CN112725022A - Hydrodewaxing method - Google Patents
Hydrodewaxing method Download PDFInfo
- Publication number
- CN112725022A CN112725022A CN201911031521.2A CN201911031521A CN112725022A CN 112725022 A CN112725022 A CN 112725022A CN 201911031521 A CN201911031521 A CN 201911031521A CN 112725022 A CN112725022 A CN 112725022A
- Authority
- CN
- China
- Prior art keywords
- hydrodewaxing
- catalyst
- reaction zone
- triisopropylbenzene
- pour point
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- VUMCUSHVMYIRMB-UHFFFAOYSA-N 1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1 VUMCUSHVMYIRMB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000005336 cracking Methods 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 16
- 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 16
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 239000003921 oil Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 230000000881 depressing effect Effects 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims 1
- 239000002283 diesel fuel Substances 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 description 16
- 239000011261 inert gas Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000007710 freezing Methods 0.000 description 7
- 239000001993 wax Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
-
- 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
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/304—Pour point, cloud point, cold flow properties
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- 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
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a hydrodewaxing method, raw waxy diesel oil passes through a hydrofining reaction zone and a hydrodewaxing reaction zone which are alternately connected in series and then is separated to obtain a low-freezing-point diesel oil product, wherein the hydrodewaxing reaction zone is filled with a dewaxing catalyst containing a ZSM-5 molecular sieve, and the cracking rate of the dewaxing catalyst to 1,3, 5-triisopropylbenzene is less than 2%. The method can obviously improve the yield of the low-freezing-point diesel.
Description
Technical Field
The invention relates to a hydrodewaxing method, in particular to a hydrodewaxing method for improving the cracking selectivity of normal paraffin and increasing the yield of diesel oil.
Background
The China is very long in the three northeast, northwest and west regions and the Tibet, etc. in winter, the demand for the diesel oil with good low-temperature fluidity is more vigorous in cold seasons, and the low-freezing point diesel oil (-20) is produced#、-35#) The efficiency of the method is remarkable, oil refining enterprises hope to increase the yield of low-freezing diesel oil products, and the economic efficiency of the enterprises is further increased.The diesel oil yield is strictly limited by the condensation point of distillate oil, and the contradiction between the diesel oil yield and the low-temperature fluidity of the diesel oil is more prominent in northern cold regions, so that the method becomes a key problem for limiting the economic benefit of northern oil refining enterprises.
In view of the reason that long-chain normal paraffin and aromatic hydrocarbon cause poor low-temperature fluidity of oil products, the improvement of the low-temperature fluidity of the oil products requires hydrogenation to destroy the structures of benzene rings and cyclane, and the oil products have cracking and isomerization performance of the long-chain paraffin, because the content of the aromatic hydrocarbon and the cyclane in diesel oil and jet fuel is not high, the over-cracking can cause the component of the oil products to be transferred to light components, and the conversion of the long-chain paraffin into the isoparaffin with better low-temperature fluidity through isomerization becomes the key for improving the low-temperature fluidity of the oil.
At present, the hydrodewaxing catalyst used usually adopts shape-selective molecular sieve and alumina binder as carriers, and adds a small amount (not more than 5% of the weight of the catalyst) of metal with dehydrogenation activity. Wherein the shape-selective molecular sieve is ZSM-5 molecular sieve. The size of a straight cylindrical pore passage of the ZSM-5 molecular sieve is 0.51 nm multiplied by 0.56nm, and the size of a zigzag pore passage is 0.54nm multiplied by 0.56 nm.
CN85100324A discloses a distillate oil hydrodewaxing catalyst and a preparation method thereof, wherein the catalyst is prepared by taking ZSM-5 zeolite molecular sieve directly synthesized by an amine-free method as a matrix, performing acid treatment, adding a binder, kneading and forming, adding an active metal component, and performing steam heat treatment. Wherein the binder is preferably small-pore alumina, the active metal component is preferably nickel, and the addition method can be impregnation, kneading and ion exchange. CN101143333A proposes a preparation method of a hydrodewaxing catalyst with certain hydrorefining function. The method makes full use of the binder component in the hydrodewaxing catalyst and takes the binder component as a carrier of the catalyst with hydrofining performance, thereby obviously improving the hydrofining performance of the catalyst. CN201010514426.0 proposes that a nano ZSM-5 molecular sieve, macroporous alumina and a binder are kneaded and formed into a carrier, then the carrier is impregnated with a load active metal, and finally the catalyst is obtained through hydrothermal treatment. CN201010514141.7 discloses a diesel hydrodewaxing method. The method comprises the following steps: the wax-containing diesel raw material sequentially passes through a hydrodewaxing catalyst bed layer and a hydrofining catalyst bed layer which are alternately and serially filled, and finally the obtained hydrofining product is separated to obtain a diesel product.
The above patent improves the product yield and product quality of the hydrodewaxing device by improving the catalyst or adjusting the process, but the diesel oil yield still needs to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrodewaxing method which can obviously improve the yield of low-freezing-point diesel.
A hydrodewaxing method is characterized in that wax-containing diesel raw oil passes through a hydrofining reaction zone and a hydrodewaxing reaction zone which are alternately connected in series and then is separated to obtain a low-freezing-point diesel product, a hydrodewaxing catalyst containing a ZSM-5 molecular sieve is filled in the hydrodewaxing reaction zone, the cracking rate of the hydrodewaxing catalyst on 1,3, 5-triisopropylbenzene is less than 2%, preferably less than 1.5%, further preferably less than 1%, specifically 0.5%, 0.8% and 0.4%, the cracking conditions are that the flow of inert gas is 100mL/min, and the volume space velocity of 1,3, 5-triisopropylbenzene liquid is 1.0h-1The reaction temperature is 350 ℃ and the normal pressure is high.
In the above method, the number of the hydrofining reaction zones is at least 1, preferably 2; the hydrodewaxing reaction zone is at least set to be 1, preferably 2, the number of the hydrofining reaction zone and the hydrodewaxing reaction zone can be the same or different, and the hydrofining reaction zone and the hydrodewaxing reaction zone are within the protection range of the application as long as the requirement of alternative setting is met, but the number of the hydrofining reaction zone and the hydrodewaxing reaction zone is preferably set to be the same.
In the method, the wax content of the wax-containing diesel raw material is 20-40 wt%, preferably 30-40 wt% relative to the total weight of the wax-containing diesel, and the wax is n-alkane containing 10-25 carbon atoms.
In the above method, the properties of the catalyst filled in the hydrorefining reaction zone are as follows: generally, metals in VIB group and/or VIII group are used as active components, alumina or silicon-containing alumina is used as a carrier, metals in VIB group are generally Mo and/or W, metals in VIII group are generally Co and/or Ni. Based on the weight of the catalyst, the content of the VIB group metal is 8-28 wt% calculated by oxide, the content of the VIII group metal is 2-15 wt% calculated by oxide, and the properties are as follows: the specific surface area is 100 to 650m 2The pore volume is 0.15-0.8 mL/g, and the types of the selectable commercial catalysts are various, such as hydrofining catalysts developed by the research and development of petrochemical industry (FRIPP) like FF series and FH-UDS series; conventional hydrotreating oxidation state catalysts may also be prepared as desired according to common general knowledge in the art.
In the above method, the operating conditions of the hydrorefining reaction zone are as follows: the reaction pressure is 6.0-20.0 MPa, the volume ratio of hydrogen to oil is 200: 1-1500: 1, and the volume airspeed is 0.1-10.0 h -1The reaction temperature is 270-460 ℃; the preferable operation conditions are that the reaction pressure is 7.0-15.0 MPa, the volume ratio of hydrogen to oil is 300: 1-1000: 1, and the volume airspeed is 0.3-8.0 h-1The reaction temperature is 315-415 ℃.
In the method, the hydrodewaxing catalyst filled in the hydrodewaxing reaction zone takes a ZSM-5 molecular sieve as an acidic component and takes VIB group and/or VIII group metals as hydrogenation active metal components. The silica-alumina molar ratio of the ZSM-5 molecular sieve is 10-150, and preferably 20-120. The VIB group metal is one or more of Mo and W, and the VIII group metal is one or more of Co and Ni. Based on the weight of the hydrodewaxing catalyst, the weight content of the hydrogenation active metal component is 1-16% in terms of oxide, and the weight content of the ZSM-5 molecular sieve is 50-85%.
In the above method, the hydrodewaxing reaction zone has the following operating conditions: the reaction pressure is 6.0-20.0 MPa, the volume ratio of hydrogen to oil is 200: 1-1500: 1, and the volume airspeed is 0.1-10.0 h-1The reaction temperature is 260-455 ℃; the preferable operation conditions are that the reaction pressure is 7.0-15.0 MPa, the volume ratio of hydrogen to oil is 300: 1-1000: 1, and the volume airspeed is 0.3-8.0 h -1The reaction temperature is 310-410 ℃.
In the method, the pour point depressing catalyst is prepared by treating the outer surface to reduce or remove the acid sites on the outer surface of the pour point depressing catalyst. For example, the high-temperature heat treatment is carried out on the pour point depressing catalyst commodity or the self-made pour point depressing catalyst by adopting macromolecular organic matters which at least can not enter the inside of the pour point depressing catalyst pore canal. The treatment can be carried out outside the reactor or inside the reactor after the catalyst is filled.
The pretreatment method adopted in the embodiment of the invention is as follows: putting a commercial grade or self-made pour point depression catalyst in a fixed bed reactor, taking 1,3, 5-triisopropylbenzene as a raw material, and controlling the volume airspeed of 1,3, 5-triisopropylbenzene liquid to be 0.5-1.0 h at the reaction temperature of 380-460 ℃ and the volume flow of nitrogen being 50-100 mL/min-1Treating for 4-12 h under the condition of (1) to obtain the final catalyst. Research results show that the process can be completely carried out on a hydrodewaxing device, the 1,3, 5-triisopropylbenzene can not cause adverse effects on a hydrofining reaction zone even passing through the hydrofining reaction zone, and pre-vulcanization and normal start-up processes are carried out after the treatment is finished.
Compared with the prior art, the hydrodewaxing method of the invention can obviously reduce side reactions and improve the yield of low-pour diesel oil.
Detailed Description
The following examples and comparative examples are given to further illustrate the effects and effects of the method of the present invention, but the following examples are not intended to limit the method of the present invention, and all% referred to in the present application are mass percentages unless otherwise specified.
The refined catalysts used in the examples and comparative examples of the present application had the following composition using alumina or silica-containing alumina as a carrier and Mo and Co as cracking components. Based on the weight of the catalyst, the Mo content is 15wt% calculated by oxide, the Co content is 5wt% calculated by oxide, and the operation conditions of the refining reaction zone are as follows: the reaction pressure is 7.0MPa, the volume ratio of hydrogen to oil is 500:1, and the volume space velocity is 1.0h -1The reaction temperature is 340 ℃; the pour point depressing catalyst before pretreatment consists of: ZSM-5 molecular sieve is used as an acidic component with the content of 10 wt%, Ni is used as a hydrogenation active metal component with the content of 7 wt% calculated by oxide, and the balance is alumina and a binder; the hydrodewaxing reaction zone operating conditions are as follows: the reaction pressure is 7.0MPa, the volume ratio of hydrogen to oil is 500:1, and the volume space velocity is 2.0 h-1The reaction temperature is 350 ℃;the properties of the waxy diesel feedstock are shown in table 1.
TABLE 1 Properties of the stock oils
Comparative example 1
The packed hydrodewaxing catalyst is not pretreated, and the volume space velocity is 1.0h when the flow rate of inert gas is 100mL/min and the liquid of 1,3, 5-triisopropylbenzene is-1The cracking rate of 1,3, 5-triisopropylbenzene is 20.4 wt% when the reaction temperature is 350 ℃ and the normal pressure is measured. The distribution and properties of the hydrodewaxing products obtained using the raw materials as shown in Table 1 are shown in Table 2.
Table 2 comparative example 1 product distribution and properties
Example 1
The packed hydrodewaxing catalyst is treated as follows: the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 0.5h when the volume flow of nitrogen is 50 mL/min, the reaction temperature is 380 DEG and the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 0.5h-1For 4 hours under the conditions of (1); the volume space velocity is 1.0h when the flow of the inert gas is 100mL/min and the 1,3, 5-triisopropylbenzene liquid is-1The cracking rate of 1,3, 5-triisopropylbenzene is 1.8 wt% when the reaction temperature is 350 ℃ and the normal pressure is measured. The distribution and properties of the hydrodewaxing products obtained using the raw materials as shown in Table 1 are shown in Table 3.
