CN101280220B - Method for producing good quality ethylene material by hydrogenation and dearomatization of benzin naphtha - Google Patents
Method for producing good quality ethylene material by hydrogenation and dearomatization of benzin naphtha Download PDFInfo
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Abstract
The invention relates to a method of producing high quality ethylene raw material through the hydrogenation and dearomatization of naphtha. Naphtha distillate is the raw oil and the single stage or a stage of series process flow is adopted; under the proper operating condition, the naphtha raw oil and hydrogen are processed in the hydrogenation reaction area to obtain the naphtha which has low sulfur, low nitrogen and low arene; wherein, at least one of the catalysts in the hydrogenation reaction area is bulk phase catalyst; the bulk phase catalyst is composed of composite oxide NixWyO z and oxide MoO3 with the weight ratio of 1:10-10:1; the composite oxide NixWyOz and oxide MoO3 account for 40%-100% of the total weight of the catalyst combination. Compared with the prior art, the method of producing high quality ethylene raw material through the hydrogenation and dearomatization of naphtha can reduce the arene content of naptha under the mild condition; thereby, the naphtha can be used as high quality ethylene raw material; the method has the advantages of improving the load machining capability and reducing the reaction temperature.
Description
Technical field
The present invention relates to a kind of petroleum naphtha hydrogenation takes off aromatic hydrocarbons the high-quality ethylene method is provided, particularly adopt catalyzer grading loading technology, use dissimilar catalyzer by grating, improve whole hydrogenation performance, can effectively carry out the aromatic hydrocarbons saturated reaction, can obviously reduce simultaneously foreign matter contents such as refining naphtha olefins and sulphur, nitrogen, improve its method as the quality product of feed ethylene.
Background technology
Coking naphtha is one of staple product of delayed coking unit, and delayed coking unit is one of heavy, that residual oil is processed most important method, thereby the output of coking naphtha is bigger.Because unsaturated hydrocarbons, sulphur, nitrogen and beavy metal impurity content are all higher in the coking naphtha, and stability is poor, be difficult to charging as subsequent processing, must be through hydrofining, can be used as feed ethylene, synthetic ammonia material after improving its stability and removing impurity widely, reform and expect and the chemical industry light oil use that wherein the hydrogenation coking naphtha is produced the raw material of ethene mainly as steam cracking.
Though the conventional coking naphtha hydrogen addition technology of employing can take off alkene to less than 5%, still leaves the aromatic hydrocarbons more than 10%, and is unfavorable to delaying ethylene cracking furnace coking, reduced the yield of ethene simultaneously.Aromaticity content mainly contains three kinds of means, i.e. hydrogenation saturation method, solvent extraction process and molecular sieve adsorption in the reduction petroleum naphtha at present.The high-temperature and high-pressure hydrogenation saturation method mainly is to use the hydrogenation catalyst of sulphided state, under the hydrogen partial pressure more than the 6.0MPa that aromatic hydrogenation is saturated, this method one is that the aromatic hydrogenation effect is undesirable, the 2nd, and existing petroleum naphtha hydrogenation device must carry out big transformation, is not the scheme of an economy; Solvent extraction process and molecular sieve adsorption also give enforcement because investment is big, energy consumption is high-leveled and difficult, have only the aromatic hydrogenation saturation method of low-temp low-pressure more satisfactory feasible.
US 4880526 discloses a kind of Ni of containing, Mo, W, the Co high reactivity is used for bulk phase catalyst of hydrotreatment and preparation method thereof, and this preparation method adopts metal to mix kneading to be equipped with technology, and the different metal component distributes under the microcosmic in mutually also inhomogeneous at body.US6299760, US6156695, US6537442, US6440888, the disclosed VIII of containing of US6652738 family/group vib active metal component are used for bulk phase catalyst of hydrotreatment and preparation method thereof, adopt and prepare the metal-powder that contains Ni-Mo or Ni-Mo-W earlier, use aluminum oxide bonding again, or the metal-powder of Ni-Mo or Ni-Mo-W is mixed back dehydration, extrusion, drying with alumina gel.Because the catalyst metal content height of this method preparation, often lack enough interactions between metal and aluminum oxide and cause catalyst strength poor.Active ingredient is made up of a large amount of metals, has some interior metal components and can not be fully utilized and cause the active ingredient loss in forming Ni-Mo or Ni-Mo-W powder process, and this problem can not be by simple bonding the solution.CN1342102A discloses a kind of mixed metal catalyst, and concrete grammar is for to obtain three kinds of reactive metal co-precipitation, and its main weak point is not find the cooperation effect between the different activities metal.US6162350, CN1339985A disclose a kind of mixed metal catalyst composition, and it is solid-state keeping at least a metal in preparation process, forms another kind of soild oxide in this solid metal compound surface reaction, finally forms the core-shell type composition.This method can not make different metal obtain good cooperation.
CN1084547A has introduced a kind of hydrodesulfurizationof of naphtha dechlorination dearsenification and the saturated process for purification of aromatic hydrocarbons.Though aromatic hydrocarbons can be reduced to less than below 1%, because dearomatization catalyst is nickel or noble metal catalyst,, must adopt two-stage method technology for preventing the catalyzer sulfur poisoning, flow process complexity, operational condition are comparatively harsh.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of petroleum naphtha hydrogenation and take off the method that aromatic hydrocarbons provides high-quality ethylene, it can reduce the operating severity in hydrofining reaction district, promptly can realize reducing working pressure, reduce temperature of reaction, increase the device processing power and prolong in the effect such as catalyzer work-ing life one or more, compare with existing petroleum naphtha hydrogenation technology, obviously improved the saturated performance of petroleum naphtha aromatic hydrocarbons.
A kind of producing good quality ethylene material by hydrogenation and dearomatization of benzin naphtha method of the present invention, comprise following content: be stock oil with the naphtha fraction, adopt single hop or one-stage serial technical process, under the hydrofining reaction condition, stock oil and hydrogen obtain low-sulfur, low nitrogen, low aromatic hydrocarbons petroleum naphtha by the hydrofining reaction district.At least comprise a kind of body phase method beds in the described hydrofining reaction district, body phase method catalyzer contains Mo, W, three kinds of metal components of Ni, and catalyzer W, Ni before sulfuration exist with the composite oxides form: Ni
xW
yO
z, z=x+3y, Mo exists with oxide form: MoO
3Composite oxides Ni
xW
yO
zThe ratio of middle x and y (atomic molar ratio) is 1: 8～8: 1, is preferably 1: 4～4: 1.Composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1: 10～10: 1, be preferably 1: 5～5: 1.Composite oxides Ni in the bulk phase catalyst
xW
yO
zWith oxide M oO
3Gross weight content be 40%～100%, be preferably 50%～80%.
The stock oil that the inventive method is used can be the virgin naphtha that obtains in the petroleum refining process, coking naphtha, and the catalytic cracking petroleum naphtha, one or more of cracking naphtha etc., the final boiling point of stock oil are not more than 220 ℃.
The hydrogenation reaction operational condition is generally reaction pressure 1.0～8.0MPa, and hydrogen to oil volume ratio is 200: 1～2500: 1, and the cumulative volume air speed is 0.5～6.0h
-1, 260 ℃～420 ℃ of temperature of reaction; Preferred operational condition is reaction pressure 3.0～6.0MPa, hydrogen to oil volume ratio 300: 1～800: 1, volume space velocity 1.0～3.0h
-1, 280～400 ℃ of temperature of reaction.Above-mentioned hydrogenation reaction operational condition is this area general knowledge, and those skilled in the art can determine concrete processing condition according to feedstock property and product property requirement.
The catalyzer in hydrofining reaction of the present invention district can all be a bulk phase catalyst, also can be the combination of conventional Hydrobon catalyst and bulk phase catalyst.During combination loading, bulk phase catalyst can be seated in the top of reaction zone, also can be seated in the bottom of reaction zone, and perhaps two types catalyzer loads at interval, the volume ratio of bulk phase catalyst and conventional catalyst is 90: 10～10: 90, preferred 20: 80～80: 20.During combination loading, preferred feed by conventional Hydrobon catalyst bed, by bulk phase catalyst bed of the present invention, helps bringing into play the catalyzer overall activity most earlier then.Catalyzer can be contained in the reactor, promptly constitutes the single hop hydrofining technology; Also can be contained in the placed in-line different reactor, promptly constitute one section series hydrogenation refining process.Wherein conventional Hydrobon catalyst can be various commercial catalysts, it generally is carrier with the aluminum oxide, so that one or more are active ingredient among W, Mo, Ni and the Co, active ingredient is generally 15%～35% in oxide weight, can contain in the auxiliary agents such as P, Si, F, B, Ti and Zr one or more simultaneously.Hydrobon catalysts such as FH-40A, the FH-40B that develops as Fushun Petrochemical Research Institute (FRIPP), FH-40C, FH-98, FH-UDS, the HC-K of Uop Inc., HC-P, S-120, the TK-557 of Topsor company, TK-915 catalyzer, the KF-756 of AKZO company, KF-757, KF-848 or the like.
Can contain in the components such as aluminum oxide, silicon oxide, amorphous aluminum silicide, phosphorous oxides, titanium oxide, Zirconium oxide, molecular sieve one or more in the bulk phase catalyst of the present invention as required, the weight content of these components in catalyzer is 0～60%, is preferably 20%～50%.The specific surface area of bulk phase catalyst is 120～400m
2/ g, pore volume are 0.10～0.50ml/g.
The preparation process of bulk phase catalyst of the present invention comprises following content: (1) coprecipitation method generates Ni
xW
yO
zThe composite oxides precursor; (2) Ni
xW
yO
zComposite oxides precursor and MoO
3Making beating mixes, filters; (3) moulding, activation are final catalyzer.
Wherein (1) described coprecipitation method generates Ni
xW
yO
zThe process of composite oxides precursor can adopt following method: with the salts solution of tungstenic, nickel, form required ratio in catalyzer and add in the glue jar, add precipitation agent and make gelatinous mixture.Precipitation agent can be inorganic or organic alkaline ammoniac compounds, is preferably ammonia, can working concentration ammoniacal liquor arbitrarily.
Add required catalyst adjuvant and add component in a step that can be in above-mentioned steps or a few step.Auxiliary agent generally comprise P, F, Ti, Si, B, Zr etc. one or more.Add component and be generally refractory porous mass and precursor thereof, as aluminum oxide and precursor (aluminium hydroxide, aluminum salt solution etc.), clay, sial, titanium oxide-magnesium oxide, molecular sieve etc.The method that adds auxiliary agent and interpolation component adopts this area ordinary method.
Though W, Mo, Ni are activity of hydrocatalyst component commonly used, find that through a large amount of The effects the performance of different fit system catalyzer has very big-difference.Particularly in the bigger bulk phase catalyst of total metal content, the different fit systems of these metals are bigger to the performance impact of catalyzer.The present invention finds by a large amount of experiments, is used for the body phase hydrogenation catalyst that the hydrocarbon material degree of depth is taken off impurity, earlier with W and Ni co-precipitation, makes Ni
xW
yO
zThe precursor of composite oxides, this composite oxides precursor again with MoO
3Making beating mixes, and adopts conventional means to prepare preformed catalyst then, and this preparation process organically cooperates element W and Ni, forms a kind of composite oxides, then with MoO
3Combination finally forms Ni
xW
yO
zThe composition of composite oxides and Mo oxide compound.The result shows when the catalyzer of this microtexture of the present invention is used for hydrocarbons hydrogenation, to have the outstanding impurity activity of taking off, and during especially for deep impurity removal process, significantly improves than the activity of such catalysts of similar chemical constitution.The mechanism that the composition of Ni-W composite oxides of the present invention and Mo oxide compound can improve catalyst activity is very not clear and definite as yet, and, in bulk phase catalyst, the content of reactive metal is higher, reactive metal exist form different fully with traditional loaded catalyst, therefore, can not be suitable for the metal cooperation theory of conventional negative supported catalyst.For example, it is generally acknowledged that Ni can promote the activity of Mo to improve, wishing has a stronger interaction between Ni and the Mo, and the present invention finds in experiment, for bulk phase catalyst, Mo and Ni is fully combined then take off impurity in the degree of depth and do not show perfect performance.The composition catalyzer of Ni-W composite oxides of the present invention and Mo oxide compound, the possible cause that takes off the unexpected raising of performance in the impurity in the degree of depth is, in the very high bulk phase catalyst of metal content, reactive metal exist form different with loaded catalyst, take off in the impurity process in the hydrocarbon raw material degree of depth, the Ni-W composite oxides have stronger hydrogenation activity after sulfuration, make to have the effective hydrogenation of complex construction macromole, eliminate and take off the sterically hindered of impurity reaction.Has the stronger impurity activity of taking off after the Mo sulfuration in the bulk phase catalyst, simple in structure, the sterically hindered little heteroatoms molecule that contains is easy to react, reduced of the interference of this part heteroatoms hydro carbons, helped the hydrogenation that Ni-W high reactivity center is used for the complex construction molecule the Ni-W hydrogenation activity.After containing the effective hydrogenation in heteroatomic complex construction macromole process Ni-W high reactivity center, take off the sterically hindered of impurity and reduce greatly, can in taking off impurity activity, remove easily in the heart.Therefore, the active centre of Ni-W composite oxides of the present invention and Mo oxide compound obtains cooperation, and combination catalyst takes off in the impurity reaction in the degree of depth and has outstanding activity.Bulk phase catalyst preparation method of the present invention does not use the salts solution of Mo, because the reaction product of Mo salts solution and precipitation agent generally has certain solubleness, has therefore avoided the loss of Mo.
Compared with prior art, characteristics of the present invention are: 1) because the present invention has used highly active bulk phase catalyst, strengthened the hydrogenation performance of hydrofining reaction district catalyzer, can effectively improve quality product, promptly under the identical operations condition, can reduce reaction pressure, reduce service temperature etc., perhaps under same reaction pressure, service temperature, increase the treatment capacity of device, perhaps reduce the usage quantity of catalyzer, thereby reduce the construction investment and the running cost of device.2) can effectively carry out the aromatic hydrocarbons saturated reaction, can obviously reduce foreign matter contents such as refining naphtha olefins and sulphur, nitrogen simultaneously, improve its quality product as feed ethylene.Those skilled in the art can carry out operational condition as required, are adapted to the demand of enterprise itself.
Embodiment
Method of the present invention is specific as follows: be stock oil with the naphtha fraction, adopt single hop or one-stage serial technical process, under the hydrofining reaction condition, stock oil and hydrogen order obtain low-sulfur, low nitrogen, low aromatic hydrocarbons petroleum naphtha by the hydrofining reaction district.At least comprise a kind of body phase method beds in the described hydrofining reaction district.
Bulk phase catalyst of the present invention can make as follows.
1, Ni
xW
yO
zComposite oxides precursor and MoO
3The preparation of mixture
In retort, add the saline solution that contains reactive metal Ni, W component by catalyst component content proportioning.Contain nickel salt and can be single nickel salt, nickelous nitrate, nickelous chloride etc.Tungstenic salt can be sodium wolframate, ammonium metawolframate etc.Mix the back, precipitation agent is added under stirring state in the said mixture, until forming collosol intermixture.Becoming the glue temperature is 30-100 ℃, and becoming the glue pH value is 7.0-10.0.Can become under the glue temperature to wear out 1-5 hour after becoming glue.Becoming in the glue thing promptly is Ni
xW
yO
zThe precursor of composite oxides.Can filter or not filter before and after becoming glue, add the solid molybdic oxide, making beating mixes, and filters then and obtains filter cake, and filter cake can wash or not wash, and filter cake dehydrates under 50-150 ℃ of condition, 0.5～24 hour time of drying, obtains Ni
xW
yO
zComposite oxides precursor and MoO
3Mixture.
Preferably 30～80 ℃ of described one-tenth glue temperature, gelation time was generally 0.5～5 hour, was preferably 0.5～3 hour, slurries pH value 7.0-9.0 preferably during cemented into bundles.Preferably 50～100 ℃ of described drying temperatures are preferably 1～8 hour time of drying.
Can add aluminum salt solution in the saline solution of Ni, W component, make the precursor that contains aluminum oxide in the throw out, aluminum salt solution can be aluminum nitrate, Tai-Ace S 150, aluminum chloride or aluminum acetate etc.Directly add aluminium hydroxide after also can becoming glue.The purpose of introducing aluminium in the catalyzer mainly is the intensity that increases catalyzer, and improves pore structure etc.In the preparation process of this mixture, can add auxiliary agent and additive etc. as required.
2, Preparation of Catalyst
The filter cake that above-mentioned drying is good rolls extruded moulding.Can or contain with water purification after the moulding and can decompose salt (as ammonium acetate) solution and wash.The activation of catalyzer comprises processes such as dry and roasting.To wash back stripe shape thing drying, roasting obtains final catalyst prod.Dry and roasting can be adopted this area normal condition, as 50～200 ℃ of dryings 1～48 hour, 450～600 ℃ of roastings 0.5～24 hour, is preferably 1～8 hour.Also can introduce auxiliary agent and additive as required in the catalyst preparation process.
Catalyst shape can be sheet, spherical, cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei), preferably cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei) as required.The diameter of carrier can be 0.8～2.0mm slice and＞the thick bar of 2.5mm.
Catalyzer has higher hydrodenitrification, hydrogenating desulfurization, the saturated isoreactivity energy of aromatic hydrocarbons.
Further specify Preparation of catalysts method of the present invention and use properties below by embodiment.Unspecified percentage composition is a weight percentage.
Embodiment 1
In retort, add 1000mL water, add nickelous chloride 40g dissolving then, add ammonium metawolframate 52g dissolving again, add zirconium oxychloride 5g dissolving again, add 10% ammoniacal liquor then and become glue, until pH value is 8, becoming the glue temperature is 50 ℃, wears out 1 hour behind the one-tenth glue, filters then, filter cake adds 600ml water purification and 16g molybdic oxide and 32g aluminium hydroxide, making beating stirs, and filters, and filter cake was 80 ℃ of dryings 5 hours, extruded moulding then, with water purification washing 3 times, wet bar is 120 ℃ of dryings 5 hours, 500 ℃ of roastings 4 hours, obtain final catalyst A, composition and main character see Table 1.
Embodiment 2
Method according to embodiment 1, press the component concentration proportioning of catalyst B in the table 1, adding aluminum chloride, nickelous chloride, sodium wolframate in retort, add 16% ammoniacal liquor then and become glue, is 9 until pH value, becoming the glue temperature is 80 ℃, wore out 3 hours after becoming glue, filter then, filter cake washs 2 times with the 500mL water purification, add water purification and molybdic oxide, making beating stirs, and filters, and filter cake was 70 ℃ of dryings 7 hours, extruded moulding then, with water purification washing 2 times, wet bar is 100 ℃ of dryings 8 hours, 550 ℃ of roastings 3 hours, obtain final catalyst B, composition and main character see Table 1.
Embodiment 3
Method according to embodiment 1, press the component concentration proportioning of catalyzer C in the table 1, in retort, add nickelous nitrate, ammonium metawolframate, aluminium hydroxide, silicon sol, add 12% ammoniacal liquor then and become glue, until pH value is 10, and becoming the glue temperature is 60 ℃, wears out 2 hours behind the one-tenth glue, filter then, filter cake adds molybdic oxide, and making beating stirs, and filters, filter cake was 120 ℃ of dryings 1 hour, extruded moulding then, wet bar is 130 ℃ of dryings 3 hours, 600 ℃ of roastings 3 hours, obtain final catalyzer C, composition and main character see Table 1.
Embodiment 4
Method according to embodiment 1, press the component concentration proportioning of catalyzer D in the table 1, in retort, add 1000mL water, add nickelous chloride 48g dissolving then, add ammonium metawolframate 40g dissolving again, adding 10% ammoniacal liquor then and become glue, is 8 until pH value, and becoming the glue temperature is 40 ℃, wore out 3 hours after becoming glue, filter then, filter cake adds 600ml water purification and 28g molybdic oxide and 17g aluminium hydroxide, and making beating stirs, filter, filter cake is 80 ℃ of dryings 5 hours, and extruded moulding then is with water purification washing 3 times, wet bar was 120 ℃ of dryings 5 hours, 500 ℃ of roastings 4 hours, obtain final catalyzer D, composition and main character see Table 1.
Comparative example
Catalyzer according to embodiment 1 is formed, and presses the disclosed method for preparing catalyst of Chinese patent CN1342102A, preparation reference agent E.
In retort, add 1000mL water, add Ammonium Heptamolybdate 25g dissolving then, add ammonium metawolframate 52g dissolving again, add 25% ammoniacal liquor then and become glue, until pH value is 10.0, and being heated to temperature is 90 ℃, drips the solution that contains the 40g nickelous chloride simultaneously in retort.The suspension liquid that forms is continued to stir 90 ℃ of temperature 30 minutes.Filter then, the filter cake hot wash, 100 ℃ of dryings 5 hours add 32g aluminium hydroxide extruded moulding then, and wet bar 500 ℃ of roastings 4 hours, obtains final reference catalyst E 100 ℃ of dryings 8 hours, and composition and main character see Table 2.Prepare catalyzer by this kind method, the molybdic oxide yield can only reach 80%, and in order to guarantee metal content and proportioning in the catalyzer, Ammonium Heptamolybdate adds 20% when feeding intake.
The catalyzer and the character of the preparation of table 1 the inventive method
| The catalyzer numbering | A | B | C | D | E |
| NiO，wt％ | 18.1 | 17.1 | 12.5 | 22.1 | 17.9 |
| WO 3，wt％ | 42.3 | 21.3 | 28.4 | 32.2 | 41.8 |
| MoO 3，wt％ | 16.5 | 57.6 | 18.6 | 28.1 | 17.0 |
| Al 2O 3，wt％ | Surplus | Surplus | Surplus | Surplus | Surplus |
| Other, wt% | ZrO 2/2.0 | Do not have | SiO 2/4.0 | TiO 2/3.0 | Do not have |
| Specific surface/m 2·g -1 | 143 | 258 | 202 | 135 | 105 |
| Pore volume/mlg -1 | 0.216 | 0.40 | 0.258 | 0.12 | 0.132 |
| Intensity/Nmm -1 | 11.5 | 11.0 | 16.7 | 18.2 | 8.6 |
Embodiment 5
Stock oil character sees Table 2, catalyst property sees Table 3, and processing condition and test-results see Table 4.Oxidized catalyst is carried out conventional sulfidizing before use.As under the 8.0MPa condition, vulcanize with the virgin naphtha that contains dithiocarbonic anhydride 2.0wt%, 230 ℃ of constant temperature 8 hours, 300 ℃ of constant temperature 10 hours, volume space velocity was 1.0h during liquid
-1, hydrogen to oil volume ratio is 500: 1.
From table 4 test-results as can be seen, adopt technology of the present invention can effectively improve the activity of Hydrobon catalyst, can reduce working pressure, reduce service temperature, perhaps improve treatment capacity, also can reduce the usage quantity of catalyzer, saved facility investment and process cost.Simultaneously because the more intense hydrogenation performance of Hydrobon catalyst makes the aromatic hydrocarbons degree of depth saturated in hydrogenating desulfurization, denitrogenation.
Table 2 stock oil character
| The stock oil title | Stock oil-1 | Stock oil-2 |
| Density (20 ℃)/gcm -3 | 0.7336 | 0.7211 |
| The boiling range scope/℃ | 34～221 | 39～200 |
| Sulphur content, wt% | 0.54 | 0.78 |
| Nitrogen content, wt% | 0.011 | 0.02 |
| Bromine valency/gBr.100g -1 | 56.0 | 68.0 |
| Aromatic hydrocarbons/v% | 12.1 | 9.9 |
The main composition and the character of table 3. Hydrobon catalyst
| Catalyzer | FH-98 | FH-40C |
| Catalyzer is formed | ||
| WO 3+MoO 3+NiO/wt％ | 29～33 | 16～22 |
| Carrier, wt% | Surplus | Surplus |
| The main character of catalyzer | ||
| Specific surface, m 2/g | 140 | ＞240 |
| Pore volume ml/g | 0.30 | 0.42 |
Table 4 embodiment 5 processing condition and test-results
| Processing condition | Process program 1 | Reference scheme 1 | Reference scheme 2 |
| Catalyzer and order | FH-98/A | FH-98 | FH-98/E |
| The catalyst loading volume ratio | 30∶70 | - | 30∶70 |
| Stock oil | Raw material 1 | Raw material 1 | Raw material 1 |
| Pressure/MPa | 4.0 | 4.0 | 4.0 |
| The inlet hydrogen to oil volume ratio | 500∶1 | 500∶1 | 500∶1 |
| Volume space velocity/h during total liquid -1 | 2.0 | 2.0 | 2.0 |
| Temperature/℃ | 260/310 | 310 | 260/310 |
| Treated gasoline | |||
| Sulphur content/μ gg -1 | ＜0.5 | ＜0.5 | ＜0.5 |
| Nitrogen content/μ gg -1 | ＜1.0 | ＜1.0 | ＜1.0 |
| Bromine valency/gBr.100g -1 | 0.07 | 0.1 | 0.08 |
| Aromatic hydrocarbons/v% | 3.0 | 9.9 | 4.8 |
Continuous table 4 embodiment 5 processing condition and test-results
| Processing condition | Process program 2 | Process program 3 | Process program 4 |
| Catalyzer and order | B | FH-40C?/C | D |
| The catalyst loading volume ratio | - | 40∶60 | - |
| Stock oil | Raw material 2 | Raw material 2 | Raw material 1 |
| Pressure/MPa | 5.0 | 5.0 | 6.0 |
| Temperature/℃ | 315 | 270/315 | 320 |
| Air speed/h -1 | 1.5 | 3.7/2.5 | 1.5 |
| The inlet hydrogen to oil volume ratio | 400∶1 | 400∶1 | 800∶1 |
| Treated gasoline | |||
| Sulphur content/μ gg -1 | ＜0.5 | ＜0.5 | ＜0.5 |
| Nitrogen content/μ gg -1 | ＜0.5 | ＜0.5 | ＜1.0 |
| Bromine valency/gBr.100g -1 | 0.1 | 0.1 | 0.08 |
| Aromatic hydrocarbons/v% | 2.5 | 3.2 | 2.1 |
Embodiment 6[has replenished the scheme of three conditions for supporting aforesaid scheme scope, please adjust if parameters such as condition are inaccurate]
Stock oil character sees Table 2, catalyst property sees Table 3, and processing condition and test-results see Table 5.Oxidized catalyst is carried out conventional sulfidizing before use, and concrete treatment condition are with embodiment 5.
Table 5 embodiment 6 processing condition and test-results
| Processing condition | Process program 5 | Process program 6 | Process program 7 |
| Catalyzer and order | FH-98/B | C/FH-40C | FH-98/D |
| The catalyst loading volume ratio | 20∶80 | 40∶60 | 70∶30 |
| Stock oil | Raw material 2 | Raw material 2 | Raw material 1 |
| Pressure/MPa | 7.0 | 5.0 | 4.0 |
| Temperature/℃ | 280/320 | 260/310 | 310 |
| Volume space velocity/h during total liquid -1 | 2.5 | 1.5 | 1.0 |
| The inlet hydrogen to oil volume ratio | 800∶1 | 400∶1 | 800∶1 |
| Treated gasoline | |||
| Sulphur content/μ gg -1 | ＜0.5 | ＜0.5 | ＜0.5 |
| Nitrogen content/μ gg -1 | ＜0.5 | ＜0.5 | ＜1.0 |
| Bromine valency/gBr.100g -1 | 0.1 | 0.1 | 0.1 |
| Aromatic hydrocarbons/v% | 2.0 | 3.5 | 2.3 |
Claims (10)
1. the method for a producing good quality ethylene material by hydrogenation and dearomatization of benzin naphtha, comprise following content: be stock oil with the naphtha fraction, adopt single hop or one-stage serial technical process, under the hydrofining reaction condition, stock oil and hydrogen obtain low-sulfur, low nitrogen, low aromatic hydrocarbons petroleum naphtha by the hydrofining reaction district; At least comprise a kind of body phase method beds in the described hydrofining reaction district, body phase method catalyzer contains Mo, W, three kinds of metal components of Ni, and catalyzer W, Ni before sulfuration exist with the composite oxides form: Ni
xW
yO
z, z=x+3y, Mo exists with oxide form: MoO
3Composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1: 10～10: 1, composite oxides Ni in the bulk phase catalyst
xW
yO
zWith oxide M oO
3Gross weight content be 40%～100%.
2. in accordance with the method for claim 1, it is characterized in that composite oxides Ni in the described bulk phase catalyst
xW
yO
zThe atomic molar ratio of middle x and y is 1: 8～8: 1, composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1: 5～5: 1, composite oxides Ni in the bulk phase catalyst
xW
yO
zWith oxide M oO
3Gross weight content be 50%～80%.
3. in accordance with the method for claim 1, it is characterized in that composite oxides Ni in the described bulk phase catalyst
xW
yO
zThe atomic molar ratio of middle x and y is 1: 4～4: 1.
4. in accordance with the method for claim 1, it is characterized in that described hydrogenation reaction operational condition is reaction pressure 1.0～8.0MPa, hydrogen to oil volume ratio is 200: 1～2500: 1, and the cumulative volume air speed is 0.5～6.0h
-1, 260 ℃～420 ℃ of temperature of reaction.
5. in accordance with the method for claim 1, it is characterized in that described hydrogenation reaction operational condition is reaction pressure 3.0～6.0MPa, hydrogen to oil volume ratio 300: 1～800: 1, volume space velocity 1.0～3.0h
-1, 280～400 ℃ of temperature of reaction.
6. in accordance with the method for claim 1, it is characterized in that described hydrofining reaction district comprises conventional Hydrobon catalyst and bulk phase catalyst, the volume ratio of bulk phase catalyst and conventional catalyst is 90: 10～10: 90.
7. according to claim 1 or 6 described methods, it is characterized in that described stock oil and hydrogen earlier by conventional Hydrobon catalyst reaction zone, then by body phase Hydrobon catalyst reaction zone.
8. in accordance with the method for claim 7, it is characterized in that described body phase Hydrobon catalyst and conventional Hydrobon catalyst volume ratio are 20: 80～80: 20.
9. in accordance with the method for claim 1, the preparation process that it is characterized in that described bulk phase catalyst comprises following content: (1) coprecipitation method generates Ni
xW
yO
zThe composite oxides precursor; (2) Ni
xW
yO
zComposite oxides precursor and MoO
3Making beating mixes, filters; (3) moulding, activation are final catalyzer.
10. in accordance with the method for claim 1, it is characterized in that described naphtha fraction is that stock oil is one or more in virgin naphtha, coking naphtha, catalytic cracking petroleum naphtha and the cracking naphtha.
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| CN102443431A (en) * | 2010-10-13 | 2012-05-09 | 天津河清化学工业有限公司 | Naphtha hydrorefining dearomatization method |
| CN102876361B (en) * | 2012-09-28 | 2015-08-26 | 西南石油大学 | A kind of coupling method of petroleum naphtha Porous deproteinized bone-vehicle fuel oil desulfurization |
| CN110129088B (en) * | 2019-05-06 | 2021-03-30 | 盘锦北方沥青燃料有限公司 | Method for producing ethylene cracking raw material by low-carbon hydrocarbon mixed hydrogenation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156695A (en) * | 1997-07-15 | 2000-12-05 | Exxon Research And Engineering Company | Nickel molybdotungstate hydrotreating catalysts |
| CN1353168A (en) * | 2000-11-03 | 2002-06-12 | 中国石油天然气股份有限公司 | Hydrorefining catalyst and its preparing process |
| CN1458233A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Process for coking full fraction oil hydrogenation refining |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156695A (en) * | 1997-07-15 | 2000-12-05 | Exxon Research And Engineering Company | Nickel molybdotungstate hydrotreating catalysts |
| CN1353168A (en) * | 2000-11-03 | 2002-06-12 | 中国石油天然气股份有限公司 | Hydrorefining catalyst and its preparing process |
| CN1458233A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Process for coking full fraction oil hydrogenation refining |
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