CN101455962A - O-phenyl phenol preparation catalyst by cyclohexanone dimer dehydrogenation and preparation method thereof - Google Patents
O-phenyl phenol preparation catalyst by cyclohexanone dimer dehydrogenation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an o-phenylphenol catalyst prepared by dehydrogenating cyclohexanone dimer, and a preparation method thereof. A carrier of the catalyst is alumina modified with rare earth oxide, and the catalyst consists of alkali oxide and precious metal which are loaded on the carrier. The invention has the most remarkable characteristic of using the alumina modified with rare earth oxide as the carrier, and another remarkable characteristic of the invention is the preparation method of the catalyst, and the method adopts an isopyknic fractional-step impregnation process, avoids competitive adsorption among components, increases the bonding strength between the components and the carrier, and the like. The catalyst has the advantages of high selectivity to o-phenylphenol, few byproducts, simple preparation process, good stability and capability of simple activation and regeneration after coking deactivation, and is an excellent high-selectivity catalyst with industrial practical value.
Description
Technical field
The present invention relates to the Catalysts and its preparation method that the dehydrogenation of a kind of cyclohexanone dimer prepares o-phenyl phenol, specifically, the carrier of this catalyst is the aluminium oxide (La of rare earth oxide lanthana modification
2O
3/ Y-Al
2O
3), carrying alkali metal oxide potassium oxide (K on the catalyst carrier
2O) and noble metal platinum (Pt).Adopt the preparation method of substep incipient impregnation, the catalyst performance of this method preparation obviously is better than co-impregnation.In fixed bed reactors catalyst is carried out reduction activation with the hydrogen of nitrogen dilution at last and make, the catalyst of reducing/regenerating is reusable behind the coking deactivation.
Background technology
O-phenyl phenol (being called for short OPP) is a kind of important, broad-spectrum meticulous organic chemical industry's product.The heat stabilizer and the flame retardant of polymer that can be used as dyestuff intermediate, plastics.Also can be used for fluoremetry triose class reagent.Have powerful sterilization, sterilization, antisepsis.
The process route of synthesizing o-phenylphenol is a lot, but because the cyclohexanone raw material is easy to get, make and utilize the process route of cyclohexanone condensation prepared cyclohexanone dimer under the catalysis of acid or alkali to simplify greatly, make cyclohexanone dimer dehydrogenation synthesizing o-phenylphenol technology more and more have competitiveness.Its process route is as follows:
The catalyst of cyclohexanone dimer dehydrogenation synthesizing o-phenylphenol employing at present mainly contains four classes: (1) copper nickel aluminium chromium metallic catalyst, make co-catalyst with alkali metal sulfates (or carbonate), alkali metal oxide; (2) make palladium (or platinum) catalyst of carrier with active C or aluminium oxide; (3) making co-catalyst with hydroxide, carbonate or the oxide of sodium (or potassium), is palladium (platinum) catalyst of carrier with aluminium oxide (or silica one aluminium oxide), and part also contains noble metals such as iridium, germanium; (4) be carrier with silica one aluminium oxide or aluminium oxide, the catalyst of load manganese, chromium, rhodium etc.
In this four classes catalyst, studying maximum is loaded noble metal catalyst, and as the loaded catalyst of platinum, palladium, germanium, iridium, carrier mainly contains aluminium oxide, activated carbon and porous silica etc.Especially alundum (Al load platinum and alkali-metal binary catalyst, noble metal only need load capacity seldom, just can show dehydrogenation activity preferably, and be also better to the selectivity of OPP.
Chinese patent CN01108229 discloses a kind of cyclohexanone synthetic method of o-phenylphenol of using, cyclohexanone dimer is carrying out dehydrogenation reaction under Catalysts Cu/MgO catalysis cheaply, dimeric initial conversion ratio is 100%, the selectivity of o-phenyl phenol is 100%, after 100 hours, dimeric conversion ratio is 94%, and the selectivity of o-phenyl phenol is 88%; Dimer carries out dehydrogenation reaction under the molecular sieve catalyst catalysis with the ion-exchange preparation, dimeric initial conversion ratio is 98%, after the selectivity of o-phenyl phenol is 100%, 200 hour, dimeric conversion ratio is 94%, and the selectivity of o-phenyl phenol is 97%.Though these two kinds of initial conversion ratios of method catalyst are than higher, poor catalyst stability, the life-span is not long.
Chinese patent CN021384339 discloses the method that a kind of cyclohexanone condensation dehydrogenation prepares o-phenyl phenol, and the cyclohexanone dimer is being loaded with dehydrogenation generation o-phenyl phenol under Pt, Pd, Ni or the Cu catalyst.Dehydrogenation reaction is under normal pressure, reduced pressure, adopts the trickle bed mode to carry out.100 ℃～330 ℃ of control reaction temperatures, the cyclohexanone dimer is dripped from the upper end that dehydrogenation catalyst reactor is housed, and finishes dehydrogenation reaction on the catalyst surface, and the yield of o-phenyl phenol can reach 75～85%.This poor catalyst stability, conversion ratio and selectivity are not high, and byproduct of reaction is many.
Chinese patent CN200610097298 discloses a kind of Cu-Mg Preparation of catalysts method that is used to prepare o-phenyl phenol, adopts coprecipitation, and conversion ratio and selectivity are also very high, but stability is bad, and the life-span is not long.
Chinese patent CN200710022479 discloses a kind of preparation technology of o-phenyl phenol, carry out dehydrogenation reaction through fixed bed reactors, the product that obtains obtains the o-phenyl phenol product through rectification under vacuum and cooling section again, article focuses on the preparation technology of o-phenyl phenol, though mention catalytic component is rare earth element, alkali metal and noble metal, but fail clearly to propose each component and the method for preparing catalyst of load on the catalyst carrier.
Chinese patent CN200710103661 discloses a kind of amino benzenes compounds synthetic method of o-phenylphenol of using, amino benzenes compounds generates biphenyl compound through diazonium coupling, obtain o-phenyl phenol through hydrolysis again, but yield is very low, life-span is very short, and diazol has a lot of hazards in dry run, is unfavorable for applying.
Chinese patent CN200610041325 discloses a kind of with silica gel and γ-Al
2O
3Be carrier, the catalyst of two or more among load Ni, Cu, Cr, the K, this catalyst are applied to the synthetic of o-phenyl phenol.The conversion ratio of cyclohexanone dimer is 96%, and the OPP yield is for only being 75%.
U.S. Pat 3933924 is openly come a kind of catalyst for preparing o-phenyl phenol, 30ml nickel chromium triangle aluminum bronze composite catalyst is loaded in the vertical fixed bed reactors, the cyclohexanone dimer is with the speed charging of 6 Grams Per Hours, and 330 ℃ of following dehydrogenations, reacting initial OPP yield is 81%; After 1000 hours, the OPP yield is 70%.
U.S. Pat 4060559, US4088702, US4080390 disclose a kind of catalyst for preparing o-phenyl phenol, with Pt-K
2O/ γ-Al
2O
3Be main component, make a series of dehydrogenations and investigate by adding an amount of hydrogen sulfide, carbon disulfide, organosulfur compound, alkali metal sulphide etc.With cyclohexanone dimer (adjacent cyclohexyl phenol) is raw material, at 300～400 ℃, keeps hydrogen 290ml/min, carries out dehydrogenation reaction under the charging rate 15.5ml/ hour condition.React after 2000 hours, feed stock conversion still can keep 100%, and the OPP selectivity is higher than 90%.
U.S. Pat 472997 discloses a kind of Catalysts and its preparation method of synthesizing o-phenylphenol, on an amount of sulfide catalyst of chromium, manganese, alkali metal compound that has been added in load, correspondingly improve sintering temperature, be impregnated in subsequently in the rhodium-containing solution, oven dry is with alkali metal soln or sulfide treatment catalyst carrier.The catalyst of making can be used for the dehydrogenation of cyclohexanone dimer.
Japan Patent JP56033034, JP76131863, JP8153632, JP83180447, JP83180448 disclose the Catalysts and its preparation method of cyclohexanone dimer dehydrogenation synthesizing o-phenylphenol, with Pt-K
2O/ γ-Al
2O
3Be main component, suitably add iridium, germanium, or replace K with sodium carbonate, potassium sulfate etc.
2The catalyst of O reacted after 4000 hours, and cyclohexanone dimer conversion ratio and o-phenyl phenol selectivity are all greater than 90%.
There is bibliographical information in Japan: with 5%Pd/C is catalyst, adopts heterogeneous intermittent reaction, keeps N
2Atmosphere is carried out cyclohexanone dimer dehydrogenation reaction under 300 ℃.Initial reaction stage has the adjacent cyclohexyl cyclohexanone of dehydrogenation product to generate, and along with the growth in reaction time, adjacent cyclohexyl phenol and OPP increase gradually, generates dibenzofurans but OPP can continue cyclisation, and the OPP selectivity is not high.
Though above-mentioned patented technology and document respectively have its characteristics, but its weak point is arranged respectively also, outstanding problem is that the o-phenyl phenol selectivity is low, technical process is unfavorable for suitability for industrialized production, poor catalyst stability, and byproduct of reaction is many, the easy coking of catalyst surface, catalyst life is not long, and that catalyst cost height, indivedual dehydrogenation products also need is molten through alkali, pickling processes just can obtain qualified products etc.
Catalyst of the present invention has then overcome the shortcoming of above-mentioned several catalyst, the aluminium oxide of the carrier that uses of this catalyst after at first as rare-earth oxide modified, rare earth oxide can not only the cover part alumina support surface hydroxyl, improve a heatable brick bed sintering character and the high-temperature stability of carrier, also have certain cracking performance and dehydrogenation; In addition, but platinum impregnated in crystal grain thinning on the alumina support of lanthana modification, improve antioxygenic property and mechanical performance etc., and can prevent grain growth.Therefore can improve the dehydrogenation of catalyst, prolong life of catalyst.Next is to adopt unique preparation section, it is soluble-salt solution → leave standstill → dry → roasting → dipping noble metal acid solution → leave standstill → dry → roasting → reduction activation → reaction of carrier → dipping alkali metal oxide, though step is many, but can make the combination securely of each component and catalyst carrier like this, bring into play its catalysis characteristics, also can avoid the competitive Adsorption between each component simultaneously.Catalyst effect is very obvious, and selectivity is very high, and accessory substance is less, and the initial conversion ratio of cyclohexanone dimer can reach 99.8% in fixed bed reactors, and the initial selectivity of o-phenyl phenol is 97%; React after 3000 hours, the selectivity of o-phenyl phenol still can reach 86.7%, and feed stock conversion maintains more than 98%.
Summary of the invention
The objective of the invention is under condition of normal pressure, the reaction that dehydrogenation prepares o-phenyl phenol for the cyclohexanone dimer provides a kind of long Catalysts and its preparation method of high activity, high selectivity and service life that has.
One of summary of the invention is the preparation method of carrier, and promptly boehmite and the water with certain metering ratio is raw material, mixes to stir and makes the boehmite slurries, after stirring evenly, adds rare-earth salts La (NO while stirring
3)
36H
2The aqueous solution of O, the back that is uniformly dispersed drips HNO
3Solution becomes collosol state through dispergation until the boehmite slurries, with this colloidal sol oven dry back roasting, is developed into 20～40 order particles after the cooling, promptly obtains La
2O
3γ-the Al of modification
2O
3
Two of summary of the invention is the Preparation of catalysts method, adopt the equal-volume step impregnation method, be soluble-salt solution → leave standstill → dry → roasting → dipping noble metal acid of carrier → dipping potassium or salting liquid → leave standstill → dry → roasting → reduction activation → reaction, each weight percentages of components of catalyst (in carrier) is: K
2O is 0.1～8%, and Pt is 0.01～6%.
Catalyst of the present invention adopts the equi-volume impregnating preparation.This method may further comprise the steps:
(1) soluble-salt of the alkali metal oxide proportion of composing according to catalyst is dissolved in a certain amount of deionized water, the catalyst carrier for preparing is flooded wherein, left standstill 3～5 hours, then 100～120 ℃ of following freeze-day with constant temperature 8～12 hours, 450～550 ℃ of following roastings 5～10 hours.
(2) again the solubility acid of noble metal or the salt proportion of composing according to catalyst is dissolved in a certain amount of deionized water, the catalyst soakage that (1) middle roasting is good wherein, left standstill 3～5 hours, then 100～120 ℃ of following freeze-day with constant temperature 8～12 hours, 450～550 ℃ of following roastings 5～10 hours.
(3) catalyst activation
Hydrogen with hydrogen or nitrogen dilution activates catalyst, under 0.1～0.5MPa pressure, carries out reduction activation 5～10 hours in 300～400 ℃ in fixed bed reactors, till reactor outlet end dry-steam.Wherein nitrogen flow is 10～60ml/min, and hydrogen flowing quantity is 6～30ml/min.
, be used for the dehydrogenation of cyclohexanone dimer and prepare o-phenyl phenol in fixed bed reactors through the catalyst of overactivation, the initial conversion ratio of cyclohexanone dimer can reach 99.8%, and the initial selectivity of o-phenyl phenol is 97%; React after 3000 hours, the selectivity of o-phenyl phenol still can reach 86.7%, and feed stock conversion maintains more than 98%.
Behind the catalyst carbon deposit inactivation, in air atmosphere, after the roasting, after pressurization heats up with the hydrogen reducing activation, be used for the dehydrogenation reaction of cyclohexanone dimer once more again.The reaction post analysis records the initial conversion ratio of raw material and still can reach more than 99% the initial selectivity 95.6% of o-phenyl phenol.
One of catalyst remarkable advantage of the present invention is, used rare-earth oxide modified aluminium oxide, improved the structural stability of aluminium oxide, increased the decentralization of noble metal at catalyst surface, reduced the consumption of noble metal, reduced the catalyst cost.
Two of catalyst remarkable advantage of the present invention is, adopts the equal-volume step impregnation method, and this preparation method can avoid the competitive Adsorption between each component, strengthens the bond strength of each component and carrier, obviously is better than each component co-impregnation.
Three of catalyst remarkable advantage of the present invention is that behind the catalyst carbon deposit inactivation, the activating and regenerating program is simple, is used for cyclohexanone dimer dehydrogenation reaction once more, and is respond well, is a kind of good high-selectivity catalyst that the industrialization practical value is arranged.
Four of catalyst remarkable advantage of the present invention is that catalyst has excellent catalytic performance, o-phenyl phenol yield and selectivity height, and operating procedure is simple, is the higher catalyst of a kind of cost performance.
The embodiment that provides below is in order to further specify the present invention, but never is limitation of the present invention.
Embodiment 1
Take by weighing 1300 gram boehmites and 1000 gram water and mix to stir and to make the boehmite slurries, after stirring evenly, add the lanthanum nitrate hexahydrate (La (NO that is dissolved in the gram of 82 in 600 ml deionized water while stirring
3)
36H
2O) aqueous solution, stirring makes it abundant dissolving, back dropping salpeter solution is uniformly dispersed, become collosol state through dispergation until the boehmite slurries, with this colloidal sol at 100～120 ℃ down after the oven dry, 500 ℃ of following roastings 6 hours, be developed into 20～40 order particles after the cooling, promptly obtain the aluminium oxide (La of lanthana modification
2O
3/ γ-Al
2O
3).
Embodiment 2
Take by weighing potassium sulfate 0.148 gram and be dissolved in the 6ml deionized water, got in the example 1 catalyst carrier 8 gram dippings 4 hours, then 100～120 ℃ of following freeze-day with constant temperature 10 hours, 500 ℃ of following roastings 6 hours; Measure the chloroplatinic acid (H of 0.02 gram/ml
2PtCl
66H
2O) solution 3.19ml adds deionized water and is made into 6ml solution, and will before the good catalyst soakage of roasting wherein 4 hours, then 100～120 ℃ of following freeze-day with constant temperature 10 hours, 500 ℃ of following roastings 6 hours.Hydrogen with nitrogen dilution activates catalyst at last, and nitrogen flow is 60ml/min, and hydrogen flowing quantity is 6ml/min.Under 0.1MPa pressure, in fixed bed reactors, carry out reduction activation 6 hours in 380 ℃, till reactor outlet end dry-steam, the cooling back is standby.
Catalyst composed as follows: (accounting for carrier percentage restatement) with active component
Catalyst performance evaluation the results are shown in Table 1.
Embodiment 3
Except the amount of potassium sulfate changes 0.296 gram into, platinum acid chloride solution changes into outside the 4.26ml.The Preparation of Catalyst condition is with embodiment 2.
Catalyst composed as follows: (accounting for carrier percentage restatement) with active component
Catalyst is formed (weight %)
Catalyst performance evaluation the results are shown in Table 1.
Embodiment 4
Except the amount of potassium sulfate changes 0.296 gram into, platinum acid chloride solution changes into outside the 5.33ml.The Preparation of Catalyst condition is with embodiment 2.
Catalyst composed as follows: (accounting for carrier percentage restatement) with active component
Catalyst performance evaluation the results are shown in Table 1.
Embodiment 5
Except the amount of potassium sulfate changes 0.148 gram into, platinum acid chloride solution changes into outside the 6.40ml.The Preparation of Catalyst condition is with embodiment 2.
Catalyst composed as follows: (accounting for carrier percentage restatement) with active component
Catalyst performance evaluation the results are shown in Table 1.
Comparative Examples 5#
Take by weighing 0.148 gram potassium sulfate, the lanthanum nitrate hexahydrate of 0.64 gram and 0.13 gram chloroplatinic acid, mixing is dissolved in 6 ml water solution.Get γ-Al
2O
3In the above-mentioned aqueous solution of carrier 8 gram dipping 4 hours, 100～120 ℃ of following freeze-day with constant temperature 10 hours, 500 ℃ of following roastings 6 hours, the hydrogen with nitrogen dilution activated catalyst at last then, and nitrogen flow is 60ml/min, and hydrogen flowing quantity is 6ml/min.Under 0.1MPa pressure, in fixed bed reactors, carry out reduction activation 6 hours in 380 ℃, till reactor outlet end dry-steam, the cooling back is standby.
This catalyst is formed with embodiment 5, and catalyst performance evaluation the results are shown in Table 1.
Embodiment 6
Except the amount of potassium sulfate changes 0.148 gram into, platinum acid chloride solution changes 5.33ml into, is dissolved in outside the 6 ml water solution.。The Preparation of Catalyst condition is with embodiment 2.
Catalyst composed as follows: (accounting for carrier percentage restatement) with active component
Catalyst performance evaluation the results are shown in Table 1.
Comparative Examples 6#
Except the amount of potassium sulfate changes 0.148 gram, H into
2PtCl
66H
2O changes into outside 0.11 gram.The Preparation of Catalyst condition is with Comparative Examples 5#.
This catalyst is formed with embodiment 6, and catalyst performance evaluation the results are shown in Table 1.
Comparative Examples 7
This Comparative Examples is that catalyst carried out reduction activation again after embodiment 6 reactivities of better catalytic activity reduced.Decaying catalyst 500 ℃ of following roastings 6 hours, is activated catalyst with the hydrogen of nitrogen dilution, and nitrogen flow is 60ml/min, and hydrogen flowing quantity is 6ml/min.Under 0.1MPa pressure, in fixed bed reactors, carry out reduction activation 6 hours in 380 ℃, till reactor outlet end dry-steam, the cooling back is standby.
This catalyst is formed with embodiment 6, and catalyst performance evaluation the results are shown in Table 1.
Each catalyst performance evaluation result of table 1
(1)
| Catalyst | Initial conversion ratio (%) | Initial selectivity (%) |
| Embodiment 2 | 95.9％ | 92.5％ |
| Embodiment 3 | 96.3％ | 90.7％ |
| Embodiment 4 | 96.0％ | 89.4％ |
| Embodiment 5 | 98.5％ | 93.0％ |
| Comparative Examples 5# | 84.5％ | 83.2％ |
| Embodiment 6 | 99.8％ | 97.0％ |
| Comparative Examples 6# | 88.2％ | 78.7％ |
| Comparative Examples 7 | 99.8％ | 95.6％ |
(1) embodiment 2～6 adopts step impregnation method to be prepared from, and Comparative Examples 1～5 is that two component co-impregnations are prepared from; To catalyst performance wherein preferably embodiment 6 catalyst carry out life assessment, after reacting 3000 hours, the selectivity of o-phenyl phenol still can reach 86.7%, feed stock conversion maintains more than 99%.
(2) Comparative Examples 7 is carried out the regeneration of reduction activation again afterwards for embodiment 6 catalyst activities reduce, and catalyst performance is estimated.The initial conversion ratio of raw material still can reach more than 99%, and the selectivity of o-phenyl phenol maintains more than 95.6%.
Claims (9)
1. one kind prepares the Catalysts and its preparation method of o-phenyl phenol by the dehydrogenation of cyclohexanone dimer, and this catalyst is characterised in that carrier is the aluminium oxide of rare-earth oxide modified, and active component is made up of the noble metal and the alkali metal oxide that are carried on the carrier.
2. catalyst according to claim 1.It is characterized in that the carrier of this catalyst is the aluminium oxide (γ-Al of rare-earth oxide modified
2O
3).Preferred lanthana (the La of rare earth oxide
2O
3), La
2O
3Content is 0.1～8%, is preferably 1%～4%.
3. according to the described catalyst of claim 1～2.It is characterized in that the main active component of catalyst is a noble metal, the preferred platinum of noble metal (Pt) is by the solubility acid of platinum or salt dipping, oven dry, roasting and obtain.
4. according to the described catalyst of claim 1～3.It is characterized in that co-catalyst is an alkali metal oxide, the preferred potassium oxide (K of alkali metal oxide
2O), by the soluble-salt dipping of potassium, oven dry, roasting and obtain.
5. according to the described catalyst of claim 1～4.It is characterized in that, (in carrier) by weight percentage, each components contents is: K
2O content is 0.1～8%, is preferably 1%～2%; Pt content is 0.01～6%, is preferably 0.3～0.6%.
6. according to the described catalyst of claim 1～2.It is characterized in that the preparation method of catalyst carrier adds lanthanum nitrate hexahydrate (La (NO for being raw material with boehmite and water
3)
36H
2O) the aqueous solution, the back that is uniformly dispersed drips salpeter solution, again behind the colloidal sol, 100～120 ℃ of oven dry down, in 500 ℃ of following roastings 6 hours, makes 20～40 order particles through dispergation, promptly obtains the alumina support (La of lanthana modification
2O
3/ γ-Al
2O
3).
7. according to the described Preparation of catalysts method of claim 1～5.It is characterized in that, adopt step impregnation, oven dry, roasting to obtain, rather than each component is mixed altogether, and dipping prepares.Above-mentioned catalyst is concrete preparation method may further comprise the steps:
(1) soluble-salt with alkali metal oxide is dissolved in a certain amount of deionized water according to the described catalyst proportion of composing of claim 5, will be wherein according to the described catalyst carrier dipping for preparing of claim 6, left standstill 3～5 hours, then 100～120 ℃ of following freeze-day with constant temperature 8～12 hours, 450～550 ℃ of following roastings 5～10 hours, it was standby to lower the temperature.
(2) again the solubility acid or the salt of noble metal is dissolved in a certain amount of deionized water according to the described catalyst proportion of composing of claim 5, the catalyst soakage that above-mentioned (1) middle roasting is good wherein, left standstill 3～5 hours, then 100～120 ℃ of following freeze-day with constant temperature 8～12 hours, 450～550 ℃ of following roastings 5～10 hours, it was standby to lower the temperature.
8. Preparation of catalysts method according to claim 7 is characterized in that, heating up through pressurization obtains catalyst of the present invention with the hydrogen reducing activation.Concrete preparation method comprises the steps: under 0.1～0.5MPa pressure, in fixed bed reactors, carry out reduction activation 5～10 hours in 300～400 ℃, wherein nitrogen flow is 10～60ml/min, and hydrogen flowing quantity is 6～30ml/min, till reactor outlet end dry-steam.
9. according to the described catalyst of claim 1～8, it is characterized in that, the reducing/regenerating of decaying catalyst comprise the steps: decaying catalyst in air atmosphere 500 ℃ of following roastings 6～15 hours, then under 0.1～0.5MPa pressure, 300～400 ℃ are carried out reduction activation 5～10 hours in fixed bed reactors, wherein nitrogen flow is 10～60ml/min, and hydrogen flowing quantity is 6～30ml/min, till reactor outlet end dry-steam.
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|---|---|---|---|
| CNA2008102074930A CN101455962A (en) | 2008-12-22 | 2008-12-22 | O-phenyl phenol preparation catalyst by cyclohexanone dimer dehydrogenation and preparation method thereof |
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|---|---|---|---|
| CNA2008102074930A CN101455962A (en) | 2008-12-22 | 2008-12-22 | O-phenyl phenol preparation catalyst by cyclohexanone dimer dehydrogenation and preparation method thereof |
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Family
ID=40767251
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103008016A (en) * | 2012-10-31 | 2013-04-03 | 上海华明高纳稀土新材料有限公司 | High-thermostability aluminum oxide and preparation method thereof |
| CN104841421A (en) * | 2015-04-15 | 2015-08-19 | 北京旭阳化工技术研究院有限公司 | Catalyst composition and preparation method thereof, and method for preparing o-phenylphenol by using catalyst composition |
| CN107073450A (en) * | 2014-11-06 | 2017-08-18 | 朗盛德国有限责任公司 | For producing o-phenyl phenol（OPP）Loaded catalyst |
| CN113736508A (en) * | 2021-08-11 | 2021-12-03 | 润和科华催化剂(上海)有限公司 | Inorganic dechlorinating agent, preparation method and application |
| CN115138363A (en) * | 2021-03-30 | 2022-10-04 | 中国科学院大连化学物理研究所 | Catalyst for preparing benzofuran-2 (3H) -ketone by catalytic dehydrogenation and preparation method thereof |
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2008
- 2008-12-22 CN CNA2008102074930A patent/CN101455962A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103008016A (en) * | 2012-10-31 | 2013-04-03 | 上海华明高纳稀土新材料有限公司 | High-thermostability aluminum oxide and preparation method thereof |
| CN103008016B (en) * | 2012-10-31 | 2015-09-23 | 上海华明高纳稀土新材料有限公司 | High thermal stability aluminum oxide and preparation method thereof |
| CN107073450A (en) * | 2014-11-06 | 2017-08-18 | 朗盛德国有限责任公司 | For producing o-phenyl phenol（OPP）Loaded catalyst |
| CN107073450B (en) * | 2014-11-06 | 2020-02-07 | 朗盛德国有限责任公司 | Supported catalyst for the production of ortho-phenylphenol (OPP) |
| CN104841421A (en) * | 2015-04-15 | 2015-08-19 | 北京旭阳化工技术研究院有限公司 | Catalyst composition and preparation method thereof, and method for preparing o-phenylphenol by using catalyst composition |
| CN115138363A (en) * | 2021-03-30 | 2022-10-04 | 中国科学院大连化学物理研究所 | Catalyst for preparing benzofuran-2 (3H) -ketone by catalytic dehydrogenation and preparation method thereof |
| CN113736508A (en) * | 2021-08-11 | 2021-12-03 | 润和科华催化剂(上海)有限公司 | Inorganic dechlorinating agent, preparation method and application |
| CN116354711A (en) * | 2023-05-30 | 2023-06-30 | 佛山市三水宏源陶瓷企业有限公司 | Rock plate with ammonia purification function and preparation method thereof |
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