CN101357338B - Co/Co-MCM-41 catalyst for olefin hydrocarbon skeletal isomerization in FCC benzin naphtha - Google Patents
Co/Co-MCM-41 catalyst for olefin hydrocarbon skeletal isomerization in FCC benzin naphtha Download PDFInfo
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Abstract
FCC naphtha contributes 35-40% share of gasoline and 85-95% share of sulfur, and is the main source of olefin and sulfide in the gasoline. If deep hydrodesulfurization can cause straight chain and single substituted olefin skeleton in the gasoline to be isomerized into branch chain and multi-substituted olefin, therefore, the loss of octane number caused by olefin saturation can be reduced. In the invention, a catalyst containing cobalt MCM-41 is prepared by the method of doping and loading, and has good olefin skeletal isomerization activity in the hydrodesulfurization condition. The catalyst is applicable to the hydroisomerization of the FCC naphtha.
Description
One, technical field:
The present invention relates to a kind of method for making and using method thereof of Co catalysts of the FCC of being used for naphtha olefin skeletal isomery.
Two, background technology:
Each country and international organization have formulated the gasoline standard of harshness more and more and have limited sulfur content in the gasoline.For example European Union will carry out Europe V standard in 2009, and wherein sulfur content requires to be reduced to below the 10ppmw, reach the standard (Appl.Catal.A.2005 the 144th volume, 143-172 page or leaf) of sweet gasoline.At present, the main method of industrial reduction sulfur in gasoline content is hydrodesulfurization, promptly makes organic sulfur compound and H in the gasoline under facing the condition of hydrogen
2Reaction generates the H that is easy to from the system separation
2S removes then.In the average formation of gasoline, the FCC naphtha accounts for 35～40%, and China is then up to 70%.Olefin(e) centent is about 50% in the FCC naphtha, and wherein the overwhelming majority is straight chain and single substituted olefine.Because other blend components do not contain alkene, perhaps contain alkene but harmonic proportion is lower, so alkene mainly comes the naphtha to FCC in the gasoline.In addition, 85～95% sulphur also mainly comes to FCC naphtha in the gasoline.In order further to reduce the sulfur content (deep hydrodesulfurizationof) in the gasoline, need more carry out hydrotreatment to the FCC naphtha under the exacting terms, this can cause wherein alkene hydrogenation greatly.Because the octane number of alkene will be higher than corresponding alkane, this will cause the heavy losses of octane number.For fear of this loss, industrial main employing selective hydrodesulfurization at present and two kinds of methods of deep hydrodesulfurizationof/octane value recovering.The former need cut raw material, and the energy consumption height can not reduce the content of alkene in the gasoline; The latter needs two reaction towers, complex process, and the energy consumption height, liquid yield is low.In recent years, someone proposes: if carry out in the hydrodesulfurization on sulphurized catalyst, make alkene generation hydroisomerizing, make straight chain, mono-substituted alkene be transformed into the higher side chain of octane number, polysubstituted alkene or alkane, just can reduce the loss of octane number (Catal.Today that causes of deep hydrodesulfurizationof, 2003 the 81st volumes, the 65-73 page or leaf).
About alkene isomerized mechanism on catalyst, a large amount of bibliographical informations is arranged.It is generally acknowledged that olefin isomerization is that to occur on the acid site, with the carbonium ion be the process of intermediate.As adopt the 1-hexene to tautomerize to the reaction of 2-hexene and 3-hexene, the generation of product 2-hexene is the result that carbonium ion takes off proton, the 3-hexene then is the product (J.Catal.2000 the 189th volume, 269-280 page or leaf) that takes off proton after the interior hydrogen migration of the molecule of carbonium ion.The skeletal isomerization of alkene it is generally acknowledged that through unimolecular mechanism bimolecular mechanism (J.Catal.1996 the 164th volume, 288-300 page or leaf) is then passed through in the generation of byproduct.According to unimolecular mechanism, the skeletal isomerization product is via protonated cyclopropane intermediate complex, and (J.Catal.1989 the 120th volume, the 182-191 page or leaf) that forms behind the proton taken off in open loop then.The intensity of raising surface acid and increase acid amount, rising temperature, the prolongation time of staying of alkene on catalyst surface all help its skeletal isomerization.But too high acid strength and temperature, the long time of staying also can cause olefin cracking.
Two kinds of situations may take place in the terminal linear olefin isomerization, and a kind of situation is a double-bond isomerism, and promptly the double-bond isomerism of carbochain end forms non-terminal linear alkene in the middle of carbochain, and its octane number is than terminal linear alkene height.But it is pointed out that under the condition of deep hydrodesulfurizationof carbon-carbon double bond is easily by complete hydrogenation, the hydrogenation products of the two is identical, is all the lower n-alkane of octane number.So double-bond isomerism does not have too big meaning under the deep hydrodesulfurizationof condition.The another kind of situation of terminal linear olefin isomerization is that linear alkene is become branched-chain alkene by isomery, is called skeletal isomerization.Branched-chain alkene has higher octane number, and under the condition of deep hydrodesulfurizationof, even if the carbon-carbon double bond of branched-chain alkene is generated alkane substitute by complete hydrogenation, its octane number is also higher, and this is significant to the octane number that keeps the FCC naphtha.
More existing reports about hydrogenation of olefins isomery under the FCC hydrodesulfurizationof of naphtha condition in document and the patent: discover that alkene is at γ-Al under hydrodesulfurizationconditions conditions
2O
3The main double-bond isomerism that takes place on the Co/Mo of load or the Ni/W catalyst does not have or rare skeletal isomerization (Ind.Eng.Chem.1955 the 47th volume, 749-172 page or leaf; Appl.Catal.B:Environ.2007 the 70th volume, the 542-547 page or leaf; Energy and Fuel, 1994 the 8th volumes, 147-150 page or leaf).This does not have help to the octane number that keeps the FCC naphtha.
Chinese patent CN1796502A discloses a kind of gasoline modifying method.This patent allows itself and the skeletal isomerization catalyst reaction, this skeletal isomerization catalyst main component be that ZSM-5 etc. has the molecular sieve that ten-ring duct molecular sieve and β zeolite etc. have the twelve-ring duct before gasoline fraction is by hydrodesulfurization.
Chinese patent CN1221314C discloses a kind of normal olefine skeletal isomerization Catalysts and its preparation method.This catalyst is a feedstock production by molecular sieve, modified kaolin, bonding agent, described molecular sieve is SAPO-11 or/and ZSM-5, modified kaolin be by kaolin through 500～800 ℃ of high-temperature roastings, acid treatment, adding magnesium chloride or/and calcium chloride or ammonium phosphate auxiliary agent are handled, calcination activation obtains.
U.S. Pat P5463160 is used for the linear chain olefin skeleton isomerism reaction with a kind of catalyst that contains molecular sieve, can selectivity positive amylene be changed into the 2-methyl butene.The aperture of used ferrierite is 0.42-0.60nm, has ten-ring and octatomic ring intersection duct.
Be that the mesoporous silicon material of representative has big specific area, mesoporous aperture that homogeneous is adjustable and stable skeleton structure with MCM-41, simultaneously, its amorphous skeleton that is easy to mix is formed and modifiable inner surface has been expanded its application as catalyst and carrier greatly.Cobalt (Co) is catalyst or an auxiliary agent commonly used in the reactions such as fuel oil hydrodesulfurization, Fischer-Tropsch synthesize.Document mainly concentrates on from n-butene the isomerization of alkene report and prepares isobutene, is used for synthesize methyl tert-butyl ether (MTBE).H.Lee etc. are used for skeletal isomerization (J.Catal.2002 the 211st volume of 1-butylene with the clinoptilolite of cobalt ions exchange, the 216-225 page or leaf), obtained 32% skeletal isomerization productive rate under the condition of hydrogen facing, but should react the selectivity lower (82%) of isobutene, needed temperature higher (450 ℃).To not find to be used for as catalyst the patent documentation of olefin skeletal isomery with Co, MCM-41 and Co/MCM-41.
Three, summary of the invention
The hydrogenation of olefins isomery is that alkene is facing the heterogeneous phenomenon that takes place under the condition of hydrogen, is characterized in that isomerization product not only comprises the double-bond isomerism and the skeletal isomerization product of alkene, also comprises the hydrogenated products of raw material and isomeric olefine.Therefore, also there is the competition of hydrogenation and isomery.Traditional Hydrobon catalyst has higher hydrogenation and desulphurizing activated, but its isomerization ability a little less than, this makes the alkene overwhelming majority in the FCC naphtha all directly be hydrogenated into alkane, loss of octane number is serious.As remedying means, industrial employing selective hydrogenation desulfurization process or deep hydrodesulfurizationof add methods such as octane value recovering workshop section, and this will cause the device technique complexity, and energy consumption is higher.Catalyst of the present invention can carry out skeletal isomerization to alkene under the condition of hydrodesulfurization, linear alkene is tautomerized to branched-chain alkene or hydroisomerizing is high-octane rating components such as branched paraffin, in hydrodesulfurization, reduces loss of octane number.We studies show that, cobalt is synthesized to obtains the mesopore material Co-MCM-41 that skeleton contains cobalt on the MCM-41 skeleton, and stronger B acid site can be introduced in its surface, can significantly improve the skeletal isomerization activity to linear alkene.In addition, we find, the catalyst that obtains behind the load C o again on the Co-MCM-41, and its olefin skeletal isomery performance is higher.Therefore we to adopt Co-MCM-41 be that carrier prepares the catalyst that is used for the olefin skeletal isomery.
Technical scheme of the present invention is as follows:
A kind of Co/Co-MCM-41 catalyst that is used for the hydrogenation of olefins isomery of FCC naphtha, it is to contain at skeleton that load has cobalt on the Co-MCM-41 of cobalt, the molal quantity of cobalt accounts for 3～30% (being the ratio Co/ (Co+Si)=3/100～30/100 of amount of substance) of the total mole number of cobalt and silicon in catalyst, it can be under the condition of hydrodesulfurization, linear alkene in the FCC naphtha is carried out skeletal isomerization, linear alkene is tautomerized to branched-chain alkene or hydroisomerizing is a branched paraffin.This catalyst is used for needing to vulcanize through original position before the hydrogenation of olefins isomery.
The Co/Co-MCM-41 Preparation of catalysts method of the hydrogenation of olefins isomery of the above-mentioned FCC of being used for naphtha is: the cabaltous nitrate hexahydrate of metering is dissolved in deionized water, the skeleton that adds metering contains the Co-MCM-41 of cobalt, stirred, place 3 hours, dried 12 hours for 120 ℃, roasting promptly got the Co/Co-MCM-41 catalyst in 3 hours in 500 ℃ air.
The mass ratio of above-mentioned cabaltous nitrate hexahydrate and water is: 0.041～0.21.
The mass ratio of above-mentioned cobalt nitrate and Co-MCM-41 is: 0.14～0.73.
The Co-MCM-41 that above-mentioned skeleton contains cobalt prepares with following method: with the CTAB (softex kw) and the Na of metering
2SiO
3Be dissolved in 80 ℃ of water, the ratio of the amount of each component materials is: CTAB: Na
2SiO
3: H
2O=1: 4: 556.Above-mentioned solution being cooled to 40 ℃, continuing to stir 1h, drip the cobalt ammonia solution of metering, is sulphur acid for adjusting pH value to 9～9.5 of 1M with concentration then, keeps 40 ℃, stirs and obtains precipitation in 3 days.With above-mentioned washing, filtration, dry in the shade, get the pink colour powder.This powder is warmed up to 550 ℃ with 1 ℃/min in moving air, roasting 5h obtains blue powder and is Co-MCM-41.
Above-mentioned cobalt ammonia solution prepares with following method: with the Co (NO of metering
3)
26H
2O is dissolved in the 80g deionized water, drips 25% ammoniacal liquor then to precipitation dissolving fully, promptly gets the cobalt ammonia solution.
The Co/Co-MCM-41 catalyst original position vulcanization process of the hydrogenation of olefins isomery of the above-mentioned FCC of being used for naphtha is: the Co/Co-MCM-41 catalyst is loaded in the tubular reactor, by hydrogen/sulfuration liquid proportional is that 300 (volume ratios) feed hydrogen, be warmed up to 150 ℃ with 2 ℃/minute speed, simultaneously system pressure is risen to 1.5MPa, begin to import sulfuration liquid, the liquid quality air speed of sulfuration liquid is 2h
-1Be warmed up to 230 ℃ with 1 ℃/min again and keep 2h, be warmed up to 320 ℃ with 1 ℃/min then and keep 4h, used sulfuration liquid is that to contain the quality percentage composition be 2% CS
2N-heptane solution.
Catalyst of the present invention is used for the method for FCC naphtha olefin skeletal isomery: CATALYST Co of the present invention/Co-MCM-41 catalyst is loaded in the reactor, cool to reaction temperature after the original position sulfuration as stated above, to vulcanize liquid and switch to the FCC naphtha, system pressure 1.0～3.0MPa, air speed 1～3h
-1, hydrogen and naphtha ratio are 200: 1～500: 1 (volume ratio), the linear alkene in the FCC naphtha can be tautomerized to branched-chain alkene or hydroisomerizing is branched paraffin., the skeletal isomerization ratio can reach 61%.
Four, the specific embodiment
The invention will be further described with following embodiment and reference example:
Embodiment 1
Get 2.33g Co (NO
3)
26H
2O is dissolved in the 80g deionized water, and dripping mass percentage concentration then is that 25% ammoniacal liquor to precipitation is dissolved fully, gets cobalt ammonia solution A.Get 14.58g CTAB and 45.47g Na
2SiO
3Be dissolved in 80 ℃, 400g deionized water, be cooled to 40 ℃ then, stir 1h, solution B.Solution A is added drop-wise to obtains suspension in the solution B, with concentration is that the dilute sulfuric acid of 1M is regulated above-mentioned suspension pH value to 9～9.5, stir 3d at 40 ℃ of constant temperature and obtain precipitation, with this washing of precipitate, filtration, dry in the shade, 550 ℃ of roasting 5h (1 ℃ of heating rate/min), obtain blue powder 5Co-MCM-41 in moving air then.Measuring its surface area is: 951m
2/ g.
Reference example 1
Get 14.58g CTAB and 45.47g Na
2SiO
3Heating for dissolving is cooled to 40 ℃ then in the 400g deionized water, stir 1h, continues to stir, adjust pH to 9～9.5,40 ℃ of constant temperature stir 3d fast, and washing, filtration are dried in the shade, 1 ℃/min temperature programming to 550 ℃, roasting 5h in moving air, white powder MCM-41.Measuring its surface area is: 1191m
2/ g.
Embodiment 2
Getting the 1.09g cobalt nitrate is dissolved in the 15.75g deionized water, the 5Co-MCM-41 that gets 5g embodiment 1 preparation again adds in the above-mentioned solution, stir 20min, place 3h, dry 12h at 120 ℃ then, 500 ℃ of roasting 3h in air (5 ℃ of heating rates/min), obtain blue powder 5Co/5Co-MCM-41, the Co content of analyzing wherein is: Co/ (Co+Si)=0.075.The 5Co/5Co-MCM-41 catalyst is sieved to 20～40 orders through compressing tablet, pulverizing, mistake, is used for determination of activity.
Reference example 2
Getting the 1.09g cobalt nitrate is dissolved in the 17.5g deionized water, the MCM-41 that gets 1 preparation of 5g reference example again adds above-mentioned solution moderate dipping, stir, leave standstill, 120 ℃ of oven dry spend the night, 5 ℃/min temperature programming to 500 ℃, roasting is 3 hours in air, compressing tablet, pulverizing, mistake are sieved to 20～40 orders then, and obtaining blue powder is oxidation state 5Co/MCM-41.
Embodiment 3
Getting 1.04g cobalt nitrate and 0.84g ammonium molybdate is dissolved in the 17.5g deionized water, the 5Co-MCM-41 that gets 5g embodiment 1 preparation again adds above-mentioned solution moderate dipping, stir, leave standstill, 120 ℃ of oven dry spend the night, 5 ℃/min temperature programming to 500 ℃, roasting is 3 hours in air, compressing tablet, pulverizing, mistake are sieved to 20～40 orders then, obtain oxidation state Hydrobon catalyst CoMo/5Co-MCM-41.
Embodiment 4
In the present embodiment, be the mould stone cerebrol with the n-heptane solution that contains 500ppmw thiophenic sulfur and 20% (quality) 1-hexene, evaluate catalysts on the small stationary bed reaction device.Be specially, the 5Co-MCM-41 of embodiment 1 preparation is loaded into the constant temperature zone of bed, tamp with 20-40 order quartz sand up and down, the catalyst loading amount is 2.7g.By hydrogen/sulfuration liquid proportional is that 300 (volume ratios) feed hydrogen, is warmed up to 150 ℃ with 2 ℃/minute speed, simultaneously system pressure is risen to 1.5MPa, begins to import sulfuration liquid, and sulfuration liquid is for containing 2%CS
2The n-heptane solution of (quality), the liquid weight air speed of sulfuration liquid is 2h
-1Be warmed up to 230 ℃ of sulfuration 2h with 1 ℃/min then, 1 ℃/min is warmed up to 320 ℃ of sulfuration 4h again.Sulfuration finishes, and the reaction bed temperature is reduced to 300 ℃, and sulfuration liquid is switched to above-mentioned mould stone cerebrol, keeps air speed, pressure and hydrogen-oil ratio constant, measures the hydroisomerizing performance of catalyst.React sampling after 5 hours, adopt the gas-chromatography off-line analysis, the results are shown in Table 1.
Embodiment 5
Press embodiment 4 identical methods and measure the hydroisomerizing performance of the 5Co/5Co-MCM-41 catalyst of embodiment 2 preparations.
Reference example 3-4
Press embodiment 4 identical methods and estimate the hydroisomerizing performance of comparative catalyst MCM-41 and 5Co/MCM-41., the results are shown in Table 1.
Reference example 5
Pressing embodiment 4 identical methods estimates industrially desulfurized with CoMo/ γ-Al
2O
3, the results are shown in Table 1.
The hydroisomerizing performance of table 1, different catalysts
| Catalyst | Conversion ratio (%) | Skeletal isomerization productive rate (%) | Hydrogenation productive rate (%) | Cracking selectivity (%) |
| MCM-41 | 92.7 | 22.5 | 22.0 | 0.7 |
| 5Co/MCM-41 | 98.1 | 46.5 | 40.6 | 2.6 |
| 5Co-MCM-41 | 93.5 | 37.7 | 42.0 | 4.2 |
| 5Co/5Co-MCM-41 | 98.1 | 61.1 | 68.5 | 4.1 |
| CoMo/γ-Al 2O 3 | 99.7 | 1.8 | 98.6 | 0.2 |
Embodiment 6
Press the hydroisomerizing performance of the identical method evaluate catalysts CoMo/5Co-MCM-41 of embodiment 4., the results are shown in Table 2.
Embodiment 7
Catalyst 5Co/5Co-MCM-41 is seated in the stage casing of bed, with industrially desulfurized with CoMo/ γ-Al
2O
3Be seated in the hypomere of bed, loading amount is 2.7g, and the centre separates with 20-40 order quartz sand, tamps three sections independent temperature controls up and down with 20-40 order quartz sand.Press the identical method of embodiment 4-5 and estimate two-stage catalytic agent performance, the results are shown in Table 2.
Table 2,1-hexene are at CoMo/ γ-Al
2O
3, nature of devulcanization in CoMo/5Co-MCM-41 and the two-stage catalytic agent and isomerization character.
| Catalyst | Thiophene conversion ratio (%) | 1-hexene skeletal isomerization productive rate (%) | 1-hexene hydrogenation productive rate (%) |
| CoMo/γ-Al 2O 3 | 96.7 | 1.8 | 98.6 |
| CoMo/5Co-MCM-41 | 93.8 | 40.7 | 74.9 |
| The two-stage catalytic agent | 98.0 | 36.5 | 91.0 |
Claims (1)
1. method of using the Co/Co-MCM-41 catalyst FCC naphtha to be carried out simultaneously the olefin skeletal isomery under hydrodesulfurizationconditions conditions, it is characterized in that: it is that the Co/Co-MCM-41 catalyst is loaded in the reactor, cool to reaction temperature after the original position sulfuration, to vulcanize liquid and switch to the FCC naphtha, linear alkene in the FCC naphtha can be tautomerized to branched-chain alkene or hydroisomerizing is branched paraffin, reacting system pressure 1.0～3.0MPa, air speed 1～3h
-1Hydrogen and naphtha volume ratio are 200: 1～500: 1, described Co/Co-MCM-41 catalyst has cobalt for load on the Co-MCM-41 that contains cobalt at skeleton, and in the catalyst molal quantity of cobalt account for cobalt and silicon total mole number 3～30%, described Co/Co-MCM-41 catalyst original position vulcanization process is: by hydrogen/sulfuration liquid volume ratio is 300 feeding hydrogen, be warmed up to 150 ℃ with 2 ℃/minute speed, simultaneously system pressure is risen to 1.5MPa, begin to import sulfuration liquid, the liquid quality air speed of sulfuration liquid is 2h
-1, be warmed up to 230 ℃ with 1 ℃/min again and keep 2h, be warmed up to 320 ℃ with 1 ℃/min then and keep 4h, used sulfuration liquid is that to contain the quality percentage composition be 2% CS
2N-heptane solution.
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| FR2988732B1 (en) * | 2012-03-29 | 2015-02-06 | IFP Energies Nouvelles | METHOD FOR SELECTIVELY HYDROGENATING A GASOLINE |
| CN106076405B (en) * | 2016-06-22 | 2018-09-18 | 北京化工大学常州先进材料研究院 | Formaldehyde catalyst and its preparation method and application in a kind of removal glyphosate mother solution |
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| WO2006002116A2 (en) * | 2004-06-17 | 2006-01-05 | Yale University | Size-controllable transition metal clusters in mcm-41 for improving chemical catalysts |
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2007
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Patent Citations (5)
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|---|---|---|---|---|
| US5232580A (en) * | 1991-06-21 | 1993-08-03 | Mobil Oil Corporation | Catalytic process for hydrocarbon cracking using synthetic mesoporous crystalline material |
| CN1318095A (en) * | 1998-08-15 | 2001-10-17 | 埃尼里塞奇公司 | Process and catalysts for upgrading of hydrocarbons boiling in naphtha range |
| CN1276408A (en) * | 1999-03-12 | 2000-12-13 | 阿吉佩罗里股份公司 | Catalyst composition for upgrading hydrocarbon mixture |
| CN1306885A (en) * | 2000-01-25 | 2001-08-08 | 大连理工大学 | Method of synthesizing medium-pore holecular sieve MCM-41 and preparing hydrogenatino and desulfurization catalyst with MCM-41 as carrier |
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