CN1330126A - Process for removing organosulfur from liquefied petroleum gas - Google Patents
Process for removing organosulfur from liquefied petroleum gas Download PDFInfo
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Abstract
A process for removing organosulfur from liquefied petroleum gas features that after hydrogen sulfide is removed, the liquefied petroleum gas passes through desulfurizing agent bed, where the organic sulfides is physically and directly adsorbed by desulfurizing agent, whose main component is the modified X-type or Y-type molecular sieve after ion exchange by high-valance metal element (La, Ce, or mixed rare-earth elements). Its advantages are simple process, high efficiency and regenerable desulfurizing agent.
Description
The present invention relates to a kind of liquefied petroleum gas (LPG) be carried out the purified method.
Along with the development of modern petrochemical technology, a lot of effective catalysts require more and more harsher to the sulphur content in the raw material.On the other hand, environmental protection standard is more and more tighter, and the total sulfur content of liquefied petroleum gas (LPG) has been proposed stricter requirement.Sulphur in the liquefied petroleum gas (LPG) can be divided into organosulfur and inorganic sulfur.Inorganic sulfur mainly is a hydrogen sulfide, adopts different sweetening agents and corresponding sulfur removal technology to be easier to remove.Organic sulfide comprises nonpolar sulfide (or claiming neutral sulfide) such as polarity sulfide mercaptan and thioether, sulphur oxygen carbon, dithiocarbonic anhydride, disulphide; The method of organic sulfide removal commonly used has hydrodesulfurization and catalytic oxidation at present.Hydrodesulfurization is to remove after the above-mentioned organosulfur in the liquefied petroleum gas (LPG) is hydroconverted into inorganic sulphide, and this method cost is higher.Catalytic oxidation is the disulfide that mercaptan is changed into no stink, uses solvent extraction, contains doctor negative requirement but the precision of desulfurization can not satisfy raw material.U.S. Pat 4204947 has been introduced a kind of method of smart mercaptan removal, use temperature height not only, and the regeneration condition harshness also can only remove mercaptan, and powerless to the organosulfur of other form.Chinese patent CN8510355.5A has introduced a kind of iron-manganese-zinc sweetening agent, though it has the advantage of organic sulfide removal kind wide ranges, desulfurization temperature is greater than 350 ℃, and so high desulfurization temperature then can't use for the desulfurization of liquefied petroleum gas (LPG).
Molecular sieve has many purposes in physics, chemistry and chemical technology, be suitable as the separation that selective adsorbent is finished each component in the mixture most, and as catalyzer.Utilize X type molecular sieve to remove H in the Sweet natural gas
2S and mercaptan are existing to be used, but can not be used for removing neutral organic sulfide.U.S. Pat 5146039 has proposed the method that the cation-modified molecular sieve of a kind of usefulness removes low levels sulfide in the hydrocarbon polymer, the used molecular sieve of this method is by copper, silver, the zinc modified cation as A type, X type or Y zeolite, can only under the condition of heating, carry out desulfurization to containing the hydrocarbon polymer that sulphur concentration is lower than 20ppm in the use, and its sulfur capacity is less.US5057473 has proposed a kind of desulfuration adsorbent of reproducible molecular sieve carrier, with copper and lanthanum successively as the modified cation of 13X type molecular sieve, ion-exchange used duration of contact is 24 and 48 hours, the temperature of ion-exchange is room temperature and 75～80 ℃, the molecular sieve of exchange back gained is used for the total sulfur that comprises hydrogen sulfide of mobile hydrocarbon polymer is removed, in the experiment that removes fuel of internal combustion engine of being lifted under about 250 ℃ of temperature, can remove 60% total sulfur through 1 hour backflow; Adopt the chemisorption method during this desulfuration adsorbent desulfurization, then adopt corresponding oxidized regenerating method during regeneration, thereby regeneration complexity and work-ing life are shorter.
The objective of the invention is: provide a kind of organic sulfide in the not hydrogen sulfide containing liquefied petroleum gas (LPG) is carried out the method that high-level efficiency removes.
The technical scheme that realizes the object of the invention is: the liquefied petroleum gas (LPG) after removing hydrogen sulfide is by the sweetening agent bed in the removal of organic sulfur from device; Under the effect of sweetening agent, the organic sulfide in the liquefied petroleum gas (LPG) is desulfurized agent and directly adsorbs with physical adsorption; Used sweetening agent is that major ingredient is modified X-type or the Y zeolite after high valence state metallic cation exchange, and high valence state metallic cation is lanthanum, cerium or mixed light rare earth element, and exchange degree is 70%～95%.
Above-mentioned sweetening agent is that the organic sulfide to liquefied petroleum gas (LPG) adsorbs under the working pressure of normal temperature and 0.6～2.0MPa; The air speed that liquefied petroleum gas (LPG) flows through the sweetening agent bed is 1～10h
-1
The removal of organic sulfur from jar that above-mentioned removal of organic sulfur from device is two parallel connections; Liquefied petroleum gas (LPG) one of them removal of organic sulfur from jar organic sulfide removal of flowing through, another removal of organic sulfur from jar is standby; When the logistics outlet that detects the removal of organic sulfur from jar contains sulphur, then will remove in the liquefied petroleum gas (LPG) operation of organic sulfide and switch to standby removal of organic sulfur from jar and carry out; At this moment, can carry out desorption and regeneration to the sweetening agent in the removal of organic sulfur from jar; When the logistics outlet that detects standby removal of organic sulfur from jar contains sulphur, then will remove in the liquefied petroleum gas (LPG) operation of organic sulfide and switch to the removal of organic sulfur from jar and carry out; At this moment, then can carry out desorption and regeneration to the sweetening agent in the standby removal of organic sulfur from jar; Alternately make sweetening agent in removal of organic sulfur from jar and the standby removal of organic sulfur from jar adsorb process with desorption, can keep removing the continuous operation of the organic sulfide operation in the liquefied petroleum gas (LPG).
Use nitrogen or catalysis drying gas that above-mentioned sweetening agent is regenerated; Regeneration temperature is 250～400 ℃, and pressure is normal pressure or negative pressure, and air speed is 100～1000h
-1The regeneration gas that has carried sulfide flows out the removal of organic sulfur from jar and deals with in addition.
Also can use 260～290 ℃ superheated vapour that above-mentioned sweetening agent is regenerated, air speed is 100～1000h
-1The regeneration gas that has carried sulfide flows out the removal of organic sulfur from jar and deals with in addition.
The exchange degree of preferred above-mentioned modified X-type molecular sieve is 82%～95%.The exchange degree of further preferred modified X-type molecular sieve is 82%～86%.
The exchange degree of preferred above-mentioned Modified Zeolite Y is 70%～75%.The exchange degree of further preferred Modified Zeolite Y is 70%～73.5%.
Above-mentioned sweetening agent finished product be shaped as spherical or cylindrical or sheet shape or cloverleaf pattern.
The present invention has positive effect: (1) molecular sieve also is called zeolite, and the original unit that constitutes zeolite is SiO
4, AlO
4Tetrahedron, wherein SiO
4The tetrahedron neutral, AlO
41 negative charge of tetrahedron band, these tetrahedron elements directly constitute secondary unit with Sauerstoffatom, constitute three grades or polyhedron by secondary unit interconnection, are made of the zeolite crystal structure of various characteristics at last the polyhedron unit.This crystalline silica-aluminate has certain cavity and duct uniformly, after dehydration, the material that can make the differing molecular size by or do not pass through, play the effect of screening different substances molecule, so zeolite is called " molecular sieve ".Because the positively charged ion in the molecular sieve is on the skeleton of zeolite, but skeleton outside and [AlO
4]
-Negatively charged ion attracts each other, so its mobility is bigger, can be exchanged by other ions.By exchange-roasting-exchange, can reach the exchange degree more than 80%.Behind intimate 100% ion-exchanged, make it have bigger adsorptive power and loading capacity.People can change physics, the chemical property of molecular sieve by the exchange different ions, thereby enlarge its application in the petroleum chemistry field.Remove in the liquefied petroleum gas (LPG) and contain water, H
2Outside the S, also contain the mercaptan sulfur thing about 100ppm.Can't remove neutral sulfide such as whole mercaptan sulfurs and thioether, thiophene with the molecular sieve of routine.But, after wherein cardioelectric field intensity strengthens greatly, neutral sulfide polarization in its vestibule, as long as the duct is enough big, just can all can be removed the organic sulfide in the liquefied petroleum gas (LPG) by molecular sieve adsorption with the later molecular sieve of different metal ion modification.Can carry out the characteristics of physical adsorption based on molecular sieve, for overcoming it to the low shortcoming of neutral organic sulfide loading capacity, one aspect of the present invention is utilized the rare earth metal positively charged ion of high valence state, molecular sieve is carried out modification, make local location raising electrostatic field intensity in the molecular sieve pore passage, neutral sulfide molecules in the liquefied petroleum gas (LPG) is polarized to be adsorbed easily thereby make, and has therefore improved loading capacity and adsorption efficiency to organic sulfide greatly; The present invention controls on the other hand and selects to make ion-exchange degree to reach 〉=70% degree, and molecular sieve is greatly improved the loading capacity and the adsorption efficiency of neutral organic sulfide.Experimental data of the present invention shows that modified molecular screen has reached 5.3% to the adsorption penetration Sulfur capacity of mercaptan sulfur.Efficiently remove sulfide in the liquefied petroleum gas (LPG) with modified molecular screen, liquefied petroleum gas (LPG) can be reached do not contain any sulfide, become no sulphur liquefied gas truly.(2) the used modified molecular screen of the present invention directly carries out coking liquefaction qi exhaustion H
2Take off the test in place of total sulfur behind the S, show that in air speed be 10h
-1, normal temperature condition under, a certain amount of molecular sieve desulfurizer has passed through the liquefied gas that contains mercaptan of 800 times of volumes, the Sulfur capacity that removes thiomethyl alcohol is near 5%.(3) experimental results show that water-content is that Sulfur capacity reaches 5.3% under the condition of 100ppm in liquefied gas; When water-content was 500ppm, it penetrates Sulfur capacity can reach 4.6%, illustrated that water-content influences Sulfur capacity, in the device actual production, should note water-content, should try one's best and remove moisture in the liquefied gas earlier.(4) method of the present invention can directly be carried out the operation of removal of organic sulfur from thing to the liquefied petroleum gas (LPG) that removes behind the hydrogen sulfide, can be directly remove water and sulfide in the liquefied gas with the fixed bed molecular sieve desulfurizer, comprise the mercaptan that directly removes in the liquefied petroleum gas (LPG), thereby technology of the present invention is simple.(5) molecular sieve desulfurizer regeneration of the present invention is convenient.Molecular sieve after absorption sulfide penetrates makes the sulfide desorption through 300 ℃ of heating, can obtain regeneration.Through absorption more than 200 times, regeneration, absorption, regeneration test, the intensity of molecular sieve is constant, and its activity reaches 95% of new agent, can continue fully to use, thereby long service life.Molecular sieve desulfurizer of the present invention can be regenerated with media such as steam, nitrogen, air, water, can carry out desorption and regeneration under normal pressure and decompression, and the decompression desorption makes regeneration more thorough, more complete.To the regeneration of molecular sieve desulfurizer bed, can purge with the nitrogen or the catalysis drying gas that are heated to 200～300 ℃ in industrial production, also available 1.0MPa superheated vapour purges regeneration, makes molecular sieve desulfurizer obtain regeneration.(6) organosulfur that gets off of the desorption of being taken away by nitrogen or catalysis drying gas or superheated vapour from the molecular sieve can be by burning back system sulphur.Also can be through overcooling, make the recovery that is condensed of the higher organosulfur of boiling point, all the other are by burning back system sulphur; Can separate by different boiling through being cooled to liquid organic sulfide, reclaim and become the organosulfur of high added value product.
Below in conjunction with specific embodiment and sweetening effectiveness test purpose of the present invention, principle and effect are described further.But content of the present invention is not limited to this fully.
(1) preparation of sweetening agent: in concrete implementation process, rare earth metal to be exchanged is prepared into nitrate or hydrochloride, nitrate or hydrochloride are made as the aqueous solution that exchanges liquid, and the concentration of exchange liquid is 0.05～0.2mol/L, the concentration of preferred 0.05～0.09mol/L.Again molecular screen primary powder is contacted and makes molecular sieve modified with the exchange liquid phase, the method of modification adopts 1. return-flow type normal pressure ion exchange method: X type or Y zeolite reflux in exchange liquid repeatedly, through once filter, wash after the exchange, dry, high-temperature roasting, and then carry out exchanging the second time, so that repeated exchanged repeatedly is up to reaching required exchange degree.Exchange and high-temperature roasting hocket, and can improve exchange degree and exchange efficiency.2. continous way normal pressure ion exchange method: be contained in molecular sieve in the packed column or on the fixed bed, metal salt solution exchanged continuously by molecular sieve, reach necessary requirement until exchange degree.In order to improve exchange degree, can raise to the packed column heating by heat conducting method and exchange temperature.Preferred exchange temperature is 81 ℃～95 ℃.3. high pressure ion exchange method is about to exchange liquid and molecular sieve places encloses container, and ion-exchange is carried out in closed system, temperature can rise to about 150～300 ℃, and under corresponding temperature, pressure is also corresponding to be improved, exchange process is strengthened, improved exchange degree and exchange efficiency.
1, with the return-flow type normal pressure ion exchange method modified X-type molecular sieve desulfurizer A that to prepare high valence state metallic cation be lanthanum ion: take by weighing the commercially available silica alumina ratio of 40g at 2.2 to 3.0 X type molecular screen primary powder, place the ground Erlenmeyer flask of 500ml, add in return that the 250ml concentration of liquid is the lanthanum nitrate hexahydrate of 0.09mol/L, the return-flow type normal pressure ion exchange method of employing is carried out swap operation: the Erlenmeyer flask that will be connected with return line placed on the electric furnace reflux 4 hours.Cooled and filtered, washing, oven dry, roasting is 2～4 hours in 490 ℃ of high temperature.After the cooling, carry out the swap operation second time, reflux after 3 hours, by analysis, record exchange degree and reach 86%.
At this moment, cooling, the molecular sieve powder that takes out after exchanging filter, wash, dry, and roasting is 2～4 hours in 490 ℃ of high temperature, makes finished product A.
2, with the return-flow type normal pressure ion exchange method modified X-type molecular sieve desulfurizer B that to prepare high valence state metallic cation be cerium ion: all the other are with embodiment 1, difference is: exchange liquid is the cerous nitrate solution of 0.1mol/L, exchange the back, exchange degree reaches 85%, makes finished product B.
3, preparing high valence state metallic cation with return-flow type normal pressure ion exchange method is the cationic modified X-type molecular sieve desulfurizer of mixed light rare earth element C: all the other are with embodiment 1, difference is: exchange liquid is the mixed light rare earth nitrate solution of 0.15mol/L, makes exchange degree and reaches 82.5% finished product C.Mixed light rare earth is produced by rare earth factory of Baotou Iron and Steel Company, and in the mixed light rare earth nitrate solution, lanthanum nitrate accounts for 50%, cerous nitrate accounts for 21%, europium nitrate accounts for 0.175%.
If will obtain the modified molecular screen of higher exchange degree (for example from 86% to 95%), can exchange and roasting by same process once more or repeatedly by two finished product A, B or the C that hand over two roasting methods to obtain above-mentioned, meet the requirements of finished product until obtaining exchange degree.
4, with the return-flow type normal pressure ion exchange method Modified Zeolite Y sweetening agent D that to prepare high valence state metallic cation be lanthanum ion: take by weighing the commercially available silica alumina ratio of 50g at the former powder of 3.0 to 5.0 Y zeolite, place the ground Erlenmeyer flask of 500ml, add in return that the 300ml concentration of liquid is in the lanthanum nitrate hexahydrate of 0.09mol/L, the return-flow type normal pressure ion exchange method of employing is carried out swap operation: the Erlenmeyer flask that will be connected with return line placed on the electric furnace reflux 5 hours.Cooled and filtered, washing, oven dry, roasting is 2～4 hours in 530 ℃ of high temperature.After the cooling, carry out the swap operation second time, reflux after 4 hours, by analysis, record exchange degree and reach 73.5%.At this moment, cooling, the molecular sieve powder that takes out after exchanging filter, wash, dry, and roasting is 2～4 hours in 530 ℃ of high temperature, makes finished product D.
5, with the return-flow type normal pressure ion exchange method Modified Zeolite Y sweetening agent E that to prepare high valence state metallic cation be cerium ion: all the other are with embodiment 4, difference is: exchange liquid is the cerous nitrate solution of 0.1mol/L, exchange the back, exchange degree reaches 72%, makes finished product E.
6, preparing high valence state metallic cation with return-flow type normal pressure ion exchange method is the cationic Modified Zeolite Y sweetening agent of mixed light rare earth element F: all the other are with embodiment 4, difference is: exchange liquid is the mixed light rare earth nitrate solution of 0.15mol/L, makes exchange degree and reaches 70.5% finished product F.Mixed light rare earth is produced by rare earth factory of Baotou Iron and Steel Company, and in the mixed light rare earth nitrate solution, lanthanum nitrate accounts for 50%, cerous nitrate accounts for 21%, europium nitrate accounts for 0.175%.
If will obtain the modified molecular screen of higher exchange degree (for example from 73.6% to 75%), can exchange and roasting by same process once more or repeatedly by two finished product D, E or the F that hand over two roasting methods to obtain above-mentioned, meet the requirements of finished product until obtaining exchange degree.
7, with the high pressure ion exchange legal system modified X-type molecular sieve desulfurizer G that to be equipped with high valence state metallic cation be lanthanum ion: the X type molecular screen primary powder that takes by weighing 40g, add in the 500ml autoclave, add 0.11mol/L lanthanum nitrate hexahydrate 250ml, temperature rises to about 250 ℃, and ion-exchange is carried out in closed system, under corresponding temperature, pressure is also corresponding to be improved, and 4 hours swap times are behind the naturally cooling, filter, washing, oven dry, 480 ℃ of roastings 2 hours, make finished product G.After measured, exchange degree reaches 88%.
8, with the high pressure ion exchange legal system Modified Zeolite Y sweetening agent G that to be equipped with high valence state metallic cation be lanthanum ion: the former powder of Y zeolite that takes by weighing 40g, add in the 500ml autoclave, add 0.06mol/L lanthanum nitrate hexahydrate 350ml, temperature rises to about 250 ℃, and ion-exchange is carried out in closed system, under corresponding temperature, pressure is also corresponding to be improved, and 3.5 hours swap times are behind the naturally cooling, filter, washing, oven dry, 550 ℃ of roastings 2 hours, make finished product H.After measured, exchange degree reaches 72%.
9, with the continous way normal pressure ion exchange method modified X-type molecular sieve desulfurizer I that to prepare high valence state metallic cation be lanthanum ion: the X type molecular screen primary powder that takes by weighing 50g, molecular screen primary powder is contained in the packed column, with the temperature of the method rising exchange column of nichrome wire energising heating.The exchange temperature of control molecular sieve is about 90 ℃.Preparation 0.06mol/L lanthanum nitrate hexahydrate makes lanthanum nitrate hexahydrate splash into molecular sieve continuously from top to bottom and exchanges, and continues exchange 5 days, makes finished product I, and after measured, exchange degree reaches 83%.
10, with the continous way normal pressure ion exchange method Modified Zeolite Y sweetening agent J that to prepare high valence state metallic cation be lanthanum ion: the former powder of Y zeolite that takes by weighing 50g, molecular screen primary powder is contained in the packed column, with the temperature of the method rising exchange column of nichrome wire energising heating.The exchange temperature of control molecular sieve is about 90 ℃.Preparation 0.08mol/L lanthanum nitrate hexahydrate makes lanthanum nitrate hexahydrate splash into molecular sieve continuously from top to bottom and exchanges, and continues exchange 6 days, makes finished product J, after measured, exchange degree reaches 70%.
11, prepare the modified molecular screen sweetening agent with return-flow type normal pressure ion exchange method
Temperature, time, concentration that relevant temperature, time, concentration conditions adopt during respectively with preparation above-mentioned finished product A～F are identical, and difference is, relevant equipment and material consumption are amplified 100 times or 1000 times respectively.When carrying out the swap operation second time, after recording ion-exchange degree and reaching requirement numerical value, cooling, the molecular sieve powder that takes out after exchanging filter, wash, dry, the shape of the sphere of required physical strength, cylindrical, sheet or cloverleaf pattern is made in machine-shaping, carries out roasting again and promptly makes the finished product sweetening agent.
12, be equipped with the modified molecular screen sweetening agent with the high pressure ion exchange legal system
Relevant temperature, time, concentration conditions are identical with temperature, time, the concentration that preparation is adopted when above-mentioned finished product G, H respectively, and difference is, relevant equipment and material consumption are amplified 100 times or 1000 times.When carrying out swap operation, after recording exchange degree and reaching requirement numerical value, cooling, the molecular sieve powder that takes out after the exchange filter, wash, dry, and the shape of the sphere of required physical strength, cylindrical, sheet or cloverleaf pattern is made in machine-shaping, carries out roasting again and promptly makes the finished product sweetening agent.
For obtaining bigger loading capacity and better adsorption effect, should note when preparing sweetening agent of the present invention: the 1. preferred X type molecular sieve of molecular sieve, the X type is compared with Y zeolite, and X type molecular sieve silica alumina ratio is low, and tradable positively charged ion is more than Y zeolite.The high-valence cationic that X type molecular sieve exchanges up is more than the Y type, so the loading capacity of modification X molecular sieve is greater than Modified Zeolite Y.2. preferred La
3+As exchange ion, because in the used high-valence cationic of modification, La
3+The polarity of the molecular sieve after the ion-exchange is the strongest, so loading capacity is bigger.3. the exchange back requires exchange degree 〉=82% for the modified X-type molecular sieve, requires exchange degree 〉=70% for Modified Zeolite Y.The molecular sieve of modification is made the desulfuration adsorbent of the sphere of required physical strength, cylindrical, sheet or cloverleaf pattern through further machine-shaping.For increasing to the intensity of product sweetening agent, after modification, can add an amount of binding agent in the molecular sieve powder, as sweet soil of sheep etc., add-on is not more than 30% (wt) of sweetening agent gross weight.
(2) laboratory removes the embodiment of the contained organic sulfide of liquefied petroleum gas (LPG)
Embodiment 1,
The reaction tube diameter 13mm of pressurization evaluating apparatus, sweetening agent is respectively above-mentioned finished product A～H, and granularity is 40 orders, and Intake Quantity is 10ml.Test conditions: air speed is 2h
-1Temperature is 20～25 ℃; Pressure is 0.8MPa.Allow the liquefied petroleum gas (LPG) that the contains organic sulfide reaction tubes by the pressurization evaluating apparatus, (lowest detection amount 〉=0.2ppm) detects the content of sulphur with Microcoulomb instrument to the liquefied petroleum gas (LPG) of import and export.
The liquefied petroleum gas (LPG) that experimental raw is used is the C-4-fraction after gas divides, and total sulfur content is 40ppm, H
2S content is 0.Organosulfur comprises: C
3H
6S, C
4H
8S, C
4H
10S, C
5H
12S, C
6H
14S, C
7H
16S, C
2H
6S
2, C
3H
8S
2, C
4H
10S
2, C
5H
12S
2, C
2H
6S
3, C
4H
7NS.C in the organosulfur
2H
6S
2≈ 72%, C
3H
8S
2≈ 8%, C
2H
6S
3≈ 14%, all the other ≈ 6%.
For comparing, also respectively former powder of X type and the former powder of Y type are tested.Test-results sees Table 1.
Table 1: sweetening effectiveness contrast table
In the process of the test, think when sulphur exists that when outlet has detected sweetening agent penetrates, the Sulfur capacity of this moment is for penetrating Sulfur capacity.
Data by table 1 can find out, it once penetrates the molecular sieve after the modification Sulfur capacity and improved 5～10 times than X type or the former powder of Y zeolite.
Regeneration tests: sample A, B, C, D, E, F, G, the H of sulfur-bearing are regenerated with 300 ℃ of high temperature nitrogen purgings, and the regeneration air speed is 500h
-1, regenerating, desulfuration efficiency still is more than 95% of original state after 200 times.
(3) suitability for industrialized production removes the embodiment of the contained organic sulfide of liquefied petroleum gas (LPG)
Embodiment 2,
Behind the LPG Desulfurization hydrogen production device, be arranged in parallel the removal of organic sulfur from jar and the standby removal of organic sulfur from jar of fixed-bed reactor structure, removal of organic sulfur from jar and standby removal of organic sulfur from jar are provided with the sweetening agent bed, the removal of organic sulfur from jar is identical with the structure of standby removal of organic sulfur from jar, diameter is 2.6 meters, highly is 10 meters, in adorn the sweetening agent A that is shaped as cloverleaf pattern of 5～6 millimeters of 16 tons of above-mentioned granularities, the aspect ratio of sweetening agent bed is 2.51, tap density is 0.68g/cm
3, the flow of control liquefied petroleum gas (LPG) is 60 tons/hour, air speed is 4.55h
-1, be under the condition of 1.2MPa at normal temperature, pressure, liquefied petroleum gas (LPG) enters the removal of organic sulfur from jar by the below.
The liquefied petroleum gas (LPG) that enters the removal of organic sulfur from jar is a catalytic liquefied petroleum gas, takes off H through N methyldiethanol amine before entering digester
2S after caustic prescrub removes remaining hydrogen sulfide, takes off post analysis H again
2The content of S is zero, and mercaptans content is 60mg/m
3, copper corrosion is defective.Moisture in the material is 1000ppm.
When liquefied petroleum gas (LPG) is passed through the sweetening agent bed, under the cationic effect of the rare earth metal of high valence state, mercaptan in the liquefied petroleum gas (LPG) is adsorbed, be desulfurized the liquefied petroleum gas (LPG) that the molecular sieve on the agent bed undertakies after the organosulfur absorption by the mode of physics and flow out fixed-bed reactor from top, by analysis, take off in the liquefied petroleum gas (LPG) of back and do not contain mercaptan, copper corrosion is qualified, becomes real no sulphur liquefied petroleum gas (LPG).
When operation detects the outlet of removal of organic sulfur from jar for some time and contains sulphur, switch to standby removal of organic sulfur from jar and carry out removing in the liquefied petroleum gas (LPG) operation of organic sulfide; Can carry out desorption and regeneration at this section to the sweetening agent in the removal of organic sulfur from jar in period; When operation detects standby removal of organic sulfur from jar outlet for some time and contains sulphur, then will remove in the liquefied petroleum gas (LPG) operation of organic sulfide and switch to the removal of organic sulfur from jar and carry out; At this moment, then can carry out desorption and regeneration to the sweetening agent in the standby removal of organic sulfur from jar; Alternately make sweetening agent in removal of organic sulfur from jar and the standby removal of organic sulfur from jar adsorb process with desorption, can keep removing the continuous operation of the organic sulfide operation in the liquefied petroleum gas (LPG).
The concrete grammar that sweetening agent is carried out periodic desorption and regeneration is: under the normal pressure, use 200～300 ℃ nitrogen or catalysis drying gas that sweetening agent is regenerated, air speed is 1000h
-1The regeneration gas outflow removal of organic sulfur from jar or the standby removal of organic sulfur from jar that have carried sulfide carry out burning disposal.
Sweetening agent is carried out the also adoptable method of periodic desorption and regeneration is: use the 1.0MPa superheated vapour that sweetening agent is regenerated, air speed is 500
-1The regeneration gas that the has carried sulfide torch of setting fire.
Embodiment 3 to embodiment 11,
All the other are identical with embodiment 2, and difference is: the sweetening agent of adorning is respectively B～J sweetening agent, and the aspect ratio of sweetening agent bed is 1.16, and air speed is 6.70h
-1
It is under normal pressure that sweetening agent is carried out periodic desorption and regeneration, uses 200～300 ℃ nitrogen or catalysis drying gas that sweetening agent is regenerated, and air speed is 200h
-1Sweetening agent is carried out the also adoptable method of periodic desorption and regeneration is: use the 1.0MPa superheated vapour that sweetening agent is regenerated, air speed is 800
-1
Embodiment 12,
Behind the LPG Desulfurization hydrogen production device, the removal of organic sulfur from jar of two fixed-bed reactor structures is set, the in parallel switching used.The diameter of removal of organic sulfur from jar is 1600mm, highly for 8000mm, in adorn the columniform sweetening agent A that is shaped as of 5～6 millimeters of 10 tons of above-mentioned granularities, the aspect ratio of sweetening agent bed is 4.15, bulk density is 0.77g/cm
3, the flow of control liquefied petroleum gas (LPG) is 20 tons/hour, air speed is 2.68h
-1, be that liquefied petroleum gas (LPG) enters fixed-bed reactor by the below under the condition of 1.2Mpa at normal temperature, pressure.
The liquefied petroleum gas (LPG) that enters the removal of organic sulfur from jar is a catalytic liquefied petroleum gas, takes off H through N methyldiethanol amine before entering the removal of organic sulfur from jar
2S after caustic prescrub removes remaining hydrogen sulfide, takes off post analysis H again
2The content of S is zero, and mercaptans content is 80mg/m
3, copper corrosion is defective.Moisture in the material is less than 1000ppm.
When liquefied petroleum gas (LPG) was passed through the sweetening agent bed, under the cationic effect of the rare earth metal of high valence state, the mercaptan in the liquefied petroleum gas (LPG) was adsorbed.By analysis, take off in the liquefied petroleum gas (LPG) of back and do not contain mercaptan, copper corrosion is qualified, becomes the liquefied petroleum gas (LPG) of no sulphur.
The blocked operation of two removal of organic sulfur from jars is identical with the method for embodiment 2, can keep removing the continuous operation of the organic sulfide operation in the liquefied petroleum gas (LPG).
The concrete grammar that sweetening agent is carried out periodic desorption and regeneration is: use 200～300 ℃ nitrogen or catalysis drying gas that sweetening agent is purged, air speed is 900h
-1Under the air-flow of a small amount of guiding gas (nitrogen or catalysis drying gas), be decompressed under the vacuum tightness of 100mmHg then, carry out desorption; The regeneration gas that has carried sulfide flows out the removal of organic sulfur from jar and carries out burning disposal.
Sweetening agent is carried out the also adoptable method of periodic desorption and regeneration is: use the 1.0MPa superheated vapour that sweetening agent is regenerated, air speed is 300h
-1
Embodiment 13 to embodiment 21,
All the other are identical with embodiment 12, and difference is: the catalyzer of adorning is respectively B～J sweetening agent, and the aspect ratio of sweetening agent bed is 3.11, and air speed is 3.57h
-1
Embodiment 22
Behind coking desulfuration of liquefied gas hydrogen production device, be arranged in parallel the removal of organic sulfur from jar and the standby removal of organic sulfur from jar of fixed-bed reactor structure, removal of organic sulfur from jar and standby removal of organic sulfur from jar are provided with the sweetening agent bed, the removal of organic sulfur from jar is identical with the structure of standby removal of organic sulfur from jar, diameter is 1200mm, highly for 8000mm, in adorn 5～6 millimeters of 6 tons of above-mentioned granularities be shaped as spheric sweetening agent A, the aspect ratio of molecular sieve bed is 5.9, and tap density is 0.75g/cm
3, the flow of control liquefied petroleum gas (LPG) is 15 tons/hour, air speed is 3.35h
-1, be under the condition of 1.0Mpa at normal temperature, pressure, liquefied petroleum gas (LPG) enters removal of organic sulfur from jar or standby removal of organic sulfur from jar by the below.
The liquefied petroleum gas (LPG) that enters the removal of organic sulfur from jar is the delayed coking liquefied petroleum gas (LPG), removes H with monoethanolamine before entering the removal of organic sulfur from jar
2Behind the S, take off post analysis H
2The content of S is zero, and mercaptans content reaches 220mg/m
3, copper corrosion is defective.
When liquefied petroleum gas (LPG) was passed through the sweetening agent bed, under the cationic effect of the rare earth metal of high valence state, the mercaptan in the liquefied petroleum gas (LPG) was adsorbed; By analysis, take off in the liquefied petroleum gas (LPG) of back and do not contain mercaptan, copper corrosion is qualified, becomes no sulphur liquefied petroleum gas (LPG).
It is identical with embodiment 2 with the process of desorption that removal of organic sulfur from jar and sweetening agent in the standby removal of organic sulfur from jar are adsorbed, thereby can keep removing the continuous operation of the organic sulfide operation in the liquefied petroleum gas (LPG).
The concrete grammar that sweetening agent is carried out periodic desorption and regeneration is: normal pressure uses 200～300 ℃ nitrogen or catalysis drying gas that sweetening agent is regenerated down, and air speed is 800h
-1The regeneration gas that has carried sulfide flows out the removal of organic sulfur from jar and carries out burning disposal.
Sweetening agent is carried out the also adoptable method of periodic desorption and regeneration is: use the 1.0MPa superheated vapour that sweetening agent is regenerated, air speed is 500～1000h
-1
Embodiment 23 to embodiment 31,
All the other are identical with embodiment 22, and difference is: the sweetening agent of adorning is respectively above-mentioned B～J sweetening agent, and the aspect ratio of sweetening agent bed is 4.42, and air speed is 4.46h
-1
Claims (10)
1, a kind of method that removes the contained organosulfur of liquefied petroleum gas (LPG) is characterized in that: the liquefied petroleum gas (LPG) after removing hydrogen sulfide is by the sweetening agent bed in the removal of organic sulfur from device; Under the effect of sweetening agent, the organic sulfide in the liquefied petroleum gas (LPG) is desulfurized agent and directly adsorbs with physical adsorption; Used sweetening agent is that major ingredient is modified X-type or the Y zeolite after high valence state metallic cation exchange, and high valence state metallic cation is lanthanum, cerium or mixed light rare earth element, and exchange degree is 70%～95%.
2, the method that removes the contained organosulfur of liquefied petroleum gas (LPG) according to claim 1 is characterized in that: sweetening agent is that the organic sulfide to liquefied petroleum gas (LPG) carries out physical adsorption under the working pressure of normal temperature and 0.6～2.0MPa; The air speed that liquefied petroleum gas (LPG) flows through the sweetening agent bed is 1～10h
-1
3, the method that removes the contained organosulfur of liquefied petroleum gas (LPG) according to claim 1 is characterized in that: the removal of organic sulfur from device is the removal of organic sulfur from jar of two parallel connections; Liquefied petroleum gas (LPG) one of them removal of organic sulfur from jar organic sulfide removal of flowing through, another removal of organic sulfur from jar is standby; When the logistics outlet that detects the removal of organic sulfur from jar contains sulphur, then will remove in the liquefied petroleum gas (LPG) operation of organic sulfide and switch to standby removal of organic sulfur from jar and carry out; At this moment, can carry out desorption and regeneration to the sweetening agent in the removal of organic sulfur from jar; When the logistics outlet that detects standby removal of organic sulfur from jar contains sulphur, then will remove in the liquefied petroleum gas (LPG) operation of organic sulfide and switch to the removal of organic sulfur from jar and carry out; At this moment, then can carry out desorption and regeneration to the sweetening agent in the standby removal of organic sulfur from jar; Alternately make sweetening agent in removal of organic sulfur from jar and the standby removal of organic sulfur from jar adsorb process with desorption, can keep removing the continuous operation of the organic sulfide operation in the liquefied petroleum gas (LPG).
4, the method that removes the contained organosulfur of liquefied petroleum gas (LPG) according to claim 3 is characterized in that: use nitrogen or catalysis drying gas that sweetening agent is regenerated; Regeneration temperature is 250～400 ℃, and pressure is normal pressure or negative pressure, and air speed is 100～1000h
-1The regeneration gas that has carried sulfide flows out the removal of organic sulfur from jar and deals with in addition.
5, the method that removes the contained organosulfur of liquefied petroleum gas (LPG) according to claim 3 is characterized in that: use 260～290 ℃ superheated vapour that sweetening agent is regenerated, air speed is 100～1000h
-1The regeneration gas that has carried sulfide flows out the removal of organic sulfur from jar and deals with in addition.
6, according to the described method that removes the contained organosulfur of liquefied petroleum gas (LPG) of one of claim 1 to 5, it is characterized in that: the exchange degree of modified X-type molecular sieve is 82%～95%.
7, the method that removes the contained organosulfur of liquefied petroleum gas (LPG) according to claim 6 is characterized in that: the exchange degree of modified X-type molecular sieve is 82%～86%.
8, according to the described method that removes the contained organosulfur of liquefied petroleum gas (LPG) of one of claim 1 to 5, it is characterized in that: the exchange degree of Modified Zeolite Y is 70%～75%.
9, the method that removes the contained organosulfur of liquefied petroleum gas (LPG) according to claim 8 is characterized in that: the exchange degree of Modified Zeolite Y is 70%～73.5%.
10, according to the described method that removes the contained organosulfur of liquefied petroleum gas (LPG) of one of claim 1 to 5, it is characterized in that: the sweetening agent finished product be shaped as spherical or cylindrical or sheet shape or cloverleaf pattern.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329485C (en) * | 2002-04-26 | 2007-08-01 | 英国石油国际有限公司 | Method and apparatus for improving the oxidative thermal stability of distillate fuel |
| CN102617281A (en) * | 2011-01-28 | 2012-08-01 | 株式会社大赛璐 | Method for removing sulfur compound from alcohol |
| CN103359760A (en) * | 2012-04-06 | 2013-10-23 | 华东理工大学 | Method for removing sodium from sodium zeolite molecular sieve through ion exchange |
| CN103614178A (en) * | 2013-10-29 | 2014-03-05 | 中国石油化工股份有限公司 | Deep desulfurization technology of refinery liquefied petroleum gas |
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| CN104645951A (en) * | 2013-11-21 | 2015-05-27 | 东营科尔特化工科技有限公司 | Regeneration method of fine desulfuration agent of liquefied petroleum gas |
| CN107057758A (en) * | 2017-06-09 | 2017-08-18 | 中石化上海工程有限公司 | The method for removing acid impurities in lighter hydrocarbons |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329485C (en) * | 2002-04-26 | 2007-08-01 | 英国石油国际有限公司 | Method and apparatus for improving the oxidative thermal stability of distillate fuel |
| CN102617281A (en) * | 2011-01-28 | 2012-08-01 | 株式会社大赛璐 | Method for removing sulfur compound from alcohol |
| CN103359760A (en) * | 2012-04-06 | 2013-10-23 | 华东理工大学 | Method for removing sodium from sodium zeolite molecular sieve through ion exchange |
| CN103666558A (en) * | 2012-09-26 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing ethylene cracking raw material by hydrogenating C4 distillate by using Ce<3+>-modified molecular sieve desulfurizer |
| CN103614178A (en) * | 2013-10-29 | 2014-03-05 | 中国石油化工股份有限公司 | Deep desulfurization technology of refinery liquefied petroleum gas |
| CN104645951A (en) * | 2013-11-21 | 2015-05-27 | 东营科尔特化工科技有限公司 | Regeneration method of fine desulfuration agent of liquefied petroleum gas |
| CN104402663A (en) * | 2014-11-05 | 2015-03-11 | 中国石油大学(北京) | Advanced alkane purifying method for removing impurities |
| CN104402663B (en) * | 2014-11-05 | 2016-05-11 | 中国石油大学(北京) | A kind of alkane impurity deep-purifying method |
| CN107057758A (en) * | 2017-06-09 | 2017-08-18 | 中石化上海工程有限公司 | The method for removing acid impurities in lighter hydrocarbons |
| CN108165321A (en) * | 2017-07-19 | 2018-06-15 | 湖北申昙环保新材料有限公司 | The purification method of coal gas |
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