CN105521815B

CN105521815B - A kind of naphtha reforming catalyst and preparation method thereof

Info

Publication number: CN105521815B
Application number: CN201410563642.2A
Authority: CN
Inventors: 刘全杰; 徐会青; 贾立明; 王伟
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2014-10-22
Filing date: 2014-10-22
Publication date: 2018-01-16
Anticipated expiration: 2034-10-22
Also published as: CN105521815A

Abstract

The invention discloses a kind of naphtha reforming catalyst and preparation method thereof, on the basis of catalyst weight, the content of the molecular sieves of MCM 36 is 20% ~ 80%, the content of zirconium oxide is 1% ~ 20%, the content of sulfate radical is 1% ~ 10%, and the content of Group IIA metal oxide is 0.1% ~ 5%, and the content of molybdenum oxide is 1% ~ 10%, the content of phosphorus pentoxide is 0.1% ~ 5%, and surplus is aluminum oxide.Preparation method is as follows：The molecular sieves of MCM 36 through Group IIA metal and modified zirconia, are mixed with aluminium hydroxide, add sulfuric acid and/or ammonium sulfate solution, kneading extruded moulding, catalyst carrier is obtained by dry and roasting, then impregnates active component, is dried, roasting obtains naphtha isomerization catalyst.The catalyst has higher activity, under the process conditions for comparing mitigation, can increase substantially the octane number of naphtha.

Description

A kind of naphtha reforming catalyst and preparation method thereof

Technical field

It is a kind of containing super acids specifically the present invention relates to a kind of naphtha reforming catalyst and preparation method Naphtha conversion carries high-octane catalyst and preparation method thereof.

Background technology

Oil is the blood of modern industry, and petrochemical industry is very important basic chemical industry, and the Atmospheric vacuum technique of refinery is given birth to The gasoline fraction of production（That is naphtha）Octane number（RON）Typically between 45 ~ 60, it is necessary to by catalytic reforming, alkylation or The reactions such as isomerization change molecular structure, increase isoparaffin and arene content, while reduce straight chain hydrocarbon content, are improved with reaching The purpose of octane number.But clean gasoline proposes strict limitation to arene content therein now, and alkylation process meeting Serious environmental pollution is produced, is extremely limited its large-scale production, isomerization process is that solve to be produced by naphtha The economic and efficient technology path of high-knock rating gasoline blend component.

Acid catalyst plays an important role in petrochemical industry, and conventional acid catalyst has liquid acid catalyst, such as sulphur Acid, hydrofluoric acid and halogen-containing solid acid catalyst.This two classes catalyst all has the problems such as pollution environment, etching apparatus, Halogen-containing solid acid catalyst, because halogen is easily lost in, therefore there is harsh control to raw material reclaimed water, it is also necessary to often mend halogen. SO₄ ^2-/ZrO₂Solid super acid catalyst it is active it is high, selectivity it is good, easily with reactant be separated, it is environmentally friendly, Not etching apparatus, the advantages that regenerating, such catalyst can be such that isomerization reaction carries out at a lower temperature, and with higher Activity, it is considered to be have very much the isomerization catalyst using future, but the deficiencies of catalyst easily inactivates be present.

CN1229368A discloses a kind of solid acid catalyst and preparation method thereof, by mediating aluminium hydroxide and hydroxide Zirconium and sulfur-containing compound, it is allowed to be molded and is calcined the zirconium oxide of generation tetragonal phase, is loading a kind of the 8th, 9 or 10 race of being selected from Metal, preferably platinum, though the catalyst introduces aluminum oxide by kneading method, tetragonal-phase zirconia is stabilized, it is used for alkane During isomerization, caused C1 ~ C4 low-carbon alkanes are more, and isomerisation selectivity is still not ideal enough.

US5095169 and US5107054, which is disclosed, uses the linear paraffin of beta zeolites and MCM-22 molecular sieves for catalyst Hygrogenating isomerization reaction.US6080904 discloses a kind of hygrogenating isomerization reaction process of linear paraffin.Used catalyst is Pt-W/ZrO₂Although also there is reaction temperature height, and octane number increase rate is also in these catalyst with certain effect The problems such as need to increasing.

The content of the invention

It is an object of the invention to provide a kind of naphtha reforming catalyst and preparation method thereof, the catalyst has very high Activity, the octane number of naphtha under the process conditions for comparing mitigation, can be increased substantially.

