CN1429890A - Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use - Google Patents
Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use Download PDFInfo
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- CN1429890A CN1429890A CN 02146005 CN02146005A CN1429890A CN 1429890 A CN1429890 A CN 1429890A CN 02146005 CN02146005 CN 02146005 CN 02146005 A CN02146005 A CN 02146005A CN 1429890 A CN1429890 A CN 1429890A
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Abstract
A selective hydrocatalyst for cracking gasoline is composed of the titanium oxide-aluminium oxide compound as carrier and palladium as active component (0.25-0.35 wt.%). Its advantages are high space speed of liquid phase (in creased by 30-40 %), high selectivity (99% or more), and high activity stability.
Description
Technical field
The present invention relates to a kind of petroleum hydrocarbon and select the hydrogenation catalyzer, more specifically to a kind of be carrier with the alumina compound that contains titanium oxide, be the catalyzer of active ingredient with the palladium metal, be mainly used in pyrolysis gasoline (C
6～C
8Cut) one stage hydrofining makes the height unsaturated hydrocarbons, changes into monoolefine as chain conjugated dienes, vinylbenzene, cyclic conjugated diene etc., also can be used for the alkynes of other petroleum hydrocarbons or the selection hydrogenation of diolefin.The invention still further relates to this Preparation of catalysts method and uses thereof.
Background technology
The catalyzer that present industrial pyrolysis gasoline one-stage hydrogenation uses mainly contains Ni/Al
2O
3Or Pd/Al
2O
3, general charging air speed was at 3.0 hours
-1Below, and the hydrogenation activity of catalyzer, diolefin hydrogenation selectivity are relatively poor.In addition, diolefin in the pyrolysis gasoline or alkynes at high temperature aggregate into colloid easily, and heavy knot makes the very fast inactivation of catalyzer at catalyst surface, cause catalyzer to have to frequently activate and regeneration.Therefore, wish that hydrogenation catalyst has higher low temperature active, make catalyzer keep suitable appearance glue ability, so that polymkeric substance is active constant before being rinsed on the surface of catalyzer, thereby prolong the work-ing life of catalyzer, this is very important in industrial production.The open CN85100761A of Chinese patent application discloses a kind of fibrous catalyst for selective hydrogenation of dienes and method for making thereof, wherein active ingredient comprises Pd or the Pt of 0.2-1% at least and comprises Na, K, Li, Mg or rare earth element a kind of of 0.05-2% at least, and the specific surface of porous fiber carrier is greater than 20m
2/ g, pore volume is greater than 0.1ml/g.Its contriver claims that this catalyzer compares with the similar pelleted catalyst of industrial present employing, the high 1-2 of a liquid air speed order of magnitude, and selectivity is near 100%; At 40 ℃ of temperature of reaction, reaction pressure 40kg/cm
2, under the liquid air speed 40ml/g.hr, 1000 hours activity of continuous operation do not descend, but its activity and stability still leave some room for improvement.The open CN1056068A of Chinese patent application discloses a kind of catalyzer that diolefin selective hydrogenation is converted into monoolefine that is used for, mainly form by nickel, sodium, sulphur and alumina supporter, wherein alumina supporter is the solid matter based on amorphous phase, and its surface-area is lower than 100m
2/ g, total pore volume is less than 1.0cm
3/ g.Its contriver claims that this catalyzer is at processing C
7-C
16The mixture of hydrocarbon the time effective especially, but its low temperature active still remains to be improved.The open CN1228402A of Chinese patent application discloses a kind of method that 2 or 3 carbyne hydrocarbon gas phase selectivity is hydrogenated into corresponding alkene in the presence of special catalyst, and this catalyzer contains palladium, at least a periodic table of elements IB family's metal and aluminum oxide.Yet the low temperature active and the selectivity of this method catalyst system therefor all have much room for improvement.
Summary of the invention
In view of above-mentioned prior art situation, the inventor selects hydrogenation to carry out research extensively and profoundly with catalyzer to pyrolysis gasoline, found that the titanium dioxide-aluminum oxide mixture that has a specified pore structure by use not only has good low temperature active and selectivity as the catalyzer that carrier obtains, and have satisfactory stability.The present invention just is being based on above discovery and is being accomplished.
Therefore, the purpose of this invention is to provide the pyrolysis gasoline selection hydrogenation catalyzer that a kind of low temperature active and selectivity are high and have good stability.
Another object of the present invention provides a kind of method for preparing above-mentioned catalyzer.
A further object of the present invention provides a kind of method of pyrolysis gasoline being selected hydrogenation.
One aspect of the present invention provides a kind of catalyzer that is used for the pyrolysis gasoline selective hydrogenation, comprise titanium dioxide-aluminum oxide mixture as carrier, and be carried on activity component metal palladium on this carrier, wherein the content of palladium metal is that the content of 0.25～0.35% (weight) and titanium oxide is 5～20% (weight) based on alumina weight based on described total catalyst weight.
The present invention provides a kind of method for preparing above-mentioned catalyzer on the other hand, comprises
(1) it is 100～200 meters with specific surface
2/ gram, pore volume are 0.5～1.5 milliliter/gram, and the most probable aperture is that the aluminum oxide of 80～200 dusts immerses in the compound titanium solution, the consumption of wherein said solution at least with the total pore volume equivalent of described aluminum oxide, and stirred 10～30 minutes;
(2) with impregnated aluminum oxide under 100-150 ℃ temperature dry 4-10 hour, in roasting temperature 4-8 hour of 500-900 ℃, make the titanium dioxide-aluminum oxide complexes carrier that contains 5-20% (weight) titanium oxide based on alumina weight then;
(3) with the titanium dioxide-aluminum oxide complexes carrier that makes in (2) with the deionized water preimpregnation of 1～1.5 times of its volume 0.3-1 hour, after filtering and draining away the water, flooded 1～4 hour with the palladium compound solution that equates with catalyzer containing metal palladium amount, the consumption of wherein said solution at least with the total pore volume equivalent of described complexes carrier, the hydrazine hydrate reduction 1～2 hour that adds 30～40% (weight) of 1～2 times of described complexes carrier volume then, filter and with deionized water wash to there not being chlorion;
(4) with the product that obtains in (3) in 100-150 ℃ dry 4-10 hour down, then in 400-600 ℃ of following roasting 4-8 hour; With
(5) be 100-150 ℃ at hydrogenation temperature, hydrogen pressure is that 2.6～3.0Mpa and hydrogen flowing quantity are reduction step (4) products obtained therefrom 6-8 hour under the condition of 35-65 ml/min.
Catalyzer of the present invention is applicable to the petroleum hydrocarbon selection hydrogenation that contains alkynes or diolefin, preferably pyrolysis gasoline is selected hydrogenation.
Of the present inventionly provide on the one hand a kind of again pyrolysis gasoline is selected the method for hydrogenation, being included in temperature is 50～60 ℃, and pressure is 2.6～3.0Mpa, and hydrogen-oil ratio is that 50: 1～80: 1 and liquid phase air speed are 8～18 hours
-1Condition under the hydrocracking gasoline stocks.
These and other purposes of the present invention, feature and advantage will become more clear after reading this specification sheets.
Detailed Description Of The Invention
Pyrolysis gasoline of the present invention selects hydrogenation with in the catalyzer, and used aluminum oxide is not had particular restriction, as long as use the specific surface area of the titanium dioxide-aluminum oxide complexes carrier that this aluminum oxide obtains to be 80-180 rice
2/ gram is preferably 120-150 rice
2/ gram; Pore volume 0.4-1.3 milliliter/gram is preferably 0.5-1.0 milliliter/gram; The most probable aperture is the 90-150 dust, is preferably the 110-140 dust.The specific surface area of preferred aluminum oxide is a 100-200 rice
2/ gram; Pore volume 0.5-1.5 milliliter/gram, more preferably 0.5-1.0 milliliter/gram; The most probable aperture is the 80-200 dust.In addition, the shape of aluminum oxide is not had particular restriction yet, for example can be cylindricality, bar shaped and spherical.
