CN106582706B - Selective hydrogenation of butadiene catalyst - Google Patents
Selective hydrogenation of butadiene catalyst Download PDFInfo
- Publication number
- CN106582706B CN106582706B CN201510661622.3A CN201510661622A CN106582706B CN 106582706 B CN106582706 B CN 106582706B CN 201510661622 A CN201510661622 A CN 201510661622A CN 106582706 B CN106582706 B CN 106582706B
- Authority
- CN
- China
- Prior art keywords
- butadiene
- catalyst
- grams
- selective hydrogenation
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/70—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
- B01J23/892—Nickel and noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to selective hydrogenation of butadiene catalyst, mainly solve that catalyst existing in the prior art is at high cost, high technical problem is lost in n-butene.The present invention is by using selective hydrogenation of butadiene catalyst, in terms of catalyst weight number, including following components: (a) 5~20 parts of metallic nickel or its oxide；(b) 0.5~4 part of IB race metal or its oxide；(c) 0~2 part of alkali metal or its oxide；(d) technical solution of 75~88 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.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 US4404124 reports one kind and adds for acetylene selection
Hydrogen is made of to the load type bimetal catalyst of ethylene Pd and Ag.Patent US4762956 reports a kind of for butadiene choosing
The palladium-based catalyst for adding hydrogen is selected, with catalyst weight, Sn or Pb containing 0.025%~1.0%Pd and 0.05%~4%,
Effectively increase the selectivity of butadiene hydrogenation, it is suppressed that olefin isomerization reaction.Degussa is proposed high level Pd catalyst
Hydrogenation process is selected for carbon four, by using low temperature and suitable hydrogen-hydrocarbon ratio, can effectively convert butadiene, while reducing and adding hydrogen mistake
The loss of butene-1 in journey.In recent years, domestic n-butene was emerged one after another using technology, is separated high-purity butene-1 and is made polyethylene list
The QSH-01 selective hydrogenation catalyst of body, alkylate oil, OCC and OMT olefin process etc., the exploitation of Shandong institute is successfully applied to alkane
The raw material pretreatment process of base carburetion.But the country is to the catalysis excellent with diene selective hydrotreating performance, butene-1 isomerization rate is low
There is also technical bottlenecks for agent and the exploitation of technique.There is resource in upstream, and there is market in downstream, for enterprise, joins in the comprehensive benefit of carbon four
With 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, at
For the economic benefit and the most effective means of the market competitiveness for improving enterprise.
The selective hydrogenation of butadiene catalyst of prior art most study is Pd loaded catalyst.Because of the catalyst system
Price is more expensive, has carried out wider research for cheap base metal type alternative catalysts in recent years.Nickel-base catalyst has
Good hydrogenation activity but selectivity is relatively poor, therefore limits its application and development.
Summary of the invention
The first technical problem to be solved by the present invention is that butene-1 isomerization rate existing in the prior art is high, catalyst
The technical issues of higher cost, provides selective hydrogenation of butadiene catalyst, which has butadiene conversion height, butene-1
The features such as low, at low cost is lost.
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: selective hydrogenation of butadiene catalyst, with catalysis
Agent parts by weight meter, including following components: (a) 5~20 parts of metallic nickel or its oxide；(b) in 0.5~4 part of IB race
One or more of metals；(c) 0~2 part of alkali metal or its oxide；(d) 75~88 parts of alumina catalyst support.
In above-mentioned technical proposal, in terms of catalyst weight number, 8~18 parts of metallic nickel or its oxide are preferably comprised.
In above-mentioned technical proposal, when Ni element is oxide pattern, one skilled in the art will appreciate that gold should be reduced into
Belong to Ni and exercises use again.
In above-mentioned technical proposal, in terms of catalyst weight number, one or more of 1~3 part IB race is preferably comprised
Metal.
In above-mentioned technical proposal, IB race metal is preferably silver or gold.
In above-mentioned technical proposal, 0.2~1 part of alkali metal or its oxide are preferably comprised
Any metal or its oxide in above-mentioned technical proposal, preferably also in lanthanum or cerium containing 0.2~2 part.
