CN1094072C - Hydrodesulphurization method of gas containing hydrocarbon, and catalyst and its application - Google Patents
Hydrodesulphurization method of gas containing hydrocarbon, and catalyst and its application Download PDFInfo
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Abstract
The present invention relates to a hydrodesulfurization process for hydrocarbon bearing gas, a catalyst for the hydrocarbon bearing gas and the applications of the hydrodesulfurization process and the catalyst. The catalyst of the present invention uses TiO2 as a carrier, and comprises a catalyst ingredient A containing the active components of nickel and molybdenum and a catalyst ingredient B containing the active components of cobalt and the molybdenum; the ingredients A, B are used by means of series connection according to a weight ratio of A to B, which is 20 to 80: 20 to 80 in the process of the hydrodesulfurization of the gas. The present invention enables each active ingredient of the catalyst to thoroughly exert respective advantages, and has the advantages of fine activity at low temperature and outstanding comprehensive advantages of the functions of the hydrogenation saturation of alkene and the conversion and catalysis of organic sulfur so as to provide a new approach for production processes of hydrogen manufacturing and synthetic ammonia manufacturing which use refinery gas as raw material.
Description
The present invention relates to a kind of hydrodesulphurizatiomethod method of gas and catalyst and application.More specifically, the present invention relates to comprise hydrodesulphurizatiomethod method of gas containing hydrocarbon and the gas Hydrobon catalyst and the application in gas containing hydrocarbon hydrogen manufacturing, system synthetic ammonia thereof of saturated hydrocarbons or unsaturated hydrocarbons.
One of Main Ingredients and Appearance of refinery gas is a unsaturated hydrocarbons.Utilize refinery gas good and cheap, resource is abundanter.In recent years, along with a large amount of exploitations of world petroleum resource, utilize to comprise that the refinery gas of coking dry gas and catalysis gas is raw material, system synthetic ammonia, hydrogen manufacturing have been subjected to people's common concern.But following two aspect problems are arranged, are perplexing always and utilizing the development of refinery gas for raw material system synthetic ammonia, hydrogen producing technology:
The one, olefin(e) centent height in the refinery gas, olefin(e) centent about 6%～10% in the general coking dry gas, olefin(e) centent can reach more than 20% in the catalysis gas, therefore in hydrogenation process, at first hydrogenation is saturated for general alkene, and emit a large amount of heat, just can reach 23～25 ℃ such as the hydrogenation of olefins temperature rise that contains 1%.Its consequence is to make the temperature of mist rise very highly, and alkene can be tied charcoal, thereby easily causes catalysqt deactivation;
The 2nd, refinery gas contains a certain amount of organosulfur compound, is example with triumph Refinery Coking dry gas, its organic sulfur content up to more than 100 to ppm more than 1000.Be in raw material system synthetic ammonia, the hydrogen production process with the refinery gas, the catalyst poisoning after organic sulfur can make in the operation.
In addition, be that the development of raw material system synthetic ammonia, hydrogen producing technology is perplexed by above-mentioned problem too with the natural gas.
Therefore, alkene in refinery gas or the natural gas and organic sulfur all need hydro-conversion and remove.But under the high situation of olefin(e) centent, want the harmful poisonous substance organic sulfur in these unstripped gas is dropped to below the 0.5ppm, can not poison with the catalyst in the assurance subsequent handling is the comparison difficulty.Prior art has been developed multiple process and the corresponding catalyst that is used for alkene and organic sulfur hydrogenation catalyst, comprises the similar catalyst of selling on the market.These catalyst all are that cobalt, nickel, three kinds of active constituents of molybdenum are supported on the alumina support and make.Employing waits two kinds of hotbed, adiabatic reactors on catalyst loading pattern.But the effect of every kind of active constituent of these catalyst can not be given full play to, and low temperature active is poor, can not adapt to the higher gas of olefin(e) centent, in case olefin(e) centent＞6%, common adiabatic reactor just can't use, and must select for use the expensive hotbed that waits to operate.
CN 1134312A (application number 95111160.4) discloses a kind of organic sulfur hydrolyst, but its desulfurization conversion ratio has only 90%, and the organic sulfur after the desulfurization falls less than below the 0.5ppm, and this catalyst more can not make hydrogenation of olefins be converted into saturated hydrocarbons.
WO 96/14152 is that CN 94100087 discloses and a kind of cobalt, two kinds of active constituents of molybdenum is supported on the Hydrobon catalyst of making on the titanium dioxide carrier.Compare with the similar catalyst that with the aluminium oxide is carrier, though this catalyst has had outstanding characteristics and effect, for example cryogenic property is good, and is described as its industrial applicability experimental example 1, and its desulfurization conversion ratio has only 90%.And it does not disclose that this catalyst is used for the refinery gas is the coking dry gas of raw material and the catalysis gas applicable cases at system synthetic ammonia, process for making hydrogen.
One of purpose of the present invention, overcome above-mentioned the deficiencies in the prior art exactly, a kind of hydrodesulphurizatiomethod method of gas containing hydrocarbon is provided, make that hydrogenation of olefins is saturated and organic sulfur conversion catalyst function synthesized advantage outstanding, make it to adapt to alkene and the higher gas of organic sulfur content, can adapt to various technological process and equipment.
Two of purpose of the present invention, provide a kind of bicomponent catalyst that is used for the gas containing hydrocarbon hydrodesulfurization, this catalyst is strong to the adaptability of raw material, low temperature active is good, every kind of active constituent of catalyst can be given full play to advantage separately, and saturated and organic sulfur conversion catalyst function synthesized advantage is outstanding for hydrogenation of olefins.
Three of purpose of the present invention provides the application of gas containing hydrocarbon hydrodesulfurization bicomponent catalyst in gas containing hydrocarbon hydrogen manufacturing, system synthetic ammonia.For with the refinery gas be raw material hydrogen manufacturing, the system synthetic ammonia production technology open up a new way.
The present invention is achieved in that
The raw material of one of the present invention's hydrodesulphurizatiomethod method of gas containing hydrocarbon also comprises saturated hydrocarbons or unsaturated hydrocarbons except that hydrogen; The used catalyst of this method is with TiO
2Be carrier, comprise nickeliferous, molybdenum active component component A, be Ni-Mo/TiO
2And contain cobalt, molybdenum active component B component, be Co-Mo/TiO
2Above-mentioned bicomponent catalyst A, the B use of in gas containing hydrocarbon hydrodesulfurization process, connecting, the weight ratio of A and B is A: B=20～80: 20～80, preferred A, B weight ratio are A: B=30～50: 50～70.
During concrete enforcement if at same reactor, such as adiabatic reactor, above-mentioned Ni-Mo/TiO
2Can be contained in the upper strata of reactor, Co-Mo/TiO
2Be contained in the lower floor of same reactor, also can adopt Co-Mo/TiO
2Be contained in above the reactor Ni-Mo/TiO
2Be contained in below the reactor.
During concrete enforcement if not in same reactor, above-mentioned Ni-Mo/TiO
2Can be contained in the isothermal bed bioreactor, and Co-Mo/TiO
2Then can be contained in the adiabatic reactor reactor of contacting with the isothermal bed bioreactor.
Concrete when implementing method of the present invention, in weight ratio, described titania support contains 60～100% TiO
2With 0～40% Al
2O
3, its specific area is 20～200m
2/ g, pore volume are 0.3～0.5ml/g, and Side pressure degree is 70～240N/cm, can several apertures be 60～200 dusts; Among the described catalytic component A, be 1～5% in the nickel content of NiO, with MoO
3The molybdenum content of meter is 5～10%; Among the catalytic component B, be 1～3% in the cobalt content of CoO, with MoO
3The molybdenum content of meter is 5～10%.
Hydrodesulphurizatiomethod method of gas containing hydrocarbon of the present invention is with that in mind:
From course of reaction, the hydrogenation of olefins saturation ratio is easier to, than just carrying out under the low reaction temperatures.And the reaction of organic sulfur hydro-conversion generally just can carried out more than 250 ℃.Along with reaction temperature raises, it is more thorough that reaction is carried out.Based on this response feature, the present invention can be at reactor upper strata filling Ni-Mo/TiO
2Catalyst, i.e. catalytic component A, the filling Co-Mo/TiO of reactor lower floor
2Catalyst, i.e. catalytic component B.Gas containing hydrocarbon enters from the reactor upper strata, carries out the saturated and fraction organic sulfur conversion of hydrogenation of olefins earlier.Along with the carrying out of olefin saturation, bed temperature improves gradually, generally rises to 380 ℃ from 240.Like this, about 360～380 ℃, this is the suitable temperature of organic sulfur hydrogenation reaction to reactor lower floor temperature just.Based on same reason, if refinery gas enters from reactor lower floor, otherwise the loading position of A, B then.
If the type of feed of hotbeds such as employing, adiabatic reactor, catalyst of the present invention such as can be contained in catalytic component A at hotbed, catalytic component B is contained in adiabatic reactor.
This shows, adopt above-mentioned scientific and reasonable catalyst loading pattern, can make that olefin(e) centent is not subjected to any restriction in the gas containing hydrocarbon, the heat that takes place in the hydrogenation of olefins saturation history is removed by thermophore, thereby keeping reaction temperature is a steady state value, can give full play to the effect of catalyst like this.This is to prolonging catalyst life, and it is all extremely favourable to improve catalyst utilization.
Simultaneously, method of the present invention is utilized catalytic component A, i.e. Ni-Mo/TiO
2Catalytic component has good hydrogenation of olefins catalytic capability and certain organic sulfur hydrogenation catalyst ability at low temperatures, can make most of hydrogenation of olefins saturated, low amounts of organic sulfur is transformed, and produce big calorimetric; And catalytic component B, i.e. Co-Mo/TiO
2Catalytic component has good organic sulfur hydrogenation catalyst function, and the saturated catalytic capability of hydrogenation of olefins is preferably also arranged under higher temperature.
Therefore, these two kinds of catalyst are had complementary advantages under different operating modes, and the levels that is contained in same reactor can better fit.This in a reactor, the method for two kinds of catalyst of filling is a kind of innovation in refinery gas hydrogen manufacturing, system ammonia synthesis process technology.Certainly, catalyst is contained in different reactor, is Ni-Mo/TiO
2Be contained in the isothermal bed bioreactor and Co-Mo/TiO
2Be contained in the adiabatic reactor reactor of contacting, can reach above-mentioned effect too with the isothermal bed bioreactor.Therefore method of the present invention can adapt to various technological requirement.
The bicomponent catalyst of the present invention's two gas containing hydrocarbon hydrodesulfurization is with TiO
2Be carrier, comprise nickeliferous, molybdenum active component component A, be Ni-Mo/TiO
2And contain cobalt, molybdenum active component B component, be Co-Mo/TiO
2
Above-mentioned titania support can contain 60～100% TiO during concrete enforcement in weight ratio
2With 0～40% Al
2O
3, its specific area is 20～200m
2/ g, preferred 60～120m
2/ g, pore volume are 0.3～0.5ml/g, and Side pressure degree is 70～240N/cm, can several apertures be 60～200 dusts, and its scope also can be controlled narrower, for example is 80～100 dusts or 100～120 dusts.During concrete enforcement among the above-mentioned catalyst catalytic component A by weight, be 1～5% in the nickel content of NiO, with MoO
3The molybdenum content of meter is 5～10%; Among the above-mentioned catalytic component B, be 1～3% in the cobalt content of CoO, with MoO
3The molybdenum content of meter is 5～10%.
Bicomponent catalyst of the present invention in use, if in same reactor, above-mentioned Ni-Mo/TiO
2Can be contained in the upper strata of reactor, Co-Mo/TiO
2Be contained in the lower floor of same reactor, vice versa; If not in same reactor, above-mentioned Ni-Mo/TiO
2Can be contained in the isothermal bed bioreactor, and Co-Mo/TiO
2Then can be contained in the adiabatic reactor reactor of contacting with the isothermal bed bioreactor.Be seated in this way in the reactor, can make the good effect of its performance.
Below catalyst of the present invention is described further:
(1) selection of carrier
The applicant has selected with TiO at last through further investigation for many years
2Carrier is as gas containing hydrocarbon and organic sulfur catalyst carrier for hydrgenating.Make carrier with it, catalyst has good low temperature active and advantages of high catalytic activity, is particularly suitable for alkene and organic sulfur hydroconversion catalyst.The physical and chemical indexes of this carrier is as follows: 1. 2. 3. 4. specific area (m of crush strength (N/cm) 60～120 of hydroscopicity (%) 35～55 of bulk density (g/ml) 0.65～0.85
2/ g) 95～150 5. pore volume (ml/g) 0.30～0.50 6. can several apertures (dust) 60～120
(2) active constituent is selected
Find according to document announcement and our practical work experience: the catalyst of Ni-Mo system has good hydrogenation of olefins saturability and organic sulfur hydrocon version functionality preferably; The catalyst of Co-Mo system has good organic sulfur hydrocon version functionality and hydrogenation of olefins saturability preferably.
The Ni-Mo/TiO of catalyst A component of the present invention
2In NiO, MoO
3Content is by weight respectively in 1～5% and 5～10% scope.
The Co-Mo/TiO of catalyst B component of the present invention
2In CoO, MoO
3Content is by weight respectively in 1～3% and 5～10% scope.
(3) preparation method's selection
Use TiO
2Preparing carriers alkene of the present invention and organic sulfur hydrogenation catalyst can be by following arbitrary methods: 1. dry pigmentation; 2. coprecipitation; 3. infusion process.
The preferred infusion process of the present invention.
Described infusion process is to make the TiO that meets the catalyst requirement earlier
2Carrier prepares dipping solution again, carrier is placed in the maceration extract soaks altogether then.Its advantage is that method is easy, and reappearance is strong.
(4) catalyst soakage condition
The selection of catalyst soakage condition will directly influence the loading of catalyst activity component.
The amount of the active constituent that supports on the catalyst is mainly determined by the hygroscopicity of titanium carrier.But, the concentration of maceration extract, dipping temperature, dip time are influential to supporting of active constituent.After carrier was determined, its hygroscopicity was also definite substantially.In the case, nickel, cobalt, molybdenum active component content and impregnation concentration are good linear relationship on the catalyst.
The relation of table 1 impregnation concentration and catalyst activity component nickel, molybdenum content
The relation of table 2 impregnation concentration and catalyst activity component cobalt, molybdenum content
Annotate: above-mentioned test, control maceration extract temperature is at 40～45 ℃, and dip time is 2 hours,
In the present invention, the concentration of maceration extract is preferably:
Preparation catalytic component A:Ni, 4.3～6.5g/100ml, MoO
3, 8～24g/100ml;
Preparation catalytic component B:Co, 1.5～3.0g/100ml, MoO
3, 8～16g/100ml.
The character of raw material nickel nitrate, cobalt nitrate and ammonium molybdate used according to the invention, when the preparation catalyst impregnating solution, good step of GPRS and maceration extract temperature avoid ammonia to volatilize in a large number, cause the maceration extract instability, cause active constituent to be separated out.
Table 3 dipping temperature and catalyst activity component NiO, MoO
3The relation of content
| Numbering | Dipping temperature (℃) | Impregnation concentration | Catalyst activity component | |||
| Ni(g/100ml) | MoO 3(g/100ml) | NiO％ | MoO 3％ | |||
| N-1 | ＜27 | 5.20 | 19.50 | Solubilizing poorly has crystallization | ||
| N-2 | 30 | 5.20 | 19.50 | 4.45 | 7.25 | |
| N-3 | 35 | 5.20 | 19.50 | 4.15 | 7.41 | |
| N-4 | 40 | 5.20 | 19.50 | 4.78 | 7.87 | |
| N-5 | 45 | 5.20 | 19.50 | 4.98 | 7.92 | |
| N-6 | ＞50 | 5.20 | 19.50 | The ammoniacal liquor volatilization, instability | ||
Table 4 dipping temperature and catalyst activity component Co, MoO
3The relation of content
| Numbering | Dipping temperature (℃) | Impregnation concentration | Catalyst activity component | ||
| Co(g/100ml) | MoO 3(g/100ml) | Co％ | MoO 3％ | ||
| H-1 | ＜27 | 1.3 | 10 | Solubilizing poorly has crystallization | |
| H-2 | 35 | 1.3 | 10 | 1.17 | 7.93 |
| H-3 | 40 | 1.3 | 10 | 1.12 | 7.74 |
| H-4 | 45 | 1.3 | 10 | 1.17 | 7.78 |
| H-5 | ＞50 | 1.3 | 10 | Ammonia volatilization, instability | |
Annotate: above-mentioned test control dip time is 2 hours
Among the present invention, preferred dipping temperature is 30～50 ℃, more preferably 38～45 ℃.If temperature is lower than 27 ℃, the active constituent solubilizing poorly has crystal to exist; Dipping temperature is higher than 50 ℃, and ammonia is volatile, the maceration extract instability.
The relation of table 5 dip time and catalyst activity component content
| Numbering | Dip time (hour) | Impregnation concentration | Catalyst activity component | ||
| Ni(g/100ml) | MoO 3(g/100ml) | NiO％ | MoO 3％ | ||
| C-1 | 1 | 4.2 | 16.1 | 3.34 | 8.50 |
| C-2 | 1.5 | 4.2 | 16.1 | 3.35 | 8.52 |
| C-3 | 2 | 4.2 | 16.1 | 3.36 | 8.55 |
| C-4 | 3 | 4.2 | 16.1 | 3.36 | 8.56 |
| C-5 | 5 | 4.2 | 16.1 | 3.38 | 8.58 |
Annotate: above-mentioned test control dipping temperature is 45 ℃
Dip time should guarantee that catalyst activity component can be penetrated into the inside of carrier, avoids catalyst to grow dim, and considers the production cycle of catalyst simultaneously.For example when preparation catalytic component A, dip time can be 1～5 hour, is preferably 2～3 hours.
(5) catalyst drying and activation condition
Dry and the activation of catalyst plays a part very important in Preparation of catalysts.Therefore, the moist catalysis behind the dipping is wanted strict control drying condition (programming rate, baking temperature, dry atmosphere, drying time), points out in many documents and will could guarantee the quality of catalyst in strict accordance with DTA, TGA curve manipulation.
Drying condition of the present invention is preferably: baking temperature is 50～150 ℃, is preferably 80～110 ℃; Be 4～16 hours drying time, is preferably 8～10 hours.
Dried catalyst (strictly say and should claim that it is a procatalyst this moment) must activation.Activation mainly is the decomposition of inorganic salts, is again active constituent miniaturization process.Therefore, activation temperature must be greater than the decomposition temperature of the inorganic salts that flood up (active constituent).In addition, also to consider the length of high temperature section constant temperature time, whether favourable to specific surface, the pore structure of keeping titanium carrier, favourable to the microcrystal miniaturization of active constituent.Catalyst activation temperature of the present invention is preferably 300～600 ℃, more preferably 400～500 ℃, most preferably is 450～500 ℃.Soak time is 2～8 hours, and wherein the high-temperature activation time is preferably 2～2.5 hours.Activation phenomenon is an oxidizing atmosphere.
Specifically, the component A of alkene of the present invention and organic sulfur hydrogenation catalyst and B can prepare by following method:
1. choose the TiO that contains weight ratio 60～100%
2With 0～40% Al
2O
3Carrier, this carrier specific area is 20～200m
2/ g, pore volume are 0.3～0.5ml/g, and Side pressure degree is 70～240N/cm, can several apertures be 60～200 dusts.
2. the solid ammonium molybdate is dissolved in the ammoniacal liquor, adds the nickel nitrate dissolving down at 30～60 ℃ then, fully stir, add the stabilizing agent ethylenediamine, continue again to stir, be mixed with active component Ni and MoO
3Weight ratio be 0.1～1.2 maceration extract.
3. the solid ammonium molybdate is dissolved in the ammoniacal liquor, adds the cobalt nitrate dissolving down at 30～50 ℃ then, fully stir, add the stabilizing agent ethylenediamine, continue again to stir, be mixed with active component Co and MoO
3Weight ratio be 0.1～0.85 maceration extract.
4. the carrier that 1. step is chosen places the described maceration extract 2. under the room temperature to 50 ℃, flooded 1～5 hour, after Separation of Solid and Liquid, 60～150 ℃ dry 4～16 hours down, 300 ℃～600 ℃ activation 1～6 hour down, make catalytic component A then.
5. the carrier that 1. step is prepared places the described maceration extract 3. under the room temperature to 50 ℃, flooded 1～5 hour, after Separation of Solid and Liquid, drying is 4～16 hours under 50～120 ℃, activate 1～6 hour down at 300 ℃～600 ℃ then, make catalytic component B.
In above-mentioned preparation method, the titania support that uses can be according to WO 96/14152 preparation, and preferably be shaped to the titania support of the trifolium-shaped of φ 3 * 3～10mm, also can need, select the titania support of any size dimension between φ 1.2～φ 3.0 for use according to the user.
Described catalytic component A and B preferably adopt dynamic infusion process.The titania support that is about to select for use places in the stainless steel hanging basket, immerses maceration extract respectively 2. or 3., makes maceration extract be in flow regime, and dipping temperature is a room temperature to 60 ℃, is preferably 35 ℃～50 ℃.Dip time is 1～5 hour, and the preferred time is 1～2.5 hour.After dipping finishes, the stainless steel hanging basket is mentioned, carry out Separation of Solid and Liquid, the catalyst after the separation carries out drying under 50～150 ℃, preferably carry out drying at 60～110 ℃.Dried catalyst activates under 300 ℃～600 ℃, and preferably 400～500 ℃ of activation down, soak time is 1～6 hour, preferred 2～3 hours.The cooling naturally of activation back promptly obtains alkene and organic sulfur hydrogenation catalyst A and B.
The present invention further provides activity rating method by the gas containing hydrocarbon Hydrobon catalyst of method for preparing.
The inventor confirms after deliberation: gas containing hydrocarbon Hydrobon catalyst of the present invention has good low temperature active and the very high saturated and organic sulfur conversion catalyst function of hydrogenation of olefins.Its activity rating program is as follows:
Coking dry gas with the triumph oil plant is an example, and gas containing hydrocarbon is through alkali cleaning and MnO
2Enter preheater after the desulfurization, before preheater, replenish H
2, the flow velocity of unstripped gas and hydrogen is controlled with control valve, and preheat temperature is adjustable, thereby can control the gas access temperature of reactor.Mist in reactor with the hydrogenation catalyst haptoreaction, and then enter ZnO desulfurizing agent bed, all inorganic sulfur (H
2S) all removed by the ZnO desulfurizing agent.The gas that comes out from reactor passes through cooler, and gas-liquid separation is after pressure-reducing valve enters gas flowmeter metering, emptying then.Described preheater can be electrical heating type, uses SCR control, makes it reach assigned temperature.Its sulfur content of gas-sample analysis, olefin(e) centent, H before the emptying
2Content is to calculate the conversion ratio of alkene and organic sulfur.
Analytical instrument in the evaluation procedure comprises:
(1) BSD-05 type wet gas flow meter is adopted in unstripped gas metering;
(2) decide sulphur content and analyse employing WKL-3 Microcoulomb instrument;
(3) the GC-14B gas chromatograph is adopted in the alkene analysis;
(4) the SP-502 gas chromatograph is adopted in the hydrogen content analysis.
Evaluation result is listed in table 6
Table 6
From table 6 evaluation result as can be seen:
| Sequence number | Air speed (time -1) | Reaction temperature (℃) | Response analysis H 2％ | Inlet | Outlet | |||
| Inlet | Focus | ∑C＝％ | ∑Sppm | ∑C＝％ | ∑Sppm | |||
| 1 | 500 | 240.0 | 351.0 | 11.3 | 5.10 | 120.0 | 0.01 | 0.2 |
| 2 | 500 | 242.0 | 370.0 | 11.5 | 5.50 | 132.0 | 0.03 | 0.2 |
| 3 | 1000 | 253.0 | 361.0 | 14.3 | 4.60 | 152.4 | 0.05 | 0.3 |
| 4 | 1000 | 250.0 | 364.8 | 12.8 | 4.80 | 150.0 | 0.04 | 0.3 |
| 5 | 1000 | 240.0 | 380.3 | 15.2 | 6.40 | 1068.6 | 0.27 | 1.1 |
| 6 | 1000 | 240.0 | 383.1 | 14.8 | 6.80 | 1182.0 | 0.26 | 1.8 |
| 7 | 1200 | 251.0 | 380.0 | 13.8 | 5.80 | 135.5 | 0.15 | 0.4 |
| 8 | 1200 | 254.0 | 383.0 | 14.1 | 5.50 | 151.0 | 0.16 | 0.3 |
1. gas containing hydrocarbon Hydrobon catalyst of the present invention, olefin(e) centent in unstripped gas＜7%, H
2Content is 11-15%, under the condition of organic sulfur content≤150ppm, can make olefin(e) centent in the exit gas≤0.04%, organic sulfur content＜0.4ppm.Even under the condition of sulfur content＞150ppm, good effect is arranged also.
2. gas containing hydrocarbon Hydrobon catalyst of the present invention has fabulous transformation function to organic sulfur, even when air speed 1000
-1, under the situation of organic sulfur content up to 1182ppm, conversion ratio still reaches 99.85%.If reduce at 500 o'clock
-1, can guarantee to export organic sulfur content＜0.5ppm.
The present invention's three is that catalyst of the present invention makes the application in wherein contained alkene and the organic sulfur hydro-conversion with the gas containing hydrocarbon when being raw material hydrogen manufacturing, system synthetic ammonia.During concrete enforcement, can load two kinds of catalyst of A, B respectively in the levels of same reactor, these two kinds of catalyst are had complementary advantages under different operating modes, can better fit.Also catalyst can be contained in different reactor, be Ni-Mo/TiO
2Be contained in the isothermal bed bioreactor and Co-Mo/TiO
2Be contained in the adiabatic reactor reactor of contacting, also can all be contained in the cold H of adiabatic reactor with the isothermal bed bioreactor
2Reaction heat is removed in circulation, can reach above-mentioned effect equally.This method is a kind of innovation in refinery gas hydrogen manufacturing, system ammonia synthesis process technology.Method of the present invention can adapt to the technology of various different alkene and organic sulfur hydro-conversion.
Embodiment
Following examples will be further described the present invention, but not will be understood that and limit the scope of the present invention.
The preparation of embodiment 1. titania supports
(1) preliminary treatment: commercially available low-grade titanium white raw material is through acid treatment, hydrolysis gets titanium oxide, and making its pH through washing is 7.0 ± 0.5, dries by the fire 8-14 hour under 110 ± 10 ℃ of temperature then, pulverize again for＜150 purpose powders standby (need not dry, adopt spray-drying also can).
(2) batching processing: 100 parts of the titanium oxides that usefulness (1) makes add 5% sesbania powder, 0.3% zinc carbonate, with the abundant mixing of blender, add 3% alumina gel then, fully mediate, extrusion was cut into trifolium-shaped or the column type bar of φ 3 * 4～8mm, 110 ± 10 ℃ of bakings 8-12 hour.
(3) roasting: above-mentioned article shaped is sent into roasting in the Muffle furnace, at 0～50mmH
2Under the O negative pressure,, promptly obtain titania support of the present invention in 450～550 ℃ of roastings 4～5 hours.
The preparation of embodiment 2. titania supports
(1) preliminary treatment: it is standby to prepare powder as the same program of embodiment 1.
(2) batching processing: with 80 parts of the titanium oxides that makes in the present embodiment (1), add 20 parts of aluminum oxides, add 5% sesbania powder again, with the abundant mixing of blender, adding 5% nitric acid then mediates for 40 parts, be extruded into trifolium-shaped or the column type bar of φ 3 * 3～10mm again, 110 ± 10 ℃ of bakings 8-14 hour.
(3) roasting: send roasting in the Muffle furnace with above-mentioned trifolium-shaped or column type bar, 450～550 ℃ of temperature, roasting 4～5 hours promptly gets titania support.
The preparation of embodiment 3 catalytic component A
(1) maceration extract preparation: earlier 27 gram ammonium molybdates are dissolved in 16% the ammoniacal liquor of 90ml, add 21 gram nickel nitrates down at 40～50 ℃ then, stir, it is fully mixed, add the 1.4ml ethylenediamine again, continue to stir, obtain containing the maceration extract of the active component of needs.
(2) Preparation of Catalyst: φ 3 * 4～8mm carrier 100 grams that embodiment 1 is made place in the stainless steel hanging basket, put into above-mentioned maceration extract, constantly move up and down 40～50 ℃ of dipping temperatures, dip time 2 hours in water-bath.Dipping finishes, and hanging basket is mentioned, and drains solution, then moist catalysis is put into the oven dry of baking railway carriage or compartment, 80～110 ℃ of baking temperatures, 8～10 hours drying times; Dried catalyst is put into Muffle furnace and is activated, 450～500 ℃ of activation temperatures, and soak time 2 hours promptly gets catalytic component A, and Ni content counts 3.1% by weight in this catalyst, MoO
3Content counts 8.3% by weight.
(3) activity rating:
Adopt adiabatic reactor as the activity rating device, evaluation result is listed in table 7:
Table 7
| Sequence number | During air speed-1 | Reaction temperature (℃) | Inlet | Outlet | |||
| Inlet | Focus | ∑C＝％ | ∑Sppm | ∑C＝％ | ∑Sppm | ||
| 1 | 1000 | 247 | 380 | 6.18 | 150.1 | 0.02 | 0.31 |
| 2 | 1000 | 241 | 372 | 5.60 | 148.1 | 0.01 | 0.30 |
| 3 | 1000 | 260 | 362 | 4.30 | 125.1 | 0.01 | 0.42 |
| 4 | 1000 | 249 | 343 | 7.20 | 192.7 | 0.08 | 0.59 |
| 5 | 1000 | 250 | 326 | 6.20 | 183.3 | 0.02 | 0.43 |
The preparation of embodiment 4. catalytic component B
(1) maceration extract preparation: 38 gram ammonium molybdates are dissolved in the ammoniacal liquor of 160ml 16%, 21 gram cobalt nitrates are dissolved in the 20ml water, then under agitation, cobalt nitrate solution is added in the ammonium molybdate solution, and heating remains between 40-50 ℃, add an amount of ethylenediamine as stabilizing agent, continue to stir, obtain activity component impregnation liquid.
(2) Preparation of Catalyst: φ 3 * 3-10mm carrier 100g that embodiment 2 is made, place in the stainless steel hanging basket, put into above-mentioned maceration extract, in water-bath, constantly move up and down, 40-50 ℃ of maceration extract temperature, dip time 2 hours after dipping finishes is mentioned hanging basket, drain, then moist catalysis is put into the oven dry of baking railway carriage or compartment, baking temperature 80-110 ℃, 8-10 hour drying time, dried catalyst is put into Muffle furnace and is activated, activation temperature 450-550 ℃, soak time is 2-2.5 hour, promptly gets catalyst B, containing the Co weight ratio in this catalyst is 1.5%, contains MoO
3Weight ratio is 8.6%.
(3) activity rating:
With thiophene is probe, measures according to the HG/T2514 standard.
Catalyst activity component cobalt, molybdenum are measured according to the HG/T2515 standard.
Evaluation result sees Table 8:
Table 8
| Numbering | Active constituent | Thiophene conversion ratio under the different temperatures | The presulfurization condition | |||
| Co％ | MoO 3％ | 250℃ | 300℃ | 350℃ | ||
| GC-1 | 1.20 | 7.56 | 70.1 | 78.3 | 88.5 | Not presulfurization |
| 67.4 | 74.1 | 96.1 | Presulfurization | |||
| GC-2 | 1.50 | 8.25 | 71.6 | 85.3 | 91.1 | Not presulfurization |
| 67.8 | 75.6 | 100 | Presulfurization | |||
| GC-3 | 1.80 | 9.86 | 85.6 | 89.2 | 96.5 | Not presulfurization |
| 75.6 | 89.0 | 100 | Presulfurization | |||
Saturated and the organic sulfur hydrogenation commercial plant sideline test of embodiment 5. refinery gas hydrogenation of olefins.
Test is raw material (a triumph oil plant) with the coking dry gas, carries out alkene and the evaluation of organic sulfur hydrogenation side line with the catalyst A and the B of preparation in embodiment 3 and 4.Olefin(e) centent in raw material≤7%, H
2Content＞10% under the condition of organic sulfur content≤150ppm, can make exit gas olefin(e) centent＜0.5%, organic sulfur content＜0.5ppm; Even when air speed 1000
-1, under the situation of organic sulfur content up to 1182ppm, the organic sulfur conversion ratio still reaches 99.85%, and the circulation H in the operation
2Amount is significantly smaller than similar catalyst.The side line evaluation shows that catalyst of the present invention has high-speed, and the bed inlet temperature is low, and the hydrogenation of olefins saturability is good, organic sulfur hydro-conversion ability advantages of higher.
Embodiment 6. carries out commercial Application on device for producing hydrogen.
At the oil plant 20000NM of Maoming petro-chemical corporation
3On/time the device for producing hydrogen,, carry out commercial Application with the catalyst of preparation in embodiment 3 and 4 anti-201 reactors of packing into.Wherein catalytic component A filling is 3.75 tons, and 9.70 tons of catalytic component B fillings amount to 15.4m
3Operation result shows, this catalyst is saturated thoroughly to hydrogenation of olefins, organic sulfur conversion ratio height, now the commercial Application situation is listed in the table below: (gas composition is the gaseous mixture of hydrocracking dry gas and coking dry gas, hydrocracking dry gas wherein: coking dry gas=1: 1 adds part light oil again and carries out hydrogen manufacturing).
Table 9 catalyst commercial Application of the present invention situation
| The test sequence number | Air speed (h - 1) | Reaction temperature (℃) | Unstripped gas | Interpretation of result | |||||
| Inlet | Focus | H 2S ppm | ∑C＝ ％ | H 2 ％ | H 2S ppm | ∑C＝ ％ | H 2 ％ | ||
| 6-1 | 260 | 360 | 2.54 | 68.97 | 0.09 | 60.72 | |||
| 7-1 | 280 | 240 | 364 | 10 | 3.04 | 66.25 | 100 | 0.28 | 63.03 |
| 8-1 | 280 | 240 | 372 | 20 | 2.53 | 58.42 | 750 | 0 | 55.25 |
| 8-2 | 280 | 240 | 369 | 20 | 4.12 | 58.58 | 1100 | 0.96 | 55.93 |
| 8-3 | 280 | 240 | 364 | 20 | 2.64 | 64.80 | 1000 | 0 | 62.31 |
| 9-1 | 280 | 240 | 362 | 20 | 3.44 | 59.93 | 2700 | 0 | 55.03 |
| 9-2 | 280 | 240 | 355 | 18 | 3.19 | 58.72 | 1050 | 0 | 55.05 |
| 9-3 | 280 | 240 | 394 | 50 | 4.16 | 57.94 | 900 | 0.21 | 57.42 |
| 10-1 | 280 | 240 | 348 | 22 | 2.40 | 55.56 | 500 | 0 | 54.00 |
| 10-2 | 280 | 240 | 381 | 15 | 3.95 | 54.66 | 650 | 0 | 53.65 |
Annotate: (1) can only be represented with the hydrogen sulfide that enters the reactor front and back because organic sulfur can't be analyzed.For example: inlet hydrogen sulfide 10ppm, outlet 100ppm, the hydrogen sulfide increase thinks that the organic sulfur conversion obtains this part hydrogen sulfide, behind subsequent reactor (anti-202/1-2) zinc oxide desulfurization hydrogen, outlet hydrogen sulfide is zero.(2) air speed in the table only is a gas space velocity.
As being that the similar catalyst of carrier is used under conditions of similarity with the aluminium oxide, about 40 ℃ of the corresponding height of inlet temperature, air speed is little about one times, and the hydrogen internal circulating load increases about 50%.
From the commercial Application situation,, utilize coking gas 265832NM to move calculating in 100 hours
3, 18373 tons in light oil is saved in conversion.
Embodiment 7. is that raw material (saturated hydrocarbons) carries out commercial Application at natural gas.
On 1.5 ten thousand tons of/year synthetic ammonia installations of Chongqing alkali amine industry parent company, load 1.67 tons of Type B catalyst.Unstripped gas is for containing CH
497.4%.Reaction temperature is that 230～280 ℃, pressure are 1.1～1.5Mpa.Air speed is 400～1000 o'clock
-1, natural gas via transforms the back organic sulfur content can be less than 0.05ppm, and this catalyst moves 4 years 06 months on commercial plant, do not carry out regeneration, and also non-resistance changes.
In sum, hydrodesulphurizatiomethod method of gas containing hydrocarbon of the present invention makes every kind of active constituent of catalyst can give full play to separately advantage, can adapt to the higher gas of alkene and organic sulfur content, can adapt to various technological process and equipment; Gas containing hydrocarbon hydrodesulfurization bicomponent catalyst of the present invention is strong to the adaptability of raw material, and low temperature active is good, and hydrogenation of olefins is saturated and organic sulfur conversion catalyst function synthesized advantage outstanding; Purposes of the present invention is for being that the hydrogen manufacturing of raw material, the production technology of system synthetic ammonia open up a new way with refinery gas etc.
Claims (7)
1. hydrodesulphurizatiomethod method of gas containing hydrocarbon, it is characterized in that: the raw material of this method also comprises saturated hydrocarbons or unsaturated hydrocarbons except that hydrogen; In weight ratio: the used catalyst carrier of this method contains 60～100% TiO
2With 0～40% Al
2O
3, that described catalyst also comprises is nickeliferous, the catalytic component A of molybdenum active component, be Ni-Mo/TiO
2And contain cobalt, molybdenum active component catalytic component B, be Co-Mo/TiO
2Among the described catalyst component A, be 1～5% in the nickel content of NiO, with MoO
3The molybdenum content of meter is 5～10%, among the catalytic component B, is 1～3% in the cobalt content of CoO, with MoO
3The molybdenum content of meter is 5～10%; Above-mentioned bicomponent catalyst A, the B use of connecting in gas containing hydrocarbon hydrodesulfurization process, the weight ratio of A and B is A: B=20～80: 20～80.
2. the method for claim 1 is characterized in that: described Ni-Mo/TiO
2Be contained in the isothermal bed bioreactor, Co-Mo/TiO
2Be contained in the adiabatic reactor reactor of contacting, perhaps Ni-Mo/TiO with the isothermal bed bioreactor
2, Co-Mo/TiO
2Layering is contained in the same adiabatic reactor.
3. the method for claim 1, it is characterized in that: described bicomponent catalyst A, B weight ratio are A: B=30～50: 50～70.
4. catalyst that is used for the gas containing hydrocarbon hydrodesulfurization is characterized in that: in weight ratio: this catalyst carrier contains 60～100% TiO
2With 0～40% Al
2O
3That described catalyst also comprises is nickeliferous, the component A of molybdenum active component, be Ni-Mo/TiO
2And contain cobalt, molybdenum active component B component, be Co-Mo/TiO
2Among the described catalytic component A, be 1～5% in the nickel content of NiO, with MoO
3The molybdenum content of meter is 5～10%, among the catalytic component B, is 1～3% in the cobalt content of CoO, with MoO
3The molybdenum content of meter is 5～10%, and the weight ratio of A and B is A: B=20～80: 20～80.
5. catalyst as claimed in claim 4, it is characterized in that: described carrier specific area is 20～200m
2/ g, pore volume are 0.3～0.5ml/g, and Side pressure degree is 70～240N/cm, can several apertures be 60～200 dusts.
6. catalyst as claimed in claim 5, it is characterized in that: wherein said carrier specific area is 60～120m
2/ g.
7. when with the hydro carbons being raw material hydrogen manufacturing, system synthetic ammonia, make application in wherein contained alkene and the organic sulfur hydro-conversion as the catalyst of one of claim 4～6.
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|---|---|---|---|---|
| US8664459B2 (en) | 2008-03-31 | 2014-03-04 | Air Products And Chemicals, Inc. | Process for hydrogenating olefins |
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| CN100363100C (en) * | 2004-02-16 | 2008-01-23 | 杨典明 | Desulfur catalyst |
| CN101173184B (en) * | 2006-11-01 | 2013-01-09 | 中国石油化工股份有限公司 | Selective hydrogenation desulfurization method for bastard gasoline |
| CN101816939B (en) * | 2009-02-27 | 2013-12-25 | 中国石油化工股份有限公司 | Catalyst for selective hydrodesulfurization and preparation method thereof |
| CN103272610B (en) * | 2013-06-08 | 2015-09-30 | 沈炳龙 | A kind of titanium base fine desulfurization catalyst and preparation method thereof and using method |
| CN105273756B (en) * | 2014-06-18 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of grading method of catalyst of coking dry gas preparing ethylene cracking material by hydrogenation |
| CN106552639A (en) * | 2016-11-29 | 2017-04-05 | 湖北荟煌科技有限公司 | A kind of hydrodesulfurization catalyst and its preparation method and application |
| CN112742403B (en) * | 2019-10-31 | 2023-03-28 | 中国石油化工股份有限公司 | Natural gas hydrodesulfurization catalyst and preparation method and application thereof |
| CN112742408B (en) * | 2019-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Dry gas hydrogenation saturated olefin and desulfurization catalyst, and preparation method and application thereof |
| CN114149835A (en) * | 2021-12-08 | 2022-03-08 | 浙江三龙催化剂有限公司 | Novel deoxidation and desulfurization process and application thereof |
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| SU1181705A1 (en) * | 1984-06-06 | 1985-09-30 | Иркутский государственный университет им.А.А.Жданова | Method of obtaining a catalyst for sulphur removal of hydrocarbon raw material |
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