In the carrier of catalyzer of the present invention, the content of titanium oxide is 5-20% (weight) based on alumina weight, preferred 8-15% (weight).
Select hydrogenation with in the catalyzer at pyrolysis gasoline of the present invention, the content of active ingredient Pd is 0.25-0.35% (weight) based on described total catalyst weight, preferred 0.28-0.32% (weight).
It is a kind of egg-shell catalyst that pyrolysis gasoline of the present invention is selected the hydrogenation catalyzer.
In Preparation of catalysts method of the present invention, used titanium compound is the titanium salt of the acetate, hydrochloride, vitriol and the nitrate that are selected from titanium or the titanic acid ester that is selected from tetraethyl titanate, metatitanic acid four n-propyls and tetrabutyl titanate.The consumption of compound titanium solution is that its volume equates with the total pore volume of aluminum oxide or greater than the total pore volume of aluminum oxide.The consumption of preferred compound titanium solution is that its volume equates with the total pore volume of aluminum oxide.If the consumption of compound titanium solution greater than the total pore volume of aluminum oxide, must filter mixture and drain earlier after dipping is finished, carry out drying then.The used solvent of preparation compound titanium solution depends on the concrete kind of used titanium compound, for example when the titanium compound that uses during as the acetate of titanium, hydrochloride, vitriol or nitrate, preferably make water or aqueous acids such as dilute sulphuric acid, rare nitric acid, dilute hydrochloric acid, acetic acid,diluted as solvent, and, preferably use aromatic hydrocarbon such as benzene, toluene or alicyclic hydrocarbon such as hexanaphthene, suberane, cyclooctane as solvent when the titanium compound that uses during as titanic acid ester.
In Preparation of catalysts method of the present invention, used palladium compound can be the disclosed any palladium compound that is suitable for making palladium catalyst of prior art, as the organic acid salt of 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.The consumption of palladium compound solution is that its volume equates with the total pore volume of complexes carrier to be impregnated or greater than the total pore volume of described carrier.The consumption of preferred palladium compound solution is that its volume equates with the total pore volume of complexes carrier.To preparing the used solvent of palladium compound solution without any particular restriction, as long as it can dissolve employed palladium compound.Preferred solvent is for example water, dilute hydrochloric acid, rare nitric acid, dilute sulphuric acid or their mixed solution.
Catalyzer of the present invention is mainly used in the selection hydrogenation of pyrolysis gasoline, for example feeding boiling range and be 80-200 ℃, diene value under the pressure of 50-60 ℃ temperature and 2.6-3.0MPa is that 30-40 gram iodine/100 gram oil and bromine valency are the stock oil of 50-70 gram bromine/100 gram oil, and the diene value of product is less than 1 gram iodine/100 gram oil.
Catalyzer of the present invention is used for pyrolysis gasoline and selects hydrogenation to have following outstanding advantage and effect:
(1) the low temperature hydrogenation specific activity of catalyzer of the present invention is the palladium catalyst height of carrier with titanium oxide or aluminum oxide only;
When (2) catalyzer of the present invention was used for pyrolysis gasoline selection hydrogenation, it was big to handle the raw material ability, and the charging air speed is than the high 30-40% of existing similar catalyst.
(3) catalyzer appearance colloidality of the present invention can be good, and hydrogenation activity is stable, can long period use.
Embodiment
Below will the present invention is further illustrated by embodiment, but these embodiment do not constitute any restriction to scope of the present invention.
The preparation of embodiment 11. carriers
Getting specific surface area is 160 meters
2/ gram, pore volume is 0.58 a milliliter/gram, the most probable aperture is cloverleaf pattern aluminum oxide 90 grams of 130 dusts, 0.557 grams per milliliter dilution heat of sulfuric acid dipping with 53 milliliters of titanium sulfates, stirred 15 minutes, after 8 hours,, make titanium dioxide-aluminum oxide mixture (A-1) in 120 ℃ of dryings in 900 ℃ of roastings 4 hours.The titanium oxide content of gained mixture is 10% (weight), and specific surface area is 144 meters
2/ gram, pore volume are 0.56 milliliter/gram, and the most probable aperture is 125 dusts.2. Preparation of catalysts
With the 100 titanium dioxide-aluminum oxide complexes carriers (A-1) that prepare previously of gram with 160 milliliters deionized water preimpregnation 0.5 hour, filter and filter solid carbon dioxide branch, immerse in 0.636 gram/100 ml water solution of 80 milliliters of Palladous chlorides, take out after 1 hour, with 145 ml concns is the hydrazine hydrate reduction 1 hour of 40% (weight), clean chlorion with deionized water, drying is 6 hours under 120 ℃, again in 500 ℃ of following roastings 4 hours.Be that 2.8Mpa, temperature are that 110 ℃ and hydrogen flowing quantity are reduction 8 hours under the condition of 40 ml/min at hydrogen pressure then.Making palladium metal content is the palladium/titanium dioxide-aluminum oxide catalyzer (C-1) of 0.3% (weight).
The preparation of embodiment 21. carriers
Immerse in the used aluminum oxide of 90 gram embodiment 1 with 0.518 grams per milliliter cyclohexane solution of 56 milliliters of tetraethyl titanates, stirred 10-20 minute, after 6 hours,, make titanium dioxide-aluminum oxide mixture (A-2) in 600 ℃ of roastings 4 hours in 120 ℃ of dryings.The titanium oxide content of gained mixture is 10% (weight), and specific surface area is 144 meters
2/ gram, pore volume are 0.56 milliliter/gram, and the most probable aperture is 125 dusts.2. Preparation of catalysts
With the 100 titanium dioxide-aluminum oxide complexes carriers (A-2) that prepare previously of gram with 150 milliliters deionized water preimpregnation 0.5 hour, filter and filter solid carbon dioxide branch, immerse in 0.636 gram/100 ml water solution of 80 milliliters of Palladous chlorides, take out after 1 hour, with the hydrazine hydrate reduction of 150 milliliter 40% (weight) 1 hour, clean chlorion with deionized water, drying is 6 hours under 120 ℃, again in 500 ℃ of following roastings 4 hours, be that 2.8Mpa, temperature are that 110 ℃ and hydrogen flowing quantity are reduction 8 hours under the condition of 40 ml/min at hydrogen pressure then.Making metal content is the palladium/titanium dioxide-aluminum oxide catalyzer (C-2) of 0.3% (weight).
The preparation of embodiment 31. carriers
Immerse in the used aluminum oxide of 170 gram embodiment 1 with 0.808 grams per milliliter cyclohexane solution of 106 milliliters of tetraethyl titanates, stirred 10-20 minute, in 120 ℃ of dryings after 6 hours, in 600 ℃ of roastings 4 hours, make titanium dioxide-aluminum oxide mixture (A-3), wherein titanium oxide content is 15% (weight), and specific surface area is 138 meters
2/ gram, pore volume are 0.51 milliliter/gram, and the most probable aperture is 120 dusts.2. Preparation of catalysts
With the 120 titanium dioxide-aluminum oxide complexes carriers (A-3) that prepare previously of gram with 180 milliliters deionized water preimpregnation 0.5 hour, filter and filter solid carbon dioxide branch, immerse in 0.636 gram/100 ml water solution of 96 milliliters of Palladous chlorides, take out after 1 hour, with the hydrazine hydrate reduction of 180 milliliter 40% (weight) 1 hour, clean chlorion with deionized water, drying is 6 hours under 120 ℃, again in 500 ℃ of following roastings 4 hours.Be that 2.8Mpa, temperature are that 110 ℃ and hydrogen flowing quantity are reduction 8 hours under the condition of 40 ml/min at hydrogen pressure then.Making Pd content is the palladium/titanium dioxide-aluminum oxide catalyzer (C-3) of 0.3% (weight).
The preparation of embodiment 41. carriers
Immerse in the used aluminum oxide of 190 gram embodiment 1 with 0.241 grams per milliliter cyclohexane solution of 119 milliliters of tetraethyl titanates, stirred 10-20 minute, in 120 ℃ of dryings after 6 hours, in 600 ℃ of roastings 4 hours, make titanium dioxide-aluminum oxide mixture (A-4), wherein titanium oxide content is 5% (weight), and specific surface area is 151 meters
2/ gram, pore volume are 0.57 milliliter/gram, and the most probable aperture is 127 dusts.2. Preparation of catalysts
With the 120 titanium dioxide-aluminum oxide complexes carriers (A-4) that prepare previously of gram with 180 milliliters deionized water preimpregnation 0.5 hour, filter and filter solid carbon dioxide branch, immerse in 0.636 gram/100 ml water solution of 96 milliliters of Palladous chlorides, take out after 1 hour, with the hydrazine hydrate reduction of 180 milliliter 40% (weight) 1 hour, clean chlorion with deionized water, drying is 6 hours under 120 ℃, again in 500 ℃ of following roastings 4 hours.Be that 2.8Mpa, temperature are that 110 ℃ and hydrogen flowing quantity are reduction 8 hours under the condition of 40 ml/min at hydrogen pressure then.Making Pd content is the palladium/titanium dioxide-aluminum oxide catalyzer (C-4) of 0.3% (weight).
Embodiment 5
Present embodiment explanation embodiment 1 gained catalyzer is at pyrolysis gasoline C
6-C
7Application in the fraction selective hydrogenation.
Getting catalyzer (C-1) 49 grams that embodiment 1 makes, is that 2.8MPa, temperature of reaction are that 55 ℃, hydrogen to oil volume ratio are that to feed diene content under 80: 1 the condition be that 21.27 gram iodine/100 gram oil, bromine valency are the pyrolysis gasoline C of 44 gram bromines/100 gram oil at hydrogen pressure
6-C
7Cut.The hydrogenation result is as shown in table 1 below.
Comparative Examples 1
Repeat the program of embodiment 5, different is that catalyzer is the LD365 that IFP is produced.The hydrogenation result is as shown in table 1 below.
Table 1 liquid phase air speed catalyst reaction time product bromine valency product diene (hour
-1) (hour) (gram bromine/100 gram oil) (gram iodine/100 gram oil) 12.0 C-1 300 17 0.4
LD365 300 19 1.316.0 C-1 300 18 0.5
LD365 300 22 2.0 annotates: the palladium content of LD365 catalyzer is 0.33% (weight).
Embodiment 6
Present embodiment explanation embodiment 2 gained catalyzer are at pyrolysis gasoline C
6-C
7Application in the fraction selective hydrogenation.
Getting catalyzer (C-2) 56 grams that embodiment 2 makes, is that 2.8MPa, temperature of reaction are that 60 ℃, hydrogen to oil volume ratio are that to feed diene content under 80: 1 the condition be that 21.27 gram iodine/100 gram oil, bromine valency are the pyrolysis gasoline C of 44 gram bromines/100 gram oil at hydrogen pressure
6-C
7Cut.The hydrogenation result is as shown in table 2 below.
Comparative Examples 2
Repeat the program of embodiment 6, different is that catalyzer is the LD365 that IFP is produced.The hydrogenation result is as shown in table 2 below.
Table 2 liquid phase air speed catalyst reaction time product bromine valency product diene (hour
-1) (hour) (gram bromine/100 gram oil) (gram iodine/100 gram oil) 12.0 C-2 200 18 0.5
LD365 200 21 1.718.0 C-2 200 20 0.9
LD365 200 28 2.5 annotates: the palladium content of LD365 catalyzer is 0.33% (weight).
Embodiment 7
Present embodiment explanation embodiment 2 and embodiment 3 gained catalyzer are at pyrolysis gasoline C
8Application in the fraction selective hydrogenation.
Getting each 56 gram of catalyzer (C-2 and C-3) that embodiment 2 and embodiment 3 make, is that 2.8MPa, temperature of reaction are that 60 ℃, hydrogen to oil volume ratio are that 80: 1, liquid phase air speed are 8.0 hours at hydrogen pressure
-1Condition under to feed diolefin content be that 19.3 gram iodine/100 gram oil, bromine valency are the pyrolysis gasoline C of 37.6 gram bromines/100 gram oil
8Cut.The hydrogenation result is as shown in table 3 below.
Comparative Examples 3
Repeat the program of embodiment 7, different is that catalyzer is the LD365 that IFP is produced.The hydrogenation result is as shown in table 3 below.
Table 3 catalyst reaction time product bromine valency product diene
(hour) (gram bromine/100 restrain oil) (gram iodine/100 gram oil) C-2 300 23.2 0.71C-3 300 21.8 0.58LD365 300 28.9 1.83 notes: the palladium content of LD365 catalyzer is 0.33% (weight).
Embodiment 8
Present embodiment explanation embodiment 2 gained catalyzer are at pyrolysis gasoline C
6-C
7Application in the fraction selective hydrogenation.
Getting catalyzer (C-2) 56 grams that embodiment 2 makes, is that 2.8MPa, temperature of reaction are that 60 ℃, hydrogen to oil volume ratio are that 60: 1, liquid phase air speed are 9 hours at hydrogen pressure
-1Condition under to feed diene content be that 21.27 gram iodine/100 gram oil, bromine valency are the pyrolysis gasoline C of 44 gram bromines/100 gram oil
6-C
7Cut.The hydrogenation result is as shown in table 4 below.
Table 4 reaction time product diene product bromine valency (hour) (gram iodine/100 gram oil) (gram bromine/100 gram oil) 100 0.1 15.5200 0.15 18.0400 0.29 18.3600 0.29 18.6800 0.31 18.41000 0.36 19.31100 0.46 19.31300 0.32 22.81400 0.46 22.61500 0.40 20.5
As can be seen from Table 4, the reaction that the present invention lasts 1500 hours with the palladium catalyst (C-2) of titanium dioxide-aluminum oxide load, activity stabilized.
Embodiment 9
Present embodiment explanation embodiment 4 gained catalyzer are at catalytic gasoline C
5Application in the cut fraction hydrogenation.
Getting catalyzer (C-4) 56 grams that embodiment 4 makes, is that 40 or 45 ℃, hydrogen to oil volume ratio are that 100: 1, liquid phase air speed are 3.0 or 4.5 hours in hydrogen pressure 2.0Mpa, temperature of reaction
-1Condition under feed C
5Content is that 99.5% (weight), diene content are that 1.2 gram iodine/100 gram oil, bromine valency are the catalytic gasoline C of 280.26 gram bromines/100 gram oil
5Cut, the hydrogenation result is as shown in table 5.
Table 5
Product diene product bromine valency
Test conditions
(gram iodine/100 gram oil) (gram bromine/100 gram oil) 40 ℃ of 0 41.42 liquid air speed of inlet temperature of reaction 3.0 hours
-10 39.69
0 42.32
0 45.54
0 44.53
45 ℃ of 0 67.12 liquid air speed of 0 45.36 inlet temperature of reaction 4.5 hours
-10 61.20
0 64.91
0 63.52
In hydrogenation process, 18～20 ℃ of catalyst bed reaction temperature rises, hydrogenation products bromine valency changes little, and reacting balance carries out.
Claims (9)
1. one kind is used for the catalyzer that pyrolysis gasoline is selected hydrogenation, comprise titanium dioxide-aluminum oxide mixture as carrier, and be carried on activity component metal palladium on the described complex carrier, wherein the content of palladium metal is that the content of 0.25-0.35% (weight) and titanium oxide is 5-20% (weight) based on alumina weight based on described total catalyst weight.
2. catalyzer according to claim 1, the specific surface area of wherein said complex carrier are 80～180 meters
2/ gram, pore volume 0.4-1.3 milliliter/gram, the most probable aperture is the 90-150 dust.
3. catalyzer according to claim 1, wherein the content of palladium metal is that the content of 0.28-0.32% (weight) and titanium oxide is 8-15% (weight) based on alumina weight based on described total catalyst weight.
4. catalyzer according to claim 1, the specific surface area that it is characterized in that described complex carrier is a 120-150 rice
2/ gram, pore volume is 0.5-1.0 milliliter/gram, the most probable aperture is the 110-140 dust.
5. method for preparing catalyzer according to claim 1 comprises:
(1) be 100-200 rice with specific surface
2/ gram, pore volume are 0.5～1.5 milliliter/gram, and the most probable aperture is that the aluminum oxide of 80～200 dusts immerses in the compound titanium solution, the consumption of wherein said solution at least with the total pore volume equivalent of described aluminum oxide, and stirring 10-30 minute;
(2) with impregnated aluminum oxide under 100-150 ℃ temperature dry 4-10 hour, in roasting temperature 4-8 hour of 500-900 ℃, make the titanium dioxide-aluminum oxide complexes carrier that contains 5-20% (weight) titanium oxide based on alumina weight then;
(3) with the titanium dioxide-aluminum oxide complexes carrier that makes in (2) with its volume 1-1.5 deionized water preimpregnation doubly 0.3-1 hour, after filtering and draining away the water, flooded 1-4 hour with the palladium compound solution that equates with catalyzer containing metal palladium amount, the consumption of wherein said solution at least with total pore volume equivalent of described complexes carrier, be incorporated as hydrazine hydrate reduction 1-2 hour of described complexes carrier volume 1-2 30-40% (weight) doubly then, filter and with deionized water wash to there not being chlorion;
(4) with the product that obtains in (3) in 100-150 ℃ dry 4-10 hour down, then in 400-600 ℃ of following roasting 4-8 hour; With
(5) be 100-150 ℃ at hydrogenation temperature, hydrogen pressure is that 2.6～3.0Mpa and hydrogen flowing quantity are reduction step (4) products obtained therefrom 6-8 hour under the condition of 35-65 ml/min.
6. according to the method for claim 5, wherein said titanium compound is the titanium salt of the acetate, hydrochloride, vitriol and the nitrate that are selected from titanium or the titanic acid ester that is selected from tetraethyl titanate, metatitanic acid four n-propyls and tetrabutyl titanate.
7. according to each described catalyzer among the claim 1-4, be used to contain the petroleum hydrocarbon selection hydrogenation of alkynes or diolefin.
8. method that pyrolysis gasoline is carried out selective hydrogenation, being included in temperature is 50～60 ℃, and pressure is 2.6～3.0Mpa, and hydrogen to oil volume ratio is that 50: 1～80: 1 and liquid phase air speed are 8～18 hours
-1Condition under the hydrocracking gasoline stocks.
9. method according to claim 8, wherein said pyrolysis gasoline raw material are that boiling range is that 80～200 ℃, diene value are that 30～40 gram iodine/100 gram oil and bromine valency are the stock oil of 50～70 gram bromines/100 gram oil.
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2002
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| CN101255358B (en) * | 2008-04-17 | 2011-12-07 | 中国石油天然气集团公司 | Selective hydrogenation catalyst and preparation method thereof |
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| CN102732294B (en) * | 2011-04-11 | 2014-09-03 | 中国石油化工股份有限公司 | Method for selective hydrogenation of cracked gasoline or its fractions through adopting Pd-Ag/Al2O3-TiO2 catalyst |
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| CN104689830B (en) * | 2013-12-09 | 2018-09-21 | 中国石油化工股份有限公司 | A kind of catalyst for alkynes and diolefin hydrogenate in mixed olefins |
| CN107486201A (en) * | 2016-06-12 | 2017-12-19 | 中国石油化工股份有限公司 | It is a kind of for the catalyst of selective hydrogenation of cracked gasoline and its preparation and application |
| CN107189812A (en) * | 2017-06-02 | 2017-09-22 | 钦州学院 | A kind of method of cracking C6 C8 cut selective hydrogenations |
| CN107189812B (en) * | 2017-06-02 | 2019-01-25 | 钦州学院 | A method of cracking C6-C8 fraction selective hydrogenation |
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| CN1184289C (en) | 2005-01-12 |
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