CN102371174A - Diphenylamine alkylation catalyst and preparation method thereof - Google Patents
Diphenylamine alkylation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a diphenylamine alkylation catalyst. The catalyst comprises, by mass, 85-99% of a molecular sieve and 1-15% of an acid, wherein the molecular sieve comprises faujasite and/or a MFI-type molecular sieve, the acid comprises an inorganic acid containing oxygen or a heteropoly acid. The catalyst is prepared by adopting an acid-containing solution to carry out saturated immersion for the molecular sieve, and carrying out treatments of dehydration and drying. The catalyst is used for the diphenylamine alkylation reaction, and has high reaction activity and reusability.
Description
Technical field
The present invention is a kind of diphenylamines alkylation catalyst and preparation method, specifically, is a kind of solid diphenylamines alkylation catalyst that contains acid and preparation method thereof.
Background technology
Chemical reaction in use and can take place and oxidation deterioration after airborne oxygen and metal surface contact in mineral oil and artificial oil, generates acidic materials, causes the corrosion of machinery equipment.In order to delay the oxidizing process of oil product, improve serviceability, effective method is in oil product, to add anti-oxidant.
Alkylated diphenylamine is a kind of octyl group and the substituted amine type of butyl mixed alkyl antioxidant; Characteristics are that oil-soluble is good, good with the functional additive compatibility of other type, use still has good antioxidant effect under higher temperature conditions, and especially the effect with the compound use of phenolic ester type antioxidant is more outstanding.Simultaneously; The quality upgrading of lubricating oil requires lubricating oil to have lower phosphorus content, means and will still less use phosphorus-containing antioxidant zinc dialkyl dithiophosphate (ZDDP); Therefore non-phosphorus antioxidant is favored gradually, and this also is the development trend of oil formula technical research.At present, alkylated diphenylamine has obtained extensive use in high-quality internal combustion engine oil product, can control oil viscosity effectively and increase and reduce sedimental generation.In addition, the application of alkylated diphenylamine in industrial lubricant also has good effect, like greases such as steam turbine oil, compressor oil, antiwear hydraulic oil, lubricating grease.
At present, the preparation alkylated diphenylamine adopts different catalyst to carry out alkylated reaction usually, and catalyst commonly used comprises AlCl
3, heteropoly acid and atlapulgite.
AlCl
3For being used for preparing the catalyst of alkylated diphenylamine the earliest; Use this catalyst can produce HCl gas usually, the alkylate that obtains contains two more substitution products, and residual the chlorine element is arranged; Color is a dark brown; Especially color is darker for the substituted diphenylamines of diisobutylene, is solid-state or paste at normal temperatures, is unfavorable for the mediation in oil product.
Heteropoly acid is the catalyst of latest development, and consumption is few during alkylated reaction, but reaction temperature is higher, the catalyst function of not decolouring, and product colour is darker, and simultaneously, unreacted diphenylamines content is higher, generally greater than 3 quality %.
Therefore; In alkylated reaction, using at present maximum is activated bauxite catalyst; General catalyst amount is 10～20 quality %, has the function of cracking diisobutylene preferably, like this in the alkylated diphenylamine product; The ratio of various products has good distribution, can make product have good mobility.
USP4824601 discloses a kind of method for preparing liquid antioxidant composition of reacting through diphenylamines and diisobutylene; This method is included in activated bauxite catalyst and exists down; Be at least in reaction temperature under 160 ℃ the condition; With diphenylamines and the diisobutylene molar ratio reaction with 1: 1.1 to 1: 2.5, this reaction proceeds to when content that 4,4 '-two uncle's octyl diphenylamine content in the final reaction mass except that catalyst are lower than 25 weight % and diphenylamines is lower than 10 weight % and accomplishes.Used atlapulgite is preferably
22B that is purchased from Laporte Industries.This method is carried out under normal pressure, and reaction temperature is higher, because the diisobutylene boiling point is 102 ℃, is liquid at normal temperatures; And diphenylamines is solid-state, and diisobutylene one gets into reaction system and gasifies immediately, refluxes, and the reactant contact is insufficient; Cause the reaction time long, the product color is darker, is dark-brown.On the other hand, the reaction speed of this reaction is along with reaction reduces gradually, when the rate of addition of diisobutylene during greater than reaction speed capacity of returns increase, make reaction temperature be lower than the control point; And when rate of addition during less than reaction speed, temperature sharply rises again, causes temperature fluctuation excessive, and it is steady that operating process is difficult to reach.
