CN101700494B - Preparation of hydrogenation catalyst and use thereof - Google Patents
Preparation of hydrogenation catalyst and use thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a hydrogenation catalyst suitable for the hydrogenation reaction of C5 petroleum resin. The method comprises the steps of: taking aluminium hydroxide, kieselguhr, pore-expanding agent and rare earth element-modified aluminium oxide as a carrier; loading bi-component noble metal on the carrier; and adjusting the catalytic activity with the rare earth element to obtain the hydrogenation catalyst with high activity and long service life. The catalyst is particularly suitable for the hydrogenation of the perchloride-containing C5 petroleum resin, thereby being capable of preparing hydrogenated petroleum resin with light hue and high softening point.
Description
Technical field
The invention belongs to preparation method and the use thereof of hydrogenation of petroleum resin catalyst, be particularly related to a kind of preparation and purposes of the hydrogenation catalyst for C 5 petroleum resin, the material carbon 5 petroleum resin is cracking accessory substance C5 fraction in the ethylene industry production process, comprise pentadiene, isoprene, amylene and a small amount of cyclopentadiene and dicyclopentadiene, above-mentioned mixing C5 fraction obtains mixing C 5 petroleum resin through catalytic polymerization.Prepared catalyst is particularly suitable for the hydrogenation process of high halogen content mixing C 5 petroleum resin in the invention, and this catalyst has high activity and permanent halogen resistant stability, can be used for producing high-quality hydrogenated carbon five petroleum resin.
Background technology
In the ethylene industry production process, can produce a large amount of cracked C 5 fractions, usually this C5 fraction is removed most of isoprene and dicyclo isoprene through the separating technology unit, copolymerization is carried out in remaining mixing C5 fraction under the cation catalyst system and catalyzing, produce and mix C 5 petroleum resin.
C 5 petroleum resin has good cohesiveness, good with grease, synthetic resin intermiscibility, application is extensive, but simultaneously owing to contain a large amount of unsaturated bonds in this resin and because the remaining catalyst of catalytic polymerization, cause thus the heat endurance of resin low, color is dark, affected its application in the high-end field, in the Application and Development of the applications such as extraordinary adhesive, coating, traffic paint, rubber, the performance of C 5 petroleum resin has been had higher requirement especially in recent years.Usually the method for modifying that adopts is that C 5 petroleum resin is carried out hydrotreatment, remaining organic or inorganic halogen in the deresinate, simultaneously unsaturated bond is carried out hydrogenation, improve thus heat endurance, the intermiscibility of resin, the resin form and aspect are improved greatly.
Three kinds of hydrogenation techniques of the general employing of Petropols catalytic hydrogenation reaction, namely starch attitude hydrogenation, spray hydrogenation and fixed bed hydrogenation, the active component of employed hydrogenation catalyst mostly is Ni, W, Mo, Mg or precious metal element Pd, Ru, Rh, Re etc., and carrier adopts aluminium oxide, clay etc. more.Development through decades, commercially produce general employing fixed-bed type hydrogenation technique, be divided into one section or two-stage hydrogenation mode, the current typing catalyst that has been applied to suitability for industrialized production has HarshawNi-0104, HarshawNi-3266E, Harshaw Ni-3210T, Engelhard 0.5%Pd/Al
2O
3Deng.
In the production of C 5 petroleum resin, adopt Friedel-Craft cation catalyst system and catalyzing to carry out catalytic polymerization more, catalyst is with anhydrous AlCl
3Be main, although naval stores is carried out the last handling processes such as alkali cleaning neutralization, washing, but halogen Cl content remaining in the resin still can have unsaturated bond to exist up to 1000～5000ppm simultaneously, and these all are to cause the resin form and aspect deeply to reach the low principal element of heat endurance.
The form and aspect of C 5 petroleum resin and softening point are the important indicators that affects its range of application and economic benefit, and for improving form and aspect and heat endurance, many companies and scientific research institutions have carried out developmental research for many years.Early stage US Patent No. 2824860 is just carried out hydrotreatment to Petropols report adopts Al such as US4328090, US4629766
2O
3Load presulfurization Ni, W or Ni, Mo makees catalyst, produce light colour petroleum resin, in addition, adopt noble metal carrier catalyst in the US Patent No. 4540480, active component mainly is selected from Pd, Rh, Ru, Re, Pt etc., these catalyst have the deficiency that also there is application in the highly active while, as early literatures Catalysis, Berkuan, Morrell and Egloff Reinhold reports among the 1940P400, remaining halogen can cause the inactivation of catalyst in the resin, even halogen Cl a small amount of in the reaction system can cause catalyst poisoning, these factors must reduce the service life of catalyst, also cause economic benefit to descend simultaneously.
The deficiency that all has self at present employed sulfuration Ni, W, Mo or noble metal carrier catalyst, the catalyst of industrial employed presulfurization Ni, W, Mo belongs to the hydrodesulfurization type catalyst, as using presulfurization Ni, W/Al among patent CN1199742A, the US6433104B1
2O
3Make the adding hydrogen into resin catalyst, although this kind catalyst has higher high active of hydrogenation catalysis, can cause the degradation reaction of too much Petropols in the course of reaction, cause the hydrogenated petroleum resin softening point to reduce too much, affect serviceability.For noble metal carrier catalyst, active component can be selected Pd, Pt, Ni, Ru, Rh, Re etc., such as CN101157029A, CN1084521A, CN1189493C, US4952639, report among the US4276396, noble metal carrier catalyst initial activity in the adding hydrogen into resin reaction is high, the degraded side reaction there is inhibitory action, but halogen Cl remaining in the material resin can be adsorbed by catalyst surface at hydrogenation process, can increase gradually the surface acidity of catalyst, finally cause the generation of resin hydrocrack, cause that the hydrogenated resin softening point descends, noble metal crystal grain generation sintering in the simultaneously use procedure, cause the minimizing of hydrogenation activity position, reduce the productive rate of hydrogenated resin, shorten catalyst service life.But the noble metal carrier catalyst reactivity is high, and reaction condition is relatively gentle, and still as first-selected catalyst, key is how to improve its halogen resistant stability and anti-caking power, with the service life of extending catalyst in the hydrogenation of petroleum resin reaction.
Domestic C 5 petroleum resin starting is late, especially mix C 5 petroleum resin and form fluctuation greatly, the halogen remaining quantity is high in the resin simultaneously, this just has higher requirement to the stability of catalyst, especially improve the anti-Cl performance of C 5 petroleum resin hydrogenation catalyst, keeping its activity and stability is the emphasis of catalyst development work, reasonably select active constituent, improve anti-caking power, be directed to simultaneously this reaction characteristics, the carrier of selecting to have suitable specific area, surface acidity, pore size and pore size distribution is also particularly important.
Summary of the invention
The object of the present invention is to provide a kind of preparation and application of mixing the C 5 petroleum resin hydrogenation catalyst, prepared catalyst not only has excellent hydrogenation reaction activity in the invention, it is unexpected that this catalyst key property of finding be to have anti-Cl stability simultaneously, under the reaction condition of high Cl content, can keep the activity stabilized of catalyst, prolonged the service life of catalyst, widened the adaptability of catalyst to material resin, use prepared catalyst among the present invention, can obtain the hydrogenated carbon five petroleum resin that the bromine valency is low, form and aspect are shallow, softening point is high.
The applicant has invented the C 5 petroleum resin hydrogenation catalyst that a kind of anti-Cl has good stability by a large amount of experimental studies,
This catalyst is to be made of composite modified alumina support and noble metal active component.
Technical method of the present invention is as follows
A kind of hydrogenation catalyst for C 5 petroleum resin is characterized in that: this catalyst comprises the composite alumina carrier of 100 weight portions and 0.5～2.0 weight portion as the noble metal of active component.
Described carrier comprises boehmite, aluminium hydroxide and diatomite.
Described carrier comprises 30～80 weight portion boehmites, 10～40 weight portion aluminium hydroxides and 10～40 weight portion diatomite; It is preferred: 40～50 weight portion boehmites, 20～30 weight portion aluminium hydroxides and 20～30 weight portion diatomite.
Described catalyst also comprises at least a rare earth metal of 0.5～2.0 weight portion, preferred 0.7～1.2 weight portion.
Described rare earth metal is one or more that are selected among La, Ce, the Sr.
Described carrier also comprises the expanding agent of 5～10 weight portions.
Described expanding agent is one or more that are selected from methylcellulose, sodium stearate, polyethylene glycol, graphite and the starch.
Described noble metal is two kinds that are selected from the VIII family element.
Described noble metal is two kinds that are selected among Pd, Ru, the Rh.
The amount of described Pd is 0.5～1.0 weight portion, preferred 0.6～0.9 weight portion.
The amount of described Ru is 0.1～1.0 weight portion, preferred 0.3～0.6 weight portion.
The amount of described Rh is 0.1～1.0 weight portion, preferred 0.4～0.8 weight portion.
It is the C 5 petroleum resin hydrogenation of 1～5000ppm that hydrogenation catalyst is used for chlorinity.
Hydrogenation catalyst is applicable to the C 5 petroleum resin hydrogenation reaction, material resin solution concentration 1～60% (wt), preferred 1～40% (wt).
Being prepared as follows of catalyst carrier:
Getting commercially available boehmite, aluminium hydroxide, diatomite and expanding agent powder mixes by a certain percentage, fully mediate after adding quantitative rare nitric acid, aging certain hour, extrusion molding on double screw extruder, roasting under the pre-set programs temperature control after dry, obtain the composite aluminium oxide of strip, it is for subsequent use that crushing screening is got certain granules degree carrier.Use the rare earth nitrate aqueous solution of the metering concentration that configures to flood in the above-mentioned carrier of weighing, carry out afterwards drying, roasting, the composite modified catalyst carrier that obtains using among the present invention.
Adopt conventional dipping method to carry out the load of active component, use the palladium bichloride of metering concentration and the mixed aqueous solution of ruthenic chloride to flood catalyst carrier, under temperature programming control, carry out roasting after dry, reduction activation in reactor before the hydrogenation reaction obtains catalyst described in the present invention.
Can obtain the catalyst of following feature, composite modified alumina support specific area 90～150m by above-mentioned preparation method
2/ g, pore volume 0.5～0.7ml/g, its mesoporous 60～200
Account for total pore volume more than 50%, the adding of aluminium hydroxide, diatomite and expanding agent is favourable to the formation of secondary pore in the roasting process, for composite carrier provides larger aperture size, can provide for the hydrogenation reaction of resin favourable reaction environment.The adding of rare earth element has improved the decentralization of active component on carrier, and the simultaneously application of bi-component active component has improved the anti-caking power of precious metal element crystallite under the high-temperature hydrogenation reaction condition, and is provided longer hydrogenation service life.
The inventor adopts the fixed bed hydrogenation technological process, find by great many of experiments, use the catalyst of said method preparation, in the C 5 petroleum resin hydrogenation reaction, has very high activity, product hydrogenated petroleum resin bromine valency＜2mg/100g, hydrogenation rate reaches 98%, product colourity＜1 (Gardner method).More outstanding is that for the C 5 petroleum resin of high Cl content, through for a long time reaction, hydrogenation rate still maintains more than 95%, illustrates that this catalyst has good anti-Cl stability.By following instance, preparation and the use of the catalyst among the present invention is described.
Catalyst activity and life assessment method:
The C 5 petroleum resin of Cl content 4728ppm is dissolved in the cyclohexane, forms the material solution of 20%～40% (wt) concentration, concentration is weight percentage.The catalyst of in the single tube fixed bed, packing into, reduction activation under temperature programming in atmosphere of hydrogen passes into material resin solution and carries out hydrogenation reaction in the reactor, reaction condition: pressure 6.0～10.0Mpa, 250～300 ℃ of bed temperatures, liquid air speed 2.0～4.0h
-1, hydrogen gas space velocity 150～200h
-1, the hydrogenation mix products obtains the product C 5 hydrogenated petroleum resin behind falling film evaporator desolvation and other accessory substance, carry out physical property and detect analysis.
Analysis and detecting instrument and operative norm:
Colour: U.S. HunterLab Colour Quest EX colorimetric analysis instrument, operative norm ASTM E313
Bromine valency: U.S. METTLER TOLEDO DL58 type titrator, operative norm ASTMD1159-93
Softening point: domestic SYD-2806F type softening point apparatus, operative norm GB/T 12007.6-1989
Chlorinity: domestic RPA-200A micro-coulometric titration instrument, the operative norm Shi Ke RIPP64 of institute
Hydrogenation saturation computation method:
Performance with above-mentioned analyzing and testing index evaluate catalysts.
Description of drawings
Fig. 1 is stability experiment stability experiment figure
Specific implementation method
A kind of hydrogenation catalyst for C 5 petroleum resin, catalyst carrier is to make with 30～80 parts of boehmites, 10～40 parts of aluminium hydroxide, 10～40 parts of former powder of diatomite and 5～10 parts of organic expanding agents forming method by routine, adopting 0.5～2.0 weight portion rare earth element that carrier is carried out pre-preg before the active constituent loading processes, with respect to 100 weight portion carriers, catalytic active component is comprised of 0.5～2.0 part of precious metal element.
Catalytic active component is selected from VIII family element, for bi-component forms, comprises two kinds of elements among Pd, Ru, the Rh.
The carrier pretreatment component is selected from rare earth element, comprises La, Sr, Ce, is made of wherein a kind of at least.
As preferably, the consisting of of said catalyst carrier: 40～50 weight portion boehmites, 20～30 weight portion aluminium hydroxides and 20～30 weight portion diatomite.Preferred 0.8～1.7 weight portion of active component, preferred 0.7～1.2 weight portion of carrier pretreatment component.
The preparation of embodiment 1 catalyst carrier
Take by weighing boehmite 500g, aluminium hydroxide 200g, diatomite 300g and 100g polyethylene glycol powder, mix, adding 276g 6% diluted nitric acid aqueous solution mediates, wore out 30 minutes under the room temperature, be shaped to φ 3 strips at banded extruder, in 120 ℃ of dryings 24 hours, afterwards in 800 ℃ of roastings 2 hours.
The strip carrier pelletizing is to φ 3 * 3 granularities, for subsequent use.
According to above-mentioned preparation method, adopt different former powder proportionings to prepare carrier 2,3,4,5 respectively, carrier forms and characterizes such as following table:
Table one support material proportioning and carrier characterize
The load of embodiment 2 active components
Take by weighing respectively 1～5 carrier 100g among the embodiment 1, add the strontium nitrate aqueous solution dipping 24 hours of 100ml (0.012g Sr/ml), in 120 ℃ of dryings 12 hours, afterwards 600 ℃ of roastings 4 hours obtained composite modified alumina support, Sr content 1.2%.
Get respectively above-mentioned 1,2,3,4,5 carrier 100g, put into respectively the mixed aqueous solution that 120ml contains palladium bichloride and ruthenic chloride, wherein palladium content 0.00125g/ml, ruthenium content 0.00083g/ml, flooded after 24 hours 120 ℃ of dryings 6 hours, repeat aforesaid operations 4 times, obtain the catalyst of load 0.6%Pd, 0.4%Ru, dry rear in 400 ℃ of roastings 4 hours, obtain corresponding C-1, C-2, C-3, C-4, C-5 catalyst.
Embodiment 3 catalyst activity evaluations
Commercially available mixing C 5 petroleum resin is dissolved in the cyclohexane solvent, forms the material solution of concentration 20% (wt), wherein chlorinity 945ppm.
Raw material mixing C 5 petroleum resin physical property such as following table:
Table two material resin physical property
| Colour (Gardner) | Chlorinity (ppm) | Bromine valency (gBr/100g) | Softening point (℃) | |
| Mix C 5 petroleum resin | 7.82 | 4728 | 70.47 | 106 |
With the catalyst of the embodiment 2 preparation single tube fixed bed reactors of packing into, 300 ℃ of reduction 4 hours in atmosphere of hydrogen make the catalyst activation under the normal pressure, carry out afterwards hydrogenation reaction.Reaction condition is as follows: 270 ℃ of temperature, pressure 8.0Mpa, liquid air speed 4.0h
-1, hydrogen gas space velocity 200h
-1, reactant mixture passes through first alkali cleaning, washing, by falling film evaporator desolvation and accessory substance, obtains the hard resin product, carries out analyzing and testing.
Hydrogenation reaction experimental result such as following table:
The evaluation of table three catalyst activity
| Catalyst | Colour (Gardner) | Chlorinity (ppm) | Bromine valency (gBr/100g) | Softening point (℃) | Hydrogenation saturation factor (%) |
| C-1 | 0.16 | 2.14 | 1.12 | 96 | 98.4％ |
| C-2 | 0.21 | 2.71 | 1.20 | 93 | 98.3％ |
| C-3 | 0.23 | 3.10 | 1.34 | 91 | 98.1％ |
| C-4 | 0.20 | 2.85 | 1.23 | 97 | 98.3％ |
| C-5 | 0.34 | 2.63 | 1.60 | 94 | 97.8％ |
Embodiment 4
Adopt catalyst C-1, input concentration is respectively 30% (wt)) and 40% (wt), other reaction conditions are with embodiment 3, and hydrogenation reaction result is as follows:
The experiment of table four different feeds concentration
| Concentration | Colour (Gardner) | Chlorinity (ppm) | Bromine valency (gBr/100g) | Softening point (℃) | Hydrogenation saturation factor (%) |
| 30％ | 0.34 | 4.00 | 1.73 | 96 | 97.8％ |
| 40％ | 0.4 | 4.10 | 1.82 | 95 | 97.5％ |
Comparative Examples 1
Adopt the method among the embodiment 1, according to different material powder proportionings, prepare respectively following carrier 6,7,8,9, the result is as follows:
The former powder proportioning of table five carrier
Adopt the carrier that obtains in the Comparative Examples 1, according to method for preparing catalyst described in the embodiment 2, difference Kaolinite Preparation of Catalyst C
-6, C
-7, C
-8, C
-9, according to catalyst activity evaluation method among the embodiment 3, carrying out hydrogenation reaction, the result is as follows:
Table six activity rating
| Catalyst | Colour (Gardner) | Chlorinity (ppm) | Bromine valency (gBr/100g) | Softening point (℃) | Hydrogenation saturation factor (%) |
| C-6 | 3.65 | 9.75 | 12.61 | 99 | 82.1％ |
| C-7 | 2.40 | 18.60 | 6.83 | 92 | 90.3％ |
| C-8 | 5.13 | 15.21 | 37.50 | 93 | 46.8％ |
| C-9 | 4.81 | 20.85 | 32.47 | 101 | 53.9％ |
Compare with embodiment 1, do not add the expanding agent modification in the carrier preparation process, the large pore size distribution of carrier reduces, on the catalyst hydrogenation activity impact significantly.
Embodiment 5
Adopt the method among the embodiment 1, the former powder amount of boehmite, aluminium hydroxide and diatomite is with reference to embodiment 1, add respectively 100g carboxymethyl cellulose powder, 100g odium stearate powder and 100g starch and make expanding agent, obtain carrier 10,11 and 12, and according to implementing method for preparing catalyst makes catalyst C-10, C-11 and C-12 in sharp 2, carry out activity rating to implement sharp 3 reaction conditions, hydrogenation reaction result is as follows:
The different expanding agent modifications of table seven are estimated
| Catalyst | Expanding agent | Colour (Gardner) | Chlorinity (ppm) | Bromine valency (gBr/100g) | Softening point (℃) | Hydrogenation saturation factor (%) |
| C-10 | Carboxymethyl cellulose | 0.36 | 3.61 | 1.79 | 93 | 97.4％ |
| C-11 | Odium stearate | 0.28 | 2.98 | 1.66 | 91 | 97.3％ |
| C-12 | Starch | 0.34 | 3.20 | 1.83 | 92 | 97.4％ |
Embodiment 6
According to carrier preparation method among the embodiment 2, prepare respectively La, Sr, Ce modified aluminium oxide supports, and according to embodiment 2 Kaolinite Preparation of Catalysts, adopt embodiment 3 appreciation conditions, hydrogenation reaction result is as follows:
Table eight activity rating
| Catalyst | Rare earth forms | Colour (Gardner) | Chlorinity (ppm) | Bromine valency (gBr/100g) | Softening point (℃) | Hydrogenation saturation factor (%) |
| C-13 | 0.7％La | 0.26 | 2.76 | 1.80 | 94 | 97.4％ |
| C-14 | 0.7％Sr | 0.29 | 3.10 | 1.65 | 92 | 97.7％ |
| C-15 | 0.7％Ce | 0.38 | 4.35 | 1.89 | 97 | 97.3％ |
| C-16 | 1.2％La | 0.34 | 4.61 | 1.94 | 90 | 97.2％ |
| C-17 | 1.2％Ce | 0.39 | 5.40 | 1.94 | 95 | 97.2％ |
Embodiment 7
Get catalyst C-1 used carrier among the embodiment 2, be prepared as follows respectively different activities component load capacity catalyst according to embodiment 2, and adopt the evaluation method of embodiment 3, catalytic reaction result is as follows:
Table nine activity rating
| Catalyst | Active component forms | Colour (Gardner) | Chlorinity (ppm) | Bromine valency (gBr/100g) | Softening point (℃) | Hydrogenation saturation factor (%) |
| C-18 | 0.5％Pd、0.2％Ru | 0.31 | 3.00 | 1.98 | 92 | 97.1％ |
| C-19 | 0.9％Pd、0.8％Ru | 0.10 | 2.10 | 1.06 | 94 | 98.5％ |
| C-20 | 0.6％Pd、0.4％Rh | 0.24 | 2.36 | 1.95 | 97 | 97.2％ |
| C-21 | 0.5％Pd、0.8％Rh | 0.29 | 2.36 | 1.95 | 97 | 97.2％ |
| C-22 | 0.2％Ru、0.8％Rh | 0.35 | 3.40 | 1.83 | 91 | 97.4％ |
| C-23 | 0.9％Ru、0.1％Rh | 0.39 | 4.10 | 1.66 | 94 | 97.6％ |
Adopt catalyst C-1, experiment condition such as embodiment 3 carry out 1500 hours Hydrogenation Experiments, experimental result such as Fig. 1: stability experiment continuously.
Claims (11)
1. hydrogenation catalyst that is used for C 5 petroleum resin, it is characterized in that: this catalyst comprises the composite alumina carrier of 100 weight portions and 0.5～2.0 weight portion as the noble metal of active component, carrier comprises 30～80 weight portion boehmites, 10～40 weight portion aluminium hydroxides and 10～40 weight portion diatomite, and it is the C 5 petroleum resin hydrogenation of 1～5000ppm that this hydrogenation catalyst is used for chlorinity.
2. according to claim 1 the hydrogenation catalyst that is used for C 5 petroleum resin, it is characterized in that: described catalyst also comprises at least a rare earth metal of 0.5～2.0 weight portion.
3. according to claim 2 the hydrogenation catalyst that is used for C 5 petroleum resin, it is characterized in that: described rare earth metal is one or more that are selected among La, Ce, the Sr.
4. according to claim 1 the hydrogenation catalyst that is used for C 5 petroleum resin, it is characterized in that: described carrier also comprises the expanding agent of 5～10 weight portions.
5. according to claim 4 the hydrogenation catalyst that is used for C 5 petroleum resin, it is characterized in that: described expanding agent is one or more that are selected from methylcellulose, sodium stearate, polyethylene glycol, graphite and the starch.
6. according to claim 1,2,3,4 or 5 hydrogenation catalyst, it is characterized in that: described noble metal is two kinds that are selected from the VIII family element.
7. according to claim 6 the hydrogenation catalyst that is used for C 5 petroleum resin, it is characterized in that: described noble metal is two kinds that are selected among Pd, Ru, the Rh.
8. according to claim 7 the hydrogenation catalyst that is used for C 5 petroleum resin, it is characterized in that: the amount of described Pd is 0.5～1.0 weight portion.
9. according to claim 7 the hydrogenation catalyst that is used for C 5 petroleum resin, it is characterized in that: the amount of described Ru is 0.1～1.0 weight portion.
10. according to claim 7 the hydrogenation catalyst that is used for C 5 petroleum resin, it is characterized in that: the amount of described Rh is 0.1～1.0 weight portion.
11. according to claim 1,2,3,4,5,7,8,9 or 10 the hydrogenation catalyst that is used for C 5 petroleum resin, it is characterized in that: the material resin solution concentration that is applicable to the C 5 petroleum resin hydrogenation reaction is 1～40% (wt).
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