CN102886262B - C4 selective acetylene hydrocarbon hydrogenation catalyst, preparation method and applications - Google Patents
C4 selective acetylene hydrocarbon hydrogenation catalyst, preparation method and applications Download PDFInfo
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- CN102886262B CN102886262B CN201110205694.9A CN201110205694A CN102886262B CN 102886262 B CN102886262 B CN 102886262B CN 201110205694 A CN201110205694 A CN 201110205694A CN 102886262 B CN102886262 B CN 102886262B
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Abstract
The present invention relates to selective acetylene hydrocarbon hydrogenation catalyst, preparation method and applications, catalyst is made up of carrier and active component.The catalyst of the present invention is used for selecting hydrogenation abjection C4 alkynes, vinylacetylene and ethyl acetylene is converted corresponding butadiene and butylene, reaches abjection and mix the purpose of the alkynes in C4.The present invention goes out catalyst and is applied in abstraction distillation separation cracking C4 device select hydrogenation containing high concentration alkynes tail gas, C4 alkynes can either be removed, make the alkynes total content 20ppm in product butadiene, reach the requirement of polymerizing butadiene, simultaneously volume increase butylene and butadiene.It is an advantage of the current invention that catalyst has good alkynes hydrogenation activity and butadiene selective, good activity and stability can be kept under conditions of a small amount of water, polymer and solvent simultaneously.
Description
Technical field
The present invention relates to a kind of catalyst, preparation method and and application, specifically, relate to a kind of C4 alkynes high-selectivity hydrogenation catalyst, preparation method and and application thereof.
Background technology
Butadiene is a kind of important basic petrochemical Organic Ingredients and synthetic rubber monomer, is one of most important component in C 4 fraction, and the status in petrochemical industry olefin feedstock is only second to ethylene and propylene.Due in its molecule containing conjugated diene key, can replace, addition, be cyclized and the reaction such as polymerization, therefore, have been widely used at the aspect such as synthetic rubber and organic synthesis tool.At present, the source of butadiene mainly has two kinds, and one is to obtain from oil plant C 4 fraction dehydrogenation, and the current a few countries of the method and area use.Another is isolated from the mixing C 4 fraction of ethylene cracker by-product, and this method is cheap, economically preponderates, and is the main source of butadiene the most in the world.
The C-4-fraction of by-product in naphtha pyrolysis process of producing ethylene, butadiene content is about 40～50%, vinylacetylene (VA) and ethyl acetylene (EA) content amount to and are about 1.0～1.5%, and other is butane (normal butane and iso-butane) and butylene (n-butene, isobutene., trans-butene-2 and cis-butene-2).Butadiene is for products such as polymerization rubber, and alkynes is then the harmful components of butadiene post-treatment, it is necessary to removed before polymerizing butadiene.
Vinylacetylene and ethyl acetylene in removing C-4-fraction typically use two kinds of methods: a kind of employing extraction rectifying method removing, another kind of method uses catalysis selective hydrogenation to make vinylacetylene and ethyl acetylene be converted into butadiene and butylene.Both approaches compares, first method technology maturation, and by industrial commonly used, its extractant is dimethylformamide (DMF), N-Methyl pyrrolidone or acetonitrile etc..But separate have a certain amount of alkene and the vinylacetylene of alkane and ethyl acetylene tail gas is inflammable and explosive, without industrial application value, torch can only be put into after diluting with other C4 appropriate hydrocarbon gas or methane and burn.Second method abroad has a small amount of assay device to report, China still belongs to experimental stage, without industrial installation.This method captivation is to turn waste into wealth, saves energy and reduce the cost, reform technique, increase yield, and economic benefit is the most considerable.
Select hydrogenation method exist two kinds of process routes, one be to carbon four material choice hydrogenation (front-end hydrogenation), two be to after extract and separate tail gas select hydrogenation (back end hydrogenation).Front-end hydrogenation refers to that raw material c4 fraction, before entering extraction device, by selecting hydrogenation that the vinylacetylene in c4 fraction and ethyl acetylene are converted into butadiene and butylene, thus reaches to purify raw material c4 fraction and the purpose of removing alkynes.The technological difficulties of front-end hydrogenation are selectivity of catalyst and stability.Because front-end hydrogenation requires to be less than 20ppm containing vinylacetylene and ethyl acetylene total amount in exported product material; and require that the loss of material butadiene is less than 1%wt; it is no more than 3%; catalyst activity and selectivity is required the strictest by this; vinylacetylene and 1; 3-butadiene is that conjugated diene is the most active; easily it is hydrogenated with; when in raw material, alkynes content is the least; 1; 3-butadiene is easily hydrogenated with and becomes butylene, thus the catalyst hydrogenation selectivity of front-end hydrogenation requires the highest, limits the method and applies in the industry.
Isolated for the extraction device tail gas containing high concentration alkynes is drawn by back end hydrogenation, after selecting hydrogenation, make vinylacetylene and ethyl acetylene be converted into corresponding alkene, then the material after hydrogenation is sent back to the feed(raw material)inlet of the first extractive distillation column, thus reaches the purpose of C4 alkynes.Tail gas after extract and separate wherein vinylacetylene and ethyl acetylene content high 20～30%, pressure is 0.11～0.15MPa, inflammable and explosive, gas component cannot pressurize (gas pressurized of high alkynes has the danger of blast), simultaneously containing impurity such as water, dimer, solvent DMF and tar in tail gas, common catalyst is easily caused pollution, reduce catalyst activity and stability, therefore, limit this Technology equally to apply in the industry.
Summary of the invention
It is an object of the invention to overcome the weak point that there is extract and separate production butadiene technology in prior art, and a kind of C4 selective acetylene hydrocarbon hydrogenation catalyst, preparation method and applications are provided.
The object of the invention can be achieved by the following measures: C4 selective acetylene hydrocarbon hydrogenation catalyst, it is made up of carrier and active component, carrier is the inorganic oxide of porous, and active component is metal or base metal: the mass content of active metal is 5～30%, and the mass content of carrier is 70～95%.
Described active component is the non-metal that passes through: the one in Ni, Co, Mo, W, Cu or two kinds, and mass content is 5～25%.
Described active component is Ni and Cu bimetallic, wherein the mass content 10～20% of Ni, and the mass content of Cu is 3～10%, and the atomic ratio of Ni and Cu is 1: 1～6: 1.
The inorganic oxide carrier of described porous is aluminium oxide, silicon oxide, titanium oxide, and carrier pore volume is 0.3～1.2ml/g, specific surface area 50～250m2/ g (BET method mensuration), the preferably inorganic oxide carrier of porous is aluminium oxide.
The preparation method of catalyst of the present invention, it is characterized in that alumina catalyst support preparation method: use boehmite industrial goods aluminum hydroxide solid elastomer, make bead through overmolding, in Muffle furnace, the speed with 200 DEG C/h heats up 700～1100 DEG C, roasting 4 hours, obtains required carrier；Using preparation catalyst, by the aqueous solution containing catalyst activity metal, impregnate above-mentioned alumina support, the carrier after dipping, 80～150 DEG C are dried 5～10 hours, proceed to carry out 300～500 DEG C of Roasting Decompositions in Muffle furnace, obtain catalyst.
The application of catalyst of the present invention, this catalyst is used for selecting hydrogenation abjection C4 alkynes, vinylacetylene and ethyl acetylene is converted, reclaim butylene and butadiene, reach the alkynes in abjection mixing C4 so that the alkynes total content in product mixing C4 is less than 20ppm, reaches the requirement of polymerizing butadiene.
Catalyst needs activation process before using: first by hydrogen 30ml/min at ambient pressure, by the speed of 100 DEG C/h, be warming up to 150～350 DEG C, and insulation carries out the activation of catalyst for 8 hours, is then down to room temperature.
The present invention compared with prior art has the advantage that catalyst of the present invention has good alkynes hydrogenation activity and butadiene selective, can keep good activity and stability under conditions of a small amount of water, polymer and solvent simultaneously；The catalyst using the present invention combines extraction rectifying method and carries out c4 cleavage separate butadiene, by increasing capacitance it is possible to increase the butylene in C 4 fraction and the yield of butadiene, reduces waste gas discharge simultaneously, protects environment；Additionally, the method of the present invention can process use difference extractant (if extractant is dimethylformamide (DMF), N-Methyl pyrrolidone or acetonitrile etc.) and separate being hydrogenated with containing high concentration alkynes tail gas, selection, remove C4 alkynes of C 4 fraction generation, reclaims butylene and butadiene.
Use single hop fixed bed reactors to catalyst activity evaluation, the activity of examination catalyst and the selectivity of generation butadiene.
Catalyst packing: by 1 gram of catalyst filling in two sections of tubular reactors that internal diameter is 8mm, catalyst particle size 10～20 mesh (i.e. particle diameter 0.4～1.5mm).
Reaction system condition is controlled as follows during evaluating catalyst:
Reaction pressure 1.0～3.0MPa, reaction liquid air speed 5～25h, reaction temperature is room temperature～200 DEG C, and product gas chromatogram carries out on-line analysis.
Accompanying drawing explanation
Fig. 1 is C4 selective acetylene hydrocarbon hydrogenation flow chart of the present invention
Detailed description of the invention
2 embodiments and 1 comparative example are set forth below, in conjunction with accompanying drawing, the present invention are described in further detail, but the present invention is not restricted by the embodiments.
Embodiment 1
The boehmite aluminum hydroxide solid elastomer using industrial goods nitrate method to prepare, makes diameter 1～2mm bead through overmolding, and in Muffle furnace, the speed program with 200 DEG C/h heats up 900 DEG C, it is incubated 4 hours, obtain alumina support, pore volume 0.62ml/g, specific surface area 124m2/ g (BET nitrogen method), 20g alumina support is put into 100ml beaker, is added the six water nickel nitrate solutions of 14.8g, add 7ml water, after being sufficiently mixed, impregnate carrier, 120 DEG C are dried 8 hours, decompose and obtain the catalyst that active component is nickel under 450 DEG C of air atmospheres.
Catalyst needs activation process before using.First by hydrogen (30ml/min) at ambient pressure, being warming up to 350 DEG C by the speed program of 100 DEG C/h, insulation carries out the activation of catalyst for 8 hours, is then down to room temperature.Reaction system condition and the result such as table 1 of selective hydrogenation reaction is controlled during evaluating catalyst.
Table 1 active component is that the C4 of Raney nickel selects hydrogenation evaluation result
By the result of table 1 it can be seen that by the effect of hydrogenation catalyst, vinylacetylene and ethyl acetylene can be converted so that the alkynes total content in product mixing C4 is less than 2%wt.Such product C4 can send back to the feed(raw material)inlet of one-section abstraction rectification in liquid form.
Comparative example 1
Using sodium metaaluminate and nitric acid to prepare boehmite aluminum hydroxide solid elastomer, make diameter 1～2mm bead through overmolding, in Muffle furnace, the speed program with 200 DEG C/h heats up 1100 DEG C, it is incubated 4 hours, obtain required carrier, pore volume 0.44ml/g, specific surface area 12m2/ g (BET nitrogen method), 20g carrier is put into 100ml beaker, is added the Palladous nitrate. containing 0.095g and 0.142g silver nitrate solution 9ml, after being sufficiently mixed, dipping carrier, 120 DEG C are dried 8 hours, and under 450 DEG C of air atmospheres, decomposition obtains active component is palladium and silver catalyst.
Catalyst needs activation process before using.First by hydrogen (30ml/min) at ambient pressure, being warming up to 100 DEG C by the speed program of 100 DEG C/h, insulation carries out the activation of catalyst for 8 hours, is then down to room temperature.
Reaction system condition and the result such as table 2 of selective hydrogenation reaction is controlled during evaluating catalyst.
Table 2 active component is that the C4 of palladium and silver catalyst selects hydrogenation evaluation result
Found out by the result of table 2: the conversion ratio containing noble metal catalyst C4 alkynes is relatively low, and the increase in time of alkynes conversion ratio and reduce, illustrate that the dimer in C4 raw material, water and solvent DMF are toxic to the hydrogenation activity of catalyst.
Embodiment 2
Using the carrier identical with embodiment 1,20g carrier puts into 100ml beaker, adds the six water nickel nitrates containing 14.80g and 2.94g copper nitrate, add 7ml water, after being sufficiently mixed, impregnate carrier, 120 DEG C are dried 8 hours, decompose and obtain the catalyst that active component is nickel and copper under 450 DEG C of air atmospheres.Catalyst activation process is with embodiment 1.Reaction system condition and the result such as table 3 of selective hydrogenation reaction is controlled during evaluating catalyst.
Table 3 active component is that the C4 of nickel and copper catalyst selects hydrogenation evaluation result
Above-mentioned reaction result is it can be seen that use Ni and Cu bimetallic catalyst, the hydrogenation butadiene selective of catalyst is high, butadiene has increment, hydrogen alkynes ratio can control to reduce, be conducive to increasing butadiene and the yield of butylene in product, and react alkynes in afterproduct and control at below 0.6%wt, alkynes total conversion is more than 95%.
Claims (4)
1. a C4 selective acetylene hydrocarbon hydrogenation catalyst, it is made up of carrier and active component, it is characterized in that: carrier is aluminium oxide, active component is Ni and Cu bimetallic, the wherein mass content 10～20% of Ni, the mass content of Cu is 3～10%, and the atomic ratio of Ni and Cu is 1:1～6:1, the mass content of carrier is 70～95%, and in catalyst, each constituent content sum is 100%.
C4 selective acetylene hydrocarbon hydrogenation catalyst the most according to claim 1, it is characterised in that: the pore volume of described aluminium oxide is 0.3～1.2mL/g, and specific surface area is 50 ~ 250m2/g。
The preparation method of C4 selective acetylene hydrocarbon hydrogenation catalyst the most according to claim 1, it is characterized in that: alumina catalyst support preparation method: use boehmite industrial goods aluminum hydroxide solid elastomer, bead is made through overmolding, in Muffle furnace, the speed with 200 DEG C/h heats up 700～1100 DEG C, roasting 4 hours, obtains required carrier；Using preparation catalyst, by the aqueous solution containing catalyst activity metal, impregnate above-mentioned alumina support, the carrier after dipping, 80～150 DEG C are dried 5～108 hours, proceed to carry out 300～500 DEG C of Roasting Decompositions in Muffle furnace, obtain catalyst.
The application of C4 selective acetylene hydrocarbon hydrogenation catalyst the most according to claim 1, this catalyst is used for selecting hydrogenation abjection C4 alkynes, vinylacetylene and ethyl acetylene is converted, reclaims butylene and butadiene, reach the alkynes in abjection mixing C4, reach to produce the requirement of polymer grade butadiene.
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| CN102728375B (en) * | 2011-04-15 | 2014-12-17 | 中国石油化工股份有限公司 | Preparation method of Mo-Ni catalyst for C4 fraction low-temperature hydrogenation |
| CN106622245A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Alkyne and diene selective hydrogenation catalyst as well as alkyne and diene selective hydrogenation method |
| CN106925275B (en) * | 2015-12-31 | 2020-01-07 | 中国石油天然气股份有限公司 | Ti-Fe-Ni selective hydrogenation catalyst, preparation method and application thereof |
| CN108187758B (en) * | 2017-12-13 | 2020-11-20 | 北京华福工程有限公司 | Catalyst for preparing butadiene from acetylene and preparation method and application thereof |
| CN108404916B (en) * | 2018-05-04 | 2020-09-11 | 河南科技学院 | Preparation method of metal cobalt catalyst and application of metal cobalt catalyst in catalyzing butadiene hydrogenation reaction |
| CN110963878B (en) * | 2018-09-30 | 2022-08-02 | 中国石油天然气股份有限公司 | Recovery method of C4 alkyne tail gas |
| US11952333B2 (en) | 2019-09-13 | 2024-04-09 | Sabic Global Technologies B.V. | Integrated systems and methods for producing 1,3-butadiene via extractive distillation, distillation, and/or selective hydrogenation |
| 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 |
| EP4238951A4 (en) | 2020-10-26 | 2024-11-13 | China Petroleum & Chem Corp | Method for selective hydrogenation of butadiene extraction tail gas and selective hydrogenation apparatus |
| CN115178262B (en) * | 2021-04-07 | 2023-04-18 | 中国石油化工股份有限公司 | Preparation method and application of C2 catalyst and C2 catalyst |
| CN115178261B (en) * | 2021-04-07 | 2023-04-18 | 中国石油化工股份有限公司 | C2 hydrogenation catalyst, preparation method and application thereof |
| CN116803502A (en) * | 2022-03-24 | 2023-09-26 | 中国石油化工股份有限公司 | Composite oxide, preparation method of composite oxide, hydrogenation catalyst and application of hydrogenation catalyst |
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| CN1235684C (en) * | 2003-10-31 | 2006-01-11 | 中国石油化工股份有限公司 | Method for preparing hydrocarbon hydroprocessing catalyst |
| US20060173224A1 (en) * | 2005-02-01 | 2006-08-03 | Catalytic Distillation Technologies | Process and catalyst for selective hydrogenation of dienes and acetylenes |
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