CN104689830A - Catalyst for selective hydrogenation of alkyne and dialkene in mixed olefins - Google Patents
Catalyst for selective hydrogenation of alkyne and dialkene in mixed olefins Download PDFInfo
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Abstract
The invention relates to a catalyst for selective hydrogenation of alkyne and dialkene in mixed olefins, and belongs to the field of petrochemical engineering. By taking TiO2-Al2O3 composite oxide as a carrier, the catalyst is loaded with a main active metal component Pd and an auxiliary active metal component Ni. A preparation method for the catalyst comprises the following steps: loading the auxiliary active metal component Ni on the carrier; and then, loading the main active metal component Pd on the carrier. The catalyst is high in hydrogenation activity and selectivity, large in green oil capacity, and stable in activity. Compared with a catalyst which is loaded with various main active components and the auxiliary active components in the prior art, the catalyst provided by the invention is reduced in type of active components, reduced in production cost and simplified in preparation process.
Description
Technical field
The present invention relates to a kind of selective hydrogenation catalyst, for the alkynes in mixed olefins and diolefin hydrogenate, belong to petrochemical industry.
Background technology
The catalyst of load P d and Ni is long-term for various hydrogenation technique, and this technique comprises selec-tive hydrogenation and the cracking of acetylene hydrocarbon compound in various hydrocarbon mixture logistics and diolefin, and the selec-tive hydrogenation etc. of catalytic gasoline.
In order to improve the selective of catalyst, the various hydrocarbon mixture logistics hydrogenation containing acetylene hydrocarbon compound and diolefin is generally adopted to bimetallic or the multicomponent catalyst of Pd or Pd and other metal compatibility, as US7,217,760B2 discloses the Pd-Ag catalyst of NH4I process, US7,009,085B2 disclose the Pd-Ag catalyst adopting P or Br modified support.
M.L.Derrien Et Al. (Studies in Surface Science and Catalyst, Vol27, Page613 (1986)), with Elsvierand K James Sasski (Petrochemical and Gas Processing, 113PTQ Autumn, 1997) think that Pt-supported catalyst has unstability for the selec-tive hydrogenation of vinylacetylene, reason is that vinylacetylene can form complex compound with Pd in hydrogenation process, Pd complex compound dissolves in hydrocarbon stream the loss causing active component Pd, makes catalyst activity reduction.
CN1604955A discloses a kind of multicomponent catalyst of selec-tive hydrogenation, comprise Pd or containing Pd and a kind of 8th race's metal is selected from Pt, Ir, Ru, Co or Ni and at least two kinds of metals are selected from Ag, Zn or Bi, the active constituent loading of catalyst is on aluminium oxide, and the BET surface area of this carrier is 20 ~ 70m
2/ g, alumina support is shaping over oxidation aluminium, and apparent bulk density is 0.7 ~ 0.8g/cm
2, be the mixed crystallization form of α, γ, θ, σ, ρ, η, κ and χ.This catalyst is for the acetylene in the various unsaturated hydrocarbons logistics of hydrogenation and alkadienes.
CN102039130A discloses a kind of selective hydrogenation catalyst, comprise porous inorganic carrier, be carried on the main active component Pd on porous carrier, Au and Ag and at least one are selected from Bi, Zr, Ce, Zn, Ni, Cu, K, Mg, Ba, Ca, Sn, Pd, Mn, La, Ti, Sr and Na helps active component, this catalyst is due to the cooperative effect of various active component, the activity and selectivity of catalyst can be made all to be significantly improved, and there is the poisoning and anti-carbon monoxide fluctuating nature of good antioxygen, it has selec-tive hydrogenation and selects Oxidation of Carbon Monoxide difunctional, it is long that this catalyst also has the regeneration period, the features such as life cycle is long, but, the active metal kind of this catalyst is many, involve great expense.
In acetylene hydrocarbon compound in various hydrocarbon mixture logistics and the selec-tive hydrogenation process of diolefin, be adsorbed on the component such as alkynes and diolefin on catalyst surface easily by hydrogenation dimerization, and then combinate form becomes C again
6~ C
24high polymer, the i.e. generation of so-called " green oil ", " green oil " blocking catalyst duct generated, causing the activity and selectivity of catalyst constantly to decline, in order to keep the activity and selectivity of catalyst, needing to adopt measures such as improving reaction temperature, corresponding is that the component such as alkynes and diolefin polymerisation is also aggravated, " green oil " growing amount increases, and causes catalyst frequent regeneration, affects the service life of catalyst.
Existing patent and the catalyst disclosed in technology, still there is activity and selectivity not high, stability is bad, namely do not solve catalyst long period and use problem, therefore, need to research and develop a kind of activity and selectivity higher, " green oil " generation can be reduced or hold " green oil " and measure large catalyst.
Summary of the invention
In order to overcome the above-mentioned problems in the prior art, the invention provides a kind of selective hydrogenation catalyst for alkynes and alkadienes in hydrocarbon mixture logistics.This catalyst has the feature of high, the selective height of low temperature active, good stability.Another object of the present invention is to provide the preparation method of described catalyst.
The invention provides a kind of catalyst for the alkynes in mixed olefins and diolefin hydrogenate, described catalyst is loaded catalyst, specifically with TiO
2-Al
2o
3composite oxides are carrier, supported active metals component Pd and Ni.Wherein Pd is main active metal, and Ni is for helping active metal.
Based on the gross weight of described catalyst, the content of Pd counts 0.005 ~ 0.8wt% with atom, preferably 0.01 ~ 0.3wt%; The content of Ni counts 1 ~ 12wt% with atom, preferably 2 ~ 10wt%.Pd and Ni all can the form of atom or compound exist.Described Pd and Ni compound can be Pd and Ni compound conventional in selective hydrogenation palladium base and nickel-base catalyst, is preferably Pd oxide and Ni oxide, as Pd
2o and NiO.
In described catalyst, TiO
2-Al
2o
3the content of composite oxide carrier is 87.2 ~ 99.9wt%.TiO in this carrier
2content is 3 ~ 30wt%, is preferably 5 ~ 20wt%.The most probable pore size of this carrier is
be preferably
pore volume is 0.50 ~ 0.64ml/g, is preferably 0.52 ~ 0.60ml/g; Specific area is 70 ~ 120m
2/ g, is preferably 80 ~ 110m
2/ g.The shape of the present invention to carrier is not particularly limited, and can be cylindricality, bar shaped, spherical or cloverleaf pattern.The specific area of described carrier, pore volume and most probable pore size are all measured by nitrogen physisorption (BET) method.
In described catalyst carrier be prepared as known technology, the preparations such as sol-gel process, aluminium salt precipitation method, coprecipitation, aluminium salt neutralisation or aluminium alcoholates Hydrolyze method can be adopted.Preparation method in the patent CN1184289 of Yanshan Mountain branch of preferred Beijing Chemical Research Institute: be 60 ~ 160m with specific surface
2/ g, pore volume is 0.50 ~ 1.5ml/g, and most probable pore size is
aluminium oxide immerse in compound titanium solution, consumption at least total pore volume equivalent with described aluminium oxide of described compound titanium solution.Leave standstill 10 ~ 30 minutes, by impregnated aluminium oxide at the temperature of 100 ~ 150 DEG C dry 4 ~ 8 hours, then in 400 ~ 600 DEG C of roasting temperatures 3 ~ 6 hours, obtained based on TiO
2-Al
2o
3composite oxides weight contains the TiO of 5 ~ 20wt%
2tiO
2-Al
2o
3composite oxide carrier.
Invention further provides the preparation method of above-mentioned selective hydrogenation catalyst.
Method for preparing catalyst of the present invention, comprises and first will help active metal component Ni load on carrier, afterwards the main active metal component Pd of load again; Or first by main active metal component Pd load on carrier, load helps active metal component Ni more afterwards.Preferably, first will help active metal component Ni load on carrier, afterwards the main active metal component Pd of load again.
In the preparation process in accordance with the present invention, the conventional method load such as dipping, spraying can be adopted for active metal component.Help the load of active metal component Ni and main active metal component Pd that substep can be taked to carry out, also can take the mode of synchronously carrying out.
