CN101134911B - Catalytic no-hydroprocessing adsorbing desulfurization for hydrocarbon oil in fluidized reactor - Google Patents
Catalytic no-hydroprocessing adsorbing desulfurization for hydrocarbon oil in fluidized reactor Download PDFInfo
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Abstract
The non-hydrocatalyzing adsorption process for desulfurizing hydrocarbon oil in a fluidizing reactor includes feeding sulfur containing hydrocarbon oil material and fluidizing medium into the fluidizing reactor, contacting with sulfur converting agent and sulfur adsorbent, separating the reacted matter flow to obtain product, regenreating the deactivated sulfur converting agent and sulfur adsorbent, and returning the regenerated sulfur converting agent and sulfur adsorbent to the fluidizing 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 92 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 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 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 fluidizing reactor, to realize the deep desulfuration of hydrocarbon ils.
The objective of the invention is to realize by following proposal: hydrocarbon oil crude material, the fluidizing medium of sulfur-bearing enter fluidizing reactor, contact with sulphur transforming agent, sulfur absorbent, the separating reaction logistics obtains product, and the sulphur transforming agent of inactivation, sulfur absorbent return described fluidizing reactor and recycle after regenerating.
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 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.
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.
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 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.
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.
Sweetening agent used in the present invention (comprising sulphur transforming agent and sulfur absorbent) for ease of fluidisation, is preferably microspheroidal, and its median size is at 20-100 μ m.Described sulphur transforming agent, sulfur absorbent are specifically formed and type of feed, have both depended on that type of reactor is also determined by feed sulphur content and reaction conditions.
Described sulfur absorbent at high temperature has adsorption to inorganic sulfur, and can reuse by oxidation regeneration.
In reactor, with sulphur transforming agent, sulfur absorbent mixed packing, sulphur transforming agent and the sulfur absorbent weight ratio in whole reactor is 0.01-100: 1.
Reaction conditions is as follows: temperature 150-600 ℃ preferred 300-550 ℃, and weight hourly space velocity 1-100h
-1Preferred 2-50h
-1, the preferred 0.2-0.6MPa of reaction pressure 0.10-0.80MPa, the preferred 5-20 of weight ratio 2-40 of sweetening agent (comprising sulphur transforming agent and sulfur absorbent) and hydrocarbon oil crude material, the preferred 0.02-0.20 of the weight ratio 0.01-1.0 of fluidizing medium and hydrocarbon oil crude material.Material behind the separating reaction, reaction product are sent into subsequent separation system and are carried out product separation, reacted two kinds of sweetening agents coke burning regeneration behind stripping, and the Returning reactor after cooling off of the sweetening agent after the regeneration recycles.
The compound reactor that fluidizing reactor of the present invention is selected from fluidized-bed, riser tube, downstriker transfer limes reactor, be made of riser tube and fluidized-bed, the compound reactor that constitutes by riser tube and downstriker transfer limes, the compound reactor that constitutes by two or more riser tubes, the compound reactor that constitutes by two or more fluidized-beds, by the compound reactor that two or more downstriker transfer limess constitute, above-mentioned every kind of reactor can be divided into two or more reaction zones.That described fluidized-bed is selected from is fixed fluidized bed, in the dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying bed, dense phase fluidized bed one or more, and preferred fluidized-bed is dense phase fluidized bed more preferably.Described riser tube be selected from the equal diameter riser tube, etc. in linear speed riser tube, the various change diameter riser tube one or more, preferred riser tube.
The present invention in fill process, can use nitrogen or/and water vapor as fluidizing medium so that reactor in Flow of Goods and Materials get up.
The sulphur transforming agent of inactivation, sulfur absorbent preferably remove the impurity of its inner absorption earlier through stripping, regenerate in oxygen-containing gas (as air) atmosphere again, and the oxidation regeneration condition is as follows: temperature is 450-800 ℃ of preferred 500-650 ℃.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.Sulphur transforming agent after the regeneration, sulfur absorbent are preferably through being cooled to 150～500 ℃ of recirculation uses.
