CN106190260A - A kind of straight-run naphtha hydrofining technology - Google Patents

A kind of straight-run naphtha hydrofining technology Download PDF

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Publication number
CN106190260A
CN106190260A CN201610692079.8A CN201610692079A CN106190260A CN 106190260 A CN106190260 A CN 106190260A CN 201610692079 A CN201610692079 A CN 201610692079A CN 106190260 A CN106190260 A CN 106190260A
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catalyst
fixed bed
mcm
bed reactors
hydrofining technology
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朱忠良
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Xishan Lvchun Plastic Products Factory
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Xishan Lvchun Plastic Products Factory
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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
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • 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
    • C10G2300/70—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
    • C10G2400/06—Gasoil

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of straight-run naphtha hydrofining technology, described technique uses fixed bed reactors, is filled with hydrogenation desulfurization and denitrogenation 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+MCM 41；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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixture；The reaction condition of described fixed bed reactors is: reaction temperature is 250 300 DEG C, and hydrogen dividing potential drop is 1.5 2.0MPa, hydrogen to oil volume ratio 80 150, volume space velocity 9 14h‑1.Straight-run naphtha total sulfur content can be controlled less than 0.5ppm by this technique.

Description

A kind of straight-run naphtha hydrofining technology
Technical field
The present invention relates to straight-run naphtha hydrodesulfurization process for refining, be specifically related to a kind of use special catalyst to carry out Straight-run naphtha hydrofining technology.
Background technology
Petroleum (chemical industry light oil) is all a kind of main raw material in oil refining and petroleum chemical industry.Petroleum is a kind of Do the refinery less than 200-250 DEG C once or the petroleum distillate of secondary operations gained, be typically derived from refinery's atmospheric and vacuum distillation Straight-run naphtha and refinery catalytic cracking, be hydrocracked, coking plant secondary operations Petroleum, some condensates are also a kind of Naphtha cut.Here it should be stressed that because Chinese Crude Oils is generally laid particular stress on, its straight-run naphtha ends content is the lowest, so Making good use of secondary operations Petroleum as petrochemical material is a critically important problem, the most also pays much attention to the degree of depth of crude oil Processing, gained secondary Petroleum is used as petroleum products blending component, replaces the raw material for petrochemical industry industry by many refineries.Therefore, First oil refining, petrochemical industry resource over all Integration are the integrated of Petroleum (including secondary operations Petroleum).
The purposes of Petroleum is many, is the primary raw material manufacturing clean gasoline, at oil in terms of petroleum refining Chemical industry aspect is to manufacture ethylene, aromatic hydrocarbons/polyester, synthesis ammonia/chemical fertilizer and the raw material of hydrogen manufacturing.In terms of quantitative relation, Petroleum makes Maximum for the quantity of oil product, secondly, aromatic hydrocarbons is less for feed ethylene.Oil product, feed ethylene, aromatic hydrocarbons material three substantially quantity ratio in the world Example is: 6.82:1:0.36.
And in an important use of straight-run naphtha, such as time as reforming raw oil, due to reforming catalyst pair Sulfur poisoning, it is therefore necessary to the sulfur content in raw material is reduced to below 0.5ppm.
Along with heaviness, the in poor quality of world's crude oil are deepened day by day, crude oil sulfur content is more and more higher, and the lightweight of high-quality is former Oil is constantly reducing.The crude oil of refinery's processing in recent years mostly is imported crude oil, and relative density increases year by year, in several years of the beginning of this century The average density of whole world refinery processing crude oil rises to about 0.8633.The problem that sulfur content is high is the most extremely serious, the current world The yield of upper sour crude oil and sour crude accounts for more than the 75% of world's crude oil total output.20th century the mid-90 whole world refinery The crude oil average sulfur content of processing is 0.9%, and the beginning of this century has increased to 1.6%.
But existing straight-run naphtha hydrofining technology for be all low sulfur product, treat with Venezuelan crude (oil) The straight-run naphtha produced for the sour crude represented, sulfur content is too high, causes desulphurizing ability limited, and catalysqt deactivation is fast. The most how straight-run naphtha process for refining is provided, can effectively the sulfur content in high-sulfur straight-run naphtha be controlled at 0.5ppm Hereinafter, to meet burning and exhausting standard, it it is a difficult problem facing of this area.
Summary of the invention
It is an object of the invention to propose a kind of straight-run naphtha hydrodesulfurization process for refining, this technique can be by straight run stone Total sulfur content in cerebrol is reduced to below 0.5ppm, to meet following process requirement and to meet burning and exhausting standard.
For reaching this purpose, the present invention by the following technical solutions:
A kind of straight-run naphtha hydrofining technology, described technique uses fixed bed reactors, fills in fixed bed reactors Being filled with hydrogenation catalyst, described catalyst includes carrier and active component.
Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+MCM-41.
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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4's Mixture.
The reaction condition of described fixed bed reactors is: reaction temperature is 250-300 DEG C, and hydrogen dividing potential drop is 1.5-2.0MPa, Hydrogen to oil volume ratio 80-150, volume space velocity 9-14h-1。
High-sulfur straight-run naphtha of the present invention refers to the straight-run naphtha that sulfur content is more than 1000ppm, such as breathes out The smooth straight-run naphtha of saxophone, its sulfur content is up to 2400ppm.
MCM-41 is ordered into mesoporous material, and its duct is that six side's ordered arrangement, size are uniform, aperture size can with synthesis time The difference adding directed agents and synthetic parts changes between 1.5～10nm, lattice parameter about 4.5nm, specific pore volume about 1mL/g, MCM-41 uniform pore diameter, has higher specific surface area (1000m2/ g) and big adsorption capacity (0.7mL/g), the most organic The free diffusing of molecule.The present invention through in numerous mesoporous materials, such as MCM-22, MCM-36, MCM-48, MCM-49, MCM56, carries out contrast test selection, finds that only MCM-41 can reach the goal of the invention of the present invention, and other mesoporous materials are all Having such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, therefore the present invention selects to use MCM-41 is as carrier basis.
