CN102816592A - Method for improving reactivity of residual oil hydrotreater - Google Patents
Method for improving reactivity of residual oil hydrotreater Download PDFInfo
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- CN102816592A CN102816592A CN2011101563630A CN201110156363A CN102816592A CN 102816592 A CN102816592 A CN 102816592A CN 2011101563630 A CN2011101563630 A CN 2011101563630A CN 201110156363 A CN201110156363 A CN 201110156363A CN 102816592 A CN102816592 A CN 102816592A
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Abstract
The invention relates to a method for improving the reactivity of a residual oil hydrotreater. A feeding port is arranged on the front portion of a desulfurizer bed of the residual oil hydrotreater. Residual oil raw materials and partial furfural extract oil accounting for 1-20 wt% of the mass of the residual oil raw materials are mixed and enter a reactor with hydrogen to be contacted with catalyst, a hydrogenation reaction is conducted, and the partial furfural extract oil enters the reactor through the feeding port added on the front portion of the desulfurizer bed. Hydrogenation reaction conditions are: temperature is 300-450 DEG C, the pressure is 10-22 MPa, hydrogen-oil ratio is 300-2000, airspeed is 0.1-1, and a protective agent, a demetalization and desulfurizer are filled sequentially. Solvent refining raw oil is one or several of atmospheric third line oil, atmospheric fourth line oil, minus first line oil, minus second line oil, minus third line oil and minus fourth line oil. The method can convert extract oil into light liquid with high added value, improves liquid flow distribution state in the hydrotreater, increases impurity desorption rate, and reduces catalyst carbon deposit.
Description
Technical field
The present invention relates to a kind of method of improving residual hydrocracking device reaction performance.
Background technology
Current, oil refining processing industry in the world is being faced with the crude resources severe challenge of heaviness and poor qualityization day by day.2008,3.42 hundred million tons of crude oil in China amount of finish, wherein the heavy crude amount of finish reaches 1.37 hundred million tons, accounts for total amount more than 40%.As everyone knows, residual oil accounts for the crude oil ratio usually 45～75%, and its character significantly is inferior to the lower gas wet goods cut of boiling range, and therefore, the crude oil deep processing is made every effort to maximize the pressure of producing light-end products and industrial chemicals and just dropped on the residual oil naturally.
Residual hydrocracking and RFCC combination are the domestic residual oil lightening methods that extensively adopts at present.Residual hydrocracking can remove most carbon residue and heteroatomss such as S, N in the residual oil, its good product quality, and the clean cargo yield is high after the entering RFCC apparatus processes, and foreign matter content is low, and catalyzer agent consumption is low.
Aspect residual hydrogenation, the inactivation of raw oil character and catalyzer is two important factors of residual hydrogenation reaction.
Aspect raw oil, residual hydrogenation is the reaction of diffusion control, and the size of raw material oil viscosity and reactant molecule all has very big influence to diffusion.If can reduce the raw material oil viscosity, reduce the reactant geometrical dimension, can improve the diffusion of raw oil, promote the reaction of residual hydrogenation.
The catalyzer factor at process aspect, is mainly reflected in carbon deposit and deposition and the depositional mode of metal on catalyzer on the catalyzer to the influence of residual hydrogenation reaction.
The deposition of metal on catalyzer depends on the metal content of raw oil, is that technology is uncontrollable.But metal sedimentary mode on residual oil hydrocatalyst then can be improved through the adjustment of technology.If can make the more even of metal deposition on the catalyzer, then can alleviate the aperture and stop up, increase the diffusion of reactant in catalyst pores, improve the residual hydrogenation speed of reaction.
Carbon deposit both can influence diffusion, and the assertive evidence that can influence catalyzer again is active.As can reduce the coke content on the catalyzer, then can slow down catalyst deactivation speed, prolong operating period.
In China, solvent treatment is the main mode of lube oil finishing, furfural treatment accounts for 75.8% of all solvent refining units, accounts for throughput.Solvent treatment is raffinated oil can production high-quality lube product through post-refining, extracts oil out and belongs to high aromatic oil, and aromaticity content is higher, and the approach that is utilized effectively is less.This part oil product is generally many ring short-side chain aromatic hydrocarbons or naphthenic hydrocarbon, is not the ideal composition of lubricating oil, but comparatively desirable as thinning oil.It is lower to extract indexs such as oily heavy metal content, carbon residue out.
Summary of the invention
The purpose of this invention is to provide a kind of through in raw oil, adding the method that solvent treatment extraction oil improves raw oil character and then improves residual hydrocracking device reaction performance.
Method provided by the invention is: before residual hydrocracking device sweetening agent bed, increase an opening for feed, extract solvent treatment out oil and carry out hydrotreatment through one or two introducing residual hydrogenation equipment in the opening for feed of feed(raw material)inlet and increase.The residual hydrocracking device can be fixed bed residual hydrocracking device, upflow fixed bed residual hydrocracking device, moving-bed residual hydrocracking device; Adopt the catalyzer grading loading, filling protective material, metal remover, sweetening agent catalyzer.Residual oil can be one or both the mixture in long residuum and the vacuum residuum, and extracting oil out is the oily 1wt%～20wt% of residual oil raw material.Solvent treatment raw oil can be for atmosphere 3rd side cut oil, normal four lines oil, first vacuum side stream, second line of distillation oil, subtract third fractional oil, subtract in the four line wet goods one or more, and solvent-refined solvent can furfural, phenol, N-Methyl pyrrolidone, preferred furfural.The oily amount of introducing through two opening for feeds of extraction can be arbitrary proportion.
The condition of residual hydrocracking device is: 300 ℃～450 ℃ of temperature, pressure 10MPa～22MPa, hydrogen-oil ratio 300～2000, air speed 0.1～1, filling protective material, metal remover, the multiple catalyzer of sweetening agent.Catalyzer generally is to be carrier with porous inorganic oxide such as aluminum oxide, and group vib and VIII family metal oxide such as W, Mo, Co optionally add the catalyzer of P, Si or F auxiliary agent or/and the oxide compound of Ni is a carrier.
Because extracting oil out, solvent treatment belongs to fraction oil, lower with respect to residual oil viscosity, join in the middle of the higher residual oil of viscosity, and can effectively reduce the viscosity of residual oil.Simultaneously, have very high aromaticity because oil is extracted in solvent treatment out, help bituminous matter to dissociate into littler structure, these have all increased the residual oil molecule and have got into the speed of catalyzer micropore, thereby can improve the decreasing ratio of metal impurities.The raising of diffusion simultaneously can also improve the distribution of metal in the catalyzer micropore, makes catalyzer can hold more metal, delays the inactivation of catalyzer.
The adding that oil is extracted in solvent treatment out will make raw oil viscosity reduce, and can improve the flow state of logistics in reactor drum, overcome the pulsation that causes because of material viscosity is excessive.
Opposite with fraction oil hydrogenation unit is, the residual hydrocracking device generally all be that rear portion bed carbon deposit is serious, and serious more near the reactor outlet carbon deposit more; This is because the hydrogenation saturating speed of colloid and oil content is very fast; And bitum saturating speed is slower, and the side chain that breaks easily, the virtue nuclear that only surplus aromaticity is higher; Thereby solubleness is more and more littler in the increasingly high environment solvent of saturation ratio, is very easy at last be deposited on form carbon deposit on the catalyzer.The adding that oil is extracted in the higher solvent treatment of aromaticity out can improve the aromaticity of solvent on every side, increases bitum peptizing power, reduces its carbon deposit on the catalyzer of rear portion.
In addition, extract oil out, can be converted into the light component of high added value through hydrotreatment.
Embodiment
The fixed bed residual hydrogenation pilot plant that the residual hydrogenation equipment that uses in embodiment and the Comparative Examples is produced as U.S. Xytel company; Device is totally four reactor drums; Each reactor drum constant temperature zone is 1L; Load protective material, metal remover, sweetening agent respectively and take off the carbon residue agent, catalyst property sees that table 1 grade mixing ratio is 5: 40: 30: 25, and catalyzer is that independently develop in the laboratory.In order to make an experiment, before the sweetening agent bed, increase a material inlet.Using the coke content on the rear catalyst is after catalyzer is drawn off from device, to use ethanol/toluene (50: 50) Suo Shi extracting 50 hours, 200 ℃ dry 5 hours down, use the Elementar elemental analyser to measure then.
Extract oil out and pick up from CNPC's refinery's furfural extraction unit, raw material has carried out the multiple-effect evaporation solvent removal and has handled and steam stripped for subtracting four lines before the oil recovery, and residual oil raw material is to subtract slag in the sand, and character is seen table 2.
Table 1 the present invention uses the main physico-chemical property of catalyzer
Table 2 test raw material oil main character
| Subtract slag in the sand | Oil is extracted in furfural treatment out | |
| Density (20 ℃), kg/m 3 | 1.02 | 0.97 |
| Viscosity (100 ℃)/mm 2·S -1 | 1476 | 34.52 |
| S，wt％ | 5.1 | 0.29 |
| Carbon residue (MCR), wt% | 20.5 | 2.38 |
| Metal (Ni+V), ppm | 148 | - |
| Group composition, wt% | ||
| Bituminous matter | 6.6 | - |
| Fragrance divides | 54.4 | 76.8 |
| Saturated branch | 11.6 | 11 |
| Colloid | 27.4 | 12.2 |
The main operational condition of table 3 residual hydrogenation equipment
Comparative Examples
Residual oil raw material gets into reactor drum with hydrogen and contacts with catalyzer and hydrogenation reaction takes place, and product separation is gas, petroleum naphtha, diesel oil and hydrogenated residue, moves after 2000 hours catalyzer to be drawn off, and measures sweetening agent and takes off the coke content in the carbon residue agent.Hydrogenated residue character and catalyst carbon deposit situation in the time of 2000 hours are seen table 4.
Embodiment 1
After residual oil raw material and 5% furfural extract oil mix, get into reactor drum with hydrogen and contact with catalyzer and hydrogenation reaction takes place, the feed(raw material)inlet access to plant that 5% furfural extract oil passes through increase reacts.Product separation is gas, petroleum naphtha, diesel oil and hydrogenated residue, moves after 2000 hours catalyzer to be drawn off, and measures sweetening agent and takes off the coke content in the carbon residue agent.Hydrogenated residue character and catalyst carbon deposit situation in the time of 2000 hours are seen table 4.
Embodiment 2
After residual oil raw material and 10% furfural extract oil mix; Getting into reactor drum with hydrogen contacts with catalyzer and hydrogenation reaction takes place; The feed(raw material)inlet access to plant reaction of 5% furfural extract oil through increasing; Product separation is gas, petroleum naphtha, diesel oil and hydrogenated residue, moves after 2000 hours catalyzer to be drawn off, and measures sweetening agent and takes off the coke content in the carbon residue agent.Hydrogenated residue character and catalyst carbon deposit situation in the time of 2000 hours are seen table 4.
Embodiment 3
After residual oil raw material and 15% furfural extract oil mix; Getting into reactor drum with hydrogen contacts with catalyzer and hydrogenation reaction takes place; The feed(raw material)inlet access to plant reaction of 5% furfural extract oil through increasing; Product separation is gas, petroleum naphtha, diesel oil and hydrogenated residue, moves after 2000 hours catalyzer to be drawn off, and measures sweetening agent and takes off the coke content in the carbon residue agent.Hydrogenated residue character and catalyst carbon deposit situation in the time of 2000 hours are seen table 4.
Can know through table 4, compare with Comparative Examples that the hydrogenated diesel oil of high added value and naphtha yield all increase to some extent, the hydrogenated residue part is handled through follow-up catalytic cracking in industry, and the petrol and diesel oil yield of high added value can increase more; The hydrogenated residue foreign matter content obviously reduces, and carbon deposit content obviously reduces on the catalyzer that draws off, and estimating running period has increased by 1～2 month.
Table 42000hr adds product and draws off the catalyst carbon deposit situation
Claims (1)
1. method of improving residual hydrocracking device reaction performance; It is characterized in that: before residual hydrocracking device sweetening agent bed, increase an opening for feed; With residual oil raw material with after accounting for the part furfural treatment extraction oil mixing of residual oil raw material weight 1～20wt%; Get into reactor drum with hydrogen and contact with catalyzer and hydrogenation reaction takes place, oil is extracted in the part furfural treatment out to be increased opening for feed and gets into reactor drum before the sweetening agent bed;
Hydrogenation conditions is: 300 ℃～450 ℃ of temperature, and pressure 10MPa～22MPa, hydrogen-oil ratio 300～2000, air speed 0.1～1 is loaded protective material, metal remover, sweetening agent catalyzer more than three kinds successively;
Described residual oil is one or both mixtures in long residuum or the vacuum residuum;
Described residual hydrocracking device is fixed bed residual hydrogenation, upflowing residual hydrogenation or moving-bed residual hydrogenation;
Described solvent treatment raw oil is atmosphere 3rd side cut oil, normal four lines oil, first vacuum side stream, second line of distillation oil, subtract third fractional oil, subtract in the four line oil one or more.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113663617A (en) * | 2021-08-13 | 2021-11-19 | 中海沥青股份有限公司 | Low-viscosity refrigerator oil base oil and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4447314A (en) * | 1982-05-05 | 1984-05-08 | Mobil Oil Corporation | Demetalation, desulfurization, and decarbonization of petroleum oils by hydrotreatment in a dual bed system prior to cracking |
| EP0537500B1 (en) * | 1991-10-09 | 1996-11-27 | Idemitsu Kosan Company Limited | A method of treatment of heavy hydrocarbon oil |
| CN1362481A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Catalyst sorting and loading method |
| CN1488719A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Heavy hydrocarbon hydroprocessing method |
| CN1597856A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Heavy slag oil fixed bed hydrogenating treatment process |
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- 2011-06-10 CN CN2011101563630A patent/CN102816592A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4447314A (en) * | 1982-05-05 | 1984-05-08 | Mobil Oil Corporation | Demetalation, desulfurization, and decarbonization of petroleum oils by hydrotreatment in a dual bed system prior to cracking |
| EP0537500B1 (en) * | 1991-10-09 | 1996-11-27 | Idemitsu Kosan Company Limited | A method of treatment of heavy hydrocarbon oil |
| CN1362481A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Catalyst sorting and loading method |
| CN1488719A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Heavy hydrocarbon hydroprocessing method |
| CN1597856A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Heavy slag oil fixed bed hydrogenating treatment process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113663617A (en) * | 2021-08-13 | 2021-11-19 | 中海沥青股份有限公司 | Low-viscosity refrigerator oil base oil and preparation method and application thereof |
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Application publication date: 20121212 |