CN106540735A - For the catalyst that benzene, methanol alkylation react - Google Patents
For the catalyst that benzene, methanol alkylation react Download PDFInfo
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- CN106540735A CN106540735A CN201510594399.5A CN201510594399A CN106540735A CN 106540735 A CN106540735 A CN 106540735A CN 201510594399 A CN201510594399 A CN 201510594399A CN 106540735 A CN106540735 A CN 106540735A
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- methanol alkylation
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 148
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 29
- 230000029936 alkylation Effects 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000002808 molecular sieve Substances 0.000 claims abstract description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 238000010306 acid treatment Methods 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 9
- 235000015165 citric acid Nutrition 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims 1
- 235000011054 acetic acid Nutrition 0.000 claims 1
- 239000011975 tartaric acid Substances 0.000 claims 1
- 235000002906 tartaric acid Nutrition 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 45
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 37
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000010791 quenching Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 9
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical class [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of catalyst reacted for benzene, methanol alkylation, in mainly solving benzene, methanol alkylation catalyst practical application, benzene conversion ratio is not high, and toluene, dimethylbenzene selective are low, the problem of poor catalyst stability.The present invention is modified by appropriate alkali process and acid treatment are carried out to HZSM-5 molecular sieves, and further loads a certain amount of oxide, preferably resolves the problem, can be used in benzene, the industrialized production of methanol alkylation reaction.
Description
Technical field
The invention belongs to the content of catalyst and field of catalytic reactions, more particularly to a kind of catalyst reacted for benzene, methanol alkylation.
Background technology
Dimethylbenzene is mainly made up of xylol, o-Dimethylbenzene and meta-xylene, is important industrial chemicals, and tool has been widely used.Wherein, xylol（PX）It is most widely used, mainly for the production of p-phthalic acid（PTA）And dimethyl terephthalate (DMT)（DMT）.PTA and DMT can further and diol reaction, then the polyester product of Jing polycondensations production is widely used in the fields such as chemical fibre, synthetic resin and plastics.The conventional production methods of PX mainly with toluene or Mixed XYLENE as raw material, by toluene disproportionation, xylene isomerization or toluene and C9The modes such as accordance transfer are realizing.Traditional handicraft has the shortcomings that low feed stock conversion, poor catalyst stability, equipment is huge, operating cost is high.Also, dimethylbenzene is mainly derived from oil at present（Refining catalytic is reformed and Aromatic Hydrocarbon United Plant）, and in world wide petroleum reserves increasingly reducing, thus the new way for seeking increasing production of xylol has an economic benefit and industrial value very much.
Alkylated reaction by benzene and methanol is the effective way of increasing production of xylol.Benzene not only can be obtained from oil, can also obtain from the deep processing of coal, coming years China's Petrochemical will be in Rapid development stage, and with reference to ethylene, aromatic hydrocarbons joint, refinery's reformation and the development of coking benzene processing project, the production capacity of China's purified petroleum benzin continues to increase.Thus estimated future China's purified petroleum benzin market will be presented the situation of production capacity surplus.On the other hand, China greatly develops Coal Chemical Industry, and production capacity of methanol is huge, has the external low price methanol import with natural gas as raw material again so that methanol market price is lower.Therefore, the downstream product such as toluene, the dimethylbenzene of high added value are directly synthesized using benzene and methanol, are worth with good commercial development.
It is all more rare at home and abroad with regard to benzene, the document of methanol alkylation catalysts research and patent.Patent CN102600887A adopts the molecular sieve carried alkaline earths of HMCM-22, the technical scheme of thulium, uses it for benzene, methanol alkylation reaction, and benzene conversion ratio is 45% or so, and methanol conversion is 90% or so, and dimethylbenzene selective is 60% or so.Patent CN102101818A loads the MoO of 3-15% with HMCM-56 molecular sieves as carrier3Or NiO, reacting for benzene, methanol alkylation, the conversion per pass of benzene is more than 45%, and toluene, the selectivity of dimethylbenzene are more than 89%.Patent CN102688771A is with HMCM-56 molecular sieves and γ-Al2O3For oxides such as complex carrier, load molybdenum, nickel, magnesium, lanthanum, boron, react for benzene, methanol alkylation, benzene conversion ratio reaches 50%, and toluene, dimethylbenzene selective reach more than 90%, but the report in terms of the patent does not have catalyst stability.These three patents use HMCM-22 and HMCM-56 molecular sieves, although benzene conversion ratio increases, but toluene, dimethylbenzene selective are still low, and poor catalyst stability.Patent CN104109065A, CN102746080A of Shanxi Hengyang Science ＆ Technology Co., Ltd. and Ningxia pagoda petrochemical industry company limited, CN101624327A etc. essentially describe separation process and the process optimization of benzene, methanol alkylation product toluene, dimethylbenzene, trimethylbenzene and benzene, are not related to catalyst research.
