CN1234666C - Preparation method of Ru-B load type catalyst - Google Patents
Preparation method of Ru-B load type catalyst Download PDFInfo
- Publication number
- CN1234666C CN1234666C CN 03109528 CN03109528A CN1234666C CN 1234666 C CN1234666 C CN 1234666C CN 03109528 CN03109528 CN 03109528 CN 03109528 A CN03109528 A CN 03109528A CN 1234666 C CN1234666 C CN 1234666C
- Authority
- CN
- China
- Prior art keywords
- zno
- catalyzer
- ruthenium
- catalyst
- zro
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing an Ru-B loaded catalyst for selective hydrogenation of aromatic hydrocarbon, which adopts ruthenium as an active component, boron as an auxiliary agent, and a single-component or a bicomponent oxide as a carrier. The method of the present invention, which is adopted to prepare the catalyst, has advantages of ruthenium dosage saving, catalyst cost reduction and catalyst efficiency improvement. The catalyst prepared by the method of the present invention has high conversion rate and high selectivity for synthesizing cycloolefin hydrocarbon by the selective hydrogenation of the aromatic hydrocarbon.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the Ru-B loaded catalyst of the synthetic cycloolefin of aromatic selective hydrogenation, wherein adopting ruthenium is active ingredient, and boron is auxiliary agent, and single component or bi component oxide are carrier.
Background technology
Cycloolefin such as tetrahydrobenzene are a kind of very important Organic Chemicals.Because it has highly active pair of key, can be used for the intermediate of fine chemicals such as medicine, food, chemistry of pesticide product, feed, polyester, nylon 6, nylon 66, purposes is very extensive.Aspect petrochemical complex, utilize tetrahydrobenzene to make raw material especially, many production technique of being set out by benzene are simplified greatly, improve resource utilization, increase social benefit.
It is synthetic that tetrahydrobenzene can pass through methods such as dehydration of cyclohexanol, cyclohexane halide dehydrohalogenation, cyclohexane dehydrogenation, but these method technical process complexity, yield is low, cost is high, can not satisfy the demand that large-scale industrialization is produced tetrahydrobenzene and related products thereof.The benzene source is abundant, with low cost, by benzene selective hydrogenation one step preparation tetrahydrobenzene technical process shortening, efficient raising, facility investment is reduced.So benzene selective hydrogenation prepares the development and application of tetrahydrobenzene technology, be subjected to paying close attention to widely.
Authorize the Ru-Zn bimetallic catalyst that discloses among the US 4665274 of industrial of Japanese Asahi Chemical Industry with precipitator method preparation, adopt this catalyzer to prepare tetrahydrobenzene by making benzene selective hydrogenation, the yield of tetrahydrobenzene can reach 50%.This catalyzer has the characteristics of high reactivity, highly selective, but insufficient is because Preparation of Catalyst efficient is low, the ruthenium utilization ratio that is unit mass is low, cause the catalyzer price very expensive, and this catalyzer is very responsive to elements such as S, Cl, Fe, As, Pb, these elements of denier just can cause catalyst deactivation, particularly sulfide, have a strong impact on the selectivity of reaction.
Deng Jingfa etc., Journal of catalysis, 1999,187, disclose among the 253-256 and used KBH
4Reduction RuCl
3The Ru-B catalyzer of preparation adopts this catalyzer to prepare tetrahydrobenzene by making benzene selective hydrogenation, and the yield of tetrahydrobenzene is 30%.This work is used for the system that benzene selective hydrogenation prepares tetrahydrobenzene with the Ru-B amorphous alloy.Deng Jingfa etc., Applied catalysis A, 1999,176,129-134 discloses and has used KBH
4Reducing loaded at SiO
2On RuCl
3The Ru-B/SiO of preparation
2Catalyzer adopts this catalyzer to prepare tetrahydrobenzene by making benzene selective hydrogenation, the yield 34% of tetrahydrobenzene.This is operated in the yield that utilizes the Ru-B amorphous alloy to improve catalyzed reaction in the loaded catalyst, but yield does not also reach industrialized demand.Liu Shouchang etc., CN 1337386A discloses with ZrO
2Be carrier, use NaBH
4Reduction RuCl
3And ZnCl
2(FeCl
3) Ru-Zn (the Fe)-B/ZrO of formulations prepared from solutions
2Catalyzer, by introducing auxiliary agent Zn and Fe, the yield that makes benzene selective hydrogenation generate tetrahydrobenzene brings up to 52%.By the above-mentioned document of quoting as can be seen, adopting B to prepare at benzene selective hydrogenation as the ruthenium-based catalyst of auxiliary agent has recently caused in the tetrahydrobenzene widely and has paid close attention to.According to XRD and dsc analysis, in above-mentioned catalyzer, formed the Ru-B amorphous alloy, electronics is transferred on the ruthenium from boron, makes the ruthenium electron rich, and the boron electron deficiency.The boron of electron deficiency easily and the lone-pair electron combination of water makes the wetting ability enhancing of catalyzer, makes tetrahydrobenzene be easy to desorption like this, thereby has improved the selectivity of tetrahydrobenzene.In existing benzene selective hydrogenation catalyzer, the introducing of B is to pass through KBH
4, NaBH
4Reduction RuCl
3And realize.Because NaBH
4And KBH
4Price more expensive, have corrodibility, and a large amount of H arranged the time in reduction
2Emit, set off an explosion easily, catalyst preparation process complexity, the therefore new preparation method of needs exploitation aromatic selective hydrogenation catalyzer.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the Ru-B loaded catalyst of the synthetic cycloolefin of aromatic selective hydrogenation, this method is included on single component or the bi component oxide carrier, adopt pickling process load active component ruthenium, and before the load active component ruthenium, afterwards or therebetween, adopt dry mix or pickling process load cocatalyst component boron compound.
The suitable ruthenium compound that is used as the active ingredient source in the inventive method is including, but not limited to ruthenium trichloride.
In the catalyzer of the inventive method preparation, in the quality percentage composition of ruthenium metal in catalyzer, the charge capacity of ruthenium is 0.1-50%, is preferably 2-10%.
The suitable boron compounds that is used as the cocatalyst component source in the inventive method is including, but not limited to boric acid, boron oxide.
In the methods of the invention, can be before the load active component ruthenium, afterwards or therebetween, adopt dry mix or pickling process load cocatalyst component boron compound, wherein preferably adopt pickling process load boric acid.In the gross weight of catalyzer, the charge capacity of boric acid is 0.1-20%, is preferably 0.5-10%.If in the quality percentage composition of boron oxide in the catalyzer, the charge capacity of boron compound is greater than 0 and smaller or equal to 20%, preferred 0.5-17%.
If load boron compound before the load active component ruthenium, then in load after the boron compound, can carry out roasting to the carrier that obtains.Maturing temperature is generally 200-700 ℃, is preferably 250-500 ℃, and roasting time was generally 2-10 hour, was preferably 2.5-5 hour.
In the methods of the invention as the suitable example of the single component of carrier or bi component oxide including, but not limited to Al
2O
3, ZrO
2, SiO
2, La
2O
3, Al
2O
3-ZnO, ZrO
2-ZnO, La
2O
3-ZnO, Fe
2O
3-ZnO, Cr
2O
3-ZnO, SiO
2-ZnO, MgO-ZnO etc. preferably comprise the bi component oxide of zinc oxide.
In load behind active ingredient source and the cocatalyst component source, generally the catalyzer that obtains is reduced to activate described catalyzer.The reduction temperature of catalyzer is generally 160-500 ℃, and preferred 200-350 ℃, the recovery time is generally 3-10h, is preferably 5-8h.
The catalyzer of the inventive method preparation can be used for the corresponding cycloolefin of selection hydrogenation preparing of many rings and mononuclear aromatics such as benzene, naphthalene, biphenyl and alkylbenzene.
Technology by the corresponding cycloolefin of selection hydrogenation preparing of many rings and mononuclear aromatics such as benzene, naphthalene, biphenyl and alkylbenzene is well known in the art.The general batch reactor that adopts, temperature of reaction 100-200 ℃, hydrogen pressure is 3-7Mpa, rotating speed is greater than 1000rpm.
Adopt the inventive method to prepare the consumption that catalyzer can be saved ruthenium, reduce the catalyzer cost, and the efficient of catalyzer is improved.Adopt the catalyst aromatic selective hydrogenation of the inventive method preparation, can be with high conversion and the synthetic cycloolefin of highly selective.At the benzene transformation efficiency is 18.66% o'clock, and the tetrahydrobenzene selectivity can reach 76.84%.
Embodiment
Further describe the present invention below in conjunction with embodiment.Be noted that these embodiment only are in order to demonstrate the invention, in office where face does not constitute limitation of the scope of the invention.
In the following example and comparing embodiment, transformation efficiency and selectivity are defined by following formula.
It is Agilent 4890D gas chromatograph that the analytical reaction product is formed employed analytical instrument.
Embodiment 1
Preparation of Catalyst
The equivalent impregnation legal system is equipped with 1.35%B/ZrO
2-ZnO.The aqueous solution that will contain 0.072g boric acid splashes into 3gZrO
2In-ZnO the carrier, stir into a paste.Keep 10h under the room temperature, put it in the baking oven 100 ℃ then and spend the night.450 ℃ of roastings are 5 hours in the retort furnace.
With conventional immersion process for preparing catalyzer 4%Ru-1.35%B/ZrO
2-ZnO.To contain 0.12gRuCl
3Solution splash in the carrier that 3g makes above, stir into a paste, keep 10h under the room temperature, 100 ℃ of dry 10h, the following 300 ℃ of reduction 5h of nitrogen atmosphere.
Evaluating catalyst
At volume is to add 60ml water, 11g Zinc vitriol, the catalyzer of the above-mentioned preparation of 3g and 40ml benzene in 500ml and the stainless steel autoclave crossed with hydrogen exchange in advance.160 ℃, 5MPa hydrogen reacts under the rotating speed 1000rpm condition.The results are shown in Table 1.
Embodiment 2
Preparation of Catalyst
With 0.072g solid boric acid and 3gZrO
2Put into retort furnace after-ZnO carrier mixes and be warming up to 700 ℃, roasting 5 hours.
With conventional immersion process for preparing catalyzer 4%Ru-1.35%B/ZrO
2-ZnO.To contain 0.12gRuCl
3Solution splash in the carrier that 3g makes above, stir into a paste, keep 10h under the room temperature, 100 ℃ of dry 10h, the following 300 ℃ of reduction 5h of nitrogen atmosphere.
The evaluating catalyst condition is identical with embodiment 1.The results are shown in Table 1.
Embodiment 3
Preparation of Catalyst
With conventional immersion process for preparing catalyzer 4%Ru/ZrO
2-ZnO.To contain 0.12gRuCl
3Solution splash in the 3g carrier, stir into a paste, keep 10h under the room temperature, 100 ℃ of dry 10h.The NaBH that will contain 0.02M NaOH under the vigorous stirring
4In the catalyzer that solution makes above splashing in 15min.Wash catalyzer to AgNO with distillation
3Check no Cl
-, get 4%Ru-B/ZrO
2The catalyzer of-ZnO.
The evaluating catalyst condition is identical with embodiment 1.The results are shown in Table 1.
The catalytic performance of catalyzer under the introducing method of table 1. different B
| The introducing method of B | Reaction times/min | Transformation efficiency/% | Selectivity/% | |
| Embodiment 1 embodiment 2 embodiment 3 | Load method dry mix NaBH 4Reduction method | 10 15 10 | 18.66 19.97 15.60 | 76.84 72.40 62.70 |
Comparing embodiment 1
Preparation of Catalyst
With conventional immersion process for preparing catalyzer 4%Ru/ZrO
2-ZnO, 6%Ru/ZrO
2-ZnO, 8%Ru/ZrO
2-ZnO.To contain 0.12g, 0.18g, 0.24g RuCl respectively
3Solution splash into 3gZrO
2In-ZnO the carrier, stir into a paste, keep 10h under the room temperature, 100 ℃ of dry 10h, the following 300 ℃ of reduction 5h of nitrogen atmosphere.
The evaluating catalyst condition is identical with embodiment 1.The results are shown in Table 2.
The different ruthenium content of metal of table 2 are to the influence of catalyst catalytic performance
| Ru quality percentage composition/% | Reaction times/min | Transformation efficiency/% | Selectivity/% |
| 4 | 15 | 18.78 | 71.56 |
| 6 | 13 | 26.60 | 60.11 |
| 8 | 11 | 23.52 | 59.80 |
Embodiment 4
Preparation of Catalyst
The solution that will contain 0.036g, 0.072g, 0.144g, 0.180g, 0.288g, 0.872g boric acid respectively splashes into 3g ZrO
2In-ZnO the carrier, stir into a paste.Keep 10h under the room temperature, put it in the baking oven 100 ℃ then and spend the night.450 ℃ of roastings are 5 hours in the retort furnace.
With conventional immersion process for preparing catalyzer 4%Ru-0.67%B/ZrO
2-ZnO, 4%Ru-1.35%B/ZrO
2-ZnO, 4%Ru-1.35%B/ZrO
2-ZnO, 4%Ru-2.70%B/ZrO
2-ZnO, 4%Ru-3.20%B/ZrO
2-ZnO, 4%Ru-5.40%B/ZrO
2-ZnO, 4%Ru-16.40%B/ZrO
2-ZnO.To contain 0.12g RuCl
3Solution splash in each carrier that 3g makes above, stir into a paste.Keep 10h under the room temperature, put it in the baking oven 100 ℃ then and spend the night.Reaction is preceding to place the following 300 ℃ of reduction 5h of nitrogen atmosphere with dried catalyzer.
The evaluating catalyst condition is identical with embodiment 1.The results are shown in Table 3.
The catalytic performance of catalyzer under the different boron oxide contents of table 3
| B 2O 3Content | Reaction times/min | Transformation efficiency/% | Selectivity/% |
| 0.67 1.35 2.70 3.20 5.40 16.40 | 15 17 8 12 15 10 | 18.91 14.04 14.43 18.32 17.08 22.88 | 70.78 77.89 76.87 82.76 80.93 71.13 |
Embodiment 5
Preparation of Catalyst
The equivalent impregnation legal system is equipped with 1.35%B/ZrO
2-ZnO.The aqueous solution that will contain 0.072 boric acid splashes into 3gZrO
2In-ZnO the carrier, stir into a paste.Keep 10h under the room temperature, put it in the baking oven 100 ℃ then and spend the night.450 ℃ of roastings are 5 hours in the retort furnace.
With conventional immersion process for preparing catalyzer 4%Ru-1.35%B/ZrO
2-ZnO.To contain 0.12g RuCl
3Solution splash in the carrier that 3g makes above, stir into a paste.Keep 10h under the room temperature, put it in the baking oven 100 ℃ then and spend the night.Reaction is preceding to place following 200 ℃, 225 ℃, 250 ℃, 275 ℃, 300 ℃ reduction of nitrogen atmosphere 5h with dried catalyzer.
The evaluating catalyst condition is identical with embodiment 1.The results are shown in Table 4.
Table 4 adopts the catalytic performance of the catalyzer of different reduction temperatures
| Reduction temperature/℃ | Reaction times/min | Transformation efficiency/% | Selectivity/% |
| 200 225 250 275 300 | 10 13 15 20 15 | 18.66 22.48 19.80 13.73 4.83 | 76.84 77.37 80.26 76.44 80.45 |
Embodiment 6
Preparation of Catalyst
The equivalent impregnation method is carried on boric acid solution on the carrier.The solution that will contain 0.072g boric acid splashes in the 3g carrier, stirs into a paste.Keep 10h under the room temperature, put it in the baking oven 100 ℃ then and spend the night.450 ℃ of roastings are 5 hours in the retort furnace.
Use the catalyzer 4%Ru-1.35%B/SiO of different carriers with conventional immersion process for preparing
2, 4%Ru-1.35%B/ZrO
2, 4%Ru-1.35%B/Al
2O
3, 4%Ru-1.35%B/La
2O
3, 4%Ru-1.35%B/SiO
2-ZnO, 4%Ru-1.35%B/ZrO
2-ZnO, 4%Ru-1.35%B/Al
2O
3-ZnO, 4%Ru-1.35%B/La
2O
3-ZnO.The reaction procatalyst is 300 ℃ of reduction 5h under nitrogen atmosphere.
The evaluating catalyst condition is identical with embodiment 1.The results are shown in Table 5.
The catalytic performance of catalyzer under table 5 different carriers
| Carrier | Reaction times/min | Transformation efficiency/% | Selectivity/% |
| ZrO 2 SiO 2 Al 2O 3 La 2O 3 ZrO 2/ZnO SiO 2/ZnO Al 2O 3/ZnO La 2O 3/ZnO | 15 20 8 30 10 60 62 30 | 18.66 19.69 23.46 39.11 25.35 12.47 16.16 17.15 | 54.28 39.04 32.20 45.02 61.14 49.68 75.12 74.06 |
Claims (10)
1. the preparation method of the Ru-B loaded catalyst of the synthetic cycloolefin of an aromatic selective hydrogenation, this method is included on single component or the bi component oxide carrier, adopt pickling process load active component ruthenium, and before the load active component ruthenium, afterwards or therebetween, load cocatalyst component boron compound.
2. method according to claim 1, wherein in the quality percentage composition of ruthenium metal in catalyzer, the charge capacity of ruthenium is 0.1-50%.
3. method according to claim 2, wherein in the quality percentage composition of ruthenium metal in catalyzer, the charge capacity of ruthenium is 2-10%.
4. method according to claim 1 wherein adopts dry mix or pickling process load cocatalyst component boron compound.
5. method according to claim 4, wherein in the quality percentage composition of boron oxide in the catalyzer, the charge capacity of boron compound is greater than 0 and smaller or equal to 20%.
6. method according to claim 5, wherein in the quality percentage composition of boron oxide in the catalyzer, the charge capacity of boron compound is 0.5-17%.
7. method according to claim 1 wherein also comprises the steps: after load active component and cocatalyst component, and catalyzer is reduced processing, and reduction temperature is 160-500 ℃.
8. method according to claim 7, wherein said reduction temperature are 200-350 ℃.
9. method according to claim 1, wherein said carrier is selected from Al
2O
3, ZrO
2, SiO
2, La
2O
3, Al
2O
3-ZnO, ZrO
2-ZnO, La
2O
3-ZnO, Fe
2O
3-ZnO, Cr
2O
3-ZnO, SiO
2-ZnO, MgO-ZnO.
10. the Ru-B loaded catalyst of each method preparation among the claim 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03109528 CN1234666C (en) | 2003-04-09 | 2003-04-09 | Preparation method of Ru-B load type catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03109528 CN1234666C (en) | 2003-04-09 | 2003-04-09 | Preparation method of Ru-B load type catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1535942A CN1535942A (en) | 2004-10-13 |
| CN1234666C true CN1234666C (en) | 2006-01-04 |
Family
ID=34319385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03109528 Expired - Fee Related CN1234666C (en) | 2003-04-09 | 2003-04-09 | Preparation method of Ru-B load type catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1234666C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103785382B (en) * | 2012-11-01 | 2016-08-03 | 中国石油化工股份有限公司 | A kind of high stability preparing cyclohexene from benzene added with hydrogen catalyst and its preparation method and application |
| CN103787817B (en) * | 2012-11-01 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of preparation method of tetrahydrobenzene |
| CN103785410B (en) * | 2012-11-01 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of benzene cyclohexene Catalysts and its preparation method and application |
| CN103301837A (en) * | 2013-06-07 | 2013-09-18 | 苏州市泰力达科技有限公司 | Method for preparing aluminum oxide loaded ruthenium catalyst |
| CN104307464B (en) * | 2014-10-24 | 2017-02-22 | 上海迅凯新材料科技有限公司 | Ruthenium-based adsorbent for deeply removing thiophene of benzene as well as preparation method and application of ruthenium-based adsorbent |
| CN110624571B (en) * | 2019-09-27 | 2022-07-05 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing 3, 5-dichloroaniline and preparation method and application thereof |
| CN113634275B (en) * | 2021-08-19 | 2023-08-22 | 浙江工业大学 | Catalyst for catalytic hydrogenation dechlorination and preparation method and application thereof |
-
2003
- 2003-04-09 CN CN 03109528 patent/CN1234666C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1535942A (en) | 2004-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101049562A (en) | Catalyst for preparing halogeno anilin through catalytic hydrogenation of halogeno nitrobenzene and preparation method | |
| CN1234666C (en) | Preparation method of Ru-B load type catalyst | |
| CN101039892A (en) | Catalysts for cycloalkanes oxidation and decomposition of cycloalkyl hydroperoxide | |
| CN1814712A (en) | Modifying catalyst for naphtha processed maferial and method therefor | |
| CN114471721A (en) | Single atom anchored TiO with metal sites2Photocatalyst and preparation method thereof | |
| CN101041139A (en) | Catalyzer for regenerating the waste lubricant oil by hydrogenation and the preparing method | |
| CN110496643A (en) | A kind of isomerization of C-8 aromatics catalyst crystal seed assistant preparation method | |
| CN106268861A (en) | A kind of magnetic hydrogenation deoxidation catalyst and preparation method thereof | |
| CN101033177A (en) | Method of synthesizing 2-ethoxy-phenol | |
| CN1100124C (en) | Aromatizing catalyst for light hydrocarbon and its preparing process | |
| CN1085115C (en) | Compound oxide catalyst for phenol hydroxylation and its preparing method | |
| CN1814347A (en) | Ethyl benzene oxidizing-dehydrogenation catalyst | |
| CN106622336B (en) | Catalyst for preparing styrene and ethylbenzene by toluene side-chain alkylation reaction and application thereof | |
| CN106316763B (en) | The method of lactone compound aromatisation production aromatic hydrocarbons | |
| CN101575253A (en) | Application of fullerene as catalyst in catalytic hydrogenation reaction of nitro aromatic compound | |
| CN1047375C (en) | Saturation hydrogenation method for olefines or aromatic hydrocarbon | |
| CN114804997B (en) | Preparation method of cyclohexylbenzene and corresponding metal catalyst | |
| CN1481935A (en) | Accelerating agent and its application in synthesizing carbolic acid using benzene and hydrogen dioxide | |
| CN111389453B (en) | Method for converting high-concentration lignin into cycloparaffin by liquid phase | |
| CN1058284C (en) | Light hydrocarbon aromatization catalyst and its preparing process | |
| CN101463016B (en) | Method for synthesizing 2,6-dimethyl piperazine | |
| CN100496728C (en) | Catalyst for preparing cyclohexene by selective benzene hydrogenation, its preparing method and use | |
| CN1168534C (en) | Prepn of catalyst for tetramethylbenzene isomerization to prepare durene | |
| CN1136975C (en) | Noble metal catalyst method of resisting Co poisoning | |
| CN1137773C (en) | Solid super acid and its prepn. |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060104 Termination date: 20150409 |
|
| EXPY | Termination of patent right or utility model |