CN1429888A - Naphtha selective hydrogenation desulfurization process and catalyst - Google Patents
Naphtha selective hydrogenation desulfurization process and catalyst Download PDFInfo
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Abstract
A selective hydrodesulfurizing process for naphtha, especially the fluidized catalytic-cracking gasoline in order to decrease the hydrogenation to olefine to maximum is disclosed. Its hydrodesulfurizing catalyst is composed of the active component (Mo and/or W and Ni and/or Co compounds) and the carrier containing spinal, active alumina and cement. Its advantages are high output rate of liquid and less loss of octane number.
Description
1. Field of the invention
The invention relates to a naphtha hydrodesulfurization process for producing gasoline products and a catalyst thereof. In particular, it relates to a process for selectively hydrodesulfurizing Fluid Catalytic Cracking (FCC) gasoline to minimize the hydrogenation of olefins therein and a catalyst therefor.
2. Background of the invention
It is well known that air pollution is a serious environmental problem, with one major source of pollution being emissions from the combustion of thousands of fuel-powered engines. Strict fuel standards have been established to reduce the emission of automotive pollutants. Sulfur-containing fuels produce sulfur dioxide and other environmental pollutants such as smoke and unhealthy substances, and acid rain can cause forest depletion, water pollution, and other environmental problems. To reduce environmental pollution, the sulfur content of the fuel has and will be severely limited, e.g., less than 100 or even 50 ppm.
Sulfur in crude oil includes aliphatic and aromatic sulfur compounds. Different hydrodesulfurization techniques have been developed for this purpose. One of them is Hydrodesulfurization (HDS), which is a catalytic reaction using hydrogen and sulfur, and a general hydrodesulfurization reaction is shown in the reaction formula 1:
reaction formula 1: hydrodesulfurization reaction
In equation 1, the sulfur-containing compound RS R' may be: a thiol, R is a hydrocarbyl group, R' is hydrogen; a sulfide or disulfide, the sulfur being linked to another sulfur on the R or R' hydrocarbyl functionality; or thiophene, and R' are connected to form a heterocyclic ring. Hydrodesulfurization reactions produce hydrogen sulfide and hydrocarbons by consuming hydrogen, the sulfur in the hydrocarbons being replaced by two hydrogen atoms. Then the sulfur content of the petroleum product obtained after separating the hydrogen sulfide is greatly reduced.
HDS is one of a series of processes known as hydrotreating, involving the introduction of hydrogen and reaction with carbon-containing compounds. The general hydrogenation reactions with oxygenates, nitrogen containing compounds, and unsaturated compounds are set forth in equations 2, 3, and 4, respectively.
Reaction formula 2: hydrodeoxygenation reaction
Reaction formula 3: hydrodenitrogenation reaction
Reaction formula 4: hydrogenation reaction
When petroleum contains sulfur, oxygen, nitrogen and unsaturated compounds, different hydrogenation reactions occur. This hydrotreating removes not only sulfur but also nitrogen and other elements such as metals. Hydrogenation is not only an environmental concern, but also other factors such as avoiding poisoning of downstream catalysts.
Because olefins contribute significantly to octane number, for example, cracked naphthas containing 20% olefins typically have higher octane numbers than normal saturated hydrocarbons. However, hydrotreating with conventional catalysts under hydrodesulfurization conditions can also result in a significant reduction in olefin content. This results in a reduction in the octane number of the product fuel, and the hydrogenated product may have to be further processed, such as by isomerization, blending of high octane components, or other processing to increase the octane number of the product. Thereby causingan increase in production cost.
Such catalysts have been reported to prevent octane degradation by selective hydrodesulfurization while simultaneously reducing olefin hydrogenation. Such as U.S. patents 4132632(Yu et al) and 4140626(Bertolacini et al). They use a specific selective hydrodesulfurization catalyst having a certain amount of group VIB and group VIII metals supported on a magnesia support.
U.S. Pat. No. 5,340,466 discloses a catalyst having a support comprising hydrotalcite and gamma-Al2O3The hydrotalcite is 70% of the weight of the carrier. When the desulfurization rate of the catalyst reaches 90%, about 30 to 40% of the olefin in the feedstock is saturated.