Table 3 example 1 product distribution and properties
Example 2
The packed hydrodewaxing catalyst is treated as follows: the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 0.5h under the conditions that the volume flow of nitrogen is 50 mL/min, the reaction temperature is 400 ℃ and the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 0.5h-1For 6 hours under the conditions of (1); under inert gasThe volume flow rate is 100mL/min, and the hourly space velocity of the 1,3, 5-triisopropylbenzene liquid is 1.0h-1The cracking rate of 1,3, 5-triisopropylbenzene is 1.2 wt% when the reaction temperature is 350 ℃ and the normal pressure is measured. The distribution and properties of the hydrodewaxing products obtained using the raw materials as shown in Table 1 are shown in Table 4.
Table 4 example 2 product distribution and properties
Example 3
The packed hydrodewaxing catalyst is treated as follows: the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 1.0h under the conditions that the volume flow of nitrogen is 100mL/min, the reaction temperature is 400 ℃ and the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 1.0h-1For 6 hours under the conditions of (1); the volume space velocity is 1.0h when the flow of the inert gas is 100mL/min and the 1,3, 5-triisopropylbenzene liquid is-1The cracking rate of 1,3, 5-triisopropylbenzene is 1.0 wt% when the reaction temperature is 350 ℃ and the normal pressure is measured. The distribution and properties of the hydrodewaxing products obtained using the raw materials as shown in Table 1 are shown in Table 5.
Table 5 example 3 product distribution and properties
| Product(s) | Naphtha (a) | Diesel oil |
| Yield wt% | 13.4 | 81.3 |
| Freezing point of | -- | -22 |
Example 4
The packed hydrodewaxing catalyst is treated as follows: the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 1.0h under the conditions that the volume flow of nitrogen is 100mL/min, the reaction temperature is 420 ℃ and the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 1.0h-1For 8 hours under the conditions of (1); the volume space velocity is 1.0h when the flow of the inert gas is 100mL/min and the 1,3, 5-triisopropylbenzene liquid is-1The cracking rate of 1,3, 5-triisopropylbenzene is 0.8 wt% when the reaction temperature is 350 ℃ and the normal pressure is measured. The distribution and properties of the hydrodewaxing products obtained using the raw materials as shown in Table 1 are shown in Table 6.
Table 6 example 4 product distribution and properties
| Product(s) | Naphtha (a) | Diesel oil |
| Yield wt% | 12.3 | 82.7 |
| Freezing point of | -- | -23 |
Example 5
The packed hydrodewaxing catalyst is treated as follows: the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 1.0h under the conditions that the volume flow of nitrogen is 100mL/min, the reaction temperature is 420 ℃ and the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 1.0h-1For 12 hours under the conditions of (1); 1,3, 5-triisopropyl at an inert gas flow rate of 100mL/minThe hourly space velocity of the benzene solution is 1.0h-1The cracking rate of 1,3, 5-triisopropylbenzene is 0.5 wt% when the reaction temperature is 350 ℃ and the normal pressure is measured. The distribution and properties of the hydrodewaxing products obtained using the raw materials as shown in Table 1 are shown in Table 7.
Table 7 example 5 product distribution and properties
| Product(s) | Naphtha (a) | Diesel oil |
| Yield wt% | 11.5 | 83.8 |
| Freezing point of | -- | -23 |
Example 6
The packed hydrodewaxing catalyst is treated as follows: the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 1.0h under the conditions that the volume flow of nitrogen is 100mL/min, the reaction temperature is 440 ℃, and the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 1.0h-1For 8 hours under the conditions of (1); the volume space velocity is 1.0h when the flow of the inert gas is 100mL/min and the 1,3, 5-triisopropylbenzene liquid is-1The cracking rate of 1,3, 5-triisopropylbenzene is 0.4 wt% when the reaction temperature is 350 ℃ and the normal pressure is measured. The distribution and properties of the hydrodewaxing products obtained using the raw materials as shown in Table 1 are shown in Table 8.
Table 8 example 6 product distribution and properties
| Product(s) | Naphtha (a) | Diesel oil |
| Yield wt% | 10.7 | 84.5 |
| Freezing point of | -- | -20 |
Example 7
The packed hydrodewaxing catalyst is treated as follows: the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 1.0h under the conditions that the volume flow of nitrogen is 100mL/min, the reaction temperature is 460 ℃ and the volume space velocity of the 1,3, 5-triisopropylbenzene liquid is 1.0h-1For 12 hours under the conditions of (1); the volume space velocity is 1.0h when the flow of the inert gas is 100mL/min and the 1,3, 5-triisopropylbenzene liquid is-1The cracking rate of 1,3, 5-triisopropylbenzene is 0.2 wt% when the reaction temperature is 350 ℃ and the normal pressure is measured. The distribution and properties of the hydrodewaxing products obtained using the raw materials as shown in Table 1 are shown in Table 9.
Table 9 example 7 product distribution and properties
| Product(s) | Naphtha (a) | Diesel oil |
| Yield wt% | 10.0 | 84.6 |
| Freezing point of | -- | -18 |
Claims (15)
1. A hydrodewaxing method is characterized in that: the wax-containing diesel raw oil passes through a hydrofining reaction zone and a hydrodewaxing reaction zone which are alternately connected in series and then is separated to obtain a low-freezing-point diesel product, wherein the hydrodewaxing reaction zone is filled with a pour point depressing catalyst containing a ZSM-5 molecular sieve, and the cracking rate of the pour point depressing catalyst on 1,3, 5-triisopropylbenzene is less than 2%.
2. The method of claim 1, wherein: the pour point depressing catalyst has a cracking rate of less than 1.5% to 1,3, 5-triisopropylbenzene.
3. The method of claim 1, wherein: the number of the hydrofining reaction zones is at least 1; the number of the hydrodewaxing reaction zones is at least 1, and the number of the hydrofining reaction zone is the same as or different from that of the hydrodewaxing reaction zone.
4. The method of claim 1, wherein: the wax-containing diesel raw material contains 20-40 wt% of wax relative to the total weight of the wax-containing diesel.
5. The method of claim 1, wherein: the properties of the catalyst filled in the hydrofining reaction zone are as follows: the VIB group and/or VIII group metal is used as an active component, and alumina or silicon-containing alumina is used as a carrier.
6. The method of claim 5, wherein: the VIB group metal is Mo and/or W, the VIII group metal is Co and/or Ni, and the content of the VIB group metal is 8-28 wt% in terms of oxide and the content of the VIII group metal is 2-15 wt% in terms of oxide based on the weight of the refined catalyst.
7. The method of claim 1, wherein: the operating conditions of the hydrofining reaction zone are as follows: the reaction pressure is 6.0-20.0 MPa, the volume ratio of hydrogen to oil is 200: 1-1500: 1, and the volume airspeed is 0.1-10.0 h -1The reaction temperature is 270-460 ℃.
8. The method of claim 7, wherein: the operating conditions of the hydrofining reaction zone are as follows: the reaction pressure is 7.0-15.0 MPa, the volume ratio of hydrogen to oil is 300: 1-1000: 1, and the volume airspeed is 0.3-8.0 h-1The reaction temperature is 315-415 ℃.
9. The method of claim 1, wherein: the hydrodewaxing catalyst filled in the hydrodewaxing reaction zone takes a ZSM-5 molecular sieve as an acidic component and takes VIB group and/or VIII group metals as hydrogenation active metal components.
10. The method of claim 9, wherein: the silicon-aluminum molar ratio of the ZSM-5 molecular sieve is 10-150, the VIB group metal is one or more of Mo and W, and the VIII group metal is one or more of Co and Ni; based on the weight of the hydrodewaxing catalyst, the weight content of the hydrogenation active metal component is 1-16% in terms of oxide, and the weight content of the ZSM-5 molecular sieve is 50-85%.
11. The method of claim 1, wherein: the operating conditions of the hydrodewaxing reaction zone are as follows: the reaction pressure is 6.0-20.0 MPa, the volume ratio of hydrogen to oil is 200: 1-1500: 1, and the volume airspeed is 0.1-10.0 h-1The reaction temperature is 260-455 ℃.
12. The method of claim 11, wherein: the operating conditions of the hydrodewaxing reaction zone are as follows: the reaction pressure is 7.0-15.0 MPa, the volume ratio of hydrogen to oil is 300: 1-1000: 1, and the volume airspeed is 0.3-8.0 h -1The reaction temperature is 310-410 ℃.
13. The method of claim 1, wherein: the pour point depressing catalyst is prepared by treating the outer surface to reduce or remove the acid sites on the outer surface of the pour point depressing catalyst.
14. The method of claim 13, wherein: the method is characterized in that macromolecule organic matters are adopted to carry out high-temperature heat treatment on pour point depressing catalyst commodities or self-made pour point depressing catalysts, the macromolecule organic matters at least need to be guaranteed not to enter the interior of pour point depressing catalyst pore channels, and the treatment process is carried out outside a reactor or in the reactor after the catalysts are filled.
15. The method of claim 14, wherein: putting a commercial grade or self-made pour point depression catalyst in a fixed bed reactor, taking 1,3, 5-triisopropylbenzene as a raw material, and controlling the volume airspeed of 1,3, 5-triisopropylbenzene liquid to be 0.5-1.0 h at the reaction temperature of 380-460 ℃ and the volume flow of nitrogen being 50-100 mL/min-1Treating for 4-12 h under the condition of (1) to obtain the final catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911031521.2A CN112725022B (en) | 2019-10-28 | 2019-10-28 | Hydrodewaxing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911031521.2A CN112725022B (en) | 2019-10-28 | 2019-10-28 | Hydrodewaxing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112725022A true CN112725022A (en) | 2021-04-30 |
| CN112725022B CN112725022B (en) | 2023-01-10 |
Family
ID=75589225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911031521.2A Active CN112725022B (en) | 2019-10-28 | 2019-10-28 | Hydrodewaxing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112725022B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116060116A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrodewaxing catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103805237A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing diesel oil with low condensation point by catalyst gradation technology |
| CN103805257A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing diesel oil with low condensation point by catalyst gradation technology |
-
2019
- 2019-10-28 CN CN201911031521.2A patent/CN112725022B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103805237A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing diesel oil with low condensation point by catalyst gradation technology |
| CN103805257A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing diesel oil with low condensation point by catalyst gradation technology |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116060116A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrodewaxing catalyst and preparation method and application thereof |
| CN116060116B (en) * | 2021-10-29 | 2024-06-04 | 中国石油化工股份有限公司 | Hydrodewaxing catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112725022B (en) | 2023-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109777514B (en) | Method for preparing aromatic hydrocarbon by catalyzing diesel oil hydrogenation conversion | |
| CN107460003B (en) | Method for increasing yield of aviation kerosene through hydrocracking | |
| CN108102709B (en) | Processing method of catalytic diesel oil | |
| CN115305105A (en) | Solvent composition prepared from waste oil and preparation method thereof | |
| CN112725022B (en) | Hydrodewaxing method | |
| CN107109255A (en) | The method for maximizing high-quality distillate | |
| CN107835847B (en) | Process for producing BTX | |
| CN104611033A (en) | Method for producing hydrogenated diesel oil with low freezing point | |
| CN111100697A (en) | Hydrocracking method of paraffin-based diesel oil | |
| CN112126465B (en) | Hydrogenation catalyst composition and method for preparing lubricating oil base oil from Fischer-Tropsch synthetic wax | |
| CN114437803B (en) | Hydrotreatment method of catalytic diesel | |
| CN104611044B (en) | The production method of lube base oil | |
| CN109777494B (en) | Method for producing high-quality gasoline and diesel oil by catalyzing diesel oil | |
| EP2516597A1 (en) | Catalytic dewaxing process | |
| CN116024014B (en) | Method for combining two hydrocracking systems | |
| CN105087064A (en) | Method for producing clean low freezing point diesel oil by treating high nitrogen diesel oil | |
| CN111763533B (en) | Method for processing heavy distillate oil | |
| CN115646540B (en) | Composite hydrocracking catalyst, preparation method thereof and preparation method of transformer oil | |
| CN115806837B (en) | Hydrocracking method for producing low-carbon light hydrocarbon and cycloalkyl special oil | |
| CN115261068B (en) | Fixed bed residuum hydrogenation method | |
| CN109988639B (en) | Method for producing gasoline and low freezing point oil by catalyst grading technology | |
| CN109988649B (en) | Method for producing gasoline and high-yield low-condensate oil by catalyst grading technology | |
| Köhler | Catalytic dewaxing with zeolites for improved profitability of ULSD production | |
| US20240093100A1 (en) | Dewaxing Catalysts And Processes Using The Same | |
| CN107177375B (en) | Hydrocracking method for producing jet fuel from straight-run diesel oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231121 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. |