This patent describes a kind of catalyst reacted for benzene, methanol alkylation, and the catalyst has good commercial development value with HZSM-5 molecular sieves as active main body Jing after alkali process and acid treatment, with high activity, high selectivity and good stability.
The content of the invention
The present invention is to solve the problems, such as that benzene, methanol alkylation catalyst activity are low, selectivity is not high, stability is poor.There is provided a kind of catalyst reacted for benzene, methanol alkylation, when the catalyst is used for benzene, methanol alkylation and reacts, with benzene high conversion rate, toluene, dimethylbenzene selective are high, the characteristics of good stability.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of catalyst reacted for benzene, methanol alkylation, by percentage to the quality：Including silica alumina ratio（SiO2/Al2O3）For 200-1000 the HZSM-5 molecular sieve 60-90% through appropriate alkali process and acid treatment, binding agent γ-Al2O3
10-40%, oxide carried amount are 1-15%.
In above-mentioned technical proposal, HZSM-5 molecular sieve silica alumina ratios（SiO2/Al2O3）Preferred scope be 200-500, by percentage to the quality：HZSM-5 molecular sieve consumptions preferred scope is 65-80%；Oxide preferred MgO, NiO, P of load2O5、CeO2In one or more, its load capacity preferred scope be 0.3%-10%；Binding agent γ-Al2O3Preferred scope be 20-35%.The preferred NaOH or KOH and NaAlO of alkali used by alkali process2、KAlO2Mixture, NaOH or KOH preferred concentrations be 0.1-0.5mol/L, NaAlO2Or KAlO2Preferred concentration is 0.005- 0.1mol/L, and the preferred 20-30 of liquid-solid ratio, number of processes be preferred 1-3 time, and the preferred 20-60min of process time, treatment temperature are preferred 50-90 DEG C.Sour optimization citric acid, oxalic acid, phosphoric acid or its mixing used by acid treatment, preferred concentration is 0.1-5mol/L, and number of processes is preferred 1-2 time, and the preferred 45-180min of process time, treatment temperature are preferred 60-90 DEG C.
The preparation method of catalyst of the present invention is as follows.
The alkali process of HZSM-5 molecular sieves and acid treatment：Molecular sieve uses alkaline solution treatment one or many first, after 120 DEG C are dried 5-12h, then acid treatment one or many, after 120 DEG C are dried 5-12h, in 450-600 DEG C of roasting 3-6h, that is, the HZSM-5 molecular sieves after processing needed for obtaining.
Catalyst preparation：It is active main body through the HZSM-5 molecular sieves of alkali process and acid treatment, adds binding agent, mix homogeneously, extruded moulding.Binding agent is γ-Al2O3, the 10-40% of catalyst gross mass is accounted for, nitric acid, Alumina gel or the Ludox that 4-30% is added in forming process is extrusion aid.After shaping of catalyst, load oxide is modified, and the predecessor of oxide used nitrate or acylate for respective metal, the method for introducing can adopt ion exchange, infusion process or mechanical mixing.Catalyst needed for drying, roasting are obtained.
The present invention by carrying out appropriate alkali process and acid treatment to HZSM-5 molecular sieves, and introduce oxide and be modified.In mass space velocity 2-60h-1, reaction temperature 400-500 DEG C, reaction pressure 0.1-0.5MPa, benzene and methanol molar ratio 0.5-2.0, carrier gas N2Benzene, the examination of methanol alkylation catalysts are carried out under conditions of flow 50ml/min.As shown by data, HZSM-5 molecular sieve Jing appropriate alkali process and acid treatment are modified, and load oxide, are remarkably improved the activity and selectivity of catalyst, and the catalyst can keep good stability, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Description of the drawings
Fig. 1 is catalyst n study on the stability figure.
Specific embodiment
【Embodiment 1-3】
Take silica alumina ratio（SiO2/Al2O3）For 300 HZSM-5 molecular sieve 30g, with 900ml 0.24mol/LNaOH and 0.012mol/L NaAlO2Mixed solution process 45min under 65 DEG C of water bath condition, 12h is dried Jing after Quench, sucking filtration, then 120min is processed under the conditions of 90 DEG C with 900ml 1.0mol/L phosphoric acid, citric acid, oxalic acid solution respectively, after Quench, sucking filtration, be dried 12h, 540 DEG C of roasting 6h.By the HZSM-5 molecular sieves after process and γ-Al2O3By 7:After 3 quality is than mix homogeneously, 10% dust technology kneading, extruded moulding is added after 120 DEG C are dried 10h, strip catalyst to be screened out the granule of 20 ~ 40 mesh, then 540 DEG C of roasting 6h of Jing.The difference of acid according to used by acid treatment, obtains Jing phosphoric acid, citric acid, catalyst A, B, C of oxalic acid treatment respectively.
【Embodiment 4】
Take silica alumina ratio（SiO2/Al2O3）For 300 HZSM-5 molecular sieve 30g, with 600ml 0.20mol/L NaOH and 0.01mol/L NaAlO2Mixed solution process 45min under 80 DEG C of water bath condition, be dried 12h Jing after Quench, sucking filtration, then process 130min under the conditions of 65 DEG C with 600ml 0.2mol/LHCl, Quench, 120 DEG C are dried 10h, 540 DEG C of roasting 5h.By the HZSM-5 molecular sieves after roasting and γ-Al2O3By 7:After 3 quality is than mix homogeneously, 4% nitric acid kneading, extruded moulding is added after being dried, after screening out the granule of 20 ~ 40 mesh, then 540 DEG C of roasting 6h, to obtain catalyst D.
【Embodiment 5】
Take silica alumina ratio（SiO2/Al2O3）For 300 HZSM-5 molecular sieve 30g, with 600ml 0.24mol/L NaOH and 0.012mol/L NaAlO2Mixed solution process 45min under 65 DEG C of water bath condition, 12h is dried Jing after Quench, sucking filtration, is then reprocessed 1 time with same method.120min, Quench, drying, roasting are processed under the conditions of 90 DEG C with 600ml 1.0mol/L citric acid solutions again after 2nd alkali process.By the HZSM-5 molecular sieves after roasting and γ-Al2O3By 7:After 3 quality is than mix homogeneously, 4% dust technology kneading, extruded moulding is added after being dried, after screening out the granule of 20 ~ 40 mesh, then 540 DEG C of roasting 6h, to obtain catalyst E.
【Embodiment 6】
Take silica alumina ratio（SiO2/Al2O3）For 300 HZSM-5 molecular sieve 30g, with 600ml 0.24mol/L NaOH and 0.012mol/L NaAlO2Mixed solution process 20min under 65 DEG C of water bath condition, 12h is dried Jing after Quench, sucking filtration, is then reprocessed 2 times with same method.120min, Quench, drying, roasting are processed under the conditions of 90 DEG C with 600ml 1.0mol/L citric acid solutions again after 3rd alkali process.By the HZSM-5 molecular sieves after roasting and γ-Al2O3By 7:After 3 quality is than mix homogeneously, 4% dust technology kneading, extruded moulding is added after being dried, after screening out the granule of 20 ~ 40 mesh, then 540 DEG C of roasting 6h, to obtain catalyst F.
【Embodiment 7】
Take silica alumina ratio（SiO2/Al2O3）For 300 HZSM-5 molecular sieve 30g, with 600ml 0.20mol/L NaOH and 0.01mol/L NaAlO2Mixed solution process 20min under 80 DEG C of water bath condition, 10h is dried Jing after Quench, sucking filtration, is then reprocessed 2 times with same method.120min, Quench, drying, roasting are processed under the conditions of 90 DEG C with 600ml 1.0mol/L citric acids again after 3rd alkali process.By the HZSM-5 molecular sieves after roasting and γ-Al2O3By 7:After 3 quality is than mix homogeneously, 4% dust technology kneading, extruded moulding is added after being dried, after screening out the granule of 20 ~ 40 mesh, then 540 DEG C of roasting 6h, to obtain catalyst G.
【Embodiment 8】
Take silica alumina ratio（SiO2/Al2O3）For 400 HZSM-5 molecular sieve 30g, with 900ml 0.24mol/LNaOH and 0.012mol/L NaAlO2Mixed solution process 45min under 65 DEG C of water bath condition, 12h is dried Jing after Quench, sucking filtration, then again with above method process 1 time.120min, Quench, drying, roasting are processed under the conditions of 90 DEG C with 900ml 1.0mol/L oxalic acid solutions again after 2nd alkali process.By the HZSM-5 molecular sieves after roasting and γ-Al2O3By 7:After 3 quality is than mix homogeneously, 4% dust technology kneading, extruded moulding is added after being dried, after screening out the granule of 20 ~ 40 mesh, then 540 DEG C of roasting 6h, to obtain catalyst H.
【Embodiment 9】
Take silica alumina ratio（SiO2/Al2O3）For 300 HZSM-5 molecular sieve 30g, with 900ml 0.24mol/L NaOH and 0.012mol/L NaAlO2Mixed solution process 2 times.120min, Quench, drying, roasting are processed under the conditions of 90 DEG C with 900ml 1.0mol/L phosphoric acid solutions again after 2nd alkali process.By the HZSM-5 molecular sieves after roasting and γ-Al2O3By 7:After 3 quality is than mix homogeneously, 4% dust technology kneading, extruded moulding is added after being dried, after screening out the granule of 20 ~ 40 mesh, then 540 DEG C of roasting 6h, to obtain catalyst I.
【Embodiment 10-18】
Take 10g catalyst A-I respectively, incipient impregnation 3.2g magnesium acetates, after dipping 24h, 120 DEG C are dried 12h, 540 DEG C of roasting 6h.6%MgO has been loaded on A-I catalyst, catalyst J-R has been obtained in order.
【Embodiment 19】
Catalyst A-I is carried out benzene, methanol alkylation activity and selectivity on fixed bed reaction evaluating apparatus to check and rate.Loaded catalyst is 2.5g, mass space velocity 8h-1, 450 DEG C of reaction temperature, reaction pressure 0.2MPa, nitrogen flow are 50ml/min, and benzene is 1.0 with methanol molar ratio.
Reaction result is listed in table 1.Wherein silica alumina ratio（SiO2/Al2O3）HZSM-5 molecular screen primary powders for 300 are designated as YF.
The conversion ratio X of benzene（B）, toluene, overall selectivity S of dimethylbenzene（TX）With total recovery Y（TX）, and the selectivity S of toluene（T）, dimethylbenzene selectivity S（X）.Their computational methods difference is as follows：
(1)
(2)
(3)
(4)
(5)
M in formula：The molal quantity of benzene in feedstock；
N：The molal quantity of benzene homologues in product；
P：The molal quantity of toluene in product；
Q：The molal quantity of dimethylbenzene in product.
Table
1
Catalyst
A-I
Reaction result
【Embodiment 20】
Catalyst J-R is carried out benzene, methanol alkylation activity and selectivity on fixed bed reaction evaluating apparatus to check and rate.Loaded catalyst is 2.5g, mass space velocity 8h-1, 450 DEG C of reaction temperature, reaction pressure 0.2MPa, nitrogen flow are 50ml/min, and benzene is 1.0 with methanol molar ratio.
Reaction result is listed in table 2.
Table
2
Catalyst
J-R
Reaction result
【Embodiment 21】
Life-span investigation is carried out on fixed bed reaction evaluating apparatus to catalyst n, loaded catalyst is 2.5g, mass space velocity 8h-1, 450 DEG C of reaction temperature, reaction pressure 0.2MPa, nitrogen flow are 50ml/min, and benzene, methanol molar ratio are 1.0.
Experimental result is as shown in Figure 1：
Catalyst life experiment in 200 hours shows that the catalyst stability is good, and the average conversion of benzene reaches 53%, and the average overall selectivity of toluene, dimethylbenzene reaches 92.50%.It is low that the catalyst successfully solves benzene, methanol alkylation catalyst benzene conversion ratio, the shortcoming that toluene, dimethylbenzene selective be not high and stability is poor, thus with good industrial application value.
Claims (8)
1. a kind of for benzene, the catalyst of methanol alkylation reaction, with HZSM-5 molecular sieves as active main body, Jing appropriate alkali process and acid treatment are modified for the catalyst, and with γ-Al2O3For binding agent, load one or more oxides and constituted, by percentage to the quality, the catalyst includes the alkali process of 60-90% and the HZSM-5 molecular sieves after acid treatment, and binding agent 10-40 %, the oxide for being loaded account for the 1-15 % of catalyst gross mass.
2. it is according to claim 1 for benzene, the catalyst of methanol alkylation reaction, it is characterised in that with silica alumina ratio (SiO2/Al2O3) be alkali process and acid treatment object for the HZSM-5 molecular sieves of 200-1000, first after Jing appropriate alkali process and acid treatment, as the active carrier that benzene, methanol alkylation react, by percentage to the quality, the consumption of HZSM-5 is 60-90%.
3. according to claim 1,2 for benzene, methanol alkylation react catalyst, it is characterised in that the alkali used by alkali process be NaOH, KOH, NaAlO2、KAlO2Deng one or more, concentration is 0.1-5mol/L.
4. according to claim 1,2 for benzene, methanol alkylation react catalyst, it is characterised in that the acid used by acid treatment be HCl, HNO3, oxalic acid, citric acid, tartaric acid, acetic acid, one or more of phosphoric acid etc., concentration is 0.1-5mol/L.
5. it is according to claim 1 for benzene, the catalyst of methanol alkylation reaction, it is characterised in that the oxide for being loaded is MgO, MoO3、P2O5、NiO、SiO2、CeO2Deng one or more, load predecessor used is corresponding nitrate or acylate, and load capacity is 1-15wt%.
6. the catalyst reacted for benzene, methanol alkylation according to claim 1,2,4,5, it is characterised in that the number of times of alkali process and acid treatment is for 1 time or repeatedly.
7. according to claim 1,2,4,5 for benzene, methanol alkylation react catalyst, it is characterised in that the time of alkali process be 10-200min, treatment temperature be 20-100 DEG C；The time of acid treatment is 30-600min, and treatment temperature is 20-100 DEG C.
8. according to claim 1,2,4,5 for benzene, methanol alkylation react catalyst, it is characterised in that the liquid-solid ratio used by alkali process and acid treatment（Amount ml/g of alkali or acid used by sieve per mole is processed）For 5-60.
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| CN106966853A (en) * | 2017-05-24 | 2017-07-21 | 兰州理工大学 | A kind of method that benzene prepares toluene with methanol alkylation |
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Inventor after: Xu Yarong Inventor after: Zhao Yanmao Inventor after: Liu Minghui Inventor after: Yang Fan Inventor after: Cao Qingsheng Inventor after: Zhou Zhuo Inventor after: Wang Meng Inventor after: Zhu Xuedong Inventor after: Feng Limei Inventor after: Wen Zhenhao Inventor after: He Xuan Inventor after: Yang Daqiang Inventor after: Wei Zhenhao Inventor after: Xia Tengfei Inventor after: Zhong Jie Inventor before: Zhu Xuedong Inventor before: Yang Fan Inventor before: Cao Qingsheng Inventor before: Zhou Zhuo Inventor before: Wang Meng Inventor before: Wen Zhenhao Inventor before: He Xuan Inventor before: Yang Daqiang Inventor before: Wei Zhenhao Inventor before: Xia Tengfei Inventor before: Zhong Jie Inventor before: Zhao Yanmao Inventor before: Liu Minghui |