The acidity of silica MCM-41 own is the most weak, is directly used as catalyst activity relatively low.Therefore, it is changed by the present invention Property, to increase its catalysis activity.The approach that MCM-41 mesopore molecular sieve is modified is by the present invention: in MCM-41 building-up process, Add Co2+Saline solution, before MCM-41 framework of molecular sieve structure is formed, by isomorphous substitution by Co2+Replace part skeleton unit Element thus embed in the skeleton of molecular sieve, improve on the whole MCM-41 mesopore molecular sieve catalysis activity, absorption and heat Mechanical stability can wait.
Although the method being modified MCM-41 mesopore molecular sieve or approach are a lot, inventor finds, the present invention urges Agent can only use doping Co2+MCM-41 could realize sulfur content as carrier and control and the balance of loss of octane number, invention People has attempted adulterating in MCM-41: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all can not Realize described effect.Exchanged Cu by ion with another modified approach of inventor2+It is supported on MCM-41 inner surfaces of pores to compare, The isomorphous substitution approach of the present invention is more stable.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 MCM-41 must control within specific content range, and its doping is with weight Meter, for the 0.56%-0.75% of MCM-41 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 straight-run naphtha desulfurized effect.More pleasurable , work as Co2+When doping in MCM-41 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, works as drafting With Co2+Doping is transverse axis, and during curve chart with target desulfurized effect as the longitudinal axis, in this content range, sulfur content can control in pole Within the scope of low, 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 MCM-41 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 straight-run naphtha can be realized and control at below 10ppm and denitrification ability notable.It is to say, 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 possess Cooperative effect.Outside this molar ratio range, or omit or replace any one component, all can not realize collaborative effect Should.
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 Cr2O3、ZrO2、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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) the catalyst facilitation to the present invention Substantially, its hydrothermal stability can be significantly improved, and improve its anti-coking deactivation, thus improve its service life.
Described Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that Cr2O3、ZrO2、 CeO2、V2O5And NbOPO4Each respective content reaches effective dose.Preferably, the Cr that the present invention uses2O3、ZrO2、 CeO2、V2O5And NbOPO4Respective 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 260-280 DEG C, and hydrogen dividing potential drop is 1.8- 2.0MPa, hydrogen to oil volume ratio 100-150, volume space velocity 9-12h-1。
Preferably, described technological process includes, raw material, after filter, surge tank, is pumped into heat exchanger by feed pump and become Product heat exchange, is mixed to form hydrogen oil mixture, again enters heating furnace with after product heat exchange with recycle hydrogen and new hydrogen after heat exchange, Being heated to reaction temperature and enter hydrofining reactor (fixed bed reactors), hydrogen oil mixture is made at catalyst in the reactor Under with, carrying out the reaction such as hydrodesulfurization, denitrogenation, product is through heat exchange more water cooled to predetermined temperature, enters high pressure and separates Device, high-pressure separator top gas phase returns recycle hydrogen surge tank as recycle hydrogen, and oil phase enters low pressure separator, low pressure separator The generation oil that bottom is drawn enters stripper after product heat exchange, and tower top oil gas enters separatory tank after air cooling, water-cooled and obtains To lighter hydrocarbons, stripping tower bottom obtains straight-run naphtha.
Preferably, described fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
The hydrofining technology of the present invention is by choosing specific catalyst, and described catalyst is by mixing hetero atom Co2+ MCM-41 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 Cr2O3、ZrO2、CeO2、V2O5With NbOPO4Mixture so that this catalyst produce cooperative effect, the hydrodesulfurization to straight-run naphtha can control to contain at total sulfur Total nitrogen content in straight-run naphtha, less than 0.5ppm, is controlled within 10ppm by amount simultaneously.
Detailed description of the invention
The hydrofining technology of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Co2+MCM-41, Co2+Doping in MCM-41 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 Become, beds is set to 3 layers, reaction bed temperature with UGU808 type temp controlled meter measure, raw material straight-run naphtha by The double plunger micro pump that Beijing Satellite Manufacturing Factory manufactures carries continuously, and hydrogen is supplied by gas cylinder and uses Beijing Sevenstar-HC D07-11A/ZM mass-flow gas meter coutroi velocity, loaded catalyst is 2kg.Reacted product cools down through water-bath room temperature Laggard row gas-liquid separation.
Raw materials used for Kazakhstan's straight-run naphtha, its sulfur content is up to 2400ppm.
Controlling reaction condition is: temperature 270 DEG C, hydrogen dividing potential drop 2.0MPa, hydrogen to oil volume ratio 150, volume space velocity 10h-1。
Testing final product, total sulfur content is reduced to 0.5ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Co2+MCM-41, Co2+Doping in MCM-41 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, total sulfur content is reduced to 0.4ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Testing final product, total sulfur content is reduced to 22ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated MCM-41, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 31ppm.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 23ppm.
Comparative example 4
By the Co in embodiment 12+Doping in MCM-41 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 27ppm.
Comparative example 5
By the Co in embodiment 12+Doping in MCM-41 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 28ppm.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion MCM-41 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 MCM-41 carrier and catalyst other Possessing cooperative effect between component, described hydrofining technology creates unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, total sulfur content is reduced to 31ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 37ppm.
Above-described embodiment and comparative example 6-7 explanation, several active component of catalyst of the hydrofining technology 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 Cr in catalyst2O3、ZrO2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 2%, 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 13.4%.
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 2.4%.
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 1.6%.
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 (7)

1. a high-sulfur straight-run naphtha hydrofining technology, described technique uses fixed bed reactors, in fixed bed reactors Being filled with hydrogenation catalyst, described catalyst includes carrier and active component, it is characterised in that
Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+MCM-41,
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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixing Thing,
The reaction condition of described fixed bed reactors is: reaction temperature is 250-300 DEG C, and hydrogen dividing potential drop is 1.5-2.0MPa, hydrogen oil Volume ratio 80-150, volume space velocity 9-14h-1。
2. hydrofining technology as claimed in claim 1, it is characterised in that hetero atom Co2+Doping be MCM-41 weight 0.63%-0.72%.
3. hydrofining technology as claimed in claim 1, it is characterised in that the total content of described active component is carrier MCM- The 3-12% of 41 weight, preferably 5-10%.
4. hydrofining technology 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. hydrofining technology as claimed in claim 1, it is characterised in that the reaction condition of described fixed bed reactors is: Reaction temperature is 260-280 DEG C, and hydrogen dividing potential drop is 1.8-2.0MPa, hydrogen to oil volume ratio 100-150, volume space velocity 9-12h-1。
6. hydrofining technology 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.
7. hydrofining technology as claimed in claim 1, it is characterised in that Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Each Content be respectively the 1-7%, preferably 2-4% of carrier quality.
CN201610692079.8A 2016-08-19 2016-08-19 A kind of straight-run naphtha hydrofining technology Pending CN106190260A (en)

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Application publication date: 20161207