CN106380365A - Hydrodesulfurization process for crude coking benzene - Google Patents
Hydrodesulfurization process for crude coking benzene Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
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Abstract
The invention discloses a hydrodesulfurization process for crude coking benzene. The process comprises the following steps: allowing a mixture of crude coking benzene and hydrogen to enter a pre-reactor from tower top, wherein the pre-reactor is filled with a Ni-Mo catalyst and has a reaction temperature of 220 to 230 DEG C and hydrogenation pressure of 3.2 to 3.8 MPa; allowing a pre-reaction product to enter a fixed-bed reactor, wherein the fixed-bed reactor is filled with a hydrodesulfurization catalyst which comprises a carrier and an active component, the carrier is a compound or mixture of MSU-G, SBA-15 and HMS the active component is a mixture of dimolybdenum nitride (Mo2N), tungsten nitride (W2N), molybdenum carbide (Mo2C) and tungsten carbide (WC), and the reaction conditions of the fixed bed reactor are that reaction temperature is 320 to 380 DEG C, hydrogen pressure is 3.0 to 3.6 MPa, a hydrogen-oil volume ratio is 500 to 800 and volume space velocity is 1.5 to 2/h; and allowing a product of a fixed-bed hydrogenation reaction to enter an extractive distillation unit so as to obtain aromatic hydrocarbons. The process enables the total sulfur content of the crude coking benzene to be 0.1 ppm or below, so requirements of extensive purposes of the crude coking benzene are met.
Description
Technical field
The present invention relates to a kind of hydrodesulfurization is and in particular to a kind of coking crude benzene hydrodesulfurization.
Background technology
Coking is one of major way of Coal dressing, also commonly referred to as the high-temperature retorting of coal, that is, by suitable coking
Bituminous coal, after proper treatment, in coke oven, isolation air is heated to 950-1050 DEG C, through drying, pyrolysis, burns and melts, bonds, solidifying
Coke is finally obtained with stages such as contractions.The volatile matter separating out in process of coking includes the chemistry such as coal gas, tar, ammonia and crude benzol and produces
Product.In addition, also containing the aromatic hydrocarbons such as a certain amount of benzene in the coal tar obtaining in coking.
Coked crude benzene refining is with coking crude benzene as raw material, through the method such as physics or chemistry removing wherein sulfur-bearing, contain
The harmful substances such as nitrogen, to obtain the high-purity benzene,toluene,xylene that can use etc. as raw material.At present, the industrial master of China
Acid wash to be adopted and hydrodesulfurization refine to crude benzol.
Catalytic hydrogenation method as coking crude benzene chemical desulfurization method, be under hydro condition by thiophene change into hydrogen sulfide and
Corresponding alkane and remove, typically in two steps, the first step：Pre-hydrotreating reaction, the main catalyst removal coking with routine
Unstable material in crude benzol is it is also possible to remove part sulphur-containing substance；Second step, main hydrogenation reaction, thiophene in removing coking crude benzene
The Major Sulfides such as fen, carbon disulfide and organic nitrogen compound.Crude benzole hydrogenation technique is divided into high-temperature hydrogenation according to catalytic reaction temperature
With two kinds of techniques of low temperature hydrogenation.
In high-temperature catalytic hydrogenation technique, most typically is exactly Lay Bristol method, i.e. Litol method, and this technique is in the sixties in 20th century
A kind of high temperature crude benzole hydrogenation method for refining successfully developed by U.S. Hu Deli (Hondry) Air Products Company, the Japanese rising sun later
Cheng company is improved to it again, defines Japanese Litol high temperature, high pressure vapor hydrogen addition technology.Crude benzol is existed by this method first
Be separated into light benzene and heavy benzol in prefractionator, light benzene enters after evaporimeter mixes with circulating hydrogen through high-pressure pump, aromatic hydrocarbon steam with
Hydrogen mixture enters pre-reactor from tower top.The hydroconversion condition of this method is：Pre-reactor temperature is 230 DEG C, and pressure is
5.7MPa, catalyst is CoMo catalyst；Main reactor temperature is 610630 DEG C, pressure is 5l0MPa, and catalyst is Cr system
Catalyst.Pre-reactor is at a lower temperature (200250 DEG C) homologues such as the styrene being easily polymerized under the condition of high temperature
Carry out hydrogenation reaction, prevent it to be polymerized in main reactor, so that catalyst activity is reduced, complete to be hydrogenated with two main reactors
Cracking, the de- reaction such as alkyl, desulfurization.The condensed cooling system of oil gas discharged by main reactor, the liquid isolated is hydrogenation
Oil, the hydrogen isolated and low molecular hydrocarbon removing H2After S, a part is sent to hydrogenation system, and a part is sent to reforming hydrogen manufacturing system
System hydrogen making.Because the alkyl on phenyl ring can be removed by Litol technique, therefore purified petroleum benzin yield can reach 114%.
Because Litol method needs to operate at high temperature under high pressure, have hydrogen embrittlement (hydrogen that at high temperature under high pressure, hydrogen decomposes is former again
Son penetrates in steel crystal grain, so that the intercrystalline atomic binding forces of steel is reduced, thus reducing elongation percentage and the section receipts of steel
Shrinkage) and hydrogen-type corrosion (at high temperature under high pressure, hydrogen molecule and hydrogen atom slowly penetrate into the fault location of steel material, assemble composition
There is hydrogenation reaction with carbon compound around after sub- defect), thus to equipment requirement will height, manufacture difficulty is larger, need from
A complete set of introduction abroad.The nineties in 20th century, Baosteel chemical industry first stage of the project of China just once the Lay Bristol method of a complete set of Introduced from Japan high
The de- alkyl hydrogenation technique of temperature, went into operation in 1986, year processes crude benzol 50,000 t, can obtain purity 99.9%, crystalline temperature 5.52
℃：, total sulphur content be less than lppm, thiophene content be less than 0.5ppm spy's purified petroleum benzin.Henan Shen Ma company is subsequently also a complete set of to introduce
The Lay Bristol method high temperature of Japan takes off alkyl hydrogenation technique.Litol law theory yield 91.53%, but in terms of actual achievement in 2004
But only have 88.96%.
Low temperature hydrogenation method mainly includes three essential elements：(purity is more than the pure hydrogen of coke-stove gas pressure-variable adsorption system
99.9%)；Hydrobon process (pre- hydrogenation and main hydrogenation)；Product purification process (extraction or extractive distillation).Due to
The product mainly obtaining in coking crude benzene low temperature hydrogenation technique is aromatic hydrocarbon and non-aromatic hydrocarbon, industrial be difficult to directly to pass through conventional
Distillating method be separated, after adding certain extractant (extractant require not formed with other components azeotropic mixture and
Boiling point is higher), can significantly change each component solubility wherein, thus changing their relative volatility and saturation steaming
Vapour pressure, then the effect separating product just can be reached by the method for distillation, technique can be divided into extractive distillation and liquid liquid extraction
Take.
Extractive distillation hydrogenation method theoretical yield is 99.41%, but only 98.30% from the point of view of actual achievement in 2004.Liquid liquid extracts
Most representational in taking technique is exactly sulfolane process, and its theoretical yield is also more than 99%.But above-mentioned process obtains
All in 0.5ppm, this is to aromatic hydrocarbon product using producing considerable restraint for purified petroleum benzin sulfur content
How a kind of hydrodesulfurization is therefore provided, effectively can control the sulfur content of coking crude benzene product in 0.1ppm
Hereinafter, to meet its application standard, it is the difficult problem that this area faces.
Content of the invention
It is an object of the invention to proposing a kind of coking crude benzene hydrodesulfurization, this technique can be by coking crude benzene
Total sulfur content is reduced to below 0.1ppm, minimum to 0.05ppm, to meet the application requirement of product.
For reaching this purpose, the present invention employs the following technical solutions：
A kind of coking crude benzene hydrodesulfurization, coking crude benzene enters pre-reactor with hydrogen mixture from tower top, pre- anti-
Answer and in device, be filled with NiMo catalyst, its reaction temperature is 220-230 DEG C, hydrogenation pressure is 3.2-3.8MPa, its product is subsequent
Enter fixed bed reactors, be filled with Hydrobon catalyst in described fixed bed reactors, described catalyst include carrier and
Active component.
Described carrier is compound or the mixture of MSU-G, SBA-15 and HMS；
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
The reaction condition of described fixed bed reactors is：Reaction temperature is 320-380 DEG C, Hydrogen Vapor Pressure 3.0-3.6MPa,
Hydrogen to oil volume ratio 500-800, volume space velocity 1.5-2h-1.
The reacted product of fixed bed hydrogenation enters extractive distillation unit, obtains aromatic hydrocarbons.
Through detection, in the aromatic hydrocarbons obtaining, total sulphur content is less than 0.1ppm, and the purity of product is also greater than 99.9%.
It should be noted that in the coking crude benzene hydrodesulfurization of present invention employing, pre-hydrotreating reaction is set using routine
Standby and technique, the improvement to coking crude benzole hydrogenation sulfur removal technology for the present invention, are more embodied in the design of main hydrogenation reaction.
An object of the present invention is that, provides the compound of a kind of 3 kinds different mesopore molecular sieves to work in coordination with effect to show
Should be with special catalytic performance, described cooperative effect shows desulfuration purification aspect, and special catalytic performance is then to show right
In the raising of the service life of catalyst and catalysis activity.
In catalyst field, according to the definition of IUPAC (IUPAC), aperture is less than the title of 2nm
For micropore；Aperture is more than the referred to as macropore of 50nm；Aperture referred to as mesoporous (or claiming mesopore) between 2 to 50nm.Mesoporous material
It is a kind of new material with huge specific surface area and three-dimensional open-framework between micropore and macropore for aperture, it has
The excellent specific property that other porous materials do not have：There is the pore passage structure of high-sequential；The single distribution in aperture, and aperture size
Can change in relative broad range；Mesoporous various shapes, hole wall composition and property controllable；Height can be obtained by optimum synthesis condition
Heat endurance and hydrothermal stability.
But in present applications ' the tail must be taken, described mesoporous material, when for catalytic field, is all single use, such as MCM system
Row, such as MCM-22, MCM-36, MCM-41, MCM-48, MCM-49, MCM56, such as MSU series, such as MSU-1, MSU-2, MSU-
4th, MSU-X, MSU-G, MSU-S, MSU-J etc., and SBA series, such as SBA-1, SBA-2, SBA-3, SBA-6, SBA-7, SBA-
8th, SBA-11, SBA-15, SBA-16 etc., and other mesoporous series etc..
Compound, such as Y/SBA-15, Y/SAPO-5 etc. of two kinds of carriers of a few studies literature research, majority is to be situated between
Based on hole-mesoporous-microporous composite molecular sieve and micropore-mesoporous-microporous composite molecular sieve.Adopt being combined to show of 3 kinds of different mesopore molecular sieves
Go out cooperative effect and the research of special catalytic performance, have not yet to see report.
The catalyst carrier of the present invention is compound or the mixture of MSU-G, SBA-15 and HMS.Described compound or mixed
In compound, the weight of MSU-G, SBA-15 and HMS is than for 1:(0.8-1.2):(0.4-0.7), preferably 1:(1-1.15):
(0.5-0.7).
MSU-G, SBA-15 and HMS mesopore molecular sieve that the present invention adopts is all the existing molecular sieve of catalytic field, and it is
Through obtaining widely studied and application in catalytic field.
MSU-G is a kind of mesopore molecular sieve with vesicle structure shape particle shape and layered framework structure, and it has height
The crosslinked and relatively thick skeleton wall of skeleton of degree and there is superpower heat endurance and hydrothermal stability, its skeleton hole with vertical
It is cross-linked with each other in layer with parallel to the hole of layer, diffusion path is very short because its vesica shell is thick.The vesica shape particle of MSU-G molecular sieve
Form facilitates reagent to enter the catalytic center of layered framework, and its catalysis activity is very high.
SBA-15 belongs to one kind of mesopore molecular sieve, has two-dimentional six side's through-hole structures, has P3mm space group.In XRD
In diffracting spectrum, main peak near about 1 °, for (10) crystal face peak.Secondary strong peak is followed successively by (11) peak and (20) peak.Other peaks are relatively
Weak, it is difficult to observe.Additionally, the silica on SBA-15 skeleton is generally amorphous state, observe not in wide-angle XRD diffraction
To obvious diffraction maximum.SBA-15 has a larger aperture (maximum up to 30nm), thicker hole wall (wall thickness is up to 6.4nm), because
And there is preferable hydrothermal stability.
Hexagonal mesoporous silicon HMS has long-range order and the relatively unordered hexagonal mesoporous duct of short distance, and its hole wall compares HCM41S
Type mesoporous material is thicker, thus hydrothermal stability is more preferably, and the relatively unordered institutional framework of short distance and aperture modulation scope be more simultaneously
Greatly, make HMS material have higher molecular transport efficiency and absorption property, be suitable in the activity as bulky molecular catalysis reaction
The heart.
The present invention, from each mesoporous material, carries out compound pairing, screens through extensive, filters out MSU-G, SBA-15
With the compound of HMS or mixing.Inventor finds, in numerous compound/mixtures, only MSU-G, SBA-15 and HMS tri-
The compound or mixing of person, just enables the collaborative lifting of hydrofinishing effect, and enables to catalysis activity not reduce for a long time, make
Can be greatly increased with the life-span.In other words, only the specific of MSU-G, SBA-15 and HMS three of the present invention is combined or mixes,
Just solve collaborative and two technical problems of service life simultaneously.Other cooperations, or not possessing synergy, or use the longevity
Life is shorter.
Described compound, can adopt being simply mixed of MSU-G, SBA-15 and HMS three, it would however also be possible to employ be combined two-by-two
Mixing afterwards, such as MSU-G/SBA-15 compound, the mixing of MSU-G/HMS and SBA-15/HMS compound.Described being combined can
To be prepared using known electrostatic matching method, ion-exchange, two step crystallization methods etc..These mesopore molecular sieves are combined with it
The preparation method of thing is the known method of catalyst field, and the present invention is no longer repeated with regard to it.
In the present invention, being particularly limited to active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Mixed proportion, inventor finds, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6):(0.28-
0.45):(0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists
In the range of being somebody's turn to do, sulfur content in coking crude benzene can be realized and control in below 0.1ppm.That is, the four of the present invention kinds of activity
Component is 1 only in mol ratio:(0.4-0.6):(0.28-0.45):(0.8-1.2), when, just possesses cooperative effect.Rub except this
Outside you are than scope, or omit or replace any one component, do not enable cooperative effect.
Preferably, two molybdenum MO are nitrogenized2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-
0.5):(0.35-0.45):(0.8-1.0), more preferably 1:(0.45-0.48):(0.4-0.45):(0.9-1.0),
Preferably 1:0.48:0.42:0.95.
The total content of described active component is the 1%-15%, preferably 3-12%, further preferred 5-10% of vehicle weight.
For example, described content can for 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%,
7.5%th, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%,
14%th, 14.5% etc..
The preparation method of described catalyst can take infusion process and other alternatives of routine, people in the art
The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.
Preferably, the reaction condition of described fixed bed reactors is：Reaction temperature is 340-360 DEG C, Hydrogen Vapor Pressure 3.2-
3.4MPa, hydrogen to oil volume ratio 600-800, volume space velocity 1.5-1.8h-1.
Preferably, described fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
The coking crude benzene hydrodesulfurization of the present invention passes through to choose specific catalyst, and described catalyst passes through to choose spy
MSU-G, SBA-15 and HMS compound/mixture of certainty ratio is as carrier, and nitridation two molybdenum choosing special ratios
MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc are as active component so that this catalyst produces cooperative effect, focusing
The hydrodesulfurization changing crude benzol can control in total sulfur content less than 0.1ppm.
Specific embodiment
The present invention is illustrated to the hydrodesulfurization of the present invention by following embodiments.
Embodiment 1
Catalyst is prepared by infusion process, carrier is the mixture of MSU-G, SBA-15 and HMS, and mixed proportion is 1:
1.1:0.5.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc is carrier
The 10% of quality, its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing is entered fixed bed reactors, the reaction tube of described reactor is by the stainless steel of internal diameter 50mm
Become, reaction bed temperature is measured with UGU808 type temp controlled meter, the twin columns that raw material light oil is manufactured by Beijing Satellite Manufacturing Factory
Plug micro pump continuous conveying, hydrogen is supplied by gas cylinder and uses Beijing Sevenstar-HC D07-11A/ZM gas mass flow gauge control
Flow velocity processed, loaded catalyst is 2kg.
Coking crude benzene enters pre-reactor with hydrogen mixture from tower top, is filled with NiMo catalyst in pre-reactor, its
Reaction temperature is 230 DEG C, and hydrogenation pressure is 3.5MPa, and its product subsequently enters described fixed bed reactors.Control main reaction bar
Part is：Reaction temperature is 340 DEG C, Hydrogen Vapor Pressure 3.4MPa, hydrogen to oil volume ratio 650, volume space velocity 1.5h-1.The product obtaining with
Enter extractive distillation unit afterwards, extractant adopts sulfolane, and extraction temperature controls at 100 DEG C, and extracting pressure controls
200kPa.
Test final product, its total sulfur content is reduced to 0.06ppm.
Embodiment 2
Catalyst is prepared by infusion process, carrier is MSU-G/SBA-15 compound, MSU-G/HMS and SBA-15/
The ratio of the mixing of HMS compound, wherein MSU-G, SBA-15 and HMS is same as Example 1.Described active component nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc is the 10% of carrier quality, and its mol ratio is 1:0.6:
0.45):1.2.
Remaining condition is same as Example 1.
Test final product, its total sulfur content is reduced to 0.03ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with MSU-G, remaining condition is constant.
Test final product, its total sulfur content is 18ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with SBA-15, remaining condition is constant.
Test final product, its total sulfur content is 16ppm.
Comparative example 3
The carrier of embodiment 1 is replaced with HMS, remaining condition is constant.
Test final product, its total sulfur content is 18ppm.
Comparative example 4
Carrier in embodiment 1 is replaced with MSU-G/SBA-15 compound, remaining condition is constant.
Test final product, its total sulfur content is 11ppm.
Comparative example 5
Carrier in embodiment 1 is replaced with SBA-15/HMS compound, remaining condition is constant.
Test final product, its total sulfur content is 21ppm.
Comparative example 6
Carrier in embodiment 1 is replaced with MSU-G/HMS compound, remaining condition is constant.
Test final product, its total sulfur content is 18ppm.
Embodiment 1 and comparative example 1-6 show, the present invention adopts MSU-G, SBA-15 and HMS compound of special ratios/mixed
Compound, as carrier, when replacing with single carrier or complex carrier two-by-two, does not all reach the technique effect of the present invention, therefore originally
MSU-G, SBA-15 and HMS compound/mixture of the special ratios of invention has as between carrier and catalyst other components
Standby cooperative effect, described hydrodesulfurization creates unforeseeable technique effect.
Comparative example 7
Omit the MO in embodiment 12N, remaining condition is constant.
Test final product, its total sulfur content is 14ppm.
Comparative example 8
Omit the WC in embodiment 1, remaining condition is constant.
Test final product, its total sulfur content is 10ppm.
Above-described embodiment and the explanation of comparative example 7-8, several activearm of catalyst of the hydrodesulfurization of the present invention divides it
Between exist specific contact, be omitted or substituted one of which or several, all can not reach the certain effects of the application it was demonstrated that its product
Give birth to cooperative effect.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in
Above-mentioned technique, that is, do not mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the art
Member is it will be clearly understood that any improvement in the present invention, the equivalence replacement to each raw material of product of the present invention and the interpolation of auxiliary element, tool
Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (6)
1. a kind of coking crude benzene hydrodesulfurization is it is characterised in that coking crude benzene is pre- anti-from tower top entrance with hydrogen mixture
Answer device, in pre-reactor, be filled with NiMo catalyst, its reaction temperature is 220-230 DEG C, hydrogenation pressure is 3.2-3.8MPa, in advance
The product of reaction enters fixed bed reactors, is filled with Hydrobon catalyst, described catalyst in described fixed bed reactors
Including carrier and active component；Described carrier is compound or the mixture of MSU-G, SBA-15 and HMS；Described active component is
Nitrogenize two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc；The reaction condition of described fixed bed reactors
For：Reaction temperature is 320-380 DEG C, Hydrogen Vapor Pressure 3.0-3.6MPa, hydrogen to oil volume ratio 500-800, volume space velocity 1.5-2h-1；
The reacted product of fixed bed hydrogenation enters extractive distillation unit, obtains aromatic hydrocarbons.
2. hydrodesulfurization as claimed in claim 1 is it is characterised in that the weight of MSU-G, SBA-15 and HMS is than for 1:
(0.8-1.2): (0.4-0.7), preferably 1: (1-1.15): (0.5-0.7).
3. hydrodesulfurization as claimed in claim 1 is it is characterised in that the total content of described active component is vehicle weight
3-12%, preferably 5-10%.
4. hydrodesulfurization as claimed in claim 1 is it is characterised in that nitrogenize two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide
Mo2The mol ratio of C and tungsten carbide wc is 1: (0.45-0.5): (0.35-0.45): (0.8-1.0), more preferably 1:
(0.45-0.48): (0.4-0.45): (0.9-1.0), most preferably 1: 0.48: 0.42: 0.95.
5. hydrodesulfurization as claimed in claim 1 is it is characterised in that the reaction condition of described fixed bed reactors is：
Reaction temperature is 340-360 DEG C, Hydrogen Vapor Pressure 3.2-3.4MPa, hydrogen to oil volume ratio 600-800, volume space velocity 1.5-1.8h-1.
6. hydrodesulfurization as claimed in claim 1 is it is characterised in that described fixed bed reactors include 1-5 catalysis
Agent bed, preferably includes 2-3 beds.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262969A (en) * | 2000-03-02 | 2000-08-16 | 南开大学 | Catalyst using TiO2 as carrier to load metal nitride Mo2N |
| CN1470327A (en) * | 2002-07-24 | 2004-01-28 | 北京石油化工学院 | Metal nitride catalyst preparing method and catalyst |
| CN1895777A (en) * | 2005-07-14 | 2007-01-17 | 北京化工大学 | Porous molecular-sieve catalyst for assembling carbide and its preparation |
| WO2013149014A1 (en) * | 2012-03-29 | 2013-10-03 | Wayne State University | Bimetal catalysts |
| CN105251527A (en) * | 2015-11-11 | 2016-01-20 | 中国石油大学(北京) | Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier |
-
2016
- 2016-08-11 CN CN201610657476.1A patent/CN106380365A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262969A (en) * | 2000-03-02 | 2000-08-16 | 南开大学 | Catalyst using TiO2 as carrier to load metal nitride Mo2N |
| CN1470327A (en) * | 2002-07-24 | 2004-01-28 | 北京石油化工学院 | Metal nitride catalyst preparing method and catalyst |
| CN1895777A (en) * | 2005-07-14 | 2007-01-17 | 北京化工大学 | Porous molecular-sieve catalyst for assembling carbide and its preparation |
| WO2013149014A1 (en) * | 2012-03-29 | 2013-10-03 | Wayne State University | Bimetal catalysts |
| CN105251527A (en) * | 2015-11-11 | 2016-01-20 | 中国石油大学(北京) | Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier |
Non-Patent Citations (14)
| Title |
|---|
| F•维拉尼: "《稀土技术及其应用》", 31 July 1986, 烃加工出版社 * |
| 中国石油化工集团公司人事部，等: "《加氢裂化装置操作工》", 30 September 2008, 中国石化出版社 * |
| 何鸣元，等: "《石油炼制和基本有机化学品合成的绿色化学》", 31 January 2006, 中国石化出版社 * |
| 姜琳琳: "全馏分FCC汽油加氢改质中改性MCM-41催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 崔克清，等: "《化工工艺及安全》", 31 May 2004, 化学工业出版社 * |
| 张文成: "改性MCM-41 分子筛的制备及加氢催化性能研究", 《第十一届全国青年催化学术会议论文集（下）》 * |
| 李静海，等: "《展望21世纪的化学工程》", 31 October 2004, 化学工业出版社 * |
| 林世雄: "《石油炼制工程（第三版）》", 31 July 2000, 化学工业出版社 * |
| 王基铭: "《石油炼制辞典》", 30 September 2013, 中国石化出版社 * |
| 王海彦，等: "《石油加工工艺学》", 31 January 2014, 中国石化出版社 * |
| 王福安，等: "《绿色过程工程引论》", 31 October 2002, 化学工业出版社 * |
| 王雷，等: "《炼油工艺学》", 31 August 2011, 中国石化出版社 * |
| 邝生鲁: "《现代精细化工高新技术与产品合成工艺》", 31 December 1997, 科学技术文献出版社 * |
| 阎子峰: "《纳米催化技术》", 31 May 2003, 化学工业出版社 * |
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