CN105521790A - Method for pre-treating low-carbon alkane dehydrogenation catalyst - Google Patents

Method for pre-treating low-carbon alkane dehydrogenation catalyst Download PDF

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Publication number
CN105521790A
CN105521790A CN201410563690.1A CN201410563690A CN105521790A CN 105521790 A CN105521790 A CN 105521790A CN 201410563690 A CN201410563690 A CN 201410563690A CN 105521790 A CN105521790 A CN 105521790A
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catalyst
dehydrogenation
accordance
temperature
dry zone
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CN105521790B (en
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王振宇
张海娟
李江红
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a method for pre-treating a low-carbon alkane dehydrogenation catalyst. The method comprises the following steps: 1) mass water absorption rate of a finished product Cr-series dehydrogenation catalyst is determined, water absorption is carried out on the catalyst for saturation; 2) semi-dry dehydration of the Cr-series dehydrogenation catalyst after water absorption for saturation is carried out to obtain the catalyst processed by semi-drying; and 3) the catalyst obtained in the step 2) is impregnated by an estersil-containing organic solvent, then is heated and dried through a program, then is calcinated to obtain the low-carbon alkane dehydrogenation catalyst. The processed catalyst has high mechanical strength, and has good conversion rate and selectivity used for a dehydrogenation reaction, the preparation method is simple, and the method is adapted to industrial application.

Description

A kind of preprocess method of catalyst for dehydrogenation of low-carbon paraffin
Technical field
The present invention relates to a kind of preprocess method of catalyst for dehydrogenation of low-carbon paraffin.
Background technology
The exploitation of North America shale gas has caused Gas Prices declining to a great extent relative to crude oil price, and condensed liquids a large amount of in shale gas (NGLs) output also increases rapidly.Be rich in the low-carbon alkanes such as ethane, propane, butane in shale gas condensed liquid, ethane can produce ethene as cracking stock, therefore only can not the demand that increases fast of propylene by FCC technology.The effective way addressed this problem by the dehydrogenating low-carbon alkane preparing low-carbon olefins in natural gas (conventional gas, shale gas, coal bed gas, combustible ice etc.).And day by day deficient along with petroleum resources, the production of propylene has been that raw material changes to the diversified technology path of raw material sources from the simple oil that relies on, also becomes a kind of trend gradually.In recent years, the technology that dehydrogenating propane produces propylene achieved large development, and particularly the technical development of dehydrogenating propane (PDH) propylene processed is very fast, has become the third-largest propylene production.
At present, dehydrogenating low-carbon alkane technology mainly comprises: anaerobic dehydrogenation and the large class of aerobic dehydrogenation two.Again based on Pt system noble metal dehydrogenation technology and Cr system De-hydrogen Technology in anaerobic dehydrogenation technology.Anaerobic dehydrogenation technology main in the world comprises: the Oleflex technique of Uop Inc., the Catofin technique of ABB Lu Musi company, the Star technique of Kang Fei (Uhde) company, the FBD-4 technique of Snamprogetti/Yarsintz company, the PDH technique etc. of Lin De/BASF AG.The leading technology adopted in new device has wherein been become with Catofin and Oleflex technique.Catalyst used in Oleflex technique is Pt system noble metal catalyst, and catalyst used in Catafin technique is Cr system dehydrogenation.Aerobic De-hydrogen Technology there is no industrialization example.
In anaerobic dehydrogenation field, Pt and Cr is as the dehydrogenation active component of generally acknowledging, studied for many years by countries in the world, the selection of its co catalysis component is also studied widely.Current research shows, Cr system dehydrogenation relative Pt system dehydrogenation, has higher dehydrogenation activity and low production cost, but less stable.And in the industrial production, mechanical strength and the wearability of the Cr system dehydrogenation being carrier with ball-type activated alumina are poor, a large amount of dust containing poisonous Cr species can be produced when reactor handling catalyst, contaminated environment and infringement health.
CN86104031A discloses the preparation method of a kind of Cr system dehydrogenation, by the solution impregnation of aluminium oxide chromium and potassium compound, with silicon compound solution dipping after drying, obtains a kind of dehydrogenation, this catalyst S iO 2content is 0.5% ~ 3%.Patent CN98117808.1 discloses a kind of dehydrogenation containing Cr, Sn, alkali metal and Si, SiO 2content is 0.08% ~ 3%.
Above-mentioned public technology load SiO 2obtain by silicon compound solution direct impregnation catalyst body.With organic solvent, estersil is dissolved, then adopt chemical vapour deposition technique (CVD) or chemical liquid deposition (CLD) to be a kind of effective way eliminating catalyst external surface acid site and meticulous modulation molecular sieve aperture size by the silicon dioxide carried method at catalyst surface (silanization), be commonly used in shape selective catalysis field.But molecular sieve catalyst is poromerics, and aperture is less than estersil molecular diameter, therefore estersil molecule cannot enter in molecular sieve pore passage, can only the Acidity of modulation molecular sieve outer surface.And aluminium oxide is mesoporous material, aperture is comparatively large, and estersil molecule can enter in aluminium oxide duct, stays the SiO in duct after roasting 2not only change duct internal structure, and can have an impact to the main co catalysis component of load, even block secondary duct, make the active component in secondary duct contact with reactant and to carry out catalytic reaction.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of pretreatment preparation method of catalyst for dehydrogenation of low-carbon paraffin, the catalytic mechanical intensity after the inventive method process is high, for the conversion ratio of dehydrogenation reaction and selective good, preparation method is simple, is suitable for commercial Application.
The preprocess method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, comprises following content:
(1) measure the quality water absorption rate of Cr system dehydrogenation, and catalyst water suction is reached capacity;
(2) water saturated for suction Cr system dehydrogenation is carried out partial desiccation dehydration, obtain the catalyst of partial desiccation process; (3), the catalyst obtained by the organic solvent solution impregnation steps (2) containing estersil, then dry through temperature programming, roasting, obtains catalyst for dehydrogenation of low-carbon paraffin.
In the inventive method, Cr system dehydrogenation described in step (1) is known for those skilled in the art, commercially available finished catalyst can be adopted or conventionally prepare, Cr system dehydrogenation general with activated alumina or pretreated activated alumina for carrier, Cr is active component, and one or more in K, Mn, Fe, Co, Ni, Cu, Zn and Ga are auxiliary agent.
In the inventive method, the partial desiccation dehydration described in step (2) is as follows: catalyst evenly tiles with on dry zone, and catalyst tiling thickness is 3 ~ 4cm, and dry zone transmission speed is 30 ~ 70m/h, preferably 45 ~ 60m/h, and dry zone length is 30 ~ 50m; Baking temperature is 120 ~ 160 DEG C, preferably 140 ~ 155 DEG C.Described dry zone is Multi-layer belt type drying machine, is the continuous chain-belt drying equipment that batch production catalyst uses.
In the inventive method, the estersil described in step (3) is one or more in methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate or many alkyl silicone grease etc.
