CN1488713A - Hydrocarbon hdyrotreating method - Google Patents
Hydrocarbon hdyrotreating method Download PDFInfo
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- CN1488713A CN1488713A CNA021331375A CN02133137A CN1488713A CN 1488713 A CN1488713 A CN 1488713A CN A021331375 A CNA021331375 A CN A021331375A CN 02133137 A CN02133137 A CN 02133137A CN 1488713 A CN1488713 A CN 1488713A
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Abstract
The present invention discloses a gas-liquid counter-current hydrocarbon hydrogenation treatment method, which is characterized by that the hydrogenation treatment reactor is graded-loaded by adoting different catalysts, the bottom portion of said reactor is loaded by high-activity catalyst easy of sulfur poisoning, said catalyst uses noble metal or reducing metal, etc. as active component generally, and has the higher functions of removing sulfur, denitrogenation and aromatic saturation, and the top portion of said reactor is loaded by general non-noble metal sulfide catalyst. As compared with existent technology said invention can greatly raise reaction activity of whole system and prolong the service life of the catalyst, and can be used to make hydrogenated treatment process of diesel oil, VGO, lubricating oil and ethylene steam cracked tail oil.
Description
1, technical field
The present invention relates to a kind of hydrocarbon hydroprocessing technique, the improving one's methods of a kind of specifically gas, liquid, solid three-phase counter-current hydrogenation technique.
2, background technology
At present, more employing hydrogen of hydrocarbons hydrogenation technology and hydrocarbon raw material also flow to current downflow, contact and carry out the fixed bed hydrogenation technology of catalyzed reaction with beds, but the hydrogen sulfide that generates in the reaction process, ammonia and hydro carbons small molecules can further react this technology, as desulfurization, denitrogenation, aromatic hydrocarbons is saturated and hydrocracking etc. has bigger restraining effect, and speed of reaction is descended.Therefore segmentation hydrogenation and/or gas-liquid counter current hydrogenation technique more and more become the emphasis of refining of petroleum area research, and the hydrogen dividing potential drop that this technology can augmenting response is in time removed the H that reaction produces
2S, NH
3
USP 5,985, and 135 propose the two-stage hydrogenation method of a kind of up-flow reactor and downflow reactor, wherein connect a stripper plant in the first stage reactor back.But this technology does not still fundamentally solve the problem that removes of obnoxious flavour, and investment is bigger.In order fundamentally to solve the problem that removes of obnoxious flavour, more oil refinery company is at research gas-liquid counter current hydrogenation technique.USP 5,183, proposed the countercurrent hydrogenation purification techniques in 556, but identical with other existing counter-current operation device, the countercurrent reaction section all adopts single catalyzer, or non-noble metal sulfide catalyst or noble metal catalyst.This catalyst loading scheme is not suitable for the deep desulfuration of stock oil, the processing treatment of taking off virtue.Reason is: the big more speed that it further reacts of stock oil reaction depth is more little, certainly will need highly active catalyzer in order to reach product requirement, as the saturated noble metal catalyst that preferably uses of aromatic hydrocarbons, if but in the whole beds of counter-current operation, used high activated catalyst such as noble metal catalyst, the catalyzer on countercurrent reaction section top could easily make catalyst deactivation because of the high hydrogen sulfide dividing potential drop.Otherwise, can reduce because of the low in hydrogen sulphide dividing potential drop easily makes catalyzer lose the sulphur activity in the bottom of countercurrent reaction section, until there not being activity if whole adverse current beds uses conventional base metal sulfide catalyst.
3, summary of the invention
In order to improve the deficiency of existing hydrocarbon raw material gas-liquid counter current hydrogenation technique, the present invention provides a kind of gas-liquid counter current hydrogenation technique of catalyzer grading loading from the catalyst loading aspect, and technology of the present invention has the saturated function of higher desulfurization, denitrogenation and aromatic hydrocarbons.
Concrete technical scheme of the present invention is as follows: under the hydrocarbon raw material hydroprocessing condition, the reverse beds that passes through of hydrogen and hydrocarbon raw material, and (1) load the highly active catalyzer of easy sulfur poisoning in the bottom of gas, liquid counter-current operation reactor, as the nitride of as-reduced metal catalyzer, noble metal catalyst, molybdenum nickel tungsten etc. or carbide catalyst etc., also can be the base metal sulfide catalyst that is difficult for losing sulphur, form the high activated catalyst bed.(2) from the hydrocarbon raw material oil-in, the conventional base metal sulfide catalyst of conversion zone filling along the paramount active catalyst bed of liquid phase feed oil flow direction is used to form the low catalytic activity beds that is difficult for sulfur poisoning.
The present invention is by impurities concentration distribution and variations such as hydrogen sulfide in investigation hydro carbons gas, the liquid countercurrent reaction procedures system, use catalyzer of different nature in different zones, optimized the service area of different activities catalyzer, different catalysts is moved under its top condition, both improved the activity of whole beds, and the more important thing is to have prolonged the catalyst life cycle.
4, embodiment
The present invention is by the activity of such catalysts grating, increased the whole catalytic activity of counter-current operation device and prolonged the running period of catalyzer.Have stronger hydrogenating desulfurization, hydrodenitrification, the saturated aromatic hydrocarbons of hydrogenation and/or hydrocracking function at the catalyzer described in (1).This class catalyzer generally all is with porous inorganic oxide such as aluminum oxide, silicon oxide, aluminium oxide-silicon oxide and/or zeolite molecular sieve, is carrier as super steady Y, β, X type, Y type and mordenite etc.Active ingredient is precious metals such as the nitride of the as-reduced metal of group vib and/or VIII family or its sulfide, precious metals such as Pt, Pd, molybdenum nickel tungsten etc. or carbide.
Be conventional catalyst than low activity catalyst described in (2) with hydrogenating desulfurization, hydrodenitrification, the saturated aromatic hydrocarbons of hydrogenation and/or hydrocracking function.This class catalyzer generally all is with porous inorganic oxide such as aluminum oxide, silicon oxide, aluminium oxide-silicon oxide and/or zeolite molecular sieve, is carrier as super steady Y, β, X type, Y type and mordenite etc.The oxide compound of group vib and/or VIII family metal oxide such as W, Mo, Co, Ni etc. is an active ingredient, optionally adds the catalyzer of other various auxiliary agents such as P, Si, elements such as F, B.
Catalyzer can be single a kind of catalyzer in above-mentioned (1) and (2), also can be according to the catalyzer gradation composition by several different performances of the difference of sulphur content in the logistics.
High activated catalyst bed of the present invention generally is whole counter-current reactor liquid phase feed oil reacting section catalyst bed volume, be high reactivity with than 20%～95%, preferred 30%～80% of low activity catalyst bed volume sum.The size of its volume mainly is provided with according to the character and the reactivity worth of reaction raw materials.Come out if stock oil is difficult for stripping at the gases such as hydrogen sulfide that generate than the low activity catalyst bed, poison for avoiding the high activated catalyst bed, the catalyzer that can load one section inert filler between two beds or be difficult for inactivation is as transition layer.Described operational condition is the processing condition that are fit to hydrocarbons hydrogenation, and operation condition is generally: temperature of reaction 240-427 ℃; Reaction pressure is 1.0-20.0MPa; Hydrogen to oil volume ratio is 50-2000; Volume space velocity is 0.1-7.5h during liquid
-1Concrete scope is relevant with stock oil boiling range scope, character and the processing purpose of being processed.Temperature, pressure, the hydrogen-oil ratio of general light ends hydrotreatment are lower, and air speed is bigger, and the temperature of heavy ends hydrotreatment, pressure, hydrogen-oil ratio are higher, and air speed is less.
The present invention is applicable to the hydrocracking of all kinds of weight distillates and residual oil, be particularly useful for temperature of reaction and be positioned at light, heavy distillate hydrotreatment within the stock oil boiling range, as diesel oil (180～390 ℃) hydrogenating desulfurization, take off the hydrotreatment processes such as raw material that virtue, bright stock or hydrogenation are produced the hydrocracking of cuts such as lubricant base, VGO, ethene steam cracking tail oil (200～465 ℃) hydrogenation (decolouring) or produced industrial chemicals, production spinning asphalt, needle coke.Also be applicable to similar procedure such as chemical industry environmental protection behind the catalyzer that the inventive method replacing suits, as MTBE production and sulfide hydrogen wastewater oxidation treatment process etc.
Following embodiment further specifies of the present invention, and it does not limit use range of the present invention.
Embodiment 1～6 and comparative example 1～4
The main hydrogenation effect of investigating hydrogenation technique of the present invention and existing countercurrent hydrogenation technology of this test.With diesel fuel desulfurization, to take off virtue be example.The catalyst system therefor physico-chemical property sees Table-1 in this test, and stock oil character sees Table-2.Hydrogenation reaction is all carried out in this test on the long run test device.Operational condition is a hydrogen to oil volume ratio: 350, and reaction pressure: 6.0MPa, temperature of reaction: 360 ℃, air speed: 2.0h
-1Catalyzer among the embodiment is: non-precious metal catalyst (A): and noble metal catalyst (B) (V: V)=V1: V2.Embodiment sees Table-3, and comparative example sees Table-4.
Table-1 catalyzer physico-chemical property
| Project | Than the low activity catalyst high activated catalyst |
| Numbering | ???????A????????????B??????????????C |
| Catalytic active component | Mo, W (sulfide) (former Pt, Pd (atomic ratio CoMoN x(Co with son than 1: 1) 1: 1) Mo atomic ratio 1: 3) |
| Shape | Trifolium bar shaped bar shaped |
| Diameter, mm | ?????2.08??????????1.2???????????1.2 |
| Specific surface area, m 2/g | ?????125???????????140???????????158 |
| Metal component, w% | ?????29????????????0.8???????????26 |
| Carrier | Contain silica alumina USY molecular sieve 4w% aluminum oxide |
Table-2 stock oil main character
| Density, kg/m 3?0.8824 |
| S，w％???????6979 |
| N，w％???????1014 |
| Aromatic hydrocarbons, w% 48.6 |
| Boiling range, ℃ |
| IBP～EBP?????185～373 |
Table-3 embodiment experimental results
| Embodiment 123456 |
| V1∶V2?????????8∶2??????7∶3??????6∶4?????5∶5??????4∶6??????3∶7 |
| Generate oil nature |
| Density, kg/m 3???0.8356????0.8356????0.8357???0.8358????0.8358????0.8359 |
| S，w％?????????19.4??????18.2??????15.5?????12.2??????11.6??????10.9 |
| N，w％??????1.0???????1.0???????1.0???????1.0???????1.0???????1.0 |
| Aromatic hydrocarbons, w% 16.2 14.2 13.2 11.3 10.1 9.8 |
| Boiling range ℃ |
| IBP～EBP????204～362??205～363??207～364??208～364??209～366??211～368 |
Table-4 comparative example experimental results
| Comparative example 1234 |
| Temperature of reaction, ℃ 350 360 360 370 |
| Catalyst B B A A |
| Generate oil nature |
| Density, kg/m 3????0.8361????0.8359????0.8356??????0.8352 |
| S，w％??????????14.3??????10.2??????20.5????????17.2 |
| N，w％??????????1.0???????1.0???????3.8?????????2.4 |
| Aromatic hydrocarbons, w% 11.6 9.2 18.2 16.6 |
| Boiling range, ℃ |
| IBP～EBP????????214～371??212～369??204～362????201～357 |
By experimental result as seen, hydrogenation effect of the present invention is far longer than single base metal sulfide catalyst effect, and is suitable with single noble metal catalyst.
Embodiment 7～12 and comparative example 4～8
The main hydrogenation effect of investigating hydrogenation technique of the present invention and existing countercurrent hydrogenation technology of this test.With diesel fuel desulfurization, to take off virtue be example.The catalyst system therefor physico-chemical property sees Table-1 in this test, and stock oil character sees Table-2.Hydrogenation reaction is all carried out in this test on the long run test device.Operational condition is a hydrogen to oil volume ratio: 350, and reaction pressure: 6.0MPa, temperature of reaction: 360 ℃, air speed: 2.0h
-1Catalyzer among the embodiment is: non-precious metal catalyst (A): and metal nitride catalyst agent (C) (V: V)=V1: V2.Embodiment sees Table-5, and comparative example sees Table-6.
Table-5 embodiment experimental results
| Embodiment 789 10 11 12 |
| V1∶V2?????????8∶2??????7∶3??????6∶4??????5∶5????????4∶6????????3∶7 |
| Generate oil nature |
| Density, kg/m 3???0.8356????0.8356????0.8357????0.8358??????0.8358??????0.8359 |
| S，w％?????????19.9??????18.7??????15.9??????12.5????????11.9????????11.3 |
| N，w％?????????1.0???????1.0???????1.0???????1.0?????????1.0?????????1.0 |
| Aromatic hydrocarbons, w% 16.8 14.6 13.8 11.7 10.8 10.2 |
| Boiling range ℃ |
| IBP～EBP???????204～362??205～363??207～364??208～365????209～367????211～368 |
Table-6 comparative example experimental results
| Comparative example 5678 |
| Temperature of reaction, ℃ 350 360 360 370 |
| Catalyzer C C A A |
| Generate oil nature |
| Density, kg/m 3????0.8360????0.8359????0.8356????0.8352 |
| S，w％??????????14.7??????10.9??????20.5??????17.2 |
| N.w％???????????1.0???????1.0???????3.8???????2.4 |
| Aromatic hydrocarbons, w% 12.3 9.7 18.2 16.6 |
| Boiling range, ℃ |
| IBP～EBP????????213～370??212～369??204～362??201～357 |
By experimental result as seen, hydrogenation effect of the present invention is far longer than single base metal sulfide catalyst effect, and is suitable with single metal nitride catalyst agent.
Embodiment 13～14 and comparative example 9～11
The main catalyst stability of investigating existing countercurrent hydrogenation technology and hydrogenation technique of the present invention of this test.The kind of catalyzer is embodiment 1～12 and comparative example 1～8 roughly the same, and catalyst loading of the present invention is: A: B=6: 4, and A: C=6: 4.Temperature of reaction is 360 ℃, and air speed is 2.0h
-1, hydrogen pressure is 6.0MPa, hydrogen-oil ratio is 350.Device running 500 hours.Test-results sees Table-7.
Table-7 stability test results
| Embodiment 13 embodiment 14 comparative examples 9 comparative examples 10 comparative examples 11 |
| Catalyzer A B of the present invention C |
| Generate oil nature |
| Density, kg/m 3?0.8357????0.8359????0.8543????0.8581????0.8554 |
| S，w％???????15.5??????17.5??????350???????482???????378 |
| N，w％???????1.0???????1.0???????58????????72????????64 |
| Aromatic hydrocarbons, w% 13.2 15.2 43.3 40.4 43.9 |
| Boiling range ℃ |
| IBP～EBP????207～364???206～363??185～369??187～370??185～370 |
By experimental result as seen, catalyst activity stability of the present invention is far longer than single catalyst loading scheme.
Claims (10)
1, a kind of hydrocarbon hdyrotreating method, under the hydrocarbon raw material hydroprocessing condition, the reverse beds that passes through of hydrogen and hydrocarbon raw material, it is characterized in that loading the catalyzer of easy sulfur poisoning, from the hydrocarbon raw material oil-in, along the conversion zone of the paramount active catalyst bed of liquid phase feed oil flow direction filling base metal sulfide catalyst in the bottom of gas, liquid counter-current operation reactor.
2,, it is characterized in that described easy sulfur poisoning catalyzer is selected from nitride or the carbide catalyst or the difficult base metal sulfide catalyst that loses sulphur of as-reduced metal catalyzer, noble metal catalyst, molybdenum nickel tungsten according to the described hydrocarbon hdyrotreating method of claim 1.
3,, it is characterized in that described easy sulfur poisoning support of the catalyst is selected from one or more in aluminum oxide, silicon oxide, aluminium oxide-silicon oxide and the zeolite molecular sieve according to claim 1 or 2 described hydrocarbon hdyrotreating methods.
4,, it is characterized in that described easy sulfur poisoning activity of such catalysts component is selected from the nitride or the carbide of the as-reduced metal of group vib and/or VIII family or its sulfide, Pt, Pd, molybdenum nickel tungsten according to claim 1 or 2 described hydrocarbon hdyrotreating methods.
5, according to the described hydrocarbon hdyrotreating method of claim 1, it is characterized in that described non-precious metal catalyst is a carrier with aluminum oxide, silicon oxide, aluminium oxide-silicon oxide and/or zeolite molecular sieve, be active constituent with group vib and/or VIII family metal.
6, according to the described hydrocarbon hdyrotreating method of claim 5, it is characterized in that described group vib metal is selected from W and/or Mo, the group VIII metal is selected from Co and/or Ni.
7,, it is characterized in that described easy sulfur poisoning catalyzer accounts for 20%～95% of catalyzer cumulative volume according to the described hydrocarbon hdyrotreating method of claim 1.
8,, it is characterized in that described easy sulfur poisoning catalyzer accounts for 30%～80% of catalyzer cumulative volume according to the described hydrocarbon hdyrotreating method of claim 7.
9, according to the described hydrocarbon hdyrotreating method of claim 1, it is characterized in that described hydrocarbon raw material hydroprocessing condition is: temperature of reaction 240-427 ℃, reaction pressure is 1.0-20.0MPa, and hydrogen to oil volume ratio is 50-2000, and volume space velocity is 0.1-7.5h during liquid
-1
10,, it is characterized in that described hydrocarbon raw material is selected from diesel oil, lubricating oil, VGO or ethene steam cracking tail oil according to the described hydrocarbon hdyrotreating method of claim 1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101089129B (en) * | 2006-06-16 | 2010-05-12 | 中国石油化工股份有限公司 | Process of selectively hydrogenating and desulfurizing inferior gasoline |
| CN101148607B (en) * | 2006-09-20 | 2010-08-18 | 中国石油化工股份有限公司 | Hydrocarbon hydroprocessing technique |
| CN101492605B (en) * | 2008-01-23 | 2012-11-21 | 中国石油化工股份有限公司 | Shale oil hydrogenation process |
| CN102911724A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Hydrogenation method for bio-oils blending diesels |
| CN103666554A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Hydroprocessing method for producing high quality solvent oil |
| CN103773437A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst grading method |
| CN103785441A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525549B (en) * | 2009-04-23 | 2013-07-03 | 中国海洋石油总公司 | Hydrocracking tail oil ultra-deep adsorbent desulfurizing and denitrifying method |
-
2002
- 2002-10-10 CN CN 02133137 patent/CN1236019C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101089129B (en) * | 2006-06-16 | 2010-05-12 | 中国石油化工股份有限公司 | Process of selectively hydrogenating and desulfurizing inferior gasoline |
| CN101148607B (en) * | 2006-09-20 | 2010-08-18 | 中国石油化工股份有限公司 | Hydrocarbon hydroprocessing technique |
| CN101492605B (en) * | 2008-01-23 | 2012-11-21 | 中国石油化工股份有限公司 | Shale oil hydrogenation process |
| CN102911724A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Hydrogenation method for bio-oils blending diesels |
| CN103666554A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Hydroprocessing method for producing high quality solvent oil |
| CN103666554B (en) * | 2012-09-05 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of hydroprocessing process producing high-quality solvent oil |
| CN103773437A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst grading method |
| CN103773437B (en) * | 2012-10-24 | 2016-02-10 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst grading method |
| CN103785441A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
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