CN101134912A - Catalytic no-hydroprocessing adsorbing desulfurization for hydrocarbon oil in fixed bed reactor - Google Patents
Catalytic no-hydroprocessing adsorbing desulfurization for hydrocarbon oil in fixed bed reactor Download PDFInfo
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Abstract
The non-hydrocatalyzing adsorption process for desulfurizing hydrocarbon oil in a fixed bed reactor includes feeding sulfur containing hydrocarbon oil material into the fixed bed reactor, contacting alternately with sulfur converting agent and sulfur adsorbent, and separating the reacted matter flow to obtain product. The process completes the catalytic conversion of organic sulfide into inorganic sulfide and the timely adsorption of inorganic sulfide cooperatively inside one reactor, and can realize deep desulfurization of gasoline in non-hydrogenation condition in the desulfurizing rate up to 95 wt%.
Description
Technical field
The present invention is belong under the situation that does not have hydrogen petroleum hydrocarbon refining, more particularly, is a kind of method that removes sulfide in hydrocarbon oil.
Background technology
Along with the pay attention to day by day of people, more and more stricter to the restriction of the sulphur content in the hydrocarbon ils to environment protection.With gasoline is example, and EPA (EPA) regulation sulphur limit value is 30 μ g/g (TierII); Europe requires content of sulfur in gasoline to be lower than 50 μ tg/g (Europe IV emission standard); China requires to carry out Europe IV emission standard in 2008 too, and content of sulfur in gasoline requires to be lower than 50 μ g/g.Thereby, the hydrocarbon ils deep desulfuration just can be meeted the requirements.
At present, the deep desulfuration of hydrocarbon ils mainly is the method that adopts hydrogenating desulfurization.Wherein selective hydrodesulfurization is the main mode that removes thiophene-type sulfide at present.US4334982, US6126814 are the reactive behavioies by control catalyst, only promote the thiophene hydrogenation and do not make the saturated method of alkene realize deep desulfuration under low octane rating loss.Another kind of hydrodesulfurizationprocess process is a deep hydrodesulfurizationof method of recovering octane value, be gasoline carry out deep desulfuration and alkene saturated in, cracking, isomerization and the alkylated reaction of second section reactor to promote low-octane hydro carbons (as normal paraffin) is set, thereby reaches the purpose of recovering octane value.
At present, non-hydrogenation process for deep desulphurization mainly contains technologies such as extracting and oxidation extraction desulfurization, catalyzed reaction desulfurization, and these technologies all need the participation of still-process, and high aromatic fraction of isolated high-sulfur or heavy sulfocompound also will depend on deep hydrodesulfurizationof.Hydrogenating desulfurization ubiquity operational condition harshness, hydrogen consumption is high, defective such as loss of octane number is arranged.
US6350422, US6350422, US6955752, US6482314, US6428685, US6346190 all utilize metal in the sorbent material or metal oxide to catch sulphur in the gasoline, generate metallic sulfide or utilize sulfide polarity to remove sulphur, the regeneration of sulfur-bearing catalyst recirculation.Though above-mentioned patent has reduced loss of octane number, reduced the hydrogen consumption, face H-H reaction yet remain, temperature of reaction height, technical process complexity.CN1583973A, CN1583972A all adopt the molecular sieve catalyst of loaded metal, and selective cracking sulfide converts it into hydrocarbon and inorganic sulphide.The catalyzed conversion desulfurization is the method for light-end products non-hydrogen cracking desulfurization, no hydrogen consumption, and no loss of octane number can be used to produce the low-sulfur processed oil, and loss of octane number is low.But the same with the mink cell focus catalytic cracking and desulfurizing, its desulfurization degree is influenced by feed sulphur content, catalyst property and depth of conversion etc., is not enough to realize deep desulfuration, and desulfurization degree is generally at 50-80%.
The catalyzed conversion desulfurization degree is except being subjected to feed sulphur content, catalyst property and depth of conversion etc. influence, and also is subjected to the influence of a large amount of inorganic sulphides of existing in the reaction oil gas.The contriver finds in the experiment of relevant gasoline sulfur catalyzed conversion research, the existence of a large amount of inorganic sulphides in the reaction oil gas, and having suppressed by the organic sulfide cracking on the one hand is the reaction of inorganic sulphide; Alkene generation secondary reaction in inorganic sulphide and the reactant flow generates new sulfide again on the other hand.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology the method for a kind of hydrocarbon ils non-hydrogen catalysis adsorption desulfurize in fixed-bed reactor, to realize the deep desulfuration of hydrocarbon ils.
The objective of the invention is to realize by following proposal: the hydrocarbon oil crude material of sulfur-bearing enters fixed-bed reactor, and sulphur transforming agent, the sulfur absorbent with filling at interval alternately contacts successively, and the separating reaction logistics obtains product.
The hydrocarbon oil crude material of described sulfur-bearing is selected from one or more the mixture in gasoline, kerosene, diesel oil, the gas oil fraction, and preferred gasoline is or/and diesel oil.Above-mentioned gasoline, kerosene, diesel oil, gas oil fraction are that its full cut is or/and its part narrow fraction.The hydrocarbon oil crude material sulphur content of described sulfur-bearing is preferably in more than the 1000 μ g/g more than 50 μ g/g.
Described sulphur transforming agent comprises molecular sieve, inorganic oxide and the optional clay that contains rare earth, serves as to calculate benchmark with the weight of sulphur transforming agent, and molecular sieve, inorganic oxide, clay account for the heavy % of heavy %, clay 0-75 of 15-60 heavy %, 10-60 respectively.
The described Y series zeolite that contains the self-contained rare earth of molecular screening of rare earth, contain rare earth the ZSM series zeolite, contain rare earth the MCM series zeolite, contain rare earth the Beta zeolite, contain one or more the mixture in the SAPO series molecular sieve of rare earth.
The wherein said Y series zeolite that contains rare earth is selected from one or more the mixture among REY, REHY, the REUSY, and preferred REY zeolite is or/and the REHY zeolite; The mixture of one or more in the ZSM-57 zeolite that the described ZSM series zeolite that contains rare earth is selected from the ZSM-5 zeolite that contains rare earth, the ZSM-8 zeolite that contains rare earth, the ZSM-11 zeolite that contains rare earth, the ZSM-22 zeolite that contains rare earth, the ZSM-23 zeolite that contains rare earth, the ZSM-48 zeolite that contains rare earth, contain rare earth preferably contains the ZSM-5 zeolite of rare earth; The SAPO-11 of the described self-contained rare earth of SAPO series molecular screening that contains rare earth, contain rare earth SAPO-34, contain one or more the mixture among the SAPO-41 of rare earth.
Described rare earth all is selected from one or more elements among La, Ce, Pr, Nd, the Sm.
The above-mentioned various molecular sieve that contains rare earth passes through preferably that other is element modified, and described other element is selected from one or more elements in the non-metallic element of metallic element, VA family of metallic element, the IIA family of metallic element, the IIB family of metallic element, the IB family of metallic element, the VIH family of metallic element, the group vib of IVB family.
Wherein the preferred Zr of the metallic element of IVB family is or/and Ti; The preferred Mo of the metallic element of group vib is or/and W; One or more elements among the preferred Fe of the metallic element of group VIII, Co, the Ni; The preferred Cu of the metallic element of IB family; The preferred Zn of metallic element of mat woven of fine bamboo strips IIB family is or/and Hg; The preferred Al of the metallic element of group III A is or/and Ga; The preferred P of the non-metallic element of VA family is or/and As.
Described inorganic oxide is selected from one or more the mixture in amorphous silicon aluminium, aluminum oxide, the silicon oxide; Described clay is selected from kaolin, halloysite, polynite, wilkinite, sepiolite, diatomite, tired one or more the mixture that takes off in the soil, preferred kaolin.
Preferred sulphur transforming agent is by constituting (all the weight with the sulphur transforming agent serves as to calculate benchmark) through the heavy % of heavy %, clay 0-75 of heavy %, inorganic oxide 10-60 of the Y series zeolite 15-60 that contains rare earth of phosphorus modification; The wherein said Y series zeolite that contains rare earth through the phosphorus modification contains with P
2O
5The phosphorus that accounts for the heavy % of this zeolite weight 0.5-8 of meter, with RE
2O
3The rare earth that accounts for the heavy % of this zeolite weight 1.0-35 of meter.
Sulphur transforming agent used in the present invention can be made different shapes, as spherical, strip or trifolium shape.Its median size is relevant with reactor diameter, is example with spherical, generally at 1～6mm, is preferably 3～5mm.
Described sulfur absorbent be selected from oxide compound, the reactive metal of gac, reactive metal oxyhydroxide, load on one or more the mixture in the oxide compound of the reactive metal on inorganic oxide, clay or the molecular sieve.
Described reactive metal all is selected from one or more metals in the metal of metal, VA family of metal, the mat woven of fine bamboo strips IVA family of metal, the IIB family of metal, the mat woven of fine bamboo strips IB family of metal, the group VIII of metallic element, the VIIB family of metal, the group vib of metal, the VB family of metal, the IVB family of metal, the IIIB family of basic metal, IIA family.
One or more metals among the preferred Li of basic metal, Na, the K wherein; One or more metals among the preferred Ca of the metal of IIA family, Mg, Sr, the Ba; The preferred Sc of metal of mat woven of fine bamboo strips IIIB family, one or more metals among La, the Ce; The preferred Zr of the metal of IVB family is or/and Ti; The preferred v of the metal of VB family; One or more metals among the preferred Cr of the metal of group vib, Mo, the W; The preferred Mn of metal of mat woven of fine bamboo strips VIlB family is or/and Re; One or more metals among the preferred Fe of the metal of group VIII, Co, the Ni; The preferred Cu of the metal of IB family; The preferred Zn of the metal of IIB family is or/and Cd; The preferred Sn of the metal of IVA family is or/and Pb; The preferred Sb of the metal of VA family is or/and Bi.
Described inorganic oxide is selected from one or more the mixture in amorphous silicon aluminium, aluminum oxide, the silicon oxide; Described clay is selected from kaolin, halloysite, polynite, wilkinite, sepiolite, diatomite, tired one or more the mixture that takes off in the soil, preferred kaolin; One or more the mixture of described molecular screening in A type molecular sieve, X type molecular sieve, Y series molecular sieve, wherein said Y series molecular screening one or more the mixture in Y type, HY type, REY type, REHY type, USY type, REUSY type zeolite.
Described sulfur absorbent at high temperature has adsorption to inorganic sulfur, and can reuse by oxidation regeneration.
The concrete composition and the type of feed of described sulphur transforming agent, sulfur absorbent had both depended on feed sulphur content, desulfurization requirement, were determined by reaction conditions again.
In reactor, according to the sulphur transforming agent. sulfur absorbent. the sulphur transforming agent. sulfur absorbent ... mode load at interval, also can adopt quartz sand dilution sulphur transforming agent.Sulphur transforming agent and the sulfur absorbent weight ratio in whole reactor is 0.01-100: 1.
Sulphur transforming agent bed and sulfur adsorbent bed operational condition are: temperature 250-600 ℃ preferred 300-550 ℃, and volume space velocity 0.1-100h
-1Preferred 1-50h
-1, the preferred 0.2-0.6MPa of pressure 0.10-0.80MPa.
Method provided by the invention can adopt newly-built intermittence or continuous fixed-bed reactor, preferably adopts idle catalytic reforming or two-stage hydrogenation fixed bed device, with the economy system investment cost.
The present invention in fill process, can use nitrogen or/and water vapor as diluent media, so that temperature keeps evenly in the bed.The volume space velocity of described diluent media is 0.01-10h
-1
The sulphur transforming agent of inactivation, sulfur absorbent remove the impurity of its inner absorption earlier through stripping, in oxygen-containing gas (as air) atmosphere, regenerate again, the oxidation regeneration condition is as follows: temperature is 450-800 ℃ of preferred 500-650 ℃, time is 1.20 minutes preferred 2-10 minute, and pressure is the preferred 0.20-0.60MPa of 0.13-1.00MPa.According to the type difference of employing sulphur transforming agent, sulfur absorbent, also need H behind the spent agent oxidation regeneration that has
2Or/and CO reduction, or with water vapor, nitrogen or other inert gas purge.The sulphur transforming agent of the heat after the regeneration, sulfur absorbent are preferably reused through cooling again.
The inactivation and the regeneration period of sulphur transforming agent, sulfur absorbent determined in requirement according to the product sulphur content, and plural fixed-bed reactor can be set.Sulphur transforming agent in a reactor, sulfur absorbent stop the charging reaction and begin regeneration in the time of need regenerating, switch to other reactor and proceed reaction, to guarantee carrying out continuously of this technological process.
The present invention compared with prior art has following unforeseeable technique effect:
1, " two dose two of a device is anti-" promptly is equipped with sulphur transforming agent, two kinds of agent of sulfur absorbent in a reactor, these two kinds of agent collaborative organosulfur of finishing in same reaction atmosphere is catalytically conveted to the function that inorganic sulfur, inorganic magnetic in time are adsorbed; Then in same regeneration atmosphere, recover active simultaneously.
When 2, adopting method provided by the invention to handle gasoline stocks, can realize deep desulfuration under the condition of non-hydrogen, the decreasing ratio of sulphur can reach more than the 95 heavy %.The content of olefin in gasoline of producing low, octane value is high.In addition, in resulting material balance, the productive rate of diesel oil+liquefied gas+gasoline is that rest part is dry gas and coke more than the 97 heavy %.
When 3, adopting method provided by the invention to handle diesel raw material, under the condition of non-hydrogen, diesel raw material has preferably takes off. and sulphur effect, desulfurization degree reach more than the 70 heavy %.The aromatic content of diesel oil of producing slightly reduces, cetane value slightly improves.
4, adopt method provided by the invention, can alleviate reaction back gas-phase product such as liquefied gas, dry gas desulfurizer load, even save desulfurizer behind the gas.
5, fixed-bed catalytic desulfurizing method by adsorption provided by the invention can adopt one or several intermittent type fixed-bed reactor or continous way fixed-bed reactor, perhaps idle catalytic reforming fixed bed device or the two-stage hydrogenation fixed bed device of refinery.
6, fixed bed sulfur method provided by the invention can be used to produce low-sulphur oil, even also can be used for the low-sulphur oil be the raw material production sweet gasoline.
Description of drawings
Accompanying drawing is that hydrocarbon ils provided by the invention takes off in fixed bed non-hydrogen catalysis absorption. the method flow synoptic diagram of sulphur.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further detailed, but does not therefore limit the present invention.
Accompanying drawing is the method flow synoptic diagram of hydrocarbon ils provided by the invention at fixed bed non-hydrogen catalysis adsorption desulfurize.Accompanying drawing adopts two fixed-bed reactor blocked operations, and one of them reactor is used for reaction, and another reactor is used for regeneration.In each fixed-bed reactor to down and on load at interval successively sulphur transforming agent-sulfur absorbent-sulphur transforming agent-sulfur absorbent-...-sulphur transforming agent. sulfur absorbent, can 3 during practical application or more fixed-bed reactor, also can load sulphur transforming agent, sulfur absorbent at interval successively from top to down, raw material is corresponding to enter reactor from top.
Hydrocarbon oil containing surphur raw material after the preheating enters fixed-bed reactor 8 through pipeline 1, pipeline 2, valve 3, pipeline 4 successively, sulphur transforming agent, sulfur absorbent with filling at interval alternately contacts successively, hydrocarbon oil containing surphur raw material, intermediate reaction logistics contact with the sulphur transforming agent and make organosulfur be catalytically conveted to inorganic sulfur, the intermediate reaction logistics contacts the inorganic sulfur that the upstream bed is generated and in time is adsorbed with sulfur absorbent, sulphur transforming agent bed and sulfur adsorbent bed operational condition are: temperature 250-550 ℃, and volume space velocity 0.1-100h
-1Pressure 0.10-0.80MPa, through repeatedly transform, after the adsorption process, final reactant flow enters separation column 17 through pipeline 10, valve 11, pipeline 12, pipeline 16 successively, and isolating dry gas, liquefied gas product, gasoline products, solar oil product, heavy gas oil product are respectively through pipeline 18, pipeline 19, pipeline 20, pipeline 21, pipeline 22 caterpillars.
When the sulphur transforming agent in the reactor 8, sulfur absorbent inactivation, shut-off valve 3 stops charging, closes threshold 11, off-stream case 8 behind the reactant flow stream sky of question response device 8.Open valve 6, valve 14 simultaneously, enable fixed-bed reactor 9.
Sulphur transforming agent in reactor 8, sulfur absorbent carries out regenerated simultaneously, hydrocarbon oil containing surphur raw material after the preheating is successively through pipeline 1, pipeline 5, valve 6, pipeline 7 enters fixed-bed reactor 9, successively with the sulphur transforming agent that loads at interval, sulfur absorbent is contact alternately, the hydrocarbon oil containing surphur raw material, the intermediate reaction logistics contacts with the sulphur transforming agent and makes organosulfur be catalytically conveted to inorganic sulfur, the intermediate reaction logistics contacts the inorganic sulfur that the upstream bed is generated and in time is adsorbed with sulfur absorbent, sulphur transforming agent bed and sulfur adsorbent bed operational condition are: temperature 250-550 ℃, and volume space velocity 0.1.100h
-1Pressure 0.10-0.80MPa, through repeatedly transform, after the adsorption process, final reactant flow enters separation column 17 through pipeline 13, valve 14, pipeline 15, pipeline 16 successively, and isolating dry gas, liquefied gas product, gasoline products, solar oil product, heavy gas oil product are respectively through pipeline 18, pipeline 19, pipeline 20, pipeline 21, pipeline 22 caterpillars.
When the sulphur transforming agent in the reactor 9, sulfur absorbent inactivation, shut-off valve 6 stops charging, the empty back of the reactant flow stream shut-off valve 14 of question response device 9, off-stream case 9.Open valve 3, valve 11 simultaneously, enable fixed-bed reactor 9 and repeat above-mentioned conversion, absorption and product separation process.
Simultaneously, open valve 27, valve 30, sulphur transforming agent, sulfur absorbent in the reactor 9 are regenerated.Oxygen-containing gas enters fixed-bed reactor 9 through pipeline 26, valve 27, pipeline 28, pipeline 7 successively, alternately contact with the sulphur transforming agent, the sulfur absorbent that load at interval successively and regenerate, regeneration condition is as follows: temperature is 450.800 ℃ preferred 500.650 ℃, time is 1-20 minute preferred 2-10 minute, and pressure is the preferred 0.20-0.60MPa of 0.13-1.00MPa.Flue gas after the regeneration is successively through pipeline 13, pipeline 29, valve 30, pipeline 31, pipeline 35 caterpillars.
Sulphur transforming agent after the regeneration, sulfur absorbent need that pipeline 26, valve 27, pipeline 28, pipeline 7 are switched to water vapor, nitrogen or other rare gas elementes and purge, and remove the oxygen containing gas in the reactor, and then carry out entering of next hydrocarbon oil crude material.
The following examples will give further instruction to method provided by the invention, but therefore not make the present invention be subjected to any restriction.
Employed feedstock property is listed in the employed sulphur transforming agent of table L among the embodiment, describe according to patent CN1583973A, preparation process is as follows: with commercially available REY zeolite (Qilu Petrochemical company catalyst plant product, silica alumina ratio 2.0) according to zeolite: ammonium nitrate: the weight ratio of deionized water=1: 1: 20 was 90 ℃ of following ion-exchanges 2 hours, filter, wash the back repeated exchanged and once obtain ammonium type REY, its Na2O content is not more than 0.15 heavy %.At room temperature the aqueous solution of above-mentioned ammonium type zeolite molecular sieve and rare earth chloride was stirred dipping 2 hours, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours.So make with RE
2O
3The content of rare earth of meter is the REY zeolite of 17.5 heavy %, and note is made zeolite ZET-3.
With 13.5 kilograms of halloysites (Suzhou china clay company Industrial products, solid content is 73 heavy %), 13.5 kilogram pseudo-boehmite (Shandong Zibo aluminium manufacturer Industrial products, solid content is 64 heavy %) even with the ZET-3 zeolite thorough mixing for preparing in advance that accounts for sulphur transforming agent weight 30 heavy %, and add extraordinary tackiness agent, structural promoter and pore-forming material, the mixing back also is put in the bonder, add suitable quantity of water, stir, in air, placed 4 hours, be shaped placement after 24 hours with the bowling machine spin, 120 ℃ of oven dry are after 3 hours in loft drier, and free Na is removed in washing
+, after drying promptly gets the sulphur transforming agent and is designated as CAT-3 (median size is 3～5mm).
Employed sulfur absorbent, with Mn, Fe as active ingredient, with γ-Al
2O
3As carrier.Its preparation method is as follows: with commercially available Fe (NO
3)
3With Mn (NO
3)
2Become certain density solution according to 1: 1 proportional arrangement of mol ratio, add the carrier γ-Al of moulding in isopyknic oil again
2O
3(median size is 3～5mm), and at room temperature dipping stirs, and again 120 ℃ of oven dry after 4 hours, roasting is 6 hours under 750 ℃ of conditions for bead.Resulting sulfur absorbent is designated as ADT-3.
Sulphur transforming agent CAT-3 and sulfur absorbent ADT-3 granularity are close with bulk density.According to sulphur transforming agent-sulfur absorbent-sulphur transforming agent-sulfur absorbent-... the mode of-sulphur transforming agent-sulfur absorbent is loaded successively, also can adopt quartz sand dilution sulphur transforming agent.
Embodiment 1
The gasoline stocks that is numbered A alternately contacts with CAT-3, ADT-3 (gross weight ratio in front and back is 0.05: 1) successively in the small stationary bed bioreactor and carries out catalyzed conversion, absorption.Main operational condition is: temperature of reaction is 400 ℃, and reactor pressure is 0.2 MPa, and the volume space velocity of gasoline stocks is 10 hours
-1, as diluent media, the volume space velocity of water vapor is 0.5 hour with water vapor
-1The desulfurization product that is obtained by reactor head obtains gaseous product and product liquid through cooling, separation.The regeneration condition of CAT-3, ADT-3 is: temperature is 550 ℃, and reactor pressure is 0.2 MPa, and the time is 5 minutes.Test conditions, product distribute and the gasoline main character is listed in table 2.
Comparative Examples 1
The raw material of Comparative Examples 1 is identical with the raw material of embodiment 1, and this raw material only contacts with sulphur transforming agent CAT-3 in the small stationary bed bioreactor and reacts.Test conditions is that temperature of reaction is 400 ℃, and reactor pressure is 0.2 MPa, and the volume space velocity of gasoline stocks is 10 hours
-1, as diluent media, the volume space velocity of water vapor is 0.50 hour with water vapor
-1Concrete testing sequence is identical with embodiment 1.Test conditions, product distribute and the gasoline main character is all listed in table 2.
As can be seen from Table 2, with respect to Comparative Examples 1, under the situation of non-hydrogen, embodiment 1 has added the catalysis adsorption desulfurize reaction of sulfur absorbent ADT-3 than the reaction desulfuration rate height that does not add sulfur absorbent, and dry gas, coke yield reduce simultaneously.
The gasoline stocks that is numbered B alternately contacts with CAT-3, ADT-3 (gross weight ratio in front and back is 1: 1) successively in the small stationary bed bioreactor and carries out catalyzed conversion, absorption.Main operational condition is: temperature of reaction is 250 ℃, and reactor pressure is 0.2 MPa, and the volume space velocity of gasoline stocks is 0.5 hour
-1, as diluent media, the volume space velocity of water vapor is 0.05 hour with water vapor
-1The desulfurization product that is obtained by reactor head obtains gaseous product and product liquid through cooling, separation.The regeneration condition of CAT-3, ADT-3 is: temperature is 450 ℃, and reactor pressure is 0.2 MPa, and the time is 10 minutes.Test conditions, product distribute and the gasoline main character is listed in table 3.As can be seen from Table 3, the desulfurization degree of gasoline is up to 93.17 heavy %.
The gasoline stocks that is numbered C alternately contacts with CAT-3, ADT-3 (gross weight ratio in front and back is 50: 1) successively in the small stationary bed bioreactor and carries out catalyzed conversion, absorption.Main operational condition is: temperature of reaction is 450 ℃, and reactor pressure is 0.4 MPa, and the volume space velocity of gasoline stocks is 80 hours
-1, as diluent media, the volume space velocity of nitrogen is 5.0 hours with nitrogen
-1The desulfurization product that is obtained by reactor head obtains gaseous product and product liquid through cooling, separation.The regeneration condition of CAT-3, ADT-3 is: temperature is 650 ℃, and reactor pressure is 0.4 MPa, and the time is 10 minutes.Test conditions, product distribute and the gasoline main character is listed in table 3.As can be seen from Table 3, the desulfurization degree of gasoline is up to 94.15 heavy %.
