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CN104946299A - Wax oil circulating hydrogenation method as well as design method and application thereof - Google Patents

Wax oil circulating hydrogenation method as well as design method and application thereof Download PDF

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Publication number
CN104946299A
CN104946299A CN201510324805.6A CN201510324805A CN104946299A CN 104946299 A CN104946299 A CN 104946299A CN 201510324805 A CN201510324805 A CN 201510324805A CN 104946299 A CN104946299 A CN 104946299A
Authority
CN
China
Prior art keywords
hydrogenation
raw material
wax oil
slurry
bed system
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510324805.6A
Other languages
Chinese (zh)
Inventor
李苏安
邓清宇
王坤朋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZHONGKE CHUANGYI TECH DEVELOPMENT Co Ltd
Original Assignee
ZHONGKE CHUANGYI TECH DEVELOPMENT Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ZHONGKE CHUANGYI TECH DEVELOPMENT Co Ltd filed Critical ZHONGKE CHUANGYI TECH DEVELOPMENT Co Ltd
Priority to CN201510324805.6A priority Critical patent/CN104946299A/en
Priority to PCT/CN2015/089854 priority patent/WO2016197476A1/en
Publication of CN104946299A publication Critical patent/CN104946299A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/24Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
    • C10G47/26Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/32Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions in the presence of hydrogen-generating compounds
    • C10G47/34Organic compounds, e.g. hydrogenated hydrocarbons

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention provides a wax oil circulating hydrogenation method as well as a design method and application thereof. The hydrogenation method comprises the following steps: mixing self-produced wax oil of a slurry bed hydrogenation reactor with partial or all raw materials to be hydrogenated, one catalyst or two catalysts to obtain raw material slurry with reduced viscosity, and enabling the raw material slurry to enter the slurry bed hydrogenation reactor for hydrogenation. The wax oil for circulating hydrogenation accounts for 4-30% by mass of the raw materials to be hydrogenated, the temperature of the raw material slurry is less than or equal to 60 DEG C and the kinematic viscosity is less than or equal to 750cSt. The method is simple and convenient to operate, automation control is convenient, the light oil yield is increased, the device operation stability is enhanced, and the repair cycle of a hydrogenation series device is prolonged.

Description

A kind of wax oil circulation method of hydrotreating and method of design thereof and purposes
Technical field
The present invention relates to a kind of wax oil circulation method of hydrotreating and method of design thereof and purposes, belong to petrochemical complex and coal chemical technology.
Background technology
In recent years, world petroleum resource worsening shortages, and the heaviness of petroleum resources and in poor quality problem are more and more obvious, but along with the quick growth of economy, society grows with each passing day to the demand of petroleum products.Heavy oil deep process technology not only effectively can utilize petroleum resources, and can improve the economic benefit of oil-processing enterprises.Current heavy oil upgrading mainly contains the techniques such as delayed coking, heavy oil fluid catalytic cracking and residual hydrogenation.The product liquid of delayed coking unit of poor quality, coke yield is high.The requirement of heavy oil fluid catalytic cracking to raw material is higher, cannot process residual oil inferior.Residual hydrogenation can process the poor residuum of high-sulfur, high carbon residue, high metal, improves the quality of liquid yield and product liquid simultaneously.Residue fixed-bed hydrogenation requires higher to the heavy metal content in residual oil, and residual oil slurry bed system hydrogenation effectively can remove sulphur, nitrogen and heavy metal in residual oil.
Meanwhile, China is the oil-poor country of a rich coal, in order to tackle current contradiction between oil supply and demand and implement energy-saving and emission-reduction policy, fully and clean utilization coal resources are important selections of guarantee energy security.Adopt gelatin liquefaction technology and oily coal mixing technology, refining coal and poor residuum are the important method solving China's energy dilemmas.Slurry bed system hydrogenation technique is the mixing core place of DCL/Direct coal liquefaction and oily coal.
Slurry bed system hydrogenator, except generating lightweight oil, also can produce the heavy wax oil of not thoroughly cracking.It is process in hydrogenation unit wax oil all being sent into next stage that some documents and patent mention way, does the operational load that can not increase paste state bed reactor like this.But no matter practical situation are is mixing at heavy-oil hydrogenation, oily coal or in direct coal liquefaction process, the mobility of the raw material of process is all poor, raw material is easily trapped in pipeline or reactor inlet and affects the progress of reaction.
Summary of the invention
Based on problems of the prior art, the invention provides a kind of wax oil circulation method of hydrotreating.Be used for self-produced wax oil to modulate the raw material or catalyzer for the treatment of hydrogenation, while reducing raw material viscosity, achieve the circulation hydrotreatment of wax oil.
Technical scheme of the present invention:
A kind of wax oil circulation method of hydrotreating, the self-produced wax oil that it is characterized in that slurry bed system hydrogenation reaction and the raw material and/or catalyst mix of partly or entirely treating hydrogenation obtain the raw material slurry that viscosity reduces, and described raw material slurry enters described slurry bed system hydrogenator circulation hydrogenation.
Treat described in preferred described wax oil accounts for that the massfraction of the raw material of hydrogenation is 4-30wt%.
Described raw material slurry is not when temperature is higher than 60 DEG C, and kinematic viscosity is not higher than 750cSt.
Preferably, the part of the self-produced wax oil of slurry bed system hydrogenation reaction with partly or entirely treat the raw material of hydrogenation or catalyzer one or both be mixed to get the raw material slurry that viscosity reduces, described raw material slurry enters described slurry bed system hydrogenator circulation hydrogenation; Another part flows in the equipment blocked because of coking or discontinuous flow in slurry bed system hydrogenation reaction technique or pipeline or interface for back flushing tamper.
Equipment preferably for back flushing comprises slurry bed system hydrogenator, vacuum furnace and/or separator.
Wherein said slurry bed system hydrogenator comprises reactor tower body, feed distributor and circulation bubble-cap, and back flushing point comprises the plate face of the grid distributor of described feed distributor and described circulation bubble-cap place.Described circulation bubble-cap place is rinsed by the flushing pipe be positioned on described reactor tower body, and described duct height is greater than or equal to described circulation height of bubble cap.
Wherein said vacuum furnace is vertical tubular structure, and back flushing point is arranged on vacuum furnace ingress, rinses the coking in decompression boiler tube.
Wherein said separator comprises the gaseous phase outlet on top and the liquid-phase outlet of bottom, and is taper bottom it, and back flushing point is the scarp of described gaseous phase outlet both sides and pyramidal structure.
The preferred interface for back flushing and pipeline comprise because coking or interruption use and produce the pipeline in dead band, thief hatch and instrumentation tap, the by-pass of variable valve, pump etc.
The purposes of above-mentioned wax oil circulation method of hydrotreating, for heavy oil hydrogenation process, direct coal liquefaction process and oily coal calendering process, described heavy oil comprises one or more combinations in heavy crude, residual oil, catalytic slurry, de-oiled asphalt and coal tar, described coal comprises one or more combinations in brown coal, bituminous coal, non-caking coal, and in described oily coal calendering process, oil is 97:3-40:60 with the proportional range of coal.
Also comprise the method for design of above-mentioned wax oil circulation method of hydrotreating.
Technique effect of the present invention:
A kind of wax oil circulation method of hydrotreating of the present invention, utilize the good feature of the mobility of wax oil, part or all of wax oil self-produced for hydrogenation technique is mixed with the raw material of poor mobile performance or the part or all of of catalyzer, the flowing property of raw material slurry formed significantly improves, viscosity reduces, and solves that the more oily coal of solids content in prior art is mixing, the problem of Flow of Goods and Materials performance difference in heavy-oil hydrogenation, direct coal liquefaction process.The raw material slurry modulated is for the hydrogenation that circulates, and wax oil is reaction, hydrogenation, cracking further together with raw material, improves light oil yield.
When the add-on of wax oil is at 5-20wt%, total viscosity of raw material can reduce 5-25 doubly.Significantly improve the mobility of raw material, solve prior art Raw and be easily trapped in pipeline or reactor inlet and the problem making to affect extent of reaction.
Accompanying drawing explanation
Fig. 1 is the wax oil circulation hydrogenation schematic diagram of the embodiment of the present invention 1;
Fig. 2 is the wax oil back flushing schematic diagram of embodiment 2 vacuum furnace.
Drawing reference numeral:
1-catalyzer; 2-coal dust; 3-residual oil; 4-circulation wax oil; 5-catalyst material configuration-system; 6-vacuum distillation tower; 7-wax oil recycle pump; 8-vacuum furnace; 9-vacuum furnace flush points.
Embodiment
For setting forth specific features of the present invention further, will be illustrated in conjunction with specific embodiments.
Embodiment 1
The wax oil of the present embodiment is the product of slurry bed system oil coal calendering process, as shown in Figure 1, the self-produced circulation wax oil 4 of slurry bed system hydrogenation is extracted out by wax oil recycle pump 7 from vacuum distillation tower 6 end and is delivered to catalyst material configuration-system 5, and treats that the coal dust 2 of hydrogenation, residual oil 3 and catalyzer 1 mix formation raw material slurry.Raw material slurry and hydrogen are blended in described raw materials furnace and heating and heat up, and repeat to enter in above-mentioned slurry bed system hydrogenation reaction equipment series and carry out circulation hydrogenation reaction.
Described wax oil except reaching the object of cracking again, can also reduce oily coal mixing in heavy oil and the viscosity of solid coal raw material, improve the mobility of raw material, make raw material smoothly by various pipeline and device.Relative to the raw material not adding self-produced wax oil, total viscosity drop, to below 500cSt, approximately reduces 5-15 doubly left and right, hydrogenation reaction is carried out smoothly, accelerates extent of reaction.
Embodiment 2
The wax oil source of the present embodiment is with embodiment 1, wherein the wax oil of 80% is through the process circulation hydrogenation as embodiment 1, the wax oil of other 20% is used for back flushing, be illustrated in figure 2 the wax oil back flushing schematic diagram of vacuum furnace, vacuum furnace flush points 9 is set in the ingress of vacuum furnace 8 and introduces recoil washing oil, coking mainly occurs in decompression boiler tube, and when detecting that the coking material in boiler tube starts wax oil back-purge system when needing to rinse, state is intermittent operation.The wax oil of back flushing rinses from bottom to top, and the pressure rinsing wax oil comes from recycle pump, without the need to arranging backwashing pump separately.
Purge oil wax oil in embodiment 2 also can replace with the mixture of diesel oil or wax oil and diesel oil.Only diesel oil is processed oil, and developing cost is high.Except vacuum furnace, can also be the miscellaneous equipment or pipeline or interface that use in heavy oil hydrogenation process, direct coal liquefaction process and oily coal calendering process, adopt continuous flushing operation or intermittent operation according to practical situation.
Conclusion:
As can be seen from above-described embodiment, a kind of wax oil circulation method of hydrotreating of the present invention, be applied to the hydrogenation process of the paste state bed reactor in heavy oil hydrogenation process, direct coal liquefaction process and oily coal calendering process, the self-produced wax oil circulation hydrogenation of hydrogenation reaction serves the dual purpose reducing solid material viscosity and hydrocracking again.Present method is easy and simple to handle, and is convenient to Automated condtrol, improves light oil yield.In addition, for the more thus easier coking of solid heavier feeds content, blocking in reaction mass heavy crude, poor residuum hydrogenation or oily coal is mixing or direct coal liquefaction process, a part of wax oil can also be transported to by recycle pump the position easily producing coking or blocking and carry out back flushing, not only self-produced wax oil is recycled more fully, the problem of coking and blocking can also be solved.
The foregoing is only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses, change can be expected easily or replace, such as, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.

Claims (10)

1. a wax oil circulation method of hydrotreating, the self-produced wax oil that it is characterized in that slurry bed system hydrogenation reaction with partly or entirely treat the raw material slurry that the raw material of hydrogenation or the mixture of raw material and catalyzer are mixed to get viscosity and reduce, described raw material slurry enters slurry bed system hydrogenator circulation hydrogenation.
2. a kind of wax oil circulation method of hydrotreating according to claim 1, is characterized in that described wax oil treats that the massfraction of the raw material of hydrogenation is 4-30wt% described in accounting for.
3. a kind of wax oil circulation method of hydrotreating according to claim 1, it is characterized in that described raw material slurry is not when temperature is higher than 60 DEG C, kinematic viscosity is not higher than 750cSt.
4. according to the purposes of the arbitrary described a kind of wax oil circulation method of hydrotreating of claim 1-3, it is characterized in that for heavy oil hydrogenation process, direct coal liquefaction process and oily coal calendering process, described heavy oil comprises one or more combinations in heavy crude, residual oil, catalytic slurry, de-oiled asphalt and coal tar, described coal comprises one or more combinations in brown coal, bituminous coal, non-caking coal, and in described oily coal calendering process, oil is 97:3-40:60 with the proportional range of coal.
5. a wax oil circulation method of hydrotreating, the part that it is characterized in that the self-produced wax oil of slurry bed system hydrogenation reaction with partly or entirely treat the raw material of hydrogenation or catalyzer one or both be mixed to get the raw material slurry that viscosity reduces, described raw material slurry enters described slurry bed system hydrogenator circulation hydrogenation; Another part flows to the equipment of the blocking in slurry bed system hydrogenation reaction technique or pipeline or interface for back flushing tamper.
6. method according to claim 5, is characterized in that comprising slurry bed system hydrogenator, vacuum furnace and separator for the equipment of back flushing.
7. method according to claim 6, is characterized in that described slurry bed system hydrogenator comprises reactor tower body, feed distributor and circulation bubble-cap, and back flushing point comprises the plate face of the grid distributor of described feed distributor and described circulation bubble-cap place.
8. a kind of slurry bed system back-flushing method according to claim 6, is characterized in that described vacuum furnace is vertical tubular structure, back flushing point be perpendicular to described vacuum furnace bottom upwards, rinse the tubular structure in described body of heater.
9. a kind of slurry bed system back-flushing method according to claim 6, it is characterized in that described separator comprises upper gaseous phase outlet and bottom heavy constituent discharge port, and be pyramidal structure bottom it, back flushing point is two lateral incline of described gaseous phase outlet both sides and described pyramidal structure.
10. a wax oil circulation hydrogenation method of design, the self-produced wax oil that it is characterized in that designing slurry bed system hydrogenation reaction with partly or entirely treat the raw material slurry that the raw material of hydrogenation or the mixture of raw material and catalyzer are mixed to get viscosity and reduce, described raw material slurry enters slurry bed system hydrogenator circulation hydrogenation.
CN201510324805.6A 2015-06-12 2015-06-12 Wax oil circulating hydrogenation method as well as design method and application thereof Pending CN104946299A (en)

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CN201510324805.6A CN104946299A (en) 2015-06-12 2015-06-12 Wax oil circulating hydrogenation method as well as design method and application thereof
PCT/CN2015/089854 WO2016197476A1 (en) 2015-06-12 2015-09-17 Wax oil circulating hydrogenation method, design method therefor, and use thereof

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109759395A (en) * 2019-03-12 2019-05-17 胜帮科技股份有限公司 A kind of backwash technique and back-purge system for catalytic hydrogenation reaction system

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CN1609170A (en) * 2003-10-24 2005-04-27 中国石油化工股份有限公司 Method of prolonging service life of heavy oil and residual oil hydrogenating catalyst
CN101396647A (en) * 2007-09-29 2009-04-01 中科合成油技术有限公司 Gas-liquid-solid three-phase suspended bed reactor for f-t synthesis and use thereof
CN102816587A (en) * 2011-06-07 2012-12-12 中国石油化工集团公司 Full wax oil under-refluxing overheat-removing and circulation ratio quantitative controlling coking-retarding apparatus and method
CN104119954A (en) * 2013-04-23 2014-10-29 中国石油化工股份有限公司 Heavy raw oil treatment method
CN104629798A (en) * 2015-02-06 2015-05-20 北京中科诚毅科技发展有限公司 Oil and coal hybrid hydrogenation refining technique and equipment

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Publication number Priority date Publication date Assignee Title
CN1297980A (en) * 1999-12-01 2001-06-06 中国石油化工集团公司 Dalayed coking method of deoiled asphalt
CN1609170A (en) * 2003-10-24 2005-04-27 中国石油化工股份有限公司 Method of prolonging service life of heavy oil and residual oil hydrogenating catalyst
CN101396647A (en) * 2007-09-29 2009-04-01 中科合成油技术有限公司 Gas-liquid-solid three-phase suspended bed reactor for f-t synthesis and use thereof
CN102816587A (en) * 2011-06-07 2012-12-12 中国石油化工集团公司 Full wax oil under-refluxing overheat-removing and circulation ratio quantitative controlling coking-retarding apparatus and method
CN104119954A (en) * 2013-04-23 2014-10-29 中国石油化工股份有限公司 Heavy raw oil treatment method
CN104629798A (en) * 2015-02-06 2015-05-20 北京中科诚毅科技发展有限公司 Oil and coal hybrid hydrogenation refining technique and equipment

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109759395A (en) * 2019-03-12 2019-05-17 胜帮科技股份有限公司 A kind of backwash technique and back-purge system for catalytic hydrogenation reaction system

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