CN106040266A - Solid acid catalyst, and preparation method and application thereof - Google Patents
Solid acid catalyst, and preparation method and application thereof Download PDFInfo
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- CN106040266A CN106040266A CN201610454940.7A CN201610454940A CN106040266A CN 106040266 A CN106040266 A CN 106040266A CN 201610454940 A CN201610454940 A CN 201610454940A CN 106040266 A CN106040266 A CN 106040266A
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/04—Preparation of esters of nitrous acid
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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
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a solid acid catalyst, and a preparation method and application thereof. The chemical formula of the catalyst is Fe2O3-ZrSO4/Al2O3, wherein iron and zirconium are active ingredients; based on the mass of a carrier, the mass fraction of the zirconium is 0.1 to 5 percent, and the mass fraction of the iron is 0.1 to 5 percent. The catalyst is prepared by adopting an impregnation method, and is obtained by respectively impregnating a zirconium salt and an iron salt on the carrier and performing high-temperature treatment. The catalyst is mainly used in a regeneration reaction of methyl nitrite; compared with a system into which the catalyst is not added, the catalytic activity of the catalyst is more obvious; the conversion rate of NO is up to 95 percent, and the selectivity of the NO is greater than 98 percent.
Description
Technical field
The present invention relates to a kind of catalyst for methyl nitrite regenerative response and preparation method thereof, mainly include using
Fe prepared by dipping method2O3-ZrSO4/Al2O3The correlation technique of loaded catalyst.
Background technology
Methyl nitrite regenerative response is a ring important in the reaction of CO gaseous oxidation coupling synthesizing dimethyl oxalate, regeneration
Reaction equation is: 4NO+O2+4CH3OH—4CH3ONO+2H2O, because having in the generation of water and raw material and existing in course of reaction
Moisture, nitric acid by-product can be generated, cause the nitrogen source of system to be run off, in order to maintain stablizing of whole response system, it is necessary to
System adds methyl nitrite or NOxGuarantee the stablizing of methyl nitrite of whole system.By-product nitric acid increase and
The device supplementing nitrogen source adds the cost of whole technique undoubtedly, it is therefore desirable to a kind of more efficient methyl nitrite regeneration techniques
Solve this difficult problem.
The patent and the document that relate to methyl nitrite regenerative response at present are less, gas disclosed in patent ZL90101447.8
Catalyze and synthesize mutually and oxalate continuous processing uses the alcohol-water solution of alcohol content more than 20% carry out the regeneration of methyl nitrite, body
Being that water content is higher, by-product nitric acid is more.Patent CN102964248A reports a kind of nitric oxide and produces and carbonylation conjunction
The method becoming dimethyl oxalate., the concentration of nitric acid needed for the method is higher, requires strict to the rotproofness of device, too high nitric acid
Concentration there is also certain potential safety hazard.It is thus desirable to by-product nitric acid can be utilized and be converted into nitrous acid by a kind of catalyst once again
Methyl ester, improves conversion ratio and the selectivity of NO further, can not only reduce cost produced by process nitric acid waste, also can reduce
The nitric acid waste pollution to environment.
Therefore, how to select a kind of suitably catalyst, methyl nitrite regenerative response is had vital effect.
Summary of the invention
The main object of the present invention is to provide a kind of solid acid catalyst and preparation method thereof, and this catalyst is used for nitrous acid
Methyl ester regenerative response process.
The solid acid catalyst that the present invention provides, its chemical formula is expressed as Fe2O3-ZrSO4/Al2O3, wherein ferrum and zirconium are for living
Property component, in terms of carrier quality, the mass fraction of zirconium is 0.1～5%, and the mass fraction of ferrum is 0.1～5%.
The preparation method of above-mentioned solid acid catalyst, specifically comprises the following steps that
A. Disulfatozirconic acid. is added the sulfuric acid solution that pH value is 1～4, the molar concentration of preparation zirconium ion be 0.01～
The zirconium salt solution of 1.0mol/l.
B. account for the mass fraction of carrier according to zirconium, alumina support impregnated in the zirconium salt solution of step A 12～36h,
Take out and dry 12～24h, be 400～800 DEG C of roastings 6～12h then at temperature, be cooled to room temperature；
Described alumina support is through pretreated ball-aluminium oxide, and its particle diameter is 1～10mm, pretreatment
Method is, according to temperature programming to 400～1300 DEG C, is cooled to room temperature after constant temperature 4～10h, and the alumina support after cooling is used
PH value be 1～4 hydrochloric acid soak 6～12h at 30～80 DEG C, fully washing is to neutral, then dries.
C. soluble ferric iron salt is added in the acid solution that pH value is 1～3, prepare the molar concentration of iron ion be 0.01～
The iron salt solutions of 1.5mol/l, described soluble ferric iron salt is ferric nitrate, ferric oxalate, iron acetate or iron chloride；Described acid is molten
Liquid is hydrochloric acid, nitric acid, sulphuric acid or acetic acid.
D accounts for the mass fraction of carrier according to ferrum, and step B is impregnated with the alumina support iron salt in step C of Disulfatozirconic acid.
Solution impregnates 12～36 hours, takes out and dry 12～24h, be 400～800 DEG C of heat treatments 6～12h then at temperature, be cooled to
Room temperature, obtains described Fe2O3-ZrSO4/Al2O3Catalyst.
This catalyst is used for methyl nitrite regenerative response and measures its catalytic performance.Use solid-bed reactor, a road
Unstripped gas is CO, NO, MN and N2Gaseous mixture, with 500～3000h-1Air speed by bed, another road unstripped gas is O2, NO/
O2=2～4 (flow-rate ratios), reaction solution is HNO3With the mixed solution of methanol, the liquid air speed per hour of liquid controls 0.1～5,
React under pressure 0.1～1MPa, room temperature condition；Unstripped gas and product are to be analyzed by gas chromatogram on-line monitoring；Unstripped gas CO:
NO:MN:N2=30:15:10:45 (gas volume ratio), NO/O2=4 (flow-rate ratios), total air speed is 1000h-1, normal temperature and pressure.Its
The change that middle NO conversion ratio and selectivity react before and after's chromatographic data by unstripped gas can calculate acquisition.
Chromatographic data analysis according to Fig. 1～3 draws, the NO gas content in embodiment 1 and embodiment 2 is less than comparative example
1, methyl nitrite gas content is higher than comparative example 1 simultaneously.Illustrate under the effect of catalyst, in embodiment 1 and embodiment 2
The conversion ratio of NO and selectivity are higher than comparative example 1.
The present invention compared with prior art, has a following remarkable result:
1., compared with tradition methyl nitrite regeneration technology, present invention employs solid acid catalyst by by-product nitric acid again
The secondary method being converted into methyl nitrite.The introducing of solid acid catalyst can make the utilization rate of methyl nitrite improve and reduce nitrogen
The loss in source.
2. metal used by the solid acid catalyst of the present invention be base metal and consumption relatively low, control at carrier quality
Within 2%, the cost of catalyst is relatively low.
3. nitric acid can be again converted to methyl nitrite under relatively low concentration of nitric acid by the solid acid catalyst of the present invention,
The conversion ratio of NO is up to 95%, and the selectivity of NO is more than 98%.
Accompanying drawing explanation
Fig. 1 is the chromatography figure that in embodiment 1, the catalyst of preparation is tested for methyl nitrite regenerative response.
Fig. 2 is the chromatography figure of the methyl nitrite regenerative response test of comparative example 1.
Fig. 3 be in embodiment 2 preparation catalyst for methyl nitrite regenerative response test chromatography figure.
It is embodied as example mode
It is further elucidated with the present invention with example below, but the invention is not restricted to example.
Embodiment 1:
The alumina particle of a diameter of for 15g 6～8mm is put in Muffle furnace and under the conditions of 600 DEG C, after roasting 6h, is cooled to room
Temperature, the hydrochloric acid of the alumina support pH=1 after cooling is washed with deionized to neutrality after soaking 2h in 60 DEG C of baking ovens, puts
Enter and be positioned in exsiccator preservation after baking oven is dried.
Weigh 0.59g Zr (SO4)24H2O puts in the dilute sulfuric acid that pH=1.5 volume is 15ml, after being sufficiently stirred for dissolving
Add the pretreated alumina support of 15g, remove solution after dipping 12h, impregnated alumina support is put into 150 DEG C of bakings
Case is dried 12h, places in Muffle furnace and is cooled to room temperature after roasting 4h under the conditions of 400 DEG C；
Weigh 0.39g Fe (NO3)3Put in the hydrochloric acid that pH=1 volume is 15ml, add after being sufficiently stirred for dissolving and loaded
The 15g alumina support of Disulfatozirconic acid., removes solution after dipping 12h, impregnated alumina support is put into 150 DEG C of oven dryings
12h, places in Muffle furnace and is cooled to room temperature after roasting 4h under the conditions of 500 DEG C, obtains required solid acid catalyst.Wherein Zr
Content is the 1% of carrier quality, and Fe content is the 0.6% of carrier quality.
Evaluating catalyst: applying the catalyst in embodiment 1 with methyl nitrite regenerative response, catalyst amount is
5ml, unstripped gas CO:NO:MN:N2=30:15:10:45 (gas volume ratio), NO/O2=4 (flow-rate ratios), total air speed is 1000h-1, normal temperature and pressure, unstripped gas and product are by gas chromatogram on-line monitoring, and chromatography figure is shown in that Fig. 2, reaction result are shown in Table 1.
Embodiment 2:
With embodiment 1, it is a difference in that Zr (SO4)24H2O mass changes 0.47g into；By Fe (NO3)3Quality changes into
0.65g.In the catalyst obtained, Zr content is the 0.8% of carrier quality, and Fe content is the 1% of carrier quality.
Evaluating catalyst process is with embodiment 1, and reaction result is shown in Table 1.
Embodiment 3:
With embodiment 1, it is a difference in that 0.59g Zr (SO4)24H2O mass changes 0.35g into, by 0.39gFe (NO3)3
Change 0.26gFeCl into3.In the catalyst obtained, Zr content is the 0.6% of carrier quality, and Fe content is the 0.8% of carrier quality.
Evaluating catalyst process is with embodiment 1, and reaction result is shown in Table 1.
Embodiment 4:
With embodiment 1, it is a difference in that 0.59g Zr (SO4)24H2O mass changes 0.47g into, by 0.39gFe (NO3)3
Change 0.64gFe into2(SO4)3.In the catalyst obtained, Zr content is the 0.8% of carrier quality, and Fe content is carrier quality
1.6%.
Evaluating catalyst process is with embodiment 1, and reaction result is shown in Table 1.
Embodiment 5:
In embodiment 1, catalyst preparation step will weigh 0.59g Zr (SO4)24H2O mass changes 0.47g into, will
0.39gFe(NO3)3Change 0.47gFe (OAc) into3I.e. cost example.Wherein Zr content is the 0.8% of carrier quality, and Fe content is for carrying
The 1.2% of weight.
Evaluating catalyst process is with embodiment 1, and reaction result is shown in Table 1.
As can be seen from Table 1: the catalyst of the present invention can promote that under relatively low content of metal NO is converted into Asia
Methyl nitrate, NO conversion ratio is significantly increased compared with not adding catalyst with selectivity, the solid acid catalyst of the present invention
The catalysis activity of excellence is shown in methyl nitrite regenerative response.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.
Comparative example 1:
Not loading catalyst in reactor.Evaluating catalyst process is with embodiment 1, and reaction result is shown in Table 1.
Table 1: catalyst catalytic performance in methyl nitrite regenerative response
Claims (4)
1. a solid acid catalyst, its chemical formula is Fe2O3-ZrSO4/Al2O3, wherein ferrum and zirconium are active component, with carrier
Quality meter, the mass fraction of zirconium is 0.1～5%, and the mass fraction of ferrum is 0.1～5%.
2. the method preparing solid acid catalyst described in claim 1, specifically comprises the following steps that
A., Disulfatozirconic acid. adds the sulfuric acid solution that pH value is 1～4, and the molar concentration of preparation zirconium ion is 0.01～1.0mol/l
Zirconium salt solution；
B. accounting for the mass fraction of carrier according to zirconium is 0.1～5%, be impregnated in by alumina support in the zirconium salt solution of step A, leaching
Stain 12～36 hours, take out and dry 12～24h, be 400～800 DEG C of roastings 6～12h then at temperature, be cooled to room temperature；
C. soluble ferric iron salt is added in the acid solution that pH value is 1～3, prepare the molar concentration of iron ion be 0.01～
The iron salt solutions of 1.5mol/l；Described soluble ferric iron salt is ferric nitrate, ferric oxalate, iron acetate or iron chloride；Described acid is molten
Liquid is hydrochloric acid, nitric acid, sulphuric acid or acetic acid.
The mass fraction that D accounts for carrier according to ferrum is 0.1～5%, and the alumina support of sulfur acid zirconium step B prepared impregnated in
In the iron salt solutions of step C, impregnate 12～36 hours, take out and dry 12～24h, be 400～800 DEG C of heat treatments 6 then at temperature
～12h, it is cooled to room temperature, i.e. obtains described Fe2O3-ZrSO4/Al2O3Catalyst.
The preparation method of solid acid catalyst the most according to claim 2, it is characterized in that described alumina support be through
Crossing pretreated ball-aluminium oxide, its particle diameter is 1～10mm, and preprocess method is, according to temperature programming to 400～
1300 DEG C, it is cooled to room temperature after constant temperature 4～10h, then soaks 6～12h with the hydrochloric acid that pH value is 1～4 at 30～80 DEG C, fully wash
Wash to neutrality, then dry.
4. an application for the solid acid catalyst described in claim 1, this catalyst is used for methyl nitrite regenerative response mistake
Journey.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497446A (en) * | 2017-09-04 | 2017-12-22 | 济南大学 | A kind of preparation method for synthesizing mixed dioctyl phthalate solid acid catalyst |
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| CN103936591A (en) * | 2014-04-14 | 2014-07-23 | 中国五环工程有限公司 | Methyl nitrite regeneration method |
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| CN1054765A (en) * | 1990-03-14 | 1991-09-25 | 中国科学院福建物质结构研究所 | Continuous process for synthesizing oxalate by gas phase catalysis |
| CN1323655A (en) * | 2000-05-11 | 2001-11-28 | 中国科学院成都有机化学研究所 | Solid acid with high selectivity and activity for esterification and its prpen. |
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Cited By (1)
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| CN107497446A (en) * | 2017-09-04 | 2017-12-22 | 济南大学 | A kind of preparation method for synthesizing mixed dioctyl phthalate solid acid catalyst |
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