CN114452978B - Hydrogenation protection catalyst and preparation method and application thereof - Google Patents
Hydrogenation protection catalyst and preparation method and application thereof Download PDFInfo
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- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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Abstract
The invention relates to the petrochemical field, and discloses a hydrogenation protection catalyst and a preparation method and application thereof. The hydrogenation protecting catalyst comprises an alumina carrier and a metal oxide active component, and the preparation method comprises the following steps: uniformly kneading pseudo-boehmite, anthracene, biotite and extrusion aid to obtain a mixture; uniformly kneading the peptizing acid solution and the mixture, shaping, drying and roasting to obtain an alumina carrier; adding a nonionic surfactant to the precursor aqueous solution of the metal oxide active component to form a mixed solution; and (3) immersing the alumina carrier in the mixed solution, and drying and roasting to obtain the hydrogenation protection catalyst. The invention uses anthracene as a pore-expanding agent, and has better pore-expanding effect. On one hand, the mechanical strength of the carrier can be improved; on the other hand, the activity stability of the downstream main catalyst can be better protected. The hydrogenation protecting catalyst of the invention can fully utilize inferior heavy oil, and the obtained mixed aromatic hydrocarbon product has high yield and low impurity content.
Description
Technical Field
The invention relates to the petrochemical field, in particular to a hydrogenation protecting catalyst and a preparation method and application thereof.
Background
At present, petroleum resources show heavy and inferior trend, the yield of heavy and inferior crude oil is increased year by year worldwide, the processing proportion of the heavy and inferior crude oil is increasingly increased, and the processing capacity of the heavy and inferior crude oil, especially the residual oil processing capacity, is urgently required to be increased.
The residual oil is the residual oil obtained by vacuum distillation of a primary processing device of a petroleum refinery in the petrochemical industry, so the residual oil is called vacuum residual oil; heavy oils obtained from the bottom of atmospheric distillation columns are sometimes also referred to as atmospheric residuum. The content of vacuum residuum in crude oil produced in China is higher, and the yield of the vacuum residuum at the temperature of more than 500 ℃ is generally 40-50%. In 2019, the national crude oil throughput was 65198.1 ten thousand tons and the vacuum residuum was about 3 hundred million tons.
The trend of the heavy crude oil resource is to put new requirements on heavy oil processing technology. In recent years, oil refining technology development institutions at home and abroad have made a great deal of work in the industrial application of fixed bed residuum hydrotreatment, ebullated bed hydrocracking and suspension bed hydrocracking technologies. At present, the fixed bed residual oil hydrogenation technology is still the main industrial application technology of residual oil processing, but has the defect of poor raw material adaptability; in order to adapt to the poor quality trend of raw materials, the hydrocracking technology of boiling bed and suspension bed has been used in industry, but the problems of high cost of equipment and operation, large investment and long return on investment are existed in the two technologies.
Hydrocracking tail oil, generally referred to as distillate from refinery hydrocrackers > 350 ℃. The hydrocracking tail oil with low BMCI can be used as raw material for preparing ethylene by steam cracking, and the tail oil with high BMCI can be used as catalytic cracking feed. For some small refineries, the economics of hydrocracking tail oil can be improved if the heavy aromatic oil is utilized in combination without ethylene cracking and catalytic cracking units.
The heavy aromatic oil mainly comes from a catalytic reforming and ethylene cracking device. Heavy aromatic hydrocarbon resources have not been fully utilized for a long time, and a small amount of heavy aromatic hydrocarbon resources are removed to be used as solvents and extracted C 9 、C 10 Except the monomer aromatic hydrocarbon, the rest is basically mixed into the inferior fuel to burn. Along with the increasing perfection of environmental protection regulations in China, blending and burning are limited. Therefore, how to effectively utilize these heavy aromatic resources and convert them into BTX (benzene, toluene, xylene) has become one of the important subjects in the technical field of aromatic hydrocarbons at home and abroad.
In the process of hydrotreating inferior heavy oil, a hydrogenation protecting catalyst is needed to protect the activity stability of a downstream main catalyst, and patents related to the hydrogenation protecting catalyst are more. Patent CN102989491B discloses a heavy oil hydrogenation protecting catalyst, a preparation method and an application method thereof, wherein the pore volume of an oxide silicon aluminum carrier is 0.98-1.15ml/g, and the specific surface is 340-380m 2 And/g. The hydrogenation protecting catalyst disclosed in patent CN103285935B has carrier containing alpha-alumina and pore volume of 0.5-0.75mL/g and specific surface area of 2-20m 2 /g, adding one or more of silicon, phosphorus, alkali or alkaline earth metals as auxiliary components. The patent CN108421548B adopts an impregnation method to load water-soluble salt of hydrogenation metal active components and an organic complexing agent on a carrier, and the hydrogenation protection catalyst has a demetallization rate of 96 percent after impregnation of a semi-finished catalyst, drying and no roasting. The hydrogenation protecting catalyst in patent CN2019109383971 comprises a metal active component and a carrier, wherein the carrier is mainly formed by mixing fullerene, naphthalene and alumina, extruding, forming, drying and roasting. The patent CN1107102C adopts sesbania powder, carbon black and other substances as pore-expanding agents, and the addition amount is 1.5-5.5wt%. The addition of conventional physical pore-expanding agents to the carrier can lead to the dispersion of the carrier pores, the macroporous part can not form continuous through pore channels, the pore channels are small in pore opening and large in pore cavity, and the mechanical strength of the catalyst can be reduced by the pore channels.
Disclosure of Invention
In order to solve the technical problems, the invention provides a hydrogenation protection catalyst, and a preparation method and application thereof.
The hydrogenation protecting catalyst adopts anthracene as a pore-expanding agent, can realize twice pore-forming in the roasting process of catalyst preparation, has better pore-expanding effect under the same adding amount, can form continuous through pore channels, and can lead the catalyst to contain more impurities and scale substances. On one hand, the problem that the mechanical strength of the carrier is reduced due to large addition amount and large particles formed during burnout of the conventional physical pore-expanding agent can be avoided; on the other hand, the activity stability of the downstream main catalyst can be better protected. The hydrogenation protecting catalyst can be applied to the processing of inferior heavy oil, and can fully utilize the inferior heavy oil, and meanwhile, the obtained mixed aromatic hydrocarbon product has high yield and low impurity content.
The specific technical scheme of the invention is as follows:
in a first aspect, the present invention provides a hydrogenation guard catalyst comprising 70 to 95wt% alumina support and 1 to 8wt% metal oxide active component; the metal oxide is cobalt and/or nickel oxide; the specific surface area of the hydrogenation protecting catalyst is 40-100 m 2 Per gram, the pore volume is 0.3-0.6 mL/g, and the crushing strength is 110-130N/cm.
The hydrogenation protection catalyst has better pore volume and continuous through pore channels, can contain more impurities and scales, and can better protect the activity stability of a downstream main catalyst. In addition, the hydrogenation protecting catalyst has better mechanical property.
In a second aspect, the present invention provides a method for preparing a hydrogenation protecting catalyst, comprising the steps of:
(1) Uniformly kneading pseudo-boehmite, anthracene, biotite and extrusion aid to obtain a mixture.
(2) And uniformly kneading the peptizing acid solution and the mixture, and shaping, drying and roasting to obtain the alumina carrier.
(3) Adding a nonionic surfactant to the precursor aqueous solution of the metal oxide active component to form a mixed solution; and then immersing the alumina carrier in the mixed solution, and then drying and roasting to obtain the hydrogenation protection catalyst.
Firstly, the hydrogenation protecting catalyst adopts an organic compound, namely anthracene, as a pore-expanding agent, and utilizes the characteristics of the anthracene to lead the anthracene to undergo a process of firstly changing into gas and finally burning out to form carbon in the roasting process of a carrier, which is different from pore-forming processes of other conventional physical pore-expanding agents such as carbon black, cellulose and the like, wherein when the anthracene is in a boiling point, the anthracene firstly becomes gas to slowly escape from the carrier, and a plurality of primary pore channels can be formed at the moment; with the rise of temperature, the fuel is finally burnt into carbon, and more secondary pore channels can be formed. The pore-forming effect of the two times is that the pore-forming agent has better pore-forming effect on the premise that the adding amount is not increased compared with that of the conventional physical pore-forming agent, can form a continuous penetrating pore canal, and can contain more impurities and scale matters. On one hand, the problem that the mechanical strength of the carrier is reduced due to large addition amount and large particles formed during burnout of the conventional physical pore-expanding agent is avoided; on the other hand, the activity stability of the downstream main catalyst can be better protected.
Secondly, the invention adopts biotite as the reinforcing agent of the hydrogenation protection catalyst, and utilizes the characteristics of small biotite particle size and large hardness to add the biotite into a carrier. The anthracene serving as the pore-expanding agent effectively avoids the decrease of the carrier strength, further improves the abrasion resistance and impact resistance of the catalyst, and inhibits the collapse phenomenon of carrier pore channels caused by water vapor in a reaction system for maintaining the relative position of active sites of the catalyst, so that the activity of the catalyst is maintained, and the service time of the catalyst is prolonged.
Preferably, in step (1): the addition amount of the anthracene is 3.1-5.0% of the weight of the alumina carrier; the adding amount of the biotite is 1.0-3.0% of the weight of the alumina carrier.
Preferably, in step (1): the extrusion aid is one or more of starch, sesbania powder, polyvinyl alcohol, methyl cellulose and polyethylene glycol, and the addition amount of the extrusion aid is 2-10wt% based on the total weight of the components.
Preferably, in step (2): the peptizing acid is one or more of nitric acid, phosphoric acid, citric acid, hydrochloric acid and acetic acid.
Preferably, in step (2): the temperature of the peptizing acid solution is 40-80 ℃, and the adding speed is 11-20 g/min.
Preferably, in step (2): the shaping is performed by extruding into a cylindrical strip shape with the equal height-diameter ratio of 5-15 mm; the drying temperature is 100-140 ℃; the roasting temperature is 350-550 ℃ and the roasting time is 5-10 h.
Preferably, in step (3): the precursor aqueous solution of the metal oxide active component is one or more of cobalt nitrate aqueous solution, cobalt acetate aqueous solution, nickel nitrate aqueous solution and basic nickel carbonate aqueous solution; the concentration of metal ions in the precursor aqueous solution is 5-40 g/100mL.
Preferably, in step (3): the addition amount of the nonionic surfactant is 2-10wt% of the alumina carrier.
Preferably, in step (3): the soaking time is 5-10 h; the drying temperature is 100-150 ℃; the roasting temperature is 400-600 ℃, and the roasting time is 2-8 h.
In a third aspect, the present invention provides an application of the hydrogenation protecting catalyst in processing inferior heavy oil, comprising the following steps: mixing heavy aromatic oil and inferior heavy oil, and distilling to separate light fraction and heavy fraction; selectively hydrofining the light fraction to produce aromatic hydrocarbon; the heavy fraction is used as pyrolysis catalytic feed; wherein, in the selective hydrofining to produce aromatic hydrocarbon, a selective hydrofining catalyst and the hydrogenation protecting catalyst are adopted.
Preferably, the selective hydrofining of the light fraction to produce aromatic hydrocarbon adopts a hydrofining reactor filled with the hydrogenation protecting catalyst and the selective hydrofining catalyst.
Preferably, the loading volume ratio of the hydrogenation protecting catalyst to the selective hydrofining catalyst is 1:2-3.
Preferably, the selective hydrofining catalyst is a catalyst for producing refined naphthalene by selective hydrofining of heavy benzol naphthalene.