U.S. patent 5,851,382 discloses a process for treating a fluid catalytic cracked naphtha containing olefins and sulfur, the catalyst bed of which contains a group VIIIB, a group VIB metal and a group IA metal on a hydrotalcite-like component support. After the reaction, the sulfur content is reduced and the olefin content is maintained at least 50%.
U.S. Pat. No. 5,525,211 discloses a catalyst having a support of K2CO3Modified magnesium aluminate spinels, K2CO3Is loaded on a carrier by an impregnation method, and active components are molybdenum and cobalt. The molybdenum and cobalt active components are loaded on the carrier by a twice-leaching method respectively. The preparation method of the catalyst is complex, and the strength of the catalyst is poor, so that the industrial application of the catalyst is limited.
It would be desirable to have a process and catalyst therefor that can economically remove sulfur from olefin-containing feedstocks such as naphtha, minimize octane number loss, and provide environmental and stable economic benefits. The selective hydrodesulfurization process and catalyst of naphtha of the invention just meet this objective.
3. Summary of the invention
The invention relates to a selective hydrodesulfurization process for naphtha and a catalyst thereof. The process of the invention can cut naphtha into light and heavy fractions according to a certain boiling point, the light fraction is subjected to mercaptan removal, etherification, alkylation or other treatments, the heavy fraction is subjected to selective hydrodesulfurization, and the treated light and heavy fractions are blended; full range naphtha can also be subjected to a full range selective hydrodesulfurization.
The active component of the catalyst contains molybdenum and/or tungsten, nickel and/or cobalt, wherein the content of the molybdenum and/or tungsten is 0.1-15 percent and the content of the nickel and/or cobalt is 0.1-10 percent calculated by metal oxide; the catalyst carrier is a composite carrier containing spinel, active alumina and cement, and its content is spinel 30-90%, cement 0.1-60% and active alumina 0.1-60%, and the contents of all the components are calculated according to the total weight of the catalyst.
In the practice of the invention, the feedstock hydrocarbons to be treated include what is known as catalytically cracked gasoline, i.e., light catalytically cracked gasoline (boiling point from C)5To 166 ℃) full range catalytically cracked gasoline (boiling point from C)5To 166 ℃ or higher), heavy catalytically cracked gasoline (boiling)Dots from 165 ℃ to 200 ℃ and the like. These hydrocarbons generally have boiling points in the gasoline range, most of which are obtained by catalytic cracking and are generally used as gasoline products. Suitable feedstocks include light, full range, heavy catalytic cracked (FCC) naphtha and gasoline fractions from visbreaking.
If gasoline cutting is required, the determination of the gasoline cutting point is generally determined according to the sulfur form and the olefin content distribution. The catalytically cracked light gasoline contains more mercaptans and olefins, while the heavy gasoline generally contains lower olefins and a high content of thiophenic sulfur. The cut point is too low, the heavy fraction with high olefin content is easily saturated in the subsequent hydrodesulfurization treatment, thereby causing great loss of octane number; if the cutting point is too high, more thiophenic sulfur enters the light fraction, and if the light fraction is treated by the conventional alkali-free deodorization method, the thiophenic sulfur is remained in the light fraction, so that the sulfur content of the gasoline can not meet the specification requirement. The cutting point is generally between 50 and 160 ℃.
The process can also be operated in batch mode for hydrodesulfurization. For example, after hydrodesulfurization of cracked naphtha for a period of time, the cracked naphtha can be replaced with a medium distillate such as light gasoline and subjected to hydrodesulfurization. After a period of time, it can be reconverted to cracked naphtha.
Under appropriate conditions, the catalyst can be used for selective hydrogenation of diolefins to form monoolefins. In this particular case, the present catalyst can be used as a guard bed in certain catalytic processes affected by diolefins. Processes in which the present catalyst may be utilized include paraffin and olefin isomerization, olefin skeletal isomerization, etherification processes, and the like.
According to experience we have noted that the products obtained with the present catalyst and process are almost as colorless as water and are therefore suitable for the production of light-colored gasoline, kerosene or diesel.