In the inventive method, the organic solvent described in step (3) is one or more in cyclohexane, cyclohexanone or hexane etc., preferred cyclohexane.
In the inventive method, in step (3), in organic solvent, the concentration of estersil is 0.0001g/ml ~ 0.01g/ml;
In the inventive method, the dipping volume ratio of step (3) organic solvent and partial desiccation catalyst is 1:1 ~ 3:1; Dip time is 1 ~ 24 hour, preferably 3 ~ 18 hours, generally adopts normal temperature dipping;
In the inventive method, step (3) temperature programming drying steps is: by room temperature with ramp to 80 ~ 130 of 0.5 ~ 5 DEG C/min DEG C and constant temperature 2 ~ 10 hours, then with ramp to 160 ~ 200 of 0.5 ~ 5 DEG C/min DEG C and constant temperature 2 ~ 5 hours; Sintering temperature is 400 ~ 800 DEG C, is preferably 500 ~ 700 DEG C; Roasting time 2 ~ 12 hours, is preferably 4 ~ 8 hours.
Catalyst application of the present invention reacts in dehydrogenating low-carbon alkane, and general process conditions are: reaction temperature is 550 ~ 650 DEG C, and pressure is generally normal pressure or negative pressure, and air speed is 100 ~ 3000h -1.
Because estersil molecular diameter is greater than the aperture of molecular sieve, thus cannot enter in molecular sieve pore passage, can only decorating molecule sieve outer surface.Therefore silanization is a kind of effective way eliminating molecular sieve catalyst outer surface acid site and meticulous modulation molecular sieve aperture size, is commonly used in shape selective catalysis field.But because the aperture of aluminium oxide is comparatively large, estersil molecule can enter in aluminium oxide duct, changes the character of active component and co catalysis component in hole.In the inventive method, adopt the method for pre-water suction that the dehydrogenation water suction of finished product Cr system is reached capacity, and through partial desiccation operation, the moisture of removing catalyst external surface, retain the moisture in catalyst duct.Then the appropriate estersil of the organic solvent dissolution do not dissolved each other with water is used, as cyclohexane.And flood semiarid catalyst, make estersil evenly be wrapped in the outer surface of catalyst, but cannot enter in duct.And roasting dry through temperature programming, obtains the Cr system dehydrogenation of outer surface load silica again.Through the catalyst surface smooth abrasion-proof of this process, mechanical strength improves greatly.Because the main cocatalyst component in catalyst duct is uninfluenced, therefore the dehydrogenation of catalyst changes hardly.The use of temperature programming drying is for the ease of reclaiming and recycling organic solvent, as cyclohexane.
Detailed description of the invention
Describe technical scheme of the present invention in detail below in conjunction with embodiment, but the invention is not restricted to following examples.
The method measuring water absorption rate in the inventive method is: take 10g finished product Cr series catalysts, is placed in dry beaker.Add appropriate amount of deionized water, start timing simultaneously, be separated with water with the sample of sub-sieve by water suction after 24h, weigh and calculated mass water absorption rate.Computing formula is as follows: W water absorption rate=(m b-m g)/m b× 100%, wherein m gthe quality before sample water suction, m bit is the quality after sample water suction.
embodiment 1
Catalyst absorbs water in advance: the water absorption rate measuring finished product Cr system dehydrogenation is 62.3%.This catalyst of 10kg is dipped in 6.23kg deionized water, makes it absorb water and reach capacity.
Catalyst partial desiccation: the catalyst reached capacity evenly is laid on dry zone by absorbing water, and thickness is 3.5cm, and controlling dry zone transmission speed is 55m/h, and baking temperature is 150 DEG C, at the uniform velocity by the dry zone of 40m length.
Silanization: 0.2kg ethyl orthosilicate is dissolved in 10L cyclohexane, and with the semiarid catalyst of this solution normal temperature dipping.Dip time is 14h.Then temperature programming drying is carried out: by the ramp to 120 DEG C of room temperature 1 DEG C/min and constant temperature 5h, then with the ramp to 180 of 0.5 DEG C/min DEG C and constant temperature 3h; Then 600 DEG C of roasting 6h.Obtain final catalyst.
In this catalyst, each element oxide accounts for catalyst gross mass percentage and is: Cr 2o 3be 15%, K 2o is 1%, CuO is 4%, Ga 2o 3be 1%, SiO 2be 0.58%.This catalyst is denoted as A.
comparative example 1
With finished product Cr system dehydrogenation for contrast medium, wherein each element oxide accounts for catalyst gross mass percentage and is: Cr 2o 3be 15%, K 2o is 1%, CuO is 4%, Ga 2o 3be 1%, SiO 2be 0.58%.This catalyst is denoted as B1.
comparative example 2
According to the method Kaolinite Preparation of Catalyst that patent CN86104031A discloses.This catalyst is denoted as B2.
comparative example 3
According to the method Kaolinite Preparation of Catalyst that patent CN98117808.1 discloses.This catalyst is denoted as B3.
embodiment 2
The pre-water absorption course of catalyst is with embodiment 1.
Catalyst partial desiccation: the catalyst reached capacity evenly is laid on dry zone by absorbing water, and thickness is 4cm, and controlling dry zone transmission speed is 50m/h, and baking temperature is 160 DEG C, at the uniform velocity by the dry zone of 40m length.
Silanization: 0.07kg ethyl orthosilicate is dissolved in 13L cyclohexane, and with the semiarid catalyst of this solution normal temperature dipping.Dip time is 14h.Then temperature programming drying is carried out: by the ramp to 120 DEG C of room temperature 0.5 DEG C/min and constant temperature 6h, then with the ramp to 180 of 1.5 DEG C/min DEG C and constant temperature 4h; Then 650 DEG C of roasting 6h.Obtain final catalyst.
In this catalyst, each element oxide accounts for catalyst gross mass percentage and is: Cr 2o 3be 15%, Ce 2o 3be 2%, La 2o 3be 2%, SiO 2be 0.21%.This catalyst is denoted as C.
Appreciation condition: catalyst volume 6.0ml, volume space velocity is 1000h -1, reaction pressure normal pressure, reaction temperature is 600 DEG C.Evaluating catalyst result (propane one way molar yield, Propylene Selectivity, mechanical strength and abrasion) lists in table 1.
Table 1 evaluating catalyst result.

Claims (9)

1. a preprocess method for catalyst for dehydrogenation of low-carbon paraffin, comprises following content: (1) measures the quality water absorption rate of Cr system dehydrogenation, and catalyst water suction is reached capacity; (2) water saturated for suction Cr system dehydrogenation is carried out partial desiccation dehydration, obtain the catalyst of partial desiccation process; (3) with the catalyst that the organic solvent solution impregnation steps (2) containing estersil obtains, then dry through temperature programming, roasting, obtains catalyst for dehydrogenation of low-carbon paraffin.
2. in accordance with the method for claim 1, it is characterized in that: the partial desiccation dehydration described in step (2) is as follows: catalyst evenly tiles with on dry zone, catalyst tiling thickness is 3 ~ 4cm, dry zone transmission speed is 30 ~ 70m/h, dry zone length is 30 ~ 50m, and baking temperature is 120 ~ 160 DEG C.
3. according to the method described in claim 1 or 2, it is characterized in that: the partial desiccation dehydration described in step (2) is as follows: catalyst evenly tiles with on dry zone, catalyst tiling thickness is 3 ~ 4cm, dry zone transmission speed is 45 ~ 60m/h, dry zone length is 30 ~ 50m, and baking temperature is 140 ~ 155 DEG C.
4. in accordance with the method for claim 1, it is characterized in that: the estersil described in step (3) is one or more in methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate or many alkyl silicone grease.
5. in accordance with the method for claim 1, it is characterized in that: the organic solvent described in step (3) is one or more in cyclohexane, cyclohexanone or hexane.
6. in accordance with the method for claim 1, it is characterized in that: in step (3), in organic solvent, the concentration of estersil is 0.0001g/ml ~ 0.01g/ml.
7. in accordance with the method for claim 1, it is characterized in that: the dipping volume ratio of step (3) organic solvent and partial desiccation catalyst is 1:1 ~ 3:1, and dip time is 1 ~ 24 hour.
8. in accordance with the method for claim 1, it is characterized in that: step (3) temperature programming drying steps is: by room temperature with ramp to 80 ~ 130 of 0.5 ~ 5 DEG C/min DEG C and constant temperature 2 ~ 10 hours, then with ramp to 160 ~ 200 of 0.5 ~ 5 DEG C/min DEG C and constant temperature 2 ~ 5 hours.
9. in accordance with the method for claim 1, it is characterized in that: the sintering temperature described in step (3) is 400 ~ 800 DEG C, roasting time 2 ~ 12 hours.
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Cited By (1)

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CN108144655A (en) * 2017-12-27 2018-06-12 北京华福工程有限公司 Produce the preparation method and purposes of aromatic hydrocarbons ceramic honeycomb body

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Publication number Priority date Publication date Assignee Title
CN108144655A (en) * 2017-12-27 2018-06-12 北京华福工程有限公司 Produce the preparation method and purposes of aromatic hydrocarbons ceramic honeycomb body
CN108144655B (en) * 2017-12-27 2020-12-22 北京华福工程有限公司 Method for producing ceramic honeycomb bodies for aromatic hydrocarbons and use thereof

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