CN101705108A - Liquid hydrocarbon mercaptan removal technique capable of deeply removing total sulfur - Google Patents
Liquid hydrocarbon mercaptan removal technique capable of deeply removing total sulfur Download PDFInfo
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- CN101705108A CN101705108A CN200910250279A CN200910250279A CN101705108A CN 101705108 A CN101705108 A CN 101705108A CN 200910250279 A CN200910250279 A CN 200910250279A CN 200910250279 A CN200910250279 A CN 200910250279A CN 101705108 A CN101705108 A CN 101705108A
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- mercaptan
- alkali
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- 238000000034 method Methods 0.000 title claims abstract description 47
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 44
- 239000007788 liquid Substances 0.000 title claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title abstract description 47
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 43
- 239000011593 sulfur Substances 0.000 title abstract description 43
- 230000008929 regeneration Effects 0.000 claims abstract description 61
- 238000011069 regeneration method Methods 0.000 claims abstract description 61
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
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- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention relates to a liquid hydrocarbon mercaptan removal technique capable of deeply removing total sulfur, in particular to a sweetening technique for liquefied gas in an oil refinery. The oil refining liquid hydrocarbon refers to components of liquefied gas and light gasoline, wherein the liquefied gas is a raw material for producing MTBE, and the light gasoline is a component for producing high-cleanness gasoline. In order to solve the problem of high total sulfur in the oil refining MTBE and the light gasoline, according to the shape and the distribution rule of sulfocompounds in the liquid hydrocarbon, processes such as functional reinforcement of a recycle solvent, three-phase mixed reinforced regeneration, regenerated catalyst and extractant separation and recycle solvent deoxidization and the like are adopted in the conventional process of liquid hydrocarbon extraction, oxidization and mercaptan removal, so the technical effects of reinforcing the mercaptan removal depth, improving carbonyl sulfide removal rate, and avoiding forming disulphide in the extracting, saving energy and reducing emission and the like are achieved. Thus, the liquid hydrocarbon can be deeply desulfurated, the problem of high total sulfur in the oil refining MTBE and the light gasoline is solved and the slag discharging quantity in the conventional process is greatly reduced.
Description
Technical field
The present invention relates to a kind of liquid hydrocarbon mercaptan removal technique, relate in particular to a kind of technology of oil refinery liquefied gas mercaptan removal.
Background technology
Oil refinery liquefied gas is mainly derived from catalytic cracking and delayed coking unit.The catalytic cracking liquefied gas is a main raw material of producing oil refining propylene and MTBE.In recent years, along with the requirement that comprehensive utilization of resources is constantly deepened, the coking liquefied gas also is used as the raw material of producing oil refining propylene and MTBE.In the production process of MTBE, as methyl alcohol, etherification reaction also can take place in mercaptan and iso-butylene, also may take place simultaneously from etherification reaction; Adding MTBE has higher factors such as solvability to sulfide than carbon four hydrocarbon, and during carbon four fractionation by distillation, the sulfide in carbon four raw materials is almost all by the enrichment of MTBE product institute behind MTBE and ether.If the incomplete words of liquefied gas desulfurizing and refining, the sulphur content of MTBE product will highly get surprising.Catalysis and coking respectively account for half in the liquefied gas raw material of the production MTBE of Shandong enterprise, and the refining back of liquefied gas total sulfur is by traditional 343mg/Nm that is not more than
3Control indexes, but the sulphur content of MTBE product is up to 1000～3000ppm.In view of MTBE to reasons such as the unstable of the dissolution characteristics of sulfide, molecular structure and self are water-soluble, desulfurization is suitable difficulty from MTBE.So deep desulfuration is very important from liquefied gas.
The content difference of each sulfide is very big in the liquefied gas, has certain rules but distribute.Wherein be mainly H
2S and mercaptan, H
2S and mercaptan are active sulphur, can be by refining the removing of alkalization extracting; And neutral sulfide contents such as carbonylsulfide and dimethyl sulfide seldom.All there is liquefaction qi exhaustion H in general enterprise
2The measure of S and mercaptan removal.Taking off H
2In the process of S and mercaptan removal, COS also can partly be removed.So as long as removed H more completely
2S and mercaptan, the total sulfur of refining back liquefied gas just can drop to lower level.General catalytic liquid gasification can drop to below the 5ppm, and the coking liquefied gas also can drop to below the 30ppm, well below the 343mg/Nm that is not more than of conventional art requirement
3Index.Yet the refining back of present most enterprises liquefied gas total sulfur is higher than theoretical value far away; Especially the coking liquefied gas can be reduced to 343mg/Nm
3Following is all less, and utmost point discrete is up to 600～800mg/Nm
3The sulfide of analyzing in the refining postindustrial liquefied gas is formed, and finds that its main component is a disulphide.As seen, liquid gas sweetening technology is unreasonable is to cause the high major cause of refining back total sulfur.
Merox extracting and oxidizing method is the mercaptan removal technique of extensive employing (see " petroleum refining engineering " third edition for details, the woods generation ruler of great talent and bold vision compiles, the 598th～600 page) of liquefied gas.Its principle is according to slightly acidic and these two characteristics of the easy oxidized generation disulfide of mercaptan negative ion of mercaptan, and reaction equation is as follows:
At first generate sodium mercaptides by highly basic (NaOH) and thiol reactant, sodium mercaptides is dissolved in the alkali lye, thereby removes from liquefied gas; Extracting has the alkali lye (being rich solvent) behind the mercaptan, can by the heating with mercaptan remove regeneration or under catalyst action bubbling air be that disulphide removes regeneration with mercaptan oxidation, regeneration has removed the alkali lye behind the mercaptan (being lean solvent) and has recycled, and can avoid the generation of a large amount of alkaline residues.
Traditional technology is dissolved in regenerated catalyst in the circulation alkali liquor to be used, so circulation alkali liquor generally is also referred to as circulation agent alkali.Traditional technology is generally used the equipment of static mixer, sieve-tray tower, packing tower or fiber (film) Shu Zuowei agent hydrocarbon contact extracting mercaptan; Regeneration adopts random packing or void tower air blast as the catalytic equipment of agent wind.Take back the extracting section again for the disulphide that prevents to generate is recycled agent alkali, traditional technology also is furnished with the solvent back suction and proposes measure, generally is to carry out back suction with the solvent of light oil after to regenerative response to carry.
At present the problem that exists of liquid gas sweetening device mainly show as take off that the back total sulfur is higher, copper corrosion and bed drain purge are big etc.Containing more disulphide in the liquefied gas of refining back is the irrational strong evidence of doctor process, and its substantive issue extracting and regeneration effect often is poor, and wherein the regeneration effect difference is a key problem.Just in time opposite with demercaptaning for gasoline, the difficult point of liquid gas sweetening reaction is regeneration.The concentration of sodium mercaptides of regenerating in the bad agent alkali that causes circulating is higher, and this has restricted the degree of depth of extraction desulfurization alcohol on the one hand, has improved the solublization of agent alkali to disulphide on the other hand again.This two aspect all is to cause the higher factor of liquefied gas refining back total sulfur.
In addition, the traditional technology regenerated catalyst is dissolved in alkali lye and recycles, and catalyzer in the alkali lye and dissolved oxygen just make the part sodium mercaptides that the side reaction of disulphide has taken place to change into when carrying out extractive reaction, and is especially remarkable in the side reaction of loading when higher of agent alkali sulphur.Adopted strict secondary back suction to propose measure behind some business regenerations, but refining back disulphide content is still very high, reason just is this.
Summary of the invention
The present invention relates to a kind of reinforcement and improved technology to conventional liquid hydrocarbon Merox extracting and oxidizing method doctor process, keeping or improving on the basis of original technology mercaptan removal level, realized that the target of total sulfur falls in the liquid hydrocarbon degree of depth, and then, provide solution for the control MTBE of quality of gasoline upgrading proposition and the problem of petroleum naphtha total sulfur.Liquid hydrocarbon of the present invention is meant liquefied gas (C3, C4 are main mixture) and the light gasoline fraction (C5, C6 are main mixture) that refinery is produced in secondary processing process, be rich in valuable active olefin in these cuts, generally be not suitable for adopting hydrofining.These cuts required to carry out sulfide removal and make with extra care before further processing or utilizing.
The present invention is in the know-why of analysing in depth traditional liquefied gas Merox extracting and oxidizing method mercaptan removal, and the refining back of liquefied gas disulphide is to cause the true basis of the high major cause of total sulfur upward to propose, mainly comprise the steps: to adopt liquid-liquor alkali extraction process to carry out mercaptan removal pending liquid hydrocarbon, to the agent alkali (being rich solvent) that contains mercaptan after the extracting, the technology that adopts agent wind oil three-phase to react through stagnant catalyst bed generation mixed oxidization together, remove regeneration after mercaptan is converted into disulphide, the agent alkali after the regeneration (being lean solvent) recycles; This technology also can may further comprise the steps:
In mercaptan removal extractant alkali, add function intensified auxiliary agent, with the ability of raising extracting mercaptan and the activity of oxidation regeneration;
The means such as combination that adopt vacuum, heating and nitrogen gas to put forward technology or these technologies are implemented deoxidation to circulating solvent;
The oxidation wind that uses in the reclaiming process is implemented to remove CO
2Preliminary cleaning.
Specify the present invention below by difference with the prior art of the present invention:
1, traditional technology adopts the circulation agent of catalyzer alkali lye as mercaptan removal.Wherein alkali lye is extractant, and catalyzer is the oxidation regeneration catalyzer.The present invention has added function intensified auxiliary agent again in as the alkali lye of circulation agent, according to effect of requirement, the add-on of function intensified auxiliary agent can change in 0.5～20wt% scope in the circulation agent, with the ability of raising extracting mercaptan and the activity of oxidation regeneration.
Wherein, described alkali lye is the alkaline aqueous solution such as NaOH, KOH or quaternary ammonium hydroxide;
Described regenerated catalyst is Co, Fe, Mo, V, Ni and/or Cu metallo phthalocyanine, be generally sulfonated phthalocyanine cobalt or poly-phthalocyanine cobalt, the add-on of regenerated catalyst can change in 50～300ppm (if no special instructions, ppm described herein is mass ratio) scope in the tradition circulation agent;
Described function intensified auxiliary agent has the extracting of helping and helps the function of catalytic regeneration, be selected from the organic compound that has hydroxyl, ketone group or carboxyl and in the quaternary amines material one or more, for example ethanol, ethylene glycol, acetone, isopropylformic acid, anthraquinone, thanomin, wherein said quaternary amines material is selected from, for example dodecyl dimethyl benzyl ammonium chloride, hydroxide octadecyl dimethyl benzyl ammonium etc.
Function intensified auxiliary agent also can increase the solubleness of carbonylsulfide in agent alkali simultaneously, has promoted the hydrolysis of carbonylsulfide and removes, thereby obtained higher desulfurization depth beyond depriving hydrogen sulphide, the mercaptan removal, and the hydrolysis reaction of carbonylsulfide in water is as follows:
Be used for the extractive contact reacts equipment of liquid-liquor alkali among the present invention and be one or more of this area static mixer, tray column or packing tower commonly used, tunica fibrosa contact reactor.
2, conventional regeneration process using agent wind two-phase mixing and contacting reaction is carried out back suction again and is carried after the reaction.In order to improve speed of response, the circulation agent need be heated to 50～60 ℃.Reclaiming process of the present invention adopts agent wind oil three-phase mixing and contacting reaction, the disulphide that regenerative response is formed can in time be transferred in the anti-extract oil, strengthened the regenerative response impellent, add the effect that helps the catalytic regeneration functional agent, thereby improved regeneration effect greatly, such reclaiming process has not only reduced the concentration of mercaptan in the reprocessing cycle solvent, has also realized normal temperature regeneration, simplify flow process and control, reduced investment and process cost.
3, the circulation agent of traditional technology is the alkali lye that contains oxide catalyst, contains sufficient dissolved oxygen in the circulation agent after the regeneration, and this part oxygen also is the factor that the oxidation side reaction takes place when causing extractive reaction.The present invention adopts the fixed bed catalyst technology, oxide catalyst is fixed in the regenerator column, thereby has obviously weakened the influence of dissolved oxygen, and the principal element of regeneration side reaction takes place when having eliminated extractive reaction.But under the situation that the smart desulfurization requirement of the degree of depth is arranged, circulating solvent is implemented deoxidation be still necessary.The present invention adopts vacuum, heating and nitrogen gas to carry or the means such as combination of these measures are implemented deoxidation to circulating solvent (being lean solvent), to prevent that dissolved oxygen in the circulating solvent is in the extractive generation that causes generating the reaction of disulphide simultaneously.Fixed bed catalyst can be a carrier with activated alumina, gac, porous resin, molecular sieve and/or carbon fiber absorption property material, and load C o, Fe, Mo, V, Ni and/or Cu metallo phthalocyanine constitute.The preferred fixed bed catalyst of the present invention is cocoanut active charcoal load sulfonated phthalocyanine cobalt or poly-phthalocyanine cobalt.