The naphtha reforming catalyst of the present invention, on the basis of catalyst weight, the contents of MCM-36 molecular sieves for 20% ~ 80%, the content of zirconium oxide is 1% ~ 20%, and the content of sulfate radical is 1% ~ 10%, and the content of Group IIA metal oxide is 0.1% ~ 5%, The content of molybdenum oxide is 1% ~ 10%, and the content of phosphorus pentoxide is 0.1% ~ 5%, and surplus is aluminum oxide.

Naphtha reforming catalyst of the present invention preferably constitute for：The content of MCM-36 molecular sieves is 30% ~ 70%, oxidation The content of zirconium is 2% ~ 15%, and the content of sulfate radical is 2% ~ 8%, and the content of Group IIA metal oxide is 0.2% ~ 3%, molybdenum oxide Content is 2% ~ 8%, and the content of phosphorus pentoxide is 0.2% ~ 3%, and surplus is aluminum oxide.

The silica of described MCM-36 molecular sieves and the mol ratio of aluminum oxide are 50 ~ total silicon；

Described Group IIA metal is selected from least one of beryllium, magnesium, calcium, strontium, barium, preferably magnesium.

The preparation method of naphtha reforming catalyst of the present invention, including following content：

（1）MCM-36 molecular sieves are added to the mixed solution containing soluble Group IIA metal compound and zirconium compounds In, the MCM-36 molecular sieves of Group IIA metal and modified zirconia are prepared using coprecipitation；

（2）By step（1）The MCM-36 molecular sieves of obtained Group IIA metal and modified zirconia are sufficiently mixed with aluminium hydroxide, Add sulfuric acid and/or ammonium sulfate solution, kneading extruded moulding, by drying and obtaining catalyst carrier after calcination process；

（3）Phosphorous and the compound loaded of molybdenum is arrived into step（2）Obtained carrier, by drying, calcination process, obtain stone Cerebrol reforming catalyst.

Step（1）Group IIA metal and the specific mistake of method of the MCM-36 molecular sieves of modified zirconia prepared by the coprecipitation Cheng Wei：MCM-36 molecular sieves are added to containing in zirconium and Group IIA metal soluble compound solution, in the condition being stirred vigorously It is lower to drop to solution ph with ammoniacal liquor as 7.0 ~ 12,0.5 ~ 4 hour is stood, separation of solid and liquid, dries, obtains Group IIA metal and zirconium changes The MCM-36 molecular sieves of property.Wherein, the soluble-salt of Group IIA metal is its chloride or nitrate；Soluble chemical combination containing zirconium Thing is Zr (NO₃)₄、ZrCl₄Or ZrOCl₂In one or more.

Step（2）Described sulfuric acid and/or the concentration of ammonium sulfate solution 0.1 ~ 2.0mol/L is calculated as with sulfate radical, it is necessary to Material kneading that can be defined by amount to have plastic paste.

Step（3）The compound of described phosphorous and molybdenum is ammonium phosphomolybdate, and mode of loading can be spraying, be coated or impregnated with Etc. mode, preferably impregnate, preferred saturation dipping in impregnation method.

Drying and roasting condition described in above step can be the same or different, described drying temperature be 25 ~ 300 DEG C, drying time is 0.5 ~ 24 hour；Described sintering temperature is 300 ~ 700 DEG C, and roasting time is 0.5 ~ 8 hour.

Catalyst of the present invention is used for the conversion process of naphtha, the process conditions of reaction：Fixed bed reactors, temperature 150 ~ 300 DEG C, 0.1 ~ 10MPa of pressure, 0.5 ~ 10h of volume space velocity^-1, hydrogen to oil volume ratio 100 ~ 2000.

The present invention has the following advantages that compared with prior art：

The carrier of catalyst of the present invention is MCM-36 molecular sieves, is a kind of molecular sieve of layer pole structure, has micropore and Jie The dual pore structure in hole, its intermediary hole are located at interlayer, are formed by the polymeric post of interlevel inorganic oxide.Existing micropore The acidity and stability of molecular sieve, while its active sites is had preferably for reactant molecule due to the mesoporous of interlayer again Accessibility.In addition, MCM-36 specific surface area is very big, and its surface is made up of 12 yuan of rings holes being relatively large in diameter, Therefore, it is possible to provide substantial amounts of active sites for reaction, the high activity of catalyst ensure that.

Zirconium oxide is tetragonal phase in catalyst of the present invention.Simple zirconium oxide starts monocline occur in 400 DEG C of roastings Crystalline phase, specific surface area decrease 100m²/ below g.After sulfuric acid oxide impregnation zirconium, there is monoclinic crystal in 600 DEG C of roastings Phase, specific surface area significantly decline therewith.The present invention makes it by being introduced into Group IIA metal in the periodic table of elements into zirconium oxide Solid solution is formed with zirconium oxide, so as to suppress transformation of the zirconium oxide from metastable state tetragonal phase to stable monocline crystalline phase, makes to urge Agent is at high temperature（750~800℃）Remain to keep larger specific surface area, improve the heat endurance of catalyst, can prevent from urging Influence of the high temperature accidentally occurred during agent use to catalyst performance, the addition of sulfate radical can form super with zirconium oxide Strong acid center, improve catalyst activity.

Embodiment

The present invention is described in detail below by embodiment, but the present invention is not limited thereto.

Wherein, MCM-36 molecular sieves are according to document disclosed in Wang Baoyu etc.（" MCM-36 Zeolite under Ultrasonic Treatment it is fast Speed synthesis ", catalysis journal, volume 28, the 5th phase, page 398 ~ 400,）Method synthesis, obtain MCM-36 silica alumina ratio（nSiO₂/ nAl₂O₃）125, specific surface area 820m², average pore size 4.8nm.

The performance evaluation condition of catalyst is as follows：On flowing fixed bed midget plant, 20 milliliters of catalyst continuously are being loaded, With naphtha after hydrofinishing（RON=53）For raw material, 210 DEG C, 2.0MPa, volume space velocity 2.0h^-1, hydrogen to oil volume ratio 500 Under the conditions of react, reaction for every eight hours for one it is constant, detect the research octane number (RON) of different constant samples respectively（RON）.

Embodiment 1

A kind of preparation method of catalyst of the present invention

（1）Take 100 grams of powderies MCM-36 molecular sieves be added to 300 milliliters it is water-soluble containing magnesium nitrate and zirconium oxychloride In liquid, with vigorous stirring, it is 8.5 that 25% concentrated ammonia liquor to solution ph, which is added dropwise, stands 2 and was as a child isolated afterwards by centrifugal process Precipitation, dried 8 hours by 120 DEG C, the MCM-36 molecular sieves of magnesium and modified zirconia are made；

（2）By step（1）The MCM-36 molecular sieves of obtained magnesium and modified zirconia are sufficiently mixed with aluminium hydroxide, add concentration For 1.0M sulfuric acid solution, kneading extrusion dries that to be calcined 3 within 4 hours and 350 DEG C small by 100 DEG C into the strip of 1.5 millimeters of diameter When processing after obtain catalyst carrier；

（3）With the solution impregnation steps containing ammonium phosphomolybdate（2）Obtained carrier, dried 6 hours and 420 DEG C by 110 DEG C Catalyst of the present invention is obtained after roasting processing in 2 hours, its composition is shown in Table 1, and reactivity worth is shown in Table 2.

Embodiment 2 ~ 6

The method that catalyst is prepared according to embodiment 1, different parts are that the composition of catalyst is different, obtain catalyst Composition be shown in Table 1, reactivity worth is shown in Table 2.

Embodiment 7 ~ 10

The method that catalyst is prepared according to embodiment 1, different parts are step（3）Middle maceration extract is three oxidations Molybdenum is dissolved in the solution obtained in phosphoric acid, and the composition of catalyst is different, and the composition for obtaining catalyst is shown in Table 1, and reactivity worth is shown in Table 2.

Comparative example 1

The method that catalyst is prepared according to embodiment 1, different parts are step（1）Without molecular sieve, catalyst Composition is different, and the composition for obtaining catalyst is shown in Table 1, and reactivity worth is shown in Table 2.

Comparative example 2

The method that catalyst is prepared according to comparative example 1, different parts are step（1）Without magnesium-containing compound, catalysis The composition of agent is different, and the composition for obtaining catalyst is shown in Table 1, and reactivity worth is shown in Table 2.

Comparative example 3

The method that catalyst is prepared according to comparative example 2, cancellation step（3）, i.e., not phosphorous and molybdenum in catalyst, catalyst Composition is different, and the composition for obtaining catalyst is shown in Table 1, and reactivity worth is shown in Table 2.

1 each embodiment of table（Comparative example）Catalyst forms.

Note：Calcium oxide,Strontium oxide strontia,Barium barium monoxide,Beryllium oxide：Magnesia=1:1（Mass ratio）,

Percentage composition described in table is weight/mass percentage composition.

2 each embodiment of table（Comparative example）The reactivity worth of catalyst.

Note：Raw material RON=53, each Time constant are 8 hours.

