CN102895990A - Light hydrocarbon aromatization catalyst and preparation method thereof - Google Patents
Light hydrocarbon aromatization catalyst and preparation method thereof Download PDFInfo
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- CN102895990A CN102895990A CN2011102152039A CN201110215203A CN102895990A CN 102895990 A CN102895990 A CN 102895990A CN 2011102152039 A CN2011102152039 A CN 2011102152039A CN 201110215203 A CN201110215203 A CN 201110215203A CN 102895990 A CN102895990 A CN 102895990A
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Abstract
The invention relates to a preparation method of a catalyst capable of transferring by-product light hydrocarbons of refinery plants into aromatic hydrocarbons or gasoline components. The active centers of the catalyst are composed of an HZSM-5 molecular sieve loaded with zinc and one of nickel, ferrum, chromium, manganese and cobalt; the loading mode of the active metals is a solid state ion exchange method; the content of zinc is 0.5 wt%-10 wt%; and the content of a second metal is 0.1 wt%-5 wt%. The catalyst has relatively high selectivity for BTX; the liquid yield can reach 68.64%; the selectivity for BTX can reach 58.28%; the liquid yield of the aromatization reaction of the catalyst is increased by 18.27%; and selectivity is increased by 18.11%. The metal loading mode employed by the method is the solid state ion exchange method, so that the metal is not easy to lose. The pore channels of the molecular sieve are unblocked via acid treatment, so that the anti-coking performance of the catalyst is improved; and the stability of the catalyst can reach longer than 120 h.
Description
Technical field:
The present invention relates to a kind of aromatizing catalyst for light hydrocarbon and preparation method.
Background technology:
In petrochemical production process, often understand the C such as by-product refinery gas, oil liquefied gas
1～C
6The low-carbon alkene components such as one-component can be converted into aromatic hydrocarbons take these low-carbon alkenes as raw material through catalytic reaction.Aromatic hydrocarbons is the important foundation raw material of petrochemical industry, sum approximately oneself of 8,000,000 kinds know in the organic compound, aromatic compound has accounted for approximately 30%, wherein BTX aromatic hydrocarbons (benzene,toluene,xylene) is called as the one-level basic organic.BTX aromatic hydrocarbons is mainly from catalytic reforming, Pintsch process ethylene by-product processed, coal processing by-product, the light hydrocarbon aromatisation, conversions between the aromatic hydrocarbons etc. because aromatic hydrocarbons and derivative thereof are important industrial chemicals and the intermediates of producing polyester, plastics, agricultural chemicals, dyestuff, also can be used as the blend component of gasoline.
In order to obtain the new source of aromatic hydrocarbons, the light-hydrocarbon aromatized research of recent domestic enlivens gradually, and this conversion has higher economic worth, day by day obtains people's attention, has become the important subject that current people pay close attention to.Many companies competitively develop this class technique in the world, develop jointly with C such as Uop Inc. of BP company
3～C
4Hydrocarbon or liquefied petroleum gas are the CYCLAR technique of raw material, Inst Francais Du Petrole and the exploitation of Salutec company
Aroforming technology etc., these techniques have mainly adopted the modified with noble metals molecular sieve catalysts such as Pt, Ga.Although these catalyst have high activity, long-life advantage, because this catalyst cost is higher, so do not obtain extensive use.
Domestic research and development to light-hydrocarbon aromatized technique also started from for 20th century, the disclosed aromatized catalyst of Chinese patent CN1069906A, CN106999A all is the ZSM-5 carried noble metal (Pt), VII transition metal of micron and the catalyst of a small amount of nonmetalloid, is mainly used in C
8～C
9Aromatisation, alkane conversion reaches 88%, and arenes selectivity is 45.6%.
Chinese patent CN1583266 discloses a kind of aromatized catalyst for transforming methane and propane, its preparation method is a kind of in zinc supported and chromium, manganese, iron, cobalt, nickel, copper, silver, platinum, molybdenum, the tungsten on HZSM-5, infusion process prepares load type bimetal catalyst, and aromatics yield is 50%～60%.
Chinese patent CN1341699A discloses zinc supported and nickel on HZSM-5, and infusion process prepares loaded catalyst, is the Zn-Ni-ZSM-5 zeolite.When mixing carbon four in fixed bed reactors, 500 ℃ of temperature, pressure 0.5～1MPa, WHSV are 1.0～1.5h
-1, when charging was reacted under the condition, liquid was received and is 60.37wt% when reacting 40 hours, and total arenes yield is 57.30wt%; Reacted 120 hours, liquid is incorporated to 47.80wt%, and total arenes yield is down to 45.34wt%.
