CN102010751A - Efficient combined production method for gasoline with ultralow sulfur and high octane value - Google Patents
Efficient combined production method for gasoline with ultralow sulfur and high octane value Download PDFInfo
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Abstract
The invention relates to an efficient combined production method for gasoline with ultralow sulfur and high octane value. The production method comprises the following steps of: performing low-temperature directional sulfur transfer reaction on a poor-quality full fraction gasoline raw material under the hydrogen condition, and then performing oil cutting and fractionation to obtain light fraction gasoline and heavy fraction gasoline, wherein the cutting and fractionation temperature is 50 to 90 DEG C; making the heavy fraction gasoline contact with a selective hydrogenation desulfurization catalyst and a supplemented desulfurization-hydrocarbon heterogeneous/aromatized catalyst; and mixing the light fraction gasoline and the treated heavy fraction gasoline to obtain a gasoline product with ultralow sulfur and high octane value. The method is suitable for modifying the poor-quality gasoline, can achieve good super-deep desulfurization and olefin reducing effects particularly for the poor-quality catalytically cracked gasoline with ultrahigh sulfur and high olefin, and can maintain or improve the octane value of the product after reaction and keep high product yield.
Description
Technical field
The present invention relates to a kind of efficient combination production method of ultra-low sulfur and high-octane number gasoline, relate in particular to a kind of refining of petroleum field and be used for the ultra-deep desulfurization-recovery octane value hydrogenation modification method of the FCC gasoline inferior of catalytic cracking (FCC) gasoline, particularly ultra-high-sulfur(UHS), high olefin.
Background technology
At present, high sulphur content and olefin(e) centent become the key issue that puzzlement world clean gasoline is produced in the catalytically cracked gasoline.Under the less situation of high-octane number component reformed gasoline and gasoline alkylate, for satisfying the clean gasoline standard-required of increasingly stringent, the hydro-upgrading of FCC gasoline just becomes one of gordian technique that clean fuel for vehicle produces.
USP 5770047, USP 5417697 etc. have introduced desulfurization based on hydrofining-cracking/single side chain hydroisomerizing, have fallen olefin process.The main thought of these technologies be with full cut FCC gasoline be cut into gently, last running, the last running of FCC gasoline is after conventional Hydrobon catalyst deep desulfuration is handled, alkene wherein all is converted into alkane, products obtained therefrom is finished alkane cracking-hydroisomerizing reaction on the zeolite based catalysts that has proper sourness through screening then, reach the purpose of improving and recovering octane value, be in harmonious proportion by the weight cut subsequently and obtain full fraction upgrading gasoline.According to the record of above-mentioned patent, the liquid yield of product of finally being in harmonious proportion is 94wt%, and gasoline research method octane value (RON) loss reaches about 2.0 units.
Though the gasoline hydrogenation modifying method that above-mentioned patent provides can realize desulfurization, the purpose of alkene is fallen, but its at stock oil in olefin(e) centent only be about 20v% and aromaticity content higher (about 30v%), be applicable to external gasoline component more, all higher for alkene and sulphur content, the oil product of aromaticity content lower (about 20v%), for example to China FCC gasoline of olefin(e) centent about up to 40v%, use this technology to carry out upgrading, in desulfurating and reducing olefinic hydrocarbon, a large amount of alkene are saturated by hydrogenation, cause the loss of octane value to increase, so the modification technology of these open reports obviously is inapplicable.So just reason, at the singularity of Chinese FCC gasoline, exploring more scientific and reasonable method for modifying is the research focus of oil refining industry all the time.
The method of the deep desulfurization olefin hydrocarbon reduction of gasoline that provides among the CN145666A (No. 02121595.2, Chinese patent application), it is exactly These characteristics at China FCC gasoline, to implement hydrogenation desulfurization and denitrogenation and the alkene heavy naphtha after saturated through Hydrobon catalyst, utilization has the HZSM-5 base octane value recovering catalyst of enough acid functions, realize the cracking of low octane rating alkane molecule and the isomerization reaction of alkane molecule, the last running that will implement upgrading then is mixed into final upgraded products may with the lighting end that cutting obtains.Introduction according to this patent, because alkene is by hydrogenation is saturated fully in first section reaction, for the octane value that recovers product need improve the cracking ability of two sections catalyzer, its cost is the significantly reduction (only being 86%) of product liquid yield, and tooling cost significantly improves.
CN 1488722A (No. 0213311.1, Chinese patent application) discloses the similar FCC gasoline hydrogenation modifying process of a kind of and above-mentioned patent.Difference is the last running of FCC gasoline after conventional Hydrobon catalyst deep desulfuration, alkene all are converted into alkane, and the gained reaction effluent is normal paraffin cracking-single side chain hydroisomerizing reaction of finishing on nanometer H β zeolite based catalysts.
The similarity of the modifying process of above two China patent all is to make through the isomerization on the zeolite based catalysts of acid function of conventional hydrorefined heavy distillate, realize normal paraffin cracking-single side chain hydroisomerizing, because HZSM-5 zeolite and nanometer H β zeolite acidity are strong, the acid amount is bigger, therefore cause cracking reaction comparatively serious, consequently suppressed single side chain isomerization reaction of alkane.
CN 1743425A (No. 200410074058.7, Chinese patent application) discloses a kind of hydrogenation modifying process at China high olefin FCC gasoline, wherein, full cut FCC gasoline through dialkene removal, alkene aromatization and replenishing three reactions of alkene upgrading falls and after, desulfurization degree is 78%, the product olefin(e) centent is that 30v%, product RON loss is 1.0 units, and product liquid is received to about 98.5wt%.But this method is primarily aimed at low sulfur-bearing FCC gasoline, and under the prerequisite that reduces the RON loss as far as possible, desulfurization degree is lower, the alkene range of decrease is little, and the products obtained therefrom difficult quality satisfies state III and state's IV clean gasoline standard, obviously is not suitable for high-sulphur stock oil.
CN 1488724A (No. 02133130.8, Chinese patent application) discloses a kind of FCC gasoline hydrofinishing/aromizing process integration based on nano zeolite catalyst.This technology is to make full cut FCC gasoline after hydrofining is alkane with most of conversion of olefines, on nano zeolite catalyst, carry out alkane aromatization again, this patent is by adopting a kind of main group that comprises, the nano level hydrogen type molecular sieve catalyzer of magnesium-yttrium-transition metal and lanthanide rare metal oxide, make upgraded products may desulfurization degree height, the alkene range of decrease is big, but the product liquid yield that this method obtains is only for about 90wt%, product RON loss is big (reaching 2.0-3.0 unit), and the nano zeolite preparation is complicated, regenerability is not good, cause the technology cost to increase, be difficult to adapt to suitability for industrialized production.
CN 1718688A (No. 200410020932.9, Chinese patent application) discloses a kind of FCC gasoline hydrogenation modifying method inferior.This patented method forms three reaction zones under the condition that hydrogen exists and temperature raises gradually, full cut FCC gasoline is contacted with three kinds of catalyzer, adopts conventional Hydrobon catalyst (6h under high charging air speed earlier
-1) take off two alkene reactions, adopt nano zeolite catalyst under high temperature (415 ℃), to carry out aromizing, isomerization reaction then, adopt Co-Mo-K-P/Al at last
2O
3Catalyzer is at high temperature (415 ℃), high-speed (40h more
-1) under carry out selective desulfurization.The advantage of this method is that the alkene and the sulphur content of the product that obtains is all lower, but product RON loss is about 3.0 units, the product liquid yield is about 94wt%, and the nano zeolite preparation is complicated, easy inactivation under the high temperature, regenerability is not good, in addition at high-speed very and yet easy inactivation of the 3rd section desulfurization catalyst under the high-temperature very, influence the reaction stability of whole technology, increased the application difficulty of suitability for industrialized production.
CN 1597865A (No. 03133992.1, Chinese patent application) discloses a kind of inferior FCC gasoline hydrogenation modifying method similar to CN 1718688A thinking.This processing method adopts conventional Hydrobon catalyst (6h under high charging air speed earlier
-1) carry out the dialkene removal reaction of full cut FCC gasoline, adopt Co-Mo-K-P/Al then
2O
3Catalyzer carries out selective desulfurization, adopts nano zeolite catalyst to carry out the alkene aromizing at last under high temperature (415 ℃).The olefin(e) centent of product that this patented method obtains is lower, but product RON loss is about 1.0 units, the weak point of above-mentioned nano zeolite still exists, and product sulphur content higher (desulfurization degree only 75%), is difficult to satisfy state III and state's IV clean gasoline standard.
CN 1769388A (No. 200410082704.4, Chinese patent application) discloses the hydrogenation modifying process of a kind of FCC of reduction gasoline sulfur and olefin(e) centent.The technology of this patent is to adopt conventional Hydrobon catalyst (6h under high charging air speed earlier
-1) carry out the dialkene removal reaction of full cut FCC gasoline, carry out prefractionation then, lighting end gasoline mainly carries out the alkene aromizing on nano zeolite catalyst, last running gasoline carries out the selective hydrodesulfurization reaction successively on low-metal content aluminium oxide catalyst and high metal content aluminium oxide catalyst, can get full fraction upgrading gasoline after at last reacted weight gasoline being mixed.The alkene and the sulphur content of product that this patented method obtains are lower, but it is about 1.5 units that the whole course of processing still makes product RON loss, and the weak point of above-mentioned nano zeolite still exists, and needs four kinds of catalyzer and supporting complicated technology, has limited its industrial application.
CN1283761C (No. 200410060574.4, Chinese patent) discloses a kind of inferior patrol hydrogenation modifying process.This technology is cut into lighting end and last running gasoline with full cut FCC gasoline earlier, then with last running gasoline at Co (Ni)-Mo/TiO
2Carry out hydrogenating desulfurization on the catalyzer, again at Co (Ni)-Mo (W)/ZSM-5-/TiO
2Carry out aromatization on the catalyzer, at last reacted weight gasoline is mixed into full fraction upgrading gasoline.Olefin(e) centent according to product that this patented method obtains is lower, but the product sulphur content is difficult to satisfy and is not higher than 50 μ g.g in state's IV standard
-1Requirement, on the other hand, this method is at high sulfur-bearing oil, in order to improve the RON of final blending product, one of key of this method is that the last running gasoline after the hydrogenating desulfurization is carried out aromizing, but aromatic hydrocarbons is the precursor of coke, and higher aromatic hydrocarbons growing amount (product aromatic hydrocarbons is higher than more than the raw material 10v%) is stable totally unfavorable to catalyzer; Moreover the support of the catalyst in this method requires with TiO
2Be main, this also makes the intensity of catalyzer significantly reduce, and is unfavorable for its long period steady running and regeneration.
In a word, low grade oilses such as China FCC gasoline at high sulfur-bearing and high olefin, though existing a lot of research all realizes desulfurating and reducing olefinic hydrocarbon at the upgrading of attempting by means of different, simultaneously keep and improve the octane value of oil product as far as possible, though these disclosed methods respectively have advantage, but explore a kind of more rational modifying process, select suitable function and active catalyzer, when keeping octane value, realize ultra-deep desulfurization and significantly fall alkene, and solve problem such as the undesirable and tooling cost height of catalyst stability, be the target that the refining of petroleum field is pursued all the time.
Summary of the invention
At the deficiencies in the prior art, the efficient combination production method that the purpose of this invention is to provide a kind of ultra-low sulfur and high-octane number gasoline, by full distillation gasoline raw material inferior is contacted with the directed sulfur transfer catalyst of low temperature under hydro condition, make lighter mercaptan and thiophene sulphur compound be converted into high boiling sulphur compound and transfer in the heavier gasoline fraction, then the inferior full distillation gasoline through the over cure transfer processing is carried out the cut cutting; The counterweight distillation gasoline is handled again, at last the last running gasoline after lighting end gasoline and the processing is mixed, and obtains the gasoline of ultra-low sulfur and high-octane number.This method is applicable to the upgrading of ultra-high-sulfur(UHS), high olefin inferior patrol, can reach inferior patrol is carried out ultra-deep desulfurization, when falling alkene, improves the product octane value and keep the effect of high product liquid yield.
For achieving the above object, the invention provides a kind of efficient combination production method of ultra-low sulfur and high-octane number gasoline, this method mainly comprises:
Make full distillation gasoline raw material inferior carry out the directed sulphur shift reaction of low temperature under hydro condition, carry out oil product cutting fractionation then, obtain lighting end gasoline and last running gasoline, the cutting cut point is 50-90 ℃;
Last running gasoline is contacted with additional desulfurization-hydro carbons isomery/aromatization catalyzer with catalyst for selectively hydrodesulfurizing;
Last running gasoline after lighting end gasoline and the processing is mixed, obtain the gasoline products of ultra-low sulfur and high-octane number.
In the efficient combination production method of ultra-low sulfur and high-octane number gasoline provided by the present invention, full distillation gasoline raw material inferior is contacted with the directed sulfur transfer catalyst of low temperature under hydro condition, make lighter mercaptan and thiophene sulphur compound be converted into high boiling sulphur compound and transfer in the heavier gasoline fraction, then the inferior full distillation gasoline through the over cure transfer processing is carried out the cut cutting, obtain lighting end gasoline and last running gasoline; Last running gasoline is at first contacted with catalyst for selectively hydrodesulfurizing carry out desulfurization, remove sulphur compounds such as thioether, alkylthrophene, thionaphthene, and then contact with additional desulfurization-hydro carbons isomery/aromatization catalyzer, further remove the thiophenic sulfur sulfides, and recover the octane value of product by isomery/aromatization effect; At last the last running gasoline after lighting end gasoline and the processing is mixed, obtain the gasoline products of ultra-low sulfur and high-octane number.
The inferior patrol that the production method of ultra-low sulfur and high-octane number gasoline provided by the invention was suitable for can comprise one or more mixture, especially ultra-high-sulfur(UHS), the FCC gasoline inferior of high olefin in catalytically cracked gasoline, coker gasoline, catalytic cracking gasoline, pressure gasoline and the steam cracking gasoline etc.
In the efficient combination production method of ultra-low sulfur and high-octane number gasoline provided by the invention, the directed sulphur shift reaction of low temperature be make sulphur compounds such as lower boiling mercaptan and thiophene by with alkene (not only refer to diolefine, also comprise monoolefine) between carry out reactions such as etherificate, alkylation and make it become weight and transfer in the gasoline last running.The directed sulphur shift reaction of this low temperature can contact realization by making gasoline stocks with sulfur transfer catalyst under hydro condition.Preferably, the reaction conditions of the directed sulphur shift reaction of low temperature is: reaction pressure 1-3MPa, liquid volume air speed 2-8h
-1, temperature of reaction 100-220 ℃, hydrogen to oil volume ratio 200-600.
In the efficient combination production method of ultra-low sulfur and high-octane number gasoline provided by the invention, by making the directed sulphur shift reaction of gasoline stocks generation low temperature, sulphur compounds such as lower boiling mercaptan and thiophene are become to be reentered in the gasoline last running, therefore, resulting gasoline lighting end need not to handle the requirement that just can satisfy the clean gasoline standard again after the cutting, save the step that lighting end is handled to gasoline, can save catalyzer and investment.And, carry out in the fixed-bed reactor of the directed sulphur shift reaction of low temperature before Cutting Tap, make sulphur transfer and gasoline fraction cutting separately carry out, can avoid the two to influence each other, guarantee the stable control of reaction conditions, thereby the lower boiling sulphur compound is transferred in the last running efficiently.
In the efficient combination production method of ultra-low sulfur and high-octane number gasoline provided by the invention, preferably, the reaction conditions (the selective hydrodesulfurization reaction conditions of last running gasoline) of last running gasoline on catalyst for selectively hydrodesulfurizing is: reaction pressure 1-3MPa, liquid volume air speed 3-6h
-1, temperature of reaction 200-300 ℃, hydrogen to oil volume ratio 200-600; Last running gasoline at the reaction conditions (the additional desulfurization of last running gasoline-hydro carbons isomery/aromatization condition) that replenishes on desulfurization-hydro carbons isomery/aromatization catalyzer is: reaction pressure 1-3MPa, liquid volume air speed 1-4h
-1, temperature of reaction 340-430 ℃, hydrogen to oil volume ratio 200-600.
In the efficient combination production method of ultra-low sulfur and high-octane number gasoline provided by the invention, adopting sulfur transfer catalyst that the full distillation gasoline of poor quality is carried out directed sulphur shifts, make sulphur compounds such as lower boiling mercaptan and thiophene be converted into high boiling sulphur compound and transfer in the gasoline last running, can guarantee that the sulphur content in the lighting end significantly reduces, and can satisfy the requirement of clean gasoline standard.In total catalyst weight, the composition of the sulfur transfer catalyst in the above-mentioned directed sulphur shift reaction comprises: transition metal oxide 2-30%, auxiliary agent 0.5-6%, zeolite 10-40%, surplus is an inorganic refractory oxide.Wherein, above-mentioned transition metal oxide is NiO, CoO, ZnO, MoO
3, WO
3With among CuO etc. one or more; Above-mentioned auxiliary agent is K
2O, MgO and La
2O
3Deng in one or more; Above-mentioned zeolite is one or more among HZSM-5, H β and the HY etc., and zeolite is the zeolite of process alkaline purification successively, ammonium exchange, hydrothermal treatment consists; Above-mentioned inorganic refractory oxide is one or more in aluminum oxide (pure alumina), silicon oxide and the siliceous aluminum oxide etc.The concrete preparation method of sulfur transfer catalyst, for example can be zeolite and inorganic oxide mixing with alkaline purification-ammonium exchange-hydrothermal treatment consists, add tackiness agent, after banded extruder extruded moulding, drying, roasting, prepare support of the catalyst, adopt pickling process carrying transition metal and auxiliary agent then, promptly get required sulfur transfer catalyst through super-dry, roasting.
In the efficient combination production method of ultra-low sulfur and high-octane number gasoline provided by the invention, for last running gasoline, at first adopt catalyst for selectively hydrodesulfurizing to carry out hydrogenation reaction, remove thioether, alkylthrophene, thionaphthene sulfides, in total catalyst weight, the weight of above-mentioned catalyst for selectively hydrodesulfurizing is formed and is comprised: MoO
310-18%, CoO2-6%, K
2O 1-7% and P
2O
52-6%, surplus is the Al-Si-Mg composite oxide carrier, and the weight of Al-Si-Mg composite oxides in catalyzer consists of Al
2O
360-75%, SiO
25-15% and MgO 3-10%.
In the efficient combination production method of ultra-low sulfur and high-octane number gasoline provided by the invention, after the counterweight distillation gasoline carries out selective hydrodesulfurization, its effluent is contacted with additional desulfurization-hydro carbons isomery/aromatization catalyzer, further remove the thiophenic sulfur sulfides, and by isomery/aromatization effect recovery product octane value, in total catalyst weight, the weight of above-mentioned additional desulfurization-hydro carbons isomery/aromatization catalyzer is formed and is comprised: MoO
34-8%, CoO 1-4%, P
2O
51-3%, modified HZSM-5 zeolite 50-70%, surplus is Al-Ti composite oxides binding agents; Wherein, the weight of Al-Ti composite oxides binding agent composition comprises: Al
2O
370-95%, TiO
25-30%.Above-mentioned modified HZSM-5 zeolite can prepare in accordance with the following methods: about temperature 500-700 ℃, the about 1-4h of steam air speed
-1Condition under, the HZSM-5 zeolite is carried out hydrothermal treatment consists about 15-50 minute; Utilize the inorganic acid solution of pH value for 1.0-4.0, the hydrothermal treatment consists product carried out 1-4 hour cleanup acid treatment about 50-90 ℃, wherein, the liquid-solid ratio of inorganic acid solution and hydrothermal treatment consists product is about 5-10mL/g; Product to cleanup acid treatment washs, after the processing of filtration, 100-120 ℃ dry 2-4 hour, 500-550 ℃ roasting 4-6 hour, makes the modified HZSM-5 zeolite then.The SiO of above-mentioned HZSM-5 zeolite
2/ Al
2O
3Mol ratio can be 30-60, is preferably 35-50; Above-mentioned mineral acid can be in nitric acid, sulfuric acid and the hydrochloric acid etc. one or more.
According to the usual phraseology of catalyst field, active ingredient on carrier that the present invention is mentioned and the catalyzer (element) content is all in its corresponding oxide.
Ultra-clean gasoline production method provided by the present invention can obtain good hydro-upgrading effect to the inferior patrol (for example FCC gasoline) of ultra-high-sulfur(UHS), high olefin, and for example: sulphur content is 1000-2500 μ g.g
-1, olefin(e) centent is the inferior patrol of 40-45v%.
Compared with prior art, the efficient combination production method of ultra-low sulfur and high-octane number gasoline provided by the present invention has following characteristics:
(1) can with sulphur content 1000-2500 μ g.g
-1, olefin(e) centent is that the inferior gasoline upgrading of 40-45v% becomes sulphur content≤10 μ g.g
-1,≤1.0 units of olefin(e) centent≤20v%, gasoline research method octane value (RON) loss premium, and product liquid yield 〉=98wt%;
(2) heat can be fully used, easy handling, and last running gasoline upgrading reactor outlet product temperature is higher, can be by utilizing heat with the method for undressed last running gasoline stocks heat exchange;
(3) in aforesaid method of the present invention, at first the full distillation gasoline of poor quality is carried out directed sulphur shift reaction, then the inferior full distillation gasoline fractionation after the over cure transfer processing is obtained lighting end gasoline and last running gasoline, the counterweight distillation gasoline carries out selective hydrodesulfurization and additional desulfurization-hydro carbons isomery/aromatic hydrocarbons successively and handles again, these multiple reactions help realizing full cut inferior patrol ultra-deep desulfurization, fall alkene, recover the effect of octane value;
(4) the efficient combination production method of above-mentioned gasoline provided by the invention is particularly useful for the inferior gasoline upgrading of ultra-high-sulfur(UHS), high olefin content, can be at ultra-deep desulfurization, alkene falls and in, improve its octane value and keep the high product liquid yield, therefore than external gasoline hydrogenation modifying method, the more suitable inferior patrol component for China of the efficient combination production method of above-mentioned gasoline provided by the invention is handled.
Description of drawings
Fig. 1 is the schematic flow sheet of the efficient combination production method of ultra-low sulfur and high-octane number gasoline provided by the present invention.
Embodiment
Understand for technical characterictic of the present invention, purpose and beneficial effect being had more clearly, existing technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as qualification practical range of the present invention.
Embodiment 1
It is 1750 μ g.g with sulphur content that present embodiment provides a kind of
-1, olefin(e) centent is ultra-high-sulfur(UHS), the high olefin full cut FCC gasoline inferior (full feedstock oil 1) of 48.4v% carries out hydro-upgrading Processing of Preparation ultra-low sulfur and high-octane number gasoline for raw material efficient combination production method.
Wherein, the composition proportion of various catalyzer is as follows, respectively in the gross weight of each catalyzer:
Sulfur transfer catalyst: 12wt%NiO-6wt%MoO
3-2wt%La
2O
3/ 20wt%HZSM-5-60wt% (Al
2O
3-SiO
2) (siliceous aluminum oxide);
Catalyst for selectively hydrodesulfurizing: 4wt%CoO-12wt%MoO
3-3wt%K
2O-2wt%P
2O
5/ 67wt%Al
2O
3-8wt%SiO
2-4wt%MgO:
Replenish desulfurization-hydro carbons isomery/aromatization catalyzer: 2wt%CoO-6wt%MoO
3-1wt%P
2O
5/ 65wt%HZSM-5-21wt%Al
2O
3-5wt%TiO
2
The concrete preparation process of sulfur transfer catalyst (catalyst I) is as follows:
At first with HZSM-5 zeolite (SiO
2/ Al
2O
3Mol ratio is 30) place the NaOH aqueous solution by the liquid-solid ratio of 10mL/g, the pH value is adjusted to 13, stirred 4 hours down in 75 ℃, filter, with the zeolite washing that leaches to neutral, 120 ℃ of dryings 3 hours; The HZSM-5 zeolite that to handle through the NaOH aqueous solution is according to zeolite: ammonium nitrate: the weight ratio of water is 1: 0.8: 10 a mixed, and in 80 ℃ of stirrings 4 hours, then product is filtered, washs, and, obtain the HZSM-5 zeolite of alkaline purification-ammonium exchange in 120 ℃ of dryings, 480 ℃ of roastings 4 hours; Above-mentioned HZSM-5 zeolite through alkaline purification and ammonium exchange is fed steam-treated 20-50 minute down at 600 ℃, obtain the HZSM-5 zeolite (the HZSM-5 zeolite of alkaline purification-ammonium exchange-hydrothermal treatment consists) of modification;
Take by weighing the 50.2g aluminum silicon powder and (contain Al
2O
392.0wt%, SiO
28.0wt%) and HZSM-5 zeolite, the 2.5g sesbania powder of the above-mentioned modification of 30.0g, its ground and mixed is even, adding 6mL mass concentration is 65% salpeter solution, in banded extruder, extrude the cloverleaf pattern bar that diameter is 2mm after fully mixed the pinching, after 4 hours, make the support of the catalyst of moulding through 4 hours, 520 ℃ roastings of 120 ℃ of dryings;
Contain NiO, MoO according to the stoichiometric ratio preparation
3And La
2O
3Nickelous nitrate, ammonium molybdate, lanthanum nitrate mixing solutions, adopt equi-volume impregnating that steeping fluid evenly is added drop-wise on the said catalyst carrier then, after 4 hours, make catalyst I through 4 hours, 520 ℃ roastings of 120 ℃ of dryings.
The concrete preparation process of catalyst for selectively hydrodesulfurizing (catalyst I I) is as follows:
Take by weighing Al-Si-Mg composite powder (moisture 25wt%) and 2g sesbania powder that 70g has suitable Al/Si/Mg ratio, its ground and mixed is even, adding 5mL mass concentration is 65% salpeter solution, fully mix and pinch back extruded moulding in banded extruder, after 4 hours, make the support of the catalyst of moulding through 3 hours, 520 ℃ roastings of 120 ℃ of dryings;
The 40g said catalyst carrier be impregnated in the mixed impregnant liquor of 35mL saltpetre and Secondary ammonium phosphate,, contain 1.5g K in this steeping fluid in oxide compound
2O and 1.0g P
2O
5, ageing was at room temperature handled 5 hours then, again 3 hours, 520 ℃ roastings of 120 ℃ of dryings 4 hours, obtained the support of the catalyst of load potassium and phosphorus;
Preparation 32.0mL contains 2.0gCoO and 6.1gMoO
3(content of each active ingredient is in oxide form, and the active ingredient in the unrestricted mixed solution exists with oxide form) Xiao Suangu and ammonium molybdate mixed solution, and adding 3.0mL mass concentration is 17% ammoniacal liquor, fully vibration is dissolved fully until solid and is made steeping fluid, support of the catalyst with above-mentioned potassium of load and phosphorus impregnated in this steeping fluid then, room temperature ageing 5 hours after 5 hours, makes catalyst I I through 3 hours, 520 ℃ calcination process of 120 ℃ of drying treatment.
Replenishing desulfurization-hydro carbons isomery/aromatization catalyzer (catalyst I II) can be according to the method preparation (full text of CN101508912A is guided to here as a reference) of CN101508912A (application number is 200910080112.1) record, and different is to carry out single mineral acid treatment (treatment condition are identical) with adopting after the hydrothermal treatment consists among the disclosed preparation method of CN101508912A after mineral acid-organic acid processing changes hydrothermal treatment consists into.
It is as follows to utilize full feedstock oil 1 upgrading to produce the process of ultra-low sulfur and high-octane number gasoline, its technical process as shown in Figure 1:
Pending raw material oil product is full feedstock oil 1, and its character is referring to table 1.The inferior full feedstock oil 1 of ultra-high-sulfur(UHS) at first carries out directed sulphur shift reaction on low temperature sulfur transfer catalyst (catalyst I), sulphur shift reaction condition is: reaction pressure 2MPa, liquid volume air speed 5h
-1, 160 ℃ of temperature of reaction, hydrogen to oil volume ratio 400; Inferior full distillation gasoline after the over cure shift reaction enters Cutting Tap and obtains lighting end gasoline and last running gasoline by the cut cutting then, and gasoline cutting cut point is 70 ℃;
Last running gasoline adopts simple serial operation, carries out on the device of two reactors in series, contacts with catalyst I I in first reactor, and the selective hydrodesulfurization reaction takes place, and reaction conditions is: reaction pressure 1.8MPa, liquid volume air speed 3h
-1, 220 ℃ of temperature of reaction, hydrogen to oil volume ratio 300; Contact with catalyst I II in second reactor, desulfurization-hydro carbons isomery/aromatization reaction takes place, reaction conditions is: reaction pressure 1.8MPa, liquid volume air speed 1.7h
-1, 360 ℃ of temperature of reaction, hydrogen to oil volume ratio 300;
After above-mentioned reaction was finished, the last running gasoline mixing with lighting end gasoline and after handling obtained light, the mediation of last running gasoline product, i.e. super low sulfur stop bracket gasoline.
In reaction process, all catalyzer are all with porcelain sand dilution, and, each reactor or reaction unit airtight qualified after, adopt conventional pre-vulcanization process to carry out prevulcanized to catalyzer, react after 400 hours sampling analysis.Table 1 has provided the nature parameters of reaction upgraded products may.
As can be seen from Table 1, method for modifying of the present invention can make the sulphur content of FCC gasoline inferior by 1750 μ g.g
-1Be reduced to 5 μ g.g
-1Olefin(e) centent is reduced to 19.8v% by 48.4v%, and isoparaffin and aromaticity content all have significantly and increase in the product, isoparaffin content is increased to 25.9v% by 17.4v%, aromaticity content is increased to 25.7v% by 16.3v%, this makes at ultra-deep desulfurization, olefin(e) centent falls and in, product research method octane value improves 0.2 unit, the blended gasoline product yield is 98.8wt%, and quality product meets the requirement of state V clean gasoline standard.
Light, last running gasoline behind full feedstock oil 1 of table 1 and the upgrading is in harmonious proportion the nature parameters of product
| Project | Full feedstock oil 1 | Gently, last running gasoline mediation product |
| Yield (wt%) | - | 98.8 |
| Density (g/mL) | 0.735 | 0.737 |
| Boiling range (℃) | 33-204 | 32-208 |
| Typical case's hydrocarbon content (v%) |
| Isoparaffin | 17.4 | 25.9 |
| Alkene | 48.4 | 19.8 |
| Aromatic hydrocarbons | 16.3 | 25.7 |
| Sulphur (μ gg -1) | 1750 | 5 |
| Diolefine (gl/100g) | 2.4 | 0.0 |
| RON | 91.3 | 91.5 |
Embodiment 2
It is 2210 μ gg with sulphur content that present embodiment provides a kind of
-1, olefin(e) centent is ultra-high-sulfur(UHS), the high olefin full cut FCC gasoline inferior (full feedstock oil 2) of 51.3v% carries out hydro-upgrading Processing of Preparation ultra-low sulfur and high-octane number gasoline for raw material efficient combination production method.
Wherein, the composition proportion of various catalyzer is as follows, respectively in the gross weight of each catalyzer:
Sulfur transfer catalyst: 10wt%NiO-7wt%MoO
3-2wt%K
2O-2wt%CuO/35wt%HZSM-5-44wt% (Al
2O
3-SiO
2) (siliceous aluminum oxide);
Catalyst for selectively hydrodesulfurizing: 3wt%CoO-14wt%MoO
3-3wt%K
2O-3wt%P
2O
5/ 67wt%Al
2O
3-5wt%SiO
2-5wt%MgO:
Replenish desulfurization-hydro carbons isomery/aromatization catalyzer: 2.5wt%CoO-8wt%MoO
3-3wt%P
2O
5/ 60wt%HZSM-5-23.5wt%Al
2O
3-3wt%TiO
2
Above-mentioned Preparation of catalysts method is identical with embodiment 1.
The process of utilizing full feedstock oil 2 upgradings to produce ultra-low sulfur and high-octane number gasoline:
The raw material oil product adopts full feedstock oil 2, and its character is referring to table 2, and the processing of reaction unit setting and catalyzer etc. are all identical with embodiment 1, and concrete reaction conditions is as follows:
Sulphur shift reaction condition is: reaction pressure 1.6MPa, liquid volume air speed 4h
-1, 140 ℃ of temperature of reaction, hydrogen to oil volume ratio 300;
Gasoline cutting cut point is 60 ℃;
The reaction conditions of the selective hydrodesulfurization reaction of last running gasoline is: reaction pressure 2MPa, liquid volume air speed 4h
-1, 240 ℃ of temperature of reaction, hydrogen to oil volume ratio 400;
The reaction conditions of the additional desulfurization of last running gasoline-hydro carbons isomery/aromatization reaction is: reaction pressure 2MPa, liquid volume air speed 2h
-1, 375 ℃ of temperature of reaction, hydrogen to oil volume ratio 400.
Table 2 has provided the nature parameters of upgrading reactor product.
The nature parameters light behind full feedstock oil 2 of table 2 and the upgrading, that last running gasoline is in harmonious proportion product
| Project | Full feedstock oil 2 | Gently, last running gasoline mediation product |
| Yield (wt%) | - | 98.6 |
| Density (g/mL) | 0.746 | 0.749 |
| Boiling range (℃) | 35-206 | 33-211 |
| Typical case's hydrocarbon content (v%) | ||
| Isoparaffin | 19.5 | 30.5 |
| Alkene | 51.3 | 18.9 |
| Aromatic hydrocarbons | 18.1 | 27.8 |
| Sulphur (μ g.g -1) | 2210 | 8 |
| Diolefine (gl/100g) | 3.5 | 0.0 |
| RON | 92.4 | 92.3 |
As can be seen from Table 2, method for modifying of the present invention can make the sulphur content of FCC gasoline inferior by 2210 μ g.g
-1Be reduced to 8 μ g.g
-1Olefin(e) centent is reduced to 18.9v% by 51.3v%, and isoparaffin and aromaticity content all have significantly and increase in the product, isoparaffin content is increased to 30.5v% by 19.5v%, aromaticity content is increased to 27.8v% by 18.1v%, this makes at ultra-deep desulfurization, olefin(e) centent falls and in, research octane number (RON) only reduces by 0.1 unit, the blended gasoline product yield is 98.6wt%, and quality product meets the requirement of state V clean gasoline standard.
Above-mentioned two embodiment show that it is sulphur content≤10 μ g.g that the efficient combination production method of ultra-low sulfur and high-octane number gasoline provided by the present invention can make ultra-high-sulfur(UHS), the oily upgrading of high olefin material inferior
-1,≤1.0 units of olefin(e) centent≤20v%, gasoline research method octane value (RON) loss state V ultra-clean gasoline product, show that the inventive method has good hydro-upgrading effect to inferior patrol, will lay the foundation for further developing of China petroleum refining industry.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; and be not intended to limit the scope of the invention; within the spirit and principles in the present invention all, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the efficient combination production method of a ultra-low sulfur and high-octane number gasoline, this method comprises:
Make full distillation gasoline raw material inferior carry out the directed sulphur shift reaction of low temperature under hydro condition, carry out oil product cutting fractionation then, obtain lighting end gasoline and last running gasoline, the cutting cut point is 50-90 ℃;
Last running gasoline is contacted with additional desulfurization-hydro carbons isomery/aromatization catalyzer with catalyst for selectively hydrodesulfurizing;
Last running gasoline after lighting end gasoline and the processing is mixed, obtain the gasoline products of ultra-low sulfur and high-octane number.
2. production method according to claim 1, wherein, the reaction conditions of the directed sulphur shift reaction of described low temperature is: reaction pressure 1-3MPa, liquid volume air speed 2-8h
-1, temperature of reaction 100-220 ℃, hydrogen to oil volume ratio 200-600.
3. production method according to claim 1, wherein, the reaction conditions of described last running gasoline on described catalyst for selectively hydrodesulfurizing is: reaction pressure 1-3MPa, liquid volume air speed 3-6h
-1, temperature of reaction 200-300 ℃, hydrogen to oil volume ratio 200-600;
Described last running gasoline at the reaction conditions that replenishes on desulfurization-hydro carbons isomery/aromatization catalyzer is: reaction pressure 1-3MPa, liquid volume air speed 1-4h
-1, temperature of reaction 340-430 ℃, hydrogen to oil volume ratio 200-600.
4. production method according to claim 1, wherein, in total catalyst weight, the composition of the sulfur transfer catalyst in the directed sulphur shift reaction of described low temperature comprises: transition metal oxide 2-30%, auxiliary agent 0.5-6%, zeolite 10-40%, and surplus is an inorganic refractory oxide; And,
Described transition metal oxide is NiO, CoO, ZnO, MoO
3, WO
3With among the CuO one or more;
Described auxiliary agent is K
2O, MgO and La
2O
3In one or more;
Described zeolite is one or more among HZSM-5, H β and the HY, and described zeolite is the zeolite through alkaline purification, ammonium exchange, hydrothermal treatment consists;
Described inorganic refractory oxide is one or more in aluminum oxide, silicon oxide and the siliceous aluminum oxide.
5. production method according to claim 1, wherein, in total catalyst weight, the composition of described catalyst for selectively hydrodesulfurizing comprises: MoO
310-18%, CoO 2-6%, K
2O 1-7% and P
2O
52-6%, surplus is the Al-Si-Mg composite oxide carrier, and the weight of Al-Si-Mg composite oxides in catalyzer consists of: Al
2O
360-75%, SiO
25-15% and MgO 3-10%.
6. production method according to claim 1, wherein, in total catalyst weight, the composition of described additional desulfurization-hydro carbons isomery/aromatization catalyzer comprises: MoO
34-8%, CoO 1-4%, P
2O
51-3%, modified HZSM-5 zeolite 50-70%, surplus is Al-Ti composite oxides binding agents.
7. according to claim 1 and 6 described production methods, wherein, the weight of Al-Ti composite oxides binding agent is formed and is comprised: Al
2O
370-95%, TiO
25-30%.
8. according to claim 1 or 6 described production methods, wherein, described modified HZSM-5 zeolite prepares in accordance with the following methods:
At 500-700 ℃, steam air speed 1-4h
-1Condition under, the HZSM-5 zeolite carried out 15-50 minute hydrothermal treatment consists;
Utilize the inorganic acid solution of pH value for 1.0-4.0, at 50-90 ℃ the hydrothermal treatment consists product is carried out 1-4 hour cleanup acid treatment, wherein, the liquid-solid ratio of inorganic acid solution and hydrothermal treatment consists product is 5-10mL/g;
Product to cleanup acid treatment washs, after the processing of filtration, 100-120 ℃ dry 2-4 hour, 500-550 ℃ roasting 4-6 hour, make described modified HZSM-5 zeolite.
9. production method according to claim 8, wherein, the SiO of described HZSM-5 zeolite
2/ Al
2O
3Mol ratio is 30-60; Described mineral acid is one or more in nitric acid, sulfuric acid and the hydrochloric acid.
10. production method according to claim 9, wherein, the SiO of described HZSM-5 zeolite
2/ Al
2O
3Mol ratio is 35-50.
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| CN104232156A (en) * | 2013-06-19 | 2014-12-24 | Ifp新能源公司 | process for producing a gasoline with a low sulphur and mercaptans content |
| CN104560166A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalytic conversion method utilizing petroleum hydrocarbon to produce high-octane gasoline |
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| CN104232156A (en) * | 2013-06-19 | 2014-12-24 | Ifp新能源公司 | process for producing a gasoline with a low sulphur and mercaptans content |
| CN104560166A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalytic conversion method utilizing petroleum hydrocarbon to produce high-octane gasoline |
| CN104560166B (en) * | 2013-10-28 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of petroleum hydrocarbon is produced the catalysis conversion method of high-knock rating gasoline |
| CN104650963A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Start-up method of FCC gasoline hydrogenation catalyst |
| CN104650963B (en) * | 2013-11-19 | 2016-06-08 | 中国石油天然气股份有限公司 | Start-up method of FCC gasoline hydrogenation catalyst |
| WO2016029401A1 (en) * | 2014-08-28 | 2016-03-03 | 中国石油大学(北京) | Mercaptan removal catalyst for light hydrocarbons, preparation method therefor, and uses thereof |
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