CN101003747A - Method for controlling concentration of sulfureted hydrogen in circulating hydrogen of hydrogenation unit - Google Patents
Method for controlling concentration of sulfureted hydrogen in circulating hydrogen of hydrogenation unit Download PDFInfo
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- CN101003747A CN101003747A CN 200610045710 CN200610045710A CN101003747A CN 101003747 A CN101003747 A CN 101003747A CN 200610045710 CN200610045710 CN 200610045710 CN 200610045710 A CN200610045710 A CN 200610045710A CN 101003747 A CN101003747 A CN 101003747A
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Abstract
This invention relates to a method for controlling H2S concentration in circulating H2 in hydrogenation apparatus. The method comprises: continuously or intermittently adding an appropriate amount of alkaline solvent into the water-injection pump inlet of hydrogenation apparatus, neutralizing H2S in circulating H2 when ammonium salt crystal is generated, and further dissolving H2S in water phase to reduce H2S concentration to an appropriate value. The method can reduce H2S concentration in circulating H2, and improve catalyst hydrogenation activity and stability. Besides, the method also has such advantages as low cost and easy operation, and can be used in the process of high-quality clean fuel production from fraction oil by hydrogenation.
Description
Technical field
The present invention relates to a kind of method of concentration of hydrogen sulfide in the recycle hydrogen of controlling in the hydrogenation unit, fraction oil hydrogenation refining production high-quality clean fuel technological process particularly, concentration of hydrogen sulfide in the Control Circulation hydrogen guarantees that the hydrogenation catalyst performance is active, prevents that hydrogenation catalyst from losing a kind of method of sulphur.
Background technology
The sustainable development of national economy has driven the fast development of automotive industry and transportation, and the objectionable impurities of motor vehicle exhaust has simultaneously become the maximum public hazards of urban air severe contamination.How effectively to control the discharging of vehicle exhaust nuisance, voluminous clean fuel is a current urgency problem to be solved.Simultaneously, owing to increasing sharply of high-sulfur crude oil with poor quality quantity, hydrogen addition technology is subjected to the attention and the favor of numerous oil refining enterprises as the direct production clean fuel.
The gasoline aspect, in order to satisfy environmental protection requirement, more and more stricter motor vehicle emission new standard has been formulated in world many countries and area, and sulphur in the gasoline and alkene have been proposed more and more strict restriction.As the new gasoline standard of European III automobile emissions standards (sulphur content ≯ 150 μ g/g, aromatic hydrocarbons ≯ 42.0v%, alkene ≯ 18.0v%).Diesel oil aspect, countries in the world are revised diesel oil standard in succession, and the relevant indexs of environmental pollution such as the sulphur content in the diesel oil, aromaticity content, cetane value and density have all been proposed stricter requirement.
In the implementation process of hydrogenation technique technology, the sulphur in the raw material generates hydrogen sulfide behind hydrodesulfurization reaction.The height of concentration of hydrogen sulfide is to catalyst activity, selectivity and the stable influence that all has in various degree in the reactive system.For the reactive metal that exists with sulphided state, contain certain density hydrogen sulfide in the system and be that reactive metal is kept sulphided state is necessary.Simultaneously, some studies show that hydrogen sulfide can promote reactions such as hydrodenitrification in the system, but there are some researches show that also too high concentration of hydrogen sulfide can suppress hydrogenation reaction, and reason may be the competitive adsorption result of hydrogen sulfide and other reactant.The general industry application practice shows, is acceptable when recycle hydrogen concentration is not higher than 1% (V) in the hydrogenation unit, and therefore, the comprehensive integral economic benefit is not very high raw material for the processing sulphur content, and recycle hydrogen is not generally established the depriving hydrogen sulphide device.
