CN102500410A - Catalyst for ethylbenzene and ethanol synthesis to realize shape-selectivity alkylation for diethylbenzene - Google Patents
Catalyst for ethylbenzene and ethanol synthesis to realize shape-selectivity alkylation for diethylbenzene Download PDFInfo
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Abstract
The invention relates to a catalyst for ethylbenzene and ethanol synthesis to realize shape-selectivity alkylation for diethylbenzene, which mainly resolves problems that existing ethylbenzene and ethanol synthesis is severe to secondary reaction such as ethylbenzene disproportionated reaction, isomerization reaction and the like in the technology of the diethylbenzene. Bioethanol can be used for replacing ethylene to resolve the problem that petrifaction raw materials are deficient. The technical scheme includes that the catalyst comprises, by weight, from 50 to 90 parts of hydrogen silicon-aluminum zeolite, from 1 to 10 parts of at least two metallic oxides of rare earth or alkaline metallic oxides and oxide binder, wherein SiO2/Al2O3 mole ratio of the hydrogen silicon-aluminum zeolite is 20-200, the hydrogen silicon-aluminum zeolite is a 10-member ring pore structure, and the problems are resolved better. Reaction conditions of the synthesis to the diethylbenzene include that reaction temperature ranges from 350 DEG C to 450 DEG C; total pressure ranges from 0.2MPa to 2.0MPa; the ratio of ethylbenzene to ethanol ranges from 2.0 to 6.0; and space velocity ranges from 1-8h-1. The catalyst is applied to ethylbenzene alkylation process for the ethylbenzene and ethanol synthesis to the diethylbenzene, and has good catalytic reaction selectivity and yield.
Description
Technical field
The present invention relates to the form selected methylation catalyst of the synthetic p-Diethylbenzene of a kind of ethylbenzene and ethanol; Said catalyst can be applied in the Chemical Manufacture of synthetic p-Diethylbenzene; Particularly can high selectivity catalysis synthetic contraposition alkyl ethylbenzene, and between avoiding, ortho position diethylbenzene production of by-products; And available bio-ethanol substitutes ethene solution petrochemical material problem in short supply.
Background technology
The p-Diethylbenzene dehydrogenation can obtain divinylbenzene, and the divinylbenzene comonomer is used to during existing polystyrene plastics produces in a large number, and the polymer of production is at proportion, hear resistance, and aspects such as transparency and shrinkage factor all are superior to simple polystyrene.Divinylbenzene also can be used as the crosslinking agent in the novel plastic material polymerization production simultaneously; In addition p-methylstyrene can with other monomer copolymerization; Can improve the hear resistance and the anti-flammability of some polymer; Can be used for engineering plastics in a large number, the manufacturing of aspects such as phthalic resin coating, thereby receive extensive attention.On the other hand, p-Diethylbenzene also is widely used as the Mixed XYLENE adsorbing separation and produces desorption eluent in the paraxylene.Also do not obtain the satisfactory method of the p-Diethylbenzene of high concentration for a long time; Obtain the product of contraposition; A kind of well behaved shape-selective catalyst must be arranged, require in duct size, grain size and the hole of zeolite catalyst acid site intensity suitable, and the acidity of outer surface is inhibited; Might make the ethylbenzene alkylated reaction break the thermodynamical equilibrium CONCENTRATION DISTRIBUTION of p-Diethylbenzene, NSC 62102, adjacent diethylbenzene product, mainly generate p-Diethylbenzene.The catalytic theory supposition is thought can make ethylbenzene and ethene vapor phase alkylation break through the restriction of thermodynamical equilibrium through the ZSM-5 of chemical modification molecular sieve, can obtain the p-Diethylbenzene of 90% above concentration, and not generate neighbour, a position diethylbenzene basically.In recent years, this important function for of research has caused the extensive interest of each company and scientific research institution, and has obtained certain progress; If can obtain further success; To produce dramatic change to the production technology of p-Diethylbenzene, to energy savings, simplified apparatus; Reduce production costs, increasing economic efficiency all has very important meaning.Catalyst technology in the application's patent obtains the p-Diethylbenzene production technology to highly selective and develops.
Chinese patent CN1045930 provides a kind of directly ZSM-5 zeolite catalyst of synthetic p-diethylbenzene of ethylbenzene/ethanol alkylation that is applicable to; It is to be that raw material is through using hydrochloric acid ion-exchange with the NaZSM-5 zeolite; With aluminium, magnesium salts modification, dry roasting again and process contain magnesium, aluminium zeolite molecular sieve catalyst; It is the directly alkylated reaction of synthetic p-diethylbenzene of raw material that modified catalyst is used for ethylbenzene/ethanol, at 360 ℃ ~ 390 ℃ of temperature, mass space velocity 6 ~ 9 h
-1, benzene alkene reaches 5 ~ 10% than the conversion ratio of ethylbenzene under 6 ~ 8 the reaction condition, and the selectivity of p-diethylbenzene reaches 95 ~ 98%.
Chinese patent CN1605390 relates to catalyst and the preparation method who is used for ethanol and the synthetic p-Diethylbenzene of ethylbenzene alkylation.Is basic thing with Si/Al than the HZSM-5 molecular sieve that is 50, through B, Mg and Co the surface acidity and the duct of catalyst is regulated, and has desirable pore-size distribution and duct inner acidic and distributes and the strong p-Diethylbenzene synthetic catalyst of anti-coking performance.Wherein the predecessor of B is a boric acid, and the predecessor of Mg is a magnesium nitrate, and the predecessor of Co is a cobalt nitrate.The mass ratio of B and HZSM-5 molecular sieve is 1%～3%, and the mass ratio of Mg and HZSM-5 molecular sieve is 0.1%～1%, and the mass ratio of Co and HZSM-5 molecular sieve is 1%～3%.The present invention compares with present similar catalyst, and it is simple to have the preparation method, and cost is low, and the p-Diethylbenzene selectivity is good, characteristics such as yield height.
Above document has all promoted the para-selectivity of product p-Diethylbenzene preferably; But the conversion of ethylbenzene of product overall selectivity is still lower; Can't satisfy the demand of actual production; And do not carry out adhesion-molded processing as fixed bde catalyst, can not adopt hydrous ethanol, realize the practical value of commercial Application thereby limited it as reaction raw materials.
Summary of the invention
The present invention mainly solves the serious problem of side reaction such as disproportionated reaction and isomerization reaction in existing ethylbenzene and the synthetic p-Diethylbenzene technology of ethene, thereby improves the effect of ethylbenzene alkylated reaction; And available biological hydrous ethanol substitutes ethene solution petrochemical material problem in short supply.The object of the present invention is to provide the form selected methylation catalyst of the synthetic p-Diethylbenzene of a kind of efficient ethylbenzene and ethanol.
In order to solve the problems of the technologies described above, the technical scheme that the present invention takes is following: the form selected methylation catalyst of the synthetic p-Diethylbenzene of a kind of ethylbenzene and ethanol comprises following component in parts by weight:
(1) SiO
2/ Al
2O
3Mol ratio is 50 ~ 90 parts of the Hydrogen Si-Al zeolites of 20 ~ 200 ten-ring pore structure;
(2) be selected from 1 ~ 10 part of at least two kinds of metal oxide in alkaline earth or the rare-earth oxide;
(3) all the other are adhesive oxides, make the gross weight umber of catalyst be 100 parts altogether.
Among the present invention; Said Hydrogen Si-Al zeolite is selected among HZSM-5, HZSM-35, HZSM-11, HSAPO-11 or the HMCM-22 any; In the liquid-phase silicone deposition surface modification of zeolite is handled, select for use polysiloxanes as modifier, the deposition of silica is the 3wt%～20wt% of Hydrogen sial weight; Polysiloxane-modified dose is selected from the reactive hydrogen radical siloxane.
Among the present invention, said alkaline earth or rare-earth oxide are selected from least two kinds of metal oxides in lanthanum, cerium, strontium, calcium, barium or the magnesium oxide.
Among the present invention, said adhesive oxides is selected from aluminium oxide or silica.
Among the present invention, ethanol can be selected from 40 wt%～95 wt% hydrous ethanols or absolute ethyl alcohol as reaction raw materials.
The synthetic p-Diethylbenzene reaction condition of the ethylbenzene of this form selected methylation catalyst and ethanol is: 350～450 ℃ of reaction temperatures; Gross pressure 0.2MPa～2.0 MPa; Ethylbenzene/ethanol 2.0 ~ 8.0; Air speed 1 ~ 8h
-1
The Preparation of catalysts of form selected methylation described in the present invention method; Concrete steps are: through the Hydrogen Si-Al zeolite; The method of adhesive oxides mixed-forming, or powdered or balling-up or granulation or extrusion modling, preferred version adopts the extrusion method of forming; Descended dry 3 hours at 120 ℃ after the moulding, then 400～600 ℃ of following roastings 4 hours.In the liquid-phase silicone deposition surface modification of zeolite is handled, adopt the normal hexane solution of reactive hydrogen radical siloxane to flood, and obtain the shape-selection and modification effect through dry, calcination process.The load operation mode of its further metal oxide can adopt before the moulding impregnating metal nitrate solution also can adopt impregnating metal nitrate solution after the moulding, the method for dipping again after the preferred moulding.Dipping is back to be descended dry 3 hours at 120 ℃, processed catalyst in 4 hours 450～600 ℃ of following roastings then.
Catalyst of the present invention uses fixed bed reactors to carry out catalytic perfomance and investigates.20 millimeters of reactor inside diameter, length 400mm stainless steel.Adopt electrical heating, temperature is controlled automatically.The bead that it is 2mm that reactor bottom is filled one section diameter is as support, catalyst filling 15 ml in the reactor, and the bead that 2mm is filled on top plays the effect of preheating and vaporization raw material.After ethylbenzene in the raw material and ethylene gas mixed, through beds generation alkylated reaction, p-Diethylbenzene and more a spot of side reaction product mainly were adjacent diethylbenzene, NSC 62102, benzene, methylbenzene and dimethyl benzene etc. from top to bottom.Catalytic reaction condition adopts: 350～450 ℃ of temperature; Gross pressure 0.2MPa～2.0 MPa; Ethylbenzene/ethanol is than 2.0 ~ 8.0; Air speed 1 ~ 8h
-1
The experimental data that reaction obtains adopts following formula to calculate.
Among the present invention; In catalyst, adopted a kind of in middle strong acidity HZSM-5, HZSM-35, HZSM-11, HSAPO-11 or the HMCM-22 zeolite as active component; And passivation its do not have the outer surface acidity position of selecting the shape function; Added simultaneously be selected from have in alkaline earth or the rare earth oxide alkalescence at least two kinds of metal oxides as the catalytic activity auxiliary agent, further improved the selectivity of molecular sieve carrier.Above-mentioned characteristic makes this catalyst synthesize in the technology of p-Diethylbenzene with ethylbenzene and ethanol alkylation, can satisfy alkylating high selectivity and conversion ratio, and keep lower ethylbenzene loss late and good stable property, has obtained actual process effect preferably.
Form selected methylation catalyst according to the invention is used for ethylbenzene and ethanol is raw material; Carry out alkylated reaction and generate p-Diethylbenzene, have the conversion ratio height, the contraposition product selectivity is high, side reaction is few, can adopt hydrous ethanol as characteristics such as reaction raw materials, catalyst stability are good.
The specific embodiment
Below through embodiment the present invention is done further elaboration.
Embodiment 1:
Adopt SiO
2/ Al
2O
3Mol ratio is 140 Hydrogen HZSM-5 molecular sieve 42 grams and 12 gram r-Al
2O
3Mix, add field mountain valley with clumps of trees and bamboo powder 1.8 grams again and mix, add the rare nitric acid of a certain amount of 3 % then and fully mediate evenly as adhesive, carry out extruded moulding, drying is 2 hours under 120 ℃, then 540 ℃ of following roastings 1 hour.After adopting the normal hexane solution of 15 % reactive hydrogen radical siloxane modifier to flood to moulded zeolite; And it is following dry 2 hours through 120 ℃; Handled in 3 hours 500 ℃ of following roastings then, the modification of liquid-phase silicone deposition surface is handled and is processed the catalyst I, and the deposition of its silica is 6.7wt%.
Embodiment 2:
The HZSM-5 molecular sieve that adopts example 1 said method to make floods in the barium nitrate aqueous solution of the magnesium nitrate of 7.0% concentration and 2.3% concentration with the molecular sieve that makes, behind the dipping, and the remaining maceration extract of elimination.120 ℃ dry 3 hours down, then 540 ℃ of following roastings 4 hours, adopt temperature programming, 3 ℃/min of heating rate is designated as catalyst I I, its magnesia load capacity is 3.2%, the barium monoxide load capacity is 1.5%.
Embodiment 3:
The HZSM-5 molecular sieve that adopts example 1 said method to make floods in the lanthanum nitrate aqueous solution of the cerous nitrate of 6.5% concentration and 5.1% concentration with the molecular sieve that makes, behind the dipping, and the remaining maceration extract of elimination.120 ℃ dry 3 hours down, then 540 ℃ of following roastings 4 hours, adopt temperature programming, 3 ℃/min of heating rate is designated as catalyst I II, its cerium oxide load capacity is 3.5%, the lanthana load capacity is 2.4%.
Embodiment 4:
Adopt Hydrogen HZSM-11 molecular screen primary powder to replace the HZSM-5 molecular screen primary powder; Make the HZSM-11 molecular sieve of moulding according to example 1 said method program and condition; Flood in the calcium nitrate aqueous solution of the strontium nitrate of 6.2% concentration and 1.2% concentration with the molecular sieve that makes; Behind the dipping, the remaining maceration extract of elimination.120 ℃ dry 3 hours down, then 540 ℃ of following roastings 4 hours, adopt temperature programming, 3 ℃/min of heating rate is designated as the catalyst IV, its strontium oxide strontia load capacity is 3.8%, the load capacity 0.5% of calcium oxide.。
Embodiment 5:
Adopt Hydrogen HSAPO-11 molecular screen primary powder to replace the HZSM-5 molecular screen primary powder; And replace aluminium oxide as binding agent with silicon dioxide gel; Make the HSAPO-11 molecular sieve of moulding according to example 1 said method program and condition; Flood in the magnesium nitrate aqueous solution of the cerous nitrate of 9.5% concentration and 1.5% concentration with the molecular sieve that makes, behind the dipping, the remaining maceration extract of elimination.Drying is 3 hours under 120 ℃, then 540 ℃ of following roastings 4 hours, adopts temperature programming, and 3 ℃/min of heating rate is designated as the catalyst V, and its cerium oxide load capacity, magnesian load capacity are respectively 7.1% and 1.0%.
Embodiment 6:
Adopt Hydrogen HMCM-22 molecular screen primary powder to replace the HZSM-5 molecular screen primary powder; Make the HMCM-22 molecular sieve of moulding according to example 1 said method program and condition; Flood in the magnesium nitrate aqueous solution of the lanthanum nitrate of 4.5% concentration and 2.4% concentration with the molecular sieve that makes; Behind the dipping, the remaining maceration extract of elimination.Drying is 3 hours under 120 ℃, then 540 ℃ of following roastings 4 hours, adopts temperature programming, and 3 ℃/min of heating rate is designated as the catalyst VI, and its lanthana, magnesian load capacity are respectively 3.3% and 1.3%.
Embodiment 7:
Adopt Hydrogen HZSM-35 molecular screen primary powder to replace the HZSM-5 molecular screen primary powder; Make the ZSM-35 molecular sieve of moulding according to example 1 said method program and condition; Flood in the calcium nitrate aqueous solution of the barium nitrate of the lanthanum nitrate of 3.6% concentration, 7.3% concentration and 6.2% concentration with the molecular sieve that makes; Behind the dipping, the remaining maceration extract of elimination.120 ℃ dry 3 hours down, then 540 ℃ of following roastings 4 hours, adopt temperature programming, 3 ℃/min of heating rate is designated as catalyst V II, the load capacity of its barium monoxide, calcium oxide is respectively 4.1% and 4.5%, the load capacity of lanthana is 2.6%.
Embodiment 8:
On fixed bed reactors, investigate its alkylation activity and selectivity with catalyst I, II, III, IV, V, VI, VII, and side reaction mainly is the degree (representing with total selection rate) of isomerization and disproportionated reaction.Reaction condition adopts: 400 ℃ of reaction temperatures; Gross pressure 1.2 MPa; Ethylbenzene/ethanol is than 4.0; Air speed 3.0 h
-140 wt%～95 wt% hydrous ethanols or absolute ethyl alcohol and industrial ethylbenzene, evaluation result is as shown in the table.
| Catalyst | Conversion of ethylbenzene/% | Selection rate/the % of p-Diethylbenzene | Overall selectivity/the % of p-Diethylbenzene |
| I (95 wt% hydrous ethanol) | 24.1 | 51.8 | 46.0 |
| II (95 wt% hydrous ethanol) | 21.3 | 96.9 | 90.6 |
| III (40 wt% hydrous ethanol) | 21.0 | 97.1 | 91.3 |
| IV (absolute ethyl alcohol) | 21.2 | 96.4 | 91.5 |
| V (65 wt% hydrous ethanol) | 21.3 | 97.2 | 91.1 |
| VI (82 wt% hydrous ethanol) | 20.9 | 96.7 | 91.6 |
| VII (56 wt% hydrous ethanol) | 20.7 | 99.0 | 91.9 。 |
Can find out after in alkaline earth or rare-earth oxide two kinds or the three kinds of metal oxide supported modifications the HZSM-5 molecular sieve with compare without the catalyst of siliceous deposits modification; Because the acidity of having regulated bore size and catalyst outer surface, modified HZSM-5 molecular sieve p-Diethylbenzene selectivity obviously improves; The HZSM-5 molecular sieve catalyst has still kept higher p-Diethylbenzene conversion ratio after the modification, and the product overall selectivity is also higher.
The above results can find out that employing Hydrogen HZSM-35, HZSM-11, HSAPO-11 or HMCM-22 molecular sieve replace the HZSM-5 molecular sieve; The HZSM-35, HZSM-11, HSAPO-11 or the HMCM-22 molecular sieve catalyst that make moulding according to same catalyst preparation method program and condition also can play similar catalytic effect, and higher p-Diethylbenzene selectivity and product overall selectivity are arranged equally; Reached the index request that commercial production is used.
Claims (6)
1. the form selected methylation catalyst of the synthetic p-Diethylbenzene of ethylbenzene and ethanol is characterized in that comprising following component in parts by weight:
(1) SiO
2/ Al
2O
3Mol ratio is 50 ~ 90 parts of the Hydrogen Si-Al zeolites of 20 ~ 200 ten-ring pore structure;
(2) be selected from 1 ~ 10 part of at least two kinds of metal oxide in alkaline earth or the rare-earth oxide;
(3) all the other are adhesive oxides, and the gross weight umber of catalyst is 100 parts altogether.
2. the form selected methylation catalyst of the synthetic p-Diethylbenzene of ethylbenzene according to claim 1 and ethanol; It is characterized in that said Hydrogen Si-Al zeolite is selected among HZSM-5, HZSM-35, HZSM-11, HSAPO-11 or the HMCM-22 any; In the liquid-phase silicone deposition surface modification of zeolite is handled, adopt polysiloxanes as modifier, the deposition of silica is with respect to the 5wt%～20wt% of Hydrogen Si-Al zeolite weight.
3. the form selected methylation catalyst of the synthetic p-Diethylbenzene of ethylbenzene according to claim 1 and ethanol is characterized in that said alkaline earth or rare-earth oxide are selected from least two kinds of metal oxides in lanthanum, cerium, strontium, calcium, barium or the magnesium oxide.
4. according to the form selected methylation catalyst of said ethylbenzene of claim 1 and the synthetic p-Diethylbenzene of ethanol, it is characterized in that adhesive oxides is selected from aluminium oxide or silica.
5. according to the form selected methylation catalyst of the synthetic p-Diethylbenzene of the said ethylbenzene of claim 1 and ethanol, it is characterized in that ethanol is selected from 40 wt%～95 wt% hydrous ethanols or absolute ethyl alcohol as reaction raw materials.
6. said liquid-phase silicone deposition surface modification at zeolite is adopted polysiloxane-modified dose in handling according to claim 2, it is characterized in that polysiloxane-modified dose is selected from the reactive hydrogen radical siloxane.
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Cited By (4)
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| CN103664474A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for synthesizing p-diethylbenzene employing ethylbenzene-ethanol alkylation reaction |
| CN103739436A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | A method of synthesizing p-diethylbenzene by alkylation of ethanol and ethylbenzene |
| CN106076404A (en) * | 2016-06-08 | 2016-11-09 | 中石化炼化工程（集团）股份有限公司 | Catalyst and preparation method thereof, application and the preparation method of durol |
| CN106179348A (en) * | 2016-07-26 | 2016-12-07 | 江苏正丹化学工业股份有限公司 | A kind of for producing the catalyst of divinylbenzene, Preparation Method And The Use |
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| CN101954293A (en) * | 2010-09-27 | 2011-01-26 | 同济大学 | Method for preparing catalyst for alkylation reaction of methylbenzene and ethylene for synthesizing paramethyl ethylbenzene |
| CN101961659A (en) * | 2010-10-08 | 2011-02-02 | 同济大学 | Shape selective alkylation catalyst for synthesizing toluene and ethanol into p-methyl ethylbenzene |
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| CN101954293A (en) * | 2010-09-27 | 2011-01-26 | 同济大学 | Method for preparing catalyst for alkylation reaction of methylbenzene and ethylene for synthesizing paramethyl ethylbenzene |
| CN101961659A (en) * | 2010-10-08 | 2011-02-02 | 同济大学 | Shape selective alkylation catalyst for synthesizing toluene and ethanol into p-methyl ethylbenzene |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103664474A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for synthesizing p-diethylbenzene employing ethylbenzene-ethanol alkylation reaction |
| CN103664474B (en) * | 2012-09-05 | 2016-01-13 | 中国石油化工股份有限公司 | The method of ethylbenzene and ethanol alkylation Reactive Synthesis p-Diethylbenzene |
| CN103739436A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | A method of synthesizing p-diethylbenzene by alkylation of ethanol and ethylbenzene |
| CN103739436B (en) * | 2012-10-17 | 2015-10-21 | 中国石油化工股份有限公司 | The method of p-Diethylbenzene is synthesized in ethanol and ethylbenzene alkylation |
| CN106076404A (en) * | 2016-06-08 | 2016-11-09 | 中石化炼化工程（集团）股份有限公司 | Catalyst and preparation method thereof, application and the preparation method of durol |
| CN106076404B (en) * | 2016-06-08 | 2019-10-18 | 中石化炼化工程（集团）股份有限公司 | The preparation method of catalyst and preparation method thereof, application and durol |
| CN106179348A (en) * | 2016-07-26 | 2016-12-07 | 江苏正丹化学工业股份有限公司 | A kind of for producing the catalyst of divinylbenzene, Preparation Method And The Use |
| CN106179348B (en) * | 2016-07-26 | 2018-09-28 | 江苏正丹化学工业股份有限公司 | A kind of catalyst, preparation method and the usage for producing divinylbenzene |
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Application publication date: 20120620 |