CN107778141B - Purification method of 1, 4-butanediol - Google Patents
Purification method of 1, 4-butanediol Download PDFInfo
- Publication number
- CN107778141B CN107778141B CN201610779939.1A CN201610779939A CN107778141B CN 107778141 B CN107778141 B CN 107778141B CN 201610779939 A CN201610779939 A CN 201610779939A CN 107778141 B CN107778141 B CN 107778141B
- Authority
- CN
- China
- Prior art keywords
- butanediol
- resin
- silver
- crude
- catalyst
- 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
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
Abstract
The invention discloses a method for purifying 1, 4-butanediol, which comprises the following steps: contacting crude 1, 4-butanediol containing aldehyde compound and/or acetal compound impurities with a silver-loaded resin catalyst under a hydrogen condition to obtain purified 1, 4-butanediol with the chroma of less than 10 APHA. The method of the invention can purify the crude 1, 4-butanediol containing aldehyde compound and/or acetal compound impurities, and reduce the chroma of the crude 1, 4-butanediol.
Description
Technical Field
The invention relates to a purification method of 1, 4-butanediol.
Background
1, 4-Butanediol (BDO) is an important basic organic chemical and fine chemical raw material, has wide application, and particularly, the derivative of the BDO is a fine chemical product with high added value and is widely used as a solvent, a medicine, a cosmetic, a plasticizer, a curing agent, a pesticide, a rust remover, artificial leather, fiber, an engineering pigment and the like. BDO is also used to make chemical products such as Tetrahydrofuran (THF), gamma-butyrolactone (GBL), and N-methyl pyrollidinone (NMP).
There are about several tens of currently known 1, 4-butanediol synthesis routes, among which Reppe method and maleic anhydride hydrogenation method are industrially high specific gravity. The Reppe method uses acetylene and formaldehyde as raw materials, firstly acetylene and formaldehyde are used for synthesizing 1, 4-butynediol under the action of a copper catalyst, and then the 1, 4-butynediol is hydrogenated to generate 1, 4-butanediol. The commercial implementation of butynediol hydrogenation to butanediol in the known Reppe process is essentially a two-stage process. The specific process for producing 1, 4-butanediol by using 1, 4-butynediol through a two-step method comprises the following steps: the first-stage hydrogenation is carried out in a suspension bed reactor or a fixed bed reactor and respectively adopts Raney Ni, modified Raney Ni or a nickel-aluminum catalyst prepared by a precipitation method, and the second-stage hydrogenation is carried out in the fixed bed reactor and adopts the nickel-aluminum catalyst. The maleic anhydride hydrogenation method is characterized in that maleic anhydride is used as a raw material, low-carbon alcohol esterification and hydrogenation are carried out to obtain 1, 4-butanediol, and low-carbon alcohol is recovered. Currently, 1, 4-butanediol is produced in the market by essentially these two processes.
However, 1, 4-butanediol products produced by either the Reppe process or the maleic anhydride hydrogenation process contain a small amount of by-products, which cause color development of 1, 4-butanediol and affect product quality.
For the Reppe process, it is known that the aldolisation of butanediol to form a large amount of condensed aldehyde and the isomerisation of butenediol to form a large amount of hydroxybutyraldehyde occur in these known hydrogenation processes, whereas the complete separation of 1, 4-butynediol, 1, 4-butenediol and derivatives thereof, for example the acetal of butanediol and the hydroxybutyraldehyde formed by the isomerisation of butenediol, from 1, 4-butanediol by distillation is difficult, but in further polymerisation applications of 1, 4-butanediol it is in most cases important that no incomplete hydrogenation products are present. And the other by-product, namely, the cyclic acetal substance, which is generated in the process of producing 1, 4-butanediol by esterifying and hydrogenating maleic anhydride, which is implemented at present, is 2- (4' -hydroxy butyl oxygen) -tetrahydrofuran with the following formula
Is difficult to avoid, especially in the later stages of operation. It was analyzed that the mechanism of formation of all the products and by-products is not clear, since 1, 4-butanediol is dehydrogenated at 220 ℃ at 150 ℃ to give hydroxybutyraldehyde, which is cyclized to give thermodynamically more stable 2-hydroxytetrahydrofuran, and 2-hydroxytetrahydrofuran is further reacted with 1, 4-butanediol to give 2- (4' -hydroxybutyloxy) -tetrahydrofuran.
Although the amount of 2- (4 '-hydroxybutyloxy) -tetrahydrofuran produced in the hydrogenation reaction process is very small, and is only 0.15-0.2% of the weight of 1, 4-butanediol product, and the normal boiling point of the substance reaches 246 ℃, and the difference between the normal boiling point of the substance and the boiling point of 1, 4-butanediol is about 20 ℃, because 2- (4' -hydroxybutyloxy) -tetrahydrofuran and the product 1, 4-butanediol form the lowest constant boiling substance, the constant boiling point is very close to that of 1, 4-butanediol, and the byproduct is difficult to be separated by simple conventional rectification. Therefore, in the industrial production process, the purity of the 1, 4-butanediol product is ensured to meet the downstream requirement only by losing the yield of the 1, 4-butanediol, so that the waste of the 1, 4-butanediol product is caused, the capacity is reduced, and the economic consideration is unreasonable.
Meanwhile, 2- (4' -hydroxybutyloxy) -tetrahydrofuran is a chromogenic substance, and the presence of very small amounts is disadvantageous for downstream applications using 1, 4-butanediol as a raw material.
In order to solve the problem of the influence of cyclic hemiacetals such as 2- (4 ' -hydroxybutyloxy) -tetrahydrofuran and cyclic holoacetals thereof on the purity of 1, 4-butanediol products, various documents have reported that the formation of 2- (4 ' -hydroxybutyloxy) -tetrahydrofuran is limited, or that irregular rectification is employed, or that the crude 1, 4-butanediol stream is subjected to further reactions to reduce the 2- (4 ' -hydroxybutyloxy) -tetrahydrofuran content.
U.S. Pat. No. 6,87224 describes a process for separating by distillation 1, 4-butanediol and a mixture of at least one 4-hydroxybutyraldehyde, a cyclic hemiacetal and a cyclic peracetal and at least one other alcohol. The process involves distilling the mixture in the presence of a basic compound such as ammonia, an amine, an alkali metal compound or an alkaline earth metal compound. Although this process is somewhat useful for solving the problems of the prior art, it is very costly to operate this process on an industrial scale due to the effect of the basic compound on the equipment.
U.S. Pat. No. 4,4383895 proposes a process for removing color-developing substances from crude 1, 4-butanediol produced by the alkynal process: the crude 1, 4-butanediol is first dehydrated and the reduced water content 1, 4-butanediol is then further rectified to remove enough color-forming substances to produce a colored product in the preparation of the polyester.
Chinese patent CN1216973A proposes a method for converting 2- (4' -hydroxybutyloxy) -tetrahydrofuran, present in minute amounts in the 1, 4-butanediol product stream, into 1, 4-butanediol. Passing a substantially anhydrous stream of 1, 4-butanediol containing a minor amount of the cyclic acetal 2- (4 '-hydroxybutyloxy) -tetrahydrofuran over a hydrogenation catalyst in the liquid phase in the presence of from 0.5% to 5% by weight of water based on the weight of the 1, 4-butanediol feed to reduce from 0.1% to 0.4% by weight of the 2- (4' -hydroxybutyloxy) -tetrahydrofuran in the 1, 4-butanediol stream to less than 0.1%; then the hydrogenated material flow is dehydrated and rectified to obtain the product 1, 4-butanediol.
While these processes are somewhat useful in addressing the problem of the presence of 2- (4' -hydroxybutyloxy) -tetrahydrofuran in the product stream of 1, 4-butanediol, certain deficiencies and disadvantages remain, both in terms of economics and efficiency of the reaction process as a whole. For example, in the method proposed in chinese patent CN1216973A, a large amount of material flow is passed through a solid catalyst in a gas-liquid form, but only 0.1% to 0.4% of the material is converted, and water is in a liquid state during the reaction, which puts high requirements on the performance of the catalyst and the operating conditions, and the reactor structure is complex, increasing the difficulty of actual operation of the plant.
Therefore, there is a need for a process that efficiently and cost effectively solves the problem of separating acetal impurities such as 2- (4' -hydroxybutyloxy) -tetrahydrofuran from a 1, 4-butanediol product stream, and that is easy to operate.
Disclosure of Invention
The invention aims to provide a method for purifying 1, 4-butanediol, which can purify crude 1, 4-butanediol containing aldehyde compound and/or acetal compound impurities and reduce the chroma of the crude 1, 4-butanediol.
In order to achieve the above object, the present invention provides a method for purifying 1, 4-butanediol, the method comprising: contacting crude 1, 4-butanediol containing aldehyde compound and/or acetal compound impurities with a silver-loaded resin catalyst under a hydrogen condition to obtain purified 1, 4-butanediol with the chroma of less than 10 APHA.
Preferably, the purified 1, 4-butanediol has an aldehyde compound and/or acetal compound impurity content of less than 0.06 wt%.
Preferably, the crude 1, 4-butanediol is prepared by the Reppe method and/or the maleic anhydride method.
Preferably, the silver content in the silver-supported resin catalyst is 0.1 to 10% by weight based on the weight of the silver-supported resin catalyst.
Preferably, the resin in the silver-supported resin catalyst is a chelate resin of a cross-linked functional polymer material of a multidentate complex.
Preferably, the chelating resin of the cross-linked functional polymer material of the multi-coordination complex is at least one selected from the group consisting of an amino phosphoric acid resin, a polystyrene resin, a polyacrylic acid resin, a polyvinyl alcohol resin and an iminodiacetic acid-based chelating resin.
Preferably, the conditions of the contacting include: the temperature is normal temperature to 120 ℃, the pressure is normal pressure to 3 MPa, the molar ratio of hydrogen to crude 1, 4-butanediol is (0.1-10), the liquid hourly volume space velocity of the crude 1, 4-butanediol is 1-20 h-1。
Preferably, the aldehyde compound comprises hydroxybutyraldehyde, and the acetal compound comprises 2- (4' -hydroxybutyloxy) -tetrahydrofuran and/or acetal.
The method of the invention can purify the crude 1, 4-butanediol containing aldehyde compound and/or acetal compound impurities, reduce the impurities in the crude 1, 4-butanediol and simultaneously reduce the chroma of the crude 1, 4-butanediol.
The method provided by the invention can be suitable for purifying the crude 1, 4-butanediol prepared by the conventional Reppe method and maleic anhydride method, and is suitable for large-scale popularization.
The catalyst of the method has simple composition, easy preparation and high activity.
The method has the advantages of mild contact conditions, less hydrogen consumption and high liquid hourly volume space velocity, so the purification cost is low and the efficiency is high.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for purifying 1, 4-butanediol, which comprises the following steps: contacting crude 1, 4-butanediol containing aldehyde compound and/or acetal compound impurities with a silver-loaded resin catalyst under a hydrogen condition to obtain purified 1, 4-butanediol with the chroma of less than 10 APHA.
According to the invention, generally speaking, the conventional crude 1, 4-butanediol has an aldehyde compound and/or acetal compound impurity content of about 0.1-0.5 wt% and a color of 20-30 or more, and the purified 1, 4-butanediol preferably has an aldehyde compound and/or acetal compound impurity content of less than 0.06 wt%, and a color of not more than 6 APHA.
According to the present invention, crude 1, 4-butanediol may be prepared by the Reppe process and/or the maleic anhydride process, as is well known to those skilled in the art. The Reppe method may include: acetylene and formaldehyde are used as raw materials, 1, 4-butynediol is firstly synthesized, the 1, 4-butynediol is hydrogenated, and then light and heavy components are removed to obtain crude 1, 4-butanediol.
According to the present invention, the silver-supported resin catalyst refers to a catalyst prepared by supporting a silver component on a resin, the supporting method of the silver component may be a coprecipitation method, an impregnation method, or the like, and the ratio of the silver component to the resin may be determined as needed, for example, the content of silver in the silver-supported resin catalyst is preferably 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the weight of the silver-supported resin catalyst. The resin is well known by those skilled in the art, the invention is not repeated, and the invention is preferably chelate resin, the mechanism of ion adsorption of the chelate resin is that functional atoms on the resin and target ions are subjected to coordination reaction to form a stable structure similar to a small molecule chelate, and the chelate resin is a high-molecular compound which selectively chelates specific ions. Compared with common resin, the chelating resin has stronger binding force with a target object and higher selectivity, is suitable for the adsorption of substances under low concentration, and is suitable for the impurity removal and refining of high-purity products. The resin is more preferably a chelate resin of a cross-linked functional polymer material of a multidentate complex, and the chelate resin of a cross-linked functional polymer material of a multidentate complex is preferably at least one selected from the group consisting of an aminophosphonic acid-based resin, a polystyrenic resin, a polyacrylic resin, a polyvinyl alcohol-based resin and an iminodiacetic acid-based chelate resin, and more preferably an aminophosphonic acid-based and/or iminodiacetic acid-based chelate resin.
According to the invention, crude 1, 4-butanediol is contacted with a catalyst, so that aldehyde compound and/or acetal compound impurities are subjected to hydrogenation reaction with hydrogen under the hydrogen condition, and the contact conditions can comprise: the temperature is normal temperature to 120 ℃, preferably 50-100 ℃, the pressure is normal pressure to 3 MPa, preferably 1-2 MPa, the molar ratio of the hydrogen to the crude 1, 4-butanediol can be (0.1-10):1, preferably (1-5):1, and the liquid hourly space velocity of the crude 1, 4-butanediol can be 1-20 hours-1Preferably 2 to 10 hours-1。
According to the present invention, it is well known to those skilled in the art that in crude 1, 4-butanediol, the aldehyde compound may comprise hydroxybutyraldehyde and the acetal compound may comprise 2- (4' -hydroxybutyloxy) -tetrahydrofuran and/or acetal.
According to the present invention, the contacting may be carried out in various existing reactors, and the present invention is not particularly limited in the form of the reactor, wherein examples of the reactor include, but are not limited to: fixed bed reactors, slurry bed reactors, tank reactors, fluidized bed reactors, and the like, preferably fixed bed reactors.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, the reagents used in the examples of the present invention are commercially available reagents, and the pressures are gauge pressures.
The composition of the crude 1, 4-butanediol and the purified 1, 4-butanediol in the embodiment of the invention is determined by a method in the 1, 4-butanediol for industrial use of national standard GB/T24768 of the people's republic of China, and the chromaticity is determined by a general method for measuring the chromaticity of chemical reagents of the national standard GB 605-1988 of the people's republic of China.
The embodiment of the invention adopts crude 1, 4-butanediol with the same unqualified chroma as a purification raw material, and the specific composition and chroma are shown in Table 1.
Example 1
100 g of amino phosphoric acid chelate resin with the mark of LSC-500 is weighed and dried for 2 hours in vacuum at the temperature of 80 ℃. Preparing 100 ml of silver nitrate water solution with the concentration of 78.7 g/L, adding 100 g of dried LSC-500 chelate resin at normal temperature under the condition of stirring, and aging for 8 hours at 60 ℃ under stirring. Introducing hydrogen into the aged mixture to perform reduction activation for 4 hours, separating the reduction-activated mixture to obtain a solid, and sequentially washing and vacuum-drying the obtained solid at 80 ℃ for 2 hours to obtain the silver-loaded resin catalyst with the silver content of 5 wt%.
A fixed bed reactor was charged with 10 grams of the silver-supported resin catalyst prepared in this example and had a liquid hourly space velocity of 2 hours at a temperature of 80 deg.C, a pressure of 2.0 MPa, and crude 1, 4-butanediol-1And purifying the crude 1, 4-butanediol with unqualified chroma under the condition that the molar ratio of the hydrogen to the crude 1, 4-butanediol is 10:1, and the composition and chroma of the obtained purified 1, 4-butanediol are shown in Table 1.
Example 2
100 g of an iminodiacetic acid-based chelate resin having a trade name of D851 was weighed and dried under vacuum at 80 ℃ for 2 hours. 100 ml of silver nitrate water solution with the concentration of 78.7 g/L is prepared, 100 g of D851 chelating resin is added under the condition of stirring at normal temperature, and the mixture is aged for 8 hours under the condition of stirring at 60 ℃. Introducing hydrogen into the aged mixture to perform reduction activation for 4 hours, separating the reduction-activated mixture to obtain a solid, and sequentially washing and vacuum-drying the obtained solid at 80 ℃ for 2 hours to obtain the silver-loaded resin catalyst with the silver content of 5 wt%.
A fixed bed reactor was charged with 10 grams of the silver-supported resin catalyst prepared in this example and had a liquid hourly space velocity of 2 hours at a temperature of 80 deg.C, a pressure of 1.0 MPa, and crude 1, 4-butanediol-1Hydrogen and crude 1, 4-butaneThe crude 1, 4-butanediol with unacceptable color was purified by treatment at a diol molar ratio of 10:1, and the composition and color of the resulting purified 1, 4-butanediol are shown in Table 1.
Example 3
100 g of polystyrene-based chelate resin with the trade name of S-930 was weighed and dried under vacuum at 80 ℃ for 2 hours. 100 ml of silver nitrate water solution with the concentration of 15.7 g/L is prepared, 100 g of S-930 chelate resin is added under the condition of stirring at normal temperature, and the mixture is aged for 8 hours under the condition of stirring at 60 ℃. Introducing hydrogen into the aged mixture to perform reduction activation for 4 hours, separating the reduction-activated mixture to obtain a solid, and sequentially washing and vacuum-drying the obtained solid at 80 ℃ for 2 hours to obtain the silver-loaded resin catalyst with the silver content of 1 wt%.
A fixed bed reactor was charged with 10 grams of the silver-supported resin catalyst prepared in this example and had a liquid hourly space velocity of 1 hour at 30 deg.C, a pressure of 3.0 MPa, and crude 1, 4-butanediol-1And purifying the crude 1, 4-butanediol with unqualified chroma under the condition that the molar ratio of the hydrogen to the crude 1, 4-butanediol is 10:1 to obtain the purified 1, 4-butanediol with the composition and chroma shown in the table 1.
Example 4
100 g of an iminodiacetic acid-based chelate resin having a trade name of D851 was weighed and dried under vacuum at 80 ℃ for 2 hours. 100 ml of silver nitrate aqueous solution with the concentration of 118.1 g/L is prepared, 100 g of D851 chelating resin is added under the condition of stirring at normal temperature, and the mixture is aged for 8 hours under the condition of stirring at 60 ℃. Introducing hydrogen into the aged mixture to perform reduction activation for 4 hours, separating the reduction-activated mixture to obtain a solid, and sequentially washing and vacuum-drying the obtained solid at 80 ℃ for 2 hours to obtain the silver-loaded resin catalyst with the silver content of 7.5 wt%.
A fixed bed reactor was charged with 10 g of the silver-supported resin catalyst obtained in the example, and the liquid hourly volume space velocity of crude 1, 4-butanediol at 100 ℃ and normal pressure was 15 hours-1The molar ratio of hydrogen to crude 1, 4-butanediol is 10:1, and crude 1, 4-butanediol with unqualified chroma is treatedButanediol was purified and the composition and color of the resulting purified 1, 4-butanediol are shown in Table 1.
Table 1 shows the composition and color of crude 1, 4-butanediol and purified 1, 4-butanediol obtained in examples 1 to 4
Claims (5)
1. A method of purifying 1, 4-butanediol, the method comprising: contacting crude 1, 4-butanediol containing aldehyde compound and acetal compound impurities with a silver-loaded resin catalyst under a hydrogen condition to obtain purified 1, 4-butanediol with the chroma of less than 10 APHA;
the silver-loaded resin catalyst is prepared by loading a silver component on resin, and the loading method of the silver component is an impregnation method;
the resin in the silver-loaded resin catalyst is a chelating resin of a cross-linked functional polymer material of a multi-coordination complex; the chelating resin of the cross-linked functional polymer material of the multi-coordination complex is at least one selected from amino phosphoric acid resin, polystyrene resin, polyacrylic acid resin, polyvinyl alcohol resin and imine diacetic acid chelating resin;
the aldehyde compound comprises hydroxybutyraldehyde, and the acetal compound comprises 2- (4' -hydroxybutyloxy) -tetrahydrofuran and/or acetal.
2. The purification process according to claim 1, wherein the purified 1, 4-butanediol has a content of aldehyde compound and/or acetal compound impurities of less than 0.06 wt.%.
3. The purification process of claim 1, wherein the crude 1, 4-butanediol is prepared by the Reppe process and/or the maleic anhydride process.
4. The purification method according to claim 1, wherein the silver content in the silver-supported resin catalyst is 0.1 to 10% by weight based on the weight of the silver-supported resin catalyst.
5. The purification process of claim 1, wherein the contacting conditions comprise: the temperature is normal temperature to 120 ℃, the pressure is normal pressure to 3 MPa, the molar ratio of hydrogen to crude 1, 4-butanediol is (0.1-10), the liquid hourly volume space velocity of the crude 1, 4-butanediol is 1-20 h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610779939.1A CN107778141B (en) | 2016-08-30 | 2016-08-30 | Purification method of 1, 4-butanediol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610779939.1A CN107778141B (en) | 2016-08-30 | 2016-08-30 | Purification method of 1, 4-butanediol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107778141A CN107778141A (en) | 2018-03-09 |
| CN107778141B true CN107778141B (en) | 2021-08-06 |
Family
ID=61450726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610779939.1A Active CN107778141B (en) | 2016-08-30 | 2016-08-30 | Purification method of 1, 4-butanediol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107778141B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851477A (en) * | 2019-01-04 | 2019-06-07 | 内蒙古东景生物环保科技有限公司 | A kind of 1,4 butanediol compositions |
| CN114436778A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing 1, 4-butanediol by acetal hydrofining |
| CN114436775A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for hydrofining 1, 4-butanediol from acetal-containing crude product |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5349540B2 (en) * | 2010-06-30 | 2013-11-20 | ローム アンド ハース カンパニー | Process for producing heterogeneous catalysts |
| EP2754490A4 (en) * | 2011-09-06 | 2014-12-10 | Sumitomo Bakelite Co | Resin-supported catalyst and method for producing resin-supported catalyst |
| CN105418371A (en) * | 2015-11-10 | 2016-03-23 | 中国石化长城能源化工（宁夏）有限公司 | Catalytic hydrogenation and decoloration method of 1,4-butanediol |
| CN105418367A (en) * | 2015-11-10 | 2016-03-23 | 中国石化长城能源化工（宁夏）有限公司 | 1,4-butanediol decoloration method |
-
2016
- 2016-08-30 CN CN201610779939.1A patent/CN107778141B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107778141A (en) | 2018-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101356166B (en) | Method for preparing 3-hydroxytetrahydrofuran by cyclodehydration | |
| US3000906A (en) | Purification of pivalolactone | |
| KR101223949B1 (en) | Process for the purification of １,４-butanediol | |
| KR101103512B1 (en) | Process for preparing of n-methyl pyrrolidone from 1,4-butanediol | |
| TWI403496B (en) | Process for obtaining ditrimethylolpropane and trimethylolpropane-enriched product streams from the secondary streams of trimethylolpropane preparation | |
| CN107778141B (en) | Purification method of 1, 4-butanediol | |
| JPS61197534A (en) | Method of purifying crude 1,4-butanediol | |
| KR101125853B1 (en) | Process for preparing of n-methyl pyrrolidone | |
| US6403844B1 (en) | Condensed phase catalytic hydrogenation of lactic acid to propylene glycol | |
| US4079068A (en) | Manufacture of tetrahydrofuran from the diacetate of 1,4-butanediol | |
| CN110642676B (en) | Method for producing 1, 2, 4-butanetriol | |
| US4864066A (en) | Preparation of alkanediols from alkynols | |
| CN112739675A (en) | Method for recovering high-quality 3-methyl-but-3-en-1-ol | |
| US2560950A (en) | Production of o-cresol derivatives | |
| US3232996A (en) | Purification of butynediol | |
| US5910612A (en) | Preparation of anhydrous 2-amino-1-methoxypropane | |
| US3184513A (en) | Production of hexamethylene glycol | |
| JP4960546B2 (en) | Purification of crude pyrrolidine | |
| US2657242A (en) | Process of making butane-1, 2, 4-triol | |
| CN111592478B (en) | Method for reducing chroma of pentaerythritol ester | |
| CN109400555B (en) | Process for α -acetyl-gamma-butyrolactone sodium salt free acetamidine hydrochloride | |
| CN109678726B (en) | Method for synthesizing trans-4-methylcyclohexylamine | |
| US3141895A (en) | Process for producing gamma-hydroxybutyronitrile and gamma-butyrolactone | |
| JP4483156B2 (en) | Method for purifying gamma-butyrolactone | |
| CN114716395A (en) | Synthesis method of 2-tert-butoxymethyl tetrahydrofuran |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |