CN104941649A - Hydrogenation catalyst for petroleum resin and preparation method and application thereof - Google Patents
Hydrogenation catalyst for petroleum resin and preparation method and application thereof Download PDFInfo
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- CN104941649A CN104941649A CN201510431240.1A CN201510431240A CN104941649A CN 104941649 A CN104941649 A CN 104941649A CN 201510431240 A CN201510431240 A CN 201510431240A CN 104941649 A CN104941649 A CN 104941649A
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- hydrogenation
- petroleum resin
- catalyst
- hydrogenation catalyst
- resin catalyst
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Abstract
The invention discloses a hydrogenation catalyst for petroleum resin and a preparation method and application thereof. A reaction device is subjected to bench scale and pilot scale tests through a high-pressure stationary bed, the catalytic performance of the hydrogenation catalyst is evaluated, and the hydrogenation catalyst is applied to industrial production. The hydrogenation catalyst is characterized in that activated carbon or silicon dioxide is used as a carrier and loads active metal nickel, nickel-molybdenum and nickel-tungsten components, the mass fraction accounts for 30-50%, a same-volume dipping method is adopted, the hydrogenation catalyst is used for C5 and C9 petroleum resin and has good low-temperature hydrogenation activity, a neutral carrier is adopted to decrease breakage of molecular chains, the variation amplitude of a softening point of a product after hydrogenation is smaller, the impurity-resisting capacity and stability of the hydrogenation catalyst are excellent, and bromine value and chroma are both within an ideal range.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of hydrogenation catalyst, this catalyst is applicable to Petropols (C5, C9) hydro-upgrading aspect.
Background technology
Carbon five, C 9 fraction are the cracking auxiliary products during industrial ethylene is produced, its efficiency utilization is the key point of the Appropriate application to petroleum resources, Petropols are that carbon five, C 9 fraction are through pretreatment, polymerization, a kind of low-molecular-weight thermoplastic resin of the explained hereafter such as distillation, it has good compatibility, caking property, resistance to water, is widely used in the industries such as rubber, adhesive, coating, papermaking, ink.Due to the difference of raw material and polymerizing condition, containing undersaturated double bond and phenyl ring in Petropols, under the effect of catalyst, it is made to be able to by hydrogenation saturated, and remove chlorine, element sulphur residual in polymerization process, and then improve colourity and the photo and thermal stability of resin, improve the quality of product.Therefore, research and development and the heavy industrialization application of carrying out hydrogenation of petroleum resin seem particularly important.
As the catalyst in hydrogenation of petroleum resin process, most important to this technique, he determines production cost and subsequent product quality.Compared to C5 hydrogenation of petroleum resin, the difficulty of C9 hydrogenation of petroleum resin is larger, because C9 Petropols are main in the form of a ring, chain structure, molecular weight is between 200 ~ 4000, sterically hindered comparatively large, activation energy needed for hydrogenation reaction improves, so need research and development to have the hydrogenation catalyst of high catalytic activity.
Current hydrogenation of petroleum resin catalyst is divided into two large classes: precious metal and base metal class, and mostly is loaded catalyst.Now carry out industrial applications mainly loading type Pd series catalysts, Ni series catalysts.Support strength because Petropols molecular weight is comparatively large, possesses hardly when the aperture of catalyst carrier for hydrgenating is less than 2nm and adds oxygen activity, so based on mesopore, also should be taken into account containing macropore or loose structure in the aperture of carrier simultaneously.Substantially there is not C-C bond fission in Pd series catalysts, its shortcoming is to impurity S
2-, Cl
-comparatively responsive, the principal element of Ni series catalysts inactivation is the reunion of active component, by changing preparation method, adding other metal promoters, improving its sulfur resistive ability and inhibit activities metal sintering, making this catalyst series advantage obvious gradually.
Patent CN103386302A discloses a kind of hydrogenation of petroleum resin catalyst, namely with Al
2o
3for carrier, carried noble metal Pd and oxides additive, the Metal Palladium crystallite that particle diameter is less than 3nm accounts for more than 90%, and its weak point is that catalyst is for impurity S
2-tolerance difference and easy poisoning and deactivation, catalyst life receives impact.
Patent CN103386308A discloses a kind of C5 hydrogenation of petroleum resin Raney nickel, with activated carbon supported Ni, add the auxiliary agents such as Zn, Co and form non-crystaline amorphous metal nano particle, reaction conversion ratio and selectively to increase, but because it adopts small-sized tank reactor to carry out intermittent reaction, do not carry out the concrete industrial applications performance test of catalyst.
Patent CN102935367A discloses a kind of palladium system C5 hydrogenation of petroleum resin catalyst, with aluminium oxide, titanium oxide composite carrier load palladium, molybdenum/tungsten active component, the mass fraction of supported palladium is 0.2-0.4%, this catalyst has low temperature hydrogenation activity, good anti-impurity ability and stability, but it supports the noble metal component of high level, production cost and expense are comparatively large, thoroughly do not solve this permanent problem.
Accordingly, need to develop a kind of applicable industrial applications, better tolerance, hydrogenation of petroleum resin catalyst with low cost, wherein, do not select acid carrier, avoid Petropols molecule chain break, cause the reduction of softening point, and carrier duct should based on hollow, the macromolecular chain being more applicable to Petropols reacts.
Summary of the invention
Inventor is by furtheing investigate discovery for a long time to hydrogenation of petroleum resin catalyst, use neutrality or basic supports, and carrying bimetallic component can give full play to concerted catalysis effect, catalyst has higher catalytic activity, and avoid the generation of side reaction in hydrogenation process, reduce molecule chain break, reduce the impact on naval stores softening point after hydrogenation, meanwhile, product colourity, bromine number are all in ideal range.
Technical scheme of the present invention is as follows:
A kind of be used for hydrogenation of petroleum resin catalyst, this is used for hydrogenation of petroleum resin catalyst and comprises carrier and load active component, active carbon or silica as carrier, load active component Ni, NiMo or NiW, quality loading is 30-50%; The specific area of hydrogenation catalyst is 200-600m
2/ g, pore volume is 0.3-0.6ml/g, and aperture is 5-110nm.
Described active carbon is wooden indefinite form granular activated carbon, first soaks with 3-5mol/L dust technology, then be neutralized to neutrality with alkali under 50 DEG C of conditions, dry; Described silica supports is graininess, by hydrochloric acid or nitric acid treatment, then spends deionized water to neutral, floods after drying.
For the preparation method of hydrogenation of petroleum resin catalyst, active carbon/silica supports is joined Ni (NO
3)
2, Ni (NO
3)
2, (NH
4)
6mo
7o
24, Ni (NO
3)
2or (NH
4)
6h
2w
12o
40the aqueous solution in, carry out incipient impregnation, impregnation concentration is according to the loading 30-50% of Ni, NiMo, NiW, and dip time is 6-10h; In Rotary Evaporators, abundant combination drying is carried out, at N after dipping is abundant
2under atmosphere, 400-550 DEG C is carried out roasting, obtains for hydrogenation of petroleum resin catalyst.
The described total pore volume of active carbon/silica supports equals mixed impregnant liquor volume used.
The application of above-mentioned hydrogenation of petroleum resin catalyst, hydrogenation of petroleum resin catalyst, Hydrogenation test is carried out in continuous fixed bed reactors, Petropols are dissolved in hexahydrotoluene or cyclohexane or Porous deproteinized bone solvent naphtha, be configured to the Petropols material solution of mass concentration 5%, 10%, 20%, loaded catalyst 300ml, reaction temperature 260-280 DEG C, pressure 12-18MPa, volume space velocity 0.6-0.9h
-1, hydrogen to oil volume ratio 700-1000, hydrogenation products, through vacuum distillation apparatus, obtains hydrogenated petroleum resin after distillation.
Petropols performance test of the present invention, employing method and standard: bromine valency is the index that (gBr/100g) weighs unsaturated hydrocarbons content in organic matter, standard: HG2231-91; Softening point adopts ring and ball method, standard: the full-automatic bituminous softening-point test device of GB/T 4507-2014, SYD-2806H type; Colourity Bian Gardner's colorimeter, standard A STMD-1544; Melt viscosity (cps) adopts NDJ-1C type rotation viscometer.
Accompanying drawing explanation
Accompanying drawing is process flow diagram of the present invention.
In figure: 1 hydrogen; 2 head tanks; 3 two ends hydrogenation fixed bed reactors A;
4 two ends hydrogenation fixed bed reactors B; 5 water pots; 6 high pressure, low pressure separator; 7 water scrubbers;
8 Water Tanks; 10 strippers; 11 products pots.
Detailed description of the invention
Below in conjunction with accompanying drawing and technical scheme, further illustrate the specific embodiment of the present invention.
Embodiment 1
1. be 300m by specific area
2/ g, pore volume 0.5ml/g, average pore size are the indefinite form granular activated carbon of 60nm, under 50 DEG C of conditions, soak 5h with 4mol/L dust technology, spend deionized water to neutral, under 100 DEG C of conditions, dry 1h. with ammonia neutralization
2. absorbent charcoal carrier is joined Ni (NO
3)
2or Ni (NO
3)
2, (NH
4)
6mo
7o
24or Ni (NO
3)
2, (NH
4)
6h
2w
12o
40carry out incipient impregnation in the aqueous solution, after dipping, in Rotary Evaporators, carry out abundant combination drying, and at N
2under atmosphere, 400-550 DEG C is carried out roasting, and heating rate 2 DEG C/min, uses the H of 15% volumetric concentration before use at catalyst
2(N
2) blender carries out reduction activation.
Ni/C, NiMo/C, NiW/C catalyst that the present embodiment is obtained, is characterized by: the mass fraction of catalyst components is: Ni 40%, Ni 35%Mo 5%, Ni 35%W 5%, and remaining is active carbon and other auxiliary agents.
Embodiment 2
Hydrogenation of petroleum resin catalyst is support type Ni, NiMo, NiW metallic catalyst, and carrier adopts SiO
2or active carbon, specific area is at 200-600m
2/ g, pore volume at 0.3-0.6ml/g, average pore size 5-110nm.Metal precursor adopts Ni (NO respectively
3)
2or Ni (NO
3)
2, (NH
4)
6mo
7o
24or Ni (NO
3)
2, (NH
4)
6h
2w
12o
40.Equi-volume impregnating is adopted to prepare load type metal catalyst through steps such as dipping-drying-roastings.At 30-50%, Mo, W metal, 5-20% is supported for Ni metal loading.High pressure fixed bed reactors are adopted to carry out pilot plant test, loaded catalyst 5ml.Following table 1 is shown in reaction process condition and product property.
As shown in Table 1, Petropols are through high pressure low temperature hydrogenation reaction, and all metallic catalyst catalytic performances are excellent, and softening point has some to reduce, and raw material bromine number obviously reduces, and illustrate that unsaturated linkage hydrogenation is abundant, product colour is also become colorless transparent by buff.
Embodiment 3
For NiMo or NiW catalyst, investigate temperature and pressure to the impact of hydrogenation of petroleum resin catalyst, wherein the loading of Ni, Mo or W is respectively 30%, 5%.Following table 2 is shown in reaction process condition and product property.Feedstock property: colourity numbers 10, bromine number 22, softening point 125 DEG C.
As shown in Table 2, because hydrogenation of petroleum resin reaction is exothermic reaction, and temperature affects positive correlation to reaction rate, and considering reaction temperature should be not too high, and reaction pressure is obvious to hydrogenation of petroleum resin influential effect, and hydrogenation pressure more high product proterties is better.Therefore, selection reaction condition is: reaction temperature 260 DEG C, reaction pressure 18MPa, volume space velocity 0.7-0.9h
-1, hydrogen to oil volume ratio 500-800.
Embodiment 4
For NiMo catalyst, hydrogenation of petroleum resin stability test is carried out to catalyst agent, chooses high pressure fixed bed pilot-plant, loaded catalyst 300ml, select the condition of cryogenic high pressure to test, following table 3 is shown in the reaction process condition and product property that within 480 hours, run.Feedstock property: colourity numbers 9, bromine number 26, softening point 120 DEG C.
The experimental result of 480 hours as shown in Table 3, adopt NiMo catalyst, Petropols are in 260 DEG C, hydrogenation reflection is carried out under 18MPa condition, from data before and after reaction relatively, the bromine number of subsequent product (480h), softening point, colourity with start to test compared with (24h) substantially constant, show that catalyst has higher catalytic activity and stability.
Claims (5)
1. for a hydrogenation of petroleum resin catalyst, it is characterized in that, this is used for hydrogenation of petroleum resin catalyst and comprises carrier and load active component, active carbon or silica as carrier, load active component Ni, NiMo or NiW, quality loading is 30-50%; The specific area of hydrogenation catalyst is 200-600m
2/ g, pore volume is 0.3-0.6ml/g, and aperture is 5-110nm.
2. according to claim 1ly it is characterized in that for hydrogenation of petroleum resin catalyst, described active carbon is wooden indefinite form granular activated carbon, first soaks with 3-5mol/L dust technology, then be neutralized to neutrality with alkali under 50 DEG C of conditions, dry; Described silica supports is graininess, by hydrochloric acid or nitric acid treatment, then spends deionized water to neutral, floods after drying.
3. the preparation method for hydrogenation of petroleum resin catalyst described in claim 1 or 2, is characterized in that, active carbon/silica supports is joined Ni (NO
3)
2, Ni (NO
3)
2, (NH
4)
6mo
7o
24, Ni (NO
3)
2or (NH
4)
6h
2w
12o
40the aqueous solution in, carry out incipient impregnation, impregnation concentration is according to the loading 30-50% of Ni, NiMo, NiW, and dip time is 6-10h; In Rotary Evaporators, abundant combination drying is carried out, at N after dipping is abundant
2under atmosphere, 400-550 DEG C is carried out roasting, obtains for hydrogenation of petroleum resin catalyst.
4. preparation method according to claim 3, is characterized in that, the described total pore volume of active carbon/silica supports equals mixed impregnant liquor volume used.
5. the application of hydrogenation of petroleum resin catalyst as claimed in claim 1 or 2, it is characterized in that: hydrogenation of petroleum resin catalyst, Hydrogenation test is carried out in continuous fixed bed reactors, Petropols are dissolved in hexahydrotoluene or cyclohexane or Porous deproteinized bone solvent naphtha, be configured to the Petropols material solution of mass concentration 5%, 10%, 20%, loaded catalyst 300ml, reaction temperature 260-280 DEG C, pressure 12-18MPa, volume space velocity 0.6-0.9h
-1, hydrogen to oil volume ratio 700-1000, hydrogenation products, through vacuum distillation apparatus, obtains hydrogenated petroleum resin after distillation.
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|---|---|---|---|
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| CN201510176463 | 2015-04-14 | ||
| CN201510431240.1A CN104941649A (en) | 2015-04-14 | 2015-07-22 | Hydrogenation catalyst for petroleum resin and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311264A (en) * | 2016-07-26 | 2017-01-11 | 厦门大学 | Silica supported nickel tungsten catalyst and preparation method and application thereof |
| CN106397673A (en) * | 2016-06-03 | 2017-02-15 | 中国石油化工股份有限公司 | Method and apparatus for continuous kettle type hydrogenation of petroleum resin |
| CN106540708A (en) * | 2016-10-25 | 2017-03-29 | 张峰 | A kind of C5Hydrogenation of petroleum resin catalyst and preparation method thereof |
| CN107880159A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of two-part preparation method of hydrogenated petroleum resin |
| CN107876056A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of hydrogenation of petroleum resin nickel catalyst, preparation method and applications |
| CN107876051A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of hydrogenation of petroleum resin palladium series catalyst, preparation method and applications |
| CN111760574A (en) * | 2020-07-30 | 2020-10-13 | 淄博鲁华泓锦新材料股份有限公司 | C9 petroleum resin hydrogenation catalyst, preparation method and application thereof |
| CN113101967A (en) * | 2021-04-15 | 2021-07-13 | 青岛中瑞泰丰新材料有限公司 | C5 and/or C9 petroleum resin two-stage hydrofining catalyst and preparation method and application thereof |
| CN113680375A (en) * | 2021-09-09 | 2021-11-23 | 中化泉州石化有限公司 | Hydrocatalyst for C-V petroleum resin and its preparing process |
| CN114602464A (en) * | 2022-04-25 | 2022-06-10 | 中化泉州能源科技有限责任公司 | Hydrocatalyst for C-V petroleum resin and its preparing process |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397673A (en) * | 2016-06-03 | 2017-02-15 | 中国石油化工股份有限公司 | Method and apparatus for continuous kettle type hydrogenation of petroleum resin |
| CN106397673B (en) * | 2016-06-03 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of method and device of continuous autoclave hydrogenation of petroleum resin |
| CN106311264B (en) * | 2016-07-26 | 2018-12-11 | 厦门大学 | A kind of silicon dioxide carried nickel tungsten catalyst and the preparation method and application thereof |
| CN106311264A (en) * | 2016-07-26 | 2017-01-11 | 厦门大学 | Silica supported nickel tungsten catalyst and preparation method and application thereof |
| CN107880159A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of two-part preparation method of hydrogenated petroleum resin |
| CN107876051A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of hydrogenation of petroleum resin palladium series catalyst, preparation method and applications |
| CN107876056A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of hydrogenation of petroleum resin nickel catalyst, preparation method and applications |
| CN106540708A (en) * | 2016-10-25 | 2017-03-29 | 张峰 | A kind of C5Hydrogenation of petroleum resin catalyst and preparation method thereof |
| CN111760574A (en) * | 2020-07-30 | 2020-10-13 | 淄博鲁华泓锦新材料股份有限公司 | C9 petroleum resin hydrogenation catalyst, preparation method and application thereof |
| CN111760574B (en) * | 2020-07-30 | 2023-04-18 | 淄博鲁华泓锦新材料集团股份有限公司 | C9 petroleum resin hydrogenation catalyst, preparation method and application thereof |
| CN113101967A (en) * | 2021-04-15 | 2021-07-13 | 青岛中瑞泰丰新材料有限公司 | C5 and/or C9 petroleum resin two-stage hydrofining catalyst and preparation method and application thereof |
| CN113680375A (en) * | 2021-09-09 | 2021-11-23 | 中化泉州石化有限公司 | Hydrocatalyst for C-V petroleum resin and its preparing process |
| CN113680375B (en) * | 2021-09-09 | 2023-08-25 | 中化泉州石化有限公司 | Carbon five petroleum resin hydrogenation catalyst and preparation method thereof |
| CN114602464A (en) * | 2022-04-25 | 2022-06-10 | 中化泉州能源科技有限责任公司 | Hydrocatalyst for C-V petroleum resin and its preparing process |
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