CN109092303A - The catalyst of selective hydrogenation of butadiene - Google Patents
The catalyst of selective hydrogenation of butadiene Download PDFInfo
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Abstract
The present invention relates to the catalyst of selective hydrogenation of butadiene, mainly solve the technical issues of high butene-1 loss existing in the prior art, catalyst higher cost and preparation process are using poisonous and harmful raw material.The present invention is by using selective hydrogenation of butadiene catalyst, in terms of catalyst weight number, including following components: (a) 0.05~0.7 part of Metal Palladium or its oxide；(b) 0.1~2 part of lanthanide series metal or its oxide；(c) technical solution of 97.3~99.85 parts of alumina catalyst support preferably solves the technical problem, can be used in the material selective hydrogenation containing butadiene.
Description
Technical field
The present invention relates to selective hydrogenation of butadiene catalyst and the selection method of hydrotreating of the material containing butadiene, are specifically related to
C 4 materials containing a small amount of butadiene are subjected to selection plus hydrogen, while removing butadiene, the selection for reducing butene-1 loss adds
Hydrogen catalyst and method of hydrotreating.
Background of invention
N-butene is the main composition of by-product-C 4 fraction of oil plant catalytic cracking, Ethylene vapor cracking and MTO device
Part, price is lower, and major consumers are in fuel and chemical field.For producing sec-butyl alcohol, methyl ethyl ketone, polyethylene Third monomer
Deng.N-butene uses of the new technology as olefin cracking, olefin(e) disproportionation technique packet continually develop success in recent years, to the need of n-butene
The amount of asking is growing day by day, arrives the year two thousand twenty according to statistics and is up to 3,570,000 t, causes to mix the separation of n-butene and the research utilized in C4
Have become an one of important development direction for chemical production technical development.
After FCC, MTO and raffinate or ether all there is number in addition to containing main components such as n-butene, isobutene, butane in carbon four
Measure (100~20000PPM) not equal diene and alkynes, these easy polymers exist will lead to n-butene reaction with (olefinic polymerization
Olefin cracking alkylation) rapid catalyst deactivation, influence device stable operation, generally require increase selection hydrogenation unit to remove
Easy polymeric component is removed, while needing to adjust butene-1 and butene-2 ratio in raw material according to product.It is well known that carbon four plus hydrogen are different
Structure reaction is simultaneous with hydrogenation.Butadiene hydrogenation reacts to form butene-1, and the reaction is rapid on a catalyst
(relative speed is equal to 1000) occurs for ground.In presence of hydrogen, two reactions occur for butene-1, and a reaction is hydroisomerization
At butene-2 (relative speed 100), this reaction requires that hydrogen is added to carry out but not consume hydrogen.Another reaction is
Hydrogenation is to generate normal butane (relative speed 10).Last reaction is that butene-2 hydrogenation directly generates normal butane, this is most
Slow reaction (relative speed 1), is substantially negligible and disregards.It can be seen that high efficiency selected hydrogenation catalyst and technique
Exploitation plays important role during carbon four appreciates and utilizes.The SHP technique of U.S. Global Oil Products Company (UOP)
(Process hydrogenates unwanted diolefins and acetylenes,Oil Gas J,1988,86
(49): 40-43 noble metal catalyst) is used, although butadiene conversion is up to 99.8%, butene-1 isomerization rate 76.1%,
But normal butane production quantity reaches 35.7%.Patent US4762956 (Novel Catalyst and Process for
Hydrogenation of Unsaturated Hydrocarbons) report a kind of palladium base for selective hydrogenation of butadiene
Catalyst, with catalyst weight, Sn or Pb containing 0.025%~1.0%Pd and 0.05%~4% effectively increase fourth
The selectivity of diolefin hydrogenation, it is suppressed that olefin isomerization reaction.Degussa is proposed high level Pd catalyst and selects for carbon four
Hydrogenation process can effectively convert butadiene by using low temperature and suitable hydrogen-hydrocarbon ratio, while reduce butene-1 in hydrogenation process
Loss.In recent years, domestic n-butene was emerged one after another using technology, is separated high-purity butene-1 and is done polyvinyl monomer, alkylate oil,
The QSH-01 selective hydrogenation catalyst of OCC and OMT olefin process etc., the exploitation of Shandong institute is successfully applied to the raw material of alkylate oil
Pretreating process.But the domestic catalyst and technique low to, butene-1 isomerization rate excellent with diene selective hydrotreating performance are opened
Return that there are technical bottlenecks.There is resource in upstream, and there is market in downstream, for enterprise, joins in carbon four and comprehensively utilizes most critical just
Surplus technology.New technology is developed, reaches or catches up with and surpass the international high standards, advanced optimize the utilization of resources, becomes and improves enterprise
Economic benefit and the most effective means of the market competitiveness.
The selective hydrogenation of butadiene catalyst of prior art most study is Pd loaded catalyst, on the one hand there is positive fourth
Higher technical problem is lost in alkene；On the other hand, existing catalyst or palladium content and catalyst bulk density are higher, improve and urge
The use cost of agent；It is exactly the palladium-based catalyst that tin or lead are modified, preparation process is more toxic using auxiliary agent, uneasy
Loopful is protected.
Summary of the invention
The first technical problem to be solved by the present invention is that high, catalyst cost is lost in butene-1 existing in the prior art
Higher and preparation process uses the technical issues of poisonous and harmful raw material, provides selective hydrogenation of butadiene catalyst, catalyst tool
There is the features such as butadiene conversion is high, butene-1 loss is low, at low cost and environmental protection comparatively safe using raw material.
The second technical problem to be solved by the present invention is the preparation method of catalyst described in one of above-mentioned technical problem.
The third technical problem to be solved by the present invention is the application of catalyst described in one of above-mentioned technical problem.
One of to solve above-mentioned technical problem, technical solution of the present invention is as follows: the catalyst of selective hydrogenation of butadiene, to urge
Agent parts by weight meter, including following components: (a) 0.05~0.7 part of Metal Palladium or its oxide；(b) 0.1~2 part of lanthanum
System or its oxide；(c) 97.3~99.85 parts of alumina catalyst support.
In above-mentioned technical proposal, in terms of catalyst weight number, 0.2~0.5 part of Metal Palladium or its oxidation are preferably comprised
Object.
In above-mentioned technical proposal, when Pd element is oxide pattern, one skilled in the art will appreciate that gold should be reduced into
Belong to Pd and exercises use again.
In above-mentioned technical proposal, in terms of catalyst weight number, 0.3~1 part lanthanide series metal or its oxidation are preferably comprised
Object；
In above-mentioned technical proposal, lanthanide series metal preferably is selected from one or both of cerium or lanthanum.More preferably simultaneously include cerium and
Lanthanum, the two have synergistic effect in terms of reducing butadiene residual volume and butene-1 loss.
To solve above-mentioned technical problem two, technical scheme is as follows:
The preparation method of catalyst described in any one of technical solution of one of above-mentioned technical problem, includes the following steps:
(1), the carrier is mixed with the solution containing lanthanide metal compound, roasting obtains catalyst precarsor I；
(2), catalyst precarsor I and the solution of containing palladium compound are impregnated, it is compound state that roasting, which obtains the Pd in catalyst,
Catalyst.
Catalyst of the present invention can be the catalyst that the Pd that step (2) obtains is compound state, and the Pd of compound state is more
Important is the oxides of Pd.It should be pointed out that being butylene-for the selective hydrogenation of butadiene in butadiene material will to be contained
Before 1 reaction, need the catalyst of compound state, reduction (or being activation) is the reduction-state catalyst that Pd is simple substance.
In above-mentioned technical proposal, it can be selected in when preparing catalyst after step (2) further include:
It (3) is reduction-state catalyst that Pd is simple substance by the catalyst reduction that Pd is oxidation state.
Pd is that the reduction-state catalyst of simple substance in the selective hydrogenation of butadiene for will contain in butadiene material is butene-1
Reaction when no longer need to capable activation.
In above-mentioned technical proposal, the temperature roasted in step (1) and/(2) is preferably 450~800 DEG C.
In above-mentioned technical proposal, the time roasted in step (1) and/(2) is preferably 3~8 hours.
In above-mentioned technical proposal, the atmosphere roasted in step (1) and/(2) is preferably oxidizing atmosphere.
In above-mentioned technical proposal, the oxidizing atmosphere is preferably air atmosphere.It is in the specific embodiment of the invention
Air atmosphere roasting.
