CN115651289B - High C A Aromatic rubber plasticizer with value and preparation method thereof - Google Patents
High C A Aromatic rubber plasticizer with value and preparation method thereof Download PDFInfo
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- 239000008036 rubber plasticizer Substances 0.000 title claims abstract description 61
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000007670 refining Methods 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 116
- 238000000034 method Methods 0.000 claims description 61
- 238000005984 hydrogenation reaction Methods 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000003223 protective agent Substances 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 9
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 claims description 4
- LCSNMIIKJKUSFF-UHFFFAOYSA-N [Ni].[Mo].[W] Chemical compound [Ni].[Mo].[W] LCSNMIIKJKUSFF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010779 crude oil Substances 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005496 tempering Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 12
- FMMWHPNWAFZXNH-UHFFFAOYSA-N ERM-AC051 Natural products C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 10
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 125000005605 benzo group Chemical group 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- LHRCREOYAASXPZ-UHFFFAOYSA-N dibenz[a,h]anthracene Chemical compound C1=CC=C2C(C=C3C=CC=4C(C3=C3)=CC=CC=4)=C3C=CC2=C1 LHRCREOYAASXPZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- -1 polycyclic aromatic compounds Chemical class 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Abstract
The invention provides a high C A The aromatic rubber plasticizer is prepared by first carrying out hydrotreatment on extract oil obtained by solvent refining in a first hydrotreatment reaction zone, and cutting light fraction to obtain heavy fraction oil A; hydrotreating the heavy deasphalted oil obtained by deasphalting the solvent in a second hydrotreating reaction zone, cutting off light fraction to obtain heavy fraction oil B, and blending the obtained heavy fraction oil A and heavy fraction oil B to obtain the high C A Aromatic rubber plasticizers of the values; the preparation method takes the mixed oil of the extracted oil obtained by solvent refining and the heavy deasphalted oil obtained by solvent deasphalting as raw materials, and successfully prepares the catalyst with higher yield, high viscosity and C through two steps of hydrotreating and blending treatment A High value and good compatibility with rubber.
Description
Technical Field
The invention belongs to the technical field of plasticizers, and particularly relates to a high C-type plasticizer A Aromatic rubber plasticizer and its preparation method and application are provided.
Background
The plasticizer has the characteristics of good effect, small dosage, high absorption speed, good compatibility with rubber, small volatility and the like, and is widely applied to rubber products. Plasticizers include paraffin-based rubber plasticizers, aromatic-based rubber plasticizers, and cycloalkyl-based rubber plasticizers, by structural classification. Wherein, the compatibility of the aromatic rubber plasticizer and the rubber is better, the produced rubber product has high strength, large addition amount and low price.
At present, the technology for producing the high aromatic rubber plasticizer mostly relates to a solvent refining process, such as a solvent deasphalting process or a furfural refining process, and the solvent refining process belongs to a separation process of physical extraction, so that the problems of low yield of a main product, low value of byproducts, high processing cost and the like are easily caused, and finally, the economic efficiency of the whole technological process is poor; meanwhile, the raw materials for producing the high aromatic rubber plasticizer are affected by gradual reduction of naphthenic base raw materials, and naphthenic base decompression wax oil which is a main raw material source is also less and less, so that the raw materials of the high aromatic rubber plasticizer are widened, the utilization rate of the naphthenic base raw materials is improved, and low added value extracted oil and heavy deasphalted oil produced in the solvent refining process are fully utilized, so that the method has great practical significance.
CN105969420a discloses a preparation method of rubber plasticizer with low content of polycyclic aromatic hydrocarbon, which takes mixed oil of vacuum distillate oil and aromatic hydrocarbon oil which is obtained by processes of solvent refining, catalytic cracking, visbreaking, thermal cracking or hydrocracking as raw materials, and obtains the rubber plasticizer product by solvent refining process. However, the rubber plasticizer product C obtained by this method A The value remains to be increased.