The present invention compared with prior art has following unforeseeable technique effect:
1, two kinds of sweetening agents being housed in a reactor is sulphur transforming agent, sulfur absorbent, and these two kinds of sweetening agents are the collaborative catalytic desulfurization function of finishing in same reaction atmosphere, recovers active then in same regeneration atmosphere simultaneously.
When 2, adopting method provided by the present invention to handle gasoline stocks, can realize deep desulfuration under the condition of no hydrogen consumption, the decreasing ratio of sulphur can reach more than the 92 weight %, and has improved gasoline octane rating when having reduced gasoline olefin.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 96 heavy %.
When 3, adopting method provided by the present invention to handle diesel raw material, under the condition of non-hydrogen, diesel raw material has sweetening effectiveness preferably, and desulfurization degree reaches 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 present invention, can alleviate gaseous product liquefied gas, dry gas desulfurizer load, even save liquefied gas, dry gas desulfurizer.
5, catalysis desulfurizing method by adsorption provided by the present invention can all be realized successive reaction and regeneration on fluidized-bed reactor.
Description of drawings
Accompanying drawing is the method flow synoptic diagram of hydrocarbon ils provided by the invention non-hydrogen catalysis adsorption desulfurize in fluidized-bed reactor.
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 non-hydrogen catalysis adsorption desulfurize in fluidized-bed reactor.Accompanying drawing adopts a fluidized-bed reactor and a revivifier.Sulphur transforming agent, sulfur absorbent mixed packing in described fluidized-bed reactor, the revivifier.
Gasoline fraction raw material after the preheating and fluidizing medium enter transfer lime 2 bottoms through pipeline 1, with contact from the sweetening agent after the regeneration of regenerator sloped tube 17, reactant flow enters the settling vessel 7 that has the dense fluidized bed bioreactor, and reaction oil gas is sent into follow-up product separation system through pipeline 8.Sweetening agent to be generated enters stripper 3, by the entrained reaction oil gas of fluidizing medium stripping sweetening agent to be generated from pipeline 4, spent agent behind the stripping enters revivifier 13 through inclined tube 5 to be generated, oxygen-containing gas is introduced revivifier through pipeline 14, sweetening agent to be generated is coke burning regeneration under the effect of oxygen-containing gas, regenerated flue gas is drawn revivifier through pipeline 12, the pyritous recycling desulfurizer enters sweetening agent water cooler 16 through pipeline 15, cooled sweetening agent returns the transfer lime bottom cycle by regenerator sloped tube 17 and uses, and loosening wind enters sweetening agent water cooler 16 through pipeline 18.
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 table 1 among the embodiment.Employed sulphur transforming agent, 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 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-1.
With 34.36 kilograms of decationized Y sieve water with 13.5 kilograms of halloysites (Suzhou china clay company Industrial products, solid content is 73 heavy %) making beating, add 13.5 kilograms of pseudo-boehmites (Shandong Zibo aluminium manufacturer Industrial products again, solid content is 64 heavy %) and 1.17 liter hydrochloric acid (concentration is 30 weight %) stir, under 75 ℃, left standstill aging 1 hour, keep pH=2-4, be cooled to 60 ℃, it is even to add the ZET-1 zeolite thorough mixing for preparing in advance that accounts for sweetening agent weight 30 heavy % respectively, spray drying forming, washing are removed free Na
+, be drying to obtain the sulphur transforming agent and be designated as CAT-1.
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
3Bead (median size is at 60 μ m), at room temperature dipping stirs, again 120 ℃ of oven dry after 4 hours, under 750 ℃ of conditions during roasting 6.Resulting sulfur absorbent is designated as ADT-1.
Sulphur transforming agent CAT-1 and sulfur absorbent ADT-1 granularity are close with bulk density.With sulphur transforming agent CAT-1 and sulfur absorbent ADT-1 mixed packing.
Embodiment 1
The gasoline stocks that is numbered A contacts with sweetening agent CAT-1, ADT-1 (gross weight ratio in front and back is 0.05: 1) in small-sized continuous fluid 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 sweetening agent (CAT-1, ADT-1) is 10 with the weight ratio of gasoline stocks, and the weight hourly space velocity of gasoline stocks is 4 hours
-1, as fluidizing medium, the weight ratio of water vapor and gasoline stocks is 0.03 with water vapor.The desulfurization product that is obtained by reactor head obtains gaseous product and product liquid through cooling, separation.The regeneration temperature of CAT-1, ADT-1 is 550 ℃, and the Returning reactor internal recycle used after the sweetening agent after the regeneration was cooled to 400 ℃.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 all identical with raw material, reaction conditions, the regeneration condition of embodiment 1, and this raw material only contacts with sulphur transforming agent CAT-1 in small-sized continuous fluid bed bioreactor and reacts.Concrete 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-1 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 contacts with CAT-1, ADT-1 (gross weight ratio in front and back is 1: 1) in small-sized continuous fluid 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 sweetening agent (CAT-1, ADT-1) is 10 with the weight ratio of gasoline stocks, and the weight hourly space velocity of gasoline stocks is 5 hours
-1, as fluidizing medium, the weight ratio of water vapor and gasoline stocks is 0.02 with water vapor.The desulfurization product that is obtained by reactor head obtains gaseous product and product liquid through cooling, separation.The regeneration temperature of CAT-1, ADT-1 is 450 ℃, and the Returning reactor internal recycle used after the sweetening agent after the regeneration was cooled to 250 ℃.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 91.61 heavy %.
The gasoline stocks that is numbered C contacts with CAT-1, ADT-1 (gross weight ratio in front and back is 50: 1) in medium-sized riser reactor and carries out catalyzed conversion, absorption.Main operational condition is: temperature of reaction is 450 ℃, and reactor pressure is 0.4 MPa, and sweetening agent (CAT-1, ADT-1) is 4 with the weight ratio of gasoline stocks, and the weight hourly space velocity of gasoline stocks is 50 hours
-1, as fluidizing medium, the weight ratio of nitrogen and gasoline stocks is 0.01 with nitrogen.The desulfurization product that is obtained by reactor head obtains gaseous product and product liquid through cooling, separation.The regeneration temperature of CAT-1, ADT-1 is 650 ℃, and the Returning reactor internal recycle used after the sweetening agent after the regeneration was cooled to 450 ℃.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 91.37 heavy %.
The diesel raw material that is numbered D contacts with CAT-1, ADT-1 (gross weight ratio in front and back is 20: 1) in small-sized continuous fluid bed bioreactor carries out catalyzed conversion, absorption.Main operational condition is: temperature of reaction is 450 ℃, and reactor pressure is 0.4 MPa, and sweetening agent (CAT-1, ADT-1) is 15 with the weight ratio of diesel raw material, and the weight hourly space velocity of diesel raw material is 3 hours
-1, as fluidizing medium, the weight ratio of water vapor and diesel raw material is 0.20 with water vapor.The desulfurization product that is obtained by reactor head obtains gaseous product and product liquid through cooling, separation.The regeneration temperature of CAT-1, ADT-1 is 550 ℃, and the Returning reactor internal recycle used after the sweetening agent after the regeneration was cooled to 450 ℃.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 73.22 heavy %.
The diesel raw material that is numbered E contacts with CAT-1, ADT-1 (gross weight ratio in front and back is 0.1: 1) in medium-sized riser reactor carries out catalyzed conversion, absorption.Main operational condition is: temperature of reaction is 550 ℃, and reactor pressure is 0.6 MPa, and sweetening agent (CAT-1, ADT-1) is 8 with the weight ratio of diesel raw material, and the weight hourly space velocity of diesel raw material is 50 hours
-1, as fluidizing medium, the weight ratio of nitrogen and diesel raw material is 0.02 with nitrogen.The desulfurization product that is obtained by reactor head obtains gaseous product and product liquid through cooling, separation.The regeneration temperature of CAT-1, ADT-1 is 700 ℃, and the Returning reactor internal recycle used after the sweetening agent after the regeneration was cooled to 500 ℃.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 72.50 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 | 191 | 195 |
| 10％ | 92 | 60 | 75 | 208 | 234 |
| 30％ | 121 | 79 | 89 | 226 | 267 |
| The raw material numbering | A | B | C | D | E |
| 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-1+ADT-1 | CAT-1 |
| Reaction conditions | ||
| Temperature, ℃ | 400 | 400 |
| Pressure, MPa | 0.2 | 0.2 |
| The gasoline weight hourly space velocity, |
4 | 4 |
| Agent-oil ratio | 10 | 10 |
| Water-oil ratio | 0.03 | 0.03 |
| Product distributes, heavy % | ||
| Dry gas | 0.34 | 0.50 |
| Liquefied gas | 1.20 | 1.66 |
| Gasoline | 92.55 | 90.16 |
| Solar oil | 2.55 | 3.54 |
| Heavy gas oil | 0.53 | 0.71 |
| Coke | 2.80 | 3.42 |
| Embodiment 1 | Comparative Examples 1 | |
| Loss | 0.03 | 0.01 |
| The gasoline main character | ||
| RON | 90.3 | 90.1 |
| MON | 80.1 | 80.2 |
| Sulphur, μ g/g | 126.2 | 352 |
| Nitrogen, μ g/g | 0.8 | 1.2 |
| Desulfurization degree, heavy % | 92.98 | 80.40 |
Table 3
| |
|
|
| Reaction conditions | ||
| Temperature, ℃ | 250 | 450 |
| Pressure, MPa | 0.2 | 0.4 |
| The gasoline weight hourly space velocity, |
5 | 50 |
| Agent-oil ratio | 10 | 4 |
| The weight ratio of fluidizing medium and gasoline stocks | Water vapor/0.02 | Nitrogen/0.01 |
| Product distributes, heavy % | ||
| Dry gas | 0.22 | 0.35 |
| Liquefied gas | 1.32 | 2.13 |
| Gasoline | 90.90 | 92.03 |
| |
|
|
| Solar oil | 3.52 | 2.47 |
| Heavy gas oil | 1.00 | 0.20 |
| Coke | 3.02 | 2.80 |
| Loss | 0.02 | 0.02 |
| The gasoline main character | ||
| RON | 92.6 | 94.6 |
| MON | 80.2 | 81.2 |
| Sulphur, μ g/g | 43.0 | 11.8 |
| Nitrogen, μ g/g | 1.0 | 0.70 |
| Desulfurization degree, heavy % | 91.61 | 91.37 |
Table 4
| |
|
|
| Reaction conditions | ||
| Temperature, ℃ | 450 | 550 |
| Pressure, MPa | 0.4 | 0.6 |
| The diesel oil weight hourly space velocity, |
3 | 50 |
| Agent- |
15 | 8 |
| The weight ratio of fluidizing medium and diesel raw material | Water vapor/0.20 | Nitrogen/0.02 |
| Product distributes, heavy % | ||
| Dry gas | 0.55 | 0.35 |
| |
|
|
| Liquefied gas | 3.87 | 3.04 |
| Gasoline | 5.78 | 3.55 |
| Solar oil | 85.86 | 89.18 |
| Heavy gas oil | / | / |
| Coke | 3.92 | 3.86 |
| Loss | 0.02 | 0.02 |
| The diesel oil main character | ||
| Sulphur, μ g/g | 310.6 | 2823.4 |
| Desulfurization degree, heavy % | 73.22 | 72.50 |
| Density, (20 ℃), kilogram/rice 3 | 881.0 | 898.9 |
| Cetane value | 31.5 | 30.2 |
Claims (20)
1. the method for hydrocarbon ils non-hydrogen catalysis adsorption desulfurize in fluidizing reactor, it is characterized in that this method comprises: the hydrocarbon oil crude material of sulfur-bearing, fluidizing medium enters fluidizing reactor, with the sulphur transforming agent, the sulfur absorbent contact, the separating reaction logistics obtains product, the sulphur transforming agent of inactivation, sulfur absorbent returns described fluidizing reactor and recycles after regenerating, wherein said sulfur absorbent is selected from gac, the oxide compound of reactive metal, the oxyhydroxide of reactive metal, load on inorganic oxide, the mixture of one or more in the oxide compound of the reactive metal on clay or the molecular sieve.
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.
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 to constitute by weighing % through heavy %, inorganic oxide 10-60 of the Y series zeolite 15-60 that contains rare earth of phosphorus modification heavy %, clay 0-75, all the weight with the sulphur transforming agent serves as to calculate benchmark; 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 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.
12. in accordance with the method for claim 11, 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 Sb 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.
13., 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; Described clay is selected from kaolin, halloysite, polynite, wilkinite, sepiolite, diatomite, tired one or more the mixture that takes off in the soil.
14. 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.
15. in accordance with the method for claim 1, it is characterized in that temperature 150-600 ℃, weight hourly space velocity 1-100h
-1, reaction pressure 0.10-0.80MPa, the weight ratio 2-40 of sulphur transforming agent, sulfur absorbent and hydrocarbon oil crude material, the weight ratio 0.01-1.0 of fluidizing medium and hydrocarbon oil crude material.
16. it is characterized in that in accordance with the method for claim 1, the sulphur transforming agent of inactivation, the oxidation regeneration temperature of sulfur absorbent are 450-800 ℃.
17. in accordance with the method for claim 1, sulphur transforming agent, the sulfur absorbent after it is characterized in that regenerating recycles through being cooled to 150～600 ℃.
18. in accordance with the method for claim 1, it is characterized in that in fill process using nitrogen or/and water vapor as fluidizing medium.
19. in accordance with the method for claim 1, the compound reactor that it is characterized in that compound reactor that described fluidizing reactor is selected from fluidized-bed, riser tube, downstriker transfer limes reactor, is made of riser tube and fluidized-bed, constitutes by riser tube and downstriker transfer limes, the compound reactor that constitutes by two or more riser tubes, the compound reactor that constitutes by two or more fluidized-beds, by the compound reactor that two or more downstriker transfer limess constitute, above-mentioned every kind of reactor can be divided into two or more reaction zones.
20. in accordance with the method for claim 19, it is characterized in that described fluidized-bed is selected from one or more in fixed fluidized bed, dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying bed, the dense phase fluidized bed, described riser tube be selected from the equal diameter riser tube, etc. in linear speed riser tube, the various change diameter riser tube one or more.
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| CN103539612B (en) * | 2012-07-12 | 2015-08-12 | 中国石油化工股份有限公司 | Desulphurization method for propylene |
| CN103540342B (en) * | 2012-07-17 | 2015-03-18 | 中国石油化工股份有限公司 | Fluidized bed reactor applied to adsorption desulfurization and application thereof |
| CN103788996B (en) * | 2012-10-29 | 2015-05-20 | 中国石油化工股份有限公司 | Adsorption desulfurization reaction device and adsorption desulfurization method |
| CN103962115B (en) * | 2014-05-21 | 2016-02-03 | 杨皓 | A kind of regeneration technology with the desulphurized aetivated carbon of Cross unit conbined usage |
| CN110760332A (en) * | 2017-07-27 | 2020-02-07 | 华东理工大学 | System for removing sulfide in oil product through cyclone reinforcement |
| CN114191965B (en) * | 2021-12-16 | 2022-11-01 | 北京博奇电力科技有限公司 | Automatic many bed layers of continuity decarbonization system of regulation |
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| CN1482210A (en) * | 2002-09-11 | 2004-03-17 | 上海博申工程技术有限公司 | Adsorption refining gasoline by catalyst cracking method |
| CN1583972A (en) * | 2003-08-20 | 2005-02-23 | 中国石油化工股份有限公司 | Method for decreasing sulfur content of hydrocarbon |
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| CN1482210A (en) * | 2002-09-11 | 2004-03-17 | 上海博申工程技术有限公司 | Adsorption refining gasoline by catalyst cracking method |
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