CN102964199B - Method for selective hydrogenation of methyl-alpha-methyl styrene - Google Patents
Method for selective hydrogenation of methyl-alpha-methyl styrene Download PDFInfo
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- CN102964199B CN102964199B CN201110256343.0A CN201110256343A CN102964199B CN 102964199 B CN102964199 B CN 102964199B CN 201110256343 A CN201110256343 A CN 201110256343A CN 102964199 B CN102964199 B CN 102964199B
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- methyl styrene
- hydrogenation
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Abstract
The invention relates to a method for selective hydrogenation of methyl-alpha-methyl styrene, which comprises the following steps: in a fixed bed reactor, allowing a feed flow containing methyl-alpha-methyl styrene to contact with a nickel catalyst in the reactor to perform one-step slow hydrogenation so as to convert the methyl-alpha-methyl styrene in the feed flow into isopropyl toluene, wherein the nickel catalyst adopts an alumina/ silica compound as a carrier and adopts metal nickel as an active component. The content of methyl-alpha-methyl styrene in the feed flow is less than or equal to 21 wt%. the hydrogenation conversion rate of the methyl-alpha-methyl styrene is up to 99.9%, and the hydrogenation selectivity is 99.9%.
Description
Technical field
The present invention relates to the selection method of hydrotreating of petroleum hydrocarbon, be specifically related to methyl-alpha-methyl styrene and select method of hydrotreating, reach the combination of high conversion and highly selective on compared with low catalyst cost.
Background technology
Methyl-alpha-methyl styrene is to produce main ingredient in the tar light oil by product of meta-cresol device, annual 12000 tons of meta-cresols and 8000 ton 2 produced, in the device of 6-d-tert-butyl-p-cresol, tar light oil by product output is 1.0～1.2 tons/meta-cresol, 1.2～1.5 tons/p-cresol, in tar light oil by product, be rich in isopropyl toluene (50～60wt%) and methyl-alpha-methyl styrene (20～30wt%), tar light oil by product carries out cutting and separating, the product that extracts 88～90wt% carries out hydrofining, make methyl-alpha-methyl styrene change into isopropyl toluene, turn back to oxidation unit oxidation, meta-cresol or p-cresol are produced in regeneration, can reduce widely device material consumption, obtain considerable economic benefit.
The alpha-methyl styrene hydrogenation that uses Reney nickel catalyzator in a kind of slurry process was disclosed in the past, but due to the loss of arene compound, a be fixed bed method of this method major part replaces, although slurry process is effective, but it needs two distillation towers and relevant device, and cooling and energy pressure, in addition, Reney nickel catalyst has transition hydrogenation to produce less desirable by product and needs frequent shortcoming of adding live catalyst.
Use noble metal catalyst to select hydrogenation to there is high conversion and highly selective methyl-alpha-methyl styrene as palladium catalyst, but noble metal catalyst is more expensive than nickel catalyst.
The open CN1793089A of Chinese patent discloses a kind of alpha-methyl styrene and has been hydrogenated into the mixed catalyst system of cumene, this system comprises and will contain the incoming flow supply response system of the alpha-methyl styrene that reaches 10%, in the first fixed bed catalyst, use nickel catalyst, make 70～95% of alpha-methyl styrene change into cumene, with in the second fixed bed catalyst, use noble metal catalyst, make alpha-methyl styrene change into cumene, but, this hydrogenation process complexity, and working cost is higher.
Summary of the invention
In order to overcome the above-mentioned problems in the prior art, the invention provides a kind of newly for methyl-alpha-methyl styrene method of hydrotreating, there is catalyzer cost low, hydroconversion condition gentleness, transformation efficiency and selectivity advantages of higher.
The invention provides a kind of methyl-alpha-methyl styrene and select method of hydrotreating, comprise: in fixed-bed reactor, contact with the nickel catalyzator in reactor containing the incoming flow of methyl-alpha-methyl styrene, by a step mild hydrogenation, make the methyl-alpha-methyl styrene in incoming flow transform generation isopropyl toluene, thereby obtain essentially no methyl-alpha-methyl styrene reactor stream fluid.
In aforesaid method, described nickel catalyzator is taking alumina/silica mixture as carrier, taking metallic nickel as active ingredient.Taking nickle atom, the catalyzer based on described is 20～50wt% to the content of activity component metal nickel described in described nickel catalyzator, is preferably 30～45wt%.In catalyzer of the present invention, nickel can exist with the form of nickle atom or sulphided state, also can exist with the form of nickel compound.Nickel compound can be the conventional nickel compound of selective hydrogenation nickel catalyst, as nickel oxide, as NiO.In a preferred embodiment of the invention, using before catalyzer of the present invention selects hydrogenation to alkene, catalyzer of the present invention reduced to processing.
Described catalyzer is loaded catalyst, and carrier is aluminium oxide-silicon oxide mixture.In carrier complexes, aluminum oxide is 1/5～1/2 of silicon oxide weight, and silicon oxide is alumina weight 2～5 times.
In the preferred embodiment of catalyzer of the present invention, catalyzer is porous material, has specific pore structure.The specific surface area of described catalyzer is 150～250m
2/ g, is preferably 180～220m
2/ g; Pore volume is 0.4～1.0ml/g, is preferably 0.5～0.9ml/g; Most probable aperture 40～120 dusts, preferably 60～100 dusts.The present invention is not particularly limited the shape of catalyzer, for example, can be cylindricality, bar shaped, spherical or cloverleaf pattern.
The preparation method of described catalyzer, preferably includes:
(1) count the mixed glue solution of the aluminum compound/silicon compound of 1/5～1/2 (weight ratio) in order to alumina/silica, under 50～70 DEG C of temperature, pH value 6.0～7.0, normal pressure and violent stirring condition, nickel salt solution is joined in described mixed glue solution, precipitate 30～40 minutes, filter, make after filter cake, with the deionized water wash of 10～20 times of filter cake volumes, filter, then wash, refilter, this process repeats four times;
(2) filter cake at the temperature of 100～150 DEG C dry 4～10 hours, in the roasting temperatures of 400～600 DEG C 4～8 hours, makes described catalyzer.
Described aluminum compound can be understood as and can obtain Al
2o
3as all aluminum compounds of support of the catalyst, can include but not limited to: organo-aluminium compound and Tai-Ace S 150, aluminum chloride and the aluminum nitrates etc. such as aluminum dialkyl, dialkylaluminum chloride, alkyl al dichloride and dialkyl group aluminum chloride are without machine aluminium compound etc.
Described silicon compound can be understood as and can obtain SiO
2as all silicon compounds of support of the catalyst, include but not limited to: CH
3siH
3deng inorganic silicon compounds such as organosilicon and Starso, silicon sol, layer silicon and instant powdery flower bulb alkali and sodium-potassium silicates.
Described nickel salt can be understood as the nickel salt that selective hydrogenation nickel catalyst adopts conventionally, can include but not limited to: the vitriol of nickel, nitrate, halogenide.Preferably single nickel salt and nickelous nitrate.The type of described nickel salt solution is not particularly limited, can be the aqueous solution, can be also the organic nickel salts solution that ethanol, benzene etc. form as solvent, but use organic nickel salts solution cost higher, and also have pollution problem, therefore the present invention preferably uses the aqueous solution of inorganic nickel.
In aforesaid method, in described incoming flow, methyl-alpha-methyl styrene content is less than or equal to 21wt%.In a specific embodiment, described incoming flow is the main logistics containing methyl-alpha-methyl styrene and isopropyl toluene in the tar light oil by product from production meta-cresol device.
In aforesaid method, the reaction conditions of preferred mild hydrogenation is: reaction pressure is 0.1～0.8MPa, preferably 0.1～0.5MPa; 20～100 DEG C of temperature of reaction, preferably 40～80 DEG C; The mol ratio of hydrogen/methyl-alpha-methyl styrene is 4～15, is preferably 5～10; Fresh feed air speed is 0.5～3h
-1with recycle ratio be 1: 1～6: 1, preferably fresh feed air speed is 1～2h
-1with recycle ratio be 2: 1～5: 1.
By aforesaid method, methyl-alpha-methyl styrene hydrogenation conversion can reach 99.5%, and hydrogenation selectivity is 99.9%, and in hydrogenation products, does not detect isopropyl methyl hexanaphthene, does not have excessive hydrogenation side reaction to produce.
Methyl provided by the invention-alpha-methyl styrene is selected method of hydrotreating, there is following outstanding advantage and effect: technique is simple, hydrogenation conditions gentleness, catalyzer cost is low and active high, methyl-alpha-methyl styrene hydrogenation selectivity is high, produces without the by product of excessive hydrogenation.
Embodiment
Below by preferred embodiment, the present invention is carried out to further elaboration, should be appreciated that preferred embodiment described herein, only for description and interpretation the present invention, is not intended to limit the present invention.
Embodiment 1
Be respectively 2000 milliliters of the mixed glue solutions of the Tai-Ace S 150 of 20.6 grams and the water glass of 103.0 grams (alumina/silica weight ratio is 1/5) in order to aluminum oxide and silicon oxide meter content, under temperature 50 C, pH value 6.0, normal pressure and violent stirring condition, to join in above-mentioned mixed glue solution taking nickel oxide content as 1000 milliliters of the nickel nitrate aqueous solutions of 76.4 grams, precipitate 30 minutes, filter, with the deionized water wash of 10 times of filter cake volumes 40 minutes, filter, wash, refilter, this process repeats four times.
Filter cake at the temperature of 100 DEG C dry 10 hours, in the roasting temperatures of 450 DEG C 8 hours, is cooled to normal temperature, pulverizes, and breaks into sheet, makes catalyst A-1 of the present invention.Data are in table 1.
Embodiment 2
Be respectively 2000 milliliters of the mixed glue solutions of the Tai-Ace S 150 of 24.55 grams and the water glass of 73.64 grams (alumina/silica weight ratio is 1/3) in order to aluminum oxide and silicon oxide meter content, under temperature 60 C, pH value 7.0, normal pressure and violent stirring condition, to join in above-mentioned mixed glue solution taking nickel oxide content as 1000 milliliters of the nickel nitrate aqueous solutions of 101.81 grams, precipitate 30 minutes, filter, with the deionized water wash of 10 times of filter cake volumes 40 minutes, filter, wash, refilter, this process repeats four times.
Filter cake at the temperature of 100 DEG C dry 10 hours, in the roasting temperatures of 500 DEG C 5 hours, is cooled to normal temperature, pulverizes, and breaks into column, makes catalyst A-2 of the present invention.Data are in table 1.
Embodiment 3
Be 2000 milliliters of the mixed glue solutions of the Tai-Ace S 150 of 28.49 grams and the water glass of 56.98 grams (alumina/silica weight ratio is 1/2) in order to aluminum oxide and silicon oxide meter content, under temperature 70 C, pH value 6.0, normal pressure and violent stirring condition, to join in above-mentioned aluminium oxide-silicon oxide glue taking nickel oxide content as 1000 milliliters of the nickel nitrate aqueous solutions of 114.53 grams, precipitate 40 minutes, filter, with the deionized water wash of 20 times of filter cake volumes 40 minutes, filter, wash, refilter, this process repeats four times.
Filter cake at the temperature of 100 DEG C dry 10 hours, in the roasting temperatures of 500 DEG C 5 hours, is cooled to normal temperature, pulverizes, and breaks into sheet, makes catalyst A-3 of the present invention.Data are in table 1.
Embodiment 4
Repeat the preparation of catalyzer in embodiment 1, different is to use nickel sulfate solution, makes catalyst B-1, and data are in table 1.
Embodiment 5
Repeat the preparation of catalyzer in embodiment 2, different is to use nickel sulfate solution, makes catalyst B-2, and data are in table 1.
Embodiment 6
Repeat the preparation of catalyzer in embodiment 3, different is to use nickel sulfate solution, makes catalyst B-3, and data are in table 1.
Embodiment 7
The catalyzer of the present embodiment explanation embodiment 1-6 gained is selected the effect of hydrogenation to methyl-alpha-methyl styrene.
Getting each 100 milliliters of catalyst A-1, A-2, A-3, B-1, B-2 and B-3 that example 1-6 makes, is 0.2MPa at hydrogen pressure, and temperature is that 420 DEG C and hydrogen flowing quantity are that under the condition of 500 milliliters, reducing catalyst 6 hours, cools to 40 DEG C of temperature of reaction.
Be 0.2MPa at hydrogen pressure, temperature is 40 DEG C, and the mol ratio of hydrogen/methyl-alpha-methyl styrene is 6, and fresh feed air speed is 1.5h
-1under the recycle ratio condition that is 3: 1, passing into methyl-alpha-methyl styrene content in fresh feed is 20.02wt%, and bromine valency is the raw material that 12.35 grams of bromine/100 gram oil and density are 0.872, and hydrogenation the results are shown in Table shown in 2.
Table 1
Table 2
Note: methyl-alpha-methyl styrene content × 100% in hydrogenation selectivity=(in raw material in methyl-alpha-methyl styrene-product methyl-alpha-methyl styrene content)/raw material, as follows.
Embodiment 8
The selection hydrogenation effect of the present embodiment explanation methyl-alpha-methyl styrene at differential responses temperature.
Get A-3 catalyzer 100ml, repeat the catalyst reduction process of embodiment 7.
Be 0.2MPa at hydrogen pressure, hydrogen/methyl-alpha-methyl styrene is 6, and fresh feed air speed is 1.5h
-1with recycle ratio be 3: 1, the reaction times is 300 hours, in the fresh feed passing into, methyl-alpha-methyl styrene content is 20.02wt%, bromine valency is that 22.35 grams of bromine/100 gram oil and density are 0.872, hydrogenation the results are shown in Table shown in 3.
Table 3
Note: hydrogenation conversion=(raw material bromine valency-product bromine valency)/raw material bromine valency × 100%, as follows.
Embodiment 9
The selection hydrogenation effect of the present embodiment explanation methyl-alpha-methyl styrene under different air speeds.
Get A-3 catalyzer 100ml, repeat the catalyst reduction process of embodiment 7.
Hydrogenation conditions and reaction raw materials are as embodiment 8, different, and temperature of reaction is 50 DEG C, fresh feed air speed 1～2h
-1, hydrogenation the results are shown in Table shown in 4.
Table 4
Embodiment 10
The selection hydrogenation effect of different methyl-alpha-methyl styrene content in the present embodiment explanation raw material.
Get A-3 catalyzer 100ml, repeat the catalyst reduction process of embodiment 7 and select hydrogenation process, the air speed of different is fresh feed is increased to 2.0h
-1, in raw material, methyl-alpha-methyl styrene content is respectively 5.06wt%, 9.85wt%, 15.18wt% and 18.27wt%.Hydrogenation the results are shown in Table 5.
Table 5
Embodiment 11
The selection hydrogenation effect of the present embodiment explanation methyl-alpha-methyl styrene under differential responses pressure.
Get A-3 catalyzer 100ml, repeat catalyst reduction process and the hydrogenation process of embodiment 7, different is to change reaction pressure, and hydrogenation the results are shown in Table 6.
Table 6
Embodiment 12
The selection hydrogenation effect of the present embodiment explanation methyl-alpha-methyl styrene under different recycle ratio conditions.
Get A-3 catalyzer 100ml, repeat catalyst reduction process and the hydrogenation process of embodiment 7, different is to change recycle ratio condition, and hydrogenation the results are shown in Table 7.
Embodiment 13
The selection hydrogenation effect of the present embodiment explanation methyl-alpha-methyl styrene under the mol ratio condition of different hydrogen/methyl-alpha-methyl styrenes.
Get A-3 catalyzer 100ml, repeat catalyst reduction process and the hydrogenation process of embodiment 7, different is the mol ratio that changes hydrogen/methyl-alpha-methyl styrene, and hydrogenation the results are shown in Table 8.
Table 7
Table 8
Embodiment 14
This example explanation methyl-alpha-methyl styrene is selected the stability of hydrogenation effect.
Get 100 milliliters of A-3 catalyzer, catalyst pretreatment process and hydrogenation process are as embodiment 7.Different, temperature is 60 DEG C, and passing into methyl-alpha-methyl styrene content in fresh feed is 21.02wt%, and bromine valency is 13.16 grams of bromine/100 gram oil, and hydrogenation the results are shown in Table shown in 9.
Table 9
It should be noted in the discussion above that by with reference to preferred embodiment, present disclosure being described, is descriptive and explanatory vocabulary but should be understood to word wherein used, instead of limited vocabulary.Can in the scope of the claims in the present invention, modify the present invention in accordance with regulations, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present disclosure of wherein describing relates to specific process for selective hydrogenation and embodiment, but and do not mean that present disclosure is limited to wherein disclosed particular case, on the contrary, present disclosure can extend to other all catalyzer, process for selective hydrogenation and application with same composition.
Claims (8)
1. the method for methyl-alpha-methyl styrene selection hydrogenation, comprise: in fixed-bed reactor, contact with the nickel catalyzator in reactor containing the incoming flow of methyl-alpha-methyl styrene, by a step mild hydrogenation, make the methyl-alpha-methyl styrene in incoming flow transform generation isopropyl toluene; Described nickel catalyzator is taking alumina/silica mixture as carrier, taking metallic nickel as active ingredient; Taking nickle atom, the catalyzer based on described is 20～50wt% to the content of activity component metal nickel described in described nickel catalyzator.
2. method according to claim 1, is characterized in that, taking nickle atom, the catalyzer based on described is 30～45wt% to the content of activity component metal nickel described in described nickel catalyzator.
3. method according to claim 1, is characterized in that, in described nickel catalyzator, aluminum oxide is 1/5～1/2 of silicon oxide weight.
4. method according to claim 1, is characterized in that, the specific surface area of described catalyzer is 180～220 meters
2/ gram, 0.5～0.9 ml/g of pore volume, most probable aperture 60～100 dusts.
5. method according to claim 1, is characterized in that, in described incoming flow, methyl-alpha-methyl styrene content is less than or equal to 21wt%.
6. method according to claim 1, is characterized in that, described mild hydrogenation condition is: reaction pressure 0.1～0.8MPa, and 20～100 DEG C of temperature of reaction, the mol ratio of hydrogen/methyl-alpha-methyl styrene is 4～15, fresh feed air speed is 0.5～3h
-1with recycle ratio be 1:1～6:1.
7. method according to claim 6, is characterized in that, described mild hydrogenation condition is: reaction pressure 0.1～0.5MPa, and 40～80 DEG C of temperature of reaction, the mol ratio of hydrogen/methyl-alpha-methyl styrene is 5～10, fresh feed air speed is 1～2h
-1with recycle ratio be 2:1～5:1.
8. method according to claim 1, is characterized in that, there is no isopropyl methyl hexanaphthene in the effluent liquid of described reactor.
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|---|---|---|---|---|
| WO2019118331A1 (en) * | 2017-12-11 | 2019-06-20 | Valvoline Licensing And Intellectual Property Llc | Scalable synthesis of hydrogenated alpha styrene dimer |
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| KR102462295B1 (en) | 2018-03-06 | 2022-11-03 | 발보린 라이센싱 앤드 인텔렉츄얼 프러퍼티 엘엘씨 | Traction fluid composition |
| WO2020186139A1 (en) | 2019-03-13 | 2020-09-17 | Valvoline Licensing And Intellectual Property Llc | Novel traction fluid with improved low temperature properties |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3878259A (en) * | 1973-04-21 | 1975-04-15 | Huels Chemische Werke Ag | Process for manufacturing cumene |
| WO2004060838A1 (en) * | 2003-01-07 | 2004-07-22 | Sumitomo Chemical Company, Limited | Method of hydrogenating aromatic compound |
| CN1732139A (en) * | 2002-12-24 | 2006-02-08 | 住友化学株式会社 | Process for producing cumene |
| CN1793089A (en) * | 2004-12-20 | 2006-06-28 | 凯洛格.布朗及鲁特有限公司 | Selective hydrogenation of alpha-methyl-styrene to cumene |
-
2011
- 2011-09-01 CN CN201110256343.0A patent/CN102964199B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3878259A (en) * | 1973-04-21 | 1975-04-15 | Huels Chemische Werke Ag | Process for manufacturing cumene |
| CN1732139A (en) * | 2002-12-24 | 2006-02-08 | 住友化学株式会社 | Process for producing cumene |
| WO2004060838A1 (en) * | 2003-01-07 | 2004-07-22 | Sumitomo Chemical Company, Limited | Method of hydrogenating aromatic compound |
| CN1793089A (en) * | 2004-12-20 | 2006-06-28 | 凯洛格.布朗及鲁特有限公司 | Selective hydrogenation of alpha-methyl-styrene to cumene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019118331A1 (en) * | 2017-12-11 | 2019-06-20 | Valvoline Licensing And Intellectual Property Llc | Scalable synthesis of hydrogenated alpha styrene dimer |
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