CN113583709a discloses a preparation method of a high-aromatic high-viscosity environment-friendly rubber plasticizer, which comprises the steps of sequentially carrying out hydrofining and hydrodewaxing on cycloalkyl vacuum residuum, and obtaining a fraction with a boiling point of more than or equal to 360 ℃ through vacuum distillation on an obtained hydrogenated liquid product, namely the high-aromatic high-viscosity environment-friendly rubber plasticizer. The preparation method adopts a combined process different from the traditional two-stage solvent process, and can solve the technical problems of low yield and contradiction between the content of the polycyclic aromatic hydrocarbon and the content of the aromatic carbon in the traditional two-stage solvent extraction process. However, the yield of the environment-friendly rubber plasticizer prepared by the method is lower, only about 60 percent, and C A The value remains to be increased.
In view of the above, a process has been developed which gives high yields and can give high C A A process for the preparation of aromatic rubber plasticizers is highly desirable.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a deviceSeed height C A The aromatic rubber plasticizer takes extract oil obtained by solvent refining and heavy deasphalted oil obtained by solvent deasphalting as raw materials, and the aromatic rubber plasticizer is successfully prepared into the aromatic rubber plasticizer with higher yield, high viscosity and C by combining hydrotreating and blending processes A The perfume-based rubber plasticizer with high value and good compatibility with rubber provides a new method for preparing the perfume-based rubber plasticizer.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a high C A A method for preparing an aromatic rubber plasticizer, the method comprising the steps of:
(1) Hydrotreating the extracted oil obtained by refining the solvent in a first hydrotreating reaction zone, and cutting off light fraction to obtain heavy fraction oil A; hydrotreating the heavy deasphalted oil obtained by deasphalting the solvent in a second hydrotreating reaction zone, and cutting off light fraction to obtain heavy fraction oil B;
(2) Blending the heavy distillate A and the heavy distillate B obtained in the step (1) to obtain the high C A Aromatic rubber plasticizers.
The preparation method provided by the invention comprises the steps of firstly carrying out hydrotreatment on extract oil obtained by solvent refining through a first hydrotreatment reaction zone, removing light fraction from the obtained hydrogenated oil to obtain heavy fraction oil A, simultaneously carrying out hydrotreatment on heavy deasphalted oil obtained by solvent deasphalting through a second hydrotreatment reaction zone, carrying out hydrotreatment on the obtained heavy fraction oil B obtained by removing light fraction from the hydrogenated oil, and then blending the heavy fraction oil A and the heavy fraction oil B obtained in the step to obtain the high C A Aromatic rubber plasticizers of the values; the preparation method takes the extracted oil obtained by solvent refining and the heavy deasphalted oil obtained by solvent deasphalting as raw materials, and the two steps of hydrotreating and blending are successfully carried out to obtain the product with higher yield, high viscosity and C A The aromatic rubber plasticizer with high value and good compatibility with rubber not only effectively expands the raw material source of the aromatic rubber plasticizer, but also utilizes low added valueThe extracted oil and the heavy deasphalted oil are used as raw materials, and the dependence on naphthenic decompression wax oil is effectively reduced.
It should be noted that both the "solvent refining" and the "hydrotreating" are conventional operations in the art in the present invention; the said "high C A Aromatic rubber plasticizers of the value "refer to C A An aromatic rubber plasticizer with a value of more than or equal to 25 percent.
Preferably, the solvent used for solvent refining in the extracted oil obtained by solvent refining comprises any one or a combination of at least two of furfural, N-methylpyrrolidone, phenol and dimethyl sulfoxide.
Preferably, the kinematic viscosity of the extracted oil obtained by refining the solvent at 100 ℃ is more than or equal to 30mm 2 S, e.g. 32mm 2 /s、34mm 2 /s、36mm 2 /s、38mm 2 /s、40mm 2 /s、42mm 2 /s、44mm 2 /s or 46mm 2 /s, etc.
Preferably, the extracted oil obtained by refining the solvent has a refractive index of 1.5300 at 20 ℃, such as 1.5400, 1.5500, 1.5600, 1.5800 or 1.6000.
Preferably, the raw materials used for solvent refining in the extracted oil obtained by solvent refining comprise vacuum distillate oil obtained by often decompressing naphthenic crude oil or intermediate crude oil.
Preferably, the vacuum distillate comprises any one or a combination of at least two of a two-wire cut, a three-wire cut or a four-wire cut.
Preferably, the kinematic viscosity of the vacuum distillate at 100 ℃ is more than or equal to 4mm 2 S, e.g. 4.5mm 2 /s、5mm 2 /s、5.5mm 2 /s、6mm 2 /s、6.5mm 2 /s、8mm 2 /s、10mm 2 /s、15mm 2 /s、18mm 2 /s、20mm 2 /s、22mm 2 /s or 24mm 2 /s, etc.
Preferably, C of the vacuum distillate A The values are 15%, for example 16%, 18%, 20%, 22%, 24%, etc.
Preferably, the solvent used for the solvent deasphalting of the resulting heavy deasphalted oil comprises propane and/or butane.
Preferably, the kinematic viscosity of the heavy deasphalted oil obtained by solvent deasphalting at 100 ℃ is more than or equal to 30mm 2 S, e.g. 32mm 2 /s、34mm 2 /s、36mm 2 /s、38mm 2 /s、40mm 2 /s、50mm 2 /s、55mm 2 /s、60mm 2 /s、65mm 2 /s or 70mm 2 /s, etc.
Preferably, the refractive index of the heavy deasphalted oil obtained by deasphalting the solvent is not less than 1.5200 at 20 ℃, for example 1.5400, 1.5600, 1.5800 or 1.6000, etc.
Preferably, the solvent deasphalting results in a heavy deasphalted oil having a char yield of 10% or less, for example 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1% or the like.
Preferably, the feedstock used for the solvent deasphalting of the resulting heavy deasphalted oil comprises naphthenic vacuum residuum and/or intermediate vacuum residuum.
Preferably, the light fraction is cut to obtain a heavy fraction oil A and the light fraction is cut to obtain a heavy fraction oil B which is more than 360 ℃ (such as 361 ℃, 363 ℃, 365 ℃, 367 ℃, 369 ℃ or the like).
Preferably, the reaction temperature of the first hydrotreatment reaction zone is 280 to 400 ℃, for example 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, or the like.
Preferably, the volume ratio of hydrogen to the extracted oil from solvent refining in the first hydroprocessing reaction zone is (600-1500): 1, such as 800:1, 1000:1, 1200:1, 1500:1, etc.
Preferably, the total volume space velocity of the first hydrotreating reaction zone is 0.2 to 2h -1 For example 0.4h -1 、0.6h -1 、0.8h -1 、1h -1 、1.2h -1 、1.4h -1 、1.6h -1 Or 1.8h -1 Etc.
Preferably, the first hydroprocessing reaction zone has a hydrogen partial pressure greater than 8MPa, for example 8.5MPa, 9MPa, 9.5MPa or 10MPa, etc.
Preferably, the catalyst used in the first hydrotreating reaction zone is a hydrofinishing catalyst.
Preferably, the hydrofining catalyst comprises any one or a combination of at least two of a molybdenum-nickel type hydrogenation catalyst, a tungsten-nickel type hydrogenation catalyst, a molybdenum-cobalt type hydrogenation catalyst or a molybdenum-tungsten-nickel type hydrogenation catalyst.
Preferably, the reaction temperature of the second hydrotreatment reaction zone is 280 to 380 ℃, such as 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, or the like
Preferably, the volume ratio of hydrogen to solvent deasphalted heavy deasphalted oil in the second hydroprocessing reaction zone is (600 to 1500): 1, such as 800:1, 1000:1, 1200:1 or 1400:1, etc.
Preferably, the total volume space velocity of the second hydrotreating reaction zone is 0.2 to 2h -1 For example 0.4h -1 、0.6h -1 、0.8h -1 、1h -1 、1.2h -1 、1.4h -1 、1.6h -1 Or 1.8h -1 Etc.
Preferably, the second hydroprocessing reaction zone has a hydrogen partial pressure greater than 8MPa, for example 8.5MPa, 9MPa, 9.5MPa or 10MPa, etc.
Preferably, the catalyst used in the second hydrotreating reaction zone is a residuum fixed bed hydrogenation catalyst system.
Preferably, the residuum fixed bed hydrogenation catalyst system includes a combination of a hydrogenation protecting agent, a hydrodemetallization catalyst, and a hydrofinishing catalyst.
Preferably, the hydrogenation protecting agent comprises a molybdenum-nickel type hydrogenation protecting agent, and more preferably a molybdenum-nickel type hydrogenation protecting agent with a total metal content of less than 5%.
Preferably, the hydrodemetallization catalyst comprises a molybdenum-nickel hydrodemetallization catalyst, more preferably a hydrodemetallization catalyst having a total metal content of less than 5%.
Preferably, the hydrofining catalyst comprises any one or a combination of at least two of a molybdenum-nickel type hydrogenation catalyst, a tungsten-nickel type hydrogenation catalyst, a molybdenum-cobalt type hydrogenation catalyst or a molybdenum-tungsten-nickel type hydrogenation catalyst.
Preferably, the mass ratio of the hydrofining catalyst to the hydrogenation protecting agent to the hydrodemetallization catalyst is 100 (0.5-10): 0.5-10.
Wherein, the mass ratio of the hydrofining catalyst to the hydrogenation protective agent can be 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8 or 100:9, etc.
The mass ratio of the hydrofining catalyst to the hydrodemetallization catalyst is 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8 or 100:9, etc.
Preferably, the mass ratio of the heavy distillate oil a to the heavy distillate oil B in the step (2) is 9:1 to 1:9, for example, 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1, 1:2, 1:4, 1:6 or 1:8, etc.
Preferably, the tempering temperature is 40 to 200 ℃, e.g. 60 ℃, 80 ℃,100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, etc.
Preferably, the tempering time is not less than 10min, such as 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, or the like.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
in a second aspect, the present invention provides a high C A An aromatic rubber plasticizer of the value obtained by the production method according to the first aspect.
Preferably, C of the aromatic rubber plasticizer A The value is more than or equal to 25 percent (such as 30 percent, 35 percent, 40 percent, 45 percent and the like), and the kinematic viscosity at 100 ℃ is more than or equal to 30mm 2 /s (e.g. 31mm 2 /s、32mm 2 /s、33mm 2 And/s, etc.), the flash point is equal to or greater than 230 ℃ (e.g., 232 ℃ or 234 ℃, etc.), the aniline point is equal to or greater than 75 ℃ (e.g., 60 ℃, 50 ℃, 40 ℃, 30 ℃, etc.), the BaP content is equal to or greater than 1mg/kg (e.g., 0.8mg/kg, 0.7mg/kg, 0.6mg/kg, 0.5mg/kg, undetected, etc.), and the PAHs is equal to or greater than 10mg/kg (e.g., 9mg/kg, 8mg/kg, 7mg/kg, 6mg/kg, 5mg/kg, 4mg/kg, 3mg/kg, undetected, etc.).
In the present invention, C A The values refer to the aromatic carbon ratio and BaP refers to benzo [a]Pyrene and PAHs refer to 8 polycyclic aromatic compounds including benzo [ a ]]Anthracene (anthracene),Benzo [ b ]]Fluoranthene, benzo [ j ]]Fluoranthene, benzo [ k ]]Fluoranthene, benzo [ e ]]Pyrene, benzo [ a ]]Pyrene, dibenzo [ a, h]Anthracene 8 polycyclic carcinogenic aromatics.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method provided by the invention comprises the steps of firstly, carrying out hydrotreatment on extract oil obtained by solvent refining through a first hydrotreatment reaction zone, removing light fraction to obtain heavy fraction oil A, carrying out hydrotreatment on heavy deasphalted oil obtained by solvent deasphalting through a second hydrotreatment reaction zone, removing light fraction to obtain heavy fraction oil B, and then blending the obtained heavy fraction oil A and heavy fraction oil B to obtain the high C A Aromatic rubber plasticizers of the values; the preparation method takes the extracted oil obtained by solvent refining and the heavy deasphalted oil obtained by solvent deasphalting as raw materials, and the two steps of hydrotreating and blending are successfully carried out to obtain the product with higher yield, high viscosity and C A An aromatic rubber plasticizer having a high value and good compatibility with rubber; specifically, the yield of the aromatic rubber plasticizer obtained by the preparation method provided by the invention is 97.5-99.3%, and the density at 20 ℃ is 0.9429-0.9831 g/cm 3 The 100 kinematic viscosity is 34.69-64.85 mm 2 S, open flash point of 232-240 ℃, C A The value is as high as 25.1-37.7%, the aniline point is 35-65 ℃, the BaP content is detected, and the PAHs content is as low as 4.7mg/kg. .
(2) The plasticizer prepared by the preparation method provided by the invention also has the advantages of no toxicity, no carcinogenic effect and high aromatic hydrocarbon content, and meets the requirement of limiting substances about environment-friendly operation oil in the automobile tire which is issued by China Petroleum and chemical industry Congress and China rubber industry Association.
(3) Meanwhile, the preparation method provided by the invention takes the mixed oil of the extracted oil obtained by solvent refining and the heavy deasphalted oil obtained by solvent deasphalting as raw materials, so that the source of the raw materials is effectively expanded, and the utilization rate of precious resources is improved; the extracted oil obtained by refining the solvent with low added value and the heavy deasphalted oil obtained by deasphalting the solvent are used as raw materials of the high-quality high-aromatic rubber plasticizer, so that the full utilization is realized, and the dependence on cycloalkyl decompression wax oil is further reduced; meanwhile, the preparation method provided by the invention has the advantages of simple process, high yield of the obtained target product and stronger market competitiveness.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Detailed information of the raw materials according to the present invention are shown in table 1:
TABLE 1
Example 1
High C A A method for preparing an aromatic rubber plasticizer, the method comprising the steps of:
(1) Hydrotreating the extracted oil obtained by refining the solvent in a hydrotreating pilot plant, wherein the catalyst adopted in the hydrotreating is ZQC-25 hydrotreating catalyst, the reaction temperature in the hydrotreating process is 350 ℃, the volume ratio of hydrogen to oil is 1000:1, and the volume space velocity is 0.5h -1 The hydrogen partial pressure is 15MPa, and the hydrogenated oil is cut after being obtained, so that the distillate oil with the temperature of more than 360 ℃ is heavy distillate oil A;
hydrotreating heavy deasphalted oil obtained by solvent deasphalting in a hydrotreating pilot plant, wherein a residual oil fixed bed hydrogenation catalyst system adopted in hydrotreating comprises ZQC-25 hydrotreating catalyst, CG series hydrogenation protecting agent and CDM series hydrodemetallization catalyst in a mass ratio of 100:0.5:0.5, wherein the reaction temperature in the hydrotreating process is 330 ℃, the volume ratio of hydrogen to oil is 1000:1, and the volume space velocity is 0.3h -1 The hydrogen partial pressure is 15MPa, and the additive is obtainedCutting the hydrogen oil to obtain distillate oil B with the temperature of more than 360 ℃;
(2) Blending the heavy distillate oil A and the heavy distillate oil B obtained in the step (1) according to the mass ratio of 1:1, wherein the blending temperature is 80 ℃, and the blending time is 20min, so as to obtain the high C A Aromatic rubber plasticizers.
Example 2
High C A A method for preparing an aromatic rubber plasticizer, the method comprising the steps of:
(1) Hydrotreating the extracted oil obtained by refining the solvent in a hydrotreating pilot plant, wherein the catalyst adopted in the hydrotreating is ZQC-25 hydrotreating catalyst, the reaction temperature in the hydrotreating process is 360 ℃, the volume ratio of hydrogen to oil is 1000:1, and the volume space velocity is 0.25h -1 The hydrogen partial pressure is 15MPa, and the hydrogenated oil is cut after being obtained, so that the distillate oil with the temperature of more than 360 ℃ is heavy distillate oil A;
hydrotreating heavy deasphalted oil obtained by solvent deasphalting in a hydrotreating pilot plant, wherein a residual oil fixed bed hydrogenation catalyst system adopted in hydrotreating comprises a ZQC-25 hydrotreating catalyst, a CG hydrogenation protecting agent and a CDM hydrodemetallization catalyst in a mass ratio of 100:0.5:0.5, wherein the reaction temperature in the hydrotreating process is 320 ℃, the volume ratio of hydrogen to oil is 1000:1, and the volume space velocity is 0.6h -1 The hydrogen partial pressure is 15MPa, and the hydrogenated oil is cut after being obtained, so that the distillate oil with the temperature of more than 360 ℃ is heavy distillate oil B;
(2) Blending the heavy distillate oil A and the heavy distillate oil B obtained in the step (1) according to the mass ratio of 6:4, wherein the blending temperature is 70 ℃, and the blending time is 15min, so as to obtain the high C A Aromatic rubber plasticizers.
Example 3
High-viscosity high-C A The aromatic rubber plasticizer was prepared in the same manner as in example 1 except that the mass ratio of the heavy fraction oil A to the heavy fraction oil B in the step (2) was 5:1, and the other raw materials, parameters and preparation methods were the same as in example 1.
Example 4
High C A The preparation method of the aromatic rubber plasticizer is different from example 1 only in that the mass ratio of the heavy fraction oil A to the heavy fraction oil B in the step (2) is 10:1, and other raw materials, parameters and preparation methods are the same as those in example 1.
Example 5
High C A The preparation method of the aromatic rubber plasticizer is different from example 1 only in that the mass ratio of the heavy fraction oil A to the heavy fraction oil B in the step (2) is 1:2.5, and other raw materials, parameters and preparation methods are the same as those of example 1.
Example 6
High C A The preparation method of the aromatic rubber plasticizer is different from example 1 only in that the mass ratio of the heavy fraction oil A to the heavy fraction oil B in the step (2) is 1:5, and other raw materials, parameters and preparation methods are the same as those in example 1.
Comparative example 1
The process for preparing aromatic rubber plasticizers differs from example 1 only in that step (2) is not added and heavy distillate B is directly blended with heavy distillate A at 80℃for 20min, and other raw materials, parameters and preparation methods are the same as in example 1.
Comparative example 2
The process for preparing aromatic rubber plasticizers differs from example 1 only in that step (2) is not added and heavy distillate A, heavy distillate B is directly blended at 80℃for 20min, and other raw materials, parameters and preparation methods are the same as in example 1.
Performance test:
(1) Yield (relative to the mixed oil)%: calculating the mass ratio of the finally obtained aromatic rubber plasticizer relative to the sum of the extracted oil obtained by solvent refining and the heavy deasphalted oil obtained by solvent deasphalting;
(2) Density at 20 ℃, g/cm 3 : testing was performed according to GB/T1884;
(3) Kinematic viscosity at 100 ℃ of mm 2 S: testing according to GB/T265;
(4) Open flash point, c: testing was performed according to GB/T3536;
(5)C A value,%: the test was performed according to SH/T0725;
(6) Aniline point, c: testing according to GB/T262;
(7) BaP content, mg/kg: testing according to the SN/T1877.3-2007 first method;
(8) PAHs content, mg/kg: the test was performed according to the SN/T1877.3-2007 first method.
The aromatic rubber plasticizers obtained in examples 1 to 6 and comparative examples 1 to 2 were tested according to the above test methods, and the test results are shown in table 2:
TABLE 2
From the data in table 2, it can be seen that: the preparation method provided by the invention uses the extracted oil obtained by solvent refining and the heavy deasphalted oil obtained by solvent deasphalting as raw materials, so that the C of the obtained aromatic rubber plasticizer is effectively improved A The values and yields also effectively reduced the PAHs content and BaP content therein.
Specifically, the yields of the aromatic rubber plasticizers obtained by the preparation methods provided in examples 1 to 6 were 97.5 to 99.3%, and the densities at 20℃were 0.9429 to 0.9831g/cm 3 The 100 kinematic viscosity is 34.69-64.85 mm 2 S, open flash point of 232-240 ℃, C A The value is as high as 25.1-37.7%, the aniline point is 35-65 ℃, the BaP content is detected, and the PAHs content is as low as 4.7mg/kg.
As can be seen from a comparison of example 1 and comparative example 1, the PAHs content and BaP of the rubber plasticizer produced by using the solvent extraction oil alone as the raw material are higher, and the product yield is lower.
As can be seen from the data of comparative example 1 and comparative example 2, it is difficult to produce high C by using heavy deasphalted oil alone as a raw material A Rubber plasticizers of the values.
In conclusion, only two raw materials are adopted to obtain the low-content PAHs and BaP and C A High viscosity with high product yieldHigh C A And (5) obtaining a rubber plasticizer product.
Applicants state that the present invention, by way of the above examples, describes a high C A The aromatic rubber plasticizer and the preparation method thereof are not limited to the above examples, i.e., the present invention must not depend on the above examples to be carried out. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (33)
1. High C A A process for the preparation of an aromatic rubber plasticizer, characterized in that it comprises the steps of:
(1) Hydrotreating the extracted oil obtained by refining the solvent in a first hydrotreating reaction zone, and cutting off light fraction to obtain heavy fraction oil A; hydrotreating the heavy deasphalted oil obtained by deasphalting the solvent in a second hydrotreating reaction zone, and cutting off light fraction to obtain heavy fraction oil B;
(2) Blending the heavy distillate A and the heavy distillate B obtained in the step (1) to obtain the high C A Aromatic rubber plasticizers of the values;
the light fraction is cut off to obtain heavy fraction oil A, and the light fraction is cut off to obtain fraction oil with the heavy fraction oil B of more than 360 ℃;
the mass ratio of the heavy distillate oil A to the heavy distillate oil B in the step (2) is 1 (0.4-8).
2. The method according to claim 1, wherein the solvent used for the solvent refining in the extracted oil obtained by the solvent refining comprises any one or a combination of at least two of furfural, N-methylpyrrolidone, phenol and dimethyl sulfoxide.
3. The process according to claim 1, wherein the extracted oil obtained by refining the solvent has a kinematic viscosity at 100 ℃ of 30mm or more 2 /s。
4. The method according to claim 1, wherein the extracted oil obtained by refining the solvent has a refractive index of 1.5300 or more at 20 ℃.
5. The method according to claim 1, wherein the raw material for solvent refining in the extract oil obtained by solvent refining comprises a vacuum distillate obtained by often decompressing naphthenic crude oil or intermediate crude oil.
6. The production method according to claim 5, wherein the vacuum distillate comprises any one of a two-wire cut, a three-wire cut, or a four-wire cut or a combination of at least two of them.
7. The process according to claim 5, wherein the vacuum distillate has a kinematic viscosity at 100 ℃ of at least 4mm 2 /s。
8. The process according to claim 5, wherein the vacuum distillate C A The value is more than or equal to 15 percent.
9. The process according to claim 1, wherein the solvent used for the heavy deasphalted oil obtained by solvent deasphalting comprises propane and/or butane.
10. The process according to claim 1, wherein the heavy deasphalted oil obtained by solvent deasphalting has a kinematic viscosity at 100 ℃ of 30mm or more 2 /s。
11. The process according to claim 1, wherein the heavy deasphalted oil obtained by deasphalting the solvent has a refractive index of not less than 1.5200 at 20 ℃.
12. The method according to claim 1, wherein the amount of carbon residue in the heavy deasphalted oil obtained by the solvent deasphalting is 10% or less.
13. The process according to claim 1, wherein the raw materials for solvent deasphalting in the heavy deasphalted oil obtained by solvent deasphalting comprise cycloalkyl vacuum residuum and/or intermediate vacuum residuum.
14. The process of claim 1 wherein the first hydroprocessing reaction zone has a reaction temperature of from 280 ℃ to 400 ℃.
15. The process of claim 1 wherein the volume ratio of hydrogen to solvent refined extract oil in the first hydroprocessing reaction zone is from (600 to 1500): 1.
16. The process of claim 1 wherein the total volume space velocity of the first hydroprocessing reaction zone is from 0.2 to 2 hours -1 。
17. The process of claim 1 wherein the first hydroprocessing reaction zone has a hydrogen partial pressure greater than 8MPa.
18. The process of claim 1 wherein the catalyst employed in the first hydroprocessing reaction zone is a hydrofinishing catalyst.
19. The method of claim 18, wherein the hydrofinishing catalyst comprises any one or a combination of at least two of a molybdenum-nickel type hydrogenation catalyst, a tungsten-nickel type hydrogenation catalyst, a molybdenum-cobalt type hydrogenation catalyst, or a molybdenum-tungsten-nickel type hydrogenation catalyst.
20. The process of claim 1 wherein the second hydroprocessing reaction zone has a reaction temperature of from 280 ℃ to 380 ℃.
21. The process of claim 1 wherein the volume ratio of hydrogen to solvent deasphalted heavy deasphalted oil in the second hydroprocessing reaction zone is from (600 to 1500): 1.
22. The process of claim 1 wherein the total volume space velocity of the second hydroprocessing reaction zone is from 0.2 to 2 hours -1 。
23. The process of claim 1 wherein the second hydroprocessing reaction zone has a hydrogen partial pressure greater than 8MPa.
24. The process of claim 1 wherein the catalyst employed in the second hydroprocessing reaction zone is a residuum fixed bed hydrogenation catalyst system.
25. The process of claim 24 wherein the residuum fixed bed hydrogenation catalyst system comprises a combination of a hydrogenation protecting agent, a hydrodemetallization catalyst, and a hydrofinishing catalyst.
26. The method of claim 25, wherein the hydro-protecting agent comprises a molybdenum-nickel type hydro-protecting agent.
27. The method of preparation of claim 25, wherein the hydrodemetallization catalyst comprises a molybdenum-nickel hydrodemetallization catalyst.
28. The method of claim 25, wherein the hydrofinishing catalyst comprises any one or a combination of at least two of a molybdenum-nickel type hydrogenation catalyst, a tungsten-nickel type hydrogenation catalyst, a molybdenum-cobalt type hydrogenation catalyst, or a molybdenum-tungsten-nickel type hydrogenation catalyst.
29. The method according to claim 25, wherein the mass ratio of the hydrofining catalyst, the hydrogenation protecting agent and the hydrodemetallization catalyst is 100 (0.5-10): 0.5-10.
30. The method of claim 1, wherein the tempering temperature is 40-200 ℃.
31. The method according to claim 1, wherein the tempering time is not less than 10min.
32. High C A An aromatic rubber plasticizer of the value, characterized in that the aromatic rubber plasticizer is prepared by the preparation method according to any one of claims 1 to 31.
33. The aromatic rubber plasticizer according to claim 32, wherein C of the aromatic rubber plasticizer A The value is more than or equal to 25 percent, and the kinematic viscosity at 100 ℃ is more than or equal to 30mm 2 And/s, the flash point is more than or equal to 230 ℃, the aniline point is less than or equal to 75 ℃, the BaP content is less than or equal to 1mg/kg, and the PAHs content is less than or equal to 10mg/kg.
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