CN105348092A - Oxalate preparation process and application thereof - Google Patents
Oxalate preparation process and application thereof Download PDFInfo
- Publication number
- CN105348092A CN105348092A CN201510631123.XA CN201510631123A CN105348092A CN 105348092 A CN105348092 A CN 105348092A CN 201510631123 A CN201510631123 A CN 201510631123A CN 105348092 A CN105348092 A CN 105348092A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- barkite
- alcohol
- reactor
- water entrainer
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
- C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides an oxalate preparation process and an application thereof. The process comprises: step one, adding oxalic acid, methanol, an ionic liquid and a water-carrying agent into a reactor, performing a reaction in the reactor and ending the reaction when the esterification rate is greater than 98%, distilling the unreacted methanol, the ionic liquid and the water-carrying agent, and reserving a first-stage product; and step two, adding the first-stage product, macromolecule alcohol and the ionic liquid and the water-carrying agent into the reactor, performing a reaction in the reactor, taking a sample from a sampling port, and ending the reaction when the esterification rate is greater than 98%, distilling the unreacted macromolecule alcohol, the ionic liquid and the water-carrying agent to produce oxalate. By synthesizing the oxalate by using a two-step method, the synthesis conversion rate of the product is improved, and the product cost is lowered; the raw materials are simple, the preparation process is convenient to operate, high in automation degree and applicable to large-scale production; the oxalate has an excellent mutual solubility with diesel; the amount of the oxalate added is small, the combustion property of diesel by using a cetane number improver is good, and no nitrogen oxides are generated in combustion, so that the preparation process is environmental-friendly and pollution-free.
Description
Technical field
The invention belongs to technical field of petrochemical industry, be specifically related to a kind of preparation technology and application thereof of barkite.
Background technology
The trend of crude oil heaviness is more and more serious, and cause the output of straight-run diesel oil to reduce, cetane value constantly declines, and diesel oil standard progressively improves for the technical indicator of cetane value.The refinery of various countries generally adopts catalytic cracking secondary processing technique, and to improve the output of lightweight oil, the Application and Development of Catalytic Cracking Technique of Heavy Oil, makes secondary processing diesel oil constituent mass decline, show as cetane value low, and oxidation stability is deteriorated.Therefore, improving diesel cetane-number is problem in the urgent need to address.
The material of cetane number improver can make cetane number improver.At present, improve diesel cetane-number and have following three kinds of methods:
1) allocate use with perfectly straight diesel oil, but straight-run production of diesel oil is limited;
2) method of shortening is utilized to improve diesel cetane-number, but costly, and cost is higher;
3) add cetane number improver, there is cost low, the simple feature of technique.
Therefore, add diesel cetane-number improver and be considered to a kind of economical and effective method to improve cetane value.China starts late for the development of cetane number improver, the positive butyl ester of isobutyl nitrate, nitric acid, isooctyl ester nitrate, cyclohexyl nitrate has been engendered from 1980, wherein isooctyl ester nitrate is universally accepted, the improving agent of these classics is alkyl nitrate ester selected type, oxynitride obnoxious flavour can be produced during burning, increase exhaust emissions, contaminate environment, and in process of production very large corrodibility is produced to equipment.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of this invention is to provide a kind of preparation technology and application thereof of barkite, this barkite and diesel oil have good mutual solubility, improve the effective of diesel combustion performance, addition is few, and raw material sources are extensive, and synthesis technique is simple, safety, do not produce oxynitride during burning, belong to a kind of diesel cetane-number improver of environmental protection.
To achieve these goals, the technical solution used in the present invention is:
A preparation technology for barkite, comprises the following steps:
1) successively oxalic acid, methyl alcohol, ionic liquid, water entrainer are added in reactor, react in a kettle., reactor temperature is 110 ~ 130 DEG C, the control reaction times is 2 ~ 3h, from thief hole sampling, when esterification yield is greater than 98%, reaction terminates, steam unreacted methyl alcohol, ionic liquid and water entrainer, retain primary product;
2) in reactor, add primary product, macromolecular alcohol and ionic liquid in step 1, water entrainer again, react in a kettle., reactor temperature is 120 ~ 140 DEG C, the control reaction times is 2 ~ 3h, from thief hole sampling, when esterification yield is greater than 98%, reaction terminates; Steam unreacted macromolecular alcohol, ionic liquid and water entrainer, this product obtained.
In described reaction mass, the mol ratio of alcohol and oxalic acid is 1.2 ~ 2.0:1.
In described preferred reaction material, the mol ratio of alcohol and oxalic acid is 1.5:1.
Described water entrainer is a kind of or two kinds of mixtures in any proportion in toluene or dimethylbenzene, and consumption is 1 ~ 2 times of oxalic acid quality.
Described macromolecular alcohol is a kind of or two kinds of mixtures in any proportion in butanols or amylalcohol, is the monohydroxy-alcohol of positive structure or isomery.
Described ionic liquid is imidazolium ionic liquid, and consumption is the 0.2wt% of oxalic acid.
The unreacted ionic liquid that step 1 can distill out by the ionic liquid in described step 2, water entrainer, water entrainer recycle.
An application for barkite, this barkite is applied to the raising of diesel cetane-number.
Compared with prior art, the invention has the beneficial effects as follows:
1) adopt the processing step of methanol esterification transesterify again to improve the transformation efficiency of product, also improve yield, both are combined, and namely shorten the reaction times, turn improve productive rate.
2) adopt ionic liquid to do catalysts, improve the transformation efficiency of product, additionally reduce the aftertreatment technology of product, reduce the production cost of product, and catalyzer can repeatedly use, and decreases three waste discharge.
3) products material is simple, and technological operation is convenient, and level of automation is high, is applicable to scale operation.
4) this barkite and diesel oil have good mutual solubility, and addition is few, and the diesel combustion performance using this barkite to improve is good, does not produce oxynitride during burning, environment friendly and pollution-free.
Embodiment
Below in conjunction with embodiment, the present invention is described further, but the solution of the present invention is not limited to following examples.
Embodiment 1
1) successively oxalic acid 181 grams, methyl alcohol 83 grams, 0.36 g of ionic liquid and water entrainer 181 grams are added in reactor, react in a kettle., reactor temperature is 110 ~ 130 DEG C, the control reaction times is 2 ~ 3h, from thief hole sampling, when esterification yield is greater than 98%, reaction terminates, steam unreacted methyl alcohol and ionic liquid water entrainer, retain primary product;
2) in reactor, add primary product, 192 grams, butanols, ionic liquid 0.36 gram and the water entrainer 181 in step 1 again, react in a kettle., reactor temperature is 120 ~ 140 DEG C, the control reaction times is 2 ~ 3h, sample from thief hole, through gas chromatographic analysis, when esterification yield is greater than 98%, reaction terminates; Steam unreacted macromolecular alcohol and ionic liquid, water entrainer, this product obtained.
Embodiment 2
1) successively oxalic acid 181 grams, methyl alcohol 96 grams, 0.36 g of ionic liquid and water entrainer 200 grams are added in reactor, react in a kettle., reactor temperature is 110 ~ 130 DEG C, the control reaction times is 2 ~ 3h, from thief hole sampling, when esterification yield is greater than 98%, reaction terminates, steam unreacted methyl alcohol and ionic liquid water entrainer, retain primary product;
2) in reactor, add primary product, amylalcohol 192 grams, ionic liquid 0.36 gram and the water entrainer 200 in step 1 again, react in a kettle., reactor temperature is 120 ~ 140 DEG C, the control reaction times is 2 ~ 3h, sample from thief hole, through gas chromatographic analysis, when esterification yield is greater than 98%, reaction terminates; Steam unreacted macromolecular alcohol and ionic liquid, water entrainer, this product obtained.
Embodiment 3
1) successively oxalic acid 181 grams, methyl alcohol 115 grams, 0.36 g of ionic liquid and water entrainer 260 grams are added in reactor, react in a kettle., reactor temperature is 110 ~ 130 DEG C, the control reaction times is 2 ~ 3h, from thief hole sampling, when esterification yield is greater than 98%, reaction terminates, steam unreacted methyl alcohol and ionic liquid water entrainer, retain primary product;
2) in reactor, add primary product, 222 grams, butanols, ionic liquid 0.36 gram and the water entrainer 260 in step 1 again, react in a kettle., reactor temperature is 120 ~ 140 DEG C, the control reaction times is 2 ~ 3h, sample from thief hole, through gas chromatographic analysis, when esterification yield is greater than 98%, reaction terminates; Steam unreacted macromolecular alcohol and ionic liquid, water entrainer, this product obtained.
By above gained sample, add diesel oil, test is actual in promoting cetane value effect, and experimental result is in table 1:
As can be seen from upper table example, add the product doing invention research, can be good at playing the effect promoting cetane value, and addition is little, so this product has good cost performance, meet the requirement of higher diesel oil standard, there is wide marketing prospect.
Claims (8)
1. a preparation technology for barkite, is characterized in that, comprises the following steps:
1) successively oxalic acid, methyl alcohol, ionic liquid, water entrainer are added in reactor, react in a kettle., reactor temperature is 110 ~ 130 DEG C, the control reaction times is 2 ~ 3h, from thief hole sampling, when esterification yield is greater than 98%, reaction terminates, steam unreacted methyl alcohol, ionic liquid and water entrainer, retain primary product;
2) in reactor, add primary product, macromolecular alcohol and ionic liquid in step 1, water entrainer again, react in a kettle., reactor temperature is 120 ~ 140 DEG C, the control reaction times is 2 ~ 3h, from thief hole sampling, when esterification yield is greater than 98%, reaction terminates; Steam unreacted macromolecular alcohol, ionic liquid and water entrainer, this product obtained.
2. the preparation technology of a kind of barkite according to claim 1, is characterized in that, in described reaction mass, the mol ratio of alcohol and oxalic acid is 1.2 ~ 2.0:1.
3. the preparation technology of a kind of barkite according to claim 1, is characterized in that, in described preferred reaction material, the mol ratio of alcohol and oxalic acid is 1.5:1.
4. the preparation technology of a kind of barkite according to claim 1, is characterized in that, described water entrainer is a kind of or two kinds of mixtures in any proportion in toluene or dimethylbenzene, and consumption is 1 ~ 2 times of oxalic acid quality.
5. the preparation technology of a kind of barkite according to claim 1, is characterized in that, described macromolecular alcohol is a kind of or two kinds of mixtures in any proportion in butanols or amylalcohol, is the monohydroxy-alcohol of positive structure or isomery.
6. the preparation technology of a kind of barkite according to claim 1, is characterized in that, described ionic liquid is imidazolium ionic liquid, and consumption is the 0.2wt% of oxalic acid.
7. the preparation technology of a kind of barkite according to claim 1, is characterized in that, the unreacted ionic liquid that step 1 can distill out by the ionic liquid in described step 2, water entrainer, water entrainer recycle.
8. an application for barkite, is characterized in that, this barkite is applied to the raising of diesel cetane-number.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510631123.XA CN105348092A (en) | 2015-09-29 | 2015-09-29 | Oxalate preparation process and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510631123.XA CN105348092A (en) | 2015-09-29 | 2015-09-29 | Oxalate preparation process and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105348092A true CN105348092A (en) | 2016-02-24 |
Family
ID=55324180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510631123.XA Pending CN105348092A (en) | 2015-09-29 | 2015-09-29 | Oxalate preparation process and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105348092A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542997A (en) * | 2016-11-14 | 2017-03-29 | 山东汇海医药化工有限公司 | A kind of method that modified graphene catalyzes and synthesizes ethyl oxalate |
| CN110511138A (en) * | 2019-09-24 | 2019-11-29 | 河北广润化工有限公司 | A kind of production technology of symmetrical oxalate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049573A (en) * | 2007-05-15 | 2007-10-10 | 武汉大学 | Ion liquid catalyst of esterification reaction, preparation method and usage |
| CN103524341A (en) * | 2013-08-26 | 2014-01-22 | 中建安装工程有限公司 | Application of Br phi nsted acid ion liquid to preparation of diphenyl oxalate |
-
2015
- 2015-09-29 CN CN201510631123.XA patent/CN105348092A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049573A (en) * | 2007-05-15 | 2007-10-10 | 武汉大学 | Ion liquid catalyst of esterification reaction, preparation method and usage |
| CN103524341A (en) * | 2013-08-26 | 2014-01-22 | 中建安装工程有限公司 | Application of Br phi nsted acid ion liquid to preparation of diphenyl oxalate |
Non-Patent Citations (1)
| Title |
|---|
| 白云波: "柴油十六烷值改进剂的评价与应用", 《精细石油化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542997A (en) * | 2016-11-14 | 2017-03-29 | 山东汇海医药化工有限公司 | A kind of method that modified graphene catalyzes and synthesizes ethyl oxalate |
| CN106542997B (en) * | 2016-11-14 | 2019-04-16 | 山东汇海医药化工有限公司 | A kind of method that modified graphene catalyzes and synthesizes diethy-aceto oxalate |
| CN110511138A (en) * | 2019-09-24 | 2019-11-29 | 河北广润化工有限公司 | A kind of production technology of symmetrical oxalate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103724201B (en) | The method of levulinate is prepared in the direct alcoholysis of a kind of catalysis biomass sugar | |
| CN104725229B (en) | The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate | |
| CN104959154B (en) | A kind of method for preparing the catalyst of levulinate and levulinate being prepared with it | |
| CN104725230B (en) | The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate | |
| CN106495105B (en) | A method of synthesis nanometer selenium material | |
| CN105728018A (en) | ZSM-5 zeolite catalyst for alkylation of benzene and methanol, preparation method and application thereof | |
| CN105348092A (en) | Oxalate preparation process and application thereof | |
| CN104190401A (en) | Molybdenum-based composite metal oxide catalyst for synthesizing propenyl alcohol by glycerol and preparation method of molybdenum-based composite metal oxide catalyst | |
| CN103342638A (en) | Preparation method of dibutyl succinate | |
| CN111135867B (en) | Metal organic iron complex, polyacid and titanium-silicon molecular sieve composite catalyst and preparation method thereof | |
| CN103566933B (en) | A kind of acetate preparation of ethanol by hydrogenating catalyst and preparation method thereof | |
| CN104399529A (en) | Alkadiene selective hydrogenation catalyst as well as preparation method and application thereof | |
| EP2810928B1 (en) | A method for synthesizing polyoxymethylene dimethyl ethers | |
| CN115449363A (en) | Preparation method of quaternary ammonium salt type high-temperature acidizing corrosion inhibitor | |
| CN108250056B (en) | Catalytic synthesis method of benzaldehyde | |
| CN103420791A (en) | Method for ethanol preparation through synthesis gas hydrogenation | |
| CN104962312B (en) | Application of 1-butyl-2, 3, 5-trimethylpyrazole tetrafluoroborate in removing organic nitrides in diesel oil | |
| CN103695053B (en) | A kind of synthetic method of diesel cetane-number improver | |
| CN103571538B (en) | The method reducing the acid corrosion of oil | |
| CN104693023B (en) | A kind of method that biomass sugar prepares levulinate | |
| CN110078687A (en) | A kind of preparation method of 2- methyltetrahydrofuran | |
| CN109364923A (en) | Copper-based water-fast catalyst M-Cu/SiO2Preparation method and application method | |
| CN104120039A (en) | Method for preparing fatty acid methyl ester through multi-stage ester exchange | |
| CN103420790B (en) | Method for ethanol preparation through oxygen-containing C2 compound hydrogenation | |
| CN112724017B (en) | Method for synthesizing asymmetric organic carbonate at room temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160224 |