The result of table 2 is shown, compared with comparative example, catalyst of the present invention is not only lived initial stage in naphtha conversion process Property it is high, and the stability of catalyst is more preferable, shows good effect.

Claims

A kind of 1. naphtha reforming catalyst, it is characterised in that：On the basis of catalyst weight, the content of MCM-36 molecular sieves is 20% ~ 80%, the content of zirconium oxide is 1% ~ 20%, and the content of sulfate radical is 1% ~ 10%, and the content of Group IIA metal oxide is 0.1% ~ 5%, the content of molybdenum oxide is 1% ~ 10%, and the content of phosphorus pentoxide is 0.1% ~ 5%, and surplus is aluminum oxide；The preparation of catalyst Method, including following content：（1）MCM-36 molecular sieves are added to containing soluble Group IIA metal compound and zirconium compounds Mixed solution in, the MCM-36 molecular sieves of Group IIA metal and modified zirconia are prepared using coprecipitation；（2）By step（1）It is made Group IIA metal and the MCM-36 molecular sieves of modified zirconia be sufficiently mixed with aluminium hydroxide, add sulfuric acid and/or ammonium sulfate be water-soluble Liquid, kneading extruded moulding, by drying and obtaining catalyst carrier after calcination process；（3）Will be phosphorous and molybdenum compound loaded To step（2）Obtained carrier, by drying, calcination process, obtain naphtha reforming catalyst.
2. according to the catalyst described in claim 1, it is characterised in that：On the basis of catalyst weight, MCM-36 molecular sieves Content is 30% ~ 70%, and the content of zirconium oxide is 2% ~ 15%, and the content of sulfate radical is 2% ~ 8%, the content of Group IIA metal oxide For 0.2% ~ 3%, the content of molybdenum oxide is 2% ~ 8%, and the content of phosphorus pentoxide is 0.2% ~ 3%, and surplus is aluminum oxide.
3. according to the catalyst described in claim 1 or 2, it is characterised in that：Described Group IIA metal be selected from beryllium, magnesium, calcium, It is one or more of in strontium or barium.
4. the preparation method of the catalyst described in a kind of claim 1 or 2, it is characterised in that including following content：（1）By MCM- 36 molecular sieves are added in the mixed solution containing soluble Group IIA metal compound and zirconium compounds, using co-precipitation legal system The MCM-36 molecular sieves of standby Group IIA metal and modified zirconia；（2）By step（1）The MCM-36 of obtained Group IIA metal and modified zirconia Molecular sieve is sufficiently mixed with aluminium hydroxide, adds sulfuric acid and/or ammonium sulfate solution, kneading extruded moulding, by drying and roasting Catalyst carrier is obtained after burning processing；（3）Phosphorous and the compound loaded of molybdenum is arrived into step（2）Obtained carrier, by drying, Calcination process, obtain naphtha reforming catalyst.
5. in accordance with the method for claim 4, it is characterised in that：Step（1）Group IIA metal prepared by the coprecipitation and The method detailed process of the MCM-36 molecular sieves of modified zirconia is：MCM-36 molecular sieves are added to can containing zirconium and Group IIA metal In soluble compound solution, it is 7.0 ~ 12 to drop to solution ph with ammoniacal liquor under conditions of being stirred vigorously, and stands 0.5 ~ 4 hour, Separation of solid and liquid, dry, obtain the MCM-36 molecular sieves of Group IIA metal and modified zirconia.
6. in accordance with the method for claim 4, it is characterised in that：Step（1）The soluble-salt of described Group IIA metal is One or more in Group IIA metal chloride or nitrate；The described soluble compound containing zirconium is Zr (NO₃)₄、ZrCl₄ Or ZrOCl₂In one or more.
7. in accordance with the method for claim 4, it is characterised in that：Step（2）Described sulfuric acid and/or ammonium sulfate solution Concentration is calculated as 0.1 ~ 2.0mol/L with sulfate radical.
8. in accordance with the method for claim 4, it is characterised in that：Described drying temperature is 25 ~ 300 DEG C, and drying time is 0.5 ~ 24 hour；Described sintering temperature is 300 ~ 700 DEG C, and roasting time is 0.5 ~ 8 hour.
9. application of the catalyst in the conversion process of naphtha described in a kind of claim 1 or 2, the process conditions of reaction： Fixed bed reactors, 150 ~ 300 DEG C, 0.1 ~ 10MPa of pressure, 0.5 ~ 10h of volume space velocity of temperature^-1, hydrogen to oil volume ratio 100 ~ 2000.