CN105439865B - The removal methods of Trace Sulfur in a kind of dibutyl phthalate/diisobutyl ester - Google Patents
The removal methods of Trace Sulfur in a kind of dibutyl phthalate/diisobutyl ester Download PDFInfo
- Publication number
- CN105439865B CN105439865B CN201510868323.7A CN201510868323A CN105439865B CN 105439865 B CN105439865 B CN 105439865B CN 201510868323 A CN201510868323 A CN 201510868323A CN 105439865 B CN105439865 B CN 105439865B
- Authority
- CN
- China
- Prior art keywords
- reaction
- desulfurizing agent
- diisobutyl
- removal methods
- dibutyl phthalate
- 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.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses in a kind of dibutyl phthalate/diisobutyl ester Trace Sulfur removal methods, after diisobutyl phthalate/diisobutyl ester is mixed by the method with hydrogen, being heated to reaction temperature carries out desulphurization reaction into the heat-insulating fixed bed reactors for being mounted with desulfurizing agent, and products therefrom can be directly used for hydrogenation reaction and prepare cyclohexanes plasticizer；Wherein SiO of the desulfurizing agent for molding2‑Al2O3、SiO2、Al2O3In the mixture of one or more；0.5 1.0ml/g of total pore volume, wherein more than 10nm pore volumes proportion are not less than 55%, and specific surface is 200 500cm2/g；The reaction condition of the desulphurization reaction is：Reaction pressure is 1～3MPa, and reaction temperature is 100～150 DEG C, and hydrogen atmosphere, hydrogen liquid volume ratio are 100～1000:1, volume liquid hourly space velocity (LHSV) is 0.1～1h‑1, in terms of diisobutyl phthalate.Simple to operate, desulfurizing agent of the invention is cheap and easy to get, long service life, significant desulfurization effect, and in product, sulfur content is less than 5ppm, and after repeatedly regenerating, in desulfurization product, sulfur content is still below 5ppm, it is adaptable to industrialized production.
Description
Technical field
The invention belongs to fine chemicals production technology, macromolecule new diseases and material molding technology field, tool
Body is 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 as conventional phthalic acid ester
Class plasticizer is industrially used widely in food, medicine and rubber etc..But, Recent study shows, adjacent benzene class plasticising
Agent has Reproductive and developmental toxicity, there is potential threat to organism nervous system, and European and American developed countries have continuously promulgated user
The statute of limitation in face and ban.Two (different) butyl ester of hexamethylene -1,2- dioctyl phthalate of DBP/DIBP hydrogenation productions is used as class environmental protection
Type plasticizer, overcomes world today's restriction with regard to adjacent benzene class plasticizer in use, can be used as the upgrading of DBP/DIBP
Succedaneum；Additionally, DIBP also has other extensive important uses, two company of Alusuisse Italia and Lummus-Crest
The solvent adopted by the ALMA fluidizations of the n butane oxidation maleic anhydride of exploitation exactly hexamethylene -1,2- diformazans
Sour diisobutyl ester, through facts have proved that it has fine qualities.
At present, the main active component in adjacent benzene class plasticizer hydrogenation catalyst is the noble metals such as Pt, Pd, Ru, noble metal
Hydrogenation catalyst is under the gentle operating condition of low temperature, low pressure, it is shown that excellent Deep catalytic Hydrogenation, but there is also valency
The defects such as lattice are expensive, catalyst Sulfur tolerance is poor, easy poisoning, require to the sulfur content in raw material higher.Patent CN
1022198688A discloses a kind of method for improving thermal stability of dibutyl/diisobutyl phthalate, it is indicated that：Current work
Industry metaplasia is produced dibutyl phthalate and diisobutyl phthalate and is still carried out as catalyst using Bronsted acid sulphuric acid
Esterification, existing non-sulfuric acid type low temperature catalyst catalysis phthalic anhydride are active relatively low with below C4 alcohol, cause reaction time long,
Catalyst is expensive, and commercial production cost increases.Production cost using sulfuric acid catalyst is relatively low, 100-140 DEG C compared with
Low temperature still has very high catalytic esterification activity, and phthalic anhydride remains to reach 99% with reaction conversion ratios of the C4 Jing after 5h, instead
Answer efficiency high, but there is also product it is neutralized-washing -ol reclaims-refined-filter etc. after operation processes, and there are still trace
Sulfur (about 100-200ppm), the presence of trace sulfur compound in product causes follow-up hydrogenation catalyst to be poisoned, rapid deactivation
(3-5d), and cannot regenerate.At present, many conducts such as activated carbon, molecular sieve, clay, metal-oxide and metal composite oxide
Adsorption desulfurizing agent is usually used in the desulfurization of oil product, but has no in the Bronsted acid sulfuric acid catalysis such as dibutyl phthalate/diisobutyl ester
Plasticizer in application in terms of Trace Sulfur removing.
The content of the invention
The purpose of the present invention is different for a kind of dibutyl phthalate/bis- of problem offer of above-mentioned prior art presence
The removal methods of Trace Sulfur in butyl ester, are effectively protected to follow-up hydrogenation catalyst.
The reaction principle of commercial production dibutyl phthalate/diisobutyl ester：
The sulfur-bearing side reaction occurred in course of reaction：
Wherein：C4H9- represent normal-butyl or isobutyl group.
Above-mentioned trace sulfur-containing compound, in dibutyl phthalate/diisobutyl ester Hydrogenation for environment-friendlyplasticizer plasticizer
During, the sulfide that cannot be regenerated with Pt, Pd, Ru isoreactivity composition generation in catalyst causes catalyst quickly to lose
It is living.
To achieve these goals, the following technical scheme that the present invention is adopted：
In a kind of dibutyl phthalate/diisobutyl ester, the removal methods of Trace Sulfur, comprise the steps：
After dibutyl phthalate/diisobutyl ester is mixed with hydrogen, it is heated to reaction temperature entrance and is mounted with desulfurization
The heat-insulating fixed bed reactors of agent carry out desulphurization reaction, dibutyl phthalate/diisobutyl ester product energy after gained desulfurization
Enough it is directly used in hydrogenation reaction and prepares cyclohexanes plasticizer；
SiO of the described desulfurizing agent for molding2-Al2O3、SiO2、Al2O3In the mixture of one or more；Total pore volume
The hole proportion of 0.5-1.0ml/g, wherein more than aperture 10nm is not less than 55%, and specific surface is 200-500cm2/g；
The reaction condition of the desulphurization reaction is：Reaction pressure is 1～3MPa, and reaction temperature is 100～150 DEG C, hydrogen
Atmosphere, hydrogen liquid volume ratio are 100～1000:1, volume liquid hourly space velocity (LHSV) (in terms of diisobutyl phthalate) 0.1～1h-1。
In removal methods of the present invention, described the cylindrically shaped of desulfurizing agent, butterfly, Herba Trifolii Pratentis or four
Leaf grass.
Described heat-insulating fixed bed reactors are two sections of fixed bed reactors in parallel, to realize being individually switched, can be real
High temperature regeneration in the device of existing desulfurizing agent.
After described desulfurizing agent adsorption saturation (about 1000h) in reactor or the outer high temperature regeneration of reactor, regeneration temperature
For 450 DEG C～550 DEG C, 4～8h of recovery time.
The inventive method is applied to the hydrogenation reaction preprocessing process that Bronsted acid sulphuric acid makees the adjacent benzene class plasticizer of catalyst.
Reaction of the sulfur-containing compound on desulfurizing agent in the present invention is that physical absorption desulfurization and chemisorbed desulfurization combine,
(10ppm can be down to) based on physical absorption desulfurization, supplemented by chemisorbed desulfurization.Chemisorbed desulphurization reaction principle：
Wherein：C4H9- represent normal-butyl or isobutyl group.
The invention has the beneficial effects as follows：1) raw material is industrial goods dibutyl phthalate/diisobutyl ester, on market often
See, be easy to get；Active silica-alumina of the desulfurizer therefor for molding, cheap and easy to get, reaction condition is gentle, be capable of achieving serialization in fixed bed
Production, simple to operate, the significant desulfurization effect of desulfurizing agent, long service life, evaluate 800h after, the still ＜ of the sulfur content in DIBP
5ppm, plays significant protective effect to follow-up hydrogenation catalyst, and desulfurized effect be far superior to traditional molecular sieve and
Activated carbon.2) it is capable of achieving after desulfurizing agent adsorption saturation in the present invention in reactor or the outer high temperature regeneration of device, regeneration temperature is 450 DEG C
～550 DEG C, 4～8h of recovery time, regeneration condition is gentle, low cost, and Jing after many regeneration, in DIBP, sulfur content is still below 5ppm,
Meet the requirement of follow-up noble metal hydrogenation catalyst.3) in the inventive method, desulfurizing agent cost is relatively low, and dibutyl phthalate/
Sulfur removal rate in diisobutyl ester is high, and reaction temperature is relatively low, is capable of achieving in reactor or the outer high temperature of device after desulfurizing agent adsorption saturation
Regeneration, it is adaptable to the large-scale industrial production such as fixed bed.
Description of the drawings
Fig. 1 is the desulfurization process figure of the diisobutyl phthalate (DIBP) of the present invention.
In figure, 1 feed pump, 2 heating furnaces, 3 desulfurization reactors, 4 gas-liquid separators, 5 hydrogenation units, 6 circulating pumps.Two in figure
Platform desulfurization reactor is used in parallel, is capable of achieving high temperature regeneration in the device of desulfurizing agent.
Specific embodiment
Below in conjunction with removing side of the embodiment to Trace Sulfur in a kind of dibutyl phthalate/diisobutyl ester of the invention
Law technology scheme is further elaborated, and embodiment is by taking diisobutyl phthalate (DIBP) as an example.
With industrial goods diisobutyl phthalate (DIBP) that purity is 99.6% as raw material, using present invention process,
Desulphurization reaction, active silica-alumina of the desulfurizing agent for molding, shape are carried out on desulfurization reactor 3 of the desulfurizing agent loadings for 100mL
Can be：Cylinder, butterfly, Herba Trifolii Pratentis or Herba Galii Bungei, in 100～150 DEG C of reaction temperature, reaction pressure 1-3MPa, hydrogen gas
Atmosphere, volume liquid hourly space velocity (LHSV) (in terms of diisobutyl phthalate) 0.1～1h-1Reaction condition under, sulfur content 1- in DIBP
5.0ppm, DIBP purity is not less than 99.5%, plant running 800h, sulfur content still ＜ 5ppm in DIBP.
Embodiment 1
With industrial goods diisobutyl phthalate (DIBP) that purity is 99.6% as raw material, sulfur content 150ppm is adopted
With present invention process, desulphurization reaction is carried out on desulfurization reactor 3 of the desulfurizing agent loadings for 100mL, desulfurizing agent is lived for butterfly
Property aluminium oxide (alumina content 100%), in 110 DEG C of reaction temperature, reaction pressure 1MPa, hydrogen liquid volume ratio 500:1, volume liquid
When air speed (in terms of diisobutyl phthalate) 0.3h-1Reaction condition under, sulfur content 2.5ppm in DIBP, DIBP purity
99.5%.
Embodiment 2
With industrial goods diisobutyl phthalate (DIBP) that purity is 99.6% as raw material, sulfur content 150ppm is adopted
With present invention process, desulphurization reaction is carried out on desulfurization reactor 3 of the desulfurizing agent loadings for 100mL, desulfurizing agent is lived for butterfly
Property sial (alumina content 80%), in 110 DEG C of reaction temperature, reaction pressure 1MPa, hydrogen liquid volume ratio 500:1, during volume liquid
Air speed (in terms of diisobutyl phthalate) 0.3h-1Reaction condition under, sulfur content 3.7ppm in DIBP, DIBP purity
99.5%.
Embodiment 3
After desulfurizing agent adsorption saturation in embodiment 1, regenerate in 500 DEG C, air atmosphere, recovery time 6h, regeneration
Catalyst re-starts absorption desulfurization, with industrial goods diisobutyl phthalate (DIBP) that purity is 99.6% as original
Material, sulfur content 150ppm, in 110 DEG C of reaction temperature, reaction pressure 1MPa, hydrogen liquid volume ratio 500:1, volume liquid hourly space velocity (LHSV) (with
Diisobutyl phthalate meter) 0.3h-1Reaction condition under, sulfur content 2.8ppm in DIBP, DIBP purity 99.5%.
The desulfurization performance that desulfurizing agent repeatedly regenerates in embodiment 1 is shown in Table many regeneration of 1, Jing, and in DIBP, sulfur content is still below
5ppm, meets the requirement of follow-up noble metal hydrogenation catalyst.
The multiple regenerative sulfur binding performance of 1 formed alumina desulfurizing agent of table
Comparative example 1
With industrial goods diisobutyl phthalate (DIBP) that purity is 99.6% as raw material, sulfur content 150ppm is adopted
With present invention process, desulphurization reaction is carried out on desulfurization reactor 3 of the desulfurizing agent loadings for 100mL, desulfurizing agent is cylinder
13X molecular sieves (molecular sieve silica alumina ratio be 5.0), in 100～150 DEG C of reaction temperature, reaction pressure 1MPa, hydrogen liquid volume ratio 500:
1, volume liquid hourly space velocity (LHSV) (in terms of diisobutyl phthalate) 0.3h-1Reaction condition under, sulfur content 7.1ppm in DIBP,
DIBP purity 99.5%.
Comparative example 2
With industrial goods diisobutyl phthalate (DIBP) that purity is 99.6% as raw material, sulfur content 150ppm is adopted
With present invention process, desulphurization reaction is carried out on desulfurization reactor 3 of the desulfurizing agent loadings for 100mL, desulfurizing agent is graininess
Cocoanut active charcoal (specific surface area 1266m2/ g, pore volume 0.97cm3/ g, average pore size 3.5nm), in 100～150 DEG C of reaction temperature,
Reaction pressure 1MPa, hydrogen liquid volume ratio 500:1, volume liquid hourly space velocity (LHSV) (in terms of diisobutyl phthalate) 0.3h-1Reaction
Under the conditions of, sulfur content 15.3ppm in DIBP, DIBP purity 99.5%.
Claims (5)
1. in a kind of dibutyl phthalate/diisobutyl ester Trace Sulfur removal methods, it is characterised in that including following step
Suddenly：
After dibutyl phthalate/diisobutyl ester is mixed with hydrogen, it is heated to reaction temperature entrance and is mounted with desulfurizing agent
Heat-insulating fixed bed reactors carry out desulphurization reaction, and after gained desulfurization, dibutyl phthalate/diisobutyl ester product can be straight
Connect cyclohexanes plasticizer is prepared for hydrogenation reaction；
Ester content in described dibutyl phthalate/diisobutyl ester is in 95wt%～99.9wt%, the content of Trace Sulfur
0-1000ppm；
SiO of the described desulfurizing agent for molding2-Al2O3、SiO2、Al2O3In the mixture of one or more；Total pore volume 0.5-
The hole proportion of 1.0mL/g, wherein more than aperture 10nm is not less than 55%, and specific surface is 200-500cm2/g；
The reaction condition of the desulphurization reaction is：Reaction pressure is 1～3MPa, and reaction temperature is 100～150 DEG C, hydrogen atmosphere,
Hydrogen liquid volume ratio is 100～1000:1, volume liquid hourly space velocity (LHSV) is 0.1～1h-1, in terms of diisobutyl phthalate.
2. removal methods according to claim 1, it is characterised in that the cylindrically shaped of described desulfurizing agent, butterfly,
Herba Trifolii Pratentis or Herba Galii Bungei.
3. removal methods according to claim 1, it is characterised in that described heat-insulating fixed bed reactors are in parallel
Two sections of fixed bed reactors, to realize being individually switched.
4. removal methods according to claim 1, it is characterised in that solid in heat-insulating after described desulfurizing agent adsorption saturation
In fixed bed reactor device or the outer high temperature regeneration of device, regeneration temperature is 450 DEG C～550 DEG C, 4～8h of recovery time.
5. the removal methods described in claim 1 increase for cyclohexanes in the adjacent benzene class plasticizer Hydrogenation of Bronsted acid sulfuric acid catalysis
Application in modeling agent, it is characterised in that the removal methods described in Jing obtain product and can be directly used for hydrogenation reaction preparing hexamethylene
Alkanes plasticizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510868323.7A CN105439865B (en) | 2015-12-01 | 2015-12-01 | The removal methods of Trace Sulfur in a kind of dibutyl phthalate/diisobutyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510868323.7A CN105439865B (en) | 2015-12-01 | 2015-12-01 | The removal methods of Trace Sulfur in a kind of dibutyl phthalate/diisobutyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105439865A CN105439865A (en) | 2016-03-30 |
| CN105439865B true CN105439865B (en) | 2017-03-29 |
Family
ID=55550569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510868323.7A Active CN105439865B (en) | 2015-12-01 | 2015-12-01 | The removal methods of Trace Sulfur in a kind of dibutyl phthalate/diisobutyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105439865B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4163111B2 (en) * | 2001-09-26 | 2008-10-08 | エボニック オクセノ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Phthalic acid alkyl ester mixture with adjusted viscosity |
| CN102219688B (en) * | 2011-05-05 | 2014-03-26 | 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
Also Published As
| Publication number | Publication date |
|---|---|
| CN105439865A (en) | 2016-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103240117B (en) | Gasoline desulfurization catalyst and preparation method thereof and gasoline desulfurization method | |
| CN104383874A (en) | Purification adsorbent based on mesoporous molecular sieve material and preparation method and application of purification adsorbent based on mesoporous molecular sieve material | |
| CN1261533C (en) | Process for adsorption desulfurization of gasoline | |
| KR20090129516A (en) | Process for reducing carbon monoxide in olefin-containing hydrocarbon feedstocks | |
| CN103614178A (en) | Deep desulfurization technology of refinery liquefied petroleum gas | |
| CN102233274B (en) | Catalyst for reducing alkene content in aromatic hydrocarbon, and a preparation method thereof | |
| CN101475430B (en) | Method for purifying ethylene from ethylene-rich gaseous mixture | |
| CN100594064C (en) | Regeneration method of catalyst for producing diphenylamine with phenylamine continuous condensation | |
| CN105439865B (en) | The removal methods of Trace Sulfur in a kind of dibutyl phthalate/diisobutyl ester | |
| CN114395417A (en) | Method for producing aromatic hydrocarbon and higher alcohol by using high-temperature Fischer-Tropsch synthetic oil as raw material | |
| CN109486509B (en) | Adsorption desulfurization catalyst and preparation method thereof | |
| CN109486508B (en) | FCC gasoline adsorption desulfurization method | |
| CN105080476A (en) | Copper and halogen-containing molecular sieve adsorbent and preparation method thereof | |
| CN104017602B (en) | A kind of reformed pre-hydrogenated tops preprocess method | |
| CN109370646B (en) | Catalytic cracking gasoline desulfurization modification method | |
| CN113385187A (en) | Pyrolysis gas deoxidation catalyst and preparation method and application thereof | |
| CN109486523B (en) | FCC gasoline desulfurization modification method | |
| CN103805236B (en) | A kind of adsorbing and desulfurizing catalytic cracking gasoline technique | |
| CN108144642A (en) | A kind of oil hydrogenation HC fuel catalyst and preparation and application | |
| CN110975523A (en) | Method for recovering n-butane in tail gas generated in preparation of maleic anhydride by butane method | |
| CN105732277A (en) | Front-depropanization front-hydrogenation method for C2 fraction | |
| CN108499526A (en) | A kind of preparation and application for removing the adsorbent of impurity in propylene oxide stream | |
| CN218345386U (en) | Device for removing oxygen-containing compounds in Fischer-Tropsch synthetic oil | |
| CN112275311A (en) | Heavy aromatic hydrocarbon lightening catalyst based on VIII group metal elements and preparation method and application thereof | |
| CN109504425B (en) | Gasoline adsorption desulfurization method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| CB02 | Change of applicant information |
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. |
|
| COR | Change of bibliographic data | ||
| TA01 | Transfer of patent application right |
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. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |