CN102010751B - 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
- Publication number
- CN102010751B CN102010751B CN201010584150.3A CN201010584150A CN102010751B CN 102010751 B CN102010751 B CN 102010751B CN 201010584150 A CN201010584150 A CN 201010584150A CN 102010751 B CN102010751 B CN 102010751B
- Authority
- CN
- China
- Prior art keywords
- gasoline
- reaction
- zeolite
- catalyst
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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 the ultra-deep desulfurization-recovery octane value hydrogenation modification method of a kind of refining of petroleum field for the FCC gasoline inferior of catalytic cracking (FCC) gasoline, particularly ultra-high-sulfur(UHS), high olefin.
Background technology
At present, in catalytically cracked gasoline, high sulphur content and olefin(e) centent become the key issue that perplexs world's clean gasoline production.At high-octane number component reformed gasoline and gasoline alkylate less in the situation that, for meeting 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 take hydrofining-cracking/mono-side chain hydroisomerizing as main desulfurization, have fallen olefin process.The main thought of these techniques be by full cut FCC gasoline be cut into gently, last running, the last running of FCC gasoline is after conventional Hydrobon catalyst deep desulfuration is processed, alkene wherein is all converted into alkane, then products obtained therefrom completes the reaction of alkane cracking-hydroisomerizing on the zeolite based catalysts through screening with proper sourness, reach the object of improving and recovering octane value, be in harmonious proportion and obtain full fraction upgrading gasoline by light and heavy fractions subsequently.According to the record of above-mentioned patent, the liquid yield of product of being finally in harmonious proportion is 94wt%, and gasoline research method octane value (RON) loss reaches 2.0 units left and right.
Although the gasoline hydrogenation modifying method that above-mentioned patent provides can realize desulfurization, the object of alkene is fallen, but its for stock oil in olefin(e) centent be only about 20v% and aromaticity content higher (30v% left and right), be applicable to external gasoline component more, all higher for alkene and sulphur content, the oil product of aromaticity content lower (20v% left and right), the for example China FCC gasoline up to 40v% left and right to olefin(e) centent, use this technique to carry out upgrading, in desulfurating and reducing olefinic hydrocarbon, a large amount of alkene is saturated by hydrogenation, cause the loss of octane value to increase, so the modification technology of these open reports is obviously inapplicable.Such reason just, for the singularity of Chinese FCC gasoline, explores the study hotspot that more scientific rational method for modifying is Oil Refining Industry all the time.
The method of the deep desulfurization olefin hydrocarbon reduction of gasoline providing in CN145666A (No. 02121595.2, Chinese patent application), it is exactly the These characteristics for China FCC gasoline, to the heavy naphtha after Hydrobon catalyst is implemented hydrogenation desulfurization and denitrogenation and olefin saturated, 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, then the last running of having implemented upgrading is mixed into final upgraded products with the lighting end that cutting obtains.According to the introduction of this patent, because alkene in first paragraph reaction is saturated by complete hydrogenation, the cracking ability that need to improve two sections of catalyzer for recovering the octane value of product, its cost is the significantly reduction (being only 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 that the last running of FCC gasoline is all converted into after alkane through conventional Hydrobon catalyst deep desulfuration, alkene, and gained reaction effluent is the normal paraffin cracking-mono-side chain hydroisomerizing reaction completing on nanometer H β zeolite based catalysts.
The similarity of the modifying process of above two China patent is all to make through the isomerization on the zeolite based catalysts of acid function of the hydrorefined heavy distillate of routine, realize normal paraffin cracking-mono-side chain hydroisomerizing, because HZSM-5 zeolite and nanometer H β zeolite acidity are strong, acid amount is larger, 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 for China high olefin FCC gasoline, wherein, full cut FCC gasoline is through dialkene removal, alkene aromatization and supplementary falling after three reaction upgradings of alkene, desulfurization degree is 78%, product olefin(e) centent is that 30v%, product RON loss is 1.0 units, and product liquid is received the left and right for 98.5wt%.But the method is mainly for low sulfur-bearing FCC gasoline, reducing as far as possible under the prerequisite of RON loss, desulfurization degree compared with low, the alkene range of decrease is little, products obtained therefrom difficult quality meets state III and state's IV clean gasoline standard, is obviously 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 technique is to make full cut FCC gasoline after hydrofining is alkane by most of conversion of olefines, on nano zeolite catalyst, carry out again alkane aromatization, this patent is by adopting one to comprise main group, the nano level hydrogen type molecular sieve catalyzer of magnesium-yttrium-transition metal and lanthanide rare metal oxide, make upgraded products desulfurization degree high, the alkene range of decrease is large, but the product liquid yield that the method obtains is only 90wt% left and right, large (reaching 2.0-3.0 unit) of product RON loss, and nano zeolite preparation is complicated, regenerability is not good, cause process costs 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, under the condition that hydrogen exists and temperature raises gradually, forms three reaction zones, and full cut FCC gasoline is contacted with three kinds of catalyzer, first adopts conventional Hydrobon catalyst (6h under high charging air speed
-1) take off two alkene reactions, then adopt nano zeolite catalyst to carry out aromizing, isomerization reaction under high temperature (415 ℃), finally adopt Co-Mo-K-P/Al
2o
3catalyzer is at high temperature (415 ℃), high-speed (40h more
-1) under carry out selective desulfurization.The advantage of the method is that alkene and the sulphur content of obtained product is all lower, but product RON loss is 3.0 unit left and right, product liquid yield is 94wt% left and right, and nano zeolite preparation is complicated, easy inactivation under high temperature, regenerability is not good, in addition at high-speed very and the yet easy inactivation of the 3rd section of desulfurization catalyst under high-temperature very, affect the reaction stability of whole technique, 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 first adopts conventional Hydrobon catalyst (6h under high charging air speed
-1) carry out the dialkene removal reaction of full cut FCC gasoline, then adopt Co-Mo-K-P/Al
2o
3catalyzer carries out selective desulfurization, finally adopts nano zeolite catalyst to carry out alkene aromizing under high temperature (415 ℃).The olefin(e) centent of product that this patented method obtains is lower, but product RON loss is 1.0 unit left and right, the weak point of above-mentioned nano zeolite still exists, and product sulphur content higher (desulfurization degree only 75%), is difficult to meet 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 technique of this patent is first to adopt conventional Hydrobon catalyst (6h under high charging air speed
-1) carry out the dialkene removal reaction of full cut FCC gasoline, then carry out prefractionation, lighting end gasoline mainly carries out alkene aromizing on nano zeolite catalyst, last running gasoline carries out successively selective hydrodesulfurization reaction on low-metal content aluminium oxide catalyst and high metal content aluminium oxide catalyst, after finally reacted weight gasoline being mixed, can obtain full fraction upgrading gasoline.Alkene and the sulphur content of product that this patented method obtains are lower, but it is 1.5 unit left and right that the whole course of processing still makes product RON loss, and the weak point of above-mentioned nano zeolite still exists, and need four kinds of catalyzer and supporting complicated technology, limited its industrial application.
CN1283761C (No. 200410060574.4, Chinese patent) discloses a kind of inferior patrol hydrogenation modifying process.This technique is first cut into lighting end and last running gasoline by full cut FCC gasoline, then by last running gasoline at Co (Ni)-Mo/TiO
2on catalyzer, carry out hydrogenating desulfurization, then at Co (Ni)-Mo (W)/ZSM-5-/TiO
2on catalyzer, carry out aromatization, finally reacted weight gasoline is mixed into full fraction upgrading gasoline.Olefin(e) centent according to product that this patented method obtains is lower, but product sulphur content is difficult to meet in state's IV standard not higher than 50 μ g.g
-1requirement, on the other hand, the method is for high sulfur crude, in order to improve the RON of final mixing prod, one of key of the method is that the last running gasoline after hydrogenating desulfurization is carried out to aromizing, but aromatic hydrocarbons is the precursor of coke, higher aromatic hydrocarbons growing amount (product aromatic hydrocarbons is higher than more than raw material 10v%) is totally unfavorable to the stability of catalyzer; Moreover the support of the catalyst in the 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, for low grade oilses such as China FCC gasoline of high sulfur-bearing and high olefin, although existing a lot of research all realizes desulfurating and reducing olefinic hydrocarbon at the upgrading of attempting by means of different, keep as far as possible and improve the octane value of oil product simultaneously, although these disclosed methods respectively have advantage, but explore the more rational modifying process of one, select suitable function and active catalyzer, in keeping octane value, realize ultra-deep desulfurization and significantly fall alkene, and solve the problems such as the undesirable and tooling cost of catalyst stability is high, all the time be the target that pursue in refining of petroleum field.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of efficient combination production method 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 be converted into high boiling sulphur compound and transfer in heavier gasoline fraction compared with light mercaptan and thiophene sulphur compound, then the full distillation gasoline of the poor quality through over cure transfer processing is carried out to cut cutting; Counterweight distillation gasoline is processed again, finally lighting end gasoline and last running gasoline after treatment is mixed, and obtains the gasoline of ultra-low sulfur and high-octane number.The method is applicable to the upgrading of ultra-high-sulfur(UHS), high olefin inferior patrol, can reach to inferior patrol is carried out ultra-deep desulfurization, when falling alkene, improves product octane value and keep the effect of higher 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, the method mainly comprises:
Make full distillation gasoline raw material inferior under hydro condition, carry out the directed sulphur shift reaction of low temperature, then carry out oil product cutting fractionation, obtain lighting end gasoline and last running gasoline, cutting cut point is 50-90 ℃;
Last running gasoline is contacted with supplementary desulfurization-hydro carbons isomery/aromatization catalyzer with catalyst for selectively hydrodesulfurizing;
Lighting end gasoline and last running gasoline after treatment are 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, first make full distillation gasoline raw material inferior contact with the directed sulfur transfer catalyst of low temperature under hydro condition, make be converted into high boiling sulphur compound and transfer in heavier gasoline fraction compared with light mercaptan and thiophene sulphur compound, then the full distillation gasoline of the poor quality through over cure transfer processing is carried out to cut cutting, obtain lighting end gasoline and last running gasoline; Make again last running gasoline first contact with catalyst for selectively hydrodesulfurizing and carry out desulfurization, remove the sulphur compounds such as thioether, alkylthrophene, thionaphthene, and then contact with supplementary desulfurization-hydro carbons isomery/aromatization catalyzer, further remove thiophenic sulfur sulfides, and recover the octane value of product by isomery/aromatization effect; Finally lighting end gasoline and last running gasoline after treatment are mixed, obtain the gasoline products of ultra-low sulfur and high-octane number.
The applicable inferior patrol of production method of ultra-low sulfur and high-octane number gasoline provided by the invention 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 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 the sulphur compounds such as lower boiling mercaptan and thiophene by with alkene (not only refer to diolefine, also comprise monoolefine) between carry out the reactions such as etherificate, alkylation and make it become weight and transfer in gasoline last running.The directed sulphur shift reaction of this low temperature can be by making gasoline stocks contact realization 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, the sulphur compounds such as lower boiling mercaptan and thiophene are become to be reentered in gasoline last running, therefore, the gasoline lighting end obtaining after cutting is without processing the requirement that just can meet clean gasoline standard again, save the step that lighting end is processed to gasoline, can save catalyzer and investment.And, in the fixed-bed reactor of the directed sulphur shift reaction of low temperature before Cutting Tap, carry out, sulphur transfer and gasoline fraction are cut apart and carry out, can avoid the two to influence each other, guarantee the stable control of reaction conditions, thereby lower boiling sulphur compound is transferred in 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 (supplementary desulfurization-hydro carbons isomery/aromatization condition of last running gasoline) supplementing 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, adopt sulfur transfer catalyst to carry out directed sulphur transfer to the full distillation gasoline of poor quality, make the sulphur compounds such as lower boiling mercaptan and thiophene be converted into high boiling sulphur compound and transfer in gasoline last running, can guarantee that the sulphur content in lighting end significantly reduces, and can meet the requirement of clean gasoline standard.In total catalyst weight, the composition of the sulfur transfer catalyst in above-mentioned directed sulphur shift reaction comprises: transition metal oxide 2-30%, auxiliary agent 0.5-6%, zeolite 10-40%, surplus is inorganic refractory oxide.Wherein, above-mentioned transition metal oxide is NiO, CoO, ZnO, MoO
3, WO
3with one or more in CuO etc.; Above-mentioned auxiliary agent is K
2o, MgO and La
2o
3deng in one or more; Above-mentioned zeolite is one or more in HZSM-5, H β and 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 silicon-containing alumina etc.The concrete preparation method of sulfur transfer catalyst, can be for example that the zeolite of alkaline purification-ammonium exchange-hydrothermal treatment consists and inorganic oxide are mixed, add tackiness agent, after banded extruder extruded moulding, dry, roasting, prepare support of the catalyst, then adopt pickling process carrying transition metal and auxiliary agent, obtain 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, first adopt catalyst for selectively hydrodesulfurizing to carry out hydrogenation reaction, remove thioether, alkylthrophene, thionaphthene sulfides, in total catalyst weight, the weight composition of above-mentioned catalyst for selectively hydrodesulfurizing comprises: MoO
310-18%, CoO2-6%, K
2o 1-7% and P
2o
52-6%, surplus is 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, counterweight distillation gasoline carries out after selective hydrodesulfurization, its effluent is contacted with supplementary desulfurization-hydro carbons isomery/aromatization catalyzer, further remove thiophenic sulfur sulfides, and recover product octane value by isomery/aromatization effect, in total catalyst weight, the weight composition of above-mentioned supplementary 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; 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: in temperature 500-700 ℃ left and right, the about 1-4h of steam air speed
-1condition under, HZSM-5 zeolite is carried out to the hydrothermal treatment consists about 15-50 minute; Utilize the inorganic acid solution that pH value is 1.0-4.0,50-90 ℃ of left and right, hydrothermal treatment consists product is carried out the cleanup acid treatment of 1-4 hour, wherein, the liquid-solid ratio of inorganic acid solution and hydrothermal treatment consists product is about 5-10mL/g; Then the product of cleanup acid treatment is washed, after the processing of filtration, 100-120 ℃ dry 2-4 hour, 500-550 ℃ roasting 4-6 hour, makes modified HZSM-5 zeolite.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 one or more in nitric acid, sulfuric acid and hydrochloric acid etc.
According to the usual phraseology of catalyst field, active ingredient on the carrier that the present invention is mentioned and catalyzer (element) content is all in its corresponding oxide.
Ultra-clean gasoline production method provided by the present invention, the inferior patrol (for example FCC gasoline) to ultra-high-sulfur(UHS), high olefin can obtain good hydro-upgrading effect, for example: sulphur content is 1000-2500 μ g.g
-1, the olefin(e) centent inferior patrol that is 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 features:
(1) can be 1000-2500 μ g.g by sulphur content
-1, olefin(e) centent is 40-45v% inferior gasoline upgrading 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, first the full distillation gasoline of poor quality is carried out to directed sulphur shift reaction, then full the poor quality after over cure transfer processing distillation gasoline fractionation is obtained to lighting end gasoline and last running gasoline, counterweight distillation gasoline carries out selective hydrodesulfurization and the processing of supplementary desulfurization-hydro carbons isomery/aromatic hydrocarbons successively again, these multiple reactions be conducive to realize 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 higher product liquid yield, therefore than external gasoline hydrogenation modifying method, the more applicable inferior patrol component for China of the efficient combination production method of above-mentioned gasoline provided by the invention is processed.
Accompanying drawing explanation
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, object and beneficial effect being had more clearly, existing technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
Embodiment 1
It is a kind of take sulphur content as 1750 μ g.g that the present embodiment provides
-1, the olefin(e) centent ultra-high-sulfur(UHS) that is 48.4v%, high olefin full cut FCC gasoline inferior (full feedstock oil 1) carry out the efficient combination production method that ultra-low sulfur and high-octane number gasoline is prepared in hydro-upgrading processing for raw material.
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) (silicon-containing alumina);
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:
Supplement 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:
First by HZSM-5 zeolite (SiO
2/ Al
2o
3mol ratio is 30) be placed in the NaOH aqueous solution by the liquid-solid ratio of 10mL/g, pH value is adjusted to 13, at 75 ℃, stir 4 hours, filter, the zeolite leaching is washed to neutral, be dried 3 hours at 120 ℃; By the HZSM-5 zeolite through the processing of the NaOH aqueous solution according to zeolite: ammonium nitrate: the ratio that the weight ratio of water is 1: 0.8: 10 is mixed, and stir 4 hours in 80 ℃, then product is filtered, washed, and in 120 ℃ of dry, 480 ℃ of roastings 4 hours, obtain the HZSM-5 zeolite of alkaline purification-ammonium exchange; The above-mentioned HZSM-5 zeolite through alkaline purification and ammonium exchange is passed into steam-treated 20-50 minute at 600 ℃, obtain the HZSM-5 zeolite (the HZSM-5 zeolite of alkaline purification-ammonium exchange-hydrothermal treatment consists) of modification;
Take 50.2g aluminum silicon powder (containing Al
2o
392.0wt%, SiO
28.0wt%) and HZSM-5 zeolite, the 2.5g sesbania powder of the above-mentioned modification of 30.0g, by even its ground and mixed, adding 6mL mass concentration is 65% salpeter solution, fully after kneading, in banded extruder, extrude the cloverleaf pattern bar that diameter is 2mm, after 4 hours, make the support of the catalyst of moulding through 120 ℃ of dry 4 hours, 520 ℃ roastings;
Contain NiO, MoO according to stoichiometric ratio preparation
3and La
2o
3nickelous nitrate, ammonium molybdate, lanthanum nitrate mixing solutions, then adopt equi-volume impregnating that steeping fluid is evenly added drop-wise in said catalyst carrier, after 4 hours, make catalyst I through 120 ℃ of dry 4 hours, 520 ℃ roastings.
The concrete preparation process of catalyst for selectively hydrodesulfurizing (catalyst I I) is as follows:
Take Al-Si-Mg composite powder (moisture 25wt%) and 2g sesbania powder that 70g has suitable Al/Si/Mg ratio, by even its ground and mixed, adding 5mL mass concentration is 65% salpeter solution, fully after kneading in banded extruder extruded moulding, after 4 hours, make the support of the catalyst of moulding through 120 ℃ of dry 3 hours, 520 ℃ roastings;
40g said catalyst carrier be impregnated in the mixed impregnant liquor of 35mL saltpetre and Secondary ammonium phosphate, in oxide compound, in this steeping fluid, contain 1.5g K
2o and 1.0g P
2o
5, then ripening 5 hours at room temperature, then 120 ℃ of dry 3 hours, 520 ℃ roastings 4 hours, obtains 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 active ingredient in unrestricted mixed solution exists with oxide form) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and ammonium molybdate mixed solution, and to add 3.0mL mass concentration be 17% ammoniacal liquor, fully vibration is made steeping fluid until solid dissolves completely, then by the impregnation of catalyst carriers of the above-mentioned potassium of load and phosphorus in this steeping fluid, room temperature ageing 5 hours, after 5 hours, makes catalyst I I through 3 hours, 520 ℃ calcination process of 120 ℃ of drying treatment.
Supplement the method preparation (full text of CN101508912A is guided to here as a reference) that desulfurization-hydro carbons isomery/aromatization catalyzer (catalyst I II) can be recorded according to CN101508912A (application number is 200910080112.1), difference is to carry out single mineral acid treatment (treatment condition are identical) after adopting the processing of mineral acid-organic acid to change hydrothermal treatment consists into after hydrothermal treatment consists in disclosed CN101508912A preparation method.
Utilize full feedstock oil 1 upgrading to produce the process of ultra-low sulfur and high-octane number gasoline as follows, 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.First the full feedstock oil 1 of poor quality of ultra-high-sulfur(UHS) carry out directed sulphur shift reaction on Sulfur-Vapor of Lower Temperature transfer catalyst (catalyst I), and 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; Then the full distillation gasoline of the poor quality after over cure shift reaction enters Cutting Tap and obtains lighting end gasoline and last running gasoline by cut cutting, and gasoline cutting cut point is 70 ℃;
Last running gasoline adopts simple serial operation, on the device of two reactors in series, carries out, and in first reactor, contacts with catalyst I I, and selective hydrodesulfurization reaction occurs, 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; In second reactor, contact with catalyst I II, the reaction of desulfurization-hydro carbons isomery/aromatization occurs, 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 completes, lighting end gasoline and last running gasoline after treatment are mixed, obtain 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.
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 in product, isoparaffin and aromaticity content all have significantly and increase, 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, blended gasoline product yield is 98.8wt%, and quality product meets the requirement of state V clean gasoline standard.
Light, last running gasoline after the full feedstock oil 1 of table 1 and 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 a kind of take sulphur content as 2210 μ gg that the present embodiment provides
-1, the olefin(e) centent ultra-high-sulfur(UHS) that is 51.3v%, high olefin full cut FCC gasoline inferior (full feedstock oil 2) carry out the efficient combination production method that ultra-low sulfur and high-octane number gasoline is prepared in hydro-upgrading processing for raw material.
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) (silicon-containing alumina);
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:
Supplement 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;
The preparation method of above-mentioned catalyzer is identical with embodiment 1.
The process of utilizing full feedstock oil 2 upgradings to produce ultra-low sulfur and high-octane number gasoline:
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 supplementary desulfurization-hydro carbons isomery/aromatization reaction of last running gasoline 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 after the full feedstock oil 2 of table 2 and upgrading, 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 in product, isoparaffin and aromaticity content all have significantly and increase, 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, blended gasoline product yield is 98.6wt%, and quality product meets the requirement of state V clean gasoline standard.
Above-mentioned two embodiment show, 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 petroleum refining industry of China.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the foregoing is only specific embodiments of the invention; the protection domain being not intended to limit the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (5)
1. an efficient combination production method for ultra-low sulfur and high-octane number gasoline, the method comprises:
Make full distillation gasoline raw material inferior under hydro condition, carry out the directed sulphur shift reaction of low temperature, then carry out oil product cutting fractionation, obtain lighting end gasoline and last running gasoline, cutting cut point is 50-90 ℃; The reaction conditions of the directed sulphur shift reaction of described low temperature is: reaction pressure 1-3M
pa, liquid volume air speed 2-8h
-1, temperature of reaction 100-220 ℃, hydrogen to oil volume ratio 200-600;
Last running gasoline is contacted with supplementary desulfurization-hydro carbons isomery/aromatization catalyzer with catalyst for selectively hydrodesulfurizing; 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 supplementing 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;
Lighting end gasoline and last running gasoline after treatment are mixed, obtain the gasoline products of ultra-low sulfur and high-octane number;
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 inorganic refractory oxide; And,
Described transition metal oxide is NiO, CoO, ZnO, MoO
3, WO
3with one or more in CuO;
Described auxiliary agent is K
2o, MgO and La
2o
3in one or more;
Described zeolite is one or more in HZSM-5, H β and HY, and described zeolite is the zeolite of process alkaline purification successively, ammonium exchange, hydrothermal treatment consists;
Described inorganic refractory oxide is one or more in aluminum oxide, silicon oxide and silicon-containing alumina;
In total catalyst weight, the composition of described catalyst for selectively hydrodesulfurizing comprises: MoO
310-18%, CoO2-6%, K
2o1-7% and P
2o
52-6%, surplus is 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 MgO3-10%;
In total catalyst weight, the composition of described supplementary desulfurization-hydro carbons isomery/aromatization catalyzer comprises: MoO
34-8%, CoO1-4%, P
2o
51-3%, modified HZSM-5 zeolite 50-70%, surplus is Al-Ti composite oxides binding agents.
2. production method according to claim 1, wherein, the weight composition of Al-Ti composite oxides binding agent comprises: Al
2o
370-95%, TiO
25-30%.
3. production method according to claim 1, wherein, the described modified HZSM-5 zeolite in the composition of described supplementary desulfurization-hydro carbons isomery/aromatization catalyzer prepares in accordance with the following methods:
At 500-700 ℃, steam air speed 1-4h
-1condition under, HZSM-5 zeolite is carried out to the hydrothermal treatment consists of 15-50 minute;
Utilize the inorganic acid solution that pH value is 1.0-4.0, at 50-90 ℃, hydrothermal treatment consists product is carried out the cleanup acid treatment of 1-4 hour, 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.
4. production method according to claim 3, 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 hydrochloric acid.
5. production method according to claim 4, wherein, the SiO of described HZSM-5 zeolite
2/ Al
2o
3mol ratio is 35-50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010584150.3A CN102010751B (en) | 2010-12-10 | 2010-12-10 | Efficient combined production method for gasoline with ultralow sulfur and high octane value |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010584150.3A CN102010751B (en) | 2010-12-10 | 2010-12-10 | Efficient combined production method for gasoline with ultralow sulfur and high octane value |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102010751A CN102010751A (en) | 2011-04-13 |
| CN102010751B true CN102010751B (en) | 2014-06-18 |
Family