When the raw material of processing high sulfur content, the concentration of hydrogen sulfide in the hydrogenation system in the recycle hydrogen will reach 1% usually, even higher.Generally need establish recycle hydrogen de sulfuration hydrogen production device this moment.The method that removes hydrogen sulfide in the prior art is more, generally can be divided into dry desulfurization and wet desulphurization, and the method that is widely used in hydrogenation unit is the pure amine absorption process in the wet desulphurization.Promptly adopt custom-designed depriving hydrogen sulphide absorption tower, adopting the tertiary alkanolamine compounds is absorption agent, removes the hydrogen sulfide in the recycle hydrogen.Its main deficiency is, needs special high pressure depriving hydrogen sulphide equipment, equipment establish money and process cost all higher.
CN1169335A discloses a kind of method that removes hydrogen sulfide from mixed gas, H 2 S-containing gas enters the absorption tower under 0.1～10.0MPa, with the absorption liquid counter current contact, hydrogen sulfide in the washing, purifying mixed gas at normal temperatures, the rich solution that has absorbed hydrogen sulfide enters regenerator column regeneration back and reuses.This invention has that sulfur capacity is big, absorption rate is fast, characteristic of low energy consumption, but investment cost is higher.
USP3,622,267 disclose and a kind ofly add Monoethanolamine MEA BASF with methyldiethanolamine and remove the method for hydrogen sulfide as absorption liquid from mixed gas, adopt the regenerate technical process of (flash distillation and stripping) of two-stage absorptions-two-stage, and the rich solution of absorbing hydrogen sulphide is to regenerator column steam heating Gas reclamation.The shortcoming of this invention is that to remove the effect of hydrogen sulfide relatively poor, and hydrogen sulfide content height in the tail gas of regeneration back must be converted into sulphur with hydrogen sulfide, and process cost obviously increases.
USP5,616,306 disclose a kind of method that removes hydrogen sulfide from mixed gas, sour gas with contain one or more organic acid solubilization iron huge legendary turtle compounds, tertiary alkanolamine compounds and one or more basic metal contact reacts and remove hydrogen sulfide.This patent has the advantages that the desulfurization treatment capacity is big, desulfuration efficiency is high, but operate continuously, but investment cost is higher.
USP5,114,562 disclose the technological process of a kind of distillate two-stage method hydrotreatment.First reactor feedstocks and hydrogen-rich gas and stream are by a kind of non-precious metal catalyst, the second reactor catalyst system therefor is that noble metal catalyst carries out the desulfurizing and eliminating aromatic hydrocarbons deeply reaction, but the concentration of hydrogen sulfide in the recycle hydrogen there is special requirement, the means of taking are to use methyldiethanolamine to remove hydrogen sulfide in the recycle hydrogen, and its major cause is that hydrogen sulfide has retardation to hydrogenation aromatics-removing.
Summary of the invention
At the deficiencies in the prior art, the present invention proposes a kind of hydrogen sulfide method that removes low, easy and simple to handle, that raising catalyst activity and stability are stablized, are beneficial in running of investing.
Find that by a large amount of experimental studies the general industry experience is thought and hydrogen sulfide acceptable concentration range in the recycle hydrogen still had different tangible influences for different reaction process.Be in particular in that for gasoline hydrogenation hydrogenation desulfurization and denitrogenation is active obviously to be reduced, particularly the performance of selective hydrogenation obviously reduces, and can only remedy by temperature raising.But for diesel oil hydrogenation, the concentration of hydrogen sulfide height is except influencing the hydrogenation desulfurization and denitrogenation activity, and is especially obvious for the influence that aromatic hydrocarbons is saturated, and because the restriction of thermodynamic(al)equilibrium, under certain pressure, the raising temperature of reaction is unfavorable for the aromatic hydrocarbons saturated reaction.Therefore, for the not high raw material hydrogenation unit of sulphur content, concentration of hydrogen sulfide still is very important in the Control Circulation hydrogen.But adopt existing recycle hydrogen de sulfuration hydrogen methods, all need establish special recycle hydrogen de sulfuration hydrogen production device, facility investment and process cost increase, and be also comparatively difficult for the transformation of existing hydrogenation unit.On the other hand, the concentration of hydrogen sulfide in the recycle hydrogen again should not be too low, and concentration of hydrogen sulfide is too low to have serious adverse influence to catalyst stability.Therefore, find the suitable concentration of hydrogen sulfide of hydrogenation unit recycle hydrogen, take into account two aspect factors, adopt simple and effective technical scheme, make hydrogenation unit realize the long period steady running.
Well known to those skilled in the artly be, the hydrogenation desulfurization and denitrogenation resultant of reaction: hydrogen sulfide and ammonia can further react and generate sulphur hydrogenation ammonia, for preventing material cooling back ammonium salt crystallization, equipment is stopped up, usually before reducing to lesser temps, injects material an amount of water, dissolving crystallized product, the equipment that prevents stops up, and the water of use is generally softening water.In general, location of water injection gas phase of high pressure hot separator in hydrogenation system enters before the interchanger, prevents that interchanger from stopping up.
Characteristics in conjunction with existing hydrogenation unit, the invention provides a kind of method of controlling hydrogenation unit recycle hydrogen concentration, concrete scheme comprises following content: add an amount of basic solvent continuously or off and at hydrogenation unit waterflood pump inlet, in dissolution system, generate in the ammonium salt crystallization, hydrogen sulfide in the recycle hydrogen is further neutralized and be dissolved in aqueous phase, make that hydrogen sulfide is reduced to suitable concentration in the recycle hydrogen.
Basic solvent can select for use various can in and the material of hydrogen sulfide, can select usually as in ammonia, alcamine compound and other water-soluble inorganic alkali or the organic bases etc. one or more.Hydramine can be methyldiethanolamine, dimethyl Monoethanolamine MEA BASF, trolamine, thanomin, diethanolamine etc.The consumption of basic solvent obtains by simple experiment according to concentration of hydrogen sulfide controlling index in the recycle hydrogen, and this is those skilled in the art's general knowledges.According to big quantity research, the optimum range that it is considered herein that concentration of hydrogen sulfide in recycle hydrogen is 10～2500 μ L/L, and in this scope, all hydrogenation units can obtain satisfied effect.Certainly, for different hydrogenation units, still can further optimize, bear below and the present invention is directed to different hydrogenation units, the recycle hydrogen concentration range of optimizing: for the gasoline hydrogenation device, concentration of hydrogen sulfide in the Control Circulation hydrogen is 500～50 μ L/L, is preferably 300～50 μ L/L, most preferably is 200～10 μ L/L; For diesel oil hydrogenation and Wax Oil Hydrogenation Unit, the concentration of hydrogen sulfide in the Control Circulation hydrogen is 2500～800 μ L/L, is preferably 2000～800 μ L/L, most preferably is 1800～500 μ L/L; For hydroeracking unit, the concentration of hydrogen sulfide in the Control Circulation hydrogen is 500～1500 μ L/L, is preferably 500～1200 μ L/L, most preferably is 500～800 μ L/L.
The inventive method is applicable to various hydrogenation units, as hydro-refining unit, hydro-upgrading unit or the hydroeracking unit etc. of raw materials such as gasoline, kerosene, diesel oil, wax oil.Water injection rate identical (about the 4m% of stock oil quality) when water injection rate can be with normal running also can be different, are generally 0.8～5 times of normal water injection rate, preferred 1.1～3 times.Can suitably adjust according to the ability of water injection equipment.
The method that the present invention controls concentration of hydrogen sulfide in the hydrogenation unit recycle hydrogen has following advantage: (1) equipment is simple, easy and simple to handle, need not increase miscellaneous equipment, only needs to add suitable alkaline matter and get final product in original rinse water.Be noted that waterflood pump and complete container pipeline etc. need have erosion resistance.(2) optimize suitable concentration of hydrogen sulfide scope in the different hydrogenation unit recycle hydrogens, optimized the response behaviour of hydrogenation system, helped improving anti-performance, improved product property, prolonged the catalyzer steady running cycle.
Description of drawings
Fig. 1 is the influence of embodiment 1 hydrogen sulfide to hydrogenation dialkene removal.
Embodiment
The detailed process of the inventive method is:
A, hydrogenation unit waterflood pump inject the softening water that is mixed with basic solvent, the hydrogen sulfide that generates with hydrogenation reaction in the basic solvent, and softening water dissolving ammonium salt prevents the obstruction of equipment.
Can improve hydrogenation activity though B, metal catalyst are operated under very low concentration of hydrogen sulfide, catalyzer mistake sulphur speeds up under this atmosphere for a long time, the active reduction.Therefore need that concentration of hydrogen sulfide prolongs the work-ing life of catalyzer in the Control Circulation hydrogen in the scope of not losing sulphur.
C, interpolation basic solvent are selected from ammonia, alcamine compound (comprising methyldiethanolamine, dimethyl Monoethanolamine MEA BASF, trolamine).
D, intermediate distillates hydrogenation of the present invention comprise gasoline, kerosene, diesel oil, wax oil hydrogenation is refining and the hydrocracking process process.It is the concentration of hydrogen sulfide span of control difference in the recycle hydrogen.
Further set forth technical scheme of the present invention below in conjunction with example.The percentage composition that relates to is a weight percentage.
Example 1
Table 1 is for injecting the relation of basic solvent concentration and hydrogen sulfide stripping.Fig. 1 is the influence of embodiment 1 hydrogen sulfide to hydrogenation dialkene removal.Basic solvent is an ammonia, and concentration is weight concentration, and water injection rate is identical with the normal running water injection rate, is the 4m% of stock oil quality.
The diolefine of table 1 gasoline stocks and treated oil removes
| Inject basic solvent concentration, wt % | 1.5 | 1.0 | 0.8 | 0 | |
| Recycle hydrogen concentration, μ L/ |
0～10 | 300～200 | 750～700 | 3000 | |
| The oil product title | Stock oil | Treated gasoline | |||
| Maleic value, gI/100g oil | 4.12 | 0.07 | 0.71 | 0.92 | 2.85 |
Processing condition: hydrogen dividing potential drop, 3.2MPa; Hydrogen to oil volume ratio, 600v/v volume space velocity, 5.0h
-1180 ℃ of temperature of reaction, catalyzer are the FH-98 Hydrobon catalyst that development Wenzhou Hua Hua company of Fushun Petrochemical Research Institute produces.
The test of example 2 diesel hydrotreating units.Basic solvent is a trolamine, and concentration is weight concentration, and water injection rate is 1.2 times of normal running water injection rate, is the 5m% of stock oil quality.
Table 2 diesel oil hydrogenation full scale plant injects the basic solvent result
| Inject basic solvent concentration, % | 2.5 | 2.0 | 0 | |
| Recycle hydrogen concentration, μ L/ |
500 | 1500 | 15000 | |
| The oil product title | Stock oil | Refined diesel oil | ||
| Density (20 ℃), g/ml | 0.8614 | 0.8350 | 0.8368 | 0.8370 |
| Boiling range, ℃/fore-running/heat up in a steamer eventually | 178/371 | 177/369 | 177/369 | 177/369 |
| Nitrogen, μ g/g | 288 | 1 | 5 | 10 |
| Sulphur, μ g/g | 12200 | 20 | 80 | 180 |
| Aromatic hydrocarbons, wt% | 36.6 | 24.0 | 25.1 | 26.7 |
| Cetane value | 46.5 | 52.0 | 51.2 | 50.1 |
Processing condition: hydrogen dividing potential drop, 6.4MPa; Hydrogen to oil volume ratio, 500v/v volume space velocity, 2.0h
-1Temperature of reaction, 360 ℃, catalyzer is the FH-98 Hydrobon catalyst that development Wenzhou Hua Hua company of Fushun Petrochemical Research Institute produces.
Claims (8)
1, a kind of method of controlling concentration of hydrogen sulfide in the hydrogenation unit recycle hydrogen, comprise following content: add an amount of basic solvent continuously or off and at hydrogenation unit waterflood pump inlet, in dissolution system, generate in the ammonium salt crystallization, hydrogen sulfide in the recycle hydrogen is further neutralized and be dissolved in aqueous phase, make that hydrogen sulfide is reduced to suitable concentration in the recycle hydrogen.
2, in accordance with the method for claim 1, it is characterized in that described basic solvent selects one or more in ammonia, the alcamine compound for use.
3, in accordance with the method for claim 1, it is characterized in that described alcamine compound is methyldiethanolamine, dimethyl Monoethanolamine MEA BASF, trolamine, thanomin or diethanolamine.
4, in accordance with the method for claim 1, the optimum range that it is characterized in that concentration of hydrogen sulfide in the described recycle hydrogen is 10～2500 μ L/L, and the consumption of basic solvent is determined according to concentration of hydrogen sulfide controlling index in the recycle hydrogen.
5, in accordance with the method for claim 1, it is characterized in that described hydrogenation unit is hydro-refining unit, hydro-upgrading unit or the hydroeracking unit of raw materials such as gasoline, kerosene, diesel oil, wax oil.
6, in accordance with the method for claim 1, it is characterized in that the concentration of hydrogen sulfide in the Control Circulation hydrogen is 500～50 μ L/L for the gasoline hydrogenation device; For diesel oil hydrogenation and Wax Oil Hydrogenation Unit, the concentration of hydrogen sulfide in the Control Circulation hydrogen is 2500～800 μ L/L; For hydroeracking unit, the concentration of hydrogen sulfide in the Control Circulation hydrogen is 1500～500 μ L/L.
7, in accordance with the method for claim 1, it is characterized in that the concentration of hydrogen sulfide in the Control Circulation hydrogen is 300～50 μ L/L for the gasoline hydrogenation device; For diesel oil hydrogenation and Wax Oil Hydrogenation Unit, the concentration of hydrogen sulfide in the Control Circulation hydrogen is 2000～800 μ L/L; For hydroeracking unit, the concentration of hydrogen sulfide in the Control Circulation hydrogen is 1200～500 μ L/L.
8, in accordance with the method for claim 1, it is characterized in that the concentration of hydrogen sulfide in the Control Circulation hydrogen is 200～10 μ L/L for the gasoline hydrogenation device; For diesel oil hydrogenation and Wax Oil Hydrogenation Unit, the concentration of hydrogen sulfide in the Control Circulation hydrogen is 1800～500 μ L/L; For hydroeracking unit, the concentration of hydrogen sulfide in the Control Circulation hydrogen is 800～500 μ L/L.
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| CNB2006100457101A CN100526432C (en) | 2006-01-19 | 2006-01-19 | Method for controlling concentration of sulfureted hydrogen in circulating hydrogen of hydrogenation unit |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942957A (en) * | 2012-10-30 | 2013-02-27 | 中国石油化工股份有限公司 | Presulfuration technology of hydrogenation unit |
| CN101676367B (en) * | 2008-09-10 | 2013-11-27 | 赫多特普索化工设备公司 | Improved hydrotreatment process |
| CN103805232A (en) * | 2012-11-14 | 2014-05-21 | 中国石油天然气股份有限公司 | Application of hydrogenation catalyst prevulcanization method in residue hydrotreating switchable reactor system |
| CN103805233A (en) * | 2012-11-14 | 2014-05-21 | 中国石油天然气股份有限公司 | Application of prevulcanization method by hydrogenation catalyst dry method in residue hydrotreating switchable reactor system |
-
2006
- 2006-01-19 CN CNB2006100457101A patent/CN100526432C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101676367B (en) * | 2008-09-10 | 2013-11-27 | 赫多特普索化工设备公司 | Improved hydrotreatment process |
| CN102942957A (en) * | 2012-10-30 | 2013-02-27 | 中国石油化工股份有限公司 | Presulfuration technology of hydrogenation unit |
| CN102942957B (en) * | 2012-10-30 | 2014-10-08 | 中国石油化工股份有限公司 | Presulfuration technology of hydrogenation unit |
| CN103805232A (en) * | 2012-11-14 | 2014-05-21 | 中国石油天然气股份有限公司 | Application of hydrogenation catalyst prevulcanization method in residue hydrotreating switchable reactor system |
| CN103805233A (en) * | 2012-11-14 | 2014-05-21 | 中国石油天然气股份有限公司 | Application of prevulcanization method by hydrogenation catalyst dry method in residue hydrotreating switchable reactor system |
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