A kind of nickel-base catalyst and the preparation method and application thereof
阅读说明：本技术 一种镍基催化剂及其制备方法与应用 (A kind of nickel-base catalyst and the preparation method and application thereof ) 是由 冯刚 王大山 张荣斌 张萌 于 2019-08-29 设计创作，主要内容包括：本发明提供一种镍基催化剂及其制备方法与应用,本发明所述的镍基催化剂,以质量百分含量计,金属Ni的含量为0.0001％至20％、其他金属的含量为0.00001％至20％、载体的含量为60％至99.999％。通过将至少含有镍元素的溶液通过湿法负载在催化剂载体上,并经过烘干、焙烧等过程制备成相应的镍基催化剂,解决了现有技术无法生产该镍基催化剂的问题,该催化剂可用于催化加氢反应中。(The present invention provides a kind of nickel-base catalyst and the preparation method and application thereof, nickel-base catalyst of the present invention, in terms of mass percentage, the content of W metal is 0.0001% to 20%, the content of other metals is 0.00001% to 20%, the content of carrier is 60% to 99.999%.By the way that the solution at least containing nickel element is loaded on a catalyst support by wet process, and corresponding nickel-base catalyst is prepared by processes such as drying, roastings, solve the problems, such as that the prior art can not produce the nickel-base catalyst, which can be used in catalytic hydrogenation reaction.)
1. a kind of nickel-base catalyst, it is characterised in that:
In terms of mass percentage, the content of W metal is 0.0001% to 20%, other metals in the nickel-base catalyst Content is 0.00001% to 20%, the content of carrier is 60% to 99.999%.
2. nickel-base catalyst according to claim 1, it is characterised in that:
The specific surface area of the nickel-base catalyst is 20m2/ g to 900m2/ g, Kong Rongwei 0.01cm3/ g to 0.55cm3/g。
3. nickel-base catalyst according to claim 1, it is characterised in that:
The carrier at least contain aluminium oxide, silica, titanium oxide, zinc oxide, magnesia, cerium oxide, lanthana, in phosphorous oxide One kind.
4. a kind of preparation method of nickel-base catalyst, which comprises the following steps:
1) it prepares at least containing the solution of nickel element, metal ion in solution concentration is 0.0001mol/L to 7mol/L, and pH value is 0.2 to 13；
2) a certain amount of carrier is weighed, the mass ratio of solution and carrier is 18:1 to 1:50, by solution obtained by step 1) and is carried Body mixing；
3) step 2) products therefrom is taken, through separation, drying 0.1 hour to 200 hours under the conditions of 20 DEG C to 250 DEG C, is then existed 250 DEG C to 800 DEG C roasting 0.2 hour to 70 hours after obtain the nickel-base catalyst.
5. the preparation method according to claim 4, it is characterised in that:
In step 1), nickel ion content is 0.01mol/L to 4.5mol/L in the solution.
6. the preparation method according to claim 4, it is characterised in that:
In step 1), at least also containing in hydrogen, tin, cobalt, iron, gallium, bismuth, silver, molybdenum, zirconium, copper, thallium, lead, titanium, manganese in the solution One kind.
7. the preparation method according to claim 4, it is characterised in that:
In step 1), the pH value of the solution is 2 to 11.
8. the preparation method according to claim 4, it is characterised in that:
In step 2), the carrier at least contains aluminium oxide, silica, titanium oxide, zinc oxide, magnesia, cerium oxide, oxidation One of lanthanum, phosphorous oxide.
9. the preparation method according to claim 4, it is characterised in that:
In step 2), the mass ratio of the solution and the carrier is 15:1 to 1:30.
10. the preparation method according to claim 4, it is characterised in that:
In step 3), drying condition is 20 DEG C to 200 DEG C, dries 2 hours to 24 hours.
11. the preparation method according to claim 4, it is characterised in that:
In step 3), roasting condition is 260 DEG C to 800 DEG C, roasts 1 hour to 40 hours.
12. a kind of method for producing ethylene, it is characterised in that:
Using nickel-base catalyst described in claims 1 to 3 any one, using the substance containing hydrogen, acetylene as raw material, anti- Answering temperature is 30 DEG C to 350 DEG C, reaction pressure 0.1MPa to 3MPa, air speed 1500h-1To 450000h-1Under conditions of with urge The contact of agent bed, reaction generate the product comprising ethylene.
13. a kind of method of acetylene in removal ethylene, it is characterised in that:
Using nickel-base catalyst described in claims 1 to 3 any one, to contain hydrogen, acetylene, nitrogen, carbon monoxide, second The substance of alkene is raw material, is 30 DEG C to 400 DEG C, reaction pressure 0.1MPa to 4.5MPa, air speed 3000h in reaction temperature-1Extremely 450000h-1Under conditions of contacted with catalyst bed, reaction generate include ethylene product.
14. a kind of method of diene hydrogenation, it is characterised in that:
Using nickel-base catalyst described in claims 1 to 3 any one, it is with the substance containing allene, butadiene, hydrogen Raw material is 50 DEG C to 450 DEG C, reaction pressure 0.1MPa to 4.5MPa, air speed 1500h in reaction temperature-1To 36000h-1's Under the conditions of contacted with catalyst bed, reaction generate comprising propylene, butylene product.
15. a kind of method of aromatic hydrogenation, using any one catalyst described in claims 1 to 3, with containing benzene, toluene, Ethylbenzene, propyl benzene, naphthalene, hydrogen substance be raw material, be 100 DEG C to 400 DEG C in reaction temperature, reaction pressure 0.1 to 10MPa is empty Speed is 5000h-1To 200000h-1Under conditions of contacted with catalyst bed, reaction generate comprising hexamethylene, hexahydrotoluene, Ethyl cyclohexane, propyl cyclohexane, naphthane, decahydronaphthalene product.
Technical field
The present invention relates to catalyst field, it is specifically related to a kind of nickel-base catalyst and the preparation method and application thereof.
Background technique
In bulk chemical, alkene occupies critically important position, is the raw material of numerous organic chemical industry's synthesis.With China Expanding economy, our demands to alkene are also growing day by day, especially ethylene.Although China's production capacity is increasing every year, according to The demand gap in China could not so be filled up.
It is usually made by petrochemical materials through catalytic cracking using ethylene as the alkene of representative.And selective hydrocatalyst It is a kind of important catalyst of petrochemical industry, is widely used in the components such as C2, C3, C4 and cracking in various types of olefins device The removing of alkynes and alkadienes in gasoline.What is applied in industry at present is mainly main active component, aluminium oxide as carrier using palladium Loaded noble metal catalyst, and the adjuvant components such as silver, copper, potassium, gold, lead, bismuth are added, to adapt to differential responses to catalytic Can requirement, prepare that activity and selectivity is higher, stability is more preferable, the lower selective hydrogenation catalyst product of cost, be always The target that scientific research personnel makes great efforts.For many years, polymer can be poisoned containing micro acetylene in the ethylene of petroleum cracking Catalyst (Chem.Rev.2014,114 (3): 1761-1782；J.Mol.Catal.A:Chem.2009,307(1–2):13- 20), so the selective hydrogenation of acetylene causes the extensive concern of people.US, 3832449 disclose the MgAl of their preparations2O4 Ni and Ni-Zn catalyst is loaded, is used directly to production ethylene using rich acetylene raw material.Density function theory shows to Ni Middle addition Au, Ag or Cu can weaken the absorption of acetylene, to improve catalyst activity；Addition Au and Ag also helps selectivity Raising.Under normal circumstances, for Ni as main catalytic active component, reactivity is sufficiently high, but selectivity is lower, leads to alkynes It does not react completely, alkene excessive hydrogenation, therefore still needs to continuously improve.
Arene content height can not only reduce the quality and Cetane number of oil product in diesel oil, also will increase in diesel combustion exhaust gas Particle emission, thus, aromatic hydrogenation receives significant attention (Chinese engineering science, 2003,5 (3): 6-14；Sinopec, 2002 (4): 22-25；Petrochemical industry dynamic, 1997,5 (3): 6-11).Aromatic hydrocarbons in oil product is broadly divided into 4 by the quantity of aromatic ring Class: mononuclear aromatics, double ring arene, thrcylic aromatic hydrocarbon and polycyclic aromatic hydrocarbon.In experimental study, Benzene and Homologues conduct is usually chosen The model reaction object of the model reaction object of mononuclear aromatics, naphthalene and its homologue as double ring arene.
Therefore this patent provides a kind of nickel-base catalyst and preparation method thereof, which can be used for producing ethylene, goes Except acetylene, diene hydrogenation and aromatic hydrogenation in ethylene.
Summary of the invention
To solve the above problems, the present invention is quasi- to develop a kind of new nickel-base catalyst and preparation method thereof, Ni conduct is chosen Main active component is made nickel-base catalyst using wet process, can be used in catalytic hydrogenation reaction.
The first technical problem to be solved by the present invention is to provide a kind of nickel-base catalyst, mainly solve in the prior art without The problem of nickel-base catalyst.
The second technical problem to be solved by the present invention is to provide the corresponding one kind of one of one kind and solution technical problem The preparation method of nickel-base catalyst, this method can be used to produce a kind of nickel-base catalyst, this can not be produced by solving the prior art The problem of nickel-base catalyst.
The third technical problem to be solved by the present invention is to provide the corresponding one kind of one of one kind and solution technical problem The method for producing ethylene.Have the advantages that feed stock conversion is high, selectivity is high, stability is good；Overcome the prior art direct The shortcomings that acetylene hydrogenation is prepared into ethylene.
The fourth technical problem to be solved by the present invention is to provide the corresponding one kind of one of one kind and solution technical problem The method for removing acetylene in ethylene.Have the advantages that feed stock conversion is high, selectivity is high, stability is good, catalyst is cheap；Overcome The disadvantages of feed stock conversion is low in acetylene technology in existing removal ethylene, selectivity is low, stability is poor, expensive catalyst.
The fifth technical problem to be solved by the present invention is to provide the corresponding one kind of one of one kind and solution technical problem The method of diene hydrogenation.Have the advantages that feed stock conversion is high, selectivity is high, stability is good；Overcome existing diene hydrogenation The disadvantages of feed stock conversion is low in technology, selectivity is low, stability is poor.
The sixth technical problem to be solved by the present invention is to provide the corresponding one kind of one of one kind and solution technical problem The method of aromatic hydrogenation.Have the advantages that feed stock conversion is high, stability is good；Raw material in existing aromatic hydrogenation technology is overcome to convert The disadvantages of rate is low, stability is poor.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of nickel-base catalyst, with quality Percentage composition meter, the content of W metal is 0.0001% to 20%, the content of other metals is 0.00001% to 20%, carrier Content be 60% to 99.999%.
Further embodiment is that the specific surface area of the catalyst is 20m2/ g to 900m2/ g, Kong Rongwei 0.01cm3/ g is extremely 0.55cm3/g；Carrier at least contains aluminium oxide, silica, titanium oxide, zinc oxide, magnesia, cerium oxide, lanthana, phosphorous oxide One of.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: a kind of preparation of nickel-base catalyst Method, comprising the following steps:
1) it prepares at least containing the solution of nickel element, metal ion in solution concentration is 0.0001mol/L to 7mol/L, pH Value is 0.2 to 13；
2) a certain amount of carrier is weighed, the mass ratio of solution and carrier is 18:1 to 1:50, by solution obtained by step 1) It is mixed with carrier；
3) step 2) products therefrom is taken, through separation, drying 0.1 hour to 200 hours under the conditions of 20 DEG C to 250 DEG C, so The nickel-base catalyst is obtained after roasting 0.2 hour to 70 hours at 250 DEG C to 800 DEG C afterwards.
Further embodiment is, in step 1), nickel ion content is 0.01mol/L to 4.5mol/L in the solution；It is molten The pH value of liquid is being 2 to 11；At least also containing in hydrogen, tin, cobalt, iron, gallium, bismuth, silver, molybdenum, zirconium, copper, thallium, lead, titanium, manganese in solution One kind.
Further embodiment is, in step 2), carrier at least contains aluminium oxide, silica, titanium oxide, zinc oxide, oxidation One of magnesium, cerium oxide, lanthana, phosphorous oxide；The mass ratio of solution and carrier is 15:1 to 1:30.
Further embodiment is, in step 3), drying condition is 20 DEG C to 200 DEG C, dries 2 hours to 24 hours；Roasting Condition is 260 DEG C to 800 DEG C, roasts 1 hour to 40 hours.
The third technical problem to be solved by the present invention, The technical solution adopted by the invention is as follows: a kind of ethylene of producing Method, using the nickel-base catalyst for solving one of technical problem, using the substance containing hydrogen, acetylene as raw material, in reaction temperature It is 30 DEG C to 350 DEG C, reaction pressure 0.1MPa to 3MPa, air speed 1500h-1To 450000h-1Under conditions of with catalyst bed Layer contact, reaction generate the product comprising ethylene.
The fourth technical problem to be solved by the present invention, The technical solution adopted by the invention is as follows: in a kind of removal ethylene The method of acetylene, using the nickel-base catalyst for solving one of technical problem, to contain hydrogen, acetylene, nitrogen, carbon monoxide, second The substance of alkene is raw material, is 30 DEG C to 400 DEG C, reaction pressure 0.1MPa to 4.5MPa, air speed 3000h in reaction temperature-1Extremely 450000h-1Under conditions of contacted with catalyst bed, reaction generate include ethylene product.
The fifth technical problem to be solved by the present invention, The technical solution adopted by the invention is as follows: a kind of diene hydrogenation Method, using the nickel-base catalyst for solving one of technical problem, using containing allene, butadiene, hydrogen substance as raw material, It is 50 DEG C to 450 DEG C, reaction pressure 0.1MPa to 4.5MPa, air speed 1500h in reaction temperature-1To 36000h-1Under conditions of It is contacted with catalyst bed, reaction generates the product comprising propylene, butylene.
The six of the technical problems to be solved by the invention, The technical solution adopted by the invention is as follows: a kind of side of aromatic hydrogenation Method is original with the substance containing benzene, toluene, ethylbenzene, propyl benzene, naphthalene, hydrogen using the nickel-base catalyst for solving one of technical problem Material is 100 DEG C to 400 DEG C in reaction temperature, reaction pressure 0.1 to 10MPa, air speed 5000h-1To 200000h-1Condition Lower to contact with catalyst bed, it includes hexamethylene, hexahydrotoluene, ethyl cyclohexane, propyl cyclohexane, tetrahydro that reaction, which generates, The product of naphthalene, decahydronaphthalene.
The present invention prepares a kind of nickel-base catalyst using the above method, and a kind of nickel-base catalyst prepared, ontology is at least Outside containing one of aluminium oxide, silica, titanium oxide, zinc oxide, magnesia, cerium oxide, lanthana, phosphorous oxide carrier, and Carrier accounts for mass ratio 60% to 99.999% in catalyst, there are also metallic nickel, tin or cobalt and corresponding oxide isoreactivity component, And in catalyst the content of activity component metal nickel account for mass ratio be 0.0001% to 20%, the content of other metals accounts for mass ratio It is 0.00001% to 20%；The specific surface area of catalyst is 20m2/ g to 900m2/ g, Kong Rongwei 0.01cm3/ g to 0.55cm3/ g.A kind of preparation method of the nickel-base catalyst provided, this method can be used to produce a kind of nickel-base catalyst, overcome existing skill Art can not produce the problem of nickel-base catalyst.The nickel-base catalyst and preparation method thereof can be used for the production field of ethylene, removal The production field of traces of acetylene in ethylene improves feed stock conversion, ethylene selectivity and catalyst stability；The nickel-base catalyst And preparation method thereof can be used for the production field of diene hydrogenation, improve feed stock conversion, olefine selective and catalyst stabilization Property.
Detailed description of the invention
Fig. 1 is the SEM of the molecular sieve carried nickel-base catalyst of the obtained ZSM-12 of preparation method of the embodiment of the present invention 1 Figure.
Fig. 2 is the nitrogen of the molecular sieve carried nickel-base catalyst of the obtained ZSM-12 of preparation method of the embodiment of the present invention 1 Isothermal adsorption desorption curve.
The invention will be further described with reference to the accompanying drawings and embodiments.
Specific embodiment
Preparation method as used in the following examples, use condition are conventional method unless otherwise specified；Following realities Reagent used in example, gas, material etc. are applied, is commercially available unless otherwise specified.
[embodiment 1]
ZSM-12 molecular sieve carried nickel-base catalyst preparation method:
(1) raw material configures: take the volumetric flask of a clean 50mL, beaker, a glass bar of a 100mL spare, Ni (the NO of 1.454g is weighed with electronic balance3)2·6H2O solid, being configured to 50mL concentration is 0.1molL-1Solution.
(2) 1g ZSM-12 molecular sieve carrier is weighed with electronic balance, by solution obtained by step (1) by soaking in equal volume Stain method is supported on carrier.
(3) step (2) products therefrom is dried overnight in air, later with the rate liter of 2 DEG C/min in Muffle furnace Temperature obtains corresponding catalyst to after continuing roasting at 500 DEG C 2.5 hours.
Gained catalyst molecular sieve carrier containing 88%ZSM-12, the content of activity component metal nickel accounts for mass ratio in catalyst It is 12%, wherein the specific surface area of catalyst is 370m2/ g, Kong Rongwei 0.25cm3/g。
[embodiment 2]
MOR molecular sieve carried nickel-base catalyst preparation method:
(1) raw material configures: take the volumetric flask of two clean 50mL, beaker, two glass bars of two 100mL spare, Weigh the Ni (NO of 2.181g respectively with electronic balance3)2·6H2O solid, 0.1753g SnCl4·5H2O is configured to 50mL concentration For 0.15molL-1Ni (NO3)2, 50mL concentration be 0.05molL-1SnCl4Solution.
(2) 1g MOR molecular sieve carrier is weighed with electronic balance, solution obtained by step (1) is passed through into equi-volume impregnating It is supported on carrier.
(3) step (2) products therefrom is dried overnight in air, later with the rate liter of 1 DEG C/min in Muffle furnace Temperature obtains corresponding catalyst to after continuing roasting at 500 DEG C 2.5 hours.
Gained catalyst molecular sieve carrier containing 97.8%MOR, the content of activity component metal nickel accounts for mass ratio in catalyst It is 2%, it is 0.2% that the content of other active metals, which accounts for mass ratio, and wherein the specific surface area of catalyst is in 307m2/ g, Kong Rongwei 0.38cm3/g。
[embodiment 3]
Beta molecular sieve carried nickel-base catalyst preparation method:
(1) raw material configures: take the volumetric flask of two clean 50mL, beaker, two glass bars of two 100mL spare, Weigh the Ni (NO of 3.635g respectively with electronic balance3)2·6H2O solid, 0.7276g Co (NO3)2·6H2O solid, is configured to 50mL concentration is 0.25molL-1Ni (NO3)2, 50mL concentration be 0.25molL-1Co (NO3)2Solution.
(2) 1g Beta molecular sieve carrier is weighed with electronic balance, solution obtained by step (1) is loaded by infusion process On carrier.
(3) by step (2) products therefrom in an oven with 12 hours dry under the conditions of 80 DEG C of temperature, finally in Muffle furnace In be warming up at 550 DEG C with the rate of 1 DEG C/min continue roasting 2 hours after obtain corresponding catalyst.
Gained catalyst molecular sieve carrier containing 94.2%Beta, the content of activity component metal nickel accounts for mass ratio in catalyst It is 5%, it is 0.8% that the content of other active metals, which accounts for mass ratio, and wherein the specific surface area of catalyst is in 569m2/ g, Kong Rongwei 0.29cm3/g。
[embodiment 4-30]
By raw materials such as nickeliferous, tin, cobalt, iron, gallium, bismuth, silver, molybdenum, zirconium, copper, thallium, lead, titanium, manganese, item is prepared according to table 1 Part is operated according to the step in embodiment, nickel-base catalyst can be obtained.
Table 1
Nickel-base catalyst is used for acetylene hydrogenation production ethylene by [embodiment 31-45].
Using hydrogen, acetylene as raw material, the nickel-base catalyst obtained using embodiment 1-15, according to table 2 reaction condition into The product rich in ethylene can be obtained in row catalyst performance evaluation.
Table 2
Nickel-base catalyst is used to remove acetylene in ethylene by [embodiment 46-60].
With hydrogen, acetylene, nitrogen, carbon monoxide, ethylene etc. for raw material, the nickel catalyst that is obtained using embodiment 16-30 Agent carries out catalyst performance evaluation according to the reaction condition of table 3, can remove acetylene in ethylene.
Table 3
Nickel-base catalyst is used for diene hydrogenation by [embodiment 61-75].
With hydrogen, allene, butadiene etc. for raw material, the nickel-base catalyst obtained using embodiment 1-30, according to table 4 Reaction condition carries out catalyst performance evaluation, and diene hydrogenation can be realized.
Table 4
Nickel-base catalyst is used for aromatic hydrogenation by [embodiment 76-90].
With hydrogen, benzene, toluene, ethylbenzene, propyl benzene, naphthalene etc. for raw material, the nickel-base catalyst obtained using embodiment 1-30 is pressed Catalyst performance evaluation is carried out according to the reaction condition of table 5, aromatic hydrogenation can be realized.
Table 5
Finally it is emphasized that the above description is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is right For those skilled in the art, the present invention can have various change and change, all within the spirits and principles of the present invention, Any modification, equivalent substitution, improvement and etc. done, should all be included in the protection scope of the present invention.