CN101323797B - Method for hydrogenation dialkene removal of catalytically cracked gasoline - Google Patents
Method for hydrogenation dialkene removal of catalytically cracked gasoline Download PDFInfo
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Abstract
The invention relates to a method for hydrodealkadiene of catalytic and cracked gasoline; the method comprises the following steps: hydrodealkadiene is carried out to catalytic and cracked gasoline distillate with an alkadiene value of 2.56gI.(100g)(-1) at the reaction temperature of 120 DEG C to 280 DEG C, a hydrogen partial pressure of 1.0Mpa to 5.0 Mpa, an liquid hourly space velocity of 1.0h(-1) to 20.0h(-1) and volume ratio of hydrogen to oil of 10 to 400; the catalyst takes alumina and Y molecular sieve as composite carriers loading 3.35 percent of cobaltous oxide, 10.03 percent of molybdenum oxide, 0.86 percent of magnesia and 1.01 percent of nickel oxide, and the total weight of the catalyst is 100 percent; atomic ratio of magnesium to cobalt and nickel is 6.8; the average value of the alkadiene of the produced oil is reduced to be less than 0.2gI.(100g)(-1); the selectivity of dealkadien reaches 95.1 percent; the octane number of the raw oil (RON) is reduced to be not more than 1, monoolefine is reduced to be not more than 3v percent and the average value of the liquid yield of the gasoline is 99.6 mass percent.
Description
Technical field
The present invention relates to a kind of method of refining of petroleum hydrogenation dialkene removal of catalytically cracked gasoline.
Background technology
Along with emission of harmful substances in the combustion tail gas is made great efforts to reduce in countries in the world, the property specification of automotive fuel (gasoline, diesel oil) is in rapid improve.Sulphur content and olefin(e) centent in the many character, particularly gasoline have been stressed in these specifications." in the gasoline and diesel fuel grades standard that world fuel standards proposes, the sulphur content of II class gasoline is＜200 μ g/g, and olefin(e) centent is＜20 μ g/g, and the sulphur content of III class gasoline is＜30 μ g/g, olefin(e) centent is＜10 (v) %.The China's current fuel standard is compared with world's clean fuel specification has very big gap, and along with China's entry into the WTO, the clean fuel standards of China also can internationalize.In China, FCC gasoline accounts for about 90% of gasoline.Sulphur content in the FCC gasoline is 300～2000 μ g/g, olefin(e) centent is 40～60 (v) %.In order to satisfy the requirement of low-sulfur and olefin(e) centent in the Future in China clean gasoline, the FCC gasoline hydrodesulfurizationmethod is essential with reducing olefin(e) centent.
Falling in the alkene research of catalytically cracked gasoline, owing to contain more diolefine in the catalytically cracked gasoline, and diolefine plays interference effect to falling olefin hydrocarbon, can influence the effect of falling alkene.Reduce in the process of olefin(e) centent at catalytically cracked gasoline; Because the temperature that reaction needed is certain; Diolefine is together with other hydro carbons generation coking reaction in the catalytically cracked gasoline, and the long-pending easily knot of the burnt matter of generation causes reaction pressure to fall at beds to increase, until stop device.Therefore need to adopt the method for selective hydrogenation that it is removed.Under the unifining condition, because the easy polymerization of alkene, the easy hydrogenation of monoolefine is saturated, improve its selectivity and adopt noble metal catalyst to carry out selective hydrogenation can the diolefine in the raw oil well to be removed.But sulphur, higher full cut or the last running catalytically cracked gasoline of nitrogen content make precious metal be easy to inactivation when adopting noble metal catalyst.Employing non-noble metal hydrogenation catalyst for refining optionally hydrogenation also can well remove the diolefine in the raw oil.
CN 1676580A discloses a kind of method for removing alkadiene by selective hydrogenation; This method is included under the hydrogen refining process condition; Distillate is contacted with catalyzer; Said catalyzer contains a kind of alumina supporter and loads on cobalt and/or nickel, molybdenum and/or tungsten and the alkaline components on this carrier, it is characterized in that the atomic ratio of said basic metal and cobalt and/or nickel is 1.3-6.Raw oil diolefine value 1.8-1.9gI/100g, processed oil diolefine value 0.5-1.0gI/100g.
CN 1631529A discloses a kind of diolefine selective hydrogenation catalyst; This catalyzer contains a kind of alumina supporter and loads on cobalt and/or nickel, molybdenum and/or tungsten and the basic metal on this carrier; It is characterized in that the bore dia in the said alumina supporter is the 55-90% that the hole of 100-200 dust accounts for total pore volume.Raw oil diolefine value 5.39gI/100g, processed oil diolefine value 0.4-1.6gI/100g.
Above-mentioned diolefine selective hydrogenation catalyst is owing to the influence of its carrier compound, and its diolefine decreasing ratio is lower, and the pressure that can not better solve next step reaction falls.
Summary of the invention
The diolefine selective hydrogenation catalyst that the purpose of this invention is to provide the higher catalytically cracked gasoline of a kind of activity reaches the method that removes the hydrogenation dialkene removal of catalytically cracked gasoline of the effect of diolefine in the catalytically cracked gasoline preferably in conjunction with proper technical conditions.
Method provided by the invention is to a kind of diolefine value 2.56gI. (100g)
-1The catalytically cracked gasoline distillate carry out hydrogenation dialkene removal, described unifining condition comprises that temperature of reaction is 120-280 ℃, is preferably 170-240 ℃, the hydrogen dividing potential drop is the 1.0-5.0 MPa, is preferably the 1.2-3.0 MPa that liquid hourly space velocity is 1.0-20.0 hour
-1, be preferably 2.0-10.0 hour
-1, hydrogen to oil volume ratio 10-400, be preferably 20-300.The atomic ratio of magnesium and cobalt and nickel is 6.8.
The catalyzer that the present invention adopted is to be complex carrier with macroporous aluminium oxide and Y molecular sieve; Load 2.0-3.5% powder blue, 6.5-11.5% molybdenum oxide, 0.3-1.0% Natural manganese dioxide, 0.5-1.5% nickel oxide; Total catalyst weight is 100%, and surplus is a complex carrier.
The macroporous aluminium oxide specification is: pore volume: 0.8-1.1; Specific surface>=230m2/g; Fe≤0.03%; Na
2O≤0.01%; Water≤10%; Cl＜0.3%.
Y molecular sieve will carry out weight exchange in 1: 1.6 with an ammonium nitrate earlier, reaches Na after the exchange
2O weight≤0.2%; The consumption weight ratio of Y molecular sieve and aluminum oxide is 50-80%.
Preferred macroporous aluminium oxide of wherein said alumina supporter or V250 powder.
Said forming method can adopt the extrusion method to carry out.Said drying, preferred temperature is 90-200 ℃, the preferred time is 1-12 hour.Said roasting, preferred temperature is 300-600 ℃, the preferred time is 1-6 hour.
Said Preparation of catalysts method comprises that the method with powder blue, nickel oxide, molybdenum oxide and Natural manganese dioxide component introducing aluminum oxide and molecular sieve complex carrier can be any known technology; Introduce with the method for the said carrier of solution impregnation that contains cobalt, nickel, molybdenum and magnesium component like method commonly used; Wherein, Be selected from cobalt and/or the nickel of group VIII, the molybdenum and the basic metal of group vib can also can be incorporated in the alumina composite carrier respectively simultaneously.
Described molybdate compound is selected from one or more in the water-soluble cpds that contains molybdenum, like in molybdenum oxide, molybdate, the paramolybdate one or more, and preferred molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein.
Described nickel compound containing is selected from one or more in the nickeliferous soluble compound, like in the soluble complexes of nickelous nitrate, nickel acetate, basic nickel carbonate, nickelous chloride and nickel one or more, and preferred nickelous nitrate, basic nickel carbonate wherein.
Described cobalt compound is selected from one or more in the soluble compound that contains cobalt, like in the soluble complexes of Xiao Suangu, Cobaltous diacetate, cobaltous dihydroxycarbonate, NSC 51149 and cobalt one or more, is preferably Xiao Suangu, cobaltous dihydroxycarbonate.
The compound of said alkali metal containing, preferred oxyhydroxide, in the inorganic or organic acid salt one or more wherein.For example be selected from Marinco H in the magnesium-containing compound, magnesium nitrate, the magnesium chloride one or more.
According to the ordinary method in this area; Described catalyzer can be in the presence of hydrogen, under 240 ℃ temperature before using; Straight-run spirit with containing 2.0% weight dithiocarbonic anhydride vulcanizes catalyzer, and condition is: hydrogen dividing potential drop 2.0 MPas, 240 ℃ of temperature, liquid hourly space velocity 4.0h
-1, hydrogen to oil volume ratio 30: 1v/v, curing time 24 hours, cool to 170 ℃ afterwards, the incision raw material reacts.Sulphur, hydrogen sulfide or sulfur-bearing raw material carry out prevulcanized, are translated into sulphided state, and cure conditions is: hydrogen dividing potential drop 2.0 MPas, liquid hourly space velocity 4.0h
-1, hydrogen to oil volume ratio 30: 1v/v, curing time 24 hours, cool to 170 ℃ afterwards, the incision raw material reacts.
Method provided by the invention is specially adapted to the catalytically cracked gasoline fraction oil hydrogenation refining, to remove diolefine wherein.
Being respectively at loaded catalyst on the evaluating apparatus of 100ml and 1 liter scale and showing through activity and estimation of stability effect, is 170-220 ℃ in temperature, and pressure 2.0MPa, hydrogen-oil ratio are 30-50, and air speed is 3.0h
-1-4.0h
-1Reaction conditions under, to diolefine value 2.56gI. (100g)
-1The catalytically cracked gasoline distillate carry out hydrogenation dialkene removal, through 2000 hours stability test, give birth to olefiant diolefine MV and be reduced to less than 0.2gI. (100g)
-1, the dialkene removal selectivity reaches 95.1%; Simultaneously, the octane value RON of raw oil reduces ≯ 1, and monoolefine reduces ≯ 3 (v%), and the liquid yield MV of gasoline is 99.6 (quality) %.The present invention is the most outstanding to be characterised in that; Compare with existing catalyzer, when catalyzer provided by the invention is used in the diolefine selective hydrogenation of catalytic cracking full distillate, reach under the lower hydrogen consumption condition in lower temperature; It is active to have higher diene hydrogenation; Than existing dialkene removal catalyzer, reduced the hydrogen consumption, increased treatment capacity.
Embodiment
Following embodiment will be described further the present invention.
Agents useful for same in the instance except that specifying, is chemically pure reagent.
Employed Y molecular sieve is wanted to exchange with a certain amount of auxiliary agent earlier among the embodiment; The practical implementation step is following: 80g an ammonium nitrate is dissolved in 500 ml deionized water, to wherein dropping into the 50gY molecular sieve, begins to stir; Be warming up to 95-100 ℃ simultaneously, constant temperature press filtration after 1 hour.After filter cake repeated above-mentioned exchange for several times, again filter cake is put into 500 ml deionized water, stir washing 1 hour, press filtration.Repeatedly for several times, in the middle of the water washing process filter cake is carried out Na
2The real-time analysis of O content is washed to Na
2O weight≤0.2% gets final product.
Big pore aluminum oxide specification is among the embodiment: pore volume: 0.8-1.1; Specific surface>=230m2/g; Fe≤0.03%; Na
2O≤0.01%; Water≤10%; Cl＜0.3%.
Embodiment 1
Take by weighing the Y molecular sieve (Na after 64g exchanges
2O weight≤0.2%), 72gV250 powder; And it is their ground and mixed is even; The dilute nitric acid solution that to add about 2ml concentration be 2g/100ml stirs into the suitable jelly of humidity, on banded extruder, is extruded into circumscribed circle diameter and is 1.6 millimeters cloverleaf pattern bar; 120 ℃ of oven dry, roasting obtained carrier ZT1 in 3 hours under 550 ℃ of air atmospheres.
Take by weighing the carrier ZT189.4g (butt) of method for preparing, be contained in Erlenmeyer flask.After the Erlenmeyer flask extracting vacuum, contain CoO2.4g, MoO with 100ml
36.8g, MgO0.7g, NiO0.7g solution spray lentamente,, left standstill 2 hours.120 ℃ of dryings are 4 hours then, and 450 ℃ of roastings 4 hours obtain catalyzer CAT1.
Embodiment 2
Take by weighing the carrier ZT189.4g (butt) of the foregoing description 1 preparation, put into 200ml molybdenum, cobalt, nickel, magnesium solution dipping.Contain CoO2.4g, MoO in the solution
36.8g, MgO0.7g, NiO0.7g, normal temperature is dipping 2 hours down, 120 ℃ of dryings are 4 hours then, 450 ℃ of roastings 4 hours obtain catalyzer CAT2.
Embodiment 3
Take by weighing the Y molecular sieve (Na after 64g exchanges
2O weight≤0.2%), the 72gV250 powder, 2g NH
4F, their ground and mixed is even, the dilute nitric acid solution that to add about 2ml concentration be 2g/100ml; Stir into the suitable jelly of humidity; On banded extruder, be extruded into circumscribed circle diameter and be 1.6 millimeters cloverleaf pattern bar, 120 ℃ of oven dry, roasting obtained carrier ZT2 in 3 hours under 550 ℃ of air atmospheres.
Take by weighing the carrier ZT284.2g (butt) of method for preparing, be contained in Erlenmeyer flask.After the Erlenmeyer flask extracting vacuum, with containing CoO3.5g, MoO
310.2g, the solution 100ml of MgO1.0g, NiO1.1g sprays lentamente,, left standstill 2 hours.120 ℃ of dryings are 4 hours then, and 450 ℃ of roastings 4 hours obtain catalyzer CAT3.
Embodiment 4
Take by weighing the carrier ZT284.2g (butt) of the foregoing description 3 preparations, put into 200ml molybdenum, cobalt, nickel, magnesium solution dipping.CoO3.5g, MoO in the solution
310.2g, MgO1.0g, NiO1.1g, normal temperature is dipping 2 hours down, 120 ℃ of dryings are 4 hours then, 450 ℃ of roastings 4 hours obtain catalyzer CAT4.
Embodiment 5
Take by weighing the Y molecular sieve (Na after 42g exchanges
2O weight≤0.2%), the 93gV250 powder, 2g NH
4F, their ground and mixed is even, the dilute nitric acid solution that to add about 2ml concentration be 2g/100ml; Stir into the suitable jelly of humidity; On banded extruder, be extruded into circumscribed circle diameter and be 1.6 millimeters cloverleaf pattern bar, 120 ℃ of oven dry, roasting obtained carrier ZT3 in 3 hours under 550 ℃ of air atmospheres.
Take by weighing the carrier ZT383.7g (butt) of method for preparing, be contained in Erlenmeyer flask.After the Erlenmeyer flask extracting vacuum, with containing CoO3g, MoO
311.5g, the solution 100ml of MgO0.3g, NiO1.5g sprays lentamente, left standstill 2 hours.120 ℃ of dryings are 4 hours then, and 450 ℃ of roastings 4 hours obtain catalyzer CAT5.
Embodiment 6
Take by weighing the carrier ZT383.7g (butt) of method for preparing, put into 200ml molybdenum, cobalt, nickel, magnesium solution dipping.Contain CoO3g, MoO in the solution
311.5g, MgO0.3g, NiO1.5g, normal temperature dipping 2 hours down, 120 ℃ of dryings are 4 hours then, 450 ℃ of roastings 4 hours obtain catalyzer CAT6.
The physico-chemical property of above-mentioned six kinds of catalyzer is seen table 1.
The catalyzer physico-chemical property of table 1 embodiment
Adopt method provided by the invention that the catalytically cracked gasoline distillate is carried out the removing alkadiene by selective hydrogenation test, raw oil character is seen table 2.Concrete grammar is: catalyst breakage is become the long particle of 3-8mm; Catalyzer 50m1. in the 100ml fixed-bed reactor, pack into before formal charging; With the straight-run spirit that contains 2.0 weight % dithiocarbonic anhydride catalyzer is vulcanized earlier, cure conditions is: hydrogen dividing potential drop 2.0 MPas, 240 ℃ of temperature, liquid hourly space velocity 4.0h
-1, hydrogen to oil volume ratio 30: 1v/v, curing time 24 hours, cool to 170 ℃ afterwards, the incision raw material reacts; React sampling analysis after 2 hours; In the estimation of stability process afterwards, temperature is adjusted gradually according to test-results, but during the stability test; Maximum temperature is not higher than 220 ℃, and product oiliness matter MV is listed in table 3.
The used catalytically cracked gasoline raw oil character of table 2 test
The evaluation test result of six kinds of catalyzer of table 3
Claims (1)
1. the method for a hydrogenation dialkene removal of catalytically cracked gasoline is characterized in that: to a kind of diolefine value 2.56gI. (100g)
-1The catalytically cracked gasoline distillate carry out hydrogenation dialkene removal, described unifining condition comprises that temperature of reaction is 120-280 ℃, the hydrogen dividing potential drop is the 1.0-5.0 MPa, liquid hourly space velocity is 1.0-20.0 hour
-1, hydrogen to oil volume ratio 10-400;
The catalyzer that adopts is to be complex carrier with macroporous aluminium oxide and Y molecular sieve, load 2.0-3.5% powder blue, 6.5-11.5% molybdenum oxide, 0.3-1.0% Natural manganese dioxide, 0.5-1.5% nickel oxide, and total catalyst weight is 100%; Surplus is a complex carrier;
The atomic ratio of magnesium and cobalt and nickel is 6.8;
Macroporous aluminium oxide is: pore volume: 0.8-1.1; Specific surface>=230m
2/ g; Fe≤0.03%; Na
2O≤0.01%; Water≤10%; Cl＜0.3%;
Y molecular sieve will carry out weight exchange in 1: 1.6 with an ammonium nitrate earlier, reaches Na after the exchange
2O weight ratio≤0.2%;
The consumption weight ratio of Y molecular sieve and aluminum oxide is 50-80%;
Straight-run spirit with containing 2.0% weight dithiocarbonic anhydride vulcanizes catalyzer, and condition is: hydrogen dividing potential drop 2.0 MPas, 240 ℃ of temperature, liquid hourly space velocity 4.0h
-1, hydrogen to oil volume ratio 30: 1v/v, curing time 24 hours, cool to 170 ℃ afterwards, the incision raw material reacts.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0736589A1 (en) * | 1995-04-05 | 1996-10-09 | Mitsubishi Oil Co., Ltd. | Process for desulfurizing a catalytically cracked gasoline |
| US20050137434A1 (en) * | 2003-12-22 | 2005-06-23 | China Petroleum & Chemical Corporation | Catalyst for selective hydrogenation of olefins and its preparation as well as use |
| CN1631529A (en) * | 2003-12-22 | 2005-06-29 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for alkadiene |
| CN1676580A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Fractional oil selective hydro-de-diene method |
-
2007
- 2007-06-13 CN CN2007101188605A patent/CN101323797B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0736589A1 (en) * | 1995-04-05 | 1996-10-09 | Mitsubishi Oil Co., Ltd. | Process for desulfurizing a catalytically cracked gasoline |
| US20050137434A1 (en) * | 2003-12-22 | 2005-06-23 | China Petroleum & Chemical Corporation | Catalyst for selective hydrogenation of olefins and its preparation as well as use |
| CN1631529A (en) * | 2003-12-22 | 2005-06-29 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for alkadiene |
| CN1676580A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Fractional oil selective hydro-de-diene method |
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