CN1302847A - Catalyst for hydrotransforming diesel oil and its preparing process - Google Patents

Catalyst for hydrotransforming diesel oil and its preparing process Download PDF

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Publication number
CN1302847A
CN1302847A CN 00110017 CN00110017A CN1302847A CN 1302847 A CN1302847 A CN 1302847A CN 00110017 CN00110017 CN 00110017 CN 00110017 A CN00110017 A CN 00110017A CN 1302847 A CN1302847 A CN 1302847A
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catalyzer
add
nickel
oxide compound
gallium
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CN1098912C (en
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宋小兵
兰玲
丁连会
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
China Petrochemical Corp
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
China Petrochemical Corp
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Abstract

A catalyst for hydrotransforming diesel oil, especially the light circulating oil (LCO) with high contents of S, N and arene and low cetane number, is prepared from one or more oxides of F, B, Si, P, Mg, Ti, Zr and Ga, alumina, molecular sieve and hydrogenating metal (W and Ni). It can greatly lower the contents of S, N and arene, and increase cetane number.

Description

Catalyst for hydrocracking diesel oil and preparation method thereof
The present invention relates to a kind of catalyst for hydrocracking diesel oil and preparation method thereof.
Along with heavy oil, the widespread use of residual oil processing technology has increased gasoline, the source of light-end products such as diesel oil, but the fraction of diesel oil foreign matter content height that obtains thus, and the storage stability is poor, and cetane value is low, needs further processing just can obtain qualified product.With the heavy oil fluid catalytic cracking is the coking that comprises of representative, poor ignition quality fuels such as thermally splitting diesel oil, be characterized in content of heteroatoms height such as sulphur, nitrogen, the aromaticity content height, cetane value is low, and the storage stability is poor, be starved of a kind of heteroatomss such as sulphur, nitrogen that can remove and satisfy the environmental regulation requirement, improve the storage stability, can increase substantially cetane value again, satisfy the novel method that quality product requires.
US4820403 has introduced the catalyzer that a kind of use hydrocracking technology is handled the method for catalytic cracking light cycle oil (LCO), and catalyst base contains the molecular sieve of 25～60m%, and hydrogenation metal is W-Ni.Its reaction characteristics is＜180 ℃ of cracking conversion rates of control, produces high-octane petroleum naphtha, desulfurization simultaneously, and impurity such as nitrogen, the diesel oil of by-product high hexadecane value, but that its shortcoming is the yield of diesel oil is low, is unfavorable for that the countries and regions of diesel fuel oil shortage are used; Simultaneously, because its product cracking degree height, the hydrogen consumption is big, has hindered in the refinery of hydrogen supply anxiety and has promoted and use.
US4871680 has introduced a kind of catalyzer that uses hydrocracking technology to handle the method for LCO, and catalyst base contains the molecular sieve of 25～60m%, and hydrogenation metal is W-Ni.Its reaction characteristics is＜180 ℃ of cracking conversion rates of control, produces high-octane petroleum naphtha, desulfurization simultaneously, and impurity such as nitrogen, the diesel oil of by-product high hexadecane value is compared with US4820403, improves activity of such catalysts by adding the gallium modified molecular screen.But its shortcoming is that the yield of diesel oil is low, and the hydrogen consumption is big.
CN96120988.7 has introduced a kind of catalyst for hydrocracking diesel oil, the characteristics of described catalyzer are to select for use a kind of molecular sieve of special pore structure, its vehicle group becomes aluminum oxide 40-80W%, amorphous aluminum silicide 0-20W%, molecular sieve 5-30W%, this patent has catalyzer by each components contents in the adjustment catalyst base good hydrothermal stability and anti-nitrogen poisoning capability, diesel yield＞95% when handling LCO, have and general similar desulfurization, denitrification percent and the mass-energy power of coming unstuck of Hydrobon catalyst, improved the cetane value of product simultaneously.With US4971680, US4820403 compares has the diesel yield height, the characteristics that the hydrogen consumption is low.Its shortcoming is that the cetane value increase rate descends more when handling the higher raw material of sulphur, nitrogen and gum level, and the product cetane value still needs further to improve.
The objective of the invention is to prepare a kind of hydrogenation conversion catalyst, compare with CN96120988.7, the increase rate of the cetane value of product is bigger under same reaction conditions, sulphur, and it is stronger that heteroatomss such as nitrogen remove ability.Because preparation method's difference can reduce the high-temperature roasting number of times, reduce the preparation energy consumption simultaneously.
Described catalyzer is a kind of dual function hydrogenation catalyst, with group VIB and group VIII metal is active ingredient, salic 30～the 70m% of this catalyzer, Y zeolite 5～30m%, fluorine 2～8%, the oxide compound 0.5～5% of one or more of boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium.Wherein the group VIB metal oxide can be the oxide compound of tungsten and/or molybdenum, and its content is 15～30m%, and the group VIII metal oxide compound can be the oxide compound of nickel and/or cobalt, and its content is 2～10m%.
This Preparation of catalysts method is:
1) will add F in liquor alumini chloridi or the alum liquor, add then boracic, silicon, phosphorus, magnesium,
The compound of titanium, zirconium, gallium.
2) add Ni, Ni can add by the mode of solvable nickel salt aqueous solution.
3) add W, W can add by the mode of the solubility tungstate aqueous solution.
4) mixed solution with above-mentioned substance is heated to 40～80 ℃, uses ammonia precipitation process.
5) 100～150 ℃ of dryings in throw out washing back.
6) throw out is removed institute and contained Tungsten oxide 99.999 18～30m% after moisture, contains nickel oxide 3～8m%, and is fluorine-containing
3～10m%, the oxide compound 1～5m% of boracic, silicon, phosphorus, magnesium, titanium, zirconium, gallium.
Dried throw out adds tackiness agent, molecular sieve, extrusion aid aftershaping, 110 ℃ of dryings, and 500 ℃ of roastings get catalyzer.
Wherein liquor alumini chloridi described in the step 1) or alum liquor concentration are by the Al that can generate 2O 3Concentration conversion＜10g/100ml, best＜5g/100ml, F can pass through HF or NH 4The F aqueous solution or BF 3The form of diethyl ether solution adds, and the solution that boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium can pass through boracic, silicon, phosphorus, magnesium, titanium, zirconium, gallium compound adds.
Step 2) solvable nickel salt can be nickelous nitrate, nickelous carbonate or nickel acetate in.
Solubility tungstate can be ammonium metawolframate, ethyl ammonium metawolframate, metatungstic acid nickel in the step 3).
Described catalyst shape can be sheet, and is spherical, strip, diameter 1.0mm～3.0mm preferably, the strip of length 3.0mm～8.0mm.
Adopt the catalyzer of the present invention can be, pressure 4.0～8.0MPa, liquid air speed 1.0～3.0h 340～400 ℃ of temperature of reaction -1, process poor ignition quality fuel under the condition of hydrogen to oil volume ratio 400～1500, the poor ignition quality fuel of being processed can be sulphur content 500 μ g/g-25000 μ g/g, the catalytic cracking light cycle oil (catalytic cracking diesel oil) of nitrogen content 100 μ g/g-1500 μ g/g.The cetane value of product can increase by 10 more than the unit, and diesel yield is greater than 95m%, and other character satisfies the diesel oil index request.
Below further specify characteristics of the present invention by example:
Comparative example 1
CN96120988.7 prepares catalyzer by patent
Get the macroporous aluminium oxide 250g that oil three factories produce, MPY zeolite (y-type zeolite, pore volume 0.438ml/g, specific surface 828 2/ g, lattice constant 2.445nm, relative crystallinity 95%, SiO 2/ Al 2O 3Than 8.17) 75g, sial (sieve and silica-sesquioxide weight ratio 1: 1) 75 and 100g tackiness agent (SB powder and an amount of rare nitric acid making beating preparation tackiness agent, SB butt 0.25 in the tackiness agent, Al 2O 3/ HNO 3Molecular ratio is 0.3, SB powder wherein is that Germany produces, and a diaspore purity is 70%) mix and pinch, add water and become can squeeze paste, extrusion becomes little of the trifolium of diameter 1.2mm on banded extruder, 110 ℃ of dryings, 550 ℃ of roastings 4 hours make carrier, carrier floods with the steeping fluid of ammonium metawolframate and nickelous nitrate preparation, 110 ℃ of dryings, 500 ℃ of roastings 4 hours, catalyst A.
Embodiment 1
Present embodiment is introduced the preparation of solution, gets a certain amount of ammonium metawolframate and adds water and be mixed with concentration for containing WO 312g/100ml solution is got a certain amount of nickelous nitrate and is added water and be mixed with concentration for containing NiO30g/100ml solution, dilution AlCl 3The aqueous solution is for containing Al 2O 33.5g/100ml.The used solution of following examples together.
Embodiment 2
Measure the above-mentioned AlCl of 2130ml 3The aqueous solution adds BF 3Diethyl ether solution contains BF 330m% (taking from Fushun No.3 Petroleum Factory's catalyst plant) 44 gram is warmed up to 70 ℃ in ventilating kitchen, caught up with ether 30 minutes, adds nickel nitrate aqueous solution 110ml, and ammonium metatungstate aqueous solution 176ml is then with 8% ammoniacal liquor PH=7～8 that neutralize.Washing is to there not being Cl -(is that 2% Silver Nitrate verifies as no white precipitate with concentration), 110 ℃ of dryings, Z1.
Embodiment 3
Measure the above-mentioned AlCl of 2130ml 3The aqueous solution, add the NH that contains F10g/100ml 4F solution 125ml is warmed up to 70 ℃ in ventilating kitchen, add nickel nitrate aqueous solution 68ml, contains the SiO of 5g/100ml 2Water glass 187ml, ammonium metatungstate aqueous solution 222ml is then with the ammoniacal liquor of 8m% PH=7～8 that neutralize.Washing is to there not being Cl -, 110 ℃ of dryings get Z2.
Embodiment 4
Get the above-mentioned AlCl of 2130ml 3The aqueous solution, adding concentration is the phosphatase 11 6g of 40m%, and adding concentration is the HF aqueous solution 173ml that contains F10g/100ml, is warmed up to 70 ℃, adds nickel nitrate aqueous solution 142ml, and ammonium metatungstate aqueous solution 182ml is then with the ammoniacal liquor of 8m% PH=7～8 that neutralize.Washing is to there not being Cl -, 110 ℃ of dryings get Z3.
Embodiment 5
Measure the above-mentioned AlCl of 2130ml 3The aqueous solution, add the NH that contains F10g/100ml 4F solution 112ml is warmed up to 70 ℃ in ventilating kitchen, add nickel nitrate aqueous solution 110ml, and adding concentration is the phosphatase 11 3g of 40m%, adds the SiO that contains 5g/100ml 2Water glass 140ml, ammonium metatungstate aqueous solution 176ml is then with the ammoniacal liquor of 8m% PH=7～8 that neutralize.Washing is to there not being Cl -, 110 ℃ of dryings get Z4.
Embodiment 6
Present embodiment is introduced the moulding of catalyzer.
SB powder and an amount of rare nitric acid making beating preparation tackiness agent, (SB butt 0.25 in the tackiness agent, Al 2O 3/ HNO 3Molecular ratio is 0.3), get Z1, Z2, Z3, each 100 gram of Z4, get the MPY zeolite 15g that oil three factories produce, sesbania powder 3 grams add 100 gram tackiness agents, and extrusion becomes little of the trifolium of diameter 1.2mm, 110 ℃ of dryings on banded extruder, 500 ℃ of roastings 4 hours make catalyzer C1, C2, C3, C4.
Embodiment 7,
Get 100 gram Z1, get the MPY zeolite 25g that oil three factories produce, sesbania powder 3 grams add the above-mentioned tackiness agent of 100 grams, and extrusion becomes little of the trifolium of diameter 1.2mm on banded extruder, 110 ℃ of dryings, and 500 ℃ of roastings 4 hours make catalyzer C5.Table 1 has been listed the composition of each catalyzer.
Table 1, the composition of catalyzer
Catalyzer A ?C1 ?C2 ?C3 ?C4 ?C5
????WO 3,m％ 22.2 ?24.0 ?27.7 ?23.2 ?23.7 22?4
????NiO,m％ 6.3 ?5.9 ?3.4 ?7.24 ?5.8 5.5
?????F,m％ ?5.0 ?5.2 ?7.35 ?4.9 4.6
???B 2O 3,m％ ?3.1 2.9
???SiO 2,m％ ?3.89 ?3.08
???P 2O 5,?m％ ?1.97 ?1.65
????MPY,m％ 10.7 ?10.7 ?10.7 ?10.7 ?10.7 16.6
Embodiment 8
Present embodiment is introduced the evaluation of catalyzer.
The evaluation of catalyzer is carried out on the 200ml hydrogenation unit, measures the 60ml catalyzer with two volumes 20～30 purpose quartz sand mixings reactor of packing into, and with the kerosene sulfuration that contains 1% dithiocarbonic anhydride, sulfuration is back control reaction conditions fully:
Temperature of reaction, ℃ 360
Volume space velocity, h -1 1.5
Reaction pressure, MPa 6.0
Hydrogen to oil volume ratio 800
Table 2 has been listed stock oil character; Table 3, table 4 were listed reaction respectively 200 hours and 1000 hours results and product property.
Table 2. stock oil character
Density (20 ℃), g/cm 3 ???0.9123
Sulphur, μ g/g ????3564
Nitrogen, μ g/g ????850
Cetane value ?????30
Boiling range (ASTM D976), ℃
??????????10％ ????233
??????????50％ ????274
??????????90％ ????353
??????????EBP ????360
Table 3. reaction result and product property (200 hours)
Catalyzer ????A ????C1 ????C2 ????C3 ????C4 ????C5
Density d 4 20,g/cm ??0.8810 ??0.8774 ??0.8766 ??0.8782 ??0.8792 ??0.8732
Sulphur, μ g/g ???108 ????66 ????52 ????83 ????91 ????69
Nitrogen, μ g/g ????8.9 ????2.3 ????2.2 ????3.7 ????6.3 ????2.5
Product cetane value amplification ???10.3 ???12.1 ???12.1 ???11.9 ???11.1 ???12.8
Less than 180 ℃ of yields, m% ????2.9 ????2.6 ????2.6 ????2.3 ????2.6 ????2.9
By table 3. as can be seen, the cetane value amplification of its product of catalyzer of the present invention is bigger, and sulphur, nitrogen decreasing ratio are higher.
Table 4. reaction result and product property (1000 hours)
Catalyzer ????A ????C1 ????C2 ????C3 ????C4 ????C5
Density d 4 20,g/cm ??0.8820 ??0.8783 ??0.8775 ??0.8793 ??0.8802 ??0.8748
Sulphur, μ g/g ???143 ????78 ????63 ????101 ????100 ????92
Nitrogen, μ g/g ???13.3 ????3.1 ????2.8 ????5.3 ????6.9 ????3.9
Product cetane value amplification ???10.2 ???12.0 ???12.1 ???11.6 ???11.1 ???12.6
Less than 180 ℃ of yields, m% ????2.9 ????2.5 ????2.6 ????2.3 ????2.6 ????2.7
As can be seen from Table 4: catalyzer of the present invention not only has satisfactory stability, and desulfurization, nitrogen removal performance are better, and it is higher to improve the diesel cetane-number amplitude.

Claims (10)

1. catalyst for hydrocracking diesel oil, with group VIB and group VIII metal is active ingredient, it is characterized in that salic 30～70m% in this catalyzer, Y zeolite 5～30m%, fluorine 2～8%, the oxide compound 0.5～5% of one or more of boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium.
2. according to the described catalyzer of claim 1, wherein the group VIB metal oxide is the oxide compound of tungsten and/or molybdenum, and the group VIII metal oxide compound is the oxide compound of nickel and/or cobalt.
3. according to the described catalyzer of claim 2, wherein the content of the oxide compound of tungsten and/or molybdenum is 15～30m%, and the content of the oxide compound of nickel and/or cobalt is 2～10m%.
4. the described Preparation of catalysts method of claim 1:
1) will add F in liquor alumini chloridi or the alum liquor, add then boracic, silicon, phosphorus, magnesium,
The compound of titanium, zirconium, gallium;
2) add Ni, Ni adds by the mode of solvable nickel salt aqueous solution;
3) add W, W adds by the mode of the solubility tungstate aqueous solution;
4) mixed solution with above-mentioned substance is heated to 40～80 ℃, uses ammonia precipitation process;
5) 100～150 ℃ of dryings in throw out washing back;
6) throw out is removed institute and contained Tungsten oxide 99.999 18～30m% after moisture, contains nickel oxide 3～8m%, and is fluorine-containing
3～10m%, the oxide compound 1～5m% of boracic, silicon, phosphorus, magnesium, titanium, zirconium, gallium;
Dried throw out adding tackiness agent, molecular sieve, extrusion aid aftershaping, drying, roasting get catalyzer.
5. according to the described preparation method of claim 4, wherein liquor alumini chloridi described in the step 1) or alum liquor concentration are by the Al that can generate 2O 3Concentration conversion＜10g/100ml.
6. according to claim 4 or 5 described preparation methods, wherein liquor alumini chloridi described in the step 1) or alum liquor concentration are by the Al that can generate 2O 3Concentration conversion＜5g/100ml.
7. according to the described preparation method of claim 4, wherein F passes through HF or NH in the step 1) 4The F aqueous solution or BF 3The form of diethyl ether solution adds, and boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium add by the solution of boracic, silicon, phosphorus, magnesium, titanium, zirconium, gallium compound.
8. according to the described preparation method of claim 4, wherein step 2) in solvable nickel salt be nickelous nitrate, nickelous carbonate or nickel acetate.
9. according to the described preparation method of claim 4, wherein solubility tungstate is ammonium metawolframate, ethyl ammonium metawolframate, metatungstic acid nickel in the step 3).
10. one kind according to the application of the described catalyzer of claim 1 in the diesel oil hydrogenation conversion process, and its processing condition are: 340～400 ℃ of temperature of reaction, pressure 4.0～8.0MPa, liquid air speed 1.0～3.0h -1, hydrogen to oil volume ratio 400～1500.
CN00110017A 2000-01-04 2000-01-04 Catalyst for hydrotransforming diesel oil and its preparing process Expired - Lifetime CN1098912C (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100389178C (en) * 2005-01-14 2008-05-21 中国石油化工股份有限公司 Fluorine-containing hydrogenation catalyst and method for preparing the same
CN100486700C (en) * 2004-07-29 2009-05-13 中国石油化工股份有限公司 Hydrogenant cracking catalyst containing zeolite, and preparation method
CN101279279B (en) * 2007-04-04 2011-04-27 中国石油化工股份有限公司 Method for selective hydrogenation
CN102451751A (en) * 2010-10-21 2012-05-16 中国石油化工股份有限公司 Light cycle oil selective hydrodesulphurization catalyst and method thereof
CN103059916A (en) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 Method for selective hydrogenation and desulfuration of light cycle oil
CN103059917A (en) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 Light cycle oil selective hydrorefining method
CN110331030A (en) * 2019-08-19 2019-10-15 福建钰融科技有限公司 A kind of regenerating waste oil degumming agent and its methods for making and using same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4971680A (en) * 1987-11-23 1990-11-20 Amoco Corporation Hydrocracking process
US4820403A (en) * 1987-11-23 1989-04-11 Amoco Corporation Hydrocracking process
CN1049679C (en) * 1996-12-10 2000-02-23 中国石油化工总公司 Catalyst for hydrogenation conversion of diesel

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100486700C (en) * 2004-07-29 2009-05-13 中国石油化工股份有限公司 Hydrogenant cracking catalyst containing zeolite, and preparation method
CN100389178C (en) * 2005-01-14 2008-05-21 中国石油化工股份有限公司 Fluorine-containing hydrogenation catalyst and method for preparing the same
CN101279279B (en) * 2007-04-04 2011-04-27 中国石油化工股份有限公司 Method for selective hydrogenation
CN102451751A (en) * 2010-10-21 2012-05-16 中国石油化工股份有限公司 Light cycle oil selective hydrodesulphurization catalyst and method thereof
CN103059916A (en) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 Method for selective hydrogenation and desulfuration of light cycle oil
CN103059917A (en) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 Light cycle oil selective hydrorefining method
CN103059917B (en) * 2011-10-24 2015-04-08 中国石油化工股份有限公司 Light cycle oil selective hydrorefining method
CN110331030A (en) * 2019-08-19 2019-10-15 福建钰融科技有限公司 A kind of regenerating waste oil degumming agent and its methods for making and using same

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