CN104151129B - The method of selective hydrogenation of alpha-methyl-styrene - Google Patents
The method of selective hydrogenation of alpha-methyl-styrene Download PDFInfo
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Abstract
The present invention relates to a kind of method of AMS selective hydrogenations, mainly solve the problems, such as in prior art, to there is poor catalyst low-temperature activity, selectivity and stability not good.Used catalyst of the present invention is in terms of parts by weight including following components：（a）0.01 ~ 1.0 part of Metal Palladium or its oxide；（b）0.01 ~ 2.0 part of at least one element or its oxide in I A or II A in the periodic table of elements；（c）0.01 ~ 20.0 part of at least one element or its oxide in IV A or V A in the periodic table of elements；（d）The technical scheme of 77～100 parts of alumina supports preferably solves the problem, can be used in the industrial production of AMS selective hydrogenations.
Description
Technical field
The present invention relates to a kind of method of selective hydrogenation of alpha-methyl-styrene, is used for isopropylbenzene especially with regard to a kind of
Accessory substance AMS during industrial manufacturing phynol/acetone is by being hydrogenated with the method for being changed into raw material isopropylbenzene.
Background technology
At present, nearly ten million ton of the yield of global isopropylbenzene, has the isopropylbenzene of 90 more than % for producing phenol and acetone.
AMS（Referred to as AMS）Hydrogenation preparing isopropylbenzene project is the supporting technology of isopropylbenzene industry manufacturing phynol/acetone, main
Accessory substance AMS during isopropylbenzene coproduction manufacturing phynol/acetone is changed into raw material isopropylbenzene by hydrogenation and returns oxidation work
Sequence is used, and so as to reduce the unit consumption of isopropylbenzene, is improved the yield of phenol, the expense that economizes in raw materials etc., can not only so be reduced raw material
Propylene and the consumption of benzene, and the technical-economic index of device can be improved.
The phynol/acetone process units for producing 10000 tons per year can 500 tons of AMS of by-product.Abroad in phynol/acetone process units
There is hydrogenation of AMS reactor.Due to the activity and selectivity of non-palladium series catalyst not high, in recent years with palladium as main or unique into
The catalyst for dividing is interesting.AMS properties are active, and stability is poor, therefore, it is intended that hydrogenation catalyst has higher low temperature active
And selectivity, appropriate appearance glue ability, to increase catalyst regeneration cycle, so as to extend catalyst service life.
Nickel, platinum, palladium, cobalt, chromated oxide and mixed metal catalyst is disclosed in United States Patent (USP) US3646235 for AMS
The purposes of hydrogenation, under conditions of 24 ~ 50 DEG C and 0.17 ~ 0.45MPa, tenor is 1 ~ 5%（Weight）Pd catalyst compared with
Good.
Chinese patent CN1793089A discloses the combination catalyst of a kind of utilization nickel catalyst and noble metal catalyst
System makes the method that AMS is selectively hydrogenated into cumene.Using commercial catalyst combination loading, in the first reaction zone, 70 ~ 95% are realized
AMS conversion, second reaction zone realize at least 95% AMS conversion.
Although combination catalyst of the prior art can reduce catalyst amount, reduces cost, its low temperature active and
Conversion ratio still needs further to be improved.
Content of the invention
The technical problem to be solved is to carry out selective adding present in prior art to AMS
A kind of problem that catalyst low-temperature activity is poor during hydrogen, selectivity and stability is not good, there is provided new AMS selectivity
The method of hydrogenation, the accessory substance AMS hydrogenation transformation being particularly used for during isopropylbenzene industry manufacturing phynol/acetone
For the method for raw material isopropylbenzene, the method has the advantages that high low temperature active, selectivity and good stability.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows：With the hydrocarbon containing AMS
Material and hydrogen be raw material, reaction temperature be 40 ~ 100 DEG C, reaction pressure be 0.3 ~ 1.0MPa, hydrocarbon material air speed be 0.5 ~
3.0 hour-1, the volume ratio of hydrogen/hydrocarbon material is 150 ~ 300：Under conditions of 1, raw material is contacted with catalyst, is reacted,
Make the AMS in raw material change into isopropylbenzene, wherein used catalyst in terms of parts by weight including following components：
（a）0.01 ~ 1.0 part of Metal Palladium or its oxide；（b）0.01 ~ 2.0 part of at least be selected from the periodic table of elements in I A or II A
Plant element or its oxide；（c）0.01 ~ 20.0 part of at least one element or its oxygen in IV A or V A in the periodic table of elements
Compound；（d）77～100 parts of alumina supports；Wherein alumina support specific surface area is 60 ~ 180 meters2/ gram, total pore volume is 0.3
~ 1.2 mls/g.
