CN106221764A - A kind of FCC gasoline hydrodesulfurization - Google Patents
A kind of FCC gasoline hydrodesulfurization Download PDFInfo
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- CN106221764A CN106221764A CN201610679321.8A CN201610679321A CN106221764A CN 106221764 A CN106221764 A CN 106221764A CN 201610679321 A CN201610679321 A CN 201610679321A CN 106221764 A CN106221764 A CN 106221764A
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- 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
- C10G67/14—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 at least two different refining steps in the absence of hydrogen
-
- 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
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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 invention discloses a kind of FCC gasoline hydrodesulfurization, described technique uses fixed bed reactors, is filled with Hydrobon catalyst in fixed bed reactors, and described catalyst includes carrier and active component;Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+SAPO 5;Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc;Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture;The reaction condition of described fixed bed reactors is: reaction temperature is 300 420 DEG C, Hydrogen Vapor Pressure 2.5 3.5MPa, hydrogen to oil volume ratio 500 800, volume space velocity 1.5 4h‑1.Total sulfur content in FCC gasoline can be reduced to below 10ppm by this technique, to meet gasoline state five standard.Meanwhile, this technique also makes the octane number of FCC gasoline significantly reduce.
Description
Technical field
The present invention relates to gasoline hydrodesulfurizationmethod technique, be specifically related to a kind of FCC gasoline hydrodesulfurization, more preferably relate to
A kind of FCC gasoline hydrodesulfurization also reduces the technique that octane number reduces amplitude.
Background technology
Entering 21st century, demand and the use of fuel oil increase substantially, and sulfur-containing compound therein is brought
Problem of environmental pollution, more cause the concern of people.The oxysulfide that sulfide in fuel oil produces through engine combustion
(SOx) be discharged in air, produce acid rain and fumes of sulphuric acid type pollution etc., cause atmospheric pollution.
Sulfur is a kind of harmful substance that nature is present in gasoline, and in gasoline product, the sulfur of more than 80% carrys out self-catalysis and splits
Changing (FCC) gasoline, along with constantly becoming of crude oil is heavy, the sulfur content in FCC gasoline also can be continuously increased.External gasoline is generally from
FCC (34%), catalytic reforming (33%), and the technique such as alkylation, isomerization and etherificate (the most totally 33%);And home-produced fuel
80% is from FCC gasoline.Due in gasoline the sulfur of 85%~95% from FCC gasoline so that the sulfur content in China's gasoline
More than external gasoline a lot.A lot of experts have carried out the research that motor vehicle exhaust emission is affected by sulfur, and result shows: if by gasoline
In sulfur content from 450 μ g g-1It is reduced to 50 μ g g-1, NO in vehicle exhaustxAverage minimizing 9%, CO averagely reduces
19%, HC averagely reduce 18%, and Toxic averagely reduces 16%.Thus, effective fuel oil hydrodesulfurization technology, to society, warp
Ji, the development of environment have important effect.
Most effective, the most economical sulfur method that hydrodesulfurization (HDS) technology is well recognized as at present, especially selective hydrogenation
Desulfurization technology, i.e. suppresses the saturated to reduce loss of octane number of alkene while the removing a large amount of sulfur-containing compound of gasoline as far as possible.
The features such as this kind of technology has operating condition and relaxes, and yield of gasoline is high, and hydrogen consumption is low and loss of octane number is little.Hydrodesulfurization technology
It is crucial that the selection of Hydrobon catalyst, the cobaltmolybdate catalyst of support type is the gasoline hydrodesulfurizationcatalyst catalyst that a class is important,
It is typically cobalt molybdenum to load on porous support (such as aluminium oxide, silicon oxide, activated carbon or its complex carrier), is widely used in adding
In hydrogen sweetening process, to obtain premium-type gasoline product.
Hydrodesulfurization (HDS) technology is to grow up the fifties, and the nineties, this technology welcome second improving and developing
Individual peak period, its technical maturity, all the time, become sulfur, nitrogen, oxygen in removing distillate, improve oil product Practical Performance with clear
The maximally efficient means of cleanliness.The activity and selectivity of catalyst is the key factor affecting hydrofinishing efficiency and the degree of depth,
Economy and environmental benefit that high performance catalyst is brought are very significant, have therefore attracted numerous enterprises and researcher to put into
In developing to efficient catalyst, the catalyst prod develop many function admirables, differing from one another.Hydrogenation technique is sent out rapidly
The basic reason of exhibition is the development of catalyst, but alkene can be caused while routine techniques desulfurization saturated and product octane number
(RON) decline, therefore desulfurization and the few selective hydrogenation new technique of loss of octane number can become what HDS method in recent years was improved
Main way.
The RESOLVE technological development of Akzo Nobel company exploitation catalytic cracking reduces the RESOLVE of content of sulfur in gasoline
Additive product series, uses high hydrogen transfer activity component and ADM-20, and cracking gasoline sulfur content can be made to reduce by 20%,
RESOLVE-700 gasoline reduces in sulfur additives currently industrial evaluation.
Exxon research engineering company is Containing Sulfur in selectively removing FCC gasoline with Akzo Nobel company joint development
The Scanfining technology of compound, and pushed this technology to industrialization in 1998.It uses traditional hydrotreating flow process, logical
Cross meticulous selecting catalyst (RT-225), make loss of octane number and hydrogen consumption reach minimum.
The Prime-G technology of France's IFP exploitation, this technology, by France studying and designing institute (IFP) exploitation, uses dual catalyst
System.Its process conditions relax, and hydrogenation of olefins activity is low, does not occur alkene saturated and cracking reaction, and liquid yield reaches 100%,
Desulfurization degree is more than 95%, and loss of octane number is few, and hydrogen consumption is low.By FCC heavy petrol hydrodesulfurization, being in harmonious proportion the gasoline product obtained can
To realize the target of sulfur content 100~150 μ g g-1;By the hydrodesulfurization respectively of FCC petroleum benzin, sulfur content 30 μ can be realized
The target of g g-1.
For the feature of domestic FCC gasoline sulfur-bearing, Fushun Petrochemical Research Institute (FRIPP) develops FCC gasoline and selects
Property hydrogen addition technology (OCT-M) and full distillation gasoline selective hydrogenation technology (FRS), device can produce sulfur nutrient and be not more than
150μg·g-1GB III gasoline.OCT-M technology, after Shijiazhuang Oil Refinery, China Petrochemical Corp. continuously runs 17 months, uses
Two kinds of prioritization schemes that FRIPP recommends, after FCC gasoline hydrogenation, sulfur nutrient reaches GB III and IV standard.
On May 5th, 2016, the issue of seven departments such as the Committee of Development and Reform, the Ministry of Finance, Chinese Ministry of Environmental Protection " accelerates product oil quality about printing and distributing
Upgrade job scheme " notice, scheme clearly expands automobile-used vapour, diesel oil state five standard performs scope.From original Jing-jin-ji region, length three
Angle, region, Pearl River Delta key cities expand 11, whole eastern region provinces and cities (Beijing, Tianjin, Hebei, Liaoning, Shanghai, river to
Soviet Union, Zhejiang, Fujian, Shandong, Guangdong and Hainan).Before 31 days October in 2015, eastern region is protected possesses manufacturing country five mark for enterprise
Quasi-motor petrol (containing ethanol petrol blend component oil), the ability of derv fuel.On January 1st, 2016 rises, and eastern region supplies comprehensively
The motor petrol (containing E10 ethanol petrol) of state five standard, derv fuel (containing B5 biodiesel) should be met.
At present, the main method reducing FCC gasoline sulfur content is catalytic desulfurhydrogenation.But hydrotreating method exists such as
Lower deficiency: (1) equipment investment is big;(2) severe reaction conditions of the de-thiophenic sulfur of hydrogenation, operating cost is high;(3) alkene is de-at hydrogenation
Easily occur saturated under the conditions of sulfur, not only consume a large amount of hydrogen, and cause octane number to reduce.FCC gasoline desulfurization degree requirement
The highest, operating condition is the harshest, and the loss of octane number is the biggest.
A kind of hydrodesulfurization is provided, can effectively the sulfur content in gasoline be controlled at below 10ppm, with
Meeting state five standard, octane number loss simultaneously is less or does not loses, and is a difficult problem facing of this area.
Summary of the invention
It is an object of the invention to propose a kind of hydrodesulfurization, this technique can be by the total sulfur content in FCC gasoline
It is reduced to below 10ppm, to meet gasoline state five standard.Meanwhile, the employing of this catalyst also makes the octane number of FCC gasoline not
Substantially reduce.
For reaching this purpose, the present invention by the following technical solutions:
A kind of FCC gasoline hydrodesulfurization, described technique uses fixed bed reactors, is filled with in fixed bed reactors
Hydrobon catalyst, described catalyst includes carrier and active component.
Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+SAPO-5.Described active component is nitridation two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.Described catalyst possibly together with catalyst aid, described in urge
Change auxiliary agent is TiO2、CeO2、V2O5And NbOPO4Mixture.
The reaction condition of described fixed bed reactors is: reaction temperature is 300-420 DEG C, Hydrogen Vapor Pressure 2.5-3.5MPa,
Hydrogen to oil volume ratio 500-800, volume space velocity 1.5-4h-1。
SAPO-5 molecular sieve is the one in SAPO (SAPO) Series Molecules sieve, and its channel system is by six sides couple
The twelve-ring that the four-membered ring of title property and hexatomic ring are constituted is constituted, and has large aperture structure, and its aperture is 0.8nm.SAPO-5
Acidic zeolite is gentle, and has faint controllability, also has cation exchange capacity (CEC).In a way, its materialization
Character not only has the characteristic of aluminophosphate molecular sieve, and also is similar to the characteristic of Si-Al zeolite.Owing to it has novel
Crystal structure, good heat stability and hydrothermal stability, in meta-xylene isomerization and normal hexane catalytic pyrolysis etc. react
Tool is widely used.But it is used for hydrofinishing rather than hydrocracking field, rarely seen document is reported.
The present invention through in numerous silicoaluminophosphamolecular molecular sieves, such as SAPO-11, SAPO-17, SAPO-20, SAPO-31,
SAPO-34, SAPO-44, SAPO-46, SAPO-47 etc., carry out contrast test selection one by one, finds that only SAPO-5 can reach
The goal of the invention of the present invention, other mesoporous materials have such-and-such defect, exist when being applied in the present invention and are difficult to gram
The technical difficulty of clothes, therefore the present invention selects to turn the SAPO-5 modification being used for being hydrocracked to do for hydrorefined carrier base
Plinth.
Inventor finds through research, for affecting the silica alumina ratio of silicoaluminophosphamolecular molecular sieves performance, phosphorus aluminum ratio, in the present invention
In, after being modified, the change of silica alumina ratio and phosphorus aluminum ratio is less to hydrofinishing influential effect, and therefore the present invention is no longer to sial
It is defined than with phosphorus aluminum ratio.For ease of the explanation present invention, typically it is defined to mol ratio and is respectively less than 1.
Owing to existing SAPO-5 molecular sieve catalytic temperature is high, and being easily caused raw material hydrocracking, therefore, the present invention is to it
Being modified, to increase its catalysis activity, reduce catalytic temperature and make it be applicable to catalytic refining, minimizing is hydrocracked.This
The bright approach to the modification of SAPO-5 mesopore molecular sieve is: introduce to the total silicon SAPO-5 mesopore molecular sieve duct inner surface of finished product
Cu2+, this approach can be exchanged Cu by ion2+It is supported on the inner surface of SAPO-5, thus improves on the whole
Catalysis activity, absorption and the Thermodynamically stable performance etc. of SAPO-5 mesopore molecular sieve.
Although the method being modified SAPO-5 mesopore molecular sieve or approach are a lot, inventor finds, the present invention urges
Agent can only use doping Cu2+SAPO-5 could realize sulfur content as carrier and control and the balance of loss of octane number, invention
People has attempted adulterating in SAPO-5: Ca2+、Fe3+、Zn2+、Ti2+、Ga3+And alkali metal etc. produces anionic surface center
Ion, finds all to realize described effect.Although described mechanism is current and unclear, but this has no effect on the reality of the present invention
Executing, inventor is according to well-known theory and it is experimentally confirmed that there is cooperative effect between itself and the active component of the present invention.
Described Co2+Doping in SAPO-5 must control within specific content range, and its doping is with weight
Meter, for the 0.56%-0.75% of SAPO-5 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%,
0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%,
0.74 etc..
Inventor finds, outside this range, can cause drastically reducing of octane number.More pleasurable, when
Co2+When doping in SAPO-5 controls in the range of 0.63%-0.72%, it is the strongest to the control of octane number, works as drafting
With Co2+Doping is transverse axis, and during curve chart with target octane number as the longitudinal axis, in this content range, sulfur content can control extremely low
Within the scope of, its desulfurized effect produced, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15% of carrier S APO-5 weight, preferably 3-12%, further preferably
5-10%.Such as, described content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%,
7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%,
13.5%, 14%, 14.5% etc..
In the present invention, it is particularly limited to active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Mixed proportion, inventor find, 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 Gai, sulfur content in FCC gasoline can be realized and control not to be decreased obviously at below 10ppm and octane number.Also
That is, four kinds of active components of the present invention are only 1:(0.4-0.6 in mol ratio): (0.28-0.45): time (0.8-1.2),
Just possesses cooperative effect.Outside this molar ratio range, or omit or replace any one component, all can not realize association
Same 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 three of the purpose of the present invention are to provide the promoter of described catalyst.Catalyst of the present invention possibly together with
Catalyst aid, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, had maturation catalyst aid, such as P, F and B etc., its
For regulating the character of carrier, weaken interaction strong between metal and carrier, improve the surface texture of catalyst, improve metal
Reducibility, promote active component to be reduced to lower valency, to improve the catalytic performance of catalyst.But above-mentioned P, F and B catalysis helps
Agent application with the carrier of the present invention with active component time, for high-sulfur component, it promotes the effect of catalytic desulfurization/refined
?.
The present invention passes through in numerous conventional cocatalyst component, and carries out in amount of activated component selecting, compounding,
Find eventually to use TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) is obvious to the catalyst facilitation of the present invention, energy
Significantly improve its hydrothermal stability, and improve its anti-coking deactivation, thus improve its service life.
Described TiO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that TiO2、CeO2、V2O5With
NbOPO4Each respective content reaches effective dose.Preferably, the TiO that the present invention uses2、CeO2、V2O5And NbOPO4
Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although there is no specific proportion requirement between catalyst aid of the present invention, but each auxiliary agent allowing for reaching
To the requirement of effective dose, the 1-7% of the content of catalyst aid effect, such as carrier quality i.e. can be played.The present invention is selecting
During find, omit or replace one or more in described auxiliary agent, all do not reach the present invention technique effect (improve water
Heat stability, reduces coking and improves service life), say, that exist between the catalyst aid of the present invention and specifically coordinate pass
System.
It is true that the present invention once attempted the niobium phosphate NbOPO in catalyst aid4Replace with five oxidation two girl Nb2O5,
Have found that while in auxiliary agent and have also been introduced Nb, but its technique effect is significantly lower than niobium phosphate NbOPO4, not only hydrothermal stability is slightly for it
Difference, its beds coking is relatively rapid, thus causes catalyst duct to block, and beds pressure drop rise is relatively
Hurry up.The present invention the most once attempted introducing other phosphate, although but this trial introduces phosphate anion, but equally exist hydro-thermal
Stability is the most slightly worse, and its beds coking is relatively rapid, thus causes catalyst duct to block, beds pressure drop
Rise relatively fast.
Although present invention introduces catalyst aid have so many advantage, but the present invention should be noted that, introduce catalysis
Auxiliary agent is only one of preferred version, even if not introducing this catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention.
Not introducing the catalyst aid particularly niobium phosphate of the present invention, it is compared to the scheme of introducing catalyst aid, and its defect is only phase
To.This defect i.e. is that it is relative to other prior aries outside the present invention relative to the defect introduced after catalyst aid,
Mentioned by the present invention had superiority or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention
Indispensable technological means, its simply further optimization to technical solution of the present invention, solve new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine
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 320-400 DEG C, Hydrogen Vapor Pressure 2.8-
3.2MPa, hydrogen to oil volume ratio 550-750, volume space velocity 1.8-3.5-1。
Preferably, described technological process includes, after FCC gasoline mixes with hydrogen, through optional heat exchanger heat exchange, then through adding
Entering fixed bed reactors after the heating of hot stove and carry out hydrodesulfurization, product separates through gas-liquid separation tower.Optionally, gas phase is returned
Returning and mix with FCC gasoline and hydrogen, liquid phase can further be refined, and such as amine washes, strip and fractional distillation etc..
Preferably, described fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
The hydrodesulfurization of the present invention is by choosing specific catalyst, and described catalyst is by mixing hetero atom Co2+
SAPO-5 as carrier, and choose the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
As active component, described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4's
Mixture so that this catalyst produces cooperative effect, the hydrodesulfurization to FCC gasoline can control at total sulfur content less than 5ppm,
Octane number reduction amplitude controls within 0.5-2% simultaneously.
Detailed description of the invention
The hydrodesulfurization of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Co2+SAPO-5, Co2+Doping in SAPO-5
Control at the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing enters fixed bed reactors, and the reaction tube of described reactor is by the stainless steel of internal diameter 50mm
Becoming, reaction bed temperature UGU808 type temp controlled meter is measured, the twin columns that raw material light oil is manufactured by Beijing Satellite Manufacturing Factory
Plug micro pump carries continuously, and hydrogen is supplied and use Beijing Sevenstar-HC D07-11A/ZM mass-flow gas meter control by gas cylinder
Flow velocity processed, loaded catalyst is 2kg.Reacted product cools down laggard row gas-liquid separation through water-bath room temperature.
Raw materials used for full fraction FCC gasoline, it contains alkene 25.3m%, aromatic hydrocarbons 40.2m%, alkane 28.8m%, grinds
The method octane number of studying carefully is 94.2, total sulfur content 660 μ g/g.
Controlling reaction condition is: temperature 370 DEG C, Hydrogen Vapor Pressure 3.0MPa, hydrogen to oil volume ratio 600, volume space velocity 3h-1。
Testing final product, its research octane number (RON) still reaches 93.8, and total sulfur content is reduced to 3ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Co2+SAPO-5, Co2+Doping in SAPO-5
Control at the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, its mol ratio is 1:0.6:0.45): 1.2.
Remaining condition is same as in Example 1.
Testing final product, its research octane number (RON) still reaches 94.0, and total sulfur content is reduced to 2ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Testing final product, its research octane number (RON) is 81, and total sulfur content is 32ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated SAPO-5, and remaining condition is constant.
Testing final product, its research octane number (RON) is 87, and total sulfur content is 36ppm.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, its research octane number (RON) is 83, and total sulfur content is 34ppm.
Comparative example 4
By the Co in embodiment 12+Doping in SAPO-5 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, its research octane number (RON) is 87, and total sulfur content is 29ppm.
Comparative example 5
By the Co in embodiment 12+Doping in SAPO-5 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, its research octane number (RON) is 82, and total sulfur content is 37ppm.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion
SAPO-5 carrier, when replacing with other known carriers of this area, or carrier is identical but Co2+During doping difference, all reach
Less than the technique effect of the present invention, the therefore Co of the certain content scope of the present invention2+Doping SAPO-5 carrier and catalyst other
Possessing cooperative effect between component, described hydrodesulfurization creates unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, its research octane number (RON) is 80, and total sulfur content is 43ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, its research octane number (RON) is 83, and total sulfur content is 38ppm.
Above-described embodiment and comparative example 6-7 explanation, several active component of catalyst of the hydrodesulfurization of the present invention it
Between there is 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 it produces
Give birth to cooperative effect.
Embodiment 3
Containing catalyst aid TiO in catalyst2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 1.5%, 1% and
3%, remaining is same as in Example 1.
Testing final product, after it uses 3 months, beds pressure drop is not any change, and uses compared to same
The beds pressure drop of time embodiment 1 reduces 15%.
Comparative example 8
Compared to embodiment 3, by NbOPO therein4Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same
The beds pressure drop executing example 1 only reduces 4.1%.
Comparative example 9
Compared to embodiment 3, by CeO therein2Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same
The beds pressure drop executing example 1 only reduces 3.8%.
Embodiment 3 shows with comparative example 8-9, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted
When one of them or several component, all can not reach the minimizing coking when present invention adds catalyst aid thus stop catalyst bed
The technique effect that lamination falling-rising is high.That is, its catalyst aid demonstrating the present invention can improve the service life of described catalyst,
And other catalyst aid effects are not as this specific catalyst aid.
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, does not i.e. 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, and the equivalence of raw material each to product of the present invention is replaced 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 (8)
1. a FCC gasoline hydrodesulfurization, it is characterised in that described technique uses fixed bed reactors, fixed bed reaction
Being filled with Hydrobon catalyst in device, described catalyst includes carrier and active component;
Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+SAPO-5;Described active component is nitridation two molybdenum MO2N、
Tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc;Described catalyst possibly together with catalyst aid, described catalyst aid
For TiO2、CeO2、V2O5And NbOPO4Mixture;
The reaction condition of described fixed bed reactors is: reaction temperature is 300-420 DEG C, Hydrogen Vapor Pressure 2.5-3.5MPa, hydrogen oil
Volume ratio 500-800, volume space velocity 1.5-4h-1。
2. hydrodesulfurization as claimed in claim 1, it is characterised in that hetero atom Co2+Doping be SAPO-5 weight
0.63%-0.72%.
3. hydrodesulfurization as claimed in claim 1, it is characterised in that the total content of described active component is carrier
The 3-12% of SAPO-5 weight, preferably 5-10%.
4. hydrodesulfurization as claimed in claim 1, 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, it is characterised in that the reaction condition of described fixed bed reactors is:
Reaction temperature is 320-400 DEG C, Hydrogen Vapor Pressure 2.8-3.2MPa, hydrogen to oil volume ratio 550-750, volume space velocity 1.8-3.5h-1, excellent
Choosing, the reaction condition of described fixed bed reactors is: temperature 370 DEG C, Hydrogen Vapor Pressure 3.0MPa, hydrogen to oil volume ratio 600, volume
Air speed 3h-1。
6. hydrodesulfurization as claimed in claim 1, it is characterised in that described technological process includes, FCC gasoline and hydrogen
After mixing, through optional heat exchanger heat exchange, then after the heating of heated stove, entrance fixed bed reactors carry out hydrodesulfurization, and reaction is produced
Thing separates through gas-liquid separation tower.
7. hydrodesulfurization as claimed in claim 1, it is characterised in that described fixed bed reactors include 1-5 catalysis
Agent bed, preferably includes 2-3 beds.
8. hydrodesulfurization as claimed in claim 1, it is characterised in that TiO2、CeO2、V2O5And NbOPO4Respective content
It is respectively the 1-7%, preferably 2-4% of carrier quality.
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