CN102732294A - 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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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, its output accounts for more than the 50 weight % of ethylene production capacity, and wherein aromaticity content accounts for 40-80 weight %, is the main source of aromatic hydrocarbons therefore.Cut C on the industrial production
8And C
9Cut through one-stage hydrogenation, is removed the height unsaturated hydrocarbons, like chain conjugated dienes, vinylbenzene, alkynes and cyclic conjugated diene class, and again through the secondary hydrogenation desulfurization, behind the organic cpds such as removal monoene and sulphur, nitrogen, oxygen, C
8Cut is used to produce YLENE, C
9Cut is used to produce aromatic solvent naphtha.C
8Cut also can be removed diolefin only through a hydrogenation, keeps most of monoene, obtains stable motor spirit admix or the higher motor spirit of octane value.
Pyrolysis gasoline C is gone up in industry at present
5-C
9The catalyzer of cut selective hydrogenation mainly is Ni/Al
2O
3Or Pd/Al
2O
3, Pd-Cr/Al is also arranged
2O
3Bimetallic catalyst.Because impurity such as As, S, O, N and colloid (high molecular polymer that unsaturated component generation polymerization such as diolefine and vinylbenzene produces) content are higher in the pyrolysis gasoline, existing catalyst deactivation is very fast, makes catalyzer have to frequent activation and regeneration.In present industrial production, pyrolysis gasoline C
5-C
9The Pd/Al that the cut selective hydrogenation is used
2O
3The shortest regeneration period of catalyzer is 7 days.Therefore, hope that hydrogenation catalyst has higher low temperature active, stronger anti-impurity is poisoned and suitable appearance glue ability, increasing the catalyst regeneration cycle, thereby prolongs catalyzer work-ing life, and this ten minutes in industrial production is important.
The open CN1665588A of one 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, and described catalyst composition has the about 0.01-0.6wt% of palladium content, and silver content is about 0.02-5wt%; And iodine content is about 10-1000ppm; Its contriver claims the fluid material of this catalyzer for the height unsaturated hydrocarbons, especially has good selectivity and transformation efficiency and lower deactivation rate for acetylene, but its anti-arsenic impurities performance still leaves some room for improvement.The open CN100506380C of Chinese patent discloses a kind of catalyzer that is used for the pyrolysis gasoline selective hydrogenation, and carrier is selected aluminum oxide for use, and the 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 a element and the oxide compound thereof among IA in the periodic table of elements or the IIA; (c) 0.01-20.0% is selected from least a element and the oxide compound thereof among IVA in the periodic table of elements or the VA.Its contriver claims the selective hydrogenation of this catalyzer for the alkynes or the diolefin of petroleum hydrocarbon, especially for the full cut (C of pyrolysis gasoline
5Hydrocarbon-do is 204 ℃ a hydrocarbon compound cut) 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, anti-high colloid and the free-water of anti-high-content performance, but its low temperature active and stability still remain to be improved.
In order to overcome the problems referred to above that exist in the prior art; Contriver of the present invention discloses a kind of catalyzer that is used for the pyrolysis gasoline selective hydrogenation in the open CN1429890A of one Chinese patent application; Comprising mixture as the titanium dioxide-aluminum oxide of 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 weight % based on said total catalyst weight.Compare with existing similar catalyst, the liquid phase air speed improves 30-40% when using this catalyzer, and selectivity is greater than 99%, and continuous operation 1500 hours is activity stabilized.Yet this catalyzer is to pyrolysis gasoline C
8, C
9The ability of preventing from heavy metal As haves much room for improvement during the last running selective hydrogenation.
Contriver of the present invention discloses a kind of pyrolysis gasoline C in the open CN1635054A of one 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, be covered on the said carrier surface earth alkali metal or its oxide compound and as metal Pd and Mo or Pd and the W of active constituent loading on said carrier; Wherein the content of earth alkali metal is 1-3 weight % based on said total catalyst weight, and Pd content is 0.24-0.35 weight % based on said total catalyst weight.This catalyzer is used for pyrolysis gasoline C
5-C
9Full cut, particularly C
8, C
9The last 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 big.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; The result finds that the catalyzer that active ingredient Pd and Ag are carried on the 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 just is being based on above discovery and is being accomplished.