4, traditional technology directly uses pressurized air as regenerating oxidation wind.CO in the atmosphere
2Content generally about 300ppm (shown in the table 1 composed as follows of dry air).CO
2Generate yellow soda ash with the alkali lye contact reacts, not only consume the life-span that NaOH in the alkali lye influence circulation agent, and the yellow soda ash that generates is lower because of solubleness, crystallization deposition endangers very big to regeneration activity on fixed bed easily at low temperatures.The present invention implements to remove CO to oxidation wind
2Preliminary cleaning, can further prolong mercaptan removal circulation agent alkali work-ing life, reduce deslagging, also can protect the activity and the life-span of regeneration fixed bed catalyst.The used alkali of extractant of the present invention preferably adopts ion film caustic soda, to reduce the content of various impurity.The present invention can adopt liming, and perhaps the mixing solutions of calcium chloride and NaOH removes CO as oxidation wind
2The preliminary cleaning absorption agent, also can adopt solid-state active metal oxide absorption agent, as activated ferric oxide, active zinc flower etc.
Table 1: the composition of dry air
| Form | ??O 2 | ?N 2 | ?Ar | ?CO 2 |
| ????V％ | ??20.93 | ?78.03 | ?0.93 | ?0.03 |
Description of drawings
Accompanying drawing 1, Fig. 2, Fig. 3, Fig. 4 are the process flow sheet of exemplary embodiments of the present invention.
Figure 1 shows that five process combination implement schema of the present invention;
Figure 2 shows that function intensified auxiliary agent and agent wind oil three-phase mixed regeneration process combination implements schema of the present invention;
Figure 3 shows that agent wind oil three-phase mixed regeneration and fixed bed catalyst process combination implement flow process of the present invention;
Figure 4 shows that fixed bed catalyst individual event implementation of processes schema of the present invention;
Wherein:
M-1. first step extracting contact reactor;
M-2. second stage extracting contact reactor;
M-3. product is washed contactor;
M-4. the agent that circulates regeneration premixer;
D-1. first step extractive reaction settlement separator;
D-2. second stage extractive reaction settlement separator;
D-3. product is washed settlement separator;
D-4. reprocessing cycle agent triphase separator;
D-5. the agent preparing tank circulates;
C-1. regeneration reactor;
C-2. oxidation wind carbonic acid gas prepurifier;
C-3. reprocessing cycle agent deoxygenator;
P-1. lean solvent pump;
P-2. half lean solvent pump;
P-3. anti-extract oil is sent pump outside.
The explanation of three kinds of states of circulation agent:
Lean solvent: through regeneration, sulfide content seldom prepares to return the circulating solvent that the extracting section is used;
Rich solvent: through the two-stage extracting, sulfide content is very high, prepares to go the regenerated circulating solvent;
Half lean solvent: through the one-level extracting, sulfide content is less, prepares to go the extractive circulation agent of next stage.
Specific embodiment
The invention will be further described to contrast accompanying drawing with embodiment below, and described embodiment just is used to help those skilled in the art to understand the present invention, rather than limit range of application of the present invention.
The present invention is above-mentioned listedly " to add function intensified auxiliary agent, agent wind oil three-phase mixed regeneration, fixed bed catalyst, lean solvent deoxidation and oxidation wind and takes off CO in the agent alkali
2Preliminary cleaning " etc. technology, can be according to composite factors such as the harsh degree of the height of raw material liquid hydrocarbon mercaptan, the total sulfur of will begging to surrender, investment amount and original device situations, flexible combination or adopt separately.
With reference to Figure of description 1, the flow process that the present invention adopts above-mentioned five process combination to implement is as follows:
Extraction desulfurization alcohol: the stock liquid gasification that removes behind the hydrogen sulfide advances one-level extractive reaction device M-1, fully contact with half lean solvent of sending here from secondary extracting settlement separator D-2, carry out the reaction of extraction desulfurization alcohol, according to mercaptans content situation in the liquefied gas, agent hydrocarbon volume ratio can be controlled between 0.1～1. then, agent hydrocarbon two-phase is advanced one-level extracting settlement separator D-1 and is separated, and the agent hydrocarbon mixture is not less than 30 minutes in the D-1 residence time; Liquefied gas after slightly taking off goes out from the D-1 roof pressure, advance secondary extractive reaction device M-2, contact and carry out smart sweetening reaction with the lean solvent after the regeneration, control agent hydrocarbon volume ratio 0.1～is 1. advanced secondary extracting settlement separator D-2 then and is carried out agent-hydrocarbon separation, the agent hydrocarbon mixture is not less than 30 minutes in the D-2 residence time. and the liquefied gas behind the smart mercaptan removal extrudes to anhydrate from the D-2 top and washes, wherein mercaptan sulfur content is lower than 3ppm, disulphide content is lower than 5ppm, generally, catalytic liquid gasification total sulfur can drop to below the 5ppm, coking liquefied gas total sulfur also can drop to below the 30ppm, thereby has realized deep desulfuration; What D-2 bottom was told is half lean solvent, by P-2 force feed isolated rich solvent that contains a large amount of mercaptan in .D-1 bottom to the M-1, is sent to regeneration section certainly and regenerates.
Washing: the liquefied gas behind the smart mercaptan removal extrudes from secondary extracting slurry tank D-2 top, with volume percent is that about 5% softening water enters product washing contactor M-3, enter settlement separate jar of D-3 separation then and cut water, the liquefied gas carrying device after the washing.
It is that the function intensified auxiliary agent of 10～15% NaOH and 10% is formulated that circulation agent alkali generally adopts weight percent.
In the C-1 is fixed bed catalyst, selects 4～8 purpose cocoanut active charcoal load sulfonated phthalocyanine cobalts for use.Wherein the charge capacity of sulfonated phthalocyanine cobalt is in 4000ppm.
The regeneration of circulation agent alkali: rich solvent goes out from force feed from the D-1 bottom, injects the oxidation wind and the anti-extract oil of preliminary cleaning before circulation agent regeneration premixer M-4, enters regenerator column C-1 and finish regenerative response behind the M-4 thorough mixing; Wherein, the injection rate of oxidation wind is 1.1～3 times of the required theoretical air requirement of mercaptan oxidation, is no more than the injection rate that 5000ppm determines anti-extract oil according to the total sulfur increase of anti-extract oil; The three-phase mixture of finishing behind the regenerative response comes out from the C-1 top, enters triphase separator D-4, and tail gas is sneaked into gas in proportion and avoided after the limits of explosion dividing the gas column branch to go out process furnace from tank deck and make fuel; The anti-extract oil that is dissolved with sulfide is crossed a jar internal partition, by pump P-3 carrying device; The regeneration lean solvent is sent from the D-4 bottom.
The lean solvent deoxidation: the regeneration lean solvent that comes from the D-4 bottom enters reprocessing cycle agent deoxygenator C-3, by vacuumize, heating or nitrogen gas are carried etc., and means are implemented deoxidation to lean solvent, dissolved oxygen in the lean solvent is reduced to below the 1ppm, then before pump P-1 delivers to secondary extractive reaction device M-2, contact with liquefied gas behind the thick mercaptan removal and to carry out smart sweetening reaction.
The preliminary cleaning of oxidation wind: the pressurized air of sending here outside installing enters the oxidation wind carbonic acid gas prepurifier C-2, absorbs or solid state chemistry absorbing and removing CO wherein by aqueous chemical
2, make CO
2Content be reduced to below the 5ppm, delivering to the M-4 previous crops is oxidation wind.
With reference to Figure of description 2, the flow process that the present invention adopts function intensified auxiliary agent and agent wind oil three-phase mixed regeneration process combination to implement is as follows:
Extraction desulfurization alcohol: the stock liquid gasification that removes behind the hydrogen sulfide advances one-level extractive reaction device M-1, fully contact with half lean solvent of sending here from secondary extracting settlement separator D-2, carry out the reaction of extraction desulfurization alcohol, according to mercaptans content situation in the liquefied gas, agent hydrocarbon volume ratio is controlled between 0.1～1.Then, agent hydrocarbon two-phase enters one-level extracting settlement separator D-1 separates, and the agent hydrocarbon mixture is not less than 30 minutes in the D-1 residence time; Liquefied gas after slightly taking off goes out from the D-1 roof pressure, advances secondary extractive reaction device M-2, contacts and carries out smart sweetening reaction, control agent hydrocarbon volume ratio 0.1～1 with lean solvent after the regeneration.Advance secondary extracting settlement separator D-2 then and carry out agent-hydrocarbon separation, the agent hydrocarbon mixture is not less than 30 minutes in the D-2 residence time.Liquefied gas behind the smart mercaptan removal extrudes to anhydrate from the D-2 top and washes, and wherein mercaptan sulfur content is lower than 3ppm, disulphide content is lower than 15ppm, and general, catalytic liquid gasification total sulfur can drop to below the 20ppm, and coking liquefied gas total sulfur also can drop to below the 60ppm; What D-2 bottom was told is half lean solvent, by the P-2 force feed to M-1.The isolated rich solvent that contains a large amount of mercaptan in D-1 bottom is sent to regeneration section certainly and regenerates.
Washing: the liquefied gas behind the smart mercaptan removal extrudes from secondary extracting slurry tank D-2 top, with volume percent is that about 5% softening water enters product washing contactor M-3, enter settlement separate jar of D-3 separation then and cut water, the liquefied gas carrying device after the washing.
Circulation agent alkali generally adopts the function intensified auxiliary agent of adding 10% in the traditional catalyst alkali lye formulated.
Do not contain the filler of supported catalyst in the regenerator column C-1, be generally metallic stuffing or void tower.
The regeneration of circulation agent alkali: rich solvent goes out from force feed from the D-1 bottom, before circulation agent regeneration premixer M-4, inject non-purification wind and anti-extract oil, behind the M-4 thorough mixing, enter regenerator column C-1 and finish regenerative response, wherein, the injection rate of oxidation wind is 1.1～3 times of the required theoretical air requirement of mercaptan oxidation, is no more than the injection rate that 5000ppm determines anti-extract oil according to the total sulfur increase of anti-extract oil; The three-phase mixture of finishing behind the regenerative response comes out from the C-1 top, enters triphase separator D-4, and tail gas divides gas column to go out to tail gas treating unit from tank deck; The anti-extract oil that is dissolved with sulfide is crossed a jar internal partition, by pump P-3 carrying device; The regeneration lean solvent is sent from the D-4 bottom.
Service data shows: raw material is that amine takes off back total sulfur 4000mg/Nm
3The coking liquefied gas, total sulfur is at 300～600mg/Nm behind mercaptan removal on the traditional technology device
3Between; After only adopting function intensified auxiliary agent and three-phase mixed regeneration technology, successfully total sulfur has been reduced to below the 40ppm; And realized normal temperature regeneration, bed drain purge has reduced one times, and liquefied gas per ton is saved heating steam 20kg.
With reference to Figure of description 3, the flow process that the present invention adopts agent wind oil three-phase mixed regeneration and fixed bed catalyst process combination to implement is as follows:
Extraction desulfurization alcohol: the stock liquid gasification that removes behind the hydrogen sulfide advances one-level extractive reaction device M-1, fully contact with half lean solvent of sending here from secondary extracting settlement separator D-2, carry out the reaction of extraction desulfurization alcohol, according to mercaptans content situation in the liquefied gas, between caning be controlled in 0.1～1, agent hydrocarbon volume ratio changes.Agent hydrocarbon two-phase is advanced one-level extracting settlement separator D-1 then and is separated, and the agent hydrocarbon mixture is not less than 30 minutes in the D-1 residence time; Liquefied gas after slightly taking off goes out from the D-1 roof pressure, advances secondary extractive reaction device M-2, contacts and carries out smart sweetening reaction, control agent hydrocarbon volume ratio 0.1～1 with lean solvent after the regeneration.Advance secondary extracting settlement separator D-2 then and carry out agent-hydrocarbon separation, the agent hydrocarbon mixture is not less than 30 minutes in the D-2 residence time.Liquefied gas behind the smart mercaptan removal extrudes to anhydrate from the D-2 top and washes, and wherein mercaptan sulfur content is lower than 5ppm, disulphide content is lower than 8ppm, and general catalytic liquid gasification total sulfur can drop to below the 20ppm, and coking liquefied gas total sulfur also can drop to below the 50ppm; What D-2 bottom was told is half lean solvent, by the P-2 force feed to M-1.The isolated rich solvent that contains a large amount of mercaptan in D-1 bottom is sent to regeneration section certainly and regenerates.
Washing: the liquefied gas behind the smart mercaptan removal extrudes from secondary extracting slurry tank D-2 top, with volume percent is that about 5% softening water enters product washing contactor M-03, enter settlement separate jar of D-3 separation then and cut water, the liquefied gas carrying device after the washing.
Circulation agent employing weight percent is 10～15% NaOH solution.
Regenerator column C-1 is catalyst fixed bed, selects 3～5 purpose cocoanut active charcoal load phthalocyanine cobalt sulphonamide for use.Wherein the charge capacity of phthalocyanine cobalt sulphonamide is in 4000ppm.
Circulation agent regeneration: rich solvent goes out from force feed from the D-1 bottom, before circulation agent regeneration premixer M-4, inject non-purification wind and anti-extract oil, behind the M-4 thorough mixing, enter regenerator column C-1 and finish regenerative response, wherein, the injection rate of oxidation wind is 1.1～3 times of the required theoretical air requirement of mercaptan oxidation, is no more than the injection rate that 5000ppm determines anti-extract oil according to the total sulfur increase of anti-extract oil; The three-phase mixture of finishing behind the regenerative response comes out from the C-1 top, enters triphase separator D-4, and tail gas divides the gas column branch to go out from tank deck and draws high altitude discharge; The anti-extract oil that is dissolved with sulfide is crossed a jar internal partition, by pump P-3 carrying device; The regeneration lean solvent is sent from D-4 bottom pump P-1.
Taking off the back total sulfur in the laboratory with an amine is 4025mg/Nm
3The coking liquefied gas be sample, adopt traditional catalyzer alkali lye to handle total sulfur and be reduced to 390mg/Nm
3, adopt fixed bed catalyst technical finesse total sulfur to be reduced to 60mg/Nm
3(being about 30ppm). analyze the decreasing ratio of finding carbonylsulfide and also reached 65%.
With reference to Figure of description 4, the present invention adopts fixed bed catalyst individual event implementation of processes flow process as follows:
Extraction desulfurization alcohol: the stock liquid gasification that removes behind the hydrogen sulfide advances one-level extractive reaction device M-1, fully contact with half lean solvent of sending here from secondary extracting settlement separator D-2, carry out the reaction of extraction desulfurization alcohol, according to mercaptans content situation in the liquefied gas, between caning be controlled in 0.1～1, agent hydrocarbon volume ratio changes.Agent hydrocarbon two-phase is advanced one-level extracting settlement separator D-1 then and is separated, and the agent hydrocarbon mixture is not less than 30 minutes in the D-1 residence time; Liquefied gas after slightly taking off goes out from the D-1 roof pressure, advances secondary extractive reaction device M-2, contacts and carries out smart sweetening reaction, control agent hydrocarbon volume ratio 0.1～1 with lean solvent after the regeneration.Advance secondary extracting settlement separator D-2 then and carry out agent-hydrocarbon separation, the agent hydrocarbon mixture is not less than 30 minutes in the D-2 residence time.Liquefied gas behind the smart mercaptan removal extrudes to anhydrate from the D-2 top and washes, and wherein mercaptan sulfur content is lower than 5ppm, disulphide content is lower than 10ppm, and general, catalytic liquid gasification total sulfur can drop to below the 25ppm, and coking liquefied gas total sulfur also can drop to below the 50ppm; What D-2 bottom was told is half lean solvent, by the P-2 force feed to M-1.The isolated rich solvent that contains a large amount of mercaptan in D-1 bottom is sent to regeneration section certainly and regenerates.
Washing: the liquefied gas behind the smart mercaptan removal extrudes from secondary extracting slurry tank D-2 top, with volume percent is that about 5% softening water enters product washing contactor M-3, enter settlement separate jar of D-3 separation then and cut water, the liquefied gas carrying device after the washing.
Alkali lye is adopted in the circulation agent, and wherein the weight percent of NaOH is 10～15%.
Regenerator column C-1 is catalyst fixed bed, selects for use the poly-phthalocyanine cobalt of 4～8 purpose cocoanut active charcoal loads to constitute.The charge capacity of wherein carrying poly-phthalocyanine cobalt is in 4000ppm.
Circulation agent regeneration: rich solvent goes out from force feed from the D-1 bottom, injects non-purification wind before circulation agent regeneration premixer M-4, enters regenerator column C-1 and finish regenerative response behind the M-4 thorough mixing; The mixture of finishing behind the regenerative response comes out from the C-1 top, enters separator D-4, and tail gas divides the gas column branch to go out aftertreatment from tank deck; The regeneration lean solvent is sent by pump P-1 from the D-4 bottom.
Taking off the back total sulfur in the laboratory with an amine is 260mg/Nm
3The catalytic liquid gasification be sample, adopt traditional catalyzer alkali lye to handle total sulfur and be reduced to 39mg/Nm
3, adopt the alkali lye processing total sulfur of catalyst-free to be reduced to 6mg/Nm
3(being about 3ppm).
The invention effect
1, fall total sulfur: wherein mercaptan sulfur content is lower than 3ppm, disulphide content is lower than 5ppm; Generally, catalytic liquefaction gas total sulfur can drop to below the 5ppm, and coking liquefied gas total sulfur also can drop to below the 30ppm, thereby has realized deep desulfuration.
2, reduce discharging: strengthen extracting and regeneration techniques measure, make the agent basic active improve four times than traditional catalyst alkali lye, deslagging is reduced to 1/4th of original bed drain purge.
3, energy-conservation: the intensifying regenerating technical measures make agent alkali realize normal temperature regeneration, the energy consumption that one ton of liquefied gas of every processing is saved 60～140MJ at least.
Claims (8)
1. the doctor process of a liquid hydrocarbon, comprise and adopt liquid-liquor alkali extraction process to carry out mercaptan removal pending liquid hydrocarbon, described dose of alkali is meant by alkali lye or the alkali lye that added function intensified auxiliary agent as extractant, extracting the agent alkali of mercaptan adopt agent wind oil three-phase that the mixed oxidization reaction takes place on the oxide catalyst fixed bed together, remove after mercaptan is converted into disulphide, thereby make the agent alkali regeneration that contains mercaptan after the extracting, the agent alkali after the regeneration enters the technology that recycles in liquid-liquor alkali extraction process.
2. the doctor process of the described liquid hydrocarbon of claim 1, it is characterized in that, also comprise function intensified auxiliary agent in the agent alkali, with the ability of raising extracting mercaptan and the activity of oxidation regeneration, the content of described function intensified auxiliary agent is 0.5～20wt%, be selected from and have hydroxyl, in the organic compound of ketone group or carboxyl and the quaternary amines material one or more, wherein said hydroxyl, the organic compound of ketone group or carboxyl is selected from ethanol, ethylene glycol, acetone, isopropylformic acid, anthraquinone and/or thanomin, wherein said quaternary amines material are selected from dodecyl dimethyl benzyl ammonium chloride and/or hydroxide octadecyl dimethyl benzyl ammonium.
3. the doctor process of the described liquid hydrocarbon of claim 1 is characterized in that, adopts the fixing described oxidation regeneration catalyzer of fixed-bed catalytic technology.
4. the doctor process of the described liquid hydrocarbon of claim 3, it is characterized in that, described oxidation regeneration catalyzer is to be carrier with activated alumina, gac, porous resin, molecular sieve and/or carbon fiber absorption property material, and load C o, Fe, Mo, V, Ni and/or Cu metallo phthalocyanine constitute.
5. the doctor process of claim 1 or 2 described liquid hydrocarbons is characterized in that, employing vacuum, heating and nitrogen gas are proposed one or more the agent alkaline solution enforcement deoxidations to recycling in the technology.
6. the doctor process of the described liquid hydrocarbon of claim 1 is characterized in that, the oxidation wind that uses in the agent alkali reclaiming process is implemented to remove CO
2Preliminary cleaning.
7. the doctor process of the described liquid hydrocarbon of claim 6 is characterized in that, adopts liming, and perhaps the mixing solutions of calcium chloride and NaOH is as removing CO
2The preliminary cleaning absorption agent, also can adopt solid-state active metal oxide absorption agent, described active metal oxide is selected from activated ferric oxide or active zinc flower.
8. the doctor process of the described liquid hydrocarbon of claim 4 is characterized in that, fixed bed catalyst is cocoanut active charcoal load sulfonated phthalocyanine cobalt or poly-phthalocyanine cobalt.
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