Compared with the prior art, the invention has the following technical effects:
(1) The hydrogenation protecting catalyst adopts an organic compound, namely anthracene, as a pore-expanding agent, and utilizes the characteristics of the anthracene to lead the anthracene to undergo a process of firstly changing into gas and finally burning out the anthracene into carbon in the roasting process of a carrier, which is different from pore-forming processes of other conventional physical pore-expanding agents such as carbon black, cellulose and the like, wherein when the anthracene is in a boiling point, the anthracene firstly becomes gas to slowly escape from the carrier, and a plurality of primary pore channels can be formed at the moment; with the rise of temperature, the fuel is finally burnt into carbon, and more secondary pore channels can be formed. The pore-forming effect of the two times is that the pore-forming agent has better pore-forming effect on the premise that the adding amount is not increased compared with that of the conventional physical pore-forming agent, can form a continuous penetrating pore canal, and can contain more impurities and scale matters. On one hand, the problem that the mechanical strength of the carrier is reduced due to large addition amount and large particles formed during burnout of the conventional physical pore-expanding agent is avoided; on the other hand, the activity stability of the downstream main catalyst can be better protected.
(2) The invention adopts biotite as the reinforcing agent of the hydrogenation protection catalyst, and utilizes the characteristics of small particle size and large hardness of biotite to add the biotite into a carrier. The anthracene serving as the pore-expanding agent effectively avoids the decrease of the carrier strength, further improves the abrasion resistance and impact resistance of the catalyst, and inhibits the collapse phenomenon of carrier pore channels caused by water vapor in a reaction system for maintaining the relative position of active sites of the catalyst, so that the activity of the catalyst is maintained, and the service time of the catalyst is prolonged.
(3) The invention mixes the inferior heavy oil, residual oil and hydrocracking tail oil with heavy aromatic oil, utilizes the dissolving power of aromatic hydrocarbon in heavy aromatic oil to residual oil and hydrocracking tail oil, enriches aromatic hydrocarbon in the latter two into light fraction through distillation, and the light fraction is catalyzed by the hydrogenation protecting catalyst and the selective hydrogenation catalyst to produce mixed aromatic hydrocarbon with high yield and low impurity content, which can be used as feed of downstream reforming device or naphthalene making device to obviously improve the combination economy of the inferior heavy oil and heavy aromatic oil.
(4) The invention provides a method with high raw material utilization rate, good product property and good comprehensive economy for residual oil, hydrogenated tail oil and heavy aromatic oil with lower added value and a hydrogenation protecting catalyst, and is very beneficial to emission reduction and synergy of refineries.
Detailed Description
The invention is further described below with reference to examples.
General examples
A hydrogenation protecting catalyst comprises 70-95 wt% of alumina carrier and l-8 wt% of metal oxide active component; the metal oxide is cobalt and/or nickel oxide; the specific surface area of the hydrogenation protecting catalyst is 40-100 m 2 Per gram, the pore volume is 0.3-0.6 mL/g, and the crushing strength is 110-130N/cm.
A method for preparing a hydrogenation protection catalyst, comprising the following steps:
(1) Uniformly kneading pseudo-boehmite, anthracene, biotite and extrusion aid to obtain a mixture. Wherein:
the addition amount of the anthracene is 3.1-5.0% of the weight of the alumina carrier; the adding amount of the biotite is 1.0-3.0% of the weight of the alumina carrier. The extrusion aid is one or more of starch, sesbania powder, polyvinyl alcohol, methyl cellulose and polyethylene glycol, and the addition amount of the extrusion aid is 2-10wt% based on the total weight of the components.
(2) Adding 40-80 ℃ peptizing solution into the mixture at the speed of 11-20 g/min, uniformly kneading, shaping, drying at 100-140 ℃, and roasting at 350-550 ℃ for 5-10 h to obtain the alumina carrier. Wherein:
the peptizing acid is one or more of nitric acid, phosphoric acid, citric acid, hydrochloric acid and acetic acid. The shaping is performed by extruding into a cylindrical strip shape with the equal height-diameter ratio of 5-15 mm;
(3) Adding nonionic surfactant (2-10wt% of alumina carrier) into precursor aqueous solution of metal oxide active component to form mixed solution; and then immersing the alumina carrier in the mixed solution for 5-10 h, and then drying at 100-150 ℃ and roasting at 400-600 ℃ for 2-8 h to obtain the hydrogenation protecting catalyst. Wherein:
the precursor aqueous solution of the metal oxide active component is one or more of cobalt nitrate aqueous solution, cobalt acetate aqueous solution, nickel nitrate aqueous solution and basic nickel carbonate aqueous solution; the concentration of metal ions in the precursor aqueous solution is 5-40 g/100mL.
The application of the hydrogenation protecting catalyst in the processing of inferior heavy oil comprises the following steps: mixing heavy aromatic oil (including but not limited to heavy aromatic byproducts in the process of producing triphenyl products) and inferior heavy oil (including atmospheric and vacuum residuum or tail oil of hydrocracking equipment in petrochemical industry) according to the mass ratio of 1:1-3, and distilling at normal pressure to separate light fraction and heavy fraction, wherein the cutting temperature is 250 ℃, namely the light fraction is less than 250 ℃, and the heavy fraction is more than 250 ℃; selectively hydrofining the light fraction to produce aromatic hydrocarbon; the heavy fraction is used as pyrolysis catalytic feed. Wherein, in the selective hydrofining to produce aromatic hydrocarbon, a hydrofining reactor filled with a hydrogenation protecting catalyst and a selective hydrofining catalyst is adopted. The filling volume ratio of the hydrogenation protecting catalyst to the selective hydrofining catalyst is 1:2-3. Selective hydrofining catalyst a catalyst for selective hydrofining of heavy benzol naphthalene to produce refined naphthalene (e.g. the catalyst disclosed in zl201810201010.X, named 1010C). The volume airspeed is 0.3-1.0 h < -1 >, the system reaction pressure hydrogen partial pressure is 4.0-6.0 MPa, the reaction temperature is 340-360 ℃, and the hydrogen-oil ratio is 500:1-1000:1.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Preparation of hydrogenation protection catalyst C1: taking 50g of pseudo-boehmite, adding 1.3g of anthracene, 0.7g of biotite and 3g of sesbania powder (extrusion aid), and uniformly kneading; dropwise adding an aqueous solution containing nitric acid (with the concentration of 60%) at 80 ℃ at the dropwise speed of 20g/min, kneading, extruding into a cylindrical strip with the height-diameter ratio of 10mm based on the uniform kneading of the four substances, drying at 140 ℃ for 7h, and roasting at 400 ℃ for 7.5h to prepare an alumina carrier; preparing aqueous solution with metal ion concentration of 10g/ml by using cobalt nitrate, adding dodecafatty alcohol polyether into the aqueous solution to obtain impregnating solution for impregnating the alumina carrier for 7.5h, drying at 125 ℃ for 3h and roasting at 500 ℃ for 5h. The final composition of the catalyst is as follows: cobalt oxide 6.4wt% and the balance alumina. Specific surface area of catalyst 56m 2 Per g, pore volume 0.56mL/g, crush strength 112N/cm. The hydrogenation protecting catalyst C1 was thus prepared.
Preparation of hydrogenation protection catalyst C2: taking 61g of pseudo-boehmite, adding 4.2g of anthracene, 2.0g of biotite and 5g of sesbania powder (extrusion aid), and uniformly kneading; dropwise adding an aqueous solution containing nitric acid (with the concentration of 50%) at the temperature of 40 ℃ at the dropwise speed of 11g/min, kneading, extruding into a cylindrical strip with the height-diameter ratio of 10mm based on the uniform kneading of the four substances, drying at the temperature of 100 ℃ for 5h, and roasting at the temperature of 550 ℃ for 5h to prepare an alumina carrier; preparing an aqueous solution with the metal ion concentration of 8g/ml by using nickel nitrate, adding dodecafatty alcohol polyether into the aqueous solution to obtain an impregnating solution, impregnating the alumina carrier for 10 hours, drying at 100 ℃ for 4 hours, and roasting at 400 ℃ for 8 hours. The final composition of the catalyst is as follows: nickel oxide 5.9wt% with the balance being aluminum oxide. Specific surface area of catalyst 75m 2 Per g, pore volume 0.41mL/g, crush strength 124N/cm. The hydrogenation protecting catalyst C2 was thus obtained.
