CN102218323B - Unsaturated hydrocarbon hydrogenation catalyst, preparation method and applications thereof - Google Patents
Unsaturated hydrocarbon hydrogenation catalyst, preparation method and applications thereof Download PDFInfo
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Abstract
The invention discloses an unsaturated hydrocarbon hydrogenation catalyst which comprises a carrier, an active component and an additive; the active component is a mixture of nickel oxides and other metal oxides; the additive is at least two out of magnesia oxide, lanthanum oxide and ceria; counted by weight percentage, the unsaturated hydrocarbon hydrogenation catalyst comprises 5-15% of nickel oxides, 1-10% of other metal oxides, 1-10% of additive and remaining quantity of carrier; and the metal oxide is one or more oxides out of molybdenum oxide, cobalt oxide and ferric oxide. The invention also discloses a preparation method and applications of the unsaturated hydrocarbon hydrogenation catalyst. The unsaturated hydrocarbon hydrogenation catalyst has the advantages of high hydrogenation precision, strong side effect resistance, good thermal stability, long service life and the like, can be used for processing tail gas in indirect coal oil production industrial and can be also used for processing unsaturated hydrocarbon in synthesis gas.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to a kind of hydrogenation of unsaturated hydrocarbons Catalysts and its preparation method and application.
Background technology
In the indirect coal liquefaction process, except producing oil, also will produce a part and contain CO, OH
4, H
2, CO
2And the industrial tail gas of unsaturated hydrocarbons etc.Also contain a certain amount of unsaturated hydrocarbons in calcium carbide furnace gas, acetylene tail gas and the coke-stove gas in addition.Utilizing its methanol or synthetic ammonia etc., both fully utilized natural resources, reduced again production cost, is a comparatively ideal raw material route.
Owing to often contain a small amount of ethene, propylene and butylene etc. in the industrial tail gas, can affect life-span and the product quality of follow-up workshop section catalyst, need be removed.The removal methods of unsaturated hydrocarbons, the domestic and foreign literature document announcement is more, most of sulphided state catalyst that adopts, the way by hydrogenation removes it, and this type of catalyst is to CO, CO in the unstripped gas
2Reaching unsaturated hydrocarbons content has certain asking, and necessary sulfur-bearing in the unstripped gas, and its scope of application is under some influence.The hydrogenation that noble metal catalyst and unvulcanised attitude catalyst also can be used for alkene is saturated, but does not generally contain CO in the unstripped gas, and in the higher situation of CO content, result of use is not quite desirable.The domestic research report that has not yet to see the indirect oils preparation industry tail gas of relevant coal hydrogenation of unsaturated hydrocarbons catalyst.
Chinese patent CN1597859A has openly reported a kind of by NiO, Co
2O
3, CuO, Fe
2O
3, TiO
2, La
2O
3With the hydrogenation catalyst that aluminium oxide forms, this catalyst adopts the infusion process preparation.Be mainly used in the hydro-conversion of oxygen and alkene in the oil from Fischer-Tropsch synthesis.This catalyst has preferably hydro-conversion effect to the oxygen in the liquid phase oil product and alkene.
Chinese patent CN1470488 introduces a kind of for fatty monoolefin hydrogenation saturated Catalysts and its preparation method and application, is applicable to C
4～C
20The fat olefins hydrogenation especially is fit to be become by light olefin such as ethene, propylene, butene oligomerization the saturated hydrogenation of gasoline.
United States Patent (USP) U.S.P6037510 has introduced a kind of for the fatty monoolefin hydrogenation saturation catalyst, with Al
2O
3, SiO
2, ZrO
2Be mixed carrier, and contain at least 50% NiO, adopt the coprecipitation preparation.
Above-mentioned three kinds of catalyst are mainly used in the hydrogenation of unsaturated hydrocarbons in the oil product, belong to liquid and solid phase reaction, have no the hydro-conversion for the gas unsaturated hydrocarbons.
Hydrogenation of unsaturated hydrocarbons catalyst and preparation method that Chinese patent CN1179788 relates to, it is saturated to be mainly used in the petroleum hydrocarbon steam cracking gas selective hydrogenation of the alkynes such as acetylene and polyene, this catalyst is take precious metal palladium as active component, by adding at least a metal or the two or more metallic combination in bismuth, rare earth metal and silver, copper, potassium, sodium, strontium, manganese, zirconium, molybdenum, cobalt, the germanium, improved the Selectivity and activety of acetylene hydrogenation generation ethene.
Chinese patent CN1253853 relates to a kind of Catalyst and process to the unsaturated compound selective hydrogenation in the hydrocarbon material flow.Specifically generate in the process of alkene alkynes and alkadienes being carried out selective hydrogenation, have higher selectively, can reduce undesirable excessive hydrogenation and generate saturated hydrocarbons such as ethane or propane.
Above catalyst all is not suitable for being rich in CO and H
2Various industrial tail gas in the full hydrogenation of the unsaturated hydrocarbons such as ethene, propylene, butylene.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, and a kind of hydrogenation of unsaturated hydrocarbons catalyst with characteristics such as the hydrogenation precision is high, anti-side reaction ability is strong, Heat stability is good, long service life is provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of hydrogenation of unsaturated hydrocarbons catalyst, comprise carrier, active component and auxiliary agent, it is characterized in that, described active component is the mixture of nickel oxide and other metal oxides, and described auxiliary agent is at least two kinds in magnesia, lanthana and the cerium oxide; The weight percent content of nickel oxide is 5%～15% in the described hydrogenation of unsaturated hydrocarbons catalyst, and the weight percent content of other metal oxides is 1%～10%, and the weight percent content of auxiliary agent is 1%～10%, and surplus is carrier; Described other metal oxides are one or more in molybdenum oxide, cobalt oxide and the iron oxide.
Above-mentioned a kind of hydrogenation of unsaturated hydrocarbons catalyst, described carrier is alundum (Al2O3), titanium dioxide or aluminum titanium composite oxide.
Above-mentioned a kind of hydrogenation of unsaturated hydrocarbons catalyst, the specific area of described carrier is 130m
2/ g～280m
2/ g, pore volume are 0.3mL/g～0.6mL/g.
Above-mentioned a kind of hydrogenation of unsaturated hydrocarbons catalyst, described carrier be shaped as bar shaped or trifolium-shaped.
The present invention also provides a kind of preparation method of hydrogenation of unsaturated hydrocarbons catalyst, it is characterized in that, the method may further comprise the steps:
(1) preliminary treatment of carrier: be under 30 ℃～60 ℃ the condition in temperature, place rare nitric acid or acetic acid to soak 2h～3h in carrier, then with deionized water the carrier after soaking is cleaned to neutral, placing temperature is that 110 ℃～120 ℃ baking oven is dried again; Perhaps with carrier with 400 ℃～600 ℃ steam treatment 3h～6h, then placing temperature is that 110 ℃～120 ℃ baking oven is dried;
(2) preparation of maceration extract: the weight percent content by each component in the catalyst takes by weighing nickel salt, molybdenum salt, cobalt salt, molysite, magnesium salts, lanthanum salt and cerium salt, and being dissolved in water after the mixing is mixed with maceration extract; Described molybdenum salt is ammonium molybdate, and described nickel salt, cobalt salt, molysite, magnesium salts, lanthanum salt and cerium salt are nitrate or acetate;
(3) preparation of catalyst: under 40 ℃～60 ℃ conditions, pretreated carrier in the step (1) placed maceration extract floods 3h～6h described in the step (2), then the carrier after will flooding is dry 10h～16h under 90 ℃～120 ℃ conditions, with dried carrier roasting 3h～6h under 360 ℃～420 ℃ conditions, obtain the hydrogenation of unsaturated hydrocarbons catalyst at last.
The mass concentration of rare nitric acid is 2%～5% described in the above-mentioned steps (1), and the mass concentration of described acetic acid is 2%～5%.
The present invention also provides a kind of hydrogenation of unsaturated hydrocarbons catalyst, and the hydrogenation of unsaturated hydrocarbons in the indirect oils preparation industry tail gas becomes the application of saturated hydrocarbons with coal in the indirect oils preparation industry of coal.
The present invention also provides a kind of hydrogenation of unsaturated hydrocarbons catalyst hydrogenation of unsaturated hydrocarbons in the industrial synthesis gas to be become the application of saturated hydrocarbons.
The present invention compared with prior art has the following advantages:
1, hydrogenation of unsaturated hydrocarbons catalyst of the present invention has taken the lead in solving the hydrogenation problem of unsaturated hydrocarbons in the indirect oils preparation industry tail gas of coal, and the gas behind the hydrogenation can be used as the raw material of synthetic ammonia or synthesizing methanol, has widened the comprehensive Utilization Ways that is rich in the CO industrial tail gas.
2, hydrogenation of unsaturated hydrocarbons catalyst of the present invention has deep hydrogenation conversion capability and stronger inhibition methanation side reaction ability, has broken through traditional hydrogenation conversion catalyst to CO in the raw material and CO
2The upper limit requirement of content 0.5%.
3, preparation method of the present invention is simple, and the method has been improved the distribution of active component, has improved activity and the heat endurance of catalyst, has reduced light-off temperature, has suppressed the generation of side reaction.
4, catalyst of the present invention has the characteristics such as the hydrogenation precision is high, anti-side reaction ability is strong, Heat stability is good, long service life.Adopt the indirect oils preparation industry tail gas of catalyst treatment coal of the present invention, the hydrogenation conversion of total unsaturated hydrocarbons such as ethene, propylene, butylene 〉=95% in the tail gas, 2 years rear catalyst activity of use etc. are all without obviously downward trend, adopt the unsaturated hydrocarbons in the catalyst treatment synthesis gas of the present invention, the hydrogenation conversion of total unsaturated hydrocarbons 〉=98%.
Below by embodiment, technical scheme of the present invention is described in further detail.
The specific embodiment
Embodiment 1
The weight percent content of nickel oxide is 8.0% in the hydrogenation of unsaturated hydrocarbons catalyst of present embodiment, and the weight percent content of other metal oxides is 5.6%, and the weight percent content of auxiliary agent is 3.0%, and surplus is carrier; Wherein other metal oxides are cobalt oxide (3.6%) and iron oxide (2.0%), and auxiliary agent is magnesia (2.4%) and lanthana (0.6%), and carrier is that specific area is 130m
2/ g, pore volume are the bar shaped alumina carrier of 0.3mL/g.
Its preparation method is:
(1) preliminary treatment of carrier: be under 40 ℃ the condition, to be 130m with specific area in temperature
2/ g, pore volume be the bar shaped alumina carrier of 0.3mL/g to place mass concentration be that 3% rare nitric acid or acetic acid soak 2.5h, then with deionized water the carrier after soaking is cleaned to neutral, placing temperature is that 120 ℃ baking oven is dried again;
(2) preparation of maceration extract: accurate weighing nickel nitrate, cobalt nitrate, ferric nitrate, magnesium nitrate, lanthanum nitrate, its consumption makes the catalyst that finally makes contain nickel oxide 8.0% (wt), cobalt oxide 3.6% (wt), iron oxide 2.0% (wt), magnesia 2.4% (wt), lanthana 0.6% (wt), being dissolved in water obtains maceration extract, and the volume of maceration extract equals the maximum that carrier absorbs;
(3) preparation of catalyst: under 60 ℃ of conditions, pretreated alumina carrier in the 100g step (1) placed maceration extract floods 3h described in the step (2), then the carrier after will flooding is dry 12h under 120 ℃ of conditions, with dried carrier roasting 4h under 380 ℃ of conditions, obtain the hydrogenation of unsaturated hydrocarbons catalyst at last.
The unsaturated hydrocarbons catalyst of present embodiment is through 500 ℃ after heat-resisting 3.5 hours, the hydrogenation activity of the heat-resisting front and back of catalyst, specific area and pore volume have no significant change, adopt the automatic X-ray diffractometer of Rigaku D/max-RC type (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is analyzed mensuration, catalyst crystalline phases illustrates that without significant change this catalyst has good heat endurance.
Embodiment 2
The hydrogenation of unsaturated hydrocarbons catalyst of present embodiment is identical with embodiment 1, and wherein difference is: other metal oxides are a kind of in molybdenum oxide, cobalt oxide and the iron oxide or three kinds, perhaps are molybdenum oxide and cobalt oxide, perhaps are molybdenum oxide and iron oxide; Auxiliary agent is magnesia and cerium oxide, perhaps is lanthana and cerium oxide, perhaps is magnesia, lanthana and cerium oxide; Used carrier is titanium dioxide or aluminum titanium composite oxide.
Its preparation method is with embodiment 1.
The unsaturated hydrocarbons catalyst of present embodiment is through 500 ℃ after heat-resisting 3.5 hours, the hydrogenation activity of the heat-resisting front and back of catalyst, specific area and pore volume have no significant change, adopt the automatic X-ray diffractometer of Rigaku D/max-RC type (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is analyzed mensuration, catalyst crystalline phases illustrates that without significant change this catalyst has good heat endurance.
Embodiment 3
The weight percent content of nickel oxide is 10.0% in the hydrogenation of unsaturated hydrocarbons catalyst of present embodiment, and the weight percent content of other metal oxides is 1.0%, and the weight percent content of auxiliary agent is 1.0%, and surplus is carrier; Wherein other metal oxides are molybdenum oxide, and auxiliary agent is lanthana (0.5%) and cerium oxide (0.5%), and carrier is that specific area is 280m
2/ g, pore volume are the granular titania-alumina mixed oxide of 0.6mL/g.
Its preparation method is:
(1) preliminary treatment of carrier: be under 30 ℃ the condition, to be 280m with specific area in temperature
2/ g, pore volume be the granular titania-alumina mixed oxide of 0.6mL/g to place mass concentration be that 2% rare nitric acid or acetic acid soak 3h, then with deionized water the carrier after soaking is cleaned to neutral, placing temperature is that 110 ℃ baking oven is dried again;
(2) preparation of maceration extract: accurate weighing nickel nitrate, ammonium molybdate, lanthanum nitrate, cerous nitrate, its consumption makes the catalyst that finally makes contain nickel oxide 10.0% (wt), molybdenum oxide 1.0% (wt), lanthana 0.5% (wt), cerium oxide 0.5% (wt), being dissolved in water obtains maceration extract, and the volume of maceration extract equals the maximum that carrier absorbs;
(3) preparation of catalyst: under 40 ℃ of conditions, pretreated titania-alumina mixed oxide in the 100g step (1) placed maceration extract floods 6h described in the step (2), then the carrier after will flooding is dry 16h under 90 ℃ of conditions, with dried carrier roasting 5h under 400 ℃ of conditions, obtain the hydrogenation of unsaturated hydrocarbons catalyst at last.
The unsaturated hydrocarbons catalyst of present embodiment is through 500 ℃ after heat-resisting 3.5 hours, the hydrogenation activity of the heat-resisting front and back of catalyst, specific area and pore volume have no significant change, adopt the automatic X-ray diffractometer of Rigaku D/max-RC type (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is analyzed mensuration, catalyst crystalline phases illustrates that without significant change this catalyst has good heat endurance.
Embodiment 4
The hydrogenation of unsaturated hydrocarbons catalyst of present embodiment is identical with embodiment 3, and wherein difference is: other metal oxides are cobalt oxide or iron oxide, perhaps are at least two kinds in molybdenum oxide, cobalt oxide and the iron oxide; Auxiliary agent is magnesia and lanthana, perhaps is magnesia and cerium oxide, perhaps is magnesia, lanthana and cerium oxide; Used carrier is alundum (Al2O3) or titanium dioxide.
Its preparation method is with embodiment 3.
The unsaturated hydrocarbons catalyst of present embodiment is through 500 ℃ after heat-resisting 3.5 hours, the hydrogenation activity of the heat-resisting front and back of catalyst, specific area and pore volume have no significant change, adopt the automatic X-ray diffractometer of Rigaku D/max-RC type (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is analyzed mensuration, catalyst crystalline phases illustrates that without significant change this catalyst has good heat endurance.
Embodiment 5
The weight percent content of nickel oxide is 5.0% in the hydrogenation of unsaturated hydrocarbons catalyst of present embodiment, and the weight percent content of other metal oxides is 10.0%, and the weight percent content of auxiliary agent is 4.3%, and surplus is carrier; Wherein other metal oxides are molybdenum oxide (3.0%), cobalt oxide (5.0%) and iron oxide (2.0%), and auxiliary agent is magnesia (3.5%) and cerium oxide (0.8%), and carrier is that specific area is 150m
2/ g, pore volume are the cloverleaf pattern titania support of 0.45mL/g.
Its preparation method is:
(1) preliminary treatment of carrier: be 150m with specific area
2/ g, pore volume are the steam treatment 6h of 400 ℃ of the cloverleaf pattern TiO 2 carrying body and functions of 0.45mL/g, and then placing temperature is that 120 ℃ baking oven is dried;
(2) preparation of maceration extract: accurate weighing nickel acetate, ammonium molybdate, cobalt acetate, ferric acetate, magnesium acetate and cerous acetate, its consumption makes the catalyst that finally makes contain nickel oxide 5.0% (wt), molybdenum oxide 3.0% (wt), cobalt oxide 5.0% (wt), iron oxide 2.0% (wt), magnesia 3.5% (wt), cerium oxide 0.8% (wt), being dissolved in water obtains maceration extract, and the volume of maceration extract equals the maximum that carrier absorbs;
(3) preparation of catalyst: under 50 ℃ of conditions, pretreated titania support in the 1000g step (1) placed maceration extract floods 6h described in the step (2), then the carrier after will flooding is dry 13h under 105 ℃ of conditions, with dried carrier roasting 6h under 360 ℃ of conditions, obtain the hydrogenation of unsaturated hydrocarbons catalyst at last.
The unsaturated hydrocarbons catalyst of present embodiment is through 500 ℃ after heat-resisting 3.5 hours, the hydrogenation activity of the heat-resisting front and back of catalyst, specific area and pore volume have no significant change, adopt the automatic X-ray diffractometer of Rigaku D/max-RC type (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is analyzed mensuration, catalyst crystalline phases illustrates that without significant change this catalyst has good heat endurance.
Embodiment 6
The hydrogenation of unsaturated hydrocarbons catalyst of present embodiment is identical with embodiment 5, and wherein difference is: other metal oxides are one or both in molybdenum oxide, cobalt oxide and the iron oxide; Auxiliary agent is magnesia and lanthana, or lanthana and cerium oxide, perhaps is magnesia, lanthana and cerium oxide; Used carrier is alundum (Al2O3) or aluminum titanium composite oxide.
Its preparation method is with embodiment 5.
The unsaturated hydrocarbons catalyst of present embodiment is through 500 ℃ after heat-resisting 3.5 hours, the hydrogenation activity of the heat-resisting front and back of catalyst, specific area and pore volume have no significant change, adopt the automatic X-ray diffractometer of Rigaku D/max-RC type (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is analyzed mensuration, catalyst crystalline phases illustrates that without significant change this catalyst has good heat endurance.
Embodiment 7
The weight percent content of nickel oxide is 12.0% in the hydrogenation of unsaturated hydrocarbons catalyst of present embodiment, and the weight percent content of other metal oxides is 9.0%, and the weight percent content of auxiliary agent is 10.0%, and surplus is carrier; Wherein other metal oxides are molybdenum oxide (1.0%) and cobalt oxide (8.0%), and auxiliary agent is magnesia (6.0%), lanthana (2.0%) and cerium oxide (2.0%), and carrier is that specific area is 220m
2/ g, pore volume are the spherical alumina carrier of 0.5mL/g.
Its preparation method is:
(1) preliminary treatment of carrier: be under 60 ℃ the condition, to be 220m with specific area in temperature
2/ g, pore volume be the spherical alumina carrier of 0.5mL/g to place mass concentration be that 5% rare nitric acid or acetic acid soak 2h, then with deionized water the carrier after soaking is cleaned to neutral, placing temperature is that 115 ℃ baking oven is dried again;
(2) preparation of maceration extract: accurate weighing nickel nitrate, ammonium molybdate, cobalt nitrate, magnesium nitrate, lanthanum nitrate and cerous nitrate, its consumption makes the catalyst that finally makes contain nickel oxide 12.0% (wt), molybdenum oxide 1.0% (wt), cobalt oxide 8.0% (wt), magnesia 6.0% (wt), lanthana 2.0% (wt), cerium oxide 2.0% (wt), being dissolved in water obtains maceration extract, and the volume of maceration extract equals the maximum that carrier absorbs;
(3) preparation of catalyst: under 50 ℃ of conditions, pretreated alumina carrier in the 1000g step (1) placed maceration extract floods 4h described in the step (2), then the carrier after will flooding is dry 16h under 90 ℃ of conditions, with dried carrier roasting 3h under 420 ℃ of conditions, obtain the hydrogenation of unsaturated hydrocarbons catalyst at last.
The unsaturated hydrocarbons catalyst of present embodiment is through 500 ℃ after heat-resisting 3.5 hours, the hydrogenation activity of the heat-resisting front and back of catalyst, specific area and pore volume have no significant change, adopt the automatic X-ray diffractometer of Rigaku D/max-RC type (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is analyzed mensuration, catalyst crystalline phases illustrates that without significant change this catalyst has good heat endurance.
Embodiment 8
The hydrogenation of unsaturated hydrocarbons catalyst of present embodiment is identical with embodiment 7, and wherein difference is: other metal oxides are a kind of in molybdenum oxide, cobalt oxide and the iron oxide or three kinds, perhaps are molybdenum oxide and iron oxide, perhaps are cobalt oxide and iron oxide; Auxiliary agent is two kinds in magnesia, lanthana and the cerium oxide; Used carrier is titanium dioxide or aluminum titanium composite oxide.
Its preparation method is with embodiment 7.
The unsaturated hydrocarbons catalyst of present embodiment is through 500 ℃ after heat-resisting 3.5 hours, the hydrogenation activity of the heat-resisting front and back of catalyst, specific area and pore volume have no significant change, adopt the automatic X-ray diffractometer of Rigaku D/max-RC type (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is analyzed mensuration, catalyst crystalline phases illustrates that without significant change this catalyst has good heat endurance.
Embodiment 9
The weight percent content of nickel oxide is 15.0% in the hydrogenation of unsaturated hydrocarbons catalyst of present embodiment, and the weight percent content of other metal oxides is 7.0%, and the weight percent content of auxiliary agent is 6.0%, and surplus is carrier; Wherein other metal oxides are molybdenum oxide (5.0%) and iron oxide (2.0%), and auxiliary agent is magnesia (4.0%) and lanthana (2.0%), and carrier is that specific area is 210m
2/ g, pore volume are the gear shape alumina carrier of 0.4mL/g.
Its preparation method is:
(1) preliminary treatment of carrier: be 210m with specific area
2/ g, pore volume be the gear shape alumina carrier of 0.4mL/g with 600 ℃ steam treatment 3h, then placing temperature is that 110 ℃ baking oven is dried;
(2) preparation of maceration extract: accurate weighing nickel acetate, ammonium molybdate, ferric acetate, magnesium acetate and lanthanum acetate, its consumption makes the catalyst that finally makes contain nickel oxide 15.0% (wt), molybdenum oxide 5.0% (wt), iron oxide 2.0% (wt), magnesia 4.0% (wt), lanthana 2.0% (wt), being dissolved in water obtains maceration extract, and the volume of maceration extract equals the maximum that carrier absorbs;
(3) preparation of catalyst: under 50 ℃ of conditions, pretreated alumina carrier in the 1000g step (1) placed maceration extract floods 4h described in the step (2), then the carrier after will flooding is dry 16h under 90 ℃ of conditions, with dried carrier roasting 3h under 420 ℃ of conditions, obtain the hydrogenation of unsaturated hydrocarbons catalyst at last.
The unsaturated hydrocarbons catalyst of present embodiment is through 500 ℃ after heat-resisting 3.5 hours, the hydrogenation activity of the heat-resisting front and back of catalyst, specific area and pore volume have no significant change, adopt the automatic X-ray diffractometer of Rigaku D/max-RC type (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is analyzed mensuration, catalyst crystalline phases illustrates that without significant change this catalyst has good heat endurance.
Embodiment 10
The hydrogenation of unsaturated hydrocarbons catalyst of present embodiment is identical with embodiment 9, and wherein difference is: other metal oxides are a kind of in molybdenum oxide, cobalt oxide and the iron oxide or three kinds, perhaps are molybdenum oxide and cobalt oxide, perhaps are cobalt oxide and iron oxide; Auxiliary agent is magnesia, lanthana and cerium oxide, perhaps is magnesia and cerium oxide, perhaps is lanthana and cerium oxide; Used carrier is titanium dioxide or aluminum titanium composite oxide.
Its preparation method is identical with embodiment 9, and wherein difference is: the temperature of steam is 500 ℃, and the steam treatment time is 5h, and oven temperature is 115 ℃.
The unsaturated hydrocarbons catalyst of present embodiment is through 500 ℃ after heat-resisting 3.5 hours, the hydrogenation activity of the heat-resisting front and back of catalyst, specific area and pore volume have no significant change, adopt the automatic X-ray diffractometer of Rigaku D/max-RC type (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is analyzed mensuration, catalyst crystalline phases illustrates that without significant change this catalyst has good heat endurance.
Embodiment 11
Hydrogenation of unsaturated hydrocarbons in the indirect oils preparation industry tail gas becomes the application of saturated hydrocarbons to the hydrogenation of unsaturated hydrocarbons catalyst with coal in the indirect oils preparation industry of coal.
Test method: 20mL hydrogenation of unsaturated hydrocarbons catalyst is packed in the fixed bed reactors, according to conventional heating reduction condition, use H
2Content is 5% hydrogen nitrogen mixed gas reduction 40 hours, then is cooled to 200 ℃～230 ℃, passes into the indirect oils preparation industry tail gas of simulation coal in fixed bed reactors, and the indirect oils preparation industry tail gas of coal forms by volume percentage and counts: CO8.3%, H
235.3%, CO
216.6%, CH
430.2%, ethene 0.60%, propylene 1.39%, n-butene 0.6%, surplus is nitrogen, and reaction temperature is 200 ℃～300 ℃, and reaction pressure is 1.0MPa～4.0MPa, and air speed is 1000h
-1～2000h
-1, result such as following table:
Table 1 catalyst is to total hydrogenation of unsaturated hydrocarbons conversion ratio of tail gas in the indirect oils preparation industry of coal
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Conversion ratio | ≥95.5％ | ≥95％ | ≥96％ | ≥96.5％ | ≥98％ | ≥98％ | ≥95％ | ≥95％ | ≥98％ | ≥98％ |
As above shown in the table, the indirect oils preparation industry tail gas of catalyst treatment coal of the present invention becomes total hydrogenation of unsaturated hydrocarbons conversion ratio of saturated hydrocarbons 〉=95% with the hydrogenation of unsaturated hydrocarbons in the tail gas, on catalyst all without obvious side reaction generation.
Embodiment 12
The hydrogenation of unsaturated hydrocarbons catalyst becomes hydrogenation of unsaturated hydrocarbons in the industrial synthesis gas application of saturated hydrocarbons.
Test method: 20mL hydrogenation of unsaturated hydrocarbons catalyst is packed in the fixed bed reactors, according to conventional heating reduction condition, use H
2Content is 5% hydrogen nitrogen mixed gas reduction 40 hours, then is cooled to 200 ℃～230 ℃, passes into simulation acetylene tail gas in fixed bed reactors, and acetylene tail gas forms by volume percentage and counts: CO27.4%, H
261.3%, CO
23.6%, CH
44.2%, acetylene 0.03%, ethene 0.60%, surplus is nitrogen, and reaction temperature is 200 ℃～300 ℃, and reaction pressure is 1.0MPa～4.0MPa, and air speed is 1000h
-1～2000h
-1
The result shows that the hydrogenation of unsaturated hydrocarbons catalyst of embodiment 1 to 10 to the total hydrogenation of unsaturated hydrocarbons conversion ratio in the synthesis gas all 〉=98% all occurs without obvious side reaction on catalyst.
The above; it only is preferred embodiment of the present invention; be not that the present invention is imposed any restrictions, every any simple modification, change and equivalent structure of above embodiment being done according to the technology of the present invention essence changes, and all still belongs in the protection domain of technical solution of the present invention.
Claims (5)
1. the application of a hydrogenation of unsaturated hydrocarbons catalyst, this hydrogenation of unsaturated hydrocarbons catalyst comprises carrier, active component and auxiliary agent, described active component is the mixture of nickel oxide and other metal oxides, and described auxiliary agent is at least two kinds in magnesia, lanthana and the cerium oxide; The weight percent content of nickel oxide is 5%～15% in the described hydrogenation of unsaturated hydrocarbons catalyst, and the weight percent content of other metal oxides is 1%～10%, and the weight percent content of auxiliary agent is 1%～10%, and surplus is carrier; Described other metal oxides are one or more in molybdenum oxide, cobalt oxide and the iron oxide; It is characterized in that, describedly be applied as the hydrogenation of unsaturated hydrocarbons catalyst hydrogenation of unsaturated hydrocarbons in the indirect oils preparation industry tail gas becomes the application of saturated hydrocarbons with coal in the indirect oils preparation industry of coal.
2. the application of a hydrogenation of unsaturated hydrocarbons catalyst, this hydrogenation of unsaturated hydrocarbons catalyst comprises carrier, active component and auxiliary agent, described active component is the mixture of nickel oxide and other metal oxides, and described auxiliary agent is at least two kinds in magnesia, lanthana and the cerium oxide; The weight percent content of nickel oxide is 5%～15% in the described hydrogenation of unsaturated hydrocarbons catalyst, and the weight percent content of other metal oxides is 1%～10%, and the weight percent content of auxiliary agent is 1%～10%, and surplus is carrier; Described other metal oxides are one or more in molybdenum oxide, cobalt oxide and the iron oxide; It is characterized in that, describedly be applied as the application that the hydrogenation of unsaturated hydrocarbons catalyst becomes hydrogenation of unsaturated hydrocarbons in the industrial synthesis gas saturated hydrocarbons.
3. the application of a kind of hydrogenation of unsaturated hydrocarbons catalyst according to claim 1 and 2 is characterized in that, described carrier is alundum (Al2O3), titanium dioxide or aluminum titanium composite oxide.
4. the application of a kind of hydrogenation of unsaturated hydrocarbons catalyst according to claim 1 and 2 is characterized in that, the specific area of described carrier is 130m
2/ g～280m
2/ g, pore volume are 0.3mL/g～0.6mL/g.
5. the application of a kind of hydrogenation of unsaturated hydrocarbons catalyst according to claim 1 and 2 is characterized in that, being shaped as of described carrier is granular, spherical, gear shape, bar shaped or cloverleaf pattern.
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| CN 201110102643 CN102218323B (en) | 2011-04-22 | 2011-04-22 | Unsaturated hydrocarbon hydrogenation catalyst, preparation method and applications thereof |
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|---|---|---|---|
| CN 201110102643 CN102218323B (en) | 2011-04-22 | 2011-04-22 | Unsaturated hydrocarbon hydrogenation catalyst, preparation method and applications thereof |
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| CN102218323B true CN102218323B (en) | 2013-01-23 |
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| CN102513114B (en) * | 2011-10-25 | 2014-11-05 | 中国海洋石油总公司 | Preparation method of poisoning-resistant catalyst for unsaturated oil hydrogenation |
| CN102633586B (en) * | 2012-03-28 | 2014-12-24 | 清华大学 | Normal hexane and preparation method for same |
| CN102895975A (en) * | 2012-10-12 | 2013-01-30 | 中国海洋石油总公司 | Method for preparing high acid value oil hydrogenation catalyst |
| CN103480380B (en) * | 2013-09-03 | 2015-04-22 | 万华化学集团股份有限公司 | Catalyst for fixed bed aniline rectification residue recycling and preparation method thereof |
| CN106927999B (en) * | 2015-12-31 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of predepropanization front-end hydrogenation technique removes alkynes method |
| CN106927993B (en) * | 2015-12-31 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of method that methanol-to-olefins product front-end hydrogenation removes alkynes |
| CN106928008B (en) * | 2015-12-31 | 2019-11-08 | 中国石油天然气股份有限公司 | A kind of front-end hydrogenation of methanol-to-olefins product removes alkynes method |
| CN106927995B (en) * | 2015-12-31 | 2019-11-08 | 中国石油天然气股份有限公司 | A kind of predepropanization front-end hydrogenation removes alkynes method |
| CN106928009B (en) * | 2015-12-31 | 2019-12-10 | 中国石油天然气股份有限公司 | Method for removing alkyne by hydrogenation before front deethanization |
| CN108246307A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of Fe-Mn selective hydrogenation catalysts, preparation method and applications |
| CN108246296A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of Fe-Co selective hydrogenation catalysts and preparation method thereof and purposes |
| CN108686667B (en) * | 2017-04-11 | 2021-03-16 | 中国人民大学 | Catalyst for microalgae thermal liquefaction denitrification and preparation method and application thereof |
| RU2656601C1 (en) * | 2017-08-08 | 2018-06-06 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Method of obtaining synthetic oil |
| RU2672269C1 (en) * | 2017-08-08 | 2018-11-13 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Catalyst for hydrogenation of olefins at producing synthetic oil and method for synthesis thereof (options) |
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| CN1272102C (en) * | 2004-07-21 | 2006-08-30 | 中国科学院山西煤炭化学研究所 | Catalyst for hyrogenating deoxidating and olefine saturating of Feather synthesizing oil and its mfg. process and application |
| CN100487086C (en) * | 2006-01-06 | 2009-05-13 | 中国石油天然气股份有限公司 | Selective nickel series hydrogenating catalyst and its preparing process and uses |
| CN100553770C (en) * | 2006-09-20 | 2009-10-28 | 中国石油化工股份有限公司上海石油化工研究院 | The Raney nickel that is used for selective hydrogenation |
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