by a separation unit I to obtain a first gas phase material, a first liquid phase material and a second liquid phase material, and the cutting point of the first liquid phase material and the second liquid phase material is 280 ℃.
The obtained first liquid phase material enters a fractionating unit I for fractionating to obtain low-carbon light hydrocarbon, light naphtha and first distillate oil (with initial distillation point being more than 175 ℃), all the first distillate oil is mixed with a second liquid phase material and a first hydrogen gas flow, the mixture enters a hydrogenation unit II for contact reaction with a hydrofining catalyst II (a refining agent II), a reaction effluent of the hydrogenation unit II is subjected to gas-liquid separation through a separating unit II to obtain a second gas phase material and a third liquid phase material, the obtained third liquid phase material enters the fractionating unit II for fractionating to obtain second distillate oil (with final distillation point being less than 175 ℃), middle distillate oil I, middle distillate oil II and tail oil, and the second distillate oil is sent to the fractionating unit I for fractionating. The specific reaction conditions and product properties are shown in table 4.
In the reaction process of this example, the aromatics saturation ratio of the hydrogenation unit I was controlled to 35.5% and the fraction conversion rate of the hydrocracking reaction unit at >350 ℃ was controlled to 44.61%.
As can be seen from Table 4, the light naphtha product has a paraffin content of 91.74% and can be used as a raw material for a high-quality ethylene production device by steam cracking; the content of naphthene and arene in the heavy naphtha product is 61.55 percent, and the heavy naphtha product can be used as a high-quality reforming material; the property of the middle distillate I of the product meets the index requirement of No. 6 large specific gravity jet fuel; the condensation point of the middle distillate II of the product is lower than-50 ℃, and the product property not only can meet the index requirement of industrial white oil, but also can meet the index requirement of refrigerating machine oil or transformer oil; the content of the tail oil alkane and the aromatic hydrocarbon of the product is 84.7%, the condensation point is-38 ℃, and the content of the aromatic hydrocarbon is less than 2%, so that the product can be used as high-quality environment-friendly refrigerating machine oil rich in naphthenes.
Example 3
Example 3 the same starting materials and process flows as in example 2 were used and the specific reaction conditions and product properties are shown in table 4.
In the reaction process of this example, the aromatics saturation ratio of the hydrogenation unit I was controlled to 35.5% and the fraction conversion rate of the hydrocracking reaction unit at >350 ℃ was controlled to 41.79%.
As can be seen from Table 4, the light naphtha product has a paraffin content of 90.18% and can be used as a raw material for a high-quality ethylene production device by steam cracking; the content of naphthene and arene in the heavy naphtha product is 60.82 percent, and the heavy naphtha product can be used as a high-quality reforming material; the property of the middle distillate I of the product meets the index requirement of No. 6 large specific gravity jet fuel; the condensation point of the middle distillate II of the product is lower than-50 ℃, and the product property not only can meet the index requirement of industrial white oil, but also can meet the index requirement of refrigerating machine oil or transformer oil; the content of the tail oil alkane and the aromatic hydrocarbon of the product is 83.5%, the condensation point is-38 ℃, and the content of the aromatic hydrocarbon is less than 2%, so that the product can be used as high-quality environment-friendly refrigerating machine oil rich in naphthenes.
Comparative example 3
Comparative example 3 adopts a one-pass process flow, wax oil raw oil and hydrogen gas mixture are sequentially contacted with a hydrogenation protective agent (protective agent), a hydrodemetallization catalyst (demetallizing agent) and a hydrofining catalyst I (refining agent I) in a hydrogenation unit I for reaction, the obtained reaction effluent enters a hydrocracking unit for reaction, the obtained reaction effluent is contacted with a hydrocracking catalyst (cracking agent 1) containing ZSM-5 molecular sieve for reaction, the reaction effluent of the hydrocracking unit directly enters a hydrogenation unit II for reaction with a hydrofining catalyst II (refining agent II) without separation, and after gas-liquid separation and fractionation of the reaction effluent of the hydrogenation unit II, low-carbon light hydrocarbons (C3-C4), light naphtha, heavy naphtha, middle distillate I, middle distillate II and tail oil are obtained; the hydrogen partial pressures of the hydrogenation unit I and the hydrogenation unit II are consistent. The specific reaction conditions and product properties are shown in table 4.
In the reaction process of the comparative example, the aromatic hydrocarbon saturation rate of the hydrogenation unit I was controlled to 57.14%, and the fraction conversion rate of the hydrocracking reaction unit at >350℃was controlled to 36.98%.
As is clear from Table 4, the light naphtha paraffin content of comparative example 3 after the reaction was 86.08%, the heavy naphtha naphthene + aromatic hydrocarbon content was 56.42%, and the middle distillate I density was 0.826g/cm 3 The product index can not meet the index requirement of No. 6 jet fuel; the condensation point of the middle distillate II of the product can meet the index requirement of a special oil product, but the paraffin content is high, the naphthene content is reduced, and the product quality is reduced to some extent; the yield of the tail oil is 51.48%, the content of naphthenes is 72.9%, the content of aromatic hydrocarbons is 6.4%, and the tail oil product cannot meet the index requirements of the base oil of the refrigerator oil.
The results show that the hydrogenation unit I can control higher aromatic saturation rate to be unfavorable for the directional conversion of wax oil raw materials; under a single-stage one-pass process, the hydrogen purity of the hydrogenation unit II is reduced, and although the higher operating pressure is adopted, aromatic compounds in the product fraction are difficult to saturate, so that the directional conversion of chain hydrocarbon and cyclic hydrocarbon in the wax oil raw material cannot be realized to produce high-quality chemical raw materials and low-aromatic environment-friendly high-added-value products.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
Claims (20)
1. A hydrocracking method for producing low-carbon light hydrocarbon and products rich in naphthenes,
after being mixed with a second hydrogen material flow, wax oil raw oil enters a hydrogenation unit I to be sequentially contacted with a hydrogenation protective agent, an optional hydrodemetallization catalyst and a hydrofining catalyst I for reaction, the reaction effluent enters a hydrocracking unit without separation and is contacted with the hydrocracking catalyst for reaction, and the reaction effluent of the hydrocracking unit is subjected to gas-liquid separation by a separation unit I to obtain a first gas-phase material, a first liquid-phase material and a second liquid-phase material, wherein the cutting point of the first liquid-phase material and the second liquid-phase material is 250-320 ℃;
the obtained first liquid phase material enters a fractionating unit I to be fractionated to at least obtain low-carbon light hydrocarbon, light naphtha, heavy naphtha and first distillate;
mixing part or all of the obtained second liquid phase material and the first distillate oil with a first hydrogen stream, enabling the mixture to enter a hydrogenation unit II to contact with a hydrofining catalyst II for reaction, carrying out gas-liquid separation on a reaction effluent of the hydrogenation unit II through a separation unit II to obtain a second gas phase material and a third liquid phase material, and fractionating the obtained third liquid phase material in a fractionation unit II to obtain at least second distillate oil, middle distillate oil I, middle distillate oil II and tail oil;
the first hydrogen stream has a hydrogen purity of at least 95% by volume and the second hydrogen stream has a hydrogen purity of at least 85% by volume;
the reaction pressure of the hydrogenation unit II is 3.0MPa to 6.0MPa higher than that of the hydrogenation unit I.
2. The method according to claim 1, wherein the initial distillation point of the wax oil raw material oil is 300-350 ℃, and the wax oil raw material oil is one or more selected from normal pressure wax oil, reduced pressure wax oil, hydrogenation wax oil, coking wax oil, catalytic cracking heavy cycle oil and deasphalting oil.
3. The method according to claim 1, wherein the hydrogenation unit I comprises the following hydrogenation protecting agent, optional hydrodemetallization catalyst and hydrofinishing catalyst I in the hydrogenation unit I in the form of a whole catalyst: 3% -10%; 0% -20%; 70% -90%.
4. The process according to claim 1, wherein the reaction conditions of hydrogenation unit I are: the reaction pressure is 3.0 MPa-20.0 MPa, the reaction temperature is 280-400 ℃, and the liquid is in liquid stateThe volume space velocity is 0.5h -1 ～6h -1 The volume ratio of hydrogen to oil is 300-2000.
5. The process according to claim 1, wherein the hydrogenation protecting agent comprises a carrier and an active metal component supported on the carrier, the carrier is one or more selected from the group consisting of alumina, silica and titania, the active metal component is one or more selected from the group consisting of group VIB metals and group VIII non-noble metals, the weight of the hydrogenation protecting agent is 0.1 to 15% by weight of the active metal component based on the weight of the hydrogenation protecting agent, the particle size of the hydrogenation protecting agent is 0.5 to 50.0mm, and the bulk density is 0.3 to 1.2g/cm 3 A specific surface area of 50 to 300m 2 /g。
6. The process according to claim 1, wherein the hydrodemetallization catalyst comprises a carrier and an active metal component supported on the carrier, the carrier is one or more selected from the group consisting of alumina, silica and titania, the active metal component is one or more selected from the group consisting of group VIB metals and group VIII non-noble metals, the weight of the hydrodemetallization catalyst is 3 to 30% by weight of the active metal component based on the weight of the hydrodemetallization catalyst, the particle size of the hydrodemetallization catalyst is 0.2 to 2.0mm, and the bulk density is 0.3 to 0.8g/cm 3 Specific surface area of 100-250 m 2 /g。
7. The process according to claim 1, wherein the hydrofinishing catalyst I is a supported catalyst, the support is alumina and/or silica-alumina, the active metal component is at least one metal selected from group VIB metals and/or at least one metal selected from group VIII metals; the VIII metal is selected from nickel and/or cobalt, the VIB metal is selected from molybdenum and/or tungsten, the content of the VIII metal is 1-15 wt% based on the total weight of the hydrofining catalyst, and the content of the VIB metal is 5-40 wt% based on oxide.
8. The process of claim 7 wherein the active metal component of hydrofinishing catalyst I is selected from two or three of nickel, molybdenum and tungsten metals.
9. The method according to claim 1, wherein in the hydrogenation unit I, the aromatic hydrocarbon saturation ratio of the raw oil is controlled to be 50% or less.
10. The process of claim 1, wherein the reaction conditions of the hydrocracking unit are: the reaction 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.
11. The process of claim 1, wherein the hydrocracking reaction unit has a distillate conversion control range of >350 ℃ of:
from 100 (wt%/mass fraction of fraction >350 ℃ in the wax oil feedstock) to 100 (wt%/mass fraction of fraction >350 ℃ in the wax oil feedstock),
wherein A is the mass fraction of alkane in the wax oil raw oil, B is the sum of the mass fractions of alkane, naphthene and monocyclic arene in the wax oil raw oil,
wherein the hydrocracking reaction unit has a fraction conversion of >350 ℃ of =100% (fraction mass fraction of >350 ℃ in the wax oil feedstock-fraction mass fraction of >350 ℃ in the reaction product of the hydrocracking reaction unit)/fraction mass fraction of >350 ℃ in the wax oil feedstock.
12. The method according to claim 1, wherein the hydrocracking catalyst comprises a support and an active metal component, the support comprises a refractory inorganic oxide and a molecular sieve, the refractory inorganic oxide is selected from one or more of silica or alumina, and the active metal component is selected from at least two metal components of group VIB metals and group VIII metals; based on the whole hydrocracking catalyst and calculated by oxide, the weight of the VIB group metal is 10-35% and the weight of the VIII group metal is 2-8%;
10 to 75 weight percent of molecular sieve based on the carrier, and the balance of heat-resistant inorganic oxide;
the molar ratio of silicon to aluminum of the molecular sieve is 20-50, and the aperture is 0.4-0.58 nm.
13. The process according to claim 12, wherein the molecular sieve is selected from one or more of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-48, ZSM-50, IM-5, MCM-22, EU-1 molecular sieves, preferably ZSM-5 molecular sieves.
14. The process of claim 1, wherein the hydrogenation unit II reaction conditions are: the reaction pressure is 6.0 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.
15. The process according to claim 1, wherein the hydrogenation unit II controls the hydrogenation depth such that the aromatic hydrocarbon content of the resulting tail oil is not more than 3%.
16. The process according to claim 1, wherein the hydrofinishing catalyst II is a supported catalyst, the support being alumina and/or silica-alumina, preferably the support being silica-alumina; the active metal component is at least one selected from VIB group metal and/or at least one selected from VIII group metal, the VIII group metal is selected from nickel and/or cobalt, the VIB group metal is selected from molybdenum and/or tungsten, the content of the VIII group metal is 1-15 wt% based on the total weight of the hydrofining catalyst II, and the content of the VIB group metal is 5-40 wt% based on oxide.
17. The process according to claim 1, characterized in that the light naphtha has an initial point of 20-30 ℃ and an end point of 65-110 ℃ and the light naphtha has a mass fraction of paraffins of at least 82%, preferably 85%;
the initial boiling point of the heavy naphtha is 65-100 ℃, the final boiling point is 155-175 ℃, and the sum of the mass fractions of naphthenes and aromatics in the heavy naphtha is at least 58%;
the distillation range of the middle distillate I is 175-300 ℃, and the mass fraction of the naphthenes in the middle distillate I is 75-87%;
the distillation range of the middle distillate II is 300-370 ℃, and the mass fraction of the naphthenes in the middle distillate II is 70-80%;
the range of the tail oil is not less than 340 ℃ at the initial boiling point, and the mass fraction of the naphthenes in the tail oil is not less than 78%.
18. The method of claim 1, wherein the second gas phase feed is a second hydrogen stream.
19. The method of claim 1, wherein the first distillate has an initial boiling point of 175 to 195 ℃; and part of the first distillate oil enters a hydrogenation unit II for reaction, and the rest part of the first distillate oil is sent to a fractionation unit II for fractionation.
20. The process according to claim 1, wherein the second distillate has a final distillation point of 175 to 195 ℃ and the second distillate is fed to the fractionation unit I for fractionation.
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