In above-mentioned technical proposal, reaction temperature is preferably 40 ~ 80 DEG C, and reaction pressure is preferably 0.5 ~ 1.0MPa, hydrocarbon
Material air speed is preferably 0.5 ~ 1.5 hour-1, the volume ratio preferably 150 ~ 250 of hydrogen/hydrocarbon material：1；Contain AMS
Hydrocarbon material in AMS by weight percentage containing 2～15 %, the isopropylbenzene of 85～98 %.
In above-mentioned technical proposal, catalyst in terms of parts by weight, the consumption of Metal Palladium or its oxide is preferably 0.1～
0.5 part；The consumption of at least one element or its oxide in I A or II A in the periodic table of elements is preferably 0.2 ~ 0.8 part；
The consumption of at least one element or its oxide in IV A or V A in the periodic table of elements is preferably 0.2 ~ 10.0 part；Catalysis
Element in agent selected from I A in the periodic table of elements is preferably potassium；Element selected from II A in the periodic table of elements is preferably calcium, magnesium or barium
At least one of；Element selected from IV A in the periodic table of elements is preferably silicon；Element selected from V A in the periodic table of elements is preferably
Phosphorus.
In above-mentioned technical proposal, alumina support specific surface area is preferably 60 ~ 150 meters2/ gram, total pore volume be preferably 0.4 ~
1.0 ml/g.Catalyst also contains 0.01 ~ 1.0 part of argent or its oxide in terms of parts by weight, preferably.In catalyst
Palladium size of microcrystal be preferably 2～5 nanometers, more preferably 2～3 nanometers.
The preparation method of carrier of the present invention includes mixing aluminum oxide, peptizing agent, water in the desired amount, after extruded moulding, first
Dry 1 ~ 24 hour at 50 ~ 120 DEG C, then roasting 1 ~ 10 hour at 800 ~ 1150 DEG C, obtains alumina support.
The preparation method of catalyst of the present invention is：First carrier presoaked with a kind of liquid that can be dissolved each other with maceration extract, then with containing
Have the salt solution impregnation of palladium, the carrier after dipping is scrubbed, dry, in atmosphere 300 ~ 600 DEG C of roastings obtain final product oxidizing catalytic
Agent finished product.Finished catalyst only need to lead to hydrogen reducing in the reactor and can use.
The metallic atom of load type metal catalyst is, metal point scattered with little particle or cluster form on carrier
Divergence has direct relation with crystallite size, and the Pd decentralization on catalyst has a kind of inverse relation with Pd particle sizes,
Catalyst hydrogenation performance is affected by Pd decentralization or Pd particles, and the life-span of catalyst or stability also can be by the shadows of Pd particles
Ring, on larger Pd particles, easily polymerization forms polycyclic aromatic hydrocarbon or polymer to alkene, and is easily covered in Pd active sites
On, the hydrogenation reaction activity of catalyst reduces；When in eggshell type distribution, Pd particles are larger, diolefin is easily in alumina surface
Coking poisoning on Pd particles；Hydrogen is in Pd/A12O3There are adsorption hydrogen and body phase absorption two kinds of absorption shapes of hydrogen on catalyst, with
The selectivity of body phase absorption hydrogen hydrogenation reaction is poor, when Pd decentralization is less, easily generates body phase absorption hydrogen.Therefore, Pd
Decentralization can not too greatly can not be too little, and moderate.Inventor is had found in research process, when Pd particles are more than 2.8nm,
The property of body phase Pd is shown, and when Pd particles are less than 1.4nm, catalyst is then quickly because the strong complexing effect with unsaturated bond
Answer and inactivate.Binding tests result, best results when inventor has found that particles of the Pd on carrier is 2-3nm.
During selective hydrogenation, diene (alkynes) hydrocarbon can occur polymerisation and generate colloid, usually cause catalysis
The blocking in agent duct, the decline of specific surface area cause catalyst activity to reduce, and this polymerisation is by the acid function of carrier
Caused, the carrier that selective hydrocatalyst should adopt surface acidity relatively low.The catalyst of the present invention is adopted to be tied with composite holes
The alumina support of structure, with relatively low acid amount, larger can several apertures, and rich abundant mesoporous.Additionally, inventor exists
Also find in research process, add some metallic elements（Such as Ag）Catalyst can be improved with modulation Pd electronic properties and structure
Active and selective.
The catalyst of the present invention has good low temperature active, selectivity and stability when for AMS selective hydrogenations,
And with good interference free performance.Using technical scheme, 60 DEG C of inlet temperature, reaction pressure 0.6Mpa,
Hydrogen/hydrocarbon material volume ratio 250, hydrocarbon material air speed 0.6 hour-1Under the conditions of, isopropylbenzene to 4% AMS
Selective hydrogenation reaction is carried out, operate nearly 400h, AMS conversion ratio is always held at 100%, and isopropylbenzene yield is more than
99%, isopropyl cyclohexane is not detected in product, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.But these embodiments are not anyway to the present invention
Scope be construed as limiting.
Specific embodiment
【Embodiment 1】
300 grams, 9 grams sesbania powders of boehmite are weighed, is mixed, added afterwards and contain poly-vinyl alcohol solution（Mass concentration is
5%）12 grams, 4.0 grams of nitric acid, concentration is 85% 2.2 grams of phosphoric acid, 2.3 grams of potassium nitrate, 270 milliliters of the aqueous solution that 12 grams of magnesium nitrate,
It is extruded into the clover of 2.5 millimeters of φ, wet bar obtains carrier Z1 through 50 DEG C of dryings 24 hours after 1000 DEG C of roastings 4 hours.Take
100 grams of carriers presoak carrier with deionized water, then drain away the water, by carrier in 0.3L PdCl2Maceration extract（The wherein matter of Pd
Amount concentration is 1g Pd/L）In impregnated, to maceration extract in colourless, drain, 120 DEG C of dryings 4 hours, 450 DEG C of roastings 4 hours,
Prepared Pd bases catalyst C1.Catalyst composition and specific surface, pore volume are shown in Table 1.
Take 100 milliliters of C1 catalyst, be 2.7 MPa in Hydrogen Vapor Pressure, temperature be 110 DEG C and hydrogen flowing quantity be 4 milliliters/
（Decigram catalyst）Under conditions of reduce 8 hours.The isopropylbenzene material containing 4% AMS is passed through, in Hydrogen Vapor Pressure
0.8MPa, 60 DEG C of inlet temperature, isopropylbenzene material air speed 0.6 hour-1, hydrogen/isopropylbenzene volume of material than 250 under conditions of enter
Row test.Hydrogenation the results are shown in Table 2.
【Embodiment 2】
300 grams of boehmite is weighed, 9 grams of sesbania powders, mixing are added afterwards and contain poly-vinyl alcohol solution（Mass concentration is
5%）12 grams, 4.0 grams of nitric acid, 1.2 grams of barium nitrate, 0.1 gram of silver nitrate, 270 milliliters of the aqueous solution of 25% 120 grams of Ludox are squeezed
Into 2.5 millimeters of clover of φ, wet bar obtains alumina support Z2 through 90 DEG C of dryings 8 hours after 900 DEG C of roastings 4 hours.Take
100 grams of carriers presoak carrier with deionized water, then drain away the water, by carrier in 0.5 L PdCl2Maceration extract（The wherein matter of Pd
Amount concentration is 1g Pd/L）In impregnated, to maceration extract in colourless, drain, 120 DEG C of dryings 4 hours, 450 DEG C of roastings 4 hours,
Prepared Pd bases catalyst C2.Catalyst composition and specific surface, pore volume are shown in Table 1.
Take 100 milliliters of C2 catalyst, be 2.7 MPa in Hydrogen Vapor Pressure, temperature be 110 DEG C and hydrogen flowing quantity be 4 milliliters/
（Decigram catalyst）Under conditions of reduce 8 hours.The isopropylbenzene material containing 4% AMS is passed through, in Hydrogen Vapor Pressure
0.8MPa, 60 DEG C of inlet temperature, isopropylbenzene material air speed 0.6 hour-1, hydrogen/isopropylbenzene volume of material than 250 under conditions of enter
Row test.Hydrogenation the results are shown in Table 2.
【Embodiment 3】
300 grams of boehmite is weighed, 9 grams of sesbania powders, mixing are added afterwards and contain poly-vinyl alcohol solution（Mass concentration is
5%）12 grams, 4.0 grams of nitric acid, 9.0 grams of calcium nitrate, concentration are 270 milliliters of the aqueous solution of 85% 5.6 grams of phosphoric acid, are extruded into 2.5 millis of φ
The clover of rice, wet bar obtain alumina support Z3 through 90 DEG C of dryings 8 hours after 1050 DEG C of roastings 4 hours.Take 100 grams of loads
Body presoaks carrier with deionized water, then drains away the water, by carrier in 0.3 L PdCl2Maceration extract（The wherein mass concentration of Pd
For 0.5 g Pd/L）In impregnated, to maceration extract in colourless, drain, 120 DEG C of dryings 4 hours, 450 DEG C of roastings 4 hours, system
Obtain Pd base catalyst C3.Catalyst composition and specific surface, pore volume are shown in Table 1.
Take 100 milliliters of C3 catalyst, be 2.7 MPa in Hydrogen Vapor Pressure, temperature be 110 DEG C and hydrogen flowing quantity be 4 milliliters/
（Decigram catalyst）Under conditions of reduce 8 hours.The isopropylbenzene material containing 4% AMS is passed through, in Hydrogen Vapor Pressure
0.8MPa, 60 DEG C of inlet temperature, isopropylbenzene material air speed 0.6 hour-1, hydrogen/isopropylbenzene volume of material than 250 under conditions of enter
Row test.Hydrogenation the results are shown in Table 2.
【Embodiment 4】
300 grams of boehmite is weighed, 9 grams of sesbania powders, mixing are added afterwards and contain poly-vinyl alcohol solution（Mass concentration is
5%）12 grams, 360 milliliters of the aqueous solution that 4.0 grams of nitric acid is extruded into the clover of 2.5 millimeters of φ, after wet bar was through 60 DEG C of dryings 8 hours
In 950 DEG C of roastings 4 hours, alumina support Z4 is obtained.Take 100 grams of carriers and carrier presoaked with deionized water, then drain away the water,
By carrier in 0.3L PdCl2Maceration extract（Wherein the mass concentration of Pd is 0.2 g Pd/L）In impregnated, to maceration extract be in nothing
Color, drains, 120 DEG C of dryings 4 hours, 450 DEG C of roastings 4 hours, and Pd base catalyst C4 are obtained.Catalyst composition and specific surface, hole
Hold and be shown in Table 1.
Take 100 milliliters of C4 catalyst, be 2.7 MPa in Hydrogen Vapor Pressure, temperature be 110 DEG C and hydrogen flowing quantity be 4 milliliters/
（Decigram catalyst）Under conditions of reduce 8 hours.The isopropylbenzene material containing 4% AMS is passed through, in Hydrogen Vapor Pressure
0.8MPa, 60 DEG C of inlet temperature, isopropylbenzene material air speed 0.6 hour-1, hydrogen/isopropylbenzene volume of material than 250 under conditions of enter
Row test.Hydrogenation the results are shown in Table 2.
【Embodiment 5】
300 grams of boehmite is weighed, 9 grams of sesbania powders, mixing are added afterwards and contain poly-vinyl alcohol solution（Mass concentration is
5%）12 grams, 4.0 grams of nitric acid, concentration is 85% 2.2 grams of phosphoric acid, 3.9 grams of potassium nitrate, 9.0 grams of calcium nitrate, 0.69 gram of silver nitrate,
270 milliliters of the aqueous solution of 25% Ludox 60, is extruded into the clover of 2.5 millimeters of φ, wet bar through 50 DEG C of dryings 24 hours after
1000 DEG C of roastings 4 hours, obtain carrier Z5.Take 100 grams of carriers and carrier is presoaked with deionized water, then drain away the water, by carrier
In 0.3L PdCl2Maceration extract（Wherein the mass concentration of Pd is 3.37 g Pd/L）In impregnated, to maceration extract in colourless, drip
Dry, 120 DEG C of dryings 4 hours, 450 DEG C of roastings 4 hours are obtained Pd base catalyst C5.Catalyst composition and specific surface, pore volume are shown in Table
1.
Take 100 milliliters of C5 catalyst, be 2.7 MPa in Hydrogen Vapor Pressure, temperature be 110 DEG C and hydrogen flowing quantity be 4 milliliters/
（Decigram catalyst）Under conditions of reduce 8 hours.The isopropylbenzene material containing 4% AMS is passed through, in Hydrogen Vapor Pressure
0.8MPa, 60 DEG C of inlet temperature, isopropylbenzene material air speed 0.6 hour-1, hydrogen/isopropylbenzene volume of material than 250 under conditions of enter
Row test.Hydrogenation the results are shown in Table 2.
【Comparative example 1】
300 grams of boehmite is weighed, 9 grams of sesbania powders, 45 grams of graphite, mixing are extruded into the clover of 2.5 millimeters of φ, wet
Bar obtains carrier D1 through 120 DEG C of dryings 4 hours after 1050 DEG C of roastings 4 hours.
Take 100 grams of carriers and carrier is presoaked with deionized water, then drain away the water, by carrier in 0.3L PdCl2Maceration extract
（Wherein the mass concentration of Pd is 1g Pd/L）In impregnated, to maceration extract in colourless, drain, 120 DEG C of dryings 4 hours, 450
DEG C roasting 4 hours, is obtained Pd base catalyst CD1.Catalyst composition and specific surface, pore volume are shown in Table 1.
Take 100 milliliters of CD1 catalyst, be 2.7 MPa in Hydrogen Vapor Pressure, temperature be 110 DEG C and hydrogen flowing quantity be 4 milliliters/
（Decigram catalyst）Under conditions of reduce 8 hours.The isopropylbenzene material containing 4% AMS is passed through, in Hydrogen Vapor Pressure
0.8MPa, 60 DEG C of inlet temperature, isopropylbenzene material air speed 0.6 hour-1, hydrogen/isopropylbenzene volume of material than 250 under conditions of enter
Row test.Hydrogenation the results are shown in Table 2.
Table 1
| Embodiment is numbered | 1 | 2 | 3 | 4 | 5 | Comparative example |
| Catalyst is numbered | C1 | C2 | C3 | C4 | C5 | CD1 |
| Bearer number | Z1 | Z2 | Z3 | Z4 | Z5 | D1 |
| Pd contents, part | 0.3 | 0.5 | 0.15 | 0.06 | 1.0 | 0.3 |
| I element A content, part | K-0.3 | 0 | 0 | 0 | K-0.5 | 0 |
| II element A content, part | Mg-0.5 | Ba-0.2 | Ca-0.5 | Mg-0.1 | Ca-0.5 | 0 |
| IV element A content, part | 0 | Si-10 | 0 | Si-3 | Si-5 | 0 |
| V element A content, part | P-0.2 | 0 | P-0.5 | 0 | P-0.2 | 0 |
| Alumina content, part | 98.7 | 89.28 | 98.85 | 99.94 | 92.7 | 99.7 |
| Silver content, part | 0 | 0.02 | 0 | 0 | 0.1 | 0 |
| Palladium size of microcrystal, nanometer | 3.9 | 2.5 | 2.9 | 3.4 | 2.1 | 6.3 |
| Specific surface, rice2/ gram | 89.4 | 134.1 | 65.0 | 100.66 | 128.96 | 102.3 |
| Pore volume, ml/g | 0.79 | 0.53 | 0.91 | 0.72 | 0.65 | 0.56 |
Table 2
【Embodiment 6】
This example demonstrates that 2 catalyst C2 of the embodiment of the present invention changes the result of the test of appreciation condition in hydrogenation of AMS.
100 milliliters of 2 catalyst C2 of Example, is 2.7 MPa in Hydrogen Vapor Pressure, and temperature is that 110 DEG C and hydrogen flowing quantity are
4 milliliters/（Decigram catalyst）Under conditions of reduce 8 hours.It is passed through the isopropylbenzene material containing 4% AMS to change
Process conditions are tested.Hydrogenation the results are shown in Table 3.
Table 3
【Embodiment 7】
This example demonstrates that 2 catalyst C2 of the embodiment of the present invention selects the result of the test of 400 hours in hydrogenation in AMS.
100 milliliters of 2 catalyst C2 of Example, is 2.7 MPa in Hydrogen Vapor Pressure, and temperature is that 110 DEG C and hydrogen flowing quantity are
4 milliliters/（Decigram catalyst）Under conditions of reduce 8 hours.The isopropylbenzene material containing 4% AMS is passed through, in hydrogen
Atmospheric pressure 0.8MPa, 60 DEG C of inlet temperature, isopropylbenzene material air speed 0.6 hour-1, hydrogen/bar of the isopropylbenzene volume of material than 250
Tested under part.Hydrogenation the results are shown in Table 4.
【Comparative example 2】
100 milliliters of 1 catalyst CD1 of comparative example is taken, is 2.7 MPa in Hydrogen Vapor Pressure, temperature is 110 DEG C and hydrogen flowing quantity
For 4 milliliters/（Decigram catalyst）Under conditions of reduce 8 hours.Carried out using raw material same as Example 7 and reaction condition
Test.Hydrogenation the results are shown in Table 4.
Table 4
Claims (7)
1. a kind of method of selective hydrogenation of alpha-methyl-styrene, with the hydrocarbon material and hydrogen containing AMS as original
Material, is 40～100 DEG C in reaction temperature, and reaction pressure is 0.3～1.0MPa, and hydrocarbon material air speed is 0.5～3.0 hour-1, hydrogen
The volume ratio of gas/hydrocarbon material is 150～300：Under conditions of 1, raw material is contacted with catalyst, is reacted, and is made in raw material
AMS changes into isopropylbenzene, wherein used catalyst in terms of parts by weight including following components：
(a) 0.01～1.0 part of Metal Palladium or its oxide；
(b) 0.01～2.0 part of at least one element or its oxide in I A or II A in the periodic table of elements；
(c) 0.01～20.0 part of at least one element or its oxide in IV A or V A in the periodic table of elements；
(d) 77～100 parts of alumina supports；
Wherein alumina support specific surface area is 60～180 meters2/ gram, total pore volume is 0.3～1.2 ml/g；
Wherein, the Alpha-Methyl benzene containing 2～15% by weight percentage in the hydrocarbon material containing AMS
Ethene, 85～98% isopropylbenzene；
Palladium size of microcrystal in the catalyst is 2～3 nanometers.
2. the method for selective hydrogenation of alpha-methyl-styrene according to claim 1, it is characterised in that the reaction temperature
For 40～80 DEG C, reaction pressure is 0.5～1.0MPa.
3. the method for selective hydrogenation of alpha-methyl-styrene according to claim 1, it is characterised in that the hydrocarbon material
Air speed is 0.5～1.5 hour-1, the volume ratio of hydrogen/hydrocarbon material is 150～250：1.
4. the method for selective hydrogenation of alpha-methyl-styrene according to claim 1, it is characterised in that the catalyst with
The consumption of parts by weight meter, Metal Palladium or its oxide is 0.1～0.5 part；In I A or II A in the periodic table of elements at least
The consumption of a kind of element or its oxide is 0.2～0.8 part；At least one element in IV A or V A in the periodic table of elements
Or the consumption of its oxide is 0.2～10.0 part.
5. the method for selective hydrogenation of alpha-methyl-styrene according to claim 1, it is characterised in that in the catalyst
It is potassium selected from the element of I A in the periodic table of elements；It is at least one of calcium, magnesium or barium selected from the element of II A in the periodic table of elements；
It is silicon selected from the element of IV A in the periodic table of elements；It is phosphorus selected from the element of V A in the periodic table of elements.
6. the method for selective hydrogenation of alpha-methyl-styrene according to claim 1, it is characterised in that the carrying alumina
Surface area per unit volume product is 60～150 meters2/ gram, total pore volume is 0.4～1.0 ml/g.
7. the method for selective hydrogenation of alpha-methyl-styrene according to claim 1, it is characterised in that the catalyst with
Parts by weight meter, also containing 0.01～1.0 part of argent or its oxide.
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