CN1701848A - Preparation of supported amorphous catalyst for pre-hydrogenation of coked crude benzol - Google Patents
Preparation of supported amorphous catalyst for pre-hydrogenation of coked crude benzol Download PDFInfo
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- CN1701848A CN1701848A CN 200510069579 CN200510069579A CN1701848A CN 1701848 A CN1701848 A CN 1701848A CN 200510069579 CN200510069579 CN 200510069579 CN 200510069579 A CN200510069579 A CN 200510069579A CN 1701848 A CN1701848 A CN 1701848A
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Abstract
The invention discloses an amorphous activator, which is used to get rid of olefin and dialkene and take hydrogenation pretreatment in coking crude benzol. After catalytic hydrogenation, the content of olefin and dialkene in product of coking crude benzol is less then 0.5ppm; the loss of benzene, toluene, xylene and other derivants of saturated benzene is less 0.5%; the activator can restrain efficiently the olefin polyreaction of coking crude benzol during HDS process, thereby prevent the phenomena of surface charring and even deactivation. It is mainly characterized in that, use vacuum impregnation method to prepare active ingredients disperse greatly on carrier surface with amorphous form, and advanced in high catalytic activity, better selectivity, long service life and low cost.
Description
Technical field the invention belongs to catalyst, is specifically related to a kind of coking crude benzene low temperature preliminary treatment selection Hydrobon catalyst that is used for.
The background technology crude benzole hydrogenation is refining to be significant process in the crude benzol processing industry, mainly adopts sulfuric acid scrubbing method and hydrofinishing method.The sulfuric acid scrubbing method is a kind of crude benzol processing method that China generally adopts at present, has shortcomings such as poor product quality, product yield are low, environmental protection difference.The hydrofinishing method not only makes good product quality, yield height, and helps environmental protection and labour protection, has an economic benefit very much and social benefit, is current state-of-the-art crude benzol processing method, and its core technology is the development of Hydrobon catalyst.
Catalyst for pre-hydrogenation is mainly used in the pre-reactor, in order to remove the compound of unstable, easy polymerization reaction take place such as cyclopentadiene, styrene in the crude benzol, make its hydrogenation saturated, but can not be with crude benzol product hydrogenations such as benzene, toluene and dimethylbenzene, therefore, this kind catalyst should have good selection hydrogenation performance; In addition, this catalyst can also partly be removed sulfur-bearing in the crude benzol, compound such as nitrogenous.Comprehensive above 2 points, the effect of catalyst for pre-hydrogenation is to separate the raw material that provides quality good with product for main hydrogenation reaction, and can protect main hydrogenating catalyst, prolongs its service life.
At present, the used catalyst for pre-hydrogenation of domestic large-scale coal chemical enterprise all depends on import, for example the M-21 catalyst of German BASF AG.At import catalyst price height, also do not apply for a patent at home and catalyst for pre-hydrogenation of coked crude benzol of the present invention is better than situations such as import catalyst on catalytic performance, the present invention proposes patent application, makes the catalyst for pre-hydrogenation of coked crude benzol production domesticization, substitutes the import like product.
Summary of the invention the purpose of this invention is to provide a kind of coking crude benzene preliminary treatment selection Hydrobon catalyst that is used for.
Main advantage of the present invention is:
1. the crude benzol preliminary treatment that the present invention relates to selects Hydrobon catalyst to have high activity, selectivity, stability and long-life.
2. the crude benzol preliminary treatment that the present invention relates to selects Hydrobon catalyst can make compound hydrogenation unstable, easily polymerization reaction take place such as cyclopentadiene in the crude benzol, styrene saturated, and the content in the product is less than 0.5ppm.
3. the crude benzol preliminary treatment that the present invention relates to selects Hydrobon catalyst can make the loss amount of benzene,toluene,xylene and other saturated benzene derivatives less than 0.5%.
4. the crude benzol preliminary treatment that the present invention relates to is selected in 240 hours runnings of Hydrobon catalyst, and active and selectivity is stablized, and does not find any deactivation phenomenom.
5. the crude benzol preliminary treatment that the present invention relates to selects Hydrobon catalyst to compare with like product (German M-21 catalyst), has better catalytic activity.
6. technology of the present invention is simple, and preparation cost is low, strong operability, suitability for industrialized.
The present invention is mainly by the following technical solutions:
The present invention adopts vacuum impregnation technology to prepare the crude benzol preliminary treatment and selects Hydrobon catalyst, prepares gained according to following step:
(1) takes by weighing Mo salt, be dissolved in the ammoniacal liquor, add ethanol, make the solution that contains Mo salt;
(2) take by weighing carrier, after the dehydration degassing, with the Mo salt solution impregnation on it;
(3) under 10～120 ℃ of temperature conditions, the carrier drying of Mo will be soaked with;
(4) under 300～700 ℃ of temperature conditions, the carrier that is soaked with active component Mo was calcined 0.5～4 hour.
(5) take by weighing Ni salt, be dissolved in the deionized water, add ethanol, make the solution that contains Ni salt;
(6) repeating step (2)～(5) join Ni in the carrier that contains Mo;
(7) take by weighing auxiliary agent, be dissolved in the deionized water, add ethanol, make compounding agent solution;
(8) repeating step (6) joins auxiliary agent in the carrier that contains Ni, Mo, thereby obtains catalyst.
Described Mo salt is selected from nitric acid molybdenum, molybdenum chloride, molybdenum trisulfate, ammonium molybdate, sodium molybdate, potassium molybdate.
Described carrier is γ-Al
2O
3, SiO
2, TiO
2, ZrO
2, diatomite, sepiolite, molecular sieve, activated carbon, CNT, specific area is 250m
2/ g～350m
2/ g, pore volume are 0.50ml/g～0.80ml/g, and the aperture is 5nm～15nm.
Described Ni salt is selected from nickel chloride, nickel nitrate, nickelous sulfate, nickel acetate, citric acid nickel.
Described auxiliary agent is one or more mixtures of W, P, B, Co, Fe, Mn.
Described prepared catalyst comprises following component (percentage by weight):
NiO 1～10% MoO
35～25% auxiliary agents 1～10 ‰ carrier remainders
Described prepared specific surface area of catalyst is 150m
2/ g～250m
2/ g, pore volume are 0.40ml/g～0.70ml/g, and the aperture is 5nm～15nm.
The service condition of described prepared catalyst is: 150～300 ℃ of temperature, pressure 1.0～4.0MPa, sample introduction air speed 1.0～3.0h
-1, hydrogen/oil=400～1200: 1 (vol).
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail.
Description of drawings
Fig. 1: the gas chromatogram of crude benzol reaction raw materials.
Fig. 2: the gas chromatogram of crude benzol behind the selective hydrogenation reaction.
The specific embodiment
Embodiment 1: will take by weighing the dried γ-Al of 8.9456g
2O
3Carrier outgased 2 hours.During this period, take by weighing the 2.2998g ammonium molybdate in a clean beaker, fully dissolve, make the solution clear, add the 4ml absolute ethyl alcohol again, stirred 1 hour, form ammonium molybdate and divide immersion liquid with 8ml 3mol/l ammoniacal liquor.Ammonium molybdate is divided on the carrier after immersion liquid is immersed in the degassing, and after dry 2 hours, calcining 2 hours in 500 ℃ Muffle furnace is again taken out after being cooled to 105 ℃, and it is standby to place drier to be cooled to room temperature.With being soaked with carrier after the calcining of ammonium molybdate, outgased 2 hours.During this period, take by weighing the 2.6452g nickel nitrate in a clean beaker, fully dissolve, make the solution clear, add the 4ml absolute ethyl alcohol again, stirred 1 hour, form nickel nitrate and divide immersion liquid with 8ml distilled water.Divide immersion liquid to be immersed in ammonium molybdate and contain on the carrier of Mo, calcining 2 hours in 500 ℃ Muffle furnace after dry 2 hours is taken out after being cooled to 105 ℃, and it is standby to place drier to be cooled to room temperature, promptly gets catalyst, and wherein NiO quality percentage composition is 6%, MoO
3The quality percentage composition is 15%.The evaluation method of this catalyst is: this catalyst breakage is got granularity 140～200 orders, getting 1.3ml, to be seated in diameter be 5.5mm, draw ratio is in 10 the fixed bed stainless steel tube reactor, and two ends filling quartz sand, this catalyst need handle through presulfurization before reaction.Reaction condition is: reaction pressure 3MPa, 210 ℃ of reaction temperatures, sample introduction air speed 1.54h
-1, hydrogen/oil=500: 1.Reactant, product its chemical composition of gas chromatographic analysis and quality percentage composition.Reaction raw materials is coking crude benzene (the quality percentage composition is: cyclopentadiene 0.3906, benzene 60.1656, toluene 21.3457, dimethylbenzene 10.1196, styrene 2.5103, other are 5.4682 years old), and its catalytic performance is referring to accompanying drawing 1, accompanying drawing 2 and following table data.
| Cyclopentadiene content in the product | Styrene-content in the product | Triphen (benzene,toluene,xylene) loss amount |
| ??～0ppm | ??0ppm | ??＜0.5％ |
Embodiment 2: the amount of the medicine that is taken by weighing in this example is identical with embodiment 1 with operation, and different is to use carrier S iO
2Replace γ-Al
2O
3, its catalytic performance sees table data.
| Cyclopentadiene content in the product | Styrene-content in the product | Triphen (benzene,toluene,xylene) loss amount |
| ??～0.5ppm | ??0ppm | ??＜0.4％ |
Embodiment 5: the amount of the medicine that is taken by weighing in this example is identical with embodiment 4 with operation, and different is to replace γ-Al with activity carbon carrier
2O
3Carrier, its catalytic performance sees table data.
| Cyclopentadiene content in the product | Styrene-content in the product | Triphen (benzene,toluene,xylene) loss amount |
| ??～0ppm | ??0ppm | ??＜0.3％ |
Embodiment 4: the amount of medicament that is taken by weighing in this example is identical with embodiment 1 with operation, and different is that carbon nanotube carrier replaces γ-Al
2O
3Carrier, its catalytic performance sees table data.
| Cyclopentadiene content in the product | Styrene-content in the product | Triphen (benzene,toluene,xylene) loss amount |
| ??0ppm | ??0ppm | ??＜0.2％ |
Embodiment 5: the medicine that is taken by weighing in this example is identical with embodiment 1 with operation, and different is to replace ammonium molybdate 2.2998g with nitric acid molybdenum 3.5427g, and its catalytic performance sees table data.
| Cyclopentadiene content in the product | Styrene-content in the product | Triphen (benzene,toluene,xylene) loss amount |
| ??～0.5ppm | ??0.1ppm | ??＜0.5％ |
Embodiment 6: the medicine that is taken by weighing in this example is identical with embodiment 1 with operation, and different is with γ-Al
2O
3Carrier 10g replaces 8.9456g, and nickel nitrate 2.4334g replaces 2.6452g, and its catalytic performance sees table data.
| Cyclopentadiene content in the product | Styrene-content in the product | Triphen (benzene,toluene,xylene) loss amount |
| ??～0.4ppm | ??0ppm | ??＜0.4％ |
Embodiment 7: the medicine that is taken by weighing in this example is identical with embodiment 1 with operation, and different is to replace nickel nitrate 2.6452g with nickel acetate 2.2637g, and its catalytic performance sees table data.
| Cyclopentadiene content in the product | Styrene-content in the product | Triphen (benzene,toluene,xylene) loss amount |
| ??～0.4ppm | ??0ppm | ??＜0.4％ |
Embodiment 8: the amount of the medicine that is taken by weighing in this example is identical with embodiment 1 with operation, different is, in preparation process, add auxiliary agent W, concrete operations are that the catalyst dehydration that will contain embodiment 1 gained outgased 2 hours, the sodium tungstate of 0.0818g is dissolved in the 8ml deionized water, add 4ml ethanol, stir and be immersed on the catalyst that contains Ni and Mo after 1 hour, calcining 2 hours in 500 ℃ Muffle furnace after dry 2 hours is taken out after being cooled to 105 ℃, it is standby to place drier to be cooled to room temperature, promptly get catalyst, wherein NiO quality percentage composition is 6%, MoO
3The quality percentage composition is 15%, WO
3The quality percentage composition is 0.5%, and its catalytic performance sees table data.
| Cyclopentadiene content in the product | Styrene-content in the product | Triphen (benzene,toluene,xylene) loss amount |
| ??～0ppm | ??0ppm | ??＜0.3％ |
Claims (10)
1. the preparation method of Hydrobon catalyst is selected in a coking crude benzene preliminary treatment, it is characterized in that according to following step preparation:
(1) takes by weighing Mo salt 1., be dissolved in the ammoniacal liquor, add ethanol, make the solution that contains Mo salt;
(2) take by weighing carrier 2., after the dehydration degassing, with the Mo salt solution impregnation on it;
(3) under 10～120 ℃ of temperature conditions, the carrier drying of Mo will be soaked with;
(4) under 300～700 ℃ of temperature conditions, the carrier that is soaked with active component Mo was calcined 0.5～4 hour.
(5) take by weighing Ni salt 3., be dissolved in the deionized water, add ethanol, make the solution that contains Ni salt;
(6) repeating step (2)～(5) join Ni in the carrier that contains Mo;
(7) take by weighing auxiliary agent 4., be dissolved in the deionized water, add ethanol, make compounding agent solution;
(8) repeating step (6) joins auxiliary agent in the carrier that contains Ni, Mo, thereby obtains catalyst.
2. preparation method according to claim 1 is characterized in that 1. described Mo salt be one or more mixtures in nitric acid molybdenum, molybdenum chloride, molybdenum trisulfate, ammonium molybdate, sodium molybdate, the potassium molybdate.
3. preparation method according to claim 1 is characterized in that 2. described carrier is γ-Al
2O
3, SiO
2, TiO
2, ZrO
2, diatomite, sepiolite, molecular sieve, activated carbon, CNT.
4. preparation method according to claim 1, it is characterized in that described carrier 2. specific area be 250m
2/ g～350m
2/ g, pore volume are 0.50ml/g～0.80ml/g, and the aperture is 5nm～15nm.
5. preparation method according to claim 1 is characterized in that described baking temperature the best is 20～70 ℃.
6. preparation method according to claim 1 is characterized in that 3. described Ni salt be one or more mixtures in nickel chloride, nickel nitrate, nickelous sulfate, nickel acetate, the citric acid nickel.
7. preparation method according to claim 1 is characterized in that 4. described auxiliary agent is one or more mixtures of W, P, B, Co, Fe, Mn.
8. preparation method according to claim 1 is characterized in that described calcining heat the best is 400～600 ℃, and calcination time the best is 1～3 hour.
9. catalyst according to claim 1 is characterized in that this kind catalyst comprises following component (percentage by weight):
NiO 1～10% MoO
35～25% auxiliary agents 1～10 ‰ carrier remainders
Best component content (percentage by weight) is:
NiO 4.5～7% MoO
310～20% auxiliary agents 4～6 ‰ carrier remainders
10. catalyst according to claim 1, specific area are 150m
2/ g～250m
2/ g, pore volume are 0.40ml/g～0.70ml/g, and the aperture is 5nm～15nm, and service condition is: 150～300 ℃ of temperature, pressure 1.0～4.0MPa, sample introduction air speed 1.0～3.0h
-1, hydrogen/oil=400～1200: 1 (vol).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510069579 CN1701848A (en) | 2005-05-17 | 2005-05-17 | Preparation of supported amorphous catalyst for pre-hydrogenation of coked crude benzol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510069579 CN1701848A (en) | 2005-05-17 | 2005-05-17 | Preparation of supported amorphous catalyst for pre-hydrogenation of coked crude benzol |
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| Publication Number | Publication Date |
|---|---|
| CN1701848A true CN1701848A (en) | 2005-11-30 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658160A (en) * | 2012-05-10 | 2012-09-12 | 无锡市强亚耐火材料有限公司 | Crude benzene hydrogenation catalyst and preparation method thereof |
| CN103789025A (en) * | 2012-11-05 | 2014-05-14 | 中国石油化工股份有限公司 | Heavy benzene hydro-upgrading method |
| CN105195164A (en) * | 2015-11-05 | 2015-12-30 | 中国石油化工股份有限公司 | Catalyst as well as preparation method and application thereof |
| CN105772004A (en) * | 2016-03-24 | 2016-07-20 | 山东成泰化工有限公司 | Benzene hydrogenation catalyst and preparation method thereof |
| CN108927143A (en) * | 2018-09-06 | 2018-12-04 | 王淑英 | A kind of preparation method for treating open-angle glaucoma pharmaceutical intermediate |
| CN112191254A (en) * | 2020-08-27 | 2021-01-08 | 安徽理工大学 | Catalyst and method for preparing 2-ethoxyphenol by catalytic depolymerization of lignin |
-
2005
- 2005-05-17 CN CN 200510069579 patent/CN1701848A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658160A (en) * | 2012-05-10 | 2012-09-12 | 无锡市强亚耐火材料有限公司 | Crude benzene hydrogenation catalyst and preparation method thereof |
| CN103789025A (en) * | 2012-11-05 | 2014-05-14 | 中国石油化工股份有限公司 | Heavy benzene hydro-upgrading method |
| CN103789025B (en) * | 2012-11-05 | 2015-07-22 | 中国石油化工股份有限公司 | Heavy benzene hydro-upgrading method |
| CN105195164A (en) * | 2015-11-05 | 2015-12-30 | 中国石油化工股份有限公司 | Catalyst as well as preparation method and application thereof |
| CN105195164B (en) * | 2015-11-05 | 2018-04-17 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method and application |
| CN105772004A (en) * | 2016-03-24 | 2016-07-20 | 山东成泰化工有限公司 | Benzene hydrogenation catalyst and preparation method thereof |
| CN108927143A (en) * | 2018-09-06 | 2018-12-04 | 王淑英 | A kind of preparation method for treating open-angle glaucoma pharmaceutical intermediate |
| CN108927143B (en) * | 2018-09-06 | 2020-01-03 | 北京宝诺康医药科技有限公司 | Preparation method of pharmaceutical intermediate for treating open-angle glaucoma |
| CN112191254A (en) * | 2020-08-27 | 2021-01-08 | 安徽理工大学 | Catalyst and method for preparing 2-ethoxyphenol by catalytic depolymerization of lignin |
| US20220062872A1 (en) * | 2020-08-27 | 2022-03-03 | Anhui University Of Science & Technology | Catalyst and Method for Preparation of 2-Ethoxyphenol by Catalytic Depolymerization of Lignin |
| US12023654B2 (en) * | 2020-08-27 | 2024-07-02 | Anhui University Of Science & Technology | Catalyst and method for preparation of 2-ethoxyphenol by catalytic depolymerization of lignin |
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