CN105536831A - Method for preparing maleic anhydride VPO catalyst through n-butane oxidation method - Google Patents

Method for preparing maleic anhydride VPO catalyst through n-butane oxidation method Download PDF

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Publication number
CN105536831A
CN105536831A CN201510943450.9A CN201510943450A CN105536831A CN 105536831 A CN105536831 A CN 105536831A CN 201510943450 A CN201510943450 A CN 201510943450A CN 105536831 A CN105536831 A CN 105536831A
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catalyst
butane
hours
preparation
molybdenum
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李大鹏
陈国福
祁洪生
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TIANJIN TIANHUAN INSTITUTE OF FINE CHEMICAL
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TIANJIN TIANHUAN INSTITUTE OF FINE CHEMICAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a method for preparing a maleic anhydride VPO catalyst through an n-butane oxidation method. The method is characterized in that catalyst precursor synthesis conditions are optimized, an iron-molybdenum-zirconium catalyst aid is synthesized, a catalyst precursor is added into a catalyst, through stoving, drying, rolling and granulation, the catalyst is molded and catalyst performances are verified through catalyst activation. The invention provides the method for preparing the maleic anhydride VPO catalyst through an n-butane oxidation method. The method has simple processes and optimizes VPO catalyst preparation conditions. Through use of the iron-molybdenum-zirconium catalyst aid and optimization of a ratio of the aid in the catalyst, catalyst activity and selectivity are improved and a butane conversion rate is improved.

Description

A kind of preparation method of n butane oxidation legal system cis-butenedioic anhydride vpo catalyst
Technical field
The present invention relates to catalyst technical field, relate generally to a kind of preparation method of n butane oxidation legal system cis-butenedioic anhydride vpo catalyst.
Background technology
Maleic anhydride (maleicanhydride writes a Chinese character in simplified form MA) is called for short cis-butenedioic anhydride, has another name called maleic anhydride, apple anhydride dehydration.Maleic anhydride system white rhomboid acicular crystal, molecular formula is C 4h 2o 3, molecular weight is 98.058, fusing point 52.8 ~ 60 DEG C, boiling point 202 DEG C, and relative density is 1.314, and flash-point 103 DEG C, easily distils.Cis-butenedioic anhydride is soluble in water, alcohol and ester, is slightly soluble in carbon tetrachloride and raw gasoline.The dust of cis-butenedioic anhydride and steam are all inflammable and explosive, have stimulation to people, and human body skin of burning.
Cis-butenedioic anhydride is a kind of important Organic Chemicals and fine chemical product, the third-largest acid anhydrides being only second to phthalic anhydride and aceticanhydride at present in the world, mainly for the production of unsaturated polyester resin, alkyd resins, for agricultural chemicals, medicine, coating, ink, lube oil additive, papermaking chemical product, textile finish, the field such as food additives and surfactant.In addition, be that raw material can also produce 1 with cis-butenedioic anhydride, 4-butanediol (BOD), gamma-butyrolacton (GBL), oxolane (THF), maleic acid, a series of broad-spectrum fine chemical products such as fumaric acid and tetrahydrochysene acid anhydrides, exploitation prospect is very wide, and its range of application is also in continuous expansion at present.
Divide by raw material along liquor-saturated production process route and mainly contain benzene catalytic oxidation, normal butane catalytic oxidation, C 4olefin catalytic oxidation method wherein benzene, as traditional raw material, has been widely used for producing along liquor-saturated, from the seventies, has caused the rise of benzene price due to rise in oil price; Increasing of unleaded gas consumption and cause the shortage of benzene resource, and benzene method causes environmental pollution serious, along with the rise of Green Chemistry and the breakthrough of other technology, with C 4alkene and normal butane are that raw material production is arisen at the historic moment along the technology of joining, the country of especially rich producing natural gas and associated gas, has a large amount of normal butane resources, and therefore normal butane method development in recent years rapidly, oneself occupies an leading position, and accounts for about 80% of total productive capacity.
Catalyst for preparing cis-anhydride by n-butane oxidation has V-P-O system, V-Mo-O system, Ti-P-O system and M o-P-O is, industrial selective oxidation of n-butane system is vanadium phosphorus oxygen composite oxide catalyst along joining the most effective catalyst, normal butane is as saturated hydrocarbons, its selective partial oxidation not only has great economic implications along joining, and to the selective oxidation of hydro carbons, there is very broad theory meaning, therefore, although the production line with normal butane being raw material is at present own through occupying leading position along joining in production, but the activity of catalyst is lower, need to be improved further the activity and selectivity of catalyst, improve reactivity and selective, increase the conversion ratio of butane.
Summary of the invention
For the problems referred to above, the invention provides a kind of preparation method of n butane oxidation legal system cis-butenedioic anhydride vpo catalyst.
The present invention solves the problems of the technologies described above adopted technical scheme:
A preparation method for n butane oxidation legal system cis-butenedioic anhydride vpo catalyst, is characterized in that,
(1) preparation of catalyst precursor
A certain proportion of solvent allyl alcohol and reducing agent isobutanol mixed liquor are joined in there-necked flask, then adds the raw material V of ball-milling treatment 2o 5, be placed on magnetic stirring apparatus and be heated to 105 DEG C, laser heating refluxes 7 hours, is then added drop-wise in flask by the phosphoric acid of 80% by a certain amount of, continues to add hot reflux 6 hours.Under being finally cooled to normal temperature, carrying out washing, filtering with ethanol, filter cake is smashed to pieces the vacuum drying chamber putting into 50 DEG C, heating rate 15 DEG C/h, after temperature rises to 120 DEG C, freeze-day with constant temperature 6 hours, obtained catalyst V PO presoma.
(2) preparation of catalyst promoter
In the ratio of iron/molybdenum/atomic percent zirconium in 1:1:1, prepare the ferric nitrate of 0.1mol/L, nitric acid molybdenum and the zirconium nitrate aqueous solution, drip concentrated ammonia liquor, obtain auburn precipitation, filter and wash with water, dried overnight at 110 DEG C, then at 800 DEG C of roasting 10h, obtain brown solid powder, i.e. catalyst promoter iron molybdenum zirconium mixed oxide.
(3) containing the preparation of auxiliary agent catalyst
After taking a certain amount of auxiliary agent with assay balance, be dissolved in a certain amount of aqueous solution, after auxiliary agent all dissolves, add in the VPO presoma of pulverizing while stirring, after mixing, in room temperature static one hour, then be placed in baking oven, dry 4 hours at about 100 DEG C, grind up art after cooling, after compression molding, then be ground into 30 orders.
(3) catalyst is shaping
When shaping of catalyst first by presoma by rolling mixing, also to add a certain amount of ethanol and graphite, then granulation, add in tablet press machine shaping.
(4) activation of catalyst
By beat sheet shaping after cyclic precursors carry out fragmentation, screen 30 object particles and put in evaluating apparatus reaction tubes, pass into butane and air gas mixture, wherein butane concentration 2.0mol%, air 98mol%, intensification per minute 3 DEG C, air speed is 2000h -1condition under, after being warmed up to 45 DEG C, keep temperature, continue be down to room temperature after 2 hours.
The invention has the advantages that: the preparation method that the invention provides a kind of n butane oxidation legal system cis-butenedioic anhydride vpo catalyst, the method is simple to operate, optimize the preparation condition of vpo catalyst, add auxiliary agent iron/molybdenum/zirconium simultaneously, optimize auxiliary agent ratio in the catalyst, improve catalyst activity and selectivity, increase the conversion ratio of butane.
Detailed description of the invention
Be clearly and completely described technical scheme of the present invention below in conjunction with embodiment, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
A preparation method for n butane oxidation legal system cis-butenedioic anhydride vpo catalyst, is characterized in that,
(1) preparation of catalyst precursor
A certain proportion of solvent allyl alcohol and reducing agent isobutanol mixed liquor are joined in there-necked flask, then adds the raw material V of ball-milling treatment 2o 5, be placed on magnetic stirring apparatus and be heated to 105 DEG C, laser heating refluxes 7 hours, is then added drop-wise in flask by the phosphoric acid of 80% by a certain amount of, continues to add hot reflux 6 hours.Under being finally cooled to normal temperature, carrying out washing, filtering with ethanol, filter cake is smashed to pieces the vacuum drying chamber putting into 50 DEG C, heating rate 15 DEG C/h, after temperature rises to 120 DEG C, freeze-day with constant temperature 6 hours, obtained catalyst V PO presoma.
(2) preparation of catalyst promoter
In the ratio of iron/molybdenum/atomic percent zirconium in 1:1:1, prepare the ferric nitrate of 0.1mol/L, nitric acid molybdenum and the zirconium nitrate aqueous solution, drip concentrated ammonia liquor, obtain auburn precipitation, filter and wash with water, dried overnight at 110 DEG C, then at 800 DEG C of roasting 10h, obtain brown solid powder, i.e. catalyst promoter iron molybdenum zirconium mixed oxide.
(3) containing the preparation of auxiliary agent catalyst
After taking a certain amount of auxiliary agent with assay balance, be dissolved in a certain amount of aqueous solution, after auxiliary agent all dissolves, add in the VPO presoma of pulverizing while stirring, after mixing, in room temperature static one hour, then be placed in baking oven, dry 4 hours at about 100 DEG C, grind up art after cooling, after compression molding, then be ground into 30 orders.
(4) catalyst is shaping
When shaping of catalyst first by presoma by rolling mixing, also to add a certain amount of ethanol and graphite, then granulation, add in tablet press machine shaping.
(5) activation of catalyst
By beat sheet shaping after cyclic precursors carry out fragmentation, screen 30 object particles and put in evaluating apparatus reaction tubes, pass into butane and air gas mixture, wherein butane concentration 2.0mol%, air 98mol%, intensification per minute 3 DEG C, air speed is 2000h -1condition under, after being warmed up to 45 DEG C, keep temperature, continue be down to room temperature after 2 hours, obtain maleic anhydride catalyst VPO.
Last it is noted that above each embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to foregoing embodiments to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.

Claims (1)

1. a preparation method for n butane oxidation legal system cis-butenedioic anhydride vpo catalyst, is characterized in that,
(1) preparation of catalyst precursor
A certain proportion of solvent allyl alcohol and reducing agent isobutanol mixed liquor are joined in there-necked flask, then adds the raw material V of ball-milling treatment 2o 5, be placed on magnetic stirring apparatus and be heated to 105 DEG C, laser heating refluxes 7 hours, is then added drop-wise in flask by the phosphoric acid of 80% by a certain amount of, continues to add hot reflux 6 hours; Under being finally cooled to normal temperature, carrying out washing, filtering with ethanol, filter cake is smashed to pieces the vacuum drying chamber putting into 50 DEG C, heating rate 15 DEG C/h, after temperature rises to 120 DEG C, freeze-day with constant temperature 6 hours, obtained catalyst V PO presoma;
(2) preparation of catalyst promoter
In the ratio of iron/molybdenum/atomic percent zirconium in 1:1:1, prepare the ferric nitrate of 0.1mol/L, nitric acid molybdenum and the zirconium nitrate aqueous solution, drip concentrated ammonia liquor, obtain auburn precipitation, filter and wash with water, dried overnight at 110 DEG C, then at 800 DEG C of roasting 10h, obtain brown solid powder, i.e. catalyst promoter iron molybdenum zirconium mixed oxide;
(3) containing the preparation of auxiliary agent catalyst
After taking a certain amount of auxiliary agent with assay balance, be dissolved in a certain amount of aqueous solution, after auxiliary agent all dissolves, add in the VPO presoma of pulverizing while stirring, after mixing, in room temperature static one hour, then be placed in baking oven, dry 4 hours at about 100 DEG C, grind up art after cooling, after compression molding, then be ground into 30 orders;
(4) catalyst is shaping
When shaping of catalyst first by presoma by rolling mixing, also to add a certain amount of ethanol and graphite, then granulation, add in tablet press machine shaping;
(5) activation of catalyst
By beat sheet shaping after cyclic precursors carry out fragmentation, screen 30 object particles and put in evaluating apparatus reaction tubes, pass into butane and air gas mixture, wherein butane concentration 2.0mol%, air 98mol%, intensification per minute 3 DEG C, air speed is 2000h -1condition under, after being warmed up to 45 DEG C, keep temperature, continue be down to room temperature after 2 hours.
CN201510943450.9A 2015-12-14 2015-12-14 Method for preparing maleic anhydride VPO catalyst through n-butane oxidation method Pending CN105536831A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106552656A (en) * 2016-11-07 2017-04-05 山东齐鲁科力化工研究院有限公司 Loaded catalyst and application thereof
CN106938197A (en) * 2016-05-25 2017-07-11 中国科学院过程工程研究所 A kind of preparation method of vanadium-phosphor oxide catalyst

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060241310A1 (en) * 2003-01-30 2006-10-26 Renshui Lan V-p-ci composite oxide catalyst precursor used for producing maleic anhydride from butance
CN104607219A (en) * 2013-11-05 2015-05-13 中国石油化工股份有限公司 Vanadium-phosphorus oxide catalyst for preparing maleic anhydride through butane oxidation, and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060241310A1 (en) * 2003-01-30 2006-10-26 Renshui Lan V-p-ci composite oxide catalyst precursor used for producing maleic anhydride from butance
CN104607219A (en) * 2013-11-05 2015-05-13 中国石油化工股份有限公司 Vanadium-phosphorus oxide catalyst for preparing maleic anhydride through butane oxidation, and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李剑锋等: "丁烷选择性氧化制顺酐铈锆复合氧化物VPO催化剂的制备", 《全国催化学术会议》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106938197A (en) * 2016-05-25 2017-07-11 中国科学院过程工程研究所 A kind of preparation method of vanadium-phosphor oxide catalyst
CN106938197B (en) * 2016-05-25 2019-12-13 中国科学院过程工程研究所 Preparation method of vanadium phosphorus oxide catalyst
CN106552656A (en) * 2016-11-07 2017-04-05 山东齐鲁科力化工研究院有限公司 Loaded catalyst and application thereof

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Application publication date: 20160504