Chinese patent CN1586721A discloses and has adopted 10～500 nanometer silica-rich zeolite, processes through steam treatment, sour reaming, obtains the carbon 4 liquid gas aromatization catalyst, aromatics yield 34%～48%.
Chinese patent CN101108364A discloses on nanometer HZSM-5 a kind of in zinc supported and thulium, europium, the erbium, and infusion process prepares aromatized catalyst, transforms n-hexane, and aromatics yield reaches 50%～57%.
It is molecular sieve molded that Chinese patent CN101530813A discloses preparation method's rare earth-ZSM-5/ZSM-11 cocrystallization, and after alkali lye, steam treatment, zinc supported obtains aromatized catalyst, catalyzed conversion carbon 4 liquid gas, aromatics yield 30%～45%.
In sum, the aromatized catalyst emphasis of prior art preparation mainly concentrates on the ZSM-5 molecular sieve with highly acid and better duct Shape-selective, but because its acidity is stronger, carbon distribution is serious, the stability of catalyst is restricted, can improve activity and selectivity to its modification, but how therefore the shortcoming that have all that metal component easily runs off, service life is long improve the aromatization activity of ZSM-5 molecular sieve catalyst, selective and service life and be the from now on developing direction of aromatizing catalyst for light hydrocarbon.
Summary of the invention:
The purpose of this invention is to provide molecular sieve catalyst of a kind of light dydrocarbon aromatization reaction and preparation method thereof, by catalyst of the present invention, can be the aromatic hydrocarbons such as benzene,toluene,xylene (BTX) with hydrocarbon conversions such as liquefied gas, refinery gas, catalyst activity metal component of the present invention be difficult for running off, the catalyst long service life.
The invention provides a kind of molecular sieve catalyst for light dydrocarbon aromatization reaction and preparation method thereof.This catalyst is comprised of molecular sieve, reactive metal, binding agent, extrusion aid etc., each component is by accounting for the molecular sieve mass percent: take the HZSM-5 molecular sieve as carrier, zinc accounts for 0.5～10% of HZSM-5 molecular sieve quality, a kind of HZSM-5 molecular sieve quality 0.1～5% that accounts in nickel, iron, chromium, manganese or the cobalt.The preparation method of this catalyst adopts the mode of loading of solid ionic exchange, with a kind of the loading on the HZSM-5 molecular sieve in zinc and nickel, iron, chromium, the manganese, improves the stability of catalyst; With acid the molecular sieve of load active component is processed again the surface acidity of regulating catalyst and dredging molecular sieve pore passage.After advancing acid treatment, the molecular sieve of modification obtains aromatized catalyst through moulding, drying, roasting.The silica alumina ratio of above-mentioned HZSM-5 molecular sieve is between 25～80.
Preparation method for aromatizing catalyst for light hydrocarbon provided by the invention, concrete steps are:
(1) the former powder of ZSM-5 uses the ammonium nitrate solution of 1mol/L at 100～110 ℃ of lower ion-exchange 3～6h, mother liquor is removed in centrifugation, with deionized water washing 3 times, 100～110 ℃ of lower dryings with at 480～580 ℃ of lower roasting 12～20h, obtain the HZSM-5 molecular sieve;
(2) product with (1) carries out the solid ionic exchange, supported active metal component zinc, and specific practice is: product and the zinc salt that accounts for its mass percent 0.5%～10% of (1) are mixed, at 400～800 ℃ of lower hydrothermal treatment consists 0.5～3h;
(3) product that (2) is obtained carries out the solid ionic exchange, load the second active metal component, specific practice is: with (2) product that obtains and the second slaine that accounts for the HZSM-5 molecular sieve percentage 0.1%～10% that obtains in (1), comprise a kind of in nickel, iron, cobalt, chromium or the manganese, mix, at 400～800 ℃ of lower hydrothermal treatment consists 0.5～3h;
(4) product that (3) is obtained carries out acid treatment, and used inorganic acid is a kind of in sulfuric acid, hydrochloric acid, the nitric acid, and concentration is 0.001～4.0mol/L.Formic acid, acetic acid, citric acid, 0.1～10%.Temperature is 10～70 ℃, static treatment, and the time is 1～20h, and is extremely neutral with the deionized water washing after acid treatment finishes, 100～115 ℃ of lower dry 2～6h;
(5) with the mixing in proportion with aluminium oxide, nitric acid to product of (4), method is routinely carried out compressing tablet or extruded moulding.The mass ratio of molecular sieve and aluminium oxide was advisable between 1: 8 to 8: 1.Zeolite after the moulding is dry 6～12h under 100～110 ℃ temperature, then carries out temperature-programmed calcination at Muffle furnace, and roasting condition is air atmosphere, and 500～600 ℃, 2～12h.
The step 2. compound of middle zinc reactive metal is Zn (NO
3)
2, ZnCl
2, ZnSO
4, Zn (Ac)
2In a kind of.
Step 2. in the temperature of hydrothermal treatment consists between 500～650 ℃, the time is 1～2h;
Step 3. nickel, iron, chromium, manganese or cobalt metal active constituent compound is Fe (NO
3)
3, FeCl
3, Fe
2(SO
4)
3Or Ni (NO
3)
2, NiCl
2, NiSO
4Or Co (NO
3)
2, CoCl
2, CoSO
4Or Gr (NO
3)
3, GrC
l3, Gr
2(SO
4)
3Or Mn (NO
3)
2, MnCl
2, MnSO
4In a kind of.
Step 3. in the temperature of hydrothermal treatment consists between 500～650 ℃, the time is 1～2h;
Step 2., 3. the method for middle hydrothermal treatment consists is: active metal salt and molecular sieve are mixed; the quartz ampoule fixed-bed reactor of packing into, the rising temperature passes into steam heat treatment 1～3h to reaction temperature under nitrogen protection; temperature is 500～650 ℃, and the steam flow is 1～500g/min.
Step 4. in used inorganic acid be a kind of in sulfuric acid, hydrochloric acid, the nitric acid, concentration is 0.001～2.0mol/L; Organic acid is a kind of in formic acid, acetic acid, the citric acid, and concentration is 0.1～10%; Treatment temperature is between 60～70 ℃, and the time is 1～3h.
The evaluation method of catalyst of the present invention is: adopting loaded catalyst is that 5ml fixed bed evaluating apparatus is estimated the activity and selectivity of catalyst.400～600 ℃ of reaction temperatures, reaction pressure 0～5MPa, charging air speed (WSHV) 0.05～10h
-1Can dilute with the silica of appropriate size during loading catalyst.Under blanket of nitrogen, be warmed up to 500 ℃ of activation, then drop to reaction temperature.Product is through cooler condensation gas-liquid separation, and gas and product liquid are all used Varian-3800 gas-chromatography (100mPONA post, flame ionic detector) analysis, and the result adopts normalization to obtain each component composition, and the mark of employing is mass percent.
The effect of invention
Catalyst of the present invention has higher selective to BTX, it is active that the ZSM-5 of Zn modification shows better aromatization, and liquid yield can reach 68.64%, BTX and selectively reach 58.28%.The introducing of the second transition metal ions, the liquid yield that has improved the catalyst aromatization has increased by 18.27%, has selectively increased by 18.11%.Metal Supported mode of the present invention is the solid ionic switching method, and metal is difficult for running off; Adopt the acid treatment mode to dredge molecular sieve pore passage, improve the anti-coking performance of catalyst, the stability of catalyst reaches more than the 120h.The present invention does not use rare Pt metal, Ga, so with low cost.
The specific embodiment
Embodiment 1:
With the former powder of the ZSM-5 of a certain amount of Si:Al=36, carry out ion-exchange 3 times with the ammonium nitrate solution of 1mol/L, wash 2 times, 110 ℃ are lower dry, and 540 ℃ of roasting 4h make the HZSM-5 molecular sieve, grind; Get prepared 20gHZSM-5 molecular sieve powder and account for the Zn (NO that its mass percent is respectively 0.5wt%, 1wt%, 3wt%, 5wt%, 10wt%
3)
2Mix, ratio accounts for the mass percent calculating of molecular sieve by the quality of metallic zinc; With the said mixture quartz ampoule fixed-bed reactor of packing into, rising temperature to 500 ℃ under nitrogen protection is used hydrothermal treatment consists 1h, and the steam flow is 100g/min, changes into the Mass Calculation of water; After the cooling again with the Fe (NO of 2wt%
3)
3Mix with molecular sieve, repeat hydrothermal treatment consists 1h; After the cooling, 60 ℃ lower is that the salpeter solution of 0.5mol/L is processed 2h with 200ml concentration, and the deionized water washing is to neutral, dry 1h under 120 ℃.The molecular sieve that obtains is mixed with the nitric acid of aluminium oxide, an amount of 0.3mol/L, the mass ratio of molecular sieve and aluminium oxide is 6: 4, extrusion, moulding, after the moulding under 110 ℃ temperature dry 12h, then in Muffle furnace with speed program to the 550 ℃ roasting 4h of 3 ℃/min, air atmosphere obtains the catalyst finished product, is denoted as Cat-A, Cat-B, Cat-C, Cat-D, Cat-E.
Embodiment 2:
The comparative example 1, ZSM-5 molecular sieve is replaced by the molecular sieve of Si:Al=50, and the load capacity of Zn is 3wt%, and other conditions are constant, and the catalyst that makes is denoted as Cat-F.
Embodiment 3:
The comparative example 1, with Fe (NO
3)
3Be replaced by Ni (NO
3)
2, Co (NO
3)
2, Gr (NO
3)
3, the load capacity of Zn is 3wt%, and other conditions are constant, and the catalyst that makes is denoted as Cat-G, Cat-H, Cat-I.
Embodiment 4:
With among the embodiment 1 with load Fe (NO
3)
3Step omit, other condition is constant, resulting catalyst is designated as Cat-J.
Embodiment 5:
With Zn (NO among the embodiment 1
3)
2The hydrothermal treatment consists time change 2h into, other condition is constant, resulting catalyst is designated as Cat-K.
Embodiment 6:
Be the Cat-C of 3wt% with the load capacity of Zn among the embodiment 1, react 40,80, under time of 120h.
Table 1 raw material forms
The different evaluating catalyst results that form of table 2
Annotate: reaction condition: 500 ℃, 0.5MPa, WSHV are 1h
-1
The investigation of table 3 catalyst Cat-C stability
Annotate: reaction condition is the same.
Claims (10)
1. aromatizing catalyst for light hydrocarbon, it is characterized in that: this catalyst components is by accounting for HZSM-5 molecular sieve carrier mass percent: zinc accounts for 0.5～10% of HZSM-5 molecular sieve quality, a kind of 0.1～5% of the HZSM-5 molecular sieve quality that accounts in nickel, iron, chromium, manganese or the cobalt.
2. the preparation method of an aromatizing catalyst for light hydrocarbon according to claim 1 is characterized in that:
1. the former powder of ZSM-5 with the ammonium nitrate solution of 0.1～1mol/L 100～110 ℃ of lower ion-exchanges 3 times, each 3～6h, mother liquor is removed in centrifugation, with deionized water washing 3 times, 100～110 ℃ of lower dryings with at 480～580 ℃ of lower roasting 12～20h, obtain the HZSM-5 molecular sieve;
2. the HZSM-5 molecular sieve that 1. step is obtained mixes with the zinc metal active constituent that accounts for its mass percent 0.5～10%, carries out solid ionic exchange 0.5～3h 400～800 ℃ of lower hydrothermal treatment consists;
The product that 3. will 2. obtain mixes with a kind of metal active constituent that accounts in nickel, iron, chromium, manganese or the cobalt of HZSM-5 molecular sieve quality 0.1～5%, carries out solid ionic exchange 0.5～3h 400～800 ℃ of lower hydrothermal treatment consists;
The product that 4. will 3. obtain is processed with organic acid or inorganic acid, and temperature is 10～70 ℃, static treatment, and the time is 1～20h, and is extremely neutral with the deionized water washing after acid treatment finishes, 100～115 ℃ of lower dry 2～6h;
5. will 4. mix in proportion with aluminium oxide, nitric acid to product, method is routinely carried out compressing tablet or extruded moulding, and the mass ratio of molecular sieve and aluminium oxide is between 1: 8～8: 1; Zeolite after the moulding is dry 1～24h under 100～110 ℃ temperature, then carries out temperature-programmed calcination at Muffle furnace, and roasting condition is air atmosphere, and 500～600 ℃, 2～12h.
3. the preparation method of aromatizing catalyst for light hydrocarbon according to claim 2 is characterized in that: step 2. in the compound of zinc reactive metal be Zn (NO
3)
2, ZnCl
2, ZnSO
4, Zn (Ac)
2In a kind of.
4. the preparation method of aromatizing catalyst for light hydrocarbon according to claim 2 is characterized in that: step 2. in the temperature of hydrothermal treatment consists between 500～650 ℃, the time is 1～2h.
5. the preparation method of aromatizing catalyst for light hydrocarbon according to claim 2, it is characterized in that: step 3. nickel, iron, chromium, manganese or cobalt metal active constituent compound is Fe (NO
3)
3, FeCl
3, Fe
2(SO
4)
3Or Ni (NO
3)
2, NiCl
2, NiSO
4Or Co (NO
3)
2, CoCl
2, CoSO
4Or Gr (NO
3)
3, GrCl
3, Gr
2(SO
4)
3Or Mn (NO
3)
2, MnCl
2, MnSO
4In a kind of.
6. the preparation method of aromatizing catalyst for light hydrocarbon according to claim 2 is characterized in that: step 3. in the temperature of hydrothermal treatment consists between 500～650 ℃, the time is 1～2h.
7. the preparation method of aromatizing catalyst for light hydrocarbon according to claim 2; it is characterized in that: step 2., 3. the method for middle hydrothermal treatment consists is: active metal salt and molecular sieve are mixed; the quartz ampoule fixed-bed reactor of packing into; the rising temperature is to reaction temperature under nitrogen protection; pass into steam heat treatment 1～3h; temperature is 500～650 ℃, and the steam flow is 1～500g/min.
8. the preparation method of aromatizing catalyst for light hydrocarbon according to claim 2 is characterized in that: step 4. in used inorganic acid be a kind of in sulfuric acid, hydrochloric acid, the nitric acid, concentration is 0.001～2.0mol/L; Organic acid is a kind of in formic acid, acetic acid, the citric acid, and concentration is 0.1～10%; Treatment temperature is between 60～70 ℃, and the time is 1～3h.
9. the preparation method of aromatizing catalyst for light hydrocarbon according to claim 2, it is characterized in that: step 5. in catalyst dry 6～12h under 110 ℃ temperature after the moulding, then in Muffle furnace with the speed program to 520 of 3 ℃/min～580 ℃, roasting 4～8h in the air atmosphere.
10. the application of an aromatizing catalyst for light hydrocarbon claimed in claim 1, it is characterized in that: be used as the catalyst that the lighter hydrocarbons of refinery's by-product is changed into aromatic hydrocarbons or gasoline component, 400～600 ℃ of reaction temperatures, reaction pressure 0～5MPa, charging air speed (WSHV) 0.05～10h
-1
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801332A (en) * | 2014-01-24 | 2015-07-29 | 上海碧科清洁能源技术有限公司 | Preparation method of catalyst for methanol to aromatics |
| CN107282088A (en) * | 2016-04-01 | 2017-10-24 | 神华集团有限责任公司 | The method of organic oxygen-containing compound olefin hydrocarbon molecules sieve catalyst and preparation method thereof and organic oxygen-containing compound alkene |
| WO2019095986A1 (en) * | 2017-11-15 | 2019-05-23 | 中国科学院大连化学物理研究所 | Method for directly producing aromatic hydrocarbon from synthesis gas |
| CN111715271A (en) * | 2019-03-21 | 2020-09-29 | 中国石油大学(北京) | Aromatization catalyst, preparation method thereof and aromatization method |
| CN112705249A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of catalyst for producing aromatic hydrocarbon, catalyst and application thereof |
| CN114749206A (en) * | 2022-06-13 | 2022-07-15 | 中国科学院山西煤炭化学研究所 | C5-C10 alkane dehydrogenation catalyst and preparation method and application thereof |
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| CN104801332A (en) * | 2014-01-24 | 2015-07-29 | 上海碧科清洁能源技术有限公司 | Preparation method of catalyst for methanol to aromatics |
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| CN107282088A (en) * | 2016-04-01 | 2017-10-24 | 神华集团有限责任公司 | The method of organic oxygen-containing compound olefin hydrocarbon molecules sieve catalyst and preparation method thereof and organic oxygen-containing compound alkene |
| WO2019095986A1 (en) * | 2017-11-15 | 2019-05-23 | 中国科学院大连化学物理研究所 | Method for directly producing aromatic hydrocarbon from synthesis gas |
| US10815162B2 (en) | 2017-11-15 | 2020-10-27 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for directly preparing aromatics from syngas |
| CN111715271A (en) * | 2019-03-21 | 2020-09-29 | 中国石油大学(北京) | Aromatization catalyst, preparation method thereof and aromatization method |
| CN112705249A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of catalyst for producing aromatic hydrocarbon, catalyst and application thereof |
| CN114749206A (en) * | 2022-06-13 | 2022-07-15 | 中国科学院山西煤炭化学研究所 | C5-C10 alkane dehydrogenation catalyst and preparation method and application thereof |
| CN114749206B (en) * | 2022-06-13 | 2022-09-23 | 中国科学院山西煤炭化学研究所 | C5-C10 alkane dehydrogenation catalyst and preparation method and application thereof |
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Application publication date: 20130130 |