Preferably, described catalyst can be prepared by the following method:
1) by TiO
2-Al
2o
3composite oxide carrier adds in nickel salt solution and floods, then dry and roasting;
2) carrier that step 1) obtains is added in palladium solution flood, then reduce, filter washing and drying obtains described catalyst.
In one particular embodiment of the present invention, described catalyst is prepared by the following method:
I) by TiO
2-Al
2o
3the composite oxide carrier nickel salt solution equal with catalyst ni content floods 1 ~ 2 hour, at the temperature of 100 ~ 150 DEG C dry 4 ~ 8 hours, then in 400 ~ 600 DEG C of roasting temperatures 3 ~ 6 hours, and obtained catalyst precarsor;
Ii) catalyst precarsor obtained in i) is measured equal palladium salt solution impregnation 1 ~ 2 hour with catalyst containing Pd, then 1 ~ 3 times that volume is described catalyst precarsor is added, concentration is that the hydrazine hydrate solution of 5 ~ 10wt% reduces 1 ~ 2 hour, filter, spend deionized water, drying 4 ~ 8 hours at the temperature of 100 ~ 150 DEG C, obtained catalyst of the present invention.
In above-mentioned preparation method, described nickel salt can be understood as the nickel salt that selective hydrogenation nickel catalyst adopts usually, can include but not limited to: the sulfate of nickel, nitrate, soluble carboxylate, hypophosphites and halide, be preferably nickelous sulfate, nickel nitrate, nickel chloride or nickel acetate.The type of described nickel salt solution is not particularly limited, and can be the aqueous solution, also can be the organic nickel salting liquid that ethanol, benzene etc. are formed as solvent.But use organic nickel salting liquid cost higher, and have environmental problem, therefore the present invention preferably uses the aqueous solution of inorganic nickel.
In above-mentioned preparation method, described palladium salt can be understood as the palladium salt that selective hydrogenation palladium series catalyst adopts usually, can include but not limited to: the nitrate of palladium, soluble carboxylate and halide, is preferably palladium nitrate, palladium bichloride, oxalic acid palladium or acid chloride.The type of described palladium salting liquid is not particularly limited, and can be the aqueous solution, also can be the organic palladium salting liquid that ethanol, benzene etc. are formed as solvent.But use organic palladium salting liquid cost higher, and have environmental problem, therefore the present invention preferably uses the aqueous solution of inorganic palladium salt.
Catalyst of the present invention is mainly used in the selec-tive hydrogenation of alkynes and alkadienes in mixed olefins, be particularly useful for the selec-tive hydrogenation of alkynes and butadiene in C4 mixed olefins, thus greatly reduce the content of alkynes and butadiene in C4 mixed olefins, reach the object of refining C4 mixed olefins.
Selective hydrogenation catalyst provided by the invention has the following advantages and effect:
(1) hydrogenation activity of catalyst and selective height.With butadiene conversion in prior art be 84%, 1-butylene selective be 45% to compare, adopt the selec-tive hydrogenation that catalyst of the present invention is used in the logistics of C4 mixed olefins, butadiene conversion can reach that 94%, 1-butylene is selective reaches 96%.
(2) catalyst holds " green oil " amount greatly, activity stabilized.The alkynes conversion ratio of selec-tive hydrogenation 100h and 1000h, butadiene conversion and the selective change of 1-butylene are little.
(3) main active component multiple with load in prior art with help the catalyst of active component and compare, catalyst provided by the invention decreases the kind of active component, reduces production cost, simplifies preparation process.
Detailed description of the invention
Below by embodiment, the present invention is further illustrated, but these embodiments do not form any restriction to scope of the present invention.
Embodiment 1
1.TiO
2-Al
2o
3prepared by composite oxide carrier
Getting BET specific surface area is 90m
2/ g, pore volume is 0.55ml/g, and most probable pore size is
al
2o
3100g, uses 55mlTiO
2content is the titanium sulfate solution dipping of 19.05g, leaves standstill 10 ~ 30 minutes, at 110 DEG C dry 6 hours, then roasting 4 hours at 480 DEG C, obtained TiO
2content is the TiO of 16wt%
2-Al
2o
3composite oxide carrier A-1;
2. catalyst precarsor preparation
Getting A-1 composite oxide carrier 100g, is the nickel nitrate solution dipping 20 ~ 30 minutes of 11.1g with 50ml NiO content, at 110 DEG C dry 6 hours, then roasting 4 hours at 450 DEG C, and obtained NiO content is the catalyst precarsor B-1 of 10wt%;
3. catalyst preparing
Get B-1 catalyst precarsor 100g, with the palladium chloride aqueous solution dipping that 85ml Pd content is 0.3g, leave standstill after 1 hour and take out, drain away the water, reduce 1 hour with the hydrazine hydrate aqueous solution that 120ml concentration is 10wt%, spend deionized water extremely without chlorion, drying 6 hours at 110 DEG C, obtained Pd content is 0.3wt%, NiO content is 10wt% and TiO
2content is the Pd-Ni/TiO of 16wt%
2-Al
2o
3catalyst C-1.
Embodiment 2 ~ 7
Method for preparing catalyst with embodiment 1, unlike change NiO, Pd and TiO
2content, respectively obtained catalyst C-2, C-3, C-4, C-5, C-6 and C-7, the active metal component in catalyst and TiO
2content in table 1.
Table 1
| Catalyst is numbered | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | C-7 |
| Pd（wt%） | 0.3 | 0.3 | 0.3 | 0.2 | 0.1 | 0.3 | 0.3 |
| NiO（wt%） | 10 | 5.0 | 12.0 | 10.0 | 10.0 | 10.0 | 10.0 |
| TiO 2（wt%） | 16.0 | 16.0 | 16.0 | 16.0 | 16.0 | 5.0 | 20.0 |
Embodiment 8
Evaluate catalysts C-1 ~ C-7 is in mixed C
4in selec-tive hydrogenation catalytic performance.
Getting each 50g of C-1 ~ C-7 catalyst, is 0.2 ~ 3.0MPa at Hydrogen Vapor Pressure, and temperature is 350 ~ 450 DEG C and hydrogen flowing quantity is reduce 6 ~ 15 hours under the condition of 20 ~ 100ml/ minute, and catalyst is activated, then cools to reaction temperature, charging is reacted.
Be 1.0MPa in reaction pressure, reaction temperature is 38 DEG C, hydrogen/(diene+alkynes)=1.2, mixed C
4feed space velocities is 3.0h
-1recycle ratio is under the condition of 15:1, pass into that iso-butane content is 1.23wt%, normal butane content is 1.84wt%, Trans-2-butene 2.30wt%, 1-butene content is 5.71wt%, isobutene content is 21.27wt%, cis-2-butene content is 24.18wt%, butadiene content is 24.25wt%, the hybrid C 4 raw material of alkynes content to be 15.48wt% and other content be 3.74wt%, reaction 1h, utilizes material after gas chromatographic analysis hydrogenation.The hydrogenation result of each catalyst is as table 2, and wherein each numerical value is mass percent.
Table 2
| Catalyst | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | C-7 |
| Alkynes conversion ratio (%) | 77.26 | 70.80 | 78.23 | 75.58 | 65.96 | 76.42 | 77.58 |
| Butadiene conversion (%) | 94.60 | 93.65 | 94.72 | 93.98 | 90.26 | 94.47 | 94.72 |
| 1-butylene selective (%) | 56.1 | 54.6 | 55.0 | 52.3 | 42.81 | 54.0 | 51.6 |
| 1-butylene (%) in product | 25.49 | 24.81 | 24.99 | 23.77 | 19.45 | 24.53 | 23.45 |
| Butadiene (%) in product | 1.31 | 1.54 | 1.28 | 1.46 | 2.36 | 1.34 | 1.28 |
| Alkynes (%) in product | 3.52 | 4.05 | 3.37 | 3.78 | 5.27 | 3.65 | 3.47 |
Butadiene conversion and 1-butylene optionally computing formula:
Table 2 illustrates compared with reaction raw materials, and use catalyst provided by the invention to carry out selective hydrogenation to hybrid C 4 raw material, in product, the content of 1-butylene improves 20%, and the content of butadiene have dropped 22 ~ 23%, and the content of alkynes decrease beyond 10%.
Embodiment 9
The LD365 palladium-based catalyst that catalyst C-1 embodiment 1 prepared and IFP produce, and the HTC-300S nickel-base catalyst that Akzo Nobel N.V. of Holland produces carries out hydrogenation contrast under the same conditions.
Get HTC-300S catalyst 50g, under Hydrogen Vapor Pressure is 0.5MPa, passes into hydrogen with the hydrogen flow rate of 250ml/min/g catalyst, whole beds is heated to 230 DEG C, keep 1 hour, catalyst is activated, then cools to reaction temperature, charging is reacted.
Respectively get C-1 and LD365 catalyst 50g, repeat the catalyst activation process of embodiment 9.Use the raw material identical with embodiment 9 and reaction condition to carry out hydrogenation reaction, the hydrogenation result of C-1, LD365 and HTC-300S tri-kinds of catalyst is as table 3.
Table 3
| Catalyst | C-1 | LD365 | HTC-300S |
| Alkynes conversion ratio (%) | 77.26 | 72.35 | 66.47 |
| Butadiene conversion (%) | 94.60 | 84.86 | 72.17 |
| 1-butylene selective (%) | 56.1 | 45.42 | 40.32 |
| 1-butylene (%) in product | 25.49 | 20.64 | 18.32 |
| Butadiene (%) in product | 1.31 | 3.67 | 6.75 |
| Alkynes (%) in product | 3.52 | 4.28 | 5.19 |
Note: the palladium content of LD365 catalyst is 0.33wt%
Table 3 illustrates, as compared to existing LD365 with HTC-300S catalyst, use catalyst provided by the invention to carry out selective hydrogenation to hybrid C 4 raw material, in product, the content of 1-butylene improves 5 ~ 7%, the content of butadiene have dropped 3 ~ 6%, and the content of alkynes have dropped 1 ~ 2%.
Embodiment 10
Getting BET specific surface area is 90m
2/ g, pore volume is 0.55ml/g, and most probable pore size is
al
2o
3carrier 100g.Weighing lanthanum nitrate, after being dissolved in water, adopt incipient impregnation carrier, then in 120 DEG C of dryings 6 hours, making final catalyst be 0.5wt% containing containing lanthanum amount.Get palladium nitrate solution, incipient impregnation method is adopted to be sprayed on by palladium nitrate solution on above-mentioned carrier, final catalyst is made to be 0.03wt% containing palladium amount, in 120 DEG C of dryings 6 hours, 480 DEG C of roastings 4 hours, meanwhile, use identical incipient impregnation method load silver and bismuth, the silver content of final catalyst and bismuth-containing amount is made to be respectively 0.09wt% and 0.03wt%, and dry, roasting.Calculate according to equivalent impregnation method, get appropriate HAuCl
3, add the Na of 0.02M
2cO
3solution, pH value is regulated to be 5.5 ~ 6.0 obtained gold solutions, spray on above-mentioned carrier, leave standstill after 12 hours, above-mentioned carrier is soaked 8 hours, with deionized water cyclic washing removing chlorion, in 120 DEG C of dryings 6 hours with the ammoniacal liquor of 2wt%, in 400 DEG C of roastings 4 hours, obtained containing 0.03Pd0.01Au0.09Ag0.09Bi0.5La/Al
2o
3catalyst B H1.
Get TiO respectively
2and SiO
2carrier 100g, according to preparing the identical method of BH1 catalyst, obtained containing 0.03Pd0.01Au0.09Ag0.09Bi0.5La/TiO
2catalyst B H2 and 0.03Pd0.01Au0.09Ag0.09Bi0.5La/SiO
2catalyst B H3.
Respectively get C-1, BH1, BH2 and BH3 catalyst 50g, repeat the catalyst activation process of embodiment 9.Use the raw material identical with embodiment 9 and reaction condition to carry out hydrogenation reaction, the results are shown in Table 4.
Table 4
As seen from Table 4, use polymetallic catalyst B H1, BH2 and BH3 for mixed C
4selec-tive hydrogenation is compared with catalyst of the present invention, the alkynes conversion ratio and the butadiene conversion that start 100 hours four kinds of catalyst are more or less the same, but, along with the increase difference of experimental period strengthens, in the experimental period of 300 hours, the alkynes conversion ratio of BH1, BH2 and BH3 have dropped 5.8%, 8.76% and 8.77% respectively, butadiene conversion have dropped 5.84%, 6.1% and 7.31% respectively, and catalyst alkynes conversion ratio of the present invention and butadiene conversion substantially constant, illustrate multimetal reforming catalyst BH1, BH2 and BH3 be used for mixed C
4hydrogenation activity is unstable.
Embodiment 11
Evaluate catalyst of the present invention to mixed C
4the stability of selec-tive hydrogenation.
C-1 catalyst 80g prepared by Example 1, repeat the catalyst activation process of embodiment 9, use the hybrid C 4 raw material identical with embodiment 9 and reaction condition to carry out hydrogenation reaction, change the reaction time, hydrogenation result is as table 5.
Table 5
As can be seen from Table 4, reaction in 1000 hours gone through by C-1 catalyst, and its activity and selectivity does not decline, and shows that C-1 catalyst of the present invention has higher appearance " green oil " ability and good stability.
In sum, the active metal kind that selective hydrogenation catalyst provided by the invention uses is few, can significantly improve the butadiene in hybrid C 4 raw material and alkynes content, have well selective.And after experiencing longer service time, still there is good stability.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (10)
1., for a catalyst for alkynes in mixed olefins and diolefin hydrogenate, described catalyst is with TiO
2-Al
2o
3composite oxides are carrier, the main active metal component Pd of load and help active metal component Ni.
2. catalyst according to claim 1, is characterized in that, based on the gross weight of described catalyst, the content of Pd counts 0.005 ~ 0.8wt% with atom, and the content of Ni counts 1 ~ 12wt% with atom.
3. catalyst according to claim 1, is characterized in that, based on the gross weight of described catalyst, the content of Pd counts 0.01 ~ 0.3wt% with atom, and the content of Ni counts 2 ~ 10wt% with atom.
4. the catalyst according to any one of claims 1 to 3, is characterized in that, in described catalyst, and TiO
2-Al
2o
3the content of composite oxide carrier is 87.2 ~ 99.9wt%.
5. catalyst according to claim 4, is characterized in that, described TiO
2-Al
2o
3tiO in composite oxide carrier
2content is 3 ~ 30wt%, is preferably 5 ~ 20wt%.
6. the catalyst according to claim 4 or 5, is characterized in that, described TiO
2-Al
2o
3the most probable pore size of composite oxide carrier is
be preferably
pore volume is 0.50 ~ 0.64ml/g, is preferably 0.52 ~ 0.60ml/g; Specific area is 70 ~ 120m
2/ g, is preferably 80 ~ 110m
2/ g.
7. the preparation method of catalyst according to any one of claim 1 ~ 6, comprises and first will help active metal component Ni load on carrier, afterwards the main active metal component Pd of load again; Or first by main active metal component Pd load on carrier, load helps active metal component Ni more afterwards.
8. method according to claim 7, is characterized in that, comprising:
1) by TiO
2-Al
2o
3composite oxide carrier adds in nickel salt solution and floods, then dry and roasting;
2) carrier that step 1) obtains is added in palladium solution flood, then reduce, filter washing and drying obtains described catalyst.
9. method according to claim 8, is characterized in that, step 2) described in reduction be pass through hydrazine hydrate reduction.
10. method according to claim 9, is characterized in that, comprising:
I) by TiO
2-Al
2o
3the composite oxide carrier nickel salt solution equal with catalyst ni content floods 1 ~ 2 hour, at the temperature of 100 ~ 150 DEG C dry 4 ~ 8 hours, then in 400 ~ 600 DEG C of roasting temperatures 3 ~ 6 hours, and obtained catalyst precarsor;
Ii) catalyst precarsor obtained in i) is measured equal palladium salt solution impregnation 1 ~ 2 hour with catalyst containing Pd, then 1 ~ 3 times that volume is described catalyst precarsor is added, concentration is that the hydrazine hydrate solution of 5 ~ 10wt% reduces 1 ~ 2 hour, filter, spend deionized water, drying 4 ~ 8 hours at the temperature of 100 ~ 150 DEG C, obtained described catalyst.
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