CN101380590A - Selective hydrogenation catalyst for carbon five fraction and preparation and use thereof - Google Patents
Selective hydrogenation catalyst for carbon five fraction and preparation and use thereof Download PDFInfo
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Abstract
The invention provides a selective hydrogenation catalyst for C5 fraction. The catalyst takes a compound of alumina and molecular sieves as a carrier and takes metals in the IA or IIA group, the VIII group, the IVA group and the IB group as active components. The compound carrier is soaked in aqueous solution of metallic compound in the IA/IIA group and is soaked in water soluble salt solution of the metals in the VIII group, nitrate solution of the metals in the IVA group and nitrate solution of the metals in the IB group by one step or multiple steps; after being soaked by one step, the compound carrier is dried for 12-20h at the temperature of 80-200 DEG.C, and then is calcined for 1-12 hours at the temperature of 350-650 DEG C. When the selective hydrogenation is carried out on unsaturated compounds in the C5 fraction by the catalyst, the transformation ratio of alkyne hydrogenation is more than or equal to 45%, the transformation ratio of dialkene is 15-35%, the content of alpha position olefin after hydrogenation is more than or equal to 15% and can meet the need of producing alpha-resin with high quality in the process of subsequent production, thus improving the quality of the alpha-resin products.
Description
Technical field
The invention belongs to chemical field, relate to a kind of hydrogenation catalyst, relate in particular to the catalyst that a kind of C5 fraction selective hydrogenation is used, also relate to this catalyst carries out selective hydrogenation to the unsaturated compound in the C5 fraction material method simultaneously.Specifically, the present invention relates to a kind of is multimetal reforming catalyst of complex carrier and preparation method thereof with aluminium oxide and molecular sieve, and relates to a kind of this catalyst carries out selective hydrogenation to alkynes in the C5 fraction and alkadienes method.
Background technology
The C5 fraction that petroleum cracking system ethylene by-product is a large amount of, its output is about 10%～30% of ethylene production capacity.The composition of C 5 fraction is very complicated, and 30 various ingredients are arranged approximately, and wherein the alkadienes total amount accounts for 40%～60% of cracking c5 cut, and these alkadienes are the important source material of producing synthetic rubber, plastics, Petropols and various fine chemical products.But because complexity is formed in C5 fraction, boiling point is approaching and easily generate azeotropic mixture each other, causes these component separation difficulty, and is still very limited to the utilization of cracking C 5 fraction at present, has most of cracking c5 to be used as fuel, caused the significant wastage of resource.For the cracking C 5 fraction more effectively is used, it is carried out the catalytic selectivity hydrotreatment, product uses as synthetic carbon five resin raw materials, can improve its added value well.The alkynes of trace and excessive alkadienes produce injurious effects to follow-up polymerization catalyst in the C5 fraction; From the high Petropols of the quality of production, the selective hydrogenation of alkynes and alkadienes generation α position monoolefine is more satisfactory in the C5 fraction in addition.
Alkynes in the C5 fraction is carried out selective hydrogenation, thereby the method that obtains carbon five dienes of high concentration has a spot of open.Promptly all or part of alkynes in the C5 fraction is carried out selective hydrogenation, especially generate desirable product in the C5 fraction by selective hydrogenation, in order to reduce the loss of corresponding valuable component, if possible, should avoid as far as possible " excessive " hydrogenation generate than the more saturated compound of desirable product and the product that contains unsaturated bond simultaneously hydrogenation generate corresponding more senior compound.For example, hydrogenation such as pentone, 2-butine, 1-pentyne in the C5 fraction are generated isoprene, 2-butylene, 1-amylene etc., perhaps make its residual content reach several μ g/g (by weight) at least, avoid " excessive " hydrogenation to make it change into more monoolefine and alkane as far as possible.But require when guaranteeing a large amount of conversions of alkynes, under the condition that the assurance alkadienes partly transforms, also there is not good solution technology and catalyst aspect that maximum generates α position alkene, this method of removing alkynes, alkadienes can be simplified carbon five separation process, but employed catalyst needs high selectivity, sufficiently high activity and sufficiently long service life, long-term to be suitable for, low-cost running.
US3,912,789 (1975) disclose a kind of liquid phase hydrogenating catalyst.This catalyst is main active constituent with copper, and for helping active constituent (as silver, platinum, palladium, nickel, manganese, cobalt, chromium and molybdenum), (specific surface is at least 10m to adopt the high-ratio surface that contains a certain amount of sodium oxide molybdena with the multivalence reactive metal
2/ g) gamma-alumina is a carrier.This catalyst life is shorter, has only 175～200 hours, needs repeatedly regeneration.The temperature of hydrogenation reaction is 50 ℃～100 ℃, and operating temperature is higher, makes C 5 diene be easy to polymerization.Catalyst selectivity is relatively poor, and the diolefin loss is bigger, and it is less to handle load.
US4,064,190 (1977) disclose a kind of gas-phase catalytic hydrogenation catalyst.This catalyst is main active constituent with the copper that loads on the zinc aluminate, with tin or plumbous for helping component.Operating temperature is 121～427 ℃, and too high operating temperature makes it have fatal shortcoming, and the reaction time is shorter, only is 0.02～5 minute.
Normally used this hydrogenation of unsaturated hydrocarbons catalyst also has noble metal catalyst, and wherein noble metal loading is on catalyst carrier.Palladium is the noble metal that often uses, and carrier is porous inorganic oxide normally, the mixture of silica, alumino-silicate, titanium dioxide, zirconium dioxide and/or these carriers for example, and what often use is aluminium oxide or silica.Promoter or other additive can also be arranged usually.
CN1410515A (2003) discloses a kind of selective hydrocatalyst and preparation method thereof and the application in C 5 fraction.This catalyst is a carrier with the aluminium oxide, comprises I B-group metal, the group VIII metal (palladium) at least a periodic table of elements and at least a alkali metal (potassium) at least a periodic table of elements.By the selectivity hydrogenation, this method is to carry out in gas phase or liquid phase to alkynes in the C5 fraction by above-mentioned catalyst, and range of reaction temperature is 30 ℃～70 ℃, and pressure limit is 0.1MPa～4.0MPa, and liquid hourly space velocity (LHSV) is 2～12m
3/ m
3.h.But this catalyst has good hydrogenation activity to alkynes, and alkadienes is hydrogenation not substantially, and α position alkene does not have relatively large raising in the product.
To the catalyst that the alkynes that is present in the C5 fraction carries out selective hydrogenation, prior art can't satisfy at alkadienes to be had under an amount of saturated situation, reduces amount of alkene maximized requirement in α position in the surplus of alkynes and the product simultaneously.
Summary of the invention
The objective of the invention is defective poor at hydrogenation of unsaturated hydrocarbons catalyst selectivity in the prior art, that the life-span short, load is little, a kind of selectivity height, good stability, long hydrogenation catalyst of life-span are provided;
A kind of this hydrogenization catalyst preparation method is provided during another object of the present invention;
A further object of the invention, it is exactly this hydrogenation catalyst carries out selective hydrogenation to alkynes in the C5 fraction and alkadienes application process, when making it carry out selective hydrogenation to cracked C 5 fraction effectively, guarantee that a large amount of conversions of alkynes and alkadienes partly transform, the product of generation is based on α position monoolefine.
(1) composition of catalyst
Selective hydrocatalyst of the present invention is that the compound with aluminium oxide and molecular sieve is a carrier, with IA in the periodic table of elements or IIA family, and VIII family, IVA family, IB family metal is an active component; Wherein, the mass percent of aluminium oxide, molecular sieve is respectively 80～99% in the complex carrier, and 1%～20%; Quality with catalyst carrier is a benchmark, and the content of IA or IIA family metal is 0.1～10%, and the content of group VIII metal is 0.05～1%, and the content of IVA family metal is 0.05～2%, and its content of I B-group metal is 0～1%.
Aluminium oxide is alpha-aluminium oxide phase or hydrated alumina phase in the described carrier.For example β-, γ-, θ-, δ-or X-aluminium oxide, boehmite, pseudobochmite or their mixture; Preferred content is 90～95%.
Molecular sieve is at least a in Y type, ZSM type, modenite, the Beta type in the described carrier, and preferred content is 5～10%.
Catalyst carrier mainly is aluminium oxide and molecular sieve complex carrier, can also comprise some other additive, for example silica, titanium dioxide, zirconium dioxide, zinc oxide and magnesia.Usually, except aluminium oxide and molecular sieve, the quality of these oxides should be less than 5%, particularly preferably is this carrier and only is made up of aluminium oxide and molecular sieve and unavoidable impurities.
The specific area of described complex carrier is 30～150m
2/ g is preferably 40～80m
2/ g; Specific pore volume is 0.45～0.65mL/g; Be preferably 0.50～0.60mL/g, average pore size is generally 5～40nm, is preferably 6～30nm; The specific area of carrier, pore volume and pore-size distribution can be optimized according to mode known in those skilled in the art.
The shape of described complex carrier can be ball-type, column type, trifolium-shaped or sheet type, and is preferred spherical.
In IA or the IIA family metal, mainly with potassium, sodium, calcium as the activity of such catalysts component, preferred potassium is as the single metal of this family, preferred content is 0.1～2% of a complex carrier quality.
In the group VIII metal, mainly with nickel, palladium, platinum, rhodium as the activity of such catalysts component, preferred palladium is the single metal of this family; Preferred content is 0.1～0.5% of a complex carrier quality.
In the IVA family metal, be the activity of such catalysts component with preferred tin, lead mainly, the best is plumbous; Preferred content is 0.1～1% of a complex carrier quality.
In the I B-group metal, preferably copper is the activity of such catalysts component, and preferred content is 0～1%.
Described active component also comprises promoter, as copper, silver or fluoride etc.; Its content is 0.5 of catalyst carrier quality～10 ‰.
(2) Preparation of catalysts
1, the preparation of complex carrier
After aluminium oxide and molecular sieve mixed in described ratio, adopt conventional forming method to carry out extrusion, compressing tablet, balling-up after, 500～1100 ℃ of following roastings 2～10 hours complex carrier;
2, Preparation of catalysts
Earlier the aqueous solution with IA family/IIA family metallic compound floods complex carrier, and the nitrate solution of using the nitrate solution of water-soluble salt solution, IVA family metal of group VIII metal and I B-group metal again once or the step impregnation complex carrier; Drying is carried out at 80～200 ℃ in each step dipping back, carries out roasting at 350～650 ℃.
Wherein IA family/IIA family metallic compound is hydroxide, the halide of this family's metal, carbonate or nitrate.
The water soluble salt of group VIII metal is the chloride or the nitrate of this family's metal.
Behind the aqueous solution dipping complex carrier with IA family/IIA family metallic compound, when adopting step impregnation, with the water-soluble salt solution dipping of group VIII metal,, use the nitrate solution dipping of I B-group metal at last earlier again with the nitrate solution dipping of IVA family metal; Each step dipping back is 80～200 ℃ of dryings 12～20 hours, then 350～650 ℃ of roastings 1～12 hour.
The used volume of each step dipping solution is as the criterion to be no more than complex carrier carrier absorption maximum volume.The present invention preferably adopts the method for each family's metal step impregnation.
Behind the aqueous solution dipping complex carrier with IA family/IIA family metallic compound, when adopting single-steeping, the pH value of the common dipping solution of the nitrate solution of group VIII metal soluble salt solution, IVA family metal and the nitrate of I B-group metal is 3～5.
Compound concentration in the dipping solution, should make the dipping finish after and impregnated carrier is converted into after the finished catalyst, the component that is deposited reaches in catalyst with carrier and calculates desirable content (composition of page catalyst that sees before).
After each step, dipping was finished, under 80～200 ℃, soaked carrier is continued drying, till the water in the carrier after impregnated is removed basically fully, to just can reach after dry 12 hours usually.Depend on the baking temperature that is adopted drying time, temperature is high more, and drying time is short more.Preferred baking temperature is 100～150 ℃, and drying time is between 12～20 hours usually.
The component that carries out roasting and mainly be that employed compound is changed into and be deposited or the parent of these components.Under the situation of utilizing metallic compound to flood, in roasting process, metallic compound mainly decomposes and generates the metal oxide remain in the catalyst.Sintering temperature in 300～650 ℃ of scopes, is preferably 350～600 ℃ usually, is preferably 450～550 ℃ especially.Usually between 1～12 hour, roasting process preferably goes on foot and surpasses 8 hours roasting time, and preferably the step was above 4 hours.Roasting process carries out in stove commonly used, for example in rotary tube furnace, carry out in tunnel oven or in Muffle furnace.Can after drying, directly calcine, needn't carry out the centre cooling dipping and dried carrier.
Three, selective hydrocatalyst carries out the technology of selective hydrogenation to the unsaturated compound in the C5 fraction
Described selecting property hydrogenation catalyst being joined in the reactor, be warming up to 60～350 ℃, is that the amount of 50:1～500:1 feeds hydrogen by the volume ratio of hydrogen and catalyst, reductase 12～20 hour; Add the C5 fraction raw material then, adjust temperature to 35～90 ℃ of reactor, pressure is to 0.1MPa～4.0MPa, and volume space velocity is 2～12h during the feeding liquid of C5 fraction
-1(volume with catalyst is a benchmark), hydrogen to oil volume ratio are that 50:1～500:1 (is preferably 150:1～250:1).
C5 fraction is carried out the process of selective hydrogenation conversion and is normally carried out in gas phase or liquid phase process, and wherein C5 fraction exists with liquid form or gas-liquid phase mixed form, and hydrogen is present in the gas phase and/or is dissolved in the liquid phase.The setting of reaction condition such as pressure, temperature, flow and hydrogen amount is converted into purpose with most of conversion of alkynes and alkadienes appropriateness.
This process can be carried out in a hydrogenation reactor, perhaps carries out in the hydrogenation reactor of a plurality of parallel connections or series connection.
In principle, catalyst after the roasting just can use, can be in hydrogenation reactor in the catalyst use or before using, utilize hydrogen or hydrogen-containing gas to handle, make the metal oxide of deposition directly be reduced into metal, just make the oxide of group VIII metal and IVA family metal all be converted into metal.This process can be carried out under the hydrogenation situation automatically.In reduction process, reduction temperature in 60～350 ℃ of scopes, is preferably 80～300 ℃ usually, is preferably 100～240 ℃ especially.Recovery time is generally 2～20 hours, preferably proceeds to many 12 hours, guarantees that the group VIII metal oxide that is deposited in the catalyst is reduced to metal fully.
The present invention compared with prior art has the following advantages:
1, catalyst of the present invention has excellent catalytic performance, has higher activity, selectivity and long service life in the process of the alkynes in the C5 fraction and alkadienes being carried out selective hydrogenation.
2, catalyst of the present invention, when the unsaturated compound in the C5 fraction is carried out selective hydrogenation, alkynes hydrogenation conversion 〉=45%, the diene hydrogenation conversion ratio is 15～35%, α position olefin(e) centent 〉=15% behind the hydrogenation, can satisfy subsequent production high-quality α-resin arts demand, thereby improve α-naval stores quality.
3, Preparation of catalysts method of the present invention is simple, easy to operate.
4, selective hydrocatalyst of the present invention is used for the C5 fraction separating technology, can shorten separation process, reduces cost of investment and energy consumption.
The specific embodiment
Embodiment one
1, the preparation of carrier S-1
(Shandong Aluminum Plant adopts Bayer process production with 1000 gram α-gibbsites; solid content 60～65wt%) and Y zeolite mixture are packed in the container of 2 liters of vibrations; wherein Y zeolite quality accounts for 5% of powder quality; make container fast by 700 ℃ of high-temperature region dehydrations; the time of staying is 0.5 second; then the gained powder is put into small-sized comminutor limit rolling water spray; be rolled into diameter and be 2～4 millimeters bead; then bead is placed under the sealing bag room temperature and place; be health 24 hours, put into 90 ℃ again; pH is hydration 8 hours in 7 the water, 120 ℃ of dryings 4 hours; 1000 ℃ of roastings get aluminium oxide-zeolite complex carrier ball, are expressed as carrier S-1.
2, the preparation of catalyst C-1
Get 100 gram carrier S-1, at ambient temperature, with the potassium nitrate aqueous solution (0.1M) oxide impregnation alumina supporter (BET surface area 75m
2/ g), drying is 12 hours under 120 ℃, and then 500 ℃ of following roastings 4 hours, take out and be cooled to room temperature; Use aqueous hydrochloric acid solution (the pH value the is 3.5) dipping of palladium bichloride again, descended dry 12 hours at 120 ℃ again, then 500 ℃ of following roastings 4 hours; At last with the aqueous solution of plumbi nitras dipping, the dipping back 120 ℃ dry 12 hours down, then 500 ℃ of following roastings 4 hours.The amount of dipping solution is the adsorbable maximum volume amount of employed carrier, the setting of the concentration of metal compound solution should make catalyst finally contain 1% potassium, 0.3% palladium and 0.3% lead (being mass percent, in the carrier quality) in dipping solution.Zhi Bei catalyst is expressed as catalyst C-1 by this way.
Embodiment two
1, the preparation of carrier S-2
Take by weighing the SB powder of 100g and the mixture of Y zeolite, wherein Y zeolite quality accounts for 5% of powder quality, with the HNO of 100ml water and 3.0g
3Mix, on the catalyst extrusion shaping machine, be extruded into the bar of diameter 1.6mm, under infrared lamp behind the dry 5h, be positioned in the baking oven 120 ℃ dry 12 hours down, 1000 ℃ of roasting 5h in muffle furnace cut into the slice of 3-8mm, are expressed as carrier S-2.
2, the preparation of catalyst C-2
Get 100 gram carrier S-2 (BET surface area 70m
2/ g), and at ambient temperature, with the potassium nitrate aqueous solution (0.1M) oxide impregnation alumina supporter (BET surface area 75m
2/ g), drying is 12 hours under 120 ℃, and then 500 ℃ of following roastings 4 hours, take out and be cooled to room temperature; Use aqueous hydrochloric acid solution (the pH value the is 3.5) dipping of palladium bichloride again, descended dry 12 hours at 120 ℃ again, then 500 ℃ of following roastings 4 hours; At last with the aqueous solution of plumbi nitras dipping, the dipping back 120 ℃ dry 12 hours down, then 500 ℃ of following roastings 4 hours.The amount of dipping solution is the adsorbable maximum volume amount of employed carrier, the setting of the concentration of metal compound solution should make catalyst finally contain 1% potassium, 0.3% palladium and 0.3% lead (being mass percent, in the carrier quality) in dipping solution.Zhi Bei catalyst is expressed as catalyst C-2 by this way.
Embodiment three
1, the preparation of carrier S-3
(Shandong Aluminum Plant adopts Bayer process production with 1000 gram α-gibbsites; solid content 60～65 heavy %) in the container of the 2 liters of vibrations of packing into; and make it fast by 700 ℃ of high-temperature region dehydrations; the time of staying is 0.5 second; then the gained powder is put into small-sized comminutor limit rolling water spray; be rolled into diameter and be 2～4 millimeters bead; then bead is placed under the sealing bag room temperature and place; be health 24 hours; put into 90 ℃, pH again and be 7 water hydration 8 hours; 120 ℃ of dryings 4 hours, 1000 ℃ of roastings get alumina balls, are expressed as carrier S-3.
2, the preparation of catalyst C-3
Get 100 gram carrier S-3 (BET surface area 55m
2/ g), repeat the preparation process of catalyst C-1 among the embodiment one.Zhi Bei catalyst is expressed as catalyst C-3 by this way.
Embodiment four
1, the preparation of carrier S-1
With embodiment one.
2, the preparation of catalyst C-4
Get 100 gram carrier S-1, repeat embodiment 4, change the setting of the concentration of metallic compound in the dipping solution, make and finally contain 1% sodium, 0.3% palladium and 0.3% lead (being mass percent) in the catalyst in the carrier quality.Zhi Bei catalyst is expressed as catalyst C-4 by this way.
Embodiment five
1, the preparation of carrier S-1
With embodiment one
2, the preparation of catalyst C-5
Get 100 gram carrier S-1 and repeat embodiment 4, change the setting of the concentration of metallic compound in the dipping solution, make and finally contain 1% potassium, 0.3% palladium and 0.3% tin (being mass percent) in the catalyst in the carrier quality.
Zhi Bei catalyst is expressed as catalyst C-5 by this way.
Embodiment six
1, the preparation of carrier S-1
With embodiment one
2, the preparation of catalyst C-6
Get 100 gram carrier S-1, at ambient temperature, with the potassium nitrate aqueous solution (0.1M) oxide impregnation alumina supporter (BET surface area 75m
2/ g), drying is 12 hours under 120 ℃, and then 500 ℃ of following roastings 4 hours, take out and be cooled to room temperature; Use the common dipping of the aqueous solution (PH-3.5) of palladium bichloride and plumbi nitras again, descended dry 12 hours at 120 ℃ again, then 500 ℃ of following roastings 4 hours.The amount of dipping solution is the adsorbable maximum volume amount of employed carrier, the setting of the concentration of metal compound solution should make catalyst finally contain 1% potassium, 0.25% palladium and 0.35% lead (being mass percent, in the carrier quality) in dipping solution.Zhi Bei catalyst is expressed as catalyst C-6 by this way.
Embodiment seven
Catalyst of the present invention carries out selective hydrogenation performance evaluation to alkynes in the C5 fraction and alkadienes
In 100 milliliters of fixed-bed reactors, respectively catalyst C-1, C-2, C-3, C-4, C-5, C-6 are carried out hydrogenation reaction performance evaluation.Wherein the C-3 catalyst is carrier with the aluminium oxide, for comparing catalyst.
In 100 milliliters of catalyst dress people reaction tubes, two ends porcelain ring filling is warming up to 100 ℃, press hydrogen and catalyst volume and fed hydrogen reducing 8 hours than the amount of 120:1, adjust bed temperature to 55 ℃, advancing C5 fraction then is that raw material reacts, and the feed weight air speed is 4h during reaction
-1, reaction temperature is 55 ℃, pressure 1.2MPa, hydrogen to oil volume ratio 150:1.
Contain 1160 μ g/g (2-butine) in the material of carbon Wuyuan, diene content is 30.4%, and monoolefine content is 24.0% (wherein monoolefine content in α position is 12.2%), and all the other are alkane component.Utilize material component after the gas chromatographic analysis selective hydrogenation.Each activity of such catalysts and selective evaluation the results are shown in Table 1.
Table 1 evaluating catalyst result
Annotate: initial reaction stage is 36 hours sample analysis results, and catalyst C-1, C-2 move 400 hours catalytic performances does not continuously have significant change.
From the last stage reaction result of table 1 as can be seen, catalyst of the present invention (C-5, when C-6) unsaturated compound in the C5 fraction being carried out selective hydrogenation, alkynes hydrogenation conversion 〉=45%, the diene hydrogenation conversion ratio is 〉=15%, α position olefin(e) centent 〉=15% behind the hydrogenation.
It can also be seen that from above-mentioned experiment, the Preparation of catalysts method is vital to the catalytic performance of catalyst, different preparation methods can produce significantly influence to activity of such catalysts, selectivity and life-span, and preparation method of the present invention is effective to Preparation of Catalyst of the present invention.Catalyst carrier also affects the catalytic performance of catalyst, the simple catalyst that with the aluminium oxide is carrier obtains has good activity aspect the alkynes hydrogenation, but it is relatively poor to be converted into aspect the monoolefine selectivity at alkadienes, purpose product α position monoolefine content in the product does not significantly increase, and it is good that experimental result shows with complex carrier of the present invention.The load component of catalyst and content thereof in the time of carrying out selective hydrogenation to cracked C 5 fraction effectively, guarantee that a large amount of conversions of alkynes and alkadienes partly transform with in the scope of determining in the present invention, and the product of generation is based on α position monoolefine.
Claims (12)
1, a kind of selective hydrocatalyst is characterized in that: its compound with aluminium oxide and molecular sieve is a carrier, with IA in the periodic table of elements or IIA family, and VIII family, IVA family, IB family metal is an active component; Wherein, the mass percent of aluminium oxide, molecular sieve is respectively 80～99% in the complex carrier, and 1%～20%; Quality with catalyst carrier is a benchmark, and the content of IA or IIA family metal is 0.1～10%, and the content of group VIII metal is 0.05～1%, and the content of IVA family metal is 0.05～2%, and its content of I B-group metal is 0～1%.
2, selective hydrocatalyst according to claim 1, it is characterized in that: described active component also comprises promoter, its addition is thought catalyst carrier quality 0.5～10 ‰; Described promoter is copper, silver or fluoride.
3, selective hydrocatalyst according to claim 1 is characterized in that: in the described carrier aluminium oxide be alpha-aluminium oxide mutually or the hydrated alumina phase.
4, selective hydrocatalyst according to claim 1 is characterized in that: molecular sieve is at least a in Y type, ZSM type, modenite, the Beta type in the described carrier.
5, selective hydrocatalyst according to claim 1, it is characterized in that: the specific area of described complex carrier is 30～150m
2/ g, specific pore volume are 0.45～0.65mL/g.
6, selective hydrocatalyst according to claim 1, it is characterized in that: described complex carrier is ball-type, column type, trifolium-shaped or sheet type.
7, the preparation method of selective hydrocatalyst according to claim 1 may further comprise the steps:
(1) preparation of complex carrier
With aluminium oxide and molecular sieve in described ratio mix, after the moulding, 500～1100 ℃ of following roastings 2～10 hours complex carrier;
(2) Preparation of catalysts: earlier the aqueous solution with IA family/IIA family metallic compound floods complex carrier, and the nitrate solution of using the nitrate solution of water-soluble salt solution, IVA family metal of group VIII metal and I B-group metal again once or the step impregnation complex carrier; Each step dipping back is 80～200 ℃ of dryings 12～20 hours, then 350～650 ℃ of roastings 1～12 hour.
8, as the preparation method of selective hydrocatalyst as described in the claim 7, it is characterized in that: described IA family/IIA family metallic compound is hydroxide, halide, carbonate or the nitrate of this family's metal.
9, as the preparation method of selective hydrocatalyst as described in the claim 7, it is characterized in that: the water soluble salt of described group VIII metal is the chloride or the nitrate of this family's metal.
10, as the preparation method of selective hydrocatalyst as described in the claim 7, it is characterized in that: in the described step (2), behind the aqueous solution dipping complex carrier with IA family/IIA family metallic compound, when adopting step impregnation, water-soluble salt solution with the group VIII metal floods earlier, with the nitrate solution dipping of IVA family metal, the nitrate solution with I B-group metal floods at last again; Drying is carried out at 80～200 ℃ in each step dipping back, carries out roasting at 350～650 ℃.
11, as the preparation method of selective hydrocatalyst as described in the claim 10, it is characterized in that: in the described step (2), when adopting single-steeping, the pH value of the nitrate solution of group VIII metal soluble salt solution, IVA family metal and the common dipping solution of I B-group metal nitrate is 3～5.
12, selective hydrocatalyst carries out process for selective hydrogenation to the unsaturated compound in the C5 fraction according to claim 1, be that described selecting property hydrogenation catalyst is joined in the reactor, be warming up to 60～350 ℃, by the volume ratio of hydrogen and catalyst is that the amount of 50:1～500:1 feeds hydrogen, reductase 12～20 hour; Add the C5 fraction raw material then, adjust temperature to 35～90 ℃ of reactor, pressure is to 0.1MPa～4.0MPa, and volume space velocity is 2～12h during the feeding liquid of C5 fraction
-1, the volume ratio of hydrogen and C5 fraction is 50:1～500:1.
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| CN106861730A (en) * | 2017-03-17 | 2017-06-20 | 钦州学院 | A kind of catalyst and preparation method for C 5 petroleum resin hydrogenation |
| CN109395738A (en) * | 2018-11-24 | 2019-03-01 | 陈泽平 | One kind being used for C 5 petroleum resin hydrogenation catalyst and preparation method |
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| CN1047962C (en) * | 1995-10-06 | 2000-01-05 | 中国石油化工总公司 | Polymetal carrying alkyl aromatic hydrocarbon isomerization catalyst |
| DE19932060A1 (en) * | 1999-07-12 | 2001-01-18 | Basf Ag | Process for the production of C¶5¶ / C¶6¶ olefins |
| CN1510020A (en) * | 2002-12-26 | 2004-07-07 | 中国石油化工股份有限公司北京燕山分 | Preparation of dihydroxy-benzene by phenol hydroxylation |
| US20050101819A1 (en) * | 2003-11-07 | 2005-05-12 | Galperin Leonid B. | Dual functional catalyst for selective opening of cyclic paraffins and process for using the catalyst |
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