CN102464543B - Application of alkyne selective hydrogenation catalyst - Google Patents
Application of alkyne selective hydrogenation catalyst Download PDFInfo
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- CN102464543B CN102464543B CN201010544652.3A CN201010544652A CN102464543B CN 102464543 B CN102464543 B CN 102464543B CN 201010544652 A CN201010544652 A CN 201010544652A CN 102464543 B CN102464543 B CN 102464543B
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Abstract
The invention provides application of an alkyne selective hydrogenation catalyst to the removal of alkyne from hydrogenation C4 distillates. The catalyst comprises a titanium oxide-aluminum oxide composite oxide carrier and the following components loaded on the carrier: a) 1 to 20 weight percent of copper, b) 0.05 to 3 weight percent of cobalt, c) 0.05 to 1 weight percent of one or more lanthanide metals, and d) optional zinc and/or nickel. When being used for alkyne selective hydrogenation, the catalyst has high activity and selectivity, and can resist sulfur poisoning and arsenic poisoning; and the using time of the catalyst is obviously prolonged. Therefore, the catalyst is particularly suitable for a selective hydrogenation process of an alkyne in a mixed C4 hydrocarbon.
Description
Technical field
The present invention relates to the application of a kind of selective acetylene hydrocarbon hydrogenation catalyst in hydrogenation and removing C-4-fraction in alkynes.Specifically, the catalyzer adopted in described application is a kind of carried copper-base selective acetylene hydrocarbon hydrogenation catalyst, this catalyzer comprises titanium dioxide-aluminum oxide composite oxide carrier, and be carried on active metal component on this carrier apart from copper, also comprise cobalt, lanthanide series metal, and optional zinc and/or nickel are as promoter metal.This catalyzer is when being used for hydrogenation and removing C
4during alkynes in cut, not only catalytic activity is high and selectivity is high, and good stability, has longer work-ing life.
Background technology
As the 1,3-butadiene of synthetic rubber raw material mainly from by product C during cracking ethylene preparation
4be isolated in cut.Synthetic rubber requires that in 1,3-butadiene raw material, alkynes total content should lower than 20ppm, and wherein vinylacetylene is lower than 5ppm, thus requires from C
4alkynes must be removed as far as possible while being separated 1,3-butadiene in cut.
Except alkynes and to be separated the method for 1,3-butadiene a lot, comprise solvent extraction process, solvent absorption, chemiadsorption, catalyst polymerization and catalysis selective hydrogenation method.Traditional technique is solvent extraction process, and this method is through an extraction, two extractions, de-light rectifying and de-heavily rectifying, and obtaining purity is the 1,3-butadiene of 99%, and wherein two extractions mainly remove vinylacetylene (VA).The C that this method removes
4alkynes need use other C
4torch burning process after hydrocarbon dilution, this will cause the very large wasting of resources.Simultaneously with the increasing of cracking severity, in C-4-fraction, alkyne concentration can be more and more higher, so the alkynes load of extraction plant increases, this can cause divinyl loss to increase, and energy consumption and compressor load rise, and operation easier increases, and danger coefficient increases.Catalysis selective hydrogenation is except the reextraction in alkynes technique not only alternative solvent extraction process extraction plant, and to reduce investment, energy-saving and cost-reducing, can also solve the mismatch problem of said apparatus, its economic advantages are taken seriously day by day.At present, the alkynes in mixed c 4 hydrocarbon-fraction can adopt the method for catalysis selective hydrogenation to remove.Secondly used catalyst mainly tends to the use noble metal catalyst that is representative with palladium, platinum, silver etc. is the non-precious metal catalyst that is representative with copper, nickel.
The difference that in hydrocarbon material flow, the selec-tive hydrogenation of alkynes forms because of raw material and the difference of object product, selected catalyzer and reaction conditions are also different.A kind of good selective hydrogenation catalyst, except will having higher hydrogenation activity, also should have satisfactory stability, and namely catalyzer will have the ability of anti-impurity and anticol matter, like this life-span of ability extending catalyst.Therefore, require that carrier will have lower acidity, less specific surface area and larger aperture.In addition, in the preparation of catalyzer, adding some auxiliary agents also can work-ing life of extending catalyst.
In the prior art, generally adopt the palladium catalyst of load on carrier (usually adopting aluminum oxide) in large quantities, and add other cocatalyst component, such as: US4,404, promotor disclosed in 124 is silver; Promotor disclosed in EP892252 is gold; DE1284403 and US4,577, promotor disclosed in 047 is chromium; US3, disclosed in 912,759 doses, promotor is copper; US3,900, promotor disclosed in 526 is iron; US3,489, promotor disclosed in 809 is rhodium; US3,325,556 promotors are lithium; And promotor disclosed in CN1151908A is potassium.In addition, promotor can also use lead or zinc etc.
Noble metal catalyst low temperature active is good, and reaction conditions is gentle, but its weak point be that catalyst activity component easily runs off, expensive, not easily regenerate, hydrogenation selectivity is slightly poor.Non-precious metal catalyst need react at a higher temperature, hydroconversion condition is harsher, but its preparation is simple, be convenient to repeated regeneration, and advantage of lower cost, and copper-based catalysts not hydrogenated olefins and diolefine substantially while selective hydration acetylene compound, olefin loss is little, hydrogenation selectivity is high, therefore still has certain research and development and is worth.In this kind of hydrogenation process, absorption semihydrogenation state free radical on a catalyst and adjacent alkynes or diolefine react and generate a kind of thick polymkeric substance (being commonly called as green oil), and it is primarily of C
6above compound composition, because of the surface that it covers catalyzer, plugs the micropore of catalyst surface, makes catalyst activity reduction, affect the work-ing life of catalyzer.Especially for conjugated diene (as 1,3-butadiene), its polyreaction is more easily carried out, thus makes catalyzer inactivation at short notice, and such catalyzer constantly regenerates just can be reused.
U.S. Patent Application Publication US3, it is catalyst based that 912,789 (1975.10.14) disclose a kind of Cu for liquid-phase hydrogenatin, and the document is declared the total alkynes content in C-4-fraction to be down to below 75ppm.This catalyzer is with containing 0.1-1.5 % by weight Na
2γ-the Al of O
2o
3for carrier, active constituent is Cu, or Cu and the promoter metal that is selected from Ag, Pt, Pd, Mn, Co, Ni, Cr and Mo combined.But the activity cycle of this catalyzer is shorter, only has 175-200 hour, needs repeated regeneration.In addition this hydrogenation catalyst be only applicable to process alkynes content lower than 0.2 % by weight C-4-fraction.
U.S. Patent Application Publication US4,440,956 (1984.4.3.) disclose another kind of copper-based catalysts.It with content be the Cu of 3-13 % by weight as main active constituent, using one or more in Ag, Pt, Pd, Mn, Co, Ni, Cr and Mo metal as promoter metal.This patent application declares that the alkynes content of C-4-fraction can be down to below 80ppm by its catalyzer, in embodiment, best except alkynes effect be 50ppm.Because above-mentioned selectivity of catalyst is poor, cause C
4in cut, 1,3-butadiene loss is comparatively large, is thus unsuitable for the selec-tive hydrogenation of the larger C-4-fraction of butadiene content except alkynes.In addition, the life-span of these catalyzer and regeneration period are all shorter, add running cost.
Therefore, for selective acetylene hydrocarbon hydrogenation copper-based catalysts, also need the activity and selectivity improving this catalyzer further, and the extending catalyst life-span.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly to selective acetylene hydrocarbon hydrogenation carried copper-base catalyst, found that, by using titanium dioxide-aluminum oxide composite oxides as carrier and by cobalt, lanthanide series metal, and the copper-based catalysts that optional zinc and/or nickel obtain as promoter metal not only has good activity and selectivity, and there is satisfactory stability.Use this catalyzer to C
4when cut carries out selec-tive hydrogenation except hydrocarbon, green oil generating amount is few, and can sulfuration resistant arseniasis; Compared with the catalyzer of prior art, life cycle and the life-span of this catalyzer increase greatly, increase nearly 0.5-1.0 times.The present invention is accomplished based on above discovery just.
Therefore, the object of this invention is to provide the application of a kind of carried copper-base catalyst in hydrogenation and removing C-4-fraction in alkynes.In this application, described catalyzer is to C
4alkynes in cut carries out selective hydrogenation, thus removing alkynes wherein, and described catalyzer not only activity and selectivity is high, and to have good stability.
Above-mentioned purpose is achieved by adopting so a kind of selective acetylene hydrocarbon hydrogenation catalyst, and this catalyzer comprises titanium dioxide-aluminum oxide composite oxide carrier and is carried on the following component on this carrier:
A) copper, its content is 1-20 % by weight based on total catalyst weight;
B) cobalt, its content is 0.05-3 % by weight based on total catalyst weight;
C) one or more lanthanide series metals, its content is 0.05-1 % by weight based on total catalyst weight; And
D) optionally, zinc and/or nickel, if use, its content is 0.05-0.3 % by weight based on total catalyst weight.
Above and other objects of the present invention, feature and advantage will become more clear after reading specification sheets of the present invention.
Be a kind of copper-based catalysts for alkynes selective hydrogenation catalyst of the present invention, it comprises titanium dioxide-aluminum oxide composite oxide carrier, belongs to loaded catalyst, and active metal component is carried on this carrier.Advantageously, this titanium dioxide-aluminum oxide composite oxide carrier is before supported active metals component, and its specific surface area is 120-150m
2/ g, pore volume is 0.5-1.0ml/g, and most probable pore size is 110-140 dust.In addition, being not particularly limited the shape of titanium dioxide-aluminum oxide composite oxide carrier, such as, can be cylindricality, spherical, bar shaped, cloverleaf pattern, gear shape, preferred cloverleaf pattern.
In the present invention, the specific surface area of carrier adopts nitrogen physisorption BET method to measure.Total pore volume adopts pressure mercury method to measure.Most probable pore size is measured by nitrogen physisorption BET method.
In titanium dioxide-aluminum oxide composite oxide carrier, advantageously, the content of titanium oxide is 5-20 % by weight based on alumina weight, preferred 8-15 % by weight.
The carrier of used catalyst of the present invention can commercial acquisition or prepared by this area ordinary method.Such as, can announce method disclosed in CN1184289C according to Chinese patent application and prepare titanium dioxide-aluminum oxide composite oxide carrier, the document is incorporated to herein as a reference at this.
The present inventor finds, by carrying out calcining the macropore carrier that can obtain low surface acidity to alumina-silica titanium composite oxide carrier at a lower temperature, the catalyzer using this carrier to prepare can improve C further
4the activity and selectivity of alkynes selective hydrogenation in cut, and can stability be improved.Thus, advantageously, be by obtaining in the temperature lower calcination of 500-900 DEG C for the titanium dioxide-aluminum oxide composite oxide carrier in the present invention.
In a preferred embodiment of the catalyzer used in the present invention, titanium dioxide-aluminum oxide composite oxides can be prepared in the following manner: be 100-200m with specific surface
2/ g, pore volume is 0.5-1.5ml/g, and most probable pore size is that the aluminum oxide of 80-200 dust immerses in compound titanium solution, and the consumption of wherein said solution is at least total pore volume equivalent with described aluminum oxide, and stirs 10-30 minute; By impregnated aluminum oxide dry 4-10 hour at the temperature of 100-150 DEG C, then in the temperature lower calcination 4-8 hour of 500-900 DEG C, the obtained alumina-silica titanium composite oxide carrier containing 5-20 % by weight titanium oxide based on alumina weight.The shape of this carrier can be cylindricality, spherical, bar shaped, cloverleaf pattern, gear shape, preferred cloverleaf pattern.
Prepare in the method for carrier above-mentioned, titanium compound used is the titanium salt being selected from the acetate of titanium, hydrochloride, sulfate and nitrate, or is selected from the titanic acid ester of tetraethyl titanate, metatitanic acid four n-propyl and tetra-n-butyl titanate.The consumption of compound titanium solution is for its volume is equal with the total pore volume of aluminum oxide or be greater than the total pore volume of aluminum oxide.The consumption of preferred compound titanium solution is that its volume is equal with the total pore volume of aluminum oxide.If the consumption of compound titanium solution is greater than the total pore volume of aluminum oxide, after having flooded, must first gained mixture be filtered and drain, then carry out drying.Prepare the concrete kind that compound titanium solution solvent used depends on titanium compound used, such as when acetate, hydrochloride, vitriol or nitrate that the titanium compound used is titanium, preferred use water or aqueous acids, if dilute sulphuric acid, dust technology, dilute hydrochloric acid, acetic acid,diluted are as solvent, and when the titanium compound used is for titanic acid ester, preferred use aromatic hydrocarbon, if benzene, toluene or alicyclic hydrocarbon are if hexanaphthene, suberane, cyclooctane are as solvent.
In the alkynes selective hydrogenation catalyst that the present invention uses, the content as the copper of active ingredient is generally 1-20 % by weight, is preferably 3-17 % by weight, is more preferably 3-8 % by weight, based on the gross weight of catalyzer.
The present invention use alkynes selective hydrogenation catalyst in, also comprise and help active metal component b) and c) and optional metal component d).Components b) be cobalt; Amount of component b) be one or more lanthanide series metals, component d) be zinc, nickel or the combination of both.
In the alkynes selective hydrogenation catalyst that the present invention uses, cobalt is as helping active metal component b), its content is generally 0.05-3 % by weight, and preferred 1-3 % by weight, based on the gross weight of catalyzer.
In the alkynes selective hydrogenation catalyst that the present invention uses, one or more lanthanide series metals are as helping active metal component c), its content is generally 0.05-1 % by weight, and preferred 0.5-1 % by weight, based on the gross weight of catalyzer.As lanthanide series metal, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu can be mentioned, preferred cerium, lanthanum, neodymium or their arbitrary combination, more preferably cerium.
In the alkynes selective hydrogenation catalyst that the present invention uses, zinc and/or nickel are optionally as helping active metal component d), if comprise component d), then its content is generally 0.05-0.3 % by weight, preferred 0.1-0.2 % by weight, based on the gross weight of catalyzer.
In order to obtain the catalyzer that the present invention uses, can using the copper as catalytically-active metals component, cobalt, lanthanide series metal, and optional zinc and/or nickel are by means commonly known in the art, such as dipping, co-precipitation, cogelledization or ion-exchange, once or be in batch dispersed on titanium dioxide-aluminum oxide composite oxide carrier.
In a preferred embodiment of the invention, the alkynes selective hydrogenation catalyst used is prepared by a method comprising the following steps: adopt the copper compound comprising solubility, the cobalt compound of solubility, the lanthanide metal compound of solubility, and hybrid infusion solution (preferred aqueous solutions) oxide impregnation titanium-alumina composite oxide carrier of the zinc of optional solubility and/or nickel compound, the titanium dioxide-aluminum oxide composite oxide carrier that drying is so flooded also is calcined, and optionally, calcinate hydrogen reducing is activated.To this, the solvent for the formation of described mixing solutions can be water, nitric acid, hydrochloric acid, ammoniacal liquor, can also with an organic solvent, as ethanol, methyl alcohol, benzene, oxalic acid, acetic acid, sherwood oil etc., preferably use water as solvent.The copper compound of solubility can be any copper compound that can dissolve formation steeping fluid, and the organic and inorganic salt of such as copper, these compounds decomposed in the catalyst calcination stage subsequently.As the example of this mantoquita, cupric nitrate, copper sulfate, cupric chloride, copper organic acid and acetylacetonate copper can be mentioned, preferred cupric nitrate.The cobalt compound of solubility can be any cobalt compound that can dissolve formation steeping fluid, and the organic and inorganic salt of such as cobalt, these compounds decomposed in the catalyst calcination stage subsequently.As the example of this cobalt salt, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobalt chloride, organic acid cobalt, acetylacetone cobalt etc. can be mentioned, preferred Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.The lanthanide metal compound of solubility can be any lanthanide metal compound that can dissolve formation steeping fluid, and the organic and inorganic salt of such as lanthanide series metal, these compounds decomposed in the catalyst calcination stage subsequently.This lanthanide metal compound comprises the nitrate of each lanthanide series metal (i.e. La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu), carbonate, vitriol, halogenide, organic acid salt or their any mixture, such as cerous nitrate, lanthanum nitrate, praseodymium nitrate.The zinc of solubility and/or nickel compound can be any zinc and/or nickel compounds that can dissolve formation steeping fluid, and the organic and inorganic salt of such as zinc and/or nickel, these compounds decomposed in the catalyst calcination stage subsequently.As the example of nickel salt, nickelous nitrate, single nickel salt, nickelous carbonate, nickelous chloride, acetylacetonate nickel and organic acid nickel can be mentioned, preferred nickelous nitrate; As the example of zinc salt, zinc nitrate, zinc sulfate, zinc chloride, zinc acetylacetonate and organic acid zinc can be mentioned, preferred zinc nitrate.
In the preparation method of used catalyst of the present invention, for the facility obtained, preferably cupric nitrate will be comprised, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, the nitrate of lanthanide series metal, and hybrid infusion solution (preferred aqueous solutions) oxide impregnation titanium-alumina composite oxide carrier of optional zinc nitrate and/or nickelous nitrate.
The dipping technique be applicable to comprises immersion, evaporative impregnation and vacuum impregnation.Preferred dipping method adopts equivalent impregnation method or excessive pickling process, preferred equivalent impregnation method.In equivalent impregnation method, according to the water-intake rate of titanium dioxide-aluminum oxide composite oxides, by the copper compound of solubility, the cobalt compound of solubility, the lanthanide metal compound of solubility, and the zinc of optional solubility and/or nickel compound are mixed with hybrid infusion solution, preferred aqueous solutions, then oxide impregnation titanium-alumina composite oxide carrier, the copper wherein contained in hybrid infusion solution, cobalt, lanthanide series metal, and the amount of metal of the amount of optional zinc and/or nickel needed for catalyzer of the present invention, and the amount of hybrid infusion solution is no more than the maximum water regain of titanium dioxide-aluminum oxide composite oxide carrier.As its name suggests, in excessive pickling process, the amount for the hybrid infusion solution (preferred aqueous solutions) of oxide impregnation titanium-alumina composite oxide carrier is greater than the maximum water regain of titanium dioxide-aluminum oxide composite oxides.Obviously, in excessive pickling process, after having flooded, first gained mixture must be filtered, then carry out drying.
After immersion, impregnated titanium dioxide-aluminum oxide composite oxide carrier is dry and calcine.This drying is carried out usually at 100-150 DEG C.Time of drying is different because of water-content, usual dry 4-10 hour.This calcining is carried out usually at 400-600 DEG C.Calcination time is generally 4-8 hour.
After calcining step, if necessary, can activate calcinate hydrogen reducing.In order to realize this hydrogen reducing activation, usually by gained calcinate at hydrogenation temperature is 100-150 DEG C, hydrogen pressure is 2.6-3.0Mpa and hydrogen flowing quantity is keep 4-8 hour under the condition of 30-65ml/min.
It is also feasible for not carrying out special hydrogen reducing activation to calcinate.Now, when this catalyzer being used for catalysis alkynes selective hydration, in catalytic reaction process, active ingredient in catalyzer starts to be exist with the form of metal oxide, in the process using hydrogen, main active ingredient Cu is converted into metallic forms, other aided metal active ingredient also changes into metallic forms in the process using hydrogen, thus reaches the object of deactivated catalyst equally.
Methylacetylene, ethylacetylene and vinylacetylene etc. are comprised by the alkynes that hydrogenation reaction is removed for catalyzer of the present invention.Thus used catalyst of the present invention is particularly suitable for C
4cut carries out acetylene hydrogenation, thus greatly reduces C
4the content of alkynes in cut, reaches refining C
4the object of cut.This catalyzer has highly selective for removing alkynes, and good stability, and work-ing life extends greatly.
In a preferred embodiment of the invention, at C
4in cut, alkynes preferably accounts for the 0.20-1.50 % by weight of cut gross weight.
As C
4cut, it is the C that obtains of petroleum cracking especially
4cut.
In a preferred embodiment of the invention, C
4cut comprises following component:
The divinyl of 40-55 % by weight,
38.0-46.6 the butylene of % by weight,
The butane of 1-5 % by weight,
The vinylacetylene of 0.50-0.90 % by weight, and
The ethylacetylene of 0.10-0.20 % by weight.
Wherein this C
4in cut, the weight percentage sum of all components is 100 % by weight.
In order to by C
4alkynes in cut carries out selective hydrogenation, and hydrogenation temperature is chosen as 40-60 DEG C usually, is preferably 50-60 DEG C; The usual 0.8-1.2Mpa of hydrogenation pressure, is preferably 0.8-1.0Mpa; Reaction raw materials air speed is generally 1.0-6.0h
-1, preferred 1.5-3.0h
-1.The consumption of hydrogen is chosen as and C usually
4in cut, the mol ratio of alkynes is 3-15, is preferably 5-10.
When catalyzer of the present invention will be used for be used for selective hydrogenation except alkynes, be applicable to the trickle bed of single hop bed, two sections of beds or other type.
Catalyzer of the present invention is used for C
4the selective hydrogenation of alkynes in cut, is relative to prior art advantage:
(1) adopt according to alumina-silica titanium composite oxide carrier provided by the invention, alumina supporter conventional in prior art can be overcome large for hydrogenation green oil generating amount, the shortcoming of hydrogenation selectivity difference, make used catalyst hydrogenation activity of the present invention and selectivity high, life cycle is long, can also sulfur resistive and arseniasis;
(2) there is synergy between Cu, Co and lanthanide series metal, make active ingredient segregation on catalyst surface, the grain diameter of catalyzer diminishes, and dispersity improves, and the reducing property of catalyzer is improved, and improves the hydrogenation activity of catalyzer; And
(3), after adding Ni and/or Zn, the hydrogenation activity improving catalyzer is conducive to.
The present invention is described further to use embodiment below.It should be pointed out that these embodiments are only exemplary, essence of the present invention and scope are not constituted any limitation.
Embodiment
Embodiment 1-Kaolinite Preparation of Catalyst 1
First titanium dioxide-aluminum oxide composite oxide carrier is prepared according to the method in the embodiment 1 of CN1184289C.Getting specific surface area is 160m
2/ g, pore volume is 0.58ml/g, most probable pore size is the cloverleaf pattern aluminum oxide 90g of 130 dusts, flood with the 0.557g/ml dilution heat of sulfuric acid of 53 milliliters of titanium sulfates, stir 15 minutes, in 120 DEG C of dryings after 8 hours, in 900 DEG C of calcinings 4 hours, obtained titanium dioxide-aluminum oxide composite oxides (A-1).The titanium oxide content of gained composite oxides is 10 % by weight, and specific surface area is 144m
2/ g, pore volume is 0.56ml/g, and most probable pore size is 125 dusts.
Preparation 63ml contains the mixed aqueous solution of cupric nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cerous nitrate and nickelous nitrate as steeping fluid, in this steeping fluid, cupric nitrate amount counts 3 % by weight with copper, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES amount counts 3 % by weight with cobalt element, cerous nitrate amount counts 0.1 % by weight with Ce elements, and amount of nickel nitrate counts 0.2 % by weight with nickel element.At ambient temperature, get 100g titanium dioxide-aluminum oxide composite oxides (A-1), with the impregnation fluid prepared above, at 120 DEG C, drying 4 hours, then calcines 4 hours at 500 DEG C, takes out and is cooled to room temperature.The catalyzer prepared by this way is expressed as catalyzer 1.
Embodiment 2-Kaolinite Preparation of Catalyst 2
Preparation 63ml contains the mixed aqueous solution of cupric nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, lanthanum nitrate and zinc nitrate as steeping fluid, in this steeping fluid, cupric nitrate amount counts 7 % by weight with copper, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES amount counts 3 % by weight with cobalt element, lanthanum nitrate amount counts 0.1 % by weight with lanthanum element, and zinc nitrate amount counts 0.2 % by weight with zinc element.At ambient temperature, get 100g titanium dioxide-aluminum oxide composite oxides (A-1), with the impregnation fluid prepared above, at 120 DEG C, drying 4 hours, then calcines 4 hours at 500 DEG C, takes out and is cooled to room temperature.The catalyzer prepared by this way is expressed as catalyzer 2.
Embodiment 3-Kaolinite Preparation of Catalyst 3
Preparation 63ml contains the mixed aqueous solution of cupric nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, neodymium nitrate and nickelous nitrate as steeping fluid, in this steeping fluid, cupric nitrate amount counts 5 % by weight with copper, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES amount counts 3 % by weight with cobalt element, neodymium nitrate amount counts 0.1 % by weight with neodymium element, and amount of nickel nitrate counts 0.2 % by weight with nickel element.At ambient temperature, get 100g titanium dioxide-aluminum oxide composite oxides (A-1), with the impregnation fluid prepared above, at 120 DEG C, drying 4 hours, then calcines 4 hours at 500 DEG C, takes out and is cooled to room temperature.The catalyzer prepared by this way is expressed as catalyzer 3.
Embodiment 4-Kaolinite Preparation of Catalyst 4
Preparation 63ml contains the mixed aqueous solution of cupric nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cerous nitrate, lanthanum nitrate and zinc nitrate as steeping fluid, in this steeping fluid, cupric nitrate amount counts 5 % by weight with copper, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES amount counts 1 % by weight with cobalt element, cerous nitrate amount counts 0.5 % by weight with Ce elements, lanthanum nitrate amount counts 0.5 % by weight with lanthanum element, and zinc nitrate amount counts 0.2 % by weight with zinc element.At ambient temperature, get 100g titanium dioxide-aluminum oxide composite oxides (A-1), the impregnation fluid prepared with 63ml above, at 120 DEG C, drying 4 hours, then calcines 4 hours at 500 DEG C, takes out and is cooled to room temperature.The catalyzer prepared by this way is expressed as catalyzer 4.
Embodiment 5-prepares comparative catalyst 5
Preparation 59ml contains the mixed aqueous solution of cupric nitrate and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES as steeping fluid, and in this steeping fluid, cupric nitrate amount counts 5 % by weight with copper, and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES amount counts 5 % by weight with cobalt element.At ambient temperature, 100g alumina supporter (BET:178m is got
2/ g, pore volume is 0.52ml/g, and most probable pore size is 84 dusts), with the impregnation fluid prepared above, at 120 DEG C, drying 4 hours, then calcines 4 hours at 500 DEG C, takes out and is cooled to room temperature.The catalyzer prepared by this way is expressed as catalyzer 5.
Embodiment 6-Kaolinite Preparation of Catalyst 6
Preparation 63ml contains the mixed aqueous solution of cupric nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cerous nitrate as steeping fluid, and in this steeping fluid, cupric nitrate amount counts 5 % by weight with copper, and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES amount counts 1 % by weight with cobalt element, and cerous nitrate amount counts 1 % by weight with Ce elements.At ambient temperature, get 100g titanium dioxide-aluminum oxide composite oxides (A-1), the impregnation fluid prepared with 63ml above, at 110 DEG C, drying 4 hours, then calcines 4 hours at 550 DEG C, takes out and is cooled to room temperature.The catalyzer prepared by this way is expressed as catalyzer 6.
Embodiment 7-prepares comparative catalyst 7
Preparation 63ml contains the mixed aqueous solution of cupric nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cerous nitrate as steeping fluid, and in this steeping fluid, cupric nitrate amount counts 5 % by weight with copper, and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES amount counts 1 % by weight with cobalt element, and cerous nitrate amount counts 1 % by weight with Ce elements.At ambient temperature, 100g alumina supporter (BET:178m is got
2/ g, pore volume is 0.52ml/g, and most probable pore size is 84 dusts), the mixed aqueous solution dipping of the steeping fluid prepared above with 63ml, at 120 DEG C, drying 4 hours, then calcines 4 hours at 450 DEG C, takes out and is cooled to room temperature.The catalyzer prepared by this way is expressed as catalyzer 7.
Embodiment 8-Kaolinite Preparation of Catalyst 8
Preparation 63ml contains the mixed aqueous solution of cupric nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cerous nitrate and zinc nitrate as steeping fluid, in this steeping fluid, cupric nitrate amount counts 17 % by weight with copper, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES amount counts 1 % by weight with cobalt element, cerous nitrate amount counts 0.5 % by weight with Ce elements, and zinc nitrate amount counts 0.1 % by weight with zinc element.At ambient temperature, get 100g titanium dioxide-aluminum oxide composite oxides (A-1), with the impregnation fluid prepared above, at 120 DEG C, drying 4 hours, then calcines 4 hours at 600 DEG C, takes out and is cooled to room temperature.The catalyzer prepared by this way is expressed as catalyzer 8.
Embodiment 9-Kaolinite Preparation of Catalyst 9
Preparation 63ml contains the mixed aqueous solution of cupric nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cerous nitrate and zinc nitrate as steeping fluid, in this steeping fluid, cupric nitrate amount counts 5 % by weight with copper, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES amount counts 1 % by weight with cobalt element, cerous nitrate amount counts 1 % by weight with Ce elements, and zinc nitrate amount counts 0.2 % by weight with zinc element.At ambient temperature, get 100g titanium dioxide-aluminum oxide composite oxides (A-1), with the impregnation fluid prepared above, at 120 DEG C, drying 4 hours, then calcines 4 hours at 450 DEG C, takes out and is cooled to room temperature.The catalyzer prepared by this way is expressed as catalyzer 9.
Embodiment 10
In the small testing device of 200ml trickle-bed reactor, the alkynes in C-4-fraction is carried out to the catalytic performance of selective hydrogenation evaluate catalysts 1-9.
C-4-fraction raw material used is the mixed pyrolysis C-4-fraction produced by chemical industry one factory of Yanshan Petrochemical company, and its composition is in table 1.
By using the beds of catalyzer 1-9 filling respectively after making raw material C-4-fraction and hydrogen mixing, catalyst packing volume is 100ml, and reaction pressure all adopts 1.0MPa; The mol ratio joining alkynes in hydrogen in C-4-fraction and C-4-fraction is 5; Temperature of reaction is 60 DEG C; The liquid air speed of material is 2.8h
-1.Utilize material after gas chromatographic analysis hydrogenation.The activity and selectivity evaluation result of each catalyzer is in table 2.
Table 1
* note: in C-4-fraction except component listed in table, also containing other trace ingredients, comprise C
5cut
Catalyst activity represents with the total surplus massfraction of VA and EA in C-4-fraction after hydrogenation and alkynes transformation efficiency; Catalyst selectivity represents with the loss of the selectivity and divinyl that generate divinyl in C-4-fraction after hydrogenation (change of reaction front and back butadiene content).
Alkynes transformation efficiency=(after 1-reaction the front alkynes content of alkynes content/reaction) × 100%
Butadiene selective=[butadiene content after reaction/(the alkynes content of butadiene content before reaction+participation reaction)] × 100%
Table 2: catalyzer composition and effect
In addition, in the selective hydrogenation of catalysis C-4-fraction, catalyzer 1 in embodiment 1, the catalyzer 2 of embodiment 2, the catalyzer 3 of embodiment 3, the catalyzer 4 of embodiment 4, the catalyzer 8 of embodiment 8 and the catalyzer 9 of embodiment run 800h catalytic performance does not continuously have considerable change yet, and catalyzer 6 continuous operating time of embodiment 6 also reaches 800h.But the comparative catalyst 5 of embodiment 5 runs and just obviously declines less than catalytic performance after 400h, comparative catalyst 7 working time of embodiment 7 is not more than 500h.
Embodiment 11
Get the catalyzer 1 of 100ml embodiment 1, use the testing apparatus of trickle-bed reactor, raw material C-4-fraction is in the same manner as in Example 10, under varying experimental conditions catalyzer 1 is carried out to the selective hydrogenation of C-4-fraction.The results are shown in Table 3.
Table 3
Claims (18)
1. the application of selective acetylene hydrocarbon hydrogenation copper-based catalysts in hydrogenation and removing C-4-fraction in alkynes, described catalyzer comprises titanium dioxide-aluminum oxide composite oxide carrier and is carried on the following component on this carrier:
A) copper, its content is 1-20 % by weight based on total catalyst weight;
B) cobalt, its content is 0.05-3 % by weight based on total catalyst weight;
C) one or more lanthanide series metals, its content is 0.05-1 % by weight based on total catalyst weight; And
D) optionally, zinc and/or nickel, if use, its content is 0.05-0.3 % by weight based on total catalyst weight, and wherein titanium dioxide-aluminum oxide composite oxide carrier is before supported active metals component, and the specific surface area of this carrier is 120-150m
2/ g, pore volume is 0.5-1.0ml/g, and most probable pore size is 110-140 dust,
Wherein be carried on component on titanium dioxide-aluminum oxide composite oxide carrier only by component a), b), c) and optional component d) form.
2. according to the application described in claim 1, it is characterized in that, component d) content be 0.1-0.2 % by weight based on total catalyst weight.
3. according to the application described in claim 1, it is characterized in that, titanium dioxide-aluminum oxide composite oxide carrier is by obtaining in the temperature lower calcination of 500-900 DEG C.
4. application according to claim 1, is characterized in that, based on total catalyst weight,
Component content a) is 3-17 % by weight; And/or
Components b) content be 1-3 % by weight; And/or
Amount of component b) content be 0.5-1 % by weight.
5. application according to claim 4, is characterized in that, based on total catalyst weight, component content a) is 3-8 % by weight.
6. application according to claim 1, is characterized in that, amount of component b) be cerium, lanthanum, neodymium or their arbitrary combination.
7. application according to claim 1, is characterized in that, in titanium dioxide-aluminum oxide composite oxide carrier, the content of titanium oxide is 5-20 % by weight based on alumina weight.
8. application according to claim 7, is characterized in that, in titanium dioxide-aluminum oxide composite oxide carrier, the content of titanium oxide is 8-15 % by weight based on alumina weight.
9. the application according to any one of claim 1-8, is characterized in that, described selective acetylene hydrocarbon hydrogenation catalyst is prepared by a method comprising the following steps:
Adopt the copper compound comprising solubility, the cobalt compound of solubility, the lanthanide metal compound of solubility, and the hybrid infusion solution impregnation titanium dioxide-aluminum oxide composite oxide carrier of the zinc of optional solubility and/or nickel compound,
The titanium dioxide-aluminum oxide composite oxide carrier that drying is so flooded also is calcined, and
Optionally, calcinate hydrogen reducing is activated.
10. application according to claim 9, is characterised in that,
Drying temperature is 100-150 DEG C, and the time is 4-10 hour; And/or
Calcining temperature is 400-600 DEG C, and the time is 4-8 hour.
11. application according to any one of claim 1-8, are characterised in that, described C
4in cut, alkynes accounts for the 0.20-1.50 % by weight of cut gross weight.
12. application according to any one of claim 1-8, are characterised in that, C
4cut comprises following component:
The divinyl of 40-55 % by weight,
38.0-46.6 the butylene of % by weight,
The butane of 1-5 % by weight,
The vinylacetylene of 0.50-0.90 % by weight, and
The ethylacetylene of 0.10-0.20 % by weight.
Wherein this C
4in cut, the weight percentage sum of all components is 100 % by weight.
13. application according to any one of claim 1-8, are characterised in that,
Hydrogenation temperature is 40-60 DEG C; And/or
Hydrogenation pressure is 0.8-1.2MPa; And/or
Reaction raw materials air speed is 1.0-6.0h
-1; And/or
The consumption of hydrogen and C
4in cut, the mol ratio of alkynes is 3-15.
14. application according to any one of claim 1-8, be characterised in that, hydrogenation temperature is 50-60 DEG C.
15. application according to any one of claim 1-8, be characterised in that, hydrogenation pressure is 0.8-1.0MPa.
16. application according to any one of claim 1-8, be characterised in that, reaction raw materials air speed is 1.5-3.0h
-1.
17. application according to any one of claim 1-8, are characterised in that, the consumption of hydrogen and C
4in cut, the mol ratio of alkynes is 5-10.
18. application according to any one of claim 1-8, are characterised in that,
Hydrogenation temperature is 50-60 DEG C; And/or
Hydrogenation pressure is 0.8-1.0MPa; And/or
Reaction raw materials air speed is 1.5-3.0h
-1; And/or
The consumption of hydrogen and C
4in cut, the mol ratio of alkynes is 5-10.
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| US20020068843A1 (en) * | 2000-09-29 | 2002-06-06 | Wei Dai | Selective hydrogenation catalyst for selectively hydrogenating of unsaturated olefin, process for preparing the same and its use |
| CN1361231A (en) * | 2000-12-29 | 2002-07-31 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst carrier and its prepn and use |
| CN1958155A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst of alkine and diolefin, preparation method and application |
| CN101428228A (en) * | 2008-09-11 | 2009-05-13 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN101433842A (en) * | 2008-09-27 | 2009-05-20 | 中国石油天然气股份有限公司 | Hydrogenation catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20020068843A1 (en) * | 2000-09-29 | 2002-06-06 | Wei Dai | Selective hydrogenation catalyst for selectively hydrogenating of unsaturated olefin, process for preparing the same and its use |
| CN1361231A (en) * | 2000-12-29 | 2002-07-31 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst carrier and its prepn and use |
| CN1958155A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst of alkine and diolefin, preparation method and application |
| CN101428228A (en) * | 2008-09-11 | 2009-05-13 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
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