CN102000613B - Method for regenerating activity of deactivated ferritic catalyst - Google Patents
Method for regenerating activity of deactivated ferritic catalyst Download PDFInfo
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Abstract
The invention provides a method for regenerating activity of a deactivated ferritic catalyst. The ferritic catalyst is a catalyst for catalyzing 2,6-xylenol to produce polyphenylene oxide and comprises Fe2O3 and In2O3. The method comprises the following steps of: introducing air into a deactivated catalyst; sintering the catalyst at the temperature of between 450 and 500 DEG C to remove coked carbon in the catalyst; crushing; thermally dissolving the crushed catalyst with 10 to 63 percent of nitric acid or a mixed liquor of the nitric acid and hydrochloric acid at the temperature of between 60 and 150 DEG C; detecting the acidulated reactive fluid; calculating according to detection results; and correspondingly adding required chromium nitrate, sodium silicate and indium.
Description
Technical field
The present invention relates to a kind of method of catalysqt deactivation regeneration, be specifically related to contain Fe
2O
3, In
2O
3The method of Fe-series catalyst inactivation regeneration.
Background technology
2, the 6-xylenol is an important monomer of producing polyphenylene oxide, and the catalyst of wherein producing usefulness is through after using, and catalyst is inactivation because accumulation is serious, and the catalyst of inactivation often is used as the waste residue processing in producing at present.
Catalyst used in the present invention is the Fe-series catalyst that is the main body with iron indium system, and main component is Fe
2O
3, In
2O
3Therefore, in decaying catalyst, contain more Fe
2O
3, In
2O
3, also contain a spot of silica, chromium oxide, and material such as calcium oxide.Wherein, In
2O
3Being than precious metal, is again the main component of catalyst, from saving resource, reduces aspects such as pollution, all must recycle decaying catalyst.
" phenol gas phase methylation catalyst single tube amplifies and regeneration test research " in " Industrial Catalysis " 2000.1 proposes: under 480 ℃, and the catalyst of bubbling air roasting inactivation in consersion unit.Though this method has certain effect, need through four regenerated catalysts, like only twice regeneration, then the regenerated catalyst life-span shorter, be no more than January through estimating; In addition, it is too frequent to regenerate, and is unfavorable for big production; The 3rd, blowing air roasting apparatus space is too small, has hidden peril of explosion to exist.
Relevant in addition " Fe
2O
3The catalytic methylation Synthetic 2; 3; The research of 5-pseudocuminol and inactivation thereof ", " reclaiming copper zinc from the synthesizing methanol dead catalyst ", " recovery of useless catalyst for methanol ", " dead catalyst reclaims new technology the methanol production " all have different regeneration methods; But find that as yet the 6-xylenol is produced the used catalyst of polyphenylene oxide to catalysis 2, the method for dissolving that method is regenerated to decaying catalyst and each composition is wherein fully reclaimed with acid.
Summary of the invention
In order to solve the problems of the technologies described above, the present invention provides a kind of method of Fe-series catalyst inactivation regeneration, and said Fe-series catalyst is catalysis 2, and the 6-xylenol is produced the used catalyst of polyphenylene oxide, and it mainly contains Fe
2O
3, In
2O
3, also contain a spot of silica, chromium oxide, and material such as calcium oxide, wherein the mol ratio of each material is respectively Fe
2O
3: In
2O
3: Cr
2O
3: SiO
2: CaO=100: 3.8: 1: 1: 0.2.
Method of the present invention comprises the steps:
1) get the catalyst of inactivation, the coking material that comprises coking carbon in the catalyst is removed in the bubbling air roasting in consersion unit, pulverizes then;
2) get the catalyst of pulverizing, add dissolving acid and carry out the heat of solution reaction, said dissolving acid is the mixed liquor of nitric acid and hydrochloric acid, and preferably chloroazotic acid makes it be converted into the nitrate of solubility and/or the solution of hydrochloride with regenerated catalyst;
3) when the quality percentage composition of dissolving acid described in the reactant liquor is counted 14-16% with nitric acid, continued stirring reaction 1.5-2.5 hour, left standstill then 46-50 hour, filter, obtain filtrating;
4) detect the content of iron, chromium, sodium and indium in the filtrating of step 3), be converted into the quality percentage composition of ferric nitrate, chromic nitrate, sodium metasilicate and indium, be respectively a, b, c and d;
5) 600/a gram filtrating, 6-(600/a) * b gram chromic nitrate, 5-(600/a) * c are restrained sodium metasilicate, and join in the reactor, stir with 6.4-(the 600/a) * d gram indium of 30-37% dissolving with hydrochloric acid; Dropwise add precipitating reagent to neutral; Placed 12-24 hour, and filtered, obtain filter cake; 6) oven dry filter cake, roasting 2-6 hour then.
Preferably, the said roasting of step 1) is at 450-500 ℃ of following roasting 4-10 hour; More preferably, at 450-475 ℃ of following roasting 4-10 hour.
Preferably, step 2) said heat of solution is 60-150 ℃ of dissolving 4-10 hour down; Preferably, the temperature of said heat of solution is 60-110 ℃; More preferably, the temperature of said heat of solution is 80-100 ℃.
Preferably, step 2) concentration of said nitric acid is 10-63%, and more preferably, the concentration of said nitric acid is 36%.
Preferably, the said precipitating reagent of step 5) is a 10-25% ammoniacal liquor.
Preferably, the temperature of the said oven dry of step 6) is 100-200 ℃, and the temperature of said roasting is 400-600 ℃.
The present invention also provides a kind of active method of Fe-series catalyst that adopts said method regeneration of estimating; This method comprises the steps: said catalyst is pressed into Φ 3mm-Φ 5mm particle; Pack into and have in the reactor of fused salt (mixture of potassium nitrate, sodium nitrate, natrium nitrosum) heating; With mol ratio be phenol: methyl alcohol: the solution reaction of water=1: 1-5: 1-5, reaction temperature are 330-380 ℃, and liquid air speed is 0.7-0.9h
-1, according to reaction result, estimate life-span, the phenol conversion and 2 of regenerated catalyst, 6-xylenol selectivity (with in the gas chromatographic detection reactant liquor 2, the content of 6-xylenol is used its conversion ratio divided by phenol then).
The method of Fe-series catalyst inactivation regeneration of the present invention has following advantage:
1. technology is simple
Adopt the acid method of dissolving that the catalyst of inactivation is regenerated, and the useful component iron in the decaying catalyst, chromium, indium are reclaimed with the form of nitrate and hydrochloride mixed liquor, simplified regeneration and reclaimed technology; Simultaneously; In the catalyst normal productive process, must raw materials such as iron, chromium, indium be handled the salify mixed liquor; And nitrate that the present invention obtains and hydrochloride mixed liquor can directly be used for the pilot process of Catalyst Production; Both simplify Preparation of catalysts technology, reduced catalyst production cost again.
2. the rate of recovery is high
Fe
2O
3, In, and the rate of recovery of chromium oxide all can reach more than 90%, the content of silica can reach more than 80%, has saved resources such as iron, chromium, indium effectively; The rate of recovery is high, easy to operate.
3. safety non-pollution
The recovery process safety is reliable, with device for absorbing tail gas, is used to absorb main waste discharge at roaster, can not cause new pollution.
4. economic benefit
During regeneration, needed main raw material are few, and the chromic nitrate, sodium metasilicate and the indium that only need to replenish respective amount get final product, and cost has only 1/10th of Preparation of Catalyst cost, is a kind of desirable method of regenerating catalyst.
5. the life of catalyst after the regeneration does not have too big difference with activity with the synthetic catalyst for preparing more than three months.
6. the size of the catalyst after the regeneration is little to the activity of such catalysts influence.
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
The specific embodiment
Embodiment 1
Get 200 gram decaying catalysts, put into Muffle furnace, remove coking material 475 ℃ of bubbling air roastings, keeping the feeding amount of air is 20L/h, insulation 4h.It is subsequent use to pulverize the back.
Get the catalyst of the above-mentioned pulverizing of 143 grams, put into the 2000ml there-necked flask that the band condenser stirs and heats, add 36% nitric acid 1000 grams 30% hydrochloric acid 300 grams, stir intensification down, 100 ℃ of insulations 8 hours.
With the content of nitric acid in the method detection reaction liquid of acid-base neutralization,, continued stirring reaction 2 hours when content reaches 15%.Stop to stir and heating, left standstill 48 hours.
Treat that temperature is cooled to room temperature, filter,, be converted into the quality percentage composition of ferric nitrate, chromic nitrate, sodium metasilicate and indium with the content of iron, chromium, sodium and indium in the atomic absorption method detection filtrating.
The content of ferric nitrate is a (47.97%) in the filtrating, and the content of chromic nitrate is b (0.45%), and the content of sodium metasilicate is c (0.32%), and indium content is d (0.48%).Stir down, in the reactor of the 20L that band stirs, add 1250 gram filtratings, 0.38 gram chromic nitrate, 1.0 gram sodium metasilicate.
With 60ml 30% dissolving with hydrochloric acid 0.4 gram indium.Join after having dissolved in the solution of above-mentioned mixing, stir after 0.5 hour, dropwise drip 15% ammoniacal liquor solution is adjusted to neutrality.Stirred again 0.5 hour, placed 24 hours.Filter.
Dry filter cake down at 180 ℃, after the oven dry, with 120 grams, 0.5% calcium oxalate dipping, 480 ℃ of roastings 4 hours, the catalyst that obtains regenerating.
Through calculating Fe
2O
3, In, and the rate of recovery of silica and chromium oxide is following: Fe
2O
3Be 90%, In is 93%, and chromium oxide is 93%, and silica is 80%.
The catalyst of regeneration is pressed into Φ 3mm particle, is encased in the single tube reactor that has fused salt (mixture of potassium nitrate, sodium nitrate, natrium nitrosum) heating, the control reaction temperature is 330 ℃, normal pressure, liquid air speed 0.9h
-1, with mol ratio be phenol: methyl alcohol: the solution reaction of water=1: 2: 1, the life-span of evaluate catalysts, phenol conversion and 2,6-xylenol selectivity, evaluation result is seen table 1.
Embodiment 2
Get 200 gram decaying catalysts, put into Muffle furnace, remove coking material 450 ℃ of bubbling air roastings, keeping the feeding amount of air is 20L/h, insulation 8h.It is subsequent use to pulverize the back.Get the catalyst of the above-mentioned pulverizing of 143 grams, put into the 2000ml there-necked flask that the band condenser stirs and heats, add 36% nitric acid 1210 grams 30% hydrochloric acid 300 grams, stir intensification down, 150 ℃ of insulations 4 hours.
With the content of nitric acid in the method detection reaction liquid of acid-base neutralization,, continued stirring reaction 1.5 hours when content reaches 15%.Stop stirring and heating, left standstill 50 hours.
Treat that temperature is cooled to room temperature, filter that the content with iron, chromium, sodium and indium in the atomic absorption method detection filtrating replenishes corresponding amount according to the method for embodiment 1 then, operates the catalyst that obtains regenerating with method.
The catalyst of regeneration is pressed into Φ 4mm particle, is encased in the single tube reactor that has fused salt (mixture of potassium nitrate, sodium nitrate, natrium nitrosum) heating, the control reaction temperature is 380 ℃, normal pressure, liquid air speed 0.9h
-1, with mol ratio be phenol: methyl alcohol: the solution reaction of water=1: 3: 1, the life-span of evaluate catalysts, phenol conversion and 2,6-xylenol selectivity, evaluation result is seen table 1.
Embodiment 3
Get 200 gram decaying catalysts, put into Muffle furnace, remove coking material 460 ℃ of bubbling air roastings, keeping the feeding amount of air is 20L/h, insulation 10h.It is subsequent use to pulverize the back.
Get the catalyst of the above-mentioned pulverizing of 143 grams, put into the 1500ml there-necked flask that the band condenser stirs and heats, add chloroazotic acid 600 grams, stir down and heat up, be incubated 8 hours at 100 ℃.
With the content of chloroazotic acid in the method detection reaction liquid of acid-base neutralization,, continued stirring reaction 2.5 hours when content reaches 15%.Stop stirring and heating, left standstill 46 hours.
Treat that temperature is cooled to room temperature, filter that the content with iron, chromium, sodium and indium in the atomic absorption method detection filtrating replenishes corresponding amount according to the method for embodiment 1 then, operates the catalyst that obtains regenerating with method.
The catalyst of regeneration is pressed into Φ 5mm particle, is encased in the single tube reactor that has fused salt (mixture of potassium nitrate, sodium nitrate, natrium nitrosum) heating, the control reaction temperature is 350 ℃, normal pressure, liquid air speed 0.9h
-1, with mol ratio be phenol: methyl alcohol: the solution reaction of water=1: 5: 1, the life-span of evaluate catalysts, phenol conversion and 2,6-xylenol selectivity, evaluation result is seen table 1.
Embodiment 4
Get 200 gram decaying catalysts, put into Muffle furnace, remove coking material 470 ℃ of bubbling air roastings, keeping the feeding amount of air is 20L/h, insulation 6h.It is subsequent use to pulverize the back.
Get the catalyst of the above-mentioned pulverizing of 143 grams, put into the 1500ml there-necked flask that the band condenser stirs and heats, add chloroazotic acid 1500 grams, stir down and heat up, be incubated 8 hours at 100 ℃.
With the content of chloroazotic acid in the method detection reaction liquid of acid-base neutralization,, continued stirring reaction 2 hours when content reaches 15%.Stop stirring and heating, left standstill 48 hours.
Treat that temperature is cooled to room temperature, filter that the content with iron, chromium, sodium and indium in the atomic absorption method detection filtrating replenishes corresponding amount according to the method for embodiment 1 then, operates the catalyst that obtains regenerating with method.
The catalyst of regeneration is pressed into Φ 3mm particle, is encased in the single tube reactor that has fused salt (mixture of potassium nitrate, sodium nitrate, natrium nitrosum) heating, the control reaction temperature is 330 ℃, normal pressure, liquid air speed 0.9h
-1, with mol ratio be phenol: methyl alcohol: the solution reaction of water=1: 3: 1, the life-span of evaluate catalysts, phenol conversion and 2,6-xylenol selectivity, evaluation result is seen table 1.
Embodiment 5
Get 200 gram decaying catalysts, put into Muffle furnace, remove coking material 475 ℃ of bubbling air roastings, keeping the feeding amount of air is 20L/h, insulation 4h.It is subsequent use to pulverize the back.
Get the catalyst of the above-mentioned pulverizing of 143 grams, put into the 1500ml there-necked flask that the band condenser stirs and heats, add 36% nitric acid 1210 grams 30% hydrochloric acid 300 grams, stir intensification down, 80 ℃ of insulations 10 hours.
With the content of nitric acid in the method detection reaction liquid of acid-base neutralization,, continued stirring reaction 2 hours when content reaches 14%.Stop stirring and heating, left standstill 48 hours.
Treat that temperature is cooled to room temperature, filter that the content with iron, chromium, sodium and indium in the atomic absorption method detection filtrating replenishes corresponding amount according to the method for embodiment 1 then, operates the catalyst that obtains regenerating with method.The catalyst of regeneration is pressed into Φ 3mm particle, is encased in the single tube reactor that has fused salt (mixture of potassium nitrate, sodium nitrate, natrium nitrosum) heating, the control reaction temperature is 380 ℃, normal pressure, liquid air speed 0.9h
-1, with mol ratio be phenol: methyl alcohol: the solution reaction of water=1: 5: 2, the life-span of evaluate catalysts, phenol conversion and 2,6-xylenol selectivity, evaluation result is seen table 1.
Embodiment 6
Get 200 gram decaying catalysts, put into Muffle furnace, remove coking material 475 ℃ of bubbling air roastings, keeping the feeding amount of air is 20L/h, insulation 4h.It is subsequent use to pulverize the back.
Get the catalyst of the above-mentioned pulverizing of 143 grams, put into the 1500ml there-necked flask that the band condenser stirs and heats, add 36% nitric acid 1210 grams and 30% hydrochloric acid, 300 grams, stir intensification down, 100 ℃ of insulations 8 hours.
With the content of nitric acid in the method detection reaction liquid of acid-base neutralization,, continued stirring reaction 2 hours when content reaches 16%.Stop stirring and heating, left standstill 48 hours.
Treat that temperature is cooled to room temperature, filter that the content with iron, chromium, sodium and indium in the atomic absorption method detection filtrating replenishes corresponding amount according to the method for embodiment 1 then, operates the catalyst that obtains regenerating with method.
The catalyst of regeneration is pressed into Φ 4mm particle, is encased in the single tube reactor that has fused salt (mixture of potassium nitrate, sodium nitrate, natrium nitrosum) heating, the control reaction temperature is 330 ℃, normal pressure, liquid air speed 0.7h
-1, with mol ratio be phenol: methyl alcohol: the solution reaction of water=1: 5: 1, the life-span of evaluate catalysts, phenol conversion and 2,6-xylenol selectivity, evaluation result is seen table 1.
Embodiment 7
Get 200 gram decaying catalysts, put into Muffle furnace, remove coking material 475 ℃ of bubbling air roastings, keeping the feeding amount of air is 20L/h, insulation 4h.It is subsequent use to pulverize the back.
Get the catalyst of the above-mentioned pulverizing of 143 grams, put into the 2000ml there-necked flask that the band condenser stirs and heats, add 42% nitric acid 1000 grams 30% hydrochloric acid 300 grams, stir intensification down, 100 ℃ of insulations 8 hours.
With the content of nitric acid in the method detection reaction liquid of acid-base neutralization,, continued stirring reaction 2 hours when content reaches 15%.Stop to stir and heating, left standstill 48 hours.
Treat that temperature is cooled to room temperature, filter that the content with iron, chromium, sodium and indium in the atomic absorption method detection filtrating replenishes corresponding amount according to the method for embodiment 1 then, operates the catalyst that obtains regenerating with method.
The catalyst of regeneration is pressed into Φ 5mm particle, is encased in the single tube reactor that has fused salt (mixture of potassium nitrate, sodium nitrate, natrium nitrosum) heating, the control reaction temperature is 330 ℃, normal pressure, liquid air speed 0.8h
-1, with mol ratio be phenol: methyl alcohol: the solution reaction of water=1: 5: 1, the life-span of evaluate catalysts, phenol conversion and 2,6-xylenol selectivity, evaluation result is seen table 1.
The evaluation of table 1 regenerated catalyst
Annotate: 1. above result uses gas chromatographic detection, the detection frequency be 2 hours once.
2. the phenol of the conversion ratio=reaction of phenol/(phenol of unreacted phenol+reaction);
3.2, the conversion ratio of the selectivity of 6-xylenol=(in the product 2,6-xylenol phenol content)/phenol
Claims (10)
1. the method for a Fe-series catalyst inactivation regeneration is characterized in that, comprises the steps:
1) get the catalyst of inactivation, bubbling air roasting in consersion unit is pulverized;
2) get the catalyst of pulverizing, add dissolving acid and carry out the heat of solution reaction, said dissolving acid is the mixed liquor of nitric acid and hydrochloric acid;
3) when the quality percentage composition of dissolving acid described in the reactant liquor is counted 14-16% with nitric acid, continued stirring reaction 1.5-2.5 hour, left standstill then 46-50 hour, filter, obtain filtrating;
4) detect the content of iron, chromium, sodium and indium in the filtrating of step 3), be converted into the quality percentage composition of ferric nitrate, chromic nitrate, sodium metasilicate and indium, be respectively a, b, c and d;
5) 600/a gram filtrating, 6-(600/a) * b gram chromic nitrate, 5-(600/a) * c are restrained sodium metasilicate, and join in the reactor, stir with 6.4-(the 600/a) * d gram indium of 30-37% dissolving with hydrochloric acid; Dropwise add precipitating reagent to neutral; Placed 12-24 hour, and filtered, obtain filter cake;
6) oven dry filter cake, roasting 2-6 hour then;
Wherein, said Fe-series catalyst is catalysis 2, and the 6-xylenol is produced the used catalyst of polyphenylene oxide, and it contains Fe
2O
3, In
2O
3, also contain a spot of silica, chromium oxide, and calcium oxide, wherein the mol ratio of each material is Fe
2O
3: In
2O
3: Cr
2O
3: SiO
2: CaO=100: 3.8: 1: 1: 0.2.
2. method according to claim 1 is characterized in that, the said roasting of step 1) is at 450-475 ℃ of following roasting 4-10 hour.
3. method according to claim 1 and 2 is characterized in that step 2) said heat of solution is 60-110 ℃ of down dissolving 4-10 hour.
4. method according to claim 3 is characterized in that step 2) temperature of said heat of solution is 80-100 ℃.
5. method according to claim 1 and 2 is characterized in that step 2) concentration of said nitric acid is 10-63%.
6. method according to claim 1 and 2 is characterized in that step 2) said dissolving acid is chloroazotic acid.
7. method according to claim 1 and 2 is characterized in that, the said precipitating reagent of step 5) is a 10-25% ammoniacal liquor.
8. method according to claim 1 and 2 is characterized in that, the temperature of the said oven dry of step 6) is 100-200 ℃.
9. method according to claim 1 and 2 is characterized in that, the temperature of the said roasting of step 6) is 400-600 ℃.
10. estimate the active method of Fe-series catalyst that the said method of claim 1-9 is regenerated for one kind; It is characterized in that; Undertaken by following step: said catalyst is pressed into Φ 3mm-Φ 5mm particle, and packing into has in the reactor of fused salt heating, with mol ratio be phenol: methyl alcohol: the solution reaction of water=1: 1-5: 1-5; Reaction temperature is 330-380 ℃, and liquid air speed is 0.7-0.9h
-1,, estimate life-span, the phenol conversion and 2 of regenerated catalyst, 6-xylenol selectivity according to reaction result.
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| CN103752354B (en) * | 2014-01-10 | 2015-09-09 | 天津市环境保护科学研究院 | A kind of renovation process for film ozone catalytic reactor inactivation Catalytic Layer |
| CN111957324A (en) * | 2020-08-13 | 2020-11-20 | 浙江工业大学 | Method for recycling waste catalyst |
Citations (4)
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|---|---|---|---|---|
| CN1034495A (en) * | 1988-01-31 | 1989-08-09 | 何新秀 | A kind of method that from the Fe-Cr HTS catalyst, reclaims siderochrome |
| CN1062330A (en) * | 1990-12-11 | 1992-07-01 | 衢州化学工业公司 | Preparation method of medium-temperature shift catalyst in hydrogen production device |
| CN101003854A (en) * | 2007-01-22 | 2007-07-25 | 中国科学院过程工程研究所 | New method for soaking out enriched ores of high indium, high iron, and high sulfur zinc |
| WO2009038379A2 (en) * | 2007-09-21 | 2009-03-26 | Research Institute Of Industrial Science & Technology | Method of manufacturing fe and ni containing material and cobalt containing material using recycling residue of spent catalyst and method of manufacturing raw material for stainless using the fe and ni containing material and method of manufacturing fe-ni alloy |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10017153C1 (en) * | 2000-04-06 | 2001-05-03 | Wacker Chemie Gmbh | Recovery of copper(I) chloride catalyst in direct synthesis of organochlorosilane involves oxidizing copper in process residue in aqueous acid and reducing resultant aqueous copper(II) chloride solution with iron |
-
2010
- 2010-11-02 CN CN201010533819A patent/CN102000613B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034495A (en) * | 1988-01-31 | 1989-08-09 | 何新秀 | A kind of method that from the Fe-Cr HTS catalyst, reclaims siderochrome |
| CN1062330A (en) * | 1990-12-11 | 1992-07-01 | 衢州化学工业公司 | Preparation method of medium-temperature shift catalyst in hydrogen production device |
| CN101003854A (en) * | 2007-01-22 | 2007-07-25 | 中国科学院过程工程研究所 | New method for soaking out enriched ores of high indium, high iron, and high sulfur zinc |
| WO2009038379A2 (en) * | 2007-09-21 | 2009-03-26 | Research Institute Of Industrial Science & Technology | Method of manufacturing fe and ni containing material and cobalt containing material using recycling residue of spent catalyst and method of manufacturing raw material for stainless using the fe and ni containing material and method of manufacturing fe-ni alloy |
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Inventor after: Li Zhengang Inventor after: Zhang Xiaolin Inventor after: Zhao Jianchao Inventor after: Liu Lin Inventor after: Liu Yonghong Inventor before: Liu Yonghong Inventor before: Li Zhengang Inventor before: Zhang Xiaolin Inventor before: Zhao Jianchao Inventor before: Liu Lin |
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Free format text: CORRECT: INVENTOR; FROM: LIU YONGHONG LI ZHENGANG ZHANG XIAOLIN ZHAO JIANZHAO LIU LIN TO: LI ZHENGANG ZHANG XIAOLIN ZHAO JIANZHAO LIU LIN LIU YONGHONG |
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Effective date of registration: 20170411 Address after: 226017 Nantong economic and Technological Development Zone, Jiangsu, Hong Kong Road, No. 118 Patentee after: Xingchen Synthetic Matrials Co., Ltd., Nantong Address before: 100083 Beijing Garden Road, No. 6201 garden hotel room, room 30, No. Patentee before: Lanxing Chemical New Material Co., Ltd. |