CN105439865A - Method for removing trace sulfur from DBP (dibutyl phthalate)/DIBP (diisobutyl phthalate) - Google Patents
Method for removing trace sulfur from DBP (dibutyl phthalate)/DIBP (diisobutyl phthalate) Download PDFInfo
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- CN105439865A CN105439865A CN201510868323.7A CN201510868323A CN105439865A CN 105439865 A CN105439865 A CN 105439865A CN 201510868323 A CN201510868323 A CN 201510868323A CN 105439865 A CN105439865 A CN 105439865A
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- reaction
- dibp
- phthalate
- diisobutyl
- removal methods
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Abstract
The invention discloses a method for removing trace sulfur from DBP (dibutyl phthalate)/DIBP (diisobutyl phthalate). The method comprises the following steps: mixing DBP/DIBP with hydrogen, heating the mixture to the reaction temperature, feeding the heated mixture into an insulation type fixed bed reactor which is filled with a desulfurizing agent for desulphurization reaction, and directly using the obtained product in hydrogenation reaction for preparing a cyclohexane plasticizer, wherein the desulfurizing agent is one or a mixture of formed SiO2-Al2O3, SiO2, Al2O3; the total pore volume of the desulfurizing agent is 0.5-1.0 ml/g, the proportion of the desulfurizing agent with the pore volume being larger than 10 nm is not lower than 55% and the specific surface area is 200-500 cm<2>/g; the desulphurization reaction condition lies in that the reaction pressure is 1-3 MPa, the reaction temperature is 100-150 DEG C, hydrogen atmosphere is required, the volume ratio of hydrogen to liquid is (100-1000):1, the liquid hourly space velocity (calculated as DIBP) is 0.1-1 h<-1>. The method for removing trace sulfur from DBP (dibutyl phthalate)/DIBP (diisobutyl phthalate) is simple in operation, the desulfurizing agent is low in cost and easily obtainable, the service life is long, the desulphurization effect is remarkable, the sulphur content in the product is lower than 5 ppm, and after multiple regeneration, the sulphur content in the desulfurization product is still lower than 5 ppm, therefore the method is suitable for industrial production.
Description
Technical field
The invention belongs to fine chemicals production technology, polymer new diseases and material molding technology field, be specifically related to the removal methods of Trace Sulfur in a kind of dibutyl phthalate/diisobutyl ester hydrogenation process.
Background technology
Dibutyl phthalate (DBP) and diisobutyl phthalate (DIBP) are used widely food, medicine and rubber etc. are industrial as conventional phthalic ester plasticizer.But Recent study shows, adjacent benzene class softening agent has Reproductive and developmental toxicity, there is potential threat to organism neural system, and European and American developed countries are continuous statute of limitation and ban of having promulgated use mutually.Hexanaphthene-1,2-dioctyl phthalate two (different) butyl ester that DBP/DIBP hydrogenation is produced, as a class environment-friendlyplasticizer plasticizer, overcomes the world today about the restriction in use of adjacent benzene class softening agent, can be used as the upgrading substitute of DBP/DIBP; In addition, DIBP also has other important use widely, the solvent hexanaphthene-1 just that the ALMA fluidization of n butane oxidation MALEIC ANHYDRIDE of AlusuisseItalia and Lummus-Crest two company exploitation adopts, 2-dioctyl phthalate diisobutyl ester, through facts have proved that it has fine qualities.
At present, main active component in adjacent benzene class softening agent hydrogenation catalyst is the precious metals such as Pt, Pd, Ru, noble metal hydrogenation catalyst is under the operational condition of low temperature, low pressure gentleness, show excellent Deep catalytic Hydrogenation, but also exist expensive, catalyzer Sulfur tolerance is poor, the easy defect such as poisoning, requires higher to the sulphur content in raw material.Patent CN1022198688A discloses a kind of method improving thermal stability of dibutyl/diisobutyl phthalate, point out: suitability for industrialized production dibutyl phthalate and diisobutyl phthalate still adopt protonic acid sulfuric acid to carry out esterification as catalyzer at present, the activity of existing non-sulfuric acid type low temperature catalyst catalysis phthalic anhydride and below C4 alcohol is lower, cause reaction time long, catalyzer is expensive, and industrial production cost increases.Adopt the production cost of sulfuric acid catalyst lower, at the lesser temps of 100-140 DEG C, still there is very high catalytic esterification active, phthalic anhydride and the C4 reaction conversion ratio after 5h still can reach 99%, reaction efficiency is high, but also there is product after the operation process such as neutralization-washing-ol recovery-refining-filtration, still there is the sulphur (about 100-200ppm) of trace, the existence of trace sulfur compound in product, cause follow-up hydrogenation catalyst poisoning, rapid deactivation (3-5d), and cannot regenerate.At present, many desulfurization being usually used in oil product as adsorption desulfurizing agent such as gac, molecular sieve, clay, metal oxide and complex metal oxides, but have no Trace Sulfur in the softening agent of the protonic acid sulfuric acid catalysis such as dibutyl phthalate/diisobutyl ester remove in application.
Summary of the invention
The object of the invention is the removal methods that Trace Sulfur in a kind of dibutyl phthalate/diisobutyl ester is provided for above-mentioned prior art Problems existing, follow-up hydrogenation catalyzer is effectively protected.
The reaction principle of industrial production dibutyl phthalate/diisobutyl ester:
The sulfur-bearing side reaction occurred in reaction process:
Wherein: C
4h
9-represent normal-butyl or isobutyl-.
Above-mentioned trace sulfocompound, at dibutyl phthalate/diisobutyl ester Hydrogenation in the process of environment-friendlyplasticizer plasticizer, generates the sulfide that cannot regenerate with Pt, Pd, Ru isoreactivity composition in catalyzer, causes rapid catalyst deactivation.
To achieve these goals, the following technical scheme of the present invention's employing:
In dibutyl phthalate/diisobutyl ester, a removal methods for Trace Sulfur, comprises the steps:
After diisobutyl phthalate/diisobutyl ester is mixed with hydrogen, be heated to temperature of reaction enter the heat-insulating fixed-bed reactor being mounted with sweetening agent and carry out desulphurization reaction, after gained desulfurization, dibutyl phthalate/diisobutyl ester product can be directly used in hydrogenation reaction and prepares cyclohexanes softening agent;
Described sweetening agent is shaping SiO
2-Al
2o
3, SiO
2, Al
2o
3in the mixture of one or more; Total pore volume 0.5-1.0ml/g, wherein more than 10nm pore volume proportion is not less than 55%, and specific surface is 200-500cm
2/ g;
The reaction conditions of described desulphurization reaction is: reaction pressure is 1 ~ 3MPa, and temperature of reaction is 100 ~ 150 DEG C, hydrogen atmosphere, and hydrogen liquid volume ratio is 100 ~ 1000:1, volume liquid hourly space velocity (in diisobutyl phthalate) 0.1 ~ 1h
-1.
In removal methods of the present invention, the shape of described sweetening agent is cylindrical, butterfly, trifolium or Herba Galii Bungei.
Described heat-insulating fixed-bed reactor are two sections of in parallel fixed-bed reactor, to realize independent switching, and high temperature regeneration in the device that can realize sweetening agent.
Described sweetening agent absorption saturated rear (about 1000h) high temperature regeneration in reactor or outside reactor, regeneration temperature is 450 DEG C ~ 550 DEG C, recovery time 4 ~ 8h.
The inventive method is applicable to the hydrogenation reaction preprocessing process that protonic acid sulfuric acid makees the adjacent benzene class softening agent of catalyzer.
In the present invention, the reaction of sulfocompound on sweetening agent is that physical adsorption desulfurization and chemisorption desulfurization combine, and physical adsorption desulfurization is main (can be down to 10ppm), and chemisorption desulfurization is auxiliary.Chemisorption desulphurization reaction principle:
Wherein: C
4h
9-represent normal-butyl or isobutyl-.
The invention has the beneficial effects as follows: 1) raw material is industrial goods dibutyl phthalate/diisobutyl esters, common on market, be easy to get; Desulfurizer therefor is shaping active silica-alumina; cheap and easy to get; reaction conditions is gentle, can realize continuous prodution on fixed bed, simple to operate; the significant desulfurization effect of sweetening agent; after long service life, evaluation 800h; sulphur content in DIBP is < 5ppm still, plays significant provide protection to follow-up hydrogenation catalyst, and sweetening effectiveness is far superior to traditional molecular sieve and gac.2) in the present invention sweetening agent absorption saturated after can in realization response device or the outer high temperature regeneration of device, regeneration temperature is 450 DEG C ~ 550 DEG C, recovery time 4 ~ 8h, regeneration condition is gentle, cost is low, after repeatedly regenerating, in DIBP, sulphur content, still lower than 5ppm, meets the requirement of follow-up noble metal hydrogenation catalyst.3) in the inventive method, sweetening agent cost is lower, sulfur removal rate in dibutyl phthalate/diisobutyl ester is high, temperature of reaction is lower, in realization response device or the outer high temperature regeneration of device, can be applicable to the large-scale industrial productions such as fixed bed after sweetening agent absorption is saturated.
Accompanying drawing explanation
Fig. 1 is the desulfurization process figure of diisobutyl phthalate of the present invention (DIBP).
In figure, 1 fresh feed pump, 2 process furnace, 3 desulphurization reactors, 4 gas-liquid separators, 5 hydrogenation unit, 6 recycle pumps.In figure, the parallel connection of two desulphurization reactors uses, high temperature regeneration in the device that can realize sweetening agent.
Embodiment
Be further elaborated the removal methods technical scheme of Trace Sulfur in a kind of dibutyl phthalate/diisobutyl ester of the present invention below in conjunction with embodiment, embodiment is for diisobutyl phthalate (DIBP).
Be that the industrial goods diisobutyl phthalate (DIBP) of 99.6% is for raw material with purity, adopt present invention process, in sweetening agent loadings be 100mL desulphurization reactor 3 on carry out desulphurization reaction, sweetening agent is shaping active silica-alumina, shape can be: cylindrical, butterfly, trifolium or Herba Galii Bungei, temperature of reaction 100 ~ 150 DEG C, and reaction pressure 1-3MPa, hydrogen atmosphere, volume liquid hourly space velocity (in diisobutyl phthalate) 0.1 ~ 1h
-1reaction conditions under, in DIBP, sulphur content 1-5.0ppm, DIBP purity is not less than 99.5%, plant running 800h, sulphur content still < 5ppm in DIBP.
Embodiment 1
Be that the industrial goods diisobutyl phthalate (DIBP) of 99.6% is for raw material with purity, sulphur content 150ppm, adopt present invention process, in sweetening agent loadings be 100mL desulphurization reactor 3 on carry out desulphurization reaction, sweetening agent is butterfly activated alumina (alumina content 100%), temperature of reaction 110 DEG C, and reaction pressure 1MPa, hydrogen liquid volume ratio 500:1, volume liquid hourly space velocity (in diisobutyl phthalate) 0.3h
-1reaction conditions under, sulphur content 2.5ppm, DIBP purity 99.5% in DIBP.
Embodiment 2
Be that the industrial goods diisobutyl phthalate (DIBP) of 99.6% is for raw material with purity, sulphur content 150ppm, adopt present invention process, in sweetening agent loadings be 100mL desulphurization reactor 3 on carry out desulphurization reaction, sweetening agent is butterfly active silica-alumina (alumina content 80%), temperature of reaction 110 DEG C, and reaction pressure 1MPa, hydrogen liquid volume ratio 500:1, volume liquid hourly space velocity (in diisobutyl phthalate) 0.3h
-1reaction conditions under, sulphur content 3.7ppm, DIBP purity 99.5% in DIBP.
Embodiment 3
After sweetening agent absorption in embodiment 1 is saturated, 500 DEG C, regenerate in air atmosphere, recovery time 6h, regeneration catalyzer re-start adsorption desulfurize experiment, with purity be the industrial goods diisobutyl phthalate (DIBP) of 99.6% for raw material, sulphur content 150ppm, temperature of reaction 110 DEG C, reaction pressure 1MPa, hydrogen liquid volume ratio 500:1, volume liquid hourly space velocity (in diisobutyl phthalate) 0.3h
-1reaction conditions under, sulphur content 2.8ppm, DIBP purity 99.5% in DIBP.
The desulfurization performance that in embodiment 1, sweetening agent repeatedly regenerates is in table 1, and through repeatedly regenerating, in DIBP, sulphur content is still lower than 5ppm, meets the requirement of follow-up noble metal hydrogenation catalyst.
Table 1 formed alumina sweetening agent repeatedly regenerative sulfur binding performance
Comparative example 1
Be that the industrial goods diisobutyl phthalate (DIBP) of 99.6% is for raw material with purity, sulphur content 150ppm, adopt present invention process, in sweetening agent loadings be 100mL desulphurization reactor 3 on carry out desulphurization reaction, sweetening agent is cylindrical 13X molecular sieve (molecular sieve silica alumina ratio is 5.0), temperature of reaction 100 ~ 150 DEG C, and reaction pressure 1MPa, hydrogen liquid volume ratio 500:1, volume liquid hourly space velocity (in diisobutyl phthalate) 0.3h
-1reaction conditions under, sulphur content 7.1ppm, DIBP purity 99.5% in DIBP.
Comparative example 2
Be that the industrial goods diisobutyl phthalate (DIBP) of 99.6% is for raw material with purity, sulphur content 150ppm, adopt present invention process, in sweetening agent loadings be 100mL desulphurization reactor 3 on carry out desulphurization reaction, sweetening agent is particulate state cocoanut active charcoal (specific surface area 1266m
2/ g, pore volume 0.97cm
3/ g, mean pore size 3.5nm), temperature of reaction 100 ~ 150 DEG C, reaction pressure 1MPa, hydrogen liquid volume ratio 500:1, volume liquid hourly space velocity (in diisobutyl phthalate) 0.3h
-1reaction conditions under, sulphur content 15.3ppm, DIBP purity 99.5% in DIBP.
Claims (6)
1. the removal methods of Trace Sulfur in dibutyl phthalate/diisobutyl ester, is characterized in that, comprise the steps:
After diisobutyl phthalate/diisobutyl ester is mixed with hydrogen, be heated to temperature of reaction enter the heat-insulating fixed-bed reactor being mounted with sweetening agent and carry out desulphurization reaction, after gained desulfurization, dibutyl phthalate/diisobutyl ester product can be directly used in hydrogenation reaction and prepares cyclohexanes softening agent;
Described sweetening agent is shaping SiO
2-Al
2o
3, SiO
2, Al
2o
3in the mixture of one or more; Total pore volume 0.5-1.0ml/g, wherein more than 10nm pore volume proportion is not less than 55%, and specific surface is 200-500cm
2/ g;
The reaction conditions of described desulphurization reaction is: reaction pressure is 1 ~ 3MPa, and temperature of reaction is 100 ~ 150 DEG C, hydrogen atmosphere, and hydrogen liquid volume ratio is 100 ~ 1000:1, and volume liquid hourly space velocity is 0.1 ~ 1h
-1, in diisobutyl phthalate.
2. removal methods according to claim 1, is characterized in that, the shape of described sweetening agent is cylindrical, butterfly, trifolium or Herba Galii Bungei.
3. removal methods according to claim 1, is characterized in that, described heat-insulating fixed-bed reactor are two sections of fixed-bed reactor in parallel, to realize independent switching.
4. removal methods according to claim 1, is characterized in that, high temperature regeneration in heat-insulating fixed-bed reactor device or outside device after described sweetening agent absorption is saturated, regeneration temperature is 450 DEG C ~ 550 DEG C, recovery time 4 ~ 8h.
5. removal methods according to claim 1, is characterized in that, the ester content in described dibutyl phthalate/diisobutyl ester at 95wt% ~ 99.9wt%, the content 0-1000ppm of Trace Sulfur.
6. the application of removal methods according to claim 1 in the adjacent benzene class softening agent preparation of protonic acid sulfuric acid catalysis, is characterized in that, obtains product can be directly used in hydrogenation reaction and prepare cyclohexanes softening agent through described removal methods.
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|---|---|---|---|
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| CN201510868323.7A CN105439865B (en) | 2015-12-01 | 2015-12-01 | The removal methods of Trace Sulfur in a kind of dibutyl phthalate/diisobutyl ester |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7323586B2 (en) * | 2001-09-26 | 2008-01-29 | Oxeno Olefinchemie Gmbh | Phthalic acid alkyl ester mixtures with controlled viscosity |
| CN102219688A (en) * | 2011-05-05 | 2011-10-19 | 江南大学 | Method for improving thermal stability of dibutyl/diisobutyl phthalate |
| CN102924277A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Method for preparing cyclohexane dioctyl phthalate dibasic esters through hydrogenation |
-
2015
- 2015-12-01 CN CN201510868323.7A patent/CN105439865B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7323586B2 (en) * | 2001-09-26 | 2008-01-29 | Oxeno Olefinchemie Gmbh | Phthalic acid alkyl ester mixtures with controlled viscosity |
| CN102219688A (en) * | 2011-05-05 | 2011-10-19 | 江南大学 | Method for improving thermal stability of dibutyl/diisobutyl phthalate |
| CN102924277A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Method for preparing cyclohexane dioctyl phthalate dibasic esters through hydrogenation |
Non-Patent Citations (1)
| Title |
|---|
| 丁金城 等: "间歇生产邻苯二甲酸二异丁酯的色度控制", 《贵州化工》 * |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: CHINA NATIONAL OFFSHORE OIL Corp. Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: CHINA NATIONAL OFFSHORE OIL Corp. Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Applicant before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161012 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: CHINA NATIONAL OFFSHORE OIL Corp. Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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