CN111097514B - Method for restoring activity of low-activity hydrogenation modified pour point depressing catalyst - Google Patents
Method for restoring activity of low-activity hydrogenation modified pour point depressing catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 230000000694 effects Effects 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 72
- 230000000881 depressing effect Effects 0.000 title claims abstract description 57
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 37
- 230000004048 modification Effects 0.000 claims abstract description 23
- 238000012986 modification Methods 0.000 claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 claims abstract description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims description 21
- 150000004767 nitrides Chemical class 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 34
- 238000009833 condensation Methods 0.000 abstract description 18
- 230000005494 condensation Effects 0.000 abstract description 18
- 230000008901 benefit Effects 0.000 abstract description 12
- 238000011084 recovery Methods 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 9
- 230000007774 longterm Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 44
- 239000003921 oil Substances 0.000 description 38
- 239000002283 diesel fuel Substances 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 13
- 230000000087 stabilizing effect Effects 0.000 description 11
- 238000004517 catalytic hydrocracking Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
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- 230000000607 poisoning effect Effects 0.000 description 5
- 238000007710 freezing Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000002199 base oil Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—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
- 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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
A method for recovering the activity of low-activity hydrogenation modified pour point depressing catalyst. The invention discloses a method for restoring the activity of a low-activity hydrogenation modified pour point depressing catalyst, which comprises the steps of introducing refined oil with the nitrogen content of 0-10 mu g/g into a low-activity hydrogenation modified pour point depressing catalyst bed layer, adjusting the reaction temperature of a modification pour point depressing section to ensure that the condensation point of a diesel product is constant to be 30-35 ℃ compared with the refined oil, and the constant time is 24-48 hours, and adjusting to a hydrogenation modified pour point depressing condition for reaction after the constant operation is finished; the low-activity hydrogenation modified pour point depression catalyst contains 5-50% of molecular sieve and 0.15-0.45% of nitrogen element by weight, wherein the molecular sieve is a beta-type molecular sieve. The method has the advantages of simple process and stable operation, and solves the problem of recovery of activity reduction of the hydro-upgrading pour point depressing catalyst caused by long-term operation according to a hydrofining mode.
Description
Technical Field
The invention relates to a method for restoring the activity of a low-activity hydrogenation modified pour point depressing catalyst, in particular to a method for restoring the activity of a hydrogenation modified pour point depressing catalyst, which causes the activity of the hydrogenation modified pour point depressing catalyst to be reduced due to long-term low-temperature operation.
Background
The hydrocracking technology is a hydrogenation process for reducing more than 10wt% of molecules in raw materials through hydrogenation reaction, and is a process for converting heavy distillate oil (VGO, CGO and DAO) into target products such as light oil, middle distillate oil and the like through hydrodesulfurization, hydrodenitrogenation, polycyclic aromatic hydrocarbon hydrosaturation and ring-opening cracking under the conditions of hydrogen, high temperature and high pressure and under the action of a catalyst. The hydrocracking technology has the advantages of strong raw material adaptability, flexible product scheme, high liquid product yield, good product quality and the like, is always favored by oil refining enterprises of various countries in the world, and has the trend of increasing year by year. Especially in the present day that environmental regulations are increasingly strict and the requirements for product quality are gradually improved, hydrocracking has become an irreplaceable important member in large families of oil refining technology, and the raw materials which can be processed by hydrocracking are wide in range, including straight-run gasoline, diesel oil, vacuum wax oil, atmospheric residue, vacuum residue and other raw materials obtained by secondary processing, such as catalytic diesel oil, catalytic clarified oil, coker diesel oil, coker wax oil and the like.
The hydro-upgrading technology can be summarized into a special hydro-cracking process in principle, and is mainly characterized in that the raw materials, reaction conditions and conversion depth are different, but the catalysts used in the core can be communicated to a certain extent, the raw materials of the hydro-upgrading technology are straight-run diesel oil, coked diesel oil, catalytic diesel oil and the like, the reaction pressure is generally medium pressure, the space velocity is slightly higher than that of the hydro-cracking technology, the hydrogen-oil ratio is slightly lower than that of the hydro-cracking technology, the production purpose is more flexible, the hydro-upgrading technology is more heavy than high-yield naphtha, more heavy than high-yield high-quality diesel oil, and has components between the two for producing low-freezing diesel oil, the hydro-upgrading isomerization pour point depression technology belongs to the hydro-upgrading technology in principle, but due to the specific catalyst characteristics and process characteristics, the hydro-upgrading technology is mainly used for producing low-freezing diesel oil products, and has strong pertinence and high applicability, so the hydro-upgrading technology is particularly suitable for the diesel oil market demand in the high and cold regions in north, the method is used for producing the low freezing point diesel oil product in winter.
Along with the change adjustment of market demands, each oil refining production enterprise can select an applicable hydro-upgrading pour point depressing technology according to the raw material characteristics and the processing balance of the oil refining production enterprise, so that the aims of improving the product quality, meeting the environmental protection demands and adapting to the market structure are fulfilled. However, since low pour point diesel oil products only have a great demand in winter, when market demand changes, enterprises generally adjust the reaction temperature of the hydro-upgrading pour point depressing device to enable the hydro-upgrading pour point depressing device to operate according to a hydrofining mode, so that the activity of the hydro-upgrading pour point depressing catalyst is obviously reduced at a lower reaction temperature, and the difficulty is increased when the hydro-upgrading pour point depressing catalyst is recovered again. The prior art does not well solve the problem of how to improve the activity of the hydro-upgrading pour point depressing catalyst.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for restoring the activity of a low-activity hydrogenation modified pour point depressing catalyst. The method has the advantages of simple process and stable operation, and solves the problem of recovery of activity reduction of the hydro-upgrading pour point depressing catalyst caused by long-term operation according to a hydrofining mode.
A method for restoring activity of a low-activity hydrogenation modification catalyst comprises the steps of introducing refined oil with the nitrogen content of 0-10 mu g/g, preferably less than 5 mu g/g into a low-activity hydrogenation modification pour point depressing catalyst bed layer, adjusting the reaction temperature of a modification pour point depressing section to ensure that the condensation point of a diesel product is constant to 30-35 ℃ compared with that of the refined oil, keeping the constant time to be 24-48 hours, and adjusting to a hydrogenation modification pour point depressing condition for reaction after the constant operation is finished; the low-activity hydrogenation modified pour point depression catalyst contains 5-50% of molecular sieve and 0.15-0.45% of nitrogen element by weight, wherein the molecular sieve is a beta-type molecular sieve.
In the above method, the nitrogen element in the low-activity hydrogenation modification catalyst is derived from an organic nitride, the organic nitride can be a basic organic nitride and a non-basic organic nitride, the proportion (by mol) of the nitrogen element derived from the basic organic nitride is preferably more than 50%, more preferably more than 60%, and the nitrogen element can be derived from the nitride in various hydrogenation modification pour point depressing raw materials.
In the method, the determination process of the nitrogen content of the low-activity hydrogenation modification catalyst is as follows: and (3) carrying out a washing process of an organic solvent (petroleum ether, ethanol or benzene and the like) on the low-activity hydrogenation modified pour point depression catalyst until no oil product exists on the surface and in the pore channel of the catalyst, and drying and then determining.
In the method, the hydrogenation modified pour point depressing feed in the hydrogenation modified pour point depressing condition is a diesel raw material subjected to hydrofining treatment, the final distillation point of the diesel raw material is generally 300-420 ℃, preferably 320-400 ℃, and the density is oneTypically at 0.96g/cm3Below, 0.94g/cm is preferable3Hereinafter, the nitrogen content is generally 0.1wt% or less, preferably 0.08wt% or less, the sulfur content is not particularly limited, and the freezing point is generally 0 ℃ or more, preferably 10 ℃ or more. The diesel oil raw material can be various straight-run or secondary processed diesel oils obtained by processing naphthenic base crude oil, intermediate base crude oil or paraffin base crude oil, and the like, can also be oil products obtained by mixing the various diesel oils, and is in an application range as long as the diesel oil raw material is any liquid-phase oil product suitable for serving as a raw material of a hydro-upgrading pour point depressing device.
In the method, the reaction temperature is adjusted to ensure that the condensation point of the diesel product is sequentially constant at 10-15 ℃, 20-25 ℃ and 30-35 ℃ compared with the reduction amplitude of the refined oil, in principle, each stage does not need to be limited to strict constant time, the adjustment is continued after the judgment is carried out by taking the condensation point of the diesel product which is not changed any more as an end point when the reaction temperature is not changed in the stage, but according to the practical application experience, the constant time of each stage is generally 24-48 hours.
In the method, the hydro-upgrading pour point depressing reaction conditions are that the operating pressure is 6.0-13.0 MPa, the volume ratio of hydrogen to oil is 300: 1-1000: 1, and the volume airspeed is 0.1-5.0 h-1(ii) a The optimal operation pressure is 7.0-12.0 MPa, the volume ratio of hydrogen to oil is 400: 1-700: 1, and the volume airspeed is 0.5-4.0 h-1。
In the method, the hydro-upgrading pour point depressing catalyst (fresh catalyst) contains 15-45 wt%, preferably 20-40 wt% of active metal oxide, and the active metal comprises one or more of Wo, Mo, Co and Ni. The hydro-upgrading pour point depressing catalyst can be selected from various conventional commercial catalysts, such as hydro-upgrading pour point depressing catalysts, such as FC-14, FC-20 and the like developed by the Fushun petrochemical research institute (FRIPP); it can also be prepared according to the common knowledge in the field, if necessary.
In the method, the process of improving the activity of the low-activity hydrogenation modified pour point depressing catalyst can be carried out on line, and is suitable for the condition that the activity of the hydrogenation modified pour point depressing catalyst is reduced due to the fact that the hydrogenation modified pour point depressing catalyst runs at low temperature according to a hydrogenation refining mode for a long time. The long-term low-temperature operation according to a hydrofining mode means that the diesel raw material is subjected to a hydrodesulfurization process under the hydrofining condition for at least 3 months continuously, the process does not limit the nitrogen content of a product at all, only the sulfur content meets the quality requirement of the product, meanwhile, the temperature of a modified pour-point depressing catalyst bed layer is basically not increased in the process, in addition, a pressure-reducing production operation mode can be adopted at certain specific time, the accurate temperature of the process is not single due to the fact that the sulfur and nitrogen content of the diesel raw material is wide, but the nitrogen content of refined oil is certainly higher than the limit of the modified catalyst on the nitrogen impurity of the preorder feeding, and the numerical value of the nitrogen is at least larger than 100 ppm.
In the method, the reaction temperature of the low-activity hydrogenation modified pour point depression catalyst is 350-400 ℃, the temperature difference T between the outlet temperature and the inlet temperature of any catalyst bed layer is lower than 5 ℃, and the weight content of nitrogen in the catalyst meets the requirement of 0.15-0.45%.
In the method, the pour point depression amplitude of the diesel product during normal production of hydro-upgrading pour point depression is 5-30 ℃, and preferably 10-25 ℃.
Aiming at the problems in the operation of the existing device, the invention carries out great innovation and creates the unique concept of restoring the activity of the hydro-upgrading pour point depressing catalyst. For a hydro-upgrading pour point depressing catalyst containing a molecular sieve, nitrogen poisoning is a key factor influencing the activity of the hydro-upgrading pour point depressing catalyst, for example, in the existing operation process, along with the extension of the operation time or the change of the operation mode, the hydro-upgrading pour point depressing catalyst is not enough in protection strength, can be poisoned by nitrides, causes the poisoning of the catalyst, generally needs to lose the use activity of the catalyst, influences the pour point depressing depth of products, has certain operation risks, causes higher reaction temperature compensation, increases the gas generation rate, changes the product distribution and seriously influences the operation period. If the reaction temperature is forcibly increased rapidly, the excessively violent reaction may cause permanent deterioration of the catalyst activity, resulting in a great reduction in the catalyst life. The recovery mode of sectional analysis is adopted, so that not only is violent reaction avoided, but also the effect of gradual release of activity can be achieved. The increase of the catalyst activity means a lower reaction temperature, the reduction of energy consumption, the reduction of gas making rate, the improvement of liquid yield, the improvement of selectivity, better product quality, the prolongation of period and other advantages. The invention aims to solve the problem that the modified pour point depressing catalyst is poisoned in the existing production during long-term low-temperature operation, the production process of the hydrogenation modified catalyst breaks through the inherent limitation, the advanced method of firstly raising the temperature excessively and resolving the concept of 'leading' reactivation by stages, then lowering the temperature for production and optimizing the process parameters is introduced, the diesel raw material is introduced and the temperature is controlled in the production process, the process of 'reactivation' by stages with low conversion rate of the modified pour point depressing catalyst is set in the temperature raising process, so that on one hand, the toxic nitride in the catalyst can be reasonably removed at a certain temperature, on the other hand, the surface of the catalyst is not easy to generate violent chemical reaction under the lower conversion depth, thereby the carbon deposition inactivation rate is also reduced, simultaneously, the removal speed of the toxic is improved, the catalyst activity is gradually recovered by the stage process, the chemical reaction is fitted to the nitride resolving process according to the requirements of the process, the method has the advantages of improving and innovating the recovery of the activity of the catalyst, fully utilizing the characteristics of physical properties of raw materials to obtain an ideal comprehensive processing effect, improving the activity of the catalyst on the basis of not influencing the operation of the device, optimizing the structure of a product, solving the problems existing in the operation process, greatly saving manpower and material resources, improving the operation flexibility of the hydrogenation modification pour point depressing device, prolonging the operation period and reducing the yield of low value-added products in the production process.
In the process, the method leads the diesel raw material subjected to hydro-upgrading and pour point depressing into the subsequent reaction after the refining process, and is directly applied to the activity recovery process of the hydro-upgrading and pour point depressing device, thereby avoiding extra investment, gradually leading the catalyst to be reactivated in advance according to the requirements, stabilizing the activity of the catalyst, utilizing the existing process of the device to cure the 'sick' upgrading and pour point depressing catalyst to the maximum extent, solving the fundamental problem of low activity of the catalyst, achieving the aim of reasonable utilization of resources, and simultaneously having the advantages of energy conservation, no need of any modification, simple process flow, convenient operation, environmental protection, low carbon and the like.
In addition, the method has good effect of restoring the activity of the catalyst, sufficient process, proper process conditions and simple selection mode, and can further accelerate the activity stability of the catalyst through the segmentation process, so that the production process is more refined and standardized, the production of by-products of devices of enterprises is reduced, higher economic benefits are created, the step of enabling the catalyst to enter a stable state is simpler and more convenient, the process is more stable, and a foundation is laid for flexible production.
Detailed Description
The action and effect of the method for restoring the activity of a low-activity hydro-upgrading pour point depressing catalyst of the present invention will be further described with reference to the following examples and comparative examples. The properties of the raw oil used in the following examples and comparative examples are shown in table 1, wherein the condensation point reduction is the difference between the properties of the diesel oil product and the diesel oil raw material, the main physicochemical properties of the catalyst used are shown in table 2, only the catalyst B is used in example 5, the catalyst A is used in the other examples and comparative examples, the hydrorefining process is included in the examples and comparative examples, and when no special mention is made, the reaction temperature is increased to refer to the hydro-upgrading condensation point reduction stage. The life evaluation of the comparative examples and examples was carried out by using the difference between the average temperature and the use limit temperature of the apparatus (here, the use limit temperature is selected to be 410 ℃), and the operation was better reflected, and the closer the difference, the shorter the life.
TABLE 1 Primary Properties of the base oils
TABLE 2 catalyst key Properties
Example 1
Introducing raw oil subjected to hydrofining treatment into a low-activity hydrogenation modification pour point depression catalyst bed layer, wherein the nitrogen content of the raw oil subjected to hydrofining treatment is-10 ppm, the low-activity hydrogenation modification pour point depression catalyst contains 5% of beta molecular sieve and 0.20% of nitrogen element by weight, the reaction temperature is increased to 380 ℃, temperature adjustment is carried out, the condensation point depression amplitude of a diesel product is controlled to be 10 ℃, and the diesel product is stabilized for 36 hours; continuously adjusting the reaction temperature, controlling the condensation point of the diesel oil product to reduce the amplitude by 20 ℃, and stabilizing for 36 hours; continuously adjusting the reaction temperature, controlling the condensation point of the diesel oil product to reduce by 30 ℃, and stabilizing for 36 hours; and (5) finishing the recovery process, adjusting the process conditions to enter normal production, and controlling the pour point depression depth to be the same as that of the comparative example 1.
Example 2
Introducing raw oil subjected to hydrofining treatment into a low-activity hydrogenation modification pour point depression catalyst bed layer, wherein the nitrogen content of the raw oil subjected to hydrofining treatment is-10 ppm, the low-activity hydrogenation modification pour point depression catalyst contains 5% of beta molecular sieve and 0.20% of nitrogen element by weight, the reaction temperature is increased to 380 ℃, temperature adjustment is carried out, the condensation point depression range of a diesel product is controlled to be 15 ℃, and the diesel product is stabilized for 36 hours; continuously adjusting the reaction temperature, controlling the condensation point of the diesel oil product to reduce by 25 ℃, and stabilizing for 36 hours; continuously adjusting the reaction temperature, controlling the condensation point of the diesel oil product to reduce by 35 ℃, and stabilizing for 36 hours; and (5) finishing the recovery process, adjusting the process conditions to enter normal production, and controlling the pour point depression depth to be the same as that of the comparative example 2.
Example 3
Introducing raw oil subjected to hydrofining treatment into a low-activity hydrogenation modification pour point depression catalyst bed layer, wherein the nitrogen content of the raw oil subjected to hydrofining treatment is-10 ppm, the low-activity hydrogenation modification pour point depression catalyst contains 5% of beta molecular sieve and 0.20% of nitrogen element by weight, the reaction temperature is increased to 380 ℃, temperature adjustment is carried out, the pour point depression of a diesel product is controlled to be 15 ℃, and the diesel product is stabilized for 24 hours; continuously adjusting the reaction temperature, controlling the condensation point of the diesel oil product to reduce by 20 ℃, and stabilizing for 24 hours; continuously adjusting the reaction temperature, controlling the condensation point of the diesel oil product to reduce by 35 ℃, and stabilizing for 24 hours; and (5) finishing the recovery process, adjusting the process conditions to enter normal production, and controlling the pour point depression depth to be the same as that of the comparative example 1.
Example 4
Introducing raw oil subjected to hydrofining treatment into a low-activity hydrogenation modification pour point depression catalyst bed layer, wherein the nitrogen content of the raw oil subjected to hydrofining treatment is-10 ppm, the low-activity hydrogenation modification pour point depression catalyst contains 5% of beta molecular sieve and 0.25% of nitrogen element by weight, the reaction temperature is increased to 380 ℃, temperature adjustment is carried out, the pour point depression of a diesel product is controlled to be 12 ℃, and the diesel product is stabilized for 36 hours; continuously adjusting the reaction temperature, controlling the condensation point of the diesel oil product to reduce by 22 ℃, and stabilizing for 48 hours; continuously adjusting the reaction temperature, controlling the condensation point of the diesel oil product to reduce by 33 ℃, and stabilizing for 24 hours; and (5) finishing the recovery process, adjusting the process conditions to enter normal production, and controlling the pour point depression depth to be the same as that of the comparative example 1.
Example 5
Introducing raw oil subjected to hydrofining treatment into a low-activity hydrogenation modified pour point depression catalyst bed layer, wherein the nitrogen content of the raw oil subjected to hydrofining treatment is-10 ppm, the low-activity hydrogenation modified pour point depression catalyst contains 25 wt% of beta molecular sieve and 0.31 wt% of nitrogen element, the reaction temperature is increased to 375 ℃, temperature adjustment is carried out, the pour point depression amplitude of a diesel product is controlled to be 10 ℃, and the diesel product is stabilized for 36 hours; continuously adjusting the reaction temperature, controlling the condensation point of the diesel oil product to reduce by 25 ℃, and stabilizing for 24 hours; continuously adjusting the reaction temperature, controlling the condensation point of the diesel oil product to reduce by 35 ℃, and stabilizing for 48 hours; and (5) finishing the recovery process, adjusting the process conditions to enter normal production, and controlling the pour point depression depth to be the same as that of the comparative example 1.
Comparative example 1
And (2) introducing the raw oil subjected to hydrofining treatment into a low-activity hydro-upgrading pour point depression catalyst bed, wherein the nitrogen content of the raw oil subjected to hydrofining treatment is-10 ppm, the low-activity hydro-upgrading catalyst contains 5 wt% of beta molecular sieve and 0.25 wt% of nitrogen element, and the activity is recovered and the raw oil enters normal production according to a mode of directly increasing the reaction temperature (about 3 ℃/h) without performing the operation of sectional excessive recovery according to the method.
Comparative example 2
And (2) introducing the raw oil subjected to hydrofining treatment into a low-activity hydro-upgrading pour point depressing catalyst bed layer, wherein the nitrogen content of the raw oil subjected to hydrofining treatment is-10 ppm, the low-activity hydro-upgrading catalyst contains 5 wt% of beta molecular sieve and 0.25 wt% of nitrogen element, the activity is restored and normal production is carried out according to a mode of directly increasing the reaction temperature (about 3 ℃/h) without carrying out the operation of sectional over-restoration according to the method, and the controlled pour point depressing depth is higher than that of comparative example 1.
The reaction effects in normal production after adjustment of the above examples and comparative examples were compared, and the results were as follows:
it can be seen from the life evaluation of the comparative example and the embodiment that, compared with the catalyst which is not used, the catalyst which is subjected to activity recovery by adopting the method of the invention has the advantages that the reaction temperature is reduced by 8 ℃ under the condition of reaching the same pour point depression depth, so that the gas production rate of the device is reduced, the economic benefit is improved, the maximum advantages are that the catalyst with high activity and low temperature can greatly prolong the service life of the device, the utilization rate of the device is improved, and in addition, the temperature matching of the refining and modifying sections can be optimized.
The embodiment and the comparative example above can see that the method has the greatest characteristic that, aiming at the problem of activity loss of the modified pour point depressing catalyst of the hydro-modified pour point depressing device caused by production balance adjustment of the existing nitrogen poisoning catalyst, especially for enterprises with high production benefit requirements, the existing process and material improvement are utilized, and the staged over-analysis of nitride is matched to carry out the activity improvement treatment of the modified pour point depressing agent, so that the problems of poisoning and activity reduction of the modified pour point depressing catalyst can be thoroughly solved, the operability and flexibility of the device are greatly enhanced, the reaction temperature is reduced, the liquid yield is improved, the product distribution is optimized, the energy consumption is reduced, the operation period is prolonged, the hidden danger caused by catalyst bed poisoning is eliminated, the investment is saved, and great advantages are provided in terms of manpower and material resources.
Claims (9)
1. A method for restoring the activity of a low-activity hydrogenation modified catalyst is characterized by comprising the following steps: introducing refined oil with the nitrogen content of 0-10 mug/g into a low-activity hydrogenation modification pour point depressing catalyst bed layer, simultaneously adjusting the reaction temperature to ensure that the pour point of a diesel product is sequentially constant at 10-15 ℃, 20-25 ℃ and 30-35 ℃ compared with the pour point of the refined oil, the constant time of each stage is 24-48 hours, and adjusting to hydrogenation modification pour point depressing conditions for reaction after the constant is finished; the low-activity hydrogenation modified pour point depression catalyst contains 5-50% of molecular sieve and 0.15-0.45% of nitrogen element by weight, wherein the molecular sieve is a beta-type molecular sieve.
2. The method of claim 1, wherein: refined oil with the nitrogen content of less than 5 mu g/g is introduced into the low-activity hydrogenation modified pour point depression catalyst bed layer.
3. The method of claim 1, wherein: the nitrogen element in the low-activity hydrogenation modification catalyst is derived from an organic nitride, and the organic nitride is a basic organic nitride and a non-basic organic nitride.
4. The method of claim 1, wherein: the proportion of nitrogen elements originating from the basic organonitrides is greater than 50% in moles.
5. The method of claim 1, wherein: the hydrogenation modification pour point depression feed in the hydrogenation modification pour point depression condition is a diesel raw material subjected to hydrofining treatment, the final distillation point of the diesel raw material is 300-420 ℃, and the density is 0.96g/cm3The nitrogen content is 0.1wt% or less.
6. The method of claim 1, wherein: the hydro-upgrading pour point depressing reaction conditions comprise that the operating pressure is 6.0-13.0 MPa, the volume ratio of hydrogen to oil is 300: 1-1000: 1, and the volume airspeed is 0.1-5.0 h-1。
7. The method of claim 1, wherein: the hydro-upgrading pour point depressing reaction conditions comprise that the operating pressure is 7.0-12.0 MPa, the volume ratio of hydrogen to oil is 400: 1-700: 1, and the volume airspeed is 0.5-4.0 h-1。
8. The method of claim 1, wherein: the hydro-upgrading pour point depressing catalyst contains 15-45 wt% of active metal oxide, and the active metal comprises one or more of W, Mo, Co and Ni.
9. The method of claim 1, wherein: the reaction temperature of the low-activity hydrogenation modified pour point depression catalyst is 350-400 ℃, and the temperature difference T between the outlet temperature and the inlet temperature of any catalyst bed is lower than 5 ℃.
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Effective date of registration: 20231016 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |