CN100467439C - Process for synthesizing dialkyldiphenylamine - Google Patents

Process for synthesizing dialkyldiphenylamine Download PDF

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Publication number
CN100467439C
CN100467439C CNB2005100474916A CN200510047491A CN100467439C CN 100467439 C CN100467439 C CN 100467439C CN B2005100474916 A CNB2005100474916 A CN B2005100474916A CN 200510047491 A CN200510047491 A CN 200510047491A CN 100467439 C CN100467439 C CN 100467439C
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pentanoic
diisobutylene
accordance
zeolite
catalyzer
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CN1951904A (en
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马皓
艾抚宾
佟明友
王海波
宋丽芝
勾连科
张淑梅
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a synthesizing method of dialkyldiphenylamine, which is characterized by the following: adopting diphenylamine and diisobutylene as raw material; making catalyst through H beta zeolite and gamma-Al2O3; operating continuously under liquid-phase condition; regenerating and recycling catalyst; reducing manufacturing cost.

Description

A kind of method of synthetic dialkyl diphenylamine
Technical field
The present invention relates to the method for the synthetic dialkyl diphenylamine of a kind of pentanoic and diisobutylene, the method for the synthetic dialkyl diphenylamine of particularly a kind of continous way.
Background technology
Dialkyl diphenylamine is a kind of high-temperature antioxidant, can be used for I. C. engine oil, turbine oil, thermal oil, hydraulic efficiency oil, and in lubricating grease and the oil fuel, also can be used in the rubber item, and it is aging to prevent that rubber thermooxidizing and elasticity from deflecting.In addition, it still is the important component of biological diesel oil anti-oxidant.
Dialkyl diphenylamine is by pentanoic and alkene, and reaction forms in the presence of catalyzer.Because the difference of raw material olefin, catalyzer and synthesis technique, the dialkyl diphenylamine structure that obtains be difference to some extent also, the branch of solid and liquid is arranged under the normal temperature.Because the liquid dialkyl diphenylamine has oil soluble good, advantages such as easy allotment, consumption has substantially exceeded the solid dialkyl diphenylamine in the actual production.
In recent ten years, along with the development of automotive industry and biofuel industry, and the continuous expansion of dialkyl diphenylamine range of application, market to the demand of dialkyl diphenylamine also growing.Traditional dialkyl diphenylamine production method is to be raw material with pentanoic and diisobutylene, is catalyzer with the aluminum chloride, adopts intermittently still reaction.As US 3,714,257 disclosed a kind of dialkyl diphenylamine production methods are exactly this kind method, and reaction product obtains after separating in this method 4, and 4 '-dioctyl diphenylamine at room temperature is a solid, and fusing point is 75～85 ℃.With nonene and pentanoic is raw material, adopts same synthetic method can obtain nonylated diphenylamine, is liquid under this product room temperature.There is following shortcoming in this method: batch production, operate cumbersome; With the aluminum chloride is catalyzer, etching apparatus; Soda acid waste residue product is arranged, contaminate environment in the production.
In order to solve aluminum chloride etching apparatus problem, and reduce contaminate environment.EP149,422 have proposed a kind of is raw material with pentanoic and diisobutylene, is catalyzer with the atlapulgite that intermittent type synthesizes the dialkyl diphenylamine method.Because normal pressure, 160 ℃ are adopted in this reaction, the continuous dropwise reaction mode of diisobutylene causes the temperature of reaction fluctuation big, the fluctuation of service problem.
It is raw material with pentanoic and diisobutylene that CN 1288000A discloses a kind of, is catalyzer with the atlapulgite, and under certain pressure, intermittent type synthesizes the dialkyl diphenylamine method.The some shortcomings part is still arranged in this method,, operate cumbersome as batch production; Catalyst levels is big, and the use etc. of can not regenerating.
Summary of the invention
In order to overcome the deficiency in the above-mentioned synthetic method, the invention provides a kind of method of synthesizing dialkyl diphenylamine by pentanoic and diisobutylene continuously.
The present invention is adopted by H β zeolite and γ-Al by the technology of pentanoic and the synthetic dialkyl diphenylamine of diisobutylene 2O 3The catalyzer of forming.
Described by H β zeolite and γ-Al 2O 3Consisting of of the catalyzer of forming:
A:H β zeolite is 50～95w%, is preferably 58～93w%;
B: surplus is γ-Al 2O 3
The SiO of H β zeolite wherein 2/ Al 2O 3The molecule mol ratio is 20～100, is preferably 20～70.
The present invention used by H β zeolite and γ-Al 2O 3The Preparation of catalysts method of forming can adopt kneading method commonly used in this area, and detailed process is as follows:
H β zeolite mixes with aluminium hydrate powder, and adds an amount of nitric acid and deionized water, and the add-on of nitric acid accounts for the 0.5wt%～2.0wt% of siccative; The add-on of deionized water is pinched mixing, extrusion is as the criterion.Afterwards, on banded extruder, mix pinch, extruded moulding, drying, roasting, wherein drying temperature is 60～110 ℃, 2h～8h; Maturing temperature is 400～580 ℃, and 3h～16h promptly obtains the present invention's catalyzer.
The inventive method can adopt batch operation of the prior art, also can adopt the continous way operation.
The inventive method preferably adopts the continous way operation, and reactant reacts under liquid-phase condition, and reaction pressure is kept by nitrogen.Pentanoic, diisobutylene and nitrogen adopt charging (promptly entering reactor from reactor head or top) on the continous way, reacted product enters gas-liquid separator from reactor lower part or bottom outflow, the gas phase of gained is a nitrogen, and the liquid phase of gained is the dialkyl diphenylamine product.Wherein, pentanoic and diisobutylene all enter reactor with liquid phase.Wherein, pentanoic can be preheating to 55～190 ℃ earlier, preferably is preheated to 55～100 ℃, enters reactor then.
Reaction conditions when adopting the continous way operation is:
Temperature of reaction, ℃: 160～200
Reaction pressure, MPa:0.4～1.2
Pentanoic feed volume air speed, h -1: 0.1～0.5
Nitrogen/oil volume ratio: 50～400
Pentanoic/diisobutylene mol ratio: 0.5～2.5
Stopper, μ g/g is greater than 20;
Preferred reaction conditions is:
Temperature of reaction, ℃: 175～185
Reaction pressure, MPa:0.8～1.0
Pentanoic feed volume air speed, h -1: 0.15～0.3
Nitrogen/oil volume ratio: 100～200
Pentanoic/diisobutylene mol ratio: 0.6～2.0
Stopper, μ g/g 20～200 μ g/g are preferably 20～30 μ g/g.
In the inventive method, can prevent the autohemagglutination of highly active diisobutylene in reaction process, thereby improve utilization ratio of raw materials with stopper.Described stopper can adopt this area stopper commonly used, such as Resorcinol or MEHQ.Stopper can add reactor separately, also can together enter reactive system with after pentanoic or diisobutylene mix, and after preferably mixing with the diisobutylene raw material, together enters reactive system.
Because the present invention has adopted by H β zeolite and γ-Al 2O 3The synthetic dialkyl diphenylamine of the catalyst of forming makes to produce and realized serialization, has simplified existing manufacturing technique, and is easy and simple to handle, is suitable for scale operation; The renewable use of catalyzer has reduced production cost of products.
Embodiment
Embodiment 1
H β zeolite (SiO with 70g 2/ Al 2O 3Molecular ratio is 30) mix with the 10g aluminium hydrate powder, and add nitric acid and deionized water, on banded extruder, mix pinch, extruded moulding, wherein the add-on of nitric acid accounts for the 0.5wt% of siccative, the add-on of deionized water is pinched mixing, extrusion is as the criterion.Bar shaped catalyst is at 50 ℃ of dry 4.0h, and 110 ℃ are descended dry 4.0h, and 550 ℃ of following roasting 4.0h promptly obtain H β zeolite-A l in muffle furnace again 2O 3Catalyzer, wherein containing H β zeolite is 92.8wt%, surplus is γ-Al 2O 3, catalyzer is numbered DPA-1.
Embodiment 2
H β zeolite (SiO with 70g 2/ Al 2O 3Molecular ratio is 42) mix with the 20g aluminium hydrate powder, and add nitric acid and deionized water, on banded extruder, mix pinch, extruded moulding, wherein the add-on of nitric acid accounts for the 1.0wt% of siccative, the add-on of deionized water is pinched mixing, extrusion is as the criterion.Bar shaped catalyst is at 50 ℃ of dry 4.0h, 110 ℃ of dry 4.0h down, and 450 ℃ of following roasting 8.0h in muffle furnace again, all the other promptly obtain H β zeolite-A l with embodiment 1 2O 3Catalyzer, wherein containing H β zeolite is 85.8wt%, surplus is γ-Al 2O 3, catalyzer is numbered DPA-2.
Embodiment 3
H β zeolite (SiO with 70g 2/ Al 2O 3Molecular ratio is 66) mix with the 20g aluminium hydrate powder, and add nitric acid and deionized water, on banded extruder, mix pinch, extruded moulding, wherein the add-on of nitric acid accounts for the 2.0wt% of siccative, the add-on of deionized water is pinched mixing, extrusion is as the criterion.Bar shaped catalyst is at 50 ℃ of dry 4.0h, 110 ℃ of dry 4.0h down, and 550 ℃ of following roasting 12h in muffle furnace again, all the other promptly obtain H β zeolite-A l with embodiment 1 2O 3Catalyzer, wherein containing H β zeolite is 85.8wt%, surplus is γ-Al 2O 3, catalyzer is numbered DPA-3.
Embodiment 4
H β zeolite (SiO with 70g 2/ Al 2O 3Molecular ratio is 78) mix with the 60g aluminium hydrate powder, and add nitric acid and deionized water, on banded extruder, mix pinch, extruded moulding, wherein the add-on of nitric acid accounts for the 2.0wt% of siccative, the add-on of deionized water is pinched mixing, extrusion is as the criterion.Bar shaped catalyst is at 50 ℃ of dry 4.0h, 110 times dry 4.0h, and 450 ℃ of following roasting 12h in muffle furnace again, all the other promptly obtain H β zeolite-A l with embodiment 1 2O 3Catalyzer, wherein containing H β zeolite is 57.8wt%, surplus is γ-Al 2O 3, catalyzer is numbered DPA-4.
Embodiment 5～8
Catalyst breakage among the embodiment 1～4 is become 8～20 orders, get a certain amount of catalyzer internal diameter 25mm that packs into, in the stainless steel reactor of long 1200mm.(2,4,4-trimethylammonium-1-amylene content is 79.5wt% for pentanoic and diisobutylene; 2,4,4-trimethylammonium-2-amylene content is 14.4wt%; Other is the hydrocarbon mixture component.Below identical), nitrogen is charging.During reaction, pentanoic is through being heated to 70 ℃, by being pumped in the reactor; Nitrogen is directly delivered in the reactor without preheating.Reacted product flows out from reactor bottom, after cooling, enters in the gas-liquid separator, and gas phase nitrogen is discharged from the separator top, and the bottom liquid phases timing sampling is formed with gas chromatographic analysis, concrete reaction conditions and the results are shown in table 1.
Table 1, reaction conditions and result
Embodiment 1 2 3 4
The catalyzer numbering DPA-1 DPA-2 DPA-3 DPA-4
The catalyzer Intake Quantity, ml 100 100 100 100
Temperature of reaction, ℃ 175 180 185 190
Reaction pressure, MPa 0.6 0.8 1.0 1.0
Pentanoic charging air speed (v) h -1 0.15 0.20 0.3 0.4
Nitrogen/oil, v 100 200 200 400
Pentanoic/diisobutylene, mol ratio 2.0 2.0 0.61 05
*The stopper add-on, μ g/g 20 20 30 40
**Product content, wt% 11.2 13.0 16.6 14.2
*Stopper is: Resorcinol
*Product content is meant 4,4 '-two uncle's octyl diphenylamines
By data in the table 1 as can be known, catalyzer of the present invention in the synthetic dialkyl diphenylamine process of pentanoic and diisobutylene, all has higher transformation efficiency and selectivity preferably.In addition, the dialkyl diphenylamine that obtains after separating of reaction product is a weak yellow liquid.
Embodiment 9
With 200ml, granularity is 8～20 purpose DPA-3 catalyzer internal diameter 25mm that pack into, in the stainless steel reactor of long 1200mm, the DPA-3 catalyzer is carried out 300 hours stable service tests.Reaction pressure is 1.0MPa, and temperature of reaction is 180 ℃, and pentanoic feed volume air speed is 0.20h -1Pentanoic and diisobutylene, nitrogen are charging.During reaction, pentanoic is through being heated to 70 ℃, by being pumped in the reactor; Nitrogen is directly delivered in the reactor without preheating.Reacted product flows out from reactor bottom, enters in the gas-liquid separator after cooling, and gas phase is a nitrogen, discharges from the separator top, and the bottom liquid phases timing sampling is formed with gas chromatographic analysis, and concrete reaction result is listed in table 2.
Table 2,300 hours stable service tests
Accumulate runtime, h 4,4 '-two uncle's octyl diphenylamine content, wt%
50 18.8
100 18.5
150 18.3
200 17.9
250 17.2
300 16.8
By table 2 data as can be known, the DPA-3 catalyzer shows active and stable preferably in 300 hours stability experiments.

Claims (10)

1, a kind of method by pentanoic and the synthetic dialkyl diphenylamine of diisobutylene, it is characterized in that adopting the continous way operation, under liquid-phase condition, react, wherein pentanoic, diisobutylene and nitrogen adopt charging on the continous way, reacted product flows out from reactor lower part or bottom, and wherein pentanoic and diisobutylene enter reactor with liquid phase; Described reaction conditions is:
Temperature of reaction, ℃: 160～200
Reaction pressure, MPa:0.4～1.2
Pentanoic feed volume air speed, h -1: 0.1～0.5
Nitrogen/oil volume ratio: 50～400
Pentanoic/diisobutylene mol ratio: 0.5～2.5
Stopper, μ g/g is greater than 20;
This method adopts by H β zeolite and γ-Al 2O 3The catalyzer of forming.
2, in accordance with the method for claim 1, it is characterized in that consisting of of described catalyzer:
A:H β zeolite is 50wt%～95wt%;
B: surplus is γ-Al 2O 3
3, in accordance with the method for claim 1, it is characterized in that consisting of of described catalyzer:
A:H β zeolite is 58wt%～93wt%;
B: surplus is γ-Al 2O 3
4,, it is characterized in that the SiO of described H β zeolite according to the arbitrary described method of claim 1～3 2/ Al 2O 3The molecule mol ratio is 20～100.
5,, it is characterized in that the SiO of described H β zeolite according to the arbitrary described method of claim 1～3 2/ Al 2O 3The molecule mol ratio is 20～70.
6, in accordance with the method for claim 1, it is characterized in that described reaction conditions is:
Temperature of reaction, ℃: 175～185
Reaction pressure, MPa:0.8～1.0
Pentanoic feed volume air speed, h -1: 0.15～0.3
Nitrogen/oil volume ratio: 100～200
Pentanoic/diisobutylene mol ratio: 0.6～2.0
Stopper, μ g/g 20～200.
7, in accordance with the method for claim 1, the add-on that it is characterized in that described stopper is 20～30 μ g/g.
8, in accordance with the method for claim 1, it is characterized in that described stopper is Resorcinol or MEHQ.
9, in accordance with the method for claim 1, after it is characterized in that described stopper and diisobutylene mixing, together enter reactive system.
10, in accordance with the method for claim 1, it is characterized in that being preheating to 55 ℃～100 ℃ earlier before described pentanoic enters reactor.
CNB2005100474916A 2005-10-19 2005-10-19 Process for synthesizing dialkyldiphenylamine Active CN100467439C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103387818B (en) * 2012-05-07 2016-01-20 山东英可利化工有限公司 Chemosynthesis alkylbenzene heat transfer oil and preparation method thereof
CN105601521B (en) * 2015-12-30 2017-09-15 天津利安隆新材料股份有限公司 A kind of preparation method of aromatic amine antioxidant 5057
CN108409583A (en) * 2018-04-25 2018-08-17 南通理工学院 A kind of preparation method of dinonyldiphenylamine antioxidant

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3714257A (en) * 1970-01-21 1973-01-30 Reichhold Chemicals Inc Method for producing dialkylated diarylamines

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3714257A (en) * 1970-01-21 1973-01-30 Reichhold Chemicals Inc Method for producing dialkylated diarylamines

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