In above-mentioned technical proposal, to obtain the better catalyst of intensity, in step (1) and/(2) before roasting, preferably
By drying.Dry condition is not particularly limited, and those skilled in the art can reasonably select.Such as, but not limited to dry
Temperature is 80~150 DEG C；The dry time is 4~24 hours.
In order to solve the above problem three, technical scheme is as follows:
Catalyst described in any one of technical solution of one of above-mentioned technical problem will contain the fourth two in butadiene material
Alkene selects the application being hydrogenated in butene-1.
Key problem in technology of the invention is the selection of catalyst, and those skilled in the art can rationally determine that above-mentioned application is reasonable
Process conditions.Such as concrete application method may is that the selection method of hydrotreating of the material containing butadiene, is included in above-mentioned technology and asks
In the presence of any one of the technical solution of one of the topic catalyst, the material containing butadiene is that raw material and hydrogen contact are reacted
Make selective hydrogenation of butadiene to monoene.
In above-mentioned technical proposal, reaction pressure is preferably 1.5~3MPa.
In above-mentioned technical proposal, reaction temperature is preferably 30~60 DEG C.
In above-mentioned technical proposal, raw material liq volume space velocity is preferably 6~20h-1。
In above-mentioned technical proposal, hydrogen/butadiene molar ratio is preferably 1.2~2.
In above-mentioned technical proposal, the material containing butadiene, which largely contains tool in molecule, and there are four carbon originals
The alkene of son, wherein containing butene-1 and butene-2 and butadiene.
In above-mentioned technical proposal, the material containing butadiene preferably is selected from the raffinate carbon after cracking ethylene device extracting butadiene
Four, one or more of carbon four or FCC, preparing light olefins from methanol device by-product C4 mix after ether.
In above-mentioned technical proposal, with raw material weight percentages, the content of butadiene is preferred > and 0 and≤0.4%.
More specific non limiting example, by weight percentage, the material contain 0.01~0.6% butadiene, 3~
25% butane, 25~55% butene-1s, 2~25% butene-2s, 0~50% isobutene, 0~10% iso-butane.
In above-mentioned technical proposal, four raw material of carbon is preferably derived from carbon four, carbon-4 or selection hydrogenating carbon after ethylene plant's ether
One or more of four mixture, refinery catalytic cracking C-4-fraction, the C_4 hydrocarbon feed composition are containing iso-butane, just
Butane, anti-butene-2, butene-1, isobutene, maleic -2 and a small amount of butadiene.Since palladium itself has stronger plus hydrogen and different
Structure activity, often will cause hydrogenation of olefins to alkane, while butene-1 isomery passes through the second metal of addition or third to butene-2
Metal can Effective Regulation palladium catalyst hydroisomerizing performance by intermetallic effective synergistic effect.By using skill of the present invention
Art scheme carries out hydrotreating under conditions of 40 DEG C of reaction temperature, pressure 2.0MPa, hydrogen/alkadienes molar ratio 1.4, outlet
Butadiene mass content < 6ppm, butene-1 are lost absolute value < 4.2, achieve preferable technical effect.
The present invention will be further described below by way of examples, but these embodiments are not anyway to this hair
Bright range is construed as limiting.
It tests raw materials used composition and is shown in Table 1.
Specific embodiment
[embodiment 1]
1, catalyst preparation
It weighs and is equivalent to 150 grams of boehmite of 110 grams of aluminium oxide, 150 grams of aluminium oxide, 15 grams of sesbania powders, mixing, it
25.0 grams of aqueous solution of nitric acid that mass concentration is 50% are added afterwards, 300 milliliters of water, are extruded intoCylindric, the wet bar warp of millimeter
110 DEG C roast 4 hours in 600 DEG C after drying 4 hours, obtain alumina support.Weigh 99.20 grams of above-mentioned carrier and containing cerium 0.30
Gram 75 grams of cerous nitrate aqueous solution mixing, it is 8 hours dry through 110 DEG C, 450 DEG C roasting 4 hours catalyst precarsor I.It will be above-mentioned
Catalyst precarsor I is mixed with 100 grams of the chlorine palladium aqueous acid containing 0.5 gram of palladium, 8 hours dry through 110 DEG C, and 450 DEG C of roastings 4 are small
When, palladium-based catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 150 DEG C, and hydrogen volume air speed is 50 small
When-1, low isomery, selective hydrogenation catalyst are obtained, concrete composition is shown in Table 2.
2, evaluating catalyst
Carry out hydroprocessing in fixed bed reactors, the catalyst of above-mentioned preparation loaded in reactor, in a continuous manner into
The selection hydroprocessing of C 4 fraction after the ether that row mass fraction containing butadiene is 0.22%.
Operating condition is as follows:
Reaction temperature: 40 DEG C
Reaction pressure: 2.2MPa
Raw material liq volume space velocity: 12h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[embodiment 2]
1, catalyst preparation, which weighs, is equivalent to 150 grams of boehmite of 110 grams of aluminium oxide, 150 grams of aluminium oxide, 15 grams of fields
25.0 grams of aqueous solution of nitric acid that mass concentration is 50% are added later, 300 milliliters of water, are extruded into for cyanines powder, mixingThe circle of millimeter
Column, wet bar roast 4 hours after 110 DEG C 4 hours dry in 600 DEG C, obtain alumina support.Weigh 99.2 grams of above-mentioned carrier
8 hours dry through 110 DEG C with 75 grams of the lanthanum nitrate aqueous solution mixing containing 0.3 gram of lanthanum, 450 DEG C obtain catalyst precarsor in roasting 4 hours
I.Above-mentioned catalyst precarsor I is mixed with 100 grams of the chlorine palladium aqueous acid containing 0.5 gram of palladium, it is 8 hours, 450 DEG C dry through 110 DEG C
Palladium-based catalyst is made in roasting 4 hours.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 150 DEG C, and hydrogen volume air speed is
50 hours-1, low isomery, selective hydrogenation catalyst are obtained, concrete composition is shown in Table 2.
2, evaluating catalyst
Carry out hydroprocessing in fixed bed reactors, the catalyst of above-mentioned preparation loaded in reactor, in a continuous manner into
The selection hydroprocessing of C 4 fraction after the ether that row mass fraction containing butadiene is 0.22%.
Operating condition is as follows:
Reaction temperature: 40 DEG C
Reaction pressure: 2.2MPa
Raw material liq volume space velocity: 12h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[embodiment 3]
1, catalyst preparation, which weighs, is equivalent to 150 grams of boehmite of 110 grams of aluminium oxide, 150 grams of aluminium oxide, 15 grams of fields
25.0 grams of aqueous solution of nitric acid that mass concentration is 50% are added later, 300 milliliters of water, are extruded into for cyanines powder, mixingThe circle of millimeter
Column, wet bar roast 4 hours after 110 DEG C 4 hours dry in 600 DEG C, obtain alumina support.Weigh above-mentioned carrier 99.20
Gram and containing 37.5 grams of cerous nitrate aqueous solution of 0.15 gram of cerium, containing 0.15 gram of lanthanum of 37.5 grams of lanthanum nitrate aqueous solution mixing, through 110 DEG C
8 hours dry, 450 DEG C obtain catalyst precarsor I in roasting 4 hours.By above-mentioned catalyst precarsor I and the chlorine palladium sour water containing 0.5 gram of palladium
100 grams of solution mixing, 8 hours dry through 110 DEG C, 450 DEG C roast 4 hours, and palladium-based catalyst is made.Hydrogen reducing is used before use
4 hours, reduction temperature was 150 DEG C, and hydrogen volume air speed is 50 hours-1, obtain low isomery, selective hydrogenation catalyst, specific group
At being shown in Table 2.
2, evaluating catalyst
Carry out hydroprocessing in fixed bed reactors, the catalyst of above-mentioned preparation loaded in reactor, in a continuous manner into
The selection hydroprocessing of C 4 fraction after the ether that row mass fraction containing butadiene is 0.22%.
Operating condition is as follows:
Reaction temperature: 40 DEG C
Reaction pressure: 2.2MPa
Raw material liq volume space velocity: 12h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[embodiment 4]
1, catalyst preparation
It weighs and is equivalent to 150 grams of boehmite of 110 grams of aluminium oxide, 150 grams of aluminium oxide, 15 grams of sesbania powders, mixing, it
25.0 grams of aqueous solution of nitric acid that mass concentration is 50% are added afterwards, 300 milliliters of water, are extruded intoCylindric, the wet bar warp of millimeter
110 DEG C roast 4 hours in 600 DEG C after drying 4 hours, obtain alumina support.Weigh 99.20 grams of above-mentioned carrier and containing cerium 0.5
Gram 75 grams of cerous nitrate aqueous solution mixing, it is 8 hours dry through 110 DEG C, 450 DEG C roasting 4 hours catalyst precarsor I.It will be above-mentioned
Catalyst precarsor I is mixed with 100 grams of the chlorine palladium aqueous acid containing 0.3 gram of palladium, 8 hours dry through 110 DEG C, and 450 DEG C of roastings 4 are small
When, palladium-based catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 150 DEG C, and hydrogen volume air speed is 50 small
When-1, low isomery, selective hydrogenation catalyst are obtained, concrete composition is shown in Table 2.
2, evaluating catalyst
Carry out hydroprocessing in fixed bed reactors, the catalyst of above-mentioned preparation loaded in reactor, in a continuous manner into
The selection hydroprocessing of C 4 fraction after the ether that row mass fraction containing butadiene is 0.22%.
Operating condition is as follows:
Reaction temperature: 40 DEG C
Reaction pressure: 2.2MPa
Raw material liq volume space velocity: 12h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[embodiment 5]
1, catalyst preparation
It weighs and is equivalent to 150 grams of boehmite of 110 grams of aluminium oxide, 150 grams of aluminium oxide, 15 grams of sesbania powders, mixing, it
25.0 grams of aqueous solution of nitric acid that mass concentration is 50% are added afterwards, 300 milliliters of water, are extruded intoCylindric, the wet bar warp of millimeter
110 DEG C roast 4 hours in 600 DEG C after drying 4 hours, obtain alumina support.Weigh 98.5 grams of above-mentioned carrier and containing 1.0 grams of cerium
75 grams of cerous nitrate aqueous solution mixing, it is 8 hours dry through 110 DEG C, 450 DEG C roasting 4 hours catalyst precarsor I.It is urged above-mentioned
Agent precursor I is mixed with 100 grams of the chlorine palladium aqueous acid containing 0.5 gram of palladium, 8 hours dry through 110 DEG C, and 450 DEG C roast 4 hours,
Palladium-based catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 150 DEG C, and hydrogen volume air speed is 50 hours-1, obtain
To low isomery, selective hydrogenation catalyst, concrete composition is shown in Table 2.
2, evaluating catalyst
Carry out hydroprocessing in fixed bed reactors, the catalyst of above-mentioned preparation loaded in reactor, in a continuous manner into
The selection hydroprocessing of C 4 fraction after the ether that row mass fraction containing butadiene is 0.22%.
Operating condition is as follows:
Reaction temperature: 40 DEG C
Reaction pressure: 2.2MPa
Raw material liq volume space velocity: 12h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[embodiment 6]
1, catalyst preparation
It weighs and is equivalent to 150 grams of boehmite of 110 grams of aluminium oxide, 150 grams of aluminium oxide, 15 grams of sesbania powders, mixing, it
25.0 grams of aqueous solution of nitric acid that mass concentration is 50% are added afterwards, 300 milliliters of water, are extruded intoCylindric, the wet bar warp of millimeter
110 DEG C roast 4 hours in 600 DEG C after drying 4 hours, obtain alumina support.Weigh 97.5 grams of above-mentioned carrier and containing 2.0 grams of cerium
75 grams of cerous nitrate aqueous solution mixing, 8 hours dry through 110 DEG C, 450 DEG C roast 4 hours.By above-mentioned carrier containing 0.5 gram of palladium
100 grams of chlorine palladium aqueous acid mixing, 8 hours dry through 110 DEG C, 450 DEG C roast 4 hours, and palladium-based catalyst is made.Use preceding use
Hydrogen reducing 4 hours, reduction temperature was 150 DEG C, and hydrogen volume air speed is 50 hours-1, obtain low isomery, selection hydrogenation catalyst
Agent, concrete composition are shown in Table 2.
2, evaluating catalyst
Carry out hydroprocessing in fixed bed reactors, the catalyst of above-mentioned preparation loaded in reactor, in a continuous manner into
The selection hydroprocessing of C 4 fraction after the ether that row mass fraction containing butadiene is 0.22%.
Operating condition is as follows:
Reaction temperature: 40 DEG C
Reaction pressure: 2.2MPa
Raw material liq volume space velocity: 15h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[embodiment 7]
1, catalyst preparation
It weighs and is equivalent to 150 grams of boehmite of 110 grams of aluminium oxide, 150 grams of aluminium oxide, 15 grams of sesbania powders, mixing, it
25.0 grams of aqueous solution of nitric acid that mass concentration is 50% are added afterwards, 300 milliliters of water, are extruded intoCylindric, the wet bar warp of millimeter
110 DEG C roast 4 hours in 600 DEG C after drying 4 hours, obtain alumina support.Weigh 98.5 grams of above-mentioned carrier and containing 1.0 grams of lanthanum
75 grams of lanthanum nitrate aqueous solution mixing, 8 hours dry through 110 DEG C, 450 DEG C roast 4 hours.By above-mentioned carrier containing 0.5 gram of palladium
100 grams of chlorine palladium aqueous acid mixing, 8 hours dry through 110 DEG C, 450 DEG C roast 4 hours, and palladium-based catalyst is made.Use preceding use
Hydrogen reducing 4 hours, reduction temperature was 150 DEG C, and hydrogen volume air speed is 50 hours-1, obtain low isomery, selection hydrogenation catalyst
Agent, concrete composition are shown in Table 2.
2, evaluating catalyst
Carry out hydroprocessing in fixed bed reactors, the catalyst of above-mentioned preparation loaded in reactor, in a continuous manner into
The selection hydroprocessing of C 4 fraction after the ether that row mass fraction containing butadiene is 0.22%.
Operating condition is as follows:
Reaction temperature: 40 DEG C
Reaction pressure: 2.2MPa
Raw material liq volume space velocity: 15h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[comparative example 1]
1, catalyst preparation
It weighs and is equivalent to 150 grams of boehmite of 110 grams of aluminium oxide, 150 grams of aluminium oxide, 15 grams of sesbania powders, mixing, it
25.0 grams of aqueous solution of nitric acid that mass concentration is 50% are added afterwards, 300 milliliters of water, are extruded intoCylindric, the wet bar warp of millimeter
110 DEG C roast 4 hours in 600 DEG C after drying 4 hours, obtain alumina support.Weigh 99.5 grams of above-mentioned carrier and containing 0.5 gram of palladium
100 grams of chlorine palladium aqueous acid mixing, 8 hours dry through 110 DEG C, 450 DEG C roast 4 hours, and palladium-based catalyst is made.Before use
With hydrogen reducing 4 hours, reduction temperature was 150 DEG C, and hydrogen volume air speed is 50 hours-1, obtain low isomery, selection hydrogenation catalyst
Agent, concrete composition are shown in Table 2.
2, evaluating catalyst
Carry out hydroprocessing in fixed bed reactors, the catalyst of above-mentioned preparation loaded in reactor, in a continuous manner into
The selection hydroprocessing of C 4 fraction after the ether that row mass fraction containing butadiene is 0.22%.
Operating condition is as follows:
Reaction temperature: 40 DEG C
Reaction pressure: 2.2MPa
Raw material liq volume space velocity: 10h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[comparative example 2]
1, catalyst preparation
It weighs and is equivalent to 150 grams of boehmite of 110 grams of aluminium oxide, 150 grams of aluminium oxide, 15 grams of sesbania powders, mixing, it
25.0 grams of aqueous solution of nitric acid that mass concentration is 50% are added afterwards, 300 milliliters of water, are extruded intoCylindric, the wet bar warp of millimeter
110 DEG C roast 4 hours in 600 DEG C after drying 4 hours, obtain alumina support.Weigh 99.2 grams of above-mentioned carrier and containing 0.8 gram of cerium
75 grams of cerous nitrate aqueous solution mixing, 8 hours dry through 110 DEG C, 450 DEG C roast 4 hours, and cerium base catalyst is made.Before use
With hydrogen reducing 4 hours, reduction temperature was 150 DEG C, and hydrogen volume air speed is 50 hours-1, obtain low isomery, selection hydrogenation catalyst
Agent, concrete composition are shown in Table 2.
2, evaluating catalyst
Carry out hydroprocessing in fixed bed reactors, the catalyst of above-mentioned preparation loaded in reactor, in a continuous manner into
The selection hydroprocessing of C 4 fraction after the ether that row mass fraction containing butadiene is 0.22%.
Operating condition is as follows:
Reaction temperature: 40 DEG C
Reaction pressure: 2.2MPa
Raw material liq volume space velocity: 10h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[comparative example 3]
1, catalyst preparation
It weighs and is equivalent to 150 grams of boehmite of 110 grams of aluminium oxide, 150 grams of aluminium oxide, 15 grams of sesbania powders, mixing, it
25.0 grams of aqueous solution of nitric acid that mass concentration is 50% are added afterwards, 300 milliliters of water, are extruded intoCylindric, the wet bar warp of millimeter
110 DEG C roast 4 hours in 600 DEG C after drying 4 hours, obtain alumina support.Weigh 98.7 grams and 0.8 gram of cupric of above-mentioned carrier
75 grams of copper nitrate aqueous solution mixing, it is 8 hours dry through 110 DEG C, 450 DEG C roasting 4 hours catalyst precarsor I.It is urged above-mentioned
Agent precursor I is mixed with 100 grams of the chlorine palladium aqueous acid containing 0.5 gram of palladium, 8 hours dry through 110 DEG C, and 450 DEG C roast 4 hours,
Palladium-based catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 150 DEG C, and hydrogen volume air speed is 50 hours-1, obtain
To low isomery, selective hydrogenation catalyst, concrete composition is shown in Table 2.
2, evaluating catalyst
Carry out hydroprocessing in fixed bed reactors, the catalyst of above-mentioned preparation loaded in reactor, in a continuous manner into
The selection hydroprocessing of C 4 fraction after the ether that row mass fraction containing butadiene is 0.22%.
Operating condition is as follows:
Reaction temperature: 40 DEG C
Reaction pressure: 2.2MPa
Raw material liq volume space velocity: 12h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 2.
Table 1
| Raw material composition | Weight forms w% |
| Butane | 14.84 |
| Iso-butane | 0.68 |
| Butene-1 | 53.34 |
| Butene-2 | 30.50 |
| Isobutene | 0.52 |
| Butadiene | 0.12 |
Table 2
Note: butene-1 percentage composition after butene-1 percentage composition-reaction before butene-1 loss absolute value unit=reaction.
Claims (10)
1. the catalyst of selective hydrogenation of butadiene, in terms of catalyst weight number, including following components:
(a) 0.05~0.7 part of Metal Palladium or its oxide；
(b) 0.1~2 part of lanthanide series metal or its oxide；
(c) 97.3~99.85 parts of alumina catalyst support.
2. catalyst according to claim 1, which is characterized in that contain 0.2~0.50 part of Metal Palladium or its oxide.
3. catalyst according to claim 1, which is characterized in that contain 0.3~1 part of group of the lanthanides earth metal or its oxidation
Object.
4. the preparation method of catalyst described in any one of claims 1 to 3, includes the following steps:
(1), the carrier is mixed with the solution containing lanthanide metal compound, roasting obtains catalyst precarsor I；
(2), catalyst precarsor I and the solution of containing palladium compound are impregnated, it is urging for compound state that roasting, which obtains the Pd in catalyst,
Agent.
5. the preparation method according to claim 4, it is characterized in that after step (2) further include:
It (3) is reduction-state catalyst that Pd is simple substance by the catalyst reduction that Pd is compound state.
6. the preparation method according to claim 4, it is characterized in that the temperature roasted in step (1) and/(2) is 450~800
℃。
7. the preparation method according to claim 4, it is characterized in that the time roasted in step (1) and/(2) is 3~8 small
When.
8. the preparation method according to claim 4, it is characterized in that the atmosphere roasted in step (1) and/(2) is oxidisability gas
Atmosphere.
9. preparation method according to claim 5, it is characterized in that the oxidizing atmosphere is air atmosphere.
10. catalyst described in any one of claims 1 to 3 is fourth that will contain the selective hydrogenation of butadiene in butadiene material
Application in alkene -1.
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