CN101134908B - Catalytic no-hydroprocessing adsorbing desulfurization for hydrocarbon oil in moving bed reactor - Google Patents
Catalytic no-hydroprocessing adsorbing desulfurization for hydrocarbon oil in moving bed reactor Download PDFInfo
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Abstract
The non-hydrocatalyzing adsorption process for desulfurizing hydrocarbon oil in a moving bed reactor includes feeding sulfur containing hydrocarbon oil material and fluidizing medium into the moving bed reactor, contacting alternately with filled sulfur converting agent and sulfur adsorbent, separating the reacted matter flow to obtain product, steam stripping the deactivated sulfur converting agent and sulfur adsorbent and burning to regenerate, and returning the regenerated sulfur converting agent and sulfur adsorbent to the moving bed reactor for circular use. 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 96 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 people's is to the pay attention to day by day of environment protection, and is more and more stricter to the restriction of the sulphur content in the hydrocarbon ils.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 g/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 through control catalyst, only promote the thiophene hydrogenation and do not make the saturated method of alkene at low octane rating loss realization deep desulfuration down.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, isomerizing and the alkylated reaction of second section reactor drum to promote low-octane hydro carbons (like 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 is harsh, the 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 MOX to catch the 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 is high, and technical process is complicated.CN1583973A, CN1583972A all adopt the sieve catalyst of loaded metal, and selective cracking sulfide converts it into hydrocarbon and inorganic sulphide.The catalyzed conversion desulfurization is the method for clean cargo non-hydro 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 BO 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 receiving feed sulphur content, catalyst property and depth of conversion etc. influence, the influence of a large amount of inorganic sulphides that also receive to exist 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-hydro catalysis adsorption desulfurize in moving-burden bed reactor, to realize the deep desulfuration of hydrocarbon ils.
The objective of the invention is to realize through following proposal: the hydrocarbon oil crude material of sulfur-bearing, diluent media get into moving-burden bed reactor; Sulphur transforming agent, sulfur absorbent with filling at interval alternately contacts successively; The separating reaction logistics obtains product; The sulphur transforming agent of inactivation, sulfur absorbent carry out coke burning regeneration behind stripping, the sulphur transforming agent after the regeneration, sulfur absorbent return moving-burden bed reactor and recycle.
The hydrocarbon oil crude material of said 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 said sulfur-bearing is preferably in more than the 1000 μ g/g more than 50 μ g/g.
Said 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 the molecular sieve, inorganic oxide, the clay that contain rare earth account for the heavy % of 15-60, the heavy % of 10-60, the heavy % of 0-75 respectively.
The said 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 said 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 said 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.
Said 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 said 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.
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 the metallic element of 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.
Said inorganic oxide is selected from one or more the mixture in amorphous silicon aluminium, aluminum oxide, the silicon oxide; Said clay is selected from kaolin, halloysite, polynite, wilkinite, sepiolite, zeyssatite, tired one or more the mixture that takes off in the soil, preferred kaolin.
Preferred sulphur transforming agent is to constitute (all the weight with the sulphur transforming agent serves as to calculate benchmark) by weighing % through the heavy % of the Y series zeolite 15-60 that contains rare earth of phosphorus modification, the heavy % of inorganic oxide 10-60, clay 0-75; 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 processed different shapes, like 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.
Said 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.
Said reactive metal all is selected from one or more metals in the metal of metal, VA family of metal, the IVA family of metal, the IIB family of metal, the 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; One or more metals among the preferred Sc of the metal of IIIB family, 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 the metal of VIIB 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.
Said inorganic oxide is selected from one or more the mixture in amorphous silicon aluminium, aluminum oxide, the silicon oxide; Said clay is selected from kaolin, halloysite, polynite, wilkinite, sepiolite, zeyssatite, tired one or more the mixture that takes off in the soil, preferred kaolin; One or more the mixture of said 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.
Said 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 said sulphur transforming agent, sulfur absorbent had both depended on feed sulphur content, desulfurization requirement, were determined by reaction conditions again.
In reactor drum, according to sulphur transforming agent-sulfur absorbent-sulphur transforming agent-sulfur absorbent ... mode load at interval, also can adopt silica sand dilution sulphur transforming agent.Sulphur transforming agent and the sulfur absorbent weight ratio in whole reactor is 0.01-100: 1.
Reaction conditions is following: temperature 250-600 ℃ preferred 300-550 ℃, and weight hourly space velocity 0.1-100h
-1Preferred 1.0-50h
-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 moving-burden bed reactor, preferably adopts idle CR moving-bed device, with the economy system investment cost.
The present invention in fill process, can use nitrogen or/and water vapor as as diluent media, so that temperature keeps evenly in the bed.The volume space velocity of said diluent media is 0.01-10h
-1
The present invention preferably is provided with plural moving-burden bed reactor, and these moving-burden bed reactors can be connected, also can be parallelly connected, and can also series-parallel connection.When all moving-burden bed reactor series connection, can level be arranged in juxtaposition, also can the vertical direction arranged superposed.No matter which kind of connecting mode these moving-burden bed reactors take, the liquid stream direction with sweetening agent (the sulphur transforming agent, the sulfur absorbent that comprise filling at interval) travel direction can be and stream or adverse current identical or on the contrary.
After the sulphur transforming agent of inactivation, sulfur absorbent come out from last moving-burden bed reactor; Remove the impurity of its inner absorption earlier through stripping; In oxygen-containing gas (like air) atmosphere, regenerate, the oxidation regeneration condition is following again: temperature is 450-800 ℃ of preferred 500-650 ℃.Type according to employing sulphur transforming agent, sulfur absorbent is different, also needs H behind the spent agent oxidation regeneration that has
2Or/and the CO reduction, or with water vapor, nitrogen or other inert gas purge.The sulphur transforming agent of the heat after the regeneration, sulfur absorbent preferably return first moving-burden bed reactor again and recycle through being cooled to 250-600 ℃.
No matter be at reactor drum or at revivifier, sulphur transforming agent, sulfur absorbent are in moving process, and the order of filling is constant at interval.
Moving-bed catalysis desulfurizing method by adsorption provided by the present invention can not established heating tube in the moving-bed, by the catalyzer that plays thermal barrier effect circulation heating between moving-bed and revivifier; When desired reaction temperature is low, also can some heat-obtaining tube banks be installed in the internal regenerator segmentation, circulate to take remaining heat away with high pressure water.
Moving-bed catalysis desulfurizing method by adsorption provided by the present invention can adopt the idle moving bed catalytic cracking device of refinery or transform idle hyperformer.
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 drum, these two kinds of agent collaborative completion organosulfur catalyzed conversion in same reaction atmosphere is the function that inorganic sulfur, inorganic sulfur 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 under the condition of non-hydro, realize deep desulfuration, the decreasing ratio of sulphur can reach more than the 96 heavy %, even can be used to produce sweet gasoline.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-hydro, diesel raw material has sweetening effectiveness preferably, and desulfurization degree reaches more than the 75 heavy %.The diesel cetane-number of producing 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.
Description of drawings
Accompanying drawing is the method flow synoptic diagram of hydrocarbon ils provided by the invention non-hydro catalysis adsorption desulfurize in moving-burden bed reactor.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further explained, but therefore do not limited the present invention.
Accompanying drawing is the method flow synoptic diagram of hydrocarbon ils provided by the invention non-hydro catalysis adsorption desulfurize in moving-burden bed reactor.The accompanying drawing signal is with a moving-burden bed reactor and a parallel placement of revivifier.In the moving-burden 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 2 during practical application or more moving-burden bed reactor; Also can load sulphur transforming agent, sulfur absorbent from top to down successively at interval, the corresponding reactor drum that gets into from top of raw material.
Hydrocarbon oil containing surphur raw material after the preheating, fluidizing medium get into moving-burden bed reactor 2 through pipeline 1, pipeline 17 after mixing respectively; Upwards replace counter current contact with sulphur transforming agent, sulfur absorbent that move down, filling at interval successively; Hydrocarbon oil containing surphur raw material, intermediate reaction logistics contact with the sulphur transforming agent and make the organosulfur catalyzed conversion is inorganic sulfur; The intermediate reaction logistics contacts the inorganic sulfur that upper reaches bed is generated and in time is adsorbed with sulfur absorbent; Reaction conditions is following: temperature 250-600 ℃, and the volume space velocity 0.1-100h of hydrocarbon oil crude material
-1, pressure 0.10-0.80MPa, the volume space velocity 0.01-10h of diluent media
-1In reaction; The intermediate reaction logistics constantly moves up in reactor drum; Sulphur transforming agent, sulfur absorbent then constantly move down in reactor drum; Through repeatedly transform, after the adsorption process, final reactant flow is extracted out through pipeline 8 from the top of reactor drum 2 and is got into separation columns 9, isolating dry gas, liquefied gas product, gasoline products, solar oil product, heavy gas oil product are respectively through pipeline 10, pipeline 11, pipeline 12, pipeline 13, pipeline 14 caterpillars.
The sulphur transforming agent of inactivation, sulfur absorbent are extracted out from the bottom of reactor drum 2; Behind stripping medium such as water vapor, nitrogen or other rare gas element strippings from pipeline 15; Get into the top of revivifier 4 through pipeline 3; Constantly move down,, under 450-800 ℃ of preferred 500-650 ℃ temperature, accomplish coke burning regeneration with the regeneration gas such as the oxygen-containing gas counter current contact that get into revivifier 4 from the bottom.Sulphur transforming agent after the regeneration, sulfur absorbent cooling (not marking among the figure) back are purged, are promoted by fluidizing medium such as water vapor, nitrogen or other rare gas elementes from pipeline 16, and the top that gets into reactor drum 2 through pipeline 7 recycles.
Following embodiment will further explain method provided by the invention, but therefore not make the present invention receive any restriction.
Employed feedstock property is listed in table 1 among the embodiment.Employed sulphur transforming agent; Describe according to patent CN1583973A; The preparation process is following: with commercially available REY zeolite (Qilu Petrochemical company catalyst plant product; Silica alumina ratio 2.0) according to zeolite: an ammonium nitrate: the weight ratio of deionized water=1: 1: 20 is 90 ℃ of following IXs 2 hours, filters, washing back repeated exchanged once obtains ammonium type REY, its Na
2O 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-5.
13.5 kilograms of halloysites (Suzhou china clay company Industrial products, solid content are 73 heavy %), 13.5 kilograms of pseudo-boehmites (Shandong Zibo aluminium manufacturer Industrial products, solid content are 64 heavy %) are even with the ZET-5 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, adds suitable quantity of water, stirs; In air, placed 4 hours; Be shaped placement after 24 hours with the bowling machine spin, and 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-5 (median size is 2～4mm).
Employed sulfur absorbent, with Mn, Fe as active ingredient, with γ-Al
2O
3As carrier.Its preparation method is following: 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 2～4mm), 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-5.
Sulphur transforming agent CAT-5 and sulfur absorbent ADT-5 granularity are close with bulk density, are coccoid, and median size is at 2～4mm.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 silica sand dilution sulphur transforming agent.
Embodiment 1
The gasoline stocks that is numbered A alternately contacts and carries out catalyzed conversion, absorption with CAT-5, ADT-5 (gross weight ratio in front and back is 0.05: 1) successively in small-sized continuous moving-burden bed reactor.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.Temperature is 550 ℃ during the regeneration of CAT-5, ADT-5, and pressure is 0.2 MPa.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-5 in small-sized continuous moving-burden bed reactor 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 fluidizing medium, as diluent media, the volume space velocity of water vapor is 0.5 with water vapor with water vapor.Concrete testing sequence is identical with embodiment 1.Test conditions, product distribute and the gasoline main character is all listed in table 2.
Can find out that from table 2 with respect to Comparative Examples 1, under the situation of non-hydro, the catalysis adsorption desulfurize reaction that embodiment 1 has added sulfur absorbent ADT-5 exceeds more than 14 percentage point than the reaction desulfuration rate that does not add sulfur absorbent, dry gas, coke yield reduce simultaneously.
Embodiment 2
The gasoline stocks that is numbered B alternately contacts and carries out catalyzed conversion, absorption with CAT-5, ADT-5 (gross weight ratio in front and back is 1: 1) successively in small-sized continuous moving-burden bed reactor.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.Temperature is 450 ℃ during the regeneration of CAT-5, ADT-5, and pressure is 0.2 MPa.Test conditions, product distribute and the gasoline main character is listed in table 3.Can find out that from table 3 desulfurization degree of gasoline is up to 93.69 heavy %.
Embodiment 3
The gasoline stocks that is numbered C alternately contacts and carries out catalyzed conversion, absorption with CAT-5, ADT-5 (gross weight ratio in front and back is 50: 1) successively in small-sized continuous moving-burden bed reactor.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.Temperature is 650 ℃ during the regeneration of CAT-5, ADT-5, and pressure is 0.4 MPa.Test conditions, product distribute and the gasoline main character is listed in table 3.Can find out that from table 3 desulfurization degree of gasoline is up to 94.74 heavy %.
Embodiment 4
The diesel raw material that is numbered D alternately contacts and carries out catalyzed conversion, absorption with CAT-5, ADT-5 (gross weight ratio in front and back is 20: 1) successively in small-sized continuous moving-burden bed reactor.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.Temperature is 550 ℃ during the regeneration of CAT-5, ADT-5, and pressure is 0.4 MPa.Test conditions, product distribute and the diesel oil main character is listed in table 4.Can find out that from table 4 desulfurization degree of diesel oil is 75.99 heavy %.
Embodiment 5
The diesel raw material that is numbered E alternately contacts and carries out catalyzed conversion, absorption with CAT-5, ADT-5 (gross weight ratio in front and back is 0.1: 1) successively in small-sized continuous moving-burden bed reactor.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.Temperature is 700 ℃ during the regeneration of CAT-5, ADT-5, and pressure is 0.6 MPa.Test conditions, product distribute and the diesel oil main character is listed in table 4.Can find out that from table 4 desulfurization degree of diesel oil is 75.32 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, ℃ | ? | ? | ? | ? | ? |
| Over point | 90 | 45 | 62 | 191 | 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-5+ADT-5 | CAT-5 |
| Reaction conditions | ? | ? |
| Temperature, ℃ | ?400 | 400 |
| Pressure, MPa | ?0.2 | 0.2 |
| The gasoline volume space velocity, hour -1 | ?10 | 10 |
| The medium volume space velocity, hour -1 | ?0.5 | 0.5 |
| Product distributes, heavy % | ? | ? |
| Dry gas | ?0.35 | 0.48 |
| Liquefied gas | ?1.31 | 1.58 |
| Gasoline | ?93.64 | 91.11 |
| Solar oil | ?2.19 | 3.15 |
| Heavy gas oil | ?0.23 | 0.51 |
| Coke | ?2.25 | 3.15 |
| Loss | ?0.03 | 0.02 |
| The gasoline main character | ? | ? |
| RON | ?90.5 | 90.1 |
| MON | ?80.2 | 80.0 |
| Sulphur, μ g/g | ?65 | 318 |
| Nitrogen, μ g/g | ?0.8 | 1.1 |
| Desulfurization degree, heavy % | ?96.38 | 82.30 |
Table 3
| ? | Embodiment 2 | Embodiment 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 | 0.21 | 0.40 |
| Liquefied gas | 1.03 | 2.10 |
| Gasoline | 92.80 | 93.05 |
| Solar oil | 3.10 | 2.12 |
| Heavy gas oil | 0.32 | 0.10 |
| Coke | 2.54 | 2.23 |
| Loss | ? | ? |
| The gasoline main character | ? | ? |
| RON | 92.6 | 94.7 |
| MON | 80.2 | 81.2 |
| Sulphur, μ g/g | 32.3 | 7.2 |
| Nitrogen, μ g/g | 0.9 | 0.8 |
| Desulfurization degree, heavy % | 93.69 | 94.74 |
Table 4
| ? | Embodiment 4 | Embodiment 5 |
| Reaction conditions | ? | ? |
| Temperature, ℃ | 450 | 550 |
| Pressure, MPa | 0.4 | 0.6 |
| The diesel oil volume space velocity, hour -1 | 3 | 10 |
| The medium volume space velocity, hour -1 | Water vapor/0.14 | Nitrogen/8.0 |
| Product distributes, heavy % | ? | ? |
| Dry gas | 0.62 | 0.65 |
| Liquefied gas | 3.32 | 2.68 |
| Gasoline | 6.34 | 4.35 |
| Solar oil | 86.19 | 88.95 |
| Heavy gas oil | / | / |
| Coke | 3.51 | 3.36 |
| Loss | 0.02 | 0.01 |
| The diesel oil main character | ? | ? |
| Sulphur, μ g/g | 278.5 | 2534.0 |
| Desulfurization degree, heavy % | 75.99 | 75.32 |
| Density, (20 ℃), kilogram/rice 3 | 879.8 | 895.2 |
| Cetane value | 32.5 | 30.2 |
Claims (20)
1. the method for hydrocarbon ils non-hydro catalysis adsorption desulfurize in moving-burden bed reactor; It is characterized in that this method comprises: the hydrocarbon oil crude material of sulfur-bearing, diluent media get into moving-burden bed reactor; Sulphur transforming agent, sulfur absorbent with filling at interval alternately contacts successively; The separating reaction logistics obtains product; The sulphur transforming agent of inactivation, sulfur absorbent carry out coke burning regeneration behind stripping, the sulphur transforming agent after the regeneration, sulfur absorbent return moving-burden bed reactor and recycle, and said 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 the molecular sieve, inorganic oxide, the clay that contain rare earth account for the heavy % of 15-60, the heavy % of 10-60, the heavy % of 0-75 respectively; Said sulphur transforming agent and the weight ratio of sulfur absorbent in whole reactor are 0.01-100: 1; Said sulphur transforming agent bed and sulfur adsorbent bed operational condition are: temperature 250-600 ℃, and volume space velocity 0.1-100h
-1, pressure 0.10-0.80MPa.
2. according to the described method of claim 1, the hydrocarbon oil crude material that it is characterized in that said sulfur-bearing is selected from one or more the mixture in gasoline, kerosene, diesel oil, the gas oil fraction.
3. according to the described method of claim 1, it is characterized in that the said 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.
4. according to the described method of claim 3, it is characterized in that the said 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 said 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 said 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.
5. according to the described method of claim 4, it is characterized in that the said Y series zeolite that contains rare earth is that the REY zeolite is or/and the REHY zeolite; The said ZSM series zeolite that contains rare earth is the ZSM-5 zeolite that contains rare earth.
6. according to described method one of among the claim 2-5, it is characterized in that said rare earth all is selected from one or more elements among La, Ce, Pr, Nd, the Sm.
7. according to described method one of among the claim 2-5; It is characterized in that the said molecular sieve that contains rare earth is element modified through other, said 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.
8. according to the described method of claim 7, 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.
9. according to the described method of claim 1, it is characterized in that said sulphur transforming agent is by weighing % and constitute through the heavy % of the Y series zeolite 15-60 that contains rare earth of phosphorus modification, the heavy % of inorganic oxide 10-60, clay 0-75; 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.
10. according to the described method of claim 1, it is characterized in that said 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.
11., it is characterized in that said 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 according to the described method of claim 10.
12., it is characterized in that said basic metal is one or more metals among Li, Na, the K according to the described method of claim 11; 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.
13. according to the described method of claim 10; It is characterized in that one or more the mixture of said molecular screening in A type molecular sieve, X type molecular sieve, Y series molecular sieve, one or more the mixture of wherein said Y series molecular screening in Y type, HY type, REY type, REHY type, USY type, REUSY type zeolite.
14., it is characterized in that said 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 1,9,10; Said clay is selected from kaolin, polynite, wilkinite, sepiolite, zeyssatite, tired one or more the mixture that takes off in the soil.
15., it is characterized in that said kaolin is halloysite according to the described method of claim 14.
16., it is characterized in that the sulphur transforming agent of inactivation, the oxidation regeneration temperature of sulfur absorbent are 450-800 ℃ according to the described method of claim 1.
17. according to the described method of claim 1, it is characterized in that in fill process using nitrogen or/and water vapor as diluent media, said diluent media volume space velocity 0.01-10h
-1
18., it is characterized in that moving-burden bed reactor is more than two, these moving-burden bed reactor series, parallel or series-parallel connections according to the described method of claim 1.
19., it is characterized in that these moving-burden bed reactor levels are arranged in juxtaposition or the vertical direction arranged superposed when all moving-burden bed reactor series connection according to the described method of claim 18.
20., it is characterized in that the liquid stream direction is identical or opposite with the travel direction of sulphur transforming agent, sulfur absorbent according to the described method of claim 18.
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| CN102031141B (en) * | 2009-09-29 | 2013-09-04 | 济南开发区星火科学技术研究院 | Method for preparing gasoline desulfurization adsorbent |
| 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 |
| US9382485B2 (en) * | 2010-09-14 | 2016-07-05 | Saudi Arabian Oil Company | Petroleum upgrading process |
| CN106675618B (en) * | 2015-11-11 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of processing method of sulphur nitrogen homogenization system and isomerate feeds |
| CN105363339B (en) * | 2015-12-08 | 2017-10-17 | 冯淑珠 | A kind of exhaust-gas treatment chimney |
| CN108187605B (en) * | 2018-01-04 | 2019-11-15 | 华南理工大学 | A kind of highly selective gasoline adsorption deep desulfurizer of support type hydroxide and preparation method thereof |
| WO2019134428A1 (en) * | 2018-01-04 | 2019-07-11 | 华南理工大学 | Supported hydroxide gasoline deep adsorption desulfurizing agent and preparation method and oxidation regeneration method therefor |
| CN111097362A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Sulfur, arsenic and phosphorus purifying agent and preparation method thereof |
| CN115805014A (en) * | 2021-09-14 | 2023-03-17 | 中国石油化工股份有限公司 | Reactor and method for desulfurizing sulfur-containing gas, and device and method for continuously desulfurizing sulfur-containing gas |
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