CN102964199A - 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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- CN102964199A CN102964199A CN2011102563430A CN201110256343A CN102964199A CN 102964199 A CN102964199 A CN 102964199A CN 2011102563430 A CN2011102563430 A CN 2011102563430A CN 201110256343 A CN201110256343 A CN 201110256343A CN 102964199 A CN102964199 A CN 102964199A
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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, in the combination that reaches high conversion and highly selective than the 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, be rich in isopropyl toluene (50～60wt%) and methyl-alpha-methyl styrene (20～30wt%) in the tar light oil by product, the 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 the oxidation unit oxidation, meta-cresol or p-cresol are produced in regeneration, can reduce widely the device material consumption, obtain considerable economic benefit.
The alpha-methyl styrene hydrogenation that uses the Reney nickel catalyzator in a kind of slurry process was disclosed in the past, but because 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 the energy of cooling and pressure, in addition, the Reney nickel catalyst has the generation of transition the hydrogenation by product of not expecting and the shortcoming that needs frequent interpolation live catalyst.
Use noble metal catalyst such as palladium catalyst to select hydrogenation to have high conversion and highly selective methyl-alpha-methyl styrene, yet noble metal catalyst is more expensive than nickel catalyst.
The open CN1793089A of Chinese patent discloses the mixed catalyst system that a kind of alpha-methyl styrene is hydrogenated into cumene, this system comprises and will contain nearly the incoming flow supply response system of 10% alpha-methyl styrene, 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 is complicated, 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 new methyl-alpha-methyl styrene method of hydrotreating that is used for, it is low to have a catalyzer cost, and hydroconversion condition is gentle, 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, to contain methyl-alpha-methyl styrene incoming flow contacts with nickel catalyzator in the reactor, by a step mild hydrogenation, methyl in the incoming flow-alpha-methyl styrene is transformed generate isopropyl toluene, thereby obtain essentially no methyl-alpha-methyl styrene reactor stream fluid.
In the aforesaid method, described nickel catalyzator is take the alumina/silica mixture as carrier, take metallic nickel as active ingredient.The content of activity component metal nickel described in the described nickel catalyzator take nickle atom based on described catalyzer as 20～50wt%, be 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 nickel compound that selective hydrogenation is commonly used with nickel catalyst, such as nickel oxide, such 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 processing.
Described catalyzer is loaded catalyst, and carrier is the aluminium oxide-silicon oxide mixture.Aluminum oxide is 1/5～1/2 of silicon oxide weight in the carrier complexes, and namely silicon oxide is 2～5 times of alumina weight.
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, preferred 60～100 dusts.The present invention does not have particular restriction to the shape of catalyzer, for example can be cylindricality, bar shaped, sphere or cloverleaf pattern.
The preparation method of described catalyzer preferably includes:
(1) counts 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 ℃ of temperature, pH value 6.0～7.0, normal pressure and violent stirring condition, nickel salt solution is joined in the described mixed glue solution, precipitate 30～40 minutes, filter, make filter cake after, deionized water wash with 10～20 times of filter cake volumes, filter, wash, refilter, this process repeats four times;
(2) filter cake is under 100～150 ℃ temperature dry 4～10 hours, in 400～600 ℃ roasting temperatures 4～8 hours, makes described catalyzer.
Described aluminum compound can be understood as and can obtain Al
2O
3All aluminum compounds as support of the catalyst can include but not limited to: the organo-aluminium compound such as aluminum dialkyl, dialkylaluminum chloride, alkyl al dichloride and dialkyl group aluminum chloride and Tai-Ace S 150, aluminum chloride and aluminum nitrate etc. are without machine aluminium compound etc.
Described silicon compound can be understood as and can obtain SiO
2All silicon compounds as support of the catalyst include but not limited to: CH
3SiH
3Deng organosilicon and Starso, silicon sol, layer silicon and the inorganic silicon compounds such as instant powdery flower bulb alkali and sodium-potassium silicate.
Described nickel salt can be understood as selective hydrogenation with the nickel salt that nickel catalyst adopts usually, 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, also can be 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, so the present invention preferably uses the aqueous solution of inorganic nickel.
In the aforesaid method, in the described incoming flow, methyl-alpha-methyl styrene content is less than or equal to 21wt%.In a specific embodiment, described incoming flow is for mainly containing the logistics of methyl-alpha-methyl styrene and isopropyl toluene in the tar light oil by product from production meta-cresol device.
In the aforesaid method, the reaction conditions of preferred mild hydrogenation is: reaction pressure is 0.1～0.8MPa, preferred 0.1～0.5MPa; 20～100 ℃ of temperature of reaction, preferred 40～80 ℃; The mol ratio of hydrogen/methyl-alpha-methyl styrene is 4～15, is preferably 5～10; The fresh feed air speed is 0.5～3h
-1With recycle ratio be 1: 1～6: 1, preferred 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 does not detect the isopropyl methyl hexanaphthene in the hydrogenation products, does not namely have the excessive hydrogenation side reaction to produce.
Methyl provided by the invention-alpha-methyl styrene is selected method of hydrotreating, have following outstanding advantage and effect: technique is simple, and hydrogenation conditions is gentle, and the catalyzer cost is low and active high, methyl-alpha-methyl styrene hydrogenation selectivity is high, without the by product generation of excessive hydrogenation.
Embodiment
Below by preferred embodiment the present invention has been carried out further elaboration, should be appreciated that preferred embodiment described herein only is used 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 water glass (the alumina/silica weight ratio is 1/5) of the Tai-Ace S 150 of 20.6 grams and 103.0 grams in order to aluminum oxide and silicon oxide meter content, under temperature 50 C, pH value 6.0, normal pressure and violent stirring condition, 1000 milliliters of nickel nitrate aqueous solutions take nickel oxide content as 76.4 grams are joined in the above-mentioned mixed glue solution, 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 under 100 ℃ temperature dry 10 hours in 450 ℃ roasting temperatures 8 hours, is cooled to normal temperature, pulverizes, and breaks into sheet, makes catalyst A of the present invention-1.Data see Table 1.
Embodiment 2
Be respectively 2000 milliliters of the mixed glue solutions of the water glass (the alumina/silica weight ratio is 1/3) of the Tai-Ace S 150 of 24.55 grams and 73.64 grams in order to aluminum oxide and silicon oxide meter content, under temperature 60 C, pH value 7.0, normal pressure and violent stirring condition, 1000 milliliters of nickel nitrate aqueous solutions take nickel oxide content as 101.81 grams are joined in the above-mentioned mixed glue solution, 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 under 100 ℃ temperature dry 10 hours in 500 ℃ roasting temperatures 5 hours, is cooled to normal temperature, pulverizes, and breaks into column, makes catalyst A of the present invention-2.Data see Table 1.
Embodiment 3
Be 2000 milliliters of the mixed glue solutions of the water glass (the alumina/silica weight ratio is 1/2) of the Tai-Ace S 150 of 28.49 grams and 56.98 grams in order to aluminum oxide and silicon oxide meter content, under temperature 70 C, pH value 6.0, normal pressure and violent stirring condition, 1000 milliliters of nickel nitrate aqueous solutions take nickel oxide content as 114.53 grams are joined in the above-mentioned aluminium oxide-silicon oxide glue, 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 under 100 ℃ temperature dry 10 hours in 500 ℃ roasting temperatures 5 hours, is cooled to normal temperature, pulverizes, and breaks into sheet, makes catalyst A of the present invention-3.Data see Table 1.
Embodiment 4
Repeat the preparation of catalyzer among the embodiment 1, different is to use nickel sulfate solution, makes catalyst B-1, and data see Table 1.
Embodiment 5
Repeat the preparation of catalyzer among the embodiment 2, different is to use nickel sulfate solution, makes catalyst B-2, and data see Table 1.
Embodiment 6
Repeat the preparation of catalyzer among the embodiment 3, different is to use nickel sulfate solution, makes catalyst B-3, and data see Table 1.
Embodiment 7
The catalyzer of 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 ℃ and hydrogen flowing quantity are that reducing catalyst 6 hours cools to 40 ℃ of temperature of reaction under 500 milliliters the condition.
Be 0.2MPa at hydrogen pressure, temperature is 40 ℃, and the mol ratio of hydrogen/methyl-alpha-methyl styrene is 6, and the fresh feed air speed is 1.5h
-1With recycle ratio be that passing into methyl in the fresh feed-alpha-methyl styrene content is 20.02wt% under 3: 1 the condition, the bromine valency is that 12.35 gram bromines/100 gram oil and density are 0.872 raw material, hydrogenation the results are shown in Table shown in 2.
Table 1
Table 2
Annotate: methyl-alpha-methyl styrene content * 100% in hydrogenation selectivity=(methyl in methyl-alpha-methyl styrene in the raw material-product-alpha-methyl styrene content)/raw material, as follows.
Embodiment 8
The selection hydrogenation effect of present embodiment explanation methyl-alpha-methyl styrene under the 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 the fresh feed air speed is 1.5h
-1With recycle ratio be 3: 1, the reaction times is 300 hours, methyl in the fresh feed that passes into-alpha-methyl styrene content is 20.02wt%, the bromine valency is that 22.35 gram bromines/100 gram oil and density are 0.872, hydrogenation the results are shown in Table shown in 3.
Table 3
Annotate: hydrogenation conversion=(raw material bromine valency-product bromine valency)/raw material bromine valency * 100%, as follows.
Embodiment 9
The selection hydrogenation effect of 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 such as embodiment 8, different is that temperature of reaction is 50 ℃, 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, methyl in the raw material-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 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 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 the recycle ratio condition, and hydrogenation the results are shown in Table 7.
Embodiment 13
The selection hydrogenation effect of present embodiment explanation methyl-alpha-methyl styrene under the mol ratio condition of different hydrogen/methyl-alpha-methyl styrene.
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 such as embodiment 7.Different is, temperature is 60 ℃, and passing into methyl in the fresh feed-alpha-methyl styrene content is 21.02wt%, and the bromine valency is 13.16 gram bromines/100 gram oil, and hydrogenation the results are shown in Table shown in 9.
Table 9
Should be noted in the discussion above that by the reference preferred embodiment present disclosure is described, is descriptive and explanatory vocabulary but should be understood to wherein used word, rather than limited vocabulary.Can in the scope of claim of the present invention, modify the present invention in accordance with regulations, and within not deviating from scope and spirit of the present invention, the present invention be revised.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 have catalyzer, process for selective hydrogenation and the application of same composition.
Claims (10)
1. a methyl-alpha-methyl styrene is selected the method for hydrogenation, comprise: in fixed-bed reactor, to contain methyl-alpha-methyl styrene incoming flow contacts with nickel catalyzator in the reactor, by a step mild hydrogenation, methyl in the incoming flow-alpha-methyl styrene is transformed generate isopropyl toluene.
2. method according to claim 1 is characterized in that, described nickel catalyzator is take the alumina/silica mixture as carrier, take metallic nickel as active ingredient.
3. method according to claim 1 and 2 is characterized in that, the content of activity component metal nickel described in the described nickel catalyzator take nickle atom based on described catalyzer as 20～50wt%.
4. the described method of any one according to claim 1～3 is characterized in that, the content of activity component metal nickel described in the described nickel catalyzator take nickle atom based on described catalyzer as 30～45wt%.
5. the described method of any one according to claim 1～4 is characterized in that, aluminum oxide is 1/5～1/2 of silicon oxide weight in the described nickel catalyzator.
6. the described method of any one according to claim 1～5 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.
7. the described method of any one according to claim 1～6 is characterized in that, methyl in the described incoming flow-alpha-methyl styrene content is less than or equal to 21wt%.
8. the described method of any one according to claim 1～7, it is characterized in that described mild hydrogenation condition is: reaction pressure 0.1～0.8MPa, 20～100 ℃ of temperature of reaction, the mol ratio of hydrogen/methyl-alpha-methyl styrene is 4～15, and the fresh feed air speed is 0.5～3h
-1With recycle ratio be 1: 1～6: 1.
9. the described method of any one according to claim 1～8, it is characterized in that described mild hydrogenation condition is: reaction pressure 0.1～0.5MPa, 40～80 ℃ of temperature of reaction, the mol ratio of hydrogen/methyl-alpha-methyl styrene is 5～10, and the fresh feed air speed is 1～2h
-1With recycle ratio be 2: 1～5: 1.
10. the described method of any one in the claim 1～9 is characterized in that, there is no the isopropyl methyl hexanaphthene in the effluent liquid of described reactor.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10696610B2 (en) | 2017-12-11 | 2020-06-30 | Valvoline Licensing And Intellectual Property Llc | Scalable synthesis of hydrogenated alpha styrene dimer |
| US10774287B2 (en) | 2018-03-06 | 2020-09-15 | Valvoline Licensing And Intellectual Property Llc | Traction fluid composition |
| US10927321B2 (en) | 2019-03-13 | 2021-02-23 | Valvoline Licensing And Intellectual Property Llc | Traction fluid with improved low temperature properties |
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|---|---|---|---|---|
| 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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10696610B2 (en) | 2017-12-11 | 2020-06-30 | Valvoline Licensing And Intellectual Property Llc | Scalable synthesis of hydrogenated alpha styrene dimer |
| CN111601857A (en) * | 2017-12-11 | 2020-08-28 | 胜牌许可和知识产权有限公司 | Scalable synthesis of hydrogenated alpha-styrene dimers |
| CN111601857B (en) * | 2017-12-11 | 2022-03-04 | 胜牌许可和知识产权有限公司 | Scalable synthesis of hydrogenated alpha-styrene dimers |
| US10774287B2 (en) | 2018-03-06 | 2020-09-15 | Valvoline Licensing And Intellectual Property Llc | Traction fluid composition |
| US10927321B2 (en) | 2019-03-13 | 2021-02-23 | Valvoline Licensing And Intellectual Property Llc | Traction fluid with improved low temperature properties |
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