In above-mentioned technical proposal, the source of metallic nickel or its oxide is not particularly limited, such as, but not limited to nickel acetate,
One or two in nickel nitrate.
Alumina support described in above-mentioned technical proposal is not particularly limited, preferred vector BET specific surface area be 110~
150m20.45~0.75ml/g of/g, Kong Rongwei, pore-size distribution account for the 50~80% of carrier total pore volume in the total pore volume of 8~20nm.
The preparation method of catalyst of the present invention is not particularly limited, and as non limiting example, includes the following steps:
(1), by boehmite (and/or aluminium oxide) and modifying agent, peptizing agent, water (or alkali metal containing aequum, lanthanum
Or the aqueous solution of cerium) mix, after extruded moulding, it is first 5~24 hours dry at 60~110 DEG C, then at 500~1000 DEG C
Roasting 4~10 hours, obtains carrier.
(2), the solution of carrier nickel compound containing aequum, IB compounds of group is impregnated, through drying, in air 450
~800 DEG C roast up to oxide type catalyst.
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 metal the compound state nickel of compound state, the IB race element reduction of compound state
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 1.2~3MPa.
In above-mentioned technical proposal, reaction temperature is preferably 30~60 DEG C.
In above-mentioned technical proposal, liquid phase air speed is preferably 6~15h-1。
In above-mentioned technical proposal, hydrogen/butadiene molar ratio is 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≤0.6%.
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, particularly, containing a small amount of in C_4 hydrocarbon charging
The sulfur-containing compound of methyl mercaptan, hydrogen sulfide.Raney nickel has the property of better resistance to impurity and poisonous substance than palladium catalyst, especially
To sulfur-containing compound, there is well adapting to property.Since nickel itself has stronger plus hydrogen and heterogeneous activity, alkene often will cause
Hydrocarbon adds hydrogen to alkane, while butene-1 isomery passes through the second metallic silver of addition or gold with nickel and form metal alloy, gold to butene-2
Or silver preferentially occupies side, rib or the step position on catalyst, it can Effective Regulation Raney nickel hydroisomerizing performance.
By using technical solution of the present invention, in 40 DEG C of reaction temperature, pressure 2.0MPa, hydrogen/alkadienes molar ratio 1.4
Under the conditions of carry out hydrotreating, export butadiene mass content < 8ppm, absolute value < 5.5 are lost in butene-1, 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 14 grams of boehmite of 10 grams of aluminium oxide, 130 grams of aluminium oxide, 9 grams of sesbania powders, mixing, later
It is added and contains 20 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration is 3.0 grams of nitric acid of 68%, 200 milliliters of water, is squeezed
AtThe trifolium-shaped carrier of millimeter, wet bar roast 4 hours after 110 DEG C 4 hours dry in 750 DEG C, obtain carrier Z1.It will
20 grams of above-mentioned carrier mix with nickel nitrate-silver nitrate mixed aqueous solution 26 of nickeliferous 14 grams and 2.0 grams of argentiferous, through 110 DEG C dry 8
Hour, 550 DEG C roast 4 hours, and Ni base catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 450 DEG C, hydrogen
Volume space velocity 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: 2.0MPa
Liquid phase air speed: 8h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[embodiment 2]
1, catalyst preparation
It weighs and is equivalent to 14 grams of boehmite of 10 grams of aluminium oxide, 130 grams of aluminium oxide, 9 grams of sesbania powders, mixing, later
It is added and contains 20 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration is 3.0 grams of nitric acid of 68%, 200 milliliters of water, is squeezed
AtThe trifolium-shaped carrier of millimeter, wet bar roast 4 hours after 110 DEG C 4 hours dry in 750 DEG C, obtain carrier Z1.It will
20 grams of above-mentioned carrier mix with nickeliferous 14 grams and 2.0 grams of argentiferous of nickel nitrate -26 grams of silver nitrate mixed aqueous solution, dry through 110 DEG C
Dry 8 hours, 550 DEG C roasted 4 hours, and Ni base catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 450 DEG C,
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: 2.0MPa
Liquid phase air speed: 8h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[embodiment 3]
1, catalyst preparation
It weighs and is equivalent to 14 grams of boehmite of 10 grams of aluminium oxide, 130 grams of aluminium oxide, 9 grams of sesbania powders, mixing, later
It is added and contains 20 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration is 3.0 grams of nitric acid of 68%, 200 milliliters of water, is squeezed
AtThe trifolium-shaped carrier of millimeter, wet bar roast 4 hours after 110 DEG C 4 hours dry in 750 DEG C, obtain carrier Z1.It will
20 grams of above-mentioned carrier and nickeliferous 14 grams and 1.0 grams of argentiferous and containing 1.0 grams of gold of nickel nitrate-silver nitrate-gold chloride mixed aqueous solution
26 grams of mixing, 8 hours dry through 110 DEG C, 550 DEG C roast 4 hours, and Ni base catalyst is made.Using preceding small with hydrogen reducing 4
When, reduction temperature is 450 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: 2.0MPa
Liquid phase air speed: 8h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[embodiment 4]
1, evaluating catalyst
It weighs and is equivalent to 14 grams of boehmite of 10 grams of aluminium oxide, 130 grams of aluminium oxide, 9 grams of sesbania powders, mixing, later
It is added and contains 20 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration is 3.0 grams of nitric acid of 68%, the nitre containing 0.5 gram of potassium
200 milliliters of sour aqueous solutions of potassium, is extruded intoThe trifolium-shaped carrier of millimeter, wet bar roast after 110 DEG C 4 hours dry in 750 DEG C
It burns 4 hours, obtains carrier Z2.20 grams of above-mentioned carrier are mixed with nickeliferous 14 grams and 2.0 grams of argentiferous of nickel nitrate-silver nitrate water-soluble
Liquid mixing, 8 hours dry through 110 DEG C, 550 DEG C roast 4 hours, and Ni base catalyst is made.It is used hydrogen reducing 4 hours using preceding,
Reduction temperature is 450 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: 2.0MPa
Liquid phase air speed: 8h-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 14 grams of boehmite of 10 grams of aluminium oxide, 130 grams of aluminium oxide, 9 grams of sesbania powders, mixing, later
Be added and contain 20 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration is 3.0 grams of nitric acid of 68%, containing 0.6 gram of potassium and
The potassium nitrate of 1.0 grams of ceriums -200 milliliters of cerous nitrate mixed aqueous solution, is extruded intoThe trifolium-shaped carrier of millimeter, wet bar is through 110
It DEG C is roasted 4 hours after dry 4 hours in 750 DEG C, obtains carrier Z3.By 20 grams and nickeliferous 14 grams and 2.0 grams of argentiferous of above-mentioned carrier
Nickel nitrate -26 grams of silver nitrate mixed aqueous solution mixing, 8 hours dry through 110 DEG C, 550 DEG C roast 4 hours, and Ni base is made and urges
Agent.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 450 DEG C, and hydrogen volume air speed is 50 hours-1, obtain low isomery,
Selective hydrogenation catalyst, 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: 2.0MPa
Liquid phase air speed: 8h-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 14 grams of boehmite of 10 grams of aluminium oxide, 130 grams of aluminium oxide, 9 grams of sesbania powders, mixing, later
Be added and contain 20 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration is 3.0 grams of nitric acid of 68%, containing 0.6 gram of potassium and
The cerous nitrate of 1.0 grams of ceriums -200 milliliters of potassium nitrate mixed aqueous solution, is extruded intoThe trifolium-shaped carrier of millimeter, wet bar is through 110
It DEG C is roasted 4 hours after dry 4 hours in 750 DEG C, obtains carrier Z3.By 20 grams and nickeliferous 14 grams and 1.0 grams of argentiferous of above-mentioned carrier
And containing 1.0 grams of gold of nickel nitrate-silver nitrate -26 grams of gold chloride mixed aqueous solution mixing, 550 DEG C roastings 8 hours dry through 110 DEG C
It burns 4 hours, Ni base catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 450 DEG C, and hydrogen volume air speed is 50
Hour-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: 2.0MPa
Liquid phase air speed: 8h-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 14 grams of boehmite of 10 grams of aluminium oxide, 130 grams of aluminium oxide, 9 grams of sesbania powders, mixing, later
It is added and contains 20 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration is 3.0 grams of nitric acid of 68%, 200 milliliters of water, is squeezed
AtThe trifolium-shaped carrier of millimeter, wet bar roast 4 hours after 110 DEG C 4 hours dry in 750 DEG C, obtain carrier Z1.It will
20 grams of above-mentioned carrier mix with nickeliferous 16 grams and 3.0 grams of argentiferous of nickel nitrate -26 grams of silver nitrate mixed aqueous solution, dry through 110 DEG C
Dry 8 hours, 550 DEG C roasted 4 hours, and Ni base catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 450 DEG C,
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: 2.0MPa
Liquid phase air speed: 8h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
[embodiment 8]
1, catalyst preparation
It weighs and is equivalent to 14 grams of boehmite of 10 grams of aluminium oxide, 130 grams of aluminium oxide, 9 grams of sesbania powders, mixing, later
It is added and contains 20 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration is 3.0 grams of nitric acid of 68%, 200 milliliters of water, is squeezed
AtThe trifolium-shaped carrier of millimeter, wet bar roast 4 hours after 110 DEG C 4 hours dry in 750 DEG C, obtain carrier Z1.It will
20 grams of above-mentioned carrier mix with nickeliferous 18 grams and 4.0 grams of argentiferous of nickel nitrate -26 grams of silver nitrate mixed aqueous solution, dry through 110 DEG C
Dry 8 hours, 550 DEG C roasted 4 hours, and Ni base catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 450 DEG C,
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: 2.0MPa
Liquid phase air speed: 8h-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 14 grams of boehmite of 10 grams of aluminium oxide, 130 grams of aluminium oxide, 9 grams of sesbania powders, mixing, later
It is added and contains 20 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration is 3.0 grams of nitric acid of 68%, 200 milliliters of water, is squeezed
AtThe trifolium-shaped carrier of millimeter, wet bar roast 4 hours after 110 DEG C 4 hours dry in 750 DEG C, obtain carrier Z1.It will
20 grams of above-mentioned carrier with nickeliferous 14 grams of nickel nitrate aqueous solution 26 grams mix, 8 hours dry through 110 DEG C, 550 DEG C roast 4 hours,
Ni base catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 450 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: 2.0MPa
Liquid phase air speed: 8h-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 14 grams of boehmite of 10 grams of aluminium oxide, 130 grams of aluminium oxide, 9 grams of sesbania powders, mixing, later
Be added and contain 20 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration is 3.0 grams of nitric acid of 68%, containing 0.5 gram of potassium and
The cerous nitrate of 0.5 gram of cerium -200 milliliters of potassium nitrate mixed aqueous solution, is extruded intoThe trifolium-shaped carrier of millimeter, wet bar is through 110
It DEG C is roasted 4 hours after dry 4 hours in 750 DEG C, obtains carrier Z1.It is water-soluble with nickeliferous 14 grams of nickel nitrate by 20 grams of above-mentioned carrier
26 grams of liquid mixing, 8 hours dry through 110 DEG C, 550 DEG C roast 4 hours, and Ni base catalyst is made.Using preceding small with hydrogen reducing 4
When, reduction temperature is 450 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: 2.0MPa
Liquid phase air speed: 8h-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 14 grams of boehmite of 10 grams of aluminium oxide, 130 grams of aluminium oxide, 9 grams of sesbania powders, mixing, later
It is added and contains 20 grams of poly-vinyl alcohol solution (mass concentration 5%), mass concentration is 3.0 grams of nitric acid of 68%, 200 milliliters of water, is squeezed
AtThe trifolium-shaped carrier of millimeter, wet bar roast 4 hours after 110 DEG C 4 hours dry in 750 DEG C, obtain carrier Z1.It will
20 grams of above-mentioned carrier mix with nickeliferous 14 grams and 5.0 grams of argentiferous of nickel nitrate -26 grams of silver nitrate mixed aqueous solution, dry through 110 DEG C
Dry 8 hours, 550 DEG C roasted 4 hours, and Ni base catalyst is made.It is used hydrogen reducing 4 hours using preceding, reduction temperature is 450 DEG C,
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: 2.0MPa
Liquid phase air speed: 8h-1
Hydrogen/butadiene molar ratio: 1.40
Specific evaluation result is shown in Table 3.
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
Table 3
Claims (12)
1. selective hydrogenation of butadiene catalyst, in terms of catalyst weight number, including following components:
(a) 5~20 parts of metallic nickel or its oxide；
(b) 0.5~4 part of IB race metal or its oxide；
(c) 0~2 part of alkali metal or its oxide；
(d) 75~88 parts of alumina catalyst support；
IB race metal is silver and gold.
2. selective hydrogenation catalyst according to claim 1, which is characterized in that contain 8~18 parts of metallic nickels or its oxygen
Compound.
3. selective hydrogenation catalyst according to claim 1, which is characterized in that containing one of 1~3 part IB race or
Several metals.
4. selective hydrogenation catalyst according to claim 1, which is characterized in that contain 0.2~1 part of alkali metal or its oxygen
Compound.
5. selective hydrogenation catalyst according to claim 1, which is characterized in that also in lanthanum or cerium containing 0.2~2 part
Any metal or its oxide.
6. the selection method of hydrotreating of the material containing butadiene, is included in the presence of any one of Claims 1 to 5 catalyst, contains
The material of butadiene is that raw material and hydrogen contact carry out reaction and make selective hydrogenation of butadiene to monoene.
7. method of hydrotreating according to claim 6, it is characterized in that being, the material containing butadiene, which contains in molecule, to be had
There are four the alkene of carbon atom, wherein containing butene-1 and butene-2 and butadiene.
8. method of hydrotreating according to claim 6, it is characterized in that be, material containing butadiene by weight percentage, fourth
Content > 0 of diene and≤0.6%.
9. method of hydrotreating according to claim 6, it is characterized in that being, material containing butadiene by weight percentage, contains
0.01~0.6% butadiene, 3~25% butane, 25~55% butene-1s, 2~25% butene-2s, 0~50% isobutene, 0~
10% iso-butane.
10. method of hydrotreating according to claim 6, it is characterized in that being, reaction pressure is 1.2~3MPa.
11. method of hydrotreating according to claim 6, it is characterized in that being, reaction temperature is 30~60 DEG C.
12. method of hydrotreating according to claim 6, which is characterized in that hydrogen/butadiene molar ratio is 1.2~2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510661622.3A CN106582706B (en) | 2015-10-14 | 2015-10-14 | Selective hydrogenation of butadiene catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510661622.3A CN106582706B (en) | 2015-10-14 | 2015-10-14 | Selective hydrogenation of butadiene catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106582706A CN106582706A (en) | 2017-04-26 |
| CN106582706B true CN106582706B (en) | 2019-09-06 |
Family
ID=58552288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510661622.3A Active CN106582706B (en) | 2015-10-14 | 2015-10-14 | Selective hydrogenation of butadiene catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106582706B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096032A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | Cracking c_4 selective hydrogenation catalyst |
| CN109092303B (en) * | 2017-06-21 | 2020-10-30 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of butadiene |
| CN109092305A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The catalyst of selective hydrogenation of butadiene |
| CN109092302B (en) * | 2017-06-21 | 2020-09-04 | 中国石油化工股份有限公司 | Method for selective hydrogenation of butadiene |
| CN111054388B (en) * | 2018-10-16 | 2022-10-14 | 中国石油化工股份有限公司 | Nickel-based carbon four-fraction selective hydrogenation catalyst and preparation method thereof |
| CN111054332B (en) * | 2018-10-16 | 2022-10-14 | 中国石油化工股份有限公司 | Preparation method of four-carbon fraction selective hydrogenation catalyst |
| CN114073960B (en) * | 2020-08-14 | 2023-11-10 | 中国石油化工股份有限公司 | Alkyne selective hydrogenation catalyst and preparation method and application thereof |
| CN114471570B (en) * | 2020-10-23 | 2024-01-30 | 中国石油化工股份有限公司 | Naphthalene selective hydrogenation catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590353A (en) * | 2003-08-26 | 2005-03-09 | 中国石化集团齐鲁石油化工公司 | Utilization method of butadiene extraction device residue |
| CN101428225A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Nickel base catalyst for producing butylene-1 with butylenes-2 hydroisomerization containing a few butadiene |
| CN102285859A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Selective hydrogenation process for C4 material flow with high concentration of butadiene |
-
2015
- 2015-10-14 CN CN201510661622.3A patent/CN106582706B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590353A (en) * | 2003-08-26 | 2005-03-09 | 中国石化集团齐鲁石油化工公司 | Utilization method of butadiene extraction device residue |
| CN101428225A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Nickel base catalyst for producing butylene-1 with butylenes-2 hydroisomerization containing a few butadiene |
| CN102285859A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Selective hydrogenation process for C4 material flow with high concentration of butadiene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106582706A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106582706B (en) | Selective hydrogenation of butadiene catalyst | |
| CN106582625B (en) | The catalyst of selective hydrogenation of butadiene | |
| CN100434168C (en) | Selective hydrogenation catalyst designed for raw gas feed streams | |
| CN106861691B (en) | A kind of preparation of hydrogenation catalyst and hydrogenation catalyst and application | |
| CN105642324B (en) | A kind of base metal selective hydrocatalyst and its preparation method and application | |
| CN104098426A (en) | Method for selective hydrogenation of carbon-containing distillate | |
| CN112007646A (en) | Carbon-tetrahydrocarbon full-hydrogenation catalyst, preparation method thereof and carbon-tetrahydrocarbon hydrogenation method | |
| CN103347986A (en) | Thio-resistant catalyst, production method and use thereof in selective hydrogenation | |
| EP2376224A1 (en) | Selective catalytic hydrogenation of alkynes to corresponding alkenes | |
| CN101348406B (en) | Hydrogenation method for cracking hydrocarbon having nine carbon atoms or more | |
| CN104449835B (en) | The method of cracking carbon nine and above hydrocarbon hydrogenation thereof | |
| CN101844081B (en) | Selective hydrogenation catalyst and application thereof | |
| CN109092298A (en) | For cracking c_4 selective hydrogenation catalyst | |
| CN101428225A (en) | Nickel base catalyst for producing butylene-1 with butylenes-2 hydroisomerization containing a few butadiene | |
| CN110508290B (en) | High-dispersion palladium/cobalt hydroxide catalyst and preparation method and application thereof | |
| CN109092305A (en) | The catalyst of selective hydrogenation of butadiene | |
| CN102936183B (en) | Method for preparing ethylene splitting material by splitting C4/C5 fraction low temperature hydrogenation | |
| CN100506379C (en) | Macropore capacity sulfur-containing nickel catalyst for selective hydrogenation | |
| CN106552647B (en) | Silver-modified Raney copper catalyst, preparation method thereof and method for selective hydrogenation and alkyne removal of carbon four-fraction | |
| CN109092302A (en) | The method of selective hydrogenation of butadiene | |
| CN103418379B (en) | Remove the Catalysts and its preparation method of alkadienes in carbon four | |
| CN104437522B (en) | C 4 olefin Hydroisomerization Catalysts and method | |
| CN109096032A (en) | Cracking c_4 selective hydrogenation catalyst | |
| CN109092303A (en) | The catalyst of selective hydrogenation of butadiene | |
| CN110639517A (en) | Catalyst for selective hydrogenation of butadiene and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |