CN1068033C - Saturated hydrogenation of olefin of reforming oil - Google Patents

Saturated hydrogenation of olefin of reforming oil Download PDF

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CN1068033C
CN1068033C CN98120381A CN98120381A CN1068033C CN 1068033 C CN1068033 C CN 1068033C CN 98120381 A CN98120381 A CN 98120381A CN 98120381 A CN98120381 A CN 98120381A CN 1068033 C CN1068033 C CN 1068033C
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group viii
metal
viii metal
boron
additive
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CN1250799A (en
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慕旭宏
张晓昕
宗保宁
马爱增
闵恩泽
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Abstract

The present invention relates to a reformed oil olefine saturation hydrogenation method. Reformed oil is in contact with hydrogen, the contact has the conditions that the temperature is from 50 to 200 DEG C, the pressure is more than 0.1MPa, the liquid hourly space velocity is from 0.1 to 20 h <-1>, and the ratio of hydrogen and water is 30. The catalyst comprises a porous carrier material, a metal of the VIII group, and one or two elements selected from boron and phosphorus. The metal of the VIII group exists in a noncrystalline alloy form, and is loaded in the porous carrier material. The weight percentage of the content of the metal of the VIII group and the boron and/or phosphorous is from 0.1 to 60%, and the atomic ratio of the metal element of the VIII group and the boron and/or the phosphorous is from 0.5 to 10.

Description

Reformed oil olefine saturation hydrogenation method
The present invention relates to the recapitalization generating oil hydrogenation process for purification, specifically about a kind of reformed oil olefine saturation hydrogenation method.
Catalytic reforming is the important process process from oil production aromatic hydrocarbons and high octane gasoline component, owing to have hydrocracking reaction in the reforming reaction process, therefore, contain small amounts of olefins in the reformed oil, for being the catalytic reforming process of purpose to produce aromatic hydrocarbons, the existence of alkene will influence the colourity and the stability of product, thereby must be removed.
At present, remove that the technology of small amounts of olefins mainly contains two kinds in the reformed oil, promptly clay-filtered technology and back end hydrogenation technology.
Clay-filtered technology is the alkene that utilizes in the carclazyte absorption aromatic hydrocarbon product, to reach the purpose of removing alkene, the carclazyte activity is lower, life cycle short, easily cause shortcomings such as environmental pollution and air speed are lower owing to exist, thereby this technology has the trend that is replaced by back end hydrogenation technology.
Traditional back end hydrogenation technology on flow process is, the generation oil of last reforming reactor outlet and hydrogen are through an interchanger, fluid temperature (F.T.) is reduced to about 330 ℃, enters the back end hydrogenation reactor that hydrogenation catalyst is housed then, make the hydrogenation of olefins that generates in the oil.Flow process is simple, energy consumption is low though back end hydrogenation technology has, do not have advantages such as " three wastes ".But along with progressively applying of two (many) metal reforming catalysts in recent years, the raising of resurfacing operation severity, this technology can influence the water chloride balance control of reforming catalyst, the pressure drop of increase recycle hydrogen system.And, because its temperature of reaction is higher, always there is the part aromatic hydrocarbons in the reformed oil saturated by hydrogenation.Simultaneously, temperature of reaction directly depends on the height of reforming reaction temperature in the back end hydrogenation technology, is difficult to control, catalyzer regeneration separately during shut-down.Therefore, develop a kind of novel saturation hydrogenating process for removing olefines from reforming produced oil,, become the problem that currency must be studied to eliminate the shortcoming that exists in the existing technology.
About the saturated hydrogenation catalyzer of alkene, summary gets up to have following several, that is:
(1) Mo-Co-Al that uses of traditional reformed oil back end hydrogenation technology 2O 3Generally about 330 ℃, temperature of reaction is too high for catalyzer, its use temperature.
(2) Raney nickel (Raney Ni) catalyzer is characterized in having higher activity, can catalysis low temperature (being lower than 220 ℃) the saturated hydrogenation reaction of alkene down.
(3) the non-loading type amorphous alloy catalyst of nickeliferous or cobalt or iron, comprising the olefine saturation hydrogenation activity apparently higher than the big surface amorphous alloy catalyst of Raney nickel (CN1,073,726A).
Because Raney nickel and amorphous alloy catalyst granularity all less (20 orders are following), be not suitable for fixed-bed reactor, and when being used for fluidized-bed reactor, granules of catalyst is easy to be taken out of by fluid, and the practical application of these two kinds of catalyzer also becomes the problem that needs solve.
For addressing the above problem CN1,152, the contriver of 605A has invented a kind of saturation hydrogenating process for removing olefines from reforming produced oil, and this technology comprises that reformed oil enters magnetically stabilized bed reactor by the bottom together with hydrogen after preheating, product is told product at last through cooling, separation.Wherein, a kind of catalyzer is housed in the magnetically stabilized bed reactor, this catalyzer is to have activity under a kind of low temperature, and has the hydrogenation catalyst of magnetic.The magnetic of described catalyzer can be provided by the magnetic that catalyst themselves had, also can be by mixing, and various complex methods such as adhesion, embedding are (as US4,687, US878, US4,541,924, US4,541,925, EP149,343 methods that provide) will have magnetic material (as be selected from nickel, cobalt, iron or its oxide compound one or more) and non-magnetic catalyst activity component compound, be prepared into matrix material, make catalyzer have magnetic.Wherein, preferred catalyzer is to have ferromagnetic hydrogenation catalyst, as contains one or more the hydrogenation catalyst that is selected from nickel, cobalt, iron or their oxide compound.More preferred catalyzer is Raney nickel catalyst and the amorphous alloy catalyst that contains nickel, cobalt, iron or their mixtures.As J.Catal.99,375, the 25Ni-P-La and the Ni-P amorphous alloy catalyst of 1986 reports, petroleum journal 7 (2), 86～89,1991 and Journal of Molecular Catalysis 5 (4), the Ni-Y-P amorphous alloy catalyst of 272～75,1991 reports and the JP86 that uses as catalyzer, 119,606 Ni-P amorphous alloy, the EP173 that disclose, the 088 Ni-Zr amorphous alloy that discloses etc.Highly preferred catalyzer is CN1,073,726A is disclosed, consist of nickel or cobalt or the iron of 86～92.5 heavy %, the rare earth of 0～3 heavy % and the big surface amorphous alloy catalyst of Ni/Co/Fe-RE-P or the CN1 of surplus phosphorus, 152,475A is disclosed, consist of the nickel of 40～91 heavy %, the high-ferromagnetic non-crystalline alloy catalyst of 2～40 heavy % iron and surplus phosphorus.Temperature of reaction is low, olefin conversion is high though this technology has, and selectivity is good, can not cause the loss and the big advantage of air speed of aromatic hydrocarbons.But the employed catalyzer of this technology is all by elementary composition amorphous alloy catalysts such as nickel, cobalt, P, rare earths, and price is higher.And this catalyzer is a kind of very tiny particle, can only be used for magnetically stabilized bed reactor, and can not be used for more conventional and investment fixed-bed reactor still less.
It is higher and can only be used for the shortcoming of magnetically stabilized bed reactor to the objective of the invention is to overcome the used amorphous alloy catalyst price of prior art, provide a kind of conversion of olefines ability higher, but catalyst system therefor is more cheap, and goes for the reformed oil olefine saturation hydrogenation method of various reactors.
Method provided by the invention is included under a kind of existence of catalyzer reformed oil is contacted with hydrogen.Wherein, the condition of described contact is 50～200 ℃ of temperature of reaction, and reaction pressure is greater than 0.1 MPa, liquid hourly space velocity 0.1～20 hour -1, hydrogen to oil volume ratio is greater than 30.Described catalyzer is a kind of carried non-crystal alloy catalyst, and this catalyzer contains a kind of porous carrier materials, a kind of group VIII metal and is selected from one or both elements in boron, the phosphorus.Described group VIII metal element exists with the form of the amorphous alloy of group VIII metal and B or group VIII metal and P and is carried in the porous carrier materials.The content of described group VIII metal and boron and/or phosphorus is 0.1～60 heavy %, and the atomic ratio of group VIII metal element and boron and/or phosphorus is 0.5～10.
According to method provided by the invention, the raising of temperature of reaction can improve the conversion of olefines rate, and under the identical situation of other conditions, the setting of temperature of reaction should change with the difference of stock oil bromine valency again, and temperature of reaction was answered corresponding raising when the bromine valency was high, and vice versa.Temperature of reaction can be 50～200 ℃, best 50～150 ℃.The raising of reaction pressure can make molecular balance move to the direction of conversion of olefines, thereby, also can improve the conversion of olefines rate.But after reaction pressure was higher than 1 MPa, it is not too obvious that reaction pressure continues to improve the effect that olefin conversion is improved.In order to cut down the consumption of energy preferred 0.1～3 MPa of the scope of reaction pressure, best 0.1～2 MPa.The raising of liquid hourly space velocity can reduce the conversion of olefines rate, and reaction velocity can be 0.1～20 hour -1, preferred 1～15 hour -1The increase of hydrogen to oil volume ratio helps molecular balance moves to the direction of conversion of olefines, and hydrogen to oil volume ratio can be greater than 30, considers energy consumption, hydrogen to oil volume ratio preferred 30～150, best 50～100.
Because method catalyst system therefor provided by the invention can be made arbitrary shape, any granularity, and part catalyzer wherein can have ferromegnetism concurrently, therefore, described contact can be carried out in the reactor of existing arbitrary form.For example, method provided by the invention can be carried out in fixed-bed reactor, fluidized-bed reactor or magnetically stabilized bed reactor.For reducing facility investment, method provided by the invention is preferably carried out in fixed-bed reactor.Can be upflowing when reformed oil and hydrogen enter reactor, also can be downflow system.Described reformed oil can be the full distillate oil of reforming and generating, and can be the benzoline of reforming and generating, and also can be the distillate before the aromatic hydrocarbons extracting.
Can also and preferably contain a kind of metal additive M in the used carried non-crystal alloy catalyst, the atomic ratio of this group VIII metal element and metal additive M is 0.1～1000, preferred 0.5～700.Described metal additive M can be except that this group VIII metal itself, can be contained BH 4 -Or H 2PO 2 -Solution be reduced into the metallic element of simple substance attitude one or more from corresponding salt.
According to an embodiment preferred of invention, described catalyzer contains a kind of metallic element, phosphorus, boron and a kind of porous carrier materials that is selected from VIII family.With the total catalyst weight is benchmark, and the content of this group VIII metal is 0.15～30 heavy %, preferred 0.5～20 heavy %, more preferred 1～15 heavy %.The content of phosphorus is 0.03～10 heavy %, preferred 0.1～5 heavy %, more preferred 0.1～2.5 heavy %.The content of boron is 0.01～3.5 heavy %, preferred 0.02～2 heavy %, more preferred 0.02～1 heavy %.Described group VIII metal exists with the form of group VIII metal-boron or group VIII metal-phosphorus amorphous alloy and is carried in the porous carrier materials.The atomic ratio of group VIII metal and phosphorus is 0.5～10 in group VIII metal-phosphorus amorphous alloy, preferred 1～5.The atomic ratio of group VIII metal and boron is 0.5～10,0.5～5 in group VIII metal-boron amorphous alloy.
In described embodiment preferred, described catalyzer can also contain a kind of metal additive M, and described metal additive M can be except that this group VIII metal itself, can be contained H 2PO 2 -Solution be reduced into the metallic element of simple substance attitude one or more from corresponding salt.Described metal additive M can exist with the form of this group VIII metal-M-phosphorus amorphous alloy, also can with this group VIII metal-phosphorus amorphous alloy and metal additive M polycrystalline mutually the form of concurrent exist.The content of metal additive M preferred 0.01～10 heavy %, more preferred 0.01～5 heavy %
Described this group VIII metal-M-phosphorus amorphous alloy or this group VIII metal-phosphorus amorphous alloy and metal additive M polycrystalline be mutually in the concurrent, (this group VIII metal+M) atomic ratio with phosphorus is 0.5～10, preferred 1～6.The atomic ratio of this group VIII metal and M can be 0.1～1000, preferred 1～1000.The atomic ratio preferred 1～5 of group VIII metal and B in the group VIII metal of described catalyzer-B amorphous alloy.
According to the above-mentioned embodiment preferred that invention provides, described Preparation of catalysts method comprises:
1. preparation contains the porous carrier materials of group VIII metal-B amorphous alloy.Be higher than solution solidifies o'clock to 100 ℃ temperature, will containing the porous support of group VIII metal and volumetric molar concentration and be 0.5～10 the BH that contains 4 -Ion solution is by 0.1～10 boron and the group VIII metal atomic ratio contact reacts that feeds intake, with the distilled water wash solid product to there not being acid group, the porous carrier materials of group VIII metal-B amorphous alloy.
2. being higher than solution solidifies o'clock to 100 ℃ temperature, will contain porous carrier materials and a kind of H of containing of group VIII metal-B amorphous alloy 2PO 2 -With group VIII metal ionic mixing solutions contact reacts.H in the mixing solutions 2PO 2 -Volumetric molar concentration be 0.01～5, group VIII metal ionic volumetric molar concentration is 0.01～5, the atomic ratio that feeds intake of phosphorus and group VIII metal is more than 0.5, and the washing solid product promptly gets the catalyzer that contains a kind of group VIII metal, phosphorus, boron and a kind of porous carrier materials to there not being acid group.
The described porous carrier materials that contains group VIII metal can be with the commercially available group VIII metal porous carrier materials that contains, also can in carrier, introduce group VIII metal with ordinary method, as making with the salt solution impregnation porous carrier materials of solubility group VIII metal, also available other method of described dipping such as kneading method replace, when porous carrier materials was the commutative type solid support material of zeolite or molecular sieve or other, the introducing of group VIII metal also can be adopted ion exchange method.Described solubility group VIII metal salt can be selected from one or more in group VIII metal muriate, vitriol, solubility carboxylate salt, the soluble complexes, preferred muriate, acetate or soluble complexes.
The described porous carrier materials that contains group VIII metal is preferably in advance 90～200 ℃ of dryings more than 3 hours.
The described BH that contains 4 -Solution can be to contain BH 4 -The aqueous solution or alcoholic solution, described BH 4 -The ionic precursor is selected from KBH 4Or NaBH 4Or its mixture.
The described porous carrier materials and the BH that will contain group VIII metal 4 -Though the catalytic temperature of solion also can be carried out being higher than 100 ℃, but, save energy reaction is higher than solution solidifies o'clock to 100 ℃ of scopes for generally being controlled at, preferably be controlled at room temperature to 50 ℃ catalytic time visual response temperature and decide, when temperature of reaction is higher, speed of response is very fast, and the reaction times can be shorter, when temperature of reaction is low, speed of response is slower, and the reaction times also can be longer.Because of reaction the time can be emitted a large amount of hydrogen, thereby no hydrogen shows that reaction finishes when emitting, and the catalytic time refers to react the time of emitting to no hydrogen of beginning.
Described porous carrier materials and the BH that contains group VIII metal 4 -The contact reacts of solion can also can will contain BH with the two direct mixing 4 -Ion solution slowly is added drop-wise in this solid support material, preferably adopts the mode that slowly drips.
In the described porous carrier materials that contains group VIII metal-B amorphous alloy, the atomic ratio of group VIII metal and B preferred 1～5.
The described H that contains 2PO 2 -Preferably contain H with group VIII metal ionic mixing solutions 2PO 2 -With the aqueous solution of group VIII metal, described H 2PO 2 -Precursor optional from or without the KH of crystal water 2PO 2Or NaH 2PO 2Or its mixture.The precursor of described group VIII metal is selected from the salt of solubility group VIII metal, as in muriate, vitriol, the solubility carboxylate salt one or more, and preferred muriate or acetate.The atomic ratio that feeds intake of phosphorus and group VIII metal is preferred more than 1 in the solution, and best 3～7.
The weight ratio of group VIII metal can be 1～1000 in described porous carrier materials that contains group VIII metal-B amorphous alloy and the solution, preferred 5～200, more preferred 5～100.
The described H that contains 2PO 2 -With the ion that can also contain metal additive M in the group VIII metal ionic mixing solutions, the ionic volumetric molar concentration preferred 0.01～3 of metal additive M, phosphorus with (atomic ratio that feeds intake of group VIII metal+M) is more than 0.5, and is preferred more than 1, more preferred 3～7.
Described metal additive M ion can be except that used the sort of group VIII metal ion, can be contained H 2PO 2 -Solution be reduced into the metal ion of simple substance attitude one or more from corresponding salt.In described metal additive M ion preferred elements periodictable IV A family metallic element, I B family metallic element, II B-group metal element, III B family metallic element, group VIB metallic element, VII B family metallic element, the metal ion of VIII family except that this group VIII metal one or more.One or more in I B family, II B-group, group VIB, VII B family, the group VIII metal ion except that Ni in the preferred elements periodictable more.Metal additive M commonly used is selected from one or more in I B family, group VIB and the group VIII metal ion except that this group VIII metal, as in iron ion, cobalt ion, cupric ion, molybdenum acid ion, wolframate radical or the metatungstic acid radical ion one or more.
The described porous carrier materials that will contain this group VIII metal-B amorphous alloy with contain H 2PO 2 -With this group VIII metal (with the ion of metal additive M) though the catalytic temperature of mixing solutions be higher than 100 ℃ also passable, be save energy, temperature of reaction generally is controlled at and is higher than solution solidifies o'clock to 100 ℃ temperature, preferred room temperature to 50 ℃.Catalytic time visual response temperature and deciding, when temperature of reaction was higher, speed of response was very fast, and the reaction times can be shorter, and when temperature of reaction was low, speed of response was slower, and the reaction times can be longer.Because of H 2PO 2Can releasing hydrogen gas when reducing the ion of this group VIII metal ion and/or metal additive M, thereby react when no hydrogen is emitted, show that reaction finishes, the catalytic time refers to react the time of emitting to no hydrogen of beginning.
The described porous carrier materials that will contain group VIII metal-B amorphous alloy with contain H 2PO 2 -With this group VIII metal ion mixing solutions contact reacts of (with the ion of metal additive M), the two directly can be mixed and leave standstill, carry out contact reacts, under agitation carry out contact reacts after also can mixing, can also will contain H 2PO 2 -Slowly drop in the porous carrier materials that contains this group VIII metal-B amorphous alloy with this group VIII metal ionic mixing solutions, preferably adopt directly and under agitation carry out catalytic mode after the mixing.
According to an embodiment preferred more of the present invention, described catalyzer is the catalyzer that contains a kind of porous carrier materials and a kind of group VIII metal and boron, described group VIII metal and boron load on the described porous carrier materials, and the form with the amorphous alloy of group VIII metal and boron exists, the content of group VIII metal and the boron % that attaches most importance to, be preferably 1～40 heavy %, wherein the atomic ratio of group VIII metal and B is 0.5～10, preferred 1～8.
This Preparation of catalysts method is included in and is higher than solution solidifies o'clock to 100 ℃ temperature range, with the BH that contains of a kind of porous carrier materials of group VIII metal and volumetric molar concentration 0.5～10 4 -Ion solution contacts with the atomic ratio that feeds intake of group VIII metal element by 0.1～10 boron.
According to another embodiment preferred more provided by the invention, described catalyzer is the catalyzer that contains a kind of porous carrier materials, a kind of group VIII metal, boron and a kind of metal additive M.In total catalyst weight, the content of this group VIII metal, boron and metal additive M is 0.1～60 heavy %, preferred 0.1～40 heavy %, more preferred 1～40 heavy %.Wherein, (this group VIII metal+M) atomic ratio with B is 0.5～10, preferred 1～8.The atomic ratio of this group VIII metal and M is 0.1～4000, preferred 0.5～100, best 0.5～25.This group VIII metal all exists with non-crystalline state, metal additive M can form amorphous alloy with this group VIII metal and boron, form with amorphous alloy exists, and metal additive M can also exist with the form of metal additive metal polycrystalline concurrent mutually by this group VIII metal-B amorphous alloy.
This Preparation of catalysts method is included in and is higher than solution solidifies o'clock to 100 ℃ scope, with the BH that contains of a kind of porous carrier materials that contains group VIII metal and metal additive M and volumetric molar concentration 0.5～10 4 -Solution by 0.1～10 boron with (atomic ratio that feeds intake of this group VIII metal+M) contacts.The atomic ratio that feeds intake of this group VIII metal and M is 0.1～80 in the described porous carrier materials that contains this group VIII metal and metal additive M.
In method catalyst system therefor provided by the invention, a kind of in described group VIII metal element chosen from Fe, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, the platinum.Described metal additive M is selected from except that this kind group VIII metal itself, can be contained BH 4 -Or H 2PO 2 -Solution be reduced into the metallic element of simple substance attitude one or more from corresponding salt.In preferred elements periodictable IV A family metallic element, I B family metallic element, II B-group metal element, III B family metallic element, group VIB metallic element, VII B family metallic element, the metallic element of VIII family except that this kind group VIII metal itself one or more.This means, if this kind group VIII metal is a nickel, described metal additive M not only can be selected from least a IV A family metallic element, I B family metallic element, II B-group metal element, III B family metallic element, group VIB metallic element, VII B family metallic element, and, can be selected from the metallic element of at least a VIII family except that nickel.If this kind group VIII metal is a palladium, described metal additive M not only can be selected from least a IV A family metallic element, I B family metallic element, II B-group metal element, III B family metallic element, group VIB metallic element, VII B family metallic element, and, can be selected from the metallic element of at least a VIII family except that palladium.A kind of in the method catalyst system therefor provided by the invention in the preferred cobalt of group VIII metal, nickel, platinum, palladium, the iridium, described metal additive M be one or more in preferred elements periodictable IV A family metallic element, I B family metallic element, II B-group metal element, III B family metallic element, group VIB metallic element, VII B family's metallic element and the VIII family metallic element except that cobalt or nickel or platinum or palladium or iridium itself more.For example, but in the described metal additive M chosen from Fe, cobalt, ruthenium, rhodium, palladium, osmium, iridium, platinum, zinc, chromium, manganese, copper, silver, molybdenum, tungsten, group of the lanthanides, actinide metals element one or more.One or more in preferably copper, zinc, manganese, silver, molybdenum, tungsten, lanthanum, cerium, samarium, neodymium, gadolinium, iron, cobalt, ruthenium, rhodium, palladium, osmium, iridium, the platinum more.One or more in iron, cobalt, copper, zinc, manganese, silver, molybdenum, tungsten, palladium, ruthenium, iridium, lanthanum, cerium, samarium, neodymium, the gadolinium particularly.
According to method provided by the invention, the group VIII metal element all exists with non-crystalline state in the catalyst system therefor, and on the x-ray diffraction spectra with CuK α target mensuration, a ℃ diffuse maximum of locating (as shown in Figure 1) is its characteristic peak in 2 θ=45.Metal additive M can form amorphous alloy with this group VIII metal element and B and/or phosphorus, form with this group VIII metal element-M-B/P amorphous alloy exists, use this moment on the x-ray diffraction spectra of CuK α target mensuration, a ℃ diffuse maximum of locating (as shown in Figure 1) is its characteristic peak in 2 θ=45.Metal additive M can also exist with the form of metal additive metal polycrystalline concurrent mutually by group VIII metal element-B/P amorphous alloy, this moment is on the x-ray diffraction spectra that CuK α target is measured, except that the 2 θ=45 ℃ characteristic peak of locating occurring, the diffraction peak (as illustrated in Figures 5 and 6) of this metal polycrystalline phase also can appear.In some cases, the peak shape of the 2 θ=45 ℃ diffuse maximum of locating changes to some extent because of the difference of carrier, when making carrier with gac, this diffuse maximum peak shape sharper (as shown in Figure 2), under other situations, this diffuse maximum may cover (shown in Fig. 3 and 4) by suppressed by vector in the diffraction peak of same position.
According to method provided by the invention, the porous carrier materials in the used carried non-crystal alloy catalyst refers to not have the porous carrier materials of oxidisability, one or more in preferred porous inorganic oxide, gac, zeolite, the molecular sieve.Described porous inorganic oxide refers to the soild oxide of II A family in the periodic table of elements, group IIIA, IV A family element, one or more in wherein preferred silicon oxide, aluminum oxide, magnesium oxide, the calcium oxide.Described zeolite, molecular sieve refers to one or more in various types of Si-Al zeolites, the hetero-atom molecular-sieve, as A type zeolite, X type zeolite, y-type zeolite, ZSM series zeolite, mordenite, Beta zeolite, omega zeolite, phosphate aluminium molecular sieve, HTS etc.Porous carrier materials commonly used is silicon oxide, aluminum oxide or gac.
Method provided by the invention has following advantage:
(1) catalyzer of method use provided by the invention can by shape, the granularity of regulating its carrier, be regulated catalyst shape, granularity easily according to different reactors.Therefore, method provided by the invention has overcome the limitation that the prior art amorphous alloy catalyst can only be used for magnetically stabilized bed reactor, can be used for various forms of reactors, and as fixed-bed reactor, its scope of application is more extensive.
(2) catalyzer of method use provided by the invention can be adjusted the specific surface of catalyzer by the specific surface of adjusting carrier, and its specific surface can be very big, and it is active and selectivity is all higher.With traditional Mo-Co/Al that can be used for fixed bed and fluidized-bed reactor 2O 3Catalyzer is compared, and method provided by the invention can be carried out the selective hydrogenation of alkene to various reformed oils under much lower temperature.
(3) catalyzer provided by the invention contains the solid support material of relatively large cheapness, and therefore, the price of catalyst system therefor is lower, thereby has reduced process cost.
Fig. 1 be method provided by the invention make the x-ray diffraction spectra of catalyzer of the amorphous alloy of carrier in order to silicon oxide;
Fig. 2 be method provided by the invention make the x-ray diffraction spectra of the amorphous alloy catalyst of carrier in order to gac;
Fig. 3 be method provided by the invention be the x-ray diffraction spectra of the amorphous alloy catalyst of carrier in order to δ-aluminum oxide;
Fig. 4 be method provided by the invention be the x-ray diffraction spectra of the amorphous alloy catalyst of carrier in order to gama-alumina;
Fig. 5 and 6 be method provided by the invention make the x-ray diffraction spectra of catalyzer of the containing metallic additive polycrystalline amorphous alloy mutually of carrier in order to silicon oxide;
Fig. 7 be method provided by the invention be the x-ray diffraction spectra of the amorphous alloy catalyst of carrier in order to Alpha-alumina;
The following examples will the present invention will be further described, but not thereby limiting the invention.
Being described as follows of used porous carrier materials in the example: used carrier 1 (numbering Z 1) be silochrom (Haiyang Chemical Plant, Qingdao's product).Carrier 2 (numbering Z 2) be Kiselgel A (Haiyang Chemical Plant, Qingdao's product).Carrier 3 (numbering Z 3) be granular active carbon (brilliance timber mill, Beijing product).Carrier 4 (numbering Z 4) be δ-aluminum oxide, this δ-aluminum oxide is that the ball-aluminium oxide (Chang Ling catalyst plant product) that is used for the CB-8 support of the catalyst obtained through 900 ℃ of roastings in 4 hours.Carrier 5 (numbering Z 5) be gama-alumina, this gama-alumina is that the ball-aluminium oxide (Chang Ling catalyst plant product) that is used for the CB-8 support of the catalyst obtained through 650 ℃ of roastings in 4 hours.Carrier 6 (numbering Z 6) be gama-alumina, this gama-alumina is that the ball-aluminium oxide (Chang Ling catalyst plant product) that is used for the CB-6 support of the catalyst obtained through 650 ℃ of roastings in 4 hours.Carrier 7 (numbering Z 7) be gama-alumina, this gama-alumina is that long strip shape aluminum oxide (Chang Ling catalyst plant product) obtained through 650 ℃ of roastings in 4 hours.Carrier 8 (numbering Z 8) be amorphous silicon oxide (silicate institute in Shanghai City provides).Carrier 9 (numbering Z 9) be Alpha-alumina.Above-mentioned carrier Z 1～Z 9Physico-chemical property list in the table 1.Wherein, specific surface and pore volume adopt cryogenic nitrogen absorption BET method to measure, and crystalline phase adopts x-ray diffraction method to measure.
Table 1
Bearer number Bearer type Specific surface, rice 2/ gram Pore volume, milliliter/gram Crystalline phase
Z 1 SiO 2 401 0.95 Amorphous
Z 2 SiO 2 672 0.39 Amorphous
Z 3 Gac 888 0.56 Amorphous
Z 4 Al 2O 3 124 0.49 δ
Z 5 Al 2O 3 153 0.47 γ
Z 6 Al 2O 3 190 0.49 γ
Z 7 Al 2O 3 175 0.44 γ
Z 8 SiO 2 180 0.89 Amorphous
Z 9 Al 2O 3 186 0.072 α
Example 1～7
The following examples illustrate method catalyst system therefor provided by the invention and preparation thereof.
(1) contains the preparation of the porous carrier materials of Ni-B crystal alloy.
Take by weighing quantitative carrier Z respectively 1～Z 5, in 100～150 ℃ of oven dry.Take by weighing quantitative four water acetic acid nickel respectively and be made into nickel acetate aqueous solution with distilled water and flood different carriers, 120 ℃ of oven dry get nickeliferous carrier.Take by weighing quantitative KBH respectively 4, and be mixed with the aqueous solution, with KBH 4The aqueous solution at room temperature is added drop-wise in the nickeliferous carrier, and reaction is carried out and releasing hydrogen gas immediately, after dripping off, treats that no hydrogen emits, and shows that reaction finishes.The solid product that obtains with distilled water wash is to not having acid group, make the porous carrier materials S that contains the Ni-B amorphous alloy 1～S 7Table 2 has provided each material consumption of preparation process, and table 3 item has provided the porous carrier materials S that contains the Ni-B amorphous alloy that obtains 1～S 7The content of Ni-B amorphous alloy, its specific surface.Wherein boron, nickel content are gone up mensuration with the molten sample of Microwave Digestion at Jarrel-Ash1000 type inductively coupled plasma direct-reading spectrometer (ICP), and specific surface and pore volume measuring method are the same.
Table 2
Carrier Nickel acetate solution KBH 4Solution Gained contains the Ni-B bearer number
Kind Consumption, gram Four water acetic acid nickel consumptions, gram Water consumption, gram KBH 4Consumption, gram Water consumption, gram
Z 1 5.0 0.2 9.0 0.11 12.0 S 1
Z 1 5.0 0.5 9.0 0.27 12.0 S 2
Z 2 5.0 0.2 9.0 0.11 12.0 S 3
Z 3 5.0 0.5 9.0 0.27 12.0 S 4
Z 4 5.0 0.2 9.0 0.11 12.0 S 5
Z 4 5.0 1.0 5.0 0.54 7.0 S 6
Z 5 5.0 0.2 5.0 0.11 7.0 S 7
Table 3
Contain the Ni-B bearer number Ni-B content, heavy % Ni and B atomic ratio Specific surface, rice 2/ gram
S 1 0.59 3.44 396
S 2 1.57 4.63 385
S 3 0.55 1.84 652
S 4 1.56 3.41 868
S 5 0.65 3.81 125
S 6 3.96 1.27 129
S 7 0.67 3.93 155
(2) Preparation of catalysts.
Take by weighing the carrier S of the quantitative Ni-B of containing amorphous alloy respectively 1～S 6, take by weighing quantitative four water acetic acid nickel and a water sodium dihydrogen phosphite (NaH respectively 2PO 2H 2O) be dissolved in the quantitative distilled water and be made into mixing solutions.With the carrier S that contains the Ni-B amorphous alloy that weighs up 1～S 6Under differing temps, join in the mixing solutions for preparing respectively, stir, reaction is carried out on carrier immediately, and releasing hydrogen gas, behind the reaction different time, when treating that no hydrogen is emitted, show that reaction finishes, the solid product that obtains with distilled water wash makes catalyzer provided by the invention to there not being acid group, and it is numbered C 1～C 7, each material consumption and reaction conditions are listed in the table 4 in the preparation process, and table 5 item has provided catalyzer C 1～C 7Composition and physico-chemical property.Catalyzer C wherein 1～C 4Just like the X-ray diffract spectral line shown in 1 among Fig. 1, catalyzer C 5X-ray diffract spectral line is as shown in Figure 2 arranged, catalyzer C 6And C 7X-ray diffract spectral line is as shown in Figure 3 arranged.
Wherein boron, nickel, phosphorus content are gone up at Jarrel-Ash1000 type inductively coupled plasma direct-reading spectrometer (ICP) with the molten sample of Microwave Digestion and are measured; The X-ray diffract spectral line of catalyzer is measured with CuK α target on Japan's D/MAX-3A type of science X-ray diffractometer, and the catalyst specific surface measuring method is the same.
Table 4
Example number Contain Ni-B amorphous alloy carrier Mixing solutions concentration, mol The mixing solutions consumption, milliliter P and Ni atomic ratio Temperature of reaction, ℃ Reaction times, hour
Kind Consumption, gram Ni 2+ H 2PO 2 -
1 S 1 5 0.10 0.10 40 1 25 3
2 S 1 5 0.10 0.70 40 7 25 3
3 S 2 5 0.05 0.40 40 8 90 1
4 S 3 5 0.10 0.40 40 4 25 3
5 S 4 5 0.12 0.48 40 4 25 2
6 S 5 5 0.14 0.56 40 4 25 3
7 S 6 5 0.22 0.88 40 4 25 1.5
Table 5
Example number The catalyzer numbering The composition of catalyzer, heavy % Specific surface rice 2/ gram
Ni The Ni of Ni-P form P B Ni/P atomic ratio in the Ni-P alloy
1 C 1 1.55 0.99 0.11 0.03 4.75 384
2 C 2 4.45 3.89 0.62 0.03 3.31 330
3 C 3 3.21 1.70 0.37 0.06 2.42 365
4 C 4 2.79 2.29 0.27 0.05 4.47 446
5 C 5 6.46 4.98 0.63 0.08 4.17 786
6 C 6 6.16 5.54 1.79 0.03 1.63 135
7 C 7 12.96 9.50 2.71 0.50 1.84 136
Example 8～26
The following examples illustrate method catalyst system therefor provided by the invention and preparation thereof.
Take by weighing the carrier S of the quantitative Ni-B of containing amorphous alloy respectively 1, S 3, S 5～S 7, take by weighing quantitative four water acetic acid nickel, a waterside sodium dihydrogen phosphite and containing metallic additive M ionic salt respectively and be dissolved in the quantitative distilled water and be made into mixing solutions.With the carrier S that contains the Ni-B amorphous alloy that weighs up 1, S 3, S 5～S 7Join under differing temps respectively in the mixing solutions for preparing, stir, reaction is carried out on carrier and releasing hydrogen gas immediately, behind the reaction different time, when treating that no hydrogen is emitted, shows that reaction finishes.The solid product that obtains with distilled water wash makes catalyzer provided by the invention to there not being acid group, and it is numbered C 8～C 18Each material consumption and reaction conditions are listed in table 6 and the table 7 in the preparation process, and table 8 item has provided catalyzer C 8～C 18Composition and physico-chemical property.Catalyzer C wherein 8～C 11, C 13, C 17And C 18Just like the X-ray diffract spectral line shown in 1 among Fig. 1, catalyzer C 12X-ray diffract spectral line is as shown in Figure 5 arranged, catalyzer C 14And C 16X-ray diffract spectral line is as shown in Figure 3 arranged; Catalyzer C 15X-ray diffract spectral line is as shown in Figure 4 arranged.
Wherein, boron, nickel, metal additive M and phosphorus content are gone up mensuration with the molten sample of Microwave Digestion at Jarrel-Ash1000 type inductively coupled plasma direct-reading spectrometer (ICP) in the catalyzer; The measuring method of catalyzer X-ray diffract spectral line and catalyst specific surface, pore volume is the same.
Table 6
Example number 8 9 10 11 12
Carrier Kind S 1 S 1 S 1 S 1 S 1
Consumption, gram 5.0 5.0 5.0 5.0 5.0
Mixing solutions Nickel acetate concentration, mol 0.15 0.15 0.15 0.15 0.15
The salt of metal additive M Na 2MoO 4 ·2H 2O Na 2WO 4 ·2H 2O Co(CH 3COO) 2 ·4H 2O FeSO 4 ·7H 2O CuSO 4 ·5H 2O
The concentration of metal additive M, mol 0.04 0.04 0.04 0.04 0.06
NaH 2PO 2Concentration, mol 1.05 1.05 0.75 0.75 0.75
The mixing solutions consumption, milliliter 40 40 40 40 40
The P and the atomic ratio that (Ni+M) feeds intake 5.53 5.53 3.95 3.95 3.95
Ni and the M atomic ratio that feeds intake 3.75 3.75 3.75 3.75 3.75
Carrier and Ni weight ratio 14.2 14.2 14.2 14.2 14.2
Temperature of reaction, ℃ 25 50 90 8 25
Reaction times, hour 3.0 2.5 1.0 10.0 3.0
Table 7
Example number 13 14 15 16 17 18
Carrier Kind S 3 S 5 S 7 S 6 S 1 S 1
Consumption, gram 5.0 5.0 5.0 5.0 5.0 5.0
Mixing solutions Nickel acetate concentration, mol 0.15 0.15 0.15 0.30 0.02 0.45
The salt of metal additive M FeSO 4 ·7H 2O FeSO 4 ·7H 2O FeSO 4 ·7H 2O CuSO 4 ·5H 2O Na 2MoO 4 ·2H 2O Na 2MoO 4 ·2H 2O
The concentration of metal additive M, mol 0.04 0.04 0.04 0.04 0.01 0.03
NaH 2PO 2Concentration, mol 0.75 0.75 0.75 1.34 0.20 3.20
The mixing solutions consumption, milliliter 40 40 40 40 40 40
The P and the atomic ratio that (Ni+M) feeds intake 3.95 3.95 3.95 3.95 6.67 6.67
Ni and the M atomic ratio that feeds intake 3.75 3.75 3.75 3.75 2.00 15.00
Carrier and Ni weight ratio 14.2 14.2 14.2 28.4 106.5 4.73
Temperature of reaction, ℃ 25 25 25 25 25 25
Reaction times, hour 3.0 3.0 3.0 1.5 3.0 3.0
Table 8
Example number The catalyzer numbering The composition of catalyzer, heavy % Specific surface rice 2/ gram The Ni/M atomic ratio (Ni+ M)/P atomic ratio
Ni The Ni of Ni-M-P or Ni-P form Additive M P B
8 C 8 6.59 6.03 Mo 0.04 0.96 0.03 384 246 3.3
9 C 9 6.65 6.09 W 0.03 0.95 0.03 374 636 3.4
10 C 10 6.61 6.05 Co 0.09 0.90 0.03 364 67 3.6
11 C 11 6.54 5.98 Fe 0.35 1.08 0.03 341 16 3.1
12 C 12 6.80 6.24 Cu 2.88 0.88 0.03 341 2 5.3
13 C 13 6.49 5.99 Fe 0.34 0.98 0.05 338 17 3.4
14 C 14 6.60 5.98 Fe 0.34 1.01 0.03 130 17 3.3
15 C 15 6.58 5.94 Fe 0.36 1.03 0.06 162 16 3.2
16 C 16 14.14 10.68 Cu 1.91 1.66 0.50 145 6 4.0
17 C 17 1.30 0.74 Mo 0.01 0.19 0.03 398 121 2.1
18 C 18 13.34 12.78 Mo 0.04 1.45 0.03 385 522 4.7
Example 19～36
The following examples illustrate method catalyst system therefor provided by the invention and preparation thereof.
Take by weighing carrier shown in the quantitatively different tables 1 respectively,, take by weighing quantitative four water acetic acid nickel respectively and be mixed with nickel acetate solution and flood different carriers in 100～150 ℃ of oven dry, 120 ℃ dry nickeliferous carrier.Take by weighing quantitative KBH respectively 4, and be mixed with the aqueous solution.With KBH 4Solution at room temperature is added drop-wise in the nickeliferous carrier, and reaction is carried out and releasing hydrogen gas immediately, after dripping off, treat that no hydrogen is emitted after, show that reaction finishes.The solid product that obtains with distilled water wash is not to there being acid group, the catalyzer that makes be numbered C 19～C 36Each material consumption is listed in the table 9 in the preparation process, and table 10 item has provided catalyzer C 19～C 36Composition and physico-chemical property.Catalyzer C wherein 19Has X-ray diffract spectral line shown among Fig. 11, catalyzer C 20Just like the diffract spectral line of X-ray shown in 2 among Fig. 1, catalyzer C 21Just like the diffract spectral line of X-ray shown in 3 among Fig. 1, catalyzer C 22, C 25, C 26, C 27, C 28And C 30Just like the diffract spectral line of X-ray shown in 4 among Fig. 1, catalyzer C 23And C 29Just like the diffract spectral line of X-ray shown in 5 among Fig. 1, catalyzer C 24Just like the diffract spectral line of X-ray shown in 6 among Fig. 1, catalyzer C 31And C 32X-ray diffract spectral line is as shown in Figure 2 arranged, catalyzer C 33X-ray diffract spectral line is as shown in Figure 3 arranged, catalyzer C 34～C 36X-ray diffract spectral line is as shown in Figure 4 arranged.
Table 9
Example number Carrier Nickel acetate solution KBH 4Solution The B/Ni atomic ratio feeds intake
Kind Consumption, gram Four water acetic acid nickel consumptions, gram Water consumption, milliliter KBH 4Consumption, gram Water consumption, milliliter
19 Z 1 5 4 9 2.16 12 2.5
20 Z 1 5 3 9 1.62 12 2.5
21 Z 1 5 2 9 1.08 12 2.5
22 Z 1 5 1 9 0.54 12 2.5
23 Z 1 5 0.5 9 0.27 12 2.5
24 Z 1 5 0.2 9 0.11 12 2.5
25 Z 1 5 1 9 0.65 12 3.0
26 Z 1 5 1 9 0.54 12 2.5
27 Z 1 5 1 9 0.43 12 2.0
28 Z 1 5 1 9 0.33 12 1.5
29 Z 1 5 1 9 0.22 12 1.0
30 Z 2 5 1 6 0.54 8 2.5
31 Z 3 5 1 8 0.54 10 2.5
32 Z 3 5 0.95 5 0.52 7 2.5
33 Z 4 5 1 5 0.54 7 2.5
34 Z 5 5 1 5 0.54 7 2.5
35 Z 6 5 1 5 0.54 7 2.5
36 Z 7 5 1 5 0.54 7 2.5
Table 10
Example number The catalyzer numbering Ni, B content in the catalyzer Specific surface rice 2/ gram
The heavy % of Ni The heavy % of B The Ni/B atomic ratio
19 C 19 8.94 0.37 4.57 301
20 C 20 7.27 0.36 3.82 321
21 C 21 5.90 0.31 3.60 324
22 C 22 3.97 0.22 3.42 341
23 C 23 1.51 0.06 3.62 384
24 C 24 0.56 0.03 3.53 395
25 C 25 3.33 0.22 2.70 364
26 C 26 3.30 0.22 2.70 365
27 C 27 3.05 0.20 2.85 367
28 C 28 2.40 0.14 3.17 374
29 C 29 1.50 0.08 3.55 385
30 C 30 2.37 0.23 1.86 451
31 C 31 3.08 0.08 7.33 815
32 C 32 4.03 0.27 3.00 131
33 C 33 3.88 0.17 4.32 129
34 C 34 3.91 0.46 1.56 177
35 C 35 3.46 0.50 1.27 201
36 C 36 3.85 0.12 5.67 194
Example 37～58
The following examples illustrate method catalyst system therefor provided by the invention and preparation thereof.
1. take by weighing carrier Z shown in the quantitatively different tables 1 respectively 1～Z 3And Z 4～Z 5, in 120 ℃ of oven dry.Take by weighing quantitative four water acetic acid nickel respectively and also mix with quantitative cupric sulfate pentahydrate, green vitriol, Cobalt diacetate tetrahydrate, four water manganous chloride, zinc chloride, Sodium Molybdate Dihydrate respectively, add quantitative deionized water respectively and be mixed with mixing solutions.Flood different carriers respectively with the mixing solutions that is made into, 120 ℃ of oven dry get carrier nickeliferous and metal additive.Take by weighing quantitative KBH respectively 4, add quantitative deionized water and be made into the aqueous solution, at room temperature with KBH 4Drips of solution is added in the carrier of nickeliferous and metal additive, and reaction is carried out and releasing hydrogen gas immediately, after dripping off, treats that no hydrogen emits, and shows that reaction finishes.The solid product that obtains with deionized water wash promptly gets catalyzer provided by the invention to there not being acid group, and it is numbered C 37～C 46Each material consumption is listed in the table 11 in the preparation process, and table 15 has provided catalyzer C 37～C 46Boron, nickel, the content and the specific surface of metal additive.Wherein, catalyzer C 37, C 39～C 43Just like the X-ray diffract spectral line shown in 4 among Fig. 1, catalyzer C 38Just like the X-ray diffract spectral line shown in 5 among Fig. 1, catalyzer C 44And C 45X-ray diffract spectral line is as shown in Figure 3 arranged, catalyzer C 46X-ray diffract spectral line is as shown in Figure 4 arranged.
2. take by weighing quantitative carrier Z respectively 1And Z 4, in 120 ℃ of oven dry.Taking by weighing quantitative four water acetic acid nickel respectively adds quantitative deionized water and is configured to the aqueous solution.Take by weighing quantitative Sodium Molybdate Dihydrate, tungstate dihydrate acid sodium and Silver Nitrate respectively, add quantitative deionized water respectively and be configured to sodium molybdate solution, sodium tungstate solution and silver nitrate solution.Flood above-mentioned carrier with the nickel acetate solution for preparing earlier, after 120 ℃ of oven dry, flood nickeliferous carrier with the sodium molybdate solution, sodium tungstate solution and the silver nitrate solution that prepare respectively again, all the other preparation processes promptly get catalyzer provided by the invention with 1., and it is numbered C 47～C 50Each material consumption is listed in the table 12 in the preparation process.Table 15 has provided catalyzer C 47～C 50Boron, nickel, the content and the specific surface of metal additive, wherein catalyzer C 47～C 48Just like the X-ray diffract spectral line shown in 4 among Fig. 1, catalyzer C 49X-ray diffract spectral line is as shown in Figure 6 arranged, catalyzer C 50X-ray diffract spectral line is as shown in Figure 3 arranged.Boron, nickel, metal additive content in the catalyzer, the x-ray diffraction spectra of catalyzer and the measuring method of specific surface are together 1..
3. take by weighing quantitative carrier Z respectively 4, in 120 ℃ of oven dry.Take by weighing quantitative four water acetic acid nickel and cupric sulfate pentahydrate respectively and add quantitative deionized water and be made into the mixing solutions that contains nickel acetate and copper sulfate.Take by weighing quantitative Silver Nitrate, add quantitative deionized water and be made into silver nitrate aqueous solution.With the solution impregnating carrier that contains nickel acetate and copper sulfate, flood with silver nitrate solution again after 120 ℃ of oven dry earlier, 120 ℃ of oven dry, all the other preparation processes get catalyzer provided by the invention with 1., and it is numbered C 51～C 56Each material consumption is listed in the table 13 in the preparation process.Table 15 item has provided catalyzer C 51～C 56Boron, nickel, the content and the specific surface of metal additive, catalyzer C 51～C 56X-ray diffract spectral line is as shown in Figure 3 arranged.The measuring method of the x-ray diffraction spectra of the content of boron, nickel metal additive, catalyzer and specific surface together 1. in the catalyzer.
4. take by weighing quantitative carrier Z respectively 1, in 120 ℃ of oven dry.Take by weighing quantitative four water acetic acid nickel, Sodium Molybdate Dihydrate, tungstate dihydrate acid sodium respectively, and add quantitative deionized water respectively and be configured to separately the aqueous solution.Difference with Sodium Molybdate Dihydrate solution, tungstate dihydrate acid sodium solution impregnated carrier, is flooded with four water acetic acid nickel respectively after 120 ℃ of oven dry earlier again, 120 ℃ of oven dry, and all the other preparation processes get catalyzer provided by the invention with 1., and it is numbered C 57～C 58Each material consumption is listed in the table 14 in the preparation process.Table 15 has provided catalyzer C 57～C 58Boron, nickel, the content and the specific surface of metal additive, catalyzer C 57～C 58Just like the X-ray diffract spectral line shown in 4 among Fig. 1.The measuring method of the x-ray diffraction spectra of the content of boron, nickel, metal additive, catalyzer and specific surface together 1. in the catalyzer.
Table 11
Example number Carrier The salt of containing metallic additive M and the solution of nickel acetate KBH 4Solution Ni and the M atomic ratio that feeds intake The atomic ratio that feeds intake of B (Ni+ M)
Kind The consumption gram Four water acetic acid nickel consumptions, gram The salt of metal additive M and consumption, gram Water consumption, gram KBH 4Consumption, gram Water consumption, gram
37 Z 1 5 1 CuSO 4·5H 2O 0.25 9 0.56 12 4.01 2.07
38 Z 1 5 1 FeSO 4·7H 2O 0.28 9 0.56 12 3.99 2.07
39 Z 1 5 1 Co(CH 3COO) 2·4H 2O 0.25 9 0.56 12 4.00 2.07
40 Z 1 5 1 MnCl 2·4H 2O 0.20 9 0.56 12 3.98 2.06
41 Z 1 5 1 ZnCl 2 0.15 9 0.56 12 3.65 2.03
42 Z 1 5 1 Na 2MoO 4·2H 2O 0.25 9 0.79 12 3.89 2.05
43 Z 2 5 1 CuSO 4·5H 2O 0.25 6 0.56 8 4.01 2.07
44 Z 4 5 1 CuSO 4·5H 2O 0.25 5 0.56 7 4.01 2.07
45 Z 4 5 1 ZnCl 2 0.15 5 0.56 7 3.65 2.03
46 Z 5 5 1 CuSO 4·5H 2O 0.25 5 0.56 7 4.01 2.07
Table 12
Example number Carrier Nickel acetate solution The salts solution of metal additive KBH 4Solution Ni and the M atomic ratio that feeds intake The atomic ratio that feeds intake of B and (Ni+ M)
Kind Consumption, gram Four water acetic acid nickel consumptions, gram Water consumption, gram The salt of metal additive and consumption, gram Water consumption, gram KBH 4Consumption, gram Water consumption, gram
47 Z 1 5 1 9 Na 2MoO 4 ·2H 2O 0.25 9 0.79 12 3.89 2.89
48 Z 1 5 1 9 Na 2WO 4·2H 2O 0.33 9 0.79 12 4.02 2.94
49 Z 1 5 1 9 AgNO 3 0.16 9 0.68 12 4.23 2.54
50 Z 4 5 1 5 AgNO 3 0.16 9 0.68 7 4.23 2.54
Table 13
Example number Carrier Contain CuSO 4Solution with nickel acetate KBH 4Solution The Ni/M atomic ratio that feeds intake The atomic ratio that feeds intake of B/ (Ni+ M)
Kind Consumption, gram Four water acetic acid nickel consumptions, gram CuSO 4 ·5H 2The O consumption, gram The water consumption gram AgNO 3Consumption, gram Water consumption, milliliter KBH 4The consumption gram Water consumption, gram
51 Z 4 5 1 0.06 5 0.04 5 0.5 7 8.41 2.06
52 Z 4 5 1 0.06 5 0.02 5 0.5 7 11.19 2.12
53 Z 4 5 1 0.12 5 0.04 5 0.5 7 5.59 1.96
54 Z 4 5 1 0.06 5 0.16 5 0.7 7 3.38 2.49
55 Z 4 5 1 0.12 5 0.16 5 0.7 7 2.81 2.38
56 Z 4 5 2.24 0.24 5 0.16 5 1.1 7 2.10 3.44
Table 14
Example number Carrier Nickel acetate solution The salts solution of metal additive KBH 4Solution Ni and the M atomic ratio that feeds intake The atomic ratio that feeds intake of B and (Ni+ M)
Kind Consumption, gram Four water acetic acid nickel consumptions, gram Water consumption, gram The salt of metal additive and consumption, gram Water consumption, gram KBH 4Consumption, gram Water consumption, gram
57 Z 1 5 1 9 Na 2MoO 4·2H 2O 0.25 9 0.79 12 3.89 2.89
58 Z 1 5 1 9 Na 2WO 4·2H 2O 0.33 9 0.79 12 4.02 2.94
Table 15
Example number The catalyzer numbering The content of Ni, B and metal additive M in the catalyzer, heavy % (Ni+M)/the B atomic ratio The Ni/M atomic ratio Specific surface, rice 2/ gram
37 C 37 Ni 3.64；Cu 1.18；B 0.22 3.76 3.39 356
38 C 38 Ni 0.37；Fe 1.09；B 0.17 5.25 3.20 358
39 C 39 Ni 3.57；Co 0.89；B 0.24 3.35 4.13 362
40 C 40 Ni 3.10；Mn 0.89；B 0.14 5.25 3.20 371
41 C 41 Ni 2.79；Zn 1.80；B 0.13 6.14 1.77 329
42 C 42 Ni 3.49；Mo 1.93；B 0.15 5.67 3.05 357
43 C 43 Ni 3.16；Cu 1.12；B 0.38 2.03 2.94 451
44 C 44 Ni 3.65；Cu 0.95；B 0.30 2.85 3.93 131
45 C 45 Ni 4.17；Zn 1.36；B 0.34 2.85 3.63 146
46 C 46 Ni 3.79；Cu 1.13；B 0.23 4.56 3.44 165
47 C 47 Ni 3.58；Mo 1.91；B 0.17 5.25 3.00 359
48 C 48 Ni 3.50；W 2.50；B 0.17 4.56 4.47 320
49 C 49 Ni 4.17；Ag 2.22；B 0.24 4.00 3.44 315
50 C 50 Ni 4.04；Ag 1.22；B 0.23 3.76 6.18 140
51 C 51 Ni 3.81；Cu 0.24； Ag 0.45；B 0.40 1.94 8.43 131
52 C 52 Ni 3.99；Cu 0.26； Ag 0.23；B 0.38 2.13 10.3 3 130
53 C 53 Ni 3.93；Cu 0.56； Ag 0.45；B 0.42 2.03 5.09 138
54 C 54 Ni 4.12；Cu 0.28 ； Ag 1.79；B 0.38 2.57 3.50 157
55 C 55 Ni 3.84；Cu 0.55； Ag 1.79；B 0.39 2.57 2.60 156
56 C 56 Ni 7.42；Cu 0.90； Ag 1.79；B 1.19 1.44 3.91 165
57 C 57 Ni 3.09；Mo 1.21；B 0.14 4.88 4.19 364
58 C 58 Ni 2.93；W 0.52；B 0.14 4.00 19.0 0 370
Example 59～60
Following example illustrates the preparation of method catalyst system therefor provided by the invention.
1. take by weighing quantitatively different above-mentioned carrier Z respectively 8And Z 9, in 120 ℃ of oven dry.Take by weighing two parts of quantitative nickelous chlorides and cobalt chloride respectively and be dissolved in the mixing solutions that is made into two parts of nickelous chlorides and cobalt chloride in two parts of quantitative deionized waters.Mixing solutions with described nickelous chloride and cobalt chloride floods described carrier Z respectively 8And Z 9, oven dry.Drip the quantitative POTASSIUM BOROHYDRIDE aqueous solution, after dripping off, treat that no hydrogen emits, with the deionized water wash solid product to there not being acid group, amorphous alloy catalyst C provided by the invention 59～C 60Each raw material consumption is listed in the table 16, and table 17 has provided catalyzer C 59～C 60Boron, nickel, metal additive content and specific surface.Wherein, catalyzer C 59Just like the X-ray diffract spectral line shown in 1 among Fig. 1.Catalyzer C 60Just like the X-ray diffract spectral line shown in 7 among Fig. 7.8 is X-ray diffract spectral lines of alpha-alumina supports among Fig. 7, and 9 is X-ray diffract spectral lines of amorphous alloy after the deduction alpha-alumina supports background among Fig. 7.
Table 16
Example number Carrier Mixing solutions The POTASSIUM BOROHYDRIDE aqueous solution Ni and the M atomic ratio that feeds intake The B and the atomic ratio that (Ni+M) feeds intake
Type Consumption, gram The nickelous chloride consumption, gram The cobalt chloride consumption, gram Water consumption, gram Concentration, mol Consumption, milliliter
59 Z 8 10 4.4 4.4 50 1 100 1.00 1.47
60 Z 9 10 4.4 4.4 50 1 100 1.00 1.47
Table 17
Example number The catalyzer numbering The content of Ni, B and metal additive M in the catalyzer, heavy % (Ni+Co)/the B atomic ratio The Ni/Co atomic ratio Specific surface, rice 2/ gram
59 C 59 Ni 10.3；Co 10.1；B 1.0 3.75 1.02 129
60 C 60 Ni 6.1；Co 7.1；B 0.77 3.15 0.86 15
Example 61～68
Following example illustrates the preparation of method catalyst system therefor provided by the invention.
Take by weighing quantitative above-mentioned carrier Z respectively 8In 120 ℃ of oven dry.The muriate that takes by weighing quantitative nickelous chloride and quantitatively different metal additive M respectively is dissolved in being made in the quantitative deionized water and contains nickel ion and metal additive M ionic mixing solutions, floods described carrier Z respectively with described mixing solutions 8, oven dry.Drip the quantitative POTASSIUM BOROHYDRIDE aqueous solution, after dripping off, treat that no hydrogen emits, with the deionized water wash solid product to there not being acid group, amorphous alloy catalyst C provided by the invention 61～C 68Each material consumption is listed in the table 18 in the preparation process.Table 19 has provided catalyzer C 61～C 68Boron, nickel, content and the specific surface of metal additive M.Catalyzer C 61～C 68All just like the X-ray diffract spectral line shown in 1 among Fig. 1.
Table 18
Example number Carrier The salt of containing metallic additive M and the solution of nickel salt KBH 4Solution Ni and the M atomic ratio that feeds intake B and the atomic ratio that feeds intake (Ni+M)
Kind Consumption, gram The nickelous chloride consumption, gram The salt of metal additive M and consumption, gram Water consumption, gram KBH 4Consumption, gram Water consumption, gram
61 Z 8 10 3.2 PdCl 2,0.4 40 5.4 100 10.95 3.72
62 Z 8 10 3.2 RuCl 3,0.4 40 5.4 100 12.83 3.76
63 Z 8 10 3.2 IrCl 4,0.7 40 5.4 100 11.79 3.73
64 Z 8 10 4.3 CeCl 3,5.0 40 5.4 100 1.63 1.87
65 Z 8 10 4.3 LaCl 3,5.0 40 5.4 100 1.63 1.87
66 Z 8 10 4.3 SmCl 3,5.0 40 5.4 100 1.71 1.90
67 Z 8 10 4.3 Nd(NO 3) 3,7.0 40 5.4 100 1.57 1.84
68 Z 8 10 4.3 Gd(NO 3) 3,7.0 40 5.4 100 1.63 1.87
Table 19
Example number The catalyzer numbering The content of Ni, B and metal additive M in the catalyzer, heavy % (Ni+ M)/B atomic ratio The Ni/M atomic ratio Specific surface, rice 2/ gram
61 C 61 Ni 10.10；Pd 1.81；B 0.64 3.19 10.11 137
62 C 62 Ni 10.00；Ru 1.68；B 0.64 3.16 10.25 146
63 C 63 Ni 10.10；Ir 3.30；B 0.65 3.15 10.02 135
64 C 64 Ni 10.20；Ce 24.30；B 1.18 3.18 1.00 125
65 C 65 Ni 10.20；La 24.00；B 1.18 3.17 1.00 125
66 C 66 Ni 10.30；Sm 26.0；B 1.19 3.16 1.02 128
67 C 67 Ni 10.2；Nd 25.00；B 1.18 3.18 1.00 122
68 C 68 Ni 10.40；Gd 27.30；B1.19 3.19 1.02 122
Example 69～70
Following example illustrates the preparation of method catalyst system therefor provided by the invention.
Take by weighing quantitative above-mentioned carrier Z respectively 8, in 120 ℃ of oven dry.Take by weighing quantitative PdCl respectively 2And LaCl 3Be dissolved in the quantitative deionized water and be made into PdCl 2And LaCl 3Mixing solutions.Flood described carrier Z with described mixing solutions 5, oven dry.Drip the quantitative POTASSIUM BOROHYDRIDE aqueous solution, after dripping off, treat that no hydrogen emits, with the deionized water wash solid product to there not being acid group, amorphous alloy catalyst C provided by the invention 69Method catalyst system therefor C provided by the invention 70The preparation method the same, just with PdCl 2And LaCl 3The RuCl that changes into 3And CeCl 3Each material consumption is listed in table 20 and 21 in the preparation process.Table 22 has provided catalyzer C 69～C 70Each component concentration and specific surface.Catalyzer C 69Just like the X-ray diffract spectral line shown in 6 among Fig. 1.Catalyzer C 70Just like the X-ray diffract spectral line shown in 1 among Fig. 1.
Table 20
Example number Carrier Mixing solutions KBH 4Solution Pd and the La atomic ratio that feeds intake B and the (atomic ratio that feeds intake of Pd+La)
Kind Consumption, gram PdCl 2Consumption, gram LaCl 3Consumption, gram Water consumption, gram Concentration, M Solution usage, milliliter
69 Z 8 10 0.084 0.1 50 1.0 21 1.00 1.47
Table 21
Example number Carrier Mixing solutions KBH 4Solution Ru and the Ce atomic ratio that feeds intake B and the (atomic ratio that feeds intake of Ru+Ce)
Kind Consumption, gram RuCl 3Consumption, gram CeCl 3, consumption, gram Water consumption, gram Concentration, M Solution usage, milliliter
70 Z 8 10 1.6 1.9 50 1.0 200 1.00 1.47
Table 22
Example number The catalyzer numbering The content of Pd or Ru, B and metal additive M in the catalyzer, heavy % (Pd or Ru+M)/the B atomic ratio Pd or Ru/M atomic ratio Specific surface, rice 2/ gram
69 C 69 Pd 0.5；La 0.6；B 0.029 3.65 1.00 139
70 C 70 Ru 8.0；Ce 9.0；B 1.43 3.22 1.00 121
Example 71～77
Following example illustrates method provided by the invention.
With 10 milliliters of granularities 0.15～0.2 millimeter catalyzer C 1～C 7Be respectively charged into internal diameter and be in 14 millimeters the fixed-bed reactor.100 ℃ of temperature of reaction, reaction pressure 1 MPa, liquid hourly space velocity 5 hours -1, be 2.1 grams/100 grams to the bromine valency under the condition of hydrogen to oil volume ratio 100, aromaticity content is that the reformed oils of 57.66 heavy % carry out hydrogenation, reaction result is listed in the table 23.Wherein, aromaticity content adopts gas chromatographic analysis.The measuring method of bromine valency is referring to " petrochemical complex analytical procedure " (RIPP test method) P172～175, Science Press, 1990
Table 23
Example number The catalyzer numbering Product bromine valency, gram/100 grams Aromaticity content, heavy %
71 C 1 0.32 57.71
72 C 2 0.26 57.70
73 C 3 0.12 57.71
74 C 4 0.08 57.68
75 C 5 0.05 57.70
76 C 6 0.18 57.67
77 C 7 0.24 57.72
Example 78～88
Following example illustrates method provided by the invention.
Method by example 70～77 is carried out hydrogenation to same reformed oil, and different is that catalyst system therefor is respectively C 8～C 18, reaction result is listed in the table 24.
Table 24
Example number The catalyzer numbering Product bromine valency, gram/100 grams Aromaticity content, heavy %
78 C 8 0.14 57.67
79 C 9 0.10 57.24
80 C 10 0.11 57.71
81 C 11 0.12 57.44
82 C 12 0.12 57.68
83 C 13 0.16 57.77
84 C 14 0.23 57.66
85 C 15 0.20 57.72
86 C 16 0.11 57.49
87 C 17 0.10 57.55
88 C 18 0.10 57.62
Example 89～106
Following example illustrates method provided by the invention.
Method by example 70～77 is carried out hydrogenation to same reformed oil, and different is that catalyst system therefor is respectively C 19～C 38, reaction result is listed in the table 25.
Table 25
Example number The catalyzer numbering Product bromine valency, gram/100 grams Aromaticity content, heavy %
89 C 19 0.08 57.66
90 C 20 0.07 57.71
91 C 21 0.05 57.64
92 C 22 0.09 57.72
93 C 23 0.11 57.71
94 C 24 0.14 57.68
95 C 25 0.09 57.68
96 C 26 0.09 57.71
97 C 27 0.11 57.59
98 C 28 0.14 57.61
99 C 29 0.19 57.66
100 C 30 0.11 57.71
101 C 31 0.17 57.69
102 C 32 0.19 57.64
103 C 33 0.21 57.62
104 C 34 0.17 57.71
105 C 35 0.17 57.74
106 C 36 0.15 57.69
Example 107～128
Following example illustrates method provided by the invention.
Method by example 70～77 is carried out hydrogenation to same reformed oil, and different is that catalyst system therefor is respectively C 37～C 58, reaction result is listed in the table 26.
Table 26
Example number The catalyzer numbering Product bromine valency, gram/100 grams Aromaticity content, heavy %
107 C 37 0.24 57.71
108 C 38 0.31 57.66
109 C 39 0.24 57.72
110 C 40 0.42 57.71
111 C 41 0.34 57.70
112 C 42 0.21 57.72
113 C 43 0.24 57.66
114 C 44 0.24 57.68
115 C 45 0.33 57.71
116 C 46 0.21 57.64
117 C 47 0.17 57.68
118 C 48 0.15 57.59
119 C 49 0.41 57.63
120 C 50 0.44 57.67
121 C 51 0.37 57.66
122 C 52 0.41 57.66
123 C 53 0.39 57.71
124 C 54 0.39 57.74
125 C 55 0.38 57.81
126 C 56 0.37 57.67
127 C 57 0.19 57.67
128 C 58 0.17 57.68
Example 129
Following example illustrates method provided by the invention.
Method by example 70～77 is carried out hydrogenation to same reformed oil, and different is that catalyst system therefor is respectively C 59, reaction result is listed in the table 27.
Table 27
Example number The catalyzer numbering Product bromine valency, gram/100 grams Aromaticity content, heavy %
129 C 59 0.44 57.71
Example 130～137
Following example illustrates method provided by the invention.
Method by example 70～77 is carried out hydrogenation to same reformed oil, and different is that catalyst system therefor is respectively C 61～C 68, reaction result is listed in the table 28.
Table 28
Example number The catalyzer numbering Product bromine valency, gram/100 grams Aromaticity content, heavy %
130 C 61 0.22 57.66
131 C 62 0.24 57.72
132 C 63 0.19 57.72
133 C 64 0.33 57.60
134 C 65 0.37 57.64
135 C 66 0.41 57.71
136 C 67 0.44 57.61
137 C 68 0.57 57.67
Example 138～139
Following example illustrates method provided by the invention.
Method by example 70～77 is carried out hydrogenation to same reformed oil, and different is that catalyst system therefor is respectively C 69～C 70, reaction result is listed in the table 29.
Table 29
Example number The catalyzer numbering Product bromine valency, gram/100 grams Aromaticity content, heavy %
138 C 69 0.14 57.67
139 C 70 0.11 57.66
Example 140～144
Following example illustrates method provided by the invention.
Method by example 70～77 is carried out hydrogenation to same reformed oil, and different is that catalyst system therefor is C 21, reaction pressure 1 MPa, liquid hourly space velocity 6 hours -1, hydrogen to oil volume ratio 120, the reaction result under the differential responses temperature is listed in the table 30.
Table 30
Example number Temperature of reaction, ℃ Product bromine valency, gram/100 grams Aromaticity content, heavy %
140 50 0.14 57.70
141 70 0.12 57.72
142 100 0.09 57.64
143 120 0.09 57.16
144 150 0.08 57.32
Example 145～148
Following example illustrates method provided by the invention.
Method by example 70～77 is carried out hydrogenation to same reformed oil, and different is that catalyst system therefor is C 21, 100 ℃ of temperature of reaction, liquid hourly space velocity 6 hours -1, hydrogen to oil volume ratio 120, the reaction result under the differential responses pressure is listed in the table 31.
Table 31
Example number Reaction pressure, MPa Product bromine valency, gram/100 grams Aromaticity content, heavy %
145 0.3 0.16 57.81
146 0.5 0.12 57.66
147 1.0 0.09 57.64
148 1.5 0.08 57.72
Example 149～152
Following example illustrates method provided by the invention.
Method by example 70～77 is carried out hydrogenation to same reformed oil, and different is that catalyst system therefor is C 21, 100 ℃ of temperature of reaction, reaction pressure 1 MPa, hydrogen to oil volume ratio 120, the reaction result under the different liquid hourly space velocitys is listed in the table 32.
Table 32
Example number Liquid hourly space velocity, hour -1 Product bromine valency, gram/100 grams Aromaticity content, heavy %
149 3 0.06 57.60
150 6 0.09 57.64
151 9 0.14 57.62
152 12 0.20 57.70
Example 153～156
Following example illustrates method provided by the invention.
Method by example 70～77 is carried out hydrogenation to same reformed oil, and different is that catalyst system therefor is C 21, 100 ℃ of temperature of reaction, reaction pressure 1 MPa, liquid hourly space velocity 6 hours -1, the reaction result under the different hydrogen to oil volume ratio is listed in the table 33.
Table 33
Example number Hydrogen to oil volume ratio Product bromine valency, gram/100 grams Aromaticity content, heavy %
153 60 0.12 57.65
154 120 0.09 57.64
155 200 0.07 57.67
156 300 0.06 57.62

Claims (27)

1. reformed oil olefine saturation hydrogenation method, this method is included under a kind of existence of catalyzer reformed oil is contacted with hydrogen, it is characterized in that, the condition of described contact is 50～200 ℃ of temperature of reaction, reaction pressure is greater than 0.1 MPa, liquid hourly space velocity 0.1～20 hour-1, hydrogen to oil volume ratio is greater than 30; Described catalyzer is a kind of carried non-crystal alloy catalyst, this catalyzer contains a kind of porous carrier materials, a kind of group VIII metal and is selected from one or both elements in boron, the phosphorus, described group VIII metal element exists with the form of the amorphous alloy of group VIII metal and boron or group VIII metal and phosphorus and is carried in the porous carrier materials, the content of described group VIII metal and boron and/or phosphorus is 0.1～60 heavy %, and the atomic ratio of group VIII metal element and boron and/or phosphorus is 0.5～10.
2. method according to claim 1, the condition that it is characterized in that described contact are 50～150 ℃ of temperature of reaction, and reaction pressure is 0.1～3 MPa, and liquid hourly space velocity is 1～15 hour-1, and hydrogen to oil volume ratio is 30～150.
3. method according to claim 2 is characterized in that described reaction pressure is 0.1～2 MPa, and hydrogen to oil volume ratio is 50～100.
4. method according to claim 1 is characterized in that described contact carries out in fixed-bed reactor.
5. method according to claim 1, it is characterized in that in the described carried non-crystal alloy catalyst except that containing a kind of porous carrier materials, a kind of group VIII metal and being selected from one or both elements in boron, the phosphorus, also contain metal additive, the atomic ratio of this group VIII metal element and metal additive is 0.1～1000, described metal additive can be contained BH except that this group VIII metal element itself 4 -Or H 2PO 2 -Solution be reduced into the metallic element of simple substance attitude one or more from corresponding salt; Described metal additive exists with the form of this group VIII metal element-metal additive-boron or phosphorus amorphous alloy, and perhaps the form with this group VIII metal element-boron or phosphorus amorphous alloy and metal additive metal polycrystalline concurrent mutually exists.
6. method according to claim 5 is characterized in that the atomic ratio of described this group VIII metal element and metal additive is 0.5～700.
7. method according to claim 1, it is characterized in that described catalyzer contains a kind of metallic element, phosphorus, boron and a kind of porous carrier materials that is selected from VIII family, with the total catalyst weight is benchmark, the content of group VIII metal is 0.15～30 heavy %, the content of phosphorus is 0.03～10 heavy %, and the content of boron is 0.01～3.5 heavy %; Group VIII metal exists with the form of group VIII metal-boron or group VIII metal-phosphorus amorphous alloy and is carried in the porous carrier materials, in group VIII metal-phosphorus amorphous alloy, the atomic ratio of group VIII metal and phosphorus is 0.5～10, in group VIII metal-boron amorphous alloy, the atomic ratio of group VIII metal and boron is 0.5～10.
8. method according to claim 7, the content that it is characterized in that described group VIII metal are 1～15 heavy %, and the content of phosphorus is 0.1～2.5 heavy %, and the content of boron is 0.02～1 heavy %.
9. method according to claim 7 is characterized in that in described group VIII metal-phosphorus amorphous alloy, the atomic ratio of group VIII metal and phosphorus is 1～5, and in group VIII metal-boron amorphous alloy, the atomic ratio of group VIII metal and boron is 0.5～5.
10. method according to claim 7 is characterized in that described catalyzer can also contain a kind of metal additive, and the content of metal additive is 0.01～10 heavy %; Described metal additive with this group VIII metal-metal additive-phosphorus amorphous alloy or this group VIII metal-phosphorus amorphous alloy and metal additive polycrystalline mutually the form of concurrent exist; Described metal additive can be except that this group VIII metal itself, can be contained H 2PO 2 -Solution be reduced into the metallic element of simple substance attitude one or more from corresponding salt; Described this group VIII metal-metal additive-phosphorus amorphous alloy or this group VIII metal-phosphorus amorphous alloy and metal additive polycrystalline are mutually in the concurrent, this group VIII metal and metal additive and atomic ratio phosphorus are 0.5～10, and the atomic ratio of this group VIII metal and metal additive is 0.1～1000; The atomic ratio of this group VIII metal and boron is 1～5 in this group VIII metal-boron amorphous alloy of described catalyzer.
11. method according to claim 10, the content that it is characterized in that described metal additive are 0.01～5 heavy %; Described this group VIII metal-metal additive-phosphorus amorphous alloy or this group VIII metal-phosphorus amorphous alloy and metal additive polycrystalline are mutually in the concurrent, the atomic ratio of this group VIII metal and metal additive and P is 1～6, and the atomic ratio of this group VIII metal and metal additive is 1～700.
12. method according to claim 1, it is characterized in that described catalyzer is the catalyzer that contains a kind of porous carrier materials and a kind of group VIII metal and boron, described group VIII metal and boron load on the described porous carrier materials, and the form with the amorphous alloy of group VIII metal and boron exists, the content of group VIII metal and boron is 0.1～60 heavy %, wherein, the atomic ratio of group VIII metal and boron is 0.5～10.
13. method according to claim 12, the content that it is characterized in that described group VIII metal and boron are 1～40 heavy %, the atomic ratio of group VIII metal and boron is 1～8.
14. method according to claim 1, it is characterized in that described catalyzer is the catalyzer that contains a kind of porous carrier materials, a kind of group VIII metal, boron and a kind of metal additive, in total catalyst weight, the content of this group VIII metal, boron and metal additive is 0.1～60 heavy %, wherein, the atomic ratio of this group VIII metal and metal additive and boron is 0.5～10, and the atomic ratio of this group VIII metal and metal additive is 0.1～1000; Described metal additive refers to except that this group VIII metal itself, can be contained BH 4 -Solution be reduced into the metallic element of simple substance attitude one or more from corresponding salt; Described this group VIII metal exists with non-crystalline state, and metal additive exists with the form of amorphous alloy, or exists with the form of this group VIII metal-boron amorphous alloy with metal additive metal polycrystalline concurrent mutually.
15. method according to claim 14, the content that it is characterized in that this group VIII metal, boron and metal additive are 0.1～40 heavy %.
16. method according to claim 15, the content that it is characterized in that this group VIII metal, boron and metal additive are 1～40 heavy %.
17. method according to claim 14, the atomic ratio that it is characterized in that this group VIII metal and metal additive and boron is 1～8; The atomic ratio of this group VIII metal and metal additive is 0.5～100.
18. method according to claim 17, the atomic ratio that it is characterized in that this group VIII metal and metal additive is 0.5～25.
19., it is characterized in that a kind of in described group VIII metal chosen from Fe, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, the platinum according to any described method in claim 1 and 5～18.
20. method according to claim 19 is characterized in that described group VIII metal is selected from a kind of in cobalt, nickel, platinum, palladium, the iridium.
21., it is characterized in that described metal additive is selected from periodic table of elements IV A family metallic element, I B family metallic element, II B-group metal element, III B family metallic element, group VIB metallic element, VII B family's metallic element and VIII family and requires in a kind of metallic element itself in the 19 described elements one or more except that right according to any described method in claim 10～11 and 14～18.
22. method according to claim 21, it is characterized in that in described metal additive chosen from Fe, cobalt, ruthenium, rhodium, palladium, osmium, iridium, platinum, zinc, chromium, manganese, copper, silver, molybdenum, tungsten, group of the lanthanides, the actinide metals element in one or more.
23. method according to claim 22 is characterized in that described metal additive is selected from one or more in copper, zinc, manganese, silver, molybdenum, tungsten, lanthanum, cerium, samarium, neodymium, gadolinium, iron, cobalt, ruthenium, rhodium, palladium, osmium, iridium, the platinum.
24. method according to claim 23 is characterized in that in described metal additive chosen from Fe, cobalt, copper, zinc, manganese, silver, molybdenum, tungsten, palladium, ruthenium, iridium, lanthanum, cerium, samarium, neodymium, the gadolinium one or more.
25., it is characterized in that described porous carrier materials is selected from one or more in porous inorganic oxide, gac, zeolite, the molecular sieve according to any described method in the claim 1,5,7,12,14.
26. method according to claim 25 is characterized in that described porous inorganic oxide is selected from one or more in silicon oxide, aluminum oxide, magnesium oxide, the calcium oxide; In A type zeolite, X type zeolite, y-type zeolite, ZSM series zeolite, mordenite, Beta zeolite, omega zeolite, phosphate aluminium molecular sieve, HTS one or more of described zeolite, molecular screening.
27. method according to claim 25 is characterized in that described porous carrier materials is silicon oxide, aluminum oxide or gac.
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CN102851075B (en) * 2011-06-30 2015-04-29 中国石油化工股份有限公司 Catalytic reforming back-end hydrogenation method
CN105601464B (en) * 2015-12-31 2017-12-05 浙江工业大学 A kind of catalytic hydrogenation method for reducing linear alkylbenzene (LAB) bromine index

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CN1163879A (en) * 1996-02-03 1997-11-05 克鲁普犹德有限公司 Procedure for generating pure aromatics from reformed gasoline and device for implementing the procedure

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