CN100512958C - Method of regenerating maleic anhydride fluidized-bed catalyst produced from n-butane oxidation - Google Patents
Method of regenerating maleic anhydride fluidized-bed catalyst produced from n-butane oxidation Download PDFInfo
- Publication number
- CN100512958C CN100512958C CNB2006100657856A CN200610065785A CN100512958C CN 100512958 C CN100512958 C CN 100512958C CN B2006100657856 A CNB2006100657856 A CN B2006100657856A CN 200610065785 A CN200610065785 A CN 200610065785A CN 100512958 C CN100512958 C CN 100512958C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- maleic anhydride
- preparation
- fluid catalyst
- butane oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a renovation process of fluidized-bed catalyst for oxidation of n-butane to maleic anhydride, which comprises the steps of: preparing precursor matrixes powder and assistant material used for raw catalyst; mixing the fine catalyst captured by the fluidized-bed device with the prepared precursor matrixes powder and assistant material; adding water soluble resin glue and agitating under the condition of aqueous thermostat; finally forming by spray drying to obtain regenerated catalyst. The regenerated catalyst of the present invention can be complemented, replacing raw catalyst, into the fluidized-bed reactor, and is equivalent with raw catalyst in activity, grain size, and intension, etc,.
Description
Technical field
The present invention relates to a kind of n butane oxidation system maleic anhydride (abbreviation cis-butenedioic anhydride) and use the Preparation of catalysts method, relate in particular to the synthetic V-P-O of using of a kind of cis-butenedioic anhydride series metal oxide Preparation of catalysts method.
Background technology
Maleic anhydride is important Organic Chemicals.Be widely used in industry such as unsaturated-resin, coating, food, agricultural chemicals, medicine, weaving at present, market is growing to the demand of cis-butenedioic anhydride.
Early stage cis-butenedioic anhydride production exploitation is to be the process route of raw material with benzene, because the price of benzene is more expensive, toxicity is big, does not also meet current more and more harsher environmental requirement, and limitation displays gradually.
For solving traditional is the defective of the synthetic maleic anhydride process of raw material with benzene, and developing with the normal butane is the process route of raw material, and has obtained developing rapidly.The n butane oxidation method is divided into two kinds of fluidized bed process and fixed bed processes.Fluidized-bed process has the advantage that the equipment investment expense is low, the raw material load is high, has broad application prospects.According to the characteristics of fluidized-bed reactor, fluid catalyst will possess characteristics such as wearability, high load capacity, easy mobility.In preparing cis-anhydride by n-butane oxidation fluidized-bed reactor real-world operation process, because collide mutually between the catalyst, wearing and tearing can cause catalyst granules to diminish, lighten, tiny catalyst can blow out reactor, in what cyclone separator at reactor rear portion tiny catalyst granules is pounced under the collection.These fine particles have that volume is little, light weight but still have big active characteristics.Annual fluidized-bed reactor all will be pounced on the many so tiny catalyst of collection, because the continuous minimizing of catalyst needs constantly to replenish new catalyst in fluidized-bed reactor.
Research about preparing cis-anhydride by n-butane oxidation fixed bed, fluid catalyst constantly develops, and has delivered many patents, as US 5,326,886, and US5,519,149, US 5,792,722, and US 6,040, and 460 etc.
Chinese patent CN1059297 provides a kind of manufacture method of V-P-O series catalysts of producing maleic anhydride by n-butane oxidation with fluid bed method, is characterized in adopting the organic solvent reducing process, with the V of technical grade
2O
5, 85% phosphoric acid is raw material, is reducing agent with the technical grade isobutanol, carries out reduction reaction in having the stirred autoclave with Steam Heating chuck of destilling tower, adopt azeotropic distillation technology and hot filter technology, reaction is after the heat filter dries filter cake, and drying makes catalyst precursor; Precursor is handled through modification, adds metal promoters, and mixing is sized mixing, and spray drying forming makes micro-spherical catalyst.
CN1090224 discloses a kind of catalyst of preparing cis-anhydride by n-butane oxidation, and it is by V
2O
5, H
3PO
4, ZnSO
4Under 90 ± 4 ℃, alcohols effect, carry out reduction reaction with the 4th component and make matrix powder; Then, in matrix powder, add modified starch and other auxiliary material, extrusion, pelletizing and make the catalyst of the shape that requires; Wherein the 4th component can be selected from rare earth compounds such as Er, Ho, Gd, Tb or Mo, Fe, transistion metal compounds such as Co, Ni.
CN1133755 discloses a kind of preparation method of oxidation of n-butane in fluidized bed catalyst for preparing cis-anhydride, and this method comprises presoma preparation and post processing process.With the vanadic anhydride is raw material, and hydrazine hydrate is a reducing agent, and phenmethylol and isobutanol are solvent, add metal promoter reactor in 105～115 ℃ down reaction waited after filtration again in 6～20 hours presoma.Presoma and Ludox, the dry loaded catalyst that gets of deionized water gelling agent slurrying get finished product through calcining and activating, moulding etc. again.
CN1303741 provides a kind of cis-butenedioic anhydride compounding vanadium, phosphorus, oxygen (VPO) Preparation of catalysts that is used for fluid bed, moving bed, consist of VPO/Ce-M, P/V is than 1.1-1.3, Ce content 0.1-50w%, M=Fe, Mn, Mo, Co, Zr, Cu, La, Bi, Ni, content 0.1-50w%.
CN1345630 provides a kind of catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof.It is by V
2O
5, H
3PO
4, ZnSO
4Make with the 4th component that is selected from Fe, Co, Mo, Ni, Cu and the 5th component that is selected from Er, Ho, Gd, Pr, Dy, Nd.During preparation, earlier with V
2O
5, H
3PO
4, ZnSO
4Under the alcohols effect, reduce, add MoO then
3And rare earth oxide continuation reaction makes matrix powder; Add binding agent and other auxiliary material then, make through moulding.
The research preparation that is mostly catalyst precursor that above-mentioned these patents provided and the forming method of fluid catalyst do not provide the method for preparing catalyst in the fluidized bed process production process for this catalyst fines regeneration that still has certain activity that produces.
Summary of the invention
Purpose of the present invention just provides a kind of preparation method who is normal butane system cis-butenedioic anhydride usefulness fluid catalyst with the tiny catalyst process processing reshaping of pouncing in the normal butane system cis-butenedioic anhydride fluidized-bed process under the collection.
Catalyst of the present invention is spent catalyst and a fluid catalyst precursor matrix powder of trapper in the fluidized-bed process being pounced on the fine powder shape that collects, be 1:(0.15-1 by weight) mix, add supplies again, through the colloid mill circular grinding, add water-soluble resin adhesive, spray drying forming makes the microballoon normal butane method cis-butenedioic anhydride fluid catalyst of regeneration.
Mentioned spent catalyst is meant in fluidized-bed process among the present invention, from fluidized-bed reactor blow out by trapper pounce on the collection under tiny catalyst.This part mainly is because catalyst becomes fluidized state in reactor, and collision mutually, wearing and tearing cause catalyst granules to diminish, and pounce on the tiny catalyst of pouncing in the acquisition means under the collection at what whirlwind of reactor back segment.This part catalyst has certain activity.
Concrete, the regenerative preparation of n butane oxidation system maleic anhydride fluid catalyst of the present invention may further comprise the steps:
A) preparation of fluid catalyst precursor matrix powder
1. with V
2O
5, dense H
3PO
4, zinc salt, alcohol compound and sulfuric acid adds in the reactor (as there-necked flask), under agitation is heated to backflow, preferably refluxes down at 90 ± 4 ℃, becomes turquoise to reactant liquor;
2. add the oxide of heavy metal Mo, the oxide of rare earth metal Er, continue to reflux 3-8 hours;
3. the reacting liquid filtering that 2. step is obtained will leach thing with the alcohol compound washing for several times, and oven dry obtains described fluid catalyst precursor matrix powder;
Wherein, the addition of each material is in element mol ratio V:P:Zn:Er:Mo=1:(1.0-1.2): (0.02-0.04): (0.006-0.008): (0.005-0.012),
Described alcohol compound is 1-5 primary alconol or secondary alcohol for the carbon atom number.
In a specific embodiments of the present invention, can after 6 hours, carry out the oxide that 2. step adds Mo, Er in the 1. described reaction of step, finish reaction after 5 hours, material is leached from reactant liquor; Carry out step 3., obtain blue fluid catalyst precursor matrix powder.
Described fluid catalyst precursor matrix powder, its active component and content are by determining on the basis that Chinese patent 00124999.1 (CN1345630) is studied: the catalyst that adopts the V-P-O system, wherein active component is Zn, Er, Mo, and each element mol ratio is: V:P:Zn:Er:Mo=1:(1.0-1.2): (0.02-0.04): (0.006-0.008): (0.005-0.012).
V in the 1. described course of reaction of step
2O
5Progressively be reduced to turquoise, turquoise of the present invention is meant V
2O
5The color of solution when being reduced between tetravalence and the pentavalent vanadium.
B) preparation of supplies
1. earlier that reducing agent is soluble in water, again with V
2O
5Add in the aqueous solution of reducing agent;
2. the ammonium salt of Zn salt, heavy metal Mo is water-soluble respectively, join step solution 1.;
3. with dense H
3PO
4Add in the step solution 2., color becomes navy blue and promptly obtains described supplies;
Wherein said reducing agent is organic acid such as formic acid, acetate, oxalic acid, tartaric acid etc., and hydrazine class such as hydrazine hydrate, acethydrazide etc., or aldehydes such as formaldehyde, acetaldehyde, propionic aldehyde, benzaldehyde etc. are preferably oxalic acid; The addition of each material is according to element mol ratio V:P:Zn:Mo=1:(1.0-1.2): (0.02-0.04): (0.005-0.020) calculate;
Because mentioned fluidized bed waste catalyst has certain activity among the present invention, but activity still can decrease than raw catelyst, in order to guarantee regenerated catalyst higher activity arranged, and needs to add a certain amount of supplies.The element ratio of supplies is based on also that V-P-O metal oxide oxidation catalyst mechanism determines, with V
2O
5, H
3PO
4For essential element and add auxiliary element and a certain amount of reducing agent.
C) preparation of regenerated catalyst
1. the fluid catalyst precursor matrix powder that spent catalyst and step a) are obtained is by weight be 1:(0.15-1), preferred 1:(0.2-0.75) mixing;
2. add the supplies that step b) obtains, put into colloid mill together, circular grinding 1-2 hour, be heated to 90-98 ℃, stirred 3-6 hours, stop heating;
3. add water-soluble resin adhesive in natural cooling process, stirring, spray shaping make described regenerated catalyst.
In the method for the invention, in the described step c), preferably behind the colloid mill circular grinding, heating in water-bath, stirring break away from the water-bath heating, naturally cooling then.
In a specific embodiments of the present invention, with spent catalyst of the present invention and described fluid catalyst precursor matrix powder by weight being 1:(0.2-0.75) mix after, add the supplies that prepare, put into colloid mill together, circular grinding 1-2 hour, make material reach careful, uniform purpose; Material is put into there-necked flask, and water-bath is heated to 90-98 ℃, stirs 4 hours, thereby reaches the minimizing material moisture, increases the purpose of material solid content; At last, break away from the water-bath heating, disposable adding water-soluble resin adhesive in natural cooling process stirred after 30 minutes, carried out the catalyst spray shaping.
Water-bath heating and interpolation water-soluble resin adhesive can well improve the granularity and the intensity of catalyst, and make catalyst that be arranged long service life.
In the preferred method of the present invention, described dense H
3PO
4Concentration be 90-110%.
Preferred described alcohol compound is an isobutanol, and described sulfuric acid is the concentrated sulfuric acid, and concentration is 95-100%, more preferably 98%.
Preferred described Zn salt is zinc sulfate.
In the preferred described step c), described water-soluble resin adhesive is selected from one or more in polyvinyl alcohol resin, POLYPROPYLENE GLYCOL resin, vinyl acetate resin and the aldehyde resin, more preferably polyvinyl alcohol resin.
Renovation process of the present invention mixes fluidized bed waste catalyst with fluid catalyst precursor matrix powder, improve the ratio of catalyst precursor matrix powder, can improve the intensity and the activity of regenerated catalyst preferably, but required expense will improve.Therefore, selecting the two weight ratio is 1:(0.15-1), preferred proportion is 1:(0.2-0.75), both satisfied the intensity and the active requirement of catalyst, also can at utmost utilize spent catalyst, saved expense.
According to the regenerated catalyst that method of the present invention is prepared, after testing, the particle size range of 80% regenerated catalyst concentrates on 40-80 μ, wear rate 0.5-3%hr
-1Move on 40ml fluid bed evaluating apparatus, resulting evaluating data is in butane concentration more than 4.0%, air speed 500hr
-1, conversion ratio 75-83%, yield 73-82% is close with import fresh catalyst catalytic performance basically.
Annual, normal butane system cis-butenedioic anhydride fluidized-bed reactor all will be pounced on the down many fine powder shape spent catalysts that still have bigger activity of the present invention of collection, can pounce on down 4～5 tons of such spent catalysts every year for the normal butane fluidized bed plant of producing ten thousand tons of cis-butenedioic anhydrides per year.Because the continuous minimizing of catalyst in reactor needs constantly to replenish new catalyst in reactor, need replenish 7 tons of raw catelysts every year approximately for ten thousand tons of devices.By the regenerated catalyst that the inventive method obtains, alternative raw catelyst adds in the reactor.Regenerated catalyst can satisfy the annual additional catalytic amount that needs basically.Because the preparing cis-anhydride by n-butane oxidation fluid catalyst costs an arm and a leg, but by regeneration save catalyst expense, thereby reduce cost.In addition, spent catalyst contains toxic heavy metal, handles difficulty, also can reduce the pollution of catalyst to environment by catalyst regeneration.
The specific embodiment
The present invention is further described with reference to the following example, but the present invention is not limited to these embodiment.
In the following embodiments, the data that relate to are measured by following method:
(1) concentration of air and normal butane and conversion ratio
Gas-chromatography (SP3400, VARIAN company makes)
(2) CO, CO
2Concentration
Gas-chromatography (SQ206, Beijing Analytical Instrument Factory makes)
Embodiment 1
In a 1000ml there-necked flask that has agitator and a spherical reflux condenser, add 55.76 gram V
2O
5, 0.883 gram MoO
3, the dense H of 3.99ml
2SO
4Stir with the 600ml isobutanol, heat temperature raising is to refluxing about 92 ℃, and in the bottle adding concentration of refluxing after 1 hour is 105% H
3PO
4Solution 81.20 grams, this moment, solution was turquoise, refluxed 6 hours again, added 0.117 gram Er in bottle
2O
3, continue to reflux 3 hours, obtain turquoise suspension, it is cooled to 40 ℃, filter with Buchner funnel, the filter cake that stays obtains fluid catalyst precursor matrix powder with washed filter cake then with three washings of 350ml isobutanol average mark altogether after 90 ℃ of oven dry.
Add 200ml distilled water in the 500ml beaker, add 40 gram oxalic acid, heating makes its dissolving, and cooling adds 33.3 gram V
2O
5, 3.71 the gram ZnSO
4.7H
2O, 1.16 gram ammonium molybdates, 0.4 gram carbonic hydroammonium are stirred to dissolving, and adding concentration is 85% H
3PO
4Solution 36.8 gram, to solution be navy blue, obtain supplies.
Getting fluid catalyst 200 grams, fluid catalyst precursor matrix powder 40 grams that waste and old imported L ONZA company produces mixes and adds the 500ml distilled water, mix with supplies and to put into colloid mill, circular grinding was emitted and is poured in the 2000ml there-necked flask in 2 hours, and water-bath is heated to 94 ℃, stirred 4 hours.Break away from the water-bath heating, the adding molecular weight is 1750 polyvinyl alcohol resin glue 30 grams, stirs 30 minutes, on two pneumatic spray drying devices (QP3 type spray dryer, the development of China Petrochemical Industry Beijing Chemical Research Institute), 280 ℃ of inlet temperatures, about 100 ℃ of outlet temperatures, the air inlet amount is about 100M
3Spray shaping makes fluid catalyst under the operating mode of/hr.
Embodiment 2
Fluid catalyst precursor matrix powder preparation process, feeding quantity are with embodiment 1.
Supplies preparation process, feeding quantity are with embodiment 1.
The fluid catalyst preparation process is with embodiment 1, and different is that fluid catalyst precursor matrix powder addition is 80 grams.
The comparative example 1
Fluid catalyst precursor matrix powder preparation process, feeding quantity are with embodiment 1.
Supplies preparation process, feeding quantity are with embodiment 1.
Fluid catalyst prepares feeding quantity with embodiment 1, and different is cancellation water-bath heating, just stirs at normal temperatures 4 hours.
The comparative example 2
Fluid catalyst precursor matrix powder preparation process, feeding quantity are with embodiment 1.
Supplies preparation process, feeding quantity are with embodiment 1.
The fluid catalyst preparation process is with embodiment 1, and different is not add polyvinyl alcohol resin glue.
The comparative example 3
Fluid catalyst precursor matrix powder preparation process, feeding quantity are with embodiment 1.
The supplies preparation process is with embodiment 1, and different is not add ammonium molybdate and carbonic hydroammonium.
Fluid catalyst preparation process, feeding quantity are with embodiment 1.
Above embodiment, comparative example and fresh import catalyst are to check and rate on the hard glass reactor fluidisation bed catalyst evaluating apparatus of 25mm at diameter, and the idol pipe of an external diameter 8mm is arranged in the reactor center position, and the lower end is the distribution grid of G1.When carrying out evaluating catalyst, at reactor bottom prepackage about 22ml (the about 60mm of the height of bed) quartz sand, to reduce the channel of unstripped gas.Loaded catalyst is 30ml (the about 85mm of the height of bed).
Process conditions and the evaluation result estimated are listed in the table below:
| Tested number | N—C° 4Volume ratio % with air | Air speed hr -1 | Focus ℃ | Conversion ratio % | Yield % | Wear rate %hr -1 |
| Embodiment 1 | 4.368 | 500 | 417 | 82.33 | 79.29 | 0.87 |
| Embodiment 2 | 4.378 | 500 | 417 | 82.02 | 80.47 | 0.91 |
| The comparative example 1 | 4.336 | 500 | 415 | 78.65 | 78.99 | 2.40 |
| The comparative example 2 | 4.392 | 500 | 416 | 79.77 | 77.89 | 2.65 |
| The comparative example 3 | 4.310 | 500 | 415 | 76.87 | 73.20 | 0.87 |
| The import fresh catalyst | 4.235 | 500 | 419 | 80.82 | 81.83 | 0.60 |
Claims (10)
1, a kind of regenerative preparation of n butane oxidation system maleic anhydride fluid catalyst may further comprise the steps:
A) preparation of fluid catalyst precursor matrix powder
1. with V
2O
5, H
3PO
4, zinc salt, alcohol compound and sulfuric acid adds in the reactor, under agitation is heated to backflow, becomes turquoise to reactant liquor;
2. add the oxide of heavy metal Mo, the oxide of rare earth metal Er, continue to reflux 3-8 hours;
3. the reacting liquid filtering that 2. step is obtained will leach thing and wash with alcohol compound, and oven dry obtains described fluid catalyst precursor matrix powder;
Wherein, the addition of each material is in element mol ratio V:P:Zn:Er:Mo=1:(1.0-1.2): (0.02-0.04): (0.006-0.008): (0.005-0.012),
Described alcohol compound is 1-5 primary alconol or secondary alcohol for the carbon atom number;
B) preparation of supplies
1. with V
2O
5Add in the aqueous solution of reducing agent;
2. the ammonium salt of Zn salt, heavy metal Mo is water-soluble respectively, join step solution 1.;
3. with dense H
3PO
4Add in the step solution 2., obtain described supplies;
Wherein said reducing agent is organic acid, hydrazine class or aldehydes; The addition of each material is according to element mol ratio V:P:Zn:Mo=1: (1.0-1.2): (0.02-0.04): (0.005-0.020) calculate;
C) preparation of regenerated catalyst
1. the fluid catalyst precursor matrix powder that spent catalyst and step a) are obtained is by weight be 1:(0.15-1) mixing;
2. add the supplies that step b) obtains, circular grinding is heated to 90-98 ℃, stirs, and stops heating;
3. add water-soluble resin adhesive in natural cooling process, stirring, spray shaping make described regenerated catalyst;
Wherein, described spent catalyst is meant the tiny catalyst of pouncing in the normal butane system cis-butenedioic anhydride fluidized-bed process under the collection.
2, the regenerative preparation of n butane oxidation system maleic anhydride fluid catalyst according to claim 1 is characterized in that described H
3PO
4Concentration is 90-110%.
3, the regenerative preparation of n butane oxidation system maleic anhydride fluid catalyst according to claim 1 is characterized in that described alcohol compound is an isobutanol, and the concentration of described sulfuric acid is 95%-100%.
4, the regenerative preparation of n butane oxidation system maleic anhydride fluid catalyst according to claim 1 is characterized in that described Zn salt is zinc sulfate.
5, the regenerative preparation of n butane oxidation system maleic anhydride fluid catalyst according to claim 1 is characterized in that in 1. reactant liquor backflow under 90 ± 4 ℃ of the step described in the described step a).
6, the regenerative preparation of n butane oxidation system maleic anhydride fluid catalyst according to claim 1 is characterized in that at the reducing agent described in the described step b) be oxalic acid.
7, the regenerative preparation of n butane oxidation system maleic anhydride fluid catalyst according to claim 1 is characterized in that in described step c) the weight ratio of described spent catalyst and precursor matrix powder is 1:(0.2-0.75).
8, the regenerative preparation of n butane oxidation system maleic anhydride fluid catalyst according to claim 1 is characterized in that in described step c), and heating in water-bath, stirring behind the circular grinding break away from the water-bath heating, naturally cooling then.
9, the regenerative preparation of n butane oxidation system maleic anhydride fluid catalyst according to claim 1, it is characterized in that in described step c) described water-soluble resin adhesive is selected from one or more in polyvinyl alcohol resin, POLYPROPYLENE GLYCOL resin, vinyl acetate resin and the aldehyde resin.
10, the regenerative preparation of n butane oxidation system maleic anhydride fluid catalyst according to claim 9 is characterized in that described water-soluble resin adhesive is a polyvinyl alcohol resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100657856A CN100512958C (en) | 2006-03-16 | 2006-03-16 | Method of regenerating maleic anhydride fluidized-bed catalyst produced from n-butane oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100657856A CN100512958C (en) | 2006-03-16 | 2006-03-16 | Method of regenerating maleic anhydride fluidized-bed catalyst produced from n-butane oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101036891A CN101036891A (en) | 2007-09-19 |
| CN100512958C true CN100512958C (en) | 2009-07-15 |
Family
ID=38888188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100657856A Active CN100512958C (en) | 2006-03-16 | 2006-03-16 | Method of regenerating maleic anhydride fluidized-bed catalyst produced from n-butane oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100512958C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691466B (en) * | 2012-09-27 | 2016-07-06 | 中国石油化工股份有限公司 | A kind of catalyst precursor and preparation method thereof and catalyst and application thereof |
| CN106311300A (en) * | 2015-06-24 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst used for preparation of maleic anhydride through oxidation of butane, and preparation and application methods thereof |
| WO2024084002A1 (en) | 2022-10-21 | 2024-04-25 | Clariant International Ltd | Mechanically stable vpo catalyst and process for the production thereof |
-
2006
- 2006-03-16 CN CNB2006100657856A patent/CN100512958C/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101036891A (en) | 2007-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101507927B (en) | Preparation method of composite oxides catalyst and use thereof in acrylic acid synthesizing process | |
| CN101594934B (en) | Method for producing catalyst moulded bodies whose active mass is a multi-element oxide | |
| CN106582652A (en) | Catalyst for ethylene glycol synthesis through gas phase hydrogenation of dimethyl oxalate, preparation method and applications thereof | |
| CN102781580A (en) | Process for preparing catalyst used in production of unsaturated aldehyde and/or unsaturated carboxylic acid by dehydration reaction of glycerin, and catalyst obtained | |
| US20060036111A1 (en) | Catalyst for synthesis of unsaturated aldehyde, production process for said catalyst, and production process for unsaturated aldehyde using said catalyst | |
| CN101554593B (en) | Method for regenerating catalyst for the production of methacrylic acid and process for preparing methacrylic acid | |
| CN105457678B (en) | Supported heteropoly compound catalyst, preparation method and applications | |
| US8507626B2 (en) | Catalyst for producing of acrylic acid, method for producing acrylic acid using the catalyst and method for producing water-absorbent resin using the acrylic acid | |
| CN105209168B (en) | Unsaturated aldehyde and/or unsaturated carboxylic acid catalyst for producing, its manufacture method and manufacture method of unsaturated aldehyde and/or unsaturated carboxylic acid | |
| CN109550515A (en) | A kind of preparation method and application of vanadium-phosphor oxide catalyst | |
| CN104437581A (en) | Catalyst for acrylic acid synthesis and preparation method of catalyst | |
| CN103736498B (en) | Propylene oxidation catalyst, preparation method and its usage | |
| CN103861640A (en) | Heteropolyacid catalyst and preparation method thereof | |
| CN103721722A (en) | Composite oxide catalyst and preparation method thereof | |
| CN111744518B (en) | Amino acid modified supported heteropolyacid salt catalyst and preparation method thereof | |
| CN100512958C (en) | Method of regenerating maleic anhydride fluidized-bed catalyst produced from n-butane oxidation | |
| CN114669306B (en) | Catalyst for preparing (methyl) acrylonitrile by (methyl) acrolein ammoxidation, and preparation method and application thereof | |
| CN101116810A (en) | Modified coal-radicle activated charcoal solid catalyst and method for preparing the same and the application in the aldehyde acetal/ketone building-up reactions | |
| CN113976179B (en) | Hollow structure catalyst and preparation method and application thereof | |
| CN107282056A (en) | The catalyst of propylene oxidative synthesis methacrylaldehyde and acrylic acid | |
| CN103418401B (en) | Catalyst for preparing acrolein by propylene oxidation method and preparation method thereof | |
| CN1978052A (en) | Iron-molybdic catalyst for preparing concentrated formaldehyde by formal oxidation and preparing method | |
| CN106732750A (en) | A kind of monomolecular dispersion heteropolyacid catalyst preparation method of methacrolein oxidation preparing isobutene acid | |
| CN104801342B (en) | A kind of heteropolyacid salt catalyst and preparation method thereof | |
| CN111545228B (en) | Microwave-assisted aging heteropolyacid salt/cerium oxide composite catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |