CN107236571B - A method of producing catalytically cracked stock - Google Patents
A method of producing catalytically cracked stock Download PDFInfo
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- CN107236571B CN107236571B CN201610186009.5A CN201610186009A CN107236571B CN 107236571 B CN107236571 B CN 107236571B CN 201610186009 A CN201610186009 A CN 201610186009A CN 107236571 B CN107236571 B CN 107236571B
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- wax oil
- raw material
- hydrodesulfurization
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- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including oxidation as the refining step in the absence of hydrogen
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
The present invention relates to refining arts, disclose a kind of method for producing catalytically cracked stock, this method comprises: (1) contacts under Hydrofinishing conditions, by wax oil raw material and hydrogen with hydrogenation catalyst, obtain hydrogenation products；(2) hydrogen sulfide in the hydrogenation products is separated, full fraction product is obtained；(3) the full fraction product is fractionated, obtains purification wax oil fraction；(4) the purification wax oil fraction is carried out non-hydrodesulfurization ether to react, obtains catalytically cracked stock.Method of the invention can selectively reduce the sulfide content for adding and being transferred in catalytically cracked gasoline in hydrogen wax oil product, to achieve the purpose that reduce content of sulfur in gasoline.
Description
Technical field
The present invention relates to refining arts, and in particular, to a method of produce catalytically cracked stock.
Background technique
As our people's living standard is continuously improved, automobile has become indispensable in common citizen life
A part.The continuous improvement of car ownership requires refinery to further increase gasoline yield.However engine quantity increase causes
Air pollution constantly aggravate, the raising of people's environmental consciousness requires refinery while increasing gasoline yield, it is necessary to reduce vapour
Heteroatomic compound in oil ingredient, especially to the biggish sulfide of air environmental pollution.Therefore, vapour is improved to a greater degree
Oil yield, reduction content of sulfur in gasoline are one of significant challenges that current refinery faces.
In general, catalytic cracking unit is the main production unit for producing gasoline fraction, catalytically cracked gasoline provides refining
90% sulfide in factory's gasoline pool.Therefore catalytic cracking unit yield of gasoline is improved, and reduces catalytic cracking unit gasoline
Sulfur content is one of the main means that refinery meets current social needs.The primary raw material wax oil of catalytic cracking unit is added
Hydrogen processing, reduces the sulfur content of catalytically cracked material, improves the hydro carbons composition of raw material, reaches reduction sulfur content of catalytic cracking gasoline
With the purpose for improving yield of gasoline.
Currently, the wax oil hydrogenation preprocess method that major refinery uses in catalyst bed filling plus hydrogen mainly by protecting
Agent, hydrodemetallization agent, Hydrobon catalyst are protected, and feedstock oil is contacted under suitable reaction condition with catalyst,
Remove most of sulfide in raw material.When wax oil sulfur content is reduced to 2000 μ g/g by conventional weighted BMO spaces method, catalysis
Cracking gasoline sulfur content can be reduced to 50 μ g/g, meet requirement of four gasoline of state to sulfur content.
However, the standard of vehicle gasoline and sulfur content in vehicle gasoline is continuously improved in environmental regulation, opened in big cities such as China Beijing, Shanghai
Begin to implement the gasoline standard that sulfur content is lower than 10 μ g/g.Harsher content of sulfur in gasoline requirement is faced, it is pre- using conventional hydro
Processing method will could make catalytic cracking as low as 600 μ g/g or less only under more exacting terms, by wax oil sulfur content
Content of sulfur in gasoline is reduced to 10 μ g/g.However, in this operating condition, the service life of catalyst is shorter, it is greatly lowered
Wax oil hydrogenation pretreatment-catalytic cracking combined device economy.In response to this, most of refineries pass through after gasoline
The method of reason further decreases sulfur content of catalytic cracking gasoline, to reach 10 μ g/g requirement below of content of sulfur in gasoline.Preceding
In the case where adding hydrogen and back end hydrogenation co-production, although can satisfy the requirement of content of sulfur in gasoline, necessarily increase investment at
This, reduces the economic benefit of refinery's entirety.
CN1313379A discloses a kind of method of poor-quality raw material for catalytic cracking weighted BMO spaces, and a kind of plus hydrogen is used to protect
Protect agent/hydrodemetallization agent/Hydrobon catalyst combination, make the tenors of gas oil feedstocks inferior, sulfur content,
Nitrogen content is greatly lowered.But the prior art is a kind of conventional wax oil hydrogenation processing method, and volume space velocity is lower, in 0.2-
1.2h-1Between, and Hydrobon catalyst is relatively simple, poor to the adaptability of raw material, refine the sulfur content of wax oil still compared with
Height, there is no the compounds that selectively removing influences sulfur content of catalytic cracking gasoline.
US5114562 discloses a kind of method that two-stage method carries out hydrodesulfurization to distillate and hydrogen is added to be saturated.This method
Using two reaction zones, desulfurizing agent is loaded in first reaction zone, second reaction zone filling adds hydrogen saturation containing noble metal
Agent, although desulfurization and aromatic hydrocarbons saturation effect are all obvious, complicated for operation, the high investment of catalyst and device, Er Qiefang
The pressure that hydrocarbon is saturated section is also higher, increases the severity of operation.And desulfurizing agent is directly seated in the first reaction zone, it is uncomfortable
Close processing nitrogen content and the higher inferior feedstock oil of polycyclic aromatic hydrocarbon content.
CN1362481A discloses the catalyst grade of a kind of hydrotreating faulty wax oil and residual oil with type of feed, this is existing
Technology uses hydrogenation protecting agent/hydrodemetallization agent/transition denitrification catalyst bed/hydrogen desulfurization agent bed/hydrodenitrogeneration
Agent bed.Wherein the denitrification catalyst bed of transition is by the catalyst and denitrification catalyst of demetalization or protective agent bed with certain
Ratio mix, compared to conventional catalyst loading pattern, such type of feed slows down the pressure drop of bed, extends
The service life of catalyst.But the denitrification catalyst bed of transition can only remove a small amount of nitride, and most of nitride fails to take off
It removes, in hydrotreating nitrogen content and the higher feedstock oil of polycyclic aromatic hydrocarbon content, nitride and polycyclic aromatic hydrocarbon in raw material are still
Stronger inhibiting effect can be generated to the Hydrogenation of bottom desulfurizing agent, and it is higher to refine wax oil sulfur content, without selectivity
Removing influences the compound of sulfur content of catalytic cracking gasoline.
Existing wax oil desulfurization technology is limited only to using the method for adding hydrogen, although this method can reduce the sulphur in raw material
Content, but do not remove targetedly and be transferred to the sulfide content of gasoline in catalytically cracked material, and cost of investment compared with
Height, is difficult to meet sulfur content of catalytic cracking gasoline and is reduced to 10 μ g/g standards below.
Summary of the invention
The purpose of the present invention is overcome the prior art to be difficult to selectively removing to influence the chemical combination of sulfur content of catalytic cracking gasoline
The defect of object provides a kind of method of new production fine quality catalytic cracking raw material oil.Method of the invention can be reduced selectively
Add the sulfide content being transferred in catalytically cracked gasoline in hydrogen wax oil product, to achieve the purpose that reduce content of sulfur in gasoline.
By the specific kenel and different sulfide of sulfide in analysis wax oil hydrogenation product in catalytic cracking reaction process
Response path after find, the thioether, thiophene and a small amount of benzothiophene in catalytically cracked material are sulfur content of catalytic cracking gasoline
Main predecessor.Thioether class sulfide is to the contribution of sulfur content of catalytic cracking gasoline mainly from two aspects: in a first aspect,
Thioether class sulfide is easier to that side chain chain-breaking reaction occurs in catalytic cracking reaction, generates thioether or the thio-alcohol vulcanization of small molecule
Object enters gasoline fraction；Second aspect, what the cleavage reaction that C-S key occurs in catalytic cracking reaction for thioether class sulfide generated
H2S, H2S, which is easier to react with the alkene that catalytic cracking reaction generates, generates mercaptan or thiophene-type sulfide, this partial vulcanization object
Easily enter gasoline fraction, to increase content of sulfur in gasoline.Therefore the thioether in catalytically cracked material is catalytically cracked gasoline sulphur
The important presoma of compound.Thiophene sulfides are easy to happen the cleavage reaction of side chain and cycloalkane in catalytic cracking reaction,
Generating portion H2The thiophene-type sulfide of S or small molecule, the latter are easily accessible gasoline fraction.Benzothiophene vulcanizes compared to thiophene-based
Because the presence of aromatic rings increases the cloud density of compound the probability of cracking reaction occurs on benzothiophene ring for object
It is very low, therefore the general cleavage reaction that side chain and saturated rings occurs, generate the benzothiophene kind sulfide for having branch, this part
The general molecular weight of sulfide is larger, only enters gasoline fraction on a small quantity.It is that structure is more complicated than benzothiophene kind sulfide
Sulfide is generally easy to happen condensation reaction, primarily enters in heavy distillat product.By analyzing the sulphur it is found that in raw material above
Ether, thiophene and benzothiophene are the main precursors of Gasoline Sulfides, and the content by reducing these three sulfide can
Significantly reduce sulfur content of catalytic cracking gasoline.
However, it was found by the inventors of the present invention that thiophene and benzothiophene kind sulfide pass through the method energy of hydrotreating
The content of such sulfide in raw material is enough significantly reduced, but thioether class sulfide is but difficult to take off by the method for hydrotreating
It removes.This mainly may be because the polarity of thioether class sulfide molecules itself is lower, and most of is chain thioether, this kind of sulfide
It is difficult to adsorb on activity of hydrocatalyst center, the probability of sulphur atom and desulphurizing activated central contact is lower, if wanted
Fall the thioether class sulfide in raw material by the method removing of hydrotreating, the condition of hydrogenation reaction is very harsh, this processing
Condition causes the economy of wax oil hydrogenation to significantly reduce.Therefore, it is necessary to develop new process, the thioether in raw material is removed
Class compound.Based on above-mentioned analysis, the present inventor has researched and developed technical solution of the present invention.
To achieve the goals above, the present invention provides a kind of method for producing catalytically cracked stock, this method comprises:
(1) under Hydrofinishing conditions, wax oil raw material and hydrogen are contacted with hydrogenation catalyst, obtains plus hydrogen produces
Object；
(2) hydrogen sulfide in the hydrogenation products is separated, full fraction product is obtained；
(3) the full fraction product is fractionated, obtains purification wax oil fraction；
(4) the purification wax oil fraction is carried out non-hydrodesulfurization ether to react, obtains catalytically cracked stock.
New wax oil processing method proposed by the present invention mainly includes two parts: first part, by hydrotreating side
Method removes most of sulfide in raw material；Second part takes off the hydrogenation products of first part by oxidizing process or other methods
Except the thioether class sulfide in raw material.
Method adaptability to raw material provided by the invention is strong, can process AGO (atmospheric gas oil), the vacuum gas oil (VGO) of high sulfur content
And high-sulfur, the coker gas oil of nitrogen content and high metal content, deep drawing vacuum gas oil (VGO) or deasphalted oil and theirs is mixed
Oil is closed, good catalytically cracked stock is obtained.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of methods for producing catalytically cracked stock, this method comprises:
(1) under Hydrofinishing conditions, wax oil raw material and hydrogen are contacted with hydrogenation catalyst, obtains plus hydrogen produces
Object；
(2) hydrogen sulfide in the hydrogenation products is separated, full fraction product is obtained；
(3) the full fraction product is fractionated, obtains purification wax oil fraction；
(4) the purification wax oil fraction is carried out non-hydrodesulfurization ether to react, obtains catalytically cracked stock.
The non-hydrodesulfurization ether reaction refers to, de- thioether reactant is carried out by way of non-plus hydrogen.
According to a kind of specific embodiment, method of the invention may further include carry out hydrofining reaction it
Before, wax oil raw material is subjected to non-hydrodesulfurization ether and is reacted.Specifically, method of the invention can also be carried out using following steps:
(1) wax oil raw material is carried out non-hydrodesulfurization ether to react, obtains desulfurization wax oil raw material；
(2) under Hydrofinishing conditions, the desulfurization wax oil raw material and hydrogen is contacted with hydrogenation catalyst, obtained
Hydrogenation products；
(3) hydrogen sulfide in the hydrogenation products is separated, full fraction product is obtained；
(4) the full fraction product is fractionated, obtains the purification wax oil fraction as catalytically cracked stock；
(5) the purification wax oil fraction is carried out non-hydrodesulfurization ether to react, obtains catalytically cracked stock.
In the case where no explanation on the contrary, " wax oil raw material " refers to the feedstock oil reacted without non-hydrodesulfurization ether；
" desulfurization wax oil raw material " refers to the feedstock oil for having been subjected to non-hydrodesulfurization ether reaction.
There is no particular limitation for method of the present invention to the hydrogen sulfide in the separation hydrogenation products, those skilled in the art
It can be carried out using at least one of conventional use of hot high score in the art, low point of heat, cold high score and cold low point；The present invention
To the isolated operating condition, also there is no particular limitation, and those skilled in the art can use item commonly used in the art
Part carries out.For example, the present invention can use, the hydrogenation products are sequentially entered into high-pressure separator and low pressure separator carries out gas
Liquid separation, resulting hydrogen-rich gas are recycled, and resulting product liquid initially enters depriving hydrogen sulphide stripper and stripped, with
And the product after stripping is subjected to subsequent processing.
To the device that the non-hydrodesulfurization ether reacts is carried out, there is no particular limitation, such as can be tank reactor
And/or tower reactor.
Preferably, the method for carrying out non-hydrodesulfurization ether reaction of the present invention is oxidizing process.It is carried out using oxidizing process non-
The operating procedure of hydrodesulfurization ether reaction may include: to connect the material of pending non-hydrodesulfurization ether reaction with oxidant
Touching, oxidant is by the polarity stronger sulfoxide type sulfide of thioether class sulfide oxidation in raw material, then uses extractant will
Sulfoxide type sulfide is extracted from mixed liquor.To realize the purpose of thioether sulphur in removing raw material.According to a kind of preferred
Specific embodiment, the non-hydrodesulfurization ether reaction of the invention are carried out using oxidizing process.It was found by the inventors of the present invention that adopting
When carrying out non-hydrodesulfurization ether reaction with oxidizing process, the sulphur in catalytically cracked material that handled by method of the invention
Content is lower.
Preferably, the oxidant that oxidizing process carries out the non-hydrodesulfurization ether reaction is selected from N (C4H9)4IO4、H2O2In extremely
Few one kind.In the present invention, it is preferred to by the oxidant such as N (C4H9)4IO4It is dissolved in alcohols solvent such as methanol and/or second
In alcohol.
Preferably, the extractant that oxidizing process carries out the non-hydrodesulfurization ether reaction is water.The water of the invention can
Think deionized water.
Preferably, the dosage weight ratio of the oxidant and the wax oil raw material is 0.01-10:1；More preferably 0.1-
2.5:1；Further preferably 0.1-1.5:1.
Preferably, using oxidizing process carry out the non-hydrodesulfurization ether reaction when, as extractant water with it is described
The dosage weight ratio of wax oil raw material is 0.05-20:1；More preferably 0.1-3.0:1；Further preferably 1.0-2.0:1.
Preferably, it is 60-200 DEG C that the condition of the non-hydrodesulfurization ether reaction, which includes: temperature,.
It is further preferred that it is 80-150 DEG C that the condition of the non-hydrodesulfurization ether reaction, which includes: temperature,.It is preferred at this
In the case of, the catalytically cracked stock sulfur content obtained by method of the invention is lower.
Preferably, it is 340-420 DEG C that the Hydrofinishing conditions, which include: temperature, and reaction hydrogen partial pressure is 6.4-12MPa；Hydrogen
Oil volume ratio is 400-1200；Volume space velocity 0.5-2.0h-1.It is further preferred that the Hydrofinishing conditions include: that temperature is
355-380 DEG C, reaction hydrogen partial pressure is 8.0-10.0MPa；Hydrogen to oil volume ratio is 600-800；Volume space velocity 1.0-1.6h-1。
In the present invention, in the case where no explanation on the contrary, pressure refers both to gauge pressure.
In the method for the invention, raw material wax oil and hydrogen is in the presence of hydrogenation catalyst, be able to carry out hydrodesulfurization,
The reactions such as hydrodenitrogeneration, the full, hydrodemetallization of aromatic hydrogenation.
The hydrogenation catalyst of the invention may include hydrogenation protecting catalyst, Hydrodemetalation catalyst and add hydrogen de-
At least one of sulfur catalyst.
Preferably, the activity in the hydrogenation catalyst containing porous, inorganic alumina support and load on the carrier
Metal component, the active metal component be selected from least one of group VIB and group VIII metallic element and it is described plus
Selectively containing the auxiliary element selected from least one of P, Si and F in hydrogen catalyst.
Selectively refer to containing the auxiliary element selected from least one of P, Si and F in the hydrogenation catalyst: adding hydrogen
The auxiliary element selected from least one of P, Si and F can be contained in catalyst, it can also be without containing choosing in hydrogenation catalyst
From the auxiliary element of at least one of P, Si and F.
It is further preferred that the active metal component is selected from least one of chromium, molybdenum, tungsten, iron, cobalt and nickel element.
Preferably, the wax oil raw material is selected from AGO (atmospheric gas oil), vacuum gas oil (VGO), deep drawing gas oil, deasphalted oil and again
At least one of recycle oil.
There is no particular limitation for the type of method of the invention to the reactor for carrying out the hydrofining reaction, can adopt
With conventional use of various types of hydrogenators in the art.
The present invention will be described in detail by way of examples below.
Below in the case where no explanation on the contrary, a variety of materials used are all from commercially available.
The exploitation of research institute of Sinopec is successively loaded in hydrogenator and by Sinopec Chang Ling
RG series guard catalyst, RM series catalyst for demetalation and the RN series Hydrobon catalyst of catalyst branch production.
The RG series guard catalyst, RM series catalyst for demetalation and RN series Hydrobon catalyst load body
Product is than being 1:2:10.
Specifically, the trade mark of the guard catalyst is RG-30A；
The trade mark of the catalyst for demetalation is RAM-100；
The trade mark of the Hydrobon catalyst is RN-410.
The property of wax oil raw material used below is as shown in table 1.
Table 1
| Wax oil raw material | A |
| Density (20 DEG C)/(g/cm3) | 0.924 |
| Sulfur content/(μ g/g) | 27000 |
| Nitrogen content/(μ g/g) | 1100 |
| C content/weight % | 85.49 |
| H content/weight % | 12.04 |
| Boiling range ASTM D-1160/ DEG C | |
| Initial boiling point | 241 |
| 50% | 469 |
| 95% | 564 |
The method that embodiment 1-3 is used to illustrate production catalytically cracked stock of the invention.
Embodiment 1
Wax oil raw material and hydrogen are concomitantly introduced into hydrogenator, are successively catalyzed with hydrogenation protecting catalyst, demetalization
Agent, Hydrobon catalyst contact, obtain hydrogenation products；By the hydrogenation products through refrigerated separation, hydrogen-rich gas is recycled,
Enter fractionating system after the hydrogen sulfide that product liquid enters in depriving hydrogen sulphide stripper removing hydrogenation products to be fractionated, after obtaining purification
Gas oil fraction (as purification wax oil fraction), the gas oil fraction after purification enters desulfurization ether device and carries out non-hydrodesulfurization
Ether reaction, obtained product are fed as catalytic cracking unit.Desulfurization ether device uses N (C4H9)4IO4Make as oxidant, water
For extractant progress.
Hydrofining reaction condition and gas oil fraction and catalysis as catalytically cracked stock are listed in table 2
The fundamental property of cracking gasoline.
Embodiment 2-3
Embodiment 2 and embodiment 3 are carried out using method similar to Example 1, the difference is that hydrofining reaction
The condition that condition and non-hydrodesulfurization ether react is different, specific as shown in table 2.
The fundamental property of the gas oil fraction and catalytically cracked gasoline of embodiment 2 and embodiment 3 is listed in Table 2 below.
Table 2
* quality/wax oil raw material quality that ratio=per hour injects deionized water is filled the water
* catalytic cracking process condition: catalytic cracking catalyst CGP-1, reaction temperature are 520 DEG C, oil ratio 6.7
The interpretation of result of embodiment 1-3: from the data of table 2 it is found that under the conditions of lower hydrogenation reaction temperature, by adding
The total sulfur content of catalytic cracking feeds after hydrogen purification and the reaction of non-hydrodesulfurization ether is reduced to 2500 μ g/g, wherein thioether class sulphur
Compound only has 10 μ g/g, and other sulfide are thiophene and benzothiophene kind sulfide, and this raw material is passed through catalytic cracking reaction
Afterwards, sulfur content of catalytic cracking gasoline is reduced to 20 μ g/g, and catalytic cracking sulphur transfer ratio is reduced to 1/125, substantially less than routinely
Hydrogenation-catalytic cracking combined technological sulphur carry-over factor.Under the conditions of higher hydrogenation reaction temperature, through the invention should
Technique, obtained catalytically cracked stock sulfur content are reduced to 1500 μ g/g, and thioether sulfur content is reduced to 4 μ g/g, by the catalysis
The sulfur content of catalytic cracking gasoline that cracked stock oil obtains is reduced to 9 μ g/g, has reached five standard of state and has wanted to content of sulfur in gasoline
It asks.
Comparative example 1
This comparative example produces catalytically cracked stock using wax oil raw material same as Example 1.It is former in the comparative example
Material oil enters hydrogenator together with hydrogen, successively with hydrogenation protecting catalyst, catalyst for demetalation, Hydrobon catalyst
Contact, obtains hydrogenation products；By the hydrogenation products through refrigerated separation, hydrogen-rich gas is recycled, and product liquid enters fractionation
System fractionation, the gas oil fraction after being refined, the gas oil fraction after purification are fed as catalytic cracking unit.
Wherein, the process conditions of hydrofining reaction and catalyst are same as Example 1.Table 3 gives this comparative example
The fundamental property of gas oil fraction after purification.
Comparative example 2
This comparative example is carried out using method similar with comparative example 1, the difference is that the condition of hydrofining reaction is not
Together, specific as shown in table 3.
The fundamental property of gas oil fraction after the purification of comparative example 2 is listed in Table 3 below.
The interpretation of result of comparative example 1-2: from the data of table 3 it is found that under the conditions of lower hydrogenation reaction temperature, merely through
Thioether class sulfide in the wax oil fraction of hydrofinishing containing 11 weight %, this raw material are urged after catalytic cracking reaction
Change cracking gasoline sulfur content and be up to 52 μ g/g, is significantly higher than the sulfur content of catalytic cracking gasoline of embodiment.It is anti-in higher plus hydrogen
Under the conditions of answering temperature, thioether class sulfide in the wax oil fraction after purification containing 9 weight %, sulfur content of catalytic cracking gasoline is
25 μ g/g, higher than the sulfur content of embodiment.
Table 3
The result of comparison the embodiment of the present invention and comparative example can be seen that using non-hydrodesulfurization ether of the invention and add
Wax oil fraction sulfur content after the purification that the technique that hydrogen process for refining combines obtains is reduced by a relatively large margin, and catalysis is split
It is significant to change content of sulfur in gasoline reduction amplitude.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (13)
1. a kind of method for producing catalytically cracked stock, this method comprises:
(1) under Hydrofinishing conditions, wax oil raw material and hydrogen is contacted with hydrogenation catalyst, obtain hydrogenation products；
(2) hydrogen sulfide in the hydrogenation products is separated, full fraction product is obtained；
(3) the full fraction product is fractionated, obtains purification wax oil fraction；
(4) the purification wax oil fraction is carried out non-hydrodesulfurization ether to react, obtains catalytically cracked stock.
2. according to the method described in claim 1, wherein, the method for carrying out the non-hydrodesulfurization ether reaction be selected from oxidizing process,
At least one of absorption method and sedimentation.
3. according to the method described in claim 1, wherein, the non-hydrodesulfurization ether reaction is carried out using oxidizing process.
4. according to the method described in claim 3, wherein, the oxidant that oxidizing process carries out the non-hydrodesulfurization ether reaction is selected from
N(C4H9)4IO4、H2O2At least one of；Extractant is water.
5. according to the method described in claim 4, wherein, the dosage weight ratio of the oxidant and the wax oil raw material is
0.01-10:1.
6. according to the method described in claim 4, wherein, the dosage weight ratio of the oxidant and the wax oil raw material is 0.1-
2.5:1.
7. according to the method described in claim 4, wherein, the dosage weight ratio of the water and the wax oil raw material is 0.05-20:
1。
8. according to the method described in claim 4, wherein, the dosage weight ratio of the water and the wax oil raw material is 0.1-3.0:
1。
9. the method according to any one of claim 3-8, wherein the condition packet of the non-hydrodesulfurization ether reaction
Include: temperature is 60-200 DEG C.
10. the method according to any one of claim 3-8, wherein the condition packet of the non-hydrodesulfurization ether reaction
Include: temperature is 80-150 DEG C.
11. according to the method described in claim 1, wherein, the Hydrofinishing conditions include: that temperature is 340-420 DEG C, reaction
Hydrogen partial pressure is 6.4-12MPa；Hydrogen to oil volume ratio is 400-1200；Volume space velocity is 0.5-2.0h-1。
12. according to the method described in claim 1, wherein, in the hydrogenation catalyst containing porous, inorganic alumina support and
The active metal component of load on the carrier, the active metal component are selected from group VIB or group VIII metallic element
At least one of and the hydrogenation catalyst in selectively containing the auxiliary element selected from least one of P, Si and F.
13. according to the method described in claim 1, wherein, the wax oil raw material is selected from AGO (atmospheric gas oil), vacuum gas oil (VGO), depth
Pull out at least one of gas oil, deasphalted oil and heavy-cycle oil.
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| CN201610186009.5A CN107236571B (en) | 2016-03-29 | 2016-03-29 | A method of producing catalytically cracked stock |
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| US6007704A (en) * | 1996-09-24 | 1999-12-28 | Institut Francais Du Petrole | Process for the production of catalytic cracking gasoline with a low sulphur content |
| CN101429457A (en) * | 2007-11-08 | 2009-05-13 | 中国石油化工股份有限公司 | Distillate hydrogenation feracity white oil method |
| CN103773486A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Combination method for raising yields of high-value products |
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| US6007704A (en) * | 1996-09-24 | 1999-12-28 | Institut Francais Du Petrole | Process for the production of catalytic cracking gasoline with a low sulphur content |
| CN101429457A (en) * | 2007-11-08 | 2009-05-13 | 中国石油化工股份有限公司 | Distillate hydrogenation feracity white oil method |
| CN103773486A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Combination method for raising yields of high-value products |
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