Therefore, the purpose of this invention is to provide a kind of method that adopts palladium-Yin/aluminium oxide-titanium oxide catalyzer to petroleum hydrocarbon, particularly pyrolysis gasoline or its cut selective hydrogenation.
One aspect of the present invention provides a kind of palladium-silver catalyst that adopts to containing the petroleum hydrocarbon of alkynes and/or diolefin; Especially the method for pyrolysis gasoline or its cut selective hydrogenation; Said catalyzer comprises the aluminium oxide-titanium oxide mixture as carrier; And be carried on active ingredient Pd and the Ag on the said complexes carrier, and wherein the content of Pd is 0.15-0.5 weight % based on the gross weight of said catalyzer, the content of Ag is 0.8-4.5 weight % based on said total catalyst weight.In the present invention, the cut of pyrolysis gasoline comprises for example C
6-C
8Cut, C
8Cut and C
9Cut.
Of the present invention these with other purpose, feature and advantage after integral body is considered the present invention, will be easy to understood by those of ordinary skill.
In the used catalyzer of the inventive method, be 0.15-0.5 weight % as the content of the palladium of catalytic active component based on the gross weight of this catalyzer, preferred 0.26-0.32 weight %.
In the used catalyzer of the inventive method, be 0.8-4.5 weight % as the content of the silver of catalytic active component based on the gross weight of this catalyzer, preferred 1.0-4.0 weight %.
In the used catalyzer of the inventive method, used aluminium oxide-titanium oxide complexes carrier there is not particular restriction, for example the specific surface area of this complexes carrier is a 50-120 rice
2/ gram, preferred 70-100 rice
2/ gram, pore volume is 0.4-1.5 milliliter/gram, preferred 0.4-1.2 milliliter/gram, the most probable aperture is the 100-260 dust, preferred 110-200 dust.Titanium oxide content is 5-20 weight %, based on the gross weight of aluminium oxide-titanium oxide complexes carrier.In addition, the shape of aluminium oxide-titanium oxide complexes carrier is not had particular restriction, for example can be cylindricality, bar shaped, sphere or cloverleaf pattern.
In the present invention, specific surface area, pore volume and most probable aperture adopt nitrogen adsorption (BET) method to measure.
Any appropriate method that the aluminium oxide-titanium oxide complexes carrier can be known by one of skill in the art such as coprecipitation method or mechanical mixing prepare the aluminium oxide-titanium oxide mixture, are configured as the carrier of desired shape then, prepare like cloverleaf pattern.As selection, the aluminium oxide-titanium oxide complexes carrier also can through on the aluminum oxide molding deposition titanium oxide or on the titanium oxide molding deposition of aluminium oxide prepare.
Need to prove that catalyzer of the present invention does not expressly comprise iodine.
The inventive method catalyst system therefor can prepare through following method:
(a) the aluminium oxide-titanium oxide complexes carrier is contained Ag source compound solution impregnation 1-4 hour that the Ag amount equates with containing at least with final catalyzer; The volume of wherein said silver-colored source compound solution is 0.8-2.5 a times of said complexes carrier pore volume equivalent volumes; Drain then; Under 100-150 ℃ temperature dry 4-20 hour, make the catalyzer work in-process; With
(b) the catalyzer work in-process that make in the step (a) are contained Pd source compound solution impregnation 1-4 hour that the Pd amount equates with containing at least with final catalyzer; The volume of wherein said palladium source compound solution is 0.8-2.0 a times of said complexes carrier pore volume equivalent volumes, and subsequent filtration is used hydrazine hydrate reduction then; Use deionized water wash; Under 100-150 ℃ temperature dry 4-20 hour then,, make the catalyzer of supported palladium and silver then in roasting temperature 3-8 hour of 400-600 ℃.
In preparing the method for catalyzer of the present invention, used aluminium oxide-titanium oxide complexes carrier can be the disclosed any aluminium oxide-titanium oxide complexes carrier that is suitable for preparing the petroleum hydrocarbon hydrogenation catalyst of prior art.Preferably, the specific surface area of this complexes carrier is a 50-120 rice
2/ gram, pore volume is 0.4-1.5 milliliter/gram, the most probable aperture is the 100-260 dust.Further preferably, in this aluminium oxide-titanium oxide complexes carrier, titanium oxide content is 5-20 weight %.
In the method for preparing the inventive method catalyst system therefor; Used palladium source compound can be the disclosed any palladium compound that is suitable for preparing palladium catalyst of prior art, like 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 such as oxalic acid palladium etc. or its mixture.The present invention for example can be 0.15-0.75 weight %, preferred 0.2-0.7 weight % to the not special restriction of the concentration of palladium source compound solution.The present invention is to the not special restriction of the type of palladium source compound solution; As long as it can be impregnated in the 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 uses the organic solution cost higher; And also have pollution problem, so the present invention preferably uses the aqueous solution of palladium source compound.
In the method for preparing the inventive method catalyst system therefor; Used silver-colored source compound can be the disclosed any silver compound that is applicable to the preparation silver catalyst of prior art, like silver oxide, oxyhydroxide, sulfide, vitriol, halogenide (like Silver monochloride and Silver monoiodide), nitrate salt and oxalate etc. or its mixture.The present invention for example can be 0.9-7 weight %, preferred 1.2-4 weight % to the not special restriction of the concentration of silver-colored source compound solution.The present invention is to the not special restriction of the type of silver-colored source compound solution; As long as it can be impregnated in the 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 uses the 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), use hydrazine hydrate reduction after the dipping, so that palladium source compound and silver-colored source compound are reduced.For this reason, Hydrazine Hydrate 80 preferably uses with the aqueous solution of 8-40 weight % or alcoholic solution such as ethanolic soln, and preferably the aqueous solution with 8-40 weight % uses.The consumption of hydrazine hydrate solution is answered the catalyzer work in-process of preparation in the submergence step (a), and preferably its consumption is that every milliliter of catalyzer work in-process use the 1-3ml hydrazine hydrate solution.Reduction with Hydrazine Hydrate 80 is carried out under 10-60 ℃ of temperature usually, and the time is generally 0.1-2 hour.After the reduction, separate, for example through filtering separation, and water, preferred deionized water wash.For example, using under the situation of Palladous chloride as the palladium source compound, use the deionized water thorough washing, up to no cl ions, this checks through silver nitrate solution and carries out.After the washing, the washed product of gained is dry under 100-150 ℃, and this carried out 4-20 hour usually.Then, will be through the exsiccant product in 400-600 ℃ of following roasting, this carried out 3-8 hour usually, made the catalyzer of supported palladium and silver.
In step (b) afterwards, randomly the supported catalyst that obtains in the step (b) is used the hydrogen reducing activation.As selection, the supported catalyst that obtains in the step (b) also can be used for restoring activation when containing the petroleum hydrocarbon of alkynes and/or diolefin, especially pyrolysis gasoline or its fraction selective hydrogenation.
Before the selective hydrogenation of carrying out petroleum hydrocarbon, advantageously the catalyzer with supported palladium and silver carries out reduction activation with hydrogen.If reduction activation is carried out in catalyst preparation stages; Then the supported catalyst that obtains in the step (b) is used the hydrogen reducing activation, 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 milliliter/gram catalyzer minute in temperature usually; 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 milliliter/gram 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 preferred the inventive method is carried out in fixed bed reactors.
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 temperature in be 25-60 ℃ with reaction pressure be 2.0-3.0MPa, hydrogen to oil volume ratio is 50: 1-200: 1 with the 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) hydrogenation activity of palladium-silver catalyst is higher than existing palladium or nickel catalyst under coldcondition;
When (2) the present invention adopts palladium-silver catalyst selective hydrogenation, has the ability of stronger anti-As, S, O, N impurity;
(3) the inventive method hydrogenation activity is stable, and palladium-silver catalyst can use by LP.
Embodiment
Through embodiment the present invention has been carried out further elaboration below, but these embodiment in no case constitute restriction to scope of the present invention.
Embodiment 1
1. the preparation of carrier
Getting specific surface area is 110 meters
2/ gram, pore volume are 0.59 milliliter/gram, and the most probable aperture is cloverleaf pattern aluminum oxide 88 grams of 130 dusts; Dilution heat of sulfuric acid dipping with 0.557 grams per milliliter of 65 milliliters of titanium sulfates stirred 15 minutes, in 120 ℃ of dryings after 8 hours; In 900 ℃ of roastings 4 hours, make the titanium dioxide-aluminum oxide mixture.The titanium oxide content of this mixture is 11.87 weight %, and specific surface area is 87 meters
2/ gram, pore volume are 0.53 milliliter/gram, and the most probable aperture is 123 dusts.
2. the half-finished preparation of catalyzer
Get titanium dioxide-aluminum oxide mixture 100 gram of above-mentioned preparation, with concentration with Ag
2O counts 0.97 gram Ag
2The silver oxalate aqueous solution of 0/100ml is poured in the described complexes carrier for 110 milliliters, stirs 20 minutes, leaves standstill 1.5 hours, drains away the water, and in 120 ℃ of dryings 10 hours, makes catalyzer work in-process A1-1.
3. Preparation of catalysts.
The catalyzer work in-process A1-1 of 90 gram fronts preparation is immersed in the palladium chloride aqueous solution that 85 milliliters of palladium content are 0.318 gram Pd/100 milliliter; 1.5 take out after hour; Leach the complexes carrier of dipping, using 120 ml concns is that the hydrazine hydrate aqueous solution of 10 weight % at room temperature reduced 1 hour, washes repeatedly with deionized water; Till clean cl ions; It is back in 120 ℃ times dry 6 hours to drain away the water, and then in 480 ℃ of following roastings 4 hours, making palladium content is that 0.30 weight %, Ag content are the Pd-Ag/TiO of 0.99 weight %
2-Al
2O
3Catalyzer (A1-2).
Embodiment 2
Repeat embodiment 1, different is: with concentration with Ag
2O counts 3.906 gram Ag
2110 milliliters of oxide impregnation titaniums of the silver oxalate aqueous solution of O/100ml-alumina compound carrier, 96 grams, and working concentration is 85 milliliters of dippings of palladium chloride aqueous solution, the 90 gram catalyzer work in-process of 0.307 gram palladium/100ml, makes catalyst B 1-2, the result sees table 1.
Embodiment 3
Repeat embodiment 1, different is: with concentration with Ag
2O counts 1.96 gram Ag
2110 milliliters of oxide impregnation titaniums of the silver oxalate aqueous solution of O/100ml-alumina compound carrier, 98 grams, and working concentration is 85 milliliters of dippings of palladium chloride aqueous solution, the 90 gram catalyzer work in-process of 0.307 gram palladium/100ml, makes catalyzer C1-2, the result sees table 1.
Embodiment 4
Repeat embodiment 1, different is: with concentration with Ag
2O counts 1.96 gram Ag
2110 milliliters of oxide impregnation titaniums of the silver oxalate aqueous solution of O/100ml-alumina compound carrier, 98 grams, and working concentration is 85 milliliters of dippings of palladium chloride aqueous solution, the 90 gram catalyzer work in-process of 0.212 gram palladium/100ml, makes catalyzer D1-2, the result sees table 1.
Embodiment 5
Repeat embodiment 1, different is: with concentration with Ag
2O counts 2.93 gram Ag
2110 milliliters of oxide impregnation titaniums of the silver oxalate aqueous solution of O/100ml-alumina compound carrier, 97 grams, and working concentration is 85 milliliters of dippings of palladium chloride aqueous solution, the 90 gram catalyzer work in-process of 0.424 gram palladium/100ml, makes catalyzer E1-2, the result sees table 1.
Table 1
Embodiment 6
The catalyzer of present embodiment illustrative embodiment 1-5 gained is at pyrolysis gasoline C
8Application in the cut selective hydrogenation.The evaluating catalyst experiment is carried out on 100ml small stationary bed hydroprocessing evaluating apparatus, and the reactor drum of this evaluating apparatus is a reaction tubes, reaction tube length 1500mm, internal diameter 25mm, loading catalyst therein.
Getting catalyst A 1-2, B1-2, C1-2, D1-2, each 75 gram of E1-2 that embodiment 1-5 makes and be loaded in the reaction tubes, is 2.8MPa in reaction pressure, and it is reduction 8 hours under the condition of 5.3 milliliters/gram catalyzer minute with hydrogen flowing quantity that temperature is 110 ℃.Be 2.8MPa in reaction pressure then, temperature in is 30 ℃, and hydrogen to oil volume ratio is 80: 1, and the liquid phase air speed is 8h
-1Condition under to feed the diene value be 23.5 gram iodine/100 gram oil, the bromine valency is 42.1 gram bromines/100 gram oil, arsenic content is the pyrolysis gasoline C of 260ppb
8Cut, hydrogenation is the result see shown in the table 2.
Table 2
Embodiment 7
The catalyst B 1-2 of present embodiment illustrative embodiment 2 gained is at pyrolysis gasoline C
8Application in the cut selective hydrogenation.
B1-2 catalyzer 54 grams of getting according to the embodiment of the invention 2 preparation are loaded in the reaction tubes, are 2.8Mpa in reaction pressure, and it is reduction 8 hours under the condition of 5.3 milliliters/gram catalyzer minute with hydrogen flowing quantity that temperature is 110 ℃.Then, be 2.8Mpa in reaction pressure, temperature in is 60 ℃, and hydrogen to oil volume ratio is 80: 1, and the liquid phase air speed is 8.0h
-1, recycle ratio (that is, the hydrogenation products that reaction tubes is discharged and the volume ratio of fresh feed) is that 3: 1 condition feeding diene value is 19.3 gram iodine/100 gram oil, and the bromine valency is that 37.6 gram bromines/100 restrain oil, and arsenic content is 260ppb, and gum level is 100mg/100ml pyrolysis gasoline C
8Cut, the hydrogenation result of catalyzer sees table 3.
Comparative Examples 1
Repeat the program of embodiment 7, different is: the LD365 palladium series catalyst that catalyzer adopts IFP to produce, the hydrogenation result sees table 3.
Comparative Examples 2
The HTC-200S nickel catalyst of getting the production of Britain Hopkinson Associates Ltd. is loaded in the reaction tubes for 72 milliliters.In reaction pressure is under the 2.8MPa, and the hydrogen flow rate feeding hydrogen with 200 ml/min milliliter catalyzer with 100 ℃ of/hour heat-up rates, is heated to 150 ℃ with whole beds, keeps 1 hour with reducing catalyst, reduces to temperature of reaction subsequently.Repeat the hydrogenation process among the embodiment 7 afterwards.The hydrogenation result sees table 3.
Table 3
Annotate: LD365 activity of such catalysts component palladium content is 0.33 weight %, and carrier is an aluminum oxide.
The active component nickel content of HTC-200S is 16 weight %, and carrier is an aluminum oxide.
Embodiment 8
Repeat embodiment 7, different is: the B1-2 catalyst consumption is changed and is made 37.5 grams.The hydrogenation result sees table 4.
Comparative Examples 3
Repeat embodiment 7; Different is: be employed in embodiment 2 preparations among the open CN1429890A of one Chinese patent application palladium/(this catalyzer is called P-C-2 to titanium dioxide-aluminum oxide catalyzer C-2 in this article; Its active ingredient Pd content is 0.3 weight %; Carrier is the titanium dioxide-aluminum oxide complexes carrier) 37.5 grams are loaded in the reaction tubes, and are 100 ℃ in temperature, and reaction pressure is that 2.6MPa and hydrogen flowing quantity are reducing catalyst 8 hours under the condition of 50 ml/min.The hydrogenation result sees table 4.
Comparative Examples 4
(this catalyzer is called P-Ni-C5 in this article to be employed in nickel/titanium dioxide-aluminum oxide catalyzer that embodiment 5 prepares in the one Chinese patent application 200910081684.4; Its active ingredient Ni content is 16.02 weight %; Carrier is the titanium dioxide-aluminum oxide complexes carrier) 37.5 grams are loaded in the reaction tubes, and are 0.5MPa in reaction pressure, and hydrogen flowing quantity is 2.7 a milliliters/gram catalyzer minute; Temperature is under 420 ℃ the condition, with catalyst reduction 20 hours; Afterwards, beds is cooled to 40 ℃, adopt DMDS to sneak into mixture that hexanaphthene obtains as vulcanized oil; And sulphur content is 0.5 weight % based on the weight of this vulcanized oil; In reaction pressure is 0.5MPa, and temperature is 40 ℃, and hydrogen flowing quantity is 2.7 a milliliters/gram catalyzer minute; The vulcanized oil inlet amount is under the condition of 1.2g/g catalyzer hour, pre-sulfide catalyst 20 hours.Repeat the hydrogenation process among the embodiment 7 afterwards.The hydrogenation result sees table 4.
Table 4
Comparative Examples 5
Explanation of this Comparative Examples 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
3Preparation of catalysts
Getting specific surface area is 88 meters
2/ gram, pore volume are 0.52 milliliter/gram, and the most probable aperture is the Al of 124 dusts
2O
3Carrier 98 gram, with concentration with Ag
2O counts 3.906 gram Ag
2The silver oxalate aqueous solution of O/100ml is poured described Al into for 110 milliliters
2O
3In the carrier, stirred 20 minutes, left standstill 1.5 hours, drain away the water,, make catalyzer work in-process F1-1 in 120 ℃ of dryings 10 hours.
The catalyzer work in-process F1-1 of 90 gram fronts preparation is immersed in the palladium chloride aqueous solution that 85 milliliters of palladium content are 0.309 gram Pd/100 milliliter; 1.5 take out after hour; Leach the complexes carrier of dipping, using 120 ml concns is that the hydrazine hydrate aqueous solution of 10 weight % at room temperature reduced 1 hour, washes repeatedly with deionized water; Till clean cl ions; It is back in 120 ℃ times dry 6 hours to drain away the water, and then in 480 ℃ of following roastings 4 hours, making palladium content is that 0.29 weight %, Ag content are the Pd-Ag/Al of 4.02 weight %
2O
3Catalyzer (F1-2).
2. performance comparison
Get the F1-2 and the B1-2 catalyzer of 54 grams respectively, the program that repeats embodiment 7 compares evaluation, and the result sees table 5.
Table 5
Embodiment 9
2 catalyst B 1-2 are at pyrolysis gasoline C for the present embodiment explanation embodiment of the invention
6-C
8Application in the cut selective hydrogenation.
B1-2 catalyzer 75 grams of getting according to embodiment 2 preparations are loaded in the reaction tubes, repeat the reduction process to catalyzer among the embodiment 7, are 2.8MPa in reaction pressure afterwards, and hydrogen to oil volume ratio is 80: 1, and the liquid phase air speed is 12.0h
-1, temperature in is under 30 ℃ the condition, and feeding the diene value is 16.50 gram iodine/100 gram oil, and the bromine valency is 28.52 gram bromines/100 gram oil, and sulphur content is 173ppm, boiling range is 81-157 ℃ pyrolysis gasoline C
6-C
8Cut, the hydrogenation result sees table 6.
Table 6
Embodiment 10
The catalyst B 1-2 of the present embodiment explanation embodiment of the invention 2 is at pyrolysis gasoline C
9Application in the last running selective hydrogenation.
B1-2 catalyzer 75 grams of getting according to embodiment 2 preparations are loaded in the reaction tubes, repeat the reduction process to catalyzer among the embodiment 7, are 2.4-2.6MPa in reaction pressure afterwards, and hydrogen to oil volume ratio is 100: 1, and the liquid phase air speed is 8.0h
-1, reactor inlet temperature is 30 ℃, temperature out is under 60-70 ℃ the condition; Feeding boiling range is 98-202 ℃, and the diene value is 9.87 gram iodine/100 gram oil, and the bromine valency is 35.67 gram bromines/100 gram oil; Arsenic content is 280ppb, and gum level is the pyrolysis gasoline C of 120mg/100ml
9Cut, the hydrogenation result sees table 7.
Table 7
Embodiment 11
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 in the fraction selective hydrogenation relatively.
Get B1-2, P-C-2 (Pd/TiO respectively
2-Al
2O
3, referring to Comparative Examples 3) and F1-2 (Pd-Ag/Al
2O
3, referring to Comparative Examples 5) and each 54 gram of catalyzer, repeat embodiment 7, different is at pyrolysis gasoline C
8Adding arsenic acid adjusting arsenic content in the cut is 330ppb, 470ppb and 528ppb, and the hydrogenation result of three kinds of catalyzer sees table 8.
Table 8
Annotate: three kinds of catalyzer use the under equal conditions experiment continuously of three hydrogenation small testing devices, and experimental period 700 hours altogether is to the pyrolysis gasoline C of different arsenic content
8Cut charging order is 330ppb, 470ppb and 528ppb successively.So product bromine valency and diene value have increase trend.
Claims (10)
1. method that adopts palladium-silver catalyst to the selective hydrogenation of petroleum hydrocarbon that contains alkynes and/or diolefin; Said catalyzer comprises the aluminium oxide-titanium oxide mixture as carrier; And be carried on active ingredient Pd and the Ag on the said complexes carrier; Wherein the content of Pd is 0.15-0.5 weight % based on the gross weight of said catalyzer, and the content of Ag is 0.8-4.5 weight % based on said total catalyst weight.
2. method according to claim 1, wherein said petroleum hydrocarbon are pyrolysis gasoline or its cut.
3. method according to claim 1 and 2, wherein the content of palladium is 0.26-0.32 weight % based on the gross weight of said catalyzer, the content of silver is 1.0-4.0 weight % based on said total catalyst weight.
4. according to each method among the claim 1-3, the specific surface area of wherein said aluminium oxide-titanium oxide complexes carrier is a 50-120 rice
2/ gram, pore volume is that 0.4-1.5 milliliter/gram and most probable aperture are the 100-260 dust.
5. according to each described method among the claim 1-4, the specific surface area of wherein said aluminium oxide-titanium oxide complexes carrier is a 70-100 rice
2/ gram, pore volume is that 0.4-1.2 milliliter/gram and most probable aperture are the 110-200 dust.
6. according to each described method among the claim 1-5, wherein titanium oxide content is 5-20 weight %, based on the gross weight of said aluminium oxide-titanium oxide complexes carrier.
7. according to each described method among the claim 1-6, wherein this method is carried out in fixed-bed reactor.
8. according to each described method among the claim 1-7, it is included in temperature is 100-150 ℃, and reaction pressure is that 2.0-5.0MPa and hydrogen flowing quantity are the said palladium-silver catalyst of reduction activation under the condition of 2.7-20 milliliter/gram catalyzer minute.
9. method according to claim 8, wherein said reduction were carried out 6-18 hour.
10. according to each described method among the claim 1-9, wherein to be 25-60 ℃ in temperature in be 2.0-3.0MPa with reaction pressure in selective hydrogenation, and hydrogen to oil volume ratio is 50: 1-200: 1 with the liquid phase air speed be 4-16h
-1Condition under carry out.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941639A (en) * | 2014-03-27 | 2015-09-30 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst and preparation method and application thereof |
| CN107497426A (en) * | 2017-08-30 | 2017-12-22 | 江苏大学 | A kind of preparation method and applications of palladium/silver alloy nanocatalyst |
| CN109718804A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | The method that selective hydrocatalyst and its application and isoprene selective hydrogenation remove alkynes |
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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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| CN104941639A (en) * | 2014-03-27 | 2015-09-30 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst and preparation method and application thereof |
| CN104941639B (en) * | 2014-03-27 | 2018-06-12 | 中国石油化工股份有限公司 | A kind of selective hydrogenation catalyst and its preparation method and application |
| CN107497426A (en) * | 2017-08-30 | 2017-12-22 | 江苏大学 | A kind of preparation method and applications of palladium/silver alloy nanocatalyst |
| CN109718804A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | The method that selective hydrocatalyst and its application and isoprene selective hydrogenation remove alkynes |
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