ID=43841084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010584150.3A Active CN102010751B (en) | 2010-12-10 | 2010-12-10 | Efficient combined production method for gasoline with ultralow sulfur and high octane value |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102010751B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2816094B1 (en) * | 2013-06-19 | 2020-04-29 | IFP Energies nouvelles | Method for producing gasoline with low sulphur and mercaptan content |
| 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 |
| 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 |
| CN107151564B (en) * | 2016-03-04 | 2019-09-17 | 中国石油大学(北京) | A kind of production method of super-low sulfur clean gasoline |
| CN107151563B (en) * | 2016-03-04 | 2019-09-17 | 中国石油大学(北京) | Couple the clean gasoline production method of ultra-deep desulfurization and the conversion of alkene high-octane rating |
| CN110157477A (en) * | 2018-08-09 | 2019-08-23 | 南京大学连云港高新技术研究院 | A kind of high olefin gasolines desulfurization of high-sulfur proposes high-octane method and apparatus |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411658A (en) * | 1991-08-15 | 1995-05-02 | Mobil Oil Corporation | Gasoline upgrading process |
| CN101508911A (en) * | 2009-03-19 | 2009-08-19 | 中国石油大学(北京) | Hydrogenation modification method for faulty gasoline |
| CN101508912A (en) * | 2009-03-19 | 2009-08-19 | 中国石油大学(北京) | Deep desulfurization-octane value recovery hydrogenation modification method for faulty gasoline |
| CN101885983A (en) * | 2010-07-02 | 2010-11-17 | 中国石油大学(北京) | Efficient coupling hydro-upgrading method for producing gasoline with ultra-low sulfur and high octane number |
| CN101885985A (en) * | 2010-07-02 | 2010-11-17 | 中国石油大学(北京) | Production method for ultra-low sulfur and high-octane number gasoline |
-
2010
- 2010-12-10 CN CN201010584150.3A patent/CN102010751B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411658A (en) * | 1991-08-15 | 1995-05-02 | Mobil Oil Corporation | Gasoline upgrading process |
| CN101508911A (en) * | 2009-03-19 | 2009-08-19 | 中国石油大学(北京) | Hydrogenation modification method for faulty gasoline |
| CN101508912A (en) * | 2009-03-19 | 2009-08-19 | 中国石油大学(北京) | Deep desulfurization-octane value recovery hydrogenation modification method for faulty gasoline |
| CN101885983A (en) * | 2010-07-02 | 2010-11-17 | 中国石油大学(北京) | Efficient coupling hydro-upgrading method for producing gasoline with ultra-low sulfur and high octane number |
| CN101885985A (en) * | 2010-07-02 | 2010-11-17 | 中国石油大学(北京) | Production method for ultra-low sulfur and high-octane number gasoline |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102010751A (en) | 2011-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101885985B (en) | Production method for ultra-low sulfur and high-octane number gasoline | |
| CN101492608B (en) | Method for deep desulfurization olefin hydrocarbon reduction of inferior gasoline | |
| CN101885983B (en) | Efficient coupling hydro-upgrading method for producing gasoline with ultra-low sulfur and high octane number | |
| CN102010751B (en) | Efficient combined production method for gasoline with ultralow sulfur and high octane value | |
| CN101845322B (en) | Production method for reducing sulfur and olefin content in gasoline | |
| CN103540349A (en) | Inferior heavy oil and residual oil hydrotreating combined process for prolonging service life of catalyst | |
| CN103789038B (en) | A kind of full cut high-sulfur inferior patrol produces the method for high-clean gasoline | |
| CN101508910A (en) | Ultra-deep desulfurization-octane value recovery hydrogenation modification method for faulty gasoline | |
| CN109022020B (en) | Method for multi-component adsorption separation of diesel oil | |
| CN103087771B (en) | Hydrogenation method for deeply desulfurizing gasoline | |
| CN101508908B (en) | Method for producing ultra-clean gasoline | |
| CN103074104B (en) | A kind of gasoline hydrodesulfurizationmethod method | |
| CN102295955B (en) | Hydro-upgrading method for inferior gasoline | |
| CN103059964B (en) | Method for producing ultra-low sulfur gasoline | |
| CN107488464A (en) | A kind of production method and production system of ultra-clean high-knock rating gasoline | |
| CN101440306A (en) | Hydro-upgrading method for FCC gasoline | |
| CN101440305B (en) | Hydro-upgrading method for FCC gasoline | |
| CN100558862C (en) | The method of white oil is produced in a kind of hydrofining | |
| CN103450935B (en) | A kind of method of producing super low-sulfur oil | |
| CN103059947B (en) | Method for production of super-clean gasoline from inferior gasoline | |
| CN103059959B (en) | Technological method for producing low sulfur gasoline | |
| CN103059956B (en) | Deep hydrodesulfurization method for catalytic gasoline | |
| CN101508911A (en) | Hydrogenation modification method for faulty gasoline | |
| CN103059953B (en) | Technological method for producing super-clean gasoline | |
| CN101508913B (en) | Deep desulfurization-octane value recovery hydrogenation modification combined method for faulty full-distillation gasoline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |