CN1302848A - Hydrogenating catalyst and its preparing process - Google Patents

Hydrogenating catalyst and its preparing process Download PDF

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Publication number
CN1302848A
CN1302848A CN 00110018 CN00110018A CN1302848A CN 1302848 A CN1302848 A CN 1302848A CN 00110018 CN00110018 CN 00110018 CN 00110018 A CN00110018 A CN 00110018A CN 1302848 A CN1302848 A CN 1302848A
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catalyzer
add
zirconium
phosphorus
magnesium
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CN1098913C (en
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宋小兵
丁连会
兰玲
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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 hydrogenating catalyst for heavy fractional oil, especially the diesel oil and pressure reducing gas oil, is prepared by carrying W and Ni on a specially prepared alumina. Said alumina is prepared through modifying by adding fluorine, and adding one or more oxide of B, Si, P, Mg, Ti, Zr, or Ga.

Description

A kind of hydrogenation catalyst and preparation method thereof
The present invention relates to a kind of hydrogenation catalyst and preparation method thereof.Be applicable to the hydrofining of heavy distillate, be specially adapted to the hydrofining of diesel oil and vacuum gas oil.
In recent years, along with the enhancing of people's environmental consciousness, market proposes higher requirement to oil quality, and hydrogen addition technology is the main means that the refinery produces the cleaning oil product, so the development of hydrogenation catalyst becomes more and more important.Simultaneously, crude quality variation in the world wide, the more difficult processing of secondary processing oil also requires catalyzer that better properties is arranged.
CN85104438 has introduced a kind of high purity aluminium oxide and has soaked fluorine and support the method that tungsten, nickel prepare hydrogenation catalyst then, prepared catalyzer fluorine-containing 1～9%, nickel oxide 1～5%, Tungsten oxide 99.999 15～38%, all the other are aluminum oxide, but the introducing of fluorine has increased the acidity of catalyzer, but influences the dispersion of metal, so the hydrogenation improved performance of catalyzer integral body is little.
CN1105953 has introduced and has soaked fluorine after a kind of high purity aluminium oxide hydrothermal treatment consists and support the method that tungsten, nickel prepare hydrogenation catalyst then, prepared catalyzer fluorine-containing 1～9%, nickel oxide 1～5%, Tungsten oxide 99.999 15～38%, all the other are aluminum oxide, aluminum oxide has improved pore structure by hydrothermal treatment consists, increased the available ratio surface of catalyzer, so activity of such catalysts improves.But overall effect is not very good, and the hydrogenation performance awaits further to improve.
Order of the present invention is that dispersion by improving hydrogenation metal is to improve the hydrogenation performance of catalyzer.Improve the structure of catalyzer and the hydrogenation performance that surface acid property increases catalyzer by one or more that add boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium, optimize the Preparation of catalysts route simultaneously, cut down the consumption of energy.
The prepared hydrogenation catalyst of the present invention is the hydrogenation activity component with group VIB and VIII family metal, fluorine, boron or silicon, phosphorus, magnesium, titanium, zirconium, gallium have been supported simultaneously, consisting of of this catalyzer: group VIB metal oxide 18～30m%, VIII family metal oxide 3～8m%, fluorine 3～10m%, boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium oxide 1～5m%, all the other are alumina catalyst supports.Wherein the group VIB metal can be W and/or Mo; Group VIII metal is Ni and/or Co.
This Preparation of catalysts method is as follows:
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) roasting got catalyzer after dry thing added the tackiness agent moulding.
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.
The step 3) solubility tungstate can be ammonium metawolframate, ethyl ammonium metawolframate, metatungstic acid nickel.
Contain Tungsten oxide 99.999 18～30m% in the catalyst material of the present invention, contain nickel oxide 3～8m%, fluorine-containing 3～10m%, the oxide compound 1～5m% of boracic, silicon, phosphorus, magnesium, titanium, zirconium, gallium.
Described catalyst shape can be sheet, and is spherical, strip, diameter 1.0mm～3.0mm preferably, the strip of length 3.0mm～8.0mm.
Catalyzer of the present invention is owing to adopt coprecipitated method preparation, and metal is scattered, and catalyst preparation process is only carried out a high-temperature roasting, and is capable of reducing energy consumption.And support fluorine in the catalyzer simultaneously, auxiliary agents such as boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium, effectively improved the hydrogenation performance of catalyzer, had higher desulfurization, denitrogenation and the matter performance of coming unstuck with comparing according to the catalyzer of CN8510438 and CN1105953 method preparation.
Further specify characteristics of the present invention below by example.
Comparative example 1
This example prepares the process of catalyzer by CN85104438.
Get SB aluminum oxide powder (a diaspore purity is 70%) 300 grams that Germany produces, 12 sesbania powder (production of Shanghai chemical reagent work), 9ml concentration is the nitric acid of 66m%, adding water 220ml stirs, be extruded into little of the trifolium of diameter 1.2mm with banded extruder, 110 ℃ of dryings, 600 ℃ of roastings 4 hours, alumina supporter.Get 14.9 gram NH 3F adds water to 60ml, and the dissolving back adds 100 gram alumina supporters, 110 ℃ of dryings, and roasting is 4 hours under 500 ℃ of air, this fluoro-containing alumina is joined contain 49.8 gram ammonium metawolframate (NH 4) 2W 4O 138H 2O (production of Zi Gong, Sichuan hard aluminium alloy factory) and 17.5 gram nitric acid nickel (NO 3) 26H 2In 60 ml waters of O (Beijing Chemical Plant's production), flooded 4 hours, 110 ℃ of dryings, roasting got catalyzer C1 in 4 hours under 500 ℃ of air.
Comparative example 2
This example prepares the process of catalyzer by CN1105953.
Get SB aluminum oxide powder (a diaspore purity is 70%) 300 grams that Germany produces, 12 sesbania powder (production of Shanghai chemical reagent work), 9ml concentration is the nitric acid of 66m%, adding water 220ml stirs, be extruded into little of the trifolium of diameter 1.2mm with banded extruder, 110 ℃ of dryings, 600 ℃ of water vapour (air: the water vapour volume ratio is 1: 6) were handled 4 hours, got alumina supporter.Get 14.9 gram NH 3F adds water to 60ml, the dissolving back adds 100 gram alumina supporters, 110 ℃ of dryings, roasting is 4 hours under 500 ℃ of air, this fluoro-containing alumina is joined in 60 ml waters that contain 49.8 gram ammonium metawolframates and 17.5 gram nickelous nitrates, flooded 4 hours, 110 ℃ of dryings, roasting got catalyzer C2 in 4 hours under 500 ℃ of air.
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 2860ml 3The aqueous solution, add 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, Z3.
Embodiment 3
Measure the above-mentioned AlCl of 2680ml 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 Z4.
Embodiment 4 gets the above-mentioned AlCl of 2680ml 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 Z5.
Embodiment 5
Measure the above-mentioned AlCl of 2680ml 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 Z6.
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 Z3, Z4, Z5, Z6 add 80 gram tackiness agents from each 100 gram, and sesbania powder 3 grams add water, and extrusion becomes little of the trifolium of diameter 1.2mm on banded extruder, 110 ℃ of dryings, 500 ℃ of roastings four hours make catalyzer C3, C4, C5, C6.
Table 1 has been listed the composition of each catalyzer.
Table 1, the composition of catalyzer:
Catalyzer C1 ?C2 ?C3 ?C4 ?C5 ?C6
????WO 3,m％ 27.0 ?27.0 ?23.8 ?27.0 ?22.7 ?23.8
????NiO,m％ 2.9 ?2.9 ?5.8 ?3.6 ?7.1 ?4.3
?????F,m％ 4.5 ?4.5 ?5.0 ?5.1 ?7.2 ?4.2
???B 2O 3,m％ ?3.1
???SiO 2,m％ ?3.2 ?3.1
???P 2O 5,m％ ?1.5 ?1.3
Embodiment 7
Present embodiment is introduced the relative reactivity evaluation procedure of catalyzer.
Adopting 180 ℃～360 ℃ triumph catalytic cracking diesel oil is raw material, the comparative evaluation activity of the hydrodenitrification of catalyzer, hydrogenating desulfurization.Be reflected on 100 milliliters of hydrogenation units and carry out.Catalyzer is packed into behind the reactor, and the kerosene with the dithiocarbonic anhydride that contains 2 volume % is handled under hydrogen earlier, makes it be converted into sulphided state, reaction then, and reaction conditions: hydrogen dividing potential drop 5.0Mpa, during air speed 2.0 -1, hydrogen/oil (volume) 500,340 ℃ of temperature of reaction, reaction result sees Table 2.
Table 2, activity rating of catalyst
Raw material and product Raw material Product
The catalyzer numbering C1 ?C2 ?C3 ?C4 ?C5 ?C6
Nitrogen content, μ g/g ?820 124 ?90 ?66 ?63 ?61 ?90
Denitrification percent, % 85 ?89 ?92 ?92 ?93 ?89
Sulphur content, μ g/g ?4050 400 ?317 ?211 ?207 ?203 ?287
Desulfurization degree, % 90 ?92 ?95 ?95 ?95 ?93
Existent gum 161 47 ?38 ?28 ?27 ?28 ?33
As can be seen from Table 2: catalyzer C3 of the present invention, C4, C5, the activity of C6 is better than CN85104438 and the described catalyzer of CN1105953.

Claims (10)

1. catalyst for hydrorefining distillate oil, this catalyzer is the hydrogenation activity component with group VIB and VIII family metal, supports a kind of in fluorine, boron or silicon, phosphorus, magnesium, titanium, zirconium, the gallium simultaneously or it is mixed into auxiliary agent.
2. according to the described catalyzer of claim 1, it consists of: group VIB metal oxide 18～30m%, and VIII family metal oxide 3～8m%, fluorine 3～10m%, boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium oxide 1～5m%, all the other are alumina catalyst supports.
3. according to the described catalyzer of claim 2, wherein the group VIB metal is W and/or Mo, and group VIII metal is Ni and/or Co.
4. 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) roasting got catalyzer after dry thing added the tackiness agent moulding.
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. according to the described catalyzer of claim 1, wherein this catalyst shape is a sheet, spherical or strip.
CN00110018A 2000-01-04 2000-01-04 Hydrogenating catalyst and its preparing process Expired - Lifetime CN1098913C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100439477C (en) * 2005-10-19 2008-12-03 中国石油化工股份有限公司 Hydroprocessing catalyst and its uses
CN101298043B (en) * 2007-04-30 2011-06-08 中国石油天然气集团公司 Hydrothermal deposition preparation of load type single metal hydrogenation catalyst
CN103191753A (en) * 2012-01-06 2013-07-10 中国石油化工股份有限公司 Preparation method of hydrotreatment catalyst
CN101590433B (en) * 2008-05-29 2014-08-13 北京三聚环保新材料股份有限公司 Modified aluminium oxide carrier, hydrogenation catalyst prepared thereby and preparation method
CN105435792A (en) * 2014-08-12 2016-03-30 中国石油化工股份有限公司 Alumina carrier, preparation method and silver catalyst
CN110639484A (en) * 2019-09-25 2020-01-03 山东金滢新材料有限公司 Preparation method of pseudo-boehmite

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1105953A (en) * 1994-01-25 1995-08-02 北方设计研究院 Method and equipment of treating waster chromium-plating water under alkaline condition

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100439477C (en) * 2005-10-19 2008-12-03 中国石油化工股份有限公司 Hydroprocessing catalyst and its uses
CN101298043B (en) * 2007-04-30 2011-06-08 中国石油天然气集团公司 Hydrothermal deposition preparation of load type single metal hydrogenation catalyst
CN101590433B (en) * 2008-05-29 2014-08-13 北京三聚环保新材料股份有限公司 Modified aluminium oxide carrier, hydrogenation catalyst prepared thereby and preparation method
CN103191753A (en) * 2012-01-06 2013-07-10 中国石油化工股份有限公司 Preparation method of hydrotreatment catalyst
CN103191753B (en) * 2012-01-06 2015-06-17 中国石油化工股份有限公司 Preparation method of hydrotreatment catalyst
CN105435792A (en) * 2014-08-12 2016-03-30 中国石油化工股份有限公司 Alumina carrier, preparation method and silver catalyst
CN105435792B (en) * 2014-08-12 2018-11-02 中国石油化工股份有限公司 Alumina support, preparation method and silver catalyst
CN110639484A (en) * 2019-09-25 2020-01-03 山东金滢新材料有限公司 Preparation method of pseudo-boehmite

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