CN102732294B - Method for selective hydrogenation of cracked gasoline or its fractions through adopting Pd-Ag/Al2O3-TiO2 catalyst - Google Patents
Method for selective hydrogenation of cracked gasoline or its fractions through adopting Pd-Ag/Al2O3-TiO2 catalyst Download PDFInfo
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- CN102732294B CN102732294B CN201110089616.7A CN201110089616A CN102732294B CN 102732294 B CN102732294 B CN 102732294B CN 201110089616 A CN201110089616 A CN 201110089616A CN 102732294 B CN102732294 B CN 102732294B
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Abstract
The invention relates to a method for selective hydrogenation of alkyne and/or diolefin contained petroleum hydrocarbons, especially cracked gasoline or its fractions, through adopting a Pd-Ag/Al2O3-TiO2 catalyst. The catalyst comprises an Al2O3-TiO2 composite as a carrier, and active components of Pd and Ag loaded on the carrier, wherein the Pd content accounts for 0.15-0.5wt% of the total weight of the catalyst, and the Ag content accounts for 0.8-4.5wt% of the total weight of the catalyst. Compared with hydrogenation methods using catalysts of the same kind, the method for the hydrogenation of the alkyne and/or diolefin contained petroleum hydrocarbons, especially the cracked gasoline or its fractions, through adopting the catalyst of the invention has the advantages of high hydrogenation selectivity at a low temperature, strong As impurity resistance, large charging capacity, and stable activity.
Description
Technical field
The present invention relates to a kind of employing palladium-Yin/aluminium oxide-titanium oxide catalyzer to petroleum hydrocarbon, particularly the method for pyrolysis gasoline or its cut selective hydrogenation.
Background technology
Pyrolysis gasoline C
5-C
9cut is the by product of ethylene industry, and according to the difference of cracking stock and cracking severity, more than its output accounts for 50 % by weight of ethylene production capacity, wherein aromaticity content accounts for 40-80 % by weight, is therefore the main source of aromatic hydrocarbons.In industrial production, cut C
8and C
9cut, through one-stage hydrogenation, removes height unsaturated hydrocarbons, as chain conjugated dienes, vinylbenzene, alkynes and cyclic conjugated diene class, then through Secondary hydrodesulfurization, removes after the organic compound such as monoene and sulphur, nitrogen, oxygen C
8cut is for the production of dimethylbenzene, C
9cut is for the production of aromatic solvent naphtha.C
8cut also can be removed diolefin only through a hydrogenation, retains most of monoene, obtains stable motor spirit admixture or the higher motor spirit of octane value.
Current industrial pyrolysis gasoline C
5-C
9the catalyzer of cut selective hydrogenation is mainly Ni/Al
2o
3or Pd/Al
2o
3, also have Pd-Cr/Al
2o
3bimetallic catalyst.Because the impurity such as As, S, O, N in pyrolysis gasoline and colloid (high molecular polymer that the unsaturated component generation polymerization such as diolefine and vinylbenzene produces) content is higher, existing catalyst deactivation is very fast, makes catalyzer have to frequent activation and regeneration.In current industrial production, pyrolysis gasoline C
5-C
9the Pd/Al that cut selective hydrogenation is used
2o
3the shortest regeneration period of catalyzer is 7 days.Therefore, wish that hydrogenation catalyst has higher low temperature active, the appearance glue ability that stronger anti-impurity is poisoning and suitable, to increase the catalyst regeneration cycle, thus extending catalyst work-ing life, this is very important in industrial production.
The open CN1665588A of Chinese patent application discloses palladium-Yin hydrogenation catalyst and preparation method thereof, solid support material is selected from aluminum oxide, silicon-dioxide, titanium oxide, zirconium white, aluminosilicate, zinc titanate and composition thereof, carrier is preferably aluminum oxide, described catalyst composition has the about 0.01-0.6wt% of palladium content, silver content is about 0.02-5wt%, and iodine content is about 10-1000ppm, its contriver claims that this catalyzer is for the fluid material of height unsaturated hydrocarbons, especially for acetylene, there is good selectivity and transformation efficiency and lower deactivation rate, but its anti-arsenic impurities performance still leaves some room for improvement.The open CN100506380C of Chinese patent discloses a kind of catalyzer for pyrolysis gasoline selective hydrogenation, and carrier is selected aluminum oxide, and catalyst activity component comprises: (a) activity component metal palladium and the oxide compound thereof of 0.01-0.5%; (b) 0.01-0.8%'s is selected from least one element and the oxide compound thereof in IA in the periodic table of elements or IIA; (c) 0.01-20.0% is selected from least one element and the oxide compound thereof in IVA in the periodic table of elements or VA.Its contriver claims that this catalyzer is for the selective hydrogenation of alkynes or the diolefin of petroleum hydrocarbon, especially for the full cut (C of pyrolysis gasoline
5hydrocarbon-do is the hydrocarbon compound cut of 204 ℃) or C
6-C
8the hydrogenation of hydrocarbon compound middle runnings has higher low temperature active, selectivity and stability, and has good freedom from jamming, resistance to high colloid and the free-water of resistance to high-content performance, but its low temperature active and stability still have much room for improvement.
In order to overcome the above-mentioned problems in the prior art, the present inventor discloses a kind of catalyzer for pyrolysis gasoline selective hydrogenation in the open CN1429890A of Chinese patent application, mixture comprising the titanium dioxide-aluminum oxide as carrier, and be carried on the activity component metal palladium on this complexes carrier, wherein the content of palladium metal is 0.25-0.35 % by weight based on described total catalyst weight.Compare with existing similar catalyst, while using this catalyzer, liquid phase air speed improves 30-40%, and selectivity is greater than 99%, and continuous operation 1500 hours is activity stabilized.Yet this catalyzer is to pyrolysis gasoline C
8, C
9during last running selective hydrogenation, the ability of preventing from heavy metal As haves much room for improvement.
The present inventor discloses a kind of pyrolysis gasoline C in the open CN1635054A of Chinese patent application
5-C
9cut, especially C
8, C
9the palladium series catalyst of last running selective hydrogenation, it comprises aluminum oxide as carrier, is covered in alkaline-earth metal or its oxide compound and the metal Pd on described carrier and Mo or Pd and W as active constituent loading on described carrier surface, wherein the content of alkaline-earth metal is 1-3 % by weight based on described total catalyst weight, and Pd content is 0.24-0.35 % by weight based on described total catalyst weight.This catalyzer is used for pyrolysis gasoline C
5-C
9full cut, particularly C
8, C
9last running selective hydrogenation process, its low temperature active is high, and anti-As, S, O and N impurity ability are strong, and charging capacity is large.Yet the stability of this catalyzer haves much room for improvement.
Summary of the invention
In view of above-mentioned prior art situation, the inventor has carried out research extensively and profoundly to petroleum hydrocarbon, particularly pyrolysis gasoline or its cut selective hydrogenation with catalyzer, found that the catalyzer that active ingredient Pd and Ag are carried on aluminium oxide-titanium oxide complexes carrier not only has high low temperature active, and anti-impurity is high with appearance glue ability, good stability.The present invention is accomplished based on above discovery just.
Therefore, the object of this invention is to provide a kind of method of palladium-Yin/aluminium oxide-titanium oxide catalyzer to petroleum hydrocarbon, particularly pyrolysis gasoline or its cut selective hydrogenation that adopt.
One aspect of the present invention provides a kind of palladium-silver catalyst that adopts to the petroleum hydrocarbon containing alkynes and/or diolefin, especially the method for pyrolysis gasoline or its cut selective hydrogenation, described catalyzer comprises the aluminium oxide-titanium oxide mixture as carrier, and be carried on active ingredient Pd and the Ag on described complexes carrier, wherein the gross weight of the content of Pd based on described catalyzer is 0.15-0.5 % by weight, and the content of Ag is 0.8-4.5 % by weight based on described total catalyst weight.In the present invention, the cut of pyrolysis gasoline comprises for example C
6-C
8cut, C
8cut and C
9cut.
These and other purposes, features and advantages of the present invention are considered, after the present invention, will be easy to be understood by persons of ordinary skill in integral body.
In the inventive method catalyzer used, the gross weight as the content of the palladium of catalytic active component based on this catalyzer is 0.15-0.5 % by weight, preferably 0.26-0.32 % by weight.
In the inventive method catalyzer used, the gross weight as the silver-colored content of catalytic active component based on this catalyzer is 0.8-4.5 % by weight, preferably 1.0-4.0 % by weight.
In the inventive method catalyzer used, aluminium oxide-titanium oxide complexes carrier used is not particularly limited, for example the specific surface area of this complexes carrier is 50-120 rice
2/ gram, preferred 70-100 rice
2/ gram, pore volume is 0.4-1.5 ml/g, preferred 0.4-1.2 ml/g, and most probable aperture is 100-260 dust, preferably 110-200 dust.Titanium oxide content is 5-20 % by weight, the gross weight based on aluminium oxide-titanium oxide complexes carrier.In addition, the shape of aluminium oxide-titanium oxide complexes carrier is not particularly limited, for example, can be cylindricality, bar shaped, spherical or cloverleaf pattern.
In the present invention, specific surface area, pore volume and most probable aperture adopt nitrogen adsorption (BET) method to measure.
Aluminium oxide-titanium oxide complexes carrier can be prepared aluminium oxide-titanium oxide mixture as coprecipitation method or mechanical mixing by any appropriate method known to those skilled in the art, is then configured as the carrier of desired shape, as prepared by cloverleaf pattern.As selection, aluminium oxide-titanium oxide complexes carrier also can by aluminum oxide molding, deposit titanium oxide or on titanium oxide molding deposition of aluminium oxide prepare.
It should be noted that, catalyzer of the present invention does not expressly comprise iodine.
The inventive method used catalyst can be prepared by the following method:
(a) aluminium oxide-titanium oxide complexes carrier is measured to the Ag source compound solution impregnation 1-4 hour that equate with final catalyzer containing Ag with containing at least, the volume of wherein said silver-colored source compound solution is 0.8-2.5 times of described complexes carrier pore volume equivalent volumes, then drain, at the temperature of 100-150 ℃, dry 4-20 hour, makes catalyzer work in-process; With
(b) the catalyzer work in-process that make in step (a) are measured to the Pd source compound solution impregnation 1-4 hour that equate with final catalyzer containing Pd with containing at least, the volume of wherein said palladium source compound solution is 0.8-2.0 times of described complexes carrier pore volume equivalent volumes, subsequent filtration, then use hydrazine hydrate reduction, with deionized water wash, then at the temperature of 100-150 ℃, be dried 4-20 hour, then in the roasting temperature 3-8 hour of 400-600 ℃, make supported palladium and silver-colored catalyzer.
In preparing the method for catalyzer of the present invention, aluminium oxide-titanium oxide complexes carrier used can be the disclosed any aluminium oxide-titanium oxide complexes carrier that is suitable for preparing petroleum hydrocarbon hydrogenation catalyst of prior art.Preferably, the specific surface area of this complexes carrier is 50-120 rice
2/ gram, pore volume is 0.4-1.5 ml/g, most probable aperture is 100-260 dust.Further preferably, in this aluminium oxide-titanium oxide complexes carrier, titanium oxide content is 5-20 % by weight.
In preparing the method for the inventive method used catalyst, palladium source compound used can be the disclosed any palladium compound that is suitable for preparing palladium catalyst of prior art, if the organic acid salt of palladium metal, Palladous chloride, Palladous nitrate, palladous sulfate, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, tetranitro palladium acid sodium, palladium is as oxalic acid palladium etc. or its mixture.The present invention is not particularly limited the concentration of palladium source compound solution, for example, can be 0.15-0.75 % by weight, preferably 0.2-0.7 % by weight.The present invention is not particularly limited the type of palladium source compound solution, as long as it can be impregnated in titanium dioxide-aluminum oxide complexes carrier, it can be the aqueous solution, also can be the organic solution that ethanol, benzene etc. form as solvent, but use organic solution cost higher, and also have pollution problem, so the present invention preferably uses the aqueous solution of palladium source compound.
In preparing the method for the inventive method used catalyst, silver-colored source compound used can be the disclosed any silver compound that is applicable to prepare silver catalyst of prior art, as silver oxide, oxyhydroxide, sulfide, vitriol, halogenide (as silver chloride and Silver iodide), nitrate and oxalate etc. or its mixture.The present invention is not particularly limited the concentration of silver-colored source compound solution, for example, can be 0.9-7 % by weight, preferably 1.2-4 % by weight.The present invention is not particularly limited the type of silver-colored source compound solution, as long as it can be impregnated in titanium dioxide-aluminum oxide complexes carrier, it can be the aqueous solution, also can be the organic solution that ethanol, benzene etc. form as solvent, but use organic solution cost higher, and also have pollution problem, so the present invention preferably uses the aqueous solution of silver-colored source compound.
In above-mentioned steps (b), after dipping, use hydrazine hydrate reduction, so that palladium source compound and silver-colored source compound are reduced.For this reason, hydrazine hydrate is preferably used as ethanolic soln with the aqueous solution of 8-40 % by weight or alcoholic solution, and preferably the aqueous solution with 8-40 % by weight is used.The consumption of hydrazine hydrate solution is answered the catalyzer work in-process of preparation in submergence step (a), and preferably its consumption is that every milliliter of catalyzer work in-process are used 1-3ml hydrazine hydrate solution.With the reduction of hydrazine hydrate, conventionally at 10-60 ℃ of temperature, carry out, the time is generally 0.1-2 hour.After reduction, separation, for example, by filtering separation, and water, preferably deionized water wash.For example, in the situation that using Palladous chloride as palladium source compound, with deionized water, fully wash, until without chlorion, this checks to carry out by silver nitrate solution.After washing, the washed product of gained is dry at 100-150 ℃, and this carries out 4-20 hour conventionally.Then, by the roasting at 400-600 ℃ of the product of drying, this carries out 3-8 hour conventionally, makes supported palladium and silver-colored catalyzer.
In step (b) afterwards, optionally the supported catalyst obtaining in step (b) is activated with hydrogen reducing.As selection, the supported catalyst obtaining in step (b) also can restore activation when petroleum hydrocarbon, especially pyrolysis gasoline for to containing alkynes and/or diolefin or its fraction selective hydrogenation.
Before carrying out the selective hydrogenation of petroleum hydrocarbon, advantageously supported palladium and silver-colored catalyzer are carried out to reduction activation with hydrogen.If reduction activation is carried out in catalyst preparation stages, the supported catalyst obtaining in step (b) is activated with hydrogen reducing, this is that 100-150 ℃, reaction pressure are that 2.0-5.0MPa and hydrogen flowing quantity are to carry out under the condition of 2.7-20 ml/g of catalyzer minute in temperature conventionally; The reduction activation time is generally 6-18 hour.
If the reduction activation of catalyzer is being close to petroleum hydrocarbon, especially carry out before the selective hydrogenation of pyrolysis gasoline or its cut, this reduction activation is that 100-150 ℃, reaction pressure are that 2.0-5.0MPa and hydrogen flowing quantity are to carry out under the condition of 2.7-20 ml/g of catalyzer minute in temperature equally; The reduction activation time is generally 6-18 hour.
In the methods of the invention, reactor is not particularly limited, but preferably the inventive method is carried out in fixed-bed reactor.
In the methods of the invention, the selective hydrogenation of petroleum hydrocarbon, especially pyrolysis gasoline or its cut is carried out under normal condition.Advantageously, this selective hydrogenation is that 25-60 ℃ and reaction pressure are 2.0-3.0MPa in temperature in, and hydrogen to oil volume ratio is 50: 1-200: 1 and liquid phase air speed be 4-16h
-1condition under carry out.In the present invention, adopt palladium-silver catalyst to petroleum hydrocarbon, especially pyrolysis gasoline or its cut selective hydrogenation have following outstanding advantage and effect:
(1) under cold condition, the hydrogenation activity of palladium-silver catalyst is higher than existing palladium or nickel catalyst;
(2), when the present invention adopts the selective hydrogenation of palladium-silver catalyst, there is the ability of stronger anti-As, S, O, N impurity;
(3) the inventive method hydrogenation activity is stable, and palladium-silver catalyst can long period be used.
Embodiment
Below by embodiment, the present invention has been carried out to further elaboration, but these embodiment are in no case construed as limiting to scope of the present invention.
Embodiment 1
1. the preparation of carrier
Getting specific surface area is 110 meters
2/ gram, pore volume is 0.59 ml/g, most probable aperture is 88 grams, the cloverleaf pattern aluminum oxide of 130 dusts, dilution heat of sulfuric acid dipping with 0.557 grams per milliliter of 65 milliliters of titanium sulfates, stirs 15 minutes, in 120 ℃ be dried 8 hours after, in 900 ℃ of roastings 4 hours, make titanium dioxide-aluminum oxide mixture.The titanium oxide content of this mixture is 11.87 % by weight, and specific surface area is 87 meters
2/ gram, pore volume is 0.53 ml/g, most probable aperture is 123 dusts.
2. the half-finished preparation of catalyzer
Get 100 grams of the titanium dioxide-aluminum oxide mixtures of above-mentioned preparation, by concentration with Ag
2o counts 0.97 gram of Ag
2110 milliliters of the silver oxalate aqueous solution of 0/100ml are poured in described complexes carrier, stir 20 minutes, and standing 1.5 hours, drain away the water, be dried 10 hours in 120 ℃, make catalyzer work in-process A1-1.
3. the preparation of catalyzer.
It is in the palladium chloride aqueous solution of 0.318 gram of Pd/100 milliliter that 90 grams of catalyzer work in-process A1-1 that prepare are above immersed to 85 milliliters of palladium content, 1.5 take out after hour, leach the complexes carrier of dipping, with the hydrazine hydrate aqueous solution that 120 ml concns are 10 % by weight, at room temperature reduce 1 hour, with deionized water, repeatedly rinse, till clean chlorion, after draining away the water, at 120 ℃, be dried 6 hours, then roasting 4 hours at 480 ℃, making palladium content is that 0.30 % by weight, Ag content are the Pd-Ag/TiO of 0.99 % by weight
2-Al
2o
3catalyzer (A1-2).
Embodiment 2
Repeat embodiment 1, different: to use concentration with Ag
2o counts 3.906 grams of Ag
296 grams, 110 milliliters of oxide impregnation titanium-alumina compound carriers of the silver oxalate aqueous solution of O/100ml, and working concentration is 90 grams of catalyzer work in-process of 85 milliliters of palladium chloride aqueous solutions dipping of 0.307 gram of palladium/100ml, makes catalyst B 1-2, the results are shown in Table 1.
Embodiment 3
Repeat embodiment 1, different: to use concentration with Ag
2o counts 1.96 grams of Ag
298 grams, 110 milliliters of oxide impregnation titanium-alumina compound carriers of the silver oxalate aqueous solution of O/100ml, and working concentration is 90 grams of catalyzer work in-process of 85 milliliters of palladium chloride aqueous solutions dipping of 0.307 gram of palladium/100ml, makes catalyzer C1-2, the results are shown in Table 1.
Embodiment 4
Repeat embodiment 1, different: to use concentration with Ag
2o counts 1.96 grams of Ag
298 grams, 110 milliliters of oxide impregnation titanium-alumina compound carriers of the silver oxalate aqueous solution of O/100ml, and working concentration is 90 grams of catalyzer work in-process of 85 milliliters of palladium chloride aqueous solutions dipping of 0.212 gram of palladium/100ml, makes catalyzer D1-2, the results are shown in Table 1.
Embodiment 5
Repeat embodiment 1, different: to use concentration with Ag
2o counts 2.93 grams of Ag
297 grams, 110 milliliters of oxide impregnation titanium-alumina compound carriers of the silver oxalate aqueous solution of O/100ml, and working concentration is 90 grams of catalyzer work in-process of 85 milliliters of palladium chloride aqueous solutions dipping of 0.424 gram of palladium/100ml, makes catalyzer E1-2, the results are shown in Table 1.
Table 1
Embodiment 6
The catalyzer of the present embodiment explanation embodiment 1-5 gained is at pyrolysis gasoline C
8application in cut selective hydrogenation.Evaluating catalyst experiment is carried out on 100ml small fixed hydrogenation evaluating apparatus, and the reactor of this evaluating apparatus is reaction tubes, reaction tube length 1500mm, internal diameter 25mm, therein loading catalyst.
Getting each 75 grams of catalyst A 1-2, B1-2, C1-2, D1-2, E1-2 that embodiment 1-5 makes and be loaded in reaction tubes, is 2.8MPa in reaction pressure, and temperature is that 110 ℃ and hydrogen flowing quantity are to reduce 8 hours under the condition of 5.3 mls/g of catalyzer minute.Then in reaction pressure, be 2.8MPa, temperature in is 30 ℃, and hydrogen to oil volume ratio is 80: 1, and liquid phase air speed is 8h
-1condition under to pass into diene value be 23.5 grams of iodine/100 gram oil, bromine valency is 42.1 grams of bromine/100 gram oil, the pyrolysis gasoline C that arsenic content is 260ppb
8cut, hydrogenation the results are shown in Table shown in 2.
Table 2
Embodiment 7
The catalyst B 1-2 of the present embodiment explanation embodiment 2 gained is at pyrolysis gasoline C
8application in cut selective hydrogenation.
Getting according to 54 grams of the B1-2 catalyzer of the embodiment of the present invention 2 preparation and be loaded in reaction tubes, is 2.8Mpa in reaction pressure, and temperature is that 110 ℃ and hydrogen flowing quantity are to reduce 8 hours under the condition of 5.3 mls/g of catalyzer minute.Then, in reaction pressure, be 2.8Mpa, temperature in is 60 ℃, and hydrogen to oil volume ratio is 80: 1, and liquid phase air speed is 8.0h
-1recycle ratio (that is, the hydrogenation products that reaction tubes is discharged and the volume ratio of fresh feed) be the condition of 3: 1 to pass into diene value be 19.3 grams of iodine/100 gram oil, bromine valency is 37.6 grams of bromine/100 gram oil, arsenic content is 260ppb, and gum level is 100mg/100ml pyrolysis gasoline C
8cut, the hydrogenation of catalyzer the results are shown in Table 3.
Comparative example 1
The program that repeats embodiment 7 is different: the LD365 palladium series catalyst that catalyzer adopts IFP to produce, hydrogenation the results are shown in Table 3.
Comparative example 2
Getting 72 milliliters of HTC-200S nickel catalysts that Britain Hopkinson Associates Ltd. produces is loaded in reaction tubes.In reaction pressure, be under 2.8MPa, with the hydrogen flow rate of 200 ml/min milliliter catalyzer, pass into hydrogen, with 100 ℃/h of heat-up rates, whole beds is heated to 150 ℃, keep 1 hour with reducing catalyst, be down to subsequently temperature of reaction.Repeat afterwards the hydrogenation process in embodiment 7.Hydrogenation the results are shown in Table 3.
Table 3
Note: the active component palladium content of LD365 catalyzer is 0.33 % by weight, carrier is aluminum oxide.
The active component nickel content of HTC-200S is 16 % by weight, and carrier is aluminum oxide.
Embodiment 8
Repeat embodiment 7, different: the consumption of B1-2 catalyzer changes does 37.5 grams.Hydrogenation the results are shown in Table 4.
Comparative example 3
Repeat embodiment 7, different: (this catalyzer is called P-C-2 in this article to adopt palladium/titanium dioxide-aluminum oxide catalyzer C-2 that in the open CN1429890A of Chinese patent application prepared by embodiment 2, its active ingredient Pd content is 0.3 % by weight, carrier is titanium dioxide-aluminum oxide complexes carrier) 37.5 grams be loaded in reaction tubes, and in temperature, be 100 ℃, reaction pressure is that 2.6MPa and hydrogen flowing quantity are reducing catalyst 8 hours under the condition of 50 ml/min.Hydrogenation the results are shown in Table 4.
Comparative example 4
(this catalyzer is called P-Ni-C5 to nickel/titanium dioxide-aluminum oxide catalyzer of employing embodiment 5 preparations in Chinese patent application 200910081684.4 in this article, its active ingredient Ni content is 16.02 % by weight, carrier is titanium dioxide-aluminum oxide complexes carrier) 37.5 grams be loaded in reaction tubes, and be 0.5MPa in reaction pressure, hydrogen flowing quantity is 2.7 mls/g of catalyzer minute, temperature is under the condition of 420 ℃, by catalyst reduction 20 hours; Afterwards, beds is cooled to 40 ℃, adopt Methyl disulfide to sneak into mixture that hexanaphthene obtains as vulcanized oil, and the weight of sulphur content based on this vulcanized oil is 0.5 % by weight, in reaction pressure, be 0.5MPa, temperature is 40 ℃, and hydrogen flowing quantity is 2.7 mls/g of catalyzer minute, vulcanized oil inlet amount is under the condition of 1.2g/g catalyzer hour, pre-sulfide catalyst 20 hours.Repeat afterwards the hydrogenation process in embodiment 7.Hydrogenation the results are shown in Table 4.
Table 4
Comparative example 5
The explanation of this comparative example and Pd-Ag/Al
2o
3the performance of the catalyst B 1-2 of the present invention that catalyzer is compared.
1.Pd-Ag/Al
2o
3the preparation of catalyzer
Getting specific surface area is 88 meters
2/ gram, pore volume is 0.52 ml/g, most probable aperture is the Al of 124 dusts
2o
398 grams, carrier, by concentration with Ag
2o counts 3.906 grams of Ag
2110 milliliters of the silver oxalate aqueous solution of O/100ml are poured described Al into
2o
3in carrier, stir 20 minutes, standing 1.5 hours, drain away the water, in 120 ℃ dry 10 hours, make catalyzer work in-process F1-1.
It is in the palladium chloride aqueous solution of 0.309 gram of Pd/100 milliliter that 90 grams of catalyzer work in-process F1-1 that prepare are above immersed to 85 milliliters of palladium content, after 1.5 hours, take out, leach the complexes carrier of dipping, with the hydrazine hydrate aqueous solution that 120 ml concns are 10 % by weight, at room temperature reduce 1 hour, with deionized water, repeatedly rinse, till clean chlorion, after draining away the water, at 120 ℃, be dried 6 hours, then roasting 4 hours at 480 ℃, making palladium content is that 0.29 % by weight, Ag content are the Pd-Ag/Al of 4.02 % by weight
2o
3catalyzer (F1-2).
2. performance comparison
Get respectively F1-2 and the B1-2 catalyzer of 54 grams, repeat the program of embodiment 7 and carry out comparative evaluation, the results are shown in Table 5.
Table 5
Embodiment 9
2 catalyst B 1-2 are at pyrolysis gasoline C for the present embodiment explanation embodiment of the present invention
6-C
8application in cut selective hydrogenation.
Getting according to 75 grams of the B1-2 catalyzer of embodiment 2 preparation and be loaded in reaction tubes, repeat the reduction process to catalyzer in embodiment 7, is 2.8MPa in reaction pressure afterwards, and hydrogen to oil volume ratio is 80: 1, and liquid phase air speed is 12.0h
-1, temperature in is that under the condition of 30 ℃, passing into diene value is 16.50 grams of iodine/100 gram oil, and bromine valency is 28.52 grams of bromine/100 gram oil, and sulphur content is 173ppm, and boiling range is the pyrolysis gasoline C of 81-157 ℃
6-C
8cut, hydrogenation the results are shown in Table 6.
Table 6
Embodiment 10
The catalyst B 1-2 of the present embodiment explanation embodiment of the present invention 2 is at pyrolysis gasoline C
9application in last running selective hydrogenation.
Getting according to 75 grams of the B1-2 catalyzer of embodiment 2 preparation and be loaded in reaction tubes, repeat the reduction process to catalyzer in embodiment 7, is 2.4-2.6MPa in reaction pressure afterwards, and hydrogen to oil volume ratio is 100: 1, and liquid phase air speed is 8.0h
-1, reactor inlet temperature is 30 ℃, temperature out is under the condition of 60-70 ℃, passing into boiling range is 98-202 ℃, and diene value is 9.87 grams of iodine/100 gram oil, and bromine valency is 35.67 grams of bromine/100 gram oil, arsenic content is 280ppb, the pyrolysis gasoline C that gum level is 120mg/100ml
9cut, hydrogenation the results are shown in Table 7.
Table 7
Embodiment 11
The present embodiment explanation catalyst B 1-2 of the present invention and comparative catalyst P-C-2 (Pd/TiO
2-Al
2o
3) and F1-2 (Pd-Ag/Al
2o
3) at pyrolysis gasoline C
8anti-arsenic Performance Ratio in fraction selective hydrogenation.
Get respectively B1-2, P-C-2 (Pd/TiO
2-Al
2o
3, referring to comparative example 3) and F1-2 (Pd-Ag/Al
2o
3, referring to comparative example 5) and each 54 grams of catalyzer, repeat embodiment 7, different is at pyrolysis gasoline C
8in cut, adding arsenic acid to regulate arsenic content is 330ppb, 470ppb and 528ppb, and the hydrogenation of three kinds of catalyzer the results are shown in Table 8.
Table 8
Note: three kinds of catalyzer are used the under equal conditions experiment continuously of three hydrogenation small testing devices, experimental period 700 hours altogether, the pyrolysis gasoline C to different arsenic content
8cut charging order is 330ppb, 470ppb and 528ppb successively.Therefore product bromine valency and diene value have increase trend.
Claims (12)
1. one kind adopts the method for palladium-silver catalyst to the selective hydrogenation of petroleum hydrocarbon containing alkynes and/or diolefin, described catalyzer comprises the aluminium oxide-titanium oxide mixture as carrier, and be carried on active ingredient Pd and the Ag on described complexes carrier, wherein the gross weight of the content of Pd based on described catalyzer is 0.15-0.5 % by weight, and the content of Ag is 0.8-4.5 % by weight based on described total catalyst weight.
2. method according to claim 1, wherein said petroleum hydrocarbon is pyrolysis gasoline or its cut.
3. method according to claim 1, wherein the gross weight of the content of palladium based on described catalyzer is 0.26-0.32 % by weight, the content of silver is 1.0-4.0 % by weight based on described total catalyst weight.
4. method according to claim 2, wherein the gross weight of the content of palladium based on described catalyzer is 0.26-0.32 % by weight, the content of silver is 1.0-4.0 % by weight based on described total catalyst weight.
5. according to the method described in any one in claim 1-4, the specific surface area of wherein said aluminium oxide-titanium oxide complexes carrier is 50-120 rice
2/ gram, it is 100-260 dust with most probable aperture that pore volume is 0.4-1.5 ml/g.
6. method according to claim 5, the specific surface area of wherein said aluminium oxide-titanium oxide complexes carrier is 70-100 rice
2/ gram, it is 110-200 dust with most probable aperture that pore volume is 0.4-1.2 ml/g.
7. according to the method described in any one in claim 1-4, wherein titanium oxide content is 5-20 % by weight, the gross weight based on described aluminium oxide-titanium oxide complexes carrier.
8. method according to claim 5, wherein titanium oxide content is 5-20 % by weight, the gross weight based on described aluminium oxide-titanium oxide complexes carrier.
9. according to the method described in any one in claim 1-4, wherein the method is carried out in fixed-bed reactor.
10. according to the method described in any one in claim 1-4, it is included in temperature is 100-150 ℃, and reaction pressure is that 2.0-5.0MPa and hydrogen flowing quantity are palladium-silver catalyst described in reduction activation under the condition of 2.7-20 ml/g of catalyzer minute.
11. methods according to claim 10,6-18 hour is carried out in wherein said reduction.
12. according to the method described in any one in claim 1-4, and wherein selective hydrogenation is that 25-60 ℃ and reaction pressure are 2.0-3.0MPa in temperature in, and hydrogen to oil volume ratio is that 50:1-200:1 and liquid phase air speed are 4-16h
-1condition under carry out.
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| CN107497426B (en) * | 2017-08-30 | 2020-06-09 | 江苏大学 | Preparation method and application of palladium/silver alloy nano catalyst |
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| CN1429890A (en) * | 2001-12-31 | 2003-07-16 | 北京燕山石油化工公司研究院 | Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use |
| CN1635054A (en) * | 2003-12-31 | 2005-07-06 | 中国石油化工股份有限公司北京燕山分公司研究院 | Catalyst for gasoline heavy fraction pyrolysis and selective hydrogenation, process for preparation and use thereof |
| CN1665588A (en) * | 2002-06-14 | 2005-09-07 | 切夫里昂菲利普化学有限责任公司 | Hydrogenation palladium-silver catalysts and methods for their preparation |
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| CN1429890A (en) * | 2001-12-31 | 2003-07-16 | 北京燕山石油化工公司研究院 | Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use |
| CN1665588A (en) * | 2002-06-14 | 2005-09-07 | 切夫里昂菲利普化学有限责任公司 | Hydrogenation palladium-silver catalysts and methods for their preparation |
| CN1635054A (en) * | 2003-12-31 | 2005-07-06 | 中国石油化工股份有限公司北京燕山分公司研究院 | Catalyst for gasoline heavy fraction pyrolysis and selective hydrogenation, process for preparation and use thereof |
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