KR20150069478A - Preparing method of lithium phosphate catalyst for dehydration of 2,3-butanediol - Google Patents
Preparing method of lithium phosphate catalyst for dehydration of 2,3-butanediol Download PDFInfo
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- KR20150069478A KR20150069478A KR1020130155927A KR20130155927A KR20150069478A KR 20150069478 A KR20150069478 A KR 20150069478A KR 1020130155927 A KR1020130155927 A KR 1020130155927A KR 20130155927 A KR20130155927 A KR 20130155927A KR 20150069478 A KR20150069478 A KR 20150069478A
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- lithium
- butanediol
- solution
- catalyst
- phosphate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 23
- 229910001386 lithium phosphate Inorganic materials 0.000 title claims abstract description 21
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000018044 dehydration Effects 0.000 title claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- -1 dibasic ammonium phosphate compound Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940116349 dibasic ammonium phosphate Drugs 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 37
- 239000000243 solution Substances 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910013553 LiNO Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920002160 Celluloid Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/12—Alkadienes
- C07C11/16—Alkadienes with four carbon atoms
-
- 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
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/10—Methyl-ethyl ketone
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
본 발명은 2,3-부탄디올의 탈수반응용 리튬포스페이트 촉매의 제조방법에 관한 것으로서, 구체적으로는 리튬포스페이트 촉매의 제조에 사용되는 전구체의 종류 및 전구체 내 리튬 및 인의 몰비를 특정 범위로 함으로써 2,3-부탄디올의 탈수 반응에서 활성도가 높은 촉매를 제조하는 방법에 관한 것이다.
The present invention relates to a process for preparing a lithium phosphate catalyst for the dehydration reaction of 2,3-butanediol. More specifically, the present invention relates to a process for preparing a lithium phosphate catalyst for 2,3- To a process for preparing a catalyst having high activity in the dehydration reaction of 3-butanediol.
2-부탄온, 메틸아세톤 등으로 불리우는 메틸에틸케톤은 증기가 강렬하고 달콤한 냄새가 나는 무색의 액체로, 각종 합성고분자 화합물의 용제, 점착제, 도료, 박리제, 세정제, 인쇄잉크용 용제, 염료용제, 휘발유의 셀룰로이드, 인조가죽, 사진필름 등의 제조 및 유기합성 중간체로 널리 사용되고 있다.Methyl ethyl ketone, called 2-butanone, methyl acetone, etc., is a colorless liquid with a strong and sweet odor. It is used as a solvent for various synthetic polymers, adhesives, paints, exfoliants, cleaners, solvents for printing inks, It is widely used for the production of celluloid of gasoline, artificial leather, photographic film and organic synthesis intermediates.
한편, 1,3-부타디엔은 무색 무취의 가연성 기체로 합성고무의 원료가 되는 매우 중요한 기초유분이다. 석유화학 기초 유분을 원료로 사용하여 1,3-부타디엔을 얻을 수 있는 공업적 방법으로는, 납사를 스팀크래킹하여 생성된 C4 유분으로부터 부타디엔을 추출하는 방법, 그리고 부탄이나 부텐을 탈수소화하는 방법, 부텐을 산화탈수소화하는 방법이 있다.On the other hand, 1,3-butadiene is a colorless odorless combustible gas, which is a very important base oil to be a raw material for synthetic rubber. Industrial methods for obtaining 1,3-butadiene using petroleum chemistry basic oil as a raw material include a method of extracting butadiene from C4 oil produced by steam cracking of naphtha, a method of dehydrogenating butane or butene, There is a method of oxidative dehydrogenation of butene.
이러한 상기 메틸에틸케톤, 1,3-부타디엔을 동시에 합성할 수 있는 방법은 2,3-부탄디올의 탈수반응이 대표적이다.The methyl ethyl ketone and 1,3-butadiene can be simultaneously synthesized by dehydration of 2,3-butanediol.
2,3-부탄디올의 탈수반응은 고온에서 황산 등 강산과 반응시킴으로써 진행할 수 있다. 그러나 이 경우 반응생성물인 메틸에틸케톤, 1.3-부타디엔의 수율이 높지 않다는 문제가 있었다.The dehydration reaction of 2,3-butanediol can proceed by reacting with strong acids such as sulfuric acid at a high temperature. However, in this case, the yield of methyl ethyl ketone and 1,3-butadiene as reaction products was not high.
따라서 반응 수율을 높일 수 있는 촉매의 개발이 시급한 실정이었다.
Therefore, it was urgently required to develop a catalyst capable of increasing the reaction yield.
본 발명의 목적은 상기와 같은 2,3-부탄디올의 탈수반응에 있어서, 반응 생성물인 메틸에틸케톤, 1,3-부타디엔의 수율이 낮다는 문제를 해결하고, 2,3-부탄디올의 탈수 반응에 있어서 생성물의 수율을 높일 수 있는, 2,3-부탄디올의 탈수반응용 리튬포스페이트 촉매의 제조방법을 제공하는데 있다.
An object of the present invention is to solve the problem that the yield of methyl ethyl ketone and 1,3-butadiene, which are reaction products, in the dehydration reaction of 2,3-butanediol is low, And a method for producing a lithium phosphate catalyst for dehydration reaction of 2,3-butanediol which can increase the yield of the product.
상기 목적을 달성하기 위한 본 발명의 일 실시예에 따른 2,3-부탄디올의 탈수반응용 촉매의 제조방법은 (a) 인산염을 포함하는 용액에 나트륨 이온을 함유하는 화합물을 혼합하여 제1용액을 제조하는 단계; (b) 리튬 이온을 함유하는 화합물이 포함된 제2용액을 제조하는 단계; 및 (c) 상기 제1용액과 제2용액을 혼합하여 생성된 침전물을 분리하고, 상기 침전물을 세척, 건조하여 리튬포스페이트 촉매를 제조하는 단계를 포함하는 것을 특징으로 한다.
In order to accomplish the above object, a method for preparing a catalyst for dehydration of 2,3-butanediol according to an embodiment of the present invention comprises the steps of: (a) mixing a solution containing a phosphate with a compound containing sodium ions, Producing; (b) preparing a second solution containing a compound containing lithium ions; And (c) separating the precipitate formed by mixing the first solution and the second solution, and washing and drying the precipitate to prepare a lithium phosphate catalyst.
본 발명에 의해 제조된 촉매는 종래의 리튬포스페이트 촉매에 비하여 미확인결정상의 비율이 적고 안정성이 우수하며, 2,3-부탄디올의 탈수 반응에 이용하는 경우, 2,3-부탄디올의 1,3-부타디엔, 메틸에틸케톤으로의 전환율이 높아져 결과적으로 높은 수율로 상기의 생성물을 수득할 수 있다.
The catalyst prepared according to the present invention has a lower ratio of unidentified crystal phases and superior stability compared to conventional lithium phosphate catalysts. When the catalyst is used for dehydration reaction of 2,3-butanediol, 1,3-butadiene, The conversion to methyl ethyl ketone is increased, and as a result, the above product can be obtained at a high yield.
기타 실시예들의 구체적인 사항들은 이하의 상세한 설명 및 도면에 포함되어 있다.The details of other embodiments are included in the following description and drawings.
본 발명의 이점 및/또는 특징, 그리고 그것들을 달성하는 방법은 후술되어 있는 실시예들 및 도면을 참조하면 명확해질 것이다. 그러나, 본 발명은 이하에서 개시되는 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 것이며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이어서, 본 발명은 청구항의 범주에 의해 정의될 뿐이다.
BRIEF DESCRIPTION OF THE DRAWINGS The advantages and / or features of the present invention and the manner of achieving them will be apparent with reference to the embodiments and drawings described hereinafter. It should be understood, however, that the invention is not limited to the disclosed embodiments, but is capable of many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, The present invention is only defined by the scope of the claims.
이하에서는 본 발명에 따른 2,3-부탄디올의 탈수반응용 촉매 및 이의 제조방법에 대하여 상세히 설명하기로 한다.
Hereinafter, the catalyst for the dehydration reaction of 2,3-butanediol according to the present invention and the production method thereof will be described in detail.
2,3-2,3-
부탄디올의Butanediol
탈수반응용 촉매의 제조방법 Method for preparing catalyst for dehydration reaction
본 발명의 일 실시예에 따른 2,3-부탄디올의 탈수반응용 촉매의 제조방법은 (a) 인산염을 포함하는 용액에 나트륨 이온을 함유하는 화합물을 혼합하여 제1용액을 제조하는 단계; (b) 리튬 이온을 함유하는 화합물이 포함된 제2용액을 제조하는 단계; 및 (c) 상기 제1용액과 제2용액을 혼합하여 생성된 침전물을 분리하고, 상기 침전물을 세척, 건조하여 리튬포스페이트 촉매를 제조하는 단계를 포함하는 것을 특징으로 한다.
The method for preparing a catalyst for dehydration of 2,3-butanediol according to an embodiment of the present invention comprises the steps of: (a) preparing a first solution by mixing a solution containing a phosphate with a compound containing sodium ions; (b) preparing a second solution containing a compound containing lithium ions; And (c) separating the precipitate formed by mixing the first solution and the second solution, and washing and drying the precipitate to prepare a lithium phosphate catalyst.
본 발명에서 상기 인산염을 포함하는 용액은 제2인산암모늄 화합물을 포함할 수 있다. In the present invention, the solution containing the phosphate may include a dibasic ammonium phosphate compound.
상기 인산염을 포함하는 제 1용액에 있어서, 용매는 물일 수 있고, 구체적으로는 증류수일 수 있다.
In the first solution containing the phosphate, the solvent may be water, specifically, distilled water.
본 발명에서 상기 나트륨 이온을 함유하는 화합물은 수산화나트륨일 수 있으며, 본 발명에서 상기 리튬 이온을 함유하는 화합물은 질산리튬일 수 있다.In the present invention, the compound containing sodium ions may be sodium hydroxide, and in the present invention, the compound containing lithium ions may be lithium nitrate.
상기 제2용액에 있어서, 용매는 물일 수 있고, 구체적으로는 증류수일 수 있다. In the second solution, the solvent may be water, specifically, may be distilled water have.
본 발명에서 상기 인산염을 포함하는 용액 내 인(P)과, 리튬 이온 함유 화합물 내 리튬(Li)의 몰비, 즉 Li/P는 0.5~1.5인 것이 바람직하다. Li/P 값이 0.5 미만인 경우에는 촉매의 산성이 염기성에 비해 상대적으로 매우 강하여 부타디엔 생성이 억제된다는 문제가 있고, 1.5를 초과하는 경우에는 과량의 리튬으로 인하여 리튬포스페이트의 생성이 어렵다는 문제가 있다.
In the present invention, the molar ratio of phosphorus (P) in the phosphate-containing solution to lithium (Li) in the lithium ion-containing compound, that is, Li / P is preferably 0.5 to 1.5. When the Li / P value is less than 0.5, there is a problem that the acidity of the catalyst is relatively strong as compared with the basicity, so that the production of butadiene is inhibited. When the Li / P value is more than 1.5, there is a problem that lithium phosphate is difficult to produce due to excessive lithium.
상기 제조된 본 발명의 촉매는 종래의 리튬포스페이트 촉매 대비 미확인 결정상이 현저히 적게 존재하므로, 기존 촉매에 비하여 높은 안정성 확보가 가능하다.
Since the prepared catalyst of the present invention has significantly few unconfirmed crystalline phases compared to the conventional lithium phosphate catalyst, it is possible to secure high stability compared to the conventional catalysts.
따라서, 본 발명에 의하여 제조된 촉매를 2,3-부탄디올의 1,3-부타디엔, 메틸에틸케톤의 생산 반응에 이용하는 경우, 반응 활성도가 높아지고 생산 반응도 높은 안정성을 유지하는 바, 결과적으로 높은 수율로 1,3-부타디엔, 메틸에틸케톤을 수득할 수 있다.
Therefore, when the catalyst prepared according to the present invention is used for the production reaction of 1,3-butadiene and 1,3-butadiene, methyl ethyl ketone increases the reaction activity and maintains high stability in the production reaction. As a result, 1,3-butadiene, and methyl ethyl ketone.
이하, 실시예를 통하여 본 발명의 촉매의 제조방법 및 제조된 촉매를 이용한 2,3-부탄디올의 탈수반응을 더욱 상세하게 설명하나, 하기 실시예는 본 발명을 보다 더 구체적으로 설명하기 위한 예시적인 것으로서, 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the process for preparing the catalyst of the present invention and the dehydration reaction of 2,3-butanediol using the catalyst thus prepared will be described in more detail with reference to the following examples. The following examples are intended to illustrate the present invention in more detail, And the contents of the present invention are not limited to the following examples.
실시예Example
실시예Example 1 One
(NH4)2HPO4 132.06g을 80~100℃, 800 mL 증류수에 첨가하여 인산염 포함 용액을 만들고, 교반중인 상기 인산염 포함 용액에 NaOH 40g을 첨가하고 용해시켜 1시간 동안 교반하여 제1용액을 제조하였다. (NH 4 ) 2 HPO 4 was added to 800 mL of distilled water at 80 to 100 ° C to prepare a phosphate-containing solution. To the phosphate-containing solution under stirring, 40 g of NaOH was added and dissolved and stirred for 1 hour to obtain a first solution .
LiNO3 34.5g을 80~100℃, 200 mL 증류수에 첨가하여 제2용액을 제조하였다.34.5 g of LiNO 3 was added to 200 mL of distilled water at 80 to 100 캜 to prepare a second solution.
상기 제1용액과 제2용액을 혼합한 후 2시간 동안 교반하고, 이후 상온으로 냉각시킨 후 침전물을 걸러내었다. 상기 침전물을 1L의 증류수로 세척한 후, 세척된 침전물을 110℃에서 18시간 충분히 건조시킨 후 500℃에서 2시간 소성하여 리튬포스페이트 촉매를 제조하고, 제조된 촉매를 2,3-부탄디올의 탈수반응에 사용하였다.
The first solution and the second solution were mixed and then stirred for 2 hours. After cooling to room temperature, the precipitate was filtered out. The precipitate was washed with 1 L of distilled water, and the washed precipitate was thoroughly dried at 110 ° C for 18 hours and calcined at 500 ° C for 2 hours to prepare a lithium phosphate catalyst. The prepared catalyst was dehydrated by 2,3-butanediol Lt; / RTI >
실시예Example 2 2
실시예 1과 동일한 방법으로 리튬포스페이트 촉매를 제조하되, LiNO3을 68.95g 사용하였다. 제조된 촉매는 2,3-부탄디올의 탈수반응에 사용하였다.
A lithium phosphate catalyst was prepared in the same manner as in Example 1 except that 68.95 g of LiNO 3 was used. The prepared catalyst was used for the dehydration reaction of 2,3-butanediol.
실시예Example 3 3
실시예 1과 동일한 방법으로 리튬포스페이트 촉매를 제조하되, LiNO3을 91.4g 사용하였다. 제조된 촉매는 2,3-부탄디올의 탈수반응에 사용하였다.
A lithium phosphate catalyst was prepared in the same manner as in Example 1 except that 91.4 g of LiNO 3 was used. The prepared catalyst was used for the dehydration reaction of 2,3-butanediol.
실시예Example 4 4
실시예 1과 동일한 방법으로 리튬포스페이트 촉매를 제조하되, LiNO3을 103.43g 사용하였다. 제조된 촉매는 2,3-부탄디올의 탈수반응에 사용하였다.
A lithium phosphate catalyst was prepared in the same manner as in Example 1 except that 103.43 g of LiNO 3 was used. The prepared catalyst was used for the dehydration reaction of 2,3-butanediol.
비교예Comparative Example 1 One
Na4P2O7·10H2O 44.6g을 100℃, 100mL에 용해시켰다. 상기 용액을 교반 하에서 LiNO3 48.3g이 용해된 400mL, 100℃ 수용액과 섞었다. 2~3 시간 교반 후, 상온으로 냉각시켰다. 냉각후 여과하여 침전물을 얻은 후, 메탄올 혹은 에탄올 용액으로 충분히 세척하여 잔류 염을 제거하였다. 상기 침전물을 110℃에서 18시간 충분히 건조하고, 이 후 500℃에서 2시간 동안 소성하여 촉매을 제조하였다. 제조된 촉매는 2,3-부탄디올의 탈수반응에 사용하였다.
44.6 g of Na 4 P 2 O 7 · 10H 2 O was dissolved in 100 mL of 100 ° C. The solution was mixed with 400 mL of an aqueous solution at 100 캜 in which 48.3 g of LiNO 3 was dissolved under stirring. After stirring for 2 to 3 hours, the mixture was cooled to room temperature. After cooling, the mixture was filtered to obtain a precipitate, which was then sufficiently washed with methanol or an ethanol solution to remove residual salts. The precipitate was sufficiently dried at 110 DEG C for 18 hours, and then calcined at 500 DEG C for 2 hours to prepare a catalyst. The prepared catalyst was used for the dehydration reaction of 2,3-butanediol.
비교예Comparative Example 2 2
Na4P2O7·10H2O 44.6g을 100℃, 100mL에 용해시켰다. 상기 용액을 교반 하에서 LiOH 16.8g이 용해된 400mL, 100℃ 수용액과 섞었다. 2~3 시간 교반 후, 상온으로 냉각시켰다. 냉각후 여과하여 침전물을 얻은 후, 메탄올 혹은 에탄올 용액으로 충분히 세척하여 잔류 염을 제거하였다. 상기 침전물을 110℃에서 18시간 충분히 건조하고, 이 후 500℃에서 2시간 동안 소성하여 촉매을 제조하였다. 제조된 촉매는 2,3-부탄디올의 탈수반응에 사용하였다.
44.6 g of Na 4 P 2 O 7 · 10H 2 O was dissolved in 100 mL of 100 ° C. The solution was mixed with 400 mL of an aqueous solution at 100 캜 in which 16.8 g of LiOH was dissolved under stirring. After stirring for 2 to 3 hours, the mixture was cooled to room temperature. After cooling, the mixture was filtered to obtain a precipitate, which was then sufficiently washed with methanol or an ethanol solution to remove residual salts. The precipitate was sufficiently dried at 110 DEG C for 18 hours, and then calcined at 500 DEG C for 2 hours to prepare a catalyst. The prepared catalyst was used for the dehydration reaction of 2,3-butanediol.
평가 - 제조된 촉매를 이용하여 2,3-Evaluation < RTI ID = 0.0 > - < / RTI &
부탄디올로부터From butandiol
1,3-부타디엔 및 메틸에틸케톤을 제조 Preparation of 1,3-butadiene and methyl ethyl ketone
(1) 제조방법(One) Manufacturing method
먼저, 2,3-부탄디올을 기화시켜 기화물을 얻고, 상기 기화물을 상기 실시예 및 비교예의 리튬포스페이트 촉매와 반응시킴으로써 1,2-부타디엔 및 메틸에틸케톤을 제조하였다. 이 때, 상기 2,3-부탄디올 기화물에 불활성 가스를 혼합하여 혼합물을 형성한 후, 상기 혼합물을 상기 제조된 리튬 포스페이트 담지 촉매와 반응시킬 수도 있다.First, 1,2-butadiene and methyl ethyl ketone were prepared by vaporizing 2,3-butanediol to obtain vaporized product and reacting the vaporized product with the lithium phosphate catalyst of the above-mentioned Examples and Comparative Examples. At this time, an inert gas may be mixed with the 2,3-butanediol vapor to form a mixture, and then the mixture may be reacted with the lithium phosphate-supported catalyst.
구체적으로, 2,3-부탄디올 용액을 펌프를 통해 일정한 속도로 증발 구역에 주입하였다. 상기 증발 구역은 2,3-부탄디올이 완전히 기화될 수 있도록 200~250℃로 유지하였다. 증발 구역에서 기화된 2,3-부탄디올 기화물, 또는 상기 2,3-부탄디올 기화물에 질소, 헬륨 또는 아르곤 가스 등의 불활성 가스가 혼합된 혼합 기체를 스테인리스 스틸 반응기 또는 석영 반응기의 상부에서 하부 쪽으로 공급되어 본 발명의 실시예, 비교예의 촉매가 포함된 촉매 층을 통과시켜 반응을 진행시켰다.
Specifically, a solution of 2,3-butanediol was pumped into the evaporation zone at a constant rate. The evaporation zone was maintained at 200-250 ° C to allow 2,3-butanediol to be completely vaporized. A mixed gas in which a 2,3-butanediol vaporized in the evaporation zone or an inert gas such as nitrogen, helium or argon gas is mixed with the 2,3-butanediol vapor is fed downward from the top of the stainless steel reactor or the quartz reactor And the reaction was carried out through a catalyst layer containing catalysts of Examples and Comparative Examples of the present invention.
(2) 결과(2) result
각 실시예 및 비교예의 촉매를 사용하고 상기 방법에 의하여 수득된 1,3-부타디엔 및 메틸에틸케톤의 전환율 및 비율, 1,3-부타디엔 및 메틸에틸케톤의 수율, 촉매의 안정성을 측정하여 하기 표 1에 나타내었다.
The conversion and ratio of 1,3-butadiene and methyl ethyl ketone obtained by the above methods, the yield of 1,3-butadiene and methyl ethyl ketone, and the stability of the catalyst were measured using the catalysts of the examples and comparative examples, Respectively.
상기 표 1에 나타난 결과로부터, 본 발명의 제조방법에 의해 제조된 촉매를 3-부탄디올의 1,3-부타디엔, 메틸에틸케톤의 생산 반응에 이용하는 경우, 반응 활성도가 높아지고 생산 반응도 높은 안정성을 유지하는 바, 결과적으로 높은 수율로 1,3-부타디엔, 메틸에틸케톤을 수득할 수 있다는 사실을 확인할 수 있었다.
From the results shown in Table 1, it can be seen that when the catalyst prepared by the production method of the present invention is used for the production reaction of 1,3-butadiene and methyl ethyl ketone of 3-butanediol, the reaction activity becomes high, As a result, it was confirmed that 1,3-butadiene and methyl ethyl ketone could be obtained at a high yield.
이상과 같이 본 발명은 비록 한정된 실시예에 의해 설명되었으나, 본 발명은 상기의 실시예에 한정되는 것은 아니며, 이는 본 발명이 속하는 분야에서 통상의 지식을 가진 자라면 이러한 기재로부터 다양한 수정 및 변형이 가능하다. 따라서, 본 발명 사상은 아래에 기재된 특허청구범위에 의해서만 파악되어야 하고, 이의 균등 또는 등가적 변형 모두는 본 발명 사상의 범주에 속한다고 할 것이다.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It is possible. Accordingly, the spirit of the present invention should be understood only in accordance with the following claims, and all equivalents or equivalent variations thereof are included in the scope of the present invention.
Claims (6)
b) 리튬 이온을 함유하는 화합물이 포함된 제2용액을 제조하는 단계; 및
c) 상기 제1용액과 제2용액을 혼합하여 생성된 침전물을 분리하고, 상기 침전물을 세척, 건조하여 리튬포스페이트 촉매를 제조하는 단계;
를 포함하는 2,3-부탄디올의 탈수반응용 리튬포스페이트 촉매의 제조방법.
a) mixing a solution containing a phosphate ion with a compound containing sodium ions to prepare a first solution;
b) preparing a second solution comprising a compound containing lithium ions; And
c) separating the precipitate formed by mixing the first solution and the second solution, washing and drying the precipitate to prepare a lithium phosphate catalyst;
Of the lithium phosphate catalyst for dehydration of 2,3-butanediol.
상기 인산염을 포함하는 용액은 제2인산암모늄 화합물을 포함하는 것을 특징으로 하는 2,3-부탄디올의 탈수반응용 리튬포스페이트 촉매의 제조방법.
The method according to claim 1,
Wherein the solution containing the phosphate comprises a dibasic ammonium phosphate compound. ≪ RTI ID = 0.0 > 11. < / RTI >
상기 나트륨 이온을 함유하는 화합물은 수산화나트륨인 것을 특징으로 하는 2,3-부탄디올의 탈수반응용 리튬포스페이트 촉매의 제조방법.
The method according to claim 1,
Wherein the compound containing sodium ions is sodium hydroxide. ≪ RTI ID = 0.0 > 11. < / RTI >
상기 리튬 이온을 함유하는 화합물은 질산리튬인 것을 특징으로 하는 2,3-부탄디올의 탈수반응용 리튬포스페이트 촉매의 제조방법.
The method according to claim 1,
Wherein the lithium ion-containing compound is lithium nitrate. 2. The process for producing a lithium phosphate catalyst for dehydration of 2,3-butanediol according to claim 1, wherein the compound containing lithium ions is lithium nitrate.
인산염을 포함하는 용액 내 인(P)과, 리튬 이온 함유 화합물 내 리튬(Li)의 몰비는 0.5~1.5인 것을 특징으로 하는 2,3-부탄디올의 탈수반응용 리튬포스페이트 촉매의 제조방법.
The method according to claim 1,
Wherein the molar ratio of phosphorus (P) in the phosphate-containing solution to lithium (Li) in the lithium ion-containing compound is 0.5 to 1.5.
A process for producing 2,3-butadiene and methyl ethyl ketone by applying lithium phosphate produced by the process of claim 1 to a dehydration reaction of 2,3-butanediol.
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| KR20110022214A (en) * | 2009-08-27 | 2011-03-07 | 한국화학연구원 | Calcium phosphate-silica catalyst for dehydration reaction of lactic acid ester and its preparation method and method for preparing acrylic compound from lactic acid ester using same |
| KR20120096125A (en) * | 2011-02-22 | 2012-08-30 | 한국화학연구원 | Fabrication method of 1,3-butadiene and 2-butanone from 2,3-butanediol |
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| KR20110022214A (en) * | 2009-08-27 | 2011-03-07 | 한국화학연구원 | Calcium phosphate-silica catalyst for dehydration reaction of lactic acid ester and its preparation method and method for preparing acrylic compound from lactic acid ester using same |
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