Preparation of hydrogenation protection catalyst C3: taking 73g of pseudo-boehmite, adding 5.0g of anthracene, 2.4g of biotite and 7g of sesbania powder (extrusion aid), and uniformly kneading; dropwise adding an aqueous solution containing nitric acid (with the concentration of 60%) at the temperature of 60 ℃ at the dropwise adding speed of 15g/min, kneading, extruding into a cylindrical strip with the height-diameter ratio of 10mm based on the uniform kneading of the four substances, drying at the temperature of 120 ℃ for 2h, and roasting at the temperature of 350 ℃ for 10h to prepare an alumina carrier; and thenPreparing aqueous solution with metal ion concentration of 12g/ml by using cobalt acetate, adding dodecafatty alcohol polyether into the aqueous solution to obtain impregnating solution, impregnating the alumina carrier for 5h, drying at 125 ℃ for 3h, and roasting at 600 ℃ for 2h. The final composition of the catalyst is as follows: 7.5wt% of cobalt oxide and the balance of aluminum oxide. Specific surface area of catalyst 94m 2 Per g, pore volume 0.38mL/g, crush strength 130N/cm. The hydrogenation protecting catalyst C3 was thus prepared. Preparation of hydrogenation protection catalyst C4: the only difference from the hydrogenation protection catalyst C2 is the replacement of anthracene with naphthalene. Specific surface area of hydrogenation protecting catalyst C4 of 158m 2 Per g, pore volume 0.24mL/g, crush strength 98N/cm.
Preparation of hydrogenation protection catalyst C5: the only difference from the hydrogenation protecting catalyst C2 is that no biotite was added. Specific surface area 82m of hydrogenation protecting catalyst C5 2 Per g, pore volume 0.46mL/g, crush strength 85N/cm.
The heavy aromatic oil used in the examples below was C split 9+ Heavy aromatic hydrocarbon raw oil, the raw material is C 9 And above aromatic hydrocarbon as main component, generally C 8- Aromatic hydrocarbons, C 9 Aromatic hydrocarbons, C 10+ Aromatic hydrocarbon, naphthalene and derivatives thereof, total aromatic hydrocarbon about 78.1%, gum 5.8mg/100g, diene 4.6g I 2 /100g。
In the following examples, the inferior heavy oil used in examples 1 and 2 was vacuum residue, and the mass ratio of the inferior heavy oil to the heavy aromatic oil was 1:2; the inferior heavy oil used in example 3 was a hydrocracked tail oil having a mass ratio to heavy aromatic oil of 1:1.5. The vacuum residuum and hydrocracked tail oil properties used are listed in Table 1.
Mixing the inferior heavy oil and the heavy aromatic oil, and then carrying out normal pressure distillation, wherein the temperature of the mixture is 250 ℃ as a cutting point to obtain light fraction with the temperature of primary distillation to 250 ℃ and heavy fraction with the temperature of more than 250 ℃.
The light fraction enters a selective hydrofining reactor and contacts the hydrogenation protecting catalyst and the selective hydrofining catalyst 1010C from top to bottom, and the filling ratio and the process conditions of the two catalysts in each example are listed in table 2; the results of the reaction after 50 hours and 2000 hours are shown in Table 3, for the nature of the non-aromatic byproducts and the final benzene and naphthalene mixtures obtained.
After gas-liquid separation, the selective hydrofining product is distilled and cut at 220 ℃ to obtain a mixed aromatic hydrocarbon product and a non-aromatic byproduct, wherein the mixed aromatic hydrocarbon product and the non-aromatic byproduct can be fed together with heavy fraction as a pyrolysis catalytic device; and (3) redistilling the mixed aromatic hydrocarbon to separate out two products of mixed benzene with the temperature of between the initial distillation and 200 ℃ and mixed naphthalene with the temperature of more than 200 ℃ which are respectively used as ideal feed for a reforming device and a naphthalene refining device.
It should be noted that the various reaction participants and process conditions used in the following examples are typical examples, but a number of experiments prove that the other types of reaction participants and process conditions listed above are applicable and achieve the technical effects claimed in the present invention.
Example 1: the hydrogenation protection catalyst C1 and the selective hydrofining catalyst 1010C are adopted, and the filling volume ratio is 1:3.
Example 2: the hydrogenation protection catalyst C2 and the selective hydrofining catalyst 1010C are adopted, and the filling volume ratio is 1:2.
Example 3: the hydrogenation protection catalyst C3 and the selective hydrofining catalyst 1010C are adopted, and the filling volume ratio is 1:3.
Comparative example 1: the hydrogenation protection catalyst C4 and the selective hydrofining catalyst 1010C are adopted, and the filling volume ratio is 1:2.
Comparative example 2: the hydrogenation protection catalyst C5 and the selective hydrofining catalyst 1010C are adopted, and the filling volume ratio is 1:2.
TABLE 1 bad heavy oil Properties
| Crude oil name | Vacuum residuum | Hydrocracking tail oil |
| Density (20 ℃ C.) kg.m -3 | 980.1 | 852.8 |
| S，μg·g -1 | 11020 | 587 |
| N，μg·g -1 | 2305 | 301 |
| Carbon residue CCR | 5.3 | - |
| Metal content, μg.g -1 | ||
| Ni+V | 62 | - |
| Fe | 12 | - |
| BMCI | - | 13.1 |
| Distillation range, DEG C | ||
| IBP/10％/30％/50％ | 231/341/405/458 | 230/-/345(15.0％) |
| 70％/90％/95％/EBP | 505(60％) | -/- |
TABLE 2 Selective hydrofinishing reaction conditions
| Scheme for the production of a semiconductor device | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Process conditions | |||||
| Hydrogen partial pressure, MPa | 6.0 | 5.0 | 4.0 | 5.0 | 5.0 |
| Reaction temperature, DEG C | 360 | 340 | 350 | 340 | 340 |
| Airspeed, h -1 | 0.3 | 0.65 | 1.0 | 0.65 | 0.65 |
| Hydrogen to oil volume ratio | 750 | 1000 | 500 | 1000 | 1000 |
TABLE 3 Properties of non-aromatic byproducts, mixed benzene and Mixed naphthalene products
In the above table, the yields of non-aromatic byproducts, mixed benzene and mixed naphthalene products were all calculated from the mixed feed (i.e., the mixture of inferior heavy oil and heavy aromatic oil mixed in proportion).
As can be seen from Table 3, after the inferior heavy oil and the heavy aromatic oil are mixed, the light fraction is distilled out and then subjected to selective hydrofining reaction, the yield of the obtained final product mixed aromatic hydrocarbon is as high as more than 76.5%, the content of triphenyl and the content of naphthalene in the mixed benzene and the mixed naphthalene product are both over 85%, the sulfur quality of the two products is very low, and the catalyst is an ideal reforming device and refined naphthalene device for feeding, can effectively reduce the processing cost of a downstream device, remarkably improves the economical efficiency of the inferior heavy oil and the heavy aromatic oil, and reflects the good impurity removal capability and activity stability of the hydrogenation protection catalyst.
In addition, in comparative example 1, in which naphthalene was used as a pore-enlarging agent, the prepared catalyst had poor activity to protect the downstream main catalyst, and had poorer activity stability, and the same level of effect of the present invention could not be achieved. The reason for this analysis is mainly: 1. naphthalene is used as a pore-enlarging agent by utilizing the characteristic of easy sublimation of naphthalene, and anthracene is used for pore-forming by utilizing the characteristic of volatilization of boiling point of anthracene, wherein the pore-forming mechanisms of naphthalene and anthracene are different; 2. the two molecules have different sizes, and naphthalene is obviously smaller than anthracene, so that the reaming effect of the two molecules is substantially influenced.
For comparative example 2, the addition of biotite was intended to enhance the catalyst strength, thereby improving the activity stability of the catalyst, and the absence of biotite component had a negative effect on the activity stability of the catalyst.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A hydrogenation protecting catalyst, characterized in that:comprises 70 to 95 weight percent of alumina carrier and 1 to 8 weight percent of metal oxide active component; the metal oxide is cobalt and/or nickel oxide; the specific surface area of the hydrogenation protecting catalyst is 40-100 m 2 Per gram, the pore volume is 0.3-0.6 mL/g, and the crushing strength is 110-130N/cm;
the preparation method of the hydrogenation protection catalyst comprises the following steps:
(1) Uniformly kneading pseudo-boehmite, anthracene, biotite and extrusion aid to obtain a mixture;
(2) Uniformly kneading the peptizing acid solution and the mixture, shaping, drying and roasting to obtain an alumina carrier;
(3) Adding a nonionic surfactant to the precursor aqueous solution of the metal oxide active component to form a mixed solution; and then immersing the alumina carrier in the mixed solution, and then drying and roasting to obtain the hydrogenation protection catalyst.
2. The hydro-protecting catalyst of claim 1, wherein: in step (1):
the addition amount of the anthracene is 3.1-5.0% of the weight of the alumina carrier; the adding amount of the biotite is 1.0-3.0% of the weight of the alumina carrier; and/or
The extrusion aid is one or more of starch, sesbania powder, polyvinyl alcohol, methyl cellulose and polyethylene glycol, and the addition amount of the extrusion aid is 2-10wt% based on the total weight of the components.
3. The hydro-protecting catalyst of claim 1, wherein: in the step (2):
the peptizing acid is one or more of nitric acid, phosphoric acid, citric acid, hydrochloric acid and acetic acid; and/or
The temperature of the peptizing acid solution is 40-80 ℃, and the adding speed is 11-20 g/min.
4. A hydrogenation protecting catalyst according to claim 1 or 3, wherein: in the step (2):
the shaping is performed by extruding into a cylindrical strip shape with the equal height-diameter ratio of 5-15 mm; and/or
The drying temperature is 100-140 ℃; and/or
The roasting temperature is 350-550 ℃ and the roasting time is 5-10 h.
5. The hydro-protecting catalyst of claim 2, wherein: in the step (3):
the precursor aqueous solution of the metal oxide active component is one or more of cobalt nitrate aqueous solution, cobalt acetate aqueous solution, nickel nitrate aqueous solution and basic nickel carbonate aqueous solution; the concentration of metal ions in the precursor aqueous solution is 5-40 g/100mL; and/or
The addition amount of the nonionic surfactant is 2-10wt% of the alumina carrier.
6. The hydro-protecting catalyst of claim 1 or 5, wherein: in the step (3):
the soaking time is 5-10 hours; and/or
The drying temperature is 100-150 ℃; and/or
The roasting temperature is 400-600 ℃, and the roasting time is 2-8 h.
7. Use of the hydro-protecting catalyst according to any one of claims 1-6 in the processing of inferior heavy oils, characterized in that it comprises the following steps: mixing heavy aromatic oil and inferior heavy oil, and distilling to separate light fraction and heavy fraction; selectively hydrofining the light fraction to produce aromatic hydrocarbon; the heavy fraction is used as pyrolysis catalytic feed; wherein, in the selective hydrofining to produce aromatic hydrocarbon, a selective hydrofining catalyst and the hydrogenation protecting catalyst are adopted.
8. The use according to claim 7, wherein: the selective hydrofining of the light fraction to produce aromatic hydrocarbon adopts a hydrofining reactor filled with the hydrogenation protecting catalyst and the selective hydrofining catalyst.
9. Use according to claim 7 or 8, characterized in that:
the selective hydrofining catalyst is a catalyst for producing refined naphthalene by selective hydrofining of heavy benzol naphthalene.
10. Use according to claim 7 or 8, characterized in that: the filling volume ratio of the hydrogenation protecting catalyst to the selective hydrofining catalyst is 1: 2-3.
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