CN1079291C - Method for prolonging service life of benzene hydrogenation homogeneous catalyst - Google Patents
Method for prolonging service life of benzene hydrogenation homogeneous catalyst Download PDFInfo
- Publication number
- CN1079291C CN1079291C CN98112633A CN98112633A CN1079291C CN 1079291 C CN1079291 C CN 1079291C CN 98112633 A CN98112633 A CN 98112633A CN 98112633 A CN98112633 A CN 98112633A CN 1079291 C CN1079291 C CN 1079291C
- Authority
- CN
- China
- Prior art keywords
- homogeneous catalyst
- service life
- benzene
- catalyst
- transition metal
- 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 - Lifetime
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002815 homogeneous catalyst Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 20
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 claims description 2
- 230000002000 scavenging effect Effects 0.000 claims 1
- -1 transition metal carboxylate Chemical class 0.000 abstract description 25
- 229910052723 transition metal Inorganic materials 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004140 cleaning Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 9
- 150000001934 cyclohexanes Chemical class 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 235000010210 aluminium Nutrition 0.000 description 2
- 230000001147 anti-toxic effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 241000883966 Astrophytum capricorne Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 208000005735 Water intoxication Diseases 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for prolonging the service life of a benzene hydrogenation homogeneous catalyst, which is characterized in that in the process of manufacturing the homogeneous catalyst, water is strictly forbidden to be added into a reaction system, and the water and impurities brought into the reaction system are reduced as much as possible. By adopting the method of timely discharging impurities and periodically cleaning the homogeneous catalyst preparation system by using an organic solvent, the impurity content in the transition metal carboxylate solution is reduced from 0.6-5% to less than 1 per mill, so that the service life of the benzene hydrogenation homogeneous catalyst is prolonged.
Description
The present invention relates to a kind of benzene hydrogenating homogeneous catalyst method in service life that improves.
According to 88105065 introductions, the preparation method of benzene hydrogenating homogeneous catalyst is: at normal temperatures and pressures, at first the 4th component water is joined in the cyclohexane solution of transition metal carboxylate, make the transition metal carboxylate by the 4th component water saturation, then the trialkyl aluminum solutions is joined among the transition metal carboxylic acid salt solution, add the 3rd component alcohols at last.The preparation of used transition metal carboxylate is with C
6～C
18Carboxylic acid and NaOH carry out saponification, generate carboxylic acid sodium salt, need not be through washing, then in the carboxylic acid sodium salt aqueous solution that generates, add the aqueous solution of transition metal inorganic salts, carry out metathesis reaction, then, under dry and filtration situation, add cyclohexane solution, the transition metal carboxylate that generates is extracted.In extraction process, finish the preparation of transition metal carboxylate cyclohexane solution simultaneously and in the transition metal carboxylate, add two technical process of the 4th component water.The 4th component water can add earlier among the transition metal carboxylic acid salt solution or in the last adding of catalyst preparation process.Adopt the distinguishing feature of above-mentioned technical process to be, the transition metal carboxylate of being produced can obtain higher yield, generally can reach more than 90%, and this is in the prior art, the fresh content of never reporting.
Triethyl aluminum and transition metal carboxylate mole ratio are 1: 1～8: 1, and be best than being 2: 1～5: 1; Weak organic acid and transition metal carboxylate mole ratio are 0.1: 1～1: 1, and be best than being 0.15: 1～0.6: 1; Water and transition metal carboxylate mole ratio are 1.8: 1～3.9: 1; The reaction temperature of producing homogeneous catalyst is 0～200 ℃, and the best is 70～160 ℃.
With the cyclohexane is solvent, prepares triethyl aluminium solution and isooctyl acid nickel solution respectively, the 4th component water is added in the isooctyl acid nickel solution again, and it is reached capacity.Equal 4.0 amounts of calculating triethyl aluminums with Al/Ni (atomic ratio), get the triethyl aluminium solution that has prepared, add in the goat's horn bottle, and then add that to contain isooctyl acid nickel amount be that (amount that wherein contains the 4th component water is with H for the isooctyl acid nickel solutions of 2.07 grams
2O/ isooctyl acid nickel mol ratio equals 2.75 and calculates), be that 0.24 amount adds the 3rd component isooctanol with isooctanol/isooctanol nickel (mol ratio), make catalyst.The 800ml benzene feedstock is added in the reactor, add in succession as the above-mentioned catalyst of making, at 180 ℃ and 7Kg/Cm
3The hydrogen branch is depressed and is carried out benzene hydrogenation, after reaction is carried out 27 minutes, no longer absorbs hydrogen, and the conversion ratio of benzene is more than 99.7%, and the purity of cyclohexane is more than 99.7%.Proceed continously hydrogen adding reaction on this basis, the reaction time of evaluate catalysts, it is 208 hours (be also referred to as life of catalyst the reaction time of catalyst) that the purity of cyclohexane is reduced to reaction time of 95% by 99.7%.This is a longest example of reaction time during patent is introduced.
This benzene hydrogenating homogeneous catalyst belongs to Ziegler (Ziegler-Natta) type catalyst, and Ziegler-type catalyst has the multiple poisonous substance that causes its loss of activity.Show that according to data the main poisonous substance of benzene hydrogenating homogeneous catalyst has H
2O, S, cl, CO, O
2Deng.The test of homogeneous catalyst water intoxication was once done by this patent side, the results are shown in following table:
Therefore, patent side requires very strict to the impurity content in hydrogenating materials-benzene and the hydrogen:
| Test number | Hydrogen water content ppm | Hydrogenation speed grams per liter branch | Add catalyst % | Hydrogenation speed grams per liter branch |
| 1 | ＜10 | 13.6 | / | / |
| 2 | 500-600 | 8.7 | 100 | 13.6 |
Benzene: H
2O＜50ppm hydrogen: H
2O＜50ppm
CO ＜10ppm CO ＜10ppm
O
2 ＜10ppm CO
2 ＜10ppm
S+cl ＜1ppm S ＜0.2ppm
cl ＜0.1ppm
When hydrogenation, also to the water content in the hydrogen further be dropped to＜20ppm.Satisfying under the above-mentioned condition, be 105 tons of right and left rings hexane/kilogram nickel the service life of benzene hydrogenating homogeneous catalyst.
Therefore, have many advantages though benzene hydrogenating homogeneous catalyst is compared with traditional Raney's nickel catalyst, it also has short partially deficiency of easy poisoning and deactivation and service life, and also very high to the quality requirement of hydrogenating materials-benzene and hydrogen.
The purpose of this invention is to provide a kind of above-mentioned benzene hydrogenating homogeneous catalyst method in service life that improves.
The present invention is achieved in that
We find in the process of using this patented technology: (impurity is mainly brought by the raw material nickel salt and is formed by side reaction when generating the transition metal carboxylate for water and impurity, and bring the Preparation of Catalyst system into by the transition metal carboxylate, and also bring a spot of water simultaneously into) very big to the quality influence of this benzene hydrogenating homogeneous catalyst.Therefore, in the benzene hydrogenating homogeneous catalyst production process, forbid to add moisture content and reduce bringing into of moisture content and impurity as far as possible.To be brought into moisture content and the impurity in the homogeneous catalyst preparation system via the transition metal carboxylic acid salt solution, except that timely discharge system, take regularly to use the method for organic solvent cleaning catalyst preparation system (equipment that refers to all contact transition metal carboxylate solution), remove it as much as possible.Behind 2～10 tons of homogeneous catalysts of every production, in the Preparation of Catalyst system, add organic solvent and soak, clean whole system, under the normal pressure, 10～40 ℃ of cleaning temperatures, every cleaning once needs 0.5～5 day.System clean up and nitrogen replacement after, can drive again.The amount that adds organic solvent is decided on homogeneous catalyst production load, produces the process units of 50 tons of homogeneous catalysts per year, and each the cleaning needs 0.5～2 ton of organic solvent.Organic solvent is optional with technical grade alcohol, ketone, alkanes, preferentially selects alkanes for use.By cleaning, can with the moisture content brought into by the transition metal carboxylic acid salt solution in the homogeneous catalyst preparation process and impurity content by 0.6～5% before cleaning drop to＜1 ‰, the quality of the homogeneous catalyst of making has obtained increasing substantially, and is in particular in antitoxin performance and on service life.
Good effect of the present invention: after implementing above-mentioned measure, the antitoxin performance and the service life of benzene hydrogenating homogeneous catalyst are improved.Satisfying: benzene: H
2O＜200ppm hydrogen: H
2O＜600ppm
CO ＜10ppm CO ＜10 ppm
O
2 ＜10ppm CO
2 ＜10 ppm
S+cl ＜1ppm S ＜0.2ppm
Under cl＜0.1ppm prerequisite, be 330～1100 tons of cyclohexanes/kilogram nickel the service life of homogeneous catalyst.
Embodiment 1. adds technical grade cyclohexane Preparation of Catalyst system from transition metal carboxylate basin produce 30 tons of homogeneous catalysts by above-mentioned process conditions after.Catalyst service life by before cleaning benzene moisture＜100ppm, hydrogen be moisture＜60 tons of cyclohexanes/kilogram nickel during 300ppm, bring up to benzene moisture＜200ppm, hydrogen be moisture＜200 tons of cyclohexanes/kilogram nickel during 600ppm.
Embodiment 2. adds technical grade cyclohexane Preparation of Catalyst system produce 8 tons of homogeneous catalysts by above-mentioned process conditions after.Catalyst service life by before cleaning benzene moisture＜200ppm, hydrogen be moisture＜180 tons of cyclohexanes/kilogram nickel during 600ppm, bring up to benzene moisture＜200ppm, hydrogen be moisture＜330 tons of cyclohexanes/kilogram nickel during 600ppm.
Embodiment 3. adds technical grade cyclohexane Preparation of Catalyst system produce 4 tons of homogeneous catalysts by above-mentioned process conditions after.Catalyst service life by before cleaning benzene moisture＜200ppm, hydrogen be moisture＜350 tons of cyclohexanes/kilogram nickel during 600Ppm, bring up to benzene moisture＜200ppm, hydrogen be moisture＜1100 tons of cyclohexanes/kilogram nickel during 600ppm.
Claims (3)
1, a kind of benzene hydrogenating homogeneous catalyst method in service life that improves, it is characterized in that: in the manufacture process of benzene hydrogenating homogeneous catalyst, forbid to add moisture content to reaction system, behind 2～10 tons of catalyst of every production, in 0.5～5 day time, clean the homogeneous catalyst preparation system with organic solvent.
2, a kind of benzene hydrogenating homogeneous catalyst method in service life that improves according to claim 1, it is characterized in that: the Clean after every time is 2～4 tons of homogeneous catalysts of every production.
3, a kind of benzene hydrogenating homogeneous catalyst method in service life that improves according to claim 1, it is characterized in that: scavenging period is 3～5 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112633A CN1079291C (en) | 1998-09-16 | 1998-09-16 | Method for prolonging service life of benzene hydrogenation homogeneous catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112633A CN1079291C (en) | 1998-09-16 | 1998-09-16 | Method for prolonging service life of benzene hydrogenation homogeneous catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1234295A CN1234295A (en) | 1999-11-10 |
| CN1079291C true CN1079291C (en) | 2002-02-20 |
Family
ID=5222468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98112633A Expired - Lifetime CN1079291C (en) | 1998-09-16 | 1998-09-16 | Method for prolonging service life of benzene hydrogenation homogeneous catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1079291C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107684929B (en) * | 2016-08-05 | 2020-12-22 | 中国石油化工股份有限公司 | Method for improving performance of benzene hydrogenation homogeneous catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE861978A (en) * | 1976-12-24 | 1978-06-19 | Inst Francais Du Petrole | PROCESS FOR HYDROGENATION OF UNSATURATED COMPOUNDS |
| CN1037729A (en) * | 1988-05-21 | 1989-12-06 | 中国石油化工总公司辽阳石油化纤公司 | A kind of benzene hydrogenating homogeneous catalyst |
| CN1121910A (en) * | 1994-02-17 | 1996-05-08 | 法国石油公司 | Catalyst and benzohydrogenization using same |
-
1998
- 1998-09-16 CN CN98112633A patent/CN1079291C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE861978A (en) * | 1976-12-24 | 1978-06-19 | Inst Francais Du Petrole | PROCESS FOR HYDROGENATION OF UNSATURATED COMPOUNDS |
| CN1037729A (en) * | 1988-05-21 | 1989-12-06 | 中国石油化工总公司辽阳石油化纤公司 | A kind of benzene hydrogenating homogeneous catalyst |
| CN1121910A (en) * | 1994-02-17 | 1996-05-08 | 法国石油公司 | Catalyst and benzohydrogenization using same |
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| Publication number | Publication date |
|---|---|
| CN1234295A (en) | 1999-11-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Chaozhong Inventor after: Zhu Zehua Inventor after: Liu Yimin Inventor after: Wang Shengkui Inventor before: Zhang Chaozhong Inventor before: Liu Yimin Inventor before: Wang Shengkui |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: ZHANG ZHAOZHONG; LIU YIMIN; WANG SHENGKUI TO: ZHANG ZHAOZHONG; ZHU ZEHUA; LIU YIMIN; WANG SHENGKUI |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHINA PETROLEUM + CHEMICAL CORPORATION Free format text: FORMER OWNER: YINGSHAN PETRO-CHEMICAL PLANT, BALING PETRO-CHEMICAL CORP. Effective date: 20090605 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20090605 Address after: Chaoyang District, Chaoyangmen, North Street, No. 22, No. Patentee after: Sinopec Corp. Address before: Hunan province Yueyang Yingshan Petrochemical Factory Patentee before: Yingshan Petro-Chemical Plant, Baling Petro-Chemical Corp. |
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| CX01 | Expiry of patent term |
Granted publication date: 20020220 |
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| CX01 | Expiry of patent term |