CN106582636A - Compound catalyst bed - Google Patents

Compound catalyst bed Download PDF

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Publication number
CN106582636A
CN106582636A CN201510661623.8A CN201510661623A CN106582636A CN 106582636 A CN106582636 A CN 106582636A CN 201510661623 A CN201510661623 A CN 201510661623A CN 106582636 A CN106582636 A CN 106582636A
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catalyst
grams
hours
carrier
oxide
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CN106582636B (en
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赵多
刘仲能
江兴华
顾国耀
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention relates to a compound catalyst bed and a method for hydro-treatment of a material containing C-C triple bond hydrocarbon to mainly solve the problems of low acetylene-hydrocarbon conversion rate and low butane yield in a reaction of hydrogenation of the C-C triple bond hydrocarbon to alkane. By adopting a technical scheme that a compound hydrogenation catalyst bed comprises a first-stage catalyst and a second-stage catalyst, the first-stage catalyst comprises a carrier 1 and palladium or an oxide thereof, and the second-stage catalyst comprises a carrier 2 and nickel or an oxide thereof, the compound catalyst bed provided by the invention well solves the technical problems and can be used for recovery utilization of the material containing the C-C triple bond hydrocarbon.

Description

Composite catalyst bed
Technical field
The present invention relates to the method for composite catalyst bed and the material hydrotreating containing triple carbon-carbon bonds hydrocarbon, more particularly to process method of hydrotreating of the acetylene by-product containing the senior alkynes such as diacetylene and vinylacetylene.
Background of invention
Gas by partial oxidation of natural acetylene process by-product partial higher alkynes gas.It mainly contains unsaturated hydrocarbons and the part C6H6 such as diacetylene (37.17V%), allylene, propine (6.74V%), vinylacetylene (10.51V%) and acetylene (19.85V%)+(25.72V%) heavy constituent.These unsaturated hydrocarbons properties are extremely unstable, such as the decomposition pressure of diacetylene is only that easily polymerization forms explosive polymerisation thing etc. for 0.02MPa, vinylacetylene, very big potential safety hazard is brought to enterprise's production, need to be diluted with substantial amounts of synthesis gas, be then sent for torch and burn.Containing more than 50% CO, H in carrier gas2Etc. component, with higher economic worth.Contain many widely used industrial chemicals in senior alkynes, but due to its complicated components, separation difficulty, it is difficult to it is fully utilized, causes the waste in resource.Therefore, no matter from the angle of production safety, or from the angle of the utilization of resources, the senior alkynes of acetylene unit is recycled, is all had great importance.
DE-A-1468206 discloses a kind of method of acetylene purification, and vinylacetylene and diacetylene are absorbed in N-Methyl pyrrolidone (NMP) solvent, with Pd/Al2O3For anti-applications catalyst, catalytic hydrogenation reaction is carried out, hydrogenated products polarity is weaker, separated easily from solvent.US4128595 discloses that one kind will contain alkynes material and inert hydrocarbon solvent is contacted with palladium-based catalyst into reactor together and carries out hydrogenation reaction, and the shortcoming of the method is that the dissolubility in varsol is poor at reaction conditions for material containing alkynes；The patent makes a declaration of, and in polar solvent such as DMF (DMF) carries out hydrogenation reaction, and catalyst deactivation rate is very fast.US2010/0016646A1 discloses a kind of diacetylene method of hydrotreating, and diacetylene is absorbed in polar solvent such as NMP or DMF, using loading type Pd/Al2O3Catalyst, 0～100 DEG C of reaction temperature, 1～40bar of pressure carries out hydrogenation reaction, obtains butane and butylene, and in running, catalyst is gradually inactivated because showing carbon distribution.Alkynes has three active keys because of which, in continuously hydrogen adding course of reaction, polymerization process easily occurs, generates green oil and colloid, cause catalyst to inactivate.Therefore a kind of new alkynes method of hydrotreating is developed, hydrogenation plant operation stability is improved, has significance.
But in prior art, alkynes conversion ratio is hydrogenated with into the reaction of alkane for hydrocarbon containing triple carbon-carbon bonds low low with butane yield.
The content of the invention
One of the technical problem to be solved in the present invention is to be hydrogenated with into the reaction of alkane that alkynes conversion ratio is low and the low problem of butane yield in prior art for hydrocarbon containing triple carbon-carbon bonds, a kind of compound hydrogenation catalyst bed is provided, the composite catalyst bed accessory has the advantages that alkynes high conversion rate and butane high income.
The two of the technical problem to be solved in the present invention are the methods of the material hydrotreating containing triple carbon-carbon bonds hydrocarbon of the catalyst using above-mentioned technical problem.
To solve one of above-mentioned technical problem, technical scheme is as follows：Compound hydrogenation catalyst bed, including first paragraph catalyst and second segment catalyst, first paragraph catalyst include carrier 1 and palladium or its oxide, and second segment catalyst includes carrier 2 and nickel or its oxide.
In above-mentioned technical proposal, the weight ratio preferably 0.5～1 of first paragraph catalyst and second segment catalyst.
In above-mentioned technical proposal, first paragraph catalyst preferably includes following components by weight percentage：
The metal Pd of (a) 0.02～0.2% or its oxide；
At least one metal in the IB from the periodic table of elements of (b) 0.04～1% or its oxide.
In above-mentioned technical proposal, when Pd elements are oxide pattern, one skilled in the art will appreciate that should be reduced into metal Pd exercises use again.
In above-mentioned technical proposal, second segment catalyst preferably includes following components by weight percentage：
The metallic nickel of (a) 10～25% or its oxide；
At least one metal in rare earth of (b) 0.2～1% or its oxide；
At least one metal in IIA in the periodic table of elements of (c) 0.2～2.0% or its oxide；
The Zr of (d) 2～5% or its oxide.
In above-mentioned technical proposal, when nickel element is oxide pattern, one skilled in the art will appreciate that should be reduced into metallic nickel exercises use again.
In above-mentioned technical proposal, carrier 1 and/or carrier 2 are not particularly limited, but preferably aluminium oxide, the more preferably 30～90m of BET specific surfaces of carrier 12/ g, pore volume are 0.65～0.85ml/g, the more preferably BET 120～200m of specific surface of carrier 22/ g, pore volume are 0.42～0.70ml/g.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The method of the material hydrotreating containing triple carbon-carbon bonds hydrocarbon, comprises the steps：
(1) one of hydrogen and material elder generation and above-mentioned technical problem first paragraph catalyst haptoreaction any one of the technical scheme is made to generate the intermediate material containing monoene；
(2) in the presence of second segment catalyst, above-mentioned intermediate products hydrogenation obtains the material containing alkane.
In above-mentioned technical proposal, the alkynes Specific amounts remained in intermediate material is not limited, but residual is more low better, and within the residual quantity 1% of preferred alkynes, intermediate material preferably comprises monoolefine, can also contain alkane.Such as but not limited to alkane and the weight ratio of monoolefine are 0.5～1.5.
In above-mentioned technical proposal, as long as can meet step (1) is first passed through and then again the step of step (2), those skilled in the art can rationally determine upper feeding, lower charging or cross-feed.For example, when select upper feeding bottom discharge when, first paragraph catalyst and second segment catalyst can be placed in same reactor, by first paragraph catalyst as second segment catalyst on；When using lower charging, first paragraph catalyst and second segment catalyst can be placed in same reactor, first paragraph catalyst is placed under second segment catalyst.Above-mentioned two-stage catalytic agent can also be placed in two reactors being connected in series.
In above-mentioned technical proposal, the reaction temperature of step (1) and/or step (2) is preferably 40～90 DEG C；More preferably 60～80 DEG C
In above-mentioned technical proposal, the reaction pressure of step (1) and/or step (2) is preferably 1.2～2.2MPa；More preferably 1.6～2.2MPa
In above-mentioned technical proposal, in step (1), the feed weight air speed of triple carbon-carbon bonds hydrocarbon is preferably 0.05～0.2h-1.More preferably 0.08～0.15h of weight space velocity-1。
In above-mentioned technical proposal, in step (1), hydrogen/triple carbon-carbon bonds hydrocarbon mol ratio is preferably 20～50.
In above-mentioned technical proposal, the material containing triple carbon-carbon bonds hydrocarbon preferably contains diluent.
In above-mentioned technical proposal, in the material, triple carbon-carbon bonds hydrocarbon preferred content is more than zero and less than 3.0% by weight；Amount of diluent is preferably 95～99%.
In above-mentioned technical proposal, the diluent may be selected from least one in N-Methyl pyrrolidone, DMF, acetone.
In above-mentioned technical proposal, hydrocarbon containing triple carbon-carbon bonds is not particularly limited, such as but not limited to propine, vinylacetylene and diacetylene etc..
More specifically non limiting example, by weight, the material contains 0.1～2% vinylacetylene, 0.1～2% benzene, 0.1～3% diacetylene, 95～99%N- methyl pyrrolidones.
The preparation method of two-stage catalytic agent carrier of the present invention is not particularly limited, and as non limiting example, comprises the steps：
Aluminium oxide and modifying agent, peptizer, water are mixed in the desired amount, after extruded moulding, is first dried 5～24 hours at 60～110 DEG C, then roasting 4～10 hours at 500～1000 DEG C, obtain carrier.
The preparation method of preferred carrier 1, including：
Aluminium oxide and modifying agent, peptizer, water are mixed in the desired amount, after extruded moulding, is first dried 5～24 hours at 60～110 DEG C, then roasting 4～10 hours at 800～1000 DEG C, obtain carrier 1.
The preparation method of preferred carrier 2, including：
Aluminium oxide and modifying agent, peptizer, water are mixed in the desired amount, after extruded moulding, is first dried 5～24 hours at 60～110 DEG C, then roasting 4～10 hours at 500～700 DEG C, obtain carrier 2.
The preparation method of two-stage catalytic agent of the present invention is not particularly limited, and used as non limiting example, the preparation method of first paragraph catalyst comprises the steps：The solution even that carrier is made into the desired amount of IB races impregnates, then drying, in atmosphere 350～500 DEG C of roastings obtain final product modified aluminium oxide supports.By the carrier be put in excess chlorination palladium solution impregnate, after filtration Jing be dried, in atmosphere 450～800 DEG C of roastings obtain final product oxidized form palladium-based catalyst.
The preparation method of two-stage catalytic agent of the present invention is not particularly limited, and used as non limiting example, the preparation method of second segment catalyst comprises the steps：The solution impregnation that first carrier cocatalyst component is made into and then the solution impregnation being made into the desired amount of nickel compound, or the solution impregnation that carrier is made into the cocatalyst component used in the desired amount of nickel compound and catalyst；Carrier drying after dipping, in atmosphere 350～500 DEG C of roastings obtain final product oxidized form nickel-base catalyst.
Above-mentioned oxidation catalyst can also be reduced, mode those skilled in the art of concrete reduction rationally can grasp, as long as the palladium or compound state nickel of compound state are reduced to metallic state.For example, the method for reducing of first paragraph catalyst of the present invention includes that 0.2～0.5MPa of pressure is warmed up to 120 DEG C with 30～60 DEG C/h heating rates, maintains 6～12h, you can.For example, the method for reducing of second segment catalyst of the present invention includes that catalyst is reduced directly on hydrogenation plant, and its reducing process condition is：0.2～0.5MPa of pressure, is warmed up to 230～280 DEG C of 3～6h of maintenance with 30～60 DEG C/h heating rates, then with the ramp of 15 DEG C/h to 330～380 DEG C, maintains 6～12h, be warmed up to 420～500 DEG C with 15 DEG C/h again afterwards, maintain 6～12h, you can.
Using the present invention, in 70 DEG C of reaction temperature, reaction pressure 1.8MPa, feed weight air speed 0.1h of triple carbon-carbon bonds hydrocarbon-1, hydrogen/alkynes mol ratio 20, alkynes conversion ratio 99.2%, butane yield 99% obtain preferable technique effect.
Below by embodiment, the invention will be further elaborated, but these embodiments are not construed as limiting to the scope of the present invention anyway.
Specific embodiment
The raw materials used higher alkyne for Sichuan vinylon plant natural gas acetylene unit by-product of experiment, specific nature are as shown in table 1.
【Embodiment 1】
1st, prepared by carrier 1
Weigh the boehmite equivalent to 12 grams of aluminium oxide, 170 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), mass concentration is 68% 4.0 grams of nitric acid, 280 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours were after 900 DEG C of roastings 4 hours, obtain the carrier Z1 that a length of 2 mm dia is 1 millimeter, specific surface area 74m2/ g, pore volume 0.72ml/g.
2nd, first paragraph catalyst preparation
1.0 grams of 100 grams of silver nitrate aqueous solution of above-mentioned 98.8 grams of carrier Z1 and argentiferous is mixed, 60 DEG C of dryings 8 hours, 450 DEG C of roastings 4 hours are obtained modified aluminium oxide supports.Then, with mix containing 100 grams of the chlorine palladium aqueous acid of 0.2 gram of palladium, after 600 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of Jing dryings 4 hours-1, first paragraph catalyst is obtained, concrete composition is shown in Table 2.
3rd, prepared by carrier 2
The boehmite equivalent to 12 grams of aluminium oxide is weighed, 69.5 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), and mass concentration is 68% 4.0 grams of nitric acid, equivalent to 0.5 gram of La2O3La (NO3)3.6H2O, equivalent to the Ca (NO of 1 gram of CaO3)2.4H2O, equivalent to 3.0 grams of ZrO2ZrOCl2.8H2O, 130 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours obtain the carrier Z2 that a length of 2 mm dia is 1 millimeter, specific surface area 147m after 700 DEG C of roastings 4 hours2/ g, pore volume 0.56ml/g.
4th, second segment catalyst preparation
Above-mentioned carrier Z2 is mixed with nickeliferous 14 grams of 90 grams of nickel ammonia solution, 60 DEG C of dryings 8 hours, after 450 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of dryings 2 hours-1, second segment catalyst is obtained, concrete composition is shown in Table 3.
5th, evaluating catalyst
Hydroprocessing is carried out in fixed bed reactors.First paragraph catalyst in reactor prepared by upper bed layer filling embodiment 1, the second segment catalyst prepared by lower bed layer filling embodiment 1, first paragraph catalyst are 0.8 with the mass ratio of second segment catalyst.Material containing triple carbon-carbon bonds hydrocarbon carries out hydroprocessing, reactor head charging, bottom discharge in a continuous manner.In experimentation, operating condition is as follows：Reaction temperature：70 DEG C, reaction pressure 1.60MPa, triple carbon-carbon bonds hydrocarbon charging weight space velocity 0.1h-1, hydrogen/triple carbon-carbon bonds hydrocarbon mol ratio 20, be carried out continuously 300 hours hydrogenation evaluate, hydrogenation average result be shown in Table 4.
【Comparative example 1】
First paragraph catalyst and second segment catalyst are placed upside down, other process conditions are identical with embodiment 1, specially：
1st, prepared by carrier 1
Weigh the boehmite equivalent to 12 grams of aluminium oxide, 170 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), mass concentration is 68% 4.0 grams of nitric acid, 280 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours were after 900 DEG C of roastings 4 hours, obtain the carrier Z1 that a length of 2 mm dia is 1 millimeter, specific surface area 74m2/ g, pore volume 0.72ml/g.
2nd, first paragraph catalyst preparation
1.0 grams of 100 grams of silver nitrate aqueous solution of above-mentioned 98.8 grams of carrier Z1 and argentiferous is mixed, 60 DEG C of dryings 8 hours, 450 DEG C of roastings 4 hours are obtained modified aluminium oxide supports.Then, with mix containing 100 grams of the chlorine palladium aqueous acid of 0.2 gram of palladium, after 600 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of Jing dryings 4 hours-1, first paragraph catalyst is obtained, concrete composition is shown in Table 2.
3rd, prepared by carrier 2
The boehmite equivalent to 12 grams of aluminium oxide is weighed, 69.5 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), and mass concentration is 68% 4.0 grams of nitric acid, equivalent to 0.5 gram of La2O3La (NO3)3.6H2O, equivalent to the Ca (NO of 1 gram of CaO3)2.4H2O, equivalent to 3.0 grams of ZrO2ZrOCl2.8H2O, 130 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours obtain the carrier Z2 that a length of 2 mm dia is 1 millimeter, specific surface area 147m after 700 DEG C of roastings 4 hours2/ g, pore volume 0.56ml/g.
4th, second segment catalyst preparation
Above-mentioned carrier Z2 is mixed with nickeliferous 14 grams of 90 grams of nickel ammonia solution, 60 DEG C of dryings 8 hours, after 450 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of dryings 2 hours-1, second segment catalyst is obtained, concrete composition is shown in Table 3.
5th, evaluating catalyst
Hydroprocessing is carried out in fixed bed reactors.Second segment catalyst in reactor prepared by upper bed layer filling embodiment 1, the first paragraph catalyst prepared by lower bed layer filling embodiment 1, first paragraph catalyst are 0.8 with the mass ratio of second segment catalyst.Material containing triple carbon-carbon bonds hydrocarbon carries out hydroprocessing, reactor head charging, bottom discharge in a continuous manner.In experimentation, operating condition is as follows：Reaction temperature：70 DEG C, reaction pressure 1.60MPa, triple carbon-carbon bonds hydrocarbon charging weight space velocity 0.1h-1, hydrogen/triple carbon-carbon bonds hydrocarbon mol ratio 20, be carried out continuously 300 hours hydrogenation evaluate, hydrogenation average result be shown in Table 4.
【Comparative example 2】
In addition to second segment catalyst is also adopted by first paragraph, other process conditions are identical with embodiment 1, specially：
1st, prepared by carrier 1
Weigh the boehmite equivalent to 12 grams of aluminium oxide, 170 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), mass concentration is 68% 4.0 grams of nitric acid, 280 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours were after 900 DEG C of roastings 4 hours, obtain the carrier Z1 that a length of 2 mm dia is 1 millimeter, specific surface area 74m2/ g, pore volume 0.72ml/g.
2nd, first paragraph catalyst preparation
1.0 grams of 100 grams of silver nitrate aqueous solution of above-mentioned 98.8 grams of carrier Z1 and argentiferous is mixed, 60 DEG C of dryings 8 hours, 450 DEG C of roastings 4 hours are obtained modified aluminium oxide supports.Then, with mix containing 100 grams of the chlorine palladium aqueous acid of 0.2 gram of palladium, after 600 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of Jing dryings 4 hours-1, first paragraph catalyst is obtained, concrete composition is shown in Table 2.
3rd, evaluating catalyst
Hydroprocessing is carried out in fixed bed reactors.First paragraph catalyst in reactor prepared by upper bed layer filling embodiment 1, lower bed layer also load first paragraph catalyst.Material containing triple carbon-carbon bonds hydrocarbon carries out hydroprocessing, reactor head charging, bottom discharge in a continuous manner.In experimentation, operating condition is as follows：Reaction temperature：70 DEG C, reaction pressure 1.60MPa, triple carbon-carbon bonds hydrocarbon charging weight space velocity 0.1h-1, hydrogen/triple carbon-carbon bonds hydrocarbon mol ratio 20, be carried out continuously 300 hours hydrogenation evaluate, hydrogenation average result be shown in Table 4.
【Comparative example 3】
In addition to first paragraph is also adopted by second segment catalyst, other process conditions are identical with embodiment 1, specially：
1st, prepared by carrier 2
The boehmite equivalent to 12 grams of aluminium oxide is weighed, 69.5 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), and mass concentration is 68% 4.0 grams of nitric acid, equivalent to 0.5 gram of La2O3La (NO3)3.6H2O, equivalent to the Ca (NO of 1 gram of CaO3)2.4H2O, equivalent to 3.0 grams of ZrO2ZrOCl2.8H2O, 130 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours obtain the carrier Z2 that a length of 2 mm dia is 1 millimeter, specific surface area 147m after 700 DEG C of roastings 4 hours2/ g, pore volume 0.56ml/g.
2nd, second segment catalyst preparation
Above-mentioned carrier Z2 is mixed with nickeliferous 14 grams of 90 grams of nickel ammonia solution, 60 DEG C of dryings 8 hours, after 450 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of dryings 2 hours-1, second segment catalyst is obtained, concrete composition is shown in Table 3.
3rd, evaluating catalyst
Hydroprocessing is carried out in fixed bed reactors.Second segment catalyst in reactor prepared by upper bed layer filling embodiment 1, the second segment catalyst prepared by lower bed layer filling embodiment 1.Material containing triple carbon-carbon bonds hydrocarbon carries out hydroprocessing, reactor head charging, bottom discharge in a continuous manner.In experimentation, operating condition is as follows：Reaction temperature：70 DEG C, reaction pressure 1.60MPa, triple carbon-carbon bonds hydrocarbon charging weight space velocity 0.1h-1, hydrogen/triple carbon-carbon bonds hydrocarbon mol ratio 20, be carried out continuously 300 hours hydrogenation evaluate, hydrogenation average result be shown in Table 4.
【Comparative example 4】
In addition to the catalyst of first paragraph and second segment catalyst are used in mixed way, other process conditions are identical with embodiment 1, specially：
1st, prepared by carrier 1
Weigh the boehmite equivalent to 12 grams of aluminium oxide, 170 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), mass concentration is 68% 4.0 grams of nitric acid, 280 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours were after 900 DEG C of roastings 4 hours, obtain the carrier Z1 that a length of 2 mm dia is 1 millimeter, specific surface area 74m2/ g, pore volume 0.72ml/g.
2nd, first paragraph catalyst preparation
1.0 grams of 100 grams of silver nitrate aqueous solution of above-mentioned 98.8 grams of carrier Z1 and argentiferous is mixed, 60 DEG C of dryings 8 hours, 450 DEG C of roastings 4 hours are obtained modified aluminium oxide supports.Then, with mix containing 100 grams of the chlorine palladium aqueous acid of 0.2 gram of palladium, after 600 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 20 hours for 110 DEG C of Jing dryings 4 hours-1, first paragraph catalyst is obtained, concrete composition is shown in Table 2.
3rd, prepared by carrier 2
The boehmite equivalent to 12 grams of aluminium oxide is weighed, 69.5 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), and mass concentration is 68% 4.0 grams of nitric acid, equivalent to 0.5 gram of La2O3La (NO3)3.6H2O, equivalent to the Ca (NO of 1 gram of CaO3)2.4H2O, equivalent to 3.0 grams of ZrO2ZrOCl2.8H2O, 130 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours obtain the carrier Z2 that a length of 2 mm dia is 1 millimeter, specific surface area 147m after 700 DEG C of roastings 4 hours2/ g, pore volume 0.56ml/g.
4th, second segment catalyst preparation
Above-mentioned carrier Z2 is mixed with nickeliferous 14 grams of 90 grams of nickel ammonia solution, 60 DEG C of dryings 8 hours, after 450 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of dryings 2 hours-1, second segment catalyst is obtained, concrete composition is shown in Table 3.
5th, evaluating catalyst
Hydroprocessing is carried out in fixed bed reactors.In reactor, upper bed layer and lower bed layer load first paragraph catalyst and the mixed catalyst of second segment catalyst prepared by embodiment 1.Material containing triple carbon-carbon bonds hydrocarbon carries out hydroprocessing, reactor head charging, bottom discharge in a continuous manner.In experimentation, operating condition is as follows：Reaction temperature：70 DEG C, reaction pressure 1.60MPa, triple carbon-carbon bonds hydrocarbon charging weight space velocity 0.1h-1, hydrogen/triple carbon-carbon bonds hydrocarbon mol ratio 20, be carried out continuously 300 hours hydrogenation evaluate, hydrogenation average result be shown in Table 4.
【Embodiment 2】
1st, prepared by carrier 1
Weigh the boehmite equivalent to 12 grams of aluminium oxide, 170 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), mass concentration is 68% 4.0 grams of nitric acid, 280 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours were after 900 DEG C of roastings 4 hours, obtain the carrier Z1 that a length of 2 mm dia is 1 millimeter, specific surface area 74m2/ g, pore volume 0.72ml/g.
2nd, first paragraph catalyst preparation
1.0 grams of 100 grams of silver nitrate aqueous solution of above-mentioned 98.8 grams of carrier Z1 and argentiferous is mixed, 60 DEG C of dryings 8 hours, 450 DEG C of roastings 4 hours are obtained modified aluminium oxide supports.Then, with mix containing 100 grams of the chlorine palladium aqueous acid of 0.2 gram of palladium, after 600 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of Jing dryings 4 hours-1, first paragraph catalyst is obtained, concrete composition is shown in Table 2.
3rd, prepared by carrier 2
The boehmite equivalent to 12 grams of aluminium oxide is weighed, 69.5 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), and mass concentration is 68% 4.0 grams of nitric acid, equivalent to 0.5 gram of Ce2O3Ce (NO3)3.6H2O, equivalent to the Ca (NO of 1 gram of CaO3)2.4H2O, equivalent to 3.0 grams of ZrO2ZrOCl2.8H2O, 130 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours obtain the carrier Z2 that a length of 2 mm dia is 1 millimeter, specific surface area 149m after 700 DEG C of roastings 4 hours2/ g, pore volume 0.56ml/g.
4th, second segment catalyst preparation
Above-mentioned carrier Z2 is mixed with nickeliferous 14 grams of 90 grams of nickel ammonia solution, 60 DEG C of dryings 8 hours, after 450 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of dryings 2 hours-1, second segment catalyst is obtained, concrete composition is shown in Table 3.
5th, evaluating catalyst
Hydroprocessing is carried out in fixed bed reactors.First paragraph catalyst in reactor prepared by upper bed layer filling embodiment 2, the second segment catalyst prepared by lower bed layer filling embodiment 2, first paragraph catalyst are 0.8 with the mass ratio of second segment catalyst.Material containing triple carbon-carbon bonds hydrocarbon carries out hydroprocessing, reactor head charging, bottom discharge in a continuous manner.In experimentation, operating condition is as follows：Reaction temperature：70 DEG C, reaction pressure 1.60MPa, triple carbon-carbon bonds hydrocarbon charging weight space velocity 0.1h-1, hydrogen/triple carbon-carbon bonds hydrocarbon mol ratio 20, be carried out continuously 300 hours hydrogenation evaluate, hydrogenation average result be shown in Table 4.
【Embodiment 3】
1st, prepared by carrier 1
Weigh the boehmite equivalent to 12 grams of aluminium oxide, 170 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), mass concentration is 68% 4.0 grams of nitric acid, 280 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours were after 900 DEG C of roastings 4 hours, obtain the carrier Z1 that a length of 2 mm dia is 1 millimeter, specific surface area 74m2/ g, pore volume 0.72ml/g.
2nd, first paragraph catalyst preparation
1.0 grams of 100 grams of silver nitrate aqueous solution of above-mentioned 98.8 grams of carrier Z1 and argentiferous is mixed, 60 DEG C of dryings 8 hours, 450 DEG C of roastings 4 hours are obtained modified aluminium oxide supports.Then, with mix containing 100 grams of the chlorine palladium aqueous acid of 0.2 gram of palladium, after 600 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of Jing dryings 4 hours-1, first paragraph catalyst is obtained, concrete composition is shown in Table 2.
3rd, prepared by carrier 2
The boehmite equivalent to 12 grams of aluminium oxide is weighed, 69.5 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), and mass concentration is 68% 4.0 grams of nitric acid, equivalent to 0.25 gram of Ce2O3Ce (NO3)3.6H2O, equivalent to 0.25 gram of La2O3La (NO3)3.6H2O, equivalent to the Ca (NO of 1 gram of CaO3)2.4H2O, equivalent to 3.0 grams of ZrO2ZrOCl2.8H2O, 130 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours obtain the carrier Z2 that a length of 2 mm dia is 1 millimeter, specific surface area 152m after 700 DEG C of roastings 4 hours2/ g, pore volume 0.58ml/g.
4th, second segment catalyst preparation
Above-mentioned carrier Z2 is mixed with nickeliferous 14 grams of 90 grams of nickel ammonia solution, 60 DEG C of dryings 8 hours, after 450 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of dryings 2 hours-1, lower bed layer second segment catalyst is obtained, concrete composition is shown in Table 3.
5th, evaluating catalyst
Hydroprocessing is carried out in fixed bed reactors.First paragraph catalyst in reactor prepared by upper bed layer filling embodiment 3, the second segment catalyst prepared by lower bed layer filling embodiment 3, first paragraph catalyst are 0.8 with the mass ratio of second segment catalyst.Material containing triple carbon-carbon bonds hydrocarbon carries out hydroprocessing, reactor head charging, bottom discharge in a continuous manner.In experimentation, operating condition is as follows：Reaction temperature：70 DEG C, reaction pressure 1.60MPa, triple carbon-carbon bonds hydrocarbon charging weight space velocity 0.1h-1, hydrogen/triple carbon-carbon bonds hydrocarbon mol ratio 20, be carried out continuously 300 hours hydrogenation evaluate, hydrogenation average result be shown in Table 4.
【Embodiment 4】
1st, prepared by carrier 1
Weigh the boehmite equivalent to 12 grams of aluminium oxide, 170 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), mass concentration is 68% 4.0 grams of nitric acid, 280 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours were after 800 DEG C of roastings 4 hours, obtain the carrier Z1 that a length of 2 mm dia is 1 millimeter, specific surface area 82m2/ g, pore volume 0.7ml/g.
2nd, first paragraph catalyst preparation
1.5 grams of 100 grams of silver nitrate aqueous solution of above-mentioned 98.2 grams of carrier Z1 and argentiferous is mixed, 60 DEG C of dryings 8 hours, 450 DEG C of roastings 4 hours are obtained modified aluminium oxide supports.Then, with mix containing 100 grams of the chlorine palladium aqueous acid of 0.3 gram of palladium, after 600 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of Jing dryings 4 hours-1, first paragraph catalyst is obtained, concrete composition is shown in Table 2.
3rd, prepared by carrier 2
The boehmite equivalent to 12 grams of aluminium oxide is weighed, 69.0 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), and mass concentration is 68% 4.0 grams of nitric acid, equivalent to 0.3 gram of La2O3La (NO3)3.6H2O, equivalent to the Ca (NO of 0.6 gram of CaO3)2.4H2O, equivalent to 4.0 grams of ZrO2ZrOCl2.8H2O, 130 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours obtain the carrier Z2 that a length of 2 mm dia is 1 millimeter, specific surface area 152m after 700 DEG C of roastings 4 hours2/ g, pore volume 0.58ml/g.
4th, second segment catalyst preparation
Above-mentioned carrier Z2 is mixed with nickeliferous 14 grams of 90 grams of nickel ammonia solution, 60 DEG C of dryings 8 hours, after 450 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of dryings 2 hours-1, second segment catalyst is obtained, concrete composition is shown in Table 3.
5th, evaluating catalyst
Hydroprocessing is carried out in fixed bed reactors.First paragraph catalyst in reactor prepared by upper bed layer filling embodiment 4, the second segment catalyst prepared by lower bed layer filling embodiment 4, first paragraph catalyst are 0.8 with the mass ratio of second segment catalyst.Material containing triple carbon-carbon bonds hydrocarbon carries out hydroprocessing, reactor head charging, bottom discharge in a continuous manner.In experimentation, operating condition is as follows：60 DEG C of reaction temperature, reaction pressure 1.80MPa, triple carbon-carbon bonds hydrocarbon charging weight space velocity 0.08h-1, hydrogen/triple carbon-carbon bonds hydrocarbon mol ratio 30, be carried out continuously 300 hours hydrogenation evaluate, hydrogenation average result be shown in Table 4.
【Embodiment 5】
1st, prepared by carrier 1
Weigh the boehmite equivalent to 12 grams of aluminium oxide, 170 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), mass concentration is 68% 4.0 grams of nitric acid, 280 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours were after 800 DEG C of roastings 4 hours, obtain the carrier Z1 that a length of 2 mm dia is 1 millimeter, specific surface area 82m2/ g, pore volume 0.7ml/g.
2nd, first paragraph catalyst preparation
1.5 grams of 100 grams of silver nitrate aqueous solution of above-mentioned 98.2 grams of carrier Z1 and argentiferous is mixed, 60 DEG C of dryings 8 hours, 450 DEG C of roastings 4 hours are obtained modified aluminium oxide supports.Then, with mix containing 100 grams of the chlorine palladium aqueous acid of 0.3 gram of palladium, after 600 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of Jing dryings 4 hours-1, first paragraph catalyst is obtained, concrete composition is shown in Table 2.
3rd, prepared by carrier 2
The boehmite equivalent to 12 grams of aluminium oxide is weighed, 69.7 grams of aluminium oxidies, 9 grams of sesbania powders, mixing are added afterwards containing 20 grams of poly-vinyl alcohol solution (mass concentration is 5%), and mass concentration is 68% 4.0 grams of nitric acid, equivalent to 0.3 gram of La2O3La (NO3)3.6H2O, equivalent to the Ca (NO of 2.0 grams of CaO3)2.4H2O, equivalent to 2.0 grams of ZrO2ZrOCl2.8H2O, 130 milliliters of water, extrusion, 120 DEG C of wet bar Jing dryings 4 hours obtain the carrier Z2 that a length of 2 mm dia is 1 millimeter, specific surface area 135m after 750 DEG C of roastings 4 hours2/ g, pore volume 0.63ml/g.
4th, second segment catalyst preparation
Above-mentioned carrier Z2 is mixed with nickeliferous 14 grams of 90 grams of nickel ammonia solution, 60 DEG C of dryings 8 hours, after 400 DEG C of roastings 4 hours, with hydrogen reducing 4 hours, 450 DEG C of reduction temperature, hydrogen volume air speed were 50 hours for 110 DEG C of dryings 2 hours-1, second segment catalyst is obtained, concrete composition is shown in Table 3.
5th, evaluating catalyst
Hydroprocessing is carried out in fixed bed reactors.First paragraph catalyst in reactor prepared by upper bed layer filling embodiment 5, the second segment catalyst prepared by lower bed layer filling embodiment 5, first paragraph catalyst are 0.8 with the mass ratio of second segment catalyst.Material containing triple carbon-carbon bonds hydrocarbon carries out hydroprocessing, reactor head charging, bottom discharge in a continuous manner.In experimentation, operating condition is as follows：80 DEG C of reaction temperature, reaction pressure 1.80MPa, triple carbon-carbon bonds hydrocarbon charging weight space velocity 0.12h-1, hydrogen/triple carbon-carbon bonds hydrocarbon mol ratio 30, be carried out continuously 300 hours hydrogenation evaluate, hydrogenation average result be shown in Table 4.
Table 1
Weight is constituted Raw material
Vinylacetylene (%) 0.5
Benzene (%) 1.0
Diacetylene (%) 1.8
N-Methyl pyrrolidone (%) 96.5
Other (%) 0.2
2 first paragraph catalyst of table is constituted
Pd, w% Ag, w%
Embodiment 1 0.2 1.0
Embodiment 2 0.2 1.0
Embodiment 3 0.2 1.0
Embodiment 4 0.3 1.5
Embodiment 5 0.3 1.5
Comparative example 1 0.2 1.0
Comparative example 2 0.2 1.0
Comparative example 3 0.2 1.0
Comparative example 4 0.2 1.0
Table 3
Table 4

Claims (10)

1. hydrogenation catalyst bed, including first paragraph catalyst and second segment catalyst are combined, and first paragraph catalyst includes Carrier 1 and palladium or its oxide, second segment catalyst include carrier 2 and nickel or its oxide.
2. catalyst bed according to claim 1, is characterized in that first paragraph catalyst with second segment catalyst Weight ratio is 0.5～1.
3. catalyst bed according to claim 1, is characterized in that first paragraph catalyst, by weight percentage Including following components：
The metal Pd of (a) 0.02～0.2% or its oxide；
At least one metal in IB in the periodic table of elements of (b) 0.04～1% or its oxide.
4. catalyst bed according to claim 1, is characterized in that second segment catalyst, by weight percentage Including following components：
The metallic nickel of (a) 10～25% or its oxide；
At least one element in rare earth of (b) 0.2～1% or its oxide；
At least one metal in IIA in the periodic table of elements of (c) 0.2～2.0% or its oxide；
The Zr of (d) 2～5% or its oxide.
5. the method for the material hydrotreating containing triple carbon-carbon bonds hydrocarbon, comprises the steps：
(1) make hydrogen and the material first and first paragraph catalyst haptoreaction any one of Claims 1 to 4 Generate the intermediate material containing monoene；
(2) in the presence of second segment catalyst, above-mentioned intermediate products hydrogenation obtains the material containing alkane.
6. method according to claim 5, is characterized in that the reaction temperature of step (1) and/or step (2) For 40～90 DEG C.
7. method according to claim 5, is characterized in that the reaction pressure of step (1) and/or step (2) For 1.2～2.2MPa.
8. method according to claim 5, is characterized in that the feed weight of triple carbon-carbon bonds hydrocarbon in step (1) is empty Speed is 0.05～0.2h-1。
9. method according to claim 5, in it is characterized in that step (1), hydrogen/triple carbon-carbon bonds hydrocarbon mol ratio is 20～50.
10. method according to claim 5, is characterized in that the material containing triple carbon-carbon bonds hydrocarbon contains diluent.
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