CN104927904A - Hydrotreating sulfur supplementing method - Google Patents
Hydrotreating sulfur supplementing method Download PDFInfo
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- CN104927904A CN104927904A CN201510275348.6A CN201510275348A CN104927904A CN 104927904 A CN104927904 A CN 104927904A CN 201510275348 A CN201510275348 A CN 201510275348A CN 104927904 A CN104927904 A CN 104927904A
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- hydrogen sulfide
- hydrogen
- hydrotreatment
- gas
- containing gas
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 13
- 239000011593 sulfur Substances 0.000 title claims abstract description 13
- 230000001502 supplementing effect Effects 0.000 title abstract 2
- 239000007789 gas Substances 0.000 claims abstract description 68
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 230000008014 freezing Effects 0.000 claims abstract description 10
- 238000007710 freezing Methods 0.000 claims abstract description 10
- 239000010865 sewage Substances 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- 239000005864 Sulphur Substances 0.000 claims description 39
- 230000008901 benefit Effects 0.000 claims description 30
- 238000004073 vulcanization Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004581 coalescence Methods 0.000 abstract 1
- 230000006835 compression Effects 0.000 abstract 1
- 238000007906 compression Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 4
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000026676 system process Effects 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PMODATROEZUNCM-UHFFFAOYSA-N CN(CCO)CCO.[N] Chemical compound CN(CCO)CCO.[N] PMODATROEZUNCM-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229940059936 lithium bromide Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Landscapes
- Gas Separation By Absorption (AREA)
Abstract
A hydrotreating sulfur supplementing method is characterized in that gas hydrogen sulfide is liquefied by using hydrogen sulfide-containing gas from sulfur-contained sewage produced by hydrotreating through a stripping tower or hydrogen sulfide-containing gas obtained by regeneration of desulfurized amine liquid and by dehydration through drying or cooling coalescence and then through compression cooling or direct freezing, fixed gas is removed by liquid separation, and finally, the liquid hydrogen sulfide is conveyed to a hydrotreating high pressure system by a pump to keep concentration of the hydrogen sulfide in circulation hydrogen of the system.
Description
Art
The present invention relates to the benefit sulphur of hydrotreater, specifically, is by injecting hydrogen sulfide to hydrotreater reactive system, to keep in reactive system recycle hydrogen hydrogen sulfide content in reasonable level.
Background technology
Hydrotreatment can comprise: the hydrotreatment of the hydrofining, hydrocracking, hydrodewaxing etc. of petroleum fractions, also the hydrotreatment of coal tar or coal, the oil fixed bed/suspension bed/ebullated bed of refining or DCL/Direct coal liquefaction etc. altogether can be comprised, i.e. the catalytic hydrogenation reaction of a series of consumption hydrogen such as sensu lato hydrogenating desulfurization, deoxidation, denitrogenation, aromatic saturation, hydrocracking.
The reactive system general flow of hydrotreatment is that raw material mixes with circulating hydrogen, enters the reactor that catalyzer is housed, hydrogenation reaction occurs after heat exchange and heating, and reaction after product, through being separated, can obtain object product as clear gusoline or industrial chemicals etc.Need in the reactive system circulating hydrogen of hydrotreatment to maintain certain concentration of hydrogen sulfide, to keep high reactivity and the selectivity of the catalyzer promoting hydrogenation reaction.
In the raw material of hydrotreatment, sulphur content is too low, or nitrogen content is too high, and in recycle hydrogen system, concentration of hydrogen sulfide can be very low, and this system needs to mend sulphur.
Traditional benefit sulphur method, be to reaction feed pump intake or to appropriate location, reactive system process furnace gangway, inject vulcanizing agent DMDS (Methyl disulfide), after DMDS injects reactive system, namely produce hydrogen sulfide with hydrogen reaction under reaction conditions, reaction formula is as follows:
CH
3-S-S-CH
3+3H
2＝2CH
4+2H
2S
Ye You enterprise, for reducing costs, adopts and injects dithiocarbonic anhydride CS
2, the method is the same with DMDS principle.
Raw material is after hydrotreatment, and the nitrogen in raw material and sulphur can hydrocracking be ammonia and hydrogen sulfide, can crystallize into salt blocking water cooler in follow-up process of cooling.Generally to be everlasting water filling before water cooler to dissolve this salt.For processing this part sour water of hydrogenation unit, setting up and putting Sulfur-containing Sewage Stripping Tower to isolate ammonia and hydrogen sulfide.Sour water stripping, namely under bottom reboiler heating condition, tower top goes out hydrogen sulfide.Stripping tower can adopt total reflux form, or tower top fills into the form of purifying waste water at the bottom of tower, with purification tower top gas hydrogen sulfide.
The reaction product of hydrotreatment, often containing hydrogen sulfide, makes final product needed desulfurization.General method is to the low point of desulfurization reacted, fuel gas desulfurization and desulfuration of liquefied gas, desulfurization adopts MDEA (nitrogen methyldiethanolamine) solution, the MDEA solution having absorbed hydrogen sulfide collects into amine liquid regenerator column top, under bottom reboiler heating condition, tower top goes out hydrogen sulfide, and the MDEA solution circulated be purified at the bottom of tower uses.MDEA solution regenerator overhead gas contains a large amount of hydrogen sulfide.
Patent 931210267 discloses a kind of benefit sulphur method of H 2 S-containing gas, is contacted with hydrocarbon ils by H 2 S-containing gas, by hydrocarbon ils dissolved hydrogen sulfide, then this hydrocarbon ils is transported to the reactive system of hydrotreatment, realizes mending sulphur.
Patent 201310374340.6 describes the H 2 S-containing gas that Sulfur-containing Sewage Stripping Tower stripping goes out, and directly compresses with membrane compressor, or by the method for hydrogen make-up compressor compresses to reactive system.
H 2 S-containing gas is dehumidified, liquefies and pumps into the method for reactive system by the introduction of this benefit sulphur method.
Prior art: the reaction feed F1 of hydrotreatment by after interchanger E1 heat exchange, then is mixed into process furnace H with the circulating hydrogen after circulating hydrogen compressor C supercharging, is controlled the temperature of reactor inlet by process furnace H.After reaction feed and circulating hydrogen carry out the series reaction such as hydrogenating desulfurization, denitrogenation, aromatic saturation, hydrocracking in several reactor R1 and R2, the reaction product of formation enters interchanger E1.After interchanger E1 and charging heat exchange, reinject water F2, for the ammonia in solubilizing reaction product, hydrogen sulfide, in storage tank D1, finally carries out the separation of Oil, Water, Gas.Wherein gas reenters compressor C as recycle hydrogen, and oil can send into fractionating section, has dissolved the sour water of hydrogen sulfide and ammonia, has discharged bottom storage tank D1, entered Sulfur-containing Sewage Stripping Tower T.
Summary of the invention
Hydrogen sulfide that analysis background technical agency continues source, as hydrotreatment the Sulfur-containing Sewage Stripping Tower that produced, or the amine liquid for desulphurization regenerator column that hydrotreatment is produced, the benefit sulphur that all can be used as hydrotreatment is selected.The sour water that discharges of preferred hydrotreatment is through the H 2 S-containing gas of stripping tower stripping gained, and because of the H 2 S-containing gas that its stripping goes out, impurities is considerably less, and pressure is also higher, is the hydrogen sulfide source of this benefit sulphur method the best.
For the sulphur of supplementary hydrotreater reactive system lacks, this benefit sulphur method, by above-mentioned preferred H 2 S-containing gas, respectively through dehumidifying, liquefaction, separatory and pressurization four steps, sends into reactive system.Make introductions all round these four steps below:
One, dehumidify.Hydrogenation type sour water, can obtain H 2 S-containing gas at tower top after stripping.Through sampling analysis, this gas sulfur hydrogen reaches more than 94%, but containing some moisture, methane, ethane, ammonia etc.The method removing ammonia is operation adjustment: generally enter purifying waste water after stripping in stripping tower teeming, to keep overhead gas hydrogen sulfide high purity, when analyzing discovery containing ammonia, only need carry a little and purifying the water yield greatly, just can dissolve wherein ammonia very well, because ammonia is very easily water-soluble.
This benefit sulphur method removes the method for moisture in H 2 S-containing gas three kinds: coalescent dehydration after (one) cooling.H 2 S-containing gas contained humidity, through cooling after coalescent, separable go out moisture.Such as 40 DEG C of hydrogen sulfide mixed gass containing saturated steam are cooled to 5 DEG C, more than 80% moisture can be removed.For preventing cooling apparatus from freezing, frozen block occurs, and what cooling temperature can be controlled at hydrogen sulfide saturated aqueous solution is above freezing.Maybe can adopt chilled brine (as lithium-bromide solution, sodium chloride solution etc.), directly contact with H 2 S-containing gas, to absorb wherein moisture.The object of this cooling step is dehydration, therefore is not cooled to make hydrogen sulfide content that the degree of liquefaction occur.(2) siccative absorption.Select silica-gel drier, or resistance to acid gas molecular sieve desiccant, all can adsorb to fall the moisture in hydrogen sulfide very well.Drying chamber can one be opened one standby, and slack tank can use factory's nitrogen, and after heating, adverse current is by siccative bed, takes away wherein moisture, realizes regeneration.(3) compound absorbs.The compound such as Vanadium Pentoxide in FLAKES, Calcium Chloride Powder Anhydrous has strong adsorption moisture ability.Hydrogen sulfide containing gas is passed into the storage tank bottom being filled with Vanadium Pentoxide in FLAKES, make it pass whole storage tank and flow out from top, in H 2 S-containing gas, namely water vapour absorbed by solid phosphorus pentoxide.It is phosphoric acid and metaphosphoric acid mixture that Vanadium Pentoxide in FLAKES forms liquid after absorbing moisture, can discharge from tank bottom.Vanadium Pentoxide in FLAKES supplements according to consumption is instant, or two storage tanks switch and use, and store enough Vanadium Pentoxide in FLAKESs, to ensure removing completely of moisture in gas.
Above-mentioned three kinds of methods, can choice for use, also can combinationally use, and such as allows H 2 S-containing gas, uses molecular sieve drying again, can extend the molecular sieve adsorption time, reduce the regeneration frequency after first cooling coalescent precipitation most of moisture.
Dehumidifying step sequence preferably cools coalescent rear drying, makes siccative with resistance to acid gas molecular sieve.
Two, liquefy.Pure hydrogen sulfide is gas in normal conditions.According to pure hydrogen sulfide saturated vapor pressure calculation formula IgP=-52.23B/T+C at different temperatures, then check in coefficient B=20.69, C=7.88, calculate the liquefaction pressure (gauge pressure) of hydrogen sulfide under differing temps as following table:
Visible according to upper table, the pressure of gas vulcanization hydrogen is higher, and liquefaction temperature is also higher.
In H 2 S-containing gas after this benefit sulphur method makes above-mentioned dehumidifying, the method for hydrogen sulfide liquefaction has two kinds: (one) pressurizes cooling.The heat-eliminating medium of such as factory's minimum temperature is recirculated water, and its temperature is 25 DEG C, and according to upper table, hydrogen sulfide sectional pressure reaches more than 2.5Mpa, can be condensed into liquid.Therefore can select the membrane compressor of zero leakage, H 2 S-containing gas is compressed to more than 2.5Mpa, then use factory's circulating water, namely gas vulcanization hydrogen become liquid, but the non-condensable gases such as methane are still gas.(2) directly freezing.Such as factory's Sulfur-containing Sewage Stripping Tower H 2 S-containing gas out, only have 0.3Mpa through dehumidifying postcure hydrogen dividing potential drop, according to upper table, need to be chilled to less than-34.5 DEG C, hydrogen sulfide could become liquid.Therefore by directly freezing for the H 2 S-containing gas after dehumidifying, refrigerant made by the refrigeration agents such as available liquid propylene, the hydrogen sulfide in H 2 S-containing gas is frozen into liquid, can obtains liquid curing hydrogen.Obviously, if factory's stripping tower gas out only has 0.1Mpa through dehumidifying postcure hydrogen dividing potential drop, need to be chilled to less than-57.3 DEG C, be limited to propylene refrigeration lowest temperature-47.7 DEG C, needing to change refrigerant is ethene, or other suitable refrigerants.
Liquefaction step sequence is preferably directly freezing, and this has larger flexibility of operation than pressurization cooling.On the other hand, the screw-type compressor selected for freezing, cools than pressurization the membrane compressor selected stable, also favourable to technology controlling and process.
Three, separatory.By the sulfide hydrogen mixture of above-mentioned post liquefaction, be incorporated in storage tank, carry out gravity settling, tank bottom enriched liquid hydrogen sulfide, the foreign gases such as methane originally can not liquefy, and are separated by storage tank, draw from tank top, can flare system be guided to, or the existing follow-up sulfur recovery processing unit of factory etc.This sulfide hydrogen mixture, also can select efficient wet cyclone, realizes thoroughly being separated of liquid curing hydrogen and foreign gas.Before noncondensable gas leaves separator, coalescer can be established, with the entrainment loss to liquid curing hydrogen during this non-condensable gas of emissions reduction.
The preferred storage tank of separatory, relies on gravity settling separation gas-liquid mixture, and equipment is simple, and be widely used, separating effect also meets processing requirement.
Four, supercharging.The first-selected pump of Liquid transfer.Consider very little (the general 500,000 tons/year of hydrotreaters of the liquid curing hydrogen amount of be injected into reactive system, flow 300L/h is enough), and consider that liquid curing hydrogen will be pressurized to the 8-25Mpa of reactive system from plant pressure about 0.3Mpa, according to factory scenario, high pressure plunger pump should be selected, cryogenic high pressure liquid delivery pump, maybe can select the hydraulic diaphragm metering pump of zero leakage.The liquid curing hydrogen collected after above-mentioned separatory is pressurizeed through pump, is transported to the reactive system of hydrotreatment.
The preferred hydraulic diaphragm metering pump of supercharging, this pump not only flow can directly read from the stroke of pump, can Long-distance Control, and zero leakage, has and leak Closed Drain facility during fault, and the hydrogen sulfide leakage of these safeguard procedures reply severe toxicity is very required.
The low temperature properties of liquid curing hydrogen after supercharging can be utilized, itself and hydrogen sulfide might as well be allowed to dehumidify or the suitable heat exchange of liquefaction step, after reclaiming cold, then send into hydrotreatment reactive system, also can not reclaim cold, be delivered directly to reactive system.Liquid curing hydrogen is in feeding reactive system process, and possible pipeline is long and by thermal evaporation, the hydrogen sulfide after gasification can continue to enter reactive system, realizes mending sulphur, does not hinder the enforcement of this benefit sulphur method, does not hinder and mends sulphur effect.
Liquid curing hydrogen injects the position of reactive system, can be the optional position entering reaction cycle hydrogen system.Preferably be injected into First reactor inlet, can directly make up needed for reaction like this, also help the corrodibility alleviated system miscellaneous equipment.
The beneficial effect of this benefit sulphur method is:
1, H 2 S-containing gas is passed through dehumidifying, be conducive to follow-up liquefaction, be more conducive to the etching problem of the Wet H2S environment alleviating follow-up pipeline equipment.
2, by liquefaction after H 2 S-containing gas dehumidifying, realize filling into of the hydrotreatment the purest hydrogen sulfide of reactive system, the hydrogen sulfide purity brought as DMDS or CS2 than factory's purchase note sulphur agent is high.
3, by hydrogen sulfide post liquefaction by pump delivery to reactive system, than with compressor investment and process cost on have saving.On the other hand, this benefit sulphur method, belongs to newly-increased part, can not have any impact when existing apparatus is transformed on existing utility.
4, this benefit sulphur method can select step sequence many, convenient according to factory's particular case adjustment or combination.Such as divide flow container, a simple container, can collect liquid curing hydrogen, is the place being separated noncondensable gas, takes into account the function of liquid curing hydrogen of having purified, or the inlet buffer of liquid curing hydrogen transferpump.
Accompanying drawing explanation
Fig. 1 is hydrotreatment principle flow chart, and the position signal of the principle figure of this benefit sulphur method (directly freezing) in hydrotreatment.
Fig. 2 is the principle flow chart of this benefit sulphur method (pressurization cooling).Its position in hydrotreatment is identical with Fig. 1.
With reference to the accompanying drawings 1 and embodiment 1, accompanying drawing 2 and embodiment 2, be described benefit sulphur method of the present invention.Wherein:
C: compressor;
D: storage tank;
E: interchanger;
F: charging, wherein F1 is the reaction feed of hydrotreatment, and F2 is the injection water of reaction product;
H: process furnace;
R: reactor;
T: tower.
Embodiment
In fig. 1.
Embodiment 1: under heating condition at the bottom of the tower of Sulfur-containing Sewage Stripping Tower, in sour water, the component such as hydrogen sulfide, water vapour, methane flows out from tower top, forms H 2 S-containing gas.This gas enters to be filled with the storage tank D2 of resistance to acid gas molecular sieve desiccant, removes wherein after water vapour, then enters H 2 S-containing gas condenser E2.At the opposite side of condenser E2, utilize liquid propene to be heated vaporization, the low temperature of minimum-47 DEG C can be formed, realize the condensing cooling to H 2 S-containing gas.(refrigeration agent is not limited to propylene).After propylene gas vaporization, cooling after can drawing back supercharging again by screw-type compressor, cooling of expanding, recycle (identical with common refrigeration, not describe in detail).H 2 S-containing gas is through condensing cooling, and the hydrogen-cooled liquid that congeals into of gas vulcanization, enters storage tank D3 together with non-condensable gas methane etc.
In storage tank D3, liquid curing hydrogen and non-condensable gas methane etc. are settlement separate, and non-condensable gas is discharged through storage tank D3 top, and the liquid curing hydrogen of enrichment bottom storage tank D3, through hydraulic diaphragm metering pump supercharging, is delivered directly to the First reactor inlet of hydrotreatment.
In fig 2.
Embodiment 2: Sulfur-containing Sewage Stripping Tower T vapour proposes H 2 S-containing gas, enter the storage tank D2 bottom being filled with Vanadium Pentoxide in FLAKES, penetrate Vanadium Pentoxide in FLAKES bed from bottom to top, remove wherein after water vapour, flow out from D2 top, form dried H 2 S-containing gas.This gas through the membrane compressor C supercharging of zero leakage, then cools through water cooler E2, enters storage tank D3, and hydrogen sulfide forms liquid and is enriched in tank bottom, and non-condensable gas is discharged as methane etc. is enriched in tank top.Liquid curing hydrogen bottom storage tank D3, through hydraulic diaphragm metering pump supercharging, is delivered directly to the First reactor inlet of hydrotreatment.
The hydrogen sulfide working cycle of this benefit sulphur method is simply described: the sour water that existing hydrotreatment is produced below, through stripping tower stripping, tower top obtains H 2 S-containing gas, drying device is dry again, and enter liquid propene vaporizer, hydrogen sulfide is condensed into liquid, after storage tank is separated with non-condensable gas, be enriched at the bottom of tank, through volume pump supercharging, to the reactor inlet of hydrotreatment.After entering reactor, promoting catalyst activation recovering, flows out with reaction product again, rinsing, forming sour water through injecting water.Therefore, this benefit sulphur method is the recycle of hydrogen sulfide, thoroughly can solve the benefit sulphur problem of hydrotreater run duration.
As mentioned above, two kinds of embodiments of this benefit sulphur method are illustrated.Those skilled in the art, completely can according to bright sulfur liquefaction of hydrogen thermometer and factory's actual conditions, as the processing parameter such as temperature, pressure, purity of stripping tower top H 2 S-containing gas, and factory's coolant temperature, determine the institute's plus-pressure size under pressurization cooling step, or the cryogenic temperature, deep cooling medium etc. when determining freezing.Therefore, this benefit sulphur method does not limit the concrete technology parameter implementing this benefit sulphur method, because those skilled in the art are easy to according to specification sheets, determines factory's optimum parameter.But as long as do not depart from fact the inventive point of this benefit sulphur method and effect can have a lot of distortion, this will be readily apparent to persons skilled in the art.Therefore, such variation is also all included within the protection domain of this benefit sulphur method.
Claims (5)
1. the benefit sulphur method of hydrotreatment, mend sulphur H 2 S-containing gas, derive from the Sulfur-containing Sewage Stripping Tower that hydrotreatment is produced, or the amine liquid for desulphurization regenerator column that hydrotreatment is produced, it is characterized in that: successively to H 2 S-containing gas dehumidifying, liquefaction, separatory and supercharging, hydrogen sulfide is transported to the reactive system of hydrotreatment.
2. benefit sulphur method as claimed in claim 1, it is characterized in that: described dehumidifying, is by cooling rear coalescent dehydration, and/or siccative absorption, and/or compound absorbs, and removes the moisture in H 2 S-containing gas.
3. benefit sulphur method as claimed in claim 1, is characterized in that: described liquefaction, is cool after pressurizeing, or directly freezing, makes gas vulcanization hydrogen become liquid.
4. benefit sulphur method as claimed in claim 1, it is characterized in that: described separatory, is by storage tank, or wet cyclone, separating liquid hydrogen sulfide and other components.
5. benefit sulphur method as claimed in claim 1, it is characterized in that: described supercharging, is by pump, by liquid curing hydrogen pressure-increasing unit to reactive system.
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| CN107488461A (en) * | 2017-09-21 | 2017-12-19 | 北京赛普泰克技术有限公司 | A kind of S Zorb systems using novel feed tank pressuring method |
| CN108441256A (en) * | 2018-03-06 | 2018-08-24 | 国家能源投资集团有限责任公司 | Benefit sulphur method and device in hydroprocessing processes |
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| CN103980935A (en) * | 2014-05-20 | 2014-08-13 | 王荣超 | Sulfur supplement technology for hydrogenation treatment |
| CN104946300A (en) * | 2015-05-28 | 2015-09-30 | 王荣超 | Sulfur supplement device for hydrotreatment |
| CN105236645A (en) * | 2015-09-14 | 2016-01-13 | 王树宽 | Hydrogenation acid water hydrogen sulfide recycling process and system thereof |
| CN106398752A (en) * | 2016-10-18 | 2017-02-15 | 山东宝塔新能源有限公司 | Device for supplementing sulfur for hydrogenation reaction by means of collecting tower top hydrogen sulfide from hydrogen sulfide removal stripping towers for hydrogenation reaction on coal tar |
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| CN104927904B (en) | 2018-07-06 |
| CN103980935A (en) | 2014-08-13 |
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