CN1288000A discloses a kind of preparation method of liquid alkyl diphenylamine; Be included under the existence of activated bauxite catalyst; 170～230 ℃ with make under the pressure that diisobutylene is in a liquid state, make diisobutylene and diphenylamines haptoreaction, in product 4; The content of 4-two uncle's octyl diphenylamines stopped reaction and collected product less than 20% o'clock.This method is than USP4824601, and the reaction time has shortened 4～5 hours, has solved the unstable problem of temperature fluctuation in the course of reaction that causes owing to the diisobutylene backflow simultaneously, and the lighter color of alkylated diphenylamine is for light yellow.But this method catalyst use amount is more, nearly about 20 weight % of diphenylamines consumption, when removing catalyst, can carry more product, has therefore reduced the output of end product.In addition, the repeat performance of this activated bauxite catalyst is relatively poor, and when reusing one time, the content of residual diphenylamines is promptly up to more than the 5 quality % in the product.
CN1995904A discloses a kind of method of synthetic dialkyl diphenylamine, comprises adopting H β zeolite and γ-Al
2O
3The catalyst of forming, reaction temperature is 175～185 ℃, reaction pressure is 0.8～1.0MPa; Adopt fixed bed to produce continuously; Catalyst service time surpasses 300 hours, and in the products therefrom 4, the content of 4-two uncle's octyl diphenylamines is less than 20%; Catalyst can carry out regeneration, but does not mention unreacted diphenylamines content in the product in the literary composition.
CN101745423A discloses the alkylation of a kind of catalyst and diphenylamines, and it is that aqueous acid below the 20 weight % contacts with atlapulgite that described catalyst uses concentration, and dehydration, drying.Described acid is selected from water-soluble inorganic acid and/or p-methyl benzenesulfonic acid.This catalyst is used for the diphenylamines alkylated reaction, and activity is still relatively poor, and the diphenylamines residual quantity is higher in the product, and it is not long that catalyst is reused the life-span.
Summary of the invention
The purpose of this invention is to provide a kind of diphenylamines alkylation catalyst and preparation method, this catalyst is used for the diphenylamines alkylated reaction, and consumption is few and repeat performance good.
Diphenylamines alkylation catalyst provided by the invention comprises the molecular sieve of 85～99 quality % and the acid of 1～15 quality %, and described molecular sieve is faujasite and/or MFI type molecular sieve, and described acid is oxygen-containing inorganic acid or heteropoly acid.
The present invention is carried on strong acid and processes catalyst on the molecular sieve, and the acidity of effectively having regulated molecular sieve distributes, and catalyst amount is few during alkylated reaction, and the alkylate that is adsorbed in the catalyst also reduces relatively, has improved the output of end product.In addition, the repeat performance of catalyst is fine, removes end product catalyst afterwards and directly reuses repeatedly, and the content of residual diphenylamines still can be controlled in the 4 quality % in the product.
The specific embodiment
The present invention loads on strong acid on the specific molecular sieve and processes catalyst.Catalyst of the present invention preferably includes the molecular sieve of 88～98 quality % and the acid of 2～12 quality %, and described acid is oxygen-containing inorganic acid or heteropoly acid, oxygen-containing inorganic acid preferably sulfuric acid or phosphoric acid, preferred phosphotungstic acid of heteropoly acid or phosphomolybdic acid.
The used molecular sieve of catalyst of the present invention is faujasite and/or MFI type molecular sieve, and when used molecular sieve was the mixture of faujasite and MFI type molecular sieve, the mass ratio of faujasite and MFI type molecular sieve was preferably 5～7: 3～5.Described faujasite molecular sieve is preferably Y zeolite, the preferred ZSM-5 of MFI type molecular sieve, and described faujasite-type molecular sieve and MFI type molecular sieve are preferably Hydrogen.The pore volume of said molecular sieve preferably is not less than 0.15cm
3/ g.
Preparation of catalysts method provided by the invention comprises with aqueous acid molecular sieve is carried out saturated dipping, then dehydration, drying.
That the used aqueous acid concentration of the inventive method is comparatively suitable is 1～20 quality %, preferred 1～12 quality %, more preferably 1～10 quality %.The temperature of saturated dipping is 20～80 ℃, preferred 2～7 hours of dip time.Baking temperature is 90～200 ℃.Described saturated dipping is the saturated adsorpting water quantity that used maceration extract volume equals to be soaked carrier, and maceration extract is just with the carrier surface complete wetting.
The present invention carries out the alkylating method of diphenylamines, comprise making diphenylamines in the presence of catalyst of the present invention, in 140～250 ℃, 0.2～0.5MPa, inert gas environment with the alkylating agent haptoreaction.Preferred reaction temperature is 150～250 ℃, more preferably 155～220 ℃.
Alkylated reaction raw material of the present invention is a diphenylamines, and the mol ratio of itself and alkylating agent is 1: 1～2, preferred 1: 1.1～1.9.The preferred diisobutylene of described alkylating agent.
In the said method, described diisobutylene preferably adds reaction system several times, and the diisobutylene amount that adds for the first time is 50～70 quality % of diisobutylene total amount.
In the described inert gas nitrogen of said method, helium and the argon gas one or more, more preferably nitrogen.
When the present invention carried out alkylated reaction, catalyst consumption was 1～10 quality % of the diphenylamines raw material total amount that adds, more preferably 2～8 quality %.When diphenylamines content in the reaction system is lower than 4 quality %, stop reaction.Generally, need unreacted diisobutylene is steamed after reaction finishes, the performance of the diisobutylene that steams is unaffected, can recycle.After diisobutylene steamed, the filtering reaction product was removed catalyst wherein while hot, obtained the mixture of faint yellow, liquid alkylated diphenylamine thus.The catalyst that filtration obtains is reusable.Also can filter the back separated earlier and obtain catalyst and product.For the color that makes alkylate does not deepen, vapo(u)rizing temperature is usually less than 150 ℃.
The alkylated diphenylamine that the inventive method makes is the mixture with following structural formula general formula,
In the formula, R
1And R
2Be the tert-butyl group or iso-octyl, and be positioned at the ortho position or the contraposition of imino group on the phenyl ring.
The alkylated diphenylamine compound that makes with catalyst of the present invention has good oil-soluble ability and antioxygenic property, can be widely used in I. C. engine oil and the industrial lubricant, and additive capacity is generally 0.01～1.0 quality %.Alkylated diphenylamine compound provided by the invention also can with the composite use of different additives to obtain better result of use.
Pass through example in detail the present invention below, but the present invention is not limited to this.
Instance 1
(1) preparation catalyst
Get HY type molecular sieve, Gu by the liquid of 0.80ml/g/than 20 ℃, to use concentration be the saturated dipping of sulfuric acid solution 2 hours of 2 quality %, dephlegmate then; 100 ℃ of dryings 2 hours; Obtain catalyst A, wherein sulfuric acid content is 1.54 quality %, and the HY molecular sieve content is 98.46 quality %.
(2) preparation alkylated diphenylamine
In the autoclave of 250ml, add 50.7 gram diphenylamines, 60.5 gram diisobutylene, 2 gram catalyst A, with nitrogen replacement reaction system three times.Begin after being warming up to 100 ℃ to stir, continue heat temperature raising to 170 ℃, when reaction system pressure reaches 0.30MPa, clock reaction 10 hours.Along with the carrying out of reaction, pressure is reduced to 0.17MPa gradually, when recording with gas chromatography that diphenylamines content is lower than 4 quality % in the reaction system, finishes reaction.With material cooling, unreacted diisobutylene and low amounts of water are removed in 140 ℃ of decompression distillation 20 minutes; Be cooled to 120 ℃; Remove by filter catalyst waste slag, obtain the faint yellow liquid thickness product of 87.9 grams, the content of residual diphenylamines is 0.829 quality % in the gas chromatographic analysis product.
Instance 2
(1) preparation catalyst
Get HY type molecular sieve, Gu by the liquid of 0.78ml/g/than 30 ℃, to use concentration be the saturated dipping of sulfuric acid solution 3 hours of 4 quality %, dephlegmate then; 120 ℃ of dryings 3 hours; Obtain catalyst B, wherein sulfuric acid content is 3.10 quality %, and the HY molecular sieve content is 96.90 quality %.
(2) preparation alkylated diphenylamine
In the autoclave of 250ml, add 50.7 gram diphenylamines, 67.2 gram diisobutylene, 3 gram catalyst B, with nitrogen replacement reaction system three times.Begin after being warming up to 100 ℃ to stir; Continue heat temperature raising to 170 ℃, when reaction system pressure reaches 0.38MPa, clock reaction 12 hours; Carrying out along with reaction; Pressure is reduced to 0.15MPa gradually, when recording with gas chromatography that diphenylamines content is lower than 4 quality % in the reaction system, finishes reaction.With material cooling, unreacted diisobutylene and low amounts of water are removed in 140 ℃ of decompression distillation 20 minutes.Be cooled to 120 ℃, remove by filter catalyst waste slag, obtain the faint yellow liquid thickness product of 88.2 grams, the content of residual diphenylamines is 0.755 quality % in the gas chromatographic analysis product.
Instance 3
(1) preparation catalyst
Get the HZSM-5 molecular sieve, Gu by the liquid of 0.78ml/g/than 40 ℃, to use concentration be the saturated dipping of phosphoric acid solution 4 hours of 5 quality %, dephlegmate then; 130 ℃ of dryings 4 hours; Obtain catalyst C, wherein phosphorus acid content is 3.85 quality %, and the HZSM-5 molecular sieve content is 96.15 quality %.
(2) preparation alkylated diphenylamine
In the autoclave of 250ml, add 50.7 gram diphenylamines, 39 gram diisobutylene, 5 gram catalyst C, with nitrogen replacement reaction system three times.Be warming up to 100 ℃ and begin to stir, continue heat temperature raising to 180 ℃, when reaction system pressure is 0.30MPa; Reaction 2 hours picks up counting; When reaction pressure is reduced to 0.18MPa, add the diisobutylene of 12.8 grams, keep 180 ℃ to continue reaction 4 hours; Add 12 gram diisobutylene again, 180 ℃ of reactions 7 hours.When recording with gas chromatography that diphenylamines content is lower than 4 quality % in the reaction system, finish reaction.With material cooling, unreacted diisobutylene and low amounts of water are removed in 150 ℃ of decompression distillation 20 minutes.Be cooled to 120 ℃, remove by filter catalyst waste slag, obtain the faint yellow liquid thickness product of 89.6 grams, the content of residual diphenylamines is 0.428 quality % in the gas chromatographic analysis product.
Instance 4
(1) preparation catalyst
Get the HZSM-5 molecular sieve; Gu by the liquid of 0.74ml/g/than 80 ℃, to use concentration be the saturated dipping of Salkowski's solution 7 hours of 10 quality %; Dephlegmate then, 190 ℃ of dryings 8 hours obtain catalyst D; Wherein phosphotungstic acid content is 7.29 quality %, and the HZSM-5 molecular sieve content is 92.71 quality %.
(2) preparation alkylated diphenylamine
In the 250ml autoclave, add 50.7 gram diphenylamines, 39 gram diisobutylene, 2 gram catalyst D, with nitrogen replacement reaction system three times.Be warming up to 100 ℃ and begin to stir, continue heat temperature raising to 180 ℃, when reaction system pressure is 0.30MPa; Reaction 2 hours picks up counting; When reaction pressure is reduced to 0.18MPa, add the diisobutylene of 12.8 grams, 180 ℃ are continued reaction 4 hours; Add 12 gram diisobutylene again, continue reaction 7 hours.When recording with gas chromatography that diphenylamines content is lower than 4 quality % in the reaction system, finish reaction.With material cooling, unreacted diisobutylene and low amounts of water are removed in 150 ℃ of decompression distillation 20 minutes.Be cooled to 140 ℃, remove by filter catalyst waste slag, obtain the faint yellow liquid thickness product of 87.8 grams, the content of residual diphenylamines is 0.729 quality % in the gas chromatographic analysis product.
Instance 5
(1) preparation catalyst
By 4: 6 mass ratioes HZSM-5 and HY molecular sieve are mixed; Gu by the liquid of 0.74ml/g/than 80 ℃, to use concentration be the saturated dipping of Salkowski's solution 7 hours of 10 quality %, dephlegmate then, 190 ℃ of dryings 8 hours; Obtain catalyst E; Wherein phosphotungstic acid content is 7.35 quality %, and the HZSM-5 molecular sieve content is 37.06 quality %, and the HY molecular sieve content is 55.59 quality %.
(2) preparation alkylated diphenylamine
In the autoclave of 250ml, add 50.7 gram diphenylamines, 39 gram diisobutylene, 2 gram catalyst E, with nitrogen replacement reaction system three times.Being warming up to 100 ℃ begins to stir; Continue heat temperature raising to 170 ℃; When reaction system pressure was 0.30MPa, the reaction 2 hours that picks up counting was when reaction pressure is reduced to 0.18MPa gradually; The diisobutylene that adds 12.8 grams continues reaction 4 hours, adds 12 gram diisobutylene then and continues reaction 7 hours.Finish reaction when recording with gas chromatography that diphenylamines content is lower than 4 quality % in the reaction system.With material cooling, unreacted diisobutylene and low amounts of water are removed in 150 ℃ of decompression distillation 20 minutes.Be cooled to 140 ℃, remove by filter catalyst waste slag, obtain the faint yellow liquid thickness product of 88.4 grams, the content of residual diphenylamines is 0.629 quality % in the gas chromatographic analysis product.
Comparative Examples 1
Method according to 1 (2) step of instance prepares alkylated diphenylamine; The different catalyst that is to use is used HY molecular sieve of (1) step; The alkylated diphenylamine output that finally obtains is 58.1 grams; The content of residual diphenylamines is 83.237 quality % in the gas chromatographic analysis product, explains that the catalyst alkylation ability is relatively poor.
Comparative Examples 2
Method by CN200810227828.5 is carried out alkylated reaction.
(1) preparation catalyst
Get atlapulgite (production of Yi County, Jinzhou oil carclazyte Co., Ltd), Gu by the liquid of 0.87ml/g/than 20 ℃, to use concentration be the saturated dipping of sulfuric acid solution 2 hours of 2 quality %, dephlegmate then, 100 ℃ of dryings 2 hours obtain catalyst F.
(2) preparation alkylated diphenylamine
In the autoclave of 250ml, add 50.7 gram diphenylamines, 60.5 gram diisobutylene, 2 gram catalyst F, with nitrogen replacement reaction system three times.Begin when being warming up to 100 ℃ to stir; Continue heat temperature raising to 170 ℃; When reaction system pressure was 0.30MPa, the reaction 10 hours that picks up counting was along with the carrying out of reaction; Pressure is reduced to 0.17MPa gradually, records with gas chromatography and finishes reaction when diphenylamines content is lower than 4 quality % in the reaction system.With the material cooling,, remove unreacted diisobutylene and low amounts of water 140 ℃ of decompression distillation 20 minutes.Material is cooled to 120 ℃, removes by filter catalyst waste slag, obtain the faint yellow liquid thickness product of 86.9 grams, the content of residual diphenylamines is 1.029 quality % in the gas chromatographic analysis product.
Reaction result shows, is the catalyst that carrier makes with the atlapulgite, and through alkylated reaction, diphenylamines content residual in the alkylate is more, explains that its reactivity worth is relatively poor.
Instance 6
Respectively the catalyst in instance 1～5 and the Comparative Examples 1～2 is repeated the diphenylamines alkylated reaction by the method for operating of each instance, investigate the service life of catalyst.Measure the content that each course of reaction finishes the residual diphenylamines in back through gas chromatography, the result sees table 1.
Table 1
Table 1 is the result show, catalyst of the present invention can be repeatedly used, and same catalyst amount has catalytic reaction effect preferably.
Instance 7
Estimate the antioxygenic property of alkylated diphenylamine.
With 150SN neutral oil is base oil, and the alkylated diphenylamine that adds each examples preparation of 0.5 quality % is modulated into oil product.Adopt rotary oxygen bomb method (ASTM D-2272) to measure the oxidation induction period of modulation oil product, the result sees table 2.
Table 2
| The alkylated diphenylamine source of using | Oxidation induction period, min |
| Instance 1 | 107 |
| Instance 2 | 103 |
| Instance 3 | 102 |
| Instance 4 | 102 |
| Instance 5 | 104 |
| Comparative Examples 2 | 103 |
Can know that by table 2 alkylated diphenylamine of the antioxygenic property of the alkylated diphenylamine that the present invention makes and the preparation of Comparative Examples 2 methods is suitable.
In sum, by the alkylated diphenylamine of Preparation of Catalyst of the present invention compared with prior art, under the suitable basically situation of antioxygenic property; Catalyst performance improves, therefore, and under same alkylate output; Can reduce catalyst amount, thereby reduce of the pollution of discarded catalyst environment.In addition, catalyst of the present invention is reused often, can reduce the Preparation of Catalyst cost.
Claims (13)
1. a diphenylamines alkylation catalyst comprises the molecular sieve of 85～99 quality % and the acid of 1～15 quality %, and described molecular sieve is faujasite and/or MFI type molecular sieve, and described acid is oxygen-containing inorganic acid or heteropoly acid.
2. according to the described catalyst of claim 1, it is characterized in that described catalyst comprises the molecular sieve of 88～98 quality % and the acid of 2～12 quality %.
3. according to claim 1 or 2 described catalyst, it is characterized in that described oxygen-containing inorganic acid is sulfuric acid or phosphoric acid, described heteropoly acid is phosphotungstic acid or phosphomolybdic acid.
4. according to claim 1 or 2 described catalyst, it is characterized in that described faujasite-type molecular sieve is a Y zeolite, MFI type molecular sieve is ZSM-5.
5. according to claim 1 or 2 described catalyst, it is characterized in that described faujasite-type molecular sieve and MFI type molecular sieve are Hydrogen.
6. the said Preparation of catalysts method of claim 1 comprises with said aqueous acid molecular sieve is carried out saturated dipping, then dehydration, drying.
7. according to the described method of claim 6, it is characterized in that described aqueous acid concentration is 1～20 quality %.
8. according to the described method of claim 6, the temperature that it is characterized in that saturated dipping is 20～80 ℃, and baking temperature is 90～200 ℃.
9. a diphenylamines alkylation comprises making diphenylamines in the presence of the described catalyst of claim 1, in 140～250 ℃, 0.2～0.5MPa, inert gas environment with the alkylating agent haptoreaction.
10. according to the described method of claim 9, it is characterized in that catalyst consumption is 1～10 quality % of the diphenylamines raw material total amount of adding.
11., it is characterized in that described alkylating agent is a diisobutylene according to the described method of claim 9.
12. according to the described method of claim 11, it is characterized in that described diisobutylene is added reaction system several times, the diisobutylene that adds for the first time is 50～70 quality % of diisobutylene total amount.
13. according to the described method of claim 9, it is characterized in that when diphenylamines content in the reaction system is lower than 4 quality %, stop reaction.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408431A (en) * | 2013-08-20 | 2013-11-27 | 天津利安隆新材料股份有限公司 | Preparation method of liquid-state aromatic amine antioxidant 5057 |
| CN105601521A (en) * | 2015-12-30 | 2016-05-25 | 天津利安隆新材料股份有限公司 | Preparation method of aromatic amine type antioxidant 5057 |
| CN108490090A (en) * | 2018-03-20 | 2018-09-04 | 苏州市信测标准技术服务有限公司 | BNST detection method of content in the products such as a kind of lubricant, ink, rubber |
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| CN113045429A (en) * | 2019-12-27 | 2021-06-29 | 中国石油天然气股份有限公司 | Method for simultaneously preparing antioxidant of butyl octyl diphenylamine and dioctyl diphenylamine and obtained product |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130478A (en) * | 2006-08-25 | 2008-02-27 | 北京石油化工学院 | Method for preparing high purity2, 6-diisopropyl naphthalene |
| CN101134905A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN101134906A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for increasing solid content of catalytic cracking catalyst slurry |
| CN101745423A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalyst and diphenylamine alkylation method |
-
2010
- 2010-08-12 CN CN201010251607.9A patent/CN102371174B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130478A (en) * | 2006-08-25 | 2008-02-27 | 北京石油化工学院 | Method for preparing high purity2, 6-diisopropyl naphthalene |
| CN101134905A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN101134906A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for increasing solid content of catalytic cracking catalyst slurry |
| CN101745423A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalyst and diphenylamine alkylation method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408431A (en) * | 2013-08-20 | 2013-11-27 | 天津利安隆新材料股份有限公司 | Preparation method of liquid-state aromatic amine antioxidant 5057 |
| CN103408431B (en) * | 2013-08-20 | 2016-01-06 | 天津利安隆新材料股份有限公司 | The preparation method of aromatic liquid amine antioxidants 5057 |
| CN105601521A (en) * | 2015-12-30 | 2016-05-25 | 天津利安隆新材料股份有限公司 | Preparation method of aromatic amine type antioxidant 5057 |
| CN108490090A (en) * | 2018-03-20 | 2018-09-04 | 苏州市信测标准技术服务有限公司 | BNST detection method of content in the products such as a kind of lubricant, ink, rubber |
| CN112023979A (en) * | 2019-06-03 | 2020-12-04 | 中石化南京化工研究院有限公司 | Catalyst for synthesizing 2-tert-butyl aniline and preparation method and application thereof |
| CN113045429A (en) * | 2019-12-27 | 2021-06-29 | 中国石油天然气股份有限公司 | Method for simultaneously preparing antioxidant of butyl octyl diphenylamine and dioctyl diphenylamine and obtained product |
| CN116060101A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Catalyst for synthesizing diphenylamine, preparation method and application thereof |
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