The selective hydrodesulfurization using the process and catalyst thereof results in a product in which a substantial portion of the olefins are not saturated and thus react with the hydrogen sulfide produced during the desulfurization process and remaining in the product to form mercaptans, which is referred to as a recombination reaction. Mercaptans formed by the recombination reaction and remaining in the naphtha product can be removed by a mercaptan removal process or converted to disulfides by an oxidation process, thereby reducing the sulfur content of the naphtha product to a lower level. Of course, if the total sulfur content of the product meets the specification, the disulfide may remain in the product. There are several mercaptan removal and oxidation processes, such as the Merox process reported in the literature.
The operating conditions for hydrodesulfurization of cracked gasoline feedstock using the process of the present invention are shown in table 1.
TABLE 1
A better range of the condition application range
Temperature, 204 ℃399260-
Total pressure, MPa 0.5-7.01.0-4.0
Hydrogen-oil ratio (V/V) 50-800200-
Liquid hourly space velocity (hr)-1) 1-15 2-5
The catalyst may be used in any form, such as a fixed bed, fluidized bed or moving bed reaction system, and the fixed bed is recommended. The catalyst is preferably in the form of a strip, sphere, tablet or granule formed by extrusion, rolling ball, flaking or the like, and preferably in the form of an extrusion such as a clover.
The carrier used by the catalyst is a composite carrier consisting of spinel, active alumina and cement. The spinel may be MgAl2O4、ZnAl2O4、CaAl2O4、CoAl2O4Or BaAl2O4More preferably MgAl2O4Spinel; the activated alumina is mainly gamma-alumina; the cement may be calcium aluminate cement, potassium cement, iron cement, etc., or a mixture thereof, more preferably calcium aluminate cement.
We have found that: the vulcanized Co-Mo catalyst loaded on the composite carrier of magnesia-alumina spinel, gamma-alumina and cement has high hydrodesulfurization selectivity to catalytically cracked gasoline. It is believed that the composite support minimizes hydrogenation of olefins while maintaining a high desulfurization rate for the catalyst. In addition, the reinforcing agent cement is added, so that the strength of the catalyst can be improved, and the catalyst has better physicochemical properties.
The carrier of the catalyst of the invention can be formed by co-extrusion or spherical carrier by spinel, mixture of gamma-alumina and cement, etc. Wherein the spinel content is 50-90%, preferably 55-80%, and the content of alumina and cement is not more than that of alumina and cement45% of the weight of the carrier. The specific surface area of the carrier can be from 10 to 500m2The pore volume is 0.1-1.5 ml/g. In general, a large specific surface area and a large pore volume are preferable.
MgAl2O4Spinels may be prepared by any method known in the art, and the preparation described in us 4,400,431 may be used as a reference for the preparation; alternatively, it can be purchased directly from the market, preferably MgAl2O4The purity of the spinel is greater than 95%. The gamma-alumina can be aluminum hydroxide dry glue powder, and has a pore volume of more than 0.7ml/g and a specific surface area of more than 350m2/g，Na2O＜0.06wt％，Fe2O3Less than 0.06 wt%, and may be prepared through high temperature roasting or purchased directly from market. The cement is a commercially available cement such as industrial calcium aluminate cement.
MgAl is added2O4Mixing spinel, aluminum hydroxide dry glue powder, calcium aluminate cement, water and dilute acid, grinding, adding in any order or simultaneously, and preparing the mixture into shape, such as column with diameter of 0.8-4mm and length of 2.5-15 mm. The cross-section of the granules may be of any shape commonly used in the art, preferably of the clover type. The catalyst carrier of the present invention can be molded by any of the conventional methods such as extrusion, rolling, and sheeting. The catalyst can be prepared by adding binder such as organic substances such as polyvinyl alcohol, stearic acid, starch, etc., or aluminum oxide, silicon oxide, titanium oxide, clay, magnesium oxide, etcAn inorganic substance. The organic binder can be removed by firing and the inorganic binder left in the final product.
Drying the formed carrier at the temperature of 100-250 ℃, preferably 110-200 ℃ for 10-30 hours, preferably 12-24 hours. Then roasting in air or inert gas at 400-600 ℃, preferably 450-550 ℃ for 0.2-6 hours, preferably 0.4-5 hours.
Because the carrier of the invention is added with cement which is a substance with high hydration strength, the strength of the carrier is greatly enhanced, and the catalyst is convenient for industrial application.
The active components of the catalyst may be supported on the support, together or separately, in any order.
The active components of the catalyst are as follows: mo and/or W, in an amount of from 0.1 to 15%, preferably from 1 to 10%, based on the respective metal oxide, based on the total weight of the final catalyst; ni and/or Co, in each case in a proportion of 0.1 to 10 wt.%, preferably 0.5 to 5 wt.%, based on the respective metal oxide, based on the total weight of the final catalyst. The catalyst active component is preferably a combination of Mo and Co. In addition, other promoters such as phosphorus, fluorine, boron and other common hydrogenation aids can be added into the catalyst, and the content of the promoters accounts for 0-10% of the total weight of the catalyst. All weight percents are calculated as elements and as the total amount of the final catalyst.
The preparation of the catalyst is suggested to be carried out from the support with molybdenum and/or tungsten and nickel and/or cobalt in aqueous solution, or else in dry or non-aqueous solution or suspension. The active components nickel and/or cobalt are preferably selected from cobalt, which may be added in solution, preferably as an aqueous solution of a cobalt salt, such as nitrate, acetate, etc., in an amount sufficient to fill the pores of the support. The active component molybdenum and/or tungsten is preferably selected from molybdenum, and can be added in the form of acetate, oxide, chloride or carbonyl salt, preferably in the form of ammonium molybdate or ammonium tetrathiomolybdate aqueous solution.
The metals may be added in any order or simultaneously using well known methods of equilibrium adsorption, impregnation, pore filling or ion exchange. The metal-loaded support is then dried at a temperature of 110-. If the addition of the metals is carried out stepwise, the support can then be dried stepwise before the next addition of the metals and also calcined.
It should be noted that the above-mentioned 'metals' are all present in the form of certain compounds, such as oxides, sulfides, carbonates, amine salts, chlorides, etc., depending on the preparation and treatment temperatures of the catalyst, without confusion among the elements. The percentages by weight of the metals indicated in the indices are calculated as metal oxides.
The catalyst can also be prepared by solid-phase synthesis techniques, for example by grinding the support and the metal compound in one or more stages, with appropriate heat treatment, and finally extruding or granulating. It should be noted that with catalysts made in this manner, the catalyst metal is present as an oxide, or a partially decomposed or partially reacted metal compound.
The contents of the components in the prepared catalyst are shown in table 2:
TABLE 2
The content range of the components (weight percent) is better, the content range (weight percent) of molybdenum and/or tungsten (calculated by oxide) is 0.1-151-10 nickel and/or cobalt (calculated by oxide) is 0.1-100.5-5
Spinel 30-9050-80 active alumina 0.1-600.1-40
0.1-600.5-40% of cement
In the embodiment of the invention, the catalyst carrier adopts magnesia-alumina spinel, active alumina and calcium aluminate cement, and the metal is added in the form of aqueous solution, for example, the metal active component is added in the form of cobalt nitrate and ammonium molybdate. The present invention is not limited to the form of the embodiments.
The prepared catalyst can be vulcanized after being loaded into a hydrodesulfurization reactor. The catalyst may be sulfided by any of the well-known methods, for example, with hydrogen sulfide-containing hydrogen, or with hydrogen-containing or hydrogen-free readily decomposable sulfur-containing compounds such as carbon disulfide, di-tert-nonyl polysulfide (TNPS) or dithiodimethane, and the sulfiding temperature may be up to 500 ℃, but is not limited thereto. The pressure may be normal pressure or higher. The atmosphere is hydrogen and the sulfidation time is 2-24 hours, e.g. 3 hours.
Alternatively, the sulfidation of the catalyst may be carried out by sulfur compounds in the process hydrogen. Or presulfiding outside the reactor, appropriately passivating, and then charging into the reactor.
Ex situ sulfiding of the catalyst may be accomplished by any of a variety of methods familiar to those skilled in the art. With these ex situ techniques, activation of the catalyst can be accomplished by introducing a sufficient amount of sulfur to heat the catalyst in a hydrogen atmosphere.
The catalyst of the invention is in contact reaction with cracked naphtha in hydrogen atmosphere under the following process conditions:
the temperature is 204 ℃ and 399 ℃, preferably 260 ℃ and 350 ℃. The pressure is 0.5-7.0MPa, preferably 1.0-4.0 MPa. The Liquid Hourly Space Velocity (LHSV) is in the range of from 1 to 15LHSV, preferably from 2 to 5 LHSV. Hydrogen to oil ratio of 50-800Nm3.m-3Preferably 200-500 Nm3.m-3。
The hydrogen used in the selective hydrodesulfurization may be pure hydrogen, or hydrogen containing inert gases or light hydrocarbons. The hydrogen not consumed in the reaction process can be recycled after separation.
The final product of selective hydrodesulfurization is to desulfurize naphtha and retain high levels of olefins, the sulfur-containing product being primarily hydrogen sulfide. Generally, the sulfur content of desulfurized naphtha is substantially reduced. Generally, the content of the active carbon can be as low as 20 percent of the original content, and even can reach below 10 percent. At the same time, the retained olefin content can reach 60%, preferably 60-90%, even better. Thus, the desulfurized naphtha retains a higher octane number than the original feed.
The removal of hydrogen sulfide gas from the desulfurized naphtha can be accomplished by any effective means. Including various methods known to those skilled in the art, typical methods include, in addition to conventional gas-liquid separation, gas purging such as hydrogen or nitrogen purging, ammonia treatment, adsorption, flashing, and the like.
The desulfurized naphtha obtained in accordance with the present invention has a very low sulfur content. Depending on the sulfur content of the feed, the hydrodesulfurization conditions, and other factors affecting desulfurization, the sulfur content of the desulfurized naphtha is typically less than 300ppm, preferably less than 150ppm, and most preferably less than 60 ppm.
Hydrodesulfurization is achieved when the HDS activity is greater than other activities, such as hydrogenation activity. HDS selectivity can be reflected by the change in sulfur content before and after hydrodesulfurization of the sulfur-containing hydrocarbon as compared to the change in the content of other components, such as olefins, before and after the reaction. Selectivity is achieved when the percentage of removed thiohydrocarbons is greater than the percentage of olefin hydrogenation after HDS. Compared with common hydrogenation catalysts, the catalyst has better HDS selectivity, and the sulfur-containing hydrocarbon removal rate of the catalyst can reach 2: 1 or even higher than that of removed olefin.
The reference standard of the analysis test index related in the embodiment of the invention is as follows: research octane number RON ASTM2699 motor octane number MON ASTM2700 catalyst compressive strength GB/T3635-83 olefin content ASTM-D1319 sulfur content GB6324.4-86 olefin saturation is calculated as the difference in olefin content before and after desulfurization of the feed divided by the olefin content before desulfurization. The desulfurization rate is calculated as the difference between the sulfur content before and after desulfurization of the material divided by the sulfur content before desulfurization.
The process of the present invention can effectively control the diene and the components capable of forming colloid, thereby making the quality of the desulfurized naphtha more stable. In most cases, the product is water-white.
4. Detailed description of the preferred embodiments
The features of the present invention will be more clearly understood by those skilled in the art from the following examples.
Comparative example 1
Step 1, commercially available magnalium spinel powder with high specific surface area (the powder is roasted at 800 ℃), and the magnalium spinel powder is fully mixed with deionized water in a grinding machine to form thick paste. Then extruded into clover strips with the diameter of phi 2.5 mm. After drying in air at 120 ℃, it was crushed to 3-6mm and then calcined in air at 550 ℃ for 4 hours. The calcined material was used for catalyst preparation. BET surface area of 160m2/g。
Step 2, 5.4 parts ammonium heptamolybdate tetrahydrate (AHM) are dissolved in 29 parts deionized water. The dried material obtained in step 1 was immersed in the solution. The impregnated material was dried in an air atmosphere at 120 ℃ for 24 hours. The dried material was calcined at 500 ℃ for 4 hours in an air stream and cooled to room temperature in air.
And 3, dissolving 4.5 parts of hexahydrate cobalt nitrate in 27 parts of water, soaking the material in the step 2, and drying the soaked material in air flow at 120 ℃ for 24 hours. The dried material was calcined in an air stream at 500 ℃ for 3 hours and cooledin air to room temperature.
Finally loading Mo, Co on catalyst in form of MoO3The weight of CoO is 6 percent and 1.5 percent of the total weight of the catalyst respectively. This is referred to as catalyst A.
Comparative example 2
The magnesia-alumina spinel product is prepared by grinding 70 parts of magnesium aluminate spinel powder, 35 parts of aluminum hydroxide dry glue powder and 50 parts of deionized water to form a thick material, extruding the thick material into clover strips with the diameter of 1.5mm, drying the clover strips in air at 120 ℃, crushing the clover strips into 3-6mm, and calcining the clover strips in air at 550 ℃ for 4 hours. The calcined material was used for catalyst preparation with a BET surface area of 180m2(ii) in terms of/g. 80ml of 25-28% ammonia water is measured, 14 g of ammonium heptamolybdate tetrahydrate is added, the mixture is stirred and dissolved, 15 g of cobalt nitrate is added, and the mixture is stirred until the solution is clear and bright. Soaking the calcined carrier in the prepared cobalt-molybdenum solution in the same volume, drying the soaked carrier in an air atmosphere at 120 ℃ for 24 hours, and then placing the carrier in an air flowCalcined at 500 ℃ for 4 hours and then cooled to room temperature in air.
Finally loading Mo, Co on catalyst in form of MoO3The weight of CoO is 6 percent and 1.5 percent of the total weight of the catalyst respectively. This is referred to as catalyst B.
Example 3
50 parts of magnesium aluminate spinel, 30 parts of aluminum hydroxide dry glue powder and 20 parts of calcium aluminate cement which are the same as those in comparative example 1 are added with a proper amount of deionized water to be mixed into a thick material, and then extruded into a clover strip with the diameter of 2.0 mm. Drying at 120 deg.C in air, crushing into 3-6mm, and calcining at 550 deg.C in air atmosphere for 4 hr to obtain carrier for catalyst preparation. 80ml of ammonia water with the concentration of 25-28% by weight is weighed, 12 g of ammonium heptamolybdate tetrahydrate is added, the mixture is stirred and dissolved, 13 g of cobalt nitrate is added, and the mixture is stirred until the solution is clear and bright. The calcined carrier is impregnated with the prepared cobalt molybdenum solution in equal volume, and the impregnated carrier is dried for 24 hours at 120 ℃ in an air atmosphere. The dried material was calcined at 500 ℃ for 4 hours in an air stream and cooled to room temperature in air.
Finally loading Mo, Co on catalyst in form of MoO3The weight of CoO is 7.5 percent and 1.4 percent of the total weight of the catalyst respectively. This is referred to as catalyst C.
Example 4
70 parts of magnesium aluminate spinel, 15 parts of aluminum hydroxide dry glue powder and 15 parts of calcium aluminate which are the same as those in comparative example 1 are added with a proper amount of deionized water to be mixed into a thick material, and then the thick material is extruded into a clover strip with the diameter of 2.0 mm. Drying at 120 deg.C in air, crushing into 3-6mm, and calcining at 550 deg.C in air atmosphere for 4 hr to obtain carrier for catalyst preparation. 80ml of ammonia water with the concentration of 25-28 weight percent is measured, 16 g of ammonium heptamolybdate tetrahydrate is added, the mixture is stirred and dissolved, 14 g of cobalt nitrate is added, and the mixture is stirred until the solution is clear and bright. The calcined carrier is impregnated with the prepared cobalt molybdenum solution in equal volume, and the impregnated carrier is dried for 24 hours at 120 ℃ in an air atmosphere. The dried material was calcined at 500 ℃for 4 hours in an air stream and cooled to room temperature in air.
Mo, Co and MoO carried on catalyst3The weight of CoO is 8.3 wt% and 1.6 wt% of the total weight of the catalyst. This is referred to as catalyst D.
Example 5 use of the catalyst in Hydrocarbon conversion
The catalysts A, B, C, D in the above examples were each 8.5 g, and the particle size was 18 to 40 mesh, and the activity was evaluated in a fixed bed micro-reverse hydrogenation evaluation apparatus. The hydrogen used in the test is steel cylinder hydrogen with a purity of 99% (m/m). Vulcanization conditions are as follows: the pressure is 2.0MPa, the temperature is 300, the hydrogen-oil ratio (v/v) is 300, and the volume space velocity is 4.0h-1. The sulphurised oil used was cyclohexane plus 6% (m/m) carbon disulphide. And (5) carrying out constant-temperature vulcanization for 6 hours. After sulfurization, the gasoline is passed into catalytic cracking gasoline with boiling range of 80-210 deg.C to obtain fraction containing 1440ppm of sulfur and 51.6 g of bromine per 100 g of oil. At the temperature of 280 ℃, the pressure of 2.0MPa and the space velocity of 4.0h-1And the volume ratio of hydrogen to oil is 300: 1.
And (3) comparison test: then adding common CoMo/Al2O3And carrying out hydrodesulfurization reaction after the hydrodesulfurization catalyst is vulcanized. The vulcanization conditions are as follows: the temperature is 300 ℃, the pressure is 2.0MPa, and the airspeed is 4.0h-1The hydrogen to oil ratio is 300: 1, the sulphurized oil is cyclohexane and 6% (m/m) carbon bisulfide, and the sulphurized time is 6 hours. Reaction conditions are as follows: 300 ℃, 2.0MPa, and the ratio of hydrogen to oil is 300: 1. The results of comparing the activity of the catalyst with that of the above catalyst are shown in Table 3.
TABLE 3 comparative results of catalyst Activity
| Catalyst and process for preparing same | Product sulfur content (ppm) | Desulfurization rate (wt％) | Olefin saturation ratio (wt％) | Strength of catalyst (N/cm) |
| Catalyst A | 220 | 84.7 | 14.2 | 60 |
| Catalyst B | 100 | 87.2 | 28.2 | 80 |
| Catalyst C | 110 | 93.1 | 23.5 | 160 |
| Catalyst D | 120 | 91.6 | 18.3 | 140 |
| CoMo/Al2O3 | 14 | ＞98 | ＞99％ | 150 |
As can be seenfrom the results in Table 3, the catalyst prepared by the present invention can maintain a high desulfurization rate, and simultaneously, can reduce the olefin saturation rate to the maximum extent, thereby reducing the octane number loss and improving the catalyst strength.
Example 6 hydrodesulfurization experiment of FCC gasoline full cut with the catalyst of the present invention
86 g of the catalyst D obtained in example 4, having a particle size of 20 to 40 mesh, was subjected to activity evaluation in a small hydrogenation evaluation apparatus. The hydrogen used in the test was reformed hydrogen with a purity of 95% (m/m). Vulcanization conditions are as follows: the pressure is 2.0MPa, the temperature is 290 ℃, the hydrogen-oil ratio (v/v) is 400, and the volume space velocity is 2.0h-1. The vulcanized oil is straight-run kerosene + 1% CS2And carrying out constant-temperature vulcanization for 5 hours. After vulcanization, the gasoline is introduced into the catalytic cracking gasoline full fraction of a victory refinery, the sulfur content of the gasoline is 860ppm, and the bromine number is 70 g of bromine per 100 g of oil. At the temperature of 260 ℃, the pressure of 2.0MPa and the space velocity of 3.0h-1Hydrogen, oil (body)Product) ratio of 400: 1. The activity results are shown in Table 4.
Table 4 results of full distillate selective hydrogenation activity data base oil properties (full distillate) RON/MON 90.3/78.6 sulfur/μ g.g-1860 product Properties (Whole fraction) RON/MON 88.3/78.4 antiknock index loss-1.1 Sulfur/μ g.g-1120
As can be seen from Table 4, the desulfurization rate of the full-range gasoline treated by the catalyst of the present invention was greater than 85%, and the antiknock index loss was only 1.1 units.
Claims (15)
1. A selective hydrodesulfurization process comprising contacting naphtha in the presence of hydrogen with a selective hydrodesulfurization catalyst under process conditions: the temperature is 204 ℃ and 399 ℃, the pressure is 0.5-7.0MPa, and the liquid hourly space velocity is 1-15LHSV, which is characterized in that the selective hydrodesulfurization catalyst contains molybdenum and/or tungsten, nickel and/or cobalt, which is loaded on a composite carrier containing spinel, active alumina and cement, wherein the content of molybdenum and/or tungsten accounts for 0.1-15% of the weight of the catalyst calculated by metal oxide, and the content of nickel and/or cobalt accounts for 0.1-10% of the weight of the catalyst calculated by metal oxide.
2、A selective hydrodesulfurization process according to claim 1 wherein the amount of hydrogen is from 50 to 800 Nm/l3.m-3。
3. A selective hydrodesulfurization process as claimed in claim 1 wherein the composite support comprises 30 to 90% spinel, 0.1 to 60% activated alumina, and 0.1 to 60% cement, based on the weight of the catalyst.
4. A selective hydrodesulfurization process according to claim 1, 2 or 3 wherein the spinel is magnesia alumina spinel.
5. A selective hydrodesulfurization process according to claim 1, 2 or 3 wherein the cement is calcium aluminate cement.
6. A selective hydrodesulfurization process according to claim 1 wherein the process conditions are: the temperature is 260 ℃ and 350 ℃, the pressure is 1.0-4.0MPa, andthe liquid hourly space velocity is 2-5 LHSV.
7. A selective hydrodesulfurization process according to claim 1 wherein the process conditions are: the temperature is 260 ℃ and 350 ℃, the pressure is 1.0-4.0MPa, the liquid hourly space velocity is 2-5LHSV, and the hydrogen-oil ratio is 200 Nm and 500 Nm8.m-8。
8. A selective hydrodesulfurization process according to claim 1 wherein said naphtha comprises light cat-cracked gasoline, full range cat-cracked gasoline or heavy cat-cracked gasoline.
9. A selective hydrodesulfurization catalyst comprising molybdenum and/or tungsten, nickel and/or cobalt on a composite support comprising spinel, activated alumina and cement, wherein the molybdenum and/or tungsten content is from 0.1 to 15% by weight of the catalyst calculated as the metal oxide and the nickel and/or cobalt content is from 0.1 to 10% by weight of the catalyst calculated as the metal oxide.
10. The catalyst of claim 9 wherein the composite support comprises 30 to 90% spinel, 0.1 to 60% activated alumina, and 0.1 to 60% cement, based on the weight of the catalyst.
11. The catalyst of claim 9 wherein the composite support comprises 50-80% spinel, 0.1-40% activated alumina, and 0.5-40% cement, based on the weight of the catalyst.
12. A catalyst as claimed in claim 9, 10 or 11, wherein the spinel is a magnesium aluminate spinel.
13. A catalyst as claimed in claim 9, 10 or 11, wherein the cement is a calcium aluminate cement.
14. The catalyst of claim 9 wherein the molybdenum oxide is present in an amount of 1 to 10% and the cobalt oxide is present in an amount of 0.5 to 5% by weight of the catalyst.
15. The catalyst of claim 9 comprising, by weight of the catalyst, from 1 to 10% molybdenum oxide, from 0.5 to 5% cobalt oxide, from 50 to 80% spinel, from 0.1 to 40% activated alumina, and from 0.5 to 40% cement.
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| CN 01142839 CN1231560C (en) | 2001-12-30 | 2001-12-30 | Naphtha selective hydrogenation desulfurization process and catalyst |
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| CN 01142839 CN1231560C (en) | 2001-12-30 | 2001-12-30 | Naphtha selective hydrogenation desulfurization process and catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103381366A (en) * | 2012-05-04 | 2013-11-06 | 中国石油天然气股份有限公司 | Hydrodeoxygenation catalyst with good hydrothermal stability and preparation and application thereof |
| CN104178211A (en) * | 2010-11-12 | 2014-12-03 | 催化蒸馏技术公司 | Selective desulfurization of fcc gasoline |
-
2001
- 2001-12-30 CN CN 01142839 patent/CN1231560C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178211A (en) * | 2010-11-12 | 2014-12-03 | 催化蒸馏技术公司 | Selective desulfurization of fcc gasoline |
| CN104178211B (en) * | 2010-11-12 | 2016-08-24 | 催化蒸馏技术公司 | The selective desulfurization of FCC gasoline |
| CN103381366A (en) * | 2012-05-04 | 2013-11-06 | 中国石油天然气股份有限公司 | Hydrodeoxygenation catalyst with good hydrothermal stability and preparation and application thereof |
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| CN1231560C (en) | 2005-12-14 |
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