CN109092305A - The catalyst of selective hydrogenation of butadiene - Google Patents
The catalyst of selective hydrogenation of butadiene Download PDFInfo
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- CN109092305A CN109092305A CN201710473436.6A CN201710473436A CN109092305A CN 109092305 A CN109092305 A CN 109092305A CN 201710473436 A CN201710473436 A CN 201710473436A CN 109092305 A CN109092305 A CN 109092305A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
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Abstract
The present invention relates to the catalyst of selective hydrogenation of butadiene, mainly solve the technical issues of high butadiene content in hydrogenation products existing in the prior art, hydrogenation reaction butene-1 loss height, catalyst higher cost and preparation process are using poisonous and harmful raw material.The present invention by using selective hydrogenation of butadiene catalyst, including carrier and following component: (a) Metal Palladium of 0.3~5g/L or its oxide；(b) the IB race metal or its oxide of 0.1~10g/L；(c) technical solution of the cerium of 1~10g/L or its oxide 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.
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.Butene-1 is mainly used as linear low density polyethylene
(LLDPE) comonomer, while can be used for producing the chemical industry such as sec-butyl alcohol, the methyl ethyl ketone of high added value as primary raw material and producing
Product；Butene-1 oligomerisation can produce carbon eight, 12 alhpa olefin of carbon, these alkene are the good raw materials for preparing surfactant.So needle
The factories of a large amount of butene-1 products is needed to butadiene is not needed, the butadiene in carbon four is changed by fourth by selection plus hydrogen
Alkene -1 is rationally to utilize the process route of the economy of this four resource of part carbon.It can be seen that high efficiency selected hydrogenation catalyst and work
The exploitation of skill plays important role during carbon four appreciates and utilizes.The especially mating high-purity butene-1 of separation, to catalysis
More stringent requirements are proposed for agent and technique.BASF, IFP and Degussa etc. are proposed corresponding carbon four and select hydrogenation catalyst
Agent and technique, but the exploitation of domestic catalyst and the technique low to, butene-1 isomerization rate excellent with diene selective hydrotreating performance
There is also technical bottlenecks.
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.SHP technique (the Oil of U.S. Global Oil Products Company (UOP)
Gas J, 1988,86 (49): 40~43) using noble metal catalyst, although butadiene conversion is up to 99.8%, butene-1 is different
Structure rate 76.1%, but normal butane production quantity reaches 35.7%.Patent US4762956 reports a kind of for butadiene selection
Add the palladium-based catalyst of hydrogen, with catalyst weight, Sn or Pb containing 0.025%~1.0%Pd and 0.05%~4% have
Effect improves the selectivity of butadiene hydrogenation, it is suppressed that olefin isomerization reaction.Degussa is proposed high level Pd catalyst use
Select hydrogenation process that can effectively convert butadiene, while reducing hydrogenation process by using low temperature and suitable hydrogen-hydrocarbon ratio in carbon four
The loss of middle butene-1.In recent years, domestic n-butene was emerged one after another using technology, separate high-purity butene-1 do polyvinyl monomer,
The QSH-01 selective hydrogenation catalyst of alkylate oil, OCC and OMT olefin process etc., the exploitation of Shandong institute is successfully applied to alkyl
The raw material pretreatment process of carburetion.But the country is to the catalyst excellent with diene selective hydrotreating performance, butene-1 isomerization rate is low
And there is also technical bottlenecks for the exploitation of technique.There is resource in upstream, and there is market in downstream, for enterprise, joins in the comprehensive utilization of carbon four
The just surplus technology of most critical.New technology is developed, reaches or catches up with and surpass the international high standards, advanced optimize the utilization of resources, become
Improve the economic benefit and the most effective means of the market competitiveness of enterprise.
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 be in hydrogenation products existing in the prior art butadiene content it is high,
The technical issues of hydrogenation reaction butene-1 loss height, catalyst higher cost and preparation process use poisonous and harmful raw material, provides
Selective hydrogenation of butadiene catalyst, the catalyst have butadiene conversion height, butene-1 loss small, at low cost and use raw material
The features such as comparatively safe environmental protection.
The second technical problem to be solved by the present invention be using above-mentioned technical problem the catalyst containing butadiene
The selection method of hydrotreating of material.
One of to solve above-mentioned technical problem, technical solution of the present invention is as follows:
The catalyst of selective hydrogenation of butadiene, including carrier and following component:
(a) Metal Palladium of 0.3~5g/L or its oxide；
(b) the IB race metal or its oxide of 0.1~10g/L；
(c) cerium of 1~10g/L or its oxide.
In above-mentioned technical proposal, in terms of catalyst weight number, the Metal Palladium or its oxide of 1~3g/L are preferably comprised.
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, IB race metal or its oxidation of 0.3~5g/L are preferably comprised
Object；
In above-mentioned technical proposal, IB race metal preferably is selected from one or both of silver or copper；Especially while containing silver and copper,
Copper and silver have synergistic effect in terms of the yield for improving monoolefine.
In above-mentioned technical proposal, the metallic cerium or its oxide of 2~6g/L are preferably comprised.
In above-mentioned technical proposal, the source of metal Pd or its oxide is not particularly limited, such as, but not limited to palladium chloride,
One or both of chlorine palladium acid etc..
Alumina support described in above-mentioned technical proposal is not particularly limited, preferred vector BET specific surface area be 110~
250m20.55~0.8cm of/g, Kong Rongwei3/g。
The preparation method of catalyst of the present invention is not particularly limited, and as non limiting example, includes the following steps:
(1), boehmite (and/or aluminium oxide) and modifying agent, peptizing agent, water are mixed, after extruded moulding, first 60
It is 5~24 hours dry at~110 DEG C, it is then roasted 4~10 hours at 300~1000 DEG C, obtains carrier.
(2) carrier is mixed with the aqueous solution of the race's element of IB containing aequum and Ce elements, 80~200 DEG C of dryings 4~
It 24 hours, is then roasted 4~10 hours at 300~1000 DEG C, obtains modified support.
(3), the palladium compound solution of modified support palladium containing aequum is impregnated, through 80~150 DEG C dry 4~24
Hour, it roasts in air up to oxide type catalyst for 450~800 DEG C.
The catalyst restores above-mentioned oxide type when can be in the preparation or for reacting, the mode specifically restored
Those skilled in the art can rationally grasp, as long as being metallic state the palladium of compound state, the IB race element reduction of compound state.
To solve above-mentioned technical problem two, technical scheme is as follows: the selection of the material containing butadiene adds hydrogen side
Method, including in the presence of any one of the technical solution of one of the above-mentioned technical problem catalyst, the material containing butadiene is original
Material and hydrogen contact, which carry out reaction, makes 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 volume air speed is preferably 6~20h-1。
In above-mentioned technical proposal, hydrogen/butadiene molar ratio is preferably 1.5~10.
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≤2.0%.
More specific non limiting example, by weight percentage, the material contain 0.01~1.0% 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 35 DEG C of reaction temperature, pressure 2.2MPa, hydrogen/alkadienes molar ratio 3.0, outlet
Butadiene mass content < 2.5ppm, butene-1 are lost absolute value < 1.0, 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 2700 grams of boehmite of 2000 grams of aluminium oxide, 180 grams of sesbania powders, mixing is added contains later
400 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration are 80 grams of nitric acid of 68%, 1600 milliliters of water, are extruded intoTrifolium-shaped carrier, wet bar roasts 4 hours after dry 4 hours through 110 DEG C in 750 DEG C, obtains carrier Z1.It will be upper
1 liter of elder generation of carrier and 1 gram of argentiferous are stated, it is small through 110 DEG C of dryings 8 containing 3 grams of cerium of silver nitrates -450 grams of cerous nitrate mixed aqueous solution mixing
When, 400 DEG C roast 4 hours.Then above-mentioned modified support is mixed with 450 grams of the chlorine palladium aqueous acid containing 1 gram of palladium, through 110 DEG C
8 hours dry, 550 DEG C roast 4 hours, and palladium-based catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 35 DEG C,
Hydrogen volume air speed is 100 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 0.30%.
Operating condition is as follows:
Reaction temperature: 35 DEG C
Reaction pressure: 2.2MPa
Raw material volume air speed: 10h-1
Hydrogen/butadiene molar ratio: 3.0
Specific evaluation result is shown in Table 3.
[embodiment 2]
1, catalyst preparation
It weighs and is equivalent to 2700 grams of boehmite of 2000 grams of aluminium oxide, 180 grams of sesbania powders, mixing is added contains later
400 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration are 80 grams of nitric acid of 68%, 1600 milliliters of water, are extruded intoTrifolium-shaped carrier, wet bar roasts 4 hours after dry 4 hours through 110 DEG C in 750 DEG C, obtains carrier Z1.It will be upper
1 liter of elder generation of carrier and 1 gram of argentiferous are stated, it is small through 110 DEG C of dryings 8 containing 4 grams of cerium of silver nitrates -450 grams of cerous nitrate mixed aqueous solution mixing
When, 400 DEG C roast 4 hours.Then above-mentioned modified support is mixed with 1600 grams of the chlorine palladium aqueous acid containing 1.2 grams of palladium, through 110
DEG C dry 8 hours, 550 DEG C roasted 4 hours, and palladium-based catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature 35
DEG C, hydrogen volume air speed is 100 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 0.30%.
Operating condition is as follows:
Reaction temperature: 35 DEG C
Reaction pressure: 2.2MPa
Raw material volume air speed: 10h-1
Hydrogen/butadiene molar ratio: 3.0
Specific evaluation result is shown in Table 3.
[embodiment 3]
1, catalyst preparation
It weighs and is equivalent to 2700 grams of boehmite of 2000 grams of aluminium oxide, 180 grams of sesbania powders, mixing is added contains later
400 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration are 80 grams of nitric acid of 68%, 1600 milliliters of water, are extruded intoTrifolium-shaped carrier, wet bar roasts 4 hours after dry 4 hours through 110 DEG C in 750 DEG C, obtains carrier Z1.It will be upper
1 liter of elder generation of carrier and 1.5 grams of cupric are stated, containing 4 grams of cerium of silver nitrates -450 grams of cerous nitrate mixed aqueous solution mixing, through 110 DEG C dry 8
Hour, 400 DEG C roast 4 hours.Then above-mentioned modified support is mixed with 450 grams of the chlorine palladium aqueous acid containing 1.5 grams of palladium, is passed through
110 DEG C drying 8 hours, 550 DEG C roast 4 hours, be made palladium-based catalyst.It is used hydrogen reducing 4 hours using preceding, reduction temperature is
35 DEG C, hydrogen volume air speed is 100 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 0.30%.
Operating condition is as follows:
Reaction temperature: 35 DEG C
Reaction pressure: 2.2MPa
Raw material volume air speed: 10h-1
Hydrogen/butadiene molar ratio: 3.0
Specific evaluation result is shown in Table 3.
[embodiment 4]
1, catalyst preparation
It weighs and is equivalent to 2700 grams of boehmite of 2000 grams of aluminium oxide, 180 grams of sesbania powders, mixing is added contains later
400 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration are 80 grams of nitric acid of 68%, 1600 milliliters of water, are extruded intoTrifolium-shaped carrier, wet bar roasts 4 hours after dry 4 hours through 110 DEG C in 750 DEG C, obtains carrier Z1.It will be upper
1 liter of elder generation of carrier and 2 grams of argentiferous are stated, it is small through 110 DEG C of dryings 8 containing 3 grams of cerium of silver nitrates -450 grams of cerous nitrate mixed aqueous solution mixing
When, 400 DEG C roast 4 hours.Then above-mentioned modified support is mixed with 450 grams of the chlorine palladium aqueous acid containing 2 grams of palladium, through 110 DEG C
8 hours dry, 550 DEG C roast 4 hours, and palladium-based catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 35 DEG C,
Hydrogen volume air speed is 100 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 0.30%.
Operating condition is as follows:
Reaction temperature: 35 DEG C
Reaction pressure: 2.2MPa
Raw material volume air speed: 10h-1
Hydrogen/butadiene molar ratio: 3.0
Specific evaluation result is shown in Table 3.
[embodiment 5]
1, catalyst preparation
It weighs and is equivalent to 2700 grams of boehmite of 2000 grams of aluminium oxide, 180 grams of sesbania powders, mixing is added contains later
400 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration are 80 grams of nitric acid of 68%, 1600 milliliters of water, are extruded intoTrifolium-shaped carrier, wet bar roasts 4 hours after dry 4 hours through 110 DEG C in 750 DEG C, obtains carrier Z1.It will be upper
1 liter of elder generation of carrier and 1 gram of argentiferous are stated, 1 gram of copper, is mixed containing 3 grams of cerium of silver nitrates -450 grams of cerous nitrate mixed aqueous solution, through 110 DEG C
8 hours dry, 400 DEG C roast 4 hours.Then above-mentioned modified support is mixed with 450 grams of the chlorine palladium aqueous acid containing 2 grams of palladium,
8 hours dry through 110 DEG C, 550 DEG C roast 4 hours, and palladium-based catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature
It is 35 DEG C, hydrogen volume air speed is 100 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 0.30%.
Operating condition is as follows:
Reaction temperature: 35 DEG C
Reaction pressure: 2.2MPa
Raw material volume air speed: 10h-1
Hydrogen/butadiene molar ratio: 3.0
Specific evaluation result is shown in Table 3.
[embodiment 6]
1, catalyst preparation
It weighs and is equivalent to 2700 grams of boehmite of 2000 grams of aluminium oxide, 180 grams of sesbania powders, mixing is added contains later
400 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration are 80 grams of nitric acid of 68%, 1600 milliliters of water, are extruded intoTrifolium-shaped carrier, wet bar roasts 4 hours after dry 4 hours through 110 DEG C in 750 DEG C, obtains carrier Z1.It will be upper
1 liter of elder generation of carrier and 2 grams of cupric are stated, it is small through 110 DEG C of dryings 8 containing 3 grams of cerium of copper nitrates -450 grams of cerous nitrate mixed aqueous solution mixing
When, 400 DEG C roast 4 hours.Then above-mentioned modified support is mixed with 450 grams of the chlorine palladium aqueous acid containing 2 grams of palladium, through 110 DEG C
8 hours dry, 550 DEG C roast 4 hours, and palladium-based catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 35 DEG C,
Hydrogen volume air speed is 100 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 0.30%.
Operating condition is as follows:
Reaction temperature: 35 DEG C
Reaction pressure: 2.2MPa
Raw material volume air speed: 10h-1
Hydrogen/butadiene molar ratio: 3.0
Specific evaluation result is shown in Table 3.
[embodiment 7]
1, catalyst preparation
It weighs and is equivalent to 2700 grams of boehmite of 2000 grams of aluminium oxide, 180 grams of sesbania powders, mixing is added contains later
400 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration are 80 grams of nitric acid of 68%, 1600 milliliters of water, are extruded intoTrifolium-shaped carrier, wet bar roasts 4 hours after dry 4 hours through 110 DEG C in 750 DEG C, obtains carrier Z1.It will be upper
1 liter of elder generation of carrier and 1 gram of argentiferous are stated, it is small through 110 DEG C of dryings 8 containing 3 grams of cerium of silver nitrates -450 grams of cerous nitrate mixed aqueous solution mixing
When, 400 DEG C roast 4 hours.Then above-mentioned modified support is mixed with 450 grams of the chlorine palladium aqueous acid containing 1 gram of palladium, through 110 DEG C
8 hours dry, 550 DEG C roast 4 hours, and palladium-based catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 35 DEG C,
Hydrogen volume air speed is 100 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 0.30%.
Operating condition is as follows:
Reaction temperature: 35 DEG C
Reaction pressure: 2.2MPa
Raw material volume air speed: 10h-1
Hydrogen/butadiene molar ratio: 3.0
Specific evaluation result is shown in Table 3.
[comparative example 1]
1, catalyst preparation
It weighs and is equivalent to 2700 grams of boehmite of 2000 grams of aluminium oxide, 180 grams of sesbania powders, mixing is added contains later
400 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration are 80 grams of nitric acid of 68%, 1600 milliliters of water, are extruded intoTrifolium-shaped carrier, wet bar roasts 4 hours after dry 4 hours through 110 DEG C in 750 DEG C, obtains carrier Z1.It will be upper
1 liter of carrier is stated to mix with 450 grams of the chlorine palladium aqueous acid containing 1.5 grams of palladium, 8 hours dry through 110 DEG C, 550 DEG C roast 4 hours,
Palladium-based catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 35 DEG C, and hydrogen volume air speed is 100 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 0.30%.
Operating condition is as follows:
Reaction temperature: 35 DEG C
Reaction pressure: 2.2MPa
Raw material volume air speed: 10h-1
Hydrogen/butadiene molar ratio: 3.0
Specific evaluation result is shown in Table 3.
[comparative example 2]
1, catalyst preparation
It weighs and is equivalent to 2700 grams of boehmite of 2000 grams of aluminium oxide, 180 grams of sesbania powders, mixing is added contains later
400 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration are 80 grams of nitric acid of 68%, 1600 milliliters of water, are extruded intoTrifolium-shaped carrier, wet bar roasts 4 hours after dry 4 hours through 110 DEG C in 750 DEG C, obtains carrier Z1.It will be upper
1 liter of elder generation of carrier is stated with 0.2 gram of cupric 450 grams of copper nitrate aqueous solution mix, 8 hours dry through 110 DEG C, and 400 DEG C of roastings 4 are small
When.Then above-mentioned modified support is mixed with 450 grams of the chlorine palladium aqueous acid containing 2 grams of palladium, it is 8 hours, 550 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 35 DEG C, and hydrogen volume air speed is
100 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 0.30%.
Operating condition is as follows:
Reaction temperature: 35 DEG C
Reaction pressure: 2.2MPa
Raw material volume air speed: 10h-1
Hydrogen/butadiene molar ratio: 3.0
Specific evaluation result is shown in Table 3.
[comparative example 3]
1, catalyst preparation
It weighs and is equivalent to 2700 grams of boehmite of 2000 grams of aluminium oxide, 180 grams of sesbania powders, mixing is added contains later
400 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration are 80 grams of nitric acid of 68%, 1600 milliliters of water, are extruded intoTrifolium-shaped carrier, wet bar roasts 4 hours after dry 4 hours through 110 DEG C in 750 DEG C, obtains carrier Z1.It will be upper
1 liter of elder generation of carrier is stated with 0.4 gram of argentiferous 450 grams of silver nitrate aqueous solution mix, 8 hours dry through 110 DEG C, and 400 DEG C of roastings 4 are small
When.Then above-mentioned modified support is mixed with 450 grams of the chlorine palladium aqueous acid containing 2 grams of palladium, it is 8 hours, 550 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 35 DEG C, and hydrogen volume air speed is
100 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 0.30%.
Operating condition is as follows:
Reaction temperature: 35 DEG C
Reaction pressure: 2.2MPa
Raw material volume air speed: 10h-1
Hydrogen/butadiene molar ratio: 3.0
Specific evaluation result is shown in Table 3.
Table 1
Table 2
Table 3
Note: butene-1 loss absolute value=(butene-1 weight percent contains in butene-1 weight percentage-product in raw material
Amount) × 100.
Claims (9)
1. the catalyst of selective hydrogenation of butadiene, including carrier and following component:
(a) Metal Palladium of 0.3~5g/L or its oxide；
(b) the IB race metal or its oxide of 0.1~10g/L；
(c) cerium of 1~10g/L or its oxide.
2. catalyst according to claim 1, which is characterized in that contain the Metal Palladium of 1~3g/L or its oxide.
3. catalyst according to claim 1, which is characterized in that IB race metal or its oxide containing 0.3~5g/L.
4. catalyst according to claim 1, which is characterized in that contain the metallic cerium of 2~6g/L or its oxide.
5. the selection method of hydrotreating of the material containing butadiene is included in the presence of any one of power 1~4 catalyst, contains butadiene
Material be raw material and hydrogen contact carry out reaction make selective hydrogenation of butadiene to monoene.
6. method of hydrotreating according to claim 5, it is characterized in that being, reaction pressure is 1.5~3MPa.
7. method of hydrotreating according to claim 5, it is characterized in that being, reaction temperature is 30~60 DEG C.
8. method of hydrotreating according to claim 5, it is characterized in that being, raw material volume air speed is 6~18h-1。
9. method of hydrotreating according to claim 5, which is characterized in that hydrogen/butadiene molar ratio is 1.5~10.
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