CN102921428A - Sulfur-containing coking liquefied gas high-temperature hydrogenation catalyst and its preparation method and use - Google Patents
Sulfur-containing coking liquefied gas high-temperature hydrogenation catalyst and its preparation method and use Download PDFInfo
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Abstract
The invention relates to a sulfur-containing coking liquefied gas high-temperature hydrogenation catalyst and its preparation method and use. The sulfur-containing coking liquefied gas high-temperature hydrogenation catalyst utilizes gamma-alumina as a carrier, comprises active components of 10.0 to 20.0% of Mo2O3 and 6.0 to 18.0% of NiO, is in a shape of a strip, a whitetip clover or a ball having the size of dia. 3*(3-5)mm and has a specific surface area of 100 to 200m<2>/g. The preparation method comprises the following steps of molybdenum loading, nickel loading, drying and calcination. The sulfur-containing coking liquefied gas high-temperature hydrogenation catalyst can be used for high-temperature hydrogenation saturation of coking liquefied gas and coking residual C4, avoids catalyst pre-vulcanization, can be directly used for high-temperature hydrogenation of coking liquefied gas and coking residual C4 after hydrogen atmosphere reduction, and avoids pre-treatment on coking liquefied gas and coking residual C4. A hydrogenation reaction feeding temperature is in a range of 180 to 230 DEG C; a reaction temperature is in a range of 280 to 300 DEG C; reaction pressure is in a range of 2.3 to 3.5MPa; a liquid hourly space velocity is in a range of 1.5 to 8.0h<-1>; a hydrogen/olefin mole ratio is (1.2 to 1.8): 1; and olefin content is less than 1% after hydrogenation.
Description
Technical field
The present invention relates to a kind of preparation and application process thereof of catalyst of coking liquefied gas high-temperature hydrogenation of Catalysts and its preparation method and the application, particularly sulfur-bearing for sulfur-bearing liquefied gas hydrogenation.
Background technology
Often decompression of refinery, catalytic cracking, delayed coking, a large amount of liquefied gas of hydrocracking unit by-product.Normal decompression, hydrocracking liquefied gas saturation degree are high, and most domestic enterprise all is used as ethylene cracking material.The catalytic cracking liquefied gas is generally isolated propane, propylene, residue C
4Because iso-butane content is higher, and be more or less the same with butenes ratio, generally produce alkylate oil, producing ethylene cracking material through hydrogenation is also arranged.Catalytic cracking residue C
4Sulfur content is lower, and the low temperature hydrogenation desulphurization cost is lower, can adopt low temperature hydrogenation explained hereafter ethylene cracking material.Delayed coking unit is take normal decompression residuum, catalytic slurry as raw material, because the more high reason of sulfur content in raw material heaviness and the crude oil, cause delayed coking liquefied gas sulfur content higher, after the desulfurization such as amine absorption, alkali cleaning, washing processing, sulfur content is still higher, particularly isolates the delayed coking residue C behind propane, the propylene
4Sulfur content is higher, has limited its development and use, and generally as industry or domestic fuel, the chemical utilization rate is not high.
Delayed coking residue C
4N-alkane 70 ~ 75%, olefin(e) centent 30 ~ 36% is than catalytic cracking residue C
4Producing ethylene cracking material through hydrogenation hydrogen consumption is low, product cracking triolefin yield is high, so delayed coking residue C
4The saturated production ethylene cracking material of hydrogenation is a kind of approach that utilizes preferably, both can make the ethylene raw lighting, has realized again coking residual C
4Chemical utilization.
Delayed coking unit is take normal decompression residuum, catalytic slurry as raw material, and the heaviness of raw material causes sulphur in its liquefied gas product, metal impurities content higher, has therefore limited its hydrogenation technique.The total sulfur mass fraction is less than 343mg/m among the LPG of GB 1174-1997 regulations
3Coking liquefied gas in refinery's extracts H through amine liquid
2S, carry out alkali cleaning with 10%NaOH, flush away is the H that goes of extracting not
2S and low-grade thioalcohol, the alkali lye that contains sodium mercaptides carry out oxidation regeneration, sedimentation with cobalt sulfonated phthalocyanine and remove behind the disulphide that mercaptan oxidation generates lixiviating and wash systemic circulation and use, and after desulfurization was processed, coking liquefied gas sulfur content was generally at 600 ~ 800mg/m
3, and sulfur speciation is take disulphide as main.Many devices undergo technological transformation to coking desulfuration of liquefied gas device for this reason, adopt the tunica fibrosa alkali cleaning to replace traditional static mixer or absorption tower caustic wash desulfuration alcohol technique, increase solvent naphtha tunica fibrosa regenerating alkali liquid extraction system, with the sulfur content in the methods such as the disulphide reduction coking liquefied gas in treated gasoline or the refined diesel oil extraction regeneration alkali lye, but the sulfur content in the coking liquefied gas is still at 100 ~ 200mg/m
3, sulfur speciation is still take disulphide as main.
To sulfur-bearing liquefied gas component hydrogenation, generally adopt molybdenum and/or tungsten, cobalt and/or Raney nickel high-temperature hydrogenation technique, or adopt noble metal catalyst or high-nickel catalyst low temperature hydrogenation technique.Adopt traditional molybdenum and/or tungsten, cobalt and/or Raney nickel high-temperature hydrogenation technique, catalyst need to become sulphided state through presulfurization, and the temperature required height of presulfiding of catalyst process, the time is long.Adopt noble metal catalyst or high-nickel catalyst low temperature hydrogenation technique, further carry out desulfurization, dehydration, dearsenification processing to raw material, to prevent catalyst poisoning.Although high-nickel catalyst increases than the noble metal catalyst sulfur resistance, still need desulfurization, dearsenification during low temperature hydrogenation.And coker feedstocks is the heavy charges such as decompression residuum, catalytic slurry, and sulphur in the coking liquefied gas, arsenic content are high, and desulfurization, sulfur speciation be take disulphide as main, and desulfurization, dearsenification cost are high.
CN 101433853A discloses a kind of hydrogenation catalyst, preparation method and application thereof, and this catalyst is take aluminium oxide as carrier, active component palladium 0.3 ~ 0.5wt%, auxiliary agent X
11.0 ~ 3.0wt% is selected among B, P, the Si one or more, auxiliary agent X
20.01 ~ 5wt% is selected among Ag, Pb, Au, Co, Cu, Bi, Ni, Pt, the Ti one or more, alkali metal and/or alkaline-earth metal 0.5 ~ 4.0wt%; Catalyst surface area 50 ~ 150m
2/ g, specific pore volume 0.2 ~ 1.0ml/g.This catalyst is specially adapted to the C of catalytic cracking process and steam cracking byproduct in process
4Cut fraction hydrogenation is saturated.This catalyst is take precious metal palladium as active component, and cost is high.And noble metal is strict to the poisonous substance such as sulphur, arsenic in the raw material.
CN 1508103A, ZL01114177.8 disclose respectively and have been applicable to C
4The catalyst of cut fraction hydrogenation, but they exist the catalyst cost high equally take noble metal as active component, to the strict defective of the poisonous substance such as sulphur, arsenic in the raw material.
CN 101037613A discloses a kind of preparation method of nickel series hydrogenating catalyst, this catalyst take aluminium oxide and or silica as carrier, adopt the method for co-precipitation to make, main active component is Ni, La, auxiliary agent X
1With carrier X
2O forms, and the weight percentage that forms in catalyst: NiO 40 ~ 70%, La
2O
32 ~ 5%, X
1O 2 ~ 5%, X
2O 20 ~ 50%, wherein X
1Be selected from Cu, Mg, Zr, X
2Be selected from Al, Si; Its specific area 80 ~ 200m
2/ g, specific pore volume 0.4 ~ 0.8ml/g, this catalyst is applicable to monoolefin hydrogenation, is particularly useful for C
9Cut fraction hydrogenation, have higher hydrogenation activity, also have certain sulfur poisoning-resistant, anti-coking performance, but high-nickel catalyst adopts coprecipitation method to produce, will pass through raw material dissolving, precipitation, filtration, washing, oven dry, moulding, roasting making step, technical process is relatively loaded down with trivial details.
In " petrochemical technology and application " " a kind of preparation of New Nickel series catalysts and application study thereof ", introduced a kind of high nickel content Ni/Al in petrochemical engineering (designing) institute, Lanzhou
2O
3-Si
2The O catalyst adopts the coprecipitation preparation, is particularly suitable for C
4Cut fraction hydrogenation.According to " scientific and technological information " the 8th interim " C in 2006
4Alkene is produced the technology research of normal butane " introduce the C of orchidization designing institute
4The hydrogenation high-nickel catalyst needs H in the control raw material
2S≤50ppm, arsenic≤50ppb, raw material need to carry out the preliminary treatment such as front adsorption dewatering, adsorption desulfurize hydrogen, absorption dearsenification.
CN 10172200014A discloses a kind of Hydrobon catalyst and preparation method and application, major catalyst is one or both among W and the Mo, helping the hydrogenation activity component is among Ni and the Co one or both, main hydrogenation activity component exists with sulphided state, helps the hydrogenation activity component to exist with the form of oxide or salt.230 ~ 330 ℃ of reaction temperatures are mainly used in catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline, pressure gasoline hydrodesulfurization, and hydrodesulfurization is selectively high, but poor to olefins hydrogenation, to be conducive to keep the octane number of gasoline products.
CN 101081998B discloses a kind of C
4The method of cut fraction hydrogenation fills in one or two fixed bed reactors C with the series connection of hydrogenation catalyst I and hydrogenation catalyst II or segmentation
4Contact with the catalyst I first after cut and hydrogen mix that to carry out diene hydrogenation saturated, then contact with the hydrogenation catalyst II and carry out impurity removal and olefin saturated.The hydrogenation catalyst I is take a kind of aluminium oxide as carrier, contains 0.5 ~ 8% heavy cobalt and/or nickel, 2 ~ 15% heavy molybdenums and/or tungsten, 2 ~ 8% heavy alkali metal; The hydrogenation catalyst II is take aluminium oxide as carrier, and active component is in oxide and take catalyst as benchmark, and its content is: tungsten 10 ~ 30% heavy, nickel 1 ~ 7% heavy, cobalt 0.01 ~ 1.0% heavy, co-catalyst 0.1 ~ 10% weights are selected from arbitrary element in magnesium, zinc, iron, the calcium.Two kinds of anti-sulphur of catalyst, anti-arsenic better performances, but catalyst I, II all need pass through presulfurization before using, under hydrogen atmosphere, injection CS
2Or DMDS carries out presulfurization under 230 ~ 370 ℃, cure time 8 ~ 32 hours, and curing temperature is high, and the time is long.
US Patent No. P4482767 discloses a kind of Pd/Al
2O
3Catalyst is used for C
3Cut fraction hydrogenation.
In sum, classify according to active component, at present to mainly contain palladium system, nickel system, cobalt-molybdenum-nickel be three classes to olefin hydrogenation catalyst.Before using, cobalt-molybdenum-nickel catalyst needs sulfuration, curing temperature high (200 ~ 360 ℃), and the time is long; The palladium series catalyst reaction temperature is low, but the noble metal catalyst cost is high, easily poisons; High-nickel catalyst need to adopt the coprecipitation preparation, compares with the load method preparation, and catalyst preparation process is complicated, loaded down with trivial details, also requires raw material carried out the preliminary treatment such as front adsorption dewatering, adsorption desulfurize hydrogen, absorption dearsenification.
For delayed coking liquefied gas or delayed coking residue C
4, adopt the high-temperature hydrogenation technology to carry out when saturated, the catalyst of present disclosed liquefied gas high-temperature hydrogenation must carry out numerous and diverse presulfurization.
For delayed coking liquefied gas or delayed coking residue C
4, adopt the low temperature hydrogenation technology to carry out when saturated, high-nickel catalyst, preparation process is complicated, loaded down with trivial details; The noble metal catalyst of employing take palladium as active component, the catalyst cost is high.Two kinds of catalyst all need raw material is carried out the preliminary treatment such as front adsorption dewatering, adsorption desulfurize, absorption dearsenification, control the impurity contents such as sulphur, As, water.And delayed coking liquefied gas or delayed coking residue C
4Characteristics be that sulfur content is high, sulfur speciation is take disulphide as main, smart desulphurization cost is high, from economic considerations, can bring certain difficulty to industrial applications.
The invention provides a kind of low cost of manufacture, active high, preparation process, the simple hydrogenation catalyst of preprocessing process and application process thereof are used for sulfur-bearing coking C
4High-temperature hydrogenation is saturated, and catalyst does not need presulfurization to process and namely can be used for hydrogenation reaction, coking liquefied gas or coking residual C after the hydrogen atmosphere reduction
4Raw material need not carry out the preliminary treatment such as desulfurization, dearsenification.
Summary of the invention
The invention provides a kind of Catalysts and its preparation method and application for coking liquefied gas high-temperature hydrogenation.Main purpose is need to carry out presulfurization when carrying out sulfur-bearing liquefied gas high-temperature hydrogenation for existing catalyst to process, or the high-nickel catalyst preparation process is complicated during sulfur-bearing liquefied gas low temperature hydrogenation, loaded down with trivial details, the noble metal catalyst cost is high, all need desulfurization of raw material during low temperature hydrogenation, the problems such as dearsenification preliminary treatment, provide a kind of cost low, hydrogenation activity is high, preparation process is relatively simple, catalyst is after the hydrogen atmosphere reduction, do not need presulfurization to process, raw material does not need catalyst and the application process of the high-temperature hydrogenation of desulfurization processing, is used for sulfur-bearing delayed coking liquefied gas and coking residual C
4High-temperature hydrogenation is saturated.
Technical scheme of the present invention is as follows:
A kind of coking liquefied gas high-temperature hydrogenation catalyst is characterized in that: catalyst is take gama-alumina as carrier, and the catalyst activity component is molybdenum, nickel, in total catalyst weight 100%, contains Mo
2O
310.0% ~ 20.0%, NiO 6.0% ~ 18.0%, and catalyst is stripe shape, trifolium-shaped or the ball-type of Ф 3 * 3 ~ 5mm, specific area 100 ~ 200m
2/ g.
The content of active component is in total catalyst weight 100%, preferred Mo
2O
313.0% ~ 16.0%, NiO10.0% ~ 13.0%.
The preparation method of catalyst of the present invention, catalyst is take gama-alumina as carrier, and the mode by dipping on the carrier after the moulding, makes active constituent loading through oven dry, roasting.
Active component is introduced in the mode of salting liquid, and the soluble-salt of nickel is nitrate, acetate, formates; The soluble-salt of molybdenum is ammonium molybdate.
Active component while or step load make finished catalyst after drying, the roasting again on carrier.Preferred step load active component.
Catalyst prepares step load on carrier, first load active component molybdenum, and then load active component nickel again after the oven dry make finished catalyst after drying, the roasting.
During load active component, 115 ~ 125 ℃ of bake out temperatures, 350 ~ 450 ℃ of sintering temperatures.118 ~ 120 ℃ of preferred bake out temperatures, 350 ~ 375 ℃ of sintering temperatures.
The application of catalyst of the present invention, catalyst reduces in hydrogen atmosphere before using, and rises to 120 ℃ with 5 ℃/min first, insulation 2h rises to 300 ℃ with 5 ℃/min again, insulation 4h, then in hydrogen atmosphere, bed temperature is down to 180 ℃, is used for sulfur-bearing liquefied gas hydrogenation reaction.
The hydrogenation reaction of sulfur-bearing liquefied gas is in thermal insulation or calandria type fixed bed reactor, and its process conditions are: 180 ~ 230 ℃ of feeding temperatures, 280 ~ 300 ℃ of reaction temperatures, reaction pressure 2.3 ~ 3.5MPa, volume liquid hourly space velocity (LHSV) 1.5 ~ 8.0h
-1, hydrogen/olefin molar ratio 1.2 ~ 1.8:1, olefin(e) centent all can be less than 1% behind the hydrogenation.
The application process of described catalyst for sulfur-bearing coking liquefied gas high-temperature hydrogenation is applicable to refinery's coking liquefied gas, coking residual C
4Deng sulfur-bearing liquefied gas high-temperature hydrogenation, olefin(e) centent is less than 1% behind the hydrogenation.
Advantage of the present invention is: the prepared catalyst of the present invention is specially adapted to sulfur-bearing liquefied gas fraction high-temperature hydrogenation, hydrogenation carries out in thermal insulation or calandria type fixed bed reactor, after catalyst reduces through hydrogen atmosphere, directly carry out hydrogenation reaction, need not pass through vulcanizing treatment, raw material does not need to carry out pre-desulfurization.
Catalyst of the present invention is carried on the mode of active component by dipping on the gamma-aluminium oxide carrier after the moulding, through oven dry, roasting, makes required delayed coking liquefied gas or/and coking residual C
4Cut high-temperature hydrogenation catalyst.
After only needing before catalyst of the present invention uses in hydrogen atmosphere, to reduce, namely can be used for hydrogenation reaction.
The specific embodiment
Further specify the present invention below by embodiment, but the present invention is not limited to embodiment, authority of the present invention is as the criterion with claims.
The preparation of catalyst: take by weighing the gamma-aluminium oxide carrier after a certain amount of moulding, make and the isopyknic load solution of carrier with the soluble-salt of nickel, the soluble-salt of molybdenum, at room temperature carrier is soaked in certain hour in this load solution, incline and the residue soak, after oven dry, roasting, make required catalyst.
Evaluating catalyst condition: 180 ~ 230 ℃ of feeding temperatures, 280 ~ 300 ℃ of reaction temperatures, reaction pressure 2.3 ~ 3.5MPa, volume liquid hourly space velocity (LHSV) 1.5 ~ 8.0h
-1, hydrogen/olefin molar ratio 1.2 ~ 1.8:1.
The required raw material of evaluating catalyst is divided into coking liquefied gas and coking residual C
4Two kinds, composition sees Table 1.
Table 1 coking liquefied gas and coking residual C
4Form
| Form (v) % | The coking liquefied gas | Coking residual C 4 |
| Propylene | 10.478 | 0.02 |
| Propane | 38.562 | 0.041 |
| Iso-butane | 8.626 | 16.915 |
| Butane | 24.597 | 48.233 |
| Anti-2 butylene | 2.164 | 4.243 |
| The 1-butylene | 6.885 | 13.501 |
| Isobutene | 5.071 | 9.944 |
| Along 2 butylene | 1.375 | 2.696 |
| Isopentane | 0.031 | 0.061 |
| Pentane | 1.017 | 1.994 |
| C 5 + | 1.2 | 2.353 |
| ∑C = | 25.993 | 30.385 |
| Hydrogen sulfide, mg/m 3 | 0.5 ----- | |
| Methyl mercaptan, mg/m 3 | 0.5 ----- | |
| COS,mg/m 3 | 8.6 | 9.0 |
| Ethyl mercaptan, mg/m 3 | 1.8 | 3.5 |
| Thiophene, mg/m 3 | 0.1 | 0.15 |
| Methyl sulfide, mg/m 3 | 3.2 | 6.4 |
| Dimethyl disulfide, mg/m 3 | 152.3 | 300 |
| Total sulfur, mg/m 3 | 167 | 319.05 |
Embodiment 1
Take by weighing the strip gamma-aluminium oxide carrier 60g (approximately 90ml) after the moulding, according to Mo on the final catalyst
2O
3Content 13.0%, NiO content 10.0% quantitatively take by weighing four water ammonium molybdates, six water nickel nitrates, are made into 90ml solution.At room temperature carrier is soaked in the solution 12 hours, inclining the residue soak.After 125 ℃ of oven dry, be divided into three parts, respectively at 350,375 ℃, 400 ℃, 450 ℃ roasting 6h.The catalyst of preparation is 1#, 2#, 3#, 4#.Specific surface area of catalyst 166.2m
2/ g, 169.8m
2/ g, 166.2m
2/ g, 146.8m
2/ g.
1#, 2#, 3#, 4# catalyst to preparation are estimated, and estimating raw material is the coking liquefied gas, the results are shown in Table 2.
The catalyst performance of the different sintering temperature preparations of table 2
Embodiment 2
Take by weighing the strip gamma-aluminium oxide carrier 60g (approximately 90ml) after the moulding, quantitatively take by weighing six water nickel nitrates according to NiO content 18.0% on the final catalyst and be made into 90ml solution, at room temperature carrier is soaked in the solution 12 hours, inclining the residue soak, in 115 ℃ of oven dry; Again according to Mo on the final catalyst
2O
3Content 20.0% takes by weighing four water ammonium molybdates and is made into 90ml solution, at room temperature the carrier after the nickel-loaded is soaked in the ammonium molybdate solution 12 hours, and inclining the residue soak, in 120 ℃ of oven dry, and 350 ℃ of roasting 6h.The catalyst of preparation is 5#.Specific surface area of catalyst 150.2m
2/ g.
The 5# catalyst is estimated, and estimating raw material is the coking liquefied gas, the results are shown in Table 3.
Embodiment 3
Take by weighing the strip gamma-aluminium oxide carrier 60g (approximately 90ml) after the moulding, according to Mo on the final catalyst
2O
3Content 16% takes by weighing four water ammonium molybdates and is made into 90ml solution, at room temperature carrier is soaked in the solution 12 hours, and inclining the residue soak, in 118 ℃ of oven dry; Take by weighing six water nickel nitrates according to NiO content on the final catalyst 13.0% again and be made into 90ml solution, at room temperature the carrier behind the load molybdenum is soaked in the nickel nitrate solution 12 hours, inclining the residue soak.In 120 ℃ of oven dry, 350 ℃ of roasting 6h.The catalyst of preparation is 6#.Specific surface area of catalyst 199.8m
2/ g.
The 6# catalyst is estimated, and estimating raw material is the coking liquefied gas, and evaluation result sees Table 3.
The standby catalyst performance of table 3 active component different loads sequential system
Embodiment 4
Take by weighing the trifolium-shaped gamma-aluminium oxide carrier III 60g (approximately 90ml) after the moulding, according to Mo on the final catalyst
2O
3Content 14% takes by weighing four water ammonium molybdates and is made into 90ml solution, at room temperature carrier is soaked in the solution 6 hours, and inclining the residue soak, in 120 ℃ of oven dry; Take by weighing six water nickel nitrates according to NiO content on the final catalyst 12% again, be made into 90ml solution, at room temperature the carrier behind the load molybdenum is soaked in the nickel nitrate solution 6 hours, inclining the residue soak.In 120 ℃ of oven dry, 350 ℃ of roasting 6h.The catalyst of preparation is 7#.Specific surface area of catalyst 188.4m
2/ g.
7# is estimated, and estimating raw material is the coking liquefied gas, and evaluation result sees Table 4.
Embodiment 5
Take by weighing the gamma-aluminium oxide carrier III 60g (approximately 90ml) after the moulding, according to Mo on the final catalyst
2O
3Content 12% takes by weighing four water ammonium molybdates and is made into 90ml solution, at room temperature carrier is soaked in the solution 4 hours, and inclining the residue soak, in 120 ℃ of oven dry; Take by weighing six water nickel nitrates according to NiO content on the final catalyst 8.0% again, be made into 90ml solution, at room temperature the carrier behind the load molybdenum is soaked in the nickel nitrate solution 4 hours, inclining the residue soak.In 120 ℃ of oven dry, 350 ℃ of roasting 6h.The catalyst of preparation is 8#.Specific surface area of catalyst 192.8m
2/ g.
8# is estimated, and estimating raw material is the coking liquefied gas, and compares with 6#, 7#, and evaluation result sees Table 4.
The catalyst performance of table 4 different loads amount
Embodiment 6
Take by weighing the gamma-aluminium oxide carrier III 60g (approximately 90ml) after the moulding, according to Mo on the final catalyst
2O
3Content 12% takes by weighing four water ammonium molybdates and is made into 90ml solution, at room temperature carrier is soaked in the solution 6 hours, and inclining the residue soak, in 120 ℃ of oven dry; Take by weighing four water acetic acid nickel according to NiO content on the final catalyst 8.0% again and be made into 90ml solution, at room temperature the carrier behind the load molybdenum is soaked in the nickel nitrate solution 6 hours, inclining the residue soak.In 120 ℃ of oven dry, 350 ℃ of roasting 6h.The catalyst of preparation is 9#.Specific surface area of catalyst 190.6m
2/ g.
The 9# catalyst is estimated, and compared with 8# evaluating catalyst result, evaluation result sees Table 5.
The catalyst performance of table 5 different material preparation
Catalyst is used
Application examples 1
Refinery's coking liquefied gas raw material is directly carried out continously hydrogen adding, use respectively coking liquefied gas, coking residual C in the table 1
4Be raw material, the 6# catalyst that makes with embodiment 3 methods carries out continously hydrogen adding investigation catalyst life.Investigation the results are shown in Table 6.
The Hydrogenation of table 6 catalyst
Claims (10)
1. sulfur-bearing coking liquefied gas high-temperature hydrogenation catalyst, it is characterized in that: catalyst is take gama-alumina as carrier, and the catalyst activity component is molybdenum, nickel, in total catalyst weight 100%, contains Mo
2O
310.0% ~ 20.0%, NiO6.0% ~ 18.0%, catalyst are stripe shape, trifolium-shaped or the ball-type of Ф 3 * 3 ~ 5mm, specific area 100 ~ 200m
2/ g.
2. hydrogenation catalyst according to claim 1, it is characterized in that: the content of active component is in total catalyst weight 100%, Mo
2O
313.0% ~ 16.0%, NiO 10.0% ~ 13.0%.
3. the preparation method of the described catalyst of claim 1 is characterized in that catalyst take gama-alumina as carrier, the mode by dipping with active constituent loading on the carrier after the moulding, through oven dry, roasting makes.
4. method as claimed in claim 3 is characterized in that, active component is introduced in the mode of salting liquid, and the soluble-salt of nickel is nitrate, acetate, formates; The soluble-salt of molybdenum is ammonium molybdate.
5. method as claimed in claim 4 is characterized in that active component while or step load on carrier, make finished catalyst after drying, the roasting again.
6. method as claimed in claim 5 is characterized in that catalyst prepares step load on carrier, first load active component molybdenum, and then load active component nickel again after the oven dry make finished catalyst after drying, the roasting.
7. method as claimed in claim 5, when it is characterized in that load active component, 115 ~ 125 ℃ of bake out temperatures, 350 ~ 450 ℃ of sintering temperatures.
8. method as claimed in claim 5, when it is characterized in that load active component, 118 ~ 120 ℃ of bake out temperatures, 350 ~ 375 ℃ of sintering temperatures.
9. the application of the described catalyst of claim 1, it is characterized in that in hydrogen atmosphere, reducing before catalyst uses, first rise to 120 ℃ with 5 ℃/min, insulation 2h, rise to 300 ℃ with 5 ℃/min again, then insulation 4h is down to 180 ℃ with bed temperature in hydrogen atmosphere, be used for sulfur-bearing liquefied gas hydrogenation reaction.
10. the application process of coking liquefied gas high-temperature hydrogenation catalyst according to claim 9, it is characterized in that: the hydrogenation reaction of sulfur-bearing liquefied gas is in thermal insulation or calandria type fixed bed reactor, its process conditions are: 180 ~ 230 ℃ of feeding temperatures, 280 ~ 300 ℃ of reaction temperatures, reaction pressure 2.3 ~ 3.5MPa, volume liquid hourly space velocity (LHSV) 1.5 ~ 8.0h
-1, hydrogen/olefin molar ratio 1.2 ~ 1.8:1, olefin(e) centent all can be less than 1% behind the hydrogenation.
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| CN106268725A (en) * | 2015-08-10 | 2017-01-04 | 中国石油化工股份有限公司 | The hydrogenation catalyst of the DCPD resin of dicyclopentadiene hot polymerization and preparation method and application in cracking of ethylene carbon 9 |
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| CN106268725A (en) * | 2015-08-10 | 2017-01-04 | 中国石油化工股份有限公司 | The hydrogenation catalyst of the DCPD resin of dicyclopentadiene hot polymerization and preparation method and application in cracking of ethylene carbon 9 |
| CN106268725B (en) * | 2015-08-10 | 2018-08-21 | 中国石油化工股份有限公司 | The hydrogenation catalyst and preparation method and application of the DCPD resins of dicyclopentadiene hot polymerization in cracking of ethylene carbon 9 |
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