The diesel raw material that is numbered D alternately contacts with CAT-3, ADT-3 (gross weight ratio in front and back is 20: 1) in small-sized continuous fixed-bed reactor successively carries out catalyzed conversion, absorption.Main operational condition is: temperature of reaction is 450 ℃, and reactor pressure is 0.4 MPa, and the volume space velocity of diesel raw material is 3 hours
-1, as diluent media, the volume space velocity of water vapor is 0.14 hour with water vapor
-1The desulfurization product that is obtained by reactor head obtains gaseous product and product liquid through cooling, separation.The regeneration condition of CAT-3, ADT-3 is: temperature is 550 ℃, and reactor pressure is 0.4 MPa, and the time is 20 minutes.Test conditions, product distribute and the diesel oil main character is listed in table 4.As can be seen from Table 4, the abdomen sulphur rate of diesel oil is 75.12 heavy %.
The diesel raw material that is numbered E alternately contacts with CAT-3, ADT-3 (gross weight ratio in front and back is 0.1: 1) in small-sized continuous fixed-bed reactor successively carries out catalyzed conversion, absorption.Main operational condition is: temperature of reaction is 550 ℃, and reactor pressure is 0.6 MPa, and the volume space velocity of diesel raw material is 10 hours
-1, as diluent media, the volume space velocity of nitrogen is 8.0 hours with nitrogen
-1The desulfurization product that is obtained by reactor head obtains gaseous product and product liquid through cooling, separation.The regeneration condition of CAT-3, ADT-3 is: temperature is 700 ℃, and reactor pressure is 0.6 MPa, and the time is 2 minutes.Test conditions, product distribute and the diesel oil main character is listed in table 4.As can be seen from Table 4, the desulfurization degree of diesel oil is 73.04 heavy %.
Table 1
| The raw material numbering | A | B | C | D | E |
| Type of feed | Gasoline | Gasoline | Gasoline | Diesel oil | Diesel oil |
| Density (20 ℃), kilogram/rice 3 | 787.5 | 726.3 | 708.3 | 886.8 | 911.6 |
| Octane value | |||||
| RON | 89.8 | 92.1 | 93.6 | ||
| MON | 78.8 | 79.2 | 79.4 | ||
| Cetane value | 29.5 | 29.0 | |||
| Sulphur, μ g/g | 1796.5 | 512.3 | 136.8 | 1160 | 10267.6 |
| Nitrogen, μ g/g | 92.4 | 109.5 | 103.6 | 682 | 878.7 |
| Carbon, heavy % | 86.28 | 86.54 | 86.46 | 88.24 | 87.68 |
| Hydrogen, heavy % | 12.98 | 13.30 | 13.15 | 11.48 | 10.80 |
| Boiling range, ℃ | |||||
| Initial boiling point | 90 | 45 | 62 | 19l | 195 |
| 10％ | 92 | 60 | 75 | 208 | 234 |
| 30％ | 121 | 79 | 89 | 226 | 267 |
| 50％ | 154 | 105 | 112 | 247 | 298 |
| 70％ | 175 | 135 | 141 | 277 | 328 |
| 90％ | 189 | 168 | 173 | 324 | 358 |
| Final boiling point | 203 | 200 | 202 | 361 | 374 |
Table 2
| Embodiment 1 | Comparative Examples 1 | |
| Sweetening agent | CAT-3+ADT-3 | CAT-3 |
| Reaction conditions | ||
| Temperature, ℃ | 400 | 400 |
| Pressure, MPa | 0.2 | 0.2 |
| The gasoline volume space velocity, |
10 | 10 |
| The medium volume space velocity, hour -1 | 0.50 | 0.50 |
| Product distributes, heavy % | ||
| Dry gas | 0.42 | 0.45 |
| Liquefied gas | 1.23 | 1.58 |
| Gasoline | 92.5 | 91.54 |
| Solar oil | 2.48 | 3.05 |
| Heavy gas oil | 0.51 | 0.45 |
| Coke | 2.84 | 2.90 |
| Loss | 0.02 | 0.03 |
| The gasoline main character | ||
| RON | 90.4 | 90.3 |
| MON | 80.2 | 80.0 |
| Sulphur, μ g/g | 75 | 248 |
| Nitrogen, μ g/g | 0.8 | 0.9 |
| Desulfurization degree, heavy % | 95.83 | 86.20 |
Table 3
| |
|
|
| Reaction conditions | ||
| Temperature, ℃ | 250 | 450 |
| Pressure, MPa | 0.2 | 0.4 |
| The gasoline volume space velocity, hour -1 | 0.5 | 80 |
| The medium volume space velocity, hour -1 | Water vapor/0.05 | Nitrogen/5.0 |
| Product distributes, heavy % | ||
| Dry gas | 0.20 | 0.45 |
| Liquefied gas | 1.00 | 2.30 |
| Gasoline | 92.05 | 92.53 |
| Solar oil | 3.36 | 2.21 |
| Heavy gas oil | 0.67 | 0.05 |
| Coke | 2.70 | 2.45 |
| Loss | 0.02 | 0.01 |
| The gasoline main character | ||
| RON | 92.5 | 94.5 |
| MON | 80.0 | 81.0 |
| Sulphur, μ g/ |
35 | 8 |
| Nitrogen, μ g/g | 1.0 | 0.8 |
| Desulfurization degree, heavy % | 93.17 | 94.15 |
Table 4
| |
|
|
| Reaction conditions | ||
| Temperature, ℃ | 450 | 550 |
| Pressure, MPa | 0.4 | 0.6 |
| The diesel oil volume space velocity, |
3 | 10 |
| The medium volume space velocity, hour -1 | Water vapor/0.14 | Nitrogen/8.0 |
| Product distributes, heavy % | ||
| Dry gas | 0.65 | 0.7O |
| Liquefied gas | 3.65 | 2.86 |
| Gasoline | 6.76 | 4.55 |
| Solar oil | 85.10 | 88.12 |
| Heavy gas oil | / | / |
| Coke | 3.82 | 3.76 |
| Loss | 0.02 | 0.01 |
| The diesel oil main character | ||
| Sulphur, μ g/g | 288.6 | 2767.8 |
| Desulfurization degree, heavy % | 75.12 | 73.04 |
| Density, (20 ℃), kilogram/rice 3 | 880.0 | 896.6 |
| Cetane value | 32.0 | 30.0 |
Claims (19)
1. the method for hydrocarbon ils non-hydrogen catalysis adsorption desulfurize in fixed-bed reactor, it is characterized in that this method comprises: the hydrocarbon oil crude material of sulfur-bearing enters fixed-bed reactor, sulphur transforming agent, sulfur absorbent with filling at interval alternately contacts successively, and the separating reaction logistics obtains product.
2. in accordance with the method for claim 1, the hydrocarbon oil crude material that it is characterized in that described sulfur-bearing is selected from one or more the mixture in gasoline, kerosene, diesel oil, the gas oil fraction, and preferred gasoline is or/and diesel oil.
3. in accordance with the method for claim 1, it is characterized in that described sulphur transforming agent comprises molecular sieve, inorganic oxide and the optional clay that contains rare earth, weight with the sulphur transforming agent serves as to calculate benchmark, and molecular sieve, inorganic oxide, clay account for the heavy % of heavy %, clay 0-75 of 15-60 heavy %, 10-60 respectively.
4. in accordance with the method for claim 3, it is characterized in that the described Y series zeolite that contains the self-contained rare earth of molecular screening of rare earth, contain rare earth the ZSM series zeolite, contain rare earth the MCM series zeolite, contain rare earth the Beta zeolite, contain one or more the mixture in the SAPO series molecular sieve of rare earth.
5. in accordance with the method for claim 4, it is characterized in that the described Y series zeolite that contains rare earth is selected from one or more the mixture among REY, REHY, the REUSY; The mixture of one or more in the ZSM-57 zeolite that the described ZSM series zeolite that contains rare earth is selected from the ZSM-5 zeolite that contains rare earth, the ZSM-8 zeolite that contains rare earth, the ZSM-11 zeolite that contains rare earth, the ZSM-22 zeolite that contains rare earth, the ZSM-23 zeolite that contains rare earth, the ZSM-48 zeolite that contains rare earth, contain rare earth; The SAPO-11 of the described self-contained rare earth of SAPO series molecular screening that contains rare earth, contain rare earth SAPO-34, contain one or more the mixture among the SAPO-41 of rare earth.
6. in accordance with the method for claim 5, it is characterized in that the described Y series zeolite that contains rare earth is that the REY zeolite is or/and the REHY zeolite; The described ZSM series zeolite that contains rare earth is the ZSM-5 zeolite that contains rare earth.
7. according to described method one of among the claim 3-6, it is characterized in that described rare earth all is selected from one or more elements among La, Ce, Pr, Nd, the Sm.
8. according to described method one of among the claim 3-6, it is characterized in that the described molecular sieve that contains rare earth passes through preferably that other is element modified, described other element is selected from one or more elements in the non-metallic element of metallic element, VA family of metallic element, the group III A of metallic element, the IIB family of metallic element, the IB family of metallic element, the group VIII of metallic element, the group vib of IVB family.
9. in accordance with the method for claim 8, the metallic element that it is characterized in that IVB family is that Zr is or/and Ti; The metallic element of group vib is that Mo is or/and W; The metallic element of group VIII is one or more elements among Fe, Co, the Ni; The metallic element of IB family is Cu; The metallic element of IIB family is that Zn is or/and Hg; The metallic element of group III A is that Al is or/and Ga; The non-metallic element of VA family is that P is or/and As.
10. in accordance with the method for claim 1, it is characterized in that described sulphur transforming agent is by constituting (all the weight with the sulphur transforming agent serves as to calculate benchmark) through the heavy % of heavy %, clay 0-75 of heavy %, inorganic oxide 10-60 of the Y series zeolite 15-60 that contains rare earth of phosphorus modification; The wherein said Y series zeolite that contains rare earth through the phosphorus modification contains with P
2O
5The phosphorus that accounts for the heavy % of this zeolite weight 0.5-8 of meter, with RE
2O
3The rare earth that accounts for the heavy % of this zeolite weight 1.0-35 of meter.
11. in accordance with the method for claim 1, it is characterized in that described sulfur absorbent is selected from the oxyhydroxide of the oxide compound of gac, reactive metal, reactive metal, loads on inorganic oxide, one or more the mixture in the oxide compound of the reactive metal on clay or the molecular sieve.
12. in accordance with the method for claim 11, it is characterized in that described reactive metal is selected from one or more metals in the metal of the metal of the metal of the metal of the metal of the metal of the metallic element of the metal of the metal of the metal of the metal of basic metal, IIA family, IIIB family, IVB family, VB family, group vib, VIIB family, group VIII, IB family, IIB family, IVA family, VA family.
13. in accordance with the method for claim 12, it is characterized in that described basic metal is one or more metals among Li, Na, the K; The metal of IIA family is one or more metals among Ca, Mg, Sr, the Ba; The metal of IIIB family is one or more metals among Sc, La, the Ce; The metal of IVB family is that Zr is or/and Ti; The metal of VB family is V; The metal of group vib is one or more metals among Cr, Mo, the W; The metal of VIIB family is that Mn is or/and Re; The metal of group VIII is one or more metals among Fe, Co, the Ni; The metal of IB family is Cu; The metal of IIB family is that Zn is or/and Cd; The metal of IVA family is that Sn is or/and Pb; The metal of VA family is that Sb is or/and Bi.
One or more the mixture of described molecular screening in A type molecular sieve, X type molecular sieve, Y series molecular sieve, wherein said Y series molecular screening one or more the mixture in Y type, HY type, REY type, REHY type, USY type, REUSY type zeolite.
14., it is characterized in that described inorganic oxide is selected from one or more the mixture in amorphous silicon aluminium, aluminum oxide, the silicon oxide according to described method one of in the claim 3,10,11; Described clay is selected from kaolin, halloysite, polynite, wilkinite, sepiolite, diatomite, tired one or more the mixture that takes off in the soil, preferred kaolin.
15. in accordance with the method for claim 1, it is characterized in that described sulphur transforming agent and the weight ratio of sulfur absorbent in whole reactor are 0.01-100: 1.
16. in accordance with the method for claim 1, it is characterized in that described sulphur transforming agent bed and sulfur adsorbent bed operational condition are: temperature 250-600 ℃, volume space velocity 0.1-100h
-1, pressure 0.10-0.80MPa.
17. it is characterized in that in accordance with the method for claim 1, the oxidation regeneration condition of sulphur transforming agent, sulfur absorbent of inactivation is as follows: temperature is 450-800 ℃, and the time is 1-20 minute, and pressure is 0.13-1.00MPa.
18. in accordance with the method for claim 1, it is characterized in that in fill process using nitrogen or/and water vapor as diluent media, described diluent media volume space velocity 0.01-10h
-1
19. in accordance with the method for claim 1, it is characterized in that being provided with plural fixed-bed reactor.Sulphur transforming agent in a reactor, sulfur absorbent stop the charging reaction and begin regeneration in the time of need regenerating, switch to other reactor and proceed reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102002413A (en) * | 2009-08-28 | 2011-04-06 | 韩国energy技术研究院 | Method for preparing an ashfree coal including a devulcanizing step |
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|---|---|---|---|---|
| CN102002413A (en) * | 2009-08-28 | 2011-04-06 | 韩国energy技术研究院 | Method for preparing an ashfree coal including a devulcanizing step |
| CN102241992A (en) * | 2010-05-14 | 2011-11-16 | 湖南省醴陵市马恋耐火泥有限公司 | Reconstruction method of 7.63 meter coke oven |
| CN104557388A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Deep desulfurization method of refinery C4 |
| CN104549140A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Ion exchange modified molecular sieve adsorbent and preparation method thereof |
| CN104549140B (en) * | 2013-10-28 | 2017-05-17 | 中国石油化工股份有限公司 | Ion exchange modified molecular sieve adsorbent and preparation method thereof |
| CN105778988A (en) * | 2016-02-23 | 2016-07-20 | 新疆恒晟能源科技有限公司 | Non-hydrogen gasoline modification method |
| CN105778988B (en) * | 2016-02-23 | 2018-03-30 | 新疆恒晟能源科技股份有限公司 | A kind of method of gasoline non-hydrogen modification |
| CN113088326A (en) * | 2021-04-22 | 2021-07-09 | 江苏大学 | Process for diesel adsorption-catalytic oxidation series ultra-deep desulfurization and denitrification |
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