CN102218323A - 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 it to produce methyl alcohol or synthetic ammonia etc., both fully utilized natural resources, reduced production cost again, is a comparatively ideal raw material route.
Owing to often contain small amount of ethylene, propylene and butylene etc. in the industrial tail gas, can influence follow-up workshop section life of catalyst and product quality, 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 under CO content condition with higher, 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 is formed, this catalyst adopts immersion process for preparing.Be mainly used in the hydro-conversion of oxygen and alkene in the oil from Fischer-Tropsch synthesis.This catalyst has hydro-conversion effect preferably to oxygen in the liquid phase oil product and alkene.
Chinese patent CN1470488 introduces a kind of be used for saturated Catalysts and its preparation method of fatty monoolefin hydrogenation and application, is applicable to C
4～C
20The fat hydrogenation of olefins is saturated, 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 fatty monoolefin hydrogenation saturation catalyst that is used for, 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, do not see the hydro-conversion that is used 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 alkynes such as acetylene and polyene, this catalyst is active component with the precious metal palladium, 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 acetylene hydrogenation and generated selectivity of ethylene and activity.
Chinese patent CN1253853 relates to a kind of Catalyst and process to the unsaturated compound selective hydrogenation in the hydrocarbon material flow.Specifically be to generate in the process of alkene alkynes and alkadienes being carried out selective hydrogenation, have higher selectivity, 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 unsaturated hydrocarbons such as ethene, propylene, butylene.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned the deficiencies in the prior art, and a kind of hydrogenation of unsaturated hydrocarbons catalyst with characteristics such as hydrogenation precision height, anti-side reaction ability are 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 a 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 (Al, 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 hydrogenation of unsaturated hydrocarbons Preparation of catalysts method, it is characterized in that this method may further comprise the steps:
(1) preliminary treatment of carrier: be under 30 ℃～60 ℃ the condition, to place rare nitric acid or acetic acid to soak 2h～3h in carrier in temperature, will clean to neutral through the carrier after soaking with deionized water then that placing temperature again is that 110 ℃～120 ℃ baking oven is dried; Perhaps with the steam treatment 3h～6h of carrier with 400 ℃～600 ℃, placing temperature then 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 catalysts: under 40 ℃～60 ℃ conditions, maceration extract floods 3h～6h described in the step (2) with placing through pretreated carrier in the step (1), then with soaked carrier 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 this method has been improved the distribution of active component, has improved activity of such catalysts and heat endurance, has reduced light-off temperature, has suppressed the generation of side reaction.
4, catalyst of the present invention has characteristics such as hydrogenation precision height, anti-side reaction ability are strong, Heat stability is good, long service life.Adopt the indirect oils preparation industry tail gas of catalyst treatment coal of the present invention, hydrogenation conversion 〉=95% of total unsaturated hydrocarbons such as ethene, propylene, butylene in the tail gas, 2 years rear catalyst activity of use etc. all do not have obvious downward trend, adopt the unsaturated hydrocarbons in the catalyst treatment synthesis gas of the present invention, hydrogenation conversion 〉=98% of total unsaturated hydrocarbons.
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 a 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 in temperature with specific area
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, will clean to neutral through the carrier after soaking with deionized water then, placing temperature again is that 120 ℃ baking oven is dried;
(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 catalysts: under 60 ℃ of conditions, maceration extract floods 3h described in the step (2) with placing through pretreated alumina carrier in the 100g step (1), then with soaked carrier 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 Japanese D/max-RC type of science (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is carried out assay determination, catalyst crystalline phases does not have significant change, illustrates that 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 Japanese D/max-RC type of science (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is carried out assay determination, catalyst crystalline phases does not have significant change, illustrates that 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 a 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 in temperature with specific area
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, will clean to neutral through the carrier after soaking with deionized water then, placing temperature again is that 110 ℃ baking oven is dried;
(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 catalysts: under 40 ℃ of conditions, maceration extract floods 6h described in the step (2) with placing through pretreated titania-alumina mixed oxide in the 100g step (1), then with soaked carrier 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 Japanese D/max-RC type of science (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is carried out assay determination, catalyst crystalline phases does not have significant change, illustrates that 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 (Al 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 Japanese D/max-RC type of science (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is carried out assay determination, catalyst crystalline phases does not have significant change, illustrates that 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 a 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: with specific area is 150m
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 placing temperature then 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 catalysts: under 50 ℃ of conditions, maceration extract floods 6h described in the step (2) with placing through pretreated titania support in the 1000g step (1), then with soaked carrier 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 Japanese D/max-RC type of science (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is carried out assay determination, catalyst crystalline phases does not have significant change, illustrates that 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 (Al 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 Japanese D/max-RC type of science (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is carried out assay determination, catalyst crystalline phases does not have significant change, illustrates that 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 a 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 in temperature with specific area
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, will clean to neutral through the carrier after soaking with deionized water then, placing temperature again is that 115 ℃ baking oven is dried;
(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 catalysts: under 50 ℃ of conditions, maceration extract floods 4h described in the step (2) with placing through pretreated alumina carrier in the 1000g step (1), then with soaked carrier 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 Japanese D/max-RC type of science (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is carried out assay determination, catalyst crystalline phases does not have significant change, illustrates that 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 Japanese D/max-RC type of science (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is carried out assay determination, catalyst crystalline phases does not have significant change, illustrates that 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 a 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: with specific area is 210m
2/ g, pore volume be the gear shape alumina carrier of 0.4mL/g with 600 ℃ steam treatment 3h, placing temperature then 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 catalysts: under 50 ℃ of conditions, maceration extract floods 4h described in the step (2) with placing through pretreated alumina carrier in the 1000g step (1), then with soaked carrier 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 Japanese D/max-RC type of science (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is carried out assay determination, catalyst crystalline phases does not have significant change, illustrates that 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 Japanese D/max-RC type of science (Cu target, pipe is pressed 40KV, pipe stream 80mA) heat-resisting front and back catalyst is carried out assay determination, catalyst crystalline phases does not have significant change, illustrates that 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,, use H according to conventional heating reduction condition
2Content is 5% hydrogen nitrogen mixed gas reduction 40 hours, is cooled to 200 ℃～230 ℃ then, feeds the indirect oils preparation industry tail gas of simulation coal in fixed bed reactors, and the indirect oils preparation industry tail gas of coal is formed by volume percentage and counted: CO8.3%, H
235.3%, CO
216.6%, CH
430.2%, ethene 0.60%, propylene 1.39%, n-butene 0.6%, surplus is a 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 〉=95% of saturated hydrocarbons with the hydrogenation of unsaturated hydrocarbons in the tail gas, does not all have tangible side reaction and take place on catalyst.
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,, use H according to conventional heating reduction condition
2Content is 5% hydrogen nitrogen mixed gas reduction 40 hours, is cooled to 200 ℃～230 ℃ then, feeds simulation acetylene tail gas in fixed bed reactors, and acetylene tail gas is formed by volume percentage and counted: CO27.4%, H
261.3%, CO
23.6%, CH
44.2%, acetylene 0.03%, ethene 0.60%, surplus is a 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% does not all have tangible side reaction and takes place on catalyst.
The above; it only is preferred embodiment of the present invention; be not that the present invention is imposed any restrictions, everyly any simple modification that above embodiment did, change and equivalent structure changed, all still belong in the protection domain of technical solution of the present invention according to the technology of the present invention essence.
Claims (8)
1. a hydrogenation of unsaturated hydrocarbons catalyst comprises 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 a carrier; Described other metal oxides are one or more in molybdenum oxide, cobalt oxide and the iron oxide.
2. a kind of hydrogenation of unsaturated hydrocarbons catalyst according to claim 1 is characterized in that described carrier is alundum (Al, titanium dioxide or aluminum titanium composite oxide.
3. a kind of hydrogenation of unsaturated hydrocarbons catalyst according to claim 1 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.
4. a kind of hydrogenation of unsaturated hydrocarbons catalyst according to claim 1 is characterized in that, being shaped as of described carrier is granular, spherical, gear shape, bar shaped or cloverleaf pattern.
5. method for preparing as hydrogenation of unsaturated hydrocarbons catalyst as described in arbitrary claim among the claim 1-4 is characterized in that this method may further comprise the steps:
(1) preliminary treatment of carrier: be under 30 ℃～60 ℃ the condition, to place rare nitric acid or acetic acid to soak 2h～3h in carrier in temperature, will clean to neutral through the carrier after soaking with deionized water then that placing temperature again is that 110 ℃～120 ℃ baking oven is dried; Perhaps with the steam treatment 3h～6h of carrier with 400 ℃～600 ℃, placing temperature then 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 catalysts: under 40 ℃～60 ℃ conditions, maceration extract floods 3h～6h described in the step (2) with placing through pretreated carrier in the step (1), then with soaked carrier 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.
6. a kind of hydrogenation of unsaturated hydrocarbons Preparation of catalysts method according to claim 5 is characterized in that the mass concentration of rare nitric acid is 2%～5% described in the step (1), and the mass concentration of described acetic acid is 2%～5%.
7. 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 for a hydrogenation of unsaturated hydrocarbons catalyst as claimed in claim 1.
8. a hydrogenation of unsaturated hydrocarbons catalyst as claimed in claim 1 becomes hydrogenation of unsaturated hydrocarbons in the industrial synthesis